American Mineralogist, Yolume 64, pages 941-944, 1979
Stoiberite,CurVrOro, a new *Hil;lffi:?,*- Izalcoyolcano, El Salvador,
RrcHano W. BTRNTEAND JoHN M. HUcHES Department of Earth Sciences, Dartmouth College Hanover, New Hampshire 03755
Abstract
Stoiberite,Cu5V2O,s, a Dewcopper vanadatemineral, occursas black platy crystalsin the oxide zone of a fumarole in Izalco volcano, El Salvador,Central America. It is monoclinic, spacegroup P2,/n, with a : 15.654(15),b : 6.054(4),c : 8.385(ll)A, and P : 102.29"(12). The mineral is opaquewith a medium reflectivity lessthan that of galena.Its calculatedden- sity is 4.96gm/cc.It is namedafter Dr. Richard E. Stoiber.
Introduction duration. Since 1958,the volcano has been inactive Naturally-occurring CurVrO,ohas been discovered exceptfor a small flank lava flow in 1966.During this in a fumarole in the summit crater of lzalco volcano. reposeperiod, the gasesand minerals of the fuma- El Salvador,Central America (13o49'N;89o38'W) roles in the summit crater have received extensive (Fig. l). ldentification of this mineral as the analog study (Stoiber and Dtirr, 1963; Stoiber and Rose, of syntheticCurVrO,o is basedon (l) electronmicro- 1970, 1974; Stoiber et al., 1975).Copper and van- probe chemical analysis, and (2) X-ray diffraction adium were found among the four distinctive ele- analysis. The new mineral is named stoiberite ments in the Izalco fumarole mineral suite. Copper (stoi" ber'it) in honor of Dr. Richard E. Stoiber, occurs in chalcocyanite (CuSOn) and chalcanthite ProfessorEmeritus of Geology at Dartmouth Col- (CuSOo'sHrO),while vanadiumoccurs in shcherbi- lege,who is noted particularly for his studiesof Cen- naite (VrOr). The compound VrO, was first noted at tral American volcanoes,fumarolic gases,and fuma- lzalco (Stoiber and Dtirr, 1963) but not named. It rolic mineral inciustations. Type specimensare was subsequentlyfound in a fumarole at Bezy- deposited in the mineral collection of the Depart- myanny Volcano, Kamchatka and named (Bori- ment of Earth Sciences,Dartmouth College and the senko,1972; Fleischer, 1973). National Museum of Natural History, Smithsonian Stoiberite is found only in the "Y" fumarole, one lnstitution, Washington,D.C. (NMNH 144942).The of five major fumarolesat Izalco (Stoiber et al., 1975, total amount of the mineral on hand is a few milli- Fig. l). ln 1964,when the mineral was first discov- grams.The mineral and mineral name have beenap- ered, the temperature of the fumarole was 450"C. proved by the Commission on New Minerals and The temperatureof the fumarole in Novembet, 1978, Mineral Names.IMA. had fallen to 89oC, and only small amounts of stoiberitewere found. The mineral occursas a black incrustationin the oxide zoneof the fumarole (fuma- Locality and occurrence role zonation describedby Stoiber and Rose, 1974). Izalco volcano is a 2-km3basaltic compositecone The crystalsare lessthan 100pm in greatestdimen- which has been intermittently active sinceits birth in sion and coat basalticbreccia fragments. 1770.The volcanorises to an altitude of 1965m. with 650 m relief. The geologyofthe volcano is described Chemistry by Meyer-Abich (1958),Rose and Stoiber (1969), The synthesisof CurVrO,o was first reported by and Stoiberet al. (1975). Brisi and Molinari (1958). They observedthat the During its brief history,Izalco has had 55 eruptive compound melts incongruently at 800oC and is one periods,ranging from 9 yearsto lessthan one year in of the five incongruentlymelting phasesin the CUO- goo3-00/.w 79 / 09r 0-094 I $02.00 941 BIRNIE AND HUGHES: STOIBERITE
metal); VrOs (V,O,); CrO, (uvarovite). No other ma- jor elementswere detected. An average of 3 mole percent chromium sub- stitutes for vanadium. The quantification of the Cr substitution is difficult because of spectral inter- ference by vanadium. The chromium is known to substitute for the vanadium because chromium in- creasesin concentration with vanadium in more van- adium-rich copper vanadates associated with stoiber- ite. The oxidation state of the Cr is not known, but is ELi \. / assumed to be Cr(VI). This assumption is made be- tzALco -vroon( i. VOLCANO cause the Cr in stoiberite occupies the vanadium sites, which are all tetrahedrally coordinated (struc- ture analysis by Shannon and Calvo, 1973).Cr(VI) is
PACIFIC the more stabilized oxidation state in a tetrahedral crystal field, and Cr(III) is not known to occupy tet- rahedrally-coordinated sites (Burns and Burns, 1975). Evidence of the compatibility of Cr(VI) in the van- Fig. l. Location oflzalco volcano, El Salvador. adium sites of stoiberite is given by the metal-oxygen bond lengths. Typical Cr(VI)-O. bond lengths are -1.65,4, VrO, systern. Fleury Q966, 1969; reported in Shan- (Burns and Burns, 1975), and values be- non and Calvo, 1973) conducted magnetic suscepti- tween 1.54and l.8lA have been reported (White and bility measurements on synthetic CurVrO,o and de- Roy, 1975). These values are consistent with the termined that the copper is divalent; therefore, the 1.724 V-Oo bond lengths in synthetic Cu,VrO,o formula can be written as 5CuO.VrOr. Single crys- (Shannon and Calvo, 1973). tals of CurVrO,o have also been synthesized by Shan- The substitution of minor amounts of the hex- non and Calvo (1973) from a melt with the composi- avalent chromium ion for the pentavalent vanadium tion 5CuO:lVrO,:6KVO3 ar 1000"C. ion poses a neutrality problem in the formula calcu- The ideal formula of stoiberite is CurVrO,o (Table lation. Brisi and Molinari (1958) described solidus l). Electron microprobe analysis of the mineral was and sub-solidus oxidation-reduction reactions in carried out using the following standards: CuO (Cu copper vanadates. Oxidation reactions ofthe sort re- quired to accommodate minor amounts of Cr(VI) in natural CurVrO,o are known to take place in the Table l. Electron-a-T"#r1;?ffof stoiberire.All valuesin oxide zone of volcanic fumaroles (Naboko, 1959), and it may be that the naturally-occurring CurVrO,o oxide has undergone a reaction of this type. The presence of Cr in stoiberite is of interest CUO 64.62 68. 0 (4) 68. 1 (6) be- cause Cr-bearing fumarole v^o. 3t .38 30.I(4) 30.3(s) minerals are rare, al- 1. 03(1) 1.0 (1) though not unknown (Naboko, 1959). Several other Cr-bearing phases have also been discovered at this 100.o0 99.13 99.4 fumarole by the authors (manuscript in preparation). *One standard deviation in narpnfhesac (1) Ideal stoiberite X-ray crystallography /?\ V ^€ I -nrr..-^^ ^f r arrdaY5es fvnA ^rUc+Al (3) I of 20 analyses of 10 crystals An X-ray diffraction pattern of stoiberite was ob- tained from a polycrystalline grain mount in a I14.6 formula (analysis (3)) on the basis of 10 oxygens: mm Gandolfi camera using CrKa radiation (tt gg gacto. oro "t4. , o6) (2.2909A, V filter) in a helium atmosphere. Correc- ideal fomula: cr5.OOV2.OOO1O tion were made for film shrinkage, and intensities were visually estimated. Powder patterns of synthetic CurVrO,o were published by Brisi and Molinari BIRNIE AND HUGHES: STOIBERITE 943
(1958; Jcpos #16-418) and Shannon and Calvo curring analog. The plates represent the front pina- (1973; Jcpns #27-1135). The diffraction pattern of coid [100]. Figure 2 is an electron microscope image stoiberite agrees with the patterns of the synthetic of a well-formed crystal of stoiberite. The orientation phase. The stoiberite pattern has been contributed to of the principal axes was determined from precession the Powder Diffraction File. The lattice constants photographs of the crystal pictured. Scanning elec- measured frorn precession photographs (MoKa radi- tron microscope examination of numerous crystals ation, 0.7 107A, Zr frlter) and those refined from Gan- showed that euhedral grains are rare and poly- dolfi patterns are listed in Table 2. crystalline aggregates are common. Some images also Stoiberite is monoclinic, uniquely determined as reveal parallel striae on the (100) face which intersect space group F2'/n. Precession photographs show ex- the D and c axes at intercepts proportional to the re- tinctions h + I # 2n for (/r0f reflections. Also in spective axial lengths. The a axial intercept could not Table 2 are the lattice constants reported for syn- be determined. These striae may represent an {ftll} thetic Cu,VrO,o. Shannon and Calvo (1973) origi- cleavage trace. nally reported an unreduced cell that conforms to the The calculated density of ideal stoiberite and the nomenclature in the International Tables for space natural Cr-bearing analog is 4.96 g/cc. This was cal- group P2,/c. The axial parameters of the unreduced culated using the X-ray cell volume and assumed cell are related to those of the proposed reduced cell Z: 4. Due to the small amount and size of the natu' by d,n,"o: [01],"o; D"^*o: [010].""; cu^..a: [00U."". rally-occurring material, density was not measured. Shannon and Calvo's cell parameters are comparable Shannon and Calvo (1973), however, report a mea- to the unreduced cell parameters if Shannon and sured density of 5.0 E/ccinthe synthetic analog;they Calvo's a and c axes are reversed to conform with the obtained Z : 4 from refined crystal structure data. convection a > c inmonoclinic crystals. Stoiberite transmits light only on thin edges. The The crystal structure of synthetic CurVrO,o was color of this transmitted light is "moderate reddish- solved by Shanon and Calvo. They describe the brown" (similar to l0 R 46, Goddard et al., 1963). structure as a network of chains of Cu-Ou octahedra Extremely weak absorption of unknown direction is and Cu-O, trigonal dipyramids linked by edge-shar- observed. In reflected light in air, stoiberite exhibits a ing of the octahedra and corner-sharing of the V-Oo weak anisotropy. The colors are not unlike "very tetrahedra. light gray" (N8, Goddard et al., 1963). A stight bluish-white pleochroism is present (estimated at 5 B Physical properties 9/l to 5 B 8.5/1, Goddard et al.,1963). The mineral Stoiberite occurs as polycrystalline aggregates has a medium reflectivity, less than that of galena. <100 pm in greatest dimension. The mineral is black Stoiberite does not fluoresce in either short- or with a metallic luster and a reddish-brown streak long-wave ultra-violet radiation. [t is soluble in di- similar to the streak of hematite. lute HrSOo. Shannon and Calvo (1973) report both plate-like and needle-like habits in synthesized Cu'VrO,o. Only the plate-like habit is observed in the naturally-oc-
Table 2. Unit-cell parameters of stoiberite and synthetic Cu5VrO'o
c(A)* B(aeq.1* v(e')
'7'7 (r) Is.69 6. 06 a ,32 to2 .3 3
l2) 15.654(15) 6.054(4) 8. 385(1r) t 02.29(l2l 7'76 (3) t5.'7r2 6. 068 8.389 lO2,34 78r
--Arc ih ^.rahfh6c6c
(I) Measured from precession photographs (2) al values from Least-squares refinement using 16 image of a well formed Gandolfi pattern (refined using LCLSQ program, Fig. 2. Scanning electron microscope Char]es l{- Burnham, Harvard UniversiLy). crystal of stoiberite. The plane surface is (100) and on it are (3) Reduced parafreteis reported on JCPDS #27-ll-35 The a axis makes an angle (B) (realuced from alata of Shannon and Calvo, 1973). marked the b and c axial directions. of 102.29' with c. BIRNIE AND HUGHES: STOIBERITE
Acknowledgments Goddard, E N., P. D. Trask, R. K. DeFord, O N. Rove, J. T. Singewald and R. M. Overbeck (1963) Rock-Color Chart. We thank John Collier and Victor Surprenant of the Thayer Huyskes-Enschede, Netherlands. School of Engineering, Dartmouth College, for their assistance in Meyer-Abich, H. (1958) Active volcanoes of Guatemala and El the use of the scanning electron microscope. We benefitted from Salvador. In F. Mooser, H. Meyer-Abich and A. R. McBirney, discussions with Larry W. Finger and Robert M. Hazen of the Calalogue of the Active Volcanoes of the World Including Solfa- Geophysical Laboratory, Carnegie Institution. Early version of tara Fields, Part VI, Cenlral America, p 39-105. International the manuscript were improved by reviews by John B. Lyons and Volcanological Association, Naples. Robert C. Reynolds. The electron microprobe analyses were per- Naboko, S L (1959) Volcanic exhalations and product oftheir re- formed at the Department of Geological Sciences, Harvard Uni- actions as exemplified by Kamchatka-Kurile volcanoes. .Bul/. versity. The research was partially supported by a grant from the Volcanol.. 20. l2l-136. Committee on Research, Dartmouth College. Rose, W. L and R. E. Stoiber (1969) The 1966 eruption of Izalco Volcano, El Salvador. J. Geophys Res., 74, 3 I I 9-3 I 30. Shannon, R. D. and C. Calvo (1973) Crystal structure of Cu5V2O,6. Acta Crystallogr., 829, 1338-1345 References Stoiber, R. E. and F Diirr (1963) Vanadium in the sublimates, Izalco volcano, El Salvador (abstr.). Geol. Soc. Am. Spec. Pap., 76, t59. Borisenko, L F. (1972\ The new mineral shcherbinaite. (in Rus- - and W. I. Rose (1970) Geochemistry of Central American sian) Zap. Vses.Mineral. Obshch., I0I, 464. volanic gas condensates. Bull. Geol. Soc.Am., 8I,2891-2912. Brisi, C. and A. Molinari (1958) Il sistema ossido ramico-ani- _ and _ (19'74) Fumarole incrustations at active Cen_ dride vanadica. Ann. Chim. (Rome), 48, 263-269 A. [transl. tral American volcanoes. Geochim. Cosmochim. Acta. 38. 495- Monicelli, Dartmouth Collegel. 5 16. Burns, V. M. and R. G. Burns (1975) Mineralogy of chromium. -, I. M. Lange and R. W Birnie (1975) The cooling Geochim. Cosmochim.Acta. 39.903-9 10. of Izalco volcano (El Salvador) 1964-19'14. Geol. Jahrb., 13, Fleischer, M. (1973) New mineral names. Am. Mineral.. j8. 560- 193-205. 562. White, W. B. and R Roy (1975) The system chromium-oxygen at Fleury, P. (1966) Sur le systdmeCuO-VrO, C.R. Acad. Sci. Paris, high oxygen pressures. Geochim. Cosmochim. Acta, 39, 803-8 17. Sir. C. 263. l3'15-1377. - (1969) Etudes sur les syst€mes V2O5-CuO ou Ag2O ou TlrO3 et sur les combinaisons interoxydes correspondantes. Rey. Chim. Miniral., 6, 819-851 (not seen; extracted from Shannon Manuscripl received, Febntary 14, 1979; and Calvo. 1973). acceptedfor publication, May 25, 1979.