Professional Documents
Culture Documents
Marine Oils With Particular Reference To Those of Canada
Marine Oils With Particular Reference To Those of Canada
MARINE OILS
WITH PARTICULAR REFERENCE
TO THOSE OF CANADA
BULLETIN NO., 89i
F Ti-/E PISS R _r E
Marine Oils
With Particular Reference to
Those of Canada
Foreword by
R. E. WALKER '
Printed in Canada by
University of Toronto Press
for the
Fisheries Research Board of Canada
Foréwoid: ,
.
.
.
IN ,1933 this Board (then tile Biological Board of Canada) published a 150-
page Bulletin, No. 37,. entitled "The 'Industrial Chemistry of Fish Oils with
Particular Reference to those of British Columbia" by H. N. Brocldesby and
0: F. Denstedt, chemists on the staff of the Pacific Fisheries Expérimental Station
of the Board.- .
In the Foreword to that Bulletin, the late Mr. J. J. Cowie, then Seeretary T
. great deal. of useful 'research TreasuofthBd,pineuatwhl
on British Columbia fish oils had been carried out at this Station (then in
information had not been made so available to the Princ.eRupt,BC)h
industry as it should be in view . of the great increaSe. in the output of British
Columbia fish oils and ,the need for finding new and wider outlets for them., It
had been felt . that a résumé and dikussion Of what had been done and was •
'being done through research towards widening the industrial uses of fish oils
woUld be of value not only to those engaged in their production, but to users
of the various kinds of oils in manufacturing processes' and in animal, feeds. With
this end in view, the authors put together much of the scattered information con-
tained in the literature on these subjects, in addition to the results .of their own -
researches, and Mr. Cowie prognosticated that the, industries on both cbasts ,of
Canada would find the Bulletin not only informative but of real-economic value.
Bulletin 37 was well received and served its purpose for' several years.
However, growing diversification of the types of marine animal oils produced
in Canada and elsewhere, as well as rapid advànces in the chémistry and •
vi
Preface .
As POINTED OUT in the Foreword, the gen,esis of this present Bulletin was Bul-
letin No. 37, written by H. N. Brocldesby and O. F. Denstedt of this Station
and published by this Board in 1933 to present in collected .form 'various data
of particular interest to preducers and processors of British Columbia fish- oils
and to users of fish oils in general.
When- it was decided several years later to prepare a more extensive Bul-
letin on' marine oils, Dr. Denstedt had meanwhile resigned from the Board's
employ. Dr. Brocklesby therefore undertook to act as Editor of the new Bulletin.
Numerous topics treated in Bulletin 37 were expanded; additional topics, in-
cluding marine mammal oils, were introduced; also, marine oils from the Cana-
dian_Atlantle coast were covered more fully than in the earlier Bulletin. Himself
a principal contributor, Dr. Brocklesby was assisted in the writing and editing
by seven, other members of the Station's staff at that time.
The compilation was published by the Board in 1941 as Bulletin 59, and in
addition to reviewing pertinent literature to the end of 1939 it in:chided results
of -considerable hitherto unpunished original work on Canadian marine oils
carried out at the Board's Atlantic and P.acific Stations.'
A continued demand for Bulletin 59 indicated the necessity of either re;-
piinting it or preparing a new Bulletin to incœporate some of the rapidly accu-
mulating new information on marine oils and -their uses. Dr. Brocklesby had:in
the meantime left' the Station's staff, and of his seven collaborators for Bul-
letin 59, only three, Drs. Bailey, Carter and Swain, were still available. A new
edition• seemed preferable to reprinting, and Dr. Bailey undertook the present
revision.
This revision is modelled largely on the previous edition, -though a' number
Of alteratiens and reauangements have been made. \ Section 11 dealing with
changes in the oils . of frozen, dried, salted, smoked, and canned fish, also of fish
meals, has been deleted as such, but much of the pertinent information has beeri
retained under other appropriate headings. Two new chapters have- been added:
Chapter 11 to describe the significance .of analytical Values for the variable and
s characteristic factors of marine oils, and Chapter 12 to list various countries'
specifications for medicinal, edible, and industrial oils.
While the revision was under way, four important developmentS occurred
that necessitated going back over much of what had been prepared, to give à
new perspective to the subject matter indicated by the new title. These de-
velopments were:
I (a) Establishment of the commercial availability of synthetic Vitamin D,
phis growing commercial development, of synthetic vitamin A, the'two vitamins
hitherto supplied principally through the medium of. fish oils. However, the
sections dealing with vitamins A and D in such oils haveS been retained with
iiew data added; for, despite the fact that the natural vitamin D in fish oils used
vii
for feed purposes is now principally considered as. a bonus to, the synthetic
vitamin D added, and synthetic vitamin A is available at a cost.ôf 15 cents per
million U.S.P. units (December, 1951) as compared with 55 cénts when it first
becarne. commercially available in 1949, the natural vitamins continue to be of
importance in the medicinal field.
(b) Failure of the British Columbia pilchard run, to materialize in com-
mercial quantities since 1947. In Bulletin. 59 man), of -the examples of production,
processing and utilization of a fish oil used British .Colnmbiâ pilchard oil as a
type of drying oil that had particular properties making it very, suitable for
numerous interesting uses. A statement dated Decembér, 1950, from the Board's
Pacific Biological Station presaged that no commercial pilchard run could be
expected during 1951 and 1952, although an eventual recurrence of the runs
was not excluded. In the present Bulletin much of the earlier information on
pilchard oil is rétained, but emphasis has been shifted in many cases to herring
oil presently in plentiful supply.
(c) The re-institution in 1948 of the whaling industry of British Columbia,
after.a lapse of several years.
(d) On March 81, 1949, Newfoundland became thetenthi province of
Canada. Much of the manuscript for the present Bulletin had been prepared..by
that time, and although it was not possible to secure comparative data for New-
foundland marine oils for inclusion in all tables dealing with production of
Canadian : oils, many data, pertaining to Newfoundland oils were inserted in
the proof of this Bulletin in order to adhere to this new significance for its title. .
Hence of the some 490 references in this. present Bullètin, about 225 are to
information accruing since Bulletin 59 was published in 1941. Pertinent litera-
ture has been reviewed to the end of 1950, and a few selected references through
1951 have been added to the proof.
Acknowledgment to all persons kindly supplying information would form
too lengthy a list for inclusion here; their helpfulness must be acknowledged as
a whole. Some specific cases are indicated in notes under certain illustrations.
Credit is also due, to Miss Irene Porter, technical assistant to I Dr. Bailey, who
performed many valuable. duties in compiling tables, arranging manuscript,
and checking. proof; and to Miss Phyllis Tweedale and others who assisted in
the typing of manuscript. Dr. Brocklesby; editor of the former edition, kindly
read the-typescript and offered valuable suggestions.
It. is the unfortunate duty of the writer of this preface to record that, Dr.
Basil E. Bailey unexpectedly passed away'before seeing the results of his labours
in printed form. He had checked the first proof, and completed his share of the
indexing. Thé writer and Dr. L. A. Swain weré confronted with carrying out the
final details of preparation for publication without the assistance of Dr. Bailey
who was instrumental in planning the present edition.
898 Richards Street NEAL M. Cnaama
Vancouver, B.C. Director, Paci fic Fisheries
December, 1951 ,Experim6ital Station
viii
Contents
, FonEWoren . . , v
'
PREFACE . VII .
' 1. , GENERAL CHEMISTRY 6F MARINE OILS, AND FATS '3
L •General definitions
,
, 3
II. Chemical définitions , ' 4
III. Isomerism . 12 .
IV. _ Miscellaneous definitions 15 ,
2. NATURE OF COMPONENT FATTY ACIDS AND COMPOSITION OF MARINE OILS ' 18
1
I.
Structure and properties of fatty acids ' 18
' (a) Physical properties 18
' • (b) Chemical properties ' • . 20 s
. ,
_ (c) Salts of the fatty.acids • . . 21 .
• (d) Properties of individual fatty acids --. 22
II. Occurrence and composition of marine animal oils . 26 ;
III. Factors influencing the composition and quantity of oils in fish '- 32
(a) Species ,
.
(b) Food •
. (c) Spawning cycle and feeding habits .• \ 39
(d) Temperature • • 43
3. VITAMINS AND OTHER NON-FAT COMPONENTS OF MARINE OILS . 46 •
' - I. Vitamins • ' , 46
, (a) Properties of vitamin A . 46 .
' (b) Properties of vitamin D ' . . • - . 54 -
(c) Methods of concentrating vitamins A and D 58
(d) Canadian sources of vitamins A and D. 60 .'
' II. Pigments 78 '
. (a) Natural pigments 78 -
(b) Properties of pigments found in fish oils _ 79 '
(c), Colour development during preparation and , storage of oil ' ' 81
' (cl) Removal of colour ,from fish oils 83
• . III. , Other non-fat components '. 84 .
• , (a) Sterols . . 84. .
,
(b) Glyceryl ethers , ' 87 '
\ (c) Phospholipides . .89
(d) Hydrocarbons 90
,. (e) Waxes and fatty alcohols ' , , . ', 93
4. METABOLISM OF FATS , . • , •• 98 .
I. Processes of fat metabolism 98
II. Effect of dietary fat ' ' 101
. III. Essential fatty acids 102
,
. IV. Alleged toxic factor in fish oils 103
V. Effect of rancidity 104
5. CHEMICAL REACTIONS AND PHYSICAL PROPERTIES OF FATS AND OILS 107
L Chemical reactions 107
(a) Hydrolysis and saponification • 107
, (b) Interesterification ' 110
-•■
(c) Hydrogenation , 114
(d) Oxidation 119
,
(e) Polymerization 124
(f) Condensation - 129
(g) Sulphation and sulphonation 130
(h) Sulphurization 133
(i) Halogenation 136
(1) Hydroxylation 138'
(k) Elaidinization 140
(1) Conjugation 142
(m) Formation .of nitrogen derivatives 143
IL Physical Properties 145
(a) Specific gravity and density 145
(b) Coefficient of cubic expansion 147
(c) IVIelting point 151
(d) Freezing point 154
(e) Titre point 155
(f) Boiling point and effect of reduced pressure , 157
(g) Refractive index 159
(h) Viscosity 161
(i) Solubility 163
(j) Surface tension 164
6. DETERIORATIVE CHANGES IN MARINE OILS 168
/ (a) Development of free fatty acids 168
(b) Oxidative rancidity 170
(c) Flavour reversion 173
(cl) Antioxidants 174
(e) Stabilization by means other than antioxidants 178
7. PRODUCTION OF MARINE OILS 180
L Fish liver oils 180
(a) Fish livers of high oil content 180
(b) Fish livers of low oil content 195
II. Fish viscera oils 198
HI. Whole fish oils and fish offal oils 199
(a) Cooking and skimming 199
(b) Batch-type pressure extractors 200
(c) Continuous-system pressure extractors • 201
(d) Centrifugal methods for the production of oil and meal 210
IV. Marine mammal oils 212
(a) Whale oils 212'
(b) Seal oil 214
8. REFINING AND PROCESSING 0,F MARINE OILS 215
I. Refining 215
(a) Removal of free fatty acids 215
(b) Cold clearing 220
(c) Bleaching 233
(d) Deodorization • 238
II. Processing 241
(a) Hydrolysis and saponification 241
(b) Hydrogenation 247
(c) Oxidation 249
(d) Bodying oils with heat 251
(e) Sulphation and sulphonation 254
(f) Sulphurization 258
(g) Fractionation 263
9. COMMERCIAL UTILIZATION OF MARINE OILS 273
I. In nutrition - 273
(a) Humhn foods 273
(b) Medicinal use 277
(c) Feeding oils 279
(d) Vitamins A and D stabilities on dry carriers 282
e) Water dispersions of vitamins ,A. and D 284
II. In industry 286
(a) Soaps and other detergents 286
(b) Paints and varnishes 289
(c) Floor coverings and oilcloth 293
.(c1) Oiled fabrics and sip-dial. materials 296
(e) Printing inks ,
297'
(f) Core oils 298
(g) Rubber manufacture 300
(h) Lubricants 302
(i) Metal-treating oils , 305
(j) Insecticides, etc. 306 ,
(k) Leather • 307
(1) Alkyd resins '308
(m) Miscellaneous uses 309
10. PROPERTIES OF SOME CANADIAN MARINE OILS • 312
I. Fish oils produced commercially 312
(a) Herring oil 812
(b) Pilchard oil 316
(c) Salmon oils 320
(d) Dogfish (grayfish) oils 327
(e) Halibut oils 328
(f) Cod liver oil and cod oil S 331
(g) Gray cod oils 335.
(h) Lingcod oils 336
(i) Black cod oils 337
(1) Red and rock cod'(rock-fish) oils 337
(k) Hake liver oil - 338
(1) Haddock liver oil 339
(n2,) Pollack liver oil • 340
(n) Shark- (other than dogfish) liver oils r - 340
(o) Radish liver oil 342
.‘
(p) Skate liver oils 343
(q) Swordfish oils 343
(r) Tuna oils 343
(s) Anchovy oil 344
II. Fish oils not commonly produced commercially 845.
(a) Mackerel oils 5
345
S
(b) Shad oils 346
(c) Eulachon oil 346
(d) Miscellaneous oils 346
xi
III. Oils of marine mammals ........... ....:............ ......... ...................... ........ ........................... 347
(a) Cetacea ............. ................................................ .................................................... 347
(b) Pinnipedia ......................... :.............. ..................................................................... 355 ,
11. SIGNIFICANCE OF ANALYTICAL VALUES ............................................................................... 359
xii
(e) Herring, sardine, shark, cod, pollack and other fish . oi l
(including calamary oil) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .: . . . . . . . . . . . . .. . . . : . . . . .. : . . .r . . . . 387
M Whale, dolphin, seal and other marine mammal oi l
(oil from Antarctic whale is not included) . . . . . . . . . . . . . :. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : ... . . . . . . . . 387
I1 . New Zealand . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... ... . . . . . . . . . . . . . 388
(a) Blended oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . 388
(b) Concentrated blended oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . : . . . . . . . . . . . . . . . . . . . . . 388
(C) Vitamin A and D concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
(d) Fish liver oils (other than groper and ling liver oils, blended oils, an d
vitamin concentrates) which conform to the requiremeints of the British
Pharmacopoeia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . ' 389
(e) Shark liver oil . . . . . . . . . . . . . . . . . : . . . . . . . .: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 9
Y . Norway . . . . . . . . . . . .. . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . 389
(a) Medicinal cod liver oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . :. . . . . . . . . . . . . . .ï . . . . . . . . . . . . . . . . : . . 389 .
.
( b ) Whale oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . 391
1I . South Africa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .r . . . . : . . . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . : . . . . . . : .: 392
(a) Cod liver oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . . . : . .398
(b) Horse mackerel ( inaasbanker ) oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . 393
YII. Sweden . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . .. 393
XIII . United States of America . . . . . . . . . . . . . . . . . . . . . . . ï . . . . . . . . . > . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . . . :~. . . . . . . . . . . . . . . . . . . . . . . 393
(a) Cod liver oil . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 3
(b) Non-destearinated cod liver oil . . . . . . . . . . . ...... . . ...... . . ...... . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
(c) Halibut liver oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . .. 395
(d) Oleovitamin A-natural vitamin A in oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . . ... ... . . . . 395
(e) Burhot liver oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . :. . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396 ' .
(f) Percomorph liver oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
(g) Shark liver oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . : 397'
.
(h) Feeding oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
, (i) Sperm oil . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . . . . . . . . . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . ., . . . . . . . . . . . . . . . . . . 39 9 .
(1) Oleovitamin A and D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . . . . . . . . 399
INDEX . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . . . . . . : . . . . . . . . . . . . . . . . . . ;'40 1
liii
MARINE OILS
WITH PARTICULAR REFERENCE
TO THOSE OF CANADA
(
CHAP'TER ONE
I. GENERAL DEFINITIONS
, Marine animal oils and fats are not chemically homogeneous materials in the
natural state. Each is a mixture of many organic chemical substances, consisting
chiefly of various liquid or solid representatives of a class of chemical compounds
that includes all pure fats and fatty oils. Unfortunately the word oi/ is applied
not -only to the true fatty oils, but also to at least two other classes of quite unre-
lated chemical substances: the petroleum (paraffin) oils, and the "non-drying"
_ ,‘
"essential" or aromatic" oils of the vegetable kingdom. Fatty oils are merely fats
that happen to be liquid at ordinary room temperatures. In industrial practice the
distinction between an oil and a fat is usually made by considering their physical
condition at a temperature of about 60°F. (15.5°C.); hence marine animal fats
and oi/s may be considered as synonymous terms for most pm-poses.
Stearine is an alternate, general term for the solid or semi-solid fats that
separate from a fatty oil upon cooling. Since, as mentioned above, marine animal
oils consist of mixtures of many individual fatty oils, the process of stearine
separation takes place in stages during cooling. The amount of stearine that
separates at any given temperature will depend on the melting points of the fats
constituting the oil. Some oils, such as raw herring oil, may contain an appre-
ciable'amount of stearine at temperatures well above 60°F., while other raw oils,
such as porpoise jaw oil, will not deposit stearine until the temPerature has fallen
considerably / below 60°F. Since the term stearine will be used extensively
throughout this Bulletin, it is desirable to emphasize that it must not be confused
with the word stearin that denotes one particular, chemically homogeneous fat.
Stearin itself may be one of the constituents of the stearine separating from cer-
tain marine oils upon cooling.
3
Certain substances that are fat-like in physical nature though not necessarily
chemically_ relaùed to fats may occur associated with the fat or other components
in various marine animal tissues. These substances include pigments (in most of
the oils), hydrocarbOns (particularly in shark liver oils) and' waxes (restricted
principally to whale oils); vitamins A and D either in the free state or combined
with fatty acids; also fatty acid compounds with sterols, phosphatides and
glyceryl ethers. Because of their solubility.in fats, they will appear in various pro-
portions in the oils recovered from such tissues. They are described and discussed
more fully in Chapter 3 and eliewhere. Small proportions of free fatty acids and
glycerol (Chapter 5) and oxidation products due to incipient breakdown of the
oil ( Chapter 6) may .also be present. Water is slightly soluble in fatty oils and
under some circumstances may occur in appreciable amounts as a colloidal sus-
pension that does not readily settle out from commercial marine oils on standing.
to the valency. An atom of hydrogen invariably has only one centre of attraction
4
or arm, which may be represented by H-, indicating a valency of one, or mono-
valency. An oxygen atom is divalent and is represented by -0-- or O=. An
example of a trivalent atom is that of nitrogen (-N =) although it can also have
a valency of five. Carbon atoms are tetravalent and for graphical purposes are
variously represented thus:
I
-c- =C= C= C
I _
Generally speaking, when atoms of two different elements unite, their vàlëncies
must be mutually satisfied. Thus. a monovalent atom may unite with one other
like or unlike monovalent atom ( H- + -H to give H-H or H2 ) ; a divalent
atom may unite with two monovalent atoms ( H- + -0- + -H to give H-0-H
or H20 ) , with one like or unlike divalent atom as in 0=0 (oxygen, 02) and
Ca=O (calcium oxide or quicklime, CaO), or with two like or unlike atoms of
valency two or more, as in the following combinations:
one remaining unoccupied valence arm and as such does not represent an actual
chemical compound, but is known as an organic radical. The condensed formula
for the example shown is variously written as CH3.CH2.CH2.CH2.CH2—,
where n = 5, CH3 ( CH2 ) 4-, or CH3 ( CH2 ),e--- where n = 4. The
formula for an organic radical is often abbreviated to the letter R. If the
unoccupied valence arm of the generalized radical C.112. 4.1— is satisfied by a
terminal monovalent atom or group of atoms, the resulting actual chemical com-
pounds (e.g., C„H2„+1—H, the hydrocarbons ) have physical and chemical proper-
ties depending on the value of n. By giving n successive values of 1,'2, 3, 4, etc.,
the compounds represente d by the resulting formulae will exhibit definite grada-
tions in physical and chemical properties and are said to form a homologous series.
Thus, there are homologous series of hydrocarbons, fatty acids, fatty alcohols, etc.
The physical property of "fattiness" or "oiliness" does not become evident in these
,acids and alcohols until n has a value of 8 or more. Expressions such as "C16 acid"
or "C18 alcohol" frequently used in this Bulletin indicate the total number of car-
bon atoms in the chain composing the molecule of the compound. This is a con-
venient way of referring to a fatty acid, or alcohol that has no simple name; their
systematic names are mentioned later.
Of the many classes of chemical compounds into which a carbon atom chain
•enters as a radical, only a few have a direct bearing on the chemical constitution
of marine animal oils. These are now briefly described.
"di-"=2, "tri-"=3, etc.) indicates the presence of two or more double bonds,,
and a suffix denotes the chemical nature of the compound. Acids are designated
by the suffix "-oic":
Stearic acid: octadec-an-oic acid •
—CH—CH=CH—CH-
+ —÷.. 1 I
Br Br Br Br
Alcohols, in the chemical sense, are chdracterized by one (or more) of the
11
1 •I I
groupings — —O—H, H — —O—H, —C—O—H giving rise to the three general
1 I I
H
types:
H ,R -
• R—C-0—H R—C—O—H
• H .
Primary Secondary Tertiary
alcohol, alcohol, alcohol,
R.CH2OH RR.CHOH RRR.COH
The term fatty alcohols is understood to mean primary alcohols having eight
or more carbon atoms in the chain.
There may be more than one alcohol group per molecule, as exemplified by
the most important alcohol in the chemistry of oils, namely glycerol (glycerin,
CILOH
1
glycerine).. Glycerol has the formula CHOH and is thus a chain of three carbon
CH2OH
atoms forming the basis for thr •e alcohol groups, one primary group at each end
and a secondary group in the centre.
The —011 part of alcohol groups is termed hydroxyl and exhibits a marked
tendency to combine with the hydrogen of the carboxyl group (—COOH) of
fatty acids. (See Esters below.)
0
H
Aldehydes are characterized by the grouping —C—H (usually abbreviated,
to —CHO), known as the aldehyde group. Aldehydes are not usually found in
fats, .but may be produced..when rancidity
. occurs (page 173).
0
I II I
Ketones are characterized by the grouping —C—C—C— and like aldehydes,
1 1
are not usually found in fats but are produced therefrom during development
of certain types of rancidity.
9
(b) COMPOUNDS RESULTING FROM UNION OF CARBON CHAIN DERIVATIVES
Esters represent by far the most important type of compound present in fish
(and marine animal) fats and oils since all pure fats, fatty oils and true waxes
are esters. They result from the chemical union of fatty acids with alcohols:
R—CH2-0H ± H- 0 —CO—R -->- R—CH 2-0—CO—R H—O—H
Alcohol Fatty acid Ester Water
The hydroxyl (-0H) of the alcohol group unites with the reactive hydrogen
(H—) of the carboxyl group of the acid to form water, leaving the remainders
(R—CH2— and —0—CO—R) of the alcohol and acid molecules united to form
the ester. The methyl esters of-fatty acids used in the separation and the iden-
tification of fatty acids from fats are thus prepared:
C17H33C00H CH3OH C17H33C00CH3 + H20
Oleic acid Methyl alcohol Methyl oleate Water
The number of alcohol groups per molecule of alcohol determines how
many molecules of fatty acids can combine with that alcohol molecule. VVhen
alcohols containing only one alcohol group unite with a molecule of a fatty acid
the resultant esters such as the above two examples are termed mono-esters, and
when certain long-chain alcohols and acids are involved, special mono-esters,
called .waxes result; e.g., CH3 ( CH2 )„COO ( C1-1 2 ) 13CH8, cetyl myristate, a wax
found in spermaceti. When the alcohol glycerol, containing three alcohol groups,
combines with fatty acids the resulting tri-esters are termed glycerides, a general
chemical term for fats and fatty oils:
cH2-0H II—O—00— ( CH 2 ) nCH3 CH2-0—00— ( CH 2 ) nCH3
t
of monoglycerides and diglycerides is doubtful and simple triglycerides are
probably uncommon. By far the larger numbe of glycerides present belong to
the rnixed triglyceride type.
MONOGLYCERIDES
CH.,O.CO.R i CH 2011 Ç11 20.CO.R., ÇlloOH ÇII20.CO.R„ ?0H
él1011 .. ÇHO.COR I CHOH ÇHO.CO.R 2 CHOH CHO.CO.R„
CH 2OH CH2OH éFI 2OH MPH éH 2OH él120H
SIMPLE DIGLYCERIDES
CH20,.CO.R 1 yll,o.co.R, cm,o.co.n 2 cii2o.co.R2 ym,o.co,R, cH2o.co.R;;
éHO.CO.R, CHOFI éllO.CO.R2 é HOH CHO.00:113 éllOH
éH2OH éH20.CO.R 1 éH2OH éH20.CO.R2 éH 2OFI él120.CO.R3
MIXED DIGLYCERIDES
CH2O.CO.R 1 CH20.CO.11 1 CH20.CO.R1
1
çH,o.CO.R i CF120.00.13 •2 CH2O.CO.R2
ÇHO.CO.R.2 éll OH CHO.CO.R„ CHOH él-10.CO.R„ è HOH
CH2OH CH 2O.CO.R2 é1120H 120.CO.R3
è1 èH2
OH é112
0.CO.R3
SIMPLE TRIGLYCERIDES
CII,O.CO.R CH20.CO.R3
ét IO.CO.R i 3 éHO.CR
20. CO.R4 20.CO.R3éF1
MIXED TRIGLYCERIDES
CH20.COR I CH20. CO.R CH.D.CO.R„ CH20.CO.113
éHO.CR, éHO.CO.R 2 éHO.CO.R., éHO.CO.R t éHO.CO.R;i -éHO.CO.Ri
éH 20.CO.R2 CH20.CO.Ri CH2o.co.rt 1 éH.,OC2R CHO.CO.R 1 éH 20.00.113
Another type of ester that does not properly fall in the class being discussed
may well be defined here. Besides combining with fatty acids, alcohols May -com-
bine With inorganic acids (acids that contain neither carbon nor the carboxyl
group, but exhibit the readily replace-able hydrogen characteristic of all acids)
to form inorg anic esters. Those of the well-known acids hydrochloric (muriatic,
11
—0
HO.), sulphuric (HH-0 > SO 2, H—O—S03H or H2504) , and phosphoric
• . ,
(H-0\
H-0— P = 0 or H3PO4 are examples of this class. Only a few inorganic
\H—O/
esters come under consideration in this Bulletin, the chief being certain phospho-
lipides (fat-like substances), and the manufactured sulphated oils:
CI-12z—O—CO—R CH2-0—CO—R
I I
CH -b —CO—R H—O—CO—R ,
I I
CH2-0-P-OH CH2-0--S 03H
. ' •
,N
1
0 OH _
Mixed phosphoric and fatty acid ester of Mixed sulphuric and fatty acid ester of
- glycerol, the parent substance of the glycerol, or one type of sulphated oil.
phospholipides.
Ethers result from chemical combination between two alcohol molecules with
•the simultaneous splitting off of one molecule of water formed, -
R—CH2-0H + H—O—CH2—R ---).- R—CH 2-0—CFI2—R + H—O—H.
Alcohol Alcohol Ether ' Water
Seme are found in,the unsaponifiable portion of fish oils as mono-ethers of glycerol,
CH2OH ' .
I
CHOH . Because there are two alcohol groups to one ether linkage in such
I
CH2-0—R ,
inolecules,, these compounds received names such as chimyl alcohol (R =-
C161-133 ), batyl alcohol (R = C181137 ) and selachyl alcohol (R = C181135 ) . They
CH9O—CO—R 1
I .
exist in the oils as diglycerides CHO—CO—R 2 but the two fatty acid portions
I
CI-19-0—R .
(—CO—R 1 and —CO—R2 ) are broken off during the saponification.
III. ISOMERISM
• The following three esters and one acid are only four of the nineteen fattY
compounds having the same condensed formula C1811 3600 with carbon atom
chains of the straight (normal) type:
H—00.0—C 1)7H 35 (heptadecyl formate)
71-115—00.0—C 10 H21 C (decyl caprylate)
II1123—00.0— 051113 C (hexyl laurate)
17}135—00.0—H C (stearic acid)
If the carbon atom chains were branched instead of straight, there could be
several thousand more such fatty substances with still the same condensed.
formula. All these compounds would have . different structural formulae and
slightly differing chemical and physical properties.
The glycerides joined by underlining in figure 1 present other examples of
structural isomerism:
CH2 .0.CO.C 15H 31 CH2OH
1
CH.O CH.O.CO.C151131
CH2OH . CH201-I
Glyceryl a-palmitate, Glyceryl /3-palmitate,
melts at 78°C. melts at 69°C.
Another kind of structural isomerism is that due to differences in the position
of the one or more double bonds in unsa.turated molecules. Examples are the two
(c) and (d) on page 7. Bothisomercfatydpnbformulae
-have the same condensed formula .C 181-13209 but ordinary linoleic acid (c) melts,
at a temperature considerably lower than the melting point of its isomer (d).
13
The significance of the conjugated position of the two double bonds in
isomer (d) has been mentioned on page 8. The chemistry of oils and fatty acids
as affected by structural isomerism arising from position of double bonds, includ-
ing conjugation, is 'of considèrable importance and is reférred to more par-
ticularly in Chapters 2 and 5.
The physical and çhemical properties of structural isomers frequently are
quite distinctly different, but isomeric glycerides differing only in the relative
positions of the fatty acid radicals usually have very similar properties, a fact
that renders the separation and recognition of .iridividual fats in a mixture very
difficult.
2>C=C<2 2>C=C<3
Groups 2 on same - side, Groups 2 on opposite side,
or cis-form or trans-form •
The above two compounds are geometriçally isomeric, and are termed cis-trans
isomers. Oleic acid, CH3 ( CH2 ); CH - CH ( CH2 ), COOH, can exist in the follow-
ing two forms:
The transformation of oleic acid into elaidic acid takes place quite readily in the.
presence of' certain reagents, the process being known as elaidinization (see
Chapter 5 ) ,' even when applied to unsaturated fatty acids other than oleic.
Carbon atoms attached by single bonds instead of by double bonds can also
give rise to a type of spatial isomerism known as optical isomerism when all four -
atoms or groups attached to one of the carbon atoms are different: ^
14
1
2-C-4.
I
3
Details of this type of isomerism are not essential for the purposes of this Bulletin,
and it need only be mentioned that the isomers are often practicallÿ indistinguish-
able except for a certain optical effect. Triglycerides of the type
CH2O.CO.R,
virtue of the carbon atom designated by the asterisk being linked by single bonds
to the four different groups: H, -O.CO.R, -CH2O.CO.Rl and -CH2O:CO.R2.
, 17
CHAPTER TWO
The chemical reactions of the fatty acids can be divided into two classes:
those typical of the carboxyl group, and those typical of the carbon chain. Both
classes of reaction will be more fully discussed in Chapter 5 of this Bulletin; but
will be outlined briefly here.
By neutralizing the acidic (carboxyl) group with basic oxides, hydroxides.
or carbonates, salts ( soaps ) are formed. With alcohols they form esters; natural
fats and oils are esters of the trihydroxy alcohol, glycerol. These two classes of
compounds of the fatty acids, namely soaps and esters, are by far the most im-
portant commercial derivatives of fats and oils. A less important reaction of the
carboxyl group is its reduction to an alcohol group by hydrogenation under
special conditions; lauryl alcôhol is obtained from lauric acid, palmityl alcohol
from palmitic acid and so on. These alcohols, which can also be made by direct
reduction of the neutral oil as well as of the fatty acids, are used in making deter-
gents. Other reactions of the carboxyl group are of less industrial interest. ,
' The chemical reactions which take place in the carbon chain are practically
restricted to the double bonds in unsaturated fatty acids. i7nsaturated acids thus
absorb oxygen to form oxides, hydroperoxides, or peroxides. Under suitable con-
ditions these may break down giving acids and aldehydes. The more unsaturated
the fatty acid, the more easily it is attacked by oxygen or other oxidizing re-
agents. Ozone reacts with unsaturated fatty acids to form ozonides which, on
boiling with water, also split up to give aldehydes and acids. This breaking up
of ozonized or otherwise oxidized unsaturated fatty acids involves a break in the
carbon èhain at the position of a double bond. By identifying the scission pro-
ducts it is therefore possible to ascertain the positions of such bonds in the chain;
hence this reaction has been. found very useful in determining the structure of
unsaturated fatty acids.
Another reaction at the double bond is that with halogenating reagents.
Bromine and iodine add on to'the double bond, giving substituted fatty acids.
The insolubility of the bromine addition products in certain solvents is useful
for identifying some of the unsaturated fatty acids, and the amount of halogeri
absorbed under specified conditions is the basis of a widely used measure of un-
saturation, the "iodine value".
With suitable catalysts, and under suitable conditions, hydrogen adds on to
the double bond giving saturated products. This reaction is the basis of an ixri-
portant process for the conversion of liquid oils to solid fats.
20
Sulphuric acid reacts at the double bond in unsaturated fatty acids, giving
a variety of products depending on the reaction, conditions. The technology of
these products is discussed in Chapter 8. Nitrous oxide when bubbled through
unsaturated fatty acids forms an unstable addition compound ;vhich immediately
breaks up to give a mixture of the trans- and cis-isosmers. The trans-acid is formed
to the extent of about 66%.
Reactions of the fatty acids as components of fish oils are, in general, similar .
in Chapter 5, in , considerable tohsenlidr.TyWbeiscud
detail.
• tion, such a solution is not a detergent. If, however, the salt gives a colloidal
solution, then detergent properties will be shown. Among the colloidal properties
,exhibited by soap solutions is that of absorbing water to form a gel. Gelling
properties start with sodium laurate and increase very rapidly with increasing
molecular weight of the fatty acid, that 4s, the higher the molecular weight of
the fatty acid the more water will its sodium salt absorb to form' a stiff gel.
Unsaturation decreases this "gelation capacity", the sodium soaps of stearic, oleic
_and linoleic acids absorbing 88.0, 3.2 and 3.3 cc. of water per gram of dry soap.
The soaps of the trans-form of the geometrical isomers have higher gelation
-capacities than the cis-forms, for example, sodium elaidate and sodium oleate
absorb, respectively, 30.0 and 3.2 cc. of water per gram of soap.
The water-soluble soaps stabilize oil-id-water types of emulsions. On the
•other hand the soaps of the alkaline earth metals, calcium, strontium, barium,
. and magnesium, tend to be more soluble in oil than they are in water and stabil-
ize the water-in-oil type of emulsion. The solubilities of the alkaline earth soaps
in oil are, in general, affected by the same conditions as affect the alkali soaps
in water.,Increasing unsaturation of the fatty acid increases the solubility of the
soap in oil as also does increase in temperature of the solution.
Copper, iron, cobalt, manganese, lead, cerium, zinc and aluminium salts of
the fatty acids are also soluble to some extent in oils but are practically insoluble
in water. Here again, the More - unsaturated the fatty acid the more soluble will
21
be the metallic soap in oil. The various applications of these soaps are‘considered
in more detail in Chapter 9.
Of particular interest, from the analytical standpoint, are the solubilities
of the,lead, lithium and sodium soaps of the fatty acids in non-aqueous solvents,
as they permit a fairly sharp séparation of various types of acids. In 95% alcohol
the lead soaps of the saturated fatty acids are soluble up to the , myristate (C14)
.which is distinctly soluble, whereas the palmitate (C 16 ) is practically insoluble.
All the lead soaps of the ,unsaturated acids up to C18 are freely soluble in 95%
alcohol; those of the fatty acids of higher molecular weight with one or two
double bonds are but sparingly soluble; with three or more double bonds the
lead salts of the fatty acids of high molecular weight are soluble.
The lithium and sodium salts of unsaturated fatty acids with three or more
double bonds are freely soluble in 95% acetone, those with one or two double
bonds are sparingly soluble and those of the saturated acids are insoluble. Al-
though the differences in solubility are not clear-cut, they afford a means of
isolating highly unsaturated fatty - acids from a complex mixture.
■
Arachidic acid. Soluble in 'ether. Soluble in hot absolute alcohol. One hun-
dred cc. of alcohol dissolve 0.45 grams at 20°C. Not -present in many fish oils,
although small: amounts have been found in the liver oils of certain sharks. When
present in any fish oils it is usually only' a trace constituent.
Behenic acid. One hundred cc. of alcohol dissolve 0:10 grams at 17°C. One
hundred cc. of ether dissolve 1.92 grams at 16°C. Even more uncommon than
arachidic acid.
Lignoceric acid. Traces have been reported in sardine and herring oils and -
in a few shark liver oils.
' Solubilities
Fatty acid , (gm./100 gm. solvent
'Welting Boiling at 10°C)
Formula Molecular point point
Common Geneva weight (°C.) (°C. at Water Ethanol Acetone
name system 760 mm.) (95 %)
The formulae and some properties of unsaturated fatty acids found combined
in marine oils are given in table 2.
-
Caproleic acid. Has one double bond in the 9 position. Melts below 0°C.
Occurs in traces in sperm whale head oil.
• Lauroleic acid. Has one double bond in the 9 position. Liquid at,room tem,
constituent of sperm whale head oil; traces also present in sperm peratu.Mino
whale blubber oil and porpoise oils.
Myristoleic acid (physeteric acid). Two forms occur in marine oils, one with
the double bond in the 9 position, the other (also known as physeteric acid)
with it in the 5 position.. The latter variety constitutes about 14% of the fatty
acids of sperm whale head oil; the former occurs in small amounts in most fish
and other marine animal oils.
Palmitoleic acid (physetoleic acid, zoomaric acid). Only one form Is çom-
mon, with the double bond in the 9 position. Melts at -1°C. Found in most fish
and other marine animal oils in amounts varying from approximately 10% to 20%.
23
Hiragonic acid. Three double bonds in the 6, 10 and 14 positions. Forms
a hexabromide which is soluble in benzene at 40°C. Has been found in Icelandic
and Japanese herring oils.
Oleic acid. When solidified, crystallizes in the alpha form (m.p. 13.4°C.)
which on standing, gradually changes to the beta form (m.p. 16.3°C.). Double
bond in the 9 position. Occurs in all fish and other marine oils, always as a major
Acid , No. of
Formula double Position of Iodine Molecular Boiling point
Comtnon name Geneva system bonds double bonds value weight (' C.)
While mest of our present ,knowledge of the composition of fish oils and
other marine animal oils has been obtained by the methyl ester distillation
method of analysis, other methods which have more recently been developed
and originally applied to other fatty oils, have also been applied.
Fatty acids with from 8 to 26 carbon atoms are found in fish oilS,' but the
most commonly occurring are those with from 14 to 24 carbon atoms. The un-
saturation is usuàlly not greater than —2H in the C14 and C16' series, —4H in the
C18 series, but in the C90, C.2' 2 and C24 series it may exceed —10H. These highly
unsaturated fatty acids are in general characteristic of marine organisms. The
total saturated fatty acids range from 10% to nearly 30% of the total fatty-acids
in the oil. The unsaponifiable matter shows great variations in both quantity and
composition. In some oils it is always less than 1%, while in others it may reach
80%. -
Analyses of some oils from teléost fishes are given in table 3: These include
oils both from whole fish and from various depots. Analyses of a number of fish
liver oils are presented in table 4. No attempt has been made in either case to
include all the published data. For more complete tabulations the reader is
referred to Lovern (1942) and Hilditch (1947). Representative analyses are
27
included in tables 3 and 4 for oil from fishes which are caught in Canadian
waters, or from similar speCies taken elsewhere. In both the body and liver oils
palmitic acid (C 10 ) is the principal saturated fatty acid.
The unsaturated fatty acids of the oils from fish and other marine animais
show greater variation in degree of unsaturation than do those of oils from other
sources. While palmitoleic (-2H) is the chief C16 unsaturated acid, small
Family Salmonidae
Salmon, Salem° solar (Scotland)
flesh (4) 0.9 5.0 11.3 1.1 0.5 9.1 (2.0) 25:7 (2.7) 26.6 (4.7) 20.8 (6.4)
mesentery (e) 3.6 14.4 2.3 0.1 7..1 (2.4) 25.3 (2.9) 28.4 (4.6) 18.8 (6.1)
liver (e) 2.7 10.9 1.6 0.7 12.3 (2.0) 32.8 (2.9) 25.8 (5.7) 13.2 (7.8)
hninature ova (f) 8.8 3,1 16.0 0.5 0.1 12.6 (2.0) 23.7 (4.0) 27.2 (8.0) 16.8 (10.4)
ripe eggs (f) 7.2 2.3 12.9 2.2 9.6 (2.0) 34.8 (2.7) 23.2 (7.6) 15.0 (11.2)
Family Pleuronectidae
Halibut, Hippoglossus hippoglossus
(North Sea), flesh (g) 1.3 4.0 14.8 0.7 trace 6.5 (2.6) 23.8 (3.0) 26.9 (5.2) 23.3 (6.5)
Turbot, Rhombus.maximus,
(North Sea), flesh (e) 2.1 3.4 15.1 2.1 0.3 8.9 (2 . 5) 21.7 (3.4) 26.6 (6.0) 21.9 (7.7)
Family Scombridae
Bluefin tuna, (tunny), Thynnus
thynnus, (North Sea),
flesh (g) 0.7 4.2 18.6 3.5 6.2 (2.7) 26.0 (3.2) 23.5 (5.5) 18.0 (6.8)
liver (g) 0 17.9 8.9 3.4 (2.5) 23.5 (2.8) 28.2 (5 .5) 18.1 (7.4)
pyloric caeca (g) 3.4 18.4 2.7 6.3 (2.7) 21.9 (3.7) 25.5 (5.5) 21.8 (6.2)
spleen (g) 0 21.0 7.0 7.0 (>2.0 27.0 (3.1) 22.0 (5.4) 16.0 (1)
heart (5) 0 25.0 3.0 4,0 (>2.0 26.0 (3.4) 25,0 (5.4) 17.0 (7.5)
Family Acipenseridae
Sturgeon, Acipenser sturio,
(Atlantic),
peritoneum (h) 7,1 14.0 0.8 0.6 23.8 (2.0) 35.8 (2.9) 12.1 (7.4) 5.8 (8.6)
liver (h) 3.0 19.2 19.5 (2.0) 39.6 (2.7) 11.8 (7.1) '6.9 (10.0)
"Numbers in brackets are the unsaturafons in ternes of -H. References: (a) BrocklesbY and Harding (1938); (5) Bjarnson and Mèara (1944);
(e) Armsttong and Allan (1924); (d) Lovern (1934a); (e) Lovern (1937); (f) Lovern (1636a); (g) Lovern (19365); (h) Lovern (1932a); (i) Hilditch and
Pathak (1949).
amounts of more highly unsaturated C16 acids may occur, for example hiragonic
acid, with three double bonds. In the Ci8 series the chief unsaturated component
is oleic acid, which has one double bond (-2H), but in this series the average
unsaturation is much higher than in the C16 .series. The C18 fatty acids which have
actually been isolated from fish oils include an octadecatrienoic acid isomeric
with linolenic acid, and moroctic or stearidonic acid, an octadecatetraenoic acid.,
In the higher series the average unsaturation varies, in the fatty acids from oils.
of the teleost fishes, from -3.8H to -10.9H. The data in table 3 show clearly the
general tendency toward greater unsaturation in the fatty acids of higher
molecular weight in the oils of teleost fishes. However, the liver oils of the elasmo-
28
branch fishes show, in some- cases, considerable difEeience to the oils of the
teleôst fishes with respect to the distribution of unsaturati(in in the fatty acids of
different molecular weight. Tsujimoto (1932) has divided the elasmobranch liver
TABLE 4. Weight percentage distribution of constituent fatty acids in fish liver oils.
Family Lanmidac
Selachii (Elasntobmnchii)
Basking shark, Cetorbinus tuasinnu
(Atlantic) (h) 32-48 2.1 13.6 3.2-- 0.5 (2;0) 11.0 (2.0) I 12.8 (2,3) 1 23.2 (4.0) 20.0 (3.6) 5,6 (5.0)
Family Squalidae
Dogfish, Squahu acaathias
(Atlantic) (a) 10.0 0.0 10.5 3.0 0 (2.0) 24.5 (2.3) 2tJ,0 (3,3) 12,0 (4,0) 6.0 (2.0)
Shark, Cenfrophores (Atlantic) (e) 50-80 1.0 13.0 2:5 trace 3.5 (2.0) 35.5 (2.1) 16.4 (2,2) 15.8 (2.3) 12.0 (3,0)
Family Scymnorhinidae
.Shark, Scymnorhinus lichia
(Europe) (c) 70-80 1,2 14.6 3.6 0.5 3.7 (2,0) 20.1 (2,0) 10.6 (2.0) 25.9 (2.1) 10.0 (2.0)
Family Scylliidae
Small spotted dogGsly
Scyflinut cmticnla (c) 2,0 1.7 15.7 3.3 4,0 (2.2) 25,3 (3.0) 24r1 (6.4) 24.8 (0.2) trace
Large spotted dogfish, Squalus
robins (g) (South Africa) 3.2 15.7 2,0 1.7 (2.0 12,6 (2.0) 40,3 (2.8) 10.7 (6.0) 13.8 (10.4)
Family Alopiidae
'Thresher shark, Alopccia tatlpes (f) 7.-1
1.8 11.0 0.5 1.5 12 0 (2.0) 10.0 (3.4) 31.0 (6.6) 17.3 (10.5)
Family Squatinidae
.t\lonk-6sh, Squatina asgefvs (e) 1,5 1,4 17.0 2,0 G.5 (2.0) 20.7 (3.0) 21.9 (6.0) 30:5 (10,2)
Family Rajidae
Skate, Raja inaculata (a) 0,3 4,0 14,0 tracc 10,5 (2.0) 20.5 (3.3) 32.5 (7.3) 18.5 (0,5)
Family Chinteridne
Ratfish, Cbinraera monztrosa (e) 37.0 8,4 7,2f •2.5 (2,0) 50.6 (2.2) 10.6 (2.9) 7.9 (3.5) 2,1 (t)
•Numbere in brackets are the unslturations in ternis of -H. "Plus 3 6, C,o; 3.2, Gz; 0.4, Cx. {Plus 1.3% C:o and 0,4% Co.
References: (a) Guha, Hilditch and Lovern ( 1030); (b) Lovern ( 1032b);
(c) Lovern (1037); (d) Lovern (1936b); (e) Hilditch and Houlbrooke
•(1028); (f) Lovern (1930); (g) Aenlle (1044); (h) Karnovsky
et at. (1048).
oils into three groups as follows: (1) those in which the unsaponifiable matter -is
from approximately 1% to 2% and consists largely of sterols, ( 2) those contam-
ing from approximately 10a/o to 30% unsaponifiable matter consisting mainly of
29
chimyl, batyl and selachyl alcohols, and (3) those with very large amounts of
unsaponifiable matter (up to 80%) containing large amounts of the unsatuxated
hydrocarbon squalene. The latter two groups shade into one another, particularly
with respect to the percentage of unsaponifidle matter in the oil, but the first
group appears to be quite distinct. On the basis of the above division the fatty
acid compositions show some well-defined differences. The samples with un-
saponifiable matter up to about 2% have unsaturated acids similar to those of the
teleost fishes. The C20 and C22 acids in particular are highly unsaturated. On the
other hand the samples with a very high content of unsaponifiable matter have
C20 and C22 acids which are mainly monoethylenic, and in addition contain mono-
ethylenic C24 acids. The dogfish, genus Squalus, with an intermediate amount of
unsaponifiable matter, contains unsaturated acids which are approximately inter-
mediate betwen the two extremes, both in regard to the unsaturation of the Co
and C22 acids and also the amounts of C24 acids.
The saturated acids do not differ significantly in the elasmobranch liver oils
with high and with low percentages of unsaponifiable matter.
The last group of oils to be considered here are those of the marine mam-
mals. Some analyses of these are given in table 5.
The blubber oils of the Balaenidae (right whales or rorquals) resemble
somewhat the liver oils of the teleost fishe's, particularly those of the Gadidae, in
composition. The most notable difference is in the unsaturated C18 acids, which
in whale oils constitute approximately 30% to 40% of the fatty acids, but in the
fish liver oils, rarely go over 30%. The amounts of unsaturated C 20 and C22 acids
in whale oils are correspondingly lower.
The head and blubber o' ils of the sperm 'whales are noted for the large
proportion of their fatty acids combined' (in the form of waxes ) with fatty alco-
hols instead of being combined with glycerol as in the glycérides so characteristic
of the fatty oils. The fàtty acid compositions, furthermore, are markedly differ-
ent from those of other marine animal oils. In the heàd ' oil (sperm oil) there are
considerable quantities of capric, lauric and lauroleic acids. The unsaturated
acids are exclusively mono-unsaturated, and in them the C14, C16 and Cis acids
predominate. Unsaturated C20 acids are present in only small amounts and the
C22 series is absent altogether. In the blubber oil of the sperm whale stearic acid
is absent, but a small quantity of lauric occurs. The unsaturated acids include an
unusually large amount of palmitoleic acid (approximately 25%) but a similar
amount of oleic acid to the blubber oils of other whales. The C20 acids are
slightly more unsaturated than those of the head oil, but markedly less so than
those of other, whale blubber oils, and in addition there is a small amount of
C22 acid with two double bonds.
The oils of the Delphinidae show some similarity to the head oil of the sperm
whale in that they contain considerable amounts of fatty acids of low molecular
weight. In the Delphinidae, however, the occurrence of large amounts of the
C5 branched-chain fatty acid, isovaleric acid, is a peculiar characteristic. It is
present in larger amounts in the head and jaw oils than in the blubber oil, but
occurs in each of those oils from each of the three representatives of the
30
Delphinidae: porpoises, dolphins and white whales. Palmitoleic acid is thé pre-
dominant unsaturated fatty acid in the oils of the Delphinidae. The unsatuiated
C14 and C18 acids are largely mono-unsaturated, but the C20 and C22 series con-
tain more highly unsaturated members.
TABLE 5. Weight percentage distribution of constituent fatty acids in marine mammal oils.
Saturated Uns.4turated•
Clt Cu CI. CIA Clé Clg C20 C22
Family Balaenidae
Whale oil (a), blubber _
Arctic, &Mena mysticetus (a) 4.1 10.5 3.5 - 18 (2.5) 33 (3) 20 (7) 11 (8)
Newfoundland, " " (a) 7.5 10.0 3.0 1.5 18 (2) 44 (2.2) - 16 (8)
Antarctic, " australis (a) 8. 0 12.0 2.3 1.5 15 (2) 43(2.3) 8 (7.5) 10.5(9)
Family Physeteridae
Antarctic spent' whale
Physeter macrocephalus '
head** (b) 14 8 2 14 (2) 15 (2) 17 (2) '6.5 (2) -
blubber (b) 5 6.5 - 4 (2) 26.5 (2) 37 (2) 19 (2.5) 1 (4)
'
Family Delphinidae
Cs 'Cis C11 CIA CIA
Porpoise
body oil (c) 13.6 3.5t 12.1 4.7 nil 4.7 (2) 27.2 (2) 16.7 (2.8) 10.5 (4.8) • 7 (4,9)
head oil (c) 20.8 4.1 15.8 7.5 0.2 4,5 (2) 20.8(2) 15.2 (2.6) 9.4 (4.5) 1.6 (4.7)
jaw oil (c) 25.3 4.6t 28:3 4,1 nil 3.2 (2) 20.3 (2) 9.3 (2.6) 4.9 (4.9) nil '
Dolphin, Phocaena connentnis ,
body oil (c) _. 3.2 1.0 7,2 8.6 0.8 4.7 (2) 25 ,•9 (2) 24.1 (3.3) 18.6 (6.5) 5.9 (7,6)
head oil (c) 13.9 2.4 12.5 11.6 0.4 2.7 (2) 25.4 (2) 15.8 (2,8) 12,7 (5,5) 2.6 (7,2)
,
White whale (beluga) (d)
Delphinaplerus toucan
body 4 - - 28,0 - _ - 51 - - 1.2
head 256 - - 29.1 - - 30.2 1 - 0.5
jaw 20 - - 14.1 - - - 51.6 - 1,3
(a) SPECIES
Atlantic ,-
lantic
CodLker Oils
Ill
DO
fish
Liver Oils
2 46
o
F- Salmon
0 185
o
t
it
?.. cob°
%a 4
a Salmon
ta
125
IL
chum
Salrt on
109
ckeYo
S Imon
265
spring
ilk
Herr ng
AA
Pilchard
50
Salmon 40
97
1.470 I P 3 • 5 6 7 8 9 1.480 I 2 3 • 5 1 7 0
REFRACTIVE INDEX
FIGURE 2. Refractive index frequency curves for ten fish oils. The numbers of samples
tested are given. (Salmon oil data from Harrison et al., 1939; cod liver oil data from Holmes
and Clough, 1927; and Atlantic halibut liver oil data from Evers, Jones and Smith, 1936.)
35
The ability of fish to produce depot fats with characteristics peculiar to their
species must mean that they can either modify their ingested fats or select their
diet, or possibly do both of these. Lovern's work on the fats of the tunny (bluefin
tuna) is particularly interesting in this regard, as this tuna is a fish that has a
body temperature about 3°C. higher than its surroundings. In examining the fats
from the pyloric caeca, heart, flesh, spleen and liver, Lovern (1936b) found for
it in comparison with the majority of marine species, the following peculiarities:
for the saturated acids, high stearic and to a less extent high palmitic acid con-
tents, and in three cases the absence of myristic acid; for the unsaturated acids,
Hexabromide
Kind of salmon Iodine value
value
Common name (with synonyms) Scientific name Lowest Highest Lowest Highest
low palmitoleic acid content and entire lack of myristoleic acid (C14) normally
present in traces in aquatic plants. In other words, there is a shift from the lower
fatty acids to the higher (and more saturated); it is probable that this shift is
related to the higher body temperature of the tunny over that of other fish.
The mechanism of the formation of the higher amounts of palmitic and
stearic acids in the fish is apparently simply addition of hydrogen to the un-
saturated members of the Cla and C18 series, since, in the oils from all the five
organs or tissues -listed above, as the stearic acid content increases, there is a
progressive decrease in the unsaturation of the Cib unsaturated acids. The high
proportion of stearic acid present is not due to the fat in the food, because the
fat of the pyloric caeca (consisting largely of food fat) has the lowest stearic
acid content.
The questions now remaining to be considered are: can fish desaturate fatty
acids to suit their particular needs; and can they synthesize fatty acids of various
carbon contents from sources other than fat? The answers to both these questions,
at least in the species investigated, appear to be in the affirmative. Lovern
(1935a) investigated the fatty components of a freshwater carp that had been
fed entirely on grasses, and another that had been fed entirely on mud; the
nutritive material for the latter being derived entirely from the decaying organic
matter in the mud. In comparing the compositions of the fat of the grasses and
those of the two kinds of carp (the mud contained no fat), he concluded that
"the evidence taken as a whole indicates that these fish are able to synthesize fat
of the desired type from carbohydrate or other sources". Other evidences, of a
36
more indirectnature, point to the ability of fish to deSaturate fats and/or tranSfer
fatty aeids selectively from one depot- fat 'to, another within its body: LeVern .
(1934a) found that the oil from the roe of Atlantic salmon - is more highly un-
saturated than the oil in other parts of the bedy, from which the roe-oil is •pre-
surnably drawn. In these laboratories Harding found the *same to hold for Pacific -
coast *salmon (see Chapter 10) . and Bailey (1934) has 'shown that in Pacific coast'
salmon, in general, the liver 'oil is Much more imSaturated than the oil from'. the
muscle.
Finally attention must be drawn to the fact that, contrary to the view held
in regard te mammals, in fish the livdr does not in all cases appear 'to be the site
of desaturation. In fish livers which. are not fat storage dePots, the oil is usually
• very highly unsaturated (for example salmon), but In other livers which are.
•, one, if not the principal, Storage depot, the "Oil is usually more saturated than-the
body, oil. There is some evidence that saturation and desaturation take place at
the site of storage, and it has been postulated that the saturation and desaturation
are controlled by a reversible enzyme system.
.
(b) FOOD
The food of all marine animal life is, in the final analysis; of vegetable 'origin-
mainly from the phytoplankton, the minute floating plants which live near the
surface of the sea, where there is enoue light to permit the'utilization of carben
'dioxide in the synthesis of carbohydrate, protein .and fat. This plant material
constitutes the food of the plankton crusta-ceans and other. minute animal &gall-
isms in the sea; these in turn form the main diet of the smaller fishes and also
many of the larger 'fishes and marine animals, including some whales. The larger
carnivorous fish live on the smaller fish. Tlais life in the. Sea; as on land, IS - de-
pendent on 'vegetable matter for its • existence. It•is of sonie interest to. . trace • the
formation ef the fats (oils) characteristic of . marine organisms -through these
sequences: The data are far from complete, but even so seine general conclusions
can be drawn with reSpect to the influence of diet on the type and quantity of fat
in fishes.'
In 1925 Tsujimoto showed that marine algal plants contain very small quan-
tities of highly' unsaturated fatty acids.'Collin et al. (1934) fonnd that the total
fatty acids of the fats from mixed' phytoplankton contained. only slight * traces of
'these characteristic highly unsaturated acids. Lovem (1935a) exaMined the fats
of green, brown, ,and red .marine algae and of a single- speeies of diatom. The
green and brown algae and the marine diatom all had fats' resembling these of
more than those of marine fish (freshwater fish oils' have greater freshwati
amounts of unsaturated C16 and C1'8 acids than marine. fish oils, but less ef.the
unsaturated Co o and C 9 2 acids), but the red algal 'fat was more similar te that of
marine fish. The, plankton crustaceans, which i form,an important link, in the suc-
thivugh which the food in the sea passes, live. on the small fleat-
cession of steps ..—.
ing algae and diatoms; and, the latter contain à ,fat with a:loW content- of
unsaturated . CodfaitY acidS and entirely lacking in 022 - acids. Yet the bulk of th•e .
37
eviClence available indicates that the plankton crustaceans which feed on ,diatoms
and other marine phytoplankton have a- fat that approximates the composition
of marine fish oils in having signifiCant amounts of -unsaturated 020 and 022 acids.
It would appear, therefore, that these-crustaceans are' able to modify the fat from
the ingested diatemS before storing it:This séems to, be true off the larger and
\ smaller forms of crùstaceans. Fish that feed on, crustaceans thus have 'accessible
to them in their diets fats containing tinsaturatecl C20 and C22 acid, but those
fish that feed on diatoms Yvould lack C22 acids, at least in important amounts, in
their diets. s ,
Before considering the diets of some important British Celumbia fishes it is
worth while to summarize an interesting experiment made by tovern (1938a)
on the controlled feeding of fish. Two lots of eels were fed separately on a low-
, and a high-fat diet. On the diet low in fat (1.1% ) the nature of the ingested fat
had no , detectable effect on the depot fat of the eéls.'But on the diet high in fat
(20.7%) the depot fat of the eel was appreCiably modified; the ingested fat was
aparently laid down with the relative proportions of the fatty acids in the various
carbon series unchanged, but the degree of unsaturation in each series was
altered, considerable saturation of the acids having taken place. The eel, there- .
fore', seeins able to bring about a hydrogenation of its ingested , fat.
Apart from the controlled experiment just described, there are few accurate
data relating the cemposition of the fat aCtually ingested by fishy to that of their
stored fat. However, the information that is available, supports the evidence for
of the ingested fat in the species concerned. Two considerablft
examples of Pacific coast fishes illustrate this point. The herring and pilchard
are closely related fishes, but their diets are censiderably different. The chief
food of the adult heriMg consists of small 'Crustaceans, "Calanus being most im-
portant in the -spring and Euphasia during thé test frif the year" (Wailes 1936).
On the ether hand, Hart (1938) stated that "Extensive food-studies on the British :
» Columbia pilchards show that the adults depend chiefly on these diatoms as
food during the summer, although the copepods remain an important secondary
food". Herring, when caught for commercial pulPoses, are rarely found feeding, -
but pilchards are caught during the active feeding period. There is a distinct
differeneè, in the - nature of the oils from these two fishes. Herring oil varies in
iodine value froni about 1 20 to 150, pilchard oil from about 170 to 190. The fat
of crustaceans, however, has a much higher iodine value than that of diatoma.,
Calculated from Loverd,s data (1935b, 1936c) the iodine values of the fatty acids
of the crustacea.n Calanus and of a :typical diatom are 212 and 156 respectively.
Thus herring appear to be able to saturate and pilchards to deSaturate their
respective ingested fats.
Finally it need hardly be mentioned that the food intake of fish -controls their
fat content. During the years when pilchards formèd an important proportion of
the fisheries of thé west coast of Canada, these fish arrived- in the early summer
and coxnmenced feeding. They fed continuously for about three Months during
which time their oil content incteaséd almest fetn'fold; the oil yield in the
- 38
reduction plants shciwed almost dailyincreases thrortghout 'the fishing seasen. On s
the other hand, purse-seined hérring'caught in British Columbia waters aré not as
and the oil yields in herring,. reduction plants ShOw gradual actively-fdng,
declines until the fish disappear. Data accumulated by various inYestigators
throughout the world show that, in general, a's fish feed they , fatten tip inprepara-
tion for the spawning period during which time their reserve fat supply forms
their only source of energy.
.39
,
tissues gradually decreases during the spawning migration, never wholly dis-
•appearing, however, even in a spawneel, dying salmon.
In a later paper Greene (1919) reported the quantitative.losses of fat by
king salmon during ;their spawning migration, as _determined .by analysing a
number of fish at various distances tip the stream in which the fish were
migrating. His results were as follows: tide ,water, 15.5% fat; 130 miles, 16.5%;
210 miles, 15.5%; 700 miles, 10.4%; and on the spawning grounds, 2.2%.
Much the same conditions yere found in pink salmon by Davidson and
•Shostrom. They pointed out that the fat content of these fish at any tirne during
their sp-awning Migration is governed by three major factors, namely (1) the
amount of stored fat in the salmon at the beginning of their migration froM the
feeding grounds in the sea, (2) . the amount of their stored fat utilized for
maintenance before being captured and (3) the amount of their stored fat used
for sexual ,develop'ment. The farther the fish have tà 'travel to reach their , spawning
grounds ,the more energy is, expended and hence the more stored fat is used for
maintenance, and also the greater is the sexual matnrity. Some idea of the effect
of these factors is given by the curves' in fig. 3, which represent the fat content
of male and female fish ,in a daily sample of ten pink salmon entering their
spawning stream from the beginning to the end of the period of the spawning
migration. In both the male and female fish there is a distinct trend ioward
depletion of fat, particularly during the latter part of thé migration period. In
regard to these data, Davidson and Shostrom say:
' k 10
k
k tu • • • •
•
\-) , -• * •••
CC 2
Li I I I 1
k.
Qà
er 5
IL.
• IV"
1 1 1 1 1 1 I
15 20 25 30 1 5 /0 /5 20 24
JULY _ AUGUST
/1/GRATI0N PER/0D
•
' FIGURE 3. Change in fat content of pinIc salmon during 1933, spawning migration at
Olive cove, Alaska (Davidson and Shostrom, 1936). Males—top; females—bottom. ,
40
The gradual increase in the fat content of the salmon during the first t`ën days of the
migration may be due to a greater growth of the incoming salmon from the standpoint
of storage of fat in their bodies. Were. it not for the fact that sexual development
begins to show its effects on the composition of the salmon that remain longer on the
seeding grounds, the fat content of the incoming salmon would no doubt first rise and
then fluctuate about a maxi.indm value during the rémainder of the migration: However,
the drain upon the eiiergy reserves of the salmon due to sexual development so shows
its effects on the fat content of the incoming salmon and the trend in this constituent
begins to fall at an ever-increasing rate.
Lovern (1934a, 1936a) has, studied the changes in composition of the oils
in the flesh and the eggs of the Atlantic salmon ( Salnzo salar ) during the spawn-
ing migration. In the case of the male salmon the stored oil was . withdrawn
selectively, as there was a loss of the fatty acids of lower molecular weight,
resulting in a rise in the C22 acids in the muscle tissues of the starving fish. In
females the same selectivity appeared, but it was not so evident, as the C22 acids
decreased in the muscle' 'oils instead of increasing. In the egg oils during all
stages. of development the degree of unsaturation of, both the C20 and C22 acids
is greater than in the muscle oils. Also, as, ripening, proceeds, there is a marked
rise in the proportion of Clg acids, while at the same time the mean unsaturation
of this group decreases.
The British Columbia herring Glu.pea pallasii spawn in the spring, between
February and April; for the preceding six months they donot feèd at all, but for
several months after spawning they eat voraciously. Hart et al. (1940) found that
the oil content reaches a maximum during July, and remains fairly constant
throughout the summer. In October it starts to. decrease, reaching its lowest
value the following spring at the time the fish spawn: The data in table 7, which
are from their paper, illustratè this trend in ,oil content. The fish constituting the
last sample, with an oil content of 4.1%, had just spawnéd. _
Lovern (1938b) studied the seasonal changes in the amount and composition,
of the oil of .the Atlantic herring. The data which' he obtained are presented in
table 8.
The oil content, like that of the Pacific herring, reached its maximum in July,
and decreased to a minimum in the spring. Although the average gross unsatura-
tion of herring oils is fairly low, the data. in table ^S show that the unsaturation
rises, with increasing, and falls with decreasing,, oil content. A. major ingredient
41 '
of the diet of this herring is the ciustacean Calanus finmarchicus, which is rich
in oil, and the oil of which is highly unsaturated. Lovern suggests that the large
intake of highly unsaturated oil during the period of intensive feeding causes a
temporary unbalancing of the fat hydrogenation with a consequent rise in the
total unsaturation.,The unsaturation of the C16 fatty acids in the herring is higher
than in the oil of the ingested crustacean, and Lovern suggests that dehydro-
genation of the C16 acids goes on during intensive feeding at the same time as
hydrogenation of higher acids.
April 8.2 115.5 8.0 15.7 0:2 4.6 ' 22.2 22.0 27.3
(2.6) (2.9) (3.9) (4.2)
June 10.7 144.2 7.3 16.7 trace 0.6 7.5' 21.1 27.3 19,5
(2.7) (3.3) (4.8) (5.7)
June 15.7 154.3 . 7.5 12.8 0.1 0.3 7'.0 21.1 30.0 21.2
(3.0) (4.8) (5.2) (4.8)
July 20.7 , 152.5 8.3 12.1 0.3 0.5 6.4 21.0 28.3 23.1
(3.9) (4.5) (5.5) (4.6)
October 12.0 129.9' 6.6 13:7 0.2 4.9 16.3 28.7 29:1
(2.8) (3.6) (4.4) (4.1)
,
April 4.0 - 147.9 5.8 12.4 0.6 4.7 17.8 31.1 27.6
(immature fish) (3.0) (3.9) . (4.3) (4.8)
•
Sample (number Oil in liver Standard
Description of fish
of fish) (mean %) deviation
pregnancy. A notable exception to this statement, and one not apparently related '
to sexual condition, is the oil content of, the so-called "mottled" livers. The great
.majority 6f dogfish livers are .of a putty-gray colour,- and these usually contain
from 66% to 80% oil. A small percentage of the livers, however, are of a dark
colour with mottled patches. These dark coloured livers contain less oil than those
having a putty-gray colour and the vitamin A content of the oil is always a great .
deal higher than that of the oil from the latter type of livers:
(d) TEMPERATURE
• It is a well-established- fact that vegetable oils from plants grown in colder
latitudes are, in general, more unsaturated than those grown in warmer parts of
the world. There is evidence to show that this generalization can also be applied
to fish oil, although with the reservation that it is only applicable to fish of the
same species.
An experimental study of the influence of environmental temperature on the
fat of eels was made by Lovern (1938a). Eels were kept for six and a half months
in tanks in which the water was maintained at two different temperatures: 14°C.
(57.2°F.) and 23°C. (73.4°F.). The yield, iodine value, and fatty acid
43
composition of the oil were then determined, His data show that the average un-
saturation of each group of unsaturated fatty acids, with the exception of the Cis
acids, was greater in the oil from the fish kept in the colder water. For the C18
acids the unsaturation was the same, within the limits of experimentàl error, for
both temperatures. However, the over-all unsaturations of the oils, as measured
by the iodine values, showed very little difference between the two, being, in fact,
slightly higher for the oil from the fish kept at the higher temperature-12L5 for
those at 23°C. and 119.1 for those àt 14°C. This was due to the greater pro-
portions of highly unsaturated fatty acids present in the oil from the fish kept
at the higher temperature.
Samples of the free oil from canned sockeye and pink salmon have been
foui-id in these laboratories to show an increase in unsaturation the farther north
the fish were caught. The differences were, however, confmed to the individual
species, the entire range of iodine value for the pink salmon being above the
range for the sockeye salmon. Attention was particularly drawn by Lovern
(1942) to the fact that the oils from different species of the same kind of fish
frorh ,widely different latitudes can have siMilar unsaturations. He pointed out
that the various fatty acid groups in the oil from tropical carp reared at Singa-
pore were fully as unsaturated as -those in the oil from the British carp. The
actual body temperature cannot be a determinirig factor in the unsaturation of
the depot fat, since, as further pointed out by Lovern, "marine mammals, such as
the baleen whales, with a relatively high body temperature deposit a depot fat
very similar to that of fish".
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BAILEY, A. E. Melting and Solidification of Fats. Interscience Publishers, Inc., New York, 1950.
BAILEY, B. E. Contr. Canad. Biol. Éish., 8, 267-274, 1934.
BAILEY, H. S., AND J. M. JonNsoN. J. Incl. Eng. Chem.. 10, 999-1001, 1918.
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HART, TESTER, D. BEALL AND J. P. ToLIN. J. Fish. Res. Bd. Can., 4, 478-490, 1940.
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AND
HoLmEs, A. D., W. Z. CLinicri. Oil Fat I d., 4, 403-409, 1927.
AND
KARNOVSKY, M. L., W. S. BAPSON, (MISS) H. M. SCHWARTZ, M. BLACK AND N. J. VAN RENS-
BURG. J. Soc. Chem. I d., 67, 104-107, 1948.
LovERN, J. A. Biochem. J., 24, 866-869, 1930; 26, 1985-19'88, 1932a; 26, 1978-1984, 1932b;
28, 1955-1960, 1934a; 28, 394-402, 1934b; 29, 1894-1897, 1935a; 29, 847-849, 19354;
30, 20-24, 1936a; 30, 2023-2026, 1936b; 30, 387-390, 1936c; 31, 755-763, 1937;
32, 1214-1224, 1938a; 32, 676-680, 1938b; Dept., Sci. and „Ind. Res. ( Great Britain)
Food Investigation, Special Report No. 51, 1942.
MARKLEY, K. S. Fatty Acids. Interscience Publishers Inc.,'New„ York, 1947.
MATUDA, S., AND S. UENO. J.S.C.I. Japan, 60, 49-55, 1939.
„
MOORE, C. W., AND C. H. CLARKE, in E. F. ARMSTRONG AND J. ALLEN. J. Soc. Chem. I d.,
43, 210T-218T, 1924.
TovAmA, Y., AND T. TSUCHIYA. Bull. Chem. Soc. Japan, 10, 296-300, 1935.
Tsujimuro, M. Chem. Umschau, 32, 125-126, 1925.
J. Soc. Chem. Incl., 51, 317-323T, 1932.
WAILES, G. H. J. Biol. Bd. Can., 1, 477-486, 1936.
.
WILLIAMS, N. V., AND N. Y. MASLOV. Schriften rentrai; Forschungsinst Lebensmittelchem, 4,
150-156, 1935. ( C.A. 30, 4707). •, „..
45
CHAPTER THREE
CHEMICALLY speaking, the term fat or fatty oil refers, as was pointed out in Chap-
ter, 1 of this 'Bulletin, to fatty acid triglycerides. There are, however, a number
of other components which are either present in the oil as it occurs in the fish or,
being oil-soluble, are extracted by the oil when it is separated from the fish
tissues. These other components include vitamins ,A and D, a number of pigments,
sterols, glyceryl ethers, phospholipides, and hydrocarbons. In addition to these,
stil other oil-soluble substances, the fatty alcohols, are present in some marine
mammal oils. All of these substances except the' hydrocarbons and hydrocarbon
pigments can, and largely do, occur as esters of fatty acids. When the oil
is saponified, the triglycerides and the phospholipides are broken down and their
constituents converted to water-soluble forms. The other substances which occur
as esters, among th,em vitamins A and D, are also split off from the fatty acids with
winch they are combined. None of them are, however, converted to water-soluble
forms, but can be extracted, together with any hydrocarbons or hydrocarbon pig-
ments which are present, from the saponification mixture by means of various
water-immiscible organic solvents. They are referred to collectively as the "un-
saponifiable matter", "unsaponifiable fraction", or simply as the "unsaponifiables".
The discussion of all these various non-fat constituents will, for convenience,
be divided into three sections: I. Vitamins, II. Pigments, and III. Other Non-fat
Components.
. VITAMINS
(a ) PROPERTIES OF VITAMIN A
(i) PHYSIOLOGICAL PROPER'LlES
It has tieen shown that yitarnin A is essential to life and health in m'ammals,
birds and reptiles, ha the reason for its frequent abundance in fishes has not been
definitely- established. Many species of fish store this vitamin in their livers and
other organs, the amounts stored generally falling within ranges fairly character-
istic for individual groups of species. The first characteristic syniptom of
a dietary deficiency of this vitamin in mammals is usually hemeralopia, or night
blindness, a decrease in the adaptability of the eyes to vision in dim light In the
next stage, the mucous membranes of the body undergo changes which result
46
'in their becoming somewhat dry and scaly . "This in turn has the effect of making
them. far more susceptible to bacterial invasion . Thus, in : vitariiin A deficiency,
various infections such as colds and other diseases - of the respiratory tract are
much more common . The eyes also 'frequently become infected, . a condition
known as xerophthalmia . This is accompanied by, the .formation of an exi .idate
at the .corners of the eyes, and along the edges of the eÿelids . Xerophthalmia must
not be confused with hemeralopia . The latter is . a primary result of vitamin A
deficiency ; the former is a secondary effect, an eye `infection resulting from
changes in the mucous . membranes of the eye, caused by vitamin A deficiency .
Among other results of a dietary deficiency of this vitamin are diarrhea,
eczéma=like skin disturbances, and degeneration of the nervous system which,
in turn, causes a staggering gait . This latter symptom has been noticed particularly
in pigs, chickens and cows .
In addition to the effects already discussed, vitamin A is essential for growth .
This was one of its earliest recognized functions, and is still used in : the. bio-assay
method for the determination of vitamin A potencies . This growth effect is prob=
ably not specific, since growth may cease or decline whenever the growing organ-
ism is not .functioning properly in all its parts, or when it is : not supplied with all
the necessary structural materials . None,the less, a deficiency of vitamin A will
retard, or, if sufficiently severe, mây entirely stop, growth in birds or anixnals
receiving an otherwise complete diet.
Furthermore, an adequate supply of vitamin A is absolutely essential fo r
reproduction and for successful_ lactation . , 1.- I
Although, in correct amounts, vitamin A is an essential for life and liealth,
excessive amounts have harmful effects . Daily dosages of 100,000 units or more
of vitamin A per day to young rats cause internal and external liaemorrhages,
and excessive fragility of the bones,, often resulting in, fractûres .~:A . typical case
of hypervitaminosis A in man was described, by Henschon (1941)? Thé patient
had been taking 30 times the normal vitamin intake and suffered from disorders
of the liver, the spleen and blood .
The biological activity of pure vitamin A from marine fish is approximately
4,000,000 U.S .P . units per gram . -
Vitamin E (tocopherol ), when fed along with vitamin A, enhances the effëct:
of the latter (Quackenbush et al., 1942 ; Hickman et al., 1942) . This effect is .
spoken of as a "sparing" action, by Hickman et al . (1944) . It has àlso' been .
ascribed to the protection of vitamin A from partial ; destruction in the digestive .
tract, since it is well known that when vitamin A and oxidized fat are fed .
simultaneously to experimental ianimals, much of thé • vitamin A in the diet is
destroyed in vivo. .
While there is evidence that'some fishes may have,the ability to syrithesize
vitamin A from simple materials, it has not yet beèn- proven ; definitely. For 'the ,
most part, however, it appears to have its origin .in plants, where it is found, not
as .the vitamin itself, but as the pigment carotene and sevéral, other pigments
closely related to it . Fishes, birds and mammals .are able to'convert some .of these !
47 -
pigments into vitamin A, so that a dietary supply of either preformed vitamin A,
or its precursors, as the pigments which are converted into vitamin A. are called,
can meet their physiological requirements. Carotene was first isolated from carrot
roots, but is of fairly wide distribution in nature. Its commonest occurrence is
in the leaves of plants where, however, its colour is masked by that of the green
pigment, chlorophyll, which is present in much greater amou.nts. It and other
vitamin A precursors are found in the minute floating plants of the sea„ the
phytoplankton. The latter constitutes the food of many zooplankton, minute ,
animal organisms living in the sea, which in turn are eaten by fish. The way in
which the carotene is passed along and converted into the vitamin A that appears'
in the fish is not definitely known, but one suggestion is that it is assimilated by
the zooplankton and converted by them into astacin, a carotenoid Pigment found
in marine forms of animal life, and passed on in that form to the fish, which• con-
vert it to vitamin A. Fish can convert carotene itself into vitamin A (Neilands,
1947), but the conversion, .at least under the conditions of this experiment, is
slow.
CH 3 CH 3
H2 C C CH3
CH 2 Vitamin A1
TABLE 10. Stability of vitamin A in halibut liver oil stored at room temperature in Open flasks,
exposed to diffuse light.
Heating in the absence of air or other sources of oxygen;causes far less des-
truction of vitamin A than when oxidation can take place. Thus if a vitamin-A
oil is deaerated by subjecting it to a vacuum to reinove the dissolved air, sub-
sequent,loss of 'vitamin A on heating! , and also during long storage at ordinary
temperatures, is less than in a non-deaerated oil.
A 'high free-fatty-acid content in a fish oil has no effect on the destruction
of vitamin A (Swain, 1948b).
Vitamin A esters are far more stable to œddation than the free alcohol form of
the -vitamin. The stability. of either form to-oxidation Can be greatly increased
by the use of substances , called antioxidants. These will also be considered in
Chapter 6 of this Bulletin, but their effect on the oxidation of vitàmin À will be
discussed here. •
Some antioxidants slow down the rate of oxidation of an oil and hence of
vitamin A, while others protect the ,vitamin A frem oxidation without greatly
decreasing the oxidation of the oil itàelf. Vegetable oilS, especially those prepared
from seeds, contain far greater quantities of natural antioxidants than do fish
oils and other oils prepared from animal„sources. . •
Saponification of an oil destroys some natural antioxidants, so that vitamin A
concentrates prepared by saponification are unstable, sinCe not only is the Vita-
min in the form of the free alcohol, which is the More unstable form, .but it lacics
the antioxidants which would assist ,in stabilizing it. .
'Various substances - are good antioxidants for . vitamin A in_.fish liver oils.
Among the best known are the tocopherols. By themselves they are fairly good
51
antioxidants for vitamin A, but when another but less effective antioxidant,
lecithin, is added along with tocopherol, the. effect of the latter is greatly in-
creased. This èffect may not be due to the lecithin itself, but to impurities which
are contained in lecithin (Slanetz and Scharf, 1945). There are several isomeric
tocopherols, individually differentiated by" the Greek letters a, /3, y, and 5. Buxton
(19-47a) found that the addition of 0.1 % of either /3- or y-tocopherol to vitamin
oils markedly decreased the loss of vitamin A and the formation of peroxides dur-
ing atmospheric ôxidation of the oil at 34.5°C. (94°F.). When 1.0% phosphatides
was added at the same time, it enhanced the effectiveness of b,oth tocopherols for
inhibiting peroxidation and vitamin A destruction. Addition of a-tocopherol,
either with or without phosphatides, protected vitamin A during the early stages
of oxidation, but did not retard the formation of peroxides; hence its protection
of vitamin A was not so prolônged as that given by either /3- or -) -tocopherol. As
an antioxidant, s-tôcopherol is more effective for fatty oils, and hence presumably
for vitamin A, than are a, /3, or 7 tocopherols.
. The effect of various antioxidants on the stability of vitamin A in shark liver
oil was investigated by Bose (1947). He found that, of those tried, the greatest
protection was given by 0.04% isobutyl gallate and 0.02^/o citric acid. While un-
treated samples, stored in dark bottles at room temperature, lost 10% of their
vitamin A in one month and 60 % within 10 months, the treated samples showed
no loss of activity during that time. However, when the loss of vitamin A had
once started, the rate of déstruction was comparable to that of the controls. ,
Nordihydroguaiaretic acid (N.D.G.A.), an antioxidant obtained from the
desert plant Larrea divaricata, has been reported by Dassow (1948) to be effec-
tive in stabilizing vitamin A in oils. Addition of 0.1 to.0.5 fo N.D.G.A. (by
weight) to an oil was effective in retarding the oxidation of vitamin A at tempera-
tures up to 97.7°C. (206.6°F.). This antioxidant was, however, much more effec-
tive when used in conjunction with citric or o-phosphoric acid. Good protection
of vitamiri,A was obtained by adding 0.1% N.D.G.A. plus 0.1 % citric acid to the
oil. Other workers, however, have found it less effective.
The, stabilization of vitamin oils and concentrates with 0.1% acetyl methyl
carbinol was patented by Simmons and Buxton in 1943 (U.S. patent 2,331,432).
The emulsification of 3 to 20 parts of blackstrap molasses with an oil to protect
the vitamin A from destruction is covered by U.S. patent 2,410,455 granted to S.
Musher in 1946.
A method of treating fat-soluble vitamin-containing marine oils by which
they are stabilized against deterioration without the addition of antioxidant, is,
described in British patent 589,688, which was grârited to National Oil Products
Co. in 1947. The method consists in treating the oil, either as such"or in a solvent,
with from 1 to. 10% of concentrated ammonium hydroxide, and subsequently
removing the ..ammonia, moisture, and solvent if one was used, by evaporation
under reduced pressure. The solvents suggested are:- CsH44, C7H,6, CsH1B,
C2HZC12, C2HC13, CÇI4, cyclohexane, C6H(6, and acetone.
Finely divided particles of various.inorganic materials in an oil cause loss of
vitamin A potency. Traces of cobalt and copper compounds greatly accelerate
52
the destruction of vitamin A; compounds of lead, iron, manganese, nickel,
aluminum, zinc, and tin also increase the rate of œddation of the vitamin, but to
a lesser extent. Treatment with other materials such as activated carben,or fuller's
earth, which do not directly affect the rate of. oxidative destruction, may speed
up the inactivation of vitamin A by removing the naturally occurring anti-
oxidants from the oil, and also cause loss of potency by removing some of the
vitamin A . itself.
More detailed information on the oxidation of oils, and on the effeets of
different antioxidants used in controlling it, sis given in-Chapters 5 and 6.
The natûre of the solvent in which it is dissolved also has a marked effect
,on the stability of vitamin A. Dann (1932) studied the effect of various natural
and artificial solvents on its destruction during aeration at 98°C. (208°F.). The
percentages which were destroyed by aeration for one hour in the different
solvents were as follows: butyl alcohol 0, amyl alcohol 22, cetyl alcohol 0, acetic <
acid 89, caproic acid 54, lauric acid 93, stearic acid 94, oleic acid 92, ethyl laurate
67, ethyl stearate 87, ethyl oleate 81, amyl acetate 23, triacetin 0, tributyrin 31,
triolein 36, coconut oil 29, peanut oil 60, 20% alcoholic potassium hydroxide 0,
sethyl alcohol (at 78°C., 172°F.) O. The important part which the solvent plays
in determining the rate of oxidation can be seen from these data. There is
apParently no relationship between the rate of oxidation of vitamin A and the
molecular constitution of the solvent, although it is worthy of note that the
vitamin was destroyed more rapidly in all the acids studied, while the rate of
-destruction in some of the alcohols and esters, and in strong alcoholic potassium
hydroxide, was negligible. The source of the vitamin A used in these experiments
was a crude cod liver oil concentrate which showed approximately 100,000 blue .
units per gram by the antiinony trichloride test. It was made up into solutions
" containing 1% of the concentrate by weight.
. Vitamin A is less susceptible to hydrogenation than might be expected from
its highly unsaturated nature. Thus, while hydrogenation at high temperatures
is very destructive, an oil containing vitamin A may be hydrogenated at low
- temperatures without appreciable loss of potency. Drunimond (1919) found
that complete inactivation of vitamin A resulted .when the oil was hydrogenated
for four hours at 250°C. (482°F.). On the other hand, Waterman and his co-
worlcers (1936) have shown that an oil may be hydrogenated at 50°C. (122°F.),
a colloidal nickel catalyst being used, without an appreciable loss of vitamin A
taking place.
Chlorination of cod liver oil was found by Diller (1938) to cause serious
.loss of vitamin A when more than 0.1% chlorine was introduced, whether by
hydrochloric acid, ammonium chloride or direct chlorination. The effect of a -
considerable number of reagents on the vitamin A in cod liver oil was investi-
gated by Cady and Luck (1930). Bubbling sulPhur dioxide through the oil
for 15 minutes at 20°C. (68°F.) destroyed most of the 'vitamin A. Treatment
swith solid sodium bisulphate at 100°C. (212°F.) in a stoppered bottle' caused
no apparent loss in 4 hours, but in 24 hours destroyed thp vitamin A. Bubbling
hydrogen sulphide' through at 100 °C. for 6 hours caused significant ,but not
53
complete destruction, and a similar treatment with ethylene had no effect. Under
the same conditions nitrous fumes, generated by the action of 20% acetic acid
on sodium nitrite, destroyed the vitamin. Neither ammonia gas bubbled through
for 25 hours, nor dry formaldehyde for 1 hour, each at 100°C., had any effect
on the vitamin, but chlorine gas destroyed it in 15 minutes at 100°C. When
• 50 cc. of the oil were shaken with 150 cc. of hydrogen peroxide for 5 minutes
dailY oyer a period of 18 days, partial destruction took 'place. Either 100 cc. of
acetyl chloride or 50 g. of phosphorus pentachleride mixed with 100 cc. of the
oil completely destroyed the vitamin A in 22 hours at room temperature. Addition
of iodine to vitamin A (in hexane) was found by Zechmeister and Polgar (1943)
to result in an increase in the spectrophotometric absorption in 'the region 240
to 280 mit.
Adsorption of vitamin A is discussed under a later subheading in the present
chapter. ( Concentration of vitamins A and D.)
Although the vitamin A potency does not decrease very much during storage
of fish livers, the stability of that vitamin is markedly lower in an oil prepared
from stored livers than in one prepared from fresh. Thus the vitamin A potency,,
of an oil prepared from stale livers decreases more rapidly, subsequent to the
preparation of the oil, than that of one prepared from fresh livers. This decrease
in stability is undoubtedly due io development of peroxides in the oil, under . the
influence of the lipoxidases in the oil. Loss of stability takes place even when
the livers are frozen, but is greater at higher temperatures.
(iii) SYNTHESIS OF 'VITAMIN A
Although a great deal of work on the synthesis of vitamin A has been
reported, it was not until 1947 that the vitamin was prepared synthetically in
a concentrated form: In that year syntheses yielding vitamin A were reported
independently from three different laboratories (van Dorp and Arens, 1947;
Isler et al., 1947; Cawley et al., 1947). Each method was stated to give a product
with similar physical and chemical properties to, and with approximately the
same biological actiVity 'as, the naturally occurring vitamin A.
Although the synthetic vitamin A now competes with high potency oil, it is.
unlikely that it will be able to compete successfully with low potency oils (feed-
ing oils), at least for some time to corne. It is worthy of note that, at the time of
writing, several years have elapsed since the first syntheses were reported, and
yet large quantities of high-potency vitamin-A fish-liver oils are,still being pro-
duced and sold. The technical difficulties in preparing synthetic vitamin A are'
considerably greater than in the preparation of synthetic vitamin D.
(b) PROPERTIES OF VITAMIN D
TABLE 11. Vitamin D potencies of various fish oils before and after saponification, expressed
irr terms of 1 gram of original oil.
After
Original oil saponification Percentage
Oil ( I.U./gm. of increase
( I.U./gm. )
original oil)
Herring .............................................. 31 58 87
Pilchard ............................................ 41 64 56
Salmon .............................................. 115 115 0
Dogfish liver .................................... 10 15 50
Black cod liver ................................ '1,100 1,630 48
Lingcod liver .................................... 2,300 4,600 100
Albacorè liver .................................. 20,000 40,000 100
Bluefin tuna liver ............................ 27,200 46,300 70
Striped tuna liver ............................ 29,600 41,800 41
Swordfish liver ................................ 8,000 8,000
56
livers of the same lot, but which had been stored at -3°C . for 3 weeks before
extraction of the oil, had the same vitamin D potency as the equivalent amount
of saponified fresh oil, and showed no further increase in . antirachitic activity
upon saponification .
The common practice of adding synthetic vitamin D3 to fish oils containing
natural vitamin D to further increase the potency has drawn attention to a very
interesting phenomenon, namely that the potency of the resulting mixture is
considerably greater than' calculated from the amount of natural and synthetic
vitamin D in it . Thus Stott and Harris (1945) obtained the result"s shown in
table 12 with cod liver oils to which synthetic vitamin D3 had been added .
Amount of syn-
Vitamin D Calculated vitamin ° Actual vitamin
thetic vitamin
content of the D potency of the D potency of the
D3 addéd to 1 gm .
cod liver oil resulting mixture, resulting mixtur e
of cod liver oil '
(LU ./gin.) (LU ./gm .) (I .U ./gm .)
(LU .)
90 80 170 206
84 81 165 245
89* 67 156 227
-*Average figures for a comprehensive series of thirteen similar blends, using eighteen pairs
of rats for each assay.
The various forms of vitamin D all belong to the group of naturally occurring
organic compounds known as sterols . They are soluble, like vitamin A; in oils
and oil solvents .
Vitamin D is more stable than vitamin A to heat, light and oxidation . Very
slight destruction of natural vitamin D occurs during storage, samples of cod
and halibut liver oils showing little or no change in antirachitic potency when
stored for 16 months in full glass bottles, either in the dark or exposed to light,
or in completely or partially filled drums . Vitamin D is, however, slowly destroyed
when the oil is heated to 200°C . (392°F .), even in the absence of air, and quite
rapidly destroyed at 450°C . (842°F.) .
Neither saponification of the oil with boiling ' 20% ' alcoholic potassium
hydroxide, nor hydrogenation at 55°C . (131°F . ) for 36 hours, using a colloidal
platinum catalyst, has any appreciable effect on vitamin D . Free fatty acids in
cod liver oil do not appear to have any effect on this .vitamin . Bills (1925) studied
the effects of various chemical agents and steam on the vitamin D in a sample
of crude Newfoundland cod liver oil . He'found that the vitamin was not affected
by hydrogen peroxidès, hydrogen sùlphide, sulphur dioxide, or formaldehyde,
but that it was rapidly destroyed by nitroiis lumes, and slowly by direct steam
or 'contact with mineral acids .
57
It.was found by Nakamiya and Koiznmi .(1940a) that D vitamins in natûral
oils are generally destroyed less rapidly than vitamin A by ultraviolét irradiation,
especially in the early stages. Low concentrations Of these vitamins were found
to favour the, destruction, -
The 'same workers (1940b) found that the increase in extinction coefficient
(wavelength not stated in the abstract) of oils is not proportional to the amount,
of synthetic. vitamin D added, except in the case of tunny liver oil.
A method by which water-soluble derivatives of vitamin D2, and possibly
other D vitamins, can be prepared was patented by Hoffmann-La Roche and
Co., in two parts in 1927 and 1928 respectively. The first ( German patent
495,450 ) covered a method of converting sterols, except cholesterol, to water-
soluble derivatives by treating with a dicarboxylic acid, or its anhydride, in
excess so as to form the acid ester, and converting this.into a salt. For example
ergosterol heated in. tetralin solutiôn ' with excess phthalic anhydride forms
ergosteryl acid phthalate. This in turn is converted into an.alkali salt, which is
water-soluble. The second patent (German patent 567,333 ) covered ultraviolet
irradiation of the sterols before or after thus converting into •water-soluble salts.
(C)- METHODS OF CONCENTRATING VITAMINS A AND D'
A large part of the. vitamins from fish oils is consumed in the form of
concentrates which are prepared by separating the. vitamins from most of the oil
in.which they are present when produced from the raw materials. The term
"concentrate" is appliedin tbe,trade to high potency oils, such as halibut liver,
lingcod liver, and other oils of high vitamin A content. Strictly speaking, however,
conçentrates are preparations which have been made from lower pôtency,ôils
by artificial means. '
The first method used for the preparation of .concentrates consisted essentially
in saponifying the oil, diluting the resultant soaps with water and extracting
the vitamins with a water-immiscible solvent, separating the solvent layer, and
distilling off the solvent. Ethyl ether, light petroleum fractions, ethylene di-
chloride and other chlorinated hydrocarbons, have all been used as solvents in
this,process. The presence,of a small amount of, oil facilitates the extraction of
the vitamins from the soaps by any of the above solvents. Thus the vitamins are
more easily extracted when the saponification is not quite complete than when
it is complete. The use of liquid sulphur dioxide as the solvent was patented by
Mitchell in 1943 (U.S. patent 2,324,012) and assigned to Colgate-Palmolive-Peet.
The saponification process has, however, been largely replaced within recent
years by other methods; especially by short-path distillation, as a means of
preparing vitamin A concentrates. In' short-path distillation the oil is distributed
as a thin film; under high vacuum, on a heated surface, and the vitamin concen-
trate, which distils 'off from it, is condensed on a coôled.surface a short distance
away. "A general review Of the method has been givenby Hickmân (1944). The
preparation of vitamin A concentrates in this way has been described by Howat
(1942a), and of the'vitamin D concentrates by the same author (-1942b).
58
Although in the saponification- prOcess of -coneentrating the vitamins-: from
A and ,vitainin: D are extracted :together,-in the Short-path. fisholbt'vamn- -
distillation proéess they can be remeved from the. oil separately..- '-
Adsorption shows inter esting posSibilities -as a means- of .coneentrating the
vitamins of fish oils. Swain (1943) foùnd that the alcohol, form Of vitaniin.A was
readily adsorbed on alumina or Silicic acid, but that the • eSterforM in which
it is mostly present in natural _oils,. is less. readily , adsorbed .than - thdiriglycerides
of the oil..Swain (1948a) subsequently feund that the„Yitainin.A in an oil- can be
converted to the alcohol form`by- methanolYsis Of the, oil. 'The yitaMin A alcehol
can then be separated from the fatty-acid Methyl esters by-adsorption. A -similar.
methodfcnraigvm_A-foshlierby'aCos"-flwed
by adsorption on alumina Was described by Karnovsky et: al. ,(1948). •
. Adsorption of, vitamin -A-. on Soa.ps formed in situ (Brocklésby and 'ktichel,
1938) offers ,possibilities as a Means of 'concentrating- the vitarnin.Snch ,a method -
would have a' great advantage' in its simPlicity and, furthermore; the oil would
-
be refined in the process of separating ,thê vitamin. , •
Chromatographic adsorption von 7fuller's eare was ,,used' by Gàjjar and
Sreenivasaya '('1945) as ,a method of Concentrating .vitamin A. A shark liVer oil
containing 10,570 I.U./gin. was passed, through a Colùrrin earth- activated
by the method of Burghardt (1931). Three, coloured' zones were ;formed,' the
top one red, the middle one orange, - -and-the bottom': ône yellow.' The adsorbent'
was Pushed dut of 'the' column, and the côleured part divided , into •five fractions, .
each of whiCh Was. ,eluted separatelY.- The eluted Material' frOm the top fraction -
had a vitamin A potency' of 211,000 J.U/gm.; • the elùted Material frona the four'
fraction below, it had, successively, vitamin À petencies-.' cif, .77,200, 5,620, - 6,550
and 8,170 I.U./gm. Thé , material in the filtra te had , a vitamin A - potency -Of
5,660, I.U./gm.
Alkali, treatment of fish' oils fer cencentrating , the vitamins, çan Be used - in
quite another ,way . than in complete - saponification and extraction. In a- patented
process (Buxton, 1946, ,U.S., patent .2,412,706, --assigned to "Nationali Oil.- Products
Company), part of the oil is sal:jellified .under careffilly,•centreiled- Conditions
whereby the vitamin A, esters are n-ot appreciably affeeted ; and ,rerriain in the
of the oil which is not saponified. Dryden and 'Buxton -(11.S.' patent- 2,404365, par.t -
1946, -assigned- to National Oil Pyochicts' Company), found that, a higher pOtency
vitamin 'ester concentrate is 'produced; arid leSs of thê-vitamin ,. \-À ester. is, -
hydrolysed; if the reaction mixture - of çaustic and is kept 'at à uniform
temperature below 35°C. (95°F.) . ' .
Of the numerous other patents is,sued for the ›préparation of vitamin' con
centrhtes from fish oils, only a few'will be cited as-illustrative of the different
types of processes, The Method, described in -British patent 393;883 (Hoffman-
La ROche and Co., 1933) cons'ists in dissolving' the raw material; :which' in the"
the unsaponifiable portion of halibut' liver 'Oil; in a water- examplgivnws
miscible solvent, for examPle methanol, and then adding, water ; With: coo- ling, and .
'59
extracting with a water-immiscible organic solyént, such as petroleum ether.
This seParates the vitamin from much of the nonvitamin materials. The product
of highest vitamin A content was obtained by diluting the methariol solution
with water to a concentration of about 80% methanol, and extracting with
petroleum -ether. U.S: patent' 2,394,968, which was issued to L. J. Van Orden
in 1946 and assigned tO the M. W. Kellogg Company, (Solexol process), covers
the preparation of concentrates from:oils by a method based on solubility, under
controlled conditions of temperature and pressure, in a solvent such as propane,
whose miscibility with the oil decreases as the temperature inCreases. A -rather
novel method was patented by E. M. Shantz in 1946 (U.S. patent 2,410,590,
assigned to Distillation Products, Inc.). It involves inter-esterification of the
triglYceridés with various esterifying agents to form 'water-soluble esters of the
fatty apids. The oil, after this treatinent, is dissolved in ether, and the fatty acid
esters are washed out with water, leaving the vitamin A and other unsaponifiable
constituents in the ether. Fractionation Of fish liver oils by extraction with 91%,
95%,or'99% isoprepanol, 95% acetone, or ,100% methanol, -was reported by
Buxton (1947b ). Each of' the solvent extract fractions had higher vitarnin A
values than the oils themselves. U.S. patent 2,41 2, 561, granted to Buxton in -
1946 and assigned to thé National Oil ProduCts Co., covers concentration of
fat-soluble - vitamins by extraction of the oil with .a. solvent from one of the
followirig classes: aliphatic or alicyclic monohyçlroxy alcohols with fro m 4 to 6
carbon atoms; esters of the same with altogether not more than 8 carbon atoms;
aliphatic .or alicyclic aldehydes with not more than 6 carbon eon's; aliphatic
_ ketones with not more than 6 carbon . atems. •
(d) CANADIAN , SOURCES OF VITM,:lINS A AND D
) RELATIVE IMPORTANCE OF CANADIAN SOURCES
Although nearly all fish,contain at least a small amount of vitamin A, and
generally soine 'vitamin D, the only fish oils now classed as vitamin -oils are those
which contain conrimercially' valuable amounts of vitamin A. The vitamin D
potency can be increased by addition of synthetic vifamin D (D3 for ponitry and
D, for hurnans),. Oils prepared from whole herting and pilchards and from salmon
offal weire formerly rised as sources of vitamins A and D for poultry, but they are
now used simply as base oils with which to blend, to standard potencies, vitamins
A and D from other sources.
In table 13 statistics are given for the landings of fish livers and viscera, and
the production of vitamin oils, in, Canada by provinces, for the years 1942 to 1949
inclusive. Additional data will be found - in the tables in Chapter 10.
Figures for "liver oil Marketed" or "Viscera oil marketed" represent the pro-
duction of such oils within the province where the livers or viscera were landed;
. the figures for "livers .marketed" or "viscera marketed" represent the amounts of
such Materials shipped as such out of the province for which they were reported,
and in which they were lançled, to othèr parts of Canada for processing (there
was an embargo on export of fish livers or visera from Canada). When the
60
TA-ErE-13. Cardian production of vitawiri oils and Taw , rnaterials.
Prov-'
Fish ince Amt. 1943 1944 1945 1946 1947 1948 1949
,
CUD, •
Livers landed P.E.I. cwt. 1,553 876 1,423 2,029 2,804 2,157 2,390
■ $ 3,390 1,824 3,212 5,294 5,797 4,314 5,000 .
N.S. cwt. 29,398 29,842 39,662 49,883 22,953 29,074 41,790
$ 96,775 107,320 133,760 167,425 78,802 96,875 135,000
N.B. cwt. 5,905 4,534 912. 7,6_10 4,811 11,304 13,340
. $' 15,509 14,371 2,736 30,340 20,949 , 58,779 57,000
P.Q. cyt. '18,906 33,995 26,928 20,086 20,604 20,186 25,740
$ 46,651 62,987 152,176 56,526 57,977 53,101 90,000
,
Livers marketed P.E.I. cwt. .... 323 736 729 1,769 1,197 1,920
$ .... 1,039 3,262 3,204 7,271 4,479 8,000
--N.S. cwt. 9,550 7,851 11,680 23,094 17,538' 19,577 24,630
$ 36,921 31,468 52,378 :101,663 85,589 76,831 102,000
N.B. cwt. .... 4,934 2,462 7,523 4,891 3,379 2,380
$ .... 15,571 7,325 , 28,980 20,059 27,072 13,000
P.Q. cwt. .... . • .. 19,436 1,964 .... 15,893 21,410
$ .... .... 59,142 7,207 53,368 90,000
Liver oil P.E.I. gal. 3,620* 2,020* 1,400* 1,352 2,836 2,966 1,390
(medicinal) $ 5,701 . 3,332 • 2,169 2,568 5,248 5,781 2,009
N.S. gal. 126,344 142,099 86,371 162,396 157,348 173,224 83,600
$ 302,085 348,670 211,592 385,252 393,766 420,656 330,000
N.B. gal. 1,960* 495* 3,328 11,995 13,359 19,037 29,600
3 2,156 816 5,807 27,615 41,881 59,967 54,000
P.Q. gal. 94,796 110,904 186,958 134,920 107,963 153,745 122,423
' $ 304,497 304,386 592,173 411,286 383,257 431,058' 253,000
, .
HALIBUT •
Livers landed N.S. cwt. 24 154 169 161 370 ' : 221 630
$ 1,680 5,415 5,436 5,397 12,553 7,079 19,000
N.B. cwt. .... .... .... .... ....
, 77 . , .. .....
$ .... .... .... .. • .
P.Q. ,cwi.. .... 307 52 116
$ .... 1,500 537 440 251 504 ....
B.C. cwt. 1,750 2,177 2,330 2,593 3,532 2,774 2,730
5 113,231 143,057 185,544 159,180 340,592 262,761 263,000
Livers marketed N.S. cwt. 115 156 169 391 289 262 ....
1 $ 6,958 . 7,475 7,998 ' 17,703 13,967 11,896 66,000t
i N.B. cwt. .... .... 3 1 .... .... ....
$ ..... .... 140 77 .... .... ....
-
P.Q. cwt. 5 .... 83 13 .... 20 ....
$ 424 .... 1,221. 728 .... 529 ....
... B.C. cwt., , 127 112 126 221 358 3 10
$ 8,887 8,040 6,308 15,052 41,986 238 1,000
Viscera landed B.C. cwt. 2,556 3,474 3,237 s 2,893 •' 4,634 4,357 4,820
$ 28,839 59,174 59,000 29,499 90,214 89,136 90,000
■
Viscera marketed B.C. cwt. 1 205 187 111 109 .... 810
5 19 2,501 3,739 1,115 1,629 . .... 12,000
*These figures do not include the re fi ned crude cod liver oil.
tData for liVers and liver oils combined in 1949 statistics. -
61
TABLE 13. (Continued).
Prov- » •
Fish ince Amt. 1943 1944 1945 1946 1947 ' 1948 1949
Viscera oil B.C. lb. 14,107 22,781 9,209 18,440 21,742 22,214 11,000,
' marketed, • $ 63,502 86,197 59,865 69,036 173,635 145,672 84,000
BLACK COD
Livers landed B.C. cwt. 533 476 •,432 566 342 653 810
$ '60,520 49,515 60,013 67,029 55,873 125,892 146,000
I
Livers maiketed B.C. cwt. 38 39 19 230 • 56 3
$ 2,045 4,273 2,782 28,505 7,961 215 3,000
Liver oil B.C. lb. 7,601 7,891 7,052 5,435 6,658 15,081 6,000
marketed s 66,209 57,776 64,323 52,538 59,351 170,337 77,000
Viscera landed B.C. cwt. 473 445 494 584 276 1,163 1,090
$ 9,497 12,716 13,849 6,036 7,504 34,602 » 40,000
Viscera oil • B.C. lb. 2,716 4,099 2,489 296 4,738 • 10,932 11,000
' marketed $ 13,851 18,920 16,323 1,304 29,508 48,573 121,000
LINGCOD ‘
Livers landed ' B.C. cwt: 1,495 1,561 1,5551,767
, ' 985' 1 . 297 1,470
'$ 170,516 265,936 282,943 • 253,116 147,429 208,518 210,000
Livers m'arketed B.C. cwt. • 382 154 242 . 221 260 ' 16 100
• $ 37,353 26,645 54,475 40,320 61,038 2,408 12,000
Liver oil B.C. lb. 13,927 20,025 ' 19,173 17,389 11,123 20,605 19,000
marketed • ,s 170,516 310,295 232,493 228,224 136,692 241,485 150,000
' Viscera landed B.C. cwt. 1,571 1,053 • 1,394 1,639 1,046 • 1,279 1,630
13,526 10,645 11,174 12,908 \ 8,899 14,211 16,000
,
Viscera marketed B.C. cwt. 136 • 115 126 111 46 ,7 ' . 50
$ • 1,140 1,147 1,224 1,334 676 79 ....
, Viscera ôil B.C. lb. 8,984 11,462 15,745 23,402 13,317 13,932 21,000
marketed $ • 3,953 8,283 8,184 10,709 • 7,147 10,515 • 8,000
'-
RED AND
ROCK COD
Livers landed B.C. cwt. 357 , • 319 401 305 139 204 • 210
'$ 24,692 25,419 32,661 261435 18,932 34,135 34,000
Liver oil B.C. lb. 356 ' 2,566 5,405 1,341 470 • 3,685 1,000
• marketed S $ 8,875 •27,166 30,886 11,622 5,181 43,777 22,000
Viscera oil B.C. lb. 194 412 ' .... 956 •»••
marketed $ 87 268 . 335 '
S 62
TABLE 13. (' COnti/ilteti).
Fish ince Amt. 1943 1944 1945 1940 1947 1948 1949
Livers landed BC. cwt. 329 122 259 554 259 141 . 290
3193 908 1,751 3,071 1,936 883 2,000
SOLE
TUNA .
Livers landed N.S. 'cwt. 3 5 10 53 ' 127 65 150
$ 75 125 240 1,400 2,818 / 3,180 6.000
,
Livers marketed N.S. cwt. , 9 19 34 193 241 - 45 ....
$ 720 800 2,020 11,415 11,726 2,121 *
SWORDFISH
Livers landed N.S. cwt. 643 496 ' 488 632 • 343 534 460
8 17,199 9,215 10,083 13,153 7,160 14,898 , 11,000
DOGFISH
(GRAYFISH)
353 ' 10
$ .... .... .... .... .... 3,192
B.C. cwt. 45,685 77,696 58,219 28,443 37,593 30,335 33,060
$‘ 1,177,411 2,661,575 1,833,210 888,075 1,087,858 1,123,397 1200,000
.,.
Livers marketed N.S. cwt: .... .... .... ... .... 137 ....
$ .... .... .... 1,362 ....
'•* •
B.C. cwt. 554 1,801 396 421 997 236 230
4 18,982 60,930 10,364 12,258 43,121 11,057 7,000
.
\Liver oil N.S. gal. 30 .... •••• .... ....
,
••••
marketed $ 20 .... .... .... .... .... ....
B.C. lb. 3,509,213 4,969,808 3,880,423 1,843,225 2,453,032 2,113,101 2,224,000
$' 2,028,875 3,661,131 2,337,267 1,098,569 1,439,861 1,634,388 1,540,000
SOUPFIN
SHARK
Livers landed B.C. cwt. .... '615 , 353 90 103 54 40
$ .... 218,337 140,103 . 23,973 28,795 18,679 8,000
Liver oil B.C. lb. 12,926 34,690 20,967 5,005 3,409 5,685 2,000
, marketeél $ 78,886 288,436 162,154 32,870 23,160 23,435; 9,000
MUD SHARK
Livers landed B.C. cwt. 1,408 842 151 .... ....
$ ... , 25,441 19,624 4,308 .... .... .
Liyver oil B.C. lb. 245,444 , 80,828 40,092 8,000 .... . . ....
marketed $ 78,298 28,650 23,506 4,755 .... .... •.•.
-
MIXED SHARK *
Livers landed N.S. cwt. .... ..... .... 6 4 8
$ .••• .... .... 30 30 200
B.C. cwt. 2,651 5,069 197 131 .... .... ....
$ 163,179 157,146 2,150 1,049 .... ....
.‘ quantity of any particular livers or viscera marketed in any province during any
one year exceeds the quantity landed, it is usually because some had been kept in
cold storage from previous seasons and ,were marketed during that year.
The figures for the Atlantic coast production of vitamin oils are not directly
• comparable with those for- the Pacific coast, since the former are reported in
imperial gallons, the latter in pounds..A gallon of fish oil Weighs about 9 lb., so
by multiplying figures for oil production on the Atlantic coast by 9, Or dividing
Pacific coast oil 'production figures by 9, they can be compared directly. The
landings of livers on the Atlantic coasf and of .livers and viscera on the Pacific
coast are both in hundredweights in table 13.
Following the incorporation of Newfoundland into Canada in April, 1949,
future landings of eastern -fish livers, as shown in the Canadian statistical tables,
will probably be somewhat higher. •
In table 14 aré given the vitamin A and D potencies of oils prepared from
furious fishes caught along the Pacific coast of Canada, and in table 15 similar
lata for fish caught off the Atlantic coast. Where available; data are also ineluded
for average oil contents. In some cases the actual fish for which the data are
reported were caught in waters off the United States or Alaska coasts, but clbsely
adjacent to Canada. Man'y of the oils are ,from 'particular -parts of the fish, for
example liver, head, eggs (roe); in some cases it is from the whole fish, and in
some cases from the "viscera", and in some from the "offal". The term viscera
includes all the internal organs except the liver, milt or eggs (roe) ; stomach and
the kidney, which is the so-called "blood clot", against the backbone of the fish.
The offal includes all the waste froni any dressing opération, *usually th. e head,
tail, fins, and all the visceral organs, with the possible exclusion of the liver.
Dogfish liver oil has been, for some years, the liver oil produced in greatest
quantity in British Columbia. It is not, however: produced commercially as a
source of Vitamin A on the Atlantic coast of Canada, because of the low average
potencY of•Ailantic dogfish liver oils. The liver oils from the Pacific coast dogfish
65
TABLE 14: Vitamin >potenciei of oils from Pacific coast fish. I;
Vitamin A Vitamin D
(11.S.P. units (LU.
per gm.) per gm.)
SELACHII (ELASMOBRANCHII)
CYCLOSTOMATA
, .
PI CES (TELEbSTÔMI)
..
Clupeidae Pilchard whole fish 5-25 100- 500 20- 100
liver 6- 8 30,000 - 65,000 200- 300
viscera 8* .... ....
flesh 15** 0 54*
Herring whole fish 5 - 25 30 - 200 25 -160
liver 3-5 30,000 - 60,000 250
viscera 12* 1,000* ....
flesh .... 0 33*
Anchovy whole fish ,12*' - 300 o' 25
Shad , liver 7 - 12 1,500 - 30,000 50 - 100
viscera 9- 15 500- 15,000 20
Salrnonidae Salmon -
Spring liver , 4- 6' 16,
000 - 40,000 100 - 500
viscera 2-6 1,500 - 8,000 100 - 200
eggs 6-13 150 - 600 40*
heads 13** 0 40*
flesh 13** , 0 - 40 35**
offal 10 - 15 1,500 - 2,000 , 50 - 150
_
Source Oil Vitamin A Vitamin D
Family Common name of oil (V (U.S.P. units (TU. per gm.)
per gm..)
-
C-0 sole liver 10 — 15 8,000-12,000 .
Curl-fin sole liver 4— 10 6,000— 15,000 ....
Dover (slirne) sole liver 4-20 2,000 — 15,000 ....
Flat-head sole liver 9 —20 2,000 — 30,000 , ....
Lemon sole liver 2-20 1,500 — 20,000 ....
Rex sole liver 6 --, 20 1,500— 10,000 150*
Rock sole liver 3— 15 2,500 — 40,000 ....
Sand sole liver 5-15 2,500-35,000 ....
Bothidae Sand dab liver 30 — 60 1,200 — 6,000 ....
Merlucciidae Hake liver 33 — 55 1,800 — 12,000 ....
Scombridae Albacorb liver 7-20 10,000 —60,000 25,000 —250,00f
Mackerel liver .... 30,000-200,000 1,400 — 5,400
offal .... 1,700* 75*
Acipenseridae Green sturgeon liver 24* 1,600* ....
viscera 1 . 6* 8,500* ....
White sturgeon liver 10— 50 10,000-15,000 ....
viscera 2— 5 10,000-25,000 ....
Anarrhichadidae Wolf fish liver 6— 10 560* ....
Cattidae Bullhead liver 13* 6,000* ....
Sciaenkfae White sea-bass liver 7-24 30,000 — 60,000 1,200— 6,000
Osmeridae Eulachon whole fish 9.8* 0 0
Plectognathi Sun-fish liver 39* 220* ....
Lampridae Moon-fish liver .... 9,500* ....
SELACHII (ELASMOBRANCHII)
I
Lamnidae Mackerel shark liver 22 - 25 500 - 6,000 ....
Squalidae Dogfish liver 13 - 75 200 - 150,000 3- 25
Rajidae Skate liver .... 1,200 - 15,000 ....
Ray liver .... 280*
PEDICULATI
PISCES (TELEOSTOMI)
70
The determination of vitamin A in whale liver oil is complicated by several
factors. There is present in it a substance kitol, which, although it has no vitamin
A activity, when heated is partly converted, as described in an earlier part of this
chapter, into vitamin A. Attention should also be drawn to the fact that when cal-
culating the vitamin A content of whale liver oils from the extinction coefficient
at 328 m,u, a conversion factor of 1200 has been used in place of the factor 1894
used for fish liver oils to calculate the potency in U.S.P. units.
The principal factor governing the vitamin A potency of fish liver oils is the
age, and thus the size and weight, of the fish. Other factors which may influence
it are the season and locality of catching, the sex of the fish, the per cent of oil, and
the colour of the oil. The last factor is, in some cases, related to the colour of the
livers. * It is difficult, from the available data, to draw general conclusions respect-
ing the vitamin D potencies of fish liver oils; but in oils prepared from the entire
fish, such as pilchard and herring oils, the vitamin D potency is governed by the
per cent of oil, which is generally related to the part of the fishing season when
the fish were caught.
In the following discussion results of investigations on factors influencing the
vitamin potencies of liver and visceral oils of Pacific coast fishes will be dealt with
first, then those concerning body oils of Pacific coast fishes, and finally, those con-
cerning the liver oils of Atlantic coast fishes.
Pugsley (1939a) studied the factors influencing the vitamin A and D
potencies of the liver oils of dogfish ( grayfish ) caught in British Columbia waters.
He concluded that the vitamin A potency was related mainly to the size, and
thus the age, of the fish; the larger or older fish yielding oils of higher vitamin A
potency than the smaller or younger fish. On the other hand, there was no re-
lationship between the size of the fish and the vitamin D potency of the liver oil
which was, furthermore, very small. The vitamin A potency of dogfish liver oil
is also related, to some extent, to the colour of the liver oil. Some of the livers are
dark brown in colour, and have a mottled appearance, while others are light
yellow or cream coloured. The former yield deeper yellow oils, with higher vita-
min A. potencies, than the latter. These points are illustrated by the data in table
17 which are from the above paper by Pugsley.
Data presented in the same paper showed that while the vitamin A potency
of the liver oils from male dogfish was higher than that from non-pregnant
females, the potency of the liver oils from pregnant females was considerably
higher than either. It was also noted that, in general, the vitamin A content was
higher in oils from fish caught in outside waters than in those caught inside the
harbour (Prince Rupert). Furthermore, when the per cent of oil in the livers was
low, its vitamin A potency was generally. higher than that of oil obtained from
fatty livers of fish taken under otherwise similar conditions. There was no
71
TABLE 17 A. Vitamin A and D potencies of dogfish liver oils in
relation to the weight of the fish.
2.65 670 • 6
5.73 5,100 , 7
9.70 45,000 4
seasonal trend in either the oil content of the livers or the vitamin potency of the
liver oil.
In a more recent paper, Sanford (1945) further substantiated the relation-
ship between the age of grayfish (dogfish) and the vitamin A potency of the liver
oil, by showing that the vitamin A potency is related to the length of the fish.
Table 18, which is copied from his report, illustrates this.
It is also stated in this paper that the vitamin A potencies of livers from
dogfish caught in more northerly waters appear to be considerably lower than
the liver potencies of fish caught off Washington and Oregon coasts.
TABLE 18. Vitamin A potencies of livers of mature female grayfish
(Sgualus suckleyi) caught in Hecate Strait, June 18, 1945.
72
. Dogfish have a single heavy spine at the front edge of each of the two dorsal
fins. Sanford and Bonham (1946) made the interesting observation that speci-
mens with blunter, shorter spines had darker cèloured livers. This difference in
spine length of fish with differently coloured livers was most noticeable among
the larger dogfish.
The factors governing the vitamin A potency of soupfin shark livers caught
off the California coast were studied by Ripley and Bolomey (1946). Some of
their results would undoubtedly be applicable to fish caught along the coast of
British Columbia, and so are included here. The percentage oil in the liver and
the vitamin A content, expressed in U.S.P. units of vitamin A in the liver, in-
creased with the length of the shark. The liver oil obtained from adult males had,
on the average, about three times more vitamin A than that from adult females.
The average total vitamin A content of the' liver of - adult male sharks was about
the same as that found in the liver of females without eggs, or containing either
fertilized or unfertilized eggs, while the total vitamin A content of the liver of
females either containing pups or which had recently delivered their pups, was
somewhat less.
« Pugsley (1939b ) studied the factors influencing the yields and vitamin A
and D potencies of the liver and viseeral .oils of the Pacific halibut. As with the
Pacific dogfish, the size of the halibut appeared to be the most important factor
determining the vitamin A potency of the. liver oil\s and, in this case, of the
visceral oils also. The oil content of neither the liver nor the viscera showed any
relation to the weight of the fish. The vitamin A potencies of these oils in relation
to the weights of the halibut are shown in fig. 4.
While the percentage of oil in the viscera did not change appreciably from
month to month, the oil content of the livers tended to be higher during the sum-
me months than in the spring and fall. There was an inverse relationship between
- the amomif of oil in the liver and the vitamin A potency of the liver oil. Thus the
vitamin A potency tended to be lower during the summer than during the pre-
ceding or following months.
The vitamin D potencies of a number of samples of halibut liver oils were
also determined. The values found showed considerable variation but were, in
general, higher during the summer than during the spring or fall. The vitamin D
potency of the liver oil did not appear to be related to the size of the fish or the
vitamin A content of the oil..
Pugsley (1939c) has also investigated the seasonal variations in the vitamin
A and D potency of the liver and visceral oils of the Pacific gray cod. He found
that during the fall and winter months there was a greater percentage of oil in the
livers, but a decreased potency of the oil in vitamins A and D, thali at other times
during the year.
In another paper, the saine author (1940) showed that the vitamin A potency
of lingcod, red, and black cod liver oils was related to the weight of the fish, the
heavier fish yielding liver oils of greater vitamin A potency. The visceral oil from
lingcod showed a similar effect, but there did not appear to be a significant
73
relationship between the vitamin A potency of the visceral oils from red or black
cod and the weight of the fish, although the vitamin A potency of the viscera
themselves showed a tendency to increase with the size of the fish.
220
200
180r
160 L I
LIVER
OIL
.
.
INTESTINE
OIL
0140
M
a 120,
ce
0
cc
Ui
a_
cs, I 00
Ui
ao
60
40
20
FicunE 4. Vitamin A content (blue value) of halibut liver and intestinal oils in relation
to increasing weight (age) of fish. (U.S.P. units=blue units X 1.6.)
74
àeasonal variation is also the predominant,factor affecting the vitamin,A and
.D potencies of the oil prepared .frorn whole pilchards. In table. 19 the oil yields
and vitamin A and D *potencies of a number of samples of pilchard oil produced
-in .British Columbia in 1937 and 1938 are . given. These data are taken from the
report by Pugsley (1942).
-The increase in yield of pilchard oil as the season progresses and the corre-
sponding decrease in vitamin D potency of the oil, is shown particularly by the
figures .for 1938. The progressive increase in yield of oil is a well established
feature of this fishery: Pugsley (1942), using statiStical methods, showed, the
close correlation between oil yield and vitamin D potency of pilchard oil.
' TABLE.19. Seasonal variations in vitamin A and D potency ançl yield of British Columbia
pilchard oil (produced at,Kildonan, B.C.).
The pilchard fishery of British Columbia; which since 1946 has been declin :
an offshore fishery. Probably the fish all belong to the saine generalingrapdly,s
population. Pilchards delivered by the fishing boats to plants located at different,
points have usually all been caught in one locality. Since all the fish move up the
coast in a general northerly direction as the season progresses, the locality of
catching is, to a great extent, a function of the time in the season when the fish
are caught. Local variation .is thus automatically ruled out as a separate factor
affecting the vitamin potency of the oil.
The herring fishery, on the °the-I-hand, is largely' an inshore fishery. There*
are many local populations of herring which differ frOM one another with respect ,
to such factors as their age-weight relationship,. vertebral count, and, so on. It
might thns be expected that locality of catching would be an important factor
in connection with the vitamin potency of herring oil. • .
The data in table 20 respecting the vitamin potency of British Columbia
■
herring oil are taken from the report of Pugsley (1938). They shov '7 no ,regularity
of variation with the season or locality of catching, or with colour. As the herring
75
fishing season progresses, the oil content of the fish gradually decreases. This has
been discussed more fully. in thé preceding chapter of this Bulletin. Pugsley
(1942) pointed out that this general downward trend in oil yield is accompanied
by a general upward trend in vitamin D potency of the oil. There is thus, just as
in the case of pilchard oil, an inverse relationship betvveen the oil content of the
fish and the vitamin D potency of the oil.
TABLE 20. Vitamin A and D potencies and colour of British Columbia herring oil.
Colour
Vitamin A Vitamin D (Lovibond units) '
Date of production Locality of catching (U.S.P. units (International
-. per gram) units per gram) Yellow Red
'p1—cm. cell.
Oils such as British 'Columbia pilchard and herring oils, which are prepared
from the whole fish, may derive an appreciable part of their vitamin A potency
from the contents of the stomach. The same may be the case with the visceral
oils when the stomach is included with the material processed. The nature of the
food of the fish may thus be a significant factor affecting the vitamin A potency
of the oil. Drummond and Gunther (1934) investigated the vitamin A and D
potencies of the oils from phytoplankton (green feed) and red feed (a type of
zooplankton). They found that the phytoplankton oil was considerably more
potent than the zooplankton oil in its growth-promoting action. This was cor-
related with a greater richness of the former in carotene which, as pointed out
in an earlier part of this chapter, is converted to vitamin A in the animal body.
Vitamin D was not pre-sent in significant amounts in either the phytoplankton or
the zooplankton, so their presence in the stomachs of the fish would have no
bearing on the vitamin D potency of the oil. Carotene, when present, would not
be included in the spectrophotometric method of testing for vitamin A. It would
show up to some extent in the antimony trichloride test, although not to its full •
value.
76
•
:MacPherson (1937) rePorted an investigation of the relationship of the oil • •
content of Newfoundlanl cod liver' and the vitamin A potency of the liver oil
to the weight, length and age of 'the fish. The Nitamin A potency Of the oil was, in
general, related torthe latter two - factors, but especially to the age,'since:a slower
growing fish could accumulate a greater quantity of vitamin A in its liver than a
more rapidly growing one of the same size. Thus. the • vitamin A -potency of the
cod liver oil produced depended mainly on the year classes constituting' the
catch. When a year's catch contained an unusnally'large proportion of small fish,
as was the case at least once, in 1935, the average vitamin A. Potency of the, cod'
liver oil was unusually low. -
The relation between the vitamin A and D potencies of cod liver oil and
various factors including the age of the fish, the part of the season when they
were caught, and the locality of catehing, were investigated by Pugsley, Morrell ,
and Kelly (1945 Anheir samples were from the Canadian-Atlantie.coast. They
found. that the older the fish, the greater was the fiotency of the liver in vitamins
A and D. An increase in ,the oil content of the liver and- of the. liver content of
the fish was accompanied by a' decrease.in the potency,of the oil in-h6th vitaming.
contentof the livers increased as .the fiShing season, advanced from-june
té October, and there were corresponding •decrCases in- the vitamin , A and D
potencies. The vitamin D potency was 'signifieantly higher:throughout the season
in the oils from fish caught in certain localities, but the vitarriin A• Potency did not
vary significantly' between localities. , • .
• Factors influencing the vitamin A potency- of the liver oils_ of the Atlantic
dogfish. (Squatas acanthia s) were studied by Tempieman (1944).-He. found. that
• in general the liver oils from immature males had -the lowest vitamin, A potencies;
those from immature. females were somewhat high•er in ipotency; those from : •
mature males next higher; while the most potent oils were tho'se froin'the livers
of pregnant females. There was; however,. considérable overlapping in the ranges
of potency shown .by the' different groups. In pregnant females the vitamin •A
potencies of the liver oils increaSèd greatly with thé size of the fish. An even more
important factor governing the vitamin' A potency of thé liver oil was the per- •
centage of oil in the liver; the., greater the oil content of the liver, the lower was:
its vitamin A potency. The •oil content tum•was found to be dependent, in any
one grouping of fish, on thé size Of theIldiVidual fish. In the saine size, sex,' and
maturity group, when the weight of the dôgfish was low, - the-weight 'of thé liver
,
was low, and its oil content also-low;but the vitamin A potency was high, and the
liVer dark in 'colour; while the reverse conditions weré true for thelarger fish . in ,
the saine gronp. • It was pôinted - out- that the mere fact Of -pregnancy , might not ,
increase the 'vitamin A potency except insofar .as it reduces the amount of. oil in
• the liver withont a corresponding reduCtion• of • the vitamin .A present, pregnant ,
feinaleS ,yielding less oil than immature feMales of the :sainè sizé group.
• • just as with the Pacific dôgfish (SqUalis Sudcleyi), , from: dark -gray livei-s
had a• cônsiderably higher vitamin A potency than oilS fro' in light-Colônred,livers,
but thé light-coloured' livers were heavier, -in the 'same ‘SiTze - grotip ef' fiSh, and
yielded more oil than ,the darker livers.•,-
77
PIGMENTS
Fish oils vary greatly in colour. Some, such as 'cod liver oil ; may be almost
colourless, vvhile others, such as salmon oil, are dark red or brown. In ,rnany of
• the inçlustries using fish oils, only light-coloured oils are acceptable, so that a
consideration of the factors governing the - colour is very important to the Pro-
ducer.. The tWo general causes of the colouration of fish oils are (1) the natural
oil-soluble pigments which océur in the fish, and (2) chemical changes in the oil
which talcé place subsequent' to the time the fish leaves the, water, producing
artificial pigments which also give it colour.
. .
- (a) NATURAL. PIGMENTS
-•,
Most of the red, orange and yellew oil-soluble pigments 'occiirring in plant
,
and animal tissues- belong to, the claSs known as the caroterioids, -the name being .
the principal pigment of carrot roots, Which was the fiÉst :derivfom'catn,
of this group' to be isolated. Thé researches of Enter, Eider and•Hellstrora (1928),•
Moore.- (1929). and others, • have shOWn that Several of thé :Carotenoid pigments
have 'yitarnin..A activity. T,hese "vitamin A preCursor" .pigments are formed in .
plants:. and cOriverted' tnthe vitamin itself, which is coleurless, in ,animalorgan- •
isms Not all -carotenoids have this phy-siological property Most of them are
without vitamin A actiVity.
- The pigment which have vitarnin A ‘activity have not been found in sig- •
nifica' .quàniities in commercial fish oils. -Pfichard ou l contains a little carotene,,,
the conimonest precursor' of 'vitamin A. The :Swedish. -wcirkers Euler, Hellstrom
and:Malmberg (1933) reported findinà a Smalramount Of carotene in salmon. oil, • :
but if has not been found in various Pacific salmon oilà which,have been exam-
ined in this laboratory. :
, A fish oil does , not, however, have to contain . a large amount of • the active
pigments to -he rich in vitamiii A, since fiShes are either. able te cenvert'the active
c-aroterioid Pigment which they get in their' food inte'vitarnin A, or .else reçeivé
it at least partially preformed from the : smaller .forms: of animal life in the sea, -
which,coneitute much-of their food. It is interesting, to note,- hoWéver, .that' the .
potency Of individual fish oils in the colotirlesS, preforrned:vitamin A is frequently, -
in proportion to their degree of pigmentation.' This isaPparently due to a parallel- •
ism .between the storage of vitamin A and the inactive caretenoid pigments in the
liver of the fish. . ,
. Of the various carotenoid.pigments, astacin; or astaxanthin as it is sometimes
called, appears to be the inost cominon,in oils of marine origin. Its, presenceiri red
whale -oil was• indicated by Schmidt -Neilsen, Sorensen, and .Trumpy • (1932) and
Burkhardt and co-workers (1934). Sorensen (1935) isOlated it from salmon oil.• •
Bailey' (1937) has shown .that the ,red Colour of both soc,keye saithon, ' (.Onco -
rhynchus nerka) and red spring salmon (0.„tshawytscha) and also thé steel- •
head (Salim,: gairdnerii) is• due to the presence i of tWo astacin-like pigments.
has also been- found in the liyers, roes and flesh of, varions othér fishes.",Asta.cin
78 ,
Biely and Chalmers (1936) indicated that the pi•inçipal yellow pigment of ,
pilchard oil was fucoxanthin,. .an inactive pigment which originates, in variou s
marine plants and reaches the pilcha rd { either directly, when it is .feeding on the
microscopic plant life of the .sea, or is transferred to , them by various small form s
of animal life in the sea, when these constitute their . food .
The pigments of several samples of pilchard oil have been studied in thi s
laboratory. Fucoxânthin was found in varying amounts in all the commercial oils ,
but was completely absent from two samples of oil prepared from the, flèsh .only.
It is thus apparent that the fucoxantbin in commercial pilchard oil must be de-
rived from the viscera, or the feed in the viscera . Pilchard oil also contàins- some
xanthophylls, pigments which . although somewhat similar, to, carotene do, no t
generally" act as precursors of vitamin A in animal nutrition . Sinall amounts o f
carotene were"present in the pilchard oils, both those prepared from the-whole
fish and from the flesh only .
When . pilchards are feeding on'the so-call ed " green feed" which consists, of
microscopic green plant material, in the sea, the oil produced from the whole
fish has a greenish colour . This tint is stated by Tompkins (1930) to be due to,
the presence of ehloroplryll,, thé green colouring matter of plants, which is dis- .
solved in the oil from the feed in the intestines of the fish .
The carotenoid pigment zèaxanthin has been.,found in halibut xoes, and
another caroteriôid pigment, taraxanthin, in the skins of a large number of di.ffer- ,
ent fishes . . Since both are oil-soluble, thé.y would be present in oil prepared, from
raw materials in which they occur . Of 54 species of fishes 'examined bÿLoinnberg
(1939) carotenoid pigments were present in the skin of all except the Atlantic
dogfish.
Threé isomeric forms of carotene are found in nature . Since their propér-
ties which are to be considered here aie largely the same for all "three, they will
be dealt with together, and referred to collectivély as carotene . Cârotené is a
hydrocarbon, its colôûr being dérived from the particular structure of the mole-
cule. Its solution in oil as well as in most organic solvents is yellow to golden
yellow, dependirig on the concentration, while the carbon disulphide solution is ~
orange-red to blood-red . Carotene solutions .are not, affected by alkalies, but the-
pigment is quite susceptible to oxidation, being rapidly destroyed when, an oil_
containing it is heated in the presence of air, and more .slowly on exposure to air
at room temperature. It is destroyed quite rapidly by peroxides in an oil . Caro .-
tene in solution is also destroyed when the solution is exposéd to light, quite
rapidly by direct sunlight, but ~ more slowly by diffûsed' light . The three, isomeric
carotenes can be characterized as a group by their absorption speçtra : Although .,
varying somëwhat between . the different carotenes, the curve has the same gen-
eral shape for each, with maximâ in carbon disulphide at; 509 to 533 mu, 477 to
496 m,u, and an inflection or maximum at about 463 .mp .
79 '
Xârithophÿlls have a molecular structure similar to caroterie, but have two
or more hydroxyl groups in the molecule. There are a number of different
xanthopliylls; but their propertiës are fairly similar so they wift be dealt with
together. Solutions ofxanthophylls in oils.and many organic solvents are yellow.
Their carbon disulphide solutions are, however, orange-red; never blood-red.
Saponification with 20% alcoholic potassium hydroxide apparently ' does not
affect xanthophylls, which can be extracted iri.the, unsaponifiable fraction, along
with the other carotenoids which are not affected by saponification, Xanthophylls
as a group can be separated from carotene by shaking a petroléum-éther solu-
tion of them with 90% methyl alcohol. The xanthophylls, are taken up in the
alcohol, while the,carotene remains in the petroleum ether. While xanthophylls
; are destroyed by oxidation, -they are, in general, not. so labile as carotene.
Zeaxarithin and taraxanthin are xankhophylls.
Fucoxanthin has a molecular structure similar to the above groups, but con-
tains six hydroxyl groups. It can be éxtracted by 70% methyl alcohol from a mix-
ture of'. carotenoids dissolved in eqiial -parts' of ethyl ether and petroleum
ether. Some xanthophyll is also extracted along with the fuçôxanthin but it
can be separated from the latter by shaking the 707o, methyl alcohol extract with
a mixture of 5 parts of petroleum ether and 1 of ethyl ether, which takes up the
- xanthophyll but not the fucoxanthin. When an ethyl ether solution of fu:coxânthin
is shakerx with 30% hydrochloric acid, the ether layer is bleached and a deep
blue colour is formed in the acid layer.. Some other pigments will under these
conditions impart a green colour to the acid layer, but, fûcoxanthin can be dis-
tinguished by the deep blue colour it produces.
'Pure fucoxanthin is insoluble in petroleum ether, but the presence of a
small amount of fatty'material allows it to dissolve in that solvent. The ethyl éther
solution - of fucoxanthin is orange-yellow; alcohol solutions have a brownish
tinge; and the carbon disulphide solution is deep red. It gives a yellow colour to
oils in which it is dissolved. Fucoxanthin solutions are less stable to_ light than
those of most other carotenoids, bleaching out quite easily. This pigment, is
apparently not affected by acid, but under certain conditions is attacked by alk.li.
It can be dissolved in very, concentrated aqueous solûtions of, potassium hy-
droxide, and cannot be extracted .from 'such solutions by ethyl ether. Heating an
oil containing fucoxanthin to 115°C. (239°F.) in the absence of air does not
destroy the pigment. Both fucoxanthin and other xanthophylls probably are
present, in fish oils as esters of ; fatty acids. Strain and Manning (1942) showed
that thore are three isomeric fucoxanthins, each showing a single spectrophoto-
metric, absorption maximum which in alcohol solution is in the vicinity of 450 mµ.
Astacin, tetraketo-/3-carotene, also occurs in fish oils in the form of esters
which, liké the oil itself, can be saponified by the action of strong alkalies. Keto-
.enol 'tautomerism gives it a hydroxyl group which can act chemically . as an
.alcohol or as an organic acid. When its ester is saponified, an alkali metal com-
pound of astacin is formed.. The latter is quite similar to the fatty acid soaps in
1 80
its behaviour, and cannot be extracted along with the unsaponifiable fraction
from. the alkali solution. The free pigment can be liberated' along with the fatty
acids by acidifying the saponified material. Under certain conditions the alkali
metal compound of astacin separates out at the alkali-ether interface When the
unsaponifiable fraction is being extracted from the soaps with ethyl ether. When
this occurs, the precipitated astacin compound can t)e isolated from the rest of
,the material for examination. According to Lederer (1935) the free pigment,
which can be liberated by acetic acid from the compound thus isolated, is in-
soluble in water, very slightly soluble in ethyl ether, petroleum ether and methyl
alcohol, somewhat more soluble in benzene and ethyl acetate, and very soluble in.
chloroform, carbon disulphide, dioxane and pyridine. Like other carotenoids its
solubility is strongly affected by the presence of fatty material. Astacin bleaches
slowly when an oil containing it is exposed to the light and is rapidly' destroyed
by aeration of the .oil at a high temperature. The absorption spectrum of astacin
has a single maximum at approximatelyS00 mu, although the exact position varies
slightly in different solvents. The physical chemistry, especially surface phe-
nomena, of astacin was investigated by Danielli and Fox (1941).,
Zeaxanthin and taraxanthin both have a molecular structure similar to other
carotenoids; the former contains two hydroxyl groups, the latter has four. The
absorption spectrum of zeaxanthin has three maxima, at 519, 483, and 450 my
in carbon disulphide solution; the absorption spectrum of taraxanthin also shows
three ,maxima, at 501, 469, and 441 mu in carbon disulphide solution.
Chlorophyll is probably the only non-carotenoid pigment occurring naturally
in fish oils. When an ethyl ether solution of chlorophyll is treated with a strong
alkali, it first turns brown, and then back to the original green, owing to the
formation of a stable alkali salt which has a green colour. This alkali salt is soluble
in water, but insoluble in ether. Thus when an oil containing chlorophyll is
saponified, the chlorophyll cannot be extracted with the unsaponifiable matter;
but remains with the soap.
The greenish colour of an oil containing chlorophyll is stable in diffused
light, but disappears when the oil is exposed to direct light, Josing muCh of its
green colour when -exposed to sunlight for even as shôrt a period as one day.
Ile
MLIZUfa ilal »Parr
1.5
10 Eu11,« . ILIUMloom
a
■11;11
6
' Fe1
RE31111 111
4
2 emu
I UMItim
0 01 0 02 003 0,04 003 0 04 007 008 009 010 0 li 0n 0.5 014 g
liver oil darlçened when stored in contact with iron for three nionths. The darken-
ing was accompanied by an increase in the 'iron content - of the oil.. Dehydration
of thè oil had some retarding effect on this colour development, but removal off
the free fatty acids followed by, dehydration caused a more - marked retardation.
Thus the oils of better "quality, whiCh are low in moisture and free fatty 'acid,
suffer less darkening as a result of contact with iron. ,
(d) REMOVAL OF COLOUR FROM FISH OILS ,
There are several physica l . and chemical principles which can be applied
to the -removal of the colour from fish oils. The Most important are adsorption,-
extraction by immiscible solvents ( -Solvents Which will not dissolve the oil),
oxidation and reduction., Although all of these are not used industrially, -each has ,
been suceessfullY used in the laboratory to remove part or all of the colour from
oils, and so they have possibilities . of application on a larger scale. The technical
methods which are now used'in the industrial decolorization of oils are described
in Chapter 8 under "Refining , (c)" (page 233).
Various solid materials . havé the property of concentrating other substances,
particularly liquids, gases or substances in - solution, at their surfaces. This
phenomenon is known as adsorption. Since it is -a surface ,effect, the activity Of
an adsorbent is not only a spécific'property depending on the particular material,
but it is a direct function orthe surface presented. In order .tô, have . a large surface
per unit weight a substance must be in a state of very fine division. This can be
accomplished either by using a finely-powdered adsorbent, Or. by precipitating
the adsorbent dirnctly in the oil in . the form of fine p-articles. Adsorbents belong-,
ing to both the above- classes can be used to remove the celourhig matters frorn
fish oils. Among the finelypowdered adsorbents there are - yaiiims "activated"
charcoals and earths which have been found suitable, while decolorization 'by,
alkali refining is an example of precipitating the adsorbent directly, in the oil in
the form of fine particles. Alkali refining- consists in neutralizing the free.fatty acid
of the oil with à concentrated solution of caustic -Soda or .càustic potash, allOwing
the soap thus formed to settle out, then drawing off, -the clear oil. While the soap
formed appears to be liquid, it is actually in the form of very small'particles' sus-
pended in the aqueous phase. These Small soap particles are. very powerful
adsorbents for the pigments in the oil. The adsorptiVe effect of soaps Was men-
tioned in connection with the concentration of vitamin A (page 59).
While the separation of pigments by their - distribution between immiscible
solvents is used to a cônsiderable extent in the study of natural piginenfis in the
laboratory, the method has not found very great industrial application since the
solubilities of some of the pigments are similar to that of the oil itself and they.-
cannot be thus separated from it. In industrial decolorization it is usually desired
to remove all the colour, or as much of it as possible; . not merely to separate certain
individual pigments. There are, howe'ver, interesting possibilities of removing
. 83
chlorophyll, the green plant pigment whiçh is sometimes found in pilchard oil,
from the oil by such a method on an'industrial scale, since chlorophÿll is soluble
in 80 /o acetone or 90% alcohol, neither of which will dissolve the oil to any
great extent.
I Both the natural pigments of the oil'and those developed in it after the time
the fish was taken from the water can be removed by adsorption. Oxidation, on
the. other han.d, will remove only the former. In bleaching an oil by oxidation,
it is also necessary to exercise considerably more care than by the other methods
since, if the process is carried too far, the oxidizing agents will attack the oil
itself, causing it to darken. Oxidation of the pigments may be carried out in
variousi ways.. An oxidizing agent such as sodium or potassium hypochlorite,
sodium, or potassium dichromate, sodium or,potassium permanganate, or sulphiiric
acid can be used in suitable concentration; or air can be blown through while
the oil is kept at a moderately' elevated temperaturé.
When an oil is reduced the natural pigments are destroyed, owing,to the
fact that their colour depends largely on the presence in the molecule of a num-
ber of conjugated double bonds which are lost when the oil is hydrogenated or
reduced by other means. Although reduction by hydrogenation. is used to con-
vert a liquid oil to a solid. fat; considerable decolorization may be accomplished
before the oil itself is, changed to an appreciable extent, since the pigments are
destroÿed. very rapidly by hydrogenation. Reduction apparently does not
affect the pigments which have been' developed in'the oil after the time the fish
was removed from the watér.
It is inadvisable to decolorize an oil which is to be used as a source of vita-
mins since most methods of' decolorization cause a loss of vita^nins as well as of
pigments. Oxidation and reduction are the most destructive. Drpmmond and
Hilditch (1930) state thât:
we are strongly of the opinion that anything of the nature of "blowing" of cod
liver oil with a view to improving its appearance is bound to have a very detrimental
result on the medicinal value of the product and may actually confer harmful properties
on the oil. I
For practical purposes, therefore, we are left with the alternatives of removal of
stearin ['stearine] and foreign matter by mechanical separation, and of'improving the
odour, flavour and colour, if necessary, by treatment with adsorbent materials such as
Fuller's earth, silica gel, charcoal, etc. We feel that, the ideal treatment would be merely
to separate stearin [stearine] and other material by chilling thé oil and expressing the
liquid portion, but we are also aware that, in some cases at all events, the product so
obtained may• be sufficiently strongly coloured and flavoured to render some further
décolorizing and deodorizing treatment desirable.
84
in water, but soluble in ether and most other organic solyents-, including oils,
thoûgh only slightly ,in cold alcohol. ,The various known sterols have a complex
molecular structure, similar to that shown below for cholesterol, the different
sterols differing only in details such as the nuinber and position of the double
bonds, and nature of the "side chain", the irn-ring part of the molecule attached
to the side of the five-carbon ring. All have a secondary alcohol group, in the
same position, capable of esterification with fatty acids. Most have one or more
double bonds which can be hydrogenated or reacted upon-by bromine and other
reagents. Individual sterols characteristic of various' marine animal tissues have
been isolated, for example, stellasterol from star fish, ostreastérol from oysters
and other mollus,es, actiniasterol from sea anemones;- but the only sterol occur-
ring in appreciable quantities in marine oils is cholesterol ( acCompanied by ib
esters).
Cholesterol (C201-144CHOH) has the -following molecular 'structure:
CH, CH,
CH— CH, ---,-CH 2-CH 2-i-H
H2 CH3 I /1-1 I -
CH,
112/C:\ VC
CH2
H 2 CH, I/ 1-1
/C\1 /C\ <CH--CH2
H2 C C Cholesterol
H
Ftox c C CH,
\C/
112 H
Cholesterol forms silky, needle-like crystals, melting at 148.5°C. (299°F.)
-when crystallized from non-aqueous solvents, and small, waxy, plate-like crystals,
-containing water of erystallization when crystallized from 80%. to 90%, alcohol.
The specific gravity of cholesterol is 1.067, the iodine, value 65.7. Its solu-
•bility in parts per 100 parts of 'solvent is: 0.25 in cold water, 1.08 in cold alcohol,
11.0 in boiling alcohol, and it is much greater in ether, beniene,, chloroform and
-other organic solvents, even when cold. Despite its low solubility in water, -true
colloidal solutions and emulsified suspensions of cholesterol in water are readily
:formed. The one double bond in cholesterol is readily hydrogenated to yield s-
cholestanol;. the crystalline dibromide addition product of cholesterol (melting
point 123°C. (253.4°F.) ) is used for identification purposes. In the natural state,
-the secondary alcohol group of cholesterol is frequently esterified with fatty acids
,such as oleic, palmitic and stearic. The saine alcohol group .may be artificially
esterified to form soluble sulphonates and other derivatives.
The intake of cholesterol or its esters in the amount ordinarily secured
throirgh the medium of medicinal fish liver oil, or fish oils for animal feeding, has
:-no undesirable effect on the organism (Kimizuka, 1938) ,. - -
Determinations of the cholesterol contents of a number. of Canadian fish
iliver oils and fish liver oils from elsewhe're gave the following results: halibut,
85
7%; lingcod, 9%; Pacific dogfish, 1 to 4%; ratfish, -29'9; monkfish, 3%; sleeper ..'
shark, 0.6%; sôupfin. shark, 2%; .'mackerel shark, 6%; marbled sculpin, 2%;
Atlantic cod ( av. ) 0.3%; Atlantiç dogfish, 3%. -Salmon: egg oil contains, approx-
imately 3% cholesterol; -commercial pilchard oil contains approximately 0.7%.
Although not a common marine animal oil, it is worthy of note that a.sample of
the -ôil- prepared from American shrimp waste was found to contain 197o
cholesterol., It is probable that oil extracted, from Canadian shrimp waste would
contain a comparable, amount.
The liver oil of the basking shark has been studied by various workers, whose
data on the cholesterol content differ widely. The oil from the liver of a basking
shark caught in British Columbia waters was found, in these laboratories, to con-
tain 2.5% cholestérol. Cholesterôl contents of from, 3.7% to 18%' have been re-
ported for, the liver - oil of thè same fish (Cetorhinus maximus) caught in other
parts of the world.
In an extensive investigation of the relationship between the percentages of
unsaponifiable matter4n various.tltlantic fish liver oils and sterol contents of this
unsaponifiable matter by Channori (1928), it was shown that the higher the per=
céntage of unsaponifiable matter in the oils, the lower was the percentage of total
sterQls in the unsaponifiable,matter.
In -the, case of the Selachii, where the greatest ranges were found, it was.
particularly observed that the sterol contents, in general, were highest when the
total ^âmount of unsap'onifi'able.matter was lowest. All sterol contents below 8%
of the unsaponifiable matter iri,the liver oils,of the Selachii were confined to one
family, the Squalidae,( including the Atlantic dogfish), in which the highest
percentages of unsaponifiables were found.
The relation between sterols and vitamin D is discussed on pages 55-56 of
this chapter. -
A study of nine species of. Japanese 'elasmobranch- fishes showed that, for
widelÿ differing species,. the ratios of cholésterol tô total unsaponifiabl,e matter
varied between narrowlimits (Uéno and Nakaguchi; 1937)'.
- Cholesterol is obtainable from the ûnsaponifiable fraction of fish liver oils, as ,
a by-product in the manufacture of vitamin A concéntrates from such oils by the
saponification process. The unsaponifiable matter containing the cholesterol and
various other constituents is dissolved in an approximately equal quantity of. hot
methyl'alco,hol, cooled to -15°to -20°C. (-1-5° to -4°F.),and kept at that tém,-
pérature overnight. The cholesterol separates as a crystalline precipitate. It is
filtered off and washed with cold absolute methyl alcohol. Halibut liver oil gives.
a good yield of cholesterol, and the preparation is simple, since there is very littlé.
other material with it which would cause interference or contaminate it. These
laboratories recently re-investigated.the recovery of choléstérol from halibut liver
oil (Kristjanson, 1951). The recovery.was simplified by using methanolpsis instead
of preliminary saponification,'. following this by an adsorption procedure, to,
separaté`the cholestérol from the_bulk of other components. -
86
A combined adsorption and extraction method for the commercial .pro-
duction of sterols from vegetable oils was described by Kraybill, Thornton and
Eldridge (1940). The method was developed for soybean„ oils, but should also
be applicable to fish oils. It consisted in adsorbing the sterols directly fro m .
the oil by aluminum silicate, eluting- ( extracting) from the oil-saturated -adsorbent
vvith- acetone, distilling off thé acetone, and extracting the sterols with methanol
from the oily concentrate thus obtained.
The possibilities of producing cholesterol from fish meal have been. investi-
gated at the Atlantic Fisheries Experimental Station. O'Leary" (1947) determined
the cholesterol contents of six samples of fish meal produced in Nova Scotia, and
found that they ranged from 0 lb. to almost 10 lb. per ton of meal. Price (1946)
worked out a process for obtaining the cholesterol from fish meal. The Meal is
first extracted with trichlorethylene, and the extract evaporated to dryness. The
phosphatides are removed by treaiment with acetone. The resultant oily material
is saponified, the unsaponifiable fraction extraCted from the saponified' material
with ether, and the ether distilled off. The extract is then're-saponified and re-
extracted with ether. Treatment of the final unsaponifiable fraction with- activated
carbon and then recrystallization from alcohol, yields pure cholesterol.
Cholesterol is used for manufacturing the closely-related sterol, 7-dehydro
cholesterol, which when irradiated is converted into vitamin D3. It is also u`sed
in manufacturing cosmetics, ointments, and other pharmaceutical products, chiefly
hormones.
Crude cholesterol can be purified 1));' heating and agitating with nitric aciçl
at 140° to 250°F. (60° to 121°C.). The resulting 'wax-like or viscous substance
is suitable for leather dressing, waterproofing, water- and acid-proof packings,
etc. (British patent 179,241, Conyers, 'Reynard, and Lanoline Extractors Ltd.,
1921).
87
A fourth ether, skesyl alcohol ("M.P. 64-65°C.) has been reported. It appears
to be the glyceryl etherof myristyl alcohol, CY4H29OH. Swain (1948a) has given
evidence of other, more highly-unsaturated glyceryl ethers in some British
Columbia fish oils.
The two remaining alcohol groups of these glyceryl ethers appear to be
almost entirely esterified with fatty acids, but as yet no definite statements can be
made as to which acids are combined with the different glyceryl ethers, since
these acids are split off during isolation of the unsaponifiable matter.
The glyceryl ether contents of a number of samples of British Columbia fish
liver, oils are given in table 21. These were determined by Morton (1944), Swain
(1945a) and Swain and McKércher (1945).
TABLE 21. Glyceryl ether content of some British Columbia fish liver oils.
The above figurés represent the percentagés of total mixed glyceryl ethers' in
the oils. The mixed glyceryl ethers of dogfish liver oil containéd from 10 to 20%
chimyl alcohol; the rest of it is mostly selachyl âlcohol.
In addition,to the fish oils,,a sample of sperm whale oil was analysed and
found to contain approximately 0.36% glyceryl ethers.
In general glyceryl ethers are not important constituents of fish oils or marine
mammal oils. From a nutritional standpoint they appear to be valueless having
neither growth-promoting nor, antirachitic properties.
The glyceryl ethers can be prepared as a group, without separating the in-
dividual members, by the method of Swain (1945b) which is briefly as follows:
--the oil is saponified, the unsaponifiable matter dissolved in petroleum ether, and
the solution passed through a vertical tube filled almost to the top with tightly-
packed âlumina. The contents of the tube are, first washed with methylene
chloride, which takes but some materials which would otherwise contaminate the
glyceryl ethers, and then with ethyl ether, which elutes the glyceryl ethers.
Little if any commercial application of the glyceryl ethers has been made in
Canada, although several patents have been taken out in other countries covering
their utilization for various purposes. The use of sulphoiiated glyceryl ethers for
cutting, cleansing and dispersing agents is the subject of a British patent (Brit.
398,818, Baldwin and Bunbury, 1933). In one American patent (U.S. 2,038;705,
Baldwin, Heilbron and Jones, 1936), it is` stated that glyceryl éthèrs are useful as
88
ingredients, of textile treatment media, and as perfume fixatives . Another (U.S .
2,101,831, Baldwin and Bunbury, 1937) covers the prodùction from selachyl .
alcohol of a product suitable for use in flax-retting,,sizing, fulling, bleaching, mor-
danting and mercerizing baths, and also as a detergent, especially for cléansing
raw wool in hard water .
(C) PHOSPHOLIPIDES
roe in such a way that they are not removed by extraction at a temperature below •
40°C. (104°F) , with non polar solvents, but can be extracted with alcohol. Thus
fairly pure phospholipides can be prepared from salmen roes by drying the latter
at a temperature not exceeding 40°C., extracting first with petroleuni ether or
other low-boiling petroleum solvent to remove the oil, and then with boiling
methyl or ethyl alcohol, which extracts the phospholipides. They can also be
obtained, from' salmon egg oil prepared by cooking and pressing the roes, since,
- after cooking, the lecithin is removed by the oil. Goss (1947) foUnd that the
lecithin can be separated from oil by washing the oil twice with 2% to 5% of
hot water, and: centrifuging/to, remove the resulting sludge of water and lecithin.
The water is removed from the lecithin at 60°C. (140°F. ) under vacuum, and
the Product bleached with : hydrogen - Peroxide. Thé residue oil 'in the lecithin
can be removed by several extractions with acétone. Two successive washings
of the oil were necessary in order to, obtain most- of the lecithin. The salmon egg
oil from which the lecithin was thus prepared' was extracted from the roes with
several successive Portions of acetone 'followed by alcohol. at 76°-79°C. (169°-
172°F. )..
, Most of the lecithin used commercially is, at the time of writing, derived
from egg yolk and vegetable sources, much ,of, it frem soybeans. Salmon roe
lecithin, if sufficiently purified to remove the fishy taste, might well be substituted
for that prepared from other sources. A method of removing the ,other fatty
substances from lecithin is described in U.S. patent 1,5 86,145, granted to Dengler
in 1926. The method consists -in combining the lecithin with cholic acid /salts,
extracting the fattir material from it with a fat solvent, and then breaking up the
lecithin—cholic acid—salt combination. Lecithin can be deodorized by treatment
with steain. or an inert gas under vacuum ( German patent 487,335, Hall, 1925).
'Lecithin is Widely used in the food, pharmacéutical and cosrnetic industries, espe-
cially for stabilizing emulsions. Since lecithin is an antioxidant as well, as an
emulsifying agent, it has the added advantage of protecting from rancification the
oil in emulsions stabilized with it. Other applications of lecithin include use in'
textile finishing and leather dressing.
(d) HYDROCARBONS
Hydrocarbons in fish oils were first recognized by Tsujimoto (1906) and
later, received some pi -eminence when a shipment , of Atlantic shark liver oil
from Lisbon was refused drç London on the grounds of alleged adulteration with
mineral hydrocarbon 'oil. Further examination disclosed that the hydrocarbons
were natural constituents of the liver oil. It is now recognized that hydrocarbons
may cônstitute 85% or More of the unsaponifiable matter of Certain shark liver
- oils.
90
The principal hydrocarbon present in the liver oil of fish belonging to the
shark family has been shovvn to be highly unsaturated, and is known as squalene
(C301-15)). Its structure as proved by synthesis reveals the presence of six un-
saturated bonds per molecule:
CHaN , / CH3
,`C CH(CH2)2C = CHçCH2)2C = CH(CH2)2CH =C(CH2)2CH = C(CH2)2CH
CH/ 1' I j CHa
CH, CH, CH, CH,
Squalene
91
Hydrocarbons/ with possibly eight unsaturated bonds have been reported as
occurring in the liver oil of a Japanese sea perch; and two unsaturated hydro-
carbons, C131-114 (orange-red crystals melting at 105 0 C, ) and CIAH ia (red crystals
melting at 126°C.), possibly of the naphthalene hydrocarbon type which would
explain their high melting points, are stated to occur in the unsaponifiable por-
tion of. a Japanese cod liver oil.
The origin of hydrocarbons in marine oils does not appear to be directly
related to the nature of the food ingested by the animal. No squalene could
be found in samples of the plankton on which many feed, and the irregular dis-
tribution of hydrocarbons in the species of fishes would indicate that these hydro-
carbons are syntheSized for some as yet unrecognizable purpose in most Selachii
(principally the family Squalidae, including the dogfishes ) but only in very small
amounts or not at all in the Pisces. One species of Squalus having 35.6% squalene
in the liver oil was-reported to contain none in the oil from the other parts of the
body; other investigators have demonstrated its presence in the fish egg oil, in
the unsaponifiables of sperm whale blubber oil, and in the peculiar reservoir of
oil found in the stomach of the small shark Scymnorhinus lichia. Over one half
of this oil is unsaponifiable matter containing 98% of squalene.
The hydrocarbon content of a number of samples of British Columbia marine
oils has been determined by Morton (1944), Swain (1945a) and Swain and Mc-
Kercher (1945), who obtained the values given in table 22.
Values for the squalene content of basking shark liver oil ranging as low as 13.8%
have been reported elsewhere, so 49% is probably near the upper limit of the
range. Squalene has been found in very small amounts in Newfoundland cod liver
oil (Drummond and Baker, 1929).
In general, squalene is found chiefly in fish liver oils with a high content of
unsaponifiables, although the converse is not necessarily true.
In an extensive investigation of the liver oils of sharks, rays, skates and
• chimaera (raffish) Tsujimoto (1932 ) drew attention to the fact that the lower
the specific gravity of the oil, the more squalene it contained. None of the oils
studied which had specific gravities above 0.9100 contained any squalene at all,
92
but those below 0.9000 showed .increasing squaléne content with decreasing
specific gravity. This effect is understandable from the specific gravity of squalene
itself, which is 0.8591 at 15°C. (59°F.) and 0.8559 at 20°C. '(68°F.). In this
work Tsiijimoto examined the liver oils from fifty-three of the sixty-odd different
species of shark found in Japanese waters, nineteen species of ray and-five species
of chimaera. Squalene was not found•in any of the rayS or chimaera, nor in thirty-
four of the sharks. The liver oils from nineteen of the sharks contained it in
amounts ranging from a "small quantity" to 84.5%. In- the case of basking shark
liver oil the squalene content covered a range of from 9.8% to 13.8%.
Squalene has been administered to rats and rabbits without resulting in any
evidence of harmful effects. Its action on man has not been fully investigated,
but it appears to be harmless, with little or no nutritive value. No antirachitic
properties have been observed, even after irradiation with ultraviolet light. It
is of interest to note that squalene-containing fishes are remarkably free from
parasites.
The hydrocarbons can be isolated from oils containing an appreciable
amount, such as basking shark liver oil, by either chromatographic adsorption or
distillation methods. When a petroleum-ether solution of the unsaponifiable mat-
ter from the oil is passed through a vertical tube filled with activated alumina,
the other constituents are held by the ahunina, while the hydrocarbons go right
through, and can be recovered from the solution by distilling off the solvent. U.S.
patent 2,169,192, granted to Baxter in 1939, describes the separation of the
hydrocarbon fraction in the concentration of vitamins A and D from fish oils
by short-path distillation.
Some of the properties of squalene are as follows. Viscosity: Ostwald viscosi-
meter-14.3 at 59°F. (15°C. ); Engler-2.4 at 77°F. (25°C. ); Redwood-91 seconds
at 59°F. (15°-C.) and 78 seconds at 70°F. (21.1°C. ). Flash point 383°F, (195°C.).
Ignition point 473°F. (245°C.). Calorific value 19,400 B.T.U. per pound. •
The principal use of squalene at the present time is for finishing natural and
artificial silks, to which it imparts an unusually brilliant sheen. Other uses which
have been suggested for it include: as a lubricant, as a carrier of perfumes, and
for filling thermometers. British Patent 345,573, granted to Bunbury and Sexton
• in 1930, describes the use of halogenated squalene for condensation with other
substances to form dyestuff intermediates, and U.S. patent 1,991,999, granted to
the same men in 1935, mentions the use of squalene ,hexàhydrobromide as an
intermediate in the manufacture of retarding agents for rubber manufacture.
The treatment of squalene-containing oils with, an excess of a sulphonating or
sulphating reagent to form products suitable for use as emulsifying agènts in the
textile, rubber, and other industries is the subject of U.S.- patent 1,961,683, granted
to Bunbury, Sexton and Stewart in 1934.
(e) WAXES AND FATTY ALÉOHOLS
Marine animal waxes are fatty acid mono-esters of fatty alcohols and are
therefore chemically distinct from the fats and fatty oils which they superficially
resemble. The word "wax" is used here in its chemical sense, for some marine
93
animal waxes are liquid at room temperatures. The term is rather loosely applied
to other types of compounds which are not true waxes; for example paraffin "wax",
which is a mixture of hydrocarbons, and Japan "wax", which is actually a fat.
The chief source of marine animal waxes is the oil found in the head cavities
and tissues .of the sperm and, to some extent, bottlenose whales, though the head
oils from both are classed together as sperm oil. Fatty alcohol esters are, also
present in the head or blubber oils of most species of marine mammals and in
small quantities from the oils of some fishes. Sperm whale oil is liquid at the body
temperature of the animal, but becomes semi-solid on cooling, owing to the
separation of a mass of fine crystals. By chilling to about 0°C. (32°F.) and press-
ing to remove the residual oil, a white crystalline substance is obtained, amount-
ing to about 12% of the original oil. This material is the spermaceti of commerce,
and consists of a mixture of true waxes, the chief constituent being cetyl myristate
(the ester C13H27C0.0C161133 from myristic acid C13H27C00H and cetyl alcohol
Ci6H330H).
The waxy portion of a marine mammal oil consists of a mixture of several or
many chemically different waxes. Thus commercial spermaceti contains, in addi-
tion to cetyl myristate, variable proportions of cetyl laurate, cetyl palmitate, and
other waxes, as well as small amounts of true fats. Sperm whale head or blubber
oils have been shown to contain waxes consisting of saturated fatty acids having
12, 14, 16, or 18 carbon atoms ( see' table 1) or mono-unsaturated fatty acids
having 12, 14, 16, 18, 20 or 22 carbon atoms ( see table 2 ) esterified with one of
the fatty alcohols listed in table 23.
The waxes are all insoluble in cold or hot water but dissolve in hot alcohol
and in most organic solvents such as ether, chloroform or benzene. When pure,
they are colourless liquids or white, waxy solids, lighter than water, and do not
oxidize and form films on exposure to air, or become rancid. However, commercial
spermaceti may turn brownish and acquire a rancid odour after long exposure
to light and air, probably due to the presence of non-wax substances as impurities.
Waxes in general are much more difficult to saponify than the fats; the resulting
alcohols, which correspond to the glycerol from fats, are, unlike it, insoluble in
water and thus hinder access of the saponifying agent to the material which still
remains unsaponified. Spermaceti requires refluxing for one hour with 15%
alcoholic alkali for complete saponification whereas most fats would be saponified
by this reagent in half an hour.
Sperm whale head oil contains, along with the waxes, approxiMately 26%
true fat; the blubber oil contains approximately 34% true fat. The differences in
the ease of saponification can be used as a basis for separating the waxes from
this fat. A short saponification converts all the true fat to soap without greatly
affecting the waxes, which can then be extracted, as esters, with any of the sol-
vents commonly used for extraction of the unsaponifiable matter ( ether, petroleum
ether, etc.).
Since waxes such as the various grades of spermaceti are mixtures of several
individual esters, their physical constants are best expressed between limits. Thus,
spermaceti may have a specific gravity of from 0.94 to 0.96 at 20°C. (68°F.),
94
0.808 to 0.816 at 99°C. (210°F.); its melting point is from 40.5° to 47.2°Ô. (104.9°
to 117.0°F.). Chemically individual waxes are difficult to isolate from the natur-
ally occurring substances, but may be prepared synthetically. The melting points
of a few synthetic waxes from saturated constituents are as follows: laury laurate
21,1°C. (70.0°F.); cetyl palmitate 55.5°C. (131.9°F.); stearyl laurate 37.2°C.
(99.0°F.); stearyl palmitate 59.4°C. (138.9°F.); cetyl myristate, 50.5°C.
(122.9°F.); and cetyl stearate 60.5°C. (140.9°F.) .. Unsatuu:ation in either the fatty
alcohol or fatty acid constituent considerably lowers the melting point, giving
rise to waxes that are liquid at room temperature. -
Fatty alcohols may be prepared, as indicated above, by the saponification' or
hydrolysis of marine animal waxes, and are also reported as existing in the free
state in some marine animal oils; sperm whale head oil has been reported to con-
tain cetyl alcohol and appreciable amounts of oleyl alcohol, the latter being also
present in small amounts in certain fish liver oils. The fatty alcaols are colourless
liquids or white microcrystalline solids with practically no odour, and a slightly
greasy feel. Some of the fatty alcohols whieh have been reported ai occurring
free or in combination in marine animal oils are shown in table 23.
Natural and synthetic fatty alcohols are used in cosmetic preparations, and
also in the manufacture of polishing compounds, defoaming agents, special soaps,
pharmaceutical products such as coatings for tablets; as emulsifiers they allow
the formation of both the 'water-in-Oland oil-in-water types, and when sulphated
or sulphonated they form other valuable detergents particularly for the fur and
leather industries.
TA L E 23. Fatty alcoho s of marine animal,origin.
Unsaturated alcohols:
Atrophyl Cn1-1 1501-1 liquid 95* 0.826
Macrocephalyl C 1 0l-1 1 ,01-1 101* 0.834
it
Odontocetyl C121-1 e0F1 157* 0.840
Physeteryl C141-1,,01-1 " .... 0.847
II
Zoômaryl Cull-LOH .... 0.850
It
Oleyl Cps1-1360H 209* ....
RIPLEY, W . E., AND R . E . BOLO\dEY . Cal. F7sh and Game Comm ., Fish Bull., 64, 39-72, 1946 .
97 . ,
CHÀPTER FOUR
V. EFFECT OF RANCIDITY
The development of rancidity, and the factors influencing it, aré dealt with
in Chapter 6 of this Bulletin, but a brief summary will be given here of the effects
on the animal organism', residting from the ingestion of rancid fats. The findings
of different workers are, in several cases, quite contradictory although in others
there is more agreement.
Lease et al. (1938) found that rancid fats inactivate vitamin A in the diet
when fed simultaneously. (The destruction of vitamin A is discussed in consider-
able detail in the preceding chapter; methods of controlling the destruction of '
vitamin A are also described there.) Pavcek and Shull (1942) found that biotin,
one of the B vitamins, is destroyed by rancid fats. Vitamin E deficiency may result
from feeding rancid oils. This was indicated by Mattill and Golumbic (1942)
who found that the addition of 3% rancid cod liver oil to the diet caused muscular
dystrophy identical with that caused by a dietary deficiency of vitamin E.
Although observable when a presumably non-rancid cod liver oil was fed, the
effect was far more marked with a definitely rancid oil.
' In addition to their effects on vitamins in the diet, rancid fats cause various
other ill effects. These include anœmia (Gyorgy et al., 1942; Burr and Barnes,
1943), retarded growth (Barnes, 1946), and resorption in pregnant females
:(Kudrjashov, 1933). This last effect might be ascribed to destruction of vitamin
E in the diet, but the author definitely stated that such was not the case. De-
generative changes have been found in the testicles of rats fed 10% to 25%
rancid fat in addition to a diet containing ample vitamin E (Kolodziejska and
Duszynska, 1939). However, Deatherage et al. (1941) reported that neither
rancid fats, their volatile oxidation products, the unsaponifiable fraction of
irradiated fats, nor some aldehydes, interfered with reproduction in female rats
receiving an adequate diet. Rancid fats (25% ) in the diets of both dogs and rats
104
were found by Whipple (1932, 1933) to cause symptoms similar to those resulting
from a low-fat diet. It was suggested that these effects were due to destruction of
unsaturated linkages. Quackenbush (1945) found that administration of 20 mg.
of oxidized wheat,germ oil or corn oil daily to rats receiving a diet in which the
only B vitamins contained were thiamine and riboflavin, resulted in prompt cure
of the acrodynia; however, in many cases this was followed a few wéeks later, by
relapse and . death. Quackenbush suggests that these results, and also those
obtained by Whipple, were due to a direct toxic effect of the rancid lard. Roffo
(1939) found that feeding rats with oils and fats which had been oxidized by
heating tended to produce cancer. Lavik and Baùmann (1941) showed that the
incidence of skin tumors due to 20-methyl cholanthrene was increased when rats
were given a liigh-fat diet. The effect was enhanced when the fat was heated for
1 hour at 300'C. (572'F.), but neither rancidity nor ultraviolet irradiation of the
fat had any effect. Ethyl laurate was as effective as natural glycerides, while
neither the unsaponifiable fraction nor glycerol had an appreciable effect. In a
later paper the same workers (1943) found that the increased tumor formation
on high-fat diets was at least partly due to the increased calorific intake.
REFERENÇES
EvANS, H. M., AND G. O. BURR. Proc. Soc. Exptl. Biol. lled., 25, 390, 1928.
EVANS, H. M., AND S. LEPKOVSxY. J. Biol. Chenz., 96, 143-156; 157-164, '1932n
Ibid., 99, 281-234, 1932.
FRnzER, A. C. Analgst, 63, 308-314, 1938.
FRAZER, A. C. Nature, 157, 414, 1946.
FRAZER, A. C.; AND H. G. SAMMONS. Biochem. J., 39, 122-128, 1945.
FRAZER, E.B., J. H. STOTHART AND H. S. GUTTERIDGE. Doin. Can. Dept. Agr. Pamphlet No.
163, 9-10, 1934.
GRAHAM, W. R., AND P. T. CUrrs. J. Dàirg Sei., 21, 45-48, 1938. - ,
GYORGY, P., R. TOMARELLI, R. P. OSTERGARD AND J. B. BROwN. J. F.tipt. Med., 76, 413-420,
1942.
HILDITCx, T. P., AND H. M. Ti-IorlrsoN. Biochem. J., 30,677-691,1936.
HUME, E. M., L. C. A. NUNN AND I. SMEDLEY-MACLEAN. Cltem. and Ind., 57, 1110, 1938.
HUME, E. M., L. C. A. NUNN, I. SMEDLEY-MACLEAN AND H. H. S\4ITH. BZOCÎteYL. J., 32, 2162-,
2177, 1938.
105
InwrN, M. H., J. WEBER AND H. SyEENaocK. J. Nutrit., 12, 365-371, 1936.
.ICNoop, F. 13eitr. Chem. Physiol. Path., 6, 150, 1904. ,
KoLoDzrEjsKA, Z., AND J. DUSZYNSKA. Acta Biol. Exptl. (Warsaw), 13, 10-23, 1939. (C.A. 36,
7085.)
KtiDajAsicov, B. A. Arch. Exptl. Path. Pharmakol., 169, 275-89, 1933. (C.A. 27, 2213.)
LAVIK, P. S., AND C. A. BAUIVIANN. Cancer Research, 1, 181-187, 1941.
Ibid., 3, 749-756, 1943.
LEACH, T. A., AND N. S. GOLDING, Sci. Agr., 12, 204-205, 1931.
LEASE, E. J., J. G. LEASE, J. WEBER AND H. STEENBOCK. J. Nutrit., 16, 571, 583, 1938.
MmasEN, L. L. J. Nutrit., 11, 471-493, 1936.
MADSEN, L. L., C. M. McCAy AND L. A. MAYNARD. Cornell Agri. Exp. Sta. Mem., 178, 1-53,
1935.
MATTILL, H. A., AND C. CoLumarc. J. Nutrition, 23, 625-631, 1942.
MAYNARD, L. A., C. M. McCAy AND L. L. MADSEN. J. Dairy Sci., 19, 49-53, 1936.
McCAY, C. M., AND L. A. MAYNAIU). J. Biol. Chem., 109, 29-37, 1935.
McCAy, C. M., H. PAUL AND L. A. MAYNARD. J. Nutrit., 15, 367-375, 1938.
MELLANBY, J. j Physiol., 64, 1, 1927.
PAVCEK, AND G. M. SHuLL. J. Biol. Chem, 146, 351-355, 1942.
P. L.,
QUACKENBUSH, F. W. Oil and Soap, 22, 836-338, 1945.
ROFFO, A. H. Prensa med. argent., 26, 619-48, 1939. (C.A. 37, 2065.)
SHAPLRO, A. H. KOSTER, D. R11.1%1%113E110 AND R. SCHOENHEIMER. Amer. J. Physiol., 117, 525-
528, 1936.
STEENBOCK, H., M. H. Lawn,' AND J. WEBER. J. Nutrit., 12, 103-111, 1936.
TANCE, U. Sci. papers, Inst. Phys. Chem. Res. (Tokyo), 20, 13-28, 1932.
TANCE, U. Sci. papers, Inst. Phys. Chem. Res. (Tokyo), 22, 1-14, 1933.
TURPEINEN, O. J. Melt., 15, 351-366, 1938.
VERKADE, P. E. Bull. Soc. Chim. Biol., 18, 989-1013, 1936.
VERZAR, F. Nutrit. Abst. Rev., 2, 441-450, 1933.
WHIPPLE, D. V. Proc. Soc. Exptl. Biol. Med., 30, 319-321, 1932.
WHIPPLE, D. V. Oil and Soap, 10, 228-229, 1933.
106
CHAPTER FIVE
One hundred parts by weight of a typical fish body oil such as pilchard,
herring, or salmon oil would, if it contained no unsaponifiable matter, yield about
95.5 parts of fatty acids and 10.5 parts . of glycerol. These yields will, however,
be reduced proportionately by whatever unsaponifiable matter the oil contains.
Data in this connection for the glycerol yields of dogfish liver oil have been re-
ported by Swain and Morton (1945).
The above equation represents a type of reaction known as hydrolysis, since
water is, as shown, the only reagent involved. The hydrolysis of an oil by water
alone at ordinary temperatures is an extremely slow process, but it is more rapid
at high temperatures. The reaction- is fairly fast with steam above 230°C.
(446°F.), although at such high temperatures there is some polymerization of
highly unsaturated oils. However, the reaction is greatly accelerated at more
moderate temperatures by various catalysts including (i) metallic oxides and
hydroxides, (ii) synthetic organic compounds, (iii) acids, (iv) enzymes.'
The difficulty of the hydrolysis of oils by water alone is partially due to the
immiscibility of water and oil. The catalyst not only increases the actual rate of
107
reaction but also, in some cases, assists in emulsifying the two phases and thus
increases the amount of contact between them. Synthetic organic compounds, and
metallic oxides and hydroxides have greater emulsifying• action than acids or
enzymes.
Many organic chemical reactions, of which the hydrolysis of a triglyceride
is an example, reach an equilibrium in which the resynthesis of the original sub-
stance proceeds at the same rate as the breakdown. The reaction may be driven
further to completion by an excess of reacting water, that is, water in actual con-
tact with the material being hydrolysed, or by removal of the fatty acids from the
reaction mixture as fast as they are formed. The same effect as removal of fatty
acids from the reaction mixture is obtained if sufficient alkali or metallic oxide is
added to the original oil to neutralize all the fatty acids formed during hydrolysis.
The alkali combines with the fatty acids as they are formed, thus making them
non-reactive as far as the hydrolysis is concerned. The product obtained in this
case, however, is soap, which is the alkali salt of fatty acids, and the .process is
called saponification. It is a special case of hydrolysis. Chemically speaking, a
soap is the alkali or other metal salt of a single fatty acid, and it is customary to
refer chemically to the "soaps" formed during saponification of an oil, since the
latter always contain not one but a number of fatty acids.
The term splitting is often used to refer to the hydrolysis of oils, as differ-
entiated from saponification. Brief accounts of the chemical aspects of various
types of hydrolysis are given here. Their technical applications are described in,
Chapter 8.
(1) HYDROLYSIS WITH METALLIC OXIDES OR HYDROXIDES
,Small amounts of various metallic oxides and hydroxides, too small for com-
plete sapopifiçation, have a catalytic effect on the hydrolysis of fats and, fatty oils
by steam under pressure. The oxides of zinc, magnesium, and calcium are the
ones most commonly employed. Zinc oxide is the most active. Lascar•ay (1939)
found that zinc oxide, magnesium oxide, calcium oxide, lithium hydroxide, sodium
hydroxide, potassium hydroxide, and ammonium hydroxide are decreasingly
active in that order. The catalyst is added to the extent of 2 to 4% of the weight
of the oil, and Water to; the extent of 30 to 60%. The mixture is heated in an
autoclave by steam under pressure to raise the temperature to from 125° to
170'C., (260' to 350'F.). The reaction is 95 % or more complete after about 6 to
10 hours. The theoretical amount of water needed for the hydrolysis is about
6% of the weight of the oil, but the large excess of water is used to drive= the
reaction fairly well to completion even though the reaction products are not
removed during the process.
.( ii ) HYDROLYSIS WITH SYNTHETIC ORGANIC CATALYSTS
Twitchell (1900 ) prepared a very active catalyst for the hydrolysis of fatty
oils, by heating 10 parts of oleic acid with 3 parts of naphthalene at 50°C., and
then treating the mixture with 30 parts of concentrated sulphuric acid. The
resultant product was washed free of uncombined sulphuric acid and dried.
108
Other similar sulphonated compounds have since been developed using different
aromatic compounds and fatty acids, in place of naphthalene and oleic acid .
One contains hydrogenated castor oil in place of the fatty acids ; some contain
no fatty material . Many are patented and sold under trade names . The amount
of catalyst used varies from 0 .5 to 1,25 Jo of the weight of the oil .
Albuminous substances in the bil were found by Trusler (1931) to poison
Twitchell catalysts, so they must be removed before hydrolysis by this method .
(V) SAPONIFICATIO N
Saponification of fats and oils with caustic soda or caustic potash is a very
old process and is carried out widely on a commercial scale since the ordinary
soaps of commerce are formed by this reaction, which can be represented by
the following equation . In saponification sufficient alkali is added to combine .
with all the fatty acids . of the oil, from approximately 12 to 14% of sodium
hydroxide (as 'a percentage of the oil) being required .
109
The reaction between canstic potash and a ,fat or oil is the same as the
above, but the soap formed with caustic potash is always softer than the cor-
responding soap formed with caustic soda. Concentrated alkali is usually used.
The reaction proceeds slowly at first but as soap is formed it promotes the
emulsification of the oil and water phases, thus speeding up the hydrolysis.
Furthermore, a concentrated soap solution will actually dissolve considerable oil
(Smith, 1932) thus accelerating the reaction still m'ore. The saponification re-
action is exothermic, and the heat generated also has an accelerating effect.
Saponification with alcoholic alkali solutions is used in the laboratory since
it is more rapid and complete than with aqueous alkali, but it is too expensive
for commercial use.
Saponification with caustic alkalies can also be carried out in an anhydrous
medium. This process, which has been described by Jacobs (1942), consists in
dissolving the oil in kerosene, adding powdered anhydrous caustic soda or
potash, and heating to 220°C. (428°F.). The reaction \ is complete in less than
fifteen minutes. The application of this process both in the laboratory and on
a plant scale is discussed by the above author.
The term "metallic soaps" is applied to the soaps of calcium, magnesium,
zinc, lead, and so on. They are insoluble in water, and have applications con-
siderably different from those of sodium and potassium soaps. They can be made
by saponification with the hydroxide or oxide of the metal. Sufficient hydroxide
or oxide must be used to combine with all the fatty acids in the triglycerides of
the oil. Lime saponification is typical of saponification with a hydroxide of this
type. Slaked lime, made into a thin paste with \water, is mixed with the oil and
heated. VVhen an oxide is used, the water added also enters into the reaction.
Actually this method of making metallic soaps is no longer of much com-
mercial importance, since these soaps are more commonly made by a reaction
between fatty acids (or their sodium or potassium soaps) and a salt of the desired
metal, usually the acetate. For example, lead soaps are made by a reaction be-
tween lead acetate and fatty acids or their sodium or potassium soaps.
The technology of soapmaking and the manufacture of metallic soaps are
discussed in Chapter 8. The use of marine oils in soaps is discussed in Chapter
9. Uses of metallic soaps, chiefly in paints and in lubricants, are also described
in Chapter 9.
(b) INTERESTERIFICATION
When excess glycerol is added to a glyceride oil and the two are heated to ;
in the presence of a small amount of any gethro25°-0C.(4378F)
one of the following catalysts: lime, 'sodium hydroxide, trisodium phosphate,
anhydrous sodium carbonate, sodium alcoholates and other alkaline catalysts (in
amounts of 0.5 to 2.0% of the oil), the fatty acids of the triglycerides distribute
themselves between the glycerol with which they are combined and the added -
glycerol, forming monoglycerides and diglycerides. Theoretically, glycerol to
the extent of approximately 5% of the triglycerides is necessary for complete
conversion to diglycerides, and approxiniately 20% for the formation of mono-
glycerides. Actually an excess is neCessary, an increasing proportion of mono-
glycerides being forrned by adding up to 30% of ,glycerol, where an equilibrium
is reached in which the triglycerides have reacted with 13.5% of their weight of
,glycerol. Additional glycerol beyond 30% does not increase the amount combined.
Under the reaction conditions given above, this equilibrimn is reached in between
.one and two hours. The soap formed by reaction between the catalyst and the -
oil can be removed by the method patented by Eckey and Clark in 1936 (U.S.
patent 2,065,520, to Proctor and Gamble Co.), which consists inadding phosphoric
acid to decompose the soaps, dehydrating the mixture by heating under a vacuum
and then filtering off the sodium phosphate, which is insoluble in the oil.
The effects of varions factors on the composition of mixtures of nionoglyc-
erides, diglycerides and triglycerides, formed by the reaction between glycerol
and hydrogenated cottonseed oil, were investigated by Feuge and Bailey (1946).
Tables for the calculation of compositions on the basis of random distribution
are given in their paper.
Monoglycerides and diglycerides can be prepared frorn sperm oil by heating
it with glycerol. Free higher alcohols are formed in the process, but thèy are
difficult to separate from the main reaction products—the monoglycerides and
diglycerides. Kawai (1940) 'found that by heating 100 gm. of sperm whale head
oil (hydroxyl value 7.1) with 32 gm. glycerol and 3 gm. zinc for 5 hours at 240°
to 250°C. (464° to 482°F.), the hydroxyl value was increased to 64.9. Heating
100 gm. of the sperm whale oil for the same time at the same temperature with
45 gm. glycerol plus 3 gm. zinc and 5 gui oleic acid gave a product with a hy-
droxyl value of 119.5.
• In preparing monoglycerides and diglycerides commercially, an aluminum,
nickel, or stainless steel tank should be used, since when ordinary steel or_ iron
tanks are used the product becomes contaminated with iron soaps which darken
it.
(iv) ESTER INTERCHANGE
35 )
e
tri 3 )
A
.
25 )
,
a R
o
15 0
- RATE OF HYDROGEN ABSORPTIO Y-
5 10 15 20 25 30 35 40 45 50 55
TIME - M1NUTE5
115
In the hydrogenation of pilchard oil, Brocklesby and .Charnley (1933) have
shown that the rate curve for hydrogenation bears a general resemblance to the
unim'olecular type and is really made up of a series of linear sections. This corre-
sponds to the results of Armstrong and Hiklitch (1920) using pure compounds.
The results obtained in the hydrogenation of pilchard oil using a nickel catalyst
at temperatures of 160 0 and 180°C. (320 0 and 356°F.) and hydrogen at atmos-
pheric pressure, are shown in fig. 6. During the reaction it was found that there
was practically no increase in saturated fatty acids until after the complete dis-
appearance of the highly unsaturated fatty acids, as indicated by the octo- and
hexa-bromide tests. •
In the hydrogenation of natural oils made up of glycerides containing
saturated, mono-, di- and poly-unsaturated fatty acids it appears that the rate
of hydrogenation of the highly unsaturated fatty acid is sufficiently rapid to go
almost completely to the lower stages of unsaturation before any appreciable
amount of hydrogenation of the mono-unsaturated acids occurs.
The hydrogenation of fats and oils with a nickel catalyst at ordinary pres-
sures of hydrogen and elevated temperatures is to a considerable degree selective,
proceeding in a step-wise manner. However, Hilditch and Terleski (1937) work-
ing with whale oil, and Harper and Hilditch (1937) worldng with cod liver oil,
found that in the hydrogenation of these oils the highly unsaturated C20 and C22
do not hydrogenate as selectively as the C16 and C18 acids.
The effects of different temperatures of reaction and pressures of hydrogen
on the rate of hydrogenation of B.C. herring oil was studied by Swain (1949,
unpublished). His results are presented in fig. 7.
The effect of hydrogenation, under the above conditions, on the naturally
occurring pigments, sterols, and vitamins is, in general, to bring about the com-
plete hydrogenation of their double bonds. However, if the process is carried
out at a low temperature, for example 50°C. (122°F.), using colloidal nickel as
the catalyst (Waterman et al., 1936) a considerable hardening of oils will take
place with little loss of colour or vitamin activity.
The technology of hydrogenation is discussed in Chapter 8.
116
140
120
W 100
J
W
Z
0
0 80
60
400 2 4 6 8 10
TIME (HOURS)
FicuxE 7. Rates of Jiydrogenation of herring oil.
-0-- 125°C.; 10-1b. pressure; 0.074% Ni.
-0- 125°C.; 60-1b. pressure; 0.074% Ni.
-^- 100°C.; 10-1b. pressure; 0.27 % Ni. ..
-^- 180°C.; 60-1b. pressure; 0.074% Ni.
-p- 180°C.; 100-1b.!pressure; 0.074% Ni.
uptake are shown in fig. 8. In several instances the hydrogenation process was
continued for several hours after the absorption of the hydrogen had ceased. In
no case was any further hydrogen taken up.
In order to give further proof to this point, a sample of highly pôlymerized
oil (cottonseed oil) was saponified and the fatty acids were converted to their
117
methyl esters. The unpolymerized esters were distilled off in a laboratory mole
cular still, and the polymerized portion was subjected to hydrogenation under
the same conditions as in the preceding experiment. No hydrogen was absorbed.
This indicates that there was no depolymerization during hydrogenation under
the stated conditions.
'a 125
100
ra
• 75
o
50
4/
• 25
,z
tti
(iii) REDUCTION
The reduction of marine oils, and their derivatives such as fatty acids or fatty
acid esters, to fatty alcohols may be accomplished with hydrogen under very
high pressures and at high temperatures in the presence of suitable ,catalysts
(Adldns, 1937). The usual catalyst for this' reaction is a combination of
copper oxide and chromium oxide (copper chromite) sometimes with small
amounts of cadmium, cerium or other metals as promotors. The nickel catalyst
with copper as a promoter, referred to under (i) above for hydrogenation at
double bonds, can also be used.
With either of the above catalysts hydrogenation at the double bonds takes
place at the same time as reduction of the actual or potential carboxyl groups to
hydroxyl groups so that the fatty alcohols obtained are fairly completely
saturated. However, Sauer and Adkins (1937) using a 'zinc chromite catalyst
obtained a 68% yield of unsaturated alcohols from oleic acid esters. Even better
yields, with very little addition of hydrogen at the double bonds, were claimed
by Richardson, in a modified high pressure hydrogenation method patented in
1945 (U.S. patent 2,375,495; to Proctor and Gamble Co.) for the reduction of
118 ,
'unsaturated fatty acids to fatty alcohols. In this modification, the essential feature
of 'which was the addition of an appreciable proportion of cadmium soap to the
unsaturated fatty acids being hydrogen'ated, 93% reduction of carboxyl of oleic
.acid was obtained with only 20% hydrogenation of. double bonds.
Fatty alcohols can also be prepared by reduction of oils, simple esters, or
fatty acids by means of nascent hydrogen formed from a liquid alcohol and
metallic sodium. The reduCing alcohol itself was formerly used as the solvent.
An improved method of carrying out this reaction was developed by Hansley
(1947). In this method the same reactants are used, but either xylene or toluene
is used as the solvent. Much smaller quantities of both sodium and alcohol are
necessary; furthermore, a practically theoretical yield of fatty alcohol is obtained.
(iv CONJUGATED HYDROGENATION
)
(d) OXIDATION •
Unsaturated oils can also react, at their double bonds, with oxygen. Tiffs may
be a slow reaction taking place during storage of an oil, and resulting in unde-
sirable changes such as rancidity, which is discussed in Chapter 6 of this Bulletin,
or it may be carried out in such a way as to produce desirable changes in the
oil making it more suitable for special applications such as paints, varnishes and
other uses (Chapter 9).
The desirable oxidatiOn when oils are used in paints or varnishes is actually
that taking place after they are applied to a surface, and it results in the forma-
tion of a tough, hard film. This action is known as drying. Only oils with a high
average degree of unsaturation will dry in this way. The unsaturation ranges of
various oils, as shown by their iodine values,' are given in table 24. The first six
oils listed have low iodine Values and do not react readily with oxygen of the air;
Thence they are known as non-drying oils, or. oils which do not oxidize to form a
film. The next few oils in the list react slowly with oxygen of the 'air and are
known as semi-drying oils, while menhaden, chinawood (tung), pilchard and
119
linseed oils are classed as drying oils since they oxidize readily to form tough,
elastic films when exposed to air. By appropriate preliminary treatment of the
oil, the subsequent rate of drying when exposed to air can be speeded up greatly,
and the properties of the resulting film modified. One of these preliminary treat-
ments is oxidation, which will be discussed under (i) just following; another is
polymerization, which is treated in the succeeding sub-heading (e) on page 124.
Iodine value,
Fat or oil range
Coconut oil 7— 11
Cacao butter 32— 41
Mutton tallow 31— 47
Beef tallow 32— 55
Lard 46— 70
Olive oil 79— 88
Peanut oil 83-100
Dogfish liver oil 100-130
Corn oil 103-130
Salmon offal oil 111-177
Soybean oil 120-141
Herring oil 113-155
Cod liver oil 1184 90
Seal oil 130-150
Menhaden oil 154-180
Chinawood (tung) oil 160-180
Pilchard oil 170-190
Linseed oil 170-204
Actually oxidation of oils includes any treatment by which they are oxidized,
so not only oxidation with air, which is the method commonly used in commercial
practice, but also the chemistry of oxidation with various chemical agents will
be discussed here.
The technology of the oxidation of oils for drying is discussed in Chapter 8;
the chemistry of their oxidation has been reviewed by Powers (1949).
-A
Among the v.arious other agents which will oxidize oils are: potassium per-
manganate, peracids, peroxides, ozone, and lead tetra-acetate.
Aqueous potassium permanganate first brings about the addition of hydroxyl
groups at the double bonds, and then breaks the carbon chain at that point, with
the formation of carboxyl groups at both sides, of the point of rupture (Lapworth
and Mottram, 1925à, 1925b). In non-aqueous solutions, such as in acetone or
glacial acetic acid, the réaction proceeds directly to rupturing the carbon chain
at the double bonds, again with the formation of carboxyl groups at both sides
of the point of rupture (Armstrong and Hilditch, 1925). This and other coddation
reactions which break the carbon chain at points of unsaturation, such as are
discussed here, are used in the study of glyceride structure.
Peracids (perbenzoic acid, persulphuric acid, peracetic acid, etc.) also
bring about hydroxylation at the double bonds, but the reaction is not so simple
or clear-cut as oxidation with permanganate. Oxidation of an uns'aturated fatty
122 '
acid with a peracid results in the formation of a variety of prodiicts the nature
of which dépend on the peracid used, the conditions under which the oxidation
is carried out, and the structure of the unsaturated fatty acid. The oxidation pro-.
ducts of fatty acids with one double bond include oxido acids, peroxido acids,
ketohydroxy acids, and dihydroxy acids. Complete rupture of the carbon'chain
apparently results only when the intermediate oxidation products are sùbjected
to extreme conditions of hydrolysis. Similar types 'of addition-oxidation products'
apparently result when more highly unsaturated fatty acids are oxidized with a
peracid, and in this case the oxidation products polymerize to some extent. Oxida-
tion of unsaturated fatty materials with peracetic acid has been reviewed -in a
paper by Findley, Swern and Scanlan (1945).
Periodic acid acts differently to the other peracids as an oxidizing agent for
fatty acids. It breaks the carbon chain of partially oxidized fatty acids, such as,
ketohydroxy or dihydroxy acids, with the formation of aldehyde or carb'oxyl
groups at the point of rupture. Details of the reaction have been discussed by
King (1936).
Peroxides will oxidize saturated fatty acids at the carboxyl end of the môle-
cule, with the formation of carbon dioxide and a f3-keto fatty acid. Cupric sul-
phate catalyses the oxidation of saturated fatty acids, by hydrogen peroxide, but
the main reaction products then are, in addition to carbon dioxide, a mixture of
isomeric substances in which unsaturated dihydroxy acids and hydroxylactones
predominate (Smedley-Maclean and Pearce, 1934).
Unsaturated oils and fatty acids are oxidized by peroxides (for example,
hydrogen peroxide), with the formation of hydroxyl groups at the double bonds,
although peroxides are not as active in this, respect as the other oxidizing re-
agents already discussed (Smedley-Maclean and Pearce,- 1931). This reaction is
catalysed by cupric sulphate, just as is the oxidation of saturated fatty àcids.
Ozone reacts with unsaturated fatty acids or glycerides at their double
bonds, forming, when the reaction is carried out in an anhydrous solvent such as
chloroform or acetic acid, solid addition products known as ozonides. The re-
action must be carried out at a low temperature (about 0°C.) since ozonides are,,
in some cases, highly explosive. These ozonides are decomposed by water, the
carbon chain rupturing at the position of the double bonds, and either aldehyde
or carboxyl groups, . depending on the conditions of the decomposition reaction,.
being formed at each side of the point of rupture. Under some conditions a
mixture of aldehydes and acids is formed. The formation of aldehydes from
various fatty acids and fatty acid esters by the action of ozone has been reviewed
by Noller and Adams (1926). A general review of ozonization of fatty acids
has been given by Markley (1947a).
Lead tetra-acetate has also been used in the oxidation of unsaturated fatty
acids to aldehydes, with rupture of the carbon chain at point of unsaturation.
However this reagent 'will not act directly on the unsaturated fatty acids; they
must first be converted to the hydroxy compounds by some other oxidizing agent,
such as dilute aqueous permanganate. Scanlon and. Swern (1940) investigated
123
the us'e of this reagent as a means of producing more valuable products from un-
saturated fatty adds and related compounds. In this work, in which they first
hydroxylated the unsaturated materials with hydrogen peroxide in glacial acetic
acid, they found that clear-cut oxidation to aldehydes occurred when hydroxy-
lated oleic acid, ethyl oleate or oleyl alcohol were treated with, lead tetracetate.
However, attempts to apply the reaction to hydroxylated olive, peanut, and lard
oils were unsatisfactory, very poor yields being obtained.
Oxidation of oils' and fatty acids with chemical agents has its greatest appli-
cations-in laboratory studies; it is not used much in commercial preparations.
(e) POLYMERIZATION
When highly unsaturated fish oils such as pilchard or sardine, or vegetable
oils such as linseed or tung, are heated to a high temperature in the absence of
air, they undergo several profound changes, chief among which is an increasè in
viscosity. The oil is said to have undergone polymerization, which means the
combination of two or more similar molecules without any change in elemental
composition. Polymerization reactions can continue, forming progressively larger
molecules, the size of which depends on the conditions of the reaction, including
the length of time it is carried out.
(i) HEAT POLYMERIZATION IN GENERAL
Drying oils can be polymerized by heating to a high temPerature without
the addition of catalysts, but by the use of various polymerization catalysts the
reaction can be speeded up greatly. Most important of these are the dryers, oxi-
dation catalysts, which have already been described in connection with oxidation
of oils, and which also catalyse heat polyinerization. Many other substances act
as catalysts for polymerization, and most of them affect the properties of the
resulting polymerized oil in different ways, so that the products are used for
different purposes. Thus sulphur dioxide gas has an accelerating effect on the
heat polymerization of oils (Waterman and van Vlodrop, 1936), and also affects
the nature of the solid dry film formed from the oil (Brocklesby and Denstedt,
1933). The catalytic action of sulphur and selenium on the heat polymerization
of drying oils vvas shown by Waterman, van Vlodrop and Althuisius (1938), who
, heat treated linseed oil both in the presence and absence of small amounts of
these elements': It was found that 0.3% was sufficient to increase the rate of
polymerization, and that oils polymerized in the presence of sulphur or selenium
remained completely clear at room temperature, whereas a polymerized oil pre-
pared under the same conditions without these elements is dark coloured. Hydro-
gen % chloride also acts as a catalyst for the heat polymerization of drying oils.
A number of polymerization catalysts for the heat polymerization of drying
oils have been patented. These include silicotungstic and tungstic acids (U.S.
patent 2,345,358, issued to Rheineck and Crecelius in 1944 and assigned to Devoe
and Reynolds ,Co. Inc.); phenanthrene-like compounds (U.S. patents 2,207,686
and 2,230,470, issued to Schwarcman in 1940 and 1941 respectively and assigned
124
to Spencer Kellogg and Sons, Inc.); and .organic compounds containing at leaSt
three aromatic rings, such as phenanthrene, anthracene, anthraquinone, and their
-derivatives • (U.S. patent 2,213,935, issued to Sorensen and Konen in 1940, and
.assigned to Archer-Daniels-Midland Co.).
A "stand oil" is one which has been bodied, usually by heat polymerization
.although blowing is sometimes used, until the oil will remain standing up,/ for a
short time at least, .without immediately falling back as a less viscous liquid
would, when something is thrust into it and it is drawn up vertically.
Although, as pointed out under the preceding heading on oxidation (d),
some polymerization takes place under the influence of oxidation, that appears
to be quite different from the polymerization taking place under the influence of
heat only. In the so-called "oxidation-polymerization" the mOlecules which com-
bine to form the polymer appear to be linked through oxygen, whereas in simple
heat polymerization, they are linked together by direct carbon-to-çarbon linkages.
"Oxidation-polymerization" is thus apparently actually not polymerization, ■ but
an addition reaction involving oxygen, and by means of which macro-molecules
are built up.
The changes taking place in bodying of pilchard oil during heat treatment
are shown in fig. 10 (Brocklesby and Denstedt, 1934). The oil was a com-
mercial sample which had been cold cleared at 6°C. (42.8°F.), and was
polymerized in an inert atmosphere at the various temperatures indicated in
the figure. Below 175°C. (347°F.) no detectable changes took place in the
heated oil. From 175° to 200°C. (347° to 392°F..) there was a slow but uni-
form decrease in unsaturation. The iodine values decreased very' rapidly during
the first 6 hours of heating at 250°C. (482°F.) after which the rate of decrease
diminished greatly. As indicated by the • iodochlorides, which are a measure of
the amount of 'highly unsaturated fatty acids in the oil, the rapid decrease in
unsaturation was due to, the 'elimination of some of the double bonds in the
tetra- and penta-ethylenic fatty acids. The saturation of these acids to the tri- or
di-ethylenic stage was complete at the end of the eighth hour at 250°C. and at
the end of the second heur at 300°C. (572°F.). Except for those of the 300°C.
run, the refractive indices showed similar, but inversé, changes to those of the
iodine values. At the higher temperature thei!e was a rapid increase in these
values after the sixteenth hour of polymerization. On, reaching this point the oil
gelled when cooled to 25°C. (77°F.).
The acid value of the Oil decreased in runs up to 200°C., probably due to the
volatilization of part, of the free fatty acids originally present in the oil. In the
250°C. (482°F.) run the acid value increased up to the fourth hour - and then
dropped rapidly. It would appear either that the fatty acids are recombined
after a certain stage in the heating, or that after the initial period of acid forma-
tion the rate decreases and those that are formed are distilled off. No large in-
creases in the amount of volatilized acidic by-products• were noted, however.
125
MOLECULAR WEIGHTS (II BENZENE) REFRACTIVE INDEX — APPARENT IODINE VALUES
r t
>11 rR.
2
0
P.
rP
5
0 IODOCHLORIDES PER CENT
C>
SPECIFIC GRAVITY AT 25. C VISCOSITIES IN POISES AT 25°C (STORMER) - ACID VALUES
Ft
):
— 7; a — — ........... r, e.
0
5
■
.7• •
StIfIONNI3WLL,
Decomposition at 300°C. was very extensive, the acid value rose rapidly, and at
the sixteenth hour reached a value of 18.
All samples from the 300°C. run and the last one of the 250°C. run deposited
a white flocculent precipitate on standing for some time at room temperature.
The amount of this deposit was not proportional to the acid value of the samples
and proved', on analysis, to be neu.tral solid glycerides which had crystallized
' out in increasing amounts • as bodying proceeded.
Decomposition of the oil was relatively slight below 200°C., and the volatile
products consisted chiefly of acidic, aldehydic and ketonic substances with
traces of hydrocarbons. At higher temperatures the decomposition was relatively
greater and the products gradually became more acidic in nature. The condensed
distillate from the runs at 250° and 300°C. consisted chiefly of free fatty acids
with a neutralization value of about 270 and an iodine value of 90. 'The substance
melted at 18°C. (64.4°F.) and appeared to be a mixture of iso-acids of the C16
and C18 series.
As with the other analytical data, there was no significant change in viscosity
at temperatures below 250°C., when it increased linearly until the sixteenth
hour, reaching a value of 8 poises. Thereafter, increase in viscosity was more
rapid, reaching 15 poises at the twenty-fourth hour. At 300°C. increase in
viscosity was very rapid, the sixth-hotr sample gelling quickly at 25°C. (77°F.).
From these data it can be concluded that the critical temperature for the
heat polymerization- of pilchard oil lies between 250 0 and 275°C. Above the
latter temperature considerable decomposition takes place, and an examination
of the fatty acids from the 300°C. run indicates that in addition to polymerization
a certain amount of condensatien also contributes to the general reaction.
An interesting study of the heat polymerization of sardine oil was reported
by Behr et al. (1937). The sample used in the investigation was an alkali-refined,
bleached and cold-cleared California sardine oil, with an iodine value of 200
and a chill ( cloud) test of 8 hours at 0°C. (32°F.). As a result of the work on
this oil, they recommend that such highly refined sardine oiis should be bodied
( for use in paints and varnishes ) at a maximum temperature of 280°C. (535°F.),
three hours being allowed for the oil to reach 249°C. (480°F.) and an additional
two hours to reach 280°C. They further recommend that a maximum viscosity
of 9 poises should be specified for these oils. Under these conditions they state
that "The polymerization of the unsaturated glycerides is canied to a reasonable
degree of completeness with a minimum gel structure and withOut the develop-
ment of a polymer cloud". According to these authors the formation of a cloudy
haze or actual precipitate in the bodied fish oils is not due to saturated glycerides
but to coagulated gel particles that are 'insoluble at room temperature in the
polymerized oiL As found by the above authors, the rate of formation and
-amount of this polymer cloud is proportional to the amount of stearine in the oil
and also to the amount of polymerization. The lower the cloud point of the cold-
cleared oil, the more polymerization it will stand before this cloudy appea;ance is
_noticed. The fact that the most highly cold-cleared oils still show this cloudiness
127
is no proof that it is not stearine, because it is difficult to remove by commercial
cold clearing all the stearine that may separate from an oil at a given temperature.
Furthermore, if a polymerized oil is given a high-temperature steam-distillation
treatment that removes the greater part of the saturated fatty acids the resulting
polymer does not show this cloudiness to the same extent.
Brocklesby (1941a) examined the precipitated material which' forms the
polymer cloud, and showed it to be saturated glycerides, at least in the case
investigated. On the basis of this he considered it to be largely stearine
which, he thought, becomes more and more insoluble in the polymerized oil
as polymerization progresses.
Mattil (1944) pointed out that the polymer cloud is probably due to the
decrease in solubility which takes place in an oil in proportion to the increase
in oxidation. He states "Often that portion of an o il which is more saturated
becomes less soluble in the oxidized unsaturated portion and either forms a
cloud, or in extreme cases, is actually precipitated". An-other possible explanatien
of polymer cloud is that some efter-interchange takes place during polymeriza-
tion, a greater proportion of more saturated triglycerides being formed. These
would tend to precipitate out as a polymer cloud.
Another matter of interest in connection with the heat polymerization of
fish oils .is the effect of stearine on the rate and extent of polymerization. Behr
(1936) has given some interesting data along these lines. In the fi rst place he
found that a crude sardine oil containing 22% saturated fatt3'r acids, after being '
cold-cleared to stand a chill test of 20 hours at 0°C. (32°F.) still contained 17%
saturated fatty acids. Further cold clearing so that the oil would stay clear 100
hours at 0°C. only reduced the saturated fatty acid content to about 16.75%,
but the loss of oil through the removal of stearine was very high. A sample of
crude sardine oil was lightly cold-cleared so that it would stand a chill test of
0.5 hours at 0°C.; a sample of the same oil was further cold-cleared to stand
a chill test of 20 hours and a third sample of the crude oil had added to it some
df the stearine removed from the first two samples. The three lots were then
polymerized under identical conditions. The viscosities and acetone-insoluble
contents of the three samples were measured. (The part which is actually poly-
merized is insoluble in acetone.) These measurements showed that the degree of
polymerization was very much greater in the case of the 20-hour chill test oil
than in the 0.5-hour chill test oil, which in turn was greater than that Of the
oil which had had stearine added to it. These results are in harmony with those
found in these laboratories by Brocklesby (1941b). A sample of Canadian
pilchard oil was cold-cleared to various degrees and the various samples were
simultaneously polymerized in an inert atmosphere. The data are given in table
25. The retarding' effect of stearine on the heat polymerization of the oil is very
marked and indicates the necessity of the cold clearing of fish oils which ale
to be used in the manufacture of bodied oils.
The technology of polymerization is discussed in Chapter 8, and uses of
polymerized oils in Chapter 9.
128
TABLE 25. Effect of stearine on polymerization of pilchard oil.
Molecular weight
Stearine removed Cloud-test on clear oil polymerized oil,
(%) A.C.S. method (°C.) Rast's method
(f) CONDENSATION
CH,( CH, )CH = CH( CH2 )7COOH C21-150H CH, (CH, )7CHCH2 ( CH2 ) 7COOH
Oleic acid Phenol
0C6115
■ Intermediate ether compound
CH2(CH2)7 CHCH2(CH2)7COOH
I
C2H4OH
10-hydroxyphenyl stearic acid
-
This reaction may be carried out With a variety of phenols and different fatty ,
acids of varying iodine value- (Niederl and Liotta; 1933).
In an experiment canied out at this Station on the condensation of pilchard
off (iodine value 164) and phenol With dry hydrogen chloride as condensing
agent, Riddell obtained a product of iodine value 11. From the change in iodine
value it Was calculated that 93% of the double bonds were saturated with phenol.
It was found that 50% of the phenyl ethers reananged to the hydroXyphenyl
stearic acid, the remainder being unchanged. Similar results were obtain.ed by
using cresol and pilchard oil..
Ry suitable control of the reaction, there may be obtained from pilchard oil
a product which contains phenol groups but retains suffidient unsaturation- to -
dry to a film when dissolved in .a thinner, for -example dipentene, mixed with
129
cobalt dryer and exposed to the air. While this product is not resistant to water,
it might have a use as a bactericidal protective coating under less drastic
conditions.
In, the glyptal type .of resin, which is prepared by the condensation of
phthalic anhydride with glycerol, the resin, may be modified by the introduction
of fatty acids to, take the place of a part of the phthalic'anhydride. This renders
the resin more soluble in oils 'and also makes it more plastic. The same result
might be obtained by the use of monoglycerides or diglycerides in place of
part or all of the glycerol. If fatty acids from drying oils are used, the resin
^will also possess some air-drying properties. The process is accomplished by
heating a suitable ' mixture of glycérol (3 equivalents) with phthalic anhydride
(2.5 equivalents) and fatty acids (0.5 equivalents) until the water formed by
the reaction: ceases to be liberated. Some results=obtained in these laboratories
with linseed- and pilchard-oil fatty acids are given in Chapter 9.
130
Unfortunately the processes. of sulphation and sulphonation, and the re-
spective sulphated and sulphonated products (sulphates and sulphonates) are
frequently confused in commercial practice (Hecking, 1938). The term "sulpho-
nation" is generally applied to both sulphated and sulphonated products. In
this Bulletin the distinction will be maintained whenever the nature of the
product is reasonably certain. The technology of sulphation and sulphonation -
is discussed in Chapter 8. Uses of sulphated and sulphonated fatty compounds
are given in Chapter 9.
I I
O-SO3H OH
Sulphated glyceride Hydroxy glyceride
or fatty acid or fatty acid
The hydroxy glycerides may remain as such, or-may undergo a very complicated
condensation or polymerization. The hydroxy fatty acids, depending on the tem-
perature ' of the sulphation process; may or may not undergo condensations
to _lactones, lactides, and related compounds. In some oils, especially highly
131
unsaturated fish oils, oxidation takes place, followed by polymerization of the oxi-
dation products (Bailey, 1945b). The sulphation of a commercial oil may there-
fore result in a mixture containing many different substances, the proportions of
which vary with the nature of the oil and the conditions of sulphation; and, al-
though a high yield of true sulphated oil is desirable, some of the by-products
remaining in the processed oil confer upon it certain properties suitable for
special applications.
(ii) SULPHATION OF FATTY ALCOHOLS
'the sulphation of a saturated fatty alcohol takes place in the same way as
that of a monoglyceride or diglyceride as indicated by the reaction at the
—C1-120H group in the following equation and, if the fatty alcohol is unsaturated,
it has been shown (Riess, 1931) that simultaneous sulphation of the double bond
and alcohol group takes place:
CH3— ( CH2 ) 7-CH=CH-( CH2 ) 7-CH2011 2112SO4
Oleyl alcohol
• CH2—( CH2 ) 7-CH-CH9- ( CH2 ) 7-CH2-0-S03H 1120
0-503H
Sulphated °ley]. sulphate
The sulphation at the double bond takes place more slowly than in the case of
unsaturated fatty acids, and the sulphate group introduced - at the point of former
unsaturation does not hydrolyse to the corresponding hydroxy compound as
readily as in the case of sulphated fatty acids (see (i) above).
(iii) SULPHONATION OF FATTY COMPOU,NDS
Sulphonation may be achieved in many ways, the commonest sulphonating
agents being sulphur trioxide (SO 3 ), oleum ( concentrated sulphuric acid con-
taining sulphur trioxide and approximating the composition of pyrosulphuric
acid, H2S207 ), and chlorosulphonic acid (C1—S0 3H). These may be used alone,
although they are usually diluted with an inert organic solvent. The general re-
action in sulphonation of unsaturated fatty compounds may be formulated as
follows: •
—HC=CH— + SO3
SO3H
Sulphonated group
Actually the reaction with most sulphonating agents is more complex, and results
in saturation of the double bond as well as sulphonation.
Sulphonation of unsaturated fdtty acids and esters . in the presence of an
organic acid anhydride or acid chloride is claimed, by Bertsch (U.S. Patent
1,923,608; 1933, assigned to H. Th. Böhme A.-G.) to sulphonate at the carbon
atom adjacent to the double bond, and towards the carboxyl end of the fatty acid
chain, without affecting the unsaturated carbon atoms.
132
Saturated oils and fatty acids are sulphonated by chlorosulphonic acid as
follows:
R—C112—R Cl—S03H —> R—CH—R HC1
I
SO3H
Su'phonated fatty alcohols may be'Prepared by some of the above reactions, -
and also. by the action of sodium' sulphite on the sodium salts of sulphated fatty
alcohols:
R—OS 03Na -I- Na2S 03 R—S 03Na -I- Na2S
Sodium salt of Sodium salt Sodium
sulphated fatty Sodium sulphite of fatty sulphate
alcohol sulphonic acid
(iv SULPHATED AND SDLPHONATED DERIVAIIVES OF FATTY, COMPOUNDS
)
•
A great many detergents and textile finishers are made by condensation of
fatty acids or fatty alcohols with other chemicals already sulphated or sulphon-
ated. The following are examples of these:
(h) SULPHURIZATION
Reaction between sulphur and saturated oils or fa tty acids may result in
ap-
alteration of . the physical properties, but little if any chemical combination
. With unsaturated
pears to take place ; the process is mainly one of polymerization
oils or fatty acids, actual chemical addition of sulphur to the double bonds takes
place and, as sulphur has certain chemical proper ti es analogous to those of
oxygen, the reaction is of the same complex nature as in the oxidation of oils or
fatty acids . The thickening and solidification which takes place during sulphur-
.
ization is due to polymerization of the sulphur addition products first formed
The reactions are thought to be as follows :
HC HC HC-S
-{- Sulphur / S
-S ;
I
1 :1 :
-CH
Only traces of hydrogen sulphide are set free, and on hydrolysing a sulphiirized
oil, the liberated Lay acids are still sulphurized . The almost complete lack of
hydrogen sulphide formation in either the • sulphurizing process or subsequent
hydrolysis indicates that little if- any substitution of hydrogen by sulphur has
taken place . If sulphurized fatty acids are heated to a sufficiently high temperature
(180°-200°C . ; 356°-392°F .), further reactiôns occur with evolution of hydrogen
sulphide .
134
HCH + Cl-S-S-Cl -> HC-S-S-Cl + HCl
I
Link in carbon Sulphur Sulpho- Hydrogen
atom chain monochloride chlorinated chloride
compound
Such reactions can continue among fatty molecules, to form trimers and higher
polymers.
In the case of unsaturated oils and fatty acids the r`eaction is rapid and ener-
getic, and may become violent if not controlled by cooling or by dilution of the
reactants with an inert solvent. Bailey (1945c) gives the following representation
of the reaction.
H H H H H H H H
I 1 1 1 1 -
-C-C=C-C- -C-C-C-C-
H H H Cl y H
S
11 H H H HH
I I 1
-C-C=C-C- S2C12 ^ -C-C-C-C-
H ^ H H,
S
H H H Cl H
I
-C-C-C=C-
I I I
H H H H H H H H
The addition reaction may take place between parts of the same glyceride mole-
cule, or between different molecules. Furthermore the sulphur monochloride itself
or some of the products formed in its reaction on unsaturated fatty acids appear
to act as simple pôlymerization catalysts. Evidence for direct polymerization as
well as linking together of oil or fatty acid molecules through sulphur was ob-
tained by Kaufmann, Baltes and Mardner (1937 ) who found that the actual
135
decrease in iodine value of the original oil is much greater than would be ex-
pected from the amount of sulphur monochloride combined. Some substitution
similar to that occurring in saturated oils when treated with sulphur xnonochloride
also appears to take place, as indicated by the liberation of some hydrogen
chlôride gas.
(iii) WITH OTHER AGENTS
Finally, the action of other sulphurizing and similar agents may be men-
tioned. Dithiocyanogen, sulphur thiocyanate, organic sulphides produced from
ethylene dichloride and calcium polysulphide, and other sulphur compounds have
been used as sulphurizing agents (British patents 284,415, A. De Waele, 1926;
313,917, J. Baer, 1928). Selenium, an element resembling sulphur in its chemical
properties, also forms a chlôride (Se 2C12 ) the "selenizing" action of which on
whale, menhaden, and cod liver oils and oleic acid was studied by Harvey and
Schuette (1928). They observed that, as judged by the rapidity of the rise in tem-
perature, selenium chloride reacts more energetically than sulphur' chloride on
various fatty oils.
(1) HALOGENATION
Two types of halogen derivatives of fatty compounds can be prepared. In
one type halogen is combined with one or more carbon atoms of the carbon
cl-fain; in the other type the halogen is combined with the carboxyl carbon atom.
The former will be referred to here as simple' halogen derivatives; the latter are
acyl halides.
( i ) SIMPLE HALOGEN DERIVATIVES
The addition of halogens ( chlorine' , bromine, and iodine) at the double
bonds of unsaturated fatty acids was mentioned briefly in Chapter 2 of this Bul-
letin. The reaction is typified by the following equation, in which X represents
one of the three halogens—chlorine, bromine or iodine:
—HC=CH— X2 —11C—CH-
( I I
XX
When oils are treated with halogens or halogenating reagents, the actual addition
takes place in much the same way as in •the fatty acids themselves; but, as might
be expected, the properties of the reaction products are different to those resulting
from the fatty acids. As well as simple addition of the halogen at the double
bonds, there may be some substitution of hydrogen in the carbon chain. Sub-
stitution in the carbon chain is typified by the following equation, in which X
represents either chlorine or bromine:
± X 2 —> —CH— ± HX
X
To prevent substitution taking place, the concentration of the reactants must be
kept low by dissolving either or both in a suitable organic solvent; the tempera-
136
ture must be kept low; the reaction mixture . must be kept in the dark; and the
reaction time must be limited since, if too prolonged, there may be substitution.
If chlorine gas is passed into a fish oil at room temperature considerable quantities
of hydrogen chloride are evolved, showing that substitution as well às addition
is taking place. The action of bromine depends on the form in which it is allowed
to react on the oil—as a dry vapour, as liquid bromine, or dissolved in one of the
many organic solvents which can be used. Thin films of fresh oil exposed in the
dark to dry bromine vapour add bromine at the double bonds without any sub-
stitution taking place, even at room temperature. Liquid bromine, or solutions
of bromine in organic solvents, cause substitution unless the reaction mixture is
kept cold, especially with oxidized or polymerized oils.. Iodine, dissolved in
chloroform or other similar solvents, alcohol, etc., adds slowly at the double bonds
of unsaturated oils, and usually complete addition is never attained. Substitution
rarely, if ever, takes place with iodine'.
Compounds Of chlorine with iodine or bromine can be prepared, which add
quantitatively at the double bonds of unsaturated oils or fatty acids. This re-
action, and other halogen addition reactions, are used extensively in the de-
termination of unsaturation and these applications will be discussed more fully
under that heading in Chapter 11.
Bromination, for both analytical and preparative work, can also be accom-
plished by means of pyridinium bi-omide perbromide ( C 5I-16-L-NBr—Br2 ). The
properties and uses of this compound are described in Bulletin 502 of the Jason
Drug Co., Brooklyn, New York.
The addition of hydrogen bromide and hydrogen chloride to fish oils has
been investigated in these laboratories by Tipson (1941 ):• Dry hydregen bromide
gas was absorbed quantitatively by dogfish liver oil. The product was a
clear, very viscous, pale yellow oil with a faint sweet smell quite unlike
the odour of the original oil. It gave no precipitate on standing oveniight
in a refrigerator. The hydrobrominated oil contained 26.2% bromine and had
a viscosity of 1.446 poises at 40°C. as contrasted with 0.325 poises for the
original oil. Dry hydrogen chloride is .not absorbed by the double bonds in un-
saturated oils. Passage of hydrogen chloride through dogfish liver oil resulted
in a small absorption (1.35% ), of chlorine that later was found to be combined
with the unsaponifiable matter present in the oil.
Substitution of bromine for hydrogen on a carbon atom adjacent to a double
bond, without any addition at the double bond itself, can be accomplished by
means of N-bromosuccinimide. The reaction is applicable to both aliphatic and
aromatic compounds. The use of this reagent with an aliphatic compound is
described by Karrer and Ringli (1947). A general description of its applications,
and a fairly complete bibliography, is given by Arapahoe Chemicals (1949).
ACYL HALIDES
( j) HYDROXYLATMN
(k) ELAIDINIZATION
Elaidinization refers to the conversion of an unsaturated fatty acid or oil
into a geometrically isomeric form of a type described on page 14. Thus, for
example, when oleic acid (melting point 16.8°C. ) is treated with a trace of nitrous
oxide, it is converted into its geometrical isomer, elaidic acid (melting point
43.7°C.). The former is the "cis" and the latter the "trans" isomer. They thus
have the same chemical composition, but differ in chemical and physical proper-
ties only because of 'the difference in their spatial 'molecular structures.
Elaidinization is a reversible reaction. An equilibrium mixture of the original
substance and its elaidinized isomer is formed, in which the proportion of the
two isomers present depends on the nature of the original material and the
efficiency of the elaidinizing catalyst. In the case of oleic acid and several other
urisaturated fatty acids equilibrium is reached when approximately two-thirds
of these fatty acids, either free or as constituents of glycerides, have been
elaidinized. If the pure elaidinized product is isolated from this mixture and
again subjected to the action of the elaidinizing reagent, approximately one
third of it is transformed back to the original substance, thus giving the same
equilibrium mixture as before.
Mono-unsaturated fatty acids which occur in fish and other marine animal
oils and are capable of undergoing elaidinization are, in addition to oleic acid
140
(C18), lauroleic (C2), myristoleic (C14), palmitoleic ( Cle,), eicosenoic (C20),
cetoleic (C22). and selacholeic (C24) acids. Naturally occurring ( cis- ) selacholeic
acid melts at 41 °,C., while the elaidinized acid (trans isomer) melts at 61'C.
Glyceryl tri-oleate ( olein ) melts at about 5'C.; the isomeric tri-elaidate ( elaidin )
melts at 40.5°C. Fatty substances containing more than one double bond in the
carbon atom chain can also be elaidinized.
Partly oxidized fatty acids, or even unsaturated fatty acids in the incipient
stages of oxidàtion through exposure to air, do not elaidinize as completely as
freshly prepared or recently distilled acids.
Elaidinizing reagents act catalytically inasmuch as very small amounts are
capable of transforming large quantities of unsaturated fatty substances: A com-
mon method consists in floating the liquid or melted fatty substance on a 70%
aqueous °solution (spec. grav. 1.42) of nitric acid acting on arsenic trioxide or
mercury at a temperature between 10° and 20°C. (50° and 68°F.). The oxides of
nitrogen liberated from the acid rapidly elaidiinize the fatty layer as they bubble
through it. The progress of the reaction is controlled by obseiving the increase iri
melting point of samples withdrawn from time to time, and on corimpletion of the
process the warm elaidinized material is washed free of acid with water. Pro-'
longed action or elevated temperature causes the formation of by-products
consisting of stable addition compounds, of the fatty substance and the nitrogen
oxides. Copper 'may be used with the nitric acid, but lowers the percentage of
elaidinized products from about 66 % to only 25 %. Oleic acid is '66% elaidinized
by agitation with cold 50% sulphuric acid to which a cold aqueous solution of
sodium nitrite is slowly added.
A modern method yielding equilibrium mixtures containing maximal amounts
of elaidinized product consists in heating fatty substances with 1°Jo of sulphur
or selenium to about 215°,C. (419°F.) for 6 hours. The same effect is pr,bduce.
by the action of 6.5% of selenium at 150°C. (302°F.) for 28 hours (Bertram,
1938, and also German patent 674,752; 1939). Equal amourits of oleic acid ` and
water heated under pressure to 220°C. (428°F.) with 3% of red phosphorus
yield an elaidinized product, snow-white as a result -of the bleaching action of
certain phosphorus compounds that are fôrmed (Rankov, 1936). The latter work
is abstracted in considerable detail in the Chemical Abstract reference given.
Difference in melting point is _ the most outstanding difference between
elaidinized oils and fatty acids and the corresponding non-elaidinized materials,
the elaidinizèd material always having the higher melting point. The, chemical
behaviour also differs, the trans isomer being in general the less reactive.
Brocklesby (1935) found that the trans isomer oxidizes more slowly than the
cis, and that halogenation with iodine monoehloride proceeds more slowly in
the case of the trans isomer. He found -the rate of hydrogenation of the tran^
isomer was a little slower than that of the 'cis. During the commercial
hydrogenation of unsaturated fats and fatty acids a partial elaidinization may
occur contributing to the increase in mel.ting point ("haxdèning"). .
141
) CONJUGATION
Conjugation was defined on page 8. Oils with conjugated double bonds
are usually referred to as conjugated oils. Althôugh conjugation and elaidiniza-
tion are both actually types of isomerization, the term isomerization, as used
in technology, generally refers only to conjugation.
A comprehensive review of both the theoretical and practical aspects of
drying-oil conjugation is given by Cowan (1949). The present Bulletin will
deal more particularly with the 'practical aspects.
Conjugated oils "dry" more rapidly than do otherwise similar non-conjugated
oils, forming films with very high resistance to moisture. Tung ( chinawood) oil
and oiticica oil are the only naturally occurring conjugated oils produced in
commercial quantities at the present time. Oils from marine sources are not
naturally conjugated, but can be converted to conjugated form by artificial means.
Isomerization from the non-conjugated to conjugated form is accompanied
by an increase in refractive index. An increase from 1.4700 to 1.4781 was observed
by Turk and Boone (1944) during isomerization of fatty acids with activated
alumina. Another feature of conjugation is the development of, absorption maxima
in the ultraviolet spectrum which are characteristic of the number of conjugated
double bonds present. Two, three and four conjugated double bonds are charac-
terized by selective absorption at approximately 233, 280 and 320 mu respectively.
Spectrophotometric absorption curves for sardine and menhaden oils, before and
after alkali isomerization, are given by Lambert and Andrews (1948).
During saponification of oils in which there are unsaturated carbon atoms
separated by one saturated carbon atom there is some isomerization to the
conjugated form. This was made evident by Moore (1937) who found that
prolonged refluxing of the fatty acids of linseed oil with 20% alcoholic potassium
hydroxide caused considérable conjugation to take place. A commercial process
based on this principle, for isomerizing, poly-unsaturated oils and fatty acids to
the conjugated form, or "conjugating" them, was developed by Bradley and
Richardson (1942). They found that unsaturated oils and fatty acids could be
thus isomerized by heating under pressure with aqueous solutions of sodium,
potassium or lithium hydroxides at temperatures of 160°-280° C. (320°-536°F.)
for 2 hours, yielding, upon acidification, Mixtures of fatty acids of which 30 to
50% was conjugated.
Activated forms of silica, silicic acid, and various metallic silicates were
found by Turk and Feldman (1943 ) to be efficient catalysts for bringing about
conjugation in non-conjugated unsaturated fatty compounds. By heating an oil
at 200°-300°C. (392°-572°F.) with 1 to 5% of such catalysts, conjugation to
the extent of 50% was obtained. Metallic oxides were used by Turk and Boone
(1944) as catalysts for this purpose. For example, heating linseed oil fatty acids
at 250°C. (482°F.) with 5% activated alumina for 4 hours resulted in the
formation of about 35% conjugated fatty acids. A patent was granted to Turk
and Boone in 1946 (U.S. patent 2,405,380) for producing conjugation in non-
142
conjugated diene or polyene fatty compounds by heating, in the presence of an
inert gas, with 2 to 20% solid magnesium silicate, until the degree of conjugation
is‘at least 15% (calculated from the increase of index of refraction).
The use of several different types of iodine compounds as catalysts for
conjugating oils and fatty acids is described in a group of patents granted to
A. W. Ralston and O. Twinsky in 1946, and assigned to Armour and Co. The
first of thése, U.S. patent 2,411,111, covers the use of amine salts of hydriodic,
acid; U.S. patent 2,411,112 covers the use of various aliphatic organic iodidés;
U.S. patent 2,411,113 covers the use of the iodides of phosphorus, tin,
aluminum, antimony and arsenic. Aluminum tri-iodide was found .especially
satisfactory; it is currently used for this purpose in industrial practice. For
example, 317 parts by weight of linoleic acid containing 30% oleic acid was
heated to 260°C. (500 0 F.) under an atmosphere of inert .gas, with continuous
stirring. When that temperature was reached, 0.15 part of -aluminum tri-iodide
was added. The reaction mixture was kept at a temperature of 260°C. for 35
minutes; 0.1 part of aluminum tri-iodide was then added. The temperature was
maintained at 260° to 270°C. for a further period of 7 minutes. Heating was-
discontinued when the rate of increase of refractive index became markedly less:
During the reaction the over-all changes were as follows: the diene value '
increased from 1.5 to 26.6; the refractive index .at 20°C. increased from 1.4668
to 1.4734; the iodine value decreased from 145 to 101. A freshly prepared
aluminum tri-iodide catalyst was even more effective; the method of iireparing
it is described in the patent. Oils as well as fatty acids can be . conjugated by
this method. A somewhat lower reaction,temperature (125°-178°C., 257°-352°F.)
was employed for carrying out isomerization tà the conjugated form when
freshly prepared catalyst was used.
Radlove et al. (1946) found that a number of catalysts, including carbon,
black, and nickel on kieselguhr, could be used to isomerize non-conjugated un-.
saturated oils, their fatty acid esters and related materials to the conjugated form..
However, a nickel catalyst prepared in a special•way on u special carbon black
was most active. A process for both isomerizing and polymerizing non-conjugated
oils by means of liquid sulphur dioxide was described by Waterman -et al..
(1948). It was successfully applied to both whale oil and herring oil.
The use of anthraquinone as a conjugation catalyst is described by Falken-
burg et al. (1948). Heating a non-conjugated oil at 285°C. (545°F.) with 2 to,
antluaquinone caused rapid isomerization to the conjugated form.
) FORMATION OF NITROGEN DERIVATIVES
A number of nitrogen derivatives, some .of which have commercial im-
portance, can be prepared from oils or fatty acids. The more important of these
- are the amides, nitriles, amines and lipoproteins. Of less importance are the -
hydrazides. Only the former group will be discussed here; the preparation and
reactions of hydrazides and azides were reported in a 'long series of papers by -
NH,
Fatty acid amides can be prepared by treating the oil with liquid ammonia
and heating to a high temperature . The ammonia "splits" the oil by ammonolysis,
analogoûs to hydrolysis. Anhydrous glycerol is formed as a by-product . Oda and
Wada (1934) found that the reaction is catalysed by ammonium chloride . They
successfully applied it to flsh oil, but were not so successful in applying it to
spermaceti, The commercial production of amides from oils by treatment with
ammonia is described by Hund and Rosenstein ( U .S . patent 2,070,991 ; Feb . 16,
1937, to . Shell Development Co .) . Amides can also be prepared by converting
the oil to fatty acids, forming the ammonium soaps and heating them . Water is
thus formed and driven o ff, and an amide is formed, according to the general
equation :
(ii) NITRILE S
(IV) LIPOPROTEINS
Cômpounds of fatty acids or other lipides with proteins are called lipo-
-proteins . :They occur naturally in many living organisms . Earlier studies of
lipoproteins were concerned- mainly with their, physiological roles . It was not
until fairly recent years that synthetic products of thistype were prepared with
a view of their commercial utilization . The rlaturally occurring lipoproteins are
,chiefly combinations of proteins with phospholipides or, to a lesser extent, wit h
144
sterol esters; the synthetic products developed for commercial use are mainly
combinations of proteins with fatty acids. °
A patent was granted to the Soc. pour l'ind. chim. à Bâle in 1936 (French
patent 805,375) for the preparation of fatty-acid and other derivatives of proteins.
They were prepared by a reaction between the protein (casein) and fatty acid
chloride, in pyridine. The same reactants were used by Gordon, Brown and
Jackson (1946), but they carried out the reaction in aqueous solution at pH 10 to
12. In this way they combined casein with saturated fatty acids from C8 ( caprylic )
to Cis (stearic), and also the unsaturated fatty acid, oleic. They also prepared
the palmitoyl derivatives of a number of other proteins including egg albumin,
zein, wheat gluten, and soybean, peanut, and cottonseed proteins. The plastic
properties of these fatty acid or protein derivatives were studied by Gordon et al.
(1946). Progressively longer-chain fatty,acid combinations with casein affected
the plastic properties as follows: water absorption is decreased; plastic flow in
the presence of 6 to 12 % water is improved; and tensile and flexual strengths
are increased.
All the above fatty acids occur in fish oils, but in view of the very different
nature of other fatty acids in such oils, they offer interesting possibilities as
sources of material for further studies along this line.
Both the chemistry of the naturally occurring lipopr.oteins, and the experi-
mental preparation of similar lipoproteins have been reviewed by Lovern (1942).
References to the experimental preparation are mostly concerned with phos-
phatide-protein complexes.
If the volume and specific gravity of an oil have been determined at some
convenient temperature, a knowledge of the coefficient of cubic expansion allows
the calculation of the volume and specific gravity at some standard temperature
such as 60°F. (15.56°C.). The-significance of this procedure in dealing with
bulk quantities of oils has already been pointed out under (a).
Each kind of marine fatty product,probably has its individual coefficient of
cubic expansion, which is known to vary sometimes even'among different samplès
of one type of product. There is an appreciable difference between•the coefficient
of a liquid fat and that of the same fat in the solid state, and the coefficient of
either varies slightly with the temperattue.,This slight variation with temperature
is usually ignored by employing the average coefficient of cubic expansion for
the range of temperatures likely to be encountered in practice, but it should be
emphasized that the average coefflcient for a liquid oil or a solid fat does not
apply over the transition range of temperatures at which the oil is solidifying
or the fat is melting, for reasons mentioned later.
The numerical value of the average coefficient of cubic expansion for a_
completely liquid fish oil between 59° and 120°F. (15° and 50°C.) lies in the
vicinity of 0.00045 per degree Fahrenheit change in temperature. This may be
approximately interpreted as stating that an oil expands (or contracts) to,the
extent of 0.00045 of its original volume for each degree Fahrenheit rise (or fall)
within the given temperature range. The coefficient per degree Centigrade is
1.8 times as great as the coefficient per degree Fahrenheit.
Providing no change from liquid to solid state (or vice versa) takes place
within a temperature range t° to T° for which the average coefficient k is
147
known, the following relations are sufficiently accurate for most practical pur-
poses and app1S7 to increase or decrease in temperature if the algebraic rules
for addition and subtraction are observed. Care must be taken to employ the
appropriate k for the temperature scale (i.e. Fahrenheit or Centigrade) being
used.
Volume at T°= volume at t° X [1 k(T° - t°)]
Spec. gray. at T° = spec. gray. at t° X [1 k(t° -T°)]
To compare the weights of a ' fixed volume of material when at two different
temperatures the second of the above relations may be used by reading "weight"
for "spec. grav.".
TABLE 26. Representative values of coefficients of cubic expansion of representative marine oils
,
Temperature Coefficient of expansion
Oil Appearance 1
° F. °C. per °F. per °C.
Offal oil
Salmon apparently solid 14 to 25 -10 to - 4 0.000370 0.000666
melting stearine 25 to 32 - 4 to 0 0.000590 0.001062
cloudy stearine 32 to 46 0 to 8 « 0.000442 0.000796
no stearine 20 to 88 - 7 to 31 ' 0.000382 0.000688
Blubber oils
,
Whale 0.00039 to 0.00042 0.00070 to 0.00075
Seal 0. 00034 to 0.00036 0.00061 to 0.00065
Porpoise 0.00036 to 0.00039 0.00065 to 0.0007é
148
Somewhat divergent and discordant numerical values for the coefficients of
.common marine oils are reported by different investigators. Values collected from
various sources are presented in table 26. The 'values shown for herring, pilchard,
salmon offal, dogfish liver, halibut liver, and rash liver oils were determined
in these laboratories from typical commercial samples produced in British
Columbia. In the case of some values reported from other laboratories it is not
evident whether or not the oil was free from stearine.
The presence of separated stearine in an oil has an immediate effect of
apparently increasing the coefficient during either cooling or warming. This
is partly attributable to the phenomenon mentioned under (a), namely that
the stearine occupies less volume (i.e. has a higher specific .gravity) than the
oil from which it was formed, at the same temperature. Since the fat is not a
simple chemical compound but rather a complex mixture, there is no sharp
freezing or melting point, and consequently the separation or 'melting of the
stearine takes place gradually with an apparent effect of increasing the rate of
-volume change per degree change of temperature. Determinations made in these
laboratories ( Carter, 1937, 1938; Frost, 1945) on various fish oils containing
stearine showed that the apparent coefficient under such conditions is higher
than when no stearine is present. These results tend to confirm those of Bolton
and - Williams (1935) who point out the errors arising in commercial practice
due to using faulty coefficients in estimating the weight of shipments of oil. No
more exact figures than are given for herring and pilchard oils containing
stearine can be quoted, since the expansion and contraction in the presence
of stearine is irregular and the coefficient varies with the amount of stearine
present. The coefficient for completely solid stearine is not greatly different from
that of the oil.
Fig. 11 illustrates the changes in- volumes and specific gravities obtained
experimentally as the temperature of a solidified sample of herring oil was raised
very slowly from 38° to 100°F. (1 0 to 38°C.) and the then liquid oil was very
slowly cooled over the same range. It will be seen that, on warming, the gradual
melting of the stearine plus its expansion on heating gave rise to a rate of volume
increase ( or specific gravity decrease) corresponding to a coefficient of expansion
of about 0.0006 as indicated by the rough parallelism of the rising temperature
curve to the line representing that coefficient in the upper key. The last trace of
stearine melted at about 94°F. (34°C.). On cooling, the straight upper portion of
the falling temperature curve indicates that the oil remained liquid to about
67°F. and exhibited a coefficient of contraction of about 0.00044; below that
temperature there was a sudden contraction due to stearine formation after
supercooling (page 154), followed by a resumption of the coefficient 0.0006 as
more stearine separated and cooled. The lower portions of the two curves do not,
coincide, due to hysteresis effect.
The use of a wrongly assumed coefficient of expansion gives rise to relatively
small errors in computing specific gravities, volumes, or weights
_ of given volumes,
as compared with the enors introduced by neglecting entirely the effect of
149
temperature on these properties. The error introduced by using a coefficient
0.0005 instead of 0.0004 for a 20°F., temperature difference is about 0.2% as
compared with an error of about 1% if the temperature effect were ignored.
Temperature, Deg. E ,
40 50 60 70 , 80 90 100
i I 1 i
- Coeff ici ent of ,
1.025 — expansion per deg.F.
0.0006 0.910
1.020 I_ Z./0.0005
0.0004
0.915
1.015
tv.Vie 0.920
1.010
_2 1.005
-V
0.925 2
0)
1.000 0.930
00011 1")
0
00010
0.995 0.0009 0.935 (5;
0008 -
0.0007 a
0.990 Coefficient of 0.940
expt,tnsi on per
cleg.C.
0.985 0.945
0980 1 1 1I 1 1 I
0 5 10 15 20 25 30 35 40
Tempèrature, Deg .C.
FIGURE 11. Effect of stearine on coefficient of cubic expansion, volume, and specifie
gravity of sample of British Columbia herring oil undergoing very slow heating and cooling.
N
920C .
N
9175 .,
A...,,
.915C .,
.9125 _ .
\
9100
9075 N
\
9050 .
N.
9025
, N
300c
.
N
8975 `.
895C
8925
890Q
• 5-c Aec .95t 40`C 45r 50 .0 55V 00V 6.5*C.
77• 66 °F 9.5•F 101 °F 113 °F 122 .F 131' F 140 °F 149*F
Tempera-lure
150
relationship is seen to be linear over this temperature range and could safely be
extended to 212°F. (1006C.). From this graph the,. specific gravity of other
samples of completely liquid pilchard oil at various temperatures may be found,
provided that the value at one temperature is known. This value would be plotted
as at A in the graph and a line drawn through this point parallel to the original
curve, as indicated by the sample dotted line through A in the figure. The specific.
gravities of the new oil may then be read from the new line for any temperature
between the limits shown. The data from which fig. 12 was drawn showed that
the sample of pilchard oil had a coefficient of cubic expansion equal to 0.000415
per °F. (0.00075yper °C.).
0 55° 131° -0
0
50° 122°
1-
z 1
3 113°
a. 45°
0
400 104° f
Id
0 10 20 30 40 50 60 70 80 90 100
• WEIGHT PALMITIC ACID IN MIXTURE (%)
FIGURE 13. Melting points of mixtures of palmitic and elaidic acids, showing lowering
of melting point and eutectic formation.
,e
temperature and sharpness of the melting point can be increased by any opera-
tion, this is an indication that a second constituent (as ,an impurity) is being
removed. Stearic acid present to the extent of 1% as an impurity in oleic acid
lowers the melting point of the latter by 0.13°C.
The lowest melting point on the curve shown in fig. 12 corresponds to a mix-
ture containing about 23.8% palmitic acid. This particular mixture is known as
a eutectic, which behaves in many ways as though it were a chemical compound
of palmitic and elaidic acids, though such is not the case. Eutectic mixtures of
some fatty compounds possess quite sharp melting points and as they sometimes
resist simple efforts to separate the two components, they have on occasion been
mistaken for new chemical entities. Not all mixtures of fatty compounds, however,
form eutectics.
Careful inspection of the change in melting point, as ,the ratio of two fatty
acids in a mixture is altered, has revealed that actual chemical compounds may
be formed in some cases, though these are unstable and apparently have little
significance in the technology of fatty oils (but see page 156).
152
Pressure. At atmospheric pressure, a solid cannot be heated above its
normal melting point. If the solid expands on melting, as do most fatty com-
pounds, an increase (or a decrease) in pressure raises (or iowers) the melting
point; for fatty acids above C r, the melting point is raised approximately 0.02°C.
(0.04°F.) for each increase of one atmosphere of pressure (14.7 lb. per sq. in.).
The corresponding value for glycerides is similar. This effect of pressure can
assume significant proportions in the hydrogenation of fatty materials under high
pressure.
Stable and unstable modifications of a solid. Pure fatty triglycerides have
been known for many years to display enatic melting points. Work ly Carter and
Malkin (1939) has shown that many triglycerides are capable of existing in four
modifications in the solid state, one unstable_vitreous ,form and three crystalline
forms. In any one triglyceride each form has its own melting point, as exemplified
by unsymmetrical palmitodilaurin, which displays the following four melting
points depending on rate of heating and previous thermal history of the sample:
unstable vitreous form, m.p. 20°C. (68°F.); unstable a-crystalline form, m.p.
33°C. (91.4°F.); unstable p-crystalline form, m.p. 43°C. (109.4°F.); stable
p-çrystalline form, m.p. 46.5°C. (115.7°F.). Symmetrical triglycerides appear to
exist in only three modifications. For example, tristearin after being eooled slowly
rnelts at about 72°C. (161.6°F.); if the liquid is chilled quickly, the unstable
vitreous solid first formed melts at 54°C. (129.2°F.), then re-solidi fies. A third
form (unstable) melts at 65°C. (149°F.).
The process of melting requires the absorption of heat, called latent heat of
fusion. When a pure crystalline substance in bulk is steadily heated, its tempera-
ture rises steadily until its melting point is reached. Its temperature then remains
almost constant (practically so if stirred) while the heat of fusion is being ab-
sorbed. Finally, after all the solid has melted, the temperature again rises steadily.
The same applies when a eutectic in bulk is heated; but in general, when a bulk
solid mixture of two or more substances (e.g. a natural fat) is heated, the
process of melting extends over a considerable temperature range and a gradual
softening is followed by the appearance of a liquid \containing suspended solid
material. The last trace of crystals of a high-melting constituent may persist until
the melting point of that constituent is almost attained. A typical example is the
melting of stearine.
Elsewhere in this Bulletin are recorded the comparative melting points of
various types of pure fatty compounds ( e.g. >fatty acids, table 1). Some estimate
of the melting points of the stable form of the various triglyceride . components of
these fats may be obtained from the data and generalizations. in table 27. The
saturated "simple" triglycerides (fig. 1) thus melt about 8°C. higher than the
fatty acid from 'which they are formed, and the longer the carbon atom chain
of the saturated fatty acid, the higher the melting point. Increasing unsaturation
in the fatty acid portion has a considerable lowering effect on the melting point.
For the types of triglycerides predominating in natural fatty oils, namely
those formed from two or three different fatty acids ; (the "mixed" trigly.cerides
153
of fig. 1), it may be stated in general that: (1) The melting point is usually lower
than that of the "simple" triglyceride of the lowest-melting fatty acid combined
in the "mixed" triglyceride. (2) The melting' point may be lower than that of the
lowest-melting fatty acid forming the triglyceride. (3) A "mixed" triglyceride
having its fatty acid radicals symmetrically attached to the glycerol portion melts
at a temperature slightly higher than that of its isomer in which the acid radicals
are unsymmetrically arranged. (4) In general, the greater the number of un-
saturated linkages in the triglycefide, the loyver the melting point.
TABLE 27. Comparison of melting points of some fatty acids and their triglycerides.
Melting point of
fatty acid (°C.) 44.2 54.4 62.9 69.6 16.3 —5 —11
Melting point of
fatty acid tri-
glyceride (°C.) 46.4 57.0 65.5 72.5 5 —13.1 —24.2
16 >
0 PILCHARD
12 > 0 SALMON
bi • HERRING
.,
) 11. '"•---bIIIIIIIIIIIM
-
4 )
4 A ,, ac nn n n ne, cn
-
— TITRE °C.
FIGURE 14. Relation between titre and iodine value in several hydrogenated fish oils.
156
increases with decrease in iodine value. The rate of change is not quite linear and
with each oil there is a tendency for the titre point to increase more slowly at the
higher stages of saturation. In the case of pilchard and herring oils • from fish
caught in British Columbia waters the highest titre obtainable is about 53°C.,
while in the case of salmon oil it may reach 56°C. The differences in the titres
of the fully hydrogenated products are most likely due to the differences in the
proportions of the fatty acids of various carbon contents. It is interesting to note,
however, that samples of honing oil produced in more northerly waters (i.e.
Alaska ) give fully hydrogenated fatty acids with titres 56°C. and over.
760
• NORMAL BOILING FOINT --)•• 1
. ( 460° F.)
700
( 238° C.)
›
tr
600 ra
c.)
ec
w
2
500
La-
o
400 e
2
300
w
I
=reco
200 Cl)
ta
cc
o .
10
Natural fats, being mixtures, have no definite boiling point under reduced
pressure; on being distilled under extremely high vacuum the separation of cer-
tain impure saturated triglycerides such as trilaurin (at 500 0 to 525°F.), tri-
myristin (at 550° to 570°F.) and tripalmitin (at 590° to 610°F.) has been
effected.
Another method of distilling below the normal boiling point is that of short-
path distillation under an extremely high vacuum. The substance does not
actually boil, but evaporates rapidly across a narrow space between heated and
cooled surfaces. By means of this method vitamins and fatty hydrocarbons are
now being distilled from fish and fish liver oils on a commercial scale (page
58). Vitamin A thus evaporates at 279°F. (137°C.) when the pressure has been
lowered to 0.00001 mm. of mercury.
158
A third method of distilling below the normal boiling point depends on the
principle that when a mixture of two completely immiscible liquids is boiled at
atmospheric pressure, each boils below its normal boiling point. Thus when
myristic acid [boiling normally at about 619°F. (326°C.) with some decom-
position] is heated with excess water or steam at atmospheric pressure, the steam
at slightly below 212°F. (100°C.) contains about 0.2% by weight of the acid,
which is readily separated from the condensate. By superheating the steam, the
proportion of myristic acid is raised to 7.f7%, and, by reducing the pressure to
TABLE 28. Effect of reduced pressure on boiling point of fatty compounds.
Boiling point
. Pressure
(mm.) (°F.) (°C.)
88 mm., the steam at about 90°F. (32°C.) contains 65.7% of the acid. Steam dis-
tillation is used commercially to a great extent in the separation of fatty acids
from hydrolysed oils, as described in another part of this Bulletin (page 269).
(g) REFRACTIVE INDEX
When a beam of light passes from air into a denser medium such as water
or oil, it is refracted towards the normal, i.e. a line at right angles to thé Inter-'
The ratio of the sines of the angles of incidence and refraction is constant face.
at the boundary of any two media. This ratio is called the refradtive index and
is usually measured with'air as the lighter medium. The refractive index is an
important physical property that, in the case of oils, is used as an analytical tool.
.Although frequently indicated by the abbreviation ref. id., it is also symbo lized
159
as n, or n L, where t is the temperature in degrees Centigrade at which it is
measured, and D refers to the sodium D line in the spectrum, the point on which
the measurement of refractive index is standardized.
The refractive index of a substance decreases with increase in temperature but
this decrease is mostly due to the decreased density. If, the density of the substance
is taken into consideration, then the refractive index is practically unaffected by
temperature. In the case of oils and fats, the refractive index depends upon the
molecular weight and degree of unsalturation of the component fatty acids, in-
creasing with increase in molecular weight and also with the number of double
bonds in the fatty acids. Fatty acids containing hydroxyl groups have a higher
refractive index than thosé containing a similar number of double bonds. Further-
more, double bonds in the conjugated position prOduce a large increase in re-
fractive index. Finally, the refractive index of a neutral fat or oil is higher than
that of the mixture of its component fatty acids.
There is a close relationship between the refractive index of an oil and the
unsaturation as measured by, the iodine value. If a series of oils is prepared from
the same sort of material by identical methods, then the unsaturation in terms
of iodine values can be calculated quite accurately from the refractive index.
Harrison et al. (1939) investigated the refractive indices and iodine values of
169 samples of oil from five species of salmon from widely varying localities.
They found that there was a coefficient of correlation of 0.9747 between these
two characteristics and suggested that the iodine value could be calculated by
the equation
Iodine value = 6929 X n — 10079.2
In the process of hydrogenation the double bonds become saturated and the
refractive index decreases. The use of this latter value has thus become of impor-
tance for rapidly estimating the degree of saturation during the hydrogenation
process. Brocklesby and Charnley (1933) found that during the hydrogenation
of pilchard oil the relationship between refractive index and iodine value (I.V.)
could be expressed by the equation:
n 0 =1.4474 + 9.6158 X 10-5 (I.V.) + 7.7998 X 10 -8 (I.V.) 2
As pointed out in other sections of this Bulletin, oxidation and polymerization
of unsaturated oils both increase the refractive index. Pickering and Cowlishaw
(1922) claim that by taking into consideration: the acid and saponification values
the refractive index can be calculated from the equation:
nD = 1.4643 — 0.000066 (sap. val.) — 0.0096 ( acid val./sap. val.)
-I- 0.000117 (I.V.)
These authors state that if the refractive index of any sample, after correction
for acidity and saponification value, lies above the curve for the iodine value •
found, it is certain that the sample is not fresh. In other words, the plot of the
above equation furnishes a means of detecting incipient oxidation. The increase
in refractive index during the polymerization of fish oils has been discussed by
Brocklesby and Denstedt (1934).
Refractive index measurements have also been used to determine the oil
160
content of seeds and other oil-bearing materials. It is based on the change in
refractive index taking place in a solvent when a knowii weight of the dried
material is extracted with a definite quantity of the solvent. It might be empha-
sized that the solvent chosen for the refractometric determination of oil content
of tissues should be one that is not associated. The density and refractive index
relationships of solutions of raw and polymerized oils in cyclohexane and dioxane
were investigated in these laboratories. Both raw and polymerized oils in cyclo-
hexane gave solutions the densities of which were a linear function of the volume
concentration. The refractive indices deviated slightly from strict linearity, prob-
ably because of slight volume changes that were undetected by the density
determinations. However, the specific refractivities (refractive index relative to
density) followed a strictly linear relationship to the weight concentration. In
dioxane both the raw and polymerized oils showed densities that were not a
linear function of the volume concentration, both curves showing a maximum
deviation at about 50^/o volume concentration. Refractive indices showed the
same type of curve, but the deviation from linearity was greater in the case
of the polymerized oil than in that of the raw oil. The specific refractivities were
again an exact linear function of the weight concentration. It was apparent that
in the dioxane solutions there was an increase in volume following the mixing
of the two components. This increase attained a maximum of 0.57% at 50^0
volume concentration.
(h) VISCOSITY
All parts of a liquid flowing through a tube do not move with the same
velocity; near the wall the liquid moves more slowly than near the centre. In the
case of lubricating oils this viscosity is a very important physical property and
it is also used to a certain extent to measure the changes taking place during the
blowing or heat treatment of drying oils. It is not used very much in connection
with oils intended for other industrial purposes.
The viscosity of oils is affected by the nature of the component fatty acids,
particularly the ratio of the saturated solid fatty acids to unsaturated liquid acids.
Oils containing fatty acids with a hydroxyl group are usually more viscous than
those lacking such acids. The manner in which the fatty acids are linked to the
glycerol molecule seems to be of some importance as far as viscosities are con-
cerned. Oils with similar fatty acid compositions may have dissimilar viscosities
due to differences in the actual glyceride structures. As a consequence, iodine
values used as a measure of the average unsaturation do not always show a linear
relationship to viscosity. Non-fatty materials such as lecithin may have a pro-
found effect on the viscosity of oils. Oils containing large amo,unts of phospho-
lipides are usually more viscous than ,those with smaller amounts. I
The viscosity of oils decreases rapidly with increase in temperature, but the
relationship is not a linear one; with increase of temperature the rate of decrease
in viscosity increases. With increase of temperature the differences between the
viscosities of different oils tend to decrease. Polymerization and oxidation both
increase the viscosity of oils.
161
Some data on the viscosities of fish,oils are given in table 29. Most of these
were determined in these laboratories with a calibrated Stormer viscometer; the
remainder are from a paper by White (1912) who used a capillary tube type of
instrument. The data bring out one or two points of interest. Removal of stearine
Observer
Brocklesby White
(25°C.) (30°C.)
So 60 70 go 90 160
O^o- 40
DEGREES CENTIGRADE.
FicunE 16. Temperature viscosity curves for pilchard oil polymerized for various times
at 250°C., as determined with Stormer viscometer. A = 16 hours, mol. wt. 1660; B 12 hours,
mol. wt. 1500; C = 6 hours, mol. wt. 1217; D = 2 hours, mol wt. 1200; E raw oil,
mol. wt. 900.
162
has a slight but measurable effect in lowering the viscosity, a greater difference
being found between the raw and the light pressed pilchard oil than between, the
latter' and the more heavily pressed oils. Sàlmon oil, although not much more
saturated than pilchard oil, has a much higher viscosity, probably on account of
the higher content, of phospholipides. The great " diff,erence between the two
samples of menhaden oil is probably due to the difference in methods of extrac-
tion, the dark sample with the high viscosity being extracted by heating at 130°C.
(266°F.) "whereby there was considerable decomposition and the oil became
quite gummy". Sperm whale oil is noted for its relatively low viscosity, a circum-
stance most likely related to the peculiar composition of this oil.
In fig. 16 the effect of polymerization and temperature on the viscosity of a
fish oil is shown. Polymerization markedly increases the viscosity; increase in tem-
perature decreases it. The most important point to be noted, however, is that the
temperature effect increases rapidly with increase in polymerization. The poly-
merized oil behaves as a colloid, the polymers losing their gel characteristics as
the température increases.
(i) SOLUBILITY
1
. , `
than is cod liver oil . As the unsaturation of the component fatty acids in an oil
increases, so does the solubility in any given solvent . If a fat containing mixed
glycerides is shaken with a solvent such as cold alcohol or acetone the clear
ctilute solution will contain more of the unsaturated glycerides than will the
insoluble residue .
In all solvents the, solubility of fats and oils increases with rise in tempera-
turé. This is particularly noticeable in the case of the alcohols and ketones . Solid
fats are much more soluble if heated in a solvent to a temperature abovè their
melting point. Usually those solvents that are completely miscible with water •
are poor solvents for oils but notable exceptions are dioxane and pyridine, which
not only will dissolve most oils but will also dissolve those that have undergone
oxidation or polymerization .
It must be emphasized that the relative solubilities of va:rious oils in a given
solvent are very much influenced by the presence of impurities, either in the
solvent or in the oil . This is particularly true of those oils containing varying
amôunts of such materials as lecithin . On the other band, a high, free fatty acid
content in an oil will also give a fictitious value for solubility . The free fatty acids
dissolve more readily than the neutral oil and the solution of the fatty acid in the
solvent in turn acts as a better solvent for the remaining neutral oil . Statements
regarding solubilities of oils in various solvents should always include a definite
description of the purity of both the oil and the solvent.
(j) SUEBACE TENSION
REFERENCES . . ■
ADKINS, H. Reactions of hydrogen with organic compounds over copper chromium oxide and
nickel catalysts. University of Wisconsin Press, 1937. -
Arapahoe Chemicals, Inc., Boulder, Colo. N-bromsuccinimide„. Çat. No. 902, 1949. .
ARMSTRONG, E. F., AND T. , P. HYLDITCH. J. Soc. Ch am. Ind., 39, 120-124T, 1920.
Ibid.,. 44, 4347T, 1925. ! .
BAc, A. yasloboino Zhiropoe Delo, 1929 ( 7 ),:40-44 ( C.A. 24, 6046).
BAILEY, A. E. Industrial Oil and Fat ProdUcts (Interscience Publishers), p. 677, I945a. • '
Ibid., p. 387, 1945b.
Ibid., p. 422, 1945c.
BAUER, S. T. Oil and Soap, 23, 1-5, 1946. •
BEHR, 0. M., C. SLIGER, E. T. MoLEAN• AND C. Smrre. Paint, Oil Ch am. Rep., Noy.11, 1937,
BEn-rnAm, S. H. Oele, Fette, VVachse, Seife Kosinetik, 1938 (7), 1-4 (C.A. 32, 7755).
BLAGONRAVOVA, A. A., M. A. ANTIPOVA, 0. N. SAVVINA AND E. M. SVETLICHNAYA. j. Applied
Chent (U.S.S.R.), 14, 192-197, 1941 (C. A. 36, 1590).
BorroN, E. R., AND K. A. WILLIAMS. Analyst, 60, 158-159, 1935.
BRADLEY, T. F., AND D. RicHAnDsoN. Ind. Eng. Chem., 34, 237-242, 1942. •
'165 •
HARRISON, R. W., A. W. Animism, S. R. POTTINGER AND C. F. Lm. U.S. Bue. Fish. Inv. Rep.,
40, 1-21, 1939.
HARVEY, E. H., AND H. A. ScnuErrE. J. Amer. Chem. Soc., 50, 2837-2840, 1928.
HEcKinà, A. Fette u. Seifèn, 45, 626-629, 1938.
Hn..nrrcu, T. P., AND J. T. TERLESKI, J. Soc. Chain. Id., 315-822T, 1937.
Jicons, J. J. Ind. Eng. Chain., 34, 322-326, 1942.
JENNINGS, G. W. J. Ind. Eng. Chem. (Anal. Ed.), 4, 262-263, 1932.
Ki.anta, P., AND W. Ftrnœ.s. Halo. Chim. Acta, 30, 863-867, 1947,
KAUFMANN, H. P., J. BALTES inn P. MiannEa. Fette u. Self en, 44, 337-340, 1937.
S. J. Soc, Chein. Ind. Japan. Suppl. Bind., 43, 428, 1940.
KING, G. J. Chem. Soc., 1936, 1788-1792, 1936.
K.fflo, K. Sci. Pap. Inst. Phys. Chain. Res. (Tokyo), 15, 127-129, 130-136, 1931 (C.A. 25, 2693).
'
LAMBERT, R. S., AND J. T. R. ANDREWS. 1.-Am. Oil. Chem. Soc., 25, 414-416, 1948.
Linwomn, A., AND E. N. Morrnim. J. Chem. Soc., 127, 1628-1632, 1925a (C.A. 19, 2930).
Ibid., 127, 1987-1989, 1925b (C.A. 20, 41).
LASCARAY, L. Fette u. Seifen., 46, 628-632, 1939.
LOVERN, J. A. Dept. Sci. Ind. Res. Food. Invest. Special Rapt. No. 52, 15-22, 24-33, 1942.
LYUBARSEH, E. L J. Applied Chain. (U.S.S.R. ), 5, 1025-1045, 1932 (C.A. 27, 1533).
MARKLEY, K. S. Fatty Acids (Interscience Publishers), 424-428, 1947a. •
Ibid., 495-496, 1947b.
Miz, W. H. Oil and Soap, 21, 197-201, 1944.
Mn,is, N. A., S. SUSSMAN, AND H. S. MASON. J. Am. Chain. Soc., 61, 1844-1847, 1939.
MoonE, T. Biochem. J., 31, 141-148, 1937.
NiunET, M., AND P. DESNIJELLE. Bull. soc. chim., 1946, 595-598, 1946 (C.A. 41, 3052).
NTEDEBL, J. B., AND C. Liorri. J. Amer. Chem. Soc., 55, 3025-3026, 1933.
NOLLER, C. R., AND R. ADAMS. J. Am. Chain. Soc., 48, 1074-1080, 1926.
Nunn, L: C. A., AND .1. SMEDLEY-MACLEAN. Biochem. J.„ 32, 1974-1981, 1938.
ODA, R., AND S. WA. J. Soc. Chem. Ind. Japan, Suppl. Binding, 37, 295-296, 1934.
.0'HAILE, G. A., AND W. J. Wrrnnow. Ind. Eng. Chain., 39, 101-104, 1947.
PICKERING, G. F., AND G. E. COWLISHAW. J. Soc. Chain. Id., 41, 74-77T, 1922.
PowEns, P. 0. Ind. Eng. Chain., 41, 304-309, 1949.
RADLOVE, S. B., H. M. TEETEn, W. H. Bonn, J. C. COWAN AND J. P. ICAss. Ind. Eng. Chem.,
38, 997-1002, 1946.
Ribucov, G. Ber., 69B, 1231-1238, 1936 (C.A. 30, 5558).
RIESS, C. Collegium, 1931, 557-588, 1931 (C.A. 26, 4583).
RUSH, V. 'A., I. L. DVINYANINKOVA AND E. I. LYUBARSKIL J. Applied Cham. ( 10,
702-708, 1937 (C.A. 31, 6493).
SAUER, J., AND H. ADKINS. J. Amer. Chain. Soc., 59, 1-3, 1937.
SCA/VLAN, J. T., AND D. SWERN. J. Am. Chain. Soc., 62, 2305-2309, 1940.
SCHAEFFER, B. B., E. T. ROE, J. A. DIXON AND W. C. AULT. J. Am. Chain. Soc., 66, 1924-1925,
1944.
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Smrrn, E. L. J. Phys. Chain., 36, 1401-1418, 1932.
,Smrrn, J. C. J. Chain. Soc., 974-980, 1939.
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25-32, 1938. •
SWAIN, L. A. Ann. Rep. Fish. Ras. Bd. Can. for 1946, 53-54, 1947.
• SwAnNI, L. A., AND B. H. MORTON. J. Fish. Ras. Bd. Can., 6, 326-333, 1945.
'TiEino, M., M. TAKAO AND M. DANZYO. J. Soc. Chem. Ind. Japan, Suppl. Binding, 43, 132-133,
1940 (C.A. 34, 6469).
166
Tresom R. S. In' "Chemistry and Technology of Marine Animal Oils." Fish. Reg. Bd. Can.
Bull., 59, 148-149, 1941.
Time,.En, R. B. Oil and Fat I d., 8, 141-143, 1931.
Tunx, A., AND P. D. Boot«. Oil and Soap, 21, 321-322, 1044. \ •
Tolls, A., AND J. Fm..MuAN. Paint, Oil, Chem. Rey., 106 (13), 10-11, 1943.
TwrrcumL, E. J. Am. Chem. Soc., 21,22-26, 1900.
VAN ANTWERPEN, F. J. Ind. Eng. Chern., 35, 126-130, 1943.
WATERMAN, H. I., AND C. VAN VLODROP. J. Soc. Chem. I d., 55, 333-34T, 1936.
WATERMAN, H. I., C. VAN VLODROP AND F. ALTirmsius. J. Soc. Chain. I d., 57, 87-89T, 1938.
WATERMAN, H. I., C. VAN VLODROP AND J. HANNEWYK. Research, 1, 183-185, 1948 (C. A. 42,
2787).
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(C.A. 31, 1645).
WarrE, G. F. J. Ind. Eng. Chain., 4, 106-110, 1912.
167
I VV,'
CHAPTER SIX
action of lipases—enzymes which are present in the tissues but which, like all
enzymes, are destroyed by heat. Hence the formation of free fatty acids takes
place chiefly during spoilage of raw material prior to processing. While oxidative
rancidity can be caused by enzymes—lipoxidases in this case—it also results from
atmospheric oxidation, and for this reason is a much bigger problem than the
development of free fatty acids. The destruction of vitamin A by rancid oils is
discussed in Chapter 3. The use of antioxidants—substances which inhibit oxi-
dation—is discussed on pages 51-53. The different types of deterioration and
ways of controlling them, including use of antioxidants, will be discussed in this
chapter.
(a) DEVELOPMENT OF FREE FATTY ACIDS
Since this is due mainly to enzymes, the lipases, which become especially
active after the death of the fish, oils prepared from putrid materials are high in
free fatty acid unless, as in the case of those from fish livers and viscera of low
oil content, they are prepared by alkali digestion. In that case the free fatty acids
are largely, although not always entirely, neutralized during production.
Lipases are present not only in the tissues of fish, but are also formed by
bacteria and other micro-organisms which can under certain conditions grow
in the oil. Jensen and Grettie (1937) showed that micro-organisms could not live
in moisture-free oil, but found that as little as 0.3% moisture in an oil enabled
them to grow.
The relationship between the time of storage (unfrozen) of raw cod livers,
and the quality of the oil produced fro- m them, was investigated by Drumm-ond
and Hilditch (1930). Some of their data are given in table 30.
These results show a marked increase in the free fatty acids and colour of
the oil produced as the time of storage of the livers increased. The storage time
of the livers had, however, no significant effect on the vitamin A content of the
oil. The yield Of oil obtained decreased steadily with increasing time of storage
of the livers, probably due to emulsification during the steaming process. Further
experiments by the same authors involved the effect of small quantities of raw
and cooked liver- tissue introduced into medicinal cod liver oils, which were then
stored for periods of time up to 13 months. This latter worlc showed fairly con-
clusively that the formation of free fatty acids was dhe to enzymes present in the
livers themselves. These authors conclude that: "Deterioration of the liver, and
168
hence, the technical quality' of the oils is due to retrOgressive changes effected by
the enzymes, etc., present within the liver tissue". ),,,Vork by Swain (1947) has
confirmed this further.
TABLE 30. .Effect of time of storage of cod livers on yield and quality of resulting oit.
Oil obtained
Approx. time of Weight of
storage at 5° C. livers Colour
(hours) (lb.) Weight Lovibond units Free fatty ,- Vitamin A
(lb.) acids (%) (U.S.P. units
Y per gram)
The oil in the muscle tissue (flesh) of fish also undergoes rapid enzymatiç
hydrolysis. This was found by Brocldesby (1933) who showed that there was an
increase in the free fatty acid content d the oil of coho salmon, both in the
minced condition and "in the round", stored respectively at 13°C.( 55°F.) and
11°C. (52°F.). The free fatty acid content of the oil from the minced flesh in-
creased from 0.2 to 2.0 in approximately 30 hours; that from the fish stored "in
the round" showed a similar increase in approximately 50 hours. The slightly
higher temperature at which the minced flesh was stored, plus the fact that there
was more bacterial contamination in the minced fish, - probably account for ,the
more rapid rate of hydrolysis.
Results of the same sort have been obtained in this laboratory in connection
with the effect of time and temperature . of • storage of whole herring on the oil
produced from them. The free fatty acid content of the oil from fresh herring
was less than 0.2, while after storage of the fish at a temperature of 2°C.(35.6°F.)
for 8 and 7 days it was 0.4 and 2.0, and at a temperature of 15°C.(60°F.) it was
3.0 and 15.4 respectively.
Enzymatic splitting of oils can take place even at temperatures below the
freezing point of the 'tissues. An increase in the free fatty acids of the oil of
stored-frozen salmon was demônstrated by Brocklesby (1933). The oil was ex-
tracted separately from the deep lateral (pink) muscle-and the superficial lateral
(dark) muscle of red spring salmon which had been held in commercial cold
storage at an average temperature of —18°C. (8.6°F.); the data which are given
in table 81 show that the development of free fatty acids was quite rapid.
The development of free fatty acid in the oil of mackerel and sardines also
stored at —13°C.(8.6°F.) was investigated by Ono (1935). He found that the
free fatty acid content increases rapidly ; but that the iodine value shows no
169
change during cold storage/ of the fish. It was shown that the hydrolysis of
neutral fat is not caused by the action of micro-organisms (moulds, bacteria,
etc.), but by a lipase vvithin the tissues themselves.
TABLE 31. Developmènt of free fatty acids in oil of red spring salmon
held in commercial cold storage for various times.
1 0.51 0.33
7 1.53 1.12
16 2.76 2.09
52 7.20 6.30
Days 0 10 28 56 63 71
Herring muscle -I- herring oil 3.6 9.3 21.0 34.5 67.0 132.6
Herring muscle (heated) + herring oil 3.6 7.7 12.7 22.6 39.6 30.7
Herring muscle -I- herring oil ± salt 3.6 10.1 20.7 63.9 157.8 270.6
Herring muscle (heated) + herring oil -I- salt 3.6 8.2 14.9 41.5 44.6 37.6
Blank 3.6 7.2 7.2 11.-7 11.4 16.3
TABLE .33. Effect of various metals and alloys present during deodorization of oil.
Peroxide value
Metal Amount after accelerated
stability tests
172
period. Most of the rancid flavour and odour develops soon after-the end of the
induction period, although some types of "flavour reversion" (see below) occur
during the induction period itself. The decrease in peroxides during later stages
of oxidation is -due to the fact that the peroxides are breaking down to other pro-
ducts more rapidly than they themselves are being formed.
Pro-oxidants are any substances which increase the rate of midation.. Paint
"driers"—substances which are added to paint oils - to increase the rate of forma-
tion of a solid film by oxidation—are pro-oxidants. Contact with various metals
has a pro-oxidant effect on oils. The action of various metals in this respect was
investigated by Ziels (1945). He measured the increase in peroxide value during
5-hour deodorization of samples of a hydrogenated cottonseed oil in contact with
granules of the various metals at 205°C. (401°F.). The results are given in
table 33.
Various organic substances also increase the rate of atniospheric oxidation
of an oil. The most important of such organic substances are fatty peroxides
which, as ,already indicated, cause autoxidation of oils. Thus, when a coating of
oil is allowed to remain on the inner, surface of equipment it becomes oxidized
and acts, as a pro-oxidant for other oil which is later handled, in the equipment.
For this reason general equipment for handling oil should-be kept especially
clean. Methods for cleaning used drums were described by` Bailey (1935).
Carotenoid pigments and chlorophyll also act as pro-oxidants ( Olcott and
Mattill, 1941).
( o ) FLAVOUR .REVERSION
173
generally odourless and flavourless; but, at least when subjected to oxidation, it
takes on a characteristic flavour. This is not exactly fishy, although it is sometimes
designated as such. A completely \hydrogenated oil does not revert thus, so the
cause appears to be definitely in the unsaturated fatty acids. The work of Lemon
(1944) indicates that this flavour results from the oxidation of an isomer of linoleic
acid, which is formed by selective hydrogenation of the double bonds in more
highly unsaturated fatty acids. Armstrong and McFarlane (1944) believe that
the reverted flavour is due actually to volatile products which are formed by
oxidative decomposition of this iso-acid.
For further information on flavour reversion the reader is referred to the
review by Bailey (1946) and the report by Lips et al. (1947).
(d) ANTIOXIDANTS
Although the greatest use of antioxidants with fish oils is . in vitamin and
feeding oils, a discussion of their more general use for fatty oils will be
included at this point. Some antioxidants are materials which occur naturally in
animal and vegetable tissues while others are synthetic substances. Included in
the naturally occurring group are some seed flours and extracts, tocopherols,
phosphatides, nordihydroguaiaretic -acid (N.D.G.A.), and gallic acid and gallates.
Synthetic substances„ with antioxidant activity for fatty oils include hydro-
' quinone, pyrogallol, catechol, alpha-napthol, p-amino benzoic acid, and various
other substances. '
Iñ some cases substances vehich by themselves have little or no antiœddant
effect, when incorporated into oils along with an antio,ddant, greatly increase
the effect of the latter. Furthermore some antioxidants when added two at a
time have a far greater effect than the sum of their individual effects at the same
concentrations. This is known as synergism. It is due to the protective effect of
one antiœddant on the ôther.
There fo ll ow short descriptions of a number of antioxidants which have been
found suitable for, or show possibilities for use in, marine oils. For further in-
formation respecting antioxidants the reader is referred to the reviews by Lund-
berg (1947), Mat-till (1947), Hilditch (1944), and Spannuth (1949). A list of
antioxidants proposed for the preservation of edible fats (with a selected bibli-
ography of papers and patents) was published by the U.S. Department of Agri-
culture, Southern Regional Research Laboratory (1944).
(i) TOCOPIIEROLS •
, There are several isomeric tocopherols, the existence of four having been
established. They are individually named by the Greek letter prefixes a-, 13 , 7 —
and —. Although fairly widely distributed, in plant tissues, the chief sources are
certain seeds, especially wheat, in which they are most concentrated in the germ.
All have antioxidant properties for fatty oils, but the extent of their activity in
this respect varies somewhat. Their effectiveness as antioxidants for lard, at
levels of both 0.02 and 0.1%, increases in the order of a-, p-, 7 and 8 toco-
—
pherols (Griewahn and Daubert, 1948). It was pointed out by Hickman (1948)
174,
- ,
that a,--tocoPherol does-not inhibit oxidation by lipoxidase, - but does inhibit side
reactions and chain reactions initiated by the lipœddase. The other tocopherols,
however, inhibit' the lipmddase activity as well as the side and chain reaction.
The chemically active parts of tocopherols depend on the phenol oxygen and
pyran oxygen of a fused phenol-pyran nucleus and the activity varies with the
number and position of methyl substituents on the phenol portion.
Tocopherols are present not only in oils of vegetable origin, but also in fish
oils. Robeson and Baxter (1942) found that a—tocopherol occurs in soupfin shark,
dogfish, Atlantic coast shark, and California jewfish liver oils. In the Atlantic
coast shark liver oil it was found to be the major antiœddant, présent to the
extent of apprœdmately 0.01% (Robeson and Baxter, 1943).
Phosphoric acid has been used in concentrations of from 0.004 to 0.1% as
a satisfactory synergist for use with tocopherols.
Other substances which are effective as synergists to tocopherol include
phosphatides, and ascorbic acid and its esters, described more fully under re-
spective headings (ii) and (If) that follow.
The addition of vegetable oils containing tocopherols to fats 'and oils for
use in edible products is permitted in Canada.
PHOSPHATIDES
Soybean phosphatides, usually referred to simply as "lecithin", have been
used for some years as antiœddants for fats and oils. Actually, pure lecithin is
ineffective as an antioxidant; the effective material includes other phosphatides
which occur along with the lecithin. The principal use of phosphatides as anti-
oxidants for fats and oils is as synergists for tocopherols. Cephalin, a phosphatide
present to the amount of about 40% in soybean phosphatides, is particularly
effective in this respect. Thus Swift et al. (1942) found that while the addition
of 0.025% a—tocopherol to methyl esters increased the stability from 5 to 85,
the further addition of 25 parts per million of cephalin increased the stability to
295.
A method of stabilizing fatty oils against rancidity by adding a phosphatide
and a sugar or molasses, and then heating, is described in U.S. patent 2,198,208
granted to Musher in 1940 and assigned to Musher Foundation, Inc. Included
in the oils mentioned were a number of fish oils: "cod liver 'oil, halibut liver oil,
mackerel oil, herring oil, etc.".
The antioxidant mixtures containing phosphatides were as follows:
1. A mixture of equal parts of lecithin and sucrose.
2. A mixture of 30% lecithin and 70% crude cane sugar.
3. A mixture of 5% lecithin and 95% blackstrap molasses. •
The antioxidant mixtures thus prepared are added to oils in amounts of from
0.05 to 5.0%. Although fairly effective when added to the oils without any sub-
sequent heating, their effectiveness is greatly increased if the oil is heated, after
adding the antioxidant, to within the temperature range 180°-400°F. (82°-
204°C.).
17 5
-The addition of lecithin to fats and oils for use in edible products is per-
. The maximum allowable addition is 0 .2The0 .inCad term "lecithin"
embraces a crude mixture of various phosphatides .
Gallic acid and gallates can be used as antioxidants for fish oils . Ethyl gal-
late at a concentration of 0 .'1% gave a protection factor of 6 for salmon oil and
4 for herring oil' (Bucher, 1945) . The use of inethyl, • ethyl, propyl, and butyl
gallates as antioxidants for fats and oils is covered by United States patent
2,255,191, which was issued to Sabalitschka and Bbhm in 1941 .
Gallic acid is not only a powerful antioxidant by itself, but can act syner-
gistically with other antioxidants (Golumbic and Mattill, 1942 ) . The synergistic
effects of gallic acid and a number of gallates were investigated by Morris et al .
(1947) . For comparative purposes N .D .G .A . was also included in the investi-
gation . At concentrations of 0 .02%, without any synergist, gallic acid and propyl
gallate were the most effective ; both N .D .G .A . and octyl gallate were somewhat
less effective ; while both dodecyl gallate and hexadecyl gallate were still less
effective . The further addition of 0 .2% isoascorbyl palmitate to fat containing
0 .02% of gallic acid, octyl gallate, hexadecyl gallate, or dodecyl gallate, increased
the effectiveness approximately 50%, and increased the effectiveness of propyl
gallate about 25% . However, it approximately doubled the effectiveness of
N .D .G.A .
The addition of propyl gallate to fats and oils for use in edible products is
permitted in Canada . The maximum allowable addition is 0 .01% .
(V) ASCORBIC ACID AND ASCORBIC .ACID ESTER S
In spite of the fact that it is only very slightly oil-soluble, ascorbic acid has
an appreciable antioxygenic effect in various fats and oils . Furthermore, it acts
synergistically with a number of other antioxidants . Golumbic and Mattill (1941)
found that although 0 .1% ascorbic acid by itself had very little antioxidant effect,
0.4%. had a markedly greater effect . Furthermore, 0 .1% ascorbic acid together
with 0 .4% /3-t0copherol caused a 60% increase in the effect of the latter . The
use as an antioxidant of a small amount (suitably 0 .1% or less) of ascorbic acid,
together with a similar small amount of a tocopherol-like substance from among
the following : hydroxycoumarans, hydroxychromans, tocopherols, alkyltocols,
A ' induction period in presence of antioxidant
Protection factor = induction period in absence of antioxidan t
176
hydroxyisocoumarans, and chroman-5, 6-quinone, was patented by Mattill and
Golumbic in 1943 (U.S. patent 2,333,655, to Lever Bros. Co.).
Fat-soluble fatty-acid esters of ascorbic acid for use as antioxidants in fats
and oils have been developed. Their preparation and use are described in U.S.
patent 2,368,435, issued to Wells and Riemenschneider in 1945, and assigned to
the United States Secretary of Agriculttire.
The use of synergistic combinations of «,-tocopherol and an ascorbyl mono-
ester of a fatty acid as antioxidants for fats and oils was patented by Riemen-
schneider and Turer in 1945 (U.S. patent 2,375,250, to United States. Secretary
of Agriculture). They were used in concentrations of 0.01 to 0.20% of a-toco-
pherol and 0.05 to 0.12^/0 of the ascorbyl monoester of a fatty acid.
A ternary synergistic antioxidant composition-three antioxidants acting
together (one of which is an ester of ascorbic acid)-was also patented by
Riemenschneider and Turer in 1945 (U.S. patent 2,383,815, to the United States
Secretary of Agriculture). The antioxidant composition comprised an ascorbyl
monoester of a saturated aliphatic monocarboxylic acid containing from 12 to 18
carbon atoms per molecule, a-tocopherol, and soybean phospholipides (com-
mercial lecithin). An antioxidant composition containing these in the following
amounts was found particularly effective: d-isoascorbyl stearate, 0.12 %; a-toco-
pherol, 0.001%; soybean phospholipides (commercial lecithin), 0.03%.
The stabilization of fatty products by the multiple synergistic antioxidant
effect of various synergists with ascorbic acid or other compounds containing
an ene-diol group is covered by a group of patents granted to F. A. Norris in
1945, and assigned to General Mills, Inc. U.S. patent 2,377,029 covers the use,
in this way, of 0.1 Jo of para-aminobenzoic acid, 0.02% of tocopherol, and 0.1 Jo
of a compound with an ene-diol grouping, such as l-ascorbic acid, or any one of
the following: isoascorbic acid, reductone, dihydroxymaleic acid, glucoascorbic
acid or araboascorbic acid. U.S. patent 2,377,030 covers the stabilization of fats
and fatty products with 0.1% of mono-, di-, or tri-ethanolamine and the saine
plus 0.1% of l-ascorbie acid or other compound having an ene-diol'grouping.
U.S. patent 2,377,031 covers the stabilization of edible fats and oils by mixtures
of para-aminobenzoic acid, a compound such as ascorbic acid,, contaiiiing an
ene-diol group, and one of several described heterocyclic oxygen compounds.
The antioxidants are used in concentrations dependent upon the resultant sta-
bility desired, but are normally not used in concentrations above 0.117'o.
Thé addition of ascorbic acid to fats and oils for use in edible products is
pez•mitted in Canada. The maximum allowable addition is 0.2%.
(Vi) GUM GUAIAC
Gum guaiac is an excellent antioxidant for animal fats and oils and hence
probably for fish oils, although it is not very effective for vegetable oils. Its use
as an antioxidant is covered by U.S. patent 1,903,12.6, issued to Newton and
Grettie in 1933. It is difficult to dissolve in an oil or fat, but can be dissolved
when the oil is hot. The stabilization of fats and oils by incorporating therein a
177
solution of gum guaiac in higher fatty acid esters containing at least one
hydroxyl group is covered by U.S. patent 2,377,610, which was granted to Brown
in 1945 and assigned to Industrial Patents. Corporation.
The addition of gum guaiacum (gum guaiac) to fats and oils for use in
ediblè products is permitted in Canada. The maximum allowable addition is
0.2 %.
(Vii) MISCELLANEOUS NATURALLY OCCURRING ANTIOXIDANTS
178
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Mimeographed Ann. Rep. Fish. Exptl. Sin. for 1948, Summary No. 4, 1948.
TAUFEL, K., AND R. MULLER. Biochem. Z., 304, 275-281, 1940.
U.S. Dept. Agr., Southern Regional Research Lab., AIC-54, 8pp., 1944. (C.A. 39, 4163).
ZIELS, N. W. U.S. Quarteimaster Corps Manua& 17-7, 109-112, 1945.
'179
CHAPTER SEVEN
FicuRE 17. Cod liver oil extractor used on board steam trawlers.
181
Pacific coast, the application of the direct-steaming methods used in the 'pro-, .
duction of Atlantic cod liver oil will be described first. Livers brought in by the
sho're fishermen, who land their catch every day, are processed at the shore
plants, whereas livers from fish caught by steam trawlers, which remain at sea
for some daÿs before landing their catch, are sometimes processed right on the
boats in small liver boilers called Patch cookers. A diagram of one of these is
shown in fig. 17.
The Patch cooker is designed so that it may be operated in both calm and
stormy weather. It consists essentially of a cylindrical vertical cooker, with a.
conical top on which is a tall narrow stack. A port in the top allows the intro--
duction of the livers. The cooker is partially filled with livers, the port is then.
closed, and steam passed in through a perforated coiled pipe inside the bottom..
After steaming for' a sufficient length of time to break down the livers, wàter is.
-forced into the cooker and the oil, which separates as a separate layer at the top,
of the cooked material, is thus forced up the stack and out through a side. pipe..
It is filtered and run into storage tanks. The cooking operation is carried out at-
atmospheric pressure; however, the source of heat is steam which is usually in--
troduced at 60 lb. per square inch (293°F.), the pressure of the ship's boilers..
These cookers make possible the production at sea of first-class cod liver oil from^
absolutely fresh livers. As in any simple steam rendering plant not all of the oil
is removed from the cooked material. I-Iowever, further processing to remove the:
residual oil is impractical at sea; the gurrv, as the residue in the cooker is called,:
is therefore usually dumped and the cookers flushed out with water, after which
they are ready for another. charge of livers. The oil yield by this method may-
run as high as 45% of the weight of the livers but will, of course, follow the-
seasonal variation of the oil content.
Diesel trawlers bring in whole livers which are rendered in large scale shore.
steam rendering plants. In storing livers aboard the large craft a suitable pre--
servative is often used. By this method the livers arrive at the shore extraction:
plant in reasonably good condition. Preservatives are used in two forms: as a_
powder and as a liquid. The powders usually used are borax and soda ash; the
liquids commonly uséd are formaldehÿde or a mixture of formaldehyde and'
acetaldehydé. Dry salts do not readily penetrate the folds of the .liver, so there-
is considerable deterioration before they become very effective, whèreas with,
liquid preservatives this is avoided.
In some commercial shore establishments the livers are ground in meat
choppers or other suitable commercial grinders, which reduces the steaming-
necessary to liberate the oil. The batch of livers or ground pulp is placed in
conical tanks equipped with a central perforated steam pipe which introduces the^
steam at a pressure of 60-100 lb. per square inch. The cookers themselves are-
maintained at atmospheric pressure. The livers are cooked until disintegrated.
The oil is then either decanted manually, by syphon, or run off by int'roducing_
water into the bottom of the cooker. A diagram of a simple shore cod-liver-oi1
rendering plant is shown in fig. 18.
182
Whichever way the oil is removed it is next strained through fine cloth into
a settling tank, which is usually made of steel or galvanized iron and equipped
with a valve 1 to 15.1 inches above the bottom for drawing off the clear oil. The
oil is left to settle for 24 hours, so that any water in it will collect at the bottom,
below the level of the valve for drawing off the clear oil. The tank should have
another valve, or drain cock, at the bottom so that the watery oil at the bottom
can be drained off. This is saved and when suffi cient has accumulated, it is
settled separately.
FIGURE 18. Simple shore rendering plant for cod liver oil. Through pipe A four holes are
drilled neax its end; through each of pipes B about forty holes are drilled, four every 2 inches
starting from near the bottom..
The oil may be sold without further processing, or it may be cold-cleared
by cooling to about 35°F.(2°C.), the exact temperature depending on the
specifications required.
Oils prepared from stale livers usually have an objectionable odour, but if
this is not very bad they can be deodorized by steam distillations under vacuum
as described on pages 238-241. The oils are sometimes heated with a
small quantity of activàted carbon or bleaching clay, or a combination of the
two materials, to give them a more brilliant sheen. Such treatment of vitamin
oils, however, has the disadvantage that it may remove some Of the vitamin A.
Partially decomposed livers are in some cases processed by the following
procedure, largely for the production of cod oil. A known quantity of livers is
placed in a cooker and 2 lb. of caustic soda dissolved in 13 gallons of water is
added per 100 lb. of livers. The mixture is then brought to a boil. It is preferable
to emulsify the mass, but not essential. A foam rises after the boiling point is
reached, and the steam is shut off at this point. The mixture is then allowed to
stand for a half hour. The free fatty acid content of the oil vqhich separates is
then determined and the amount of additional caustic soda necessary to neutral-
183
ize these free fatty acids is calculated as follows: for each per cent of free fatty
acids per 100 gallons of livers, 1 lb. of câustic soda is added, dissolved in 5 pints
of water. For example, 250 gallons of livers with 3.3% free fatty acids would
250
require: 3.3 X -= 8.25 lb. of caustic soda, dissolved in 8.25 X 5 = 41 pints, or
100
5 gallons, of water. The calculated amount of alkali is added, the mixture
brought to a boil, and then allowed to settle. If too much caustic has already
been added, some oil with a free fatty acid content, or more livers containing oil
with a high free fatty acid content, may be added. The mixture is again brought
to a boil and allowed to stand for '2 hours before drawing off the oil.
A liver cooker somewhat similar in nature, except for, the fact that a supply
of steam from a.` separate source such as the ship's boiler is not required for its
operation, was developed by Labrie and Fougere (1937) at the Gaspé Fisheries
Experimental Station of the Fisheries Research Board of Canada. The Labrie
cooker allows the production of first-grade medicinal oil on a relatively small
scale.
The principle of this apparatus, a diagram of which is shown in fig. 19, is
that of a percolator in which the extracting agent is steam, instead of boiling,
water. The whole is constructed from galvanized sheet iron, and can be heated
on an ordinary stove or over a fire. The lower reservoir is filled with 3 quarts
of water. On boiling, the "steam formed reaches the livers, which are in the
upper perforated reservoir through the pipe Z, entering Z throUgh the holes X,
and entering the upper reservoir through the holes Y. As it is rendered, the oil
flows through the perforations C in the outside of the upper reservoir, down the
annular space, and out through the opening at B. The outer cylinder is insulated
with a layer of asbestos. The galvanized-iron cylinder in which the livers are
placed is pierced with holes 1/12 inch in diameter .and spaced 3‘ inch apart.
This cylinder is supported in the apparatus by the steam pipe and turns on ball
bearings. The steam pipe is also fixed solidly to the two ends of the apparatus.
Thus the cylinder which contains the livers can be turned easily around the steam
pipe which acts as an axis. A simple arrangement, consisting of a sleeve which
fits over the steam pipe, permits shutting of the holes Y during filling of the
cylinder with livers. The sleeve is lowered by means of an iron wire handle until
it shuts off the holes. A rubber or cork stopper at the top Of the steampipe acts as
a safety valve.
To operate the apparatus water is placed in the lower reservoir and the
whole unit placed on a stove. When the water in the lower reservoir begins
to boil, livers are placed in the upper cylinder, the sleeve is raised, and the
top of the steam pipe is closed with the stopper D. Boiling is continued for
about 5 hours during which time fresh lots of livers are added. It is necessary
to agitate the livers from time to time with a stick, to ensure that all the livers
come in contact with the steam. Towards the end of the operation the cylinder
can be turned easily by the handle E. Boiling is continued for as long
as oil flows from the cylinder. It is possible to obtain 80% of the oil contained
in cod or similar livers with this apparatus without having to press the residue.
184
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185
O
From the oil outlet the oil flows through a cloth-bag strainer into a separator,
which consists simply of a galvanized iron box fitted with two outlets, one •at
the bottom, and one half way up the side.' After separation, the oil is run off
through the side outlet, a suitable oil level being maintained by adjustment of
the water level in the tanks by means of the bottom outlet.
The chief advantage of this extractor is the fact that good commercial oil
can be produced by it without the necessity of a steam'boiler. An apparatus with
external dimensions of 32 X 16 inches, having a cylinder 24 X 13 inches, should
have a capacity of 25 gallons of livers. every 6 hours. The apparatus is simple
and easy to construct; it could be built readily by almost any sheet-metal shop.
(iii) DIRECT-STEAM METHODS USED ON THE PACIFIC COAST
Direct steaming is used in British Columbia to prepare the oil from shark,
dogfish, and raffish livers. It is, however, sometimes combined with other proces-
ses to prepare the oil in fractions of different potency and to recover the oil left
in the liver residue after the greater part has been removed.
'The liver oil plants on the Pacific coast consist basically of a disintegrator
to break up the livers; cookers, or digesters as they are also called; and centri-
fuges to separate and clarify the oil. In the disintegrators the livers are broken
up by rapidly revolving arms which force them through a perforated screen.
The digesters are open vertical tanks fitted with mixers and open steam coils.
Some also have closed steam cous. Although some are made of wood, digesters
are far more commonly made of iron, with a conical bottom. In small plants a
two-phase tubular-bowl type of centrifuge, such as the Sharples Super-centrifuge,
has been found satisfactory. This type of centrifuge, in which the two liquid
phases are separated in a long cylindrical bowl, is particularly suitable for plants
in which small batches of different oils are being run, since it can be started and
stopped quickly and the bowl is removed easily for cleaning out the solids which
separate as a layer along the inside surface. For large-scale fish-liver-oil plants,
however, a three-phase continuously-sludging type of centrifuge such as the
DeLaval "Nozzle-Matic" or the Shar'ples "Nozljector" is generally preferred.
Although considerably more expensive, they have far greater capacities but re-
quire a two-phase centrifuge, usually of the disc type, for clarifying or "polishing"
the oil after it has been separated, since they do not give so clear-cut a separa-
tion as the two-phase tubular-bowl type of centrifuge. The oil separated in a
two-phase cylindrical-bowl centrifuge is sometimes put through a two-phase
- disc-type machine to clarify it, but this is not so necessary as with the oil
separated in a three-phase continuously 'sludging centrifuge. This general type
of plant with one or other type of centrifugal system referred to above is used
for fish livers of both high and low oil content.
Before proceeding to a discussion of the process itself an outline of the
principles of centrifugal separation, and descriptions of the three types of centri-
fuges mentioned above will be given — two-phase tuhular-bowl, three-phase con-
tinuously-sludging, and two-phase disc-type centrifuges.
186
While mixtures of immiscible liquids such as oil and water can be separated
into their individual components by settling, the separation can be greatly
speeded up by the application of centrifugal force, that is, by the use of cen-
trifuges. In these machines the mixture is rotated at high speed, the heavier
component or components being forced to the outside. The centrifugal effect is
represented by the force exerted on a mass of 1 lb. at the periphery of the cen-
2
trifugal bowl. The formula by which this force can be calculated is C= DN
5866
where D is the diameter of the bowl in feet, N is the speed of the bowl in revolu-
tions per minute, and C is the centrifugal effect in pounds exerted on 1 lb. at the
periphery. The relationship between the centrifugal effect and the linear velocity
2
V is given by the equation C = 57888D ' The centrifugal effect is thus propor-
tional to the square of the number of revolutions per unit time, and directly
proportional to the diameter of the bowl. The type of bowl chosen for breaking
oil-in-water emulsions depends on a number of factors other than the actual
centrifugal force developed. These factors are briefly discussed in the following
paragraphs.
187
The two-phase tubular-bowl centrifuge is illustrated in cut-away form in
fig. 20. The bowl—the part which rotates—is a long, narrow tube-like cylinder in
this particular centrifuge. Two liquids ( oil and water) can be separated in it
continuously; suspended solids are also separated, although these build up on the
inside of the bowl, gradually cutting down the capacity. Eventually a point is
reached at which the centrifuge has to be stopped and the bowl changed. Two
bowls are provided so that one can be cleaned out while the other is in operation.
The machine can be quicldy and easily stopped and started up again and, fur-
thermore, changing the bowls is a simple matter. This centrifuge is well suited
to small scale operations, particularly for operations involving small batches of
different oils which must be kept separate. Up to a maximum of 500 gallons of
liquid per hour can be put through, the actual rate depending on the extent of
emulsification and on the amount of suspended solids.
189
changing over to the next lot. The capa.city of these machines is up to 2,500'
gallons per hour, depending on the character of the liquid being put through.
However, as already pointed out, the oil separated in them is somewhat cloudy
and hence requires clarification.
A two-phase centrifuge of the type used for clarifying fish oils is shown in
fig. 22. Such machines are sometimes called simply "clarifiers" and are also re-
ferred to as "purifiers" and as "polishers", since they "polish" the oil, i.e. remove
the cloudiness. The boVd is fitted with discs, like that of a three-phase continu-
ously-sludging centrifuge, but it is considerably smaller and does not have
nozzles around the edge. Any solids in the oil collect inside the bowl, and the
machine has to be shut down occasionally so that the accumulated solids can be
FicunE 28. Flow diagram for fish liver oil plant. (Courtesy DeLaval Separator Company.)
, 1. disintegrator; 2. steaming kettle; 3. water inlet; 4. agitator; 5. steam inlet; 6. DeLaval SVK
Separator; 7. sludge and water discharge; 8. oil discharge; 9. oil storage tank; 10. DeLaval
Fish' Oil Purifier; 11. water discharge; 12. finished oil discharge.
190
cleaned out. These solids build up far more slowly if some hot water, at 195°F.
to 210°F., is run through along with the oil. Disc-type oil-clarifying centrifuges'
are made with capacities of 600, 800, and 1,000 gallons of liquid per hour.
Although the actual amount of ,oil going through is cut down when some hot
water is run through at the same time, the loss in capacity may be more than
offset by the greater length of time the machine can be operated without shutting
down to clean out the accumulated solids.
A diagrammatic flow-sheet of a fish liver oil plant with a three-phase con-
tinuously-sludging centrifuge followed by an oil clarifier is shown in fig. 23.
The livers are put through a disintegrator and the ground material is pumped
or run into the digesters, where it is cooked with live steam until liquefied. This
usually takes about 10 to 15 minutes. In plants using a three-phase centrifuge,
as indicated by ( 6 ) in fig. 23, the cooked material runs directly through this cen-
trifuge; the oil goes directly to the clarifying centrifuge, as shown in the diagram,
and thence to storage; the water and the sludge of solids are rejected.
A somewhat different practice is used for processing high-oil-content livers
in plants equipped with two-phase tubular-bowl centrifuges instead of the th'ree-
phase machine. The grinding and cooking of the livers is the same, but, after
being cooked, the livers are allowed to settle until the oil rises to the surface.
This oil is then pumped or drawn off and put through the centrifuge to separate
the suspended moisture and particles of liver tissue. After pumping off the oil,
the residue in the digesters is treated with 2% sodium carbonate or 1% sodium
hydroxide (percentages on the basis of the original livers), and again heated
with live steam until liquefied. This sets free the remaining oil. The entire con-
tents of the digester are then run through the centrifuge -to separate this residual
oil.
The oil thus obtained by alkali digestion of the residue has a higher vitamin
A potency than that from steaming only, since the vitamin is associated with
the tissues in the liver rather than with the oil and the latter merely dissolves it out
when set free by such processes as steaming or alkali digestion. It was found by
Bailey (1941) that oils with even greater gradation in vitamin A potency could
be' obtained by mixing thoroughly into minced raw dogfish livers either 10% of
fine-ground sodium chloride or 2% of powdered anhydrous calcium chloride,
allowing the material thus treated to stand for an hour, and removing the oil
which then separated. Either salt or calcium chloride (especially the latter)
caused a large proportion of the oil, containing but little vitamin A, to separate
from the raw livers, so that subsequent portions of the oil, obtained by steaming
and by alkali digestion, were richer in vitamin A. When calcium chloride is used,
sodium carbonate must not be used for the subsequent digestion of the liver,
since a precipitate of calcium carbonate is formed. Even sodium hydroxide has
to be used sparingly after calcium chloride treatment.
Other modifications of the stearning process for extracting oil from dogfish
livers are given on page 194.
191
( iv ) EXTRACTION WITHOUT HE'AT
A large plant which was established some years ago at Rimouski, Que-
bec, uses a method by which cod liver oil is produced without steaming the
livers. The process, which is essentially one of ebld flotation, is described in
Canadian Chemistry and Process Industries, volume 27, page 555 (October,
1943). The following description is based on that article. The livers processed
at this plant are preserved by the fishermen with a patented preservative (U.S.
patent 2,107,245; Hoplçinson, 1938), which is distributed to them by the company
operating the plant. It is used in the proportion of 1 gallon to 5 gallons of livers.
In addition to preserving the livers it coagulates the liver proteins.
In the actual extraction process the livers first' pass along a conveyor belt,
where most of the preservative drains away. The remaining preservative is read-
ily separated later in the process, since it is soluble in water but insoluble in oil.
After inspection on the conveyor belt, the livers are very finely ground and mixed
with water at the proper temperature in a flotation tank. The oil from the livers
rapidly separates to form an oil layer containing about 0.5% protein and water.
The crude oil is stored under an atmosphere of nitrogen to prevent oxidation
while awaiting further refining operations, which are also carried out under an
atmosphere of nitrogen. The refining consists of first subjecting the oil to a con-
tinuous dehydration process in which it is in contact with the heated zone for
approximately only 7 seconds. B esidual protein and other foreign matter are next
removed by very fine filtration. The oil is then ready for cold clearing and subse-
quent blending to desired potencies. Satisfactory extraction of both the oil and
vitamins A and D is claimed for this process.
Another method for producing cod liver oil without the use of heat is that
patented by Wentworth in 1938 (U.S. patent 2,134,163), which has been success-
fully applied by a plant at Yarmouth, Nova Scotia. In this method the livers, after
being washed with a brine, are mechanically disintegrated and mixed with a
smaller quantity of dry beet pulp or dehydrated cereal-grain pulp. The dry
material which is added to the livers takes up the moisture and so assists in
liberating the oil.. It also facilitates thé pressing of the ground liver tissue. The
first oil which separates is run off and most of the remainder is recovered by cold
pressing. Samples , of cod liver oil made by this process and by the steaming
process from portions of a thoroughly mixed lot of livers have been found iden-
tical in vitamin A potency. After standing in a reftigerator for one year in filled
bottles, the acid values of these oils were both less than 1.0.
A method for the production of non-freezing medicinal cod liver oil from
cod livers without the use of heat is described in U.S. Patent 1,519,779, E. M.
Johnson, 1924. The fresh livers are cooled to a temperature several degrees below
the freezing point and the oil is pressed from them while they are frozen. The
apparatus described for carrying this out includes a jacketed glass-lined tank hi
which the livers are placed. A freezing mixture is circulated through the jacket to
freeze the contents. The frozen mass is then pressed to separate the oil, the livers
being kept frozen during pressing. It is claimed that this procedure yields a larger
192
quantity of first, rade oil having less odour and colour than that made by the
steaming process. '
This process for manufacturing cod liver oil has béen studied by Stewart,
as reported by Leim (1931), at the Atlantic Fisheries Experimental Station.
He found that by freezing and pressing, more oil could be obtained from
a given sample of livers than could be skimmed from the cooking kettle
wheri a• similar amount of the same livers was stearned. Furthermore, the
pressed frozen liver material still contained a quantity of oil that could be re-
covered by other means as a second grade oil. It is claimed that the vitamin
potency of the oil made by pressing the frozen livers is the same as that made
by the steaming 'method. The chief advantage of the freezing process is that
the oil expressed from the frozen livers does not have to be subjected to cooling
and filtration for removal of the stearine.
A very novel process for extracting- fish liver oils `without the use of heat
was patented by R. F. Shropshire in 1949 (U.S. patent 2,473,453, to Submarine
Signal Co.). It consists of subjecting the coarsely-ground fish liver to a high-
power compressional wave vibration. This brings about the release of the oil,
which is then recovered by the usual means.,
The fat-splitting enzymes found in fish are very active; -in loW-temperature
methods of liver oil extraction these enzymes may not be destroyed. As pointed
out by Drummond and Hilditch (1930), it is.a wise precaution to heat such oils
promptly after extraction in order to inactivate these enzymes. This step is some-
times refened to - in commercial practice as "sterilization". Cod liver oils produced
in Canada by cold processes are subsequently heated to inactivate the f at-
splitting enzymes.
( "V ) COOKING UNDER VACUUM WITH INDIRECT HEAT
It was formerly believed that !loss of vitamin A occurred during -treatment
of fish livers with direct steam. It is now known that such is not the case if the
livers are fresh but, on the basis of that earlier idea, plants were designed to
operate under reduced pressures and at comparatively low temperatures:with-
out direct contact between steam and the livers. They have been used to some
extent in the Atlantic cod.liver oil induStry but little, if at all, on the Pacific Coast
of Canada. It was also claimed that a higher yield of oil was obtained than by
simple direct steaming. The cook-er was sunounded‘ by a jacket through which
low-pressure steam or hot water was circulated to heat the contents. These cook-
ers were made in both vertical and horizontal slyles. Typical of the former was
the Scott Patent Vacuum Boiler. This is a jacketed cooker fitted with stirring
paddles and designed to operate under reduced pressure. The livers are fed into
the cooker through a controlled feed valve. Owing to the combination of low
pressure (which hastens the rupture of the cells) and mechanical agitatioil > ren-
dering of the livers takes place quite rapidly. Processing of the material can be
'watched through sight glasses in the cooker. The apparatus is equipped with
a decanting pipe through which the oil that separates on the surface can be
removed.
193
The liver "foots",= as the residue from which the oil has been separated by
cooking processes is called, are run off through a drain in the boftom and can be
treated by otb.er means, such as alkali digestion or solvent extraction, to recover
the oil remaining in them.
There are many other designs of equiprnent for the low-pressure extraction
of cod and similar liver oils. They all consist essentially of jacketed cookers with
mechanical stirrers, and can be operated under reduced pressures although•they
may also be operated at atmospheric pressure.
Processes for producing fish liver oil by cooking under vacuum with indirect
heat are used very little in Canada.
194
hydration of the proteins has taken place, setting free the oil, so that the material
is now a suspension of hydiated protein in oil. The oil can be separated easily
from the hydrated proteins, which form a paste-like residue, by centrifuging. It
should be possible to carry out this separation as a continuous process by use of
a Super-D-Canter, which is described on page 211, or as a semi-continuous
process by the use of an imperforate basket ,centrifuge of the self-dumping type.
(b) FISH LIVERS OF Low Oit. CONTENT
Some materials such as halibut, lingcod, black cod, tuna and similar, fish
livers are included in this category. All these livers have two common char-
acteristics: they have a low oil content (between approximately 5 and 25%) and
the oil is not set free to any great extent by simple steaming. The steaming
methods such as are used for high-oil-content livers are of little value with them
and more elaborate methods have to be used. When oils were fint prepared
commercially from livers of this type, solvent-extraction methods were used, but
these were quickly superseded by methods in which the liver proteins were con-
yerted into a water-soluble form from which the oil coidd be more easily
s'eparated.
(i) DIGESTION METHODS
Digestion methods are by far the most commonly used for the production of
oils from fish livers of low oil content. A general description of the type of plant
used for this process has already been given on page 191. The livers are first passed
through the disintegrator and pumped to thé digester, where the pH is adjusted
to 8.7-10.5 by the addition of 1-2% sodium carbonate or 0.5-1% sodium hydrox-
ide, several additions of alkali being made with stin:ing until the pH remains
steacl. The mixture is then steamed with live steam until the Whole mass be-
comes liquid. This usually requires about 45 minutes but varies with the raw
material. The contents of the digester, while still hot, are run through the cen-
trifuge which for low-oil-content livers is usually of the two-phase, tubular-bowl
type. Brocklesby and Green (1937) pointed out that the aqueous liquid from the
separation of the oil from the digested liver material retains a considerable
quantity of vital-inn A, and reported that this could be recovered from the "wash
liquor", as the aqueous fraction is sometimes called, by extracting with another
oil containing little or no vitamin A. It is rnow common practice to run this
aqueous liquid separated Érom the oil in processing low-oil-content livers of high
vitamin potency back into the digestion tank, or a similar tank, provided with
mèans for heating and mixing, and to extract it thoroughly with herring oil,
salmon oil, or some other oil of similar characteristics and of low vitarnin content.
This oil, which in this process is called the "wash oil" or "picicup oil", thus takes
up the vitamin A which would otherwise be lost. The same pickup' ' o il can be
used several times for extracting the residnal vitamin A from the aqueous liquid,
and its potency thus built up. If the livers which are being processed have under-
gone considerable autolysis before processing, several successive treatments with
wash oil may be necessary. In this case the same oil should not be used - for each
195'
extraction, but oils of progressively lower vitamin A content, i .e . oils which have
been through the process fewer times, should be employed . Commercial salmon
oil (prepared from cannery offal) or herring off are very suitable for use as
pickup oils . Pilchard oil, owing to its greater susceptibility to oxidation, is not
so suitable . It is difficult to thus re-extract the aqueous fraction when a three-
phase continuously-sludging type of centrifuge is used ; since considerable water
must be added whenrunning the steamed or digested liver material through this
machine, there is consequently much dilution . For this reason the two-phase
tubular-bowl centrifuge is usually preferred for low-off-content livers of high
vitamin potency.
Although much autolysis of the livers is undesirable, a slight degree of
autolysis greatly facilitates alkali digestion . Absolutely fresh livers cannot be
liquefied directly by that process . Preliminary digestion by a proteolytic enzyme
such as pepsin is necessary. This may be carried out by the method of Brocklesby
and Green (1934) : The livers are minced and diluted with an equal volume of
water, and sufficient 25% hydrochloric acid is added to bring the pH to between
1 .2 and 1 .5 . The pH is maintained within this range during digestion by further-
additions of acid if necessary. Commercial pepsin to the amount of 0.05-0 .1~/0 of
the weight of the fresh livers is dissolved in a little warm water and
thoroughly mixed in . The mixture is then maintained at a temperature of
43°-49°C . (110°-120°F .) for a period of 24 to 4$ hours, during which time it i
. The end of this preliminary digestion can be ascertained by mak-stiredlowy
ing small samples slightly alkaline, and heating in a test tube . When the sample
liquefies easily, the digestion is complete . The rest of the process is, the same as
that for ordinary alkali digestion, except that additional alkali is required to
neutralize, the acid which was added . It is preferable to use sodium hydroxide
rather than sodium carbonate for making it alkaline, since if the latter is used,
much frothing occurs due to the carbon dioxide formed and the material may
even overflow the digestion tank . The low pH maintained during the digestion
with pepsin prevents any bacterial action and since-the optimum for fat-splitting
enzymes is above pH 5, the action of any of these enzymes in the liver is in-
hibited . The concentration of hydrochloric acid used in the process is so low that
there is no chemical hydrolysis of the oil during the process and consequently,
if the oil in the livers, is low in free fatty acids to begin with, no -troublesome
emulsions are encountered when alkali is added .
A digestion process using the vegetable enzyme papain for the production,
of fish liver oil is described in U .S . patent 1,922,484, granted to L . W. Mapson,
J. McCurdy and H . O . Nolan in 1933 . It has not, however, proved as satisfactory
as the pepsin process outlined above .
More récent enzyme-digestion methods developed for the production of
fish liver oils are those covered by U .S . patents 2,395,790 and 2,406,249, both of,
which were granted to Parfentjev in 1946 . The method described in the first of
these patents consists of recovering the oil mechanically after subjecting raw fish
livers to proteolytic digestion with hog pepsin or fish stomach juice at a pH o f
196
1.5 to 5.0. The oil is clarified by treating with 1.0. to 10,0% by • weight of
magnesium malate, agitating, and filtering. In the process covered by the .
second patent, raw fish livers are minced and the pH is adjusted, to 1.5-2.0 by
addition of hydrochloric acid. Hog pepsin is then added in the ratio of 1 part to ,
1700 parts of liver weight. The mixture is next warmed to 90°-100°F. (32°-38°C.)
for 2 to 3 hours and allowed to stand for 3 days at 70°-80°F. (21°-27°C.). The
temperature is then raised to 98°F. (37°C.), and -the oil and aqueous layers are,
decanted or siphoned off from the sediment. The oil remaining in the latter can ;
be separated by filtration at 37°-40°F. (3°-4.5°C.).. The oil and water are sepa-
rated by decantation and centrifuging. Filtration of the oil, through soft filter
paper eliminates the necessity of alkali treatment. The patent includes the use ,
of fish stomach juice or ground fish stomach tissue instead of hog pepsin: The oil ‘,
obtained by this process is said to be stable.
The equipment used for the pepsin- digestion process is somewhat diffeyent
to that for simple alkali digestion. The digestion tank should be of some açid- ;
and should be jacketed so that the -mixture can, be maintained jresitngmal,
at a uniform, temperature by circulating warm water through the jacket. Means . ,
should be provided for keeping this water at a constant temperature. The tank ?
should have a cover and some sort of mixing device. . - i
In a method patented by. C. W. Kaufman in 1945 (U.S. patent 2,380;847, -
to General Seafoods Corp.) fish livers are preserved and stored with added sub-.:
stances which-inhibit the lipolytic enzymes and prevent bacterial decomposition
but allow the proteolytic enzymes in the livers. to act. Thus the livers are digested.,
and a high-quality fish liver oil of light colour and lOw free fatty 'acid content ,
is obtairied. The preservative is 3-12% ethyl alcohol with a water-soluble bac- -
as acetic acid, propionic acid, borax, sodium salicylate, "bromo. - tericdsuh
phenolic" acid, monochloracetic acid, or sodium arsenate., One-half part of the
preservative is generally used for one part of the raw material. Storage of the '
livers for 3 to 5 weeks results in complete digestion. The oil is then removed by.'
centrifuging and refined with sodium hydroxide; the product obtained is a light-
yellow oil containing less than 0.1% -free fatty acid.
With some livers of very low oil content, for example salmon livers, the'
most suitable methods for obtaining the vitamins are extraction with another oil—,
a pickup oil as described above. There are various methods of treating the liver
material in this process. It may.be finely ground, then thoroughly mixed with the
solvent oil, and steamed; or it may be digested by alkali, by enzymes, or by both, -
and subsequently mixed with the solVent oil. In all cases, the oil is separated from
the liver residue by centrifugal methods.
(ii ) SOLVENT EXTRACTION OF LIVER OILS
The fact that several patents have been taken,.out during recent years for
solvent extraction of fish liver oils shows that there iS still interest in this method,
even though it is not used extensively in Canada as a commercial method, for
production of oils from marine materials.
197
The extraction of vitamin A by means of a "pickup oil" as described under
the immediately preceding sub-heading is, strictly speaking, a solvent extraction
method. However, the term "solvent extraction" is generally applied simply to
extraction with a volatile organic solvent, and will be so used in this Bulletin.,
One patent (U.S. patent 2,078,404) which was issued to C. Nielson in 1937
and assigned to Abbott Laboratories, describes a method in which the livers are
steamed at a temperature not substantially above 100°C. (212°F.) and the watery
liquid, which usually separates when fish livers of low oil content are steamed,
is drained off. The pasty liver material is then frozen and the oil extracted with
à solvent such as ethyl ether. The latter should be peroxide-free. The livers are
protected from air during the whole process. An excellent yield of good quality
oil is obtained by this method, although the oil is darker in colour than that
obtained by digestion methods.
U.S. patent 2,345,099, granted to Buxton of National Oil Products Company
in 1944, covers the preliminary warming of the livers with acetic acid followed
by extraction with an organic solvent 'such as ethylene dichloride. The extract
is filtered, the acetic acid removed from it by washing with water, and the sol-
vent distilled off. It is stated that the acetic acid has a penetrating effect on the
liver cells, thus accomplishing a more ;efficient release of the oils.
Another -extraction method is described in U.S. patent 2,067,279, which was
granted to Nitardy and Jones in 1937 and assigned to E. R. Squibb and Sons, as
follows :
The oil is obtained by extracting^the liver (the protein of which has been coagulated
by processes or agents nôn-injurious to vitamins A and D, as by cooking or by adding
alkali) with a solvent, preferably one selected from the group consisting of ethylene
dichloride, trichlorethylene, and dichlorethyl ether. The extraction is made, preferably
after adjusting the weight ratio of water to dry' (which is used to mean water-free and
oil-free) liver in the extraction mass between 2 and 4 of the former to 1 of the latter,
the adjustment being effected by adding water to the extraction mass to supply a
deficiency, or by evaporating with heat and/or under reduced pressure, to remove an
excess.
The reason for adjusting the ratio of water to `.`dry" liver is to maximize the
completeness and speed with which the solvent separates from the liver tissue.
Solvent-extracted oils, even from fresh livers, are usually darker than oil
prepared by alkali digestion methods. The material causing this dark colour can
be separated, without appreciably affecting the vitamin A potency, by shaking
the oil with a solution of aluminum sulphate under suitable conditions. The
material thus separated appears to be a protein or protein-like substance, since
not only aluminum sulphate but other protein precipitants have the same effect.
The viscera of various fishes including halibut, lingcod, black cod, red cod,
rock-fish, and swordfish contain considérable amounts of vitamin A. However,
they generally contain very little oil, making the extraction of the vitamin from
198
them somewhat more difficult than from the corresponding livers. It is generally
accomplished by extracting with a pickup .oil as described on page 195. The
viscera are put through a disintegrator and the ground material is pumped into ,
digestion tanks where it is treated by the alkali digestion process, the same as
for fish livers of low oil content. An oil low in vitamin A is then thoroughly mixed
with the digestion material, and the mixture centrifuged. Extractions with fresh
batches of the extracting oil are repeated until, from his experience, the operator
knows that little or no more vitamin would be obtained by further treatment.
The viscera, as used for vitamin Oil production, do not include the stomach,
the liver, or the milt or roe if present in the fish. All the remaining visceral organs
are included.
Solvent-extraction methods, whia have already been described in connection
with the production of oil from fish livers of low oil content, are also used for
fish viscera. It is claimed that better total yields of vitamin A are obtained by
this means than by the use of a pickup oil as described above. Furtherniore
the oil produced by solvent extraction has, of Course, a higher vitamin A potency
than that produced by the latter method.
Oil from oily fish such as herring and pilchards, as well as from the offal
resulting from canning or other processing of these fishes and salmon, is most
commonly produced in "reduction plants" employing a batch- or continuous-
type system of cooking and pressing. Skimming and centrifugal methods, as
described under (a) and (b) below, are sometimes used instead of pressing.
Solvent extraction by methods already described is also sometimes employed
where oily fish material is available in relatively small quantities only. While
the oil obtained by solvent extraction is darlcer in colour and generally of a poorer
quality than that prepared by other methods, the meal is usually of better quality.
Fish meal prepared by solvent extraction processes generally contains not over
2% of oil, thus being comparable to the "white fish meal" prepared by simply
drying and grinding non-oily fish material such as the trimmings of Atlantic cod,
haddock, and so on; whereas meal made from oily fish material by cooking and
pressing methods generally contains over 2% residual oil. ,
(a) COOKING AND SKIMMING
Simple cooking and skimming lias been used to obtain the oil from salmon
offal in canneries where there is not enough raw material available to justify the
installation of presses for the preparation of both meal and oil. The short season
during which salmon canneries operate makes it uneconomical to go to the ex-
pense of installing more elaborate equipment. The offal is sometimes transported
to the nearest reduction plant.
In this type of process no meal is made, but the residual material, after
skimming the oil, is simply dumped. Such a process can thus only be used in
places where tidal or river water will carry away the waste efficiently.
199
■ '"''The equipment used in British Columbia for producing salmon oil in this
"Way comprises a pressure cooker in which the offal is cooked with live steam,
'and tWo small settling tanks. The capacity of the cooker, which is equipped with
' an agitator, is approximately one ton of offal. No grinding is done, material,being
1 - dumped directly into the cooker. One per cent of calcium chloride (lump or
»flake) is added with the charge.
The charge is heated with live steam for 10 minutes at 15 lb. pressure. The
agitator is then turned on, and the pressure cooking continued for 20 minutes
longer. After this 'cooking the agitator and steam are turned off and the pressure
is lowered by slowly blowing off stearn over a further period of 20 minutes. Water
is then run into,the bottom of the cooker to float off the oil into the settling tanks.
' The last of the oil is carefully skimmed off the remaining material in the cooker
before dumping the residue through a large valve in the bottom.
The settling of the oil is also a batch process. After standing in the settling
tanks for at least an hour, the élear oil is slcimmed off and put in drums, while
the • debrig and water which have settled out are dumped.
Emulsions that sometimes form in the cooker may be broken by the addi-
tion of more calcium chloride to the charge and further cooking under steam'
pressure. ,
A procesg for producing oil from salmon he-adS, without the use of steam
nder pressure, was outlined by Anderson (1945). It consists in grinding up the
heads, adding a quantity of 3.5% sodium hydroxide solution equal in volume to
0% of the volume of the fish material, and then cooking at a temperature of
180°F. io 200° F. (82°C. to 93°C.) for about 30 minutes. The mixture is agitated
gently throughout the cooking process; the digest is then diluted to three times
,'its volume. After settling for 15 minutes the oil layer and upper quarter of the
Water layer are dram'm off, passed through a 60-mesh screen, and centrifuged. An
alternative method of separating the oil from the diluted digest would be to
allow it to settle until a clear-cut oil layer had separated, and to run that off in
the same Way as in the preceding process. When the digestion is carried out at
a iemperature of 200°F. (93°C.) the tendency to form an emulsion is minim-
It,was pointed out that the eggs. do not submit readily to alkali digestion.
The " suggestion was made that, for convenience, only the heads be used as raw
matelial, since they can be most easily segregated from the eggs and the rest of
the offal. Most of 'the Oil is contained in the heads and eggs. A method for the
production of salmon egg oil is described on page 325.
- 200
for transporting the material from one piece of equipment to the next in. the
procéss, but the cobkers and presses handle only one charge at a time. This type
of plant has certain advantages over continuous systems. In factories where a
great variety of raw màterial has to be handled, the batch system permits greater
flexibility in the time and conditions of cooking, pressure and rate of pressing,
etc. Each batçh of raw material can be put through under the most suitable
conditions.
There are many different designs of batch cookers. Some of these use live
steam, while some are jacketed, and many can be operated either under pressure
or a partial vacuum. Pressure cooking has the advantage of being more rapid,
and furthermore, the "glue" or gelatinous material which may cause the cooked
fish or fish offal to stick to the press cloths is broken down. In cooking with live
steam, pressures of 10 to 20 lb. per square inch are most satisfactory. At much
higher pressures the material darkens. If wet pressing is being used, the cooking
time is relatively short. In some systems, however, the moisture is all removed
by vacuum cooking, and the oil pressed out of the dried material. In such cases
,the cooking time may extend to 6 or 7 hours. Steam pressures in the jacket of
such cookers vary from 40 to 80 lb. per square inch in different installations and
with different raw materials: Oils prepared by this process, which is called dry
rendering, are very dark coloured irrespective of the nature or degree^ of fresh-
ness of the raw material.
Hydraulic presses are usually used in batch systems. They may be used with
a curb or with press cloths. The former is a low cylinder made of strong vertical
slats with very narrow openings between them, and reinforced with circular iron
bands on the outside so that they will withstand great pressure. The material
to be pressed is dumped into the curb and a hydraulically opei•àt6d rain,
which fits closely inside the curb, forces the liquid out between the slats.
Press cloths are usually heavy canvas or jute cloths which are placed in a
form and filled with the material to be pressed, the ends folded over, and the
filled cloths stacked one above the other in the press, with fluted dividers be-
tween them to allow,the liquid to drain away from the middle part.
If the cooked fish is pressed wet, the oil and water mixture is pumped to
settling tanks for separation. The use ofcentrifugal pumps should be avoided,
since dissolved nitrogenous materials may cause emulsification of the oil and
water. The oil expressed from dry-pressed fish usually contains some finely-
divided protein material and a little water. For this reason it is allowed to stand
in a tank heated with closed steam coils until the debris and water have settled
out; then the clear oil is pumped to storage.
This type of reduction plant is generally used where fish such as herring,
sardines, and pilchards are being processed. It is also used for handling salmon
cannery offal, sole and other filleting waste, and at least one such plant success-
fully processes dogfish carcasses and whole ratfish. The equipment consists essen-
201
tially of continuous cookers, presses, driers, and oil-separating equipment. A flow
diagram of a plant of this type is shown in fig. 24, and illustrations of a typical
plant in fig. 25.
UNIT TO
FINISHED
FOOTS ro,L.
WHOLE CONTINUOUS
eSS , STOR A GE
FISH SCREW
STORAGE PRESS geBrie glii'RESS
I LIQUOR
u,
PRESS CAKE
RAW FISH
_I TO SeCKWAT ER PLANT
OR SEW E R
VERTICAL SETTLING TANK "".
/ r.. HEATING CENTRIFUGE
MILL OR CENTRIFUGE - TANKS - SYSTEM-OIL
'ef
SYSTEM S OPTIONAL RECOVERY-
AIR EXHAUST TO
FLUFFED CENTRIFUGE FINISHED
PRESS CAKE OIL
DRIER STORAGE
EXHAUST ROTARY STEAM TUBE DRIER
FAN OIL POLISHER
It
TO STICKWATER
PLANT
OR SEWER
DRY MEAL SACK I NG
DEODORIZER
CYCLONE
TO SEWER MEAL
yERTICAL BLOWER
MILL SAC.KED
C"-- MEAL
GROUND MEAL
FiounE 24. Flow diagram for a continuous fish-reduction plant. ( Courtesy Enterprise
Engine and Foundry Company.)
The cdokers are long stationary cylinders through which the fish are passed
continuously by a revolving screw arrangement and revolving paddles. The live
steam used for cooking is introduced into the cooker thrciugh small inlet pipes
placed at equal intervals along .the cooker as shown in fig. 25B. There are two
steam manifolds; each one for half the length of the cooker; thus the steam sup-
plied to each half can be controlled separately. Suitable arrangements at the feed
and diScharge ports of the cooker prevent the escape of steam. Furthermore, the
cooker becomes choked with fish so that a pressure of steam can be developed in
it. The cooking process has to be carried out correctly since the pressing properties
of the cooked material depend on it. If undercooked, the oil and water will not
separate'properly from the flesh in the press; if overcooked, it becomes very soft
and will not develop a "head" in the press, running through without pressing.
The pressure of steam during cooking depends on the nature of the fish being
processed. For whole herring or pilchards it is in some cases about 10 lb. per
square inch on the feed end, and 5 lb. per square inch on the discharge end of the
cooker, although lower pressures are sometimes used. Salmon cannery offal, when
202
processed in this type of plant, has to be given far more cooking; in fact many
operators when processing it slow the cooker down to about half the normal
speed by changing the driving sprocket on the end: Dogfish carcasses and whole
ratfish or -skates on the other hand require a very short cook, otherwise they
become so soft that they will not press at all. Short cooldng is accomfflished by
speeding up the cooker, and by turning on the steam only in the manifold that
supplies steam to the second or discharge end. Trouble has been experienced
in processing dogfish carcasses and skates with this type of plant due to the
skins, which are very tough, becoming wound tightly around the screw in the
cooker. This trouble can be overcome by putting the carcasses first through a
'log", which consists of a rapidly revolving cylinder with kniVes projecting from,
it and almost touching a number of stationary knives. If the carcasses are very
fresh the process is facilitated by putting them .not only through the hog but also
through a hasher, a machine similar to an ordinary ldtchen mincer, but much
larger. Hogging or hashing also facilitates the processing of salmon cannery offal
since it breaks up the solid bony structure of the head, making it easier to cook.
Raffish do not require hogging, but can simply be put through the - hasher and
then the cooker. Even hashing is unnecessary with them, unless they are quite
fresh..Whole herrings, pilchards or similar fish, Or the waste from canning them
do not require any particular maceration.
From the cooker the material passes through a "pre-drain" device in which
much of the liquid is separated. The solids 'pass from this into the feed box of a
continuous screw press. A diagram of one type of continuous press is shown in
fig. 26. There are several different types of screw presses.. One type consists
essentially of two screws of different pitches working within a horizontal curb,
and turning at different speeds. The feed screw, as the screw in the first half is
called, is built on a shaft of uniform diameter and has a slightly higher pitch than
the pressure screw, which is built on a tapering shaft. The diameter of this shaft
increases toward the discharge end of the machine. Another type of screw press
has only one screw; in it not only does the diameter of the shaft increase, but the
pitch of the screw decreases considerably toward the discharge end. The dis-
charge takes place through an annular opening at the end of the pressure screw,
the size of this opening being regulated by a pressure cone which can be moved
in or out. The curbs are built in two ways. In the earlier designs, the curbs con-
sisted of horizontal slats, very close together, held in position by heavy metal
bands around the outside. These steel slats were slightly wider on the inner side
and, since they were arranged lengthwise, the distance between them was
greater on the outside than the inside..This minimized the possibility of the curb
becoming plugged with small pieces of flesh forced through the openings. An-
other design of curb consists of perforated brass cylinders strengthened by a
metal frameworlc that makes it,possible to use veiy high pressures. The holes in
this cylinder are tapered, the smaller opening being on the inside, thus prevent-
ing them from plugging. In the operation of the press the cooked material is
203
FIGURE 25. Modern fish-reduction plant. (A) cooker and oil recovery systems; (B) ad-
justing steam pressure on cooker.
204
wry 'r
FIGURE 25. (C) cooker and continuous press; (D) centrifuges and fish meal drier.
(Courtesy B.C. Packers Ltd.)
205
forced forward by the more rapidly revolving feed screw, or by the higher pitch
of the screw in the first half, and then subjected to a gradually increasing pres-
sure in the second half due to -the increasing diameter of, the shaft .
:3 ; - - -- _ -
An entirely different design of press has been introduced within recent years
into fish reduction plants in place of the screw press, and is proving very satis-
factory. This press, as shown in fig . 27, consists of two very heavy, gear wheels
set at a small angle to one another with perforated cast steel plates fitted into
positions between the spokes so that the inner face of each wheel is a flat surface
with large perforations in it; over each of these surfaces is a finely perforatéd
brass screen in the,form of a dise covering the entire surface from the axle
to the outer edge . Each of the press wheels is backed by three trunions . The
cooked fish enters the press at the top from a-hopper or,a pressure feed screw ;
it is pressed at the bottom, where the wheels are closest together, between the
screens covering the perforated plates . The press cake is discharged on the side
opposite to that at which it enters . This type of press is known as the "P & L"
press.
The "press liquor", as the liquid which flows from any type of press is called,
consists of a mixture of oil and "stick water". The latter, the aqueous fraction,
usually has considerable quantities of dissolved nitrogenous materials in it,
especially when the fish or fish waste being processed is somewhat decomposed .
Regardless of the condition of the raw material, however, the press liquor usually
contains not only dissolved substances, but also some suspended protein material
in the form of fine particles which have been squeezed through the press . To
206
separate this the press liquor is passed through a "foots-recovery" system. There
are various widely differing designs of equipment for this, but the type most
commonly used in British Columbia consists of a rotating fine-mesh screen in the
form of a long hollow hexagon or cylinder, operated in conjunction with a small
FIGURE 27. New type press. (Courtesy P. & L. Welding & Machine Works, Inc.)
continuous press of special design. The rotating screen varies in over-all dimension
according to the capacity of the plant; but it must be large enough to handle
efficiently the amount of press liquor which is put through it. If it is too small
the screen will clog and the efficiency will be lowered. The screen itself is
usually Monel-metal screening of 60 meshes to the inch. The solids from this
are sent to the small press, the liquid to the oil-separating system.
Other methods of separating the suspended solids from the press liquor
include the use of (1) a rapidly vibrating fine-mesh screen which, like the rotat-
ing screen, is used in conjunction with a small, specially designed press, (2) an
imperforate basket-type centrifuge, or (S) a recently-designed special horizontal
centrifuge. This last machine has also been tried in place of a press for the
primary separation of solids and liquids, and is discussed more fully on pages
210-212.
The oil and water become emulsified to some extent as they are squeezed
out through the fine apertures of the press, and the tendency to form emulsions
207
is. increased by the dissolved nitrôgenous constituents, the protein decomposition
products, in the stick water. Thus the more putrid the raw material becomes
before pressing, the more trouble will be experienced with emulsion formation
in.the press liquor.
The oil is separated from the stick water either in a system of settling tanks,
by a three-phase continuously-sludgirig centrifuge, or by a combination of both.
Three-phase, continuously-sludging centrifuges have already been described in
connection with vitamin-oil production (page 188). Two-phase tubular-bowl
centrifuges, commonly used in vitamin-oil plants, were tried out in reduction
plants," but did not prove very satisfactory. The three-phase centrifuges in which
the solids are continuously sludged off have since been developed, and have been
found much more satisfactory than tubular-bowl centrifuges for press liquor.
Settling systems for separating the oil from the stick water consist of a num-
ber of tanks set clôselÿ together in a row, with each successive tank slightly lower
than the one before it so that the overflow from one can run directly into the
next. There are usually five such tanks, each equipped with a closed -steam coil
for heating its contents, and having a water inlet near the conical bottom. The
first tank has in addition an open steam coil. A typical settling system of a Pacifie
coast reduction plant is shown diagramatically in fig. 28.
T T,
(
Sc
• Sc
Sc. Sc. ^
I+icusn 28. Diagram of a settling system for separating oil from aciueous fraction of press
liquor.
The, first tank (tank A) is called the "breaking tank", since the emulsiori
coming from the press is broken, or largely broken, in it. The press liquor enters
the system through the pipe E and, by means of an adjustable spout on the end
208
of the pipe, is delivered into the breaking tank (tank A) 12 to 18 inches below
the level of the overflow F. In this way the surface of the liquid is kept still and
the oil has an opportunity to rise. The overflow F is generally a shallow open
trough. The oil, usually containing some water and solids in suspensien, over-
flows into tank B, and the stick water is discharged from tank A through the
pipe M. The tanks B, C and D are really purifying tanks, the oil passing from
B to the bottom of C, which is partially filled with hot water. The water assists
in washing out any suspended solid particles which have not been separated in
the foots-recovery equipment. The oil fleated off from tank C is similarly passed
into the bottom of D, where it is again heated with hot water. Finally it is run
into tanks T1 or T2 which . are also equipped with closed steam coils; it is heated
there to a high temperatme to drive off any water remaining in it. From there. it
is pumped to storage tanks. At the end of the day's operation, water is run into
tanks A, B, C, and D to float off all the oil, and after sldmming this off, the -valves
at the bottom of each tank are opened and the tanks drained and washed out.
Heating is usually sufficient to break the emulsion of oil and stick water
which comes from the press b it, if difficulty is experienced, salt is also added.
This assists in breaking the emulsion.
In British Columbia the use of settling systems for separating the oil from
the press liquor in fish reduction plants has largely given way,, during recent
years, to the use of centrifuges. The latter separate the oil from the press liquor
more completely and hence give a better yield. The initial cost of a centrifugal
oil-separating system is, however, much greater than that of a settling system,-
so the latter still has its place in small plants where the full capacity of a cen-
trifugal separator would net be used. The three-phase continuously-sludging
type of centrifuge (see page 188), such as the SharpleÈ Nozljector and the
DeLaval Nozzle-Matic, is used for primary separation . of oil from press liquor. In
these machines the oil and Water phases are separated., and finely divided solid
particles suspended in the press liquor are removed continuously through nozzles
fitted into the periphery of the bowl. The openings in these nozzles are very fine
(about 0.055 inch in diameter), hence complete removal of all larger particles
by efficient solids-recovery equipment before the „press 11qt -tor reaches the cen-
trifuge is very important.
The oil as it comes from the three-phase continuously-sludging centrifuge
usually requires further clarification. A two-phase disc-type centrifuge is gen-
erally used in fish reduction plants to clarify or "polish" the oil coining from the
primary separation, just as it is in liver-oil plants. In the clarifying centrifuge the
solids are not removed continuously, but build up inside the bowl. This neces-
sitates occasional shut-downs for cleaning out. The solids can, however, be
washed out continuously to a large extent and the time between shut-downs for
cleaning out the bowl greatly prolonged, by running hot water (195° to 210°F.,
91° to 99°C.) through the.machine along with the oil.
Many reduction plants equipped with 'centrifuges for separating the oil from
the press liquor have settling tanks as -well in case of emergency such as mechan-
209
ical breakdown. Furthermore, in some plants a combination of settling tanks and
centrifuges is used for carrying out the separation. There are various ways in
which this can be done, for example as -follows:
PRESS LIQUOR
SETTLING TANKS
STICK WATER TO
FOOTS-RECOVERY UNIT .
SOLIDS TO
FOOTS PRESS
SOLIDS TO LIQUIDS TO
DRIER I 3-PHASE CENTRIFUGE
This particular= arrangement has the advantage that the solids coming from
the foots press have a lower oil content than when the press liquor is run directly
from the main press to the foots-recovery unit, as shown in fig. 24.
(d) CENTRIFUGAL METHOD FOR THE PRODUCTION OF OIL AND MEAL
This method must not be confused with the use of centrifuges for separating
the oil from the press liquor. It is one in which the liquid fraction, corresponding
to the press liquor in a plant using a press, is separated from the solid part of the
cooked fish or fish offal by centrifugal means. A batch process in which such a
separation was made in a perforate-type basket centrifuge has been used to a
limited extent in fish reduction, but it was never very successful; the separation
of the oil from the solid material was much less complete than with a press.
However, a piece of equipment has been developed by the Sharples Corporation
to perform the same function as the press in the reduction process, but using
centrifugal force instead of pressure. It was first developed for foots recovery
210
but has since been applied to this other use. Although not yet wholly successful
in place of the press, it has interesting possibilities for that purpose if modified
further. This machine, to which the makers have given the name Super-D-Canter,
is illustrated in cut-away form in fig. 29. The type shown in the figure consists
hour. Passage through two sets of these presses converts the blubber into
a semi-fluid brei which can be rendered, at least by open steaming, more rapidly
than blubber in the form of fumps. In British Columbia a "hog" (see page 203)
is used for disintegrating the blubber before steaming in open cookers. Disin-
tegration before cooking under pressure is not necessary.
Pressure cookers are made in both vertical and horizontal types. The ver-
tical types are from 12 to 18 feet high and from 6 to 9 feet in diameter; they are
built to stand pressures of 60 to 90 pounds per square inch. These cookers are
usually made with suitable strainers to remove debris from the liquid which
separates. The oil, along with the stick water, is withdrawn periodically through
petcocks in the side of the cooker and passed through a separatory systein some-
what Similar to that used for the press liquor in fish reduction plants, i.e. settling
tanks and/or centrifuges.
The horizontal type of pressure cooker—often called a rotary digester—is
usually semi- or wholly continuous. It is gradually replacing all other types. A
typical design of rotary digester is shown in fig. 30. The cut-up blubber is• fed
into the sluices A and A1 from which it falls through an automatic opening
device into the preheaters immediately below. In the preheaters the blubber is
subjected to live steam. The valve leading from the preheater to the extractor
is automatically opened when the pressure in the preheater becomes greater
than that in the extractor. The extractor itself consists of a heavy 'iron tank inside
which is a perforated cylinder attached to a heavy shaft. The perforated cylinder
is open at both ends and the material from the preheaters is fed into both ends
while the cylinder is rotating. The action of the high pressure and temperature,
plus the action of the cylinder as it rotates, releases the oil and water and converts
212
the solid part of the blubber into a fluid brei. The mixture of oil, 'water and sus-
pended solids runs tlu-ough the perforations into the bottom of the extractor;
it is continuoiisly removed through a suitable pressure valve, and then passed
through a separatory system to separate the oil from the stick water.
---•••••••,19!
1,1
Is-sujf. 1111114-141
11X1-W I tre.
mi
FIGURE 30. Rotary digester for whale blubber. _
The production of whale blubber oil by finely mincing the blubber, heating
it to 57°-58°C. (135°-136°F.) and pressing it in an expeller press was patented
by D. A. Hansen in 1943 (Norwegian patent 67,042).
The -oil in the head of the sperm whale is liquid at the b`ody temperature of
the living mammal; but when the body has cooled after killing, the oil partially
,solidifies due to the large amount of spermaceti wax in it. Thus, if a sperm w . hale
is still warm when brought in, the head oil will be liquid and can be drawn off
,directly. However, if the whale has cooled, the head oil will be in the form of a
semi-solid mass which must be heated before it can be tanked. Some of the sperm
whale head oil is containéd in the so-called "junk", a gelatinous material from
which the oil can be pressed. The crude 'sperm oil of commerce is a mixture of
-the head and blubbers oils of the sperm ihale; refined 43erm oil is simply the
head oil.
The bones, from which considérable oil is obtained, are sawn up into chunks
and cooked, under pressure, together with a certain amount of blubber, in a
.rotary digester. Rendering of the mixture is complete in 3 hours at 45 pounds
steam pressure. A special method for preparing the oil from whale bones by
means of rotary digesters is described in British patent 536,328 ; granted jointly
to Aktiebolaet Separator, Lever Brothers and Unilever Ltd., and B. R. Bostock
in 1941.
The oil from whale meat can be obtained by putting.the meat through a
reduction plant similar to that used for whole fish or fish offal (pages 201-210). A
.method of recovering the oil from whale meat by means of rotary digesters was
patented in 1940 by The Southern Whaling and Sealing Co. Ltd. and B. R.
Bostock (British patent 521,521).
The oil from whalelivers can be produced by methods described in the part
,of this chapter dealing with fish livers of low oil content (page 195). A solvent-
,
213
extraction metho d for the production of whale liver oil was patented in 1947 by
United Whalers Ltd.\ and A. J. V. Underwood (British patent 585,304).
The oil in the remaining visceral organs can be obtained in sever. al different
ways, for example: coolcMg in open cookers with live steam, or pressure cooking
in a rotary digester.
Among the most advanced designs in whaling establishments are those in
the large "mother ships" operating in the Antarctic. In these floating factories
every part of the process is continuous and the finished oil is run directly into
storage tanks in the hold of the vessel. Provision is made for keeping the various •
oil separate. gradesof
(b) SEAL ,OM
In the sealing industry the 'blubber and pelt are removed together from the
carcass at the time of catching, and Tut in the hold of the sealing vessel. The
blfibber is removed from the pelt sometime after landing, and the oil is prepared
from the former usually by open steaming, although other methods can be used.
The effects of storage of the pelts before the blubber is removed and the oil
prepared was investigated by Riou (1948). At the same time a study was made
of various factors in the preparation of the oil from the blubber. It was found
that the longer the pelts are stored before removal and processing of the blubber,
the higher is the free acidity of the oil obtained. During storage of the pelts the
surface of the blubber becomes oxidized. When unoxidized blubber is rendered,
either under steam pressure or in a double boiler heated by steam at atmospheric
pressure, a clear oil separates, but when oxidized blubber is rendered emulsions
form. This emulsification is particularly bad when the rendering is done at high
temperatures and pressures. Rioù recommended that the raw blubber be finely
hashed so that it can be satisfactorily rendered at a relatively low ;temperature
to reduce the formation of emulsions. The oil darkens considerably during the
rendering of oxidized blubber, but unoxidized blubber yields a light-coloured oil.
REFERENCES
ANDEnsoN, L. Fishery Market News, 7, (4), 4-7, 1945.
BAILEY, B. E. Pacific Fish. Exptl. Stn., Ind. Memo. No. 6, 8-10, 1941.
BROCKLESBY, H. N. The Chemistry and Technology of Marine .Animal Oils, Fish. Res. Bd.
Can. Bull. 59, 218, 1941.
BROCKLESRY, H. N. AND K. GREEN , Biol. Bd. Gan. Pao. Prog. Rep., 22, 8-10, 1934.
Ibid. 33, 7, 1937.
BurLEn, C. U.S. Fishery Leaflet, 233, 1948.
DRUMMOND, J. C. AND T. P. Hmnrrcu. Gr. Brit. Empire Market Bd. Rep., 35, 1-129, 1930.
HARIUSON, R. W. AND W. S. HAMM. Pacific Fisherman, 39 (9), 37-39, 1 941.
LAnrun, A. AND H. FOUGERE. Biol. Bd. Can. Atl. Prog. Rep., 21, 6-8, 1937.
LEIM, A. H. Biol. Bd. Can. Atl. Prog. Rep., 1, 9, 1931.
Rion, L. Mimeographed Ann. Rep. Caspé Fish. Exptl. Stn. for 1948. Appendix No. 19, 1048.
TRESSLER, D. K. AND J. MCW. LEMON. Marine Products of Commerce. Reinhold Publishing
Corp., New York, 1951.
VANDENIIEUVEL, F. A. Fish Res. Bd. Gan. Atl. Prog. Rep., 48, 4-7, 1950.
214
CHAPTER EIGHT.
I. REFINING
Free fatty acids in oils may be removed-in a variety of ways, but in com-
mercial practice refining with caustic soda is the method most commonly used.
Various other methods, such as esterification of the free fatty acids, or removal
with solvents or by steam distillation, are also described briefly.
(1) ALKALI REFINING
This can be carried out either in a batch or in a continuous process, and con-
sists simply in adding to the oil sufficient aquebus alkali to combine with all the
free fatty acids present. The soap formed has certain adsorbent properties, given
in detail later, and usually canies down withjt a certain amount of colouring
matter, finely dispersed tissue material, etc., and a little of the neutral oil itself.
Some decolorization is therefore effected by this treatment. A typical alkali-
refining plant is shown in fig. 31. A charge of oil is pumped to the refining tank,
which is equipped with suitable variable-speed agitators. The caustic' soda -solu-
tion is pumped from the dissolving tank to the measuring tank and sufficient
solution run into the oil to neutralize the free fatty :acids present. The strength
of the caustic soda' solution should be between 10 0 and 24° Baumé (7-18%),
although stronger solutions are used with oils containing more than 10% of free
fatty acids. Usually a small excess (1-5% ) of alkali over that required for exact
215
neutralization of the free fatty acids is addéd, particularly if the oil to be refine d
is very dark .
FIGURE 31 . Alkali-refining and bleaching plant . (Courtesy Wurster & Sanger, Inc . )
Although the temperature at which the, refining is carried out varies with
the nature of the oil, it is generally kept fairly low-from about 68° to 75°F .
(20° to 24°C.)-during nèutralization*sô that the caustic soda will combine only
with the free fatty acids, and not saponify any of the oil . Stirring must be effi-
cient but not rapid enough to cause emulsification of the soapstock with the oil :
After all the alkali has been added, stirring is discontinued and the charge in the
neutralization tank left until the soapstock has settled, usually ovérnight, although
a shorter period may be used. Heating to a temperature of about 120°F . (49°C . )
hastens the separation of the soapstock . The addition of a small amount of salt
brine also facilitates the separation . After,thorough settling, the soapstock is
drawn off and the refined oil washèd, first with a salt brine and then several times
with hot water . A variation in the method consists in drawing off the clear re=
fined oil, after settling, into another tank for washing, leaving the soapstock in
the neutralization tank . The soapstock is then heated, causing separation of the
small amount of oil usually entrained in it .
Some bleaching of the oil may take place during alkali refining . This is
greatest when- the soap is formed in very small particles, and least when it
"grains" out in larger particles . In the grained condition adsorption by the soaps
is at a minimum . -
By varying the concentration of the caustic soda, the temperature of the oil,
and the rapidity of stirring, conditions may be found under which a minimu m
216
amount of nentral oil will be entrained ana the formation of slow-breaking
emulsions also avoided. The optimum conditions vary with different types of oils,
but for marine oils it can be stated that, in general, low temperatures, fairly high
concentrations of alkali, and slow stiffing, are most satisfactory.
The washing of the alkali-refined oil with hot water does not necessarily
remove all colloidally dispersed soap, and several methods have been introdueed
to remove the last traces of such material. In addition to the use of centrifuges,
filtering unwashed oil through filter presses containing special filter ,paper has
been found satisfactory, particularly when filter aids such as asbestos fibre or
diatomaceous earth are used. It is essential that the filter aid be dry and added
in sufficient amount to absorb the moisture associated with the colloidally dis-
persed soap.
Sodium carbonate (soda ash) is sometimes eMployed for-alkali refining. The
amount of decolorization of the oil is less than with canstic soda, but usually
a higher yield of neutral oil is obtained. The soda-ash solution should be heated
to boiling and the oil at 176°F. (80°C.) added to the 'slowly stirred solution. The
mixture may be heated with either open or closed steam coils. In the former case
any tendency for the sodium soaps to emulsify is overcôme by the addition of
sodium chloride (salt) while in the latter case heating is continued until the
moisture content of the soap decreases sufficiently to make the latter rise to the
top of the oil. The second method gives larger yields of neutral oil.
Slaked lime can also be used for alkali refining. The lime is usually added
in the form of a thick cream and the mixture heated with closed steam coils so
that the greater part of the water is removed. When sufficiently dehydrated, the
calcium soaps can be removed by filtration.
Batch methods of alkali refining, as described above, are suitable for small-.
and intermediate-scale operations, but for very large-scale opeations continuous
alkali-refining processes are taking their place. In the continuous process the
requisite amount of alkali is mixed with the oil, the mixture is heated and then
passed through a continuous centrifuge to separate the foots from the refined
oil. The latter is then washed with hot water and pased through another con-
tinuous centrifuge.
Before leaving the subject of the alkali refining of oil, attention must be
drawn to the great adsorptive capacity of the nascent soaps formed in the oil.
The decolorizing effect of alkali fefining is due to the adsorption of the pigments
and other colouring matter in the oil by the soaps formed. Nascent soaps can also
adsorb vitamin A. Brocklesby and Kuchef (1938) investigated the factors affect-
ing the adsorption of v• itamin A by the nascent soaps formed in the alkali refining
of fish oil. The most important single factor was found to be the water:soap ratio,
the adsorption' increasing with increase of this ratio up to values of 1500:1, as
shown in fig. 32. The amount of adsorption, at equal water:soap ratios, was
inversely proportional to the temperature within the range studied, 104° to
158°F. (40° to 70°C.), and directly proportional to the free-fatty-acid content of
the oil, i.e. to the amount of soap formed. The removal of vitamin A by adsorption
217
varied with the amount- which was originally present in the oil. This can be
seen from the data shown in fig. 33. The lower the original vitamin A potency of
the oil the greater was the percentage loss during alkali refining under otherwise
identical conditions.
- 50
M
o
x
E 40
a>
n Sodium Sou
le"
1-1 Poto=slum S ap
20
10 n ^ 5n F nn 75 n m on 12 50 15( 0
Water:Soap Ratio
FzcuRE 32. Effect of water-soap ratio on adsorption of vitamin A during alkali refining.
It is only the nascent soaps-those actually formed in the oil during alkali
refining-that have these high adsorptive capacities. Preformed soaps added to
a vitamin A oil adsorb far less of the vitamin than is adsorbed by the same soap
formed directly in the oil.
The adsorbed material, either pigment or vitamin A, cannot be removed
easily from the soap without first destroying thé colloidal properties of the lattér;
solvents such as ethyl ether or light petroleum will remove scarcely any of the
adsorbed material. Vitamin A can, however, be recovered from the soaps by
dissolving them in another batch of oil. None the less it is very important to take
the phenomenon of vitamin A adsorption by nascent soaps. into consideration
when treating vitamin A-containing oils with alkaline solutions. When alkali
refining such oils particular attention should be given to doing so under con-
ditions which will result in minimum adsorption of the vitamin.
218
(ii ) VACUUM-STEAM DISTILLATION
This is rarely, if ever, employed exclusively for the removal of free fatty
acids. It is used as a method of deodorization, and when an oil is thus deodorized ,
some removal of free fatty acids is simultaneously effected. It is not possible to
lower the free-fatty-acid content below approximately 025% by this method and,
for edible oils, alkali-refining is preferred. For industrial marine oils which have
to be deodorized, however, the shnultaneous lowering in the free-fatty-acid con-
tent may be sufficient and in some cases the alkali-refining step may then not be
necessary. Methods and equipment for the vacuum—steam treatment of oils are
dealt with on pages 238-241.
75
65
55
45
35 1.■■•
0 10 20 30 40 • 50
Original Potency in Units per Grain x /0-3
Fromm 33. Variation of vitamin A removal with original potency of oil.
ESTERIFICATION
Although this has long been recognized as a possible means of eliminating
the free fatty acids in oils, little attention was given to its' commercial application
until quite recent years. It involves the interaction of an alcohol with the free
fatty acids; if the esterification is with methyl or ethyl alcohol, the resulting esters
may be removed by vacuum distillation; if the esterification is with glycerol, they
may be left in the oil.
The disadvantages in the older methods of esterifying the free fatty acids
in an oil with glycerol include the very high temperature required, the strong
acid catalyst, and the large excess of glycerol which is necessary to drive the
reaction to completion. Improved methods for forming glycerides and/or other
esters of the free fatty acids hi oils have more recently been developed. One such
.method is by ester interchange (see page 118), for example by heating the oil
219
with a calculated amount of anôther oil or fat containing glycerides of low-
molecular-weight fatty acids (such as palm oil). The low-molecular-weight fatty
acids liberated from the added oil by the exchange reaction are removed by steam
distillation. A satisfactory method of converting the free fatty acids in an oil into
the esters of low-molec,ular-weight alcohols was patented in 1946 by Bradshaw
and Meuly of E. I. Dupont de Nemours and Co. (U.S. patent 2,398,492). It con-
sists in treating the oil with dimethyl- or diethyl-sulphate and sufficient quantity
of -sodium carbonate, sodium bicarbonate, potassium carbonate, or other similar
alkali, to neutralize the sulphuric acid formed in the reaction.
( iv) SOLVENT SEPARATION
Free fatty acids can also be removed from an oil by certain solvents. Various
solvents, among them alcohol, dilute acetone, and methyl formate dissolve the
fatty acids to a greater extent than they dissolve the oil itself, and can thus be
used for extracting the former directly from the latter.
Alkali refining of oil dissolved in a solvent is used in a commercial process
( Solexol process) for the combined refining and fractionation of oils (see page
267); liquid propane is the solvent used.
220
Various factors in connectiCn with the .cold clearing of fish oils were studied
by Swain (1941a). His findings are given unCler the ensuing sub-headings (i) to
.(iv) inclusive.
•
(i) STEARINE CONTENT OF SOME COMMERCIAL OILS
A series of experiments was carried out to determine the' stearine content of
various oils at various temperatures. This was undertaken mainly to try to find
out, if possible, the temperatures to which an oil should be cooled to separate
given amounts of stearine. However, it was found that the variations between
individual samples of the same oils were too great for any such predictions to
be made.
The oils Were first warmed until any stearine in t.hem was melted, and then
filtered to remove any suspended matter. For each expel-in-lent the filtered oil was
maintained at 140°F. (60°C.) for 4 hours in a water bath, after which duplicate
50-gm. samples were weighed into bottles which were 'then stoppered and re-
turned to the water bath. After cooling at room temperature overnight, tle water
bath was transferred to a cold room at the desired temperature and left for 24
hours. The oil was then filtered in the cold room through a cloth in a Büchner
funnel, with 'vacuum. The results are shUwn in table 34.
These data bring out several interesting points One is that the stearine con-
tent of honing oil is high in comparison with that of other fish oils. Furthermore,
the stearine content of the hening oil samples from north central B.C. shows an
increase during the season, as the fish approach the spawning period. Cod liver
oil samples 1 and 2 contrast the effects of two processes of extraction which are
described in Chapter 7; in the Wentworth process the livers are not heated. •
(ii) EFFECT OF COOLING RATE ON THE STEARINE OF HERRING AND PILCHARD OILS
221
TABLE 34. Stearine content of various oils at various temperatures (percentages).
(°F.) 60 53 48 39 37
Temperature
(°C.) 16 • 15 4
,
Source of oil
Herring (1937)
North Central 13_,C. coast, early 2.8 3.8 solid
(iodine value 154.2)
North Central B.C. coast, midseason and late 4.8 thiek
, (iodine value 141.2)
North Central B.C. coast, late 4.7 8.7 solid
(iodine value 139.3)
Central B.C. coast, early , 1.4 2.3 solid
late 2.8 11.4 thick
Commercial sample 6.8
Pllch'ard
August, 1938 24.8
September, 1938 29.5 .
Commercial sample 17.0 23.0
Sardine, 1 32.2
‘‘ 2 29.4 42.4
Halibut, liver 0 0
" head 7.7
Dogfish liver .
Dec. .2,1936 1.1
July 6,1937 . 1.4
July 27,1937 ' trace
Cod liver
1. Wentworth process trace 12.0
2. Steam process 1.3 16.7
3. Commercial wintered 0*
4. Commercial unwintered '
7.0 - 15.0
5. Commercial 0 8.7
6. Commercial , 0.6 14.6
222
The yields of stearine for the two constant rates of cooling are shown in fig.
34. The yield of stearine from herring oil at the faster rate of cooling was less at
any given terriperature, than at the slower rate. For pilchard oil, however, the two
curves for the yields cross each other. At the slower rate of cooling the two final
points in the herring-oil curve and the two points rather remote from the pilchard-
oil curve show the final yields after standing at 38°F. (3°C.) for 2 months. Thus
3 weeks, during which time the temperature was falling, was not sufficient time
for crystallization to reach an equilibrium in either oil. However, at the faster rate
of cooling the stearine yields at 34°F. (1°C.), obtained after standing 3 weeE_s at
that temperature, showed .an increase for herring oil but no change for pilcliard
^oil.
rc
76
38
I
- X STEARINE _- +
FicuaE 34. Effect of temperature on stearine content of pilchard and herring oils at two
rates of cooling.
224
A somewhat similar experiment was carried out earlier by Brocklesby,
Riddell and O'Neill at this Station, using pilchard oil from the same, stock . In
this experiment 200-gm . sanlples of previously heated 'oil were placed in a water
bath at 90 9 F . (32°C .), which was then allowed to cool irI a room maintained at
41°F . (5°C .) . The rate of cooling was therefore high at first and decreased
steadily . Stearine appeared at 56°F . (13'C .) at a time when the oil was cooling at
the rate of 16°F . (9°C .) per day . The stearine-temperature curve was linear,
there being 19 .3% stearine . at 41°F . (5°C .) . After standing a week at this tem-
perature the stearine content had increased to 27 .8% .
Other examples which show the dependence of stearine yield on conditions
of cooling are the two values for "Pilchard oil, commercial sample" in table 34,
which were determined on samples from the same stock of oil as was used in the
preceding experiments . Neither value lies on any of the three stearine-temperature
curves 'for pilchard oils which have been described. -
(iii) FILTERING PROPERTIES OF I3ERRING- AND PILCHARD-OIL STEARINES
During the course of these experiments on cooling rates the time required
for filtration was noted for e? ch sample . At the slôwer rate of cooling the samples
at the higher temperatures filtered in a matter of minutes while some at the'- lower
temperatures required as long as 2 hours . The samples which had stood for 2
months at 38'F . (3 .3°C .), and which contained the large crystals, filtered in less
than a minute . At the faster rate of cooling all samples filtered within 4 minutes .
These data indicate, as might be expected, that speed of filtration increased with
crystal size .
The effect of stirring on the formation of stearine crystals was investigated .
Duplicate 200-gm . samples of herring oil from the same batch of, oil as used in
the experiment on rate of cooling were heated and allowed to cool in a bath of
water originally at 127°F . (53°C .) . One sample was stirred slowly ; the other
was allow to stand undisturbed . The stirred sample showed the presence of
stearine at 60°F . (16°C .), the unstirred sample at 57°F . (14°C.) . After 13 hours
the temperature had reached 45°F . (7°C.) and the samples were photographed
(row 5 of fig . 35) and filtered . The stirred sample required 50 minutes to filter
and yielded 32 .8% stearine, while the unstirred sample reqiiired 2 minutes and
yielded 41 .7% stearine . In this experiment stirring incrèased, the time required
for filtering and decreased the yield of stearine ; the photomicrographs show that .
the unstirred sample contained better formed and slightly larger crystals .
Further observations on stirring were made, this time on pilchard oil- . One
of the samples in the "3°F . per day" cooling experiment was vibrated con-
tinuously . After 3 weeks of continuous cooling this sample and a_comparable
non-vibrated sample were photographed and filtered at 34 .5°F . The vibrated
sample was full of stearine, required 120 minutes to filter, and yielded 30 .40/"0
stearine. A comparable non-vibrated sample was one-third filled with stearine,
required 50 minutes to filter, and yielded 16 .5% stearine. As with herring oil
the sample which was motionless during cooling contained better formed and
somewhat larger crystals (row 5 of figure 35), and filtered more rapidly . -
225
An earlier 'experiment, in which 25-gm. samples of pilchard oil were cooled
for three hours in,water at 48°F. (9°C.), showed a yield of 7.5% stearine when
the oil was motionless and°10.5% when stirred.
Since "filter aids" ("diâtomaceous earth or similar materials) are frequently
used to speed filtration and "polish" oils by removing very small suspended
particles, the effect of their addition on the rate of filtration of stearine-containing
pilchard oil was deterinined in these laboratories. In these experiments 3-litre
samples of' filtered oil which had been filtered at room temperature were left in
a cold room at the desired éold-clearing temperature for 24 hours. Each was then
filtered in a small filter press in the cold room, under 10 lb. air pressure, with a
coarse canvas filter cloth. In some cases 0.32% by weight of a ,commercial filter
aid was added to the oil before it was cooled, and in some cases the same quan-
tity was added immediately before filtration. The volume of filtrate was noted at
five-minute intervals; the volume-time curves are shown in figs. 36 and 37.
Ficvr(E 36. Effect of filter aid on the filtering properties of pilchard-oil stearine.
It is evident from these curves that the rate of filtration of oil without filter
aid decreased with lower temperature. It can also be seen that in these experi-
ments the presence of a filter aid decreased the rate of filtration of the oil, par-
ticularly when added after stearine had separated. This may be due to the coarse-
ness of the canvas used, since the filter aid, composed of particles far smaller
than the stearine crystals, may have penetrated into the canvas, diminishing the
size of its pores and therefore decreasing the filtration rate. A finer canvas might
lead to different results. It is also possible that the pores between the particles
of stearine were similarly reduced in size, reducing the filtration rate. Possibly
the addition of a filter aid of particle size comparable to that of the stearine cry-
stals might lead to better filtration.
An attempt to filter a sample oE herring oil repeatedly at successively lower
temperatures to simplify Btration was unsuccessful. Filtration of 'a sample first
at 60°F. (16°C. ), then filtering the filtrate at 58°F. (15°C. ), and the second fil-
trate at 55°F. (13°C.) yielded a total of 18.7% stearine with filtering time of
226
more than 100 minutes, and the third filtrate wa's unfilterable at 50°F. (10°C.). A
sample from the same stock of oil, cooled under the same Conditions but filleted
only at 50°F., required 40 minutes to filter, yielding 25.7% stearine.
1.6
i NO FILTER AID, 5. C. ,
g,
d
,
wo.8 Z. LTER AI D ADDED BEFORE COOLING, •C
o
3. NO FILTER AID, 4.C.
Fioun.E 37. Effect of filter aid on the filtering properties of pilchard-oil stearine.
dear, viscous supernatant oil was poured off from the stearine that had been
solidly compacted as it progressively formed. The iodine values of the original
oil and this rigorously "cold-cleared" oil were respectively 145.2 and 197.8.
It is evident from the foregoing experiments that the' formation of stearine
in a condition suitable for its separation from the cleared oil is not a simple prob-
lem. While v,ery rapid cooling to a low temperature produces a mixture which
227
cannot be filtered, the stearine obtained at the same temperature by slow cooling
is more readily separable. It is also evident that, notwithstanding their great
utility in clarifying an oil, filter aids are not beneficial in the separation of
stearine.
In all the cold-clearing experiments described so far crude oil was used.
The effect of alkali refining on the subsequent stearine separation has been
investigated by Brocklesby and Denstedt (1933); fig. 38 is taken from their work.
These photomicrographs, taken after identical cooling of crude and alkali-refined
samples of pilchard oil, show that alkali refining greatly increases the size and
perfection of the crystals formed. It is therefore preferable to precede cold clear-
ing by alkali refining.
FIGURE 38. Stearine crystals from (a) crude pilchard oil, (b) alkali-refined pilchard oil.
18
•
12
ga
ID ---- . -...- On an An
FmunE 39. Iodine value of stearine and cold-cleared oil of achard and herring' as
increasing amounts of stearine are removed.
TABLE 35
A. Saturated fatty acid content of pilchard oil cold cleared at several temperatures.
(°F.) 68 46 40 34
Temperature of cold clearing
(°C.) 20 8 4.5
B. Saturated fatty acid content of cleared pilchard oil and stearine formed in
acetone 'solution at several temperatures.
(°F.) 28.5 23 14 5 —4
Temperature of crystallization
(°C.) —2 —5 —10 —15 —20
of cissing of the films, i.e. their failure to remain uniformly spread. These errors
xeduee the statistical value of the measurements, but there was nevertheless a
trend tomiard increased hardnéss of the film as increasing amounts of stearine
were removed from the oil. The difference between the hardness of the first and
the last samples is statistically valid.
The effect of stearine removal on polymerization is described in Chapter 5, I.
) INDUSTRIAL COLD CLEARING
For the cold clearing of oils on a commercial scale two pieces of equipment
are needed, a cooling tank and a filter press or other device for separating the
stearine from the liquid oil. The oil can be cooled by several methods. Cold brine
may be circulated through coils directly in contact with the oil in an insulated
tank, or through the jacket of a jacketed insulated tank. Recently developed
refrigerants have made possible the direct expansion of the refrigerant into the
coils to _produce temperatures suitable for cold clearing. Another arrangement
is to have the cooling tank in a cold room, so that the heat is removed from the
230
oil by the air in the room. The room is kept at a low temperature by suitably
placed cooling coils. The cooling of the oil is slOwer and more uniform by this
method than with either cooling coili or jacketed tank. As pointed out under
sub-heading (iii) above, the more slowly the oil is cooled the more satisfactory
is the subsequent filtration. For this reason cooling in a tank in a cold room ii
the preferred method. The most easily filterable stearine is obtained when the
oil is cooled to the desired temperature over a period of at least one week. This
is accomplished by gradually lowering the temperature of the room.
After cooling, the mixture of oil and stearine is either run by gravity flow,
forced by compressed air, or pumped, to a filter press. This is usually located in
a room separate from the cooling tanks, especially if the cold-room method of,
cooling the oil is used, to avoid the variations in cold-room temperature which
would result from the opening and closing of the door. The filtering room
must be kept cold, but it need not be as cold as the cooling room. It has be,en
found in industrial practice that if the temperature of the filtering room is not
more than 8°F. (4.5°C.) above the temperature to which the oil is cooled, the
stearine will not melt.
In operating the filter, the cloths are covered with heavy crinkly paper,
similar to paper towelling but much heavier. This greatly facilitates the removal
of the press cake. During filtration the inflow pressure gradually increases. A run
is usually stopped when the pressure reaches 50 lb. per sq. in., the press cakes
then being removed from the filter. If the trough in wlaich the dear oil is col-
lected in the filter is deeper at one end than the other, any water in the oil will
collect at the deep end. The oil is pumped off at the shallow end, while a drain-
cocic is provided for running off the water at the deep end.--
( vi) INHIBITION OF STEARINE FORMATION
Cold clearing is sometimes carried out for the purpose of obtaining an ofl
which will remain clear at winter temperatures. A means of inhibiting the de-
position of stearine subsequent to cold clearing would be desirable in order to
avoid the very low temperature at which the oil would otherwise have to be
cleared, and the consequent small yield of cleared oil.
The addition of 0.1 to 0.5% of blovvn cacao butter to olive oil is said to
have this effect (U.S. patent 2,097,720; Clayton, l3ack, More and Johnson, 1937
assigned to Cross and Blackwell Ltd.). In another report on the method, Clayton
and some of his co-workers (1937) found that a sample of olive oil containing
1.0% of blown cacao butter remained clear and readily pourable for at least
4 years at 35° to 39°F. (2° to 4°C.), while a control sample set solid in a few
hours. This material did not, however, inhibit stearine formation in peanut or
cottonseed oils. These workers found that blown beef tallow had a similar effect
to blown cacao butter in inhibiting stearine-formation in olive oil; blown cotton-
seed oil was slightly effective. It was suggested that the oxidized material added
to the oil is adsorbed on the surface of clusters of stearine molecules, while they
are still very minute in size, vvith the result that the stearine separates out in
231
Q01.1oida1 rather than crystalline form. In an experiment carried outr in these
laboratories, neither blown cacao butter nor blown herring oil had any effect
on stearine formation in herring oil. The use of blown oils, if found at all effective
for inhibiting stearine formation in fish oils, would be limiteci since œddized oils
accelerate the development of rancidity and destroy vitamin A.
Another method of stabilizing cold-cleared oils against clouding is described
in V.S. patent 2,425,001, which was granted to F. P. Parkin and G. N. Walker
of the Minnesota Linseed Oil Co. in 1947. The oil is first cooled to a temperature
at which it clouds but above which no actual stearine is formed. This cloud, it is
stated, is composed of minor constituents such as phospholipides, waxes, and
pigments: The cloudy materials are remo'ved by adding 0.5 to 5.0% of an aqueous
solution of an electrolyte to the cooled oil, and then centrifuging. The subse-
quently cold-cleared oil is claimed to- be more stable against clouding than one
not • given this preliminary treatment before cold clearing. A paint or varnish
prepared from a drying oil (linseed oil) treated in this way dried more
quickly and gave a harder and less- tacky film. In an example given in the
patent, 800 lb. of linseed oil was cooled to 50°F. (10°C.) and mixed thoroughly
fôr 30 minutes with 18 lb. àf water containing 2 lb.. of calcium chloride. The
en'iulsion • thus formed was allowed to settle, and the oil separated by centri-
fuging. Since fish oils contain phospholipides and pigments the method should
be applicable to them.
The formation of • stearine in pilchard oil is delayed by washing the .oil,
Under suitable conditions, with dilute permanganate solution. Since permanganate
is an oxidizing agent, it possibly forms from the oil itself a product with similar
stabilizing properties -to the blown fats mentioned above. Herring oil separated
from acid-treated reduction-plant liquors also shows delayed stearine formation.
An oil which has been alkali refined at a relatively low temperature some-
exhibits slightly delayed stearine deposition. An. experiment was carried
Wit at•this Station to determine the extent of delay in stearine formation in
herring oil by this treatment when applied at several temperatures. A litre of
warm, clear herring oil was thoroughly mixed and cooled at a rate not exceeding
8°F. (4.5°C.) per day. Samples were withdrawn at 70°F. (21°C.), 60°F. (16°C.),
51°F. (14°C.) and 50°F. (10°C.). Each sample was divided and one portion
Was mixed with dilute sodium carbonate solution containing sufficient sodium
chloride to grain out the soapproduced. This mixture and the untreated portion
were immediately and simultaneously centrifuged for a half hour at 2,500 r.p.m.
In each case the room and reagent temperatures were the same as that of the
oil so as to prevent any change in the stearine on that account, although the
temperature in the centrifuge did rise a few degrees owing to the heat of the
Motor. The separation of stearine by centrifuging was incomplete in the control
samples at the two lower temperatures. On the other hand, the alkali-treated
samples all gave a good separation readily in the centrifuge, the mixture of soap
and stearine forming a solid cake betvveen the oil and the water layers. The
restilting oil, however, contained a cloudiness which settled out with time as a
232
flocculent precipitate. A portion of this oil was then heated for an hour in boiling
water, which increased the amount of precipitate in the 60°F. sample and re-
moved it in the 50°F. sample.
The various samples obtained were cooled at the rate of 8°F. (4.5°C.) per
day, or slower, after preliminary warming to about 120°F. (49°C.) The tempera-
tures at which stearine crystals first appeared are shown-in table 36. Only the
sample alkali treated at 50°F. showed delay in stearine formation, and in this
case the control contained stearine even though centrifuged for an extra period
of 15 minutes.
(c) BLEACHING
The terms bleaching and decolorizing are used synonymously for the pro-
cess of removing colour from oils.
Colour in unprocessed marine oils is due to naturally occurring pigments
or to deterioration changes. The latter include spoilage of the raw material prior -
to prpduction of the oil, faulty production methods, and oxidation of the oil
during storage. Overheating, especially if the oil is in contact with rusty iron,
causes darkening. Contamination with -even' a véiy small amount of fuel oil also
233
causes considerable darkening of fish oil and other fatty oils . Various methods
of processing oils cause darkening . This is especially true of oxidation by blowing .
Oils can be bleached by various methods, but the most commonly used
method for marine oils is a physical process, adsorption of the colouring matters
with 'an activated earth, sometimes accompanied by carbon . Another physical
method, although not practised to any great extent, is heating the oil under
vacuum . Chemical methods can also be used but they are not in general as
satisfactory as adsorption .
The decolorization of seal oil by steam distillation, by adsorption with
fuller's earth, and by treatment with various chemicals was studied by Dugal and
Cardin (1949) .
Various clays or earths such as fuller's earth have the property of adsorbing
the colouring matters from oils-both the natural pigments and those resulting
from oxidation and other causes . The activity of such earths in this respect is
greatly increased by treatment with sulphuric acid or hydrochloric acid and then
drying . Methods for carrying out such activation have been described- by
Burghardt (1931) and in U .S . patents 1,776,990 (W . S . Baylis, 1930, to Filtrol
Co . of California) ; 1,819,496 (W . S . Baylis, 1931, to Filtrol Co . of California) ;
1,929,113 (J . D . Haseman, 1933) ; 1,980,569 (D . S . Belden and W. Kelley, 1934,
to Filtrol Co . of California) . Commercially activated earths are also available
and are commonly used . In bleaching oils by this means, 3 Jo to 5~/0 of the
activated earth is added to the ôil, which is then heated to 150°-260°F . (65°-
%
130°C .), maintained at the temperature for 15 to 60 minutes with continuous
stirring, and then filtered .
The bleaching activity of several British Columbia earths on pilchard oil
was •studied by Brocklesby and Moore (1933), a comparison being made with
a standard activated earth . Data from their paper are given in table 37 . In èach
Colour
Amount Optimum Colour remaining
use d temperature . removed (Lovibond)
Type of earth % (Duboscq)
(°C .) (°F.) % Y R
234
case the optimum proportion of earth and the optimum temperature had been
determined by preliminary tests. In the experiments reported the oil was stirred
with the optimum amount of adsorbent at the optimum temperature for 15
minutes and then filtered. The bentonite was activated by treating 670 gm. of the
earth with 434 cc. of concentrated hydrochloric acid, adding 3 volumes of water
to the mixture, and boiling for 6 hours.
The amounts of colour in pilchard oil which had been bleached with differ-
ent samples of Canadian bentonite are given in table 38. In each case the oil was
stirred with the earth at 120°C. (248°F.) for 5 minutes. The bentonites were
acid, each requiring a different acid con- activedbyolngwhrci
centration and a different time of boiling for best results.
TABLE 38. Decolorization of pilchard oil with bentonites (Gallay 1938), measured
in yellow (Y) and red (R) units.
Residual colour
Amount (Lovibond)
Source of clay used
(%) Y R
Commercial bleaching of fish oils is generally done by heating the oil with
3% of an activated earth at 200°-230°F. for a period long enough to decolor-
ize it.
It has been claimed that' the presence of soap or alkali in an oil lowers the
efficiency of bleaching earths, and that the presence of soap during bleaching
results in an increase in free-fatty-acid content. Since bleaching is often carried
out after alkali refining, care should be taken to ensure complete removal of the
soap from the refined oil before bleaching.
The addition of a small amount of water (1 to 10%) has been recommended
to improve bleaching.
Decolorizing carbon is not ordinarily used by itself for the bleaching of
oils, but is sometimes employed along with an earth to improve the bleaching.
The ratio of carbon to earth used is from 1:20 to 1:10. Carbon removes sub-
stances which earths do not, so the two together are more effective than either
alone.
A process and apparatus for the continuous bleaching of oils by means of
adsorbing earths,. with or without carbon, is described in U.S. patent 2,428,082,
235
which was granted to R. R. King, S. E. Pack and F. W. Wharton in 1947, and
assigned to Mrs. Tucker's Foods, Inc. An important step in this process is a pre-
liminary de-aeration of the mixture of oil and adsorbent, which gives improved
results.
Considerable decolorization of an oil may accompany alkali refining. This
is due to adsorption of the colouring matters, especially the naturally occurring
pigments, on the nascent soaps formed within the oil during that process. How-
ever, bleaching by this means is not reliable, since the conditions under which
the alkali refining is carried out, greatly affect the removal of the colour from the
oil. Thus if a uniformly light-coloured product is desired other means of bleach-
ing are usuall.y used, even.for alkali-refined oils. .
A number of patents, including U.S. patents 2,003,076 (W. Gensecke, 1935,
to American Lurgi Corp.); 2,110,789 (B. Clayton and B. H. Thurman, 1938);
2,122,260 (L. C. Moore and A. C. Norman, 1928); and British patent 327,990
(A. Glover and C. Couche, 1938, to Co-operative Wholesale Society Ltd.), cover
the bleaching of oils by heating to 450°-500°F. (232°-260°C.) in a vacuum. In
two of these, an inert gas is simultaneously passed through the oil. With the
more unsaturated fish oils, heating thus,"even under the vacuum, would lead to
polymerization if prolonged.
A diagram of a bleaching plant, combined with an alkali-refiniiig plant, is
shown in fig. 31 on page 216.
Chemicâl methods 'of bleaching oils are'limited in their scope since, while
they destroy or decolorize the naturally occurring pigments, they have little or
no efEect on other colouring matters such as those resulting from oxidation of the
oil, spoilage of the raw material, and so on.
Oxidation is one of the most commonly.used chemical methods ôf -bleaching
oils, but it has the disadvantage that the antioxidants imthé oil are also destroyed,
and some oxidation of the oil itself may take place as well. Oxidation by blowing
air through an oil can be used to destroy the natural pigments in it; but unless
care is taken to stop the process as soon as the pigments have been destroyed,
the oil itself may darken by oxidation.
Sodium dichromate is used to some extent for bleaching oils. The use of this
reagent has been described by Thomssen and Kemp (1937) as follows: "
Bleaching is conducted in a lead-lined tank, equipped with perforated coils for the
injection of both steam and air. The charge consists of one ton of oi1. The oil is brought
to a temperature of 110°F., and 40 pôunds of fine dry salt are sprinkled into the tank.
Then there are added 40 pounds of concentrated commercial, hydrochloric acid, and 17
pounds of sodium dichromate dissolved in 45 pounds of the same acid. The latter
solution is added slowly, over a period of about three hours; the charge is agitated with
air during the addition of the dichromate solution, and for one hour thereafter. At the
end of this time,'agitation is stopped and the aqueous phase is allowed to settle to the
bottom of the tank, from which it is drawn off. Water to the amount of 40 gallons is
236
then added, and the charge is agitated- and- heated with open steam to 150°-160°F.,
after which the operatioh is completed by allowing thé contents of the tank to settle
overnight. .„
Hydrogen peroxide is a useful .clreiniCal for oil decolorization Since it de-
composes into water and oxygen leaving no . other residue. An oil, heated to
100°-175°F. ( 38b-80° C. )„ is treated with 0.5% to 2.0% of 30% or 45% hydro-
gen peroxide, which is açlded slowly with stirring to the :cil: Stiging is continued
tor 2, to. 5 hours until the required decolorization is effected. A smaller amount -
of hydrogen. peroxid e. is required if the oil is first acidified with 1% of 70% sul-
phuric acid. The simultaneous or successive addition of equal quantities of hydro-
gen. p-eroxide- and acetic anhYdride .is -covered by German patent 632,516 (P.
LangenkamÈ,. to Firma ; E. Merck, 1936). Austrian ,,patent 109,719 (F, - Gruber,.
1928) describes the combined use of hydrogen peroxide' and more or less in-
soluble peroxides, such às that of barium. Thè use of hydrogen peroxide together
with phosphoric acid is Covered by British patent 577,879, granted' tO. Laver Bros.
arid -Unilever Ltd. in 1946. The- use of organic peroxide is described in U.S. patent
1;838,707 (Rollhaus and Stoddard, to. Pilot Labs'., Inc„ 1932). . Two different
patents, Austrian 137,324 (Osterreichische cbern. Werke G.m.b.H., 1934); and
French 762,166 (Soc. des produits peroxydes, 1934), cover .the use of any peroxide
followed by an adsorbent. -
Other oxidizing agents which have been used for destroying the pigments
in fatty oils include: calcium or sodium hypochlorite (Rritish patent 444,813,
Mathieson Alkali Wàrks, 1936), -a mixture cif, alkali chlôrite - and persulphate ,
(U-.S. patents 2,433,661-2, Hampel.... to Mathieson Alkali Works, Inc., 1947).
Peracetic acid can be used as an oxidiling agent for decolôrizing oils.
Hydrogenation or reduction by other ineans also has . a, decolorizing effect
on the pigments in oils. Even a small amount of. hydrdgenation ehininates the
colour of carotenoid pigments, which are chiefly responsible . for the natural
6i:dour of fish oils. Zinc dust and acetic acid, -.both separately, and together, also
hava been used for this purpose. . •
Several chemical methods for ded-cilorizing - Oils wera ,tried out by Swain',
(1941b). . The results are sunarnarized iff table 3): It should be mentioned that
neither concentration, temperature, nor,tha time;of . reacticin in these experiments
. „ . , .
was necessarily -at 'the optimum. - -
Greenish emulsions produced by the action of potassium dichromate werd
very difficult to break in the case of pilchard oil, 'being resistant even to centri,
Filtering. with a filter aid cleared them fairly well. With duplicate samples fugin-.
of salmon oil; the: emulsion formed in one remained stable on filtering,- while the,
other cleared to _some' extent. The use of 70% sulphuric acid preceding hydrogen
peroxide treatment caused an immediate blackening in,both oils, which could not,
be removed by filtering. Sixteen percent 'sulphurie acid; 'hoWeVer, cans'ed no de-.
colorization..Of the methods tried, acidified hydrogen peroxide seemed, to, give the
best results. .The •advantage of the presence of acid is ',shown .by .comParing
2 37
experiments 11 and 12 in table 39. The efféct of increased temperature and
time is evident on comparing' 9, 10 and 12. Comparison of 2, 3, and 4 shows that
glacial acetic acid, soluble in both oils, caused some decolorization and was
almost as effective alone as when added with zinc.
TABLE 39. Decolorization of pilchard and salmon oils with chemicals, measured
by Lovibond units of yellow (Y) and red (R).
I
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FYcuxx 40. Oil-deodorizing plant (batch system). (Courtesy Wurster & Sanger, Inc.)
239
The oil is heated in the deodorizing tank„ superheated steam is introduced
at the, bottom and remoye'd: at the top by means -of the :vacuum purnp. The
vacuum should be as complete as possible; it is best maintained by multiple:eage
steam 'ejectors. The 'process is usually carried out at a temperature of from 425°
to 475°F. (218° to 246°C.). Several hours are generallY required for satisfactory
deodorization by the batch process.
PROWo-Arro VAcenel
DefERATOR eYerreo
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SYSTEIY
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FiGunE 41., Continuous oil-decrdorizing - plant. ( Courtesy Wurster & Sanger, Inc.)
240
The vacuum should be maintained and steàm bloi,vn through the oil during
the entire heating period. Steaming under vacuum while the temperature of the
oil is being raised carries off the dissolved oxygen ,which might otherwise cause
darkening.
. A diagram of a continuous deodorizing plant is shown in fig. 41. The oil is
deodorized as it flows , downward over the plates in the deodorizing tower by the
superheated steam rising through the tower. One of the advantages of continuous
deodorizing is that heat exchangers can be used, with resulting economy of heat.
The actual loss of oil during deodorization is, according to Wurster and
Stockmann (1942), very small. They state that it is seldom ever 0.1%, with a
maximum of less than 0.5%. A small amount of oil may be carried over by
entrainment, usually less than 0.5%, and this can be recovered.
For a more detailed discussion of deodorization the reader is referred to
Bailey (1945, pp. 5347557), also to Dugal and Cardin (1951).
According to Ebisawa (Japanese patent 91,076, 1931) fish oils are deodor-
ized, decolorized and stabilized by adding about 5% dry calcium hydrmide
( slaked lime) . and 5% calcium oxide (quicklime), agitating, and filtering. Since
both of these can combine with the free fatty acids, at least partial alkali reffiling
, -
should Occur simultaneously.
Hydrogenation of fi§h oils substantially eliminates the fishy odour, providing
no non-oil fishy material is present. Since in commercial practice all such im-
purities are removed before hydrogenating, the hydrogenated oil has no fishy
odour.
II. PROCESSING
In the following pages brief descriptions are given of the more important
processes by which fish oils, and other marine animal oils are converted into
forms suitable for various industrial and commercial applications. For more
detailed descriptions of the processes the reader is refened to "Industrial Oil and
Fat Products" by Bailey (1945) and to other, specialized references given therein.
(a) HYDROLYSIS AND SAPONIFICATION
The chemistry of hydrolysis and saponification of oils has been discussed in
Chapter 5; some technieal aspects of these processes as applicable to the con-
version of marine animal oils into fatty acids, soaps, and glycerol are now pre-
sented. Marine animal waxes such as sperm oil which, as pointed out in Part III
of Chapter 3 differ from glyceride oils, can also be hydrolysed - or saponified,
although with greater difficulty than in the case of ordinary glyceride oils. Fatty
alcohols were formerly thus olitained commercially from spermaceti, sperm oil
and other waxes, but are now prepared by other means as described in Chapter 5.
This has eliminated the necessity of relying on natural waxes as raw materials for
such alcohols; and furthermore, except where some specific fatty acid oecurring ii
Such waXes is desired, fatty acids are more readily obtainable from glyceride oils,
so hydrolysis or saponification of sperin oil is no longer as important as it was.
241
Fat splitting is the trade expression for the hydrolysis of fats and fatty oils
to yield free fatty acids and glycerol. When alkaline catalysts are used [see (ii)
below], the catalyst may combine with a small proportion of the fatty acids, but
the process is still substantially a hydrolysis, with fatty acids and glycerol as
products. The term hydrolysis, although it has in general wider implication, is
used here to refer to the breakdown of fats and fatty oils into fatty acids and
glycerol. The term saponifi cation is here employed to designate the reaction
between oils and sufficient alkali to combine with all the fatty acids therein,
both free and combined, to yield chiefly soaps and glycerol. Saponification is
thus a process of fat splitting accompanied by essentially simultaneous soap
formation. The soaps formed may be the desired product, or they may be later
neutralized with a mineral acid to liberate the fatty acids, although fatty acids
are seldom prepared commercially in this way.
Large quantities of glycerol are now produced by other means, so its pro-
duction as a by-produCt of hydrolysis and saponification has lost some of its
economic importance.
The principal fat-splitting processes used commercially are: autoclaving
with steam alone; heating with alkali, or metallic oxides, insufficient for complete
saponification; use of Twitchell reagents; use of lipolytic enzymes. Autoclaving
with acids was formerly used as a commercial method Of fat-splitting, but it is
no longer piactised. The principal commercial saponification processes are cold
saponification, pan boiling, and the continuous process.
Before describing these processes some generalities Concerning the factors
influencing the rate and completeness of hydrolytic reactions may be emphasized;
saponifying processes imply completeness of reaction.
Although fats are considered as insoluble in.water, there is 'nevertheless a
slight mutual solubility which increases perceptibly with increase in temperature.
Conflicting views have been expressed on the question of whether the initial
stages of hydrolysis of a 'melted fat (i.e. oil) take place at the interfaces between
the oil and the water, in the oil-in-water solution, or in the water-in-eil solution.
Views expressed by Lascaray (1939b) favour the lasi-mentioned reaction; but
in each case the hydrolysis would be assisted by increased temperature and by
agitation, the latter to provide an interfacial area between the two liquids suffi-
cient to allow a reasonable rate of reaction or mutual solution.
Kaufmann and Keller (1937) demonstrated that an incrèase in temperature
increases the rate but not the equilibrium completeness of hydrolysis of a fat by
water alone, when other conditions (e.g. agitation) are equal:
140°C.(284°F.) 3.6% hydrolysis in 20 hours,
77.5% -(maximum) in 108 hours;
185°C.(365°F.) 77.5% (maximum) in 20 hours;
205°C.(401°F.) 3.1% hydrolysis in 2 hours,
77.5% (maximum) in 11 hours.
The completeness of the hydrolysis is thus independent of the'temperature, but
is increased by an increase in the ratio of water to oil:
242
Water:oil = 1:6 (Temp)205°C.) maximum hydrolysis 63.3%; .
Water: oil = 1:3 ( Temp. 205° C.) maximum hydrolysis 77.5%;
Water: oil = 1:2 _( Temp. 150° C ) maximum hydrolysis 84.9%.
,Lascaray (1939a) investigated the effects of small amounts of alkaline
catalysts on the rate and completeness of hydrolysis.. In carrying the ratios of
water to oil beyond the limits investigated by Kaufmann and Keller, the follow-
ing data, obtained when using 0.5% caustic soda and a temperature of 185°C.
with uniform agitation, show a fm-ther increase in completeness of the reaction
at equilibrium:
, Water:oil = 3:5 gave 90% hydrolysis in 8 hours;
Water:oil .-_---_- 1:1 gave 94-70 hydrolysis in 8 hours;
Water:oil .= 2:1 gave 95% hydrolysis in 8 hours.
Increase in the amount of catalyst caused an increase in the rate of
hydrolysis; 1% caustic soda gave substantially the same degree of hydrolysis in
5 ho.urs as 0.5% gave in 8 hours. The completeness of the reaction was slightly
increased by the additional amounts of catalyst, an effect due to a displacement
of the equilibrium by the combination of some of the free fatty acids to form
soaps. This effect with apparently small amounts of catalysts is , greater than
would at first appear, because of the great difference between tlie lew Molecular
weights of the usual . hydrolytic catalysts and the high molecular weights of fatty .
for a typical fish oil, the percentage of fatty acids fixed as soaps are acids.Thu,
as follows, using of each catalyst an amount equal to 1% by weight of the oil:
Zinc Magnesium Calcium Lithium Caustic Canstic
oxide oxide oxide hydroxide soda potash
7.2 14.5 , 10.1 12.2 7.3 5.2
The foregoing catalysts are arranged in the order of decreasing efficiency found
by Lascaray (1939a) when investigating their promotion' of the autoclave hy-
drolysis of an animal fat at 185°C. (365°F.). Zinc oxide increased the rate of
reaCtion much more than 'any of the others, a result corresponding with the
observation that water is very much more soluble in fat in the presence of zinc
oxide than in the absence of 'a catalyst.
Not all of the fat-splitting processes to be described are suited to the treat-
ment of all marine oils. In any process involving a temperature over 300°F. for
an appreciable length of time, the highly unsaturated fatty acids of many fish
body oils such as pilchard, herring, and menhaden oils and some fish liver oils
are prone to undergo oxidation, polymerization, or even partial decoMposition,
with consequent darkening and acquisition of other undesirable properties. The
fatty acids of marine mammal oils such.as whale 'oil are not so subjeet to such
changes. Fish oils that have.been hydrogenated prior to hydrolysis or saponifica-
tion undergo splitting with little if any alterayon of their component fatty acids.
If the fatty acids are to be used as such, any da‘rk colour acqmired during the
fat splitting is usually removable by methods described under "Bleaching" (pages
233-238).
243
(1) AUTOCLAVING WITH STEAM ALONE
This method requires such high temperatures that it is not gelierally suitable
for the treatment of fish oils since, due to the presence of highly unsaturated fatty
acids in them, some polymerization takes place . Whale oil and hydrogenated
fish oils are somewhat more amenable to the process, but the fatty acids re-
covered have a tendency to be dark in colour . The oil is heated with live steam
at 200 to 220 pounds pressure per square inch, corresponding to temperatures
of about 198 ° to 202°C . (388' to 395'F .) . Water up to 60% of the weight of
the oil is sometimes added prior to the introduction of the steam . Mechanical
mixing is not used, but the steam is distributed by fine jets, and a slight con-
tinuoils escapement facilitates agitation . A variation of this process involves,
blowing superheated steam into the oil preheated to about 300°C . (570°F .) at
which temperature both the fatty acids and the glycerol are volatilized with the
steam and condensed separately in the order given . The Hoffman fat-splitting
reaction is a continuous process involving hydrolysis at 220°C . to 260°C, (430°
to 500°F .) of a water-emulsified purified fat under 800 to 900 pounds pressure
per square inch . The product is then passed into a high-vacuum expansion zone
where the fatty acids distill, whereas the unsaponified residues remain liquid .
The reaction is complete in 6 to 12 hours . When the reaction is carried out below
232°C . (450°F .) light-coloured fatty acids can be produced, but above that
temperature there is some darkening and ,polymerization .
SAPONIFICATION
This method is more commonly used than autoclaving with steam alone
since the reaction is nnuch faster. It is carried out commercially both as a batch
process and as a continuous process . The former is better adapted to small-scale
operations, the latter to operations handling at least a carload of oil per day .
Furthermore, much higher temperatures are used in the continuous process,
making it unsuitable for treatment of fish oils containing appreciable amounts
of highly unsaturated fatty acids .
In the batch process an autoclave is charged to about 75% of its capacity
with a mixture of 75,7o oil, 21 to 22 % water, and as a catalyst 3 to 4~/o zinc oxide .
Other catalysts including calcium, barium, and magnesium oxides were formerly
used, but have been largely supplanted by zinc oxide . A small amount of zinc
dust is also added frequently. This does not act as a catalyst for the hydrolysis
but prevents the resultant fatty acids from darkening unduly during the process .
Steam at 100 pounds pressure is admitted to the a :u:toclave, and raises the tem-
perature to about 140°C . (285°F .) . After 5 hours the hydrolysis is 90 to 93a/o
complete, and after 12 liôurs 98 to 99% complete. As previously pointed but,
part of the liberated fatty àcids will be fixed as metal soaps . These fatty acids
may be recovered by b6iling with dilute sulphuric acid . '
The continuous process is carried out in a tower, the oil being introduced
near the .bottom and the water near the top, so that they flow counter-current t o
244
each other. Before introduction into the tower the oil is .treated with the requis
. ite
amount of zinc- oxide and heated with mixing until the catalyst:, has completely
dissolved by forming zinc soaps. The oil and water are each subjected to a high
hydrauliC pressure and then heated, by direct steam injection, the oil to 260°C.
(495°F.) and the water to 250°C. (480°F.). They are then pumped into the
tower as already described, and in carefully controlled proportionality. The re-
action is greatly facilitated by the fact that as the water flows downward it car-
ries with it the glycerol formed in the reaction, whereas the fatty acids rise. This
separation of the-products drives the reaction more rapidly to:completion.
(iii) HYDROLYSIS BY TWITCHELL REAGENTS •
The Twitchell process is a catalytic process in which the catalyst is any one
of a number .of sulphonated compounds sueh as those desciibed on page 108
-under - the heading "Hydrolysis with synthetic organic Catalysts". These are
known collectively as 'Twitchell reagents". The chief advantage of the process
is the simple equipment required. Disadvantages are the length of time required
for completion of the reaction, se) that the over-a ll -capacity of the equipment
used is low; greater variation in'the behaviour of different batches than in other
fat-splitting methods; and discoloration of the fatty acids. The fatty acids pro-
duced by.the Twitchell method were formerly very dark, but modified Twitchell
xeagents giving lighter-coloured, products have now been developed.
The process is . carried out in open tank, either wooden or concrete being
-used since Twitchell reagents attack many metals. A charge of oil, togetheewith 40
to 100% of its weight of water, plus 0.5 to 1.0% of Twitchell reagent, based on
-the weight of the oil, is run into the tank, and gentle mixing-at 100°C. (212°F.)
is maintained by" passing:in live steam. The hydrolysis is practically complete in
.24 to 60 hours depending on the oil being processed. The -addition of from 0.5
to 2.0% of 75% sulphuric acid to the mixture is claimed to 'accelerate hydrolysis.
It is also considered advantageous to interruPt the hydrolysis when about half
.completed, to allow settling, and run off as much as possible of the aqueolis layer
containing glycerol, and then resume heating after making up to volume with
-water.
Modifications of the basic prOcess have been developed; for example that
described in United States patent 1,976,376 (E. F. Spellmeyer, 1934) in which
• an alternating electric current of 0.25 amperes at 3 to 5 volts is said to reduce
the time of hydrolysis at 100°C. (212°F.). It is claimed that the reaction is 77%
. complete in 3 hours, 91% complete in 6 hours and totally completed in 9 hours.
Nitrogenous impurities in an oil must be removed before splitting by the
Twitchell process, since they have a poisoning effect on the catalyst. They can
be removed by boiling the charge with dilute sulphuric acid.
- In this process the exothermic nature of the reaction between caustic alkalies
and fats is utilized to supply the heat necessary to complete the saponification.
It is suitable for small-scale operations, and is used for the production of certain
types of soaps where the recovery of glycerol is unimportant or undesirable. The
fat is heated to 40° to 60°C. (104° to 140°F.) in an open vessel and the pre-
determined amount (or a very slight excess) of strong caustic soda or potash
solution is run in with rapid agitation. When the emulsion which forms has
become sufficiently viscous, it is run into moulds and allowed to stand in a warm
room Where the reaction proceeds for a further 24 to 48 hours with some spon-
taneous elevation in temperature. A modification involves mixing the fat with the
theoretical amount of "powdered caustic alkali at the above temperatures, and
then initiating the reaction by the addition of an amount of water less than the
weight of alkali used. Soft soaps (potassium soaps) are usually made by this
process.
(vi) PAN-BOLLING PROCESS
This is the process most commonly used for the manufacture of soap from
any fat, including suitable clarified or hydrogenated marine animal oils. Many
variations and refinements of the process are in use, but the procedure in general
is to raise the temperature of the fat to about 100°C. (212°F.) by passing in live
steam. The theoretical amount (or a very slight excess) of caustic soda or potash,
as a 10 to 32% solution depending on the method used, is then cautiously run
in to secure emulsification without allowing any temporary local excess in con-
centration of alkali which would tend to break the emulsion and delay saponifica-
tion. Gentle boiling With steam is continued for several hours, and the reaction
is completed in 12 to 24 hours.
three are batch processes and the other two are continuous processes.
•
(i) BY MECFIANICAL AGITATION
This type of plant uses a steel tank fitted with openings suitable for inspec-
tion, introduction and discharge of oil and injection of hydrogen, and with coils
247
for use with steam under pressure for initiating the reaction. In addition there is
provided a , suitable mechanical agitator. The hydrogen is admitted slowly as
required to maintain the desired pressure, and mixing is provided by the agitator..
The packing glands required by this type of hydrogenator introduce the possi-
bility of leakage of hyçlrogen with its attendant loss and danger.
(ii) BY AGITATION WITH HYDROGEN
This type of plant is similar to that used in mechanical agitation except that
no provision is made for stirring. The hydrogen is introduced at the bottom of
the tank so that it agitates the oil as it passes through it. The hydrogen is with-
drawn from the top of the tank, recompressed and recirculated through the oil.
There are no packing glands in this system, thus reducing the possdility of loss
of hydrogen.
111111M11131111 "'.
— Znidi f m Ewe if
I Iii
—l"
Viremban
( V. ) BAMAG-SAROC PROCESS
The important feature of this process IS the rapid and intimate mixing of
the three phases: liquid oil, solid catalyst, and gaseous hydrogen. Due to the ,
intimate mixing, the réaction takes place very quicidy. After it is completed, the
catalyst is separated from the hydrogenated .oil by filtration or centrifugation.
The exothermic nature of the reaction is made use of to heat the incoming oil.
This is accomplished in a heat exchanger, where the incoming oil is heated by ,
the hot outgoing oil. The process is more fully described in the recent Bainag
Bulletin No. 032 (Bamag Ltd., London S.W26, England)„'
,
(c) OXIDATION
( i) OXIDATIO N PROCESSES
A IDoiled oil is a drying oil with which has been incorporated a suitable,
amount of drier by means of a heat treatment and, depending-upon the product
desired, which has. been blown for some time. Blowing during the incorporation
of the driers produces a product that is partially oxidized and polymerized and
that Will:dry more quickly' than raw oil to give a harder and more lustrous film.
Thi'isimportant in varnish technolog)',.' The length of time ofllowing depends
upijn the viscosity desired.
The p' rocess in general consists in raising the temperature of the oil to about
105°C., (220°F.) and gradually adding the drier with agitation by a stream of
air. the temperature is maintained until a clear solution is obtained. As this
pro.cesS 'gives a product that is dark in colour owing to extensive -mddation, a
small quantity of frequently incorporated with the driers, which are then
mixed with the main portion at as low a temperature as possible, usually not
above 95°C. (200°F.). In this maUner a product of lighter colour is obtained.
The driers often added are lead oxide, cobalt oxide or acetate, and manganese
oxide or borate. The neWer procedures consist in using the soluble soaps, resinates,
249
naphthenates and linoleates of the foregoing metals. They are soluble in the oil
and may be incorporated at much lower temperatures to produce products of
light colour. Heat is usually applied by means of dosed steam coils to prevent
the undue darkening caused by local overheating which would occur with direct
firing. -
In order to produce a cheaper prbduct, the drier is sometimes added to the
oil at about 35°C. (95°F.) and the mixture vigorously agitated by an air blast
to obtain a homogeneous mixture. During the blowing the oil must be cooled to
prevent an excessive rise in temperature.
(ii) BLOWN OIL
These oils are produced in a similair manner to boiled oils but the blowing
process is continued longer to make a more highly polymerized oil of high vis-
cosity. The oil is blown with air at a temperature of about 90°C. (194°F.) and
the oxidation soon becomes so rapid that the temperature .rises considerably,
whereupon cooling water is circulated through the coils to prevent further rise
with consequent darkening. A vigorous current of air is necessary to produce a
viscons oil in a short time, and also to assist in carrying off some of the volatile
acidic oxidation products. By careful working, an oil may be, obtained with an
acid value below 10. Being partly oxidized, these oils dry rapidly, but the film
formed is less durable than from oils polyMerized by heat alone. However, blown
oils wet certain pigments such as white lead and the ochres better than does raw
or boiled oil.
Pilchard oil may be blown satisfactorily to produce. oils of high viscosity or
solid gels, but it does not body as ,rapidly as linseed oil, several days at 125°C.
(257°F.) being required to produce a solid gel, When blowing was canied out
at 250°C. (482°F.), the viscosity of the oil increased very slowly until the tenth
hour, when the values rapidly increased to a final value of 28.4 poises, which was
reached at the end of 22 hours. During the preliminary heating before blowing
was started, the acid value rose from 1.5 to 8.1, but during the vigorous blowing
it dropped until it reached an almost cons,tant value of 3.
(iii) SHOWER BATH AND SivIACKER PROCESS
This is a modification of the cblowing process and is carried to the limit of
oxidation by air with the production of a rubbery mass. The oil containing driers
is maintained at 50°C. (122°F.) and passed in a shower through the air from
the perforated bottom of a tank or trough. It is then collected in a lower tank and
re-sprayed until it becomes too thicic to re-cycle, when it is transferred to a
steam-jacketed agitator or "smacker". Here it is agitated violently with a strong
stream of air at 55°C. (131°F.) until it becomes a crumbly mass, when it is
"stoved" or heated for several days at 40°C. (104°F.). The product is used in
the manufacture of linoleum.
(iv) on„
SCRIM
Ânother method of securing the linoxyn" or oxidized solid oil is to permit
the oil (containing driers) to flow over a mass of loose cotton fabric or "scrim",
suspended in a room maintained at 38°C. (100°F.). Because of the large amount
250
of surface exposed the oil dries as it flows over the cotton and that which drips
from the fabric is collected and the process repeated until a coating of half an
inch of solidified oil is obtained. This is stripped off and shredded through rolls.
"Bôdying" is the term used in industrial practice for the heat polymerization
of drying oils; it refers to the thickening or development of "body" in an oil.
An oil which has been so heavily bodied that it will "stand" (i.e. will not fall back
immediately when a rod is thrust into it and withdrawn) is called a stand oil..
These are used in the manufacture of products such as printing inks, and certain
types of varnish. Bodied oils used in the manufacture of printing inks are called
lithographic varnish. The methods used for the production of bodied oils vary
with the type of product desired.
( ii ) TOP-PICRING
In this process bodied oils are made by heating the oil until the flash point
of the vapours formed by its decomposition is reached. The vapours are ignited
and heating continued until the desired body in the oil is reached. If carefully
made, a top-fired oil will be lighter in colour than one made in an open kettle
without top-firing. Bodied oils prepared in this way are used for certain types
of printing inks.
254
(containing dissolved sulphur triœdde) tends to increase the ratio of sulphonated
to sulphated products, but they have to be used with caution since oils will char
very easily with them.
(ii) PROPORTION OF SULPHURIC ACID TO OIL
In common sulphating processes the weight of acid used is about 35% of
the weight of the oil. In thus treating oleic acid, a product containing between
5% and 7% of combined SO 3 as sulphuric half ester is obtained. In experiments
using 70% by weight of sulphuric acid, the combined SO3 content of sulphated
oleic acid was not materially increased (Sunderland, 1935).
(iii) RATE OF ADDITION OF SULPHURIC ACID TO OIL
The action of sulphuric acid on unsaturated fatty oils and acids produces
considerable heat and the processes may roughly be divided into two classes,
depending on whether the sulphuric acid is added slowly in an endeavour to
maintain a low temperature, or quickly with a consequent considerable rise in
temperature. The distinction is exemplified by the descriptions of typical "high"
and "quick" sulphation processes to follow (vi). A third method consists of a
"factor" process analogous to that described for sulphurization in which the
whole amount of acid is added to a portion of the oil and the vigour of the
reaction controlled by judicious addition of portions of the remaining cold oil.
(iv) TEMPERATURE OF REACTION
256
by Kapoor and Mathur (1945). The 'product -thus obtained is stated to have
improved emulsifying, wetting, and hard-water-resisting properties due to the
presenee of chlorhydrins in the chlorinated oils.
Developments in the teclmology of sulphonation from 1941 to the, earlier
part of 1947 were reviewed by Lisk (1948), and from the earlier part of 1947
to about the end of 1948' by the same author (1949).
The corrosive action of sulphuric acid on sulphating equipment has been
studied by several investigators. Iron and steel are attacked rather rapidly through'
continual removal of the protective layer of hydrated ixon oxide (Welwart, 1933).
Average depths of corrosion of nickel, monel and inconel metals after subjection
to one hundred sulphation batches containing 66° Baumé sulphuric acid at
temperatures of 16° to 60°C.. (61° to 140°F.) followed by water and alkali
washes were found to be, as follows (Friend, 1939):
( f ) SULPHURIZATION
The chemistry of sulphurization was'discussed in Chapter 5. The technology
of the process, especially as applied to oils of marine origin, is discussed here.
Raw, cold-cleared, refined, or partially blown oils are mixed with the requi-
site amount of powdered or pulverized sulphur and heated in closed vessels with
vigorous agitation. Uniform heating by means of a surrounding heat-transferring
medium is desirable to avoid scorching as the viscosity of the mass increases.
Semi-solid factices may be cooled in the reaction.vessel, while solid factices are
usually removed, crushed and allowed to cool in the air.
Takano (1939) has. investigated the formation of "brown" factice from
herring and sardine oils under such conditions with the results shown in table
40, A. For both oils, the factice obtained by using smaller amounts of sulphur or
lower temperatures was soft and somewhat tacky; that obtained by using more
sulphilr or higher temperatures was bard, brittle, and of dark colour. The amount
258
TABLE 40. Sulphurization of fish oils.
A. With sulphur.
Herring oil (acid value, 0.87; iodine value, 109.3; saponification Value; 188.5)
Sulphur ,
added to oil Heating H2S Combined Free Acetone
(gm. per 100 Temperature time evolved sulphur sulphur extract
gm. of oil) (°C.) (min.) (%) (V, (%) (%)
Sardine oil (acid value, 0.64; iodine value, 173.2 saponification value, 196.5)
-
20 164-165 60 0.01 13.7 1.47 46.1
25 60 0.04 16.8 1.9637.5
30 " 60 0.08 18.3 3.43 ' 28.2
35 ig 60 0.15 19.6 3.78 27.1
40 u 60 0.20 20.5 5.89 - 29.8
20 170-173 30 0.08 13.7 1.56 ' 38.3
25 30 0.12 16.7 .... 30.2
30 ,. 30 0.26 17.9 3.31 31.2
20 180-184 30 0.19 13.5 1.78 - 39.4
25 , 30 0.34 15,5 2.41 34.8
30 " 30 0.36 17.2 , 3.02 33.9
20 190-192 30 0.22 13.0 1.84 38.6
259
of acetone-soluble material was considered rather high for factices of satisfactory
quality," a circumstance that may be ascribed to the presence of various com-
ponents with conspicuously different degrees of unsaturation in these oils. Sardine
oil required in general a larger amount of sulphur and showed a more rapid
coagulation than herring oil 'under the same conditions. The prolonged heating
given to the last three samples, of herring oil, although too long for technical use,
showed that the content of acetone-soluble material may be reduced to satis-
factory proportions concomitant with a desired lowering of free-sulphur content.
Herring oil (acid value 0.87; iodine value. 109.3; saponification value, 188.5)
Sardine oil (acid value, 0.64; iodine value, 173.2; saponification value, 196.5)
TABLE 42. Reactivity of some oils and fatty acids with sulphur monochloride.
Rise in temperature
Material Reagent added of reaction Nature of product
(% by weight) (° C. per min.)
Both sulphur monochloride and sulphur are used for producing factices for
the paint and varnish industry. The use of factices in paint and varnish demands
the property of causing the products to be ( 1) little absorbed by porous materials
that are being coated, (2) capable of thorough drying even in thick layers,
(3) capable of giving considerable film thicicness with consequent better re-
sistance to water and weathering. The use of blown oils and driers together with
a small amount of sulphur for producing improved drying oil has been mentioned
(page 253), and although desirable products, sometimes liquid, are purposely
made by under-sulphurizing, or blowing, or both, the opinion has been expressed
(Brust, 1938) that the full amount of reagent should be used to attain a greater
degree of polymerization, since the larger the molecule the better the guarantee
of the satisfactoriness of the prodiict. If blowing is carried too far, too little
reagent is apt to be used. Special types of varnishes (spar) and paint incorpo-
262
rating factices have the property of "settine almost as soon as applied, and
although one coat may not yet be "dry", a second coat can be applied very soon
after. German patent 596,400 claims that the solution of factices in drying oils
ai high temperatures provides a suitable rust-proofing paint, while the German
patent 621,400 describes the solution of fish-oil factices at low temperatures for
the same purpose. -
The use of certain (unsaturated) fish oils for producing factices for paint
and varnishes has been criticized severely on account of their.tendency to liberate
considerable quantities of hydrogen chloride when treated with sulphur mono-
chloride. This evolution of acid may slowly continue in the finished product,
with detriment to the adhesion of the film on metallic surfaces. This objection
does not apply, however, to factices prepared from fish oils and sulphur, or to
the factices prepared from fish oils by suitable modificationsrof other sulphurizing
processes, such as first blowing the oil with a drier, and using only 3 to 4% of
sulphur monochloride (Osnos and Golovistikov, 1932).
( g) FRACTIONATION
Within recent years commercial processes have been developed for sepa-
rating oils into fractions with higher and lower degrees of unsaturation ( and
thus higher and lower iodine values) than those of the original oils, such
fractions being more suitable for various applications. Fractionation is not only
applied to the oils themselves, but to the fatty acids prepared from them, and in
this case separations can be made into fractions containing different numbers
of carbon atoms ( and hence with different freezing and boiling points), as well
as into fractions with different degrees of unsaturation. Separation into fractions
with different degrees of unsaturation is effected, in the case both of the oils and
of the fatty acids, by fractional crystallization or by extraction with immiscible
solvents; separation into fractions with different numbers of carbon' atoms, which
can be done mrith fatty acids or their mono-esters, although not so easily with
the oils, is accomplished by fractional distillation. Differences in the unsaturation
of fractions obtained by distillation are chiefly due to differences in the average
unsaturation of fatty acid fractions with different carbon number, since fraction-
ation by distillation cannot be made on the basis of unsaturation alone.
Fish oils offer great possibilities for commercial fractionation. As was shovvn
in Chapter 2, the fatty acids which enter into the çomposition of marine 'oils
cover a far wider range both of .unsaturation and of carb.on-chain length, and
permit separation into fractions having these properties to a higher degree, than
do oils of land origin.
(i) FRACTIONAL CRYSTALLIZATION
Fractional crystallization has already been discussed in connection with
refining ( cold clearing). Further fractionation of an oil or mixed fatty acids into
fractions with different degrees of unsaturation can be accomplished by crystal-
lization from solvents. Among the solvents which have been used for this purpose
263
are: 90% methailol=Emersôl process -(Kistler et al., 1946; and U.S. patent
2,293,676, L. D. Meyers and V. J. Muckerheide, 1942, assigned to Emery Indus-
tries Inc.); petroleum naphtha (Bailey et al., 1943); petroleum ether, hexane,
amylene, acetone, or methanol (U.S. patent 2,340,104,,J. B. Brown, 1944, assigned
to Ohio State University Research Foundation). British patent 582,557; granted
to Lever Bros. and Unilever Ltd. in 1946, covers fractional crystâ.llizatioli of fatty
oils by-chilling a solution of the oil in any solvent which will dissolve it. In this
patent it is stated that the higher the ratio of solvent to oil, the greater will be
the spread between the iodine values of the fractions separated. I
::' Solubilities of a number of different fatty acids in various organic solvents
at low temperatures were reported by Foréman and Brown (1944).
The results obtained in !thè: low-temperature crystallization of fish-oil fatty
;acids^were given in'the abôve.U,S. patent,2,340,104: -Exàtnples of the data are
sho\^vn in table 43. The yield d^ta-and
, filtrate iodine vàlues refer to the filtrate
TABLE 43. Fractional crystallization of fish oil fatty acids from various solvents.
Yield
Original . Concentration in Filtrate
1VIi,xed fatty iodine Solvent (gm./100 cc. Temp. Filtrate iodine
âEids used value solvent) (° C.) (°^o) value
;I .
,after removal of the solvent, the yields being expressed as percentages of the
mixed1atty acids used. it-is pointed out that, of the solvents tried, methanol and
^etliânql, are less desirable than the others -sincé they have a slight tendency to
foxm esters with the fatty acids. While acetone was found more' effective than
tlie.liyclrocarbon solvénts in segregating highly unsaturated fatty acids, the
products obtained using the former.were generally darker in colour than the
original ôil, whereas those obtained when solvents of the latter type were used
were ùsually as light or lighter than the original oil.
As an. example of the results obtained in . fractioxlal crystallization of fish oil
fattÿ acids, b,^, the ' Emersol process, Blaw-Knox '(1945) states that sardine-oil
mixed fatty acids with an iodine value of 160.0 yielded 25% solid fatty acids
with an iodine value of 30.0, and 75% liquid fatty acids with an iodine value of
201.5.
,. Equipment for thecontiriuous processing of mixed fatty acids by the crystal-
lizat:ion from solvents is described by Kistler et al. (1946).
(ii) LÎQUID-LIQUID EXTRACTION
Fractionation of oils or fatty acids into fractions with different degrees of un-
saturation by liquid-liquid extraction, a. process often referred to as segregation,
264
can be done in several different waÿs . The oil can be extracted with one solvent, or
it can be extracted simultaneôusly with two immiscible solvents, one of which
has a greater tendency to dissolve the more unsaturated, and the other one the
less unsaturated, constituents of the oil . The extraction may be carried out as a
single-stage batch process, as a countercurrent batch process, as a multiple-stage
process, or as a continuous co-current or countercurrent process . In multiple-stage
extraction a number of successive extractions with fresh lots of solvent are made .
In actual practice continuous countercurrent extraction is carried out in a vertical
tower packed with Raschig rings or other suitable packing material (see Cairns,
1948) . A packed tower for laboratory work on countercurrent extraction has
been described by Varteressian and Fenske (1936) ; Bewick, Currah and Beamish
(1948) describe a laboratory liquid-liquid extractor for the rapid evaluation
of solvent-extraction processes. Semi=commercial and full-scale commercial plants
for extraction of fatty oils are described by Kenyon, Gloyer and Georgian (1948) .
The transfer of solute between two immiscible liquids may be regarded
as molecular diffusion through- two liquid films . These films are the parts of the
two liquids through which there are gradients in composition from the compo-
sition in the main body of each liquid to that at each side of the interface . If the
solubility of the solute is far greater in the liquid being used for extraction than
in the liquid being extracted, only one film need be considered-that of the liquid
being extracted-since the other film offers negligible resistance to the transfer
of solute . In any case the rate of transfer of the solute from one liquid to the
other is directly related to the concentrations of the solute in the two liquids,
the area of surface through which the diffusion takes place, that is, the area of
contact between the two liquids, and to the diffusion coefficients of the solute
through the two liquid films . The diffusion coefficients are related to, although
not always directly proportional to, the relative solubilities,of the solute in the
two liquids .
A review of the theory of liquid-liquid extraction is. beyond the scope of
this Bulletin ; a detailed treatise on this theory, including graphical solutions of
particular problems encountered in practice, is given on pages 729 to 753 of the
"Chemical Engineers' Handbook" referred `to in the introduction to this .chapter
(page 215) .
The fractionation of cils or fatty acids by liquid-liquid extraction into
fractions with different degrees of unsaturation depèinds mainly on the fact that
polar solvents dissolve the more highly unsaturated fatty acids or glycerides to
a far greater extent than the less highly unsaturated fatty acids or glycerides .
The material extracted by the polar solvent is generally referred to as the extract,
while the remainder is called the raffinate . Furfural is a solvent widely
used for commercial solvent segregation on this basis . Its use- for this purpose
is covered by U .S . patents 2,200,390 (1940), 2,200,391 (1940), 2,278,309 (1942),
2,291,461 (1942), 2,313,636 (1943), and 2,316,512 (1943), all of which were
granted to S . E . Freemari, and assigned to the Pittsburgh Plate Glass Co . The
process is further described by Gloyer (1948,' 1949) and Kenyon, Gloyer and
Georgian (1948) . It can be carried out as a single-solvent process, or as a
265
two-solvent process using naphtha as the second solvent. In either case part of the
extract product ( extract without removal of solvent) may be "refluxed"—fed back
into the tower at a point near that at which the extract is drawn off.
Data for the fractionation of sardine oil by countercurrent extraction with
furfural in a packed 45-foot column are given by Gloyer (1948). Using 6 parts
of furfural to 1 of sardine oil (iodine value 190), and refluxing 0.48 parts of the
extract product, an extract with an iodine value of 230 was obtained, while the
raffinate had an iodine value of 145. The extract amounted to 55% of the original
oil, the rernaining 45% being raffinate. Data for the fractionation of dogfish
liver oil, including both iodine value and vitamin A, are included in the same
paper. In this case a more complicated two-tower system was used for the
extraction. Two solvents, furfural and naphtha were employed, different pro-
portions of each being refluxed. In addition to the extract and the raffinate, a
third fraction, which'was designated the by-product fraction, was separated. The
latter fraction consisted almost entirely Of fatty acids. The data reported are
given in table 44.
TABLE 44 Fractionation of dogfish liver oil by furfural—naphtha extraction
\
Vitamin A
Fraction Yield (%) Iodine value Acid value
% total
Units/gm. vitamin A
The use of a number of different polar solvents for fractionation of fatty oils
is covered in U.S. patent 2,313,636 ( see above), data being included in the
patent for the fractionation of menhaden oil by several different solvents and
pairs of solvents. These data are given in table 45.
TABLE 45. Iodine values of menhaden oils fractionated by liquid—liquid extraction.
Iodine values
Solvent
Original Extract Raffinate
266
The possibilities of methanol as a solvent for the commercial fractionation
of fatty oils by liquid—liquid extraction were investigated by Kleinsmith and
Kraybill (1943). Methanol extracted preferentially the more highly unsaturated
portions of the oils. Although the paper was mainly concerned with the use of
methanol for liquid—liquid extraction, a number of other solvents were also tried
for the purpose. Of those tested, nitroethane, acetonitrile, and methyl formate
were found particularly effeetive.
The fractionation _of fish liver oils by extraction with 91%, 95%, and 99%
isopropanol, 95% acetone, and 100% methanol was investigated by Buxton
(1947). The solvent extracts had a higher content of unsaponifiable matter and
of free fatty acids, a higher iodine value, and a higher vitamin A potency than
either the original oil or the residual fractions.
Although polar solvents are used in most processes for liquid—liquid fraction-
ation of oils, a non-polar solvent, liquid propane, is the only solvent employed
in one such process (Solexol Process). The segregation of an oil into fractions
with high and low iodine values by this process depends on the fact that, while
oils are miscible in all proportions with such solvents as liquid propane at room
temperature, as the temperature is raised the selubility of the oil in the solvent
decreases progressively until at the critical point. [95.6°C. (206°F.) for propane]
it is completely insoluble. Different constituents or fractions of an oil precipitate
preferentially at different temperatures; thus, by suitably controlling the con-
centration, temperature and pressure, an oil can be fractionated in many different
ways. The process, which is adapted only to large-scale operation, is described
by Passino ( 1949), whose data for the fractionation of sardine oil and cod liver
oil are given in table 46.
Two runs with cod liver oil are included; both were made with the same oil,
but by changing the conditions considerable variation in yield and iodine value
was produced without changing the vitaMin A potencies of the different fractions.
In each case the cod liver oil was alkali refined as part of the process; the sardine
oil was not so treated. The first fraction separated from the latter oil, as well as
from most of the other oils mentioned in the paper, was very dark coloured. This
fraction is called the "colour bodies" since it contains most of the colouring
matter in the oil. The data in table 46 show clearly that the segregation of the
glycerides is on the basis of unsaturation, not molecular weight. They also show
that there is segregation of the unsaponifiable constituents, and that the free,
fatty acids are Concentrated especially in the high-vitamin fraction.
The drying and non-drying constituents of an oil can be segregated by first
polymerizing the oil, then extracting with a solvent in which the non-polymerized
material is soluble but the polymerized material insoluble. The following solvents
are suitable for this purpose: ketones (for example acetone), higher alcohols
(for example butyl acohol or amyl alcohol), amyl acetate. The process was first
described by Rossmann (1937), who applied it to linseed oil. Its application to
fish oils is covered by U.S. patent 2,239,692, granted to O. M. Behr in 1941, and
assigned to the Vegetable Oil Products Co.
267
; Polymerization followed by segregation with acétone was used by Privett,
Pringle and McFarlane (1945) in preparing a stable type of edible shortening
from linseed oil. The oil was first polymerizéd by heating at 270-275'C. (018-
527'F.) for 12-15 hours with continuous passage of carbon dioxide through
A. Sardine oil
it. Extrâction with acetone yielded 60-65% of acetone-soluble oil which on hydro-
genation made an excellent shortening. The polymerized fraction was thought
to have possibilities for use as a paint and varnish oil. This was subsequently
268
investigated by Privett, McFarlane and Gass (1947). .They heated a sample of
linseed oil for 123 hours at 270°C. (518°F.) with a stteam of carbon dimdde
bubbling through it. The oil thus polymerized was extracted at 5°C. (41°E)
with three successive portions of acetone ,( solvent:oil ratio = 8:1). The first
acetone-soluble fraction was suitable, as before, for the Manufacture of shorten7
the third fraction was found satisfactory as a paint oe, while the residual ing;
acetone-insoluble material had properties which shoWed that it Would be particu-
-
(iii) DISTILLATION
Distillation of fatt), acids is cattied out under vacuum at an absolute pressure:
of about 100 mm. Steam is introduced into the still to assist in vaporiZing them..
The temperature of distillation is. fronl 232.° to 260°C. (450i. to 500°F.). In dis-1
tilling fatty acids prepared from fish oils the distillation temperature" should be,
kept. as low as possible to minimize the formation of "stearin pitch", as the un4i
distillable residue of polymerized fatty acids which is formed in the still is called
Due to the highly unsaturated nature of some of the fatty acids from fish oiW
they readily polymerize if too high a temperature is used.
When hot, fatty acids are very corrosive to ordinary steels, so fatty . acid'
stills must be constructed 'of speCial alloy steel.
A diagram of a fatty acid distillation plant is shown in fig. 43. -
Commercial distillation of fatty aciçls is done to a large extent ,simply as 4
means of producing lighter-coloured fatty acids—that is, separating -them from
the accompanying impurities. Within recent years, however, fractional distillation_
on a. commercial scale has developed to a considerable extent. In this case the
basic method of vaporization is the same as in simple distillation, although dif.
ferent equipment is used, and the fatty acicls, vapériieçl at a high teMperature
under vacuum and usually with steam, are passed through a fractionating column
instead of being simply condensed. New equipment for vaporizing fatty acids
by "flash" evaporation without the Use of steam is described by Keleti (1948).
Molecular distillation is used to separate the vitamins and other components'.
fromatyils,bunpretsd,comialyngretxfo'
the fractionation of fatty acids. Its use as a means. of separating vitamins from
fish oils has already been mentioned on page 58.
26,9
■
( RE—ESTERIFICATION
The re-esterification of fractionated fatty acids with glycerol to produce tri-
glyceride oils with specific properties has been developed commercially to a
considerable extent within recent years. The process is carried out by heating
equivalent quantities of fatty acids and glycerol, with a small amount of catalyst,
to 175-225°C. (347-437°F.). The reaction is conducted under vacuum to remove
vAPOR
scpume.
eirlY §=e
SIWPPING
[OLOM
Sr.e.é/7
4=.•
leAfeR
,r ---------
(
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171
—411-- •-•1 .1
11_
li 1
1i i;)œ.0 VAPOM.W7
Mee .1717,0[05
ft. tOde
i 11i
L13 e3
rcr0
atm.
ceenalan
0,5a1.1Pcy
S.L
fre.0
P
00500000 I
, -! ...® enIrTY
FicunE 43. Continuous fatty-acid distillation plant. ( Courtesy Wurster (Sz Sanger, Inc. )
270
BAIU.EY, A. E. Industrial Oil And Fat Products. Interscience Publishers, New York, 1945.
BAILEY, A. E., R. O. FEUGE, E. A. `KRAEMER, AND S. T. BAUER, Oil and Soap, 20, 129-132,,1943.
BEHR, O. M. Ind. Eng. Chem., 28, 299-301, 1936.
BEwICK, H. A., J. E. CuRRAH AnD F. E. BEAMISH. Anal. Chem., 20, 740-743, 1948.
Blaw-Knox Company, Blaw-Knox Bulletin, 2051, p. 17, 1945.
BoLTON, E. R. J. Soc. Chem. Ind., 46, 444-446T, 1927.
BROCKLESBY, H. N. The Chemistry and Technology of Marine Animai Oils. Fish: Re% Bd.
Can. Bull. 59, 293-294, 1941.
BROCKLESBY, H. N. AND O. F. DENSTEDT. Bull. Biol. Bd. Can. 37, 1-150,1933.
BROCKLESBY, H. N. AND C. C. KuCHÈL. J. Fish. Res. Bd. Can., 4, 174-183, 1938.
BROCKLESBY, H. N. AND L. P. MoORE. Contr. Canad. Biol. Fish., 7, 415-424, 1933.
BROCKLESBY, H. N., W. A. RIDDELL AND K. F. HARDING. Ann. Rep. Biol. Bd. Can. for 1986,
40, 1937.
BRUST, A. Fette u. Self en, 45, 635-636, 1938. ., _ - .
BURGHABDT, O. Ind. Eng. Chem., 23, 800-802, 1931.
BURTON, •D. AND G.. F. ROBERTSHAw: Sulphated Oils and Allied Products. Chémical Publishing
Co., Inc., New York, 1940.
BUXTON, L. O. J. Am. Oil Chem. Soc., 24, 106-116; 1947.
CAmNS; W. A. Can. Chem. Process Ind., 32, 314-317, 1948.
CLAYTON, W., S. BACK, R. 1. JOHNSON AND J. F. MORSE. J. Soc. Chem. Ind., 56, 196-199T,
1937.
COFFEY, S. J. Soc. Chem. Ind., 40, 19-20T, 1921.
DENSTEDT,•O. F. AND H.N. BROCKLESBY. J. B2ol. Bd. Can., 2, 13-40,1936.
DIIGAL, L. C. AND A. CARDIN. J. Fish. Res. Bd. Can., 7,471-489,1949.
Ibid., 8, 189-194,1951.
FAwsrrT, C. J. Soc. Chem. Ind., 7, 552, 1888.
FOREMAN, H. D. AND J. B. BROWN. Oil and Soap, 21, 183-187,-1944.
FRIEND, W. Z. Chem. and Met. Eng., 46,260-262,1939.
GALLAY, W. Can.j. Res., 16B, 6-34,1938.
GLOYER, S. W. Ind. Eng. Chem., 40, 228-236, 1948.
J. Am. Oil Chem. Soc., 26, 162-166, 1949.
HARVEY, E. H. AND H. A. SCHUETTE. I1Ul. Eng. Chem., 23, 675-676, 1931,
HEUBLYUM, R. Peintures, pigments, vernis, 12, 1-3,1935 (C.A. 29, 3537).
KAPOOR, P. C. AND K. B. L. MATHUR. J. Indian Chern. Soc. Ind.. and News. Ed., 8, 94-103,
1945 (C.A. 40, 6273).
KAUFMANrI, H. P., J. BALTES AND P. MARDNER. Fette u. Set f en, 44, 390=394, 1937.
KAUFMANN, H. P. AND M. C. KELLER. Fette u. Self en, 44, 42-47, 1937.
KAUFMANN, H. P. AND P. MARDNER. Fette u. Seifen, 45, 177-179, 1938.
KELETI, C. Can. Chem. Process Ind., 32, 630-632, 1948.
KENYON, R. L., S. W. GLOYER, AND C. C. GEORGIAN. Ind. Eng. Chem., 40, 1162-1170, 1948._
KISTLER, R. E., V. J. MUCKERHEIDE AND L.,D. MEYERS. Oil and Soap, 23, 146-150, 1946.
KLEINSMI7T3, A. W. AND H. R. KRAYBILL. Itd. Eng. Chem., 35, 674-676, 1943.
LASCARAY, L. Fette u. Seifen, 46, 628-632, 1939a.
Ibid.,. 46, 533-536, 1939b.
LISK, G. F. Ind. Eng. Chem., 40, 1671-1683, 1948.
Ibid., 41, 1923-1934, 1949.
LusH, E. J. Ind. Chemist, 3, 249-256, 1927.
MATTIELLO, J. J. AND L. T. WoRg. Nail. Paint, Varnish and Lacquer Assoc. Circ: No. 502„
1936
MATTIL, W. A. Oil and Soap, 21, 197-201, 1944.
MEISTER. Farbeti-Zig., 37, 945-947, 1932 (C.A., 26, 3390). •
OsNos, J. AND J. CoLovisnxov. Masloboino-Zhirovoe Delo, 1932, 23-33, 54-57, 60-73, 1932
, (C.A., 26, 6161:6162). *
PASSINO, H. J. Ind. Eng. Chain., 41, 280-287, 1949.
PRIVETT, A. S., W. D. MCFARLANE AND J. H..GASS. J. Am. Oil Chem. Soc., 24, 204-209, 1947.
Piny-Err, A. S., R. B. PRINGLE AND W. D. MCFARLANE. Oil and Soap, 22, 287-289, 1945.
RIESS, C. Collegium, 1931, 557-588, 1931.
RossmANN, E. A. Angew. Chem., 50, 246-248, 1937.
SUNDERLAND, A. E. Soap, 11 (10), 61-64, 71, 1935; 11. (11), 61-64, 1935; 11 (12), 67-69,
1935.
SwAr«, L. A. In Fish. Ras. Bd. Can. Bull. 59, 262-274, 1941a.
Ibid.., 59, 2747277, 1941b.
TAKANO, M. J. 'Soc. Chem.,Ind. (Japan), Suppl. Binding, 42, 210-212B, 1939.
ri'HomssEN, E. G. AND C. R. KEMP. Modern Soap Making. MacNair-Dorland Co., New York,
pp. 30-32,1937.
VARTERESSIAN, K. A. AND M. R. FENSKE" Ind. Eng. Che/72., 28, 928-933, 1936.
WELWART. Seifensieder-Ztg., 60, 400-401, 1933.
WOCASEK, J J AND J. R. Komi. J. Am. Oil Chem. Soc. 25, 335-337, 1948.
WURSTER, O. H. AND G. J. STOCKMANN. Processing Oils and Fats. Wurster and Sanger, Inc.,
Chicago, 1942.
272
CHAPTER NINE
I. IN NUTRITION
(a) HUMAN FOODS
The digestion and utilization of fats and oils in the body (metabolism) is
treated in some detail in Chapter 4. In the present chapter the term "utilization"
refers to the different ways in which oils are applied.
(i) CANNING. 'OILS
Various fish oils are added to canned fish to improve the product and
increase its acceptability. The two principal types of canning oil are salmon oil
for adding to canned salmon, and -specially processed herring oil or cod-liver
oil for adding to canned sardines, anchovies, and similar fish. ,
When salmon is low in oil content, oil prepared from the same species is
sometimes added during canning. It is essential that this oil be prepared from
fresh material, and that all visceral organs, with the exception of the roe, be
excluded from the raw material. If these precautions a're not observed, the oil
may taint the contents of the can. The oil for this purpose is prepared chiefly
273
from the salmon trimmings (heads, tails, and fins ) but a little roe oil is some-
times also added to improve the colour.
Specially prepared herring oil is used in Norway as a substitute for olive
oil in canning sardines. An important feature of the method of preparing this oil
for use in canning is a slight polymerization, which stabilizes it against rancidity
and also slightly increases both the viscosity and the cloud point. The r.aw herring
oil is first cold cleared, and then alkali refined and filtered with filter aid. It is
next polymerized and finally deodorized by treating, under vacuum, with super-
heated steam. Although full details of the method used in Norway have not been
published, it has been stated to consist in polymerizing the oil at a temperature
of 280°-300°C. (536°-572°F.) for 8 to 12 hours. The following specifications for
polymerized herring oils used in the Norwegian canning industry for the packing
of sardines were reported by Ronold and Taarland in the March, 1947, issue of the
Norwegian Canners Export Journal as cited by Hamm (1947), and from these
specifications certain deductions can be made respecting the polymerization
process.
1. The oil shall be clear, that is, carefully filtered, free from moisture, slime
and other impurities.
2. The colour shall be from pale yellow to golden yellow.
3. The odour and taste shall be dean, good and tenable.
4. Only insignificant amounts of solid fat shall separate with cooling to 6°C.
for three days.
5. The viscosity at 25°C. shall be between 80 and 140 centipoises.
6. The content of free fatty acids calculated as oleic acid) shall not be
over 0.3 gram per 100 grams of oil.
7. The saponification number shall be between 180 and 200.
8. The iodine number ( determined by Wijs method) sha ll be between 95
and 110.
9. The polybromide number shall not be over 2.0 (calculated as grams of
polybromides per 100 grams of oil).
10. The content of unsaponifiable matter shall not be over 1.0 gram per
100 grams of oil.
11. The rancidity number shall not be over 2 red Lovibond units by the
quantitative Kreiss test.
12. Saponification with N/2 alcoholic KOH shall 'produce' a yellow coloured
and not a dark brown coloured mixture.
13. The ash content shall not be over 30 milligrams per liter_ of oil.
The fact that the polybromide number of the canning bils must not be over
2.0 ( specification No. 9) indicates that polymerization is carried to the point
where the highly unsaturated fatty acids in the triglycerides have been com-
bined as polymers.
Since the characteristics of herring oils from northern Europe are fairly
similar to those in othe/ r parts of the world, it would appear from the above
274
TABLE 47. Consumption of fish oils, etc., in the manufacturing industries of Canada during the years 1942-1949.
I
Unit 1942 1943 1944 1945 • 1946 , 1947 1948 1949
of
measure Quantity Value Quantity Value Quantity Value Quantity Value Quantity Value Quantity Value Quantity Value Quantity Value
s' $, $ $ $ $ $ $
Cod oil used in:
Leather tanneries gal. 35,199 30,562 41,372 39,324 34,472 • 32,924 45,424 43,832 30,495 • 28,980 19,408 29,271 22,619 39,152 20,877 33,135
Miscellaneous chemicals lb. 881,461 61,401 1,015,920 97,541 1,298,948 127,050 1,150,245 116,091 963,074 161,284 489,606 75,406 478,594 79,698 404,603 66,041
Cod liver oil used in:
Medicinal and pharmaceutical
preparations gal. 92,029 245,309 92,916 280,085 84,150 262,815 87,769 245,378 88,831 282,992
lb. 902,578 270,707 509,461 168,593 998,053 305,004
-Foods, miscellaneous gal. 9,617 35,434 .
Feeds, stock and poultry gal. 111,359 259,060 Reported under "Other fish ils" in years 1943-1949 in 1.
Cod oil, sulphonated, used in:
_
Leather tanneries gal. 78,690 73,345 82,451 75,329 112,723 110,807 99,210 100,644 99,722 111,390 81,939 107,998 73,825 106,763 115,607 156,976
Fish oil, hydrogenated, used in:
Acids, alkalies, etc. (chiefly) lb. 2,469,588 197,567 2,220,720 199,865 2,064,818 180,672 1,541,490 134,880 736,880 64,477 1,080,000 , 142,020 ' 2,539,740 393,660 , 1,106,270 98,126
Other fish oils used in:
Leather tanneries gal. 48,191 30,599 134,719 114,580 69,056 53,348 125,468 116,810 183,967 180,606 178,171 208,707 -- 119,379 159,695 76,422 103,209
Meat packing industry '
(shortening) lb. • 274,356 25,561 32,982 5,776 8,770,442 794,923 6,744,538 587,711 5,508,599 479,542 -
Paints gal. 116,062 101,742 71,219 50,823 57,886 43,811
lb. 746,083 61,537 300,679 32,298 160,662 23,008 393,838 37,226 370,368 55,128
Soaps lb. 10,568,347 815,908 9,185,949 564,270 6,344,904 412,574 5,834,688 340,897 3,102,738 185,165 4,147,237 327,374 10,565,219 1,443,241 2,199,876 294,187
Feeds, stock and poultry gal. 207,428 271,567 444,908 894,894 -
tons ,--- 2,987 1,382,295 3,033 1,605,038 3,631 1,851,193 3,889 2,207,001 2,444 1,586,734 2,144 1,162,054
Miscellaneous chemicals lb. 2,682,930 174,847 -1,944,115 152,917 1,821,454 132,463 1,045,046 78,824 1,454,722 120,897 1,450,669 134,673 2,188,434 301,569 2,146,090 219,171
Miscellaneous textiles lb. 20,015 3,138 6,769 635 6,791 585 19,895 1,957 38,332 5,073 123,038 29,725 61,539 13,387
Fish oil for refining used in: •
Fish curing and packing gal. 250,150 268,959 214,837 423,018 245,014 216,272 510,615 429,547 308,136 271,265
Whale oil used in: , .
Meat packing industry
(shortening) lb. 7,645,207 762,074 8,147,106 853,059 7,525,935 806,191 10,767,203 ' 1,237,125 13,504,436 1,479,147 18,792,142 2,748,460 25,585,138 5,205,770 7,018,497 1,318,679
Soaps and washing compounds lb. - 177,081 13,483 1,295,396 81,129 1,866,796 101,833 90,843 10,435 221,422 14,772 2,418,698 236,511 380,269 40,065 151,482 23,442
Sperm oil used in:
'Miscellaneous chemicals lb. 1,301,351 124,413 846,643 83,015 335,514 47,840 278,528 36,551 599,141 127,997 398,067 63,585
Seal oil used in:
Meat packing (shortening) lb. - 307,891 - 34,149 1,669,353 144,070 264,930 22,594 1,338,030 115,338 775,092 - 122,954 2,882,963 499,701 661,693 97,662
Soaps and washing compounds lb. 688,381 48,564 305,069 19,032 11,150 378 22,551 2,228 419,723 22,580 107,335 12,495 29,235 2,958
Herring oil used in:
Fish curing and packing gal. 900 1,170 270 511
Meat packing industry lb. 375,020 58,343 1,680,000 233,200 10,747,978 1,115,459
Pilchard oil used in:
Meat packing industry lb. - 287,400 59,205 1,342,570 347,122
'
Other marine oils used in:
Meat packing industry
(shortening) lb. 4,639,167 381,096 7,104,437 655,603 30,000 4,377 5 884,425 s 27,865 165,871 20,556 15,000 3,450
(ii) MARGARINE
Margarine is a solid emulsion of processed milk and hydrogenated oil or
other suitable fat, with small amounts of salt, lecithin, butter flavour ( diacetyl),
and vitamins A and (sometimes ) D incorporated into it. The fat content should
be about 80%. The addition of vitamins A and D to margarine was formerly
not permitted in the United States, although they have been 'added for some years
in Europe, but 'vitamin A equivalent to the amount found in butter is now
allowed. Canada now permits the addition of between 9000 and 45,000 Inter-
national Units of vitamin A and -between 1800 and 9000 International Units of
vitamin D,per pound of margarine (potencies must be declared). The lecithin
acts both as an emulsifying agent, stabilizing 'the emulsion and preventing
"bleeding" of the milk from it, and as an antioxidant, inhibitirig the development
of rancidity.
It might be expected that the fish odour and flavour of fish oils would pre-
clude their use as ,raw materials for margarine manufacture; but the odour and
flavour are due to certain highly unsaturated fatty acids which are converted to
moi'e saturated, non-odorous forms by hydrogenation to the degree necessary
for use in margarine.
275
(iii) COOKING FAT S
Cooking fats are used for ordinary and deep-fat frying . Some oils and fats
decompose at a relatively low temperature, giving off very irritating fumes and
at the same time accumulating non-volatile decomposition products . An oil or
fat to be used for this purpose must thus have a high decomposition temperature,
which is indicated by a high smoking temperature (smoke point) . The smoke
point, which for commercial purposes is always expressed in degrees Fahrenheit,
should be above 375°F . Since the smoke point of fish oils is ordinarily less than
that, such oils must be hydrogenated to be used'as cooking fats . Hydrogenation
also eliminates the characteristic fishy odour and flavour which would otherwise
make them quite unsuitable .
The amounts of different fats and oils used in the United States for the
manufacture of cooking fats, oils, and compounds during the years 1937 to 1944
inclusive are given in table 48. This is compiled from reports of the United States
Bureau of Agricultural Economics .
TAB1,E 48 . Fats and oils (in thousands of pounds) used in the manufacture of cooking
fats, oils, and compounds, in the United States, 1937-1944 .
Cottonseed oil 1,162,596 1,051,347 904,950 823,359 888,733 693,564 572,208 489,880
Soybean oil 90,798 137,133 201,599 212,317 215 ;967 335,555 568,405 620,257
Peanut oil 58,141 52,402 51,713 22,516 81,905 37,817 50,886 67,249
Cdrn oil 1,611 399 1,453 746 62 4,093 6,356 5,393
Linseed oil 1,522 6 - - - - 7,084 30 0
TOTAL DOMESTI C
VEGETABLE2 1,314,668 1,241,287 1,159,715 1,058,938 1,182,667 1,071,029 1,204,939 1,177,079
Tallow, edible 66,278 74,251 56,671 39,595 41,227 55,777 78,552 59,75 2
Olcostearine 29,664 32,845 25,574 16,940 23,103 30,701 29,726 22,39 3
Lard 915 2,825 7,398 16,786 50,7876 61,6326 36,4076 38,7276
Oleo oil 242 291 470 880 1,282 663 2,660 2,69 1
TOTAL ANIMAL 97,099 110,212 90,113 74,201 116,399 148,773 147,345 123,56 5
Fish oils 21,289 16,529 20,321 10,902 6,165 5,750 12,584 2,764
Mariné mammal oils 66 48 12 - - -
TOTAL FAT AND OILS 1,604,841 1,517,299 1,406,318 1,196,424 1,418,109 1,285,259 1,370,625 1,309,03 9
276
( iv) SHORTENING
These are fats used in baking pastry and similar products. Originally lard
was used exclusively, but modern shortenings consist mainly of hydrogenated
fats. Vegetable oils are the principal raw materials, but both whale oil and fish
oils have been included in making shortenings for the bakery trade and have
proven quite satisfactory. Fish oils for use in shortenings are hydrogenated to an
iodine value of 85 to 90.
One of the important properties of a shortening is that it must . be plastic at
room temperature, so that it can be easily mixed with bakery mixes. Plasticity
-
is developed largely by Imeading the shortening after chilling it, but is greatly
improved by making it from several different fats and oils with specific properties,
instead of from only one fat.
The amounts of different fats and oils used in the manufacture of shortenings
in the United States in the years 1938 to 1948 are listed in table 49. These statistics
.are from "Animal and Vegetable Fats and Oils", published by the U.S. Bureau.
of Census, Washington, D.C.
TABLE 49. Oils and fats (in millions of pounds) consumed in the manufacture of shortenings in
• the United States.
Oil or fat 1938 1939 1940 1941 1942 1943 1944 1945 1946 1947 1948
Cottonseed oil 1,051 905 823 889 694 572 489 487 502 300 321
Soybean oil „ 137 202 212 216 336 568 620 683 744 705 708
Palm oil 115 113 33 86 29 0 0 0 0 0 0
Peanut oil 52 52 23 82 38 51 . 61 51 42 65 56
Coconut oil 26 21 18 22 ' 5 0 0 0 17 87 48
Corn oil 0 1 1 0 4 6 5 2 3 3 4
Sesame oil 5 1 0 0 0 0 0 0 0 0 2
Rapeseed oil 1 1 0 0 0 0 0 0 0 0 0
Linseed oil 0 0 0 0 0 7 0 0 0 0 0
Oleostearine 33 26 17 23 31 30 22 24 13 19 15
Edible tallow 66 57 40 41 56 79 60 79 44 44 29
Lard and rendered pork fat 1 7 17 51 62 36 39 23 20 101 114
_
Fish oils 21 20 11 , 6 6 12 3 3 1 0 0
Other oils 1 . 1 1 1 26 8 9 22 7 2 5
1,517 1,406 1,196 1,418 1,287 1,371 1,309 1,375 1,396 1,326 1,302
Oils from marine sources may be used as substitutes for several of the vege-
table oils listed in the above table. Whale, herring or salmon oils could be used
in place of cottonseed oil; beluga blubber oil could replace palm oil.
(b) MEDICINAL USE
Adequate amounts of both vitamins A and D are necessary throughout life
for the normal functioning of the body. Studies of the amounts of vitamin A
277
,
required by humans were made by the Vitamin A Subcommittee of the Accessory
Food Factois Committee in 1945 for the British Ministry of Food, with con-
scientious objectors to military service as the subjects. It was found that a dietary
intake of 2500 International units (I.U.) of vitamin A per day was sufficient for
the maintenance of normal human adults. Remington (1945) gave the adult
human requirement as 5000 U.S.13: units. per day, that for growing children as
1500 to 5000 U.S.P. units, and for pregnant and lactating women as 6000 to 8000
units. The human requirement for vitamin D, unlike that for vitamin A, is
greatest in infancy. It was reported by Escudero (1944) that children of 1 month,
12 months, 22 months and 33 months of age require respectively 250, 1500, 2000
and 500 LU. of vitamin D per day. The vitanlin D requirements of pregnant and
lactating women have been given by Remington (1945) as 400 to 800 I.U. per
day.
Although cod liver oil was for many years the common medicinal source of
vitamins A and D, during the decade from 1930 to 1940 various other oils were
introduced. Halibut liver oil, the vitamin A potency of which is much higher than
that of cod liver oil, was the first of these to be placed on the retail market.
Halibut liver oil was soon followed by other oils, some similar, some lower and
a few higher, in vitamin A potency. The commercial practice of selling oils on
the basis of their vitamin A potency (see below), rather than as individual oils
with individual prices, was developed later. Cod liver oil is an exception to this.
Even though it is much lower in vitamin potency than halibut liver oil and most
other vitamin oils, and the dosage consequently much higher, it was' so well
established as the common medicinal oil before any others were introduced that
,large quantities of it are still sold. The balance between the amounts of vitamins
A and D nàurally occurring in cod liver oils is excellent for providing the body
with the right amounts of each. Halibut liver oil and many other oils, especially
those of the Selachii ( dogfish and sharks) contain proportionally less vitamin D
' in relation to their vitamin A content. To make up for this, synthetic, vitamin D
is added to them. Cod liver oil with synthetic vitamin D is also sold on the retail
markets for medicinal use in cases requiring especially high dosages or vitamin
D. Cod liver oils fortified with small amounts of high-vitamin-A potency fish
liver oils have also been marketed. Most high potency oils, or "concentrates" as
they are called in the trade, are sold to the consumer either in capsules contain-
ing sufficient quantities of both vitamin A and D so that one capsule will provide
a day's requirement, or along with other vitamins in "multiple" vitamin capsules
and special preparations. ,Halibut liver oil is retailed in ordinary liquid forin,
though mostly in capsules, both plain or with added vitamin D.
The liyer oils from fishes of the percomorph family including the tunas,
albacore, and mackerel contain, in addition to a high content of vitamin A,
much more vitamin D than is found in most other fish liver oils. For several
years they were sold as such under the name "Percomorph Liver Oil" or "Oleum
Percomorphum" but during' the last few years they have been almost entirely
displaced, as a source of vitamin D, by synthetic vitamin D, and they are now
278
used siinply as vitamin A "concentrates" in multiple vitamin capsules 'and. other
vitamin preparations. Some 'are also blended with cod liver oil and sold as "Cod
-
The term "feeding oir is used commercially to designate oils used as sources
of vitamins A and D in poultry and animal feeding; it distinguishes them from
"vitamin oils". The latter term refers to oils of higher vitannin potency,, which
are used both in human nutrition ând for blending with non-vitamin oils to
produce blends suita- ble for use as feeding oils.
Cod liver oil, generally of a crude grade, was the first fish oil commonly
used to introduce vitamins A and D into poultry and animal feeds. During the
years between 1930 and 1935 pilchard oil, the oil prepared from whole pilchards,
was tried as a substitute and for some years was widely used, especially in
poultry feeding, since its potencies in both vitamins are near enough to those
of a low grade cod liver oil to allow similar usages. Later the practice
developed of fortifying an oil—usually herring oil—with additional vitamin
A and Da ( the forin of vitamin D active for chicicens—see below) to definite
potencies of each. Dogfish liver oil is usually used as the source of vitamin A.
This oil and synthetic vitamin D3 are,blended with herring, salmon, or pilchard
oils. The latter three, although they contain small amounts of vitamins A and D,
are now regarded as containing no vitamins, and are called "base oils", in making
up feeding-oil blends. The vitamins in them are regarded simply as a factor of
safety in case the feeding oil should lose some of its vitamin potency befoie being
used.
Instead of blending vitamin A oil and synthetic viiamin D3 with a base oil,
some feeding oil producers have, during recent years, been mixing them with a dry
carrier to about the same potency per unit of weight as 'a feeding oil. This is
discussed on page 282.
(i) POULTRY
The use of fish oils as vitamin supplements in poultry feeding is now well
established; but whereas it was formerly customary for farmers themselves to mix
270
the oil into the feed, the trend is now toward the use of mixed feeds into which
,
Ols'son (1949) found that White Leghorn chicks require 250-300 chicic units
of vitamin D per kilogram of feed; Rhode Island Red chicks require 2.7 times
as much, and White Sussex 1.6 times as much.
Bills et al. (1937) showed that not only does the concentration of vitamin D
vary widely in the liver oils of fish of different species, but that there are a
number of different, although closely related, substances with vitamin D activity
occurring in fish oils. They found that, rat unit for rat unit, the vitamin D in the
oil from whole sardines and the liver oils of halibut, round-nosed sole, lingcod,
black sea-bass; and the New England tuna, was similar to cod liver oil vitamin D
- -
in effectiveness for chickens; the vitamin D in the liver oils of white sea-bass,
sablefish (black cod), swordfish, dogfish, and basking shark was more effective
for chickens than the vitamin D of cod liver oil. Several of the tunas, notably
the albacore, striped tuna, California bluefin, and California bonito, were found
to have liv-er oils the vitamin D 6f which was definitely less effective for
chickens 'than for rats. It has long been known that different synthetic forms of
vitamin D differ greatly in their effectiveness, rat unit for rat unit, with chickens;
thus vitamin D3, which is similar to the vitamin D of cod liver oil in its effective-
ness for chickens, is over 30 times as effective for chickens as 'vitamin D2. For
these reasons it is essential that vitamin D potency of materials for feeding to
chickens be determined on chicks. The A.O.A.C. unit is, as indicated above, the
official vitamin D unit on this continent for poultry-feeding materials.
The recommended amounts of vitamins A and D for turkeys are given by
Lloyd and Biely (1947) as 4000 I.U. of vitamin A and 800 A.O.A.C. units of
vitamin D per pound of feed. The relative efficacies of the different forms of
,
vitamin D are not the same in turkeys as in chickens. Both Boucher (1944) and
Bird (1944) found that vitamin D3 is approximately twice as effective for turkeys
as the same number of chick (A.O.A.C.) units of cod liver oil. Thus the A.O.A.C.
unit, which is determined with chicks, is not an accurate measure of the vitamin
D potency for turkeys. However, the recommended amount of 800 A.O.A.C.
units should be adequate, regardless of which form of vitamin D is used. Since
several workere have shown independently that 400 A.O.A.C. units .per day is
280
sufficient for turkey poults, the 800 units would be adequate if a form less active
for turkeys was used. White Holland poults require 700-800 chick units of vitamin
D per kilogram of feed, according to Olsson (1949).
The vitamin D requirements of ducklings were found by Fritz et al. (1941)
to be approximately the same as those of chicks. Peking ducklings were fôund to
require 800 chick units of vitamin D per kilogram of feed, white Italian goslings
require 300 chick units, while goslings having a more rapid growth such as the
Toulouse require more than 350 (Olsson, 1949).
There are several disadvantages in the use of base oils as carriers of vitamins
A and D for poultry feeding, and, in order to overcome"the disadvantages, in-
creasing amounts of those vitamins are being used stabilized on dry carriers to
the same potencies as in feeding oils. These "dry vitamin A and D" premixes are
mixed directly into feeds in the same proportion as the equivalent feeding oils.
The first disadvantage of using the vitamins dissolved in a base oil is`, their
instability, especially that 'of vitamin A, after the oil has been incorporated into
a feed. Another disadvantage is the fact that it is more important for the farmer
to feed his birds additional protein than oil, so the base oil in which the vitamins
are dissolved is generally an unnecessary adjunct to the ration. However, a
diluent of some sort must be employed as it would be impossible to mix into feeds
the more . potent vitamin oils,which are used as the sources of vitamin A, and the.
synthetic vitamin D. Fish body oils have, in the past, been the most commonly
used diluent.,
Dry vitamin D premixes have -been on, the market for some, time, since
vitamin D is the easier. ôf the two to stabilize against oxidation, but later
dry premixes containing both vitamins A and D were introduced. Three
commer.cial, preparations;, of. vitamin D 'on dry carriers for use in mixing
feeds for farm animals in Hungary -were described by Becker (1941). They
consisted of vitamin D2 (calciferol) on barley oilcake or alfalfa meal, and con-
tained from 150 to 800 I.U. of vitamin D per gram. He recommended, however,
that the vitamin D content of such preparations should be from 80 to 100 I.U.
per gram, with the latter figure as'a maximum: A dry vitamin D premix in which
natural or synthetic vitamin D is incorporated into oil-bearing seed particles
from which the oil has been expressed, such as cottonseed or oatmeal flour, was
patented by Broid and Dumbrow of National Oil Products Co. in 1942 (U.S.
patent 2,283,531).
Fritz ei, al. (1942) found that a stable vitamin D.premix can be made by
282 '
first mixing the vitamin D concentrate with soybean meal, and then coating the
particles with either calcium stearate or hydrogenated fat. It is essential that
the impregnated particles should be completely covered by the impervious cdat-
ing, since otherwise it will not give efficient protection. The use of n-propyl
gallate together with j3-aminoethanol bound to a glycerophosphoric radical as
antioxidants for vitamin A in a dry supplement (premix) for poultry and animal
feeds is covered by U.S. patent 2,394,456, granted to Korner and Loomis in 1946
(assigned to the Sihno Chemical Corp.). The dry premix is prepared by dis-
solving 0.1% of n-propyl gallate in a vitamin-containing fish oil at 60°C. (140°F.),
cooling and adding 0.15% of the p-aminoethanol combined with glycerophos-
phate, and stirring until it is dissolved. The treated oil is then stirred into a
coinmercial soybean meal. The stabilizing effect of the second antioxidant is
very small when used alone, but it greatly increased the effect of the n-propyl,
gallate as a stabilizer. It is stated that both are biologically harmless, and are
odourless and tasteleis in thé proportions used.
A method- of stabilizing vitamins A and D in a dry premix is covered by
U.S. patent 2,401,293, granted to Buxton, and Konen of National Oil Products
Co. in 1946. It consists in mixing a concentrate of vitamin A and/or vitamin D
with a crude vegetable oil, and incorporating the product thus obtained into a
vegetable substance having a high affinity for fat, the total amount of fatty
'material incorporated being controlled to yield a substantially non-oily product
containing not more than 30% of fatty material. The vegetable materials into
which the vitamins may be incorporated include wheat . germ presscake flour,
dried distillers grain solubles, and linseed oil presscake. The vegetable oil sub-
sequently added should be one high in antioxidants, but with a low iodine value.
A stabilized dry vitamin A and D preparation is described in a later patent by
the same company (U.S. patent 2,427,520 to Broid and Buxton in 1947). It is
prepared from molasses and syrups, and finely ground vegetable materials mixed
with calcium oxide. The molasses should preferably, although not necessarily,
have a reading between about 43° and 45° Bé. (specific gravity 1.42 to 1.45).
In an example "given, 400 parts of linseed oil meal and 150 parts of powdered
quicklime are thoroughly mixed and de-aerated in a mechanical mixer under a
vacuum of 27 inches; the vacuum is released and 450 parts of molasses containing
10% of fish liver mixed with it is incorporated, and the xnass is dried under
vacuum and ground to a suitable particle size.
In the preparation of dry vitamin A and D premixes there are several factors
which must be considered. The vitamins A and D must be stable both when the
premix is stored as such and also after it has been incorporated into a mixed
feed. Not only must the vitamins be stable against loss of activity, but the oil
containing them, by which they were•introduced into• the premix, must not
"bleed", that is, run out of the carrier. Also the vitamins in the premix must be
as efficiently absorbed and as effective for poultry and animals when it has been
blended into a mixed feed, as the vitamins which are introduced into the feed
by direct addition of feeding oil. Thus, before any new formula for a dry vitamin
283
A and D premix can be used commerdally it must be iested with birds and
animals, preferably the ones for which it is to be used. Finally, the premix must
, not contain any toxic ingredients.
Vitamin A rapidly loses its activity when an oil containing it is dispersed on
powdered materials, especially on finely powdered granular materials. It is soon
inactivated by, for example, the following: calcium carbonate, calcium hypo-
phosphite, rnagnesium citrate, sodium hypophosphite, ferrous sulphate, and ferric
oxide, mineral supplements that might be added to feeds.
Although vitamin A is the less stable of the two, vitamin D is also quite
rapidly destroyed when dispersed on various dry powdered materials, unless
specially stabilized thereon. The losses are greatest on inorganic materials such
as calcium carbonate, oyster shell, sand, salt, kaolin, or fuller's earth, the different
forms of vitamin D apparently being equally susceptible to destruction wheri
thus dispersed. Fritz et al. (1942) found that vitamin D is far more stable on
some of the common dry ingredients of poultry feeds than on others. Thus the
vitamin D of a high potency fish liver oil concentrate rapidly lost its activity
when dispersed,on various mineral substances, sucrose or dried whey, but it was
very stable on soybean meal, ground yellow corn, and on "dried stick", which is
the residue left after drying "stick water"—the aqueous effluent from fish re-
duction plants. The stability was intermediate on dried skim milk and on liver
meal. Addition of smaller amounts of a mineral mixture used in poultry feeds,
or of calcium carbonate or dried whey to a premix of the fish liver oil and ground
yellow corn caused rapid loss of activity; some loss of vitamin D activity occurred
when the mineral mixture or dried whey was added to a premix of the fish
liver oil and soybean meal; but no change in the vitamin D potency took place,
over a four-month period, when 25% calcium carbonate was added to the soy-
bean meal premix. Milby and Thompson (1944) found that vitamin D premixed
vvith calcium carbonate and stored for three and a half weeks before incorpo-
rating it into a poultry ration lost over half of its activity, and storage for 12
weeks caused almost complete 'loss of activity. When vitamin D was s premixed
with ground barley, alfalfa leaf meal, meat and bone scraps, cottonseed meal,
soybean meal, dried buttermilk and salt, each separately, and the premixes were
stored separately for 12 weekd before mixing into the ration, little or no vitamin •
D activity was lost.
With regard to the ability of the birds or animals to absorb and uiili7e the
vitamins, it should be pointed out that due to the phytin which it contains too
much oatmeal in the ration inhibits the effectiveness of vitamin D. It has also
been reported (Hauge, Hilton and Wilbur, 1937) that soybeans contain a factor
which decreases the effectiveness of the vitamin A in the ration of cows. Others
have since carried out similar experiments with soybeans, but have not found
this inhibitory effect on the utilization of vitamin A.
285
A process patented by Wechslér and Dumbrow of National Oil Products (U .S .
patent 2,276,531; 1942) consists in partial saponification of a vitamin-containing
oil, such as cod liver oil, .with potassium hydroxide . Another watér-dispersible
vitamin composition was patented by Lipsius, also of the National Oil Products
Co ., in 1943 (U .S . patent 2,311,554) . The vitamins are mixed with a vehicle
prepared by refluxing ethyl alcohol for about an hour with a small proportion'of
gum arabic or the like . The use of this vehicle with vitamins A, B, C, D, and G .
is éovered in the patent .'Vitàmin A and D emulsions suitablé for u"se with stock
and poultry feeds were prepared by Lubarsky of the Vitamol Co. (U .S . patent .
2,321,400 ; 1943) by emulsifying a fish liver oil concentrate with blackstrap
molasses . British patent 561,179, granted to, M. Talbott in 1944, describes the :
preparation of a vitamins A- and D-containing emulsion by agitating togèther
under ,vacuum a erude,sugar syrup or molasses and materials containing the,
fat-soluble vitamins, such -as fish liver oil or a concentrate therefrom, artificially
activated forms of vitamin D, and so on .
A purely mechanical method of dispersing a vitamin oil in water for in-
corporation into farm feeds is used in the procéss covered by U .S . patent-
2,395,067 granted to Richardson of - the California Packing Co. in .1946 . The oil
containing, vitamins A and D' at relatively high- potencies is emulsified with
water by a special device as it is added to the feed into which it is being incorpo-
rated. Enough water to distribute the oil efficiently in the feed is used ., This oil
amounts to less than 1~/0 of the weight of the feed, so that the oil content of the
latter is kept low . I
II . IN INDUSTR Y
The term detergent means simply "cleansing agent" . Soaps° are by far the
most commonly used detergents, but others have been developed for special
purposes ; they will be discussed separately below .
(i) soAP s
As described in Chapters 5 and 8, the treatment of fats or fatty,oils with
sufficient alkali under' suitable conditions results in the formation of soap. Fish
oils are, as was stated, hydrogenated to an iodine value of 70 to 80 for use in
soap . Hydrogenating not only hardens the oil, but also eliminates the fishy odour .
Prior to 1940 whale oil ( except from the sperm whale) was much more widely
used than fish oils for the manufacture of soap, but during the war the shortage
-of whale oil and other oils previously used in soapmaking resulted in a consider-
able increase in--the use of fish oils for that purpose . In 1946 over three million
pounds of herring and pilchard oils (including . the stearine from them) were
used in .Canada for soap manufacture . Commercial salmon oil can also be used
for this purpose . Fish oil stearine is used to a greater extent than fish oil itself
in the soap industry, since it requires very littlehydrogenating before makin g
286
into soap, and furthermore there are fewer other outlets for it than for the liquid
portion of the oil. The effects of hydrogenation, ipolyinerization, and combined
polymerization and hydrogenation of pilchard oil on the detergent efficiency of
soap made from it, and also the effects of soap concentration, temperature and
time of washing, were studied .by Brocklesby, Riddell, and Rogers (1941). For
the washing tests they used pieces of cotton sheeting soiled under uniform
conditions with a mixture of carbon black, Nujol and a hardened fat in carbon.
tetrachloride. These were washed in a machine which gave concordant results
on corresponding samples. The amount of cleansing was measured by means of
40 60
Minutes Hours Polymerized
15
13
II
2 2
Stage of HydrOgenation Stage of Hydrogenation
YrcunE 44. Effect of various factors on the washing efficiency (L 1 —L2 ) of pilchard-oil soap.
287
a reflection photometer, using a photoelectric cell to measure the reflected
light. The cell was of the same , type as used in the Evelyn colorimeter, and the
readings were observed on a similar galvanometer. Readings were taken on the
test pieces of cloth before and after washing, the efficiency of washing being
recorded in terms of the difference L, — L, of the "L value" where L = optical
density = 2 — log G, G being the galvanometer reading. The results are shown
in fig. 44.
There was little effect in varying the concentration of soap from 0.1 to 1.0%,
but beyond that there was a decrease in washing efficiency, and for these tests
the concentration of 0.25% was adopted, Similarly the temperature of washing
caused little difference from 25° to 40°C. (77° to 104°F.), vvith a marked de-
crease in efficiency above these temperatures when the soap from the mixed,
fatty acids of pilchard oil was used. Washing for varying lengths of time showed
a preliminary rapid increase in, whiteness up to 20 minutes and with longer
washing a steady but slower whitening, and on the basis of this information a
washing time of 30 minutes was adopted.
Polymerization decreased the detergent value of soaps from such an oil as
compared with the raw oil, hot there appeared to be little difference in value as
- the polymerization was continued from 4 to 24 hours. The results of washing with
soaps prepared from pilchard oil polymerized for varying lengths of time are
shown in fig. 44d.
The detergent efficiency of the soap was increased by hydrogenation of the
oil from which it was made, until the highly unsaturated fatty acids had been
reduced to the mono-unsaturated stage, after which further hydrogenation de-
creased the solubility to such an extent that the soaps obtained were not so effective
• in washing. However, properly controlled hydrogenation of fish oils may be used
to produce a soap stock which can be used to advantage, when blended with
other oils, for the production of laundry soaps.
The effect of hydrogenation of the polymerized oils was also studied and,
while the results were not as conclusive as might be desired, there appeared to
be little change in the value of the soaps as detergents', as compared with the
results of hydrogenation of unpolymerized pilchard oil. The results of these tests
are shown in fig. 44e and f, where two stages of hydrogenation are indicated.
The first stage was carried to the extent that all highly unsaturated acids should
be removed, and the second stage was such that only monoethylenic bonds should
remain in any fatty acid residue.
In commercial practice the introduction of antioxidants to prevent rancidity
has increased the stability of soap to aa, considerable extent and many individual
compounds and types of compounds have been patented for this purpoie.
Catalysis of oxidation due to traces of copper and iron from the boiling
kettles has been largely eliminated by the use of nickel or stainless steel in the
fabrication of soap-boiling equipment.
For descriptions of the various ldnds of soap which are produced com-
mercially the reader is referred to Bailey . (1945).
288
(ii) SPECIAL DETERGENTS ,
Fish oils and other marine animal oils can be used in the preparation of
.several different types of non-soap detergents, which are formed by introducing
various chemical groups into fatty compounds to increase their solubility and,
otherwise modify their properties. The chemical groups most commonly employed
are sulphate and sulphonate; others include hydroxyl, amine and substituted,
alnine, amide and substituted amide. There are many different kinds of non-
soap detergents and detergents in which soap forms only a minor part, but only
type exanriples will be given here. For example the sodium alkyl sulphates,
which are used for washing with hard water, are made by sulphating fatty
alcohols and neutralizing the product with sodium hydroxide. The fatty alcohols,
used can be prepared by the saponification of sperm oil, or by the reduction of
fatty acids (page 118). Another type of hard-water detergent is described in
German patent 745,555, which was granted to A. Doser, of the I. G. Farbenin-
dustrie A.G., in 1943. It consists of a mixture of high-molecular-weight hydroxy-
alkylated. amides of aliphatic chlorobenzylated amino-sulphonic ,acids. Since
some fatty acids prepared from fish oils are highly unsaturated, thus allowing
the introduction of more of the solubilizing.hydroxyl groups than into fatty
acids from other sources, these fish oil fatty acids should be particularly suitable
for preparation of such hydroxylated products. A detergent composition for use
in bard water, patented by J. Cunder of the National Oil Products Co. in 1947
(U.S. patent 2,414,452), consists principally of sulphated fatty materials with a
smaller proportion of soaps of high-molecular-weight fatty acids, such as those
from hydrogenated fish oil. A typical composition given as an example in the
patent was 54% highly sulphated oleic acid (moisture 38% on total oil, SO3 15.5ojo '
on dry weight of oil), 6% caustic soda (50% aq.), 4% sodium resinate
(anhydrous powder), 36% sodium soap (anhydrous powder, from hydrogenated -
sardine oil with an iodine value of 8).
A dry-cleaning composition prepared from cetyl alcohol, or other ingredients,
was patented by L. H. Flett of Allied Chemical and Dye Corp. in 1943 (U.S.
2,290,870). It is the ammonium, alkali metal, alkaline earth metal or "organic
ammonium" salt of a sulphonated aliphatic fafty alcohol such, as cetyl alcohol
or lauryl alcohol. This product is used in an emulsion of water in a volatile dry-
cleaning solvent.
(b) PAINTS AND VARNISHES
(i) USES OF FISH OILS IN PAINTS AND VARNISI3ES -
Practically all fish oils will absorb oxygen on exposure to air, and certain
such oils (notably those from menhaden, California sardine, and Canadian
pilchard) will eventually dry to a solid. film. The last=named was the only Cana-
dian fish oil used to any great extent in paints, approximately 275,000 lb.: being
used in Canada during the year 194G. The cold-cleared but otherwise untreated
oils are vely slow drying, and give a film which is rather soft and "tacky" (slightly
sticky). When heat-bodied they dry faster and give a harder film than the raw
289
oils. These properties are all made use 'of in the application of fish oils in paint
manufacture.
Lightly cold-cleared pilchai'd oil is used in smoke-stack paints, in which it ,
stands up to the heat better than other drying oils such as linseed oil. It is also
used in paints for structural steel and other applications where rust prevention
is a primary consideration. It may be used by itself or mixed with tung oil or
linseed oil, or with both.
Pilchard oil is also used along with linseed oil in house paints. It slows down
the rate of drying (Mattil, 1944) and hence assists in "levelling" or eliminating
brush marks and other irregularities from the finish. For this particular appli-
cation, and for others requiring an oil which will dry to a hard, non-tacky film,
pilchard oil is bodied under vacuum. By this means the oil is bodied with a mini-
mum of oxidation, so there is less polymer cloud (page 127) in it than in oil
bodied by blowing or by heating in an open kettle; hence the resulting film is
superior. Furthermore, the vacuum assists in removing non-drying constituents,
and in deodorizing the oil. Driers (page 122) are generally incorporated in
bodied pilchard oil during the heat treatment.
- There are various types of varnishes, the principal types being the oil varn-
ishes and the spirit varnishes. The oil varnishes contain a drying oil such as boiled
linseed, tung or pilchard oil, resins, and a thinner such as turpentine; spirit
varnishes contain resins and a volatile solvent. Thus the only application of fish
oils in varnishes is in the former type. For this purpose pilchard oil, after cold
clearing, may be steam distilled under vacuum to remove the non-drying con-
stituents; at the same time it is very heavily bodied. Very poor yields are obtained
in this process, which limits the usefulness of pilchard oil as a varnish component.
Factices (sulphurized oils) are also used in oil varnishes to some extent.
A recently developed rust-proof paint, which can be applied directly as a
priming coat over a rusted surface, contains fish oil as its base. Before incor-
porating into the paint, the oil is specially treated to eliminate, the fishy odour
and to °therm, . ise improve its properties.
The processes of segregating, fish oils by solvents, or of converting to fatty
acids and then fractionally distilling and re-esterifying these (pages 264-270), have
been developed largely within recent years as a commercial means of separating
them into drying and non-drying fractions. The drying fraction is used as a sub-
stitute for linseed or tung oil in paints and varnishes; the non-drying fractions
can be used for such purposes as the manufacture of shortening or soap.
Pilchard oil is used in shingle stain. Salmon oil can be substituted for soy-
bean oil, which is used in baked enamels and to a small extent in other paints.
Experimental results on weathering and other tests of fish oil paints, as
carried out over several years at these laboratories by Brocklesby and Denstedt,
were described quite fully on pages 320 to 345 of the previous edition of this
Bulletin. These details have not been included in the present edition; multilithed
reproductions of these pages can be obtained by writing to the Pacific Fisheries
Experimental Station, Vancouver, B.C.
290
(ff ) INFLUENCE OF VARIOUS MAIERLUS ON THE DRYING OF PILCHARD OIL
The drying of an oil to form a paint film is, as mentioned in a previous 'sec-
tion, the result of oxidation of the oil when spread on a surface in a thin layer.
The influence of various substances On the oxygen absorption of raw . pilchard
oil under such conditions was studied by Denstedt and Brocklesby (1935).
Although bodied oils are used for paints, this work with raw oils is indicative of
the relative effects of the various substances on the rate of drying. Driers were
prepared by making soàps of pilchard-oil fatty acids and various metals. These
metallic soaps were made by adding solutions of inorganic salts of the different
metals to aqueous solutions of the potassium soaps of pilchard oil fatty acids. The
soaps precipitated out, some as hard, horny masses, others in a more spongy form.
These soaps were then dissolved in pilchard oil ( about 65 grams of the moist
soap in 270 grams of oil) by heating in an inert atmosphere for two hours at
160°C. (320°F.). Relatively few showed any outstanding effects. The most active
were the soaps of cobalt and manganese, foll6wed by copper, iron, cerium,
aluminium, and lead. Since cobalt and manganese showed so much superiority
in catalytic activity, tests were made to find optimal concentrations and tempera-
tures of incorporation. The results showed that the maximal effects were given
by amounts of soap corresponding to approximately 0.05% cobalt oxide and
from 0.15 to 0.20% manganese oxide incorporated in the oil at a temperature of
125°C. (257°F.).
. Some pigments used in paint manufacture have an effect on the rate of
oxidation of the oil vehicle. In some cases this is due to. adsorption of the drier
by the pigment, while in others the pigment itself may exert an accelerating
action. This tendency was investigated by thoroughly grinding , 10 grams of the
pigment in 100 grams of pilchard oil, heating the mixture for 15 minutes at 160°C.
(320°F.), cooling and determining the oxygen absorption in the usual manner.
In general, the results were similar to those obtained with linseed oil. The
adsorptive effect of inert materials was shown by treating pilchard oil containing
cobalt and manganese "driers" with Filtrol. If the linoleates of these metals
are dissolved in the oil, little if any of the metallic soap is removed by the
Filtrol; but if small amounts of the oxides are incorporated in thd'oil by heating,
they become colloidally dispersed forming clear solutions from which the oxides
can be removed by treatment with Filtrol. ' ,
Cobalt and manganese surpass all common metals in their activity as drying
catalysts. Cobalt is superior in some ways to manganese. It is more active as a
, drier, causes less darkening, and produces harder, less tacky films. On account
of their activity both these metals sometimes cause surface or "skin" drying.
Lead, cerium, iron, and copper are in a class by themselves as drying catalysts
for pilchard oil because of certain effects they have on gelation and solidification.
Although driers prepared from these metals eliminate the induction period (time
during which oxygen is very slowly absorbed at the beginning of the oxiciation),,
they have little effect on the rate of subsequent oxygen absorption. They cause
a rather rapid increase in viscosity to the stage where the film is ahnost semi-
- 291
solid. After remaining in this state for some time the film solidifies rather abruptly.
This'is particularly noticeable with cerium driers. Copper and iron tend to pro-
mote disintegration of the dried film, and -hence cerium and` lea.d are the only
driers which can be used satisfactorily to prômote-uniform drying and to,counter-
act skin, drying. Antimony, nickel and tin showed a slight tendency to harden the
film but ,not immediately after drying.
A. Hardness
Films made from raw and cold-cleared pilchard .oil are inferior in hardness
and tensile' strength to those made from lins-eed oil. On the other hand the former
possess greater flexibility and ,stretching capacity than do Éhe latter. Unfortun-
ately any treatment that improves hardness usually detràcts from flexibility.
Another defect of fish-oil films is their tackiness, which persists even when driers
are used. Films made from fish oil alone therefore collect dust rapidly and become
dull. Softness 'and tackiness have a common origin in the incompleteness of film
structure which is due to the presence of excess amounts of non-drying com-
ponents. ,
The effects of various driers on the relative hardness of pilchard-oil films
were 'investigated in these laboratories. Cerium and cobalt used together gave
the hardest film of all the driers tested. It is interesting to note that cobalt lino-
leate gave a much harder film than the cobalt soaps of pilchard oil fatty acids,
The hardening effect of ferrous sulphate on films is well known to paint tech-
nologists.
- Treatment of pilchard oil with sulphur dioxide gas accelerates drying, most
films becoming dust-dry in about two hours less than the untreated samples.
The hardness of the resulting films is about 100% greater than those of the un-
treated. However, 'films, of sulphur-dioxide-treated pilchard oil are stiffer and
more easily, cracked on bending, being only about two-thirds as durable as the
untreated. Oven baking of' films is a method of improving hardness and reducing
tackiness, with obvious limits of application.
011ClOih is a coitein .cloth -coated on one side with a mixture of drying oils
and a filler such as whiting dr China 'whiting. It is stitnewhat similar to flooreloth -
ex. cept that it is' thinner and far more flexible, and is usually varnished or waxed
to giVe it a rMire àloSsy surface. Its principal uses are for covering 'Shelves, tables,
a'rul -walls. in Places 'where special protection is needed. The flex'ibility is attained
partly by the .use of certain Proportions of suitably bodied pilchard or other fish
oil, and partly bÿ the use of plactieizers such as solid fats or fatty acids.
'Pilchard 'urid 'similar fish: oilS can be used for the manufactûre of patént
leather in miteh the s-ame-way as in 'oilcloth, but using as a base a Specially pre-
pà.red leather instead of cloth..
(d) OILED FABRICS AND SIMILAR MATERIALS
(1) WATERPROOFED FABRICS . .
' These are madie„ by thoroughly impregnating.fabric with a drying :oil-or a
mixture of drying oils. Several-successive applications of dry-ing oil may .he
made, allowing eaeh, to dry before' applying the next. Silks and linens are the-
fiibrics usually used as the base, although .cotton iS sometimes :u sed. Highly un-
saturated fish oils are partidularly suitable for this purpose. ,They .form 'a film
which is practically 'n6n4acky, .and the oiled fabries.made from thern are more
flékible and less'prone to crack than those made.froin linseed, tung, or perilla oils.
Fabrics treated With cold-elea:red pilchard oil with,no chier added appear to stand
uP better to long expoSurelô wet weather than those treated with similar oil con-
taining small arhounts of cobalt or manganese driers. Samples of oiled-fabrics pre-
pared. .in -these labôratories . from pilchard and linseed oil were examined over a
period- of five y. ears: Fabrics oiled with linseedôil became .brittle after a period of
,
about one'year,. and could stand very little handling without cracking. A sample of
silk oiled with cold-cleared pilchard oil without driers was still soft and pliable .
after a period of five years. A similar sample containing a small amount of cobalt
drier was slightly discoloured, and more brittle than the one without any drier.
This conSists' iii-Ltréating the jute with. an eniulsion of oil and water before
Carding and 'Spinning, tô soften and hibricate the fibérs;Whale and fish oils were
formerly-uSed for this purpose, but mineral ôfiS haVelo a large extent replaeed
fatty-oils, partly because they are cheaper, and partly* because they do not turn
rancid, Spetin ôil should; hoWeVer; be more satisfactory than Mineral 'oils ; because
if cati be more 'easily emillsified, thereby allOwing better wetting of the- fibres.
FINISHING,,COTTON,' ETC. •
• - A' very small amount .sulphonated sperm or seal: oil is applied to the
. surface of both-Cotton and rayon thread during spinning. This is called a finishing
oil; although its ftmétion is to act as .a .lubricant for the thread. Fish 'oils are
rarely if ever Used for this purpose.
296
(iv) OILED FISHING GEAR
Oiled cords and threads, as used in fishing tackle and .the like, are usually
made with a raw linseed oil, applied without any driers but dried in cabinets,
thoroughly aired and heated to 100° to 150°C . (212°=302°F .) . Heavÿ-pressed
pilchard oil can be utilized to advantage in this case asthe elasticity and extensi-
bility of the oil film prevents cracking. The steam-distilled polymeiized product
from pilchard oil, when dissolved in a suitable solvent such, as dipentene, is also
of value for oiled cords, having the added advantage of producing a waterproof
filin that is `still resistant to cracking . In the treatment of textile fishing nets
cuprous oxide has found extensive use, This material is usually incorporated in
a homogeneous' mixture, of which tar is a common constituent . Experiments with
the use of certain amounts of fish oils showed that they helped to, form a mixture
that could be applied easily, but there was some evidénce that they diminishè d
the strepgth of the twine .
in Europe, tanned cotton fishing nets have been treated with shark liver oils
contàiriing largé amounts of unshponifiable matter (chiefly squalene) . The results
are stated to be similar to those 'in which linseéd oil is used .
( f ) Coim. Oas
^ , _ .
Sand cores are used for forming the cavities in iron or steel' castings, as for
instance the hollow sections of steam or hot-water radiators. The core is set in the
sand mould and the molten metal run in between them to form the shèll. Altlioûgh
many types of cores are used; sand cores find the widest application. These cores
consist of sharp-grained sand mixed with a drying or semi-drying oil. The mixture
is moulded in a wooden pattern and baked in an oven to oxidize the oil which
dries through polymerization and oxidation to bind the-sand particles together
into a solid mass. The sand is usually dampened with about 6% of water to
facilitate mixing of the oil. A water-soluble binder such as casein or dextrin is
also used to 'impart some strength to the core before it is baked. The baking of
^ 298
the core simulates in many respects the baking of oil-varnish films, and an oil or
mixture of oils that gives a firm, hard, baked-varnish film will usually be found
satisfactory for core-oil manufacture. Linseed oil was formerly regarded as the
standard material for cores, but during recent years other oils including fish oils
have been used.
Core manufacture is not fully standardized and consequently many foundries
have their own ideas as to what constitutes a satisfactory cure; but in general the
following characteristics are desirable. The core should have mechanical strength.
Transverse strength when measured by breaking a bar 1 inch sqare and 8 inches
long supported on 6-inch centres should be from 25 to 50 pounds per ,square inch.
Tensile strength as measured on a standard cement tester should run from 150 to
225 pounds per square inch. It is claimed that low permeability in sand cores gives
a better finish to the casting. In practice the cores are sufficiently vented to the
outside to permit egress of gases, but a certain permeability is required to allow
the gases to reach the vents and thus prevent the formation of gas pockets.
Finally, although the time required for baking is not of paramount importance,
a quick-baking core allows faster production and a certain saving in heat require-
Ments.
Although linseed oil has been used for the base of core oils for many years,
efforts to reduce the cost of such core oils have resulted in mixtures of linseed
with other vegetable oils, resins and mineral oils being marketed. A satisfactory
core oil is made, according to U.S. patent 1,822,411 granted to E. H. McCardle
in 1931, by reacting resin glyceryl ester with a semi-drying oil haying an iodine
value of 100 or over at a temperature between 260 0 and 305°C. (500 0 and
580°F.). Glyceryl esters of the highly unsaturated fatty acids of fish oils (Arineur
and Company's Neo-fat No. 19) are also recommended as a core oil.
Since it is possible to produce hard films by baking pilchard-oil films, it is
reasonable to suppose that pilchard oil would be a suitable oil for core maldng.
Also, since raw pilchard oil films are softer than those of linseed oil, it might be
expected that this characteristic would be reflected in the nature of pilchard-011
cores. Experimental work done in these and other laboratories fully confirm sand
these expectations. Details of the results of many of these experiments were
described quite fully on pages 349 to 352 of the previous edition of this Bulletin.
i'hese details have not been included in the present edition; multilithed reprà-
ductions of these pages can be obtained by writing to the Pacific Fisheries
Experimental Station, Vancouver, B.C.
Balced pilchard-011 films can be made as hard and strong as linseed-oil films
and it should be possible to get cores of satisfactory strength when made with
this oil. The fact that factory-made cores containing pilchard oil are as strong as
linseed-oil cores made up with the same sand and baked under similar conditions
shows that the baking technique is of some importance. 'Also it has been sug-
gested that pilchard oil should be mixed with the sand at temperatures slightly
higher than room temperature. It should be remembered that tensile- and
transverse-strength measurements are nUt the only criteria of judging satisfactory
299
cores. Many of the pilchard-oil cores made during the experiments. were judged
to be satisfactory by practical core makers. Cores that are too hard, are som'e-
times difficult to remove from the casting. Given a certain degree of hardness,
the practical core maker seems to be particularly interested in the permeability
and friability. The latter characteristic determines the resistance to crumbling
and therefore the retention of sharp edges. In this respect pilchard-ou l cores
were found to be as satisfactory as either linseed- or perilla-oil cores.
(g) RUBBER MANUFACTURE
STEABIC ACID SUBSTITUTES
Large quantities of stearic acid, or stearic acid substitutes are used in rubber
manufacture. Formerly just stearic acid was used, but within recent years the
fatty acids of fully hydrogenated fish oils have been used instead to a consider-
able extent. Approximately 165,000 lb. of fully hydrogenated herring and pilchard
oils (including the ste,arine from them) was used by the rubber industry in
Canada during the year 1946. Simple hydrolysis of the fully hydrogenated fish
oils yields the stearic acid substitute. The subsequent pressing which is necessary
with ordinary stearic acid to remove the liquid fatty acids is not necessary since;
if completely hydrogenated, there are no liquid fatty acids present.
Stearic acid is not unique in its rubber-compounding properties. Other
saturated fatty acids with fewer carbon atoms, such as lauric, myristic, and
palmitic acids have been found satisfactory. Fatty acids of higher carbon number,
have also been found to be efficient. As shown in Chapter 2 fish oils contain
unsaturated fatty acids of high carbon number and when such acids are saturated
with hydrogen so that the iodine value is 10 or less, it has been found both
experimentally, and in practice that they are as efficient, pound for pound, as
double-pressed stearic acid. Furthermore, the hydrogenation process makes
300
possible production of a more saturated product of more uniform quality than,
is possible. by the .physical process of cold pressing. The lower content of un-
saturated fatty acids favours the aging of the rubber with less tendency to bloom.
Cônsequently fatty acids from 'hydrogenated marine oils are recognized as
standard materials for rubber processing.
Hydrogenated fish-oil fatty acids have been prepared:.in these laboratories
and the products tested by the National Research Laboratories,in Ottawa through
the..courtesy of Dr. G. S. Whitby. Table 50 shows the characteristics of ,the
samples tested. Commenting on the rubber-compounding tests _made on these.
samples, the National Research Council reports: "It cap be stated that Nos. '1
and, 2 are slightly inferior and that.. 3 and 4 are about equal with the advantage,,
if any,_.in favour of ntimber 3". The report, stàtes -further as a conclusion: "AlJ
the samples of hydrogenated pilchard oil fatty acids submitted are. satisfactoiÿ;
for use in rubber compounding, number 3 being the best.and the one rriost likely
to find acceptançé by the rubber industry". •
Canadian. fish oils suitable for the manufacture of hyd'rogenated fatty acids
for rubber manufacture include pilchard, herring, halibut head, and salmon oils.-.
All these oils are relatively low in unsaponifiable, matter; when almost.:,completel.y;
hydrôgenated they yield ;fatty acids..with, the titre points - showA.in table The
relatiônship, of titre to coiripositi,onhas already -been discussed on page_156,,
All these- hy.drogenated fatty acids meet the usual specifications . demanded^
by, the rubber_ industrry,,in respect. to unsaturation, titré point, unsaponifiàbie
matter and saponifiçation_ value.,
TABLE 51.. Titres of fatty acids from hydrogenated B.C. fisli oils. ..
Herring Stalmon• .
oil oil
.., .
Iodine value . . .. . . . . . : . . . :'. . . . . . . . A.4 1.4
i
Titre point (°C.) . . . . . . . . : . . . . . : : 53.5 55.8'7'
Cutting oils are applied to the'tools for thé cutting, drilling, or machining
of metals, They have a number of functions, chief of which are to lubricate and
çoôl the cutting edge; they also serve to wash away the particles of detached
métal. Although there are a large number of cutting oils in use, they may be
divided into two generâl types, the so-called soluble or emulsifying oils; and
the straight non-emulsifying oils. According to Huffman, Harding, and Oldaére
(19M) thé fundamen'tal characteristics to be considered in selecting an oil of
either of these types are as follows: soluble cutting oils (1) ability to emulsify,
(2) tendency to rémain emulsified, and (3) tendency to prevent corrosion (such
as rusting) and give a satisfactory finish; non-emulsi f ying cutting oils (1) amount
and nature; of the saponifiable part of the oil, and (2) amount of combined
.sulphur. ,
In the manufacture of soluble cutting oils, mineral oils are mixed with
fatty oils, fatty açids,. alkali. and water. Resin acids are sometimes used in the
place of fatty acids. Water is usually added before immediate use, the quantity,
.added depending upon the nature of the emulsion required. Emulsifying agents
-other than alkali soaps are sometimes used; these usually consist of sulphonated
:fish oils. in a typical formula 9 gallons of mineral oil,,3 gâllons of resin oil and
1 gallon of oleic acid are mixed with 4 ounces of sodium hydroxide dissolved
in lquart of water and a quart of -alcohol. Water is then added to the mixture
:as required. Practically all emulsifying oils contain the sodium, potassium or
'.ammonium soaps of oleic acid and for this purpose the fatty acids from partially
-hydrogenated fish oil should prove satisfactory. The main consideration is that
the alkali soap should not tend to precipitate out and should- give a good emulsion
-with the mineral oil.
Lard oil was for many years the standard cutting oil, but various substitutes
are now used. Non-emulsifying cutting oils are usually mixtures of a fatty oil
: â.nd mineral ôils with or without free or combined sulphur. The sulphur is coin-
-monly combined with the lard oil or other fatty oil and the sulphurized product
. dissolved in the mineral oil. A heavy-duty cutting oil is made as follows: 26 parts
'by weight of herring oil are mixed with 10 parts of sulphur and heated to 150°C.
( about 300°F. ) until all the sulphur is combined. A soft rubbery mass, a form
. of factice (page 134), is produced, which is then dissolved in 80 parts' of mineral
<oil by heating to about 65°C. (150°F.)-, Other unsaturatëd fish oils may be used
304 -
in place of herring oil; experiments in thesnlaboratories showed pilchard stearine
(iodine value about 120) to be suitable for this . purpose. Such sulphurized fish
oils are dissolved in mineral oils usually in amounts up to 10%. This type of
lubricant is suitable for iron and steel cutting but may not be used on brass
owing to the action of the sulphur on the copper.
Thread-cutting oils are sometimes made from certain .marine oils. A typical
oil for this purpose is made by mixing 20 parts by weight of whale oil with 5
parts of tallow oil and 75 parts of mineral oil. In such mixtures the oiliness factor
is of extreme importance and the use of fatty oils is practically esSential: Various
fish oils may be used in place of whale oil, particularly those of medium un-
saturation. Any tendency towards rancidity may be prevented by the use of
suitable antioxidants.
A stainless cutting oil can be made by adding 0.5 to 1.0% lecithin to an
oil prepared from sulphurized sperm and petroleum oil (U.S. patent 2,412,131
by T. W. Culmer, 1946, to Ohio Oil Corp.). The lecithin prevents the active
sulphur from causing stains.
Wire drawing compounds are used to lubricate and cool the dies used in
that imecess, so they are similar in function to cutting oils, and Will be included
here. A drawing compound suitable for use in various metal-forming operations
. was patented by E. A. Nill in 1943 (U.S. patent 2,326,387, to the H. A. Mont-
gomery Co.). The principal component was sulphonated tall oil, but it contained
also from 10 to 30% of sulphonated sperm oil to Make it more plastic. The
compound thus prepared can be used with mineral oil, water, or other admixtures.
iv) MISCELLANEOUS LUBRICANTS
(
The jaw oil of porpoises and dolphins has for many years been -used_ as a
lubricant for watches and other fine instruments. These oils have the properties
of great oiliness and low viscosity; they remain liquid at very low temperatures,
and they are chemically stable at relatively high temperatures—that is, they are
non-gumming. A similar oil can be preparecP from thé jaw lobes of the beluga,:
Sperm oil from which the spermaceti wax has been removed is used as a
lubricant for high-speed spindles and looms. This oil shows very little tendency
to oxidize when exposed to air and has a very low viscosity, with high "oiliness".
Ratfish liver oil is' used by many fishermen and others on the coast of British
Columbia as a "gun oil" for lubricating firearms. It is apparently quite satisfac-
tory, and might well be used more extensively for that purpose.
( i ) METAL-TREATING OMS
( i ) TIN PLATE
In tin plating, the finished sheets are given a coating of oil to prevent
oxidation of the tin and to dissolve any tin oxide on the surface. Palm oil is
most commonly used,for this purpose, mainly because it is cheap and has been
found satisfactory. Collins and Clarke (1920), in an effort to find some fat that
lyould successfully replace palm oil, investigated the use of hydrogenated cotton-
305
• seed. oil and hydrogenated herring oil. The former material was used in a plant
for a considerable time (12 weeks) and the operation was somewhat better than with
palm oil. The iodine value of the hardened oil was 13. A herring oil hydrogenated
to an iodine value of 60 was investigated by laboratory methods, and it was
found that the product showed less tendency to polymerize or lose weight when
heated than either palm oil or the hydrogenated cottonseed oil. These authors
concluded that a herring oil hydrogenated to a lower iodine value than 60 would
probably prove superior to hardened cottonseed oil for use in tin pots.
(ii)" QUENCHING OF STEEL
This is in some cases carried out by immersing the heated metal in a bath of
oil. Whale oil was originally used for this purpose but recent developments in
this field indicate that mixtures of oils can be made that are superior in their
quenching properties to any single oil. Mineral oils also can be used for quench-
ing high-speed tools. Some of the cheaper semi- or non-drying vegetable oils are
more or less satisfactory for any type of steel quenching. However, blends of
mineral oil with fatty oils are cheaper and of greater general utility. The fatty
oil is used to an extent of about 25% of the mixture and is preferably one that
will not turn rancid or form gum when heated. Partially hydrogenated fish oils
are satisfactory for this purpose.
) INSECTICIDES, ETC.
Fish oils such as raw pilchard oil, which form a s ticky adherent film, are
used in sôme insecticides to hold the toxic materials on the leaves so that they
cannot be washed off by rain. The term adhesive is applied to fish oils in this con-
nection. The experimental work which led up to the use of fisl-; oils in sprays for
the control of the cod li ng moth was outlined by Webster, Marshall, Miller and
Hansberry (1932), and Marshall (1937). The preparation of such sprays has been
described by Marshall and Groves (1988). Herring oil is particularly suitable
for this purpose.
The use of fish oils in fruit-tree sprays is mentioned in many reports. Haller,
Cassil and Murray (1938) state that the addition of fish-oil or mineral-oil emul-
sion to the first two lead arsenate sprays and of fish oil to late-cover sprays of
casein lime does not greatly influence the removal of the lead residue• at harvest
time. Black (1936) claims that ,apple and pear trees sprayed about four weeks
before blossoming with a raw linseed-oil or seal-oil emulsion produced an earlier,
more prolific, and more even bloom, by which the crop was considerably en-
hanced in value. Zappe and Stoddard (1937) report that sprays made with 3
pounds of lead arsenate, 10 pounds of hydratéd lime, and 100 gallons of water,
with an adhesive of fish oil gave excellent control of curculio, codling moth, and
other chewing insects in Connecticut orchards. Hood (1929) claims that the use
of fish oils as an adhesive in lead-arsenated sprays for gypsy-moth extermination
and general control work permits the reduction in quantity of lead required.
Fish oil is also a gocid,adhesive for Bordeaux mixture. Miller (1937) found that
300
foliage injury resulting from the -treatment of walnut trees *as ahnost completely
eliminated by the addition of emulsions of salmon oil or of certain kinds of
mineral oil to the spray. U.S. patent 2,127,380 granted to F. Dearborn, 1938,
which was assigned to the people of the United States for free use, describes
the preparation of an insecticide by reacting a solution of an alkali-metal
arsenite with an inorganic cupric salt and an alkali-metal salt of fatty acids from
vegetable, animal or fish oils. The resulting product can be used as sprays for
foliage. The reaction product of thiodiphenylamine with an unsaturated fatty
oil such as soybean or fish oil is described in U.S. patent 2,127,039 granted to
F. Lindstaedt, 1938, for use as a 5% solution in mineral oil in horticultural sprays.
Another way in which fish oils are utilized in this field is for the preparation
of tree-banding compounds, which ara used in preventing infestation of trees
by larvae from the ground. Semi-drying fish oils such as herring oil would
probably be best for this purpose. Canadian patent 284,093 describes the pro-
duction, of a paper for use in tree-banding. The paper is covered with a compo-
sition consisting of 1 part of rubber latex, 3/2 part of fish oil, 15 parts of mineral
oil, Y2 part of rosin, and 1 part of molasses or other sweetening material.
For some purposes treated fish oils themselves have toxic properties. For
example, a phenolated pilchard oil which was effective in protecting submerged
wooden structures against the attacks of marine boring organisms was prepared
by Riddell (1937). (See also page 129.)
A review of the insecticidal applications of fatty acids, soaps and glycerides
is given by Thornssen and Doner (1941): It covers toxicities, plant tolerances, and
uses as stickers (adhesives ) and activators.
The recently-developed insecticide Icriown familiarly as "DDT" is more ,
soluble in organic liquids (including fatty oils) than in water. It is frequently
employed, dIssolved in a non-aqueous solvent or• emulified with water. The
possibilities of utilizing the particular physical properties of certain fish oils as
an application medium do not seem to have been explored.
(k) LEATHER
Large quantities of marine oils are used by the leather industry, both as
tanning agents and for softening thé leather. The two functions are quite sepa-
rate. In oil tanning the unsaturated molecules or their oxidation, prodUcts actually
react chemically with the skin, whereas in softening ("stuffing"), the oil only
lubricates, and hence softens, the leather.
(i) on., TANNAGE
This process is used for preparing chamois, buff, Japanese white Napa, buck-
slcin, Moch, fur skins, deer skins, and other soft leathers. The moist "splits" are im-
pregnated with a drying oil by swabbing or mechanical beating. This treatment
is interrupted from time to time by hanging up the skins to talce uP the oil '
through evaporation of some of the moisture. The skins are finally either hung
up in warm rooms having a temperature of about 1007. (38°C.), piled loosely,
307
or stored in an enclosed space. Oxidation of the oil occurs, and some of the
oxidation products combine chemically with the collagen and other nitrogenous
constituents of the skin to produce the desired "tanning" effect. If piled or stored,
heat is generated spontaneously and the temperature has to be kept below
about 130°F. (55°C.). The skins are then soaked in warm water and, by hydraulic
pressing, a certain excess of free fat or grease known as "moellon" is recovered.
They may also be scoured with alkaline solutions and pressed to remove the
remaining- excess of free fatty materials which, when recovered from the alkali
by acidification, is known as "sod oil". Final drying, working, bleaching and
buffing of the skins yields a finished product that is very soft and open.
Only oils of marine origin are commonly used in oil tanning; cod, herring,
pilchard, salrnon, wliale, seal, and sharlc oils are preferred. Mineral oils have no
"tanning" powers; linseed and similar vegetable oils are not satisfactory. The
superiority of marine oils is thought to be due to the presence of suitable unsatur-
ated and saturated fatty acids in the same molecule. Marine oils contain more
highly unsaturated fatty acids, and a greater proportion of saturated fatty acids,
than do vegetable oils, the unsaturation of which is mainly due to fatty acids' of
intermediate unsaturation. The fatty acids tend to be evenly distributed in the
triglyceride molecules. Thus many of the molecules will contain both satUrated and
highly unsaturated fatty acids. The latter combine chemically with the leather
and the former, which are hence not removed during the degreasing operation,
have a lubricating or softening effect on the leather.
Fish oil for use in the chamoising of leather should, according« to Barrett
(1942) have an iodine value of 145 to 165, an acidity of 9 to 14%, and a specific
gravity of 0.925.
( ii) STUFFING OF LEATHER
Leathers prochiced by tanning procedures other than oil fanning require the
application of oil at some stage of the process. The function of this oil, as
already pointed out, is to soften the tanned hides; the pr,ocesses of applying it
are called "stuffing". Fish oils, particularly cod oil, and sulphonated cod, salmon,
halibut-hehd, dogfish-body, seal, and sperm oils tare used in stuffing. Light
leathers are oiled by the "fat-liquoring" process. In this, oil is applied to the
tanned hides as an emulsion in water stabilized by the sulphonated oil. "Drum
stuffing" is similar except ,that the leather is tumbled with the fat liquor, usually
at a high temperature, in a drum. Heavy leathers are treated by rubbing with
an oily paste ("dubbin") of cod oil and tallow. Although cod oil is preferred,
salmon oil and seme shark and whale oils are also used.
( 1) ALKYD RESINS
Fatty acids of both the drying and non-drying types are used to modify the
properties of the resins formed by the interaction of glycerol or other polyhydric
/ substances with phthalic acid or similar dibasic acids. Fatty acids produce a
tougher and less brittle resin and, if drying fatty acids are used, the resulting
308
resin will have drying properties . . Distilled unsaturated fatty acids from fish
oils, which have an iodine value of 250 and a mean molecular weight of over
800, are now available commercially in the United States . The makers claiin that
these fatty acids produce resins that have "excellent air-drying properties and are
very similar to resins made with chinawood oil" . In addition it is claimed that
the tendency of the resin to gel during formation is less when these highly
unsaturated fatty acids are used than when chinawoo.d is employed. The use of
alkyd resins causes rapid drying and the formation of a hard lustrous film . They
are particularly recommended for baking enamels .
Several years ago . some experiments were carried out in these laboratories
on the use of pilchard-oil fatty acids as modifiers of alkyd resins . The fatty acids
used were as follows : Series A, total fatty . acids from cold-cleared pilchard oil ;
series B, liquid fatty acids from pilchard oil ; series C, free fatty acids from
steam-distilled pilchard oil ; series D, free fatty acids from vacuum-polymerized
pilchard oil; and series E, the total fatty acids .from linseed oil . These .fatty acids
were used to replace a portion of the phthalic acid, each acid being used in
two proportions, namely 0.5 and 1 .0 equivalents . The condensations were made,
at 210°C . (410°F.), the reaction being followed by acid-value . determinations .
When the reaction was completed, as indicated by constant acid values, the
resins were plated out and their drying properties ascertained . In all cases the
use of 0 .5 equivalents of fatty acids with 2 .5 equivalents of phthalic acid and 3 of
glycerol gave the best results . While the linseed-oil fatty acids gave the harder
films, those made from pilchard-oil fatty acids were also satisfactory . The liquid
fatty acids gave resins whose films were much harder than those of the total
fatty acids and about two-thirds as hard as the linseed-oil resin films . The fatty
acids of vacuum-bodied pilchard oil also yielded satisfactory resin films, the
hardness approaching those of the linseed-oil resins . With the exception of- the
resins made with the total fatty acids of pilchard oil, all the other fish-oil fatty
acid resins had good gloss and in addition were, definitely less brittle than those
of the linseed-oil fatty acids . The fish-oil resins did not dry so rapidly as those
of linseed oil and took slightly longer to reach their maximum hardness .
The uses for marine oils as described in this and the ;preceding twelve sub-
secti ons do not exhaust already-applied or possible -uses, but indicate ,the wide-
spread applications of the diversified products from such oils . Reference to the
Index will disclose other- uses mentioned in various connecti ons in other chapters .
Spelm , oil is used for impregnating air-conditioning filters . During the war,
when sperm oil was scarce, ratfish liver oil was tried as a subs titute, but it was
quite unsatisfâctory. It gave the fi ltered air a fishy od 6 ur, whereas spèrln oil
is odourless .
Solid marine animal waxes ( comnnerciai sperinaceti ) are used for "super-
fatting" special soaps, and as a cons ti tuent of various cosmetics such as cold
creams and face creams, also in polishing compounds .
309
Pilchard oil could be used in place of sardine oil in a "tree-wound dressing",
a formula for which has been given as follows:
Resin 7 parts
Sardine oil 3 parts
Copper sbap 3 parts
Another possible use of fish oils according to Harrison (1931) could be as a
substitute for the asphalt commonly employed for impregnating "mulch papers"
used as artificial soil coverings in vegetable and small-fruit gardens.
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• BARRETT, B. Leather Trades Rev., 75, 1125-30, 1942.
I BucicEn, J. Meztig- azdasagi Kutatasok, 14, 4-9, 1941.
, BERGMANN, E. A. Ind. E;Ig. Chain., 39, 4987500, 1947.
BILLS, C. E., O. N. MASSENGALE, M. IMBODEN AND H. HALL. J. Nutrit., 13, 435-452, 1937.
BIRD, H. R. J. Nutrition, 27, 377-383, 1944.
BLACK, M. W. Farming S. Africa, 11, 77-79, 1936.
• BOUCHER, R. V. J. Nutrition, 27, 403-413, 1944.
BROCKLESBY, H. N., W. A. RIDDELL AND N. I. RocEus. Reported in Fish. Ras. Bd. of Cam. Bull.,
59, 357-359, 1941.
CHALM1ERS, W. AND J. BIELY. Poultry Science, 26, 535-536, 1947.
COLLINS, W. D. AND W. É. CLARKE. Ind. Eng. Chem., 12, 149-152, 1920.
DENSTEDT, O. F. AND H. N. BROCKLESBY. J. Biol. Bd. Can., 1, 487-496, 1935.
Ibid., 2, 13-40, 1936.
Escoorao, P. Pub. inst. nacl. nutricion (Buenos Aires) Pub. Cient., CPa6, 109-117; 118-141 ,
1944.
Fars-z, F. Fette u. Seifen, 45, 88-90, 1938.
FRITZ, J. C., W. ARCHER AND D. BAuxun. Poultry Sci., 20, 151-154, 1941.
Film, J. c., J. L. HALPIN, J. H: HOOPER AND E. H. KnAmicE. 'Ind. Eng. Chem., 34, 979-982,
1942:
GEORGI, C. W. AND J. B. STUCKER. J. Am. Oil Chant. Soc., 24, 15-18, 1947.
GUILBERT, H. R., R. F. MILLER AND E. H. HUGHES. J. Nutrition, 13, 543-564, 1937.
HAIN, G. M., AND E. E. STONE. Ind. Eng. Chem., 39, 506-507, 1947.
• HALLER, M. H., C. C. CASSIL AND C. W. MURRAY, U.S. Dept. Agri. Tech. Bull., 62, 1-31, 1938.
HAMM, W. S. Commercial Fish. Rev., 9(5), 12-17, 1947.
HAnnism, R. W. U.S. Bar. Fish. Inv. Rep., 7, 1-78, 1931.
HART, G. H. AND H. R. GUILBERT. Calif. ,Agr. Exp. Ste. Bull., 560, 1933.
HAUGE, S. M., J. H. HILTON AND J. W. WILBUR. Purdue (Incl.) Agr. Expt. Sta. Rapt. of the
Director, 1937, 8-9, 40.
HILTON, J. H., j. W. WILBUR AND S. M. HAUGE. J. Dairy Sci., 27, 631-632, 1944.
HOLMES, A. D., F. TRIPP AND G. H. SATTERFIELD. Am. J. Physiol., 123, 693-700, 1938.
HOOD, C. E. U.S. Dep. Agri. Tech. Bull., 111, 1-28, 1929.
HUFFMAN, W. D., C. B. HAnnuva AND W. H. OLDACRE. Iron Age, 134, 36-38, 1934.
JAKOBSEN, F. AND R. NERGAARD. Tids. Kiimi, Bergvesen Met., 3, 68-74, 1943.
JonmoN, D. W. AND L. S. PALMER. J. Agr. Research, 63, 639, 648, 1941.
310
KAEMPFE, G. Farben-Ztg., 40, 1009, 1935 (C.A. 30, 883).
KUWATA, T., H. MATUBARA AND S. AsAnARA. J. Soc. Chem. Ind. (Japan), Suppl. bind.,
43, 80-82, 1940.
LLOYD, E. A. AND J. RIELY, Practical Poultry Feeding, B.C. Dept. Agr. Bull., No. 107, 1947.
MARSHALL, J. Wash. Agri. Expt. Sta. Tech. Bull., 350, 1-88, 1937.
MARSHALL, J. AND K. GROVES. Wash. State Coll. Exp. Bull., 232, 1-7, 1938.
MATrn.., W. H. Oil and Soap, 21, 197-201, 1944.
MILLER, P. W. Oregon State Hort. Sci-Ann. Rep., 29, 119-143, 1937.
MILBY, T. T. AND R. B. THOMPSON. Poultry Sci., 23, 405-7, 1944.
OLsson, N. Kgl. Lantbruks-Hogskol. Ann., 16, 1-38, 1949 (C.A. •44, 196).
REIN:laNCTON, R. E. The Western-Levine Vitamin Chart, 1945.
RIDDELL, W. A. Fish. Ras. Bd. Can., Pac. Prog. Rep., No. 31, 14-15, 1937.
RONOID, A. A. AND T. TAAFtLAND. Tids. Hermetikind, 34, 49-51,- 1948.
ScnoNnEndEn, R. AND F. BREUSCH. Z. physiol. Chem., 211, 19-22, 1932.
ScnwrrzEn, M. K. Oleagineux, 3, 251-252, 1948.
Smrrn, S. E. J. Nutrition, 24, 97-107, 1942.
Soars, A. E., M. SnEruvrAN, J. LICHTBLAIT, S. SNOW AND B. KRAMER. J. Nutrition, 35,
225-238, 1948.
TANAKA, Y., R. KOBAYASHI AND T. TSUEIMA. J. Soc. Chem. Ind. (Japan), Supp/. bind.,
38, 440-442, 1935.
TrumussEn, E. G. AND M. H. DONER. Soap Sani. Chain., 17(4), 94-98, 1941.
WAriss, G. C. South Dakota Agr. Ea:p. Sta., 53id Ann. Rapt., 37-40, 1940.
WEBsTEn, R. L., J. MARSHALL, C. E. MILLER AND T. R. HANSBERRY. Proc. 28th Ann. Meet,
Wash. State Hort. Assoc., 48-64, 1932. .
ELESI, H. H. Nature, 156, 238, 1945.
WnE
Worm, L. T., C. SWAN, A. WASMUTH AND J. MATTIELLO. Ind. Eng. Chain ., 28, 1022-1024, 1936.
.
ZAPPE, M. P. ANn E. M. STODDARD. Conn. Agri. Exp. Ste. Bull., 396, 364-366, 1937.
311
CHAPTER TEN
The lierring, Çlupea pallcisi% caught along the British Columbia coast is 'â
member of the family Clupeidae to which the pilchard also belongs. But wheréas.
the oil content of pilchards increases during the period when they are fished in
British Columbia, that of, herring decreases. This is due to differences in the
I parts. of their respective annual cycles during which each is fished. Practically
all the herring caught in British Columbia waters are taken prior to spawning,.
and thus their oil content decreases as the fishing season advances. During the.
active feeding period the oil content of whole herring may run as high as 19%,.
but it may drop almost as low as 4% after spawning (Hart et al. 1938). Faetors.
affecting the oil content of herring"are discussed in greater detail on pages 41-42.
Herring investigations conducted since 1929 by the Pacific Biologicà.l Station
have shown the existence of several more or less separate herring populations.
along the British Columbia coast. The herring fishery generally extends from
late September to early March; attempts have been made at developing a summer
fishery but they have not proven commercially successful.
A regular herring fishery off the lower east coast of Vancouver Island com-
mences during the latter part of September or early October. It is consistent and
usually extends over a period of six weeks to three months, with the Satellite
Channel-Swanson Channel and Nanoose Bay areâs generally being the chief
i contributors. The start of herring fishing' on the west coast of Vancouver Island
is governedlargely by the progress of the lower easti coast fishery; it is usually not
until after the peak of this fishery that a large number of seine boats move to the
west coast areas. The bulk of the catch on the west coast is taken from the Barkley
312
and Nootka Sound areas, with Clayoquot, Kyuquot and Quatsino Sound areas
providing highly variable fishing. Regular, but relatively small, fisheries usually
develop in the middle and upper east coast of Vancouver Island. The.fisherY in
the central British Columbia coast area is generally active from Jamiary to early
March after the hening fleet has completed operations on the lower east coast
and the west coast of Vancouver Island. In recent years spawning ground surveys
• have indicated appreciable quantities of herring along the northern 'coast; the
fishery depends on economic conditions and the time at which the herring
become available in relation to the opening and closing- of the fishing season.
In some years the catches are small or negligible, whereas in others (e.g.
December, 1950) very large catches have been made.
The quantities and values- Of herring oil produced during the years 1927 to
1951 in British Columbia are given in table 52. Herring are used not only for
reduction, but also for mining, dry salting, kippering, and so en.. The price and
demand for the various products made from them largely govern the quantities
used for these various products, including oil and meal. This- Consideration
TABLE 52. Quantities and values of herring oil produced in British Columbia
1927-1951.
*Preliminary data:
313
accounts to some extent for the variations in the amounts of oil produced in -
different years.
Herring oil is prepared in British Columbia not only by reduction of -whole
fish, but also by reduction of herring cannery offal. Furthermore, considerable
amounts of oil are obtained as a diréct by-product of the canning process. In
that process the open cans of fish are given a short steaming upside down on trays,
to drain off part of the water and oil. The oil is recovered by passing the liquid
which collects in the retort either through settling tanks or through centrifuges.
The herring.on the Atlantic coast, Clupea harengus, is used principally for
food and bait. The smaller herring, known as sardine herring, is canned in large
quantities in southern New Brunswick,'the pack being known as Canadian sar-.
dines. The offal from this cannery operation, together with fish too small or other
wise unsuitable for canning, is put through a continuous reduction process and
converted to meal and oil. The total herring-oil production on the east coast
during recent years ranges from about 50,000 gallons to 150,000 gallons per year,
mainly from New Brunswick.
Table 53 contains a list of the general chemical characteristics and range of
values of British Columbia herring oil-data derived from samples of oil obtained
from various reduction plants in different localities along the British Columbia
coast and analysed in these laboratories.
The oil expressed frorn the herring varies from a light yellow to a reddish
brown in colour. It deposits large amounts of stearine at ordinary temperatures.
Although Brocklesbÿ,(1941) found considerable variation in iodine value
among herring oils produced in, different localities along the British Columbia
coast, more recent work at this Station has shown little variation in that re-
spect between bulk shipments of the oil from different localities. Brocklesby's
data for the iodine values of herring oils produced in different localities were as
314
follows; Butedale (northern B.C. coast) 141.7, Kyuquot Sound (west coast of
Vancouver Island) 140.3, Barldey Sonnd (west coast of Vancouver Island) 154.4,
and Swanson Channel (south-easf Vancouver Island) 129.0. Iodine values of
samples from 32 bulk shipments of herring oil from a number, of British Columbia
plants during 1948 are given in table 54. While the dates of the shipments are not
s trictly representative of the times the oils were produced, they cover the entire
year, and thus show the variations which may be expected in shipments of herring
oil. Apparently the variations among individual lots of oil are overcome by the
•
mixing in large tanks. Neither local nor regular seasonal variation is shown by
these data.
TABLE 54. Iodine values of British Columbia herring oil, bulk shipments, 1948.
. In 'table $5 are given some data . showing the average quality of bulk Com-
mercial shipments of British Columbia herring oil during the years 1936 to 1939.
It is obvious from these figures that a high uniform quality is maintained• in the
production of this oil. Free fatty acid contents as high as ,5% - have been found
in herring oil, but this is unusual; in general it is rnuch lower. The variations" in
colour are mosi likely due to natural causes, since an oil- that is darkened-
owing to improper processing usually shows a large, increase in - red colour. The
average annual ranges in moisture content are •remarkably uniform but con-
siderable individual variations were found. The moisture content to a certain
extent reflects the length of time and the temperature at which the oil has been
tanked. It has but little significance in regard to the quality df commercially
315
"dry" oil. No analyses for years later than 1939 are shown in table 55 beeâuse • it
has been observed that the ranges shown therein ;Would be little altered by data
from bulk commercial shipments in more recent years while the trend has been
to blend individual, batches of herring oil to méet specifications. This decreases
differences in analyses between different shipments of oil to a given ,ortler.
Average colour ,
(Lovibond units, 1-in. cell) yellow 25.0 21.3 29.3 20.7
(Lovibond units, 1-in. cell) red 2.5 2.3 2.3 2.5
Colour range ,
(Lovibond units, 1-in. cell) yellow 23.0-27.0 21.0-22.0 25.0-35.0 20,0-25.0
(Lovibond units, 1-in. cell) red 2.1-2.7 1.8-3.4 2.2-2.4 2.0-3.2
Average moisture (%) 0.31 0.57 0.46 0.33
Moisture (%) (range) 0.12-0.52 0.25-0.80 0.31-0.54 0.09-0.65
Ether-insol. matter (%) 0.01 ' 0.01 0.01 0.01
Free fatty acid (%) (ay.) 0.65 0.53 0.45 0.52
Free fatty acid (%) (range) 0.28-0.90 0.39-0.70 0.39-0.1 0.31-0.67
Several samples of commercial Atlantic coast herring oil have been examined
in these laboratories. Most of these had a rather dark colour and a strong odour.
The free-fatty-add contents were higher than those found for Pacific coast herring
oil. One or two experimentak lots of Atlantic coast hening oil have also been
examined. These were of excellent quality, being light in colour, low' in free fatty
acids and moisture, and practically free from , odour. Thus the dark colour of the
commercial oils could be attributableto spoilage of the raw material before
processing, or to overheating during processing, or to both. •
The uses of herring oil are discussed in the preceding chapter, but for con-
venience will be summarized here. Raw herring oil contains so much stearine
that its use is mainly limited to hydrogenation for subsequent use in the manu-
facture of soaps, shortenings and çooking fats, lubricating greases, and other
applications of hydrogenated fats sùch as in the manufacture of stearic acid for
the rubber industry. The raw oil is also used as a cutting oil, and is sulphonated
for use in the leather industry. Cold-cleared herring oil is use'd in feeding oils,
insecticides, tree-banding compounds, and in the manufacture of linoleurh
and oilcloth. Herring oil stearine is hydrogenated and used for the same purposes
as the hydrogenated raw oil.
317
I
The fish are caught by purse seines and transported immediately to reduction
plants where the entire fish are processed by a continuous system (pages
201-210) . The amount of oil in the fish varies with the season ; during the earlier
part of the summer the yield averages about 12 gallons to the ton (617o), but
towards the fall it increases to as much as 50 gallons to the ton . The oil thus pro-
duced is the raw pilchard oil of commerce. A more detailed discussion of the
changes in oil content of pilchards is given on pages 42-43 .
Seasonal samples of pilchard oil for the years 1929 And 1937 analysed in these
laboratories failed to show any constant trend, in, characteristics with advance in.
season . From table 57 it is evident that in 1929 there was a regular increase in
urisaturation (iodine value) from July 2 to about September 15, but for the year
1937 no such trend existed . This lack of any definite trend in unsaturation wa s
TABLE 5 7. Seasonal variation in unsaturation (iodine value) of pilchard and sardine oils . \
July 2 173 .2 Aug. 1- 4 176 .7 Aug. 16-21 185 .0 Nov . l' 188.6
Aug . 2 177 .3 Aug. 7-11 175 .8 Aug. 22-28 186 .8 Nov . 13 187.6
Aug . 9 179 .3 Aug. 13-20 176 .2 Aug. 28-Sep .4182 .4 Nov . 27 189.5
Aug . 16 180 .3 Aug., 28-Sep .2 176 .3 Sept . 5-11 187 .3 Dec. 1 190.7
Aug . 16 181 .9 Sept . 3- 7 173 .0 Sept . 12-18 188 .4 Dec. 28 182 .8
Sept . 3 183 .2 Sept . 7-14 177 .0 Sept . 27-Oct.2189 .5 Feb . 11 178 .4
Sept . 15 183 .4 Sept . 14-19 175 .5 Oct. 3- 9 188 .4 Feb . 22 176 .1
Oct . 7 182 .3 Oct . 13' 178:2 Nov. 29-Dec .4188 .5 Mar . 1 173 .5
Dec . 5-11 189 .8 Mar. 8 185 .3
Mar. 11 181 .1
Apr. 14 170 . 9
318
■
also borne out by the analyses of Califôrnia sardine oil for 1937-1938, although
there was a slight indication of a lowering of the iodine value towards the end
of-the season in the southern area. The higher average unsaturation of California
sardine oil over that of British Columbia pilchard oil is, however, quite marked.
As a result of analyses of samples of commercial pilchard Oil carried out in
these laboratories over a- period of ten years the limiting values of certain l
chemical and physical characteristics can be given. These are shown in table 58,
from which it can be seen that the greatest variation in chemical properties lies
in the unsaturation, the iodine value ranging from 170 to 188. The unsaponifiable,
matter varies over a small range. Pilchard oils differ considerably in degree of
colour, and although not indicated by the data in the table, they , sometimes have
a greenish tinge. This is due to chlorophyll, the green colouring matter of plants;
it is dissolved in the oil from the "green feed" which is sometimes present in the
intestine of the fish. The variation in vitamin content has been discussed on
page 75. In spite of the high unsaturation of pilchard oil., it deposits a con-
siderable amount of stearine at ordinary temperatures. The commercial oil is
also very low in nitrogenous matter, an average of 0.004% nitrogen being found
for several samples. This amount is partly due to ,suspended matter and can he
reduced by filtration or refining. Analyses of four selected samples of pilchard oil
are shown in table 59.
and 12 lb. per case. The oil yields for sockeye and pink -sahnoii offal aye -found
to be within the range given by Harrison et al., but that for chum salmon bffal
is much smaller, about 7 gallons per ton. Seine of the circumstanceS contributing
to these discrepancies rnay be enumerated. The canning of tips and tails and
other edible portions of fish left by the iron chink,. while not being a general
practice in all canneries, undoubtedly reduces the total offal - available in some
plants. The large amount of water used to flush the offal from the iron chink
tends to make, a very fluid mixture in the offal bin. These bins are never Water-
tight, and it is the opinion of some operators that`much of the loss occurs at this
point, the water washing away oil and soluble proteins. This is particularly
noticeable if the offal is not removed immediately, autolytic and bacterial decom-
position increasing the amount of liquid products that are lost through the floor
of the bin. It is also a fact that the yield of' offal per case of sainion, packed is
higher in those reduction plants that are operated in conjUnetion with a cannery
than in those- that are situated some distance from the cannery and which, there-
fore, cannot get the offal in as fresh a condition:. Similarly, it has been observed
that in a particulài: case of a reduction plant operating at some distance from the
canneries supplying the offal, daily collection àf the offal (which was -therefore
in good condition) gave a higher yield of offal per case of fish packed than when
it was collected only once or twice a week.
The offal from most cif the British Columbia salmon camieries is flow utilized,
at least for the production of oil, although the solids are in some instances still
thrown away. As described on pages 199-200, at some , canneries the offal is cooked
under pressure, the liberated oil is skimmeçl off, and the solids are discarded.
However, a number of the larger canneries at various points along the çoast are
equipped with regular reduction planté for the production of meal and oil; not
only is the offal from these canneries themselves processed in their 'reduction
plants, but the,offal from other canneries in the same locality is hauled to them
on scows. -
I'll-eduction data for salmon oil preduced in relation to the number of
cases of cannesd salmon packed in British Columbia for the years 1932 to 1950
inclusive are given in table 62.
Commercial salmon oil is quite deeply coloured, ranging from a cherry red
te a light amber depending upon the species of fish and upon whether total waste
or selected parts of the waste are used. The most deeply :coloured oils are obtained
• 321
--
TABLE 62. Production data for salmon oil and canned salmon in British Columbia.
*Includes a considerable quantity canned from cold-storage stocks of fish caught in 1946.
**Preliminary data.
from coho and sockeye salmon; the least coloured are from chum and pink sal-
mon. Other fish oils such as pilchard and herring normally have but little red in
their colour çomposition. If a deeper red colour is produced by oxidation during
322 •
manufacture these oils are of much less .conimercial value, since this red colour
adds to the diffi culty of subsequent refilling. Most of the colour in salmon oil can
be removed by methods described on pages 233-238. The natural colour is also
removed in the early stages - of the process of hydrôgenation.
The.general characteristics of commercial salmon Oil are shown in table 63.
Considerable variation is evident in the =saturation of commercial salmon oil,
as shown by the wide range in iodine values._This is chiefly due to the number
of different species of salmon used for production of the commercial oil. 'Since
the species predominating varies at different times during the season, the oil
produced from the o ff al will vary 'correspondingly. The variation in properties
of oil obtained from different species of salmon can be seen from table 64, com-
piled from the data of Harrison et al. (1939). As pointed out by those workers
it is noticeable that in general- the longer the life cygle of a species, the more
highly unsaturated is the oil obtained from it.
TABLE 64. Characteristic ranges in properties of oils from various species cif salmon.
Chinook Pink or
or spring Sockeye humpback ' Coho Chum
Not only does the =saturation of salmon oil vary with species and with the
locality of catching, but there is also considerable variation in the oil from the
various fat depots of the fish, so that the characteristics of the commercial oil
will vary according to the proportions of the different waste materials in the
offal. In table 65 are given data for the chemical characteristics of the oils from
eight different fat depots in the coho salnion. The liver oil is noticeably more
unsaturated than most of the storage fats, as is shown by thé high iodine value
and the low content of saturated fatty acids. This is in direct contradiction to the
. findings of Lovern (1934) for other fish. The highly unsaiurated nature of salmon
liver oil was well showriby Bailey (1934) who found in examining several di ff erent
samples of oil from all species that the average iodine value , was 207.2. The hie
iodine value and relatively high saturated-fatty-acid content of the true glyceride
portion of the egg oil would seem sto indicate the présence of a fair amount of
very highly unsaturated fatty acIdS; the egg ôil was separated into two fractions
based on their solubility in acetone—the triglycerides are soluble in acetone while
the lecithin is not. The sidn oil and dark-muscle oil are more unsaturated than
323
TABLE 65. Characteristics-of oils from various fat depots of coho salmon.
the oil from muscle nearer the bone. The total head oil appears to be more
highly ,unsaturated than the oils of either of the constituent parts studied, which
would lead to the conclusion that there must be a part of the head where very
highly unsaturated oil occurs. Variation in deposition of storage fats in salmon
was likewise found for, ten red spring salmon examined in these laboratories.
The data showed that the oil from the pink muscle is generally more unsaturated ,
than that from the dark muscle; also that the oil from the flesh near the head
is more unsaturated than that from near the tail.
' Salmon oil can be oxidized, but it is not a drying oil. From analytical data
obtained in these laboratories it was found that when red-spring-salmon oil was
subjected to continuous blowing with air at 100°C. (212°F.), the delgree of un-
saturation steadily decreased, while the viscosity and molecular weight increased.'
The final product was very viscous but did not gel. It had an 'oxidized-fatty-acid
content of 13.8%. Raw salmon oil exposed to the air never dries to a non-tacicy
film; samples exposed for several months become thick and viscous, but retain
their fluid nature.
When hydrogenated, salmon oil forms a white, odourless fat. It can be
hydrogenated quite readily, as shown in table 66. A concentration of 0.7% nickel
catalyst was used, with a hydrogen pressure of 30 lb. and a temperature of
180°C. (356°F.).
A very important feature of salmon oil is its low stearine content. Conse-
quently, high yields of cold-cleared oil are obtained. But as already pointed out
it is not; even when cold cleared, a drying oil.
324
Raw salmon Oil is chiefly sulphonated to produce a very good material for
offing, rather than dressing, leather. Cold-cleared salmon oil is used in feeding .
in the manufacture of soaps, shortenings: oils.Hydrgenatmoilsud
, and cooking fats, and as a quenching oil. The fatty acids of fully hydrogenated
salmon oil are pure white and, as noted in table 66, have a titre of over 55°C.
Certain industries require solid fatty acids with titres approximately 55°C., and
these can thus be prepared from:salmon oil. For further ,details about uses of
salmon oil see Chapter 9.
This oil is not regularly available on the open market but it has been pre-
pared by commercial fish-oil producers to fill special orders. The eggs contain
from 6 to 15% oil and a considerable amount of lecithin, part of which may be
extracted along with the oil.
The oil can be prepared from salmon eggs by grinding them ( with care fo
avoid emulsification), adding an approximately equal volume of either
sodium chloride, 4% sodium sulphate, or 2% monosodium phosphate, and pass-
ing the mixture through a centrifuge. The mixture may be warmed slightly before
centrifuging, but it must not be heated sufficiently to coagulate any of the protein.
A solvent-extraction method for the prepâration of salmon egg oil on a
commercial scale has been described by Jones et al. (1948). It was canied out
' as follows: Raw salmon eggs were ground up and mixed with ,4 parts by.volume
of acetone, the mixture being stirred intermittently over a period, of 4 hours (it
was pointed out that continuous stirring should reduce the time required for
efficient extraction); the acetone extraction was repeated three times. The
the water and most of the fatty 'material. After the acetone acetonrmvd
extractions, the material was given a final extraction with ethyl alcohol at 76 —
78°C. (168.8 — 172.4°F.). The ethyl alcohol was distilled off separately from the
final extract, and the extracted material thus obtained was added to the com-
bined acetone extracts. The acetone was distilled off from the combined extracts,
which contained the oil, lecithin, and water; most of the acetone came off by heat-
ing to 60°C. ,(140°F.). Removal of the acetone caused the oil and water to separate
into , two layers; the oil was remeved by decantation. The lecithin was separated
from the oil by dissolving the latter in -ether, and adding acetone until no -further
precipitate formed. The ether solution of oil was decanted off from the sludge of
lecithin, and the sblvents were distilled off from the fractions thus separated.
The cholesterol content of salmon eggs was also' investigated, but the
amounts present were found to be too small for commercial exploitation.
Further information' respecting both cholesterol and lecithin, is given on
pages 84-87 and 89-90.
Salmon egg oils have very outstanding properties. In the first place they have
a deeper red colour than the oils froin the flesh of the corresponding specieà..
Sockeye and doh() egg oils in particulàr are deeply coloured. Another interesting
property is the fact that some salmon egg oils will remain liquid at very. loVe
325
temperatures. Two samples of sockeye egg oil kept in a cold room at -30°F.
(-34.4°C.) at this Station for a period of over a year deposited only. a small
amount of stearine, leaving a clear non-viscous oil above. The characteristics of
egg oils from different species of salmon are summarized in table 67, compiled
from the data of Lee and Tolle (1934) and Harrison et al. (1939).
^
Pink or Chum, dog
Spring Sockeye Coho or keta
humpback
Salmon liver oil is not a regularly available commercial product, but small
amounts, have been prepared in the past, particularly during the war years. The
quantities and values of salmon liver oil produced in British Columbia are shown
in table 13. Data for the oil contents of the livers and the vitamin A and D
potencies of the liver oils are given in table 14.
TABLE 69. Quantities and values of dogfish liver and body oils produced in British Columbia,
1930-1950.
There was no relationship whatever between the amounts of liver and body
oils produced, as can be seen froM the figures for the years when• they were
327
reported separately. This is due to the fishermen's practice of removing the livers-
at sea and throwing the carcasses overboard, the low price paid for the latter
making it unattractive to bring them in. The only two plants on the British
Columbia coast which had been reducing dogfish carcasses in recent years-both
batch plants-closed down in 1945, and all the carcasses are now thrown away at
sea by the fishermen. The carcasses can, however, in spite of the general impres-
sion to the contrary, be processed in an ordinary continuous reduction plant by
the method described on pages 201-210.
• The characteristics of dogfish liver and body oils produced on the Pacific
coast and some data for Atlantic dogfish liver oil are given in table 70.
Pacific Atlantic
<,
Liver oil Body oil Liver oil
( e) HALIBUT OILS •
Halibut are common to both the Atlantic and Pacific oceans, although the
Atlantic halibut (Hippo glossus hippo glossus) is a different species • from the
Pacific halibut (H. stenolepis). Much smaller amounts are landed on the Atlantic
328
coast than on the Pacific coast. The Pacific halibut fishery is regulated under' an
international agreement between Canada and the United States, the catch for
each country being limited to a definite quota each year. Halibut are _caught
some distance off shore, mainly outside territorial limits, so Canadian and
American fishermen fish to a large extent in the same localities. The Pacific•coast
halibut fishing grounds are divided into four areas, two of which, Areas 1 and 4,
are fished very little, the bulk of the quantity landed being caught.in Areas 2 and
3. The areas all have defined limits: in general the Area 2 fishing grounds are
off the coast of British -Columbia and Southeastern Alaska, Area 3 to the north-
west and farther off shore.
Three different oils are produced as by-products of the halibut fishery: liver,
viscera, and head (offal) oils.^ The fish are eviscerated at sea, but the heads are
left on until brought into port. When a load of halibut is landed, the heads are
cut off and hauled to a reduction plant where they are converted to oil and meal.
The livers and viscera are processed in vitamin oil plants. The quantities and
values of halibut liver, viscera, and head oils produced in British Columbia
during the years 1937 to 1949 are given in table 71. The British Columbia landings
of halibut livers constitute the greater part of the total quantity landed in Canada.
Very little halibut liver oil is produced on the Atlantic coast of Canada, most of
the livers landed there being sold for processing elsewhere.
TABLE 71. Quantities and values of halibut oils produced in British Columbia, 1937-1950.
This is produced from the raw or frozen livers by methods outlined on pages
195-198. Halibut livers constitute from about 1 to 2.5% of the weight of the round
329
fish. The livers of Area 2 halibut contain about 15 to 30% oil, while those of hali-
but caught in Area 3 contain from about 8 to 20% oil. When prepared by diges-
tion methods, the oil has a clear yellow colour; when prepared by solvent
extraction it is dark brown Some characteristics of the oil prepared by digestion
methods, the more common process, are given in table 72.
, The iodine values of different samples of halibut liver oil vary greatly, as
can be seen from the data in this table. Haines and, Drummond (1936) found a
direct relationship between the iodine value and vitamin A potency of oils from
any one of several general localities (West Greenland, Labrador, Iceland). The
data of Pugsley (1939) for Pacific halibut showed no such relationship but did
indicate some parallelism between the percentage of unsaponifiable matter and
the vitamin A potency. Vitamin A itseff has a high iodine value, but the variations
in vitamin A content of the oils are not sufficient to account for the variations in
iodine value, even of the oils examined by Haines and Drummond.
I-IEAD OIL
This oil, which is alsô refened to as "halibut offal oil", is produced in re-
duction plants from halibut heads collected at fresh and frozen fish establishments.
The heads constitute from 10 to 12% of the weight of the fish, and have an oil
content ranging from 10 to 20%. As produced in reduction plants halibut head
oil usually contains some salmon oil since the fish dealers usually handle fresh
salmon also, and the heads are mixed indiscriminately. However, some samples
of pure halibut head oil have been produced cdtimercially and many samples
have been prepared in this Station.
Some of the characteristics of halibut head -oil are shown in table 72. It is
a clear pale-yellow liquid that deposits but little stearine in spite of its relatively
low unsataration and high content of saturated fatty acids. The iodine value of
samples examined over a period of years has shown a variation of only about
13 units. It is low in unsaponifiable matter and contains but little vitamin A or D.
Halibut head oil does not oxidize to a dry film but becomes thick and .stiCky.
This adhesive characteristic, which prevents its use in the ,pretective coating
industries, is• of value when the oil is used fer insecticide sprays and for tree-
banding compounds. The oil can be sulphonated and the product used as an
emulsifier and fat-liqrtoring .agent in the leather industry. The low content of
unsaponifiable matter warrants the use of the oil in the hydrogenation proèess,
and the hardened oil (or its fatty acids) makes a good.substitute for commercial
stearic acid.
TABLE 73. Quantities and values of cpd liver oil and cod oil,produced on the Atlantic coast
of Canada (exclusive of Newfoundland), 1929-1949 .
Year
Quantity Value Quantity Value
(gal .) $ (gal . ) $
332
to 1949 are given in table 73; similar data for Newfoundland during the years
1938 to 1950 are given in table 74.
TABLE 74. Quantities and values of cod liver oil and cod oils produced in Newfoundland
during the years 1938 to 1950.
•
Year Medicinal cod liver oil Poultry cod oil Common cod Oil
Cod liver oil and cod oil are differentiated basically by freshness of the
livers and the method of preparation, which in turn affect the quality of the oil
produced. Cod liver oils are made from fresh livers by steam-rendering or low
temperature methods; only the highest quality oils are used for human con-
sumption. Cod oils are generally made by sun-rotting or fire-cooldng methods,-
and sometimes by steam rendering. Even when steam rendered, an oil may
be of too low a grade for any nutritional use if the livers from which it was
made were putrid, in which case it is ,sold as çod oil. Production methods for
cod oil and cod liver oil are described on pages 180-195.,
The effect of various methods of production on the quality of the oil is very
well brought out by analyses made by Brocldesby and co-workers on a number
of samples of cod liver oil collected by Canadian Departinent of Fisheries
Inspectois. The results of these analyses are given in table 75. The difference
between sun-rendered samples and those prepared by steam processing is_ very
marked. The former samples were aaracterized by high acid values and a dark
colour; most of them had a bad odour. The first-run samples from the steam-
rendering process were of uniformly high grade, as far as colour and acid value
are concerned; the second-run oils, which were obtained' by further settling of
the liver residue after skimming the first run oil, had higher acid values and in
one case a higher colour. Some of the iodine values -were considerably below
333
the'range generally found for cod liver oils, probably due to the presence of
some haddock liver oil; which has a much lower unsaturation. The vitamin A
potencies of the few, saznples assayed varied over a wide range, but since in-
sufficient data were available regarding the sizes of fish and the yields of
oil obtained, little significance can be attached to these values. It is noteworthy,
however, that the potency of the "stove-rendered" sample was markedly lower
than that of any of the others. Furthermore, the great variations in vitamin A.
potency emphasize the importance of blending oils to obtain a more standâ.rd
potency.
TABLE 75. Properties of Canadian Atlantic cod liver oils and cod oils; effects of various
production methods.
Colour
(Lovibond units) Iodiné value Free fatty Vitamin A
Description of sample
yellôw red acid (%) (U.S.P. units/gm.)
334
In table 76 are given some ranges of analytical values for cod liver and cod
- oils produced on the Atlantic coast. •
The term "destearinated cod liver oil" refers to -oil which has been cold
cleared, usually at about 35°F. (2°C.), the exact temperature' depending on the
specifications; a non-destearinated cod liver oil is one which has nôt been cold
cleared. Steam-refined crude cod liver oil is a lower grade .oil which has beeri'
deodorized by vacuum—steam distillation so that it meets the requirements for
a medicinal or feeding oil. This cannot be done with very« low grade oils, sincd
even•when refined they will not meet reqUirements.
Most of the cod oil produced in Canada is sulphonated for use in the tanning
industry for dressing certain types of leather, and to some extent in the manu-
facture of wetting agents and other surface-active compounds.
( h LINGCOD OILS
)
336
Lingcod liver oil prepared by alkali digestion has a light yellow colour.
Characteristics of lingcod liver oil are given in table 78. The unsaturation varies
over a wide range, slightly below that of halibut liver oil. The unsaponifiable
matter rarely exceeds 10% averaging slightly over 5%. The saturated fatty acid
content falls within the range commonly found for fish liver oils.
Lingcod viscera oil generally contains from 10,000 to 175,000 U.S.P. units
of vitamin A, and from 100 to 200 International units of vitamin D per gm. Both
lingcod liver and viscera oils are used for the manufacture of medicinal prepara-
tions.
( i) BLACK-COD OILS
Atlantic Pacific
338
along the Pacific coast from California to Alaska . Hake liver oil is only produced
on the Atlantic coast; the quantities produced and the values are given in table
13.
Data for the ranges in the characteristics of Atlantic hake liver oils, and for
the analysis of one sample of Pacific hake liver oil are given in table 79 .
Atlantic hake liver oils- cannot profitably be used alone in the preparatio n
of medicinal oil . They deposit so much stearine on cooling that the yield of
clear oil is low . For this reason the better grades are blended with other oils to
produce a mixture suitable for use in poultry or animal nutrition, lower grades
being used in the leather and other industries . ,
TABLE 80 . Characteristics of haddock, pollack and mixed (cod, pollack, hake and cusk
mixture) liver oils.
In general the physical and chemical characteristics of haddock liver oil are
similar to those of Atlantic cod liver oil, but its average potencies in both vitami n
339
A and D are lower. Probably haddock liver oils are sometimes sold as poultry-
grade cod liver oil and as cod oil, since not only are the liver oils similar in
physical and chemical characteristics, but haddock belongs to the same family
as cod.
Although some shark liver oil is produced on the Atlantic coast of Canada,
much greater quantities are produced in British Columbia.
The most outstanding feature of shark liver oils is the tremendous variation
in vitamin A potency between different species of shark. Thus while basking
shark liver oil contains little vitamin A, sometimes none at all, soupfin shark liver
oil is very rich in it. The liver oils of other sharks have vitamin A potencies
intermediate between these two extremes.
(i) SOUPFIN SHARK LIVER 011,
The soupfin shark, Galeorhinus galeus, is caught on the Pacific coast from
southern 'California to northern British Columbia. It is a medium-size shark,
reaching a maximum length of slightly over 6 feet. It was not actively fished
before 1937, any landed being caught merely incidentally to other fisheries.
However, with the discovery about 1937 that the liver oil is very rich in vitamin
A, an extensive fishery developed immediately. At first the fishery was chiefly in
California waters, but later these sharks were sought after by the fishermen in
British Columbia, and a small fishery developed there. The quantities and value
of soupfin shark livers landed, and of soupfin sharlc liver produced in British
Columbia during the years 1942 to 1948 are given in .table 13.
The livers of adult male soupfin sharks constitute approximately 10% of the
weight of the fish; the livers of the adult females average slightly higher but are
far more variable. The oil content of the male liver is in general from 25 to 70%,
that of the female from 35 to 80%. A remarlcable feature of these oils is that the
liver oils from the males have considerably higher vitamin A potencies than
those from the females. The former range from 45,000 to 200,000 U.S.P. units of
vitamin A per gram, the latter from 15,000 to 40,000 U.S.P. units. The generally
340
higher oil yield from the female livers partly compensates for the lower vitamin
A potency, but Bolomey et al. (1946) state that the livers of the adult male
soupfin sharks contain on the average over two and a half times more vitamin
A per pound of liver than do the females. -
The high vitamin A potency of the oil, together with the high oil content
of the livers and the higli percentage of liver in the fish, make soupfin sharks,
especially th, males, very valuable. The oil is all used as a source of vitamin A.
Like all Elasmobranch fishes, the.oils of the soupfin sharks contain very little
vitamin D.
(ii) MUD SHA.RK LIVER OIL
The mud shark, Hexanchus gr,iseus, is caught on the Pacific coast from
southern California to Northern British Columbia. It is quite a large shark,
sometimes reaching a length of over 26 feet, although usually it is considerably
smaller. The quantities and values of mud shark livers landed, and of mud shark
liver oil produced in British Columbia are giv.en in table .13:
Mud shark liver oil contains from 30 to 70% oil and the oil contains from
1,000 to 9,000 U.S.P. units of vitamin A per gram. It is used in feeding oils and
for the preparations of vitamin concentrates. J
(iii) OTIIRR SfiARK LIVER OILS
Several other sharks are caught in British Columbia waters, but only in small
numbers. They include principally the brown shark, Apristurus brunneus; the
blue shark, Prionace glauca; the sleeper shark, Somniosus microcephalus; the
Pacific mackerel shark (recently named Lamna ditropis and called the salmon
shark); and the basking shark, Cetorhinus maximus.
The oil contents of various shark livers and the vitamin A potencies of the
liver oils are given in table 14. The livers, like those of most sharks; generally
constitute on the average from 8 to 10% of the weight of the fish. Analyses of
samples of liver oils from some of these sharks and from the spotted cow shark,
Notorynchus cepedianus, caught only occasionally on the British Columbia
coast, are given in table 81.
TABLE 81. Characteristics of liver oils from sharks, ratfish,.and skate.
Colour
Free
(Lov. units,
Sp. gr. fatty Unsap.
Iodine Sap. 1-in: cell)
(15°C.) acid inatter
va l ue va l ue
Yellow Red
1 . 341
The liver oils of the blue, sleeper, and mackerel sharks are 'generally'used
along with mud shark or dogfish liVer oils as sources of Vitamin A, either as
constituents of feeding oils or for the preparation of vitamin A 'concentrates.
Basking sharlc liver oil, however, because of its negligible vitamin A content, is.
used industrially, chiefly as a sulphonating oil for the tanning industry. Another
use of basking shark liver oil is as a source of squalene (page 91). Swain and
McKercher (1945) found that 93.6% of the unsaponifiable matter of a sample
of basking shark liver oil was squalene. Since the oil contained 52.2% unsaponi-
fiable matter thé squalene constituted apprOximately - 49% of the whole oil.
For statistical purposes all shark liver oils other than those from soupfin and
mud s'harks are grouped together under one heading "mixed sharlc liver oils".
Statistics for their production and value are given in table 13.
The raffish, Hydrolagus colliei, is common on the Pacific Coaà from California
to Alaska. Although not especially fished to any great extent, it is caught in
considerable numbers along with other fishes, particularly dogfish. Trawl fisher-
men have stated, however, that very large quantities of ratfish can be caught by
trawling in certain localities; thus, if a profitable outlet for the oil could be
found, the fish might be obtained in this way. The livers of ratfish are relatively
large, constituting, on the average, approximately 15% of the weight of the
fish; they contain about 80% oil. Thus on the basis of the live oil alone the
whole fish contain about 12% oil. To obtain the oil the whole fish can be put
through an ordinary reduction plant, using the modified process described on
pages 201-210:
"Sinall amounts of raffish liver oil have been produced in British Columbia
during recent years: none was repérted for 1943 or preceding years, but in 1944
the production was 68,939 lb., with a value of $7,526; in 1945 it was 25,546 lb.,
valued at $2,206; and in 1946 it was 9,988 lb., valued at $1,165. Some character-
istics of ratfish liver' oil are given in table 81. The oil deposits very little stearine
until cooled to quite a low temperature, but it is not very highly unsatur-
ated. One sample deposited 3.4% stearine when cooled to 34°F. (1.7°C.);
another clouded at 26.6°F. (-3°C.) and solidified at 11.4°F. (-12°C.). The oil
oxidizes 'slowly, and for this reason as well as because of its fluidity at relatively
low temperatures it is used to some extent as a lubricant for 'guns and fine
machinery. In many places along the British Columbia coast fishermen and
loggers use ratfish liver oil as a rubbing oil for muscular complaints. The high
content of unsaponifiable matter malces the hydrogenated oil of little value for
food or soap-making purposes. However, the raw or partially hydrogenated oil
sulphonates well. Swain (1948) found that the unsaponifiable matter from a
sample of raffish liver oil contained approximately 68% glyceryl ethers. This
may point the way to other uses.
342
(p) SxnrE Livrai Oris I
A number of different species of skate are caught in British Columbia waters,
but the only skates taken in appreciable amounts are the long-nosed skate, Raja
rhina, and the, big skate, Raja binoculata. Skate livers contain from 30 to 60%
oil, but the commercially important species,in British Columbia yield oils very
low in vitamin A. Foi' that reason the oil is used. only for industrial purposes,
chiefly as a sulphonating oil. '
Prior to 1942 no skate liver oil was reported in the fisheries statistics for
British Columbia, but in 1942, 1943, 1944 and 1945 the quantities produced were
respectively 7,397; 4,118; 5,030; and 2,092 lb., with values of $835; $1,198; $1,006;
and $216. Since then production has been negligible.
Some characteristics of skate liver oil are given in table 81. The data are from
a paper by Tsujimoto (1936) and show that this oil varies widely in unsaturation.
Samples of British Columbia skate liver oils analysed in these laboratories showed
values intermediate between the limits given by Tsujimoto. In spite of the high
unsaturation of some samples they did not display any outstanding drying
properties, films expospd to the' air remaining sticky f-or several years.
343
TABLE 82.,, Characteristics of Atlantic swordfish, Atlantic bluefin tuna, and Pacifie albacore
tuna liver oils.
distance south, but the albacore, Thunnus alalunga, predominates in the landings.
since it is caught directly off the British Columbia coast.
At. thé present time no tuna livers are separated and saved in British;
Columbia, since these fish are sold in the rôund-just as they are caught. On the
Atlantic coast of Canada, tuna livers are saved and tuna liver oil is produced.
The quantities and values of tuna livers landed and marketed, and tuna liver
oil produced in Canada during the years 1942 to 1948 are given in table 13:
Some characteristics of a sample of Pacific albacore tuna liver oil, and of a
commercial tuna liver oil from fish caught off the northeastern United States are-
given in table 82. !
Atlantic coasti tuna livers constitute from about 1 to 1.8% of the weight of-
the fish, the viscera from about 1 to 2%; the oil content of the liver ranges from,
approximately 9 to 35U/o, that of the viscera from about 2 to 407o. Pacific coast
albacore tuna contain approximately 1.5 to 2^/0 of liver with an oil content
Tanging from about 7 to 20^/0.
Tuna liver oils are not only rich in vitamin D, but their vitamin D is pre-
dominantly D3i the form utilized by chickens (see page 55). That form has-
been synthesized within recent years, and the synthetic product now supplies,
the commercial requirements. When formerly vitamin D3 had to be obtained
from natural sources, tuna liver oils were in great demand for blending in poultry
oil to supply the so-called "chick vitamin D". Now, however, they are sold
mainly on the basis of their vitamin A content, since synthetic vitamin D3 is
quite cheap.
345
of oil prepared from macicerel cannery offal was found to contain 1,700 U.S.P.
units of vitamin A and 75 International units of vitamin D per gram.
(b) SHAD OILS
The shad, Alosa sapidissima, belongs to the family Clupeidae, although it is
considerably larger than most members of that family; it reaches a length of
2 féet 6 inches. It is an anadromous fish spending most of its life in the ocean but
ascending the rivers to spawn. Although caught on both coasts of Canada, the
catch on neither coast is large.
No oil is produced commercially from shad or shad offal in Canada. Pugsley
et al. (1942) investigated the liver, viscera, body and offal oils of two small lots
of Atlantic shad. Their data are summarized in table 84.
TABLE 84. Yields and vitamin data for had liver, viscei a, body and offal oils.
( EULACHON OIL
This oil is produced almost solely by the North Pacific coast Indians from
the very oily eulachon, Thaleichthys pacificus, a species of smelt. VVhen the fish
enter the rivers to spawn, large quantities are netted by the natives who merely
boil the -fish and skim off the oil, which is used entirely by the Indians them-
selves and is regarded highly as a food.
Some characteristics of eulachon oil are given in table 85. The oil is of a
light yellow coleur and sets to a buttery solid when cooled to 10°C. (50°F.). It
contains practically no vitamin A or D, in spite of the claims that have been
made for its medicinal properties.
PACIFIC COAST
Albacore body 1.4860 198 0:1 186
Anchovy 1.4789 171 0.2 187 0.5
Crab viscera 180 0.1 188 3.6 75
Eulachon body 127 - 164 17.6
Flounder head - 1.3 197 1.5 28 2.5
Flounder liver - 1.4892 152 3,8
Halibut skin 198 1.7 1.5
Monk-fish liver 147 0.5 184 - 3.6 75 , 60
Perch liver 1.4751 131 1.8
Sardine liver 1.4815- 185- 3.0- 177- 3.-
1.4838 194 7.0 186 5.3
Sea cucumber 89 130 15.4
.Sole liver 111 0.3 194 5.7 20 1.2
Starfish 141 14.5
Sturgeon body 90 0.2 202 0.6 13 1.2
Sturgeon liver 95 169 15.9 90 18
Sun-fish liver 166 1.0 194 1.7
ATLANTIC COAST
Jew-fish liver 0.7 128 37.7 :45 2.5
Mackerel body 1.4773 147 0.8 ----
Under this heading are included the whales, poipoises,, dolphins, and
belugas (white whales), all of which belong to the order _Cetacea, and the seals
and sea lions, which belong to the Pinnipedia, a suborder of the Carnivora. All
marine mammals are warm-blooded, and in order to maintain their body tem-
perature they have a thick layer of fatty tissue immediately under the skin. This
layer, which is the blubber, is the principal source of oil.
(a) CETACEA
( i ) .WHALE ons
The whales are divided into two main groups: the Mystacoceti, or baleen
whales, and the Odontoceti, or toothed whales. The first group includes the
and right whales; the sperm whale sulphr-botm(e),finackIpbs
- 347
is the most important member of the latter group, although another member, the
_ bottlenose whale, is also caught occasionally, principally in the Atlantic Ocean.
All the baleen whales yield oil from the blubber and the bones. Sperm
whales yield oil from the blubber, bones, and also frorn a cavity in the head
which contains a large quantity of a special kind of oil. The latter, called sperm
oil, difFers from a txue fatty oil in that it consists mainly of esters of fatty
alcohols, approximately 74% of the fatty acids being combined in that form, the
remaining 26% as triglycerides. The blubber and bone oils also contain esters
of fatty alcohols, but in smaller proportions than the head oil.)
The average- yields of oils from different whales are given in table 86.
Yield of oil
Species of whale Origin
(gal. per whale) _
BRITISH COLUMBIA
1922 38 4 94 50 1 187, 283,314
1923 94 62 166 78 53 2B 455 706,514
1924 83 56 125 47 100 3 414 645,657
1925 76 29 135 40 68 3B ! 351 ,556,939
1926 80 14 124 25 25 1R 269 468,206
1927 82 10 138 21 7 258 437,967
1928 83 47 140 21 13 1B 305 571,914
1929 146 16 168 67 113 407 712,597
q
1930 147 10 62 12 89 32 0 525,533
1931 Not operating
1932 Not operating
1933 190 17 1 209 509,310 96,197
1934 265 71 14 350 813,724 159,270
1935 175 20 1 202 426,772 189,390
1936 311 48 14 2 370 763,740 144,751
1937 265 44 7 317 662,355 197,227
1938 25 2 50 4 31 0 5 43,378 162,70 8
1939 Not operating
1940 126 2 90 2 •220 361,620
1941 233 1 67 27 328 566,505
1942 130 1 25 7 16 3 2,351,114
194 3 69 15 7 91 137,432
1944-47 Not operating -
1948 28 40 112 2 - 182 284,000
1949 69 2 105 76 3 - 255 392,000
*
1950 40 4 150 95 24 1 31 4
NEWFOUNDLAN D
1949 53 30 425 11 J23 38 580 1,029,031
1950 29 16 408 16 16. 175 660 877,869
*Production in British Columbia for 1948 ind 1949 are from Norwegian Whaling Gazette Year-
book ; production in 1950 and values for 1948-1950 are not available for release .
\
Colour
(Lovibond units,
Oil F.F.A. Iodine Sap. Unsap. Saturate d 1-in cell)
val. val. mat. , fatty acid
(%) (%) ' (%) Yel. Red
_
No. 1 whale oil 1-2 118 '185 2.9 18.5 10 2
Sperm whale oil 1-2 76 135 30-40 11.6 5 0.5
Unsaponifi-
Saponifica- Iodine Refractive
able matter
The oil of Acid value
tion value value index nD40 • (%)
TABLE 91. Yields and vitamin A potencies of whale livers and liver oils.
351
DOLPHIN OILS
Dolphins are a smaller type of sea mammal than whales. There ,is consider-
able variation in size between different individual varieties. Only one species, the
striped dolphin, Lagenorhynchus obliquidens, has been found in British Columbia
waters, and that very rarely. A larger variety, the so-called blackfish, which is
actually a dolphin, is present in considerable numbers along the Atlantic coast
of Canada. While not used comrnércially in Canada, it is caught near Cape Cod,
in the United States, for commercial purposes. Its value lies principally in the
oils obtained from the two fatty lobes adjacent to the articulation of the jaws.
The jaw oil, as pointed out on page 22; contains a considerable amount of com-
bined isovaleric acid. This fatty acid, which is present in the form of glycerides,
gives the oil properties that make it particularly suitable for the lubrication of
watches, clocks, and other fine instruments. A similar oil is obtained from the
a large fatty mass extending from the spout hole to the beak. "melonrjuk,
Oil is also prepared from the blubber, but its properties are different to those of
- the head and jaw oils.
In preparing each of the latter two oils the fatty tissue is minced and cooked
in water at a temperature not exceeding 82°C. (180°F.); the blubber oil can be
obtained by cooking in boiling water or under steam pressure.
Analyses of the oils from the common dolphin, Delphinus delphis, are given
in table 92 from the data of Marcelet (1926) and Klein and Stigol (1930). The
high Reichert-Meissl values and high saponification values of the jaw and head
oils indicate the presence of a high proportion of loW-molecular-weight fatty
acids, mainly isovaleric ‘acid, in these oils.
TABLE 92. Characteristics of oils of the common dolphin (taken from lobes at the articulation
of the jaws, fatty tissue inside upper part of head, tissue surrounding the skull, and blubber).
•
Around
Jaws Head Blubber
skull
Puncochar (1946) has described the Cape Cod dolphin fishery, and the
- preparation and nature of the jaw and head oil. It is stated that specifications
for oil of this type generally require that it contain not more than 0.3% free fatty-
acid and have a pour point of —20°F.
352
(iii) BELUGA OILS
The beluga, or white whale as it is sometimes called, DelphinaptentS leucas,
is not a true whale, but a species of large dolphin. It has been taken commercially
in the Gulf of St. Lawrence for many years; commercial utilization has also re-
cently been started in Hudson Bay. In table 93 are given statistics for the
number of belugas landed and the quantities and values of beluga oil produced in
Canada during the years 1937 to 1951 inclusive. This production to 1947 was in
Quebec; since 1949 it has been in Manitoba.
TABLE 93. Number of belugas landed, quantities and values of oil produced, in Canada 1937-1951.
The oil from belugas is obtained principally from the blubber. Some charac-
teristics of this oil and the jaw oil are given in table 94 (A), and the viscosity of
one sample each of beluga body and head oils at different temperatures in table
94 (B). •
TABLE 94 (A). Characteristics of beluga oils.
Beluga oil has low cloud and pour points in spite of the low Reichert-Meissl
and iodine values. Apparently the relatively high saponification value, which in
353
Tab'le 94 (B). Viscosities of beluga oils.
,
Temperature Viscosity in 'centipoises .
28 82.5 41 33
37.8 100.0 30 24
65.6 150.0 17 12
100.0 212.0 10 9
view of'the low Reichert-Meissl value indicates a fairly low molecular weight of
the fatty acids as a whole, thus accounts for the low-clouding temperature. Beluga
livers contain approximately 0.4 to 4.0% oil; the vitamin A potency of oil
ranges from 6000 to 40,000 U.S.P. units per gram.
(iv) ronpœsE ons
Porpoises are small marine mammals, quite similar to dolphins, but with a
maximum length of only about 5 feet. Two varieties are found in British Columbia
waters, the harbour porpoise, Phocoena vomerina, and the Da11 porpoise,
Phocoena dalli. It is doubtful if even the two together are present in sufficient
numbers for commercial exploitation.
A small porpoise industry was carried on in the Province of Quebec up to
the year 1936. Statistics for_the number of porpoises landed, and the quantities
and values of the oil produced in Canada from 1930 to 1936 are given in table 95.
TABLE 95. Number of porpoises landed, quantities and values of oil produced, in Canada
1930-1936.
The oils from a porpoise caught in the vicinity. of Prince Rupert were pre-
pared and studied by Sunderland (1932). This porpoise was about 5 feet long
and weighed 145 lb. The oils from the -upper and lower jaws, skull, and blubber,
were expressed semi-quantitatively and the following yields were obtained:
upper jaw oil, 3X oz.; lower jaw oil, 2X oz.; skull oil, 1 3 oz.; blubber oil, 14 lb.
354
These oils were analysed with results shown in table 96. Porpoise jaw oils, like
dolphin jaw oils, are peculiar in that they cantain considerable proportions of
combined fatty acids of low molecular weight, principally isovaleric acid. The
valuable lubricating properties of these oils depend to a certain extent on the
presence of these fatty acids, the proportion of which is shown by the Reichert-
Meissl values, high saponification values, and low solidification points. From the
data in table 96 it may be concluded that the oil from the upper jaw contains the
largest proportion of acids of low molecular weight, with slightly less in oil from
the lower jaw. The blubber oil contains more of these acids than do the head oils,
and in addition has a relatively low unsaturation.
(b) PINNIPDDIA
TABLE 97. Number of hair seals landed, quantities and values of oil produced, in Canada
1930-1950.
As already pointed out, the Atlantic seals are captured during the winter.
The skins with the blubber attached are separated from the carcasses, and allowed
to freeze naturally. At the rendering plant the skins are removed from the blub-
ber, which is then ground up and rendered with steam under a pressure of 10
to 15 pounds. The oil produced is divided into three grades: the brown oil with
356
a free-fatty-acid content above 5%; the straw-coloured oil with a free-fatty-acid
content between 1.5 and 5%, and the pale oil.with a free-fatty-acid content below
1.5%. The decolorization and deodorization of these oils have been intensively
studied by Dugal and Cardin .(1949; 1951).
Characteristics of the oils from Pacific hair and fur seals, and from the
Atlantic hair seal, are given in table 98, compiled from the data of Egloff and
Nelson (1933), Pugsley and Harding (1938) and Riou (1947).
Seal oils are used chiefly for hydrogenating to Make various. products, and
in the manufacture of soap. Lower grades are sulphonated and used in cotton
and rayon finishing.,
- Seal livers contain very little oil, but the oil prepared from them, especially
that from fur seal livers, has a fairly high average vitamin A potency. Both the
oil content and the vitamin A potency are, however, subject to wide variations
The livers of male fur seals contain from 0.2 to 2.2% oil; the vitamin A potency
of the oil ranges from about 13,000 to 400,000 U.S.P. units of vitamin A per gram.
Hair seal livers contain from 1.8 to 3.3% oil with a vitamin A potency ranging
from about 10,000 to 55,000 U.S.P. units per gram.
(ii) SEA LION OILS
Sreller's sea lion, Eumetopias jubata, is found in considerable numbers
along the coast of British Columbia. Sea lions are considerably larger than seals,
and can be captured more easily since they spend a considerably longer period
out of the water while having their young. Sufficient numbers could probably be
taken to warrant the establishment of a plant for producing oil and meal. While
such a plant would have to be located close to the sea lion rookeries, any seals ,
obtainlecuds z.
357
Some characteristics of sea lion blubber oil are given in table 98.
Sea lion livers contain from about 2 to 4% of oil with vitamin A potency
ranging from about 15,000 to 30,000 U.S.P. units per gram.
REFERENCES
359
CHAPTER ELEVEN
THE term analysis usually refers to the determination of the actual composition,
of a material. In the case of fats and fatty oils the determination of the actual
composition is long and tedious; but a number of physical and chemical. tests
for various factors related to the composition give,,sufl'icient information for most
purposes. While detailed studies of the composition are sometimes carried out,,
the tests referred to are much more commonly used. Although the examination
of an oil is thus ordinarily not an analysis in the usual sense, the term oil analysis
is applied to it.
While some of the tests and measurements were develbped specifically for
use with marine oils, most of them were originally devised for other oils or for
fatty oils in general.
The present treatment of the subject is divided into two -parts. The first part
deals with factors which, due to natural causes, improper processing, or deteriora-
tion of the oil, may vary widely; in the second part the so-called "characteristics",
factors which are more or less constant in any particular kind of oil, are
discussed. .
The object of the present chapter is to explain the meaning of the various
determinations, not to describe the actual laboratory procedures. Some specific
references are given to the latter, especially to methods particularly suitable for
fish oils. In general, however, for details of laboratory methods the reader is
referred to the following: Official and Tentative Methods of the American Oil
Chemists' Society (American Oil Chémists' Society, 35 East Wacker Drive,
Chicago 1, Ill.); the chapter on Oils, Fats and Waxes in the Official and Tentative
Methods of Analysis of the Association of Official Agricultural Chemists ( Asso-
ciation of Official Agricultural Chemists, P.O. Box 540, Benjamin Franklin Station,
Washington 4, D.C.) ; methods published by the American Society for Testing
Materials, 1916 Race St., Philadelphia 3, Pa. '
In assessing the data obtained in the analysis of an oil there are several
considerations which must be taken into account. In the first place it must be
remembered that no matter how accurately an analysis is carried out, its repre-
sentation of the actual lot of material is limited by the accuracy of the sampling.
For accurate work a container or tank of oil should be mixed thoroughly.imme-
diately before sampling. When that is not possible, the sample should be a com-
posite of several taken at different depths representing a vertical section of the
359
contents of the container. This is particularly important when the oil has been
standing in the container for some time and there is no opportunity of mixing it,
since under such conditions some semi-solid stearine may have settled to the
bottom.
The next consideration is that of significant figures for values, and the degree
of accuracy obtainable in a determination. When the first two digits in a value
are reliable while the reliability of the third is détubtful, the value is said to be
accurate to two significant figures. Similarly, when the first three digits are re-
liable but the fourth doubtful, it is said to be accurate to three significant figures.
The number of significant figures is independent of the decimal point. Thus the
saponification value of an oil, when expressed in the customary manner as milli-
grams of potassium hydrœdde per gram of oil, may have been determined with
an accuracy of three significant figures ( for example 97.6), or to four sig-nificant
figures (for example 184.3). If it should be expressed in grams of potassium
hydroxide per gram of oil, instead of in milligrams, the values corresponding to
the above would be 0.0976 and 0.1843, but the number of significant figures in
each would be unchanged. To obtain the final significant figure a result is cal-
culated one figure beyond it. For example, if the result of an analytical détermina-
' tion is caldulated as 0.242, and the third figure is not definite but may be in error
by as much as -±-2 (that is, the result lies between 0.240 and 0.244), the value is
taken as 0.24. If it had come out as, say, 0.247, it would be taken as 0.25.
I. VARIABLE FACTORS
(a) CoLoun
Colour in oils is due to naturally occm-ring pigments, to deterioration
changes, and to contamination. Deterioration changes include spoilage of the
raw material prior to production of the oil, faulty production methods, and oxida-
tion of the oil during storage. Contamination with fuel oil, iron compounds and
other adventitious materials may give rise to darkening or colour development.
For the measurement of colour, Lovibond colour glasses have usually been
employed, values being expressed in terms of Lovibond units and the thickness
of the cell used. The thicicness of the cell, for commercial measurement of oil
colours, is generally 1 inch. 'This is the standard method of determining colour
of oils for shipment to Great Britain. In scientific work Lovibond units are usually
measured and expressed in terms of a 1-centimetre cell.
The use of spectrophotometric measurements instead of Lovibond colour
glasses for determining colours of oils has been under consideration and study
'by the American Oil Chemists' Society for several years. A spectrophotometric
method for the determination of colour of fatty oils has been reported by Presnell
(1949). Several methods for recording the colour of fish oils were compared by
Bucher et al. (1946).
In the United States the colours of oils are frequently expressed in ferms of
360
the F .A.C . standard colour ampoules .' In ûsing these a comparator block should
be employed, or alternatively they may be permanently mounted in rows in an
open-sided box, with a clear glass panel in front and suitable lighting (prefer-
ably fluorescent tubes) behind . The ampoules should be spaced at such a dis-
tance apart that a test tube of the saine diameter containing the oil to be graded,
when held in front of the clear glass panel, just covers the space between the
two standards most nearly matching the colour of the sample .
While the colotu of oils to be sold to domestic markets may be measured
in a Lovibond tintometer, a somewhat simpler procedure, carried out âs follows,
is more customary . Every season an analyst will select as a standard a fresh
average sample of good quality for each type of oil which he is called upon to
examine . Such an oil is sometimes designated as F .A.Q . (fair average quality,
see page 377) for the season represented . These standards will vary somewhat
in depth of colour from year to year, but by comparing a sample of oil with
the standard chosen as representative of the ôil produced during the same year,
the analyst can determine whether the sample under examination is of satis-
factory quality with respect to its colour . If satisfactorÿ, it is designated "light" .
The' actual depth of colour in a herring or pilchard oil designated as "light"
according to this method varies from year to year, since the . average colour
varies, depending largely on the nature of the feed in the fish when caught .
The comparison is made by pouring the standard oil into a large test tube to
a depth of 2 or 3 inches, filling a similar test tube to just the same depth with
the oil to be examined, and viewing them together vertically against a brightly-
lighted white background .
This method is generally applied in British Columbia only to herring and
pilchard oils, although it would be equally applicable to other light-coloured
oils . A dark colour in liver oils is not necessarily an index of deterioration ; on
the contrary, if the oil is of good quality, it usually indicates 1 high vitamin A
potency when comparisons are made among samples of the oil from one species
of fish. Salmon oils vary greatly in pigmentation' depending on the variety or
varieties of salmon waste from"which they are produced . The variations are too
great to permit the use of this simple method of colour grading . Lovibond colour
glasses can be used to measure the colour of salmon body oil and other dark-
coloured oils .
Free fatty acids result from the hydrolytic breakdown of neutral oils . Oils
prepared from putrefied material without the use of alkali are often high in free
fatty acids; an oil freshly prepared from good quality material should contain
only a negligible amount, but upon standing, particularly if it contains an appre-
ciable amount of water, free fatty acids will be formed . Their development is
hastened by various agencies such as light, enzymes not destroyed during process-
°Obtainable from Swift and Company, Technical Division, Union Stockyards, Chicago,
Illinois, U .S .A .
361
ing, and bacteria. The free acid content is thus an index of the extent of deteriora-
tion of an bil, and provides a criterion for judging the quality. Oils prepared by
alkali digestion are neutral, even if prepared from putrid materials, since the
free fatty acids are neutralized during the preparation.
The free acidity of an oil is expressed either as (a) the number of milli-
grams of potassium hydroxide required to neutralize the free fatty acids in 1
gram of oil, or as (b) percentage of free fatty acid in terms of oleic acid.
A numerical value expressed as (a) is exactly 1.9878 times, or for all prac-
tical purposes twice, the numerical value expressed as (b). Although the term
"acid value" usually refers to (a), that usage is not strictly adhered to, and it is
sometimes used in reference to (b). The ,latter is, however, more commonly
designated as "% free fatty acid" or simply as "free fatty acid". Occasionally the
term "acid number" may be encountered; its usage is generally synonymous with
"acid value".
(c) ATMOSPHERIC OXIDATION; RANCIDITY
These phenomena, -discussed on pages 170-172, may arise as a result of
deteriorative changes in the raw tissue materials before the oil is separated, or as
a result of improper preparation or storage of the oil.. An initial manifestation
of theSe changes is an addition of oxygen to the unsaturated fatty acid 'com-
ponents, with formation of peroxides; these are detectable by one or other of the
variations of the "peroxide test". Breakdown of peroxides is evidenced by the
appearance of aldehydes, which contribute to a f'rancid" flavour and odour.
Various tests such a's the Kreis, Schiff, Lea and others are used in detecting and
determining these aldehydes. The value of these tests for peroxides and aldehydes
lies not only in their assessment of the deteriorative changes that already may
have taken place, but also in the information they yield concerning possible
further deterioration that may take place, with or without the benefit of anti-
oxidants, or stabilizers such as described on pages 174478. Peroxide values are
commonly expressed as millimoles (milligrams' X 16) of reactive oxygen per kilo-
gram of oil ( Markley, 1947), and should be regarded as an index, rather than an
absolute measure, of oxidation.
( d ) MOISTURE
The moisture content of fish oils varies considerably depending on the con-
dition of the raw material, the method of production and the amount of refining.
As a rule, it is higher in oils prepared from material which has undergone some
preliminary decomposition, and in those which, due to improper processing, con-
tain suspended materials such as tissue or gelatin (sometimes referred to by
reduction-plant men as "glue"), since these as well as decomposition products
not only absorb water but also act as emulsifying agents for water in the oil.
However, even without the presence of such suspended matter, an oil may con-
tain up to 0.5% moisture and yet remain dear at room temperature; larger
adounts give it a cloudy appearance.
362
There are'several methods by which the moisture content can be determined.
One method is to heat 'a weighed sample of the oil to constant weight in a
vacuum oven. The results obtained by this method are usually reported as
"moisture and volatile matter" since any non-aqueous volatile constituents pres-
ent will also be removed. Another method of determining "moisture and volatile
matter" consists in heating a sample of the oil in a hot air oven for 30 minutes at
101°C. (214°F.). This method would not be so satisfactory for highly unsaturated
oils as the. vacuum-oven method, since sufficient oxygen maY be absorbed to
appreciably affect the results.
The Kingman Distillation Method, one of the official methods of the Ameri-
can Oil Chemists' Society, consists in distilling off the water from the sample
with a high-boiling, water-immiscible liquid and collecting the distillate in a
calibrated sedimentation tube with a side arm which returns the medium to the
distilling ,flask while the water is trapped in the calibrated tube.
(e) CLOUD, COLD, AND FLOW TESTS
( CLOUD TEST ( CLOUD POINT)
The cloud test, or cloud point as it is also called, is the temperature at
which an oil shows a slight permanent cloud when it is cooled fairly rapidly
after being heated. The official cloud-test method of the American Oil Chemists'
Society specifies that the oil shall be heated to 130°C. (266°F.) immediately
before maldng the test.' Values obtained in determinations carried out by the
method officially described as the cloud test are sometimes referred to as the
cold test, but the latter is officially quite a different test (see below).
Clouding of an oil at a higher temperature than that shown by the cloud test
on a sample drawn from it is generally due to moisture. To check this, a fresh
sample should be cooled without the preliminary heating, and the cloud point
noted. It is then heated to 130°C. to drive off the moisture, and again cooled. A
difference of more than a few degrees in the resulting cloud points is due to
moisture. Small differences are due to the fact that heating causes an oil to give
an abnormally low cloud test for several hours afterwards.
(ii) COLD TEST
The cold test, as described in the Official and Tentative Methods of the
American Oil Chemists' Society, statos merely that the oil shall remain clear when
a 4-oz. sample bottle of it is cooled_ in a water and ice bath—that is, at 0°C.
(32°F.)—for 5 3 hours. Actually the oil might have to be cooled to a much lower
temperature to produce clouding, bit as long as it remains clear at 0°C. for 53 .
hours it passes the official cold test.
(iii) PLOW TEST (POUR POINT)
The flow test, also known as the pour point,- is the lowest temperature at
which the oil will just flow under specified conditions. The method entails
solidifying the oil in a partia lly-fi ll ed oil sample bottle and then allowing it to
warm up at room temperature until the oil will just flow from one end of the
bottle to the other when inverted.
363
(f) SOAP
While fresh oils prepared without the use of alkali do not Contain soap, liver
oils prepared by alkali-digestion methods and any oils which have been alkali
refined may contain appreciable amounts. It can be determined by the Durst
method as modified by Harvey, et al. (1938).
(g) NITROGEN
Calculated
(According
Compound Determined
to
Kaufmann)
367
linolenic acid was equivalent to less than two thirds of the unsaturation. The data
in table 99, from the paper by Hilditch and Murti, illustrate this.
(iii) IBENE ( MALEIC ANHYDRIDE ) VALUE
The diene or maleic anhydride value is used to measure the amount of un-
saturation due to conjugated double bonds in oils or fatty acids. The basis of the
determination is the quantitative reaction between maleic anhydride and com-
pounds with conjugated double bonds, whereby stable addition products are
formed.
Unfortunately maleic anhydride reacts not only with conjugated double
bonds but also with hydroxy acids, amino acids, phosphatides, saturated alcohols .,
and the oxidation products of unsaturated fatty acids.
Diene values are expressed as the percentage iodine equivalent to the maleic
anhydride absorbed.
(iv) INSOLUBLE BROMIDES
Bromine reacts with the double bonds of unsaturated fatty acids, each
double bond adding on two atoms of the reagent. The bromides so formed differ
greatly in their solubility relations in different solvents. Based on this are methods
for estimating the distribution of unsaturation among various unsaturated fatty
acids of fatty oils. Table 100 gives a general idea of the solubilities.
Solubility in
Nature of ' Bromide
Petroleum Ethyl
fatty acid formed Chloroform
spirits ether
Monoethylenic Dibromides Soluble Soluble Soluble
(oleic)
Di-ethylenic Tetrabromides Soluble warm Soluble Soluble
(linoleic) Insoluble cold
Tri-ethylenic Hexabromides Insoluble 'Almost Soluble
(linolenic) insoluble
Tetra-ethylenic Octabromides Insoluble Practically Insoluble
insoluble
Penta-ethylenic Deca- and higher Insoluble Insoluble Insoluble
and higher bromides
The solubilities given in table 100 are only approximate; none of the com-
pounds indicated as "insoluble" are absolutely so. In precipitating any particular
bromide or group of bromides it is customary first to saturate with these bromides
the solvent from which they are to be precipitated, at the temperature àt which
the precipitation is to be carried out. This eliminates the error which would
•otherwise be introduced by their slight solubility. The bromides used for saturat-
ing the solvent are prepared non-quantitatively from the same materials and by
:the same method.
368
From table 100 it can be seen that if à mixture of various fatty acids is
brominated in cold petroleum spirits, those bromides which are insoluble (tetra-,
hexa-, octa- and deca-) will precipitate and can be filtered off, washed, dried,
and weighed. Similarly, if brominated in ethyl ether the hexa-, oeta- and deca‘
bromides are precipitated, while in chloroform the octa- and decabromides
separate out. The precipitation of the insoluble bromides, therefore, forms the
basis for rough estimation of the different proportions of the various unsaturated
fatty acids present.
The data obtained in insoluble bromide determinations are expressed in
terms of the precipitated bromides, as percentages of the material under examina-
tion.
Unfortunately the bromination method of determining the distribution of
unsaturation suffers from the inherent defect that only a part of thè bromine
addition product of each unsaturated fatty acid is insoluble in the solvents
discussed; part is simultaneonsly converted into an isomeric soluble bromide.
Matthews, Brode and Brown (1941b) found while the theoretical tetrabromide
value of linoleic acid and hexabromide value of linolenic acid tare respectively,
214.2 and 273.7, the corresponding actual values of carefully purified samples
were 102.9 for linoleic and 96.0 for linolenie acid. On the basis of these values
the percentage of fatty acid with two double bonds in a mixture can be calculated
(Tetrabromide value ) x (100)
by the formula and the percentage of fatty acid
102.9
(Hexabromide value) X (100)
with three double bonds from the formula
96.0
Although there are as yet few data available respecting the actual per-
centages of insoluble octa- and decabromides. formed from fatty acids with four
and five double bonds, there is little doubt that they fall considerably short of
the theoretical values.
While hexabromides are the highest bromides yielded by vegetable
oils, fish oils are aaracterized by the presence of fatty acids yielding octa- and
even higher bromides. For this reason the "octabromide test" is frequently used
by commercial analysts in detecting the presence of fish oils in vegetable oils.
A method for the determination of bromides insoluble in petroleum spirits
is described by Brown and Frankel (1938); methods for determining ether-
insoluble bromides are described by Bailey and Johnson (1918), Shinowara and
Brown (1938), and White and Brown (1949); a method for chloroform-insoluble
bromides is given. by Eisenschiml and Copthorne (1910). A method for ether-
insoluble bromides which involves brominating in chloroform, then distilling off
the chloroform, and exicacting the residue with ethyl ether, is described by
Steele and Washburn (1920).
From table 100 it might appear that the determination of the tetra-, hexa-,
and higher bromides céuld be made in the same sample by precipitating them
all together in petroleum spirits, and then dissolving out the tetrabromides by
369
extracting the precipitate with ethY1 ether, then the hexabromides by extracting
with chloroform; but this procedure is not satisfactory, since, on treatment with
the second solvent, the residue undergoes decomposition with the evolution of
hydrobromic acid and the formation of a gummy brown residue. By making
three separate determinations, however, and taking the difference between the
respective values so found, the amounts of tetra-, hexa-, octa- and higher
bromides may be estimated.
The term "hexabromide number" or "hexabromide value" is often used to
designate simply the total ether-insoluble bromides, and the term "tetrabromide
value" is similarly taken as the total of the bromides insoluble in petroleum
spirits. Strictly speaking, however, the hexabromide number or hexabromide
value should refer to the ether-insoluble bromides less the chloroform-insoluble
bromides; and the tetrabromide value should refer to the petroleum-insoluble
bromides less the ether-insoluble bromides. The values are used in this stricter
sense in the present Bulletin.
The percentage yields obtained by direct bromination of fish oil fatty acids
in ether and in petroleum spirits ( separately) were used, together with examina-
tion of all the fractions of bromides, for identifying various fish oils (cod, herring,
etc.) by Bélopolskii and Maksimov (1931, 1932).
~ C) SAPONIFICATION EQUIVALENT
( d ) EsTER VALUE
While the greater portion of most fats and fatty oils can be converted into
soap and glycerine by treatment with caustic alkali, there is always a certain
amount of material present which cannot be thus rendered water soluble . To
this material, which contains a number of diûerent' substances, the term "un-
saponifiable matter" is collectively applied . The commonest constituents of, the
unsaponifiable matter of fish oils are cholesterol and pigments but, in addition,
hydrocarbons, vitamins A and D, high-Inolecular-weight fatty alcohols and
glyceryl ethers may occur .
Although the percentage of unsaponifiable matter in fish oils is, subject to
wide variations, in general the body and liver oils of the Teleostomi contain
relatively little, usually less than 2 .5%, while the body and liver oils of the
Elasmobranclùi (sharks, dogfish, skates) contain larger amounts . There are,
however, exceptions in either case ; the liver of the halibut, one of the Teleostomi,
for example, contains from 5 to 167o . Shark liver oils mostly contain between
5 and 25%, although basking shark liver oils have more (see table, 81), but
skate liver oils contain only about 1 to 5% .
The oils from two species of whale, the bottlenose and the sperm, are very
high in unsaponifiable matter since they contain fatty acid esters of high-
molecular-weight alcohols in considerable amounts . These alcohols, when set
371
free by saponification, form the greater part of the unsaponifiable matter in such
oils.
The presence of much unsaponifiable matter is undesirable in drying oils
since the unsaponifiable constituents are all non-drying, and is also undesirable io,
oils to be used for soapmaking since the yield of soap is lowered by the amount
of the unsaponifiables present. In general, a minimal pêrcentage of unsaponifiable
matter is desirable, except in vitamin A oils. In an oil having a vitamin A potency
of 200,000 U.S.P. units per gram the vitamin amounts to about 5% of the weight
of the oil, so it is obvious that a low content of unsaponifiable matter is impossible
in an oil which is rich in that vitamin. On the other hand an oil containing
200,000 International units of vitamin D per gram would contain by weight only
0.5% of this vitamin.
Unsaponifiable matter also includes any mineral oil or resin oil present as
adulterants or contaminants.
The percentage of unsaponifiable matter in an oil is determined by saponify-
ing the oil, diluting the soaps with water and extracting the soap solution with a
suitable solvent, washing the extract to remove the traces of dissolved soap, dis-
tilling off the solvent and weighing the residue. Of the various solvents which have
been tried only two, petroleum spirits and ethyl ether, are at all commonly used
for the determination of unsaponifiable matter, and of them the latter is the
one usually employed. Very careful standardization of conditions is necessary in
either case as otherwise the results may show considerable discrepancies.
While the majority of oils contain only fatty acids of inoderately high
molecular weight, which are quite insoluble in water, a few contain fatty acids
of low molecular weight which are water soluble. The chief water-soluble fatty
acids which have been found in oils are butyric; iso-valeric, caproic, caprylic,
capric, and caproleic. The solubility decreases as the molecular weight increases,
so that while butyric acid is infinitely soluble, capric dissolves to the extent of
only one part in a thousand parts of boiling water. Only three of the above
mentioned acids have been found in marine oils: iso-valeric in the jaw oils of
porpoises and dolphins, caproleic and capric in sperm whale head oil.
The soluble acids are expressed as a percentage of the oil, in terms of
butyric acid. The arbitrary expression in terms of butyric acid is merely a con-
venience. Although a standard procedure, it is really erroneous for marine oils,
since they do not contain butyric acid. The insoluble acids are also expressed
as a percentage, but they are determined by direct weighing so no arbitrary mode
of expression is necessary.
There is no sharp line of division between the fatty acids which are volatile
with steam and those which are not, and it is not possible to effect more than an
apprœdmate separation by any method of distillation unless it is rigidly
standardized or the distillation continued for a very long time. By carefully
standardizing the procedure, however, fairly constant proportions of the acids
can be distilled. The Reichert-Meissl value, which represents the amount of
water-soluble fatty acids volatile with steam, is expressed as the number of cubic
centimetres of tenth-normal alkali required to titrate the. soluble fatty acids
obtained from 5 gm. of oil by steam distillation of the fatty acids under pre-
scribed conditions. The Polenske value is the number of cubic céntimetres of
tenth-normal base required to titrate the insoluble fatty acids distilled in the
course of the Reichert-Meissl determination.
Just as in. the case of the soluble acids determination, significantly high
Reichert-Meissl values are given by only a few marine animal oils, chiefly those
373
from the jaw lobes of porpoises and dolphins and that from the head of the
sperm whale.
Values obtained with oxidized and rancid oils have no significance in
assessing the original amount of volatile fatty acids in an oil. Partially oxidized
non-volatile fatty acids are broken down during a steam distillation to forms
which will distil with steam.
The only solid fatty acid components in the glycerides of untreated fish oils
are saturated, but elaidinized or hydrogenated oils may contain unsaturated solid
fatty acids. The determination of the- saturated or solid fatty acids, while not a
widely used characteristic, is useful as an indication of the composition.
Their amount can be determined by either of two widely different basic
procedures. One is the Bertram method or its modifications, which consists in
oxidizing the unsaturated fatty acids with potassium permanganate and separating
the solid saturated fatty acids from the liquid acids so formed, as the magnesium
soaps. The other is the Twitchell method or one of its modifications. In the
Twitchell method differences in the solubilities of the lead soaps in alcohol are
used to separate the solid and liquid fatty acids.
REFERENCES
374
CHAPTER TWELVE
I. AUSTRALIA ( 1948 )
There are no official specifications for the import of fish oils into Australia.
However, the specifications laid down in the British Pharmacopoeia are generally
used to cover the import of fish-liver and other medicinal Oils. Other fish oils are
imported on the basis of specifications agreed upon between the importer and
the overseas supplier.
III. CANADA
(a) COD LIVER, OIL ( DEPARTMENT OF NATIONAL -HEALTH AND WELFARE ) (1949)
No person shall sell cod liver oil in a package unless both the inner and the
outer labels thereof carry, legibly and conspicuously, a statement
1. In International Units per gram of both the vitamin A and the vitamin D
content, and
2. Of the recommended dosage that, irrespective of the age of the consumer,
shall not exceed per day two teaspoonfuls or
10,000 International Units of vitamin A, and
2,000 International Units of vitamin D.
375
(b) HALIBUT LIVER OIL (DEPARTMENT OF NATIONAL HEALTH AND WELFARE)
(1949)
Description-Halibut Liver Oil shall be the fixed oil extracted from the fresh,
or suitably preserved liver of the halibut, Hippoglossus hippoglossus Linn., and
other species of Hippoglossus. It is a yellow to brownish-yellow oily liquid,
possessing a slightly fishy, but not rancid odour, and a fishy taste. Halibut Liver
Oil shall contain not less than '60,000 International Units of vitamin A per gram;
and shall conform to the following specifications.
Solubility-Halibut Liver Oil is slightly soluble in alcohol (90%o); and is
miscible with ether, with chloroform, with carbon disulphide and with ethyl
acetate.
Test for identity-Dissolve 1 drop of Halibut Liver Oil in 1 cc. of chloroform
and shake the mixture with 1 drop of sulphuric acid; a blue colour is produced,
which changes to violet, then to dark green, and finally to black.
Specific gravity-The specific gravity of the oil at 25°C. (77°F.) shall be not
lower than 0.920 and not higher than 0.930.
Iodine value-The iodine value of the oil shall be not lower than 125 and not
higher than 155.
Acid value-The acid value of .the oil shall not be greater than 2.8 (i.e. 1.4%,
calculated as oleic acid).
Unsaponifiable matter-The oil shall contain not less than 7% and not more
than 13.5% unsaponifiable matter.
Saponification value-The saponification value of the oil shall be not lower than
160 and not higher than 180.
Storage-Halibut Liver Oil should be kept in a well-filled, well-closed con-
tainer, from which air has been excluded, and in a dark, cool place.
Most sales of these oils, both domestic and foreign, are made on what is com-
monly referred to as the F.A.Q. (Fair Average Quality) basis; the actual details
being agreed upon between buyer and seller at the time of making their contract.
That is, certain limiting values for various factors in connection with the oil are
agreed upon and pro-rata penalties (i.e. price deductions) are set for any devia-
tions from these limits. (See also page 361.)
In general the F.A.Q. specifications for British Columbia herring and pilchard
oils are as follows.
377
Domestic F.A.Q. Contracts:
Free fatty acids—maximum 1.5 to 2.0%.
Combined mineral oil and impurities—maximum 1.0%.
The oil must be free from contamination, fuel oil and/or mineral oil.
'Contracts for F.A.Q. sales to Europe:
Free fatty acids—basis of 2%, maximum 3%.
Combined moisture and impurities—maximum 0.5%.
Iodine value—pilchard oil, 170;
—herring ,oil, not specified.
The oil must be 97% saponifiable.
If the herring or pilchard oil produced in any particular season differs very
markedly in any of the above factors or in appearance from that produced in
other years, it is customary to sell it on the basis of F.A.Q. (Season). In that case
allowance is made for the difference. Sales contracts should always specify
whether the basis is F.A.Q. (Season) or simply F.A.Q.
IV. DENMARK
(a) COD LIVER Ou ( DANISH PHARMACOPOEIA ) ( 1949)
The fat oil exuded from the fresh, cleaned livers of different cod-fish, in
particular Gadus callarias Linn., without or during the lowest possible steam
heating, and which—by cooling at a temperature below 0°C. (32°F.) and then
filtering—has been freed from the solid matter separated at this temperature.
Liver oil should be biologically controlled both with regard to its content
of vitamin A and with regard to its content of vitamin D3 according to the regu-
lations of the Ministry of the Interior for biological control of liver oil; it should
contain at least 750 International Units of vitamin A and at least 75 International
Units of vitamin D per gram.
Designation—Oleum jecoris aselli.
Description—Liver oil is a clear and pale yellow oil with a characteristic taste
and odour. The oil should not have a rancid odour or taste. VVhen allowed to
stand in thin layers exposed to the air the liver oil forms a tough mass.
Solubility—Almost insoluble in water, moderately soluble in absolute alcohol,
very light-soluble in boiling absolute alcohol, very heavy-soluble in pure alcohol,
can be mixed in all proportions with ether and chloreform and with petroleum
ether and vaseline . ,
Specific gravity—From 0.917 to 0.926.
Refractive index—From 1.477 to 1.481.
Saponification value-174 to 197. (i.e., 12.40 to 14.05 cc. of 0.5 N alcoholic
potassium hydroxide is required to saponify 2.000 gm. of liver oil.)
Iodine value—In the determination of the iodine value of 0.2000 gm. of liver
oil frpm 23.65 to 28.40 cc. of 0.1 N bromate should be used.
Unsaponifiable matter—From 0.5 to 1.4%.
378
Co/our—Liver oil should keep within the limit test for colour with the following
colour standard: 2.00 Co + 23.00 Fe + 75.00 acid.
Peroxide value—In the determination of peroxide in liver oil 0.40 cc. of 0.01 N
thiosulphate should at most be used.
Acid value—In the determination of the acid value of 5.00 gm. of liver oil 1.07
cc. of 0.1 N sodium hydrœdde should at most be used.
Cold test-10 cc. of liver oil should be clear after cooling for 4 hours in a test
tube in an ice bath.
Miscellaneous tests-3 drops of fuming ni tr ic acid should at once give a red or
purple colour after addition to a few drops of liver oil on a watch-glass, and
stirring by means of a glass spatula. Upon standing this colour changes through
orange into brownish-yellow or blue colour (seal oil, fish oils).
—Liver oil should not give reactions indicating cottonseed oil.
—Liver oil should not give reactions indicating sesame oil.
—2.0 gm. of liver oil should not leave a greater ignited residue than 0.0005
V. FRANCE ( 1949 )
No official specifications for marine oils.
382
Unsaponifiable matter—The oil shall not contain more than 3% Of 'unsaponi-
fiable matter, unless ofherwise agreed between purchaser and vendor .,
Cold test—The cloud point shall be agreed between purchaser and Vendor.
384
(C ) VITAMIN A OIL
1. Vitamin A' Oil is a fixed oil obtained from fresh livers of marine fishes and
animals or its vitamin concentrate dissolved in Cod Liver Oil or vegetable oil.
2. Vitamin A Oil is a yellow or brownish-yèllow and clear or ttubid liquid. Its
acid value is not more than 5.0.
3. 0.5 grams of Vitamin A Oil shall be soluble in 3 cc. of chloroform.
4. When 0.06 grams of Vitamin A Oil is tested by the same method as in the third
clause of "Cod Liver Oil", the saine results shall be obtained.
5. Bottle shall be filled with Vitamin A Oil and tightly corked. Or Vitamin A Oil
shall be preserved in a bottle from which air is expelled. Store in dark cool place.
(e) HERRING, SARDINE, SHARK, COD, POLLACK AND OTHER FISH OIL (INCLUDING
CALAMARY OIL )
Admitted grade
Test
First grade Second grade Third grade
Acid value Free fatty acid not Free fatty acid not Free fatty acid
more than 3% more than 10% above 10%
Impurity Water, residue and Water, residue and Water, residue and
impurity are not impurity are not impurity are, not
contained contained contained
WHALE, DOLPHIN, SEAL AND OTHER MARINE MAMMAL OIL (OIL FROM
Admitted grade
Test
First grade Second grade . Third grade
Acid value Free fatty acid not Free fatty acid not Free fatty acid
more than 3% more than 10% above 10%
Impurity Water, residue and. Water, residue and Water, residue and
impurity are not impurity are not impurity are not
contained contained - contained
387
IX. NEW ZEALAND
( NEW ZEALAND STANDARD INSTITUTE ) ( 1948)
(a) BLENDED OIL
Designation—Oleum Mixtum.
Preparation—Oleum Mixtum shall consist of a solution of vitamins A and D
obtained from a suitable fish liver oil or a blend of fish liver oils, provided that:
Vitamin D may be added as vitamin D2 or vitamin D3.
A suitable vegetable oil may be added.
Acid value—The acid value shall not be greater than 2.5%.
Unsaponifiable matter—The unsaponifiable matter shall not be more than 10%.
Vitamin content—The vitamin A content shall be not less than 1,000 Inter-
national Units per gram. The vitamin D content shall be not less than 100 Inter-
national Units per gram.
(b) CONCENTRATED BLENDED Ou.
D esignation—Oleum Mixtum Concentratum.
Preparation—Oleum Mixtum Concentratum shall consist of a concentrated
solution of vitamins A and D obtained from fish liver oil or a blend of fish liver
oils, provided that:
Vitamin D may be added as vitamin D2 or vitamin Ds.
A suitable vegetable oil may be added.
Acid value—The acid value shall not be greater than 2 5%.
Unsaponifiable matter—The unsaponifiable matter shall not be more than 10%.
Vitamin content—The vitamin A content shall be not less than 4,000 Inter-
national Units per gram. The vitamin D content shall be not less than 500 Inter-
national Units per gram.
385
■
Free fatty, acids
Oil grade calculated as oleic acid
1
2 '
3 15%
4 30%
Unsaponifiable matter—The oil shall contain not more than 2.0% of unsaponi-
fiable matter, when extracted with ethyl ether under specified conditions.
VIII. JAPAN
(PuBLic HEALTH AND WELFARE SECTION, SCAP, 1950)
, (a) Con LIVER Om
1. Cod Liver Oil is the partially destearinated fixed oil obtained from fresh
livers of Gadus macrocephalus Tlle sius, Theragra chalcogramma and other
species of the Family ( Gadidae).
2. Cod Liver Oil is yellow or golden yellow clear liquid and has a characteristic
slight odour and feeble taste. Its acid value is not more than 3.0.
3. Accurately weigh 1 *gram of Cod Liver Oil and 0.2 grams of Standard Cod
Liver Oil in each 10-cc. volumetric flask and dissolve in 10 cc. of pure chloro-
form at 20°C. Take 0.2 cc. of each solution in two small test tubes of about 0.8
cm. diameter and add 2 cc. of antimony trichloride T.S. respectively. Compare
' the coloration within 30 seconds, the coloration of Cod Liver Oil shall not be
weaker than that of Standard Cod Liver Oil.
4. Cod Liver Oil has not an unpleasant rancid odour and taste. Cod Liver 011
remains clear and does not separate stearine after about 3 hours at 0°C.
5. Add 10 cc. of nitric acid to 2 grams of Cod Liver Oil and add 1 gram of
powdered sodium nitrate in small portions. After standing for 10 hours in cool
place, it must remain clear.
6. Cod Liver Oil has not an unpleasant odour when it is warmed.
7. Bottle shall be' filled with Cod Liver Oil and tightly corIced. Or Cod Liver Oil
shall be preserved in bottle from which air has been expelled. Store in dark cool
• place.
1. Strong Liver Oil is the simple or mixed oil obtained from fresh livers of marine
fishes and animals.
2. Strong Liver Oil is , a yellow clear liquid. Its acid value is not more than 3.0.
3. When 0.2 grams of Strong Liver Oil is tested by the same method as in the
third clause of "Cod Liver Oil", the same result shall be obtained.
4. Bottle shall be filled with Strong Liver Oil and tightly corked. Or Strong
Liver Oil shall be preserved in bottle from which air has been expelled. Store in
dark cool place.
386
- .centTate prepared by saponification, distillation, or extraction of such oil, or by
-distillation or extraction of such unsaponifiable matter from any other source of
the antirachitic substance found in fish livers.
Acid value—The acid value shall not be greater than 2.5%.
Vitamin content—The vitamin A content shall be not less than 25,000 Inter-
'national Units per gram. The vitamin D content shall be not less than 2,500
International Units per gram.
-
(d) 17ISH LIVER OILS .( OTHER THAN GROPER AND LING LIVER OILS., BLENDED OILS,
AND VITAMIN CONCENTRATES ) WHICH CONFORM TO THE REQUIREMENTS OF
THE BRITISH PHARMACOPOEIA
All oils in this group shall conform to the requirements as set out in the
British Pharmacopoeia, 2nd Issue, 1932 edition and addenda thereto, as cited in
the Regulations, 1946, under the Sale of Food and Drugs Act, 1908, or any
amendment thereto for the time being operative.
X. NORWAY
(a) MEDICINAL COD LIVER OIL (NORSICE STANDARDISERINGS-FORBUND) (1947)
Description—Norwegian Steam-rendeied Medicinal Cod Liver 011, Control
Standard A: liver from Gadus morrhua.
Norwegian Medicinal Cod Liver Oil, Control Standard .B; Norwegian Medi-
cinal Cod Liver Oil, Raw, Control Standard C; Norwegian Medicinal Cod Liver
Oil, Pale, Control Standard C: Gad-us morrhua and other Gadidae.
Medicinal Cod Liver Oil "Not Under Control Standard": Below control
standard.
389
Iodine value-
Norwegian Steam-rendered Medicinal Cod Liver Oil,
Control Standard A: From 162.0 to 173.0
Control Standard B: From 160.0 to 180.0
Norwegian Medicinal Cod Liver Oil, Raw,
Control Standard C: From 160.0 to 180.0
Norwegian Medicinal Cod Liver 011, Pale,
Control Standard C: From 160.0 to 180.0
- Norwegian Medicinal Cod Liver Oil "Not Under Control Standard",
Below control standard: From 158.0 to 186.0
Saponification value-
Norwegian Steam-rendered Medicinal Cod Liver Oil,
Control Standard A: From 182.0 to 188.0
Control Standard B: From 182.0 to 190.0
•
Norwegian Medicinal Cod Liver Oil, Raw,
•
Control Standard C: From 182.0 to 190.0
Norwegian Medicinal Cod Liver Oil, Pale,
Control Standard C: From 182.0 to 190.0
NorWegian Medicinal Cod Liver Oil "Not Under Control Standard",
Below control standard: From 180.0 to 190.0
Unsaponifiable matter-
Norwegian Steam-rendered Medicinal Cod Liver Oil,
Control Standard A: Up to 1.40%
Control Standard B: Up to 1.40%
Norwegian Medicinal Cod Liver Oil, Raw,
Control Standard C: Up to 1.50%
Norwegian Medicinal Cod Liver Oil, Pale,
Control Standard C: Up to 1.50%
Norwegian Medicinal Cod Liver Oil, "Not Under Control Standard",
Below control standard: Up to 1.40%
Free fatty acids-
Norwegian Steam-rendered Medicinal 'Cod Liver Oil,
Control Standard A: Below 0.8%
Control Standard B: Below 1.0%
Norwegian Medicinal Cod Liver Oil, Raw,
Control Standard C: Above 1.0%
Norwegian Medicinal Cod Liver Oil, Pale,
Control Standard C: Above 1.0%
Norwegian Medicinal Cod Liver Oil "Not Under Control Standaffl",
Below control standard: Below 1.4%
Odour and taste—The cod liver oil shall have an odour and taste satisfactory
for the respective grades. It shall not be rotten or have any foreign off-taste.
390
Kreiss value (oxidation)-
Norwegian Steam-relidered Medicinal Cod Liver Oil,
Control Standard A : Below 10 red units (Loviboncl)
Control Standard B : Below 10 red units (Lovibond)
Norwegian Medicinal Cod Liver Oil, Raw ,
Control Standard C : Below 12 red units (Lovibond)
Norwegian Medicinal Cod Liver Oil, Pale,
Control Standard C : Below 12 red units (Lovibond )
What the stand¢rd covers-This standard applies only to whale oil, i .e., the oil
obtained from the various parts of baleen whales .
The standard- includes three quality classifications of such an oil, which
classification is to be indicated as follows :
No . 1 Whale oil
No . 2 Whale oi
. 3 Whale oillNo
and which differ chiefly as regards the various requirements with respect to free
fatty acids and colour.
The standard includes only the reqùiiements which whale oil must meet in
each of these 'grades, for instance, if in a contract reference is made `to this
standard, or when one of the above descriptions is used . The standard can
therefore apply as an integral part of a contract but does not contain the usual
determination or all of the determinations of a teclnlical nature, which such a
contract includes .
Description-(refers to all three classifications )
The oil must be obtained exclusivelv from the various parts of baleen
whales, of which the most important kinds are :
Blue whale (Balaenoptera niiasculus)
Fin whale (Balaenoptera physalus) ,
Humpback whale (Megaptera nodosa) .
Sei whale (Balaenoptera borealis )
Moisture and inapurities=No . 1 and No . 2 whale oils must not contain
more than 0 .5% and No . 3 whale oil shall contain not more than l % moisture
and/or impurities .
391
In case it does not meet the requirernents with respect to moisture and/or
impurities the oil shall not be considered outside the present standard as long as
the moisture and/or impurities content do not exceed 10%. It stipulates only that
the buyer is allowed a reduction in the price he is to pay for the oil having not
more than 0.5% and I% moisture and/or impurities, respectively.
Acid content—The oil must have no mineral and organic acids added. For the
various grades the oil must not contain any greater percentages of free fatty
acid (calculated as oleic acid) than the following values:
No. 1 whale oil .
No. 2 whale oil
No. 3 whale oil 15%
The requirements given here as regard § free fatty acids shall not alone
determine whether a certain oil belongs in one or another of the grades No. I,
No. 2 or No. 3, and whether it is entitled to a corresponding description, since the
colour requirement is also a deciding factor ,in this respect.
If an oil according to its colour belongs in a certain grade, the oil shall be
considered as belonging in the grade determined by its colour, even if it as far
as the free fatty acids are concerned meets the requirements .of the next lower
grade than the free fatty acids requiréments in such a case, only stipulate that
the buyer when purchasing is allowed a reasonable price reduction "fair allow-
ance". -
Colour—The colour of the oil, with the exception given below, shall not exceed
the following values for the various grades:
The requirements given here as regards the colour shall not alone determine
whether an oil belongs in one or another quality grade No. I, 2 or 3, and whether
it is entitled to a corresponding description, since the free fatty acid requirements
are deciding factors.
If an oil, from the standpoint of its free fatty acids„ should belong to a
certain grade, the oil shall be considered as belonging to the class decided by its
free fatty acid Content, even if it as far as the colour is concerned only meets the
requirements of the next lower class; that the colour requirement has not been
fulfilled only stipulates that the purchaser when the oil is sold is granted a
reasonable price reduction ("fair allowance").
Cod Liver Oil is the partially destearinated fixed oil obtained from fresh
liver of Gadus morrhua Linn., and other species of the family Gadidae. Cod
Liver Oil contains in each gram not less than 850 U.S.P. Units of Vitalnin A and'
not less than 85 U.S.P. Units of Vitamin D.
The Vitamin A potency and Vitamin D potency of .Cod Liver Oil, when
designated on the label, shall be expressed in "United States Pharmacopoeia
Units" per gram of oil and may be referred to as "U.S.P. Units."
Cod Liver Oil may be flavoured by the addition of not more than 1^/0 of
any one or any mixture of flavouring substances recognized in this pharmacopoeia.
Description-Cod Liver Oil is a thin, oily liquid, and has a characteristic,
slightly fishy, but not a rancid, odour, and a fishy taste.
Soliability-Cod Liver Oil is slightly soluble in alcohol, but is freely soluble in
ether, in chloroform, in carbon disulphide; and in ethyl acetate.
393
Specific gravity—The specific gravity of Cod Liver Oil is not less than 0.918
and not more than 0.927.
Co/our—When viewed transversely in a tall, cylindrical, standard oil-sample
bottle of colourless glass of about 120 cc. capacity, the colour of Cod Liver Oil -
shall not be more intense than that of a mixture of 11 cc. of cobaltous chloride
C.S., 76 cc. of ferric chloride C.S., and 33 cc. of distilled water, in a similar bottle
of the same internal diameter.
Non-destearinated [sic] cod liver oil—Fill a tall, cylindrical, standard oil-sample
bottle of about 120 cc. capacity with Cod Liver. Oil, at a temperature between
23°C. and 28°C. (73°F. and 80.6°F.), stopper, and immerse the bottle in a mix-
ture of ice and water for 3 hours: the oil remains clear and does not deposit
stearine.
Unsaponifiable matter—Cod Liver Oil contains not more than 1.3% of un-
saponifiable matter.
Saponification value—The saponification value of Cod Liver Oil is not less than
180 and not more than 192. When carbon dioxide has been used as a preservative,
the oil must be exposed in a shallow dish in a vacuum desiccator for 24 hours
before weighing the sample for determination of the saponification value.
Iodine value—The iodine value of Cod Liver Oil is not less than 145 and not
more than 180.
Acid value—Dissolve 2 grams of Cod Liver Oil, accurately weighed, in 30 cc.
of a mixture of equal volumes of akohol and ether, the mixture having been
previously neutralized with tenth-normal sodium hydroxide, using 5 drops of
phenolphthalein T.S. as the indicator. Boil the oil solution gently under a reflux
condenser for 10 minutes. Cool, and titrate the mixture with tenth-normal sodium
hydroxide to the production of a pink colour which persists after shaking for 30
seconds: not more than 1 cc. of tenth-normal sodium hydroxide is required
[i.e. 1.4% free fatty a'cid].
The oil extracted from the livers of the Burbot (Lota maculosa), family
Gadidae. It is biologically assayed to have a potency of not less than 4,480 units
of vitamin A (U.S.P. ), per gram and of not less than 640 units of vitamin D
( U.S.P. ) per gram.
fishÿ;
Description-Burbot liver oil is a pale, yellow, oily liquid. It has a slightly,
but not rancid, odour, and a fishy taste.
Solubility-It is slightly soluble in_ alcohol, but is soluble in ether, chloroform,
benzene, carbon disulphide and ethyl acetate.,
Specific gravity-From 0.921 to 0.927.
Refractive index-From 1.479 to 1.482 at 20°C.i (68°F.).
Test for identity-A solution of one drop of the oil in 1 cc. of chloroform, when
shaken with one drop of sulphuric acid, acquires a light purple colour, changirig
to purple, dark green and finally brown. Treat 5 cc. of oil with 5 cc. of benzene
and centrifuge for 25 minutes at 25°C. (77°F.): no precipitate forms and a clear
solution remains.
Cold test-Fill a tall, " cylindrical, standard oil-sample bottle of about 120 cc.
capacity with burbot liver oil at a temperature between 23°C. and 28°C. (73.4°F.
and 82.4°F. ), stopper, and immerse the bottle in a mixttire of ice and water for
five hours: the oil remains fluid and forms no deposit.
Free acidity-Not more than 1.4% free fatty acid when determined by the
method described above under the heading "COD LIVER OIL (UNITED STATES
PFIARMACOPOEIA ) ".
Unsaponifiable matter-Not less than 0.9 % or more than 3.0%.
Saponification value-Not less , than 184 or more than 196.
Iodine value-Not less than 155 or more than 180.
A blend contâining the fixed oils obtained from the fresh or freshly frozen
livers of the percomorph fishes, containing not more than 50% of other fish liver
396
oil. It has a potency of not less than 60,000 units of vitamin A (U.S.P. ) per gram
( spectrophotometric ) and of not less than 8,500 units of vitamin D (U.S.P. ) per
gram.
Description-Percomorph liver oil, 50% in fish liver oil, is a yellow to brownish-
yellow oily liquid. It has a slightly fishy, but not rancid, odour; and fishy taste.
Solubility-It is slightly soluble in alcohol, but is soluble in ether, chloroform,
benzene, carbon disulphide and ethyl acetate.
Specific gravity-From 0.918 to 0.930.
Re f ractive index-From 0.1480 to 0.1485 at 200C. (680F.).
Test for identity-A solution of one drop of the oil in 1 cc. of chloroform, when
shaken with one drop of sulphuric acid, acquires a blue colour, changing to
violet, dark green and finally brown. -Treat 5 cc. of oil with 5 cc. of benzene and
centrifuge for 25 minutes at 25°C.: no precipitate forins and a'clear solution
remains.
Cold test-Fill a tall, cylindric, standard oil-sample bottle of about 120 cc.
càpacity with percomorph liver oil, 50% in fish liver oil, at a temperature be-
tween 23°C. and 28°C. (73.4°F. and 82.4°F.); stopper, and immerse the bottle.
in a mixture of ice and distilled water for five hours: the oil remains fluid and
forms no deposit.
Free acidity-Not more than 1.4% free fatty acid when determined by. the
method described under the heading "CoD LIVER OIL (UNITED STATES PHARMA-
COPOEIA)".
Unsaponifiable matter-from 3.5 to 9.OcIo; it is semi-solid in appearance.
Saponification value-From 165 to 186.
° Iodine value-From 145 to 180.
UNDILUTED PERCOMORPH LIVER Om-The undiluted fixed oil obtained from
the fresh livers of the percomorph fishes, and used in the preparation of per-
comorph liver oil, 50% in fish liver oil, conforms to the following constants as
determined by U.S.P. methods: specific gravity, from 0.924 to 0.930 at 25°C.;
refractive index,•from 1.484 to 1.490 at 20°C.; free acid in 2 gm., equivalent to
not more than 1 cc. of tenth-normal sodium hydroxide; unsaponifiable matter,
not less than 7 nor more than 13% (semi-solid in appeararice ); sapoliification
value not less than 168 nor more than 180; iodine value, not less than 145 nor
more than 180.
The oil extracted from`the livers of the shark, mainly of the variety Hypoprion
breuirostri.s (lemon), but any or all of the following varieties may be included:
Odontaspis littoralis (sand), Isu.rtcs piinctatus (mackerel), Triakis semifasciata
(leopard), Sphyrna zygaena (hammerhead), Carcharias obscurus (dusky),
Ginglymostonua cirratum (nurse), Carcharias milberti (white), and Carcharias
limbatus (black tip). It is biologically assayed and has a potency of not lessF than
16,500 units of vitamin A (U.S.P. ) per gram and of not less than 40 units of
vitamin D (U.S.P. ) per gram.
397
Description—Sliark liver oil is an amber to brown oily liquid possessing a fishy
odour and taste.
• Solubility—It is insoluble in water, slightly soluble in alcohol and soluble in
chloroform, ether, benzene, ethyl acetate and carbon disulphide.
Specific gravity—From 0.917 to 0.923 at 25°C. (77°F.).
Refractive index—From 1.475 to 1.480 at 20°C. (68°F.).
Test for identity—A solution of one drop of the oil in 1 cc. of chloroform, when
shaken with one drop of sulphuric acid, acquires a light violet colour, changing
to purple and finally brown or blue. Transfer 5 cc. of oil to a centrifuge tube and
add 5 cc. of benzene; centrifuge for 25 minutes• at 25°C. (77°F.) : no prebipitate
forms and a clear solution remains.
Cloud test—Fill a tall,_,cylindrical, standard oil-sample bottle of about 120 cc.
capacity with shark liver oil and immerse in a water bath at about 10°C. ( 50°F. ) :
the oil becomes turbid at about 15°C. (59°F.), but it becomes fluid and clear
when the bath is then warmed to 45°C. (113°F.).
Free acidity—Not more than 1.4% free fatty acid when determined by the
method described above under the heading "Con LIVER Ou. ( UNITED STATES
PHARMACOPOEIA )".
Unsaponifiable matter—Not less than 3.0% nor more than 6.0%.
Saponification value—Not less than 170 nor more than 187.
Iodine value—Not less than 125 nor more than 145. \
400
Index -
Where information on an. index entry extends to the following page, only the -first of
the two consecutive page numbers is given; where the information extends over three or
more pages inclusive page numbers are given.
ABSORPTION, definition, 15 Acids, inorganic:
Acetyl value, 372 as catalysts in hydrolysis, 109
Acid value; 361 definitions, 11
Acidity. (pH), definition, 16 Acids, saturated fatty, 22:
Acids as antioxidants, 174, 176 caprylic, 157
Acids, fatty, 4, 6-8, 18-44: characteristics, 22
absorption in metabolism, 98-106 crystalliza.tion forms, 19
alcohols from, 118 definition, 7
in alkyd resins, 308 halogenation, 136-138
boiling point, 157-159 hydroxylation, 138-140
brominated, solubility, 368 isovaleric, 30, 852, 355
cliaracteristics, 18-26, 145-167 lauric, 300
condensation reactions, 129 in marine animal oils; 28
crystallization, 19, 264 measurement, 374
definition, 6 metallic soaps, 343
distillation by steam, 269 rnyristic, 300 '
essential, in nutrition, 102 palmitic, 300
esterification, 270 stearic: see Stearic acid
' esters: see Esters sulphurization, 134
eutectic mixtures, 152 uses (see also Soaps), 300
free: see Acids, free fatty Acids, unsaturated fatty, 20, 23-26:
insoluble, measurement, 373 action of reagents on, 136-142, 208
in interesterification, 111 characteristics, 23-26
melting points, 19, 150-154, 303 definition, 7
nitrogen compounds from, 143-145 elaidinization, 14
nomenclature, systematic, 7, 23, 24 halogenation, 136-138
orientation at surfaces, 18 hydrogenation: , see Hydrogenation ,
oxidation in metabolism, 100 hydroxylation, 138-140
oxidation rate, 121 linoleic (linolic), isomers in marine oils,,
reduction to fatty alcohels, 118 1, 174
re-esterification, 270 linolenic, isomers in marine oils, 7
in resins, 130, 309 in marine animal oils, 28,
salts: see Soaps and Driers sulphation and sulphonation, 131
segregation, 264-269 sulphurization, 134-136
separation by metallic salts, 21, 374 Addition reactions, definition, 8, 16
separation by physical methods, 264, 290 Adhesives (in insecticides), 306
soaps (see also Soaps), 21 Adsorption:
solid, measurement, 374 decolorizing by, 234
soluble, measurement, 373 definition, 15
solubility, 163 effect of adsorbent on oil, 183 '
solubility of brorninated, 368 of vitamin A, 183, 217-219
surface tension, 165 Albacore oils:
unsaturation, effect on properties, 18-26 body, 347
. uses (see also Soàps), 300, 307 liver, 68, 278, 344
Acids, free fatty, 4: Alcohols (see also Glyceryl ethers), defini-
development during deterioration, 168-170 tion and cômpounds, 9-12, 111
by enzymatic action, 168-170 Alcohols, fatty, 9:
measurement, 361 cetyl, properties and uses, 159, 289, 298
removal, 215-220 condensation reactions, 133
401
from fatty acids, 118 production, 198
laaffyl, 289 statistics, 62
nomenclature, systematic, 7-9 Black cod viscera, statistics, 62
occurrence, characteristics, uses, 46, 93-95 Black rock-fish oils, vitamins, 67, 337
stearyl, 159 Blackfish (a dolphin), 352
sulphated and sulphonated, 132, 289 Bleaching, 216, 233:
Alcoholysis, 111 chemical methods, 236-238
Aldehydes: physical methods, 234-236
definition, 9 Blown oils, 120, 249, 250, 290, 294, 297
from oxidation of acids, 123 Blubber oils: see under Beluga, Porpoise, Sea
Alkali digestion of fish livers, 183, 191, 194, lion, Seal, Whale
195 Blue shark liver oil vitamins, 66
Alkali refining, 215, 218: Blue *hale:
effect on cold clearing, 228 characteristics of oils, 350
effect on colour, 216, 236 statistics, 349
Alkalinity (pH), definition, 16 Bluefin tuna: see Tuna oils
Alkyd resins, fatty acids in, 308 Bodied oils: see Polymerized oils
Alopecia vulpes (thresher shark) liver oil, 29, Boiled oils, 249
66 Boiling point, 157-159
Alosa sapidissima (shad) oils, 66, 69, 346 Bonds, double (unsaturated or ethylenic):
Amides, 144, 289 conjugated, 8
Amines, 144, 289 definition and properties, 6-9
Analysis, definition and sampling for, 359 elaidinization reaction, 14, 140
Analytical values, significance, 359-374 halogenation, 136
Anchovy oil: hydrogenation, 115
characteristics, 66, 344, 347 hydroxylation, 131, 138-140
statistics, 345 sulphation and sulphonation, 131
Anhydro vitamin A, 49 sulphurization, 134
Animal feeds, oils in, 279-286 Bonito liver oil, 280
Anoplopoma fimbria: see under Black cod Bottlenose whale oils, characteristics, 350
- Antioxidants, 51-53, 174-178, 275, 282-284: Brevoortia tyrannus: see Menhaden oil
for animal feeds, 282-284 Brill liver oil vitamins, 67
Apristurus brunneus (brown shark), 341 Bromides, insoluble, 368-370
Ascorbic acid as antioxidant, 176 .Bromine, action on fish oils, 137
Astacin, 78 Brown shark, 341
Australian specifications for oils, 375 Bullhead liver oil vitamins, 68
Autocatalytic action, definition, 15 Burbot liver oil specifications, U.S.A., 296
Autolysis of livers, effect on alkali digestion, Burning point, 365
196
Autoxidation, 171 • Callorhinus ursina cyanocephala: see under
Seal
BACT4RIA, in oils, 168, 170 ' Canadian coast sources of vitamins, 66-70
Balaena spp.: see Whale oils Canadian specifications for oils, 375-378
Basking shark liver oils, characteristics, 29, Canning, oils used in, 273-275
66, 88, 92, 341 Carbohydrates, relation to fats in metabolism,
Bass (sea) liver oils, vitamins, 68, 280 98 .
Batyl alcohol, 12, 87 Carbon atom chains:
Belgian specification for oils, 375 definition and derivatives, 6-14
Beluga (white whale) oils: effect of oxygen on, 171
characteristics, 31, 70, 353 length and boiling point, 157
statistics, 353 length and specific gravity, 147
uses, 301, 305 Carboxyl group, definition, 6
yield, 348 Carotene, 78, 281
Black cod livers, statistics, 62 Carriers for vitamins in feeds, 282-286
Black cod liver oil: Catalysts:
characteristics, 67, 280, 336 definition, 15
statistics, 62 for conjugation, 142
Black 'cod viscera oil: for elaidinization, 141
characteristics, 67, 336 for hydrogenation, 8, 115, 118
402
for hydrolysis, 107-109 Great Britain, 382
for .hydroxylation, 13 9 Japan, 387
for interesterification, 11 1 statistics, 33 2
for oxida ti on, 121, 173, 249, 290-292, 296 sulphation and sulphonation, 254-25 8
for polymeriza tion, 124 sulphurization, 259
Centrifuges : Coho sahnon oils, 35, 67, 321-326
in oil-breaking systems, 186-191, 210-212 Cold clearing, 220-233 :
principles of, 186 cooling rate, effect in, 221-225
'Centrophorus sp. (Atlantic shark) liver oil, 29 definition, 220
Cetyl alcohol, 159, 289, 298 - and degree of unsaturation, 22 8
Cetorhinus mcra;hnats : see Basking shark liver and drying of pilchard oil, 229, 29 2
oil s effect on chemical properties, 228-23 0
Characteristics of oils ; effect on polymerization, 12 8
définition, 359 industrial, 183, 230
determination, 366-374 Cold pressed oil : 'see Cold clearin g
Chemistry, general, of marine fatty cbm- Cold test, 363
pounds, 3-1 9 Colloids, definition, 16
Chimaera monstrosa: see under Ratfish Colour :
Chimyl alcohol, 12, 87 concentration in solvent extraction, 26 7
Chlorine, action on fish oils, 137, 303 development in oils, 81-83
Chlorophyll, 79, 8 1 effect of storage, 168,
Cholesterol, 55, 85-87, 325 measurement, 360
Chum salmon oils, 35, 36, 66, 323-326 origin, 233
Cis-trans isomerism, 1 4 removal from oils, 83, 216, 233-23 8
Cloud in polymerized oils, 127-129 Concentrates : see Vitamin concentrate s
Cloud test, 36 3 Condensation reactions, 129
Clûpèa harengus (Atlantic herring), 41, 314, Conjugated bonds, 8, -14 2
31 6 Conjugated hydrogenation, 119
Clupea pallasii : see under Herring Contamination by fuel oil, 36 5
Cod liver oil (Atlantic) : Contrac ti on of oils, 147-151
as animal feeding oil, 279, 282, 332 Cooking fats, 27 6
characteristics, 148, 162, 222, 331-335 Core oils, 298-300
composition, 2 9 Cosmetics, 87, 90, 95, 30 9
fractionation, 267, 268 Crab viscera oil characteristics, 34 7
hydrogenation, 116 Cusk liver oil, 332
medicinal uses, 278, 332 Cutting oils, 804
production methods, 180-195
effect on quality, 333 DARK nivsNC, of oils during storage, 16 8
statistics, 61, 332 Decolorizing, 216, 233-238
sulphurization, 259, 261 Definitions, 3-17 -
toxicity, 10 3 Defoaming .ageirts, fatty alcohols as, 9 5
uses, 332 Delphinapterus leucas : see Beluga oil s
vitamins, 55, 69, 278, 282 Delplzinus delphis (dolphin) oils, 31, 305,
Cod liver oil specifications : 352, 387
Canada, 375 Denmark - specifications for oils, 37 8
Denmark, 37 8 Density ( see also Specific gravity), 145
Great Britain, 380, 381 Déodorization, 172, 183, 219, . 238-241, 275,
Japan, 38 6 29 0
Norway; 389-391 Detergents ( see also Soaps), 286-289
U.S .A., 394, 39 8 Deterioration : see Acids, free fatty ; also
Cod liver oils (Pacific) : ttancîdit
characteristics, 67, 280, .335-338 y Diene value determination, 36 8
statistics, 62 Dietary fats, 98-106
Cod livers (Atlantic), statistics, 61 Distillation : -
Cod oil (Atlantic) ; deodorization by, 240
characteristics, 33 4 indùstrial 158 269
in leather industry, 30 8 by molecular evâporation, 58-60, 158, 269 ;
production methods, 180, 183, 833 29 8
specifications : under reduced pressure, 157-159
403
with steam, 159, 269 in hydi'-olYsis, 242
Dog salmon oils: see Chum salmon oils. Ergosterol, 55
Dogfish body oil,: Essential fatty acids in nutrition, 102
characteristics, 66, 328 Esterification, 219, 270
in leather industry, 308 Esters (see also Glycerides):
production, 201-210 definition, 10
statistics, 32 inorganic, 11
Dogfish liver oil: interchange, 110-114, 269
in animal feéding; 279 for separation of fatty acids, 264-269, 290
characteristics, 148, 162, 164, 222, 327 of unskionifiables, 46, 85, 88
composition, 29, 88, 92 Ester value, 371
effect of sexual condition, 89 Ethanolysis, 111
fractionation, 266 Ethers:
statistics, 64, 327 ' aromatic, of fatty acids, 129
sulphation and sulphonation, 257 definition, 12
sulphurized, in 'rubber industry, 301 in marine animal oils, 46, 87-89
vitamins, 49, 66, 69, 72„ 74, 278, 327 Eulachon oil characteristics, 68, 346
Dogfish livers, statistics, 64 Eumotopias jubata (sea lion) oils, 70, 357
Dogfish viscera oil vitamins, 66 Eutectics, formation from fatty acids, 152
Dolph,in oils: Exothermic reaction, definition, 16
characteristics from various tissues, 352 Expansion, coefficient of cubic, 147-151
composition, 31 -
specifications, Japan, 387 FACTICES, 133, 258-263, 290, 301, 303, 304
uses, 305 Farm animais, vitamins A and D in feeding,
Double bond: see Bonds, double 279-286
Driers and oxidation of oils, 121, 173, 24 9, Fats:
290-292, 296 definition, 8, 10
Drying properties: metabolism, 98-106
effect of oxidation on, 119-122 modification by fish, 36, 88
of pilchard oil, 290-293 stabilization, 174-178
for printing inks, 297 solubility in water, 242
of salmon oil, 290, 324 unstable modifications, 153
' Fat-splitting: see Hydrolysis
EEL OILS, vitamins, 69 Fatty acids: see Acids, fatty
Egg oils, characteristics, 66, 323-326 Fatty oils, definition, 3, 10
Elaidinization, 14, 140 Feeding oils (for animals), facing 274, 279-
Emulsifying agents: 286
lecithin as, 90, 275 Feeding oils, specificatiOns:
sulphated compounds as, 93, 304 Canada, 376
Emulsions: , Great Britain, 382
in cutting oils, 304 U.S.A., 398
definition, 16 Filter aids:
in hydrolysis and saponification, 108, 110 in soap removal, 217
in insecticides, 306 in stearine removal,' 226
stickwater, 206, 209 Filtering properties of stearine, 225-228
of vitamins in animal feeds, 284-286 Finback whale oils:
Endothermic reaction, definition, 16 characteristics, 350
Engraidis mordax (anchovy) oils, 66, 344, yield, 348
347 Finishing oils, 296
Enzymes: Fire point, 365
definition, 15 Fish stomach juice in liver digestion, 197
deteriorative effects of lipases, 168-170 Fishing gear, oiling of, 297
digestion of livers by 196 Flash point, 365
effect on rancidity, 168-171 Flavour of oil, cause and removal, 275
hydrolysis of oils by, 109, 169, 245 Flavour reversion, 173
in low-temperature-processed livers, 193 Floor _covering materials, 293-296
oxidizing (lipoxidases), 171 Flounder oils, characteristics, 67, 347
Equilibrium reactions: Flow test, 363
in elaidinization, 140 • Foods, oils as human, 273-279
404
Formulae, types of chemical, 5-8 HADDOCK LIVER OIL, 332:
Fractionation: characteristics, 69, 339
by crystallization, 263 composition, 29
by distillation, 269 Hag-fish liver oil vitamins, 66
by liquid-liquid extraction, 264-269 Hake liver oil, 332:
France, specifications for oils, 379 characteristics, 68, 69, 338, 339
Free fatty acid removal: composition, 29
by alkali refining, 215-218 statistics, 63
by esterification, 219 Hake livers, statistics, 63
by solvent separation, 220 Halibut fishery, 328
by vacuum-steam distillation, 219 Hali but head (offal) oil:
vitamin A removal in, 218 characteristics, 67, 164, 222, 330
Free fatty acids: see Acids, free fatty statistics, 329
Freezing point: see Melting point sulphation and sulphonation, 254, 258, 308
Fucoxanthin, 79, 80 sulphurized, 301 .
Fuel oil contamination, 365 Halibut liver oil:
Fur-bearing animals, vitamin oils in feeding in animal feeding, 280
of, 281 characteristics, 148, 222, 329
Fur industry, sulphated compounds in, 95 composition, 29, 92
Fur seal: see under Seal specifications:
Canada, 376
Gadus aeglifinus (haddock) liver oil, 29, 69, Great Britain, 380
332, 339 U.S.A., 395
Gadus macrocephatus (gray cod) oils, 63, 67, statistics, 61, 329
335 vitamins, 49, 67, 69, 278, 280
Gadus morrhua: see Cod liver oil, Atlantic vitamin stability, 51
Gadus pollachius: see Pollack li ver oil Halibut livers, sta tistics, 61
Galearhinus gal eus: see Soupfin shark liver Halibut slcin oil characteristics, 347
oil Halibut viscera, statistics, 61
Gallic acid and gallates as antioxidants, 176 Halibut viscera oil:
Gel: characteristics, 67, 330
definition, 16 production, 198
formation in oils, 127, 251 statistics, 61, 329
German specifications for oils, 379 Halichoerus grypus: see under Seal
Glycerides: Halogenated oils, uses, 298, 303
boiling points, 158 Halogenation of fish oils, 136-138:
definitions and types, 10-13, 31 to prevent rancidity, 178
interesterification, 110-114 Harbour seal: see under Seal
separation, 88, 264, 269 Herring:
unstable forms, melting points, 153 fishery, 312
-Glycerol (glycerine), 4, 109: food, 38
esters: see Glycerides oil content during maturation, 41, 312
ethers (glyceryl ethers), 12, 46, 87-89 uses, 314
recovery in hydrolysis and saponification, Herring (Atlantic), 41, 314, 316
107, 242 Herring oil:
structure, 9 in canning, 274
yield from typical fatty oil, 107 characte ri stics, 76, 146, 148-150, 162, 164,
Glyceryl ethers, 12, 46, 87-89 312-316
Gravity oil-separation system, 208 commercial, quality of, 315
Gray cod livers, statistics, 63 composition, 28, 42, 312
Gray cod oils: contamination by fuel oil, 82
characteristics, 67, 335 - fractionation, 264
statistics, 63 hydrogenated, 116, 156, 300
Gray whale oils: production, 199-212, 314
characteristics, 350 rancidity development in, 170
yield, 348 specifications:
Greases: see Lubricants British Columbia, 377
Green cod: see Pollack Japan, 387
Gum guaiac as an antioxidant, 177 U.S.A., 398
405
statistics, 313 Insoluble bromides, 368-370
stearine, 146, 149, 155, 221-232, 314 Iodine value (see also Unsaturation):
sulphation and sulphonation, 254, 258 effect of oxidation and polymerization on,
sulphurization, 258-261, 304 120, 126
uses, 195, 274, 279, 286, 298, 300, 304, determination, 366
306, 308, 316 of oils in rubber industry, 300
vitamins, 66, 69, 76 and refractive index, 34, 160
Herring oil (Atlantic), .properties, 316 and titre point, 156
Hexabromide value, 370 Irradiation and formation of vitamin D, 55
Hexanchus griseus (mud shark) oils, 64, 66, Isomerism:
341 conjugation, 14, 142
Hippoglossus spp.: see under Ha libut geometrical, or cis-trans, 14, 19, 140
Horse mackerel (Atlantic): see Tuna oils of hydroxylated fatty acids, 139
Horse mackerel oil specifications, South optical, 14
Africa, 393 structural, 7, 11-14
Humpback salmon: see Pink salmon
Humpbacic whale oils: JAPANESE SPECIFICATIONS FOR OILS, 386
characteristics, 350, 351 Jew-fish liver oil:
yield, 348 characteristics, 347
Hydrocarbons, 4, 6, 90-93: neovitamin A in, 49
separation from oils, 159 Jute oils for batching, 296
Hydrogenated oils, uses, 275-277, 287, 289,
300, 302-304, 306 KETONES, definition, 9
Hydrogenation, 8, 114-119, 247-249: Killer whale oil yield, 378
catalysts, 115, 247-249 Kitol, 49, 351
conjugated, 119
decolorization during, 237 LACTMES from hydroxy fatty acids, 131
deodorization during, 241, 275 Lactones -from hydroxy fatty acids, 131
effect on titre point, 156 Lagenorhynchus obliquidens (dolphin) oils,
flavour reversion in, 173 31, 305, 352, 387
of herring oil, 116 Lamna ditropis: see Mackerel shark
industrial, 247-249 Lamprey liver oil vitamins, 66
of oils, composition changes during, 275 Large spotted dogfish liver oil, composition, 29
of pilchard oil, 115, 118 Latent heat of fusion, 153
polymerization of oils and, 116-118, 288 Leather industry, 87, 251, 296, 301
rancidity control by, 173 Lecithin:
_ of salmon oil, 324 effect on solubility of oils, 164
Hydrolagus see under Ratfish effect on viscosity of oils, 161
Hydrolysis, 107-109, 241-246: occurrence, properties, uses, 89, 175, 275,
by acids, 108, 242 305
by allcali catalysts, 108, 243 Lingcod liver oil:
distinction from saponification, 108, 242 characteristics, 88, 92, 336
by enzymes, 108, 169, 245 statistics, 62
rate and completeness of, 242 vitamins, 67, 280
by Twitchell and similar reagents, 108, 245 Lingcod livers, statistics, 62
by water and steam, 107, 242, 244 Lingcod viscera oil:
Hydroperoxides, formation by o xi dation, 1 71 production, 198
Hydroxyl group, defini ti on, 9 vitamins, 67
Hydroxyl value, 372 Linoleums, 250, 251, 294
Hydroxylation, 138-140: Linoxyn, 250, 294
through sulphation, 131 Lipases, 168-170:
in fish tissues, 168
IrmucTrvE PERIOD, 16, 173, 291 hydrolysis of fats bY, 170, 245
Industrial hydrogenation plants, 247-249 temperature effect on, 170
IndustTial oxidation, 120, 122, 249-251, 308 Lipoproteins, 144
Inhibitors: see Antio xi dants Lipoxidases, 170
Inks, printing, 297 Lithographic varnishes, 251
Insecticides, 306 Liver oils (see also Production of liver oil,
Interesterification, 110-114, 269 and under name of fishes):
406
fractionation, 267 Mulch papers, 310
Liver preservation, 182
Lubricants, 138, 296, 302-305 NEOVITAM1N A, 49
New Zealand specifications for oils, 388
MACKEREL BODY OIL CHARACTERISTICS, 347 Nitriles, 144
Mackerel liver oil: Nitrogen derivatives of fatty material, 143-
characteristics, 345 145
vitamins, 68, 69, 278 Nitrogen determination, 364
Macicerel sharlc liver oil: Nomenclature, systematic, of fatty acids and
characteristics, 88, 92, 341 alcohols, 7-9
vitnmins, 66, 69 Non-fat components, 46-97
Maleic anhydride value, 368 Non-saponifiables: see Unsaponifiable matter
Marbled sculpin liver oil characteristics, 88, Nordihydrog-uaiaretic acid (N.D.G.A.) as an
92 antioxidant, 176
Margarine, 275 Norwegian specifications for oils, 389-392
Marine manunal oiLs, production, 212-214 Notorynchus cepeclianus (spotted cow shark )
Melanogrammus aeglefinus (haddock) liver liver oil, 66, 341
oil, 29, 69, 332, 339 Nutritional uses of oiLs:
Melting point, 19, 150-154: for animals, 279-286
of mixtures of fatty compounds, 152, :303 for humans, 273-279
raising of, by elaidinization, 140
Menhaden oil: ODOUR OF FLSH °us:
characteristics, 69, 148, 162, 289 cause and removal, 183, 275
composition, 28 from rancidity, 173
fractionation, 264, 266 Offal oil production, 199-212
sulphtnization, 259 Oil analysis, 359-374
uses, 251, 289, 298 Oil content of tissues:
Meduccius spp.: see under Hake factors affecting, 32
Metabo li sm of fats, 98-106: by refractive index, 160
absorption, 98-100 Oil gels, 251
dietary fat and, 101 Oil separation (see also Production):
effect of rancidity, 104 by centrifuges, 186-191, 210-212
essential fatty acids, 102 by gravity, 208
toxicity of fish oils and, 103 Oilcloth, 296
Metabolism of fatty acids, 98-103 Oiled fabrics, 296
Metallic oxides: Oils, fatty: see Fats
for bodying, 298 Oils, fish:
in hydrolysis and saponification, 108 percentage yields, 66-69
Metals, relative effect on rancidity, 172 statistics for, 61-65
Metall ic soaps, 21: Oils, marine mammal, percentage yields, 69
definition, 110 Oleic acid, 7, 24:
as driers, 122, 291 condensation reactions, 129
uses in industry, 303, 307 elaic-lini7ation, 14, 141
Methanolysis, 112 hydroxylation; 139
Methyl esters of fatty acids, 10, 112 soaps, 304
Micro-organisms in oils, 168 sulphation and sulphonation, 133, 289
Molecular distillation, 93, 158, 298: sulphurization, 262
fatty acid fractionation, 269 Oleovitamin A specifi cations, U.S.A., 395
vitamin concentrates by, 58 Oncorhynchus spp.: see under Salmon
Molecular weight, effect of oxidation and Ophiodon elongatus: see under Lingcod
polymerization, 121, 126 Orco whale oil yield, 348
Molecule, definition, 4 Oxidation of oils (see also Rancidity), 119-
Monk-fish liver oil: 124:
characteristics, 69, 347 by air, 120-122, 171, 250
composition, 29 by bleaching, 236
Moon-fish liver oil vitamins, 67 effect of driers, 121, 172, 249, 290-296
Mud shark liver oil: industrial, 120-122, 249-251, 308
characteristics, 66, 341 by lipoxidases, 170
statistics, 64 • by oxidizing agents other than air, 122-124
407
by peroxides, 171, 237 drying of, 290-294, 296
of pilchard, with air, 121, 250 hydrogenated, 116, 118, 156, 160, 300
pro-oxidants, 173 polymerization, 121, 125-129, 253
and refractive index, 121, 126 processing, 258, 289-296, 301, 305
tests for, 362 production, 199-212
Oxides, metallic, 108, 298 specifications:
Oxygen absorption and rancidity, 171 British Columbia, 377
Ozone, oxidation of oils by, 123 South Africa, 393
U.S.A., 398
PALvxs AND vnaivrsHEs, 251, 289-293, 297:. statistics, 317
driers, 173, 290-292 stearine, 221-229, 232
factices, 262, 290 toxicity, 103
statistics, facing 274, 289 uses, 129, 251, 279, 286-296, 298, 301,.
Papain, liver digestion with, 196 306-310, 319
Pepsin, liver digestion with, 196 vitamins, 66, 75
Peptization, definition, 16 yield, effect of season, 42
Perch liver oil characteristics, 347 Pink salmon oils:
Percomorph liver oils: characteristics, 35, 67, 323-326
specifications for U.S.A., 396 effect of spawning mfigration, 40
vitamins, 278 effect of temperature on iodine values, 44
Peroxide value, 362 Pliability of oiled fabrics, 296
Peroxides: Pneumatophorus diego: see under Mackerel
oxidation of oils by, 122-124, 171 Polenske value, 373
rancidity and, 171 Polishing compounds, 95, 309
vitamin A destruction and, 50-52 Pollachius virens: see Pollack liver oil
pH: Pollack liver oil, 332, 340:
definition, 16 characteristics, 69, 339
in liver digestion, 194-196 composition, 29
Pharmaceutical products (see also under specifications, Japan, 387
Vitamins ) : Polymer cloud, 127-129, 290
cholesterol in, 87 Polymerization, 124-129, 249-254:
fatty alcohols in, 95 cloudiness in fish oils by, 127
fatty materials in, 309 definition, 124
Phoca vitulina richardii: see under Seal electrical, 302
Phocaena commuais ( dolphin ) oils, 31, 305, gel formation and, 127
352, 387 by heat, property changes of oils during,
Phocaena spp.: see under Porpoise 124-129
Phospholipides (phosphatides), 12, 46, 89, hydrogenation effect on, 116-118, 288
161: industrial, 120, 249-254, 295
as antioxidants, 175 by oxidation, 120, 125
Physeter macrocephalus: see under Whale of pilchard oil by heat, 125 .
Phytoplankton fatty acids, 37 refractive index and, 125, 160
Pickup oil, 195, 198, 330 of sardine oil by heat, 127
Pigments, 46, 78-84: stearine and, 127-129
carotenoid, relation to vitamin A, 47 during sulphation and sulphonation, 131
definition, 4 by sulphur and selenium, 124, 134-136
effect on paint oils, 291 viscosity and, 121, 127, 162
in fish oils, 78 Polymerized oils:
properties, 79-81 segregation by solvents, 267-269
in relation to rancidity, 81-83, 173 structure and properties, 160
removal, 83 uses, 274, 288, 290, 297, 302
Pilchard fishery, 38, 42, 317 Porpoise oils:
Pilchard oil (see also Sardine oil): characteristics, 70, 222, 354
alkali refining and stearine crystals, 228 composition, 31
bleaching, 234, 237 statistics, 354
blowing, 119-121, 250 uses, 301, 305
characteristics, 146, 148, 150, 162, 316-320 Poultry, vitamins A and D in feeding of,
cold-cleared, 128, 229, 290 279-286
composition, 28, 86 Pour point, 302, 363.
408
Preservatives, 182, 192 characteristics under .specific oils), 347-
Press, continuous, for oil production, 203-206 353
Pressed oil: see Cold clearing
Pressure effect on boiling point, 157-159 QUENCHING OILS, 306
Prionace glauca.(blue shark) liver oil, 66
RAFFINATE, 265
Piinting inks, 251, 297 •
Pristane, 159 •
Raja spp.: see Skate liver oils
Rancid fats, effect of ingesting, 104
Processing of oils, 215, 24 1-270:
Rancidity, 168, 170-179:
bodying by heat, 251-254 -
antioxidants, 174-178, 275
fractionation, 263-270
changes due to, 170-179
hydrogenation, 247-249
control of bacterial, by pre„servatives, 182,
hydrolysis, 241-245
192
oxidation, 249-251
enzymes and, 168-170
polymerization, 251-254
flavour reversion caused by, 173
saponification 246
and free fatty acids in cold-stored fish,
sulphation and sulphonation, 254-253
168-170
sulphurization, 258-263
lipoxidases and, 170
Production of fish and offal oils: - metals and development of, 172.
batch-type pressure extraction, 199 methods for determination, 362 •
centrifugal method, 210-212 oxidative, 170-174'
continuous plants, 201-212 oxygen absorption during development,
cooking and skimming, 199 171
effect of tissue spoilage, 364 pigments and, 81-83, 173 •
emulsions in, 207-210 preservatives for control of bacterial, 182,
presses, continuous, 201-210 192
from 'salmon eggs, 325 . Prevention, 174-178, 275
Production of liver oils: pro-oxidant, effeet on, 173 -
aboard trawlers, 181 sodium chloride, effect on, 170
acid digestion, 194 in soaps, 288
alkali digestion, 183, 191, 194 tests for, 362
Atlantic, 180-186, 192, 193 vitamin A in relation td, 170
batch-type cookers for, 180-186 Raffish oil, sulphation and sulphonation, 254
centrifuges, 186-191 Raffish liver oil:
effect of autolysis, 196 characteristics, 66, 222, 341
effect of tissue spoilage, 364 composition, 29, 88,. 92, 342
enzyme digestion, 196 statistics, 342 -
extraction without heat, 180, 192 uses, 301, 305, 342
Labrie's cooker for, from cod, 184-186 . Ray liver oil vitamins, 69
from livers of high oil content, 180-195 Red, and rock cod livers, statistics, 62
from livers, of low oil content, 195-198 Red and rock cod oils, characteristics, 67,
low pressure method, 193 337
oil-solvent (pickup oil) extraction, 195-197 Red cod liver oil:
Pacific, 186-191 . characteristics, 67, 336-338
Patch cooker for; 182 statistics, 62
rotting processes, 180 Red cod .viscera, statistics, 62 -
solvent extraction, 197 Red cod viscera oil:
solvents, effect on nature of oil, 199 production, 198
steam processes, 180-191 - statistics, 62
température effect on oil rendering,' 193 vitamins, 67
by vibration, 193 Reduction by hydrogenation, 118
vitamin A loss in, 183, 217-219 Reduction plants, 199-214
Wentworth process, 192 Red whale oil pigments, 78
Production of viscera oils, 198 Re-esterification, 276
Promoters for catalysts, 115 Refining, 215-241:
Pro-oxidants, 173 . alkali, 215-218, 228, 236
Properties of fish oils (see also characteristics bleaching, 216, 233-238
under specific oils), 312-347 cold clearing, 220-233 ,
Properties of marine mammal oils (see also deodorization:- see Deodorization
409
free fatty acid removal, 215-229 characteristics, 222, 318
Refractive index, 34, 159-161: fractionation, 266, 268
effect of oxidation and polymerization, polymerization by heat, 127
121-126 specifications, Japan, 387
relation to iodine value, 160 uses, 258-261, 280, 289, 294, 298, 303,
Refrigerated oil: see Cold clearing 310
Reichert-Mdissl value, 373 vitamins, 280
Resins, drying, 130, 308 Sarçlinops caerulea:'see under Pilchard and
Rhombus maximus (turbot) oils, 28, 69 Sardine:
Right whale oil, yield, 348 , Scomber scombrus: see under Mackerel -
Rock-fish oils, characteristics, 337 Scrim oil, 250
- Rosefish offal oils, vitamins, 69 Scyllium canicula (small spotted dogfish) ,
Rubber industry, 300 liver oil, 29
Rust prevention with fish oil paints, 290 Scymnorhinus lichia (shark) liver oil, 29 -
Sea bass liver oils, vitamins, 68, 280 .
SABLE-FISH: see under Black cod Sea cucurnber oil characteristics, 347
Salmo. salar (Atlantic salmon), 28, 41 Sea lion oils, characteristics, 70, 357
Salmon, oil content during spawning, 39-41 Seal blubber oil: -
Salmon, canned: characteristics of various, 148, 357
oil added to, 273 production, 214, 356
• oil in, 322 , uses, 301
statistics, 322 vitamins, 70
Salmon egg oil: Seal liver oil vitamins, 70, 357
• characteristics, 66, 325 Seal oils, 355-357:
composition and production of Pacific, 325 bleaching, 234
composition of . Atlantic, 28 characteristics, 70, 355
Salmon liver oil: composition, 31
characteristics, 66, 326 specifications, Japan, 387
composition of Atlantic, 28 statistics, 356
production, 197 sulphation and sulphonation, 254
specifications for feeding oils, U.S.A., 398 sulphurization, 262
statistics, 63 uses, 296, 306, 308
Salmon livers, statistics, 63 Sebastodes spp. (rock fishes), 337
Salmon oil ( offal oil), 320-325: Sei whale oils, characteristics, 350
bleaching, 238 Selachyl alcohol, 12, 87, 89
'hydrogenated, 156, 301, 324 Separation of oil (see also under Production):
pigments, 78, 321 by centrifuges, 186-191, 210-212
• production, 199-212 by gravity, 208
specifications for feeding oils, -U.S.A., 398 Shad oils, 66, 69, 346
statistics, 321 Shark liver oils:
sulphation and sulphonation, 254, 258 characteristics of various, 148, 340-342
unsaturation in relation to temperature, 44 composition, 29, 88, 92
unsaturation in relation to various tissues, specifications:
323 New Zealand, 389 .
uses, 195, 273, 279, 301, 307, 321, 325 U.S.A., 397
vitamins, 66 statistics, 64, 65
Salmon viscera statistics, 63 uses, 297, 308
Salmon -viscera oils: vitamins, 49, 66, 69, 278-280
statistics, 63 Shark livers, statistics, 64
vitamins, 66 Shortenings, production and ,proPerties, 277
Sampling for analysis, 359 Skate liver oil:
Sand cores, 298-300 characteristics, 341-343
Sand -dab liver oil vitamins, 68 composition, 29
Saponification (see also Hydrolysis), 109, 246: uses, 301
distinction from hydrolysis, 108, 242 vitamins, 66, 69
Saponification equivalent, 371 Skesyl alcohol, 88
Saponification value, 370 Sleeper shark liver oils:
Sardine liver oil characteristics, 347 characteristics: 66, 341
Sardine oil (see alsô Pilchard oil): composition, 88, 92
410
Sniall spotted dogfish liver oil, 29 sapoiiificltion, 246
Smoke point, 276, 365 specificàtiôns, Great Britain, 384
Soap, nascent, properties, 217 spermaceti and other waxes from, 94; 348
Soaps (see also DetergentsY, 6, 21, 241-246, sulphation and sulphonation, 255; 258, 308
286-288: sulphurization, 259, 262, 305
detergent action, 287 uses, 296, 305, 308, 309
deteiniination, 364 vitamins, 70
effect on bleaching, 235 yield, 348
industry, 109, 241, 309 Splitting of fats: see Hydrolysis and
metallic, 21, 110, 122, 291, 303, 307 Saponification
presence in oils, 364 ' Spotted "cow shark liver oil characteristics,
saponification of fats for, 109, 242; 245 66, 341
sulphated and sulphonated, 133, 289 Spraying compounds (insecticides), 306
Sockeye salmon oils: Spring salmon oils:
charlcteristics,.35, 36, 323, 326 characteristics, 35, 36, 66, 328, 326
effect of temperature on iodine value, 44 effect of spawning migration, 39
Sol, definition, 16 Squalene, 91-93, 159, 297
Sole liver oils: Squalus spp.: see arnder Dogfish
characteristics, 347 Sqaralina ¢ngelus (monk fish) liver oil, 29,
statistics, 63 6^, 347
vitamins in various, 67, 68, 380 Stand oil, 125, 251
Sole livers, statistics, 63 Starfish oil characteristics, 347
Solubility of oils, '163, 265 Stearic acid, 7, 22, 23:
Solvent extraction: composition of commercial, 300
of fatty acids and of oils, 264-269 hydroxylated, 139
of livers, 197 in rubber industry, 300
plants for, .265 sulphurization, 262
of viscera, 199 Stearin, distinction from stearine, 3, 220
Solvents for oil extraction, 198, 267 "Stearin pitch", 269
Soinniosus naicrocephalus: see Sleeper shark Stearine:
Soupfin shark liver oil: content in some commercial oils, 221
characteristics, 66, 88, 92, 340 crystals, 224, 228
statistics; 64 definition, 3, 220
Specific gravity, 145-151: and drying of pilchard oil, 229, 295
effect of polymerization, 126 effect of cooling rate, 221-225
effect of stearine formation, 149 effect on polymerization, 127-129
effect of temperature, 145, 150 effect on volume and specific gravity,
Specifications, 375-399: 149-151, '
Australia, 375 filtering properties, 225-228
Belgium, 375 formation, 3, 154, 225, 231-233
Canada,-375-378 in herring oil, 154
Denmark, 378 iodine value, 229, 300
France, .379 and polymerization, 127-129
Great Britain, 380-386 removal, 225-228, 230
japan, 386 unsaturated fatty acids in, 229
New Zealand, 388 uses, 286, 300
Norway, 274, 389-392 Steel quenching oils, 306
South Africa, 392 Sterols, 46, 85-87:
Sweden, 393 relation to vitamin D, 55
Sperinaceti: 'Stickwaters, 206, 209
characteristics, 94, 147, 213 Storage of fish, deteriorative effect on oil,
occurrence, 94, 348 168-170
uses, 95, 309 Stuffing oils for leather industry, 308
Sperm liver oil, 351: Sturgeon oils (Atlantic), composition, 28
vitamins, 70 Sturgeon oils (Pacific), characteristics, 68, 347
Sperm oil: Substitution reaction, definition, 16
characteristics, 70, 92, 147, 162, 164, 350 Subvitamin A, 49
compositiôn, 31, 94 Sulphated and sulphonated products, 12:
free fatty alcohols in, 05 uses, 245, 289, 296, 298, 304
411
• Sulphation and sulphonation, 130-133, UNSAPONIFIABLE MATTER (unsaponifiables),
254-258: 4C-97:
corrosion rates of' equipment for, 257 components, 46
of fatty compounds, 132 concentration by solvent extraction, 267
suitability of fish oils for, 257 definition, 46
Sulphur as a polymerizing catalyst, 124, 253 determination, 371
Sulphur-bottom whale oil: percentage of, in marine oils: see under
characteristics, 350 specific fishes
statistics, 349 Unsaturation, 366-370:
Sulphurization, 133-136, 258-263 _ definition, 7
Sulphurized products: see Factices effect of climate on, 43
Sun-fish liver oil characteristics, 68, 347 effect on • physical properties, 19, 156,
Supercooling and effect on stearine formation, 263-269 •
154 as measured by iodine value (see also under
Surface tension of oils, 164 specific oils), 8
Swordfish livers, statistics, 64 methods of measuring, 366-370
Swordfish oils: of oils in paint industry, 289-296
characteristics, 69, 280, 343 terminology, 17
production, 198 Urophycis spp.: see Hake
statistics, 64
Synergism, definition, 174
'VACUUM DISTILLATION: see under Distillation
Valency, definition, 4
TANNING INDUSTRY, 307 Varnishes: see Paints and varnishes
Taraxanthin, 79, 81 Viscera oils production, 198
Temperature, effect on physical properties Viscosity, 161-163
of oils, 145-151 effect of polymerization on, 1213 '126
Textiles, sulphated and sulphonated cora- of oils,' 162
1 pounds in, 296 Vitamin A, 46-54, 58-77:
Thaleichthys pacificus ( eulachon) oil, 68, adsorption, 59, 183, 217
346 - antioxidants and, 51
Thiocyanogen value, 367 biological activity, 47
Thresher shark liver oil: carotenoid pigments and, 47, 78
composition, 29 characteristics, 48-54
vitamins, 66 clinical application, 277-279
Thunnus alalunga (albacore) oils, 68, 278, concentrating, methods of, 58-60
344, 347 destruction by rancidity, 170
Thunnus (Thynnus) thynnus: see under Tuna effect of heat, light and oxidation, 50
Titre point, 155,157' effect of various treatments, 53
Tocopherols as antiokidants, 174 esters, 50
Tom cod liver oil vitamins, 67 in feed oils, 279-286
Toxicity: loss during production of oils, 183
excess vitamin A, 47 , physiological properties, 46-48, 277-282
excess vitamin D, 55 potencies of Canadian oils, 66-70
fish oils, 103 potency, factors influencing, 71-77
Tree-banding compounds, 307 requirements, 278-281
Tree-wound dressing, 310 specifications, Japan, 387
Tuna liver oils: stability, 50-54, 282-286
statistics, 64 structure, 48
vitamins, 69, 278, 280 synthesis, 54
Tuna livers, statistics, 64 toxicity of excess, 47
Tuna (bluefin) (horse mackerel, tunny) oils: . units, 70, 279
aaracteristics, 69, 343 Vitamin A2, 48
composition, 28, 29, 36 Vitamin A and vitamin D, 4, 58-77:
specifications for feeding oils, U.S.A., 398 in animal feeding, 279-280
Turbot oils: concentrating, methods of, 58-60
composition, 28, 29 in margarine, 275
vitamins, 69 oil specifications:
Twitchell reagents, hydrolysis by, 109, 245 Canada, 376
412
Denmarlc, 379 WATER ru Ons, 4
Great Britain, 382 Waterproofing, 87,' 296 -
New Zealand, 388 Waxes, 93-95:
U.S.A., 398 definition and structure, 93 ,
potencies of Canadian oils, 66-70 relation to unsaponifiablei, 4
sources of medicinal, 278 saponification, 241
sources on Canadian coasts, 60-71 spermaceti, 94, 348
stability on dry carriers, 282-284 sulphation of fatty alcohols from, 132
water dispersions, 284-286 uses, 309
Vitamin concentrates: Whale blubber oil:
definition and uses, 278 production, 212
preparation, 58-60, 266-269 vitamins, 70
specifications: Whale liver oil:
New Zealand, 388 kitol in, 49
U.S.A., 395, 398 production, 214
Vitamin D: vitamins, 70, 351
biological activity, 55, 57 yield, 351
characteristics, 57 Whale oils• (see also Sperm oil):
clinical application, 277-279 characteristics, '162, 222, 347-351
, concentrating, methods of, 58-60 composition, 30, 31
in feeds, 279-286 hydrogenated, 116
multiple nature, 55, 58, 279-282 hydroxylated, '139
physiological properties, 54-57, 277-282 specifièations:
potencies of Canadian oils, 66-70 - . Great Britain, 385
potency factors influencing, 71-77 japan, 387
, relation to sterols, 55 Norway, 391
requirements, 278-281 statistics, 348
specifications for feeding oils, U.S.A., 398 sulphation and sulphonation, 258 .
.0 stability, 57, 282-286 sulphurization, 259, 262
synthetic, 55, 279 uses, 251, 286, 294, 298, 305, 308, 350
toxicity of excess, -- 55 yield, 348
water-soluble, 58 White whale oils: see Beluga oils
Vitamin D2, 58, 280, 282 Whiting liver oil vitamins, 69 •
Vitamin D8, 55, 57, 279 Wintered oil: see Cold clearing
Vitamin F, 103 'Wolf-fish liver oil vitamins, 68, 69
Vitamin potencies of Canadian fish oils,
66-70: XA1\111-10PHYLL, 79 _
factors influencing, 71-77 Xiphias glaclius: see 'under Swordfish
Volume, effect of temperatüre and stearine ZEAXANTHIN,' 79, 81
séparation, 146-151 Zooplankton fatty acids, 38, 42
413
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