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APR T JAN 2 2 200F IN REPLY REFER TO: UNITED STATES CrTsnS DEPARTMENT OF THE INTERIOR GEOLOGICAL SURVEY WASHINGTON 25. D. C. AEC-203/5 January 13, 1955 &r» T* H. Johnson, Director Division of Research U. S. Atomic Energy Commission l6th Street and Constitution Avenue, N. W. Washington 25, D. C. Dear Dr. Johnson: Transmitted herewith is one copy of TEI-^57> "The occurrence and properties of metatyuyamunite Ca(U02 )2(V(>4)2'3-5 KgO*" by T. ¥, Stern, L. R. Stieff, M, N. Girhard, and Robert Meyrowitz, September 195k. We plan to submit this report for publication in the American Mineralogist, Sincerely yours, +*f W. H. Bradley Chief Geologist NOTE APR T JAN 2 2 200f Geology and Mineralogy This document consists of 50 pages including pages 8a, l6a, and 22a. Series Ac UNITED STATES DEPARTMENT OF THE INTERIOR' GEOLOGICAL SURVEY THE OCCURRENCE AND PROPERTIES OF METATYUIAMUNITE By T. W. Stern, L. R* Stieff , M* N. Girhard, and Robert Meyrowitz September 1951*- Trace Elements Investigations Report This preliminary report is distributed ¥ithout editorial and technical review for conformity with official standards and nomenclatureo It is not for public inspection or quotation. *This report concerns work done on behalf of the Division of Research of the U» S* Atomic Energy Commission* USGS - GEOLOGY AID MINERALOGY Distribution (Series A) No. of copies Argonne National Laboratory .....<,...........•,............•».... 1 Atomic Energy Commission, Washington .•*•.......•....«......•... 2 Battelle Memorial Institute, Columbus ....„,,».....*........,.... 1 Carbide and Carbon Chemicals Company, Y-12 Area ................ 1 Division of Raw Materials, Albuquerque ..,.......».,.,•••.»••«.. 1 Division of Raw Materials, Butte ............................... 1 Division of Raw Materials, Denver ..•*....••••....c....... 0 ..... 1 Division of Raw Materials, Douglas ...«,.*«....».«.........«.... 1 Division of Raw Materials, Hot Springs ... *.„.<,. ................ 1 Division of Raw Materials, Ishpeming »•.....«.»•.•.«.•....*.•».. 1 Division of Raw Materials, Phoenix .«,*.,........... 00 ....«<><,.... 1 Division of Raw Jfeterials, Richfield ....•..•••»..••.......»•... 1 Division of Raw Materials, Salt lake City .....•,..••»•..••.»... 1 Division of Raw Materials, Washington ,>....»»*»...OO.B,,..,,.*.... 5 Division of Research, Washington <>»«>«»«*.o.<,c.o...»<r<,.a« a ....0*0,, 1 Dow Chemical Company, Pittsburg O o..ooo»..o««»o«..eo..<.«..»»<,... 1 Exploration Division, Grand Junction Operations Office ••,....., 6 Grand Junction Operations Office .»o.ooo.«...oo. 0 .ft..>«,e.«.«o..» 1 National Lead Company, Winchester 0 .o 000 <,o...».,».o.c,..aB<»oo.«<...» 1 Technical Information Service, Oak Ridge .•*.....,.•...»»....... 6 Tennessee Valley Authority, Wilson Dam ,«,»..« a «oo...«,........... 1 U. S. Geological Survey; Fuels Branch, Washington .......»..». <>.....<>. <,»<........«...».».. 1 Geochemistry and Petrology Branch, Washington •..•...,..,..»•.». 20 Geophysics Branch, Washington ...•••..•»..»»...»*o.....»*•.•••.. 1 Mineral Deposits Branch, Washington e •..«,..<,.<,. .o 0 .«.oo».. 0 ...» 2 Eo Ho Bailey, Menlo Park .<>,»•.a...*.<>..•.<>•«•..»»*o»»».oo»B.»*.t. 1 A 0 L» Brokaw, Grand Junction »o««.»«.o 0 .o..0*0..•«»...•••.•»«.«. 2 J 0 ,R» Cooper, Denver .00.o»..e.»o.o..«oo°e..•».••••»••••••«•«.•» 1 N 0 Mo Denson, Denver eo. 0 «,.«> ........,.o.».«...». t,.« (>...r»..c B aoee 1 C. Eo Button, Madison „........ ...<,..».«... .o..............o..o. 1 We L«, Emerick, Plant City ....,.«..,.»....,..«»......oo.•••»»••* 1 L, S. Gardner, Albuquerque .„<,<>,,...o«» ( ..o«.«»••••»••«»•<>»««•••* 1 MO R. Klepper, Washington . O ce 0t>o 0 c«..« e o 0 »«,.e.o.o 0 . 0 «««..ooc«>o 1 Ao H. Koschmann, Denver ..<>.,>,,,>«,.<,.».....•..<>.,»«.».•»....<.• ».«•. 1 R. A« Laurence, Knoxville ....o.».....*.o-...»».*..»o.«.......... 1 D. M. Lemmon, Washington o. C o.- 0 .».«o C . s .. 0 <,a.o 0... c 0 . , 0 ........... 1 J. D. -Love 5, Laramie 0 «i>»..»..ooo...«... a o.o..e.»...«............ 1 P. Co Patton, Denver .„...«......„.<>»..»...<>».......»..»......... 2 J. Fo Powers, Salt Lake City .»....,,..•»...............•.*...•• 1 Q s Do Singewald, Beltsville » aa o».o.....*»....•...»••............ 1 J. F o Smith, Jr., Denver O o..<, ooe .».»c».. ..*<...»..«......».»...* 1 A. E. Weissenborn, Spokane .»o.».*ee...o.o 4 o.e»».••••••»..»»..». 1 XJ-J-iTV-'v^ « i/O]-lV©3/ ocyoec<r0a»oo&o«0«€^ec)oei>-4>o«»9»a9oe9Ooo0fre(r*fr0fr^o<reA» £. TEPCO, RPS ? Washington, (including master) ..................... 3 CONTENTS Page Abstract ...........*.........................<>............ 5 Introduction .............................................. 6 Occurrence of metatyuyamunite ............................. j Physical properties ........... ...... ......«.....«».«.«.... 9 Optical properties ,«.»..... ...«..*.».o. ................... 9 Chemical composition ...................................... n Water content c. ........................................... 12 X-ray diffraction data ....... .«...,..<,..«,. D ^ .............. 15 Base exchange .............. , . 0 . .. ......... <> ............. e . 21 Radium- uranium age ....... »....*.. ..............o.......... 23 Acknowledgments . ... e ...... o ......... e .. o .......... e ....... 25 Literature cited ........ 0 ..... e .......... o ...... e ... o ..... 25 ILLUSTRATIONS Page Figure 1. Graph of number of moles of -water as a function of the partial pressure of water .............. Plate 1. "/Photomicrograph of bladed crystalline meta*- tyuyamunite, Small Spot mine, Calamity Mesa, Mesa County, Colo. ....... ... e .... ............. 8 2. X-ray diffraction powder patterns of meta­ tyuyamunite and tyuyamunite .................... 16 3. X-ray diffraction powder patterns of meta­ tyuyamunite, base -exchanged metatyuyamunite, and camotite ..................................... .22 TABLES Page Table 1 0 Optical properties of tyuyamunite and meta- « 10 2» Variation in optical properties of tyuyamunite and metatyuyamunite from Small Spot mine caused by hydration and dehydration «,. e0 o«>0 ceeeo 0 .«,.«> o» 0<> ».o... 11 Je Semiquantitative spectrographic analyses of meta~ oo«oeooeooi>e»ooe»oocxoo»oaeeeooee<>ee(>oe<>«e» 12 -. Chemical analyses of tyuyamunite and metatyuyamunite . 15 o X-ray powder diffraction data for metatyuyamunite 17 6*. Radium content , departure from eq.uilibrium? and radium-uranium age of metatyuyamunite specimens . 0 „ , . THE OCCURRENCE AND PROPERTIES OF METATYUYAMUNXTE By T. ¥„ Stern, L* R0 .Stieff , M. N0 Girhard, and Robert Meyrowitz Metatyuyamunite rCa(U0i— 2 )2(V04)2 e 3~5 HaO"|,-J a new mineral, is a dehydration product ©f tyuyamunite rCa(XJQ2)2(V04)2»5~8*5. HgOjo This lower hydrate of tyuyamunite has been collected from more than 35 localities on the Colorado Plateaus and from several localities in Fall River County 5 S 0 Dako, and Campbell and Johnson Counties, Wyo* The optical properties and specific gravity of metatyuyamunite and tyuyamunite are significantly different, Metatyuyamunite samples from two localities in Mesa County 9 Colo^ have been chemically analyzed,. The hydration of metatyuyamujaite has been e;mmined as a function of water vapor pressure. Plateaus on the dehydration curve are at values of 5 and 80 5 moles of water per mole of CaCuOg^CVQ^go Metatyuyamunite was rehydrated to tyuyamunite by placing it in a moist atmosphere a The X-ray diffraction powder pattern, of metatyuyaminite and tyuyamunite are distinctly different, indicating a change in phase 0 Base exchange studies show that the meta­ tyuyamunite structure may contain several percent potassium. X-ray diffraction powder patterns of this base -exchanged product do not reveal the presence of carnotite 5 rK2 (U02 )2(V04)2 e l=i5 HgOj. Two samples of metatyuyamunite from Mesa County , Colo 0? are not in radium- iiranium equilibrium and their Ra/U ages are 25^000 and 150,000 years. INTRODUCTION Variations in the water content of tyuyamunite have "been studied by Hillebrand (192^, p. 202), Rohde (1925, p. 557), and Murata, Cisney, Stieff, and Zworykin (1950, p. 5; 1951, p. 525). Merwin (192k, p. 210) found that the density of the mineral increases as it is dehydrated. An analogous variation in the water content of minerals of the torbernite and metatorbernite groups has "been discussed in papers by Beintema (1958» p. 155), Frondel, J. W., (1951, p. 2^9), Frondel (1951, P- 678, 68l), Mrose (1950, p. 529), and Nuffield and Milne (1955, p. kj6]. The water content of sengierite (Vaes and Kerr, 19^9, P. 109) should be studied when and if sufficient amounts of the mineral can be made available. Both the torbernite group and synthetic KU02V04 have a layer type structure (Beintema, 1958, p. 155; Sundberg and Sillen, 1950, p. 557). In KU02V04, sheets of (U02V04 )~ are separated by K layers, Tyuyamunite Ca(U02 ) 2 (V04) 2 «5-8.5 H20 has a layer structure with the metal-oxygen sheets bonded together by Ca++ ions. This layer structure is stable for values of nH20 up to 8.5 and the water content ranges zeolitically down to 5» The hydration-dehydration effect is reversible in the range 5*8.5 H20. Metatyuyamunite, a new mineral, contains 5-5 moles of water per mole of Ca(U02 ) 2 (V04 )2 and has distinct X-ray powder diffraction pattern and optical properties. Various hydrates within the range of stability have been found in nature, and unless specimens are collected in moisture- proof containers, they may dehydrate before they are examined in the laboratory. Crystal lattice studies of tyuyamunite, carnotite, and sengierite have been made by Gabrielle Donnay and J« D* H. Donnay (X,'5!:
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