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The Geochemistry of Rhenium, With Special Reference To Its Occurrence in Molybdenite
The Geochemistry of Rhenium, With Special Reference To Its Occurrence in Molybdenite
The Geochemistry of Rhenium, With Special Reference To Its Occurrence in Molybdenite
MICHAEL FLEISCHER
ABSTRACT
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
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)
RI-IENIUM IN MOLYBDENITES
TABLE 2
TABLE 2---Continued
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
Re eontemt, ppm
Type of occurrence No. of samples
Range Average
TABLE 4
(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
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
1. Ahrens, L. H., 1952, The use of ionizationpotentials,I. Ionic radii of the elements:
Geochim. et Cosmochim. Acta, v. 2, p. 155-169.
2. Aminoff, G., 1943, En rheniumrikmolybdenglans:
Geol. F6ren. StockholmF6rh., v. 65,
p. 71-72.
3. Bibikova,V. I., 1946, Rheniumin dustsof the molybdenum
divisionof the Balkhash
works: Tsvetnye Metall., v. 19, no. 4, p. 44-48. (in Russian)
4. Boyd,G. E., and Larson,Q. V., 1956,Reporton the occurrence
of technetium
on the
earth's crust: Jour. Phys. Chemistry,v. 60, p. 707-715.
5. Brown, H. S., and Goldberg,E. C., 1949, A new determination
of the relative abundance
of rhenium in Nature: Phys. Rev., v. 76, p. 1260-1261.
6. Creasey,S.C., 1957, Geologyand resources,p. 6-15 in Mclnnis, Wilmer, Molybdenum,
a materials survey: U.S. Bur. Mines Inf. Cite. 7784.
7. Druce, J. G. F., 1948, Rhenium: Cambridge,University Press,92 p.
8. Geilmann,W., Lange, G., and Barttlingck, H., 1948, Ueber den Rheniumgehalteiniger
MolybdSnminerale:Neues Jahrb. Mineral., Geol., Monatsh.,Abt. A, 1945-1948, p. 3-9.
9. Goldschmidt,V. M., 1937, Geochemisehe Ve•teilungsgesetzeder Elemente IX. Die Men-
genverh51tnisse der Elemente und der Atom-Arten: Norske Videnskaps-Akad.Oslo,
Skrifter, Mat.-Nat. KI., no. 4, p. 1-148.
10. Herr, Willrid, and Metz, Erich, 1955, Eine neue Metbodezur Altersbestlmmung
yon
Rhenium-haltigenMineralien mittels Neutronaktivierung: Zeitschr. Naturforschung,v.
10a, p. 613-615.
11. Hiskey, C. F., and Meloche,V. W., 1940, Determinationof rhenium in molybdenite
minerals: Ind. and Eng. Chemistry, Anal. Ed., v. 12, p. 503-506.
12. Hurd, L. C., and Hiskey,C. F., 1938,The determination
of rhenium. Estimationin pyro-
lusite: Ind. and Eng. Chemistry, Anal. Ed., v. 10, p. 623-626.
THE GEOCHEMISTRY OF RHENIUM 1413
13. Kaiser, E. P., Herring, B. F., and Rabbitt, J. C., 1954, Minor elements in some rocks,
ores, and mill and smelter products: U.S. Geol. Survey TEI-415, p. 1-119, issued by
U.S. Atomic Energy Comm. Tech. Inf. Service Extension, Oak Ridge, Tenn.
14. Meixner, Heinz, 1935, Woher starerot das Molybd/in auf den Blei-Zink-Lagerst/itten?:
Carinthia II, p. 182.
15. Morgan, Gilbert, and Davi•s, G. R., 1938, Residual affinity and co-ordination. XL. Some
complex compoundsof rhenium: Chem. Soc. London Jour., p. 1858-1861.
16. Nodclack, Ida, and Noddack, Walter, 1931, Die Geochemie des Rheniums: Zeitschr. phys.
Chem., v. A154, p. 207-244.
17. Noddack, Ida, and Noddack, Walter, 1932, The element rhenium: Uspekhi Khim., v. 1, p.
699; quoted by Studenikova and Zolotareva.
18. Petersen, R. G., Hamilton, J. C., and Myers, A. T. (1959), An occurrence of rhenium,
associatedwith uraninite, in Coconino County, Arizona: Ecom G•oI.., v. 54, p. 254-267.
19. Schroll, E., 1949, t•ber die Anreicherung yon Mo and V in der Hutzone der Pb-Zn Lager-
st•tten Bleiberg-Kreuth in K/irnten: Geol. Bundesanstalt (Austria) Verhandl., 1949,
20 p.
20. Sen, Sujata, 1957, Estimation of molybdenum and rhenium in Indian eolumbite: Science
and Culture (India), v. 23, p. 318-319; Chem. Abstracts, v. 52, p. 19775 (1958).
21. Sims, C. T., Wyler, E. N., Gaines, G. B., and Rosenbaum,D. M., 1956, A survey of the
literature on rhenium: Wright Air Development Center, WADC Tech. Rept. 56-319,
ASTIA Document No. AD 110596, p. 1-224.
22. Studenikova,Z. V., and Zolotareva, V. A., 1958, Rhenium in molybdenitesof the Tymy-
Auz deposit: Geokhimiya, 1958, No. 1, p. 81-85; translation in Geochemistry, 1958,
No. 1, p. 109-115.
23. Tribalat, Suzanne, 1957, Rh6nium et teehn6tium: Gauthier-Villars, Paris, 172 p.
24. Vanderwilt, J. W., 1942, The occurrenceand production of molybdenum: Colorado School
of Mines Quart., v. 37, no. 4, p. 1-78.
25. Vinogradov, A. P., 1956, The regularity of distribution of the chemical elements in the
Earth's crust, Geokhimiya, 1956, No. 1, p. 1-52; translation by S. Botcharsky,
U.K.A.E.A. (Harwell), A.E.R.E. Lib/Trans. 795, 63 p. (1957).