THOMSON 1965 Air Pollution

Air Pollution: A Review for Conservation Chemists
Author(s): Garry Thomson

Source: Studies in Conservation, Vol. 10, No. 4 (Nov., 1965), pp. 147-167
Published by: Taylor & Francis, Ltd. on behalf of the International Institute for
Conservation of Historic and Artistic Works
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GARRY THOMSON
Air Pollution-A Review for Conservation

Chemists
THE UNIT OF MEASUREMENT 147 Effects of Hydrogen Sulphide 155
Effects of Ammonia I56
POLLUTANTS PRESENT IN THE ATMOSPHERE 148 Ozone Formation in Polluted Air 156
Sulphur Dioxide 148 Electrostatic Precipitators 157
Hydrogen Sulphide 149 Effects of Ozone and Nitrogen Oxides
Ammonia 149
Ozone and Nitrogen Dioxide 149 METHODS OF CONTROL 159
Aerosols I50 Removal of Aerosols 159
Removal of Sulphur Dioxide 161
AIR CHEMISTRY AND EFFECTS 152 Removal of Oxidants 162
Oxidation of Sulphur Dioxide 152
A Note on pH and Acidity 154 THE FUTURE 162
Effects of Sulphur Dioxide 154
MOST of the evil effects of the dirt and acid
given environme
gases in town air on art and architectureof
have proportion be
been recognized in a general way for more A great deal of i
than a century. This article attempts to on
bring these matters
further detail into the picture by including
is manifestly obj
some very interesting recent work
isin a deposited fro
summary of basic information. We are sticks
con- tenaciou
cerned with those substances in air, other than
through the effec
oxygen, which are known to have pernicious
quantity of dirt
effects on museum material. Substances cities
which to the poi
becomes
are poisonous only to living matter, as far as the chi
is known, such as carbon monoxide, are We not know that su
included. paper, cotton, an
A sense of proportion with regard to butthe we know n
mode
many possible causes of damage is essential to of action in
good conservation. Once museums have got
methods of rem
over the major stage of preventing deteriora-
small scale. Ozon
tion taking place, as it were, under ourAngeles
eyes- smogs to
or more literally within times less thanofa widespread oc
decade-conservators must increasingly therely increased num
on record-keeping and instrumental measure-
know it attacks or
ment as the only possible checks on for slow sure whether
change and on the purity of the environment.
in the slow destr
To establish that damage is caused by visible
THE UNIT OF MEASUREMENT
light, by ultraviolet light, by transport and
photography, by dirt, air pollution, etc.,
When is the concentration of one po
not sufficient. Damage by one agent mayquoted
occur in different units in differ
at I/iooth the rate of damage by another in a it becomes very difficult to
cations
147
148 Garry Thomson
figure in mind at all. And 00 oo g when the
of 'pencil lead' is the sort concentra-
of quantity
tions of several substances
transferred areto papereachin writing quoted
one word. in
different units, comparison becomes
I ooo000 g of soot might thoroughly arduous.
blacken
To take one example, one the concentration
square centimetre of paper. I ooo0 g of a of
sulphur dioxide typical
gas suchof andioxide
as sulphur urban winter
could be stored
in the industrial partswithout
of compression
the world in a sphere justmay
under a be
centimetre
quoted in any one of the in diameter.
ways This amount is in
shown fre- the
table below: quently found in each cubic metre of London
town air during smogs.
TABLE I
I 000ooog/m3 of sulphur dioxide is just about
CONVERSION TABLE FOR SULPHUR DIOXIDE CONCENTRA- detectable by smell. However, though it
TIONS [I] appears to have a highly pungent odour in the
laboratory, certain other substances are detect-
able at far lower levels. Fortunately these do
600oog/m3 - micrograms per cubic metre not normally occur in polluted air [2].
60 mg/Ioo m3 - milligrams per Ioo cubic metres
0-21 ppm - parts per million by volume
21 pp Ioo m - parts per Ioo million by volume POLLUTANTS PRESENT IN THE
Approx. 5-5 mg SO3 per Ioo cm2 per day- referring
ATMOSPHERE
to a standard measurement using lead peroxide
cylinders.
There is very little point in attem
define the composition of a 'pure, u
atmosphere'. For our purposes th
Other units using pounds, gallons, etc.,
approach is to regard any minor con
are not beyond the bounds of possibility in
of the atmosphere, whether man-mad
English-language publications. Water vapour
which might do harm to the common
in air, for instance, is still commonly quoted
materials as a pollutant. Oxygen,
in grains per pound.
responsible for much damage, is not
Solid particles must, of course, be measured
constituent and cannot obviously be
by weight, so that, if we are to choose one unit
as a pollutant.
for all pollutants, the pollutants must be
Not all pollutants are man-made.
measured by weight, not by volume. A
notably, is produced almost entire
volume of air is more easily visualized than a
upper atmosphere, though we wo
weight of air, so that the preference narrows
little cause to complain of it bu
down to weight per unit volume. A little
additional ground-level production
manipulation will show that the quantities of
Angeles-type smogs. Surprisingly, h
impurity actually encountered in air are most
sulphide (sulphuretted hydrogen) is stil
conveniently quoted in itg/m3 (micrograms per of non-industrial origin (see below).
cubic metre). Figures will then range from less
than io for low pollution to over a thousand
Sulphur Dioxide, SO,
for smog.
Though one cubic metre is easily visualized, Any impression that the mineral ex
being the amount of air in a cube of I metre techniques of today have reduced
side (I m3~ I-3 yd3), I'pg is a very small the minimum is immediately banishe
quantity indeed. Air with only I [g of solid repugnant fact that sulphur product
matter per cubic metre is substantially particle- phuric acid and all other forms of
free air, purer than is to befound in the country- produced by the chemical industry) i
side on a clear windless day. exceeded by the amount of sulphur pou
Air Pollution-A Review for Conservation Chemists 149
the atmosphere as sulphur dioxide waste from significant amounts of H2S a
burning fuel [4]. given off by rubber and other m
Though sulphur dioxide gas may itself might find themselves in show
cause the fading of a few dyes [5], its real
destructive action begins after its conversion to
Ammonia, NH3
sulphuric acid (see p. 152). Ammonia, like hydrogen sulp
This sulphur dioxide is produced almost duced by both man and nature.
entirely by the burning of fuel, predomi- tions do not fluctuate widely b
nantly coal and coke, and to a lesser extent and summer, falling mostly wit
automobile fuels. Domestic fires in Great 5-20 ~g/m3.
Britain emit considerably less than industrial However, in urban conditions, where the
furnaces, the ratio being about I/5 [6]. water in raindrops and adsorbed on solid
Quantities of sulphur dioxide to be expected particles is acid, the major part of the ammonia
are summarized in Table II (see also Fig. I). will be found in this water as ammonium
From experience in the National Gallery [7] sulphate (see p. 153).
and the Victoria and Albert Museum [8] the
concentration of sulphur dioxide inside a Ozone and Nitrogen Dioxide, 03 and NO2
non-air-conditioned room may be from 50 We now come to one of the most chemic-
to ioo% of the outside concentration. ally interesting and potentially dangerous
pollutants, ozone, and its precursor in the town
TABLE II
atmosphere, nitrogen dioxide.
Sulphur Dioxide-Typical Concentrations Before the arrival of very large numbers of
(micrograms per cubic metre) cars in Los Angeles, California, ozone was
widely regarded as a stimulating and health-
giving constituent of seaside air. Certainly it
Highest recorded (London smog
of 1962) 5 66o was not regarded as a poison, in low as well
Industrial towns inas winter
in high concentrations
more [Io]. than 400
Small towns in winter Prior to this automobile age ozone was
Large towns in formed
summers up
almost exclusively in the to
upper atmos- 30
Country and maritime air away
phere, in greatest concentration at a height of
from industry 0-25
about 25 km [11], by the action of ultraviolet
light on oxygen. Mixing by air currents brings
this ozone down to earth.
Hydrogen Sulphide, HS
The winter smog of cities like Los Angeles,
Hydrogen sulphide (sulphuretted hydrogen),
which receive plenty of sunshine, is different
the enemy of silver, cannot to
beand
escaped from
rather worse than inLondon smogs.
the countryside. Both contain large quantities of soot and sul-
It appears from the rather scanty
phur dioxide, data
but the smogs of Los Angeles
available that this gas is certainly
contain, in produced
addition, irritantin
amounts of ozone,
both town and countryside, in the former
nitrogen dioxide, and organic oxidants.
from industrial activities, and in
Most of thethe latter
nitrogen dioxide comes from
from biological activity incarswamps, shallow
exhausts [12], and ozone is produced from
lakes, and intertidal flats [9]. it by the action of sunlight. Further details are
Variations are too irregular and
given localized
on p. to
156. Whereas the background
tabulate, ranging from less than
levels I todioxide
of nitrogen about outside towns are
10 Iog/m3, with an average of less
similar than
to those 5. One
of ozone, both can rise in Los
should remember, on the other hand, that
Angeles smogs at noon to I ooo /g/m3, and
I50 Garry Thomson
are commonly found at seen
a few cover their
hundred wind
Lg/m3.
their window-sills,
The range of concentrations which are bu
likely to occur in towns in winter
museums is those
is for as
follows (in ~g/m3): enter all parts of a room
-smoke in other word
A knowledge
Nitrogen oxides: Los Angeles, Cin- of th
cinnati, Baltimore
aerosol 2oo-600 particles is imp
it we cannot assess
London, Frankfurt 10-30 how efficient an air-
Ozone: Los Angeles filtration system should be. Air chemists speak
(daytime smog) 1oo-300 of three ranges of size: 'giant', 'large', and
London 20 'Aitken' particles:
Organic gases: Los Angeles 70-4
GIANT LARGE IAITKEN
In countryside conditions nitrogen oxid
radius in microns I o01
concentration falls to very low values
London suburbs,
Florida, less than 6). Tho
the ozone/nitrogen oxides
Giant ratio
particles range is
fromactu
I to
anything
higher in London than in Losmuch larger settling
Angeles it w
be incorrect to deduce
source that ozone
of production. produc
Large particle
(see p. 156) occurs to any extent in Lon
i to o.I t range, and Aitken p
20 [tg/m3 of ozone anything
is about smaller,
the though
expected there
for non-polluted air. Inlimit
lower other words
of about subs
o0-0oo05 , s
tially all the London
smaller
ozonethanhas
this been
rapidly prod
becom
in the upper atmosphere by the actio
larger particles.
short-wavelength ultraviolet
Urban air contains radiation
roughly the
of Giant and
oxygen [iI]. This natural Large particles.
process of But
oz
formation results in a fairly
that uniform
a Giant particle weighs sea-
abou
as much
distribution of ozone as a Largeslightly
generally and a millionhi t
than the London figure-say s50og/m3,
as an Aitken particle, the arrival of
or less
was the sole important Giant particles
source until the can alte
ad
of the internal combustion engine.
weight distribution. In any case G
will be effectively trapped in
Aerosols
filter system.
The term 'aerosol' covers the
Of greater minute
interest is thesol
pro
Aitken particles-those
particles in the atmosphere which below are l o
Only 'high efficiency'
enough to remain suspended in still filters
air. are
U
fortunately they deal
do with
notthese.
remain
Yet, fromin the
data ki
by R.
for ever because when E. Waller
they hit[13], we must c
a surface t
often stick there, to from
form5 to 15% of the a
eventually aerosol
layer m
black dirt which cannot
micron be dusted
radius off.
in London air consi
This solid matter in
particlestowns
[I4]. is mainly com
posed of carbon black Smoke,
(fine though composed
particlesmainly of carbon,
of carbo
produced by the includes other materials of interest
incomplete to the
combustio
fuels and rendered conservator.
sticky Chief by
among these are adsorbed
a proportio
tarry material. sulphur dioxide, ammonium sulphate, and
iron, though in
Londoners and dwellers traces other
of many otherlarge
elements cit
know that plenty of particles
are present big
[I 5]. There are enough
also certain to be t
TYPICAL LEVELS OF AIR POLLUTION
- up to 4000-
Smog
700
Industrio/l Towns-Winter
Small C/tles - Wnter

Large Ci/tes- Summer
5-50
Natural Background--Rural
SULPHUR DIOXIDE or AEROSOL
400
Los Angeles-type Smogs
NI/TROGEN OXIDES
Los Angeles- type Smogs
OZONE
normally below 20
NITROGEN OX/DES, OZONE, AMMON/A, HYDROGEN SULPHIDE
(each square represents lOOug/ccm3)

FIG. I.
present, as solids in museum air, suspendedatmospheric hazes in the countryside has been
particles of ash, building and soil dust, and
proposed by F. W. Went [16]. The blue haze,
fibre fragments. The importance of sharp often called a 'heat haze', which is to be seen
fragments in abrading textile material as itover the distant countryside on sunny days is
moves under changes in humidity has not formed from volatile products given off by
been evaluated. shrubs and trees. Its origin is not connected
Before closing this section, two natural with human activities. This volatile aromatic
sources of suspended particles should be men-
material is acted on by sunlight to form oily
tioned: plants and sea-spray. polymers, which condense into particles in the
An extremely interesting explanation of
Aitken range of size (radius less than o'I
152 Garry Thomson
atmospheric
microns). A haze of particles in this water
sizedroplets;
range (3) ph
tion in the gaseous
scatters blue light preferentially, and state.
is there-
fore blue in colour. Correspondingly it passes
(I) Catalytic oxidation in water-ab
more red light, causingmaterials
particularly red
occurs, for sun- in pap
instance,
sets. It is important to note that
cellulosic water
textiles. Thisvapour
presumably ta
cannot give a blue haze.in adsorbed
Cloud waterdroplets
water (amounting to a
by weight
are very much larger (radius of the cellulose
greater than 2 fibre at
microns). They scatter all colours and
temperatures equally and in the
humidities)
of, e.g., iron as
therefore appear white or grey. However the follows:
next stage in the life of these organic particles
SO-- +H2O+2Fe+++
is very likely to be condensation of water =
SO- +2H+ +2Fe++
vapour round them to form cumulus clouds
followed by re-oxidation
or, with a low-level temperature of the ferrous iron.
inversion,
morning ground mists.The Their
process isfinal fate
exothermic, and is is no by
followed
less interesting. There is convincing
further evidence
release of heat as the sulphuric acid is
to suggest that, afterhydrated
precipitation on energies
[20]. No large activation the are
involved.over
ground, they accumulate The process therefore does
millions of not
require light, andof
years, eventually to form-deposits in fact takes place readily in
petroleum.
This is all incidental to the
conservation. But
dark [21]. Traces of other it besides
metals
is worth noting that organiciron-manganese and copper
particles for instance-
originat-
ing from plants in this way will catalyse the reaction
probably [21, 22], and there is
contribute
a background mass in the evidence
air of to show
aboutthat conversion
5 Eg/m3. is concen-
Finally, sea-spray produces by
trated in the evaporation
areas where iron is present [231
and will not(with
particles of sodium chloride take placetraces
in the absence
of of
a catalyst
other salts) small enough [24].
to remain suspended.
Their importance to metallic corrosion
Further aspects in
of the effect of sulphur
museums situated near dioxide
the on cellulosics
coast iswill be reviewed
clear on
[17].
Sea-salt concentrations p. of154. up to I ooo00g/m0
have been observed close (2) to Catalytic
the oxidation
coast in air-borne
[i8], but water
this concentration drops droplets has been closely
rapidly a fewstudied kilo-
by Junge and
Ryan [21], and many
metres inland. Hence, although of their conclusions
sea-salt par- can
be usefullytheir
ticles can penetrate far inland, applied toimportance
process (I) above.
compared with urban sources Oxidation doesof not take place in the absence
chloride is
small. of a catalyst, but appropriate amounts of iron,
not to mention other catalytic metals, are to
AIR CHEMISTRY AND EFFECTS be expected in polluted atmospheres [25].
The oxidation is not photosensitive within the
Oxidation of Sulphur Dioxide ordinary range of sunlight illumination levels.
Of great interest
A proportion of the sulphur dioxide in theis the finding that oxidation
atmosphere becomes convertedalmost
to sulphuric
ceases when the pH in the droplet falls
acid, a very strong acid rendered more
to about 2-2, though this could be expected
in a general
dangerous than other equally strong acids way
such from the presence of hydro-
gen ions on
as hydrochloric acid by its involatility [I9].the right-hand side of the equation
Atmospheric sulphur dioxide underis known to
process (I) above. If this were the end
undergo conversion to sulphuric of the matter
acid the mechanism would not suffice
by three
routes: (I) catalytic oxidation in water-
to account for the known quantities of sul-
absorbent materials; (2) catalyticphate in rain-water,
oxidation in which are about two
Air Pollution--A Review for Conservation Chemists 153
orders of magnitude greater than experiment- favoured. Under these conditions bloom may
ally predicted on this basis. But ammonia is grow in much the same way as ammonium
present in the atmosphere and would im- sulphate accumulates in airborne droplets,
mediately be taken up, allowing the pH to iron being inevitably supplied by industrial
rise and the reaction to continue. It has been dust. The photosensitivity of the process may
shown by Junge that a rise in pH does indeed be due to the fact that the oxidation of the
allow the reaction to build up sulphate, and varnish surface is accelerated by light. Finally
that the reactants are present in polluted there is some evidence that a thick film is
atmospheres in sufficient amounts to account more likely to bloom, so that we cannot
for the known quantities of ammonium ignore the possibility that certain bloom-
sulphate present in rain-water. Over the forming constituents migrate to the surface.
U.S.A. the average concentration of sulphate (3) Photo-oxidation of sulphur dioxide in the
gaseous state certainly occurs, but the reaction
is about 3 mg per litre of atmospheric moisture,
existing in almost stoichiometric proportions mechanism is uncertain [29].
with NH4, but with a balance on the acid side, The rate is proportional to the SO, concen-
especially over towns, resulting in a rain- tration (oxygen being in excess) and amounts
water pH usually lying between 4 and 5. The to about o-I to o'2% conversion per hour in
pH can, in fact, never rise above 5-6, unless intense natural sunlight [21]. Estimates of the
alkali is present, because of the presence of actual half-life of sulphur dioxide and Junge's
carbon dioxide [26]. Nevertheless, Junge con- investigation of the catalytic conversion in
cludes that 'in most polluted atmospheres droplets in icate that the catalytic process is
SO4- is the major constituent which reduces by far th most important, at any rate in
the pH' [27]. polluted atmospheres [30].
This mechanism whereby ammonium sul- Evidence that the major part of the acid in
phate accumulates in atmospheric moisture is paper and cellulose textiles (other than that
interesting in connection with the formation due to manufacture) is derived from sulphur
of 'bloom' on certain kinds of varnish surface dioxide oxidized in situ by process (I) above is
[28]. Bloom consists of uniformly distributed as follows.
particles of moist ammonium sulphate which (A) The actual concentration of sulphuric
grow in size, passing through the aerosol acid in polluted air (as opposed to rain-water
range (sub-micron to a few microns in radius). which does not normally reach museum ob-
Exposure to light increases rate of growth, jects!) is only a fraction of the sulphur diox-
which occurs at normal temperatures and ide concentration. Readings at the National
humidities. The varnishes which favour bloom Gallery, London, in 1959 showed a weight
formation are the chemically unstable types, ratio H2SO4/SO2 of about I/5o, though they
characterized by dammar and mastic. Bloom also indicated that the acid gained ready access
usually occurs in the first months of varnish to the inside of the building (non-air-condi-
life, old varnishes becoming immune. It is tioned rooms) [31].
likely that bloom formation is favoured only (B) Sulphuric acid does not appear in pure
at certain water contact angles-droplets filter paper under conditions-a few weeks
either evaporating on non-polar surfaces or
in 2"5% sulphur dioxide-where amounts of
spreading on highly polar surfaces. But, due up to I% develop in newsprint or filter paper
to their chemical instability, bloom-prone containing iron [32].
varnishes pass through all stages of polarity, There are many other published results
starting very non-polar and ending with a which, while not affording unambiguous
highly oxidized surface. Thus, at some stage evidence for conversion of SO, to H2SO, in
during oxidation bloom formation should be situ, show that sulphate is formed [33], acidic
154 Garry Thomson
material and sulphates appear
the paper, [34],
as has SO,
quiteis
com
chemically absorbed, increasingly sowhere
it is pretty clear where the f
particles of iron are present
2. Acid[22], etc.
paper ingredients. A
the end of the 17th centur
A Note on pH and Aciditysize so as to improve writi
been misleading,
The pH scale is sometimes the chief source
con-of aci
centrating as it does an enormous
more variation
potent by the later
within the compass of alum-rosin size. Chlorides
a few digits. Thus
chemists keep their fingers outdecomposition
bleaches, and of acids
stronger than about pH low-grade
i, and alkalis stronger
wood pulp are o
than about pH 13, each 3.
6 Sulphur
points on either
dioxide side
gas, as al
of neutrality (pH 7). But an acidity
Curiously enough,of pH
in 4spi
cannot even be detectedamount of published
by taste (e.g. 5 mgma
sulphuric acid per litre), which is fortunate
deterioration, it does not yet
since this degree of acidity is commonly
the present author at any
attained in old paper and urban
factors (2)rainwater.
and (3) against eac
While Barrow
The acidity of paper exposed to urban supposes
air
account
(e.g. the edges of old books), offor only
peat a small
bogs in p
north-western England [35], and
deterioration' of the
[38], urban
extra
ness at about
rain-water is very commonly the edges
pH 4. ofThe
pages
major source of acid diffused
in each in appears
[33], andto be
the sup
industrial SO2, and in books
each case
in thethis
sameis edition
partly ke
neutralized by ammonia or another
as opposed weak
to the town [39] s
base. that SO2 is important [40].
TABLE III
Cotton and linen. Being a
Some Approximate pH Values
cellulose fibres-spun instea
vegetable textiles must follow
lines of deterioration as pape
Sulphuric acid, 50 g/1 0-3 tiles get dirtier than book p
Sulphuric acid, 5 g1 I-2 are
Sulphur dioxide, saturated solution 1'5 more exposed so we can
Alum (Io g/l) 3-2 to be more dangerous to the
Carbon dioxide, saturated solution 3-8 Figures are available to
Vinegar and cider 2"4-3"4
Bog water from Lake District, England 3'7-4'1
acidity in urban atmosphe
Rain 4-6
loss in strength of cellulose
Cultivable soils 6-5-8 example:
TABLE IV
Effects of Sulphur Dioxide
Comparison of strength of cotton patterns exposed in
Paper. Evidence that acid in paper causes its
different locations for I 300 sun hours [41]
deterioration is conclusive, and has been
known to be so at least since the 1930s [36].
The most complete data are by Barrow,
Retained strength
whose recent work is summarized in [37].
I. Unexposed
There are, however, not I00
one, but three
2. Clean air 75
possible sources of acid: 3. Moderately conta
4. Suburban
I. Acid inks, usually iron-gall industrialWhere
types. air 12
the printed letters actually make holes in
As with paper, serious damage by SO, can alkali or salt-must be present. Conseq
be regarded as proven, but the mechanism is corrosion will be speeded by (a) s
not certain. A slow dark conversion to dioxide because it forms acid solutio
(b) soot which aids the adsorption o
sulphuric acid followed by hydrolytic attack,
as with paper, can be assumed, but Little [41] [45]1.
emphasizes the importance of sunlight in The corrosion of copper and bronze in air
accelerating this attack. can proceed in five possible directions: to the
Sulphur dioxide may cause slow damage tobasic forms of carbonate, chloride, and
other textiles, but the effect is far smaller than
sulphate, to oxide or to sulphide. Of these by
on cellulose. The other main organic material far the commonest is the sulphate, even near
the sea coast [46]. (Corrosion of buried copper
to suffer is leather, at any rate leather tanned in
certain established ways [3]. For the effect is ofa different story. Here sulphate is un-
sulphur dioxide on dyes see [5]. common, the usual surface corrosion being
Plaster, limestone, and marble. Asked to pick carbonate or chloride. There is commonly
the most tragic examples of attack by sulphur an underlayer of cuprous oxide.)
dioxide, many might cite those Italian frescoes Below certain critical relative humidities,
which now find themselves within industrialsulphur dioxide corrosion of both iron and
zones.
copper appears to be very slow or absent.
Reports by Tintori, Sayre and Majewski
These are 60% for iron, and 63% for copper
[42] demonstrate that 'attack by acidic
[47]. gases
has been the predominant cause of Summarizing,
the rela-sulphur dioxide is a major
tively rapid decay that has occurred during
corrosion agent on iron and copper.
the present century' on the Giotto frescoes in
EffectsIn
the Scrovegni Chapel at Padua. of Hydrogen
trueSulphide, H,S
frescoes the pigment is bonded to the H2S issurface
present at very much lower concen-
by calcium carbonate formed from the
trations thanlimeSO2-typically I/Iooth of the
SO2 concentration
plaster by the action of carbon dioxide. Thein urban winter conditions.
conversion of carbonate to sulphate H2Sresults in both silver and copper,
rapidly attacks
a doubling of volume, so that the though surface
in the case of copper, as we have seen,
expands, flakes and powders. Decay wasnot
sulphate worst
sulphide is the corrosion product.
where water seepage occurred. The effect ofH2S on copper in towns is small
The erosion of limestone is to becompared
seen to inSO2 all
attack.
temperate-zone cities. ArchitectsSilver have the
tarnish, on the other hand, is silver
choice of exposing the stone to the action
sulphide. From theofknown stability of silver
rain so that it 'washes its own compounds,
face', or we of
would not expect either
protecting it under cornices, mouldings, oror oxide to accumulate.
sulphate, carbonate,
other forms of shelter. In the former case thereby
But we cannot the assume that tarnish
stone is kept free of soot but slowly eroded
results only from attack by H2S. It is possible
away by acid rain-water (pH of that urban rainsilver, the end product
SO2 also attacks
usually about 4), and in the latter it will not be silver sulphide [48].
being in this case also
able to avoid SO2 attack but may be Lest anyone should suppose that the con-
subjected
to flaking caused by repeated recrystallization
centration of some of the rarer pollutants, such
of the calcium sulphate which is allowed
as H2S tolow to worry about, it
and 03 is too
accumulate [43, 44]. can theoretically be demonstrated, for in-
Metals. Iron rusts by an electrochemical
stance, that every atom in a silver surface will
process. For this to occur, water plus some-
be hit about twice a second by a molecule of
thing to make it conduct electricity-an acid,
H2 S at a concentration of 5 /g/m3 [49].
I56 Garry Thomson
Effects of Ammonia From the mass of data, some of
Cellulose is degraded collected
by both over
acidthe
andpast decade or
alkaline conditions (by ing outline canIt
hydrolysis). beis
drawn.
Motor
possible to imagine that if no fossil vehicle engines diff
fuels were
fired
to be burnt, rainwater and furnaces water
absorbed in that they prod
would become alkaline, substantial
and ammoniaquantities
a of (A) n
(B) gaseous
noxious museum contaminant. However organic
it has material. P
tionspresent
already been shown that under of either of these may
condi-
volume of the
tions, at any rate in towns, water absorbedexhaust gases i
petrol engines
into cellulose and other non-alkaline [so]. The organ
materials
is acidic because of the sists of acetylene,
predominance ofhydrocarbo
saturated),
sulphur dioxide. Any ammonia and aldehydes in
also absorbed
parable quantities.
merely reduces the acidity. Ammonium
Nitric oxide is,
sulphate or bisulphate is hygroscopic however, a ph
and
thereby plays the chief part stable compound,
in the formationand its co
smog is far
of bloom on paintings varnished with naturaltoo low for its
nitrogen dioxide
resins (p. 153). This is about as far as we can by direct co
implicate ammonia in the deterioration of in eleme
oxygen, as described
museum materials, except textbooks [51].
where present in
Nevertheless it is reported that
abnormally high concentration.
just before sunrise in Los Ang
Ozone Formation in Polluted Air
start coming into the town, th
It has already been stated of that,
nitricfrom
oxide the
and hydrocarbo
human point of view, the but after
worst sunrise
smogs the NO decr
are
NO2
produced in large towns with builds
a lot up [52].
of cars and Though
a sunny climate-Los Angeles being
of NO to NO2 the
occurs when
typical representative. These smogs
containing causeare irradiat
olefins
tory, the mechanisms
serious eye irritation. Consequently much by w
research has been concentrated on the
are not yet chemical
clear. It is definit
olefinic
reactions which result in eye hydrocarbons
irritants. These must be
therefore
form only a small proportion summarize
of the total this stag
impurities, and are not likely to be of the
NO+olefins->NO
same importance in the museum as they are to
The appearance of NO2 is th
the human eye.
trouble. As Cvetanovid has ob
The most important museum poison specific
is now generally accepted tha
to Los Angeles-type smogs is almost certainly
solar radiation by nitrogen dio
ozone. But without the production of nitrogen
responsible for the initiati
oxides by road vehicles abnormal concentra-
reactions which lead to smo
tions of ozone would never appear [12].
Los Angeles)'.
Therefore we must first examine the produc-
This key reaction can be represented as
tion of these nitrogen oxides. Nitrogen forms a
follows:
variety of oxides, but only two of them need
NO2 +hv->NO+O ... (ii)
be considered here, since they are the only two
which appear in significant quantities in
polluted air-nitric oxide (NO)
O+O,(+M)
Reaction and
-Oa(+M) ... (iii)
nitrogen
(ii) indicates that, in the presence of
dioxide (NO,, sometimes sunlight,
known NO,as willnitrogen
revert partly to NO with
peroxide). the production of a very reactive oxygen
atom. This O atom then combines quickly efficiency in removing aerosol particles
and almost completely with an oxygen higher than that of all but the finest fabr
molecule to form ozone, 03. Another mole- filters (see Fig. 3). Its operation is briefly
cule, M (usually a nitrogen or another oxygen follows.
molecule), must be at hand to take away the The incoming dusty air passes through a
energy given up in the reaction, otherwise the screen consisting of wires charged to a positive
ozone would fly apart as soon as formed. voltage of about Io ooo volts (the ionizing
Only a tiny proportion of the O atoms pro- voltage) and the dust particles are thereby
duced by reaction (ii) react with hydrocarbons given a positive charge. Nearby plates charged
or other materials. Though these reactions negatively (the collector plates) attract and
may be important in the production of eye hold the positively-charged dust particles.
irritants, our interest centres on the production At intervals the electricity supply is dis-
of ozone. We need not therefore pursue connected and the dust on the negative plates
further the many other reactions which occur is removed by tapping and/or washing.
in polluted air [55]. The most effective method of producing
It should be emphasized that reaction (ii) is ozone in the laboratory is by passing a high-
photochemical--ozone is not formed in the voltage electric discharge through a stream of
absence of sunlight, and this is generally air, so that it is no surprise to learn that
accounted the chief reason why London, for electrostatic precipitators, as well as cleaning
instance, does not get Los Angeles-type smogs. the air, produce some ozone (and nitrogen
To summarize this section, the chemical oxides).
reactions in polluted air which lead to ozone Fig. 2 shows that, with the precipitator
formation are as follows: working correctly, ozone concentration is
motor vehicle engines->NO +olefins likely to be at least doubled, but if for any
sunlight reason the ionizing voltage rises or a high
NO +olefins----NO2 . .. (i) local potential gradient appears, ozone produc-
sunlight tion rises sharply. But even the doubling of
NO2- -NO+O ... (ii) ozone concentration seems very undesirable.
Electrostatic precipitators cannot, therefore,
O +02(+M)-Os3(+M) ... be(iii) recommended for use in museums, except
for exhibits known to be unaffected.
At present it seems that the active organic
material also found with ozone in Los Angeles-
Effects of Ozone and Nitrogen Oxides
type smogs occurs in such small amounts
compared with ozone that its presence
Ozoneinhas a very specific action on organic
museums can be ignored. materials. It will attack and break open any
double bond between carbon atoms (e.g. an
Electrostatic Precipitators unsaturated carbon chain):
If the reader wishes to convince himself that
ozone is an objectionable pollutant he should O
turn to the next column, where the action of 03 / ultimately

ozone on organic material is briefly reviewed, o---CH=CH~
I I
---- C
for we must now consider another possible 0-0
source of ozone which has actually been
introduced into museums. ---COOH HOOC---
The electrostatic precipitator is a very
effective machine for removing dust from In the
in- long carbon chains which compose
rubber,
coming air. Though its installation is costly its a double bond occurs after every
158 Garry Thomson
300
200
o normcal
voltage
100
ozone
produced by
electrostatic
precipitator
sng voge 4 (k ot)

0. fonising voltage 14 (kilovolts) 16
FIG. 2. Test of an electrostatic precipitator. The ozone concentration shown is the total out-
put minus the background concentration. Collector plate voltage maintained at about half
ionizing voltage [56].
fourth carbon atom in the chain. Rubber is normal concentrations [59]. Results indicate
therefore very sensitive to ozone. The ozone that substantial modification may occur in a
molecule contains three oxygen atoms, and short time, e.g. a cotton sample at 50% moisture
oxygen gas two, but ozone cracking and the content, after a 5o-day exposure to ozone at
photooxidation of rubber by oxygen are two about 100oog/m3, lost 20% of its breaking
distinguishable processes. Photooxidation con- strength. The report referred to concluded,
verts the surface of rubber to a non-elastic nevertheless, that in exterior weathering the
material. Ozone cracking will occur in the effect of ozone is small compared with other
dark, but is only noticeable when rubber is modes of deterioration. Though museum
stretched. Ozone cracking causes no visible cellulose is not subjected to these humidities,
change in the surface, but deep cracks at right- the effect of ozone on cellulose should not be
angles to the line of stretch [57]. ignored when considering, for instance, the
All unsaturated organic material is sensitive use of electrostatic precipitators (p. 157).
to photooxidation as well as attack by ozone, Ozone is also a dye-fading agent [6o0]. The
and probably the former is overwhelmingly chief targets of the nitrogen oxides also appear
more important. The unstable natural-resin to be dyed fabrics. In the case of nitrogen
varnishes are the commonest museum examples oxides, these act together with the acidic
of such material. Ozone attacks saturated conditions resulting from SO2 contamination
hydrocarbon polymers at room temperature, to cause fading of certain dyes on wool [6i].
the preferred site being at branch points in the It is difficult to judge on present analytical
chain (tertiary hydrogens) [58]. evidence whether ozone and the nitrogen
Damp cellulose is also attacked by ozone at oxides could take a significant part in museum
TABLE V
Summary of Effects of Pollutant Gases
Important (I) or
Gas Formula Known to affect: probably minor (M) in
normal situations
Sulphur dioxide SO2 Cellulose (paper, cotton, linen), leather, plaster

limestone, marble, iron, copper, bronze I
silver?
Hydrogen sulphide H2S silver I

(sulphuretted hydrogen) copper and bronze M
Ozone 03 natural rubber I
all organic material (p
certain dyes M
Nitrogen oxides mainly
NO, NO2 certain dyes M
fading. Probably herethe

toodust out; and
their electrostatic
effect is negl p
which transfer electric
gible compared to photooxidation charges
(thoug
particles so that
in the days of gas illumination thisthey
wasarenot
pulled
s
One can assume thisair stream. If
simply the air is fabric
because not filt
unexposed to light museum
are not air will contain about
usually faded as m
though they are still accessible
pended dirt as the to pollutan
air outside.
gases. In the present state of the art
However museums exposed
necessary to to Los Angeles-
investigate the various d
although
type smogs or to badly there is no reason
maintained why
electr
static precipitators cyclone
may filters
have should
to take
not bethe
brou
effects into consideration.
efficiencyIn both
in the these
future. situ
Electrostati
tions other oxidising of an efficiency
entities, suchintermediate
as hydrog b
peroxide, are certainly formed,
best and and
the worst dry migh
filters, but
well play their partgiven on p. 157
in both dyethey are to be
fading anr
tendering of textiles. undesirable in museums.
Of the various dry filters on th
METHODS OF CONTROL we require to know:
(a) what efficiency is it reasonable
Removal of Aerosols (b) what kinds of filter are the most
The first and most obvious task in cleaning
this efficiency?
(c) what proportion of dirt is a
air is to remove the suspended solid particles-
moved?
the aerosols. These can be filtered out by
passing the air through one of a variety
Efficiency. of concern is simply
Our ultimate
devices, which include dry filtersthe proportion
(composed by weight
of of dirt which gets
felt, woven material, cotton wool, glass fibre,
through the filter irrespective of particle size.
The very
plastic foam, etc.); viscous filters smallest particles,
in which the weight for weight,
dust is removed in a coating are
ofat oil
leastor other as the largest. But
as important
filters which
liquid on the filter; cyclone filters which stopspin
substantially all the dirt
I6o Garry Thomson
offer more resistance to Fig.the
3 comparesflow of filters
a set of Vokes' air, in re-
quiring more powerful fans,
Methylene Blue Test and
efficiency clog
and resistancemore
to aireven
easily in bad conditions, flow. Vokes' technical
with staff find that the
properly
arranged pre-filters. Furthermore there
rural air pollution at their factory, comes
containing
only small
a limit beyond which there is quantities
no sense of soot from
innearby
going
because of the dirt brought in quite
Guildford, corresponds by museum
closely to the
visitors and through Methylene
opening doors.
Blue particle cloud It is
for efficiency
possible to install filters which
tests, but remove
that the efficiency of all filters risesmore
than 99-995% by weight as soon
of as additional
incomingsoot is introduced. aerosol
Soot
(e.g. Vokes H66). But such
particlesfilters
are commonly in find
the sub-microntheir
range,toxic
application where specific but tend to clump together. They are
particles are to
be removed-in hospitals, consequently for example,
more easily trapped than their and
in laboratories handlingsizeradioactive
would suggest, and by their materials.
presence in
However to extract information
the filter increase itsfrom manu-
efficiency against the
facturers' leaflets which will
particles allow one make
that follow.
But evenanother
of filter to be compared with if we take this is intonotaccountin
the
results of a test
the least easy and frequently conducted at the National
impossible. Even
where results of a standardized test
Gallery during the are
winterquoted,
of I959 by P. J.
these must still be related-with
Lawther and R. E. considerable
Waller of the Medical
uncertainty-to stopping power for Pollution
Research Council Air Unit are
real urban
dirt. surprising [7]. The filters for the air-condi-
There is in fact a range of 'test dusts', tioned rooms of the National Gallery are
different ones for different countries, which Vokes' Standard Kompak or equivalent. Daily
are used to give meaningful figures for readings of aerosol pollution and filtration
efficiency. There is also an understandable efficiency were taken over a two-month
tendency for manufacturers to quote tests period from February to April, using a stan-
using a dust coarse enough to give a flattering dard stain technique on Whatman no. i filter
figure for all their filters. British Standard paper. These showed considerable variation in
Test Dust no. 2, for instance, gives a figure of efficiency (percentage by weight of dust
over 90go% efficiency for all filters of interest to stopped) which was, nevertheless, always
museums. B.S. Test Dust no. i-the Methy- higher than 90% except on two occasions
lene Blue Test [62]-on the other hand can be immediately after filter changes, when it is
used to test filters in the highest efficiency supposed that some unfiltered dust may have
range. The American D.O.P. (dioctyl phthalate) slipped into the ducts. Efficiency appeared to
test is said to give roughly equivalent figures. be in the 90-97% range for most of the time
In a survey of the technical leaflets on [63].
filters made in various countries the firm of 9o% of the National Gallery air is recircu-
Vokes (Guildford, Surrey, England) will be lated, and this will naturally raise efficiency if
found exceptional in providing very complete new dirt is not injected. Also the air passes
data on their wide range of filters. All except through a particularly thorough spray which
the coarsest are rated by the Methylene Blue could remove hydrophilic dirt. Fig. 3 shows
Test, which is uncomplimentary to all but the that the Standard Kompak tested above could
most efficient filters. Something will therefore be greatly improved on with a small increase in
have been achieved if we can (I) use these resistance to air-flow by using the UniVee B
figures for scaling a range of filters, and (2) or equivalent grade. Better filtration still is
relate the Methylene Blue Test to efficiency obtained at the sacrifice of dust capacity with
against real dirt in the air. the UniVee A. But one hesitates to assume on
100 Absolute A 66 -
Absolute A 22
Electrostatic
precipitator
efficiency
about here
80 - i /ni Vee A
Z 60 /ni Vee 8
' Standard Kompak
/Uni Ve C
2C
20
0 1s2 3 4 5
Pressur
FIG. 3. Me
efficiency
represents
factors
the Some day, perhaps before coal has been

result
use that
completely replaced by nuclear fuel, sulphur b
overdioxide will be effectively
95% removed from
of waste gases at source. But in spite of much
instal
work on economical methods there is little
emphasi
monitor
sign of progress yet [6].
museum environment. Theoretically there are many ways of
eliminating sulphur dioxide from a room or
Removal of Sulphur Dioxide building, such as the use of various alkalis for
There is a strong case for removing sulphur scrubbing the incoming air. Whereas an
dioxide from all urban museums in industrial- industrial process must pay for itself by sulphur
ized countries. Damage by sulphur dioxide has recovery, this is less important on a small scale.
been surveyed on p. 154. In practice two methods have been explored:
162 Garry Thomson
from buildings
(I) washing with untreated orhas been proved in practice,
alkaline water,
secondly because
(2) adsorption on activated one is uncertain whether
charcoal.
this would be worth while except
(I) Washing. The air-conditioning within theat
plant
the National Gallery Los
has already
Angeles-type smog beltsbeen men-
or where electro-
tioned as subjecting static
allprecipitators
incoming are in use. air at all
times to a very thorough Some work has been done on This
spray. filters which
was
designed for the sole purpose of
successfully prevent the humidifying
arrest of plant growth
the air. But the Medical Research
in polluted Council
air [66]. Activated carbon, test
alu-
quoted above [7] showed that and
minium turnings, this spray
steel wool were found of
plain water also removed sulphur
effective. Polythene dioxide
fibre, cellulose sponges,
with an efficiency of and glass wool
about impregnated with
95-97% over ferrous
the
period February-March sulphate or 1959. This
stannous chloride was a
were without
effect. and
surprisingly high result, Althoughoneit is assumed
should that plant
not
poisons are associated with
conclude that all air-conditioning high oxidant
sprays will
give this bonus. In fact Kimberly and Emley
levels, it is not at all certain which pollutants
are to spray
[64] ascertained that the blame, and sulphur
for dioxide may also
air-condi-
tioning the Folger Shakespeare
play a part. One would notLibrary
expect ozone, at
Washington removed only
from about
its low boiling half
point, to the
be strongly
adsorbedunless
incoming sulphur dioxide on activated it
carbon,
was though the
made
alkaline. They recommended large surface areaaof pH of might
this material between
favour
8-5 to 9. All sulphur dioxide was removed at a
catalytic decomposition.
pH of 8-6 or greater, but The many
a pH devicesgreater
now being developed
than to 9
might damage metals such remove asnoxious
zinc fumes
by from car engines are
corrosion.
The alkaline material added to the water all designed with the aim of oxidizing in-
included corrosion inhibitors. completely burnt fuel, and are not concerned
(2) Adsorption. Two firms known by thewith the removal of oxidants.
author to market activated carbon filters are Ozone is strongly absorbed by unsaturated
Vokes of Guildford, England, and Filtration organic material such as turpentine and is very
Products of Canada, Toronto. Both were soluble in fats. The construction of a cheap and
marketed as odour-removers, and their effi- effective ozone absorber should not be diffi-
ciency against sulphur dioxide does not seem cult, and further work should be done on the
to be as high as is desirable unless the air is importance of this measure in cities with high
continuously recirculated through them [65]. ozone levels.
THE FUTURE
Removal of Oxidants
'Oxidant' is here a term of analytical con- It is sad to sift through the sourc
venience. Oxidant gases are all those gases in for this article and to find so small a
polluted air which are capable of oxidizingtion from one class of beneficiaries-those
potassium iodide to iodine when bubbled whose work is the care of antiquities.
through a solution at room temperature. A limited aim for scientific conservation
Chief among these is ozone, but nitrogen research could be something on the following
dioxide, hydrogen peroxide and a complicatedlines. To obtain a clear picture, quantitative
variety of organic ozonides must also be in- where possible, of the relative importance of
cluded. removal of dirt, sulphur dioxide, and other
The recommendations in this section will be pollutants for various classes of antiquities.
found to be very vague, firstly because no This will certainly involve a good deal of
method of removing ozone conveniently work on the chemical reactions involved.
These conservation measures should be related member of the staff at regular intervals for
in turn to the other major control-controls of checking.
radiation, relative humidity, and biological No one need regret that the museum, once
hazards. a palace for the display of trophies, is becoming
Adequate control of air pollution is useless in one of its aspects a machine for conserva-
without adequate monitoring. If sulphur di- tion. Concurrent with this evolution more
oxide is to be removed it must be seen to be thought than ever before is being given to the
removed, and the same holds for all the other better display of antiquities. There sc ems little
aspects of environmental control mentioned reason why display should to be threatened by
above. Monitoring need not be continuous, considerations of conservation.
and can be manual or automatic, but in every GARRY THOMSON
case it should be regular and the information National Gallery,
collected should be passed to an appointed London
Notes and References
I The conversion factor from volume per unit Air Pollutant (no date), p. 6. Sulphur dioxide dis-
volume to weight per unit volume is different for charged into the air (in 1962)= 6-o9 and (in 1963)
each gas: -6-37 million tons. Ratio domestic/industrial
molecular weight g/ production - about 1/5.
I pp Ioo m = w2.24Lg g/m3 7 Unpublished report by P. J. LAWTHER and R. E.
2 A. R. MEETHAM, Atmospheric Pollution, Pergamon, WALLER, Air Pollution at the National Gallery, 1959.
London (1952), p. 133, 140. Mercaptan is detectable 8 T. PADFIELD, private communication.
at 0o04 tg/m3, and vanillin at 2 1o-0-4~g/m3. Two 9 JUNGE (ref. 4 above, pp. 65-6) concludes that most
pollutants detectable by smell at lower levels than H2S is produced biologically, but this does not
sulphur dioxide are hydrogen sulphide at 30 ig/m3 tally with data given by J. T. MINSTER (Nature,
[3] and acrolein (from diesel exhausts) at a few 199 (August 3, 1963), pp. 474-5) obtained over 21
hundred tqg/m3. The limit of sensitivity may years in north-west suburban London, which
have been reached by certain male moths, who correlate increased H2S concentrations with wind
need only receive a few hundred molecules (per- from industrially polluted areas.
haps Io-14tLg/m3) of a female's scent to exhibit Io We are concerned in this report with the health of
signs of excitement. antiquities, not of human beings. However, because
3 C. H. GILES, Chemistry and Industry, May 9, 1964, many people still regard ozone as health-giving, to
p. 772. the extent that electrical devices for producing
4 CHRISTIAN E. JUNGE, Air Chemistry and Radio- ozone in the home are still on the market, the
activity, Academic Press, New York and London following is quoted. J. W. A. BRANT and S. R. G.
(1963), P. 71. Total U.S. sulphur emission 26 HILL, writing on human respiratory disease in Los
million tons/year. Total U.S. sulphur production Angeles (Air and Water Pollution, 8, no. 5 (1964),
p. 259), find that 'respiratory dysfunction increased
19 million tons/year. (Total as SO4, year 1957.)
5 C. H. GILES, 'The Fading of Colouring Matters', directly and cumulatively with increased total
1964 Delft Conference, LI.IC., 2nd edn. stencilled pre- oxidant (in the atmosphere) over a four-week time
prints (from I.I.C., c/o National Gallery, London, lag . . . The authors believe that ozone rather than
W.C.2), p. 8. Fading by sulphur dioxide 'is not other chemicals which comprise total oxidant is
common within the textile trade at the present time, responsible ... although there is no experimental
perhaps because some of the susceptible dyes are less evidence to conclusively prove this.'
used than formerly, but it might of course occur in 11 JUNGE, ref. 4 above, pp. 37-59.
museum specimens'. The original colour is restored 12 W. L. FAITH (ed.), Air Pollution Foundation Final
by weak ammonia solution. Report (I96I), p. 25. 'two thirds of the nitrogen
6 National Society for Clean Air, 1964-1965 Clean oxides in the air come from motor vehicles. ...
Air Year Book, p. 38; and. (also N.S.C.A.) Sulphur Nitrogen dioxide, together with hydrocarbons and
Dioxide-an Examination of Sulphur Dioxide as an their derivatives are the principal smog-forming
164 Garry Thomson
contaminants. In the presence of sunshine
an important these
contaminant o
materials react to form ozone.
evenNo other
where it method
could have a s
disease,of
of forming significant amounts for instance,
ozone in thecause
chloride, has never, so far a
lower atmosphere is known.'
13 The range of 5 to 15% wasbeen
deduced
tracedby tothe
theauthor
presence
from unpublished curves of particle
phere. size chloride
Sodium distribu-
particl
tion for typical London pollution
air can, ofcompiled
course, be byhighly
R. E. WALIER, Medical Research Council Air
Pollution Unit. The higher20SO3+H20--H2SO4+
SO2+--02--SO3+22-5
figure corresponds to kca
49 kca
heavier pollution. H2SO4+water to infinite di
21 CHR.
14 JUNGE, ref. 4 above, p. 118, gives E. JUNGE
a figure and
for T. G. R
Aitken
Oxidation
particles of not more than 'o to 200% ofin the
Solution
aerosoland its
substance'. He considers that the Aitken
Chemistry', particles
Quart. J. of the
are chiefly a product of industry and that
Soc. 84(1958), pp. their
46-55.
'concentration can even be used
F. E. as an index
GARTRELL of'Atm
et al.,
SO2
pollution' (p. 157). They must in Coal-burning
form, therefore, a Pow
small but definite proportion of the deposited
American Industrial dirt.Hygie
15 JUNGE, ref. 4 above, Tables,
pp. 113-120. pp. 178-9. Estimates
based on rather scanty 22data
F. LYTH HUDSON
are as and W. D. MILNER, 'The am-
follows: Perman-
monium sulphate 2% by weightence of Paper-the Use of Radioactive
of aerosol, ironSulphur3to
or 4%. Ammonia and sulphur trioxide
Study the Pick-up of Sulphur Dioxidequite by Paper',
closely balance each other to
Paper form
Technology, (NH4)2SO4,
2, no. 2 (I96I), pp. 155-61.
23 HUDSON
though in some cases there is an and MILNERof
excess (ref.sulphuric
22 above, p. 157)
acid corresponding to the partial
exposed formation
paper to radioactive of
sulphur dioxide.
(NH4)HSO4 (Junge, p. 337).After
Thistwo hours in a current
gives rainof air water
to remove free
its acid reaction. Data on chloride, whether
sulphur dioxide the as HCI
paper was autoradiographed
or salts, are too scarce toandgive reliable
subsequently developed infigures.
potassium ferro-
Roughly one might estimate cyanide.
thatThe iron and copper spots
chloride on the paper
concen-
corresponded
tration, gaseous and particulate, is to black spots on
I/Ioth of the sulphur
autoradiograph,
dioxide+sulphate (Junge, though
Fig. 41,
there p. 175)
was general darkening (Meet-
as well.
ham, ref. 2 above, Table, p.
24 GILES, 135).
ref. 3 above, p.Only
773. a small
25 JUNGE,
proportion of this chloride is of ref.maritime
4 above, pp. 178-9. origin.
16 F. W. WENT, 'Organic Matter
26 90% of thein the
dissolved CO2Atmosphere,
is undissociated, Io% is
and its Possible Relation toionized
Petroleum Formation',
to HCO3 , and the C03- concentration is
Proc. N.A.S., 46 (1960), pp. 212-21;
negligible F. 21W.
(Junge, ref. above,WENT,
p. 54). Except
for a few What,
'Atmospheric Hazes: Whence, 'alkali islands'Whither?'
noted in Scandinavia,
Penguin Science Survey B, rainwater
Penguin has beenBooks, London
found always acid in reaction.
(1964), pp. 212-29. 27 JUNGE, ref. 4 above, p. 339.
17 WILLIAM BOUSTEAD, 28
'The Conservation
N. BROMMELLE, Depart-
'Bloom in Varnished Paintings,
ment of the New South Wales
Museums Art
J., 55(1956), Gallery,
pp. 263-6; GARRY THOMSON,
'Some Picture Varnishes',
Australia', Studies in Conservation, 5 (1960), Studies in
p.Conservation,
121.
18 JUNGE, ref. 4 above, p. 158.3(1957-8), pp. 68-71.
19 Hydrochloric acid is a 29gas
Energetically
at room the easiest temperature
path is by either of the
(B.Pt. --840C) and, althoughfollowing
itroutes, both having
forms a anconstant
activation energy
boiling mixture with water at
of 135 20% HC1, it could
kcals/mole:
SO2-_SO+O
never accumulate on surfaces in normal atmospheres
since it would continually be lost SO2-S+ 02
by non-replace-
135 kcals correspondsboils
ment. Sulphuric acid, in contrast, to short UVat radiation
about
33o0C-for comparison (2dibutyl phthalate,
oo00 A), a region of the spectrum not absorbed a
common plasticiser, boils at
by sulphur 3400C-and
dioxide. will
However sulphur dioxide
absorbs
therefore readily accumulate inradiation in the near-UV corresponding
absorbent materials. to
If aerial droplets contain 85-95
chloride,
kcals, and the reactionand sulphur
dioxide is present, hydrochloricSO2+ acid 02-SO4gas will be
is said to be plausible.
liberated as the sulphur dioxide This would be followed
is oxidised byby the
reaction withp.
chlorine (JUNGE, ref. 4 above, a second
69). molecule
Butof oxygen:
though
SO4+ O2-SO3-
traces of HC1 are frequently present 03O
in air, it is not
(PHILIP A. LEIGHTON, Photochemistry ofAir Pollution, in Conservation, 8 (1963), pp. 37-54. Quotation is
Academic Press, New York and London (I96I), from p. 51.
pp. 61, 236). 43 S. B. HAMILTON et al., 'A Qualitative Study of
30 JUNGE, ref. 4 above, pp. 68, 339. Some Buildings in the London Area', National
31 See ref. 7 above. There was actually a higher ratio Building Studies Special Report 33, Dept. of Scientific
of H2SO4 to SO2 in foggy winter weather than in and Industrial Research: Building Research Station,
April, suggesting that photochemical oxidation is H.M.S.O., London (1964), pp. 50, 123.
not the major process here. Other work shows, on 44 F. I. G. RAWLINS, 'The Cleaning of Stonework
the contrary, that conversion is favoured in damp, Studies in Conservation, 3 (1957-8), p. 19.
foggy conditions. See, for instance, F. E. GARTRELL 45 U. R. EVANS, 'Electrochemical Mechanism of
et al., 'Atmospheric Oxidation of SO2 in Coal- Atmospheric Rusting', Nature, 206, no. 4988
burning Power Plant Plumes', American Industrial (June 5, 1965), p. 980. The mechanism of atmos-
Hygiene Assoc., 24(I963), pp. 113-20. pheric rusting with SO2 present is described.
32 GILES, ref. 3 above, p. 773. Moist unpolluted air produces little damage,
33 W. H. LANGWELL, 'Permanence of Paper: Part 5', though after rusting has commenced by the SO2
Proc. Technical Section of the British Paper and Board mechanism, a continued supply of SO2 is un-
Makers' Assoc., 37, pt. 3(1956), pp. 495-500. necessary.
34 T. D. JARRELL et al, 'Deterioration of Paper as 46 For example the Statue of Liberty, though standing
Indicated by Gas Chamber Tests', Technical Bulletin, on the sea front, is patinated with sulphate not
no. 605(1938), U.S. Dept. of Agriculture, Washing- chloride: D. H. OSBORN, Materials in Design
ton.
Engineering (June 1963), pp. 80-81.
35 E. GORHAM, 'Free Acid in British Soils', Nature,
47 W. H. J. VERNON, Trans. Faraday Soc. 27 (1931),
181 (II January 1958), p. io6. pp. 255, 582, and 31 (1935), p. 1668.
36 T. D. JARRELL et al., 'The Effect of Inorganic 48
Acids
H. H. UHLIG, Corrosion Handbook (1948), pp. 15,
on the Physical Properties of Waterleaf Rag Bond 319; L. E. PRICE and G. J. THOMAS, Trans. Electro-
Paper', Technical Bulletin, no. 334 (1932), U.S. chemical Soc., 76 (1939), p. 329.
Dept. of Agriculture, Washington. 49 Number of molecules of gas striking I cm2 of
37 Permanence/Durability of the Book, Vol. 2: 'Test surface per second
Data of Naturally Aged Papers', W. J. Barrow cn
Research Laboratory, Richmond, Virginia (1964). 4

38 W. J. BARROW and R. C. SPROULL, 'Permanence (GLASSTONE,
of Physical Chemistry, 2nd edn., 1956, p.
Book Paper', Science, 129(1959), p. 1075. 278). At 200C, 760 mm Hg, c(average velocity of
39 A. E. KIMBERLY and B. W. SCRIBNER, 'Summary molecules) 5 x 104 cm/sec
Report of NBS Research on Preservation of n (number of molecules per cm3) = 2-5X Io19
Records', National Bureau of Standards Misc. Pub. cn
(new edn.), M.144, Washington (1937), P. 11i. whence4 -- - approx. 3 X 1023

40 A third view is taken by H. P. DIxsON and J. C.
At an H2S concentration of 0-4 pp Ioo m (about
NELSON, 'An Accelerated Study of Several Writing
6 ~g/m3) number of H2S molecules striking I cm2
Papers', Tappi, 45, no. Io (October 1962), pp. 753-
of surface per sec
60o. They suppose that acidic ingredients such as
rosin-alum size are of secondary importance for 3 x Io23X 0'4
108
strength (tear and fold), provided that 'the fibre

quality, the refining, the sheet formation, and the The spacing between Ag atoms is about
rest of the paper-making steps are maintained at a(4X Io-8cm), therefore number of Ag atom
level consistent with maximum bonded area and c2 I IO16
tensile strength'. But it is difficult to reconcile this (4x 10-8)2 16
with Barrow's data (ref. 37 above, vols. I and 3)Therefore number of H2S molecules striking
on improved permanence following deacidifica-Ag atom per sec
tion. 1-2X ol015 16
41 A. H. LITTLE, 'Deterioration of Textile Materials', 10- 16 about 2.
1964 Delft Conference, LI.C., 2nd edn. stencilled
50 W. L. FAITH (ed.), Air Pollution Foundation
preprints (from I.I.C., c/o National Gallery, London
no. 21 (1957), p. 46.
W.C.2), p. 77. 51 Published analyses of exhaust gases from
42 L. TINToRI, E. V. SAYRE and L. J. MAJEWSKI, vehicle engines have frequently quoted
'Studies for the Preservation of the Frescoes by
oxide as 'nitrogen oxides', on the assumpti
Giotto in the Scrovegni Chapel at Padua', Studies
both nitric oxide, NO, and nitrogen dioxid
166 Garry Thomson
61 GILES, ref. 5(e.g.
are produced in the combustion above, p. 8.ref. 50o above).
In air, NO is oxidized to 62NO2 by
Unexpectedly the
the very well
largest and the very studied
smallest
dark third-order reaction particles
(C. in N. the aerosol range are trapped more
HINSHELWOOD,
Kinetics of Chemical Change, easily than a group
Oxfordof intermediate(1940),
size. The
pp. 140-5). However the Methylene
rate Blue ofTest this(B.S. Testreaction,
Dust no. I)
depending on the square of produces
the particles
NO predominantly in this most
concentration,
drops to a negligible figure elusive
at the range-theconcentrations
mass median size of the test to
particles52
be found in polluted air (ref. is about 0-2 microns radius.
below, pp. The184-6),
large
and at the high temperature of are
aerosol particles the
trapped combustion
in filters by their
chamber NO is very much the
inertia: favoured
the air stream changes direction oxide.
many
Recent analyses show in fact times within that almost
the filter, but all
these particles tend to the
combined nitrogen in exhaust proceed in straight gases leaves
lines, thereby hitting and the
combustion chamber as NO
adhering (ref.
to the filter. 53
Particles in below).
the Aitken range
This is subsequently photochemically oxidized
(less than about o-I micron radius) conform to the to
NO2 in polluted air only where
movement ofolefins
the air stream, butare present
are jostled about
by Brownian movement, eventually hitting the
(ref. 52 below, pp. 254-74).
52 PHILIP A. LEIGHTON, Photochemistry
filter if the path length and of
pore sizeAir Pollution,
are favourable.
See, for and
Academic Press, New York instance, H.London
L. GREEN and W. R.(I96I),
LANE,
p. 274. Particulate Clouds, 2nd edn., 1964, Spon, London,
53 J. HAWKINS et al., 'Oxidesp. 213. In of Nitrogen
the Methylene inof Diesel
Blue Test a fine spray
methylene blue14,
Exhaust', Air Pollution Control, solution no.
is discharged into a duct.
I (January
1964), pp. 34-38. The moisture evaporates and the spray becomes a
54 R. J. CVETANOVIC, Air Pollution Control,
cloud of particles. Samples of the air upstream14,
and no. 6
(1964), p. 209. downstream of the filter are taken on filter paper,
55 LEIGHTON, ref. 52 above, steamedp.
to bring
15o.out the Over
blue colour, and com-
99-7% of
the atomic oxygen reacts withpared. molecular oxygen to
form ozone. JUNGE, ref. 63 I have4made a small allowance
above, p. for 357:
the fact that
'The
photodissociation of ozone is no.slow
Whatman I paper passesand
perhaps 2%does
by weight not
of the aerosol.
substantially decrease the ozone concentration, but
the nitric oxide-ozone reaction
64 A. E. KIMBERLYlimits the
and A. L. EMLEY, 'A Studyconcen-
of the
tration of ozone which canRemoval of Sulphur Dioxide
coexist with from NO2.'
Library Air',
56 The information on which Nationalfig.
Bureau of2 Standards
was Misc. Pub. 142,
constructed
is based on work carried Washington
out at (1933). the Admiralty
65 A in
Materials Laboratory (U.K.) test of1962,
the Vokes Activated
andis Carbonused
Pack by thewith
U.K. Ministry of Public Building and Works gave
permission of the Navy Department.
57 N. GRASSIE, Chemistry of60o%
High
removal ofPolymer
sulphur dioxide at I oooDegradation
cu.ft/min,
Processes, Butterworths,4 inch water gauge. R.(1956),
London E. TUFFLEY and P.
p. A. 261;
ZORAB (Lancet,
J. CRABTREE and A. R. KEMP, February 22, 1964, P. 415)
'Weathering of give aSoft
Vulcanized Rubber', Ind. figure
Eng. of 40-45% sulphur dioxide
Chem. 38 removal for a
(1946),
pp. 278-96. smaller unit in the shape of a box with I cm thick
58 Y. LANDLER and P. LEBEL, 'Modifications des packs of activated carbon, at 16o0cu.ft/min.
Polyol6fines Satures par l'Ozone; Symposium Efficiency is of course dependent on residence time
iiber Makromolekiile in Wiesbaden, Sektion IVA within the filter, and is greatly improved at slower
(1959); H. C. BEACHELL and S. P. NEMPHOS, than the rated air speeds.
'Ozone Chemistry and Technology', Advances in 66 H. T. FREEBAIRN, 'Removal of Toxic Gases in
Chemistry Series no. 21 (1959). Smog with Metal Filters', J. Air Pollution Control
59 H. BOGATY et al., 'The Oxidation of Cellulose by Assoc. 13(1963), pp. 218-19; H. M. HULL and F. W.
Ozone in Small Concentrations', Textile Research WENT, 'Life Processes in Plants as Affected by Air
J., 22 (February 1952), pp. 81-83. Pollution', Proc. Second National Air Pollution
60 V. S. SALVIN,J. Soc. Dyers and Colourists, 79 (1963), Symposium, Pasadena, Calif. (1952), p. 124.
p. 687.
della composizione delle particelle solide sopese
POLLUTION ATMOSPHERIQUE-REVUE aria. L'anidride solforosa e principalmente dannosa
POUR LES CHIMISTES DE LA CONSERVATION che viene trasformata in acido solforico e si discut
meccanismo della trasformazione nell'aria e su sost
L'examen des principales sources de polluants atmos-
quali la carta. L'a avanza una possibile tesi sul m
nismo
pheriques: reactions chimiques dans I'air et effets della formazione dell'annebbiamento sulle ver
chimi-
ques sur les mat'riaux de musee. La Fig. I indique des I filtri d'aria con precipitatore elettrosta
dei quadri.
chiffres caract6ristiques de concentration. L'ozone, qui
producono ozono, il che li rende controindicati
se formait autrefois dans la haute atmosph&e,impieghi
apparait generali di museo. Nella Tabella V si da
aujourd'hui dans les grandes villes oii circulent sommario
de nom- degli effetti dei gas inquinatori. Nelle ult
breuses automobiles. Il s'agit d'une reaction des oxydes
sezioni si discute lo smaltimento della polvere e
d'azote et d'hydrocarbones des gaz d'6chappement fumo,des dell' anidride solforosa e degla ossidanti.
voitures, en presence de la lumiere du soleil. On donne
certains details sur la composition des particules DIEsolides
VERUNREINIGUNG DER LUFT-EIN
suspendues dans l'air. L'anhydride sulfureux est surtout
BEITRAG FOR RESTAURATOREN
nuisible en raison de sa transformation en acide sulfuri-
que. Les mecanismes de cette transformation dans I'air et
Es werden die wichtigsten Stoffe erwihnt, die die
sur des substances telles que le papier sont examines.
Luft verunreinigen, sowie die chemischen Reaktionen,
L'auteur sugg"re un m1canisme possible de la formation
die sie ausl6sen, und deren Auswirkungen aufMuseums-
de bleut6 sur le vernis des tableaux. Les filtres " air '
gegenstinde. Typische Werte fiir die Konzentration
precipitation 6lectrostatique produisent de l'ozone, ce
dieser Stoffe in der Luft sind aus Abb. I ersichtlich. Das
qui les rend inadmissibles dans les musdes. Le tableau 5
Ozon, das gew6hnlich in der oberen Atmosphire
r6sume les effets des gaz polluants. Les dernieres sections
ensteht, bildet sich nun auch in Stidten, wo es sehr viele
traitent de la suppression des poussieres et de la fumte, de
Kraftfahrzeuge gibt; es ensteht, wenn das Stickstoffoxyd
l'anhydride sulfureux et des oxydants.
un die Kohlenwasserstoffe der Auspuffgase unter der
Einwirkung des Sonnenlichts miteinander reagieren.
INQUINAMENTO DELL' ARIA-RASSEGNA PER Schwefeldioxyd ist hauptsichlich deswegen schlidlich,
weil daraus Schwefelsiure entsteht. Es werden die
I CHIMICI DELLA CONSERVAZIONE
Ursachen fiir diese Reaktion an der Luft untersucht,
sowie deren
Rassegna delle sorgenti, delle reazioni chimiche nell' Auswirkung auf bestimmte Stoffe, zum
aria e degli effetti chimici sui materiali dei Beispiel
museiPapier.
dei Es werden Bedingungen untersucht, die
maggiori agenti inquinatori dell'aria. Nella Fig I si
m6glicherweise dazu fiihren, daB Firnisse wolkig wer-
riportano cifre tipiche di concentrazione.den. L'ozono,
Elektrostatische Luftfilter erzeugen Ozon; sie sind
precedentemente formato nell'atmosfera superiore,
deshalb fiir die allgemeine Verwendung in Museen
oggi compare nelle cittat con una forte circolazione auto-In Tabelle V wird die Wirkung der Abgase
ungeeignet.
mobilistica mediante una reazione tra ossidi in e der
idrocar-
Luft dargestellt. Der letzte Abschnitt befaf3t sich
buri provenienti dagli scarichi degli autoveicoli in
mit der Entfernung von Staub, Rauch, Schwefeldioxyd
presenza della luce solare. Si riportano alcuni und
particolari
Oxydationsmitteln.

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Air Pollution: A Review for Conservation Chemists

Author(s): Garry Thomson

Air Pollution-A Review for Conservation

Small C/tles - Wnter

Los Angeles-type Smogs

Los Angeles- type Smogs

NITROGEN OX/DES, OZONE, AMMON/A, HYDROGEN SULPHIDE

(each square represents lOOug/ccm3)

turn to the next column, where the action of 03 / ultimately

sng voge 4 (k ot)

Summary of Effects of Pollutant Gases

Sulphur dioxide SO2 Cellulose (paper, cotton, linen), leather, plaster

Hydrogen sulphide H2S silver I

fading. Probably herethe

' Standard Kompak

the Some day, perhaps before coal has been

Notes and References

Research Laboratory, Richmond, Virginia (1964). 4

(new edn.), M.144, Washington (1937), P. 11i. whence4 -- - approx. 3 X 1023

strength (tear and fold), provided that 'the fibre

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