Economic Geology

Vol. 54, 1959, pp. 1406-1415

THE GEOCHEMISTRY OF RHENIUM, WITH SPECIAL

REFERENCE TO ITS OCCURRENCE IN
MOLYBDENITE •

MICHAEL FLEISCHER

ABSTRACT

Little has been addedto our knowledgeof the geochemistryof rhenium

sincethe work of Noddackand Noddack (16) in 1931, exceptthat many
determinationshave beenpublishedof the rhenium contentof molybdenite,
the only presentsource. These determinations,150 in all, have been as-
sembled. The rheniumcontentof molybdeniterangesfrom noneto 3,250
ppm Re, and varies widely, even in samplesfrom a single deposit. No
generalizationsare yet possibleas to correlationsof rhenium content
with geologicalconditionsof formation. Other possiblesourcesof rhen-
ium are consideredbriefly.

INTRODUCTION

RaENIUM, the element of atomic number 75, is one of the rarest of the
chemicalelementsand wasnot discovered until 1925,althoughmanyprevious
investigators
had claimedproof of findingit. The historyof thesestudiesis
summarizedby Druce (7).
Rheniumis placedin Column7B of the periodictable of elementsbelow
manganeseand technetium; the latter element has not yet been proved to
exist in nature. Rhenium in the periodictable is adjacenthorizontallyto
tungstenand to the platinummetalsand diagonallyto molybdenum;it might
thereforebe expectedto showsomegeochemical associations
with manganese,
tungsten,the platinum metals, and molybdenum.In fact, the association
with molybdenumis marked; there is evidenceof only a slight degree of
associationwith manganese,the platinum metals, and tungsten.
Chemically,rheniumis known in the valencestates-- 1, q- 1, q- 2, q- 3,
q- 4, q- 5, q- 6, and q- 7; of these,the q- 4 and q- 7 statesare the most stable
and the most important. The ionic radii are given by Ahrens (1) as Re+4
0.72, Re+• 0.56 A; thesemay be comparedwith Mo+40.70, W +• 0.70, Mn+•
0.60, Mo+60.62, W +60.62 A. From theseit would be reasonableto expect
that rheniumcouldbe associated with quadrivalentmolybdenum and tungsten
and, to a lesserdegree,with quadrivalentmanganese. It is probablytrue
that size of ionic radiushas little to do with the possibleentry of rhenium
into the mineralsmolybdeniteand tungstenite,in which the bondingis cova-
lent; however,ReS2 has a crystalstructurevery similarto thoseof MoS2
andWS2. Surveysof the literatureon rheniumhaverecentlybeenpublished
(21, 23).
• Publication authorized by the Director, U.S. Geological Survey. Paper presented at
the meeting of the A.I.M.E., Los Angeles, May 1958.
1406
 THE GEOCHEMISTRY OF RHENIUM 1407

RI-IENIUM IN ROCKS AND METEORITES

Our presentknowledgeof the geochemistryof rhenium rests almost en-

tirely on the work of Ida and Walter Noddack (16), with the exceptionof
new analysesof molybdeniteand a few other determinationsmentionedlater.
These investigatorsstatethat they analyzedsome1,600 samplesof minerals
and rocks,but they actuallypublishedanalysesof only 220 samples,in many
of which rhenium was not found. The abundance of rhenium in the Earth's
crust,given in nearly all referenceworks as 0.001 ppm, is basedon a single
determinationby the Noddackson a compositesampleof 110 igneousrocks.
One is temptedto speculatethat this value may be one or two ordersof mag-
nitude too low, as seemsto be true for their data on meteoritesdiscussedbe-
low. Vinogradov (25) quotesunpublishedwork by Basitova2 as giving
0.06 ppm Re in basicrocksand 0.006 ppm Re in acidic rocks,yielding an
averageof about0.01 ppm, which is one order of magnitudehigher than the
Noddacks'figure.
The data on meteoritesare given in Table 1. The recentdeterminations
are two orders of magnitudehigher than the Noddacks'.
TABLE 1

RHENIUi•[ CONTENT OF METEORITES IN PARTS PER MILLION

Reference
Iron meteorites (avg. of 16) 0.008 (16)
Troilites (avg. of 7) 0.001 (16)
Stony meteorites 0.0008 (16)
Iron meteorites (avg. of 5) 0.6 4-0.2 t (5)
Iron meteorite (one) ,•2 (9)

Determinations ranged from 0.335 to 1.95 ppm.

RI-IENIUM IN MOLYBDENITES

Of the manymineralsanalyzedby the Noddacks,. molybdenitehad by far

the highestcontentof rheniumand many analyseshave sincebeenpublished.
The dataare widelyscattered;someanalyseshaveappearedin papersdealing
with the radioactivityof rheniumand somein papersdealingwith the search
for technetium. It hasthereforeseemedworthwhileto assemble theseanalyses
in Table 2, in which the arrangementis by the countryof origin. The ac-
ruracy of someof the older analysesmay be questionable.
Data on someof thesedepositsare givenby Vanderwilt (24) and Creasey
(6). No generalizations are evidentas to the rheniumcontentand the type
of geological
occurrence.For example,the rheniumcontents of molybdenites
from porphyrycopperdeposits rangefrom the low figures(0-50 ppm) at
Bagdad,CopperCreek,and CopperHill, Arizona;Chino,New Mexico;and
Bingham,Utah; to the 100-150ppmrangeof Cananea,Mexico,andKounrad,
U.S.S.R., the 150-688 ppm of Miami, Arizona,to the singledeterminationof
1,030ppmat the NevadaConsolidated mine. It is alsoevidentthat thereis
wide variationin samplesfrom a single deposit. Unfortunately,with the
2 The reference is not identified, but a recent paper (22) cites a thesis by S. M. Basitova
(1950) on the geochemistryof rhenium.
1408 MICHAEL FLEISCHER

TABLE 2

RHENIUM CONTENT OF MOLYBDENITES

(Most samples were concentrates)

Source Re,ppm MoS2

content
Wt. % Reference

1. "u. s.A." 140 83.8 (8)

2. Arizona, Bagdad 20 -- (13)
3. Arizona, Copper Hill mine, Yavapai County 30 -- (13)
4. Arizona, Copper Creek 40 -- (11)
5. Arizona, Copper Creek 27.5 -- (11)
6. Arizona, Copper Creek 0 -- (11)
7. Arizona, Copper Creek• 20 -- (13)
8. Arizona, Miami, Gila County 152 -- (4)
9. Arizona, Miami, Gila County 150 -- (4)
10. Arizona, Miami, Gila County 297 -- (4)
11. Arizona, Miami, Gila County 688 -- (4)
12. Not stated 2 70 -- (11)
13. Not stated2 325 -- (11)
14. Not stated • 597 -- (11)
15. "Colorado" 1.8 -- (15)
15. Colorado, Climax 5 -- (11)
17. Colorado, Climax 1.2 -- (11)
18. Colorado, Climax 28 82.5 (8)
19. Colorado, Climax .20 -- (4)
20. New Mexico, Chino mine 17.5 -- (11)
21. New Mexico, Questa 7.5 -- (11)
22. New Mexico, Questa 7.5 -- (11)
23. New Mexico, •uesta 7.5 -- (11)
24. New Mexico, Questa 9 -- (11)
25. New Mexico, Questa 12.5 -- (11)
26. Nevada, McGill a 1030 -- (4)
27. Utah, Bingham 31 -- (11)
28. Utah, Bingham 44 -- (11)
29. Utah, Garfield none -- (11)
30. Utah, Garfield none -- (11)
31. Utah, Garfield 3.5 -- (11)
32. Utah, Garfield 6 -- (11)
33. Utah, Garfield 7 -- (11)
34. Utah, Garfield 37 -- (11)
35. "Canada" 20.4 99.6 (8)
36. Mexico, Cananea 120 92.1 (8)
37. "Brazil" 12.5 -- (11)
38. "Bolivia" 0.05 -- (16)
39. Chile, San Antonio 519 -- (10)
40. "Peru" 36 73.2 (8)
41. "Finland" 18 83.0 (8)
42. Sweden,Lainejaur 2500 -- (2)
43. "Norway" 8 91.9 (8)
44. Norway, Arendal 1400 98.6 (8)
45. Norway, Bandkeli 1.2 -- (17)
46. Norway, Drammon 7.5 -- (17)
47. Norway, Flekkefjord 12.1 97.2 (8)
48. Norway, Flekkefjord 5.0 -- (11)
49. Norway, Flekkefjord, Knaben mine 13.3 94.6 (8)
50. Norway, Flekkefjord,I•naben mine 1.4 -- (17)
51. Norway, Hvaleroyene 90 98.7 (8)
52. Norway,Lir 2 -- (17)
53. Norway, Lofoten 509 -- (10)
54. Norway, Moos 0.6 -- (17)
55. Norway, Nummedalen 811 -- (10)
 THE GEOCHEMISTRY OF RHENIUM 1409

TABLE 2---Continued

Source Re,ppm MoS2

content
Wt. % Reference
56. Norway, Stavanger (avg. of 2) 3035 98.2 (8)
57. Norway, Stavanger (avg. of 2) 3130 -- (10)
58. Unknown, perhaps Stayanger 3250 98.5 (8)
59. Unknown, perhaps Stayanger 3040 98.0 (8)
60. Norway, Telemark 21 -- (16)
51. Germany, Manafeld shale ,•100 -- (9)
52. "Altenburg" 44 82.2 (8)
53. "Mine di Gonnesfadiga" 19.8 92.8 (8)
64. "Bulgaria" 5 46.5 (8)
55. Turkey, Keskin 50 98.4 (8)
56. U.S.S.R., "Siberia" 0.6 -- (16)
57. U.S.S.R., Kazakhstan, Chikoi 1.2 70.3 (3)
58. U.S.S.R., Kazakhstan, Kounrad (1941) 150 -- (3)
59. U.S.S.R., Kazakhstan, Kounrad (1943) 100 20.1 (3)
70. U.S.S.R., Kazakhstan, Kounrad (1944) 100 16.9 (3)
71. U.S.S.R., Kazakhstan, Kounrad (1945) 150 82.1 (3)
12. U.S.S.R., Kazakhstan, Tyrny-Auz 10 -- (3)
?3. U.S.S.R., Kazakhstan, Tyrny-Auz 2 -- (3)
14. U.S.S.R., Kazakhstan, Tyrny-Auz • 0-8 -- (22)
15. U.S.S.R., Umal'ta 5 -- (3)
16. "Japan" 10 -- (16)
?7. Japan, Shirakawa 9.6 98.2 (8)
?8. "Australia" 110 -- (15)
19. Australia, New South Wales 2.5 -- (17)
80. Australia, New South Wales, Kingsgate 48 -- (10)
81. German East Africa s 2710 98.2 (8)
82. Unknown 17.8 96.4 (8)

x Locality given as Childs-Aldwinkle mine.

2 Placed here in the table becauseit seemsa reasonableguessthat these came from Miami.
8A smelter is located at McGill. Sample presumably from Nevada Con. mine, near Ely,
Nevada.
s Analyses of 69 samples given. See Table 3.
8 Stated elsewhere in same reference. to be South West Africa.

exception
of the samples
fromthe Tyrny-Auzdeposit,
thereare no geological
data on the samples,mostof which are concentrates.
The onlystudyof thevariationof rheniumcontentas relatedto geological
occurrence
is that of Studenikovaand Zolotareva(22), who analyzed69
molybdenites
from the Tyrny-Auz deposit. Their resultsare summarizedin
Table3. The rangeof rheniumcontentis rathersmall,with oneexception,
andthedepositis of an unusualtype,sothat theresultsare not veryindicative.
Similarstudiesof samplescollected
with goodgeological controlfrom such
depositsas Miami wouldbe very desirable. It wouldalsobe of greatinterest
to havedeterminations of rheniumin samplesof the amorphous form of MoS2,
jordisite.
Referenceson the recoveryof rheniumfrom molybdenitesmeltersare
givenby Simset al. (21). Rheniumvolatilizes as oxideduringthe roasting
of the molybdeniteand is enrichedin the flue dusts. Bibikova(3) gives
analysesof variousflue dustsobtainedby roastingore containing100 ppm
Re; thesecontained12, 30, 150, 360, and 2,000 ppm Re, and Cottrell dusts
 1410 MICHAEL FLEISCHER

TABLE 3

RItENIUM IN MOLYBDENITES OF TxmNv-Auz (1room (22))

Re eontemt, ppm
Type of occurrence No. of samples
Range Average

1. Skarns 13 0.13-8.0 3.8

2. Leucocratic granite 6 0-0.1 0.1
3. Quartz veinlets in biotite hornfels 7 2-5 3.4
4. Quartz veinlet in leucocratic granite 1 1.8 1.8
5. Quartz veinlets in skarn 7 0-8 2.7
6. Quartz-feldspar veinlets in biotite hornfels 6 1-3.5 2.2
7. Skarn veinlets 10 0-7 3.7
8. Quartz-garnet veinlets in leucocratic granites 8 0-6 2.5
9. Quartz-garnet veinlets in skarns 10 0-8 4.9
10. Veinlets in El'dzhurtinsk granites 1 140 140

contained900 ppm Re. Boyd and Larson (4) reported3,130 ppm Re in a

flue dustfrom Miami and statedthat other samplescontainedup to 2 percent
Re.
RuE•IUM t• MOL¾•VATV,

One mightreasonably expectthat rheniumwouldbe presentin appreciable

amountsin molybdateminerals; the ionic radii of sexivalent rhenium must
be close to that of sexivalentmolybdenumand the ionization potentialsof
Mo+øand Re+7are also close. The availableanalyses,collectedin Table 4,
show that this is not the case.
It is an intriguing problem as to whether molybdenumand rhenium
separateduringtheir oxidationfrom the quadrivalentstate. There has been
considerableuncertainty as to the origin of wulfenite in ore deposits. At
presentthe prevailingbeliefis that it wasformedby reactionof lead in the
ore depositwith molybdenumleachedfrom overlyingsediments,especially
shales. (See Schroll (19), Meixner (14), and many referencescited by
them.) If this is correct,the molybdenum
and rheniumof wulfeniteare not

TABLE 4

RHENIUM IN MOLYBDATE MINERALS

Locality Re, ppm PbMoO4, % Reference

1. Wulfenite, Mammoth mine, Arizona 0.12 49.7 (8)

2. Wulfenite, Red Cloud mine, Arizona 0.38 78.4 (8)
3. Wulfenite, Bennett mine, N. Mex. 0.37 71.5 (8)
4. Wulfenite, Zacatecas, Mexico 0.05 7.7 (8)
5. Wulfenite, Atacama, Chile 0.06 16.8 (8)
6. Wulfenite, Bleiberg, Austria 0 --

(16)
7. Wulfenite, Bleiberg, Austria 0.88 47.8 (8)
8. Wulfenite, Bleiberg, Austria 0.62 58.5 (8)
9. Wulfenite, Partenkirchen 0.25 7.7 (8)
10. Wulfenite, Garmisch 1.25 56.6 (8)
11. Molybdenum ocher, Knaben, Norway 0 --

(16)
 THE GEOCHEMISTRY OF RHENIUM 1411

deriveddirectlyfrom oxidationof molybdenite. It would be of great interest

to have determinationsof the Mo/Re ratio in bituminousshales;none has
yet beenmade.
Relative solubilitiesof molybdenumand rhenium compoundsmay play
an importantrole in this apparentseparation. The recentreport by Peter-
sen, Hamilton, and Myers (18) of rhenium contentsup to 0.1 percentin
Triassicsedimentaryrocksfrom CoconinoCounty,Arizona, is of particular
interest,becausethey report it to be associatedwith molybdenumand ura-
nium, and becausethey found that the rheniumwas, at least in part, in a
water-solubleform (R%O, ?).

RHENIUM IN OTHER MINERALS

No mineral other than molybdeniteor wulœenite(analysescalculatedto

pure mineral) has been[oundto containas muchas 2 ppm Re. Below are
listedsomeof the mineralsin whichasmuchas 0.01 ppmRe hasbeenreported.
The Noddacks
(16) reported
0.02ppmin a scheelite
andthesameamount
in a wolœramite.The very rare mineraltungstenite,WS2, reportedœromonly
two localitiesin the world, seemedto be a likely host mineral [or rhenium,
but a spectrographic analysismadeby Harry Bastronoœthe U.S. Geological
Surveyshowedno rheniumin a sampleœromthe type locality,Emma mine,
Utah. However, the sensitivityoœthe analysiswas low, perhaps50-100
ppm Re.
The Noddacksreportedno rheniumin the œewmanganesemineralsthey
studied,a somewhatsurprisingresultin view oœthe relationshipin the Peri-
odic Table. Hurd and Hiskey (12) analyzed80 samplesoœ"pyrolusite"
from many localitiesand œound 0.1 ppm Re in 7 samples,0.2 ppm in one
sample. One might predictwith someconfidence that rheniumis likely to
be presentin smallamountsin the flue dustsoœsmeltersthat roastmanganese
oxides or carbonates.
The Noddacks(16) found 0-1 ppm Re in 5 sampleso[ platinumgroup
minerals and ores, but Boyd and Larson (4) found none in an osmiridium
concentrate from SouthAfrica. The Noddacksalsoreported0.01-0.08 ppm
Re in about 15 different sulfides,includingchalcopyrite,argentite,and mar-
casite. The selenidesclausthalite(PbSe) and berzelianite(Cu2Se) were
especiallyhigh in rhenium(0.8 ppm, 0.2 ppm). They alsofound0.01-0.02
ppm Re in cassiterite,rutile, and chromite.
The Noddacks(16) also found concentrations of rheniumin somepeg-
matiteminerals,notablyin the alvitevariety of zircon (up to 0.6 ppm Re),
gadolinite(up to 1.1 ppmRe), thortveitite(0.6 ppm Re), columbite-tantalite
(0.03-0.2 ppm Re), and in complextantalatemiobates (fergusonite,euxenite,
samarskite)(0.01-0.02 ppm Re). Sen (20) recentlyfound 0.26 ppm Re
in a columbite. Boyd and Larson (4) found no rhenium'in a sampleof
yttrotantalite.
Thesefragmentaryresultsindicatethat rheniumconcentrates somewhatin
hydrothermalore4ormingsolutionsand in late-stagepegmatiticsolutions.
1412 MICHAEL FLEISCHER

POSSIBLE FUTURE SOURCES OF RItENIU/•

The total productionof the world was guessedin 1956 (21, p. 166) to
be of the order of magnitudeof 1,000 to 2,000 poundsof metal per year, all
derivedfrom the smeltingof molybdenite.This was estimatedto be a small
fraction,perhaps5-10 percent,of the potentialproduction. Obviouslythe
first stepin increasing
productionis to installrecoveryprocessesin existing
molybdenite
smelters. It is possiblealso that presentrecoveriescouldbe
improved.
The work of the Noddacksdoesnot suggestany other potential source.
Perhapsevenmorediscouraging is the fact that the spectrographic
analyses
published
by Kaiseret al. (13) of nearly1,000samplesof smelterproducts
showedrheniumonly in molybdenites.These analyseswere, however,of
comparatively
lowsensitivity (perhaps20-50ppmRe) andit is quitepossible
thata goodsource hasbeenoverlooked.It shouldnot be forgottenthat the
maximumcontentin molybdenite in Table 2 is 150 timesthat reportedby
the Noddacks. Systematicanalysesof the flue dustscollectedin smelters
usingoxidizingroastsof sulfideminerals
maywellturnupa source of rhenium
not now guessed.
ACKNOWLSr•:MENTS

I am indebtedto Dr. GeorgeSwitzerof the U.S. NationalMuseumfor

the loan of the type specimen
of tungstenite and to Harry Basttonof the
U.S. Geological Survey,whoanalyzedit for rhenium.
U.S. GEOLOGICALSURVEY,
WASHINGTON, D.C.,
March 31, 1959
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 THE GEOCHEMISTRY OF RHENIUM 1413

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