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On Studtite and Lts Composition

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On Studtite and Lts Composition American Mineralogist, Volume 59, pages 166-171, 1974 On Studtiteand lts Composition Kunr WarpNre Institut filr Mineralogie und Kristallchemie der Uniuersitiit Stuttgart Abstract The investigation of studtite from the uranium deposit of Menzenschwand in the Black Forest shows that this ill-defined species is not a uranyl carbonate as hitherto assumed but a hydrous uranium oxide of monoclinic symmetry. It is identical with a synthetic uranium com- pound which is regarded as peroxide hydrate UO.'4 H"o (Sato, 1961). If this interpretation is correct, studtite would be the first peroxide mineral found in nature. Unit-cell dimensions of the mineral from Menzenschwandare: a 11.85,D 6.80,c 4.25 AP93"5l',2 =2, spacegroup C2, Cm, or C2/m, density (calc) 3.64 g/cc. Strongestlines of the powder Patternare 5.93 (10), 3.40 (8), 2.96 (6). The X-ray data agree closely with those given by Debets (1963) for the synthetic compound. The structure of studtite probably consists of O-U-O-U-O chains in the direction of the c-axis as in caseof a-UOg. When heated to 60'C, studtite is transformed into a dihydrate, UO.'2 HrO with loss of 2 H,O. This dihydrate, which is alsg known as a synthetic compound, is orthorhombic with a 6.51, b 8.78,c 4.21 A, Z = 2, spacegroup probably Immm, density (calc) 4.67 g/cc. Strongestlines of the powder pattern: 5.24 (10) , 4.41 (7 ) , 3.54 ( 8 ) . A brief description is also given of a presumably new siliciferous mineral occurring at Menzenschwand associatedwith studtite and uranophane. Introduction Mode of Occurrence The mineral studtite is an ill-defined secondary The mode of occurrenceof studtite at Menzen- uranium mineral. It was describedby Vaes (L947) schwand closely resemblesthat of the mineral at as a hydratedcarbonate of uranium,on the basisof Shinkolobwe.It forms aggregatesand crustsof min- qualitative tests. The mineral had been found as ute needle-likecrystals that frequently show a more aggregatesof thin fibers on uranophaneand ruther- or lessradial fibrousstructure (Fig. 1). The needles fordine at Shinkolobwe,Katanga. The optical prop- are elongated along the c-axis but lack observable ertiesgiven by Vaesled to the conclusionthat studtite crystal faces. Their maximum length approaches is orthorhombic (Frondel, 1958). The scantydata 0.5 mm; maximumthickness is about 10 pm. publishedby Vaes were later supplementedby Guil- The mineral is foun{ on barite, quartz, hematite, lemin (1958), who furnishedX-ray powder spac- and limonite associatedwith billietite, uranophane, ing data for the mineralfrom Katanga. rutherfordine,and other secondaryuranium minerals. The optical and X-ray data publishedby Vaes and In one caseit is intimately intergrownwith urano- Guillemin permitted the present author to identify phane and the unknown mineral describedbelow. In studtite amongthe secondaryminerals of the uranium another it occurs as younger crusts on uranophane. deposit at Menzenschwandin the Southern Black Forest (Walenta, 1960; 1963). The first specimen Chemical Composition of studtite found at this locality dates from 1959. A preliminary chemical investigation, however, Studtiteis slowly acted on by cold 1:1 HCI and showedthat the mineralis not a carbonate(Walenta, cold 1:1 HNOB, whereasit is more rapidly soluble 1967). Vaes evidentlyinvestigated an impure sam- in cold 1 :1 HzSOe.No effervescencewas observed ple. This may alsobe indicatedby the small amount during dissolution. Minute crystals of the lower of lead in his materialwhich he thoughtmight be due hydrate (p. 169) precipitatefrom the solution in to inclusions.Such impurities could alsohave caused HCI after partial evaporationof the solvent at room the evolution of carbon dioxide when the mineral temperature. was treatedwith acid. Electron microprobe and microchemicalanalyses r66 ON STUDTITE AND ITS COMPOSITION 167 zone of uranium depositsas a member of a normal secondaryparagenesis is astonishing.It would be the first natural occurrenceof a peroxide compound. Becausethe existenceo,f such a compoundin nature seemed unlikely, it was thought possible that its interpretation as peroxide might be wrong and an- other formula, UO2(OH)2.4 }J2O = UOs.5 HzO, interpreting it as hydroxide, was taken into con- sideration. However, all chemical tests carried out speakin favor of the peroxidenature of the synthetic compoundand the mineral. If for instanceMnO2 is addedto a solutionof the compoundin dilute HsSOa, gas is given off with effervescence.With KI the solu- tion yields a precipitate of iodine, and a solution of FIc. 1. Studtite forming aggregatesof needlelike crystals KMnOa is decolorizedby it. on limonite, Menzenschwand,Southern Black Forest. Mag- If studtite is indeed a peroxide, the question re- nification about 60 X. tnains of how it formed under natural conditions. Although this problem is not yet solved,possibly the small amountsof hydrogenperoxide known to occur revealedonly uranium as a major constituent.Tests in rain water and snow are responsible.Another for other cationsand anionswere negative. possibility is an organic source of the hydrogen A spectrographicanalysis performed by H. Wilk, peroxide. ChemischesUntersuchungsamt der Stadt Stuttgart, yielded similar results, though a number of other Physical and Optical Properties elementswere detectedin minor amounts(Mg, Cu, The needle-likeyellow crystals exhibit no distinct Ni, Zn, Al, Si) and in traces(Ca, Co, Fe, Mn, Bi, cleavage,are soft, and translucent to transparent. Sb, Sn). In part their presencemay be ascribedto Studite does not fluorescein ultraviolet light. The impurities. calculateddensity is 3.64 g/cc. The attempt to de- The qualitative chemical analysesreveal that termine the density of the natural mineral by means studtite is not a carbonateand that no cations other of heavy liquids was not successfulbecause the than uranium play an essentialrole in its structure. crystals were too small. The density of the artificial Its true nature was recognized when the powder compoundas measuredby tfe pycnometermethod pattern of pure studtite proved identical with that is 3.58 g/cc, in reasonableagreement with the cal- of a synthetic hydrous uranium oxide, the formula culatedvalue. of whichis thoughtto be UO+.4 HzO (Sato,1961; The optical propertiesare summarizedin Table 1. Debets, 1963). Likewise, the powder diagrams of Becausethe small crystals were not suitable for ob- UO4-2 HzO as obtainedby heatingstudtite to 60'C taining polarization figures,the optical characterand are identical to those of the similarly dehydrated the optical axial angle 2V c,ouldnot be determined synthetic compound. directly. Yaes (1947) states2V to be large; how- Chemicallythe compoundUOa.4 H2O generally is regarded as uranium peroxide hydrate (Katz and Tenre 1. Optical Properties of Studtite Rabinowitch,I95I; Sato, 1961). Thus its formula 'H2O2.3 is alsowritten UOB H2O.It can be obtained Studtite as a light yellow precipitate by addition of hydrogen Shinkolobwe Menzenschwand peroxide to a concentratedsolution of uranyl nitrate (Vaes, 1947) (Present study) or uranyl acetate.Peroxo-uranates are formed by a 1.545 a L.537 t 0.003 treating the compoundsimultaneously with hydrogen B r..sss peroxide and alkalies. Heating of the uranium per- y l-. 68 y 1.680! 0.003 oxide leadsfirst to a lower hydrate and then to UOg Nearly colorless with evolution of oxygen and water. 2V Taxge The presenceof this compound in the oxidized Z paraLleL to elongatlon 168 KURT WALENTA ever, this is not consistentwith the indicesof refrac- Tesrs 2. X-ray Powder Data for Natural and Synthetic tion he determined.The indicesof refraction c and p Studtite do not differ greatly, as confirmed by the present Studtlte Synthetic study, so the mineral must be optically positive and Menzensctred sbLDkolobre Uo4 ' 4 H2o (Piesent study) (qri11*in' 195E) (Debets, 1953)* have a small2V. a <il r** a <fil r*t 4 111 7*** 171 The extinction of the crystals is parallel and not 7.53 at oblique. The Z 5.93 10 5.91 w st 5.88 100 200,110 acute bisectrix coincides with the 4.2) W W 1.ZJ L2 00t- c axis so that the monoclinic symmetry cannot be J. t> w 3.58 w 3.55 10 20L recognizedby the optical properties. This behavior 3.49 2 drf. 3.49 19 111 3.40 310 is explained by the fact that the lattice shows a J'4u t 3.40 8 3.39 32 020,111 marked pseudohexagonalsymmetry for the c axis. J. J4 5 20L The pseudosymmetryevidently influencesthe optical 3.22 w to D 2.95 5 400 2.98 v propertiesto such a degreethat they resemblethose 2.96 6 w 2.94 8 220 of a uniaxial positive crystal. 2,72 0.5 2.73 5 311 2.66 1 2.648 7 021 2.60 1 2.588 6 31t X-Ray Investigation 2,49 2 2.53 v F 2.500 5 40L 2.44 2 2.457 6 22L 2,37 3 2.380 5 22t X-ray porvder diffraction data for studtite from 2.356 5 40r Menzenschwandand Shinkolobwe as well as the 2.234 5 510 2.23 6 2.27 v w 2.228 5 420 indexedpattern for the syntheticcompound are listed 2.220 4 130 in Table 2.aThe unit-cell dimensions 2.L2 1 2.127 w v 2.118 002 of natural stud- 2,026 6 5r1 2.O2 5 2.042 y w tite and the synthetic compound are given in Table 2.OLz 11 LLz,42L r.974 10 131,112,600 3. The d-spacingsof the powder pattern and the 1.970 5 broad L.955 w L.957 10 330,r31,202 unit-cell dimensions of studtite and the synthetic t.934 3 1. 931 8 42L,sLL L.844 3L2 compound are the samewithin limits of error. 1.837 0.5 dif, 1.832 I 501 The powder pattern given by Guillemin (1958, r.797 1 1.798 5 33L,022 r.755 2 1,758 5 33L,312 p.
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