Nomenclature of the Alunite Supergroupis Com- Mineralogy (Palache Et Al

Home , Alunite, Beudantite, Corkite, Hidalgoite, Jarosite, Osarizawaite

1323

The Canarlian Mineralogist Vol. 37.pp. 1323-1341t I999)

NOMENCLATUREOF THE ALUNITE SUPERGROUP

JOHN L. JAMBORS

Depat'tmentof Earth and OceanSciences, University of British Columbia,Vancouver, British ColumbiaV6T lZ4, Canadn

Aesrnlcr

The alunite supergroupconsists of more than 40 mineral specieswith the general formula DG3(ZO4)2(OH,H2O)6,in which D is occupiedby monovalent (e.g., K, Na, NHa, H3O), divalent (e.g., Ca, Ba, Pb), ortrivalent (e.g., Bi, REE) ions, G is typically A13* or Fe3+,and Zis 56*, Ass*, or Ps*. The current nomenclature classification is unusual in that, within the temary system defined by the SOa, AsOa, and POa apices, compositions are divided into five fields rather than the three that are conventionally recom- mended for such systemsby the Commission on New Minerals and Mineral Names (CNMMN) of the International Mineralogical Association. The current compositional boundaries are arbitrary, and the supergroupis examined to determine the repercussions that would ensuefrom adoption of a conventional ternary compositional system.As a result ofthe review, severalinconsistencies have been revealed; for example, beaverite and osarizawaite, which are commonly formulated as Pb(Cu,Fe)3(SO+)z(OH)eand Pb(Cu,Al)dSOa)z(OH)0, respectively, not only have formula Fe > Cu and Al > Cu, but the amount of substitutional Cu also is variable. Beaverite is therefore compositionally equivalent to Cu-bearing plumbojarosite. The CNMMN system also permits the introduction of new mineral namesif a supercell is present;within the alunite supergroup,the supercell is typically manifested by a doubling of the c axis to -34 A, and the effect is evident on X-ray powder pattems by the appearanceof a diffraction line_orpeak at 11 A. In addition to the supercell, however, severalother departuresfrom the standardtrigonal cell with spacegroup R3n have been observed To accommodate these structural variations, thereby minimizing the introduction of numerous potential new mineral names, the possibility of incorporating a suffix modifier is explored. To keep within CNMMN nomenclature protocols, potential solutions are offered, but none is proposed.

Keywortls'. alunite supergroup,nomenclature, alunite group, beudantite group, crandallite group, compositions, sffuctures.

)OMMAIRE

Le supergroupe de l'alunite comprend plus de quarante espbces min6rales rdpondant h la formule gdndrale DQ(TOD2(OH,H2O)6; le site D contient des ions monovalents (e.g., K, Na, NHa, H3O), divalents (e.g.,Ca, Ba, Pb), ou trivalents (e g , Bi, tenes rares), G contient en gdndral A13+ou Fe3*,et lreprdsente 56+,As5+, ou Ps*. Le systbmede classification en vigueur actuellement est anomal: dans le contexte d'un systbme temaire d6fini par les p6les SO+, AsO+, et PO+, les compositions sont rdparties en cinq domaines plutOt que trois, comme le recommande la Commission sur les Nouveaux Mindraux et Noms de Mindraux de I'Association Min6ralogique Internationale. La ddlimitation des divers champs est arbitraire. Les r6percussionsde l'adoption d'un systbme temaire de nomenclature de ce supergroupe sont ici passdessous revue. Plusieurs cas de non concor- dance sont relevds; d titre d'exemple, la beaverite et 1'osarizawaite,auxquelles on attribue couramment les formules Pb(Cu,Fe)3(SOa)2(OH)6et Pb(Cu,Al)3(SOa)2(OH)6,respectivement, ont une teneur en Fe et en Al supdrieured celle du Cu, mais cette teneur en cuivre peut aussiOtre variable. La beaverite serait donc dquivalente en composition d une plumbojarosite cuprifBre. Le systdme en place actuellement permet I'introduction de nouveaux noms de mindraux si une supermaille est manifestde. Au sein du supergoupede 1'alunite, la pr6senced'une supermaille se voit par le d6doublagede la pdriode c jusqu'd environ 34 A, et par la prdsence d'un pic ou d'une raie d 11 A dans un spectre de diffraction. En plus de la supermaille, toutefois, on observe plusieurs autres 6cafts par rapport h la maille trigonale standarddans le groupe spatialR3m. Afin d'accommoder ces variations structurales,et ainsi de minimiser l'introduction potentielle de piusieurs nouveaux noms de mindraux, il est possible d'ajouter un suffixe au nom. Afin de satisfaire aux exigeancesde la Commission, des solutions possibles au dilemne sont prdsentdes,mais aucune n'est proposde.

(Traduit par la Rddaction)

Mots-clds: supergroupede l'alunite, nomenclature, groupe de l'alunite, groupe de la beudantite, groupe de la crandallite, compo- s1t10ns.structures.

E E-mail address:jlj @wimsey com t324 THE CANADIAN MINERALOGIST

INrnooucrroN meaningful compositional boundary, and that mutual substitutions of SO+, PO+, and AsOa are extensive The alunite supergroup consists of three mineral within the alunite supergroup.To rationalize the previ- groups that, combined, contain more than 40 mineral ously indefinite boundaries between the SOa-dominant specieswith the generalformila DGz(TOr,)z(OH,H2O)6, and other membersof the family, Scott (1987) proposed wherein D representscations with a coordination num- that the boundariesbe set at 0.5 formula (SO+)zand l 5 ber greater or equal to 9, and G and T represent sites formula (SOa)z;these values arc 25Vo and 75Voof total with octahedral and tetrahedral coordination, respec- TO4, as shown in Figure 1. The proposal was accepted tively (Smith et al.1998). The supergroup consists of by the Commission on New Minerals and Mineral the alunite group, the beudantite group, and the Names (CNMMN). The effect of Scott's classification crandallite group (Mandarino 1999). In all three, the ? is that each SO+-AsO+-POa "ternary" diagram incor- in_(7Oa)2 is dominated by one or more of 56*, As5*, or porates five compositional fields and mineral names, P'*. The alunite group is characterizedby (SOa)2-domi- four of which are partly governed by the POa-AsOa nant minerals, whereas in the beudantite group, one of binary dividing line (Fig. 1). Nov6k et al. (1994) pro- the two SOa groups is replaced by POa or AsOa. In the posed that the SOa-POa-AsOa held be divided into six crandallite group, the (7Oa)2represents one or both of units (Fig. 1), a system that requires the redefinition of POa and AsO+. Thus the change from the alunite to the several minerals. Their system has not been submitted beudantite group, and thence to the crandallite group, to the CNMMN for a vote, but its usagehas been propa- can be viewed as a progression from (SO+)2,to (SO4) gated in several publications (Nov6k & Jansa 1997, (POa) or (SO+)(AsO+),and thence to either (POa)2or Novilk e/ a|.1997,1998, Sejkoraet al.1998). (AsO+)2.This progressionfollows thatinThe Systemof The nomenclature of the alunite supergroupis com- Mineralogy (Palache et al. I95l), wherein the alunite plex and promisesto be increasingly so if the CNMMN- group is classihedwith the sulfates,the beudantitegroup approved system is not modified to take account of the falls within the category of "compound phosphates, crystal-structurevariations that have beenrecognized to etc." , andtheplumbogummite group is equivalent to the occur within the supergroup. In the following discus- current crandallite group. In the beudantite group, a sion, the nomenclature is evaluatedto explore not only small departure from the 1:1 ratio for (?Oa):(7Oa) was what happens in a ternary compositional system, but recognized (Palache et al. l95l), and this variation is also to explore the repercussionsof designatingthe crys- evident in all of the compositions listed therein. For tal-structure variations by suffixes. In the compositional example, the two compositions chosen for beudantite system herein, the ternary series is divided into three sensustrictohave SO3 contents of 12.30and 74.82wt%a, equal fields (Fig. 1, left), which is in accord with cur- whereas the appropriate value is 11.24 wt%ofor rent CNMMN recommendations for naming ternary (SOa):(AsOa)= 1:1. Under the currentrules of nomen- solid-solutions that are complete and without structural clature for such a binary system,these compositions fail order of the ions defining the end members (Nickel to meet the "5OVorule" in that they are sulfate-domr- 1992). nant rather than precisely at the 50:50 boundary that separatesthem from the arsenate-dominantmineral spe- Tun, AluNrrB Gnoup cies. Compositions of someof the other minerals within the group, however, exceed the 50Vo reqtirement and The minerals of the alunite group are listed in fall within the PO+-dominantfield. Table l. Figure 2 shows that little substitution of SO+ After publication of The System of Mineralogy, it by POa and AsOa occurs for members in which D is became apparentthat the l:1 ratio of anions was not a monovalent; where D is divalent, however, TOa substi-

As04 Poa AsO4

Ftc. l. Left diagram shows the nomenclature schemefor complete tema-rysolid-solutions according to recommendationsby the CNMMN (Nickel 1992). Middle diagram is the systemin current use for the alunite supergroup(Scott 1987), and the diagram on the right shows the composition fields proposed by Novdk et al (1994). NOMENCLATURE OF THE ALUNITE SUPERGROUP 1325

TABLE I MINERALS OF IIIE ALIINITE GROTJP(CURRENI USAGE) tution may be substantial, and these minerals a"redis- cussed separately.In the synthetic alunite-jarosite se- aluite jrosite ries, Fe-for-Al solid solution is complete (Brophy et al. KAls(S0rl(0rr)6 KFq(soa),(olD5 1962, Hartig et al. 1984); although natural members mtroaluite mlrojao$te NaAL(s01),(0l{)6 N&Fe3(SOJdOH)6 with intermediate compositions are known (Palache er monioaluite moniojuosite al. 1951, van Tassel 1958), the degree of Fe-for-Al (NlI4)Aq(SO1L(Orr)5 (NHr)Fq(soXoH)6 schlossmcherite hydronim jrcsite substitution in most occuffences is limited, and composi- (H'o,ca)Al'(so.)"(ol0" Gr.O)re(so.)doH)6 tions are close to those of either the Fe or Al end-members. ilgentojmsite AeFq(so.),(OH)" Solid solution involving K+, Na+, and (H3O)+is ex- doEllchtrite tensive in both alunite andjarosite (Brophy et al. 1962, rlFq(soa),(oH). & Sheridan 1965, Kubisz 1960, oseiawaite b@vqite Parker 1962, Brophy Pb(Al,Cu)3(SO4)r(OEII2O)6 Pb(Fe,cu[SO,),(OH,H,O)" 1970, Stoffregen & Cygan 1990,Liet al. 1992). Substi- plMbojilosit€* has been shown by Scott PbFe(SOJr(oII)o tution involving K+ and Pb2* minuiite* (1987) to be extensive in alunite, and by de Oliveira et (NaCa,K),AUsoa)a(olo' al. (1996) and Roca et al. (1999) to be equally exten- humgite* CaAl6(Sq)4(OI{)n sive in jarosite. The incorporation of NHa in ammonio- ualthisite+ alunite (Altaner et al. 1988) and ammoniojarosite BaAL(SO)(oII)u (Odum er al. 1982) seemsto be mainly at the expense of K+ and (H:O)*. Apparent deficiencies in K + Na + * Length of c unit-cell pdameter is double that of the other members of group the NH+ D-site occupancy are generally attributed to (Hso)*.

unchanged: soo iarosite natrojarosite hydroniumjarosite K:jarosite Fe>Al ammoniojarosite Na: natrojarosite argentojarosite HrO: hydroniumjarosite dorallcharite NHo:ammoniojarosite Ag: argentojarosite Tl: dorallcharite

AsOo

geo: Na:natroalunite, minamiite Al >Fe alunite HrO: schlossmacherite natroalunite,minamiite NHo:ammonioalunite schlossmacherite SO, SOo .ttonio"lrnit"

Frc. 2. Minerals of the alunite supergroup with monovalent ions predominant as the D-site cation. Left diagram shows the current system of nomenclature, and diagram on the right shows the effects of adopting a ternary system. Minerals with Fe > Al and with Al > Fe are, respectively, jarosite - alunite, natrojarosite - natroalunite, ammoniojarosite - ammonioalunite, hydronium jarosite - schlossmacherite.Argentojarosite and dorallcharite do not have Al > Fe analogues. r326 THE CANADIAN MINERALOGIST

Natural argentojarosite is generally near the end- regardedminamiite to be compositionally equivalent to member composition, although in synthetic systemsthe calcian natroalunite, but with the c axis doubled in solid solution between Ag-Pb (t H3O) and Ag-K minamiite. A plot by Matsubara et al. (1998) of Na + K (+ H:O) has been shown to be complete (Ildefonse el (alunite-natroalunite) versus Ca (huangite) does not al. 1986, Dutrizac & Jambor 1984). The Tl+ member, show significant compositional gapsto be presentin the dorallcharite, is known only from one locality, and the series.Because of small grain-size,however, X-ray data mean occupancy of the D site is (TlosrKole) (Bali6 have not been obtained for all compositions. Thus, if Zuntd et al. 1994).The remaining membersof the alunite ordering of Ca is assumedto be the sole cause for the group, except minamiite and schlossmacherite,contain doubling of c, the lower limit to trigger the change has a predominance of divalent D-site cations. As these not been established. minerals present some difficulties in nomenclature,the speciesare discussedindividually. B eaverite and os arizaw aite

Minamiite Beaverite is typically assignedthe formula PbCuFez (SO+)z(OH)eor Pb(Cuz*,Fer+,AD3(SO4)2(OH)6@alache The ideal formula of minamiite is (Na,Ca,K)2A16 et al. 1951, Gaines et al. 1997). Osaizawaite is the Al- (SO4)4(OH)12.Chemical analysis of the type specimen dominant analogue of beaverite, i.e., Al > Fe (Taguchi gave (Nasa6K0 1eCa6 1atr6 r+):o s:Al: l1(SO4)2(OH)570 1961).As all compositionsof beaveriteand osarizawaite on the basis of SOa - 2, and the ideal formula of the have Fe > Cu or Al > Cu, the respectiveformulas should crystal used for the X-ray structure study (Ossakaer al. be written as Pb(Fe,Cu,Al)3(SO4)2(OH)6and Pb(Al,Cu, 1982) was determined to be (Na636K0 tCaoztloz)>ogz Fe)3(SOa)2(OH)0.Most compositions of beaverite have AI3(SO4)2(OH)6.The n in the formula representsva- Cu:(Fe,Al) near 33:67, but both higher and lower val- canciesthat compensatefor the presenceof the divalent ues have been reported (van Tassel 1958, Yakhontova ion (Ca2*) in the D position. The mineral was deter- et al. 1988,Breidenstein et a\.7992). As summarized mined to-be trigonal. spacegroup R3m- a = 6.98| . c = by Yakhontova et al. (1988), the values of the relevant 33.490 A. Thus, type minamiite is compositionally ratio range from 36:64 to 25:75. equivalent to a Ca-rich natroalunite, but the c axis in As for beaverite, most analysesof the Al > Fe ana- minamiite is doubled becauseof oartial order of the D logue, osarizawaite,indicate Cu:(Al,Fe) near 33:67. cations. This results in a superstructure that yields a However, Paar et al. (1980) reported an occurrence of characteristicpowder-diffraction line (or peak) at about osarizawaite for which the ratio is 25:75. [The mineral 11 A (Okadaet al.1987). described by Cortelezzi (1977) as osarizawaite seems Although type minamiite is Na-dominant (Ossakaer to be a Pb-Cu-rich alunite, requiring re-analysisl. al. 1982), the same authors subsequently synthesized the The compositional variations in beaverite- Ca-dominant analogue, and they explicitly referred to osarizawaiteindicate that the ratio of divalent (Cu2+and the end-member composition of minamiite as CaosAl3 Zn2+1to trivalent (Fe3+and Al3*) ions need not be (SO4)2(OH)6(Ossaka et al. 1987, Okada et al. 1987). strictly 33:67 . In synthetic beaverite-plumbojarosite, Nevertheless,although Ossakaet al. (1987) showed that substitution of Cu2* for Fe3* was found to be complete extensive substitution involving Na-K-Ca occurs rn over the rangeCu:Fe = 0:100to Cu:Fe= 33:67 (Jambor natural minamiite. none of the comoositions indicated a & Dutrizac 1985). Up to 0.76 mol (Zn + CLr)has been predominanceof Ca as the D-site iation. reported for Pb-rich alunite (Scott 1987). For corkite, Most minerals of the alunite group have D occupied which is also in the supergroupand is describedfarther by a monovalent ion, and for these minerals the substi- below, substitution of 0.42 to 0.64 mol Cu has been re- tution of SOa by POa or AsOa is exrremely limited ported by de Bruiyn et al. (199O) and Tsvetanova (Fig. 2). Adoption of a ternary system SOa-POa-AsOa (1995),respectively. for theseminerals thereforewould not affect the nomen- Giuseppetti & Tadini (1980) solved the structure of clature of the existing species.The three divalent ele- osarizawaite of composition Pb(Alr 62Cu6esFes 3s ments predominating at the D site in the alunite-group Zn6s2)23ss(SO+)z(OH)oin space group R3nz, which minerals are Ba. Ca. and Pb. requires that the Cu and Al-Fe be disordered. X-ray powder-diffraction patterns reported for natural Huangite and wahhierite beaverite-osarizawaite have so far conformed to a basic cell of a = -7, c =-tZ A, but as Cu2*decreases, Pb The mineral with Ca predominant, ideally Caa5Al3 content also must decreaseto maintain charge balance. (SO4)2(OH)6,was named huangite, and that with Ba At some point, therefore, the unit cell must transform to predominant, ideally Ba65AI3(SO4)2(OH)6, was named the doubled c of -34 A that is commonly accepted as walthierite (Li et al. 1992). X-ray powder patterns of characteristic of plumbojarosite. In synthetic plumbo- both minerals show an 11 A diffraction effect, indicar jarosite-beaverite,however, doubled cells appearedran- ing that their c axis is doubled to 33-34 A. Acceptance domly along the series (Jambor & Dutrizac 1983). of huangite as a new mineral indicated that the CNMMN NOMENCLATURE OF THE ALUNITE SUPERGROUP t327

In terms of composition, beaverite is a Cu-rich TABLE 2 MINERALS OF TIIE BEUDANTITE GROIJP(CIJRRENT USAGE) plumbojarosite. All occurrences of natural plumbojarosite have so far been reported to have a doubled c b@dutite corkite rbre3[(As,S)OJdOH,HTO)5 PbFe[(P,S)OJ,(OH,H,o)6 axis, but in synthetic hydronium-b-earing plumbo- hidalgoite hinsdalite jarosite, the c may be either 17 or 34 A, apparently de- PbAl3(As,S)O4],(OH,n 0)6 PbAl3t@,s)orl,(orlE 0)6 kenmlitzite srubqgite pending on whether Pb is ordered or disordered. The (sr,ce)Al.t(nqs)oJloH,Eo)6 srAl,lG,s)O-l,(oEH'o)" degreeof order can be variable, and this is readily indi- woodhouwite cated in intensity CaAl3[(P, S)O.],(OH,II'o). by variations the ofthe 11 A diffrac- gallobeudmtite tion line or peak in the X-ray pattern. PbGa3(As, S)O4]2(OH,H,O)6

Schlossmacherite Either As or S my be predominaot in (A5,S)O4, ud eiths P or S may be predonimt in (P,S)O, Schlossmacherite contains substantial amounts of both SO+and AsO+; thus the mineral has been variably assignedto the alunite group (Gaines et al. 1997) or the beudantite group (Mandarino 1999; Table 2). Recalcu- nant in D (threemembers for eachofthese cations),four lation of the only analytical data available (Schmetzer members have Pb dominant, and the remainder has REE, et al. 1980) gives [(H3O)6:zno zsCao26Na6 67K6.05 Ca, or Th dominant. As in the alunite group, a primary 516s1Ba6 sll;1 oo (Alz eaFe602Cu6 06)>3 02 [(SO+)rsr distinction rests on whether the proportion of Fe is (AsO+)0.+ql(OH)szo on the basis of TOa = 2 and after greater than that of Al or vice versa. reassignmentof Cu from the D to the G position. The formula conforms with that generalizedby the authors Ba predominance (Schmetzer et al. 1980). The ratio of SOa:AsO+is 75.6:24.4,thus placing schlossmacheritein the SOa- The Ba-dominant member of the alunite group is AsOa-dominant field in Figure 2. The mineral is there- walthierite BaosAI3(SO4)2(OH)0, and its relationship to fore the Al-dominant analogue of hydronium jarosite. other Ba-dominant members of the alunite supergroup Cell dimensions ate a = 6.998, c = 16.67 A. is shown in Figure 3. AlthoughLiet al. (1992) obtained a = 7.08, c = 1'7.18A by electron-diffraction study of Tue CneNoallrrE GRoUP walthiedte, X-ray powder pattemsof bulk samplesshow an ll A diffraction peak, requiring that the length of c The minerals of the crandallite group are listed in be doubled. The inconsistency was attributed to disor- Table 3. Nine of the members have Ba. Sr. or Ca domi- der induced by the electron-diffraction beam.

TABLE 3. MINERALS OF THE CRANDALLITE GROI.]P (CTJRRENTUSAGE)

Al>Fe Fe>Al gorceixite rsnogor@ixite dusrertite BaAlj(Po1)eq.orD(oII)6 BaAL(AsO{XASO3.OID(OlI)6 BaFes(AsOJdOH)6 qmdallite reocmdallite CaAl3[PO3(O1D(OI'rJ],(OID6 CaAl3[AsO j(On(OID;)]r(OIt6 goyuite dmogoyete b@uite STALIPO3(On(OH)rrl,(OH)6 SrAl[AsO.(O,"(OH)'J] {0II)6 Srre(PO,),(OH,H,O)6 philipsbomite kintorcite wEnitite plMbogwite pbpe@o.),(oEEo)6 PbAl3@o4)'(oH,r{'o)6 PbAl3(AsO4XOH,IIP)6 PbFq(.csoaXOH,ILo)6 florencit€-(Ce) trsofloretrcite-(Ce) CeAIr(POo)r(OHL CeAl(AsO'),(OtI)c florscite-(La) "dsoflorflcits(La)"* LaA[(PO1)b(OFD6 LaA13(As04),(OlD5 floretrcite-(Nd) "usmoflorscite-(Nd)"* NdAteo4)'(or{)6 NdAl3(A504)2(0II)6 waylmdite "ilsrcwylmdite"f zakite (Bi, Ca)AL@Or,SiO,),(OH)e @i,Ca)Al (AsOo),(OH,IlO). BiFeeoXoH). e'.lsttssite (ThPb)ALeO4,SiO4)'(oIr)6 Othes

springcr@kite BaV3eOaL(OH,ILO)6

* not CNMMN-approved, but included here for completeness. t328 THE CANADIAN MINERALOGIST

soo soo

Fe >Al

dussertite Poo AsOo POo

sorceixite arsenogorceixiter/ arsenogorceixite \

walthierite

soo soo

FIc. 3. Minerals of the alunite supergroupwith Ba as the predominant D-site cation. Left diagram shows the cunent nomenclature, and diagram on right shows the effects of adopting a temary system. "Weilerite" is not a valid species(see text).

The main concem in the Ba-dominant group is sub- Ca predominance stitution atthe T site; for walthierite, such substitution was not detected (Li et al. 1992). Likewise, composi- All Ca-dominant minerals in the alunite supergroup tions of gorceixite are typically close to, or at, the POa are also Al-dominant (Fig. a). Numerous compositions end-member. For arsenogorceixite,however, the type of crandallite are near that of the POa end-member.but material shows AsOa:POq = 74:26 (Walenta & Dunn substitution of S for P is extensive, and compositions 1993).The AsOa (arsenogorceixite)and PO4(gorceixite) extend well into the current field for woodhouseite end-membershave been synthesizedby Schwab et al. (Stoffregen & Alpers 1987, Spcitl 1990, Li et al. 1992), (1990,1991). including compositions with formula SO+> PO+ (Wise "Weilerite" is included as a valid species in some 1975). For arsenocrandallite(Walenta 1981), the type modern compilations (Clark 1993, Gaines er al. 1997), material contains substantial Si in the Z position: but the mineral was discredited by the CNMMN (IMA (Aso qqPozsSio z6). The As:P ratio is 57:43, which is well 1968). As no quantitative chemical data had been pub- within the field for arsenocrandallite. lished for the mineral (Fleischer 1962, 1967), the posr- Adoption of a temary system for the Ca-Al-domi- tion on the AsO+-SO+join is uncertain, and the mineral nant minerals would pose the problem of whether may have been identical to the more recently described woodhouseite or huangite is to be used to designatethe arsenogorceixite.The removal of "weilerite" from the SOa end-member. Type woodhouseite has POa:SOa= system is appropriate, thus leaving a gap between 54:46 (Lemmon 1937), but it has long been accepted gorceixite-arsenogorceixite and walthierite (Fig. 3). that either formula S or P can be predominant. The only Dussertite is the only known member with Fe > A1, composition given by Palache et al. (1951) has P > S, thus theoretically allowing six additional names to be but more modern analyses,by electron microprobe, of introduced in the left diagram of Figure 3. In a ternary woodhouseite from the type locality have shown both system, the potential six are reduced to two. formula P > S and S > P (Wise 1975). Moreover. the NOMENCLATURE OF THE ALUNITE SUPERGROUP 1329

Soo

AsO, POo crandallite arsenocrandallite crandallite arsenocrandalIite

woodhouseite

soo soo

Frc. 4. Minerals of the alunite supergroupwith Ca as the predominant D-site cation. Left diagram shows the cu[ent nomenclature, and diagram on right shows the effects of adopting a ternary system.

current CNMMN-approved nomenclature extends the the compositions probably straddle the aforementioned composition of woodhouseite well into the SOa-domi- boundary. The formula of the unnamed mineral rs nant field (Fig. a). Accordingly, woodhouseitehas been (SrzsrBao oo)Fe: r:(PO+)r :s(SO+)o os(OH,H2O),, which adopted to designatethe field with S > P in the ternary places the mineral well beyond the field of benauite. If system (Fig. 4). Scott's (1987) nomenclature systemis to be adheredto, benauiterequires redefinition as ideally SrFe3[e,S)O4]2 Sr predominance (OH,H2O)6.The field shown Bboccupied by benauitein Figure 5 would therefore remain vaguint. The minerals with Sr predominant in the D site are For the Al-dominant group. (Fig. 5), goyazite and shown in Figure 5. The two minerals with Fe > A1 are svanbergitehave long beenusedto indicate the POa and benauite and an associatedunnamed mineral richer in PO+-SO+ minerals, respectively. For svanbergite, the SOa (Walenta et al. 1996). The empirical formula for compositions listed in Palache et al. (1951) have for- benauite is (Sre67Ba6 16Pbs e7Ca6 61Ko ot):,0 sz (Fezgo mula P > S, but compositions with S > P also are known Alo o:):z s: [(PO+)r+s(SO+)o as(AsO4)0 04](OH,H2O)8 3, (Wise 1975); the CNMMN-approved system accepts which was simplified by Walenta et al. (1996) as that either S or P may predominate (Fig. 5). Type SrFe3(POa)2(OH,HzO)0.The proportion of atoms in the arsenogoyazite(Walenta & Dunn 1984) has AsOa:PO+ T site, however,is P:S:As = 74:24:2,which placesthe = 64:36, but the pure end-member has also been de- mineral just beyond the boundary designatedby the sim- scribed (Zhang et al. 1987). Kemmlitzite (Hak et al. plified formula, and into the field of the unnamed SOa- 1969) was regardedby Fleischer (1970) to be the arsen- richer mineral (Fig. 5). The rangein compositions(wt7o) ate analogue of svanbergite; analysis of type material, reported by Walenta et al. (1996) is PzOs l'1 .98-19.93 however, gave [(AsO+)oes@Oa)6 a2(SOa)s 3e(SiOa)s 1e] (mean 18.53used to calculatethe formula), As2O50.64- 11e3, which places kemmlitzite in the field of arseno- 0.94 (mean0.78), SO3 6.24-:7.37 (mean 6.79), and thus goyazite(Fig. 5). Re-examinationof the holotype speci- 1330 THE CANADIAN MINERALOGIST

soo soo

/ a"n^uit a Poo AsOo PO,

covazite ^"tloo'o'^'n"/ arsenogoyazrte \

soo soo

Ftc 5. Minerals of the alunite supergroupwith Sr as the predominant D-site cation. Left diagram shows the current nomenclature; unnamed mineral is that of Walenta et al ( 1996), point "a" is the composition of type arsenogoyazite,and "k" is that for t)?e kemmlitzite. Right diagram shows the effects of adopting a ternary system.

men of kemmlitzite has shown it to be zoned and inho- zairite (van Wambeke 1975) are within the designated mogeneous (Novdk et al. 1994). Kemmlitzite predates compositional fields. "Arsenowaylandite" is an unoffi- arsenogoyazite,and the latter was specifically defined cial name (Scharm et al.1994) that has not been sub- as occupying the AsOa-dominant field because adop- mitted to the CNMMN for approval. The anhydrous tion of the current (Scott) system of nomenclature had composition for ZOa = 2 vaies from (Bi68esr005 the effect of entrenching kemmlitzite as representative Caoos)>o s7 (Al2 e6Fe610) [(AsOa)1 or(SO+)o zz@O+)o rr] of SOa-richcompositions (Fig. 5). Such a SOa-richcom- to (Bi6eeSrs 65)1 1 6a(A12 e6Fe6 ea) [(AsO+) r sr(SO+)ors,. position has been reported by Nov6k et al. (1997). ln view of the reported zoning and lack of homogeneity in Pb predominance type kemmlitzite, retention of the name arsenogoyazite would seem,arguably, to be preferred. In a ternary sys- Figure 7 is illustrative of the profusion of mineral tem, therefore, the most appropriate names are consid- names possible as the compositional fields within the ered to be goyazite, arsenogoyazite,and svanbergitefor alunite supergroup are frlled. For Fe-dominant miner- the Al-dominant members, and benauite for the Fe- als, plumbojarosite, corkite, and beudantite have been dominant mineral with POa greater than AsOa or SOa in use for many years, and corkite and beudantite oc- (Fie.s). cupy the bulk ofthe field. Segnitite (Birch et al. 1992) and kintoreite (Pring et al. 1995) occupy the SOa-poor Bi predominance fields that opened only as a consequenceof the adoption of the current CNMMN-approved system of no- Minerals with Bi predominant in D are shown in menclature.For Al-dominant minerals,plumbogummite Figure 6. Analyses of waylandite (Clark et al. 1986i)and and hinsdalitehave beenknown for many years(Palache NOMENCLATURE OF THE ATUNITE SUPERGROUP r33r

soo SO,

AsOo POo waylandite "arsenowayl

SO,

FIc. 6. Minerals of the alunite supergroup with Bi as the predominant D-site cation Left diagram shows current nomenclature, and that on the right shows the effects of adopting a temary system. "Arsenowaylandite" (Scharm et aI. 1994) is not an approved name.

et al. l95l). Hidalgoite has the formula ratio SOa:AsOa SO+join as shown in Figure 7. The consequenceis that = 59:47, and the mineral was specifically named as the the field for hidalgoite, which includes the composition arsenate analogue of hinsdalite (Smith er al. 1953). oftype hidalgoite, would be overlappedby the new field Philipsbornite (Walenta et al. 1982) is somewhat for hinsdalite. Therefore, as was done for arseno- unusual in its high Cr content in TO+, for which goyazite,philipsbornite would be retained to designate AsOa:CrOa:SO+= 76:19 5. The small freld at the SO+ the As-dominant member. apex (Figs. 7, 8) has beenreferred to as "plumboalunite" (Novrik et al. 1994) and "plumbian alunite" (Sejkora er REE predominance al. 1998). However, if it is acceptedthat (Cu + Zn) substitution is non-essential,then the Pb-Al sulfate in this The REE-bearing minerals are characterized by a field is osarizawaite. predominanceof trivalent cations in D, and it has been Adoption of a ternary system for the Pb-dominant suggested(Scott 1987) that such minerals be classified members would pose some difficulties. In the system as the florencite group. Accepted minerals within the with Fe predominant in G, corkite and beudantite have group (Fig. 9) are florencite-(Ce), florencite-(La), priority, thereby requiring the abandonment of the re- fl orencite-(Nd), and arsenoflorencite-(Ce). Composi- cently named kintoreite and segnitite.In the systemwith tions corresponding to the La and Nd analogues of Al predominant in G, plumbogummite and hinsdalite arsenoflorencite-(Ce)have been reported by Scharm er have priority. Osarizawaite was named as the Al ana- al. (1991,1994), but the new nameshave not been sub- logue ofbeaverite, but the requirement, as will be dis- mitted to the CNMMN for approval. Adoption of a ter- cussed, is that neither be retained as a mineral name. nary system for the REE-dominant members would not Plumbogummite and hinsdalite thus occupy the PO+- affect the current nomenclature. 1332 THE CANADIAN MINERALOGIST

soo soo

rmbojarosite

plumbojarosite

/ kintor"it" segnitite beudantite Poo soo Po. ohilivsbornite plumbogummite philipsbornite \lumbogummite ,/

AI arizawaite

soo soo

Ftc. 7. Minerals of the alunite supergroupwith Pb predominant as the D-site cation. Left diagram shows current nomenclature. The mineral at the A1-SO4 apex is osarizawaiteif it is acceptedthat Cu is non-essential.Compositions are shown by Sejkora 'plumboalunite" et al. (1998) as extending into this field, which has been named by Nov6k e/ a/. (1994) Diagram on right shows the results of adopting a temary system.

Other minerals Other analogues

Eylettersite is considefedto be a Th-dominant mem- Numerous members of the alunite supergroup have ber of the crandallite group, with P as the main cation in been synthesized.Among those not known as minerals 70+ (Table 3). Hqryever, the calculated formulas also are the Rb* and Hg2+ analogues of jarosite; the Hg- incorporate substantiai(H+O+) in ZOa,and show exces- dominant and Pb-dominant phases described by sive Al (>3.5 mol) for G (Van Wambeke 1972). Such a Dutizac & Kaiman (1976) and Dutrizac et al. (1980) G-cation excess is untenable for an alunite-type min- are indexed with c = 33 A, but no diffraction line at 11 eral, and eylettersite is considered to need restudy. A was reported. Mumme & Scott (1966) also noted that Gallobeudantitewas defined ashaving subequalval- the 11 A line is absent from their synthetic plumbo- ues of AsOa and SO+, and a predominance of Ga in G jarosite. (Jambor et al. 1996). However, ZO4 compositions ex- Tananaevet al. (1961) preparedanalogues with Na, tend into the fields encompassedby Ga analogues of K, Rb, H3O, and NHa in D, and Ga in G. Only small segnitite, corkite, and kintoreite, thus permitting the in- amounts of various divalent metals other than Cu2+and troduction of three additional new names for the Ga- Znz* have been reported to be taken up by the alunite dominant minerals. The distribution of 7Oa values in supergroup. The In3+, V3*, and Cr3* analogues have the Ga minerals is such that adoption of a ternary sys- been synthesized (Dutrizac 1982, Dt;trizac & Dinardo tem would not reduce the number of potential new 1983,T,engauer et al. 1994):up to 0.6 mol V3* and 0.18 names.Also presentwith gallobeudantiteis the Ga ana- mol Crr* have beenreported in natural gorceixite (Johan logue of arsenocrandallite. et al. 1995), and Vr+ predominates at the G site in NOMENCLATIJRE OF THE ALUNITE SUPERGROUP r333

Stnucrunel Asprcrs

The classification of the alunite supergroup dis- cussedto this point hasbeen mainly chemical, and structural aspectshave been largely ignored. Numerous single-crystal X-ray structure studiesof the supergroup have been done, and the findings are summarized in Table 4. Most of these studies have revealed that the minerals have trigonal symmetry, with a x 7, c = 17 A, space group R3m, but several exceptions have been documented. The structures of alunite, jarosite, and plumbo- (1937), a -^ jarosite were first determinedby Hendricks who n)\-/4 concluded that becausealunite andjarosite show strong pyroelectric properties, their spacegroup must be R3m rather than R3m. In co_ntrast,plumbojarosite was determined to belong to R3m, and the Pb atoms showed an ordered arrangement that had the effect of doubling the c axis, i.e., the typical cell of a = 7, c = 17 A increased loa=7,cx34A. In addition to the data given in Table 4, severalstud- ies of synthetic analogues have been done, either by single-crystal or Rietveld methods. All of the studies, both on minerals and their synthetic equivalents,and on those not known as minerals, confirm that the basic topology of the structure remains the same regardlessof SO, chemical composition. Even where a monoclinic or triclinic system has been established, the structures are pseudotrigonal. Frc. 8 Compositionsof mineralswithin the Pb-dominant strongly field, asin Figure7, illustratingthe extensive range of ZOa The basic structural motif of the supergroupconsists solid solution Solidcircles: abridged data from Sejkoraer of TOa tetrahedra and variably distorted R-cation octa- al. (1998);open squares are compositions from Rattrayel hedra, the latter corner-shared to form sheets perpen- al. (1996\. dicular to the c axis. Substitutionsinvolving G therefore mainly affect the a dimension, and a increasesas Fe- for-Al substitutionincreases. The ZO+tetrahedra, which are aligned along [001], occur as two crystallographi- springcreekite (Table 3 ; Kolitsch et al. 1999a). Substan- cally independent sets within a layer; one set of TOa tial Sbs*-for-Fe3+ substitution in dussertite has been points upward along c, and this set altemates with an- documentedby Kolitsch et al. (1999b). other pointing downward. The oxygen and hydroxyl The vanadate(Tudo et al. 1973), chromate (Powers form an icosahedron,amidst which is the D cation. For et al. 1976, Cudennec et al. 1980), and selenate compositions with identical T tn TOq,the length of c is (Dutrizac et al. 1981, Breitinger et al.1997) analogues mainly influenced by the size of the D cation. have been synthesized,and substantial Cr has been re- Symmetry changes arise principally becauseof or- ported in the Z site in philipsbornite (Walenta et al. der-disorder relationships among the 7Oa tetrahedra,or 1982). Some analysesreveal Si, which has been as- because of order-disorder or distortion involving D signedeither as SiO+(as in kemmlitzite and eylettersite) sites. To maintain the space grotp R3m, the SO+-PO+- or as amorphous SiO2. Other substitutions, such as Nb AsO+ tetrahedra must be disordered; ordering, as has (Lottermoser 1990) and CO3, are possible but generally been found in corkite and gallobeudantite, reduces the not significant; analysesshowing percentagequantities symmetry to R3m. of CO2 (e.9., Frirtsch 1967) predatethe widespreaduse A second principal effect is related to the presence ofthe electron microprobe, and the high valuesreported of a divalent cation in D. In such a case, the standard in a few older analysesmay be the result of inclusions -7|+162+jarosite-type formula D*G3*3(SOa)2(OH)6becomes either of carbonateminerals. t(soo)r(og)ul, (ordered) or, D2* 112G3*3(Soa)2 Substitution of Cl for OH is rarely reported and, (OH)o (disordered). Thus in plumbojarosite, for example, where detected,amounts are small. Accounts of F sub- the D-site cation is Pb2*,and to maintain electroneutral- stitution are more cofirmon, and up to 4.'l wtVo F has ity, half of the D sites are vacant. Ordering of the Pb been determined to be present in gorceixite (Taylor et and thesevacancies produces a supercell,which is mani- al. 1984\. fested as a doubling of the c axis to 33-34 A. r334 THE CANADIAN MINERALOGIST Soo soo

Fe)Al fe>Al

AsOo PO, AsOu arsenoflorencite{Ce) florencite-(Ce) arsenofloren cite-(Ce) _(Nd)* -(La)*

Al >Fe Al )Fe

sou 500Soo

Frc 9. Minerals of the alunite-jarosite supergroup with REE as the predominant D-site cations. "Arsenoflorencite-(La)*" un6 "arsenoflorencite-(Nd;*" *" names (Scharm et al. 1991, 1994) that have not been submitted to the CNMMN for a vote. Diagram on right shows the effects of adopting a temiuy system.

A third principal effect is related to the charge of the Szymafiski (1985) has pointed out additional aspects ZOa group. Where ZOa is POa or AsOa rather than SOa, relevant to the crystal chemistry of the alunite super- an extra proton is required to maintain charge balance. group. Among these is the report by Loiacono et al. In crandallite, Blount (1974) concluded that the formula (1982) that the space group of their natural alunite is takes the form CaAl3[PO 30 1p(OH) 1p]2(OH)6, thereby R3m. For hydronium jarosite - schlossmacherite, achieving compensation by having partial substitution Szymafiski(1985) pointed out that "... the hydronium of hydroxyl for oxygen of the PO+ tetrahedron. ion, whether it remains in its original H3O+ form or Radoslovich (1982), however, determined that such a whether it is reduced to water, cannot have a centre of configuration would not be permitted in gorceixite be- symmetry and cannot be located at a centre of symme- cause of the larger size of Ba. He therefore concluded try. Any hydronium-for-cation substitution will destroy that the formula of gorceixite is best represented by the symmetry, and reduce the space group to R3m or BaAl3eO4)(PO3.OHXOH)6. lower. This is not to say that the hydrogen atoms of the It is possible, therefore, that order may exist without hydronium ion or the water molecule cannot be statisti- the necessity of having the 7 site occupied by different cally distributed or dynamically disordered, and hence elements (As, P, S). Furthermore, the crystal-structure give the structure the overall appearanceof having a determination (R = 0.0195) of unnamed PbFe3GO4)2 centre of symmetry." (OH,H2O)6 by J.T. Szymanski (Table 4) revealed that As with hydronium, the NHa ion cannot be accom- distortion at the Pb sites leads to two indeoendent Pb modated within R3m (Arkhipenko et al. 1985, Sema et atoms in the structure. Thus, a ruperstru.ture is formed al. 1986).However, as discussedby Szymahski (1985), in this mineral without the necessiw of havine D-site in the absenceofincontrovertible sfuctural data, the space vacancres. group of alunite minerals should be consideredas R3m. NOMENCLATURE OF THE ALUNITE SUPERGROUP I 335

TABLE 4 SINGLB-CRYSTALX-RAY STRUCTURESTTIDIES OF MINERALS IN TIIE ALUMTE SUPERGROTJP

Compositio4 oments a,L c, A spaegroup Ref.

alunite @mpo$uoDnor grvm 6970 17 27 Rim 1 natroalsite (Nao,slqrJAls(SO),(OH)6 6 990 16095 Bm 2 mimiite (Nao*Ig rCa".rrtrnr)Alr(Sq)r(O$. 6 981 33 490 R3m 3 4 JilOSrte not givq; synthetic 1 305 l7 l9O Rlm not giv€n;mtural 7304 17268 Rim 5 gorccixite monoclinic 6 [email protected](OID6 monoclinic* Cm 7 qmdallite Cao"At*P,*; CaAlrlPO3(O@(OIDdlr(OID6 7 005 16192 Rlm 8 woodhouseite not givm; CaAI,(PO*)(SO4XOID5 6 993 16386 Bm 9 goyuite not givm; SrAI3[PO3(O,"(OID,J]2(OI06 ? 015 16558 Rlm 10 svmbergite rot givs; SrAL(POa)(SO4XOID6 6992 16567 Rim 5 os@awilte Pb(Al, .rCuo,rFeo ,lq d(SO1)r(OH)5 70'15 17 I Rlm 1l plmbojaosite trot givd; structurefomula u below 720 3360 Rim 12 PboJq *So *; Pb[Fe(sOJr(o]D51, 7 3055 33 675 Em 13 bfldatite Pboe(FqsCuo@zrboilSO).lAsOJ.'(0II)6d 1 339 17 034 R1m 14 Pb,*(Fe,"Alo*)(AsOJr odsO4te(OEHp)6 7 3l5l I7 0355 Rlm 15 Pb,.(FerorAlorr)(AsO,)r B(SO)0'(OH,ILO)6 triclinic** 15 corkite Pbo*(Fer"Cuo *)(PO4)I.6(SOJ0*(Asq)o ml(OH)6q 7 ZaO 16821 R3m 16 hin$datite PbALleo,), 3r(so{Lcl(orr,H,o)5 7 029 16789 Rim f'l galobildantite Pbl u(Gal fAli laFeoszno ilGei 6XAsO{)r&(SQI *(OIO" 7 225 1703 R3m 18 " plmbogwite PbALI(PoJ, s(Aso)o,J(oI!H,o). 7 039 16761 Bm 17 't '19 kirio!eite PbFq(POJ',(AsOn)ur(SO4)03(OII,Hp)6 331,0 16885 Bm du$ertite Ba(Fd.' s4sb*o,b)3(Aso"),(ollHp). 7 410 l'l 484 Rlm 20 nnnnrBed PbooFq n,@Oo),,,(SOn)o ,(OI1I4O)' ,, 7 28A5 33 680 R3m 21 florencite-(Ce) (CeoalrorNdo,rSmo*Car*)A1r(PO,l(OlD. 6912 16-261 Bm 22

* a 12 195,b 7 o4o,c ? 055A 0 125 l0' S@slro BlEnchdd (1989) * * q 7 3r9, b 7 309,c 17032 A, a 90 004,p 90 022,y 11997 4" Referenes:7 Wngetdl.(1965),2 Okedaetal0982), 3 O$ska"t4l. (1982),4 Mf,chetti&Sabeli(1976), 5 Kato &M{m(1977),6 Radoslovich&Slade(1980),? Radostovich(1982), E Blout(1974),9 Kato097l, 1977)' l0 Ksto (1971,198?), 1 I Giuseppetti& Tadini(1980), 12 Hendricks(1937), who alsogave reflrlts for aluite edjeositq 13 Szf- miski (1985), 14 Giuseppelti& Tadini(1989), 15 SzJmiski (1988), 16 Giuseppetti& Tadini(1987), 17Kolitsh etdl.(1999c), 78 lanboretal (1996), 19 Khdirueta/. (1997),20 Kolitsch€tdl (1999b),2l IMANo 93-039, 22 Kato(1990)

Formula calculations Significance of the supercell

Various methods have been used to calculate the Regardless of symmetry variations (Table 4), the formulas of minerals in the alunite supergroup.Among topology of the unit cell of all minerals in the family the most common are normalization to 14 oxygen at- can be related to a rhombohedral cell that has hexago- oms, or to TO4 = 2. Some authors (e.g., Scharm et al. nal dimensions of a x 7, c N l7 A. The development of 1991,Novrik & Jansa1997, Sejkoraet al. 1998)have a supercell with c = 2 X l7 A can arise becauseof or- used G3(IOa)2 = 5. Use of TOa - 2 is preferred here dering ofD-site cations, regardlessof whether D con- becausenonstoichiometry in both D and G is common, tains vacanciesor is filled completely. Moreover, order particularly in synthetic samples. To paraphrase does not require the presence of a combination of Szymafrski(1985), use of ZO4 = 2 has a sound struc- monovalent and divalent cationsin D, but can take place tural basisbecause "... it is inconceivableto visualizea solely with monovalent ions (Dutrizac & Jambor 1984). stablejarosite structure with vacanciesin the [TOa] lay- Many rapidly crystallized syntheticproducts show signs ers as well." of an ordered structure,and it is inconceivablethat some A second difficulty in formula calculations is that of the commonly more slowly crystallized natural min- hydronium cannot be determineddirectly. This problem erals would not be ordered.On the other hand, synthetic is not significant for most of the minerals in the super- Pb-H3O systemsshow various degreesof disorder, and group, but it doesemphasize the precarious statusof the synthetic plumbojarosite without detectablediffraction sole composition available for schlossmacherite, for effects due to a superstructureis well known. At the which D is [(H:O)o :zno z8ca026].Ia0 07Ko s5Sr6 slBao s1l. opposite extreme, in their X-ray structure studies both r336 THE CANADIAN MINERALOGIST

Hendricks (1937) and Szymairski (1985) used plumbo- like structure.For minerals of the alunite supergroup,a jarosite from the Tintic Standardmine, Utah, for which similarly simplified system of nomenclature system an exceptionally high degreeof order was found; in the could be adopted such that: (a) no modifier accompany case of the latter author at least, the material was se- the mineral name if the unit cell has not been deter- lected specifically becauseX-ray powder patterns had mined, or if only one structure type is known; (b) if there previously indicated an exceptionally high degree of is a need to distinguish between the conventional cell order to be present. and the supercell, the former should be designated lc, If minerals in the alunite supergroup are to be named and the latter 2c, each followed by the standard simply on the presenceor absenceof the c-axis super- (CNMMN-approved) abbreviation for the unircell type structure, the potential for the introduction of "trivial" [1: hexagonal,rt: rhombohedral, M: monoclinic, A: tri- names will increase enormously. I believe that detec- clinic (anorthic), erc.l. Note that it is important to retain tion of the superstructurewill become more common the c to avoid confusion with the nomenclature desig- once there is an increasedawareness of the sisnificance nations for polytypes. Thus, for example, rhombohedral of the I I A powder-diffraction line or peak. plumbojarositelacking a superstructurewould be named plumbojarosite-lcR, and that with a superstructure Recol,rlr,rewoauoNsoN Noprexcr-erunE would be plumbojarosite-2cR. Monoclinic gorceixite remains as gorceixite, but if a doubled c axis for the If the proliferation of mineral names in the alunite monoclinic cell were to be found, the nomenclature supergroup is to be avoided, two properties or factors would distinguish gorceixite-7cM and gorceixite-2cM. must be addressed:(a) crystallographic, and (b) chemi- It has not yet been proved that gorceixite with a con- cal. In some casesthese factors are independent,as for ventional rhombohedral cell exists, but such a mineral example minamiite and as-yet-unnamedmineral IMA would simply be designatedas gorceixite-lcR. No. 93-039, both of which are distinguished from Adoption of such a system would involve the fol- previously named minerals solely on the presence of lowing nomenclaturechanges or revisionsin: standard cell versus supercell relationships. The fund- 1. Minamiite, which is fundamentally different from amental topology of the alunite structure remains the natroalunite only in order-disorder relationships, is same regardlessof space group or symmetry changes. natroalunite-2cR. The fundamental cell is rhombohedral, space group 2. Monoclinic gorceixite, assuming that the rhom- R3m, with a x 7 and c = 17 A as expressedwitli hex- bohedral form also exists, would not be entitled to a agonal parameters.Slight distortion of this cell can lead trivial name. to orthorhombic (Jambor & Dutrizac 1983), monoclinic 3. Triclinic crandallite, reported by Cowgill et al. (Radoslovich 1982),or triclinic (Szymairski 1988)poly- (1963), ifverified, would be designatedcrandallite-lcA. morphs, and patterns of order of various kinds can lead 4. Triclinic beudantite reported by Szymafiski to a doubling of c. (1988) would be designatedwith the suffix lcA. 5. Unnamed rhombohedral mineral IMA No. 93- Crystallo graphic aspects 039 would likewise adopt the appropriate already established name, together with the suffix 2cR. Various systems have been used to accommodate 6. Beaverite is cuprian plumbojarosite without su- structural changeswithin a mineral group while main- perstructure reflections. Beaverite is therefore cuprian taining a comprehensible nomenclature. For example, plumbojarosite-1cR. Pring et al. (1990) used the CNMMN-approved name 7. Orthorhombic jarosite with the doubled c and baumhauerite-2a to designate a silver-bearing mineral composition K6e6Fe2qo(SO+)z(OH)616 (Jambor & having a superstructurederived from a baunihauerite- Dfiizac 1983) is jarosite-2co.

TABLE 5 SI]MMARY OF POTENTIALLY CHANGED NOMENCLATURE FOR A TERNARY COMPOSITIONAL SYSTEM

Previous nue Prwiously wmed

mitmiite nahoalunil€-2cI triclinic qedallite crmd.llite 1cl huugite woodhoureite-2cR triclinic beudmtite b@ddtite- lc,{ kef,nrlitzite menogoyuite rhombohedral kiatoreite corkite2cR b@vqite cupriu plufi$ojdositelcR orthorhombic juosite jtosite-2co kintoreite @rkite segilwe bodmtite hidalgoite hinsdalite osrizawaite hinsdalite NOMENCLATURE OF THE ALUNITE SUPERGROUP r337

Compositional aspects (b) Osarizawaite:Cu:(Al,Fe) is not 1:2, and Al rs predominant. Two approachesare used, namely, (a) an evaluation (c) Minamiite is compositionally equivalent to in terms of the existing (Scott 1987) system of nomen- natroalunite. but has c ! 33 A. Mineral IMA No. 93- clature, and (b) an evaluation on the basis of a ternary 039 (Table 4) could be given a trivial name on identical compositional system.Neither systemtakes into account grounds. possible miscibility gaps, which have not been proved (d) Benauite: the compositional field doesnot coin- to exist within the alunite supergroup, although such a cide with that of the ideal formula. possibility is highly likely. For example, Stoffregen & (e) Eylettersite requiresre-examination becausethe Cygan (1990) have argued that a miscibility gap may formula(s) exceed acceptablelimits for minerals of the exist on the simple alunite-natroalunite binary join if alunite supergroup. theseminerals crystallize under equilibrium conditions. (f) The possible triclinic analogue of crandallite Under nonequilibrium conditions, however, a gap is not (Cowgill et al. 1963, Blount 1974) requires re-exami- evident.Numerous proposalsfor miscibility gapsamong nation both with respectto composition and symmetry; minerals other than the alunite supergroupcan be found no single-crystal X-ray study has been done, and the in the literature, but in many casesthe purported gaps formula deviates significantly from that of the alunite simply reflect plots of existing chemical data, without supergroup. good evidencethat the gapscannot be breached.For the (g) Orpheite, a Pb-Al phosphate-sulfate, is vari- alunite supergroup,it is likely that it will be many years ously classified as in (Gaines et al. 1997) or out before miscibility gaps can be incontrovertibly demon- (Mandarino 1999) of the alunite supergroup.Fleischer strated to exist. This aspect,therefore, is not taken into (in Fleischer et al. 7976) concluded that orpheite is considerationin this review of nomenclature;neverthe- hinsdalite, but orpheite has retained speciesstatus. less, it is evident that, over the long term, the multicom- paftment systemin current use for alunite nomenclature AcrNowrsocrvsrvrs would fare less well in terms of avoiding complexity than would a ternary system. The initial version of the manuscript was examined If a ternary system of nomenclature,combined with by, among others,J.E. Dutrizac, J.D. Grice, U. Kolitsch, the superstructure-symmetrynotation, were adoptedfor J.A. Mandarino, E.H. Nickel, and A.C. Roberts. I am the alunite supergroup,the following would result: grateful for their comments and, in some cases, their 1. Alunite group with monovalent ions in D: re- strong encouragementto continue to pursue the nomen- moval of minamiite, beaverite, and osarizawaite, and clature issues.I am also thankful to W.D. Birch for his expansion of the compositional fields as shown in Fig- appreciable input during the formative stages of this ure 2 (right). review, to P. Bayliss for incisive and useful refereecom- 2. Ba predominant in D (Fig. 3): the compositional ments, and to R.F. Martin both for editorial comments field available for a "weilerite"-t1pe mineral disappears. and for acceptingthat this review of nomenclaturemer- 3. Ca predominant in D (Fig. 4): huangite is ited airing. Acknowledgement is not intended to imply woodhouseite-2cR. agreementwith the views that have been expressed. 4. Sr predominant in D (Fig. 5): kemmlitzite is no longer retained. RrpBnsNcBs 5. Bi predominant in D (Fig. 6): no change other than expansion of the compositional fields. Ar-raNnn,S P.,FrrzpArRrcK, J.J., KnonN, M.D., Bnrrt B,P.M., 6. Pb predominant in D (Fig. 7): for Fe > A1, corkite HAvBA,D.O., coss, J.H. & Bnown,Z.A. (1988):Ammo- and beudantite have priority, so that kintoreite and nium in alunitesAm Mineral.73, I45-I52. segnititeare no longer retained.Similarly, hinsdalite has AnKureeuro,D.K., DBvv.crrrne,E.T. & PAL'cHrK,N.A. priority over hidalgoite, and the latter is no longer re- (1985):Local symmetryof ammoniumions in the struc- tained. tureof aluniteand jarosite.ln Crystal Chemistry and Struc- 7. REE predominant in D (Fig. 8): no change other tural Typomorphismof Minerals.Nauka, Leningrad, Rus- than expansion of the compositional fields. sia(151-155; in Russ). The nomenclature changes are summarized rn Table 5. Ber-leZuNr6, T., MoELo,Y , LoNean,Z. & MrcrsH-sEN,H. (1994):Dorallcharite, Tls 3K62Fe3(SOa)2(OH)6, a new CoNcrusroNs memberof thejarosite-alunite family. Eur. J. Mineral.6, 255-263. Independentof any new nomenclatureproposals, the BrncH,W.D., pnrNc, A. & GlrEsousB,B.M. (1gg2):Segnitite, following minerals and namesrequire reappraisal: pbFe3H(AsOa)2(OH)6,a new mineral in thelusungite group (a) Beaverite: Cu:(Fe,Al) is not 1:2, and Fe is pre- from BrokenHill, New SouthWales. A11stralia.Am. Min_ dominant. era1.77.656-659. 1338 THE CANADIAN MINERALOGIST

BL,qNcHeno,F.N. (1989): New X-ray powder data for & -(1981): Selenateanalogues gorceixite, BaA1:(PO+)z(OH)5.H2O, an evaluation of d- of jarosite-type compounds. Hy drometall 6, 327-337 spacingsand intensities, pseudosymmetryand its influence on the f,lgure of merit. P ow de r Diffrac tion 4, 22'7-230 & JAMBoR.J.L (1984): Formation and characterization of argentojarosite and plumbojarosite and their rel- Br-ouNr, A.M. (1974): The crystal structure of crandallite.Arn. evance to metallurgical processing. In Proc. Second Int. Mineral. 59,4l-47. Congress on Applied Mineralogy in the Minerals Industry (W.C. Park, D M. Hausen & R.D. Hagni, eds.). AIME, BnBrlBNsrBru, B., ScHLUTER,J. & Gssuenl, G. (1992): On New York. N.Y. (507-530). beaverite:new occurrence,chemical data, and crystal struc- trne. N eue s Jahrb. M ineral., M onats h., 213-220. & KAIMAN, S (1976): Synthesis and properties of jarosite-typecompounds Can.Mineral. 14, 151-158. BnlrrrNcBn, D.K., KnlnclsrElN, R., BocNER,A., ScHwAB, R.G., Pnapr,T.H., Mosn, J. & Scturow, H. (1997): Vi- Fr-rtscHsn. M 0962): New mineral names.An. Mineral- 47 , brational spectra of synthetic minerals of the alunite and 414-420. crandallite type. J. Molecular Structure 4081409,28'7-290. -(1967): New mineral names Am. Mineral. 52,1579- Bnopsv, G.P., Scorr, E.S & SNu-r-cnovr, R.A (1962): 1589. Sulfate studies. II. Solid solution between alunite and jarosite 4m. Mineral 47,112-126. (1970): New mineral names.Am. Mineral. 55,317' 323. & SnBnoeN, M.F. (1965): Sulfate studies. IV. The jarosite - natrojarosite - hydronium jarosite solid solution PABST,A., Menoannro, J.A., Ctuo, G.Y. & Cernr, series.Am. Mineral. 50, 1595-1607 L.J |1976i: New mineral names.Am. Mineral.6l,174-186

Cr-enr, A.M. (1993): Hey's Mineral Index. Chapman & Hall, FORrscH,E.B. (1967): "Plumbogummite" from Roughten Gill, New York. N.Y Cumberland. Mineral. Mag 36,530- 538.

CoupBn,A.G., Erraenrv, P.G & FBnn,E.E. (1986): GerNes,R.V., SrrNNsn,H.C.W., Foono, E.E, MASON,B & Waylandite: new data from an occurrencein Cornwall, with RosENZwEIG,A. (1997): Dana's New Mineralogy. lohn a note on "agnesite".Mineral. Mag.50,731-733 Wiley & Sons, New York, N Y.

ConrsI-pzzI. C R. (1977): Occurrence of osarizawaite in Ar- GrusreeEtr, G. & Teorxr, C (1980): The crystal structure of genlina.N eue s J ahrb. M ineral., M onat sh., 39- 44. osarizawaite.Neues Jahrb. Mineral, Monatsh.,401-40'7'

Cowcnr-, U.M., HurcsINsoN, G E & JoENsuu,O. (1963): An & - (1987): Corkite, PbFe:(SO+)(PO+) apparently triclinic dimorph of crandallite from a tropical (OH)0, its crystal structue and ordered arrangement of the swamp sediment in El Pat6n, Gtatemala. Am. Mineral.48, tetrahedralcation s. N eues Jahrb. M iner al., M omt sh., 7 | -81- lt44-1153. & - ( 1989):Beudantite: PbFe3(So4XAso4) CurBNNnc,Y., Rrou, A, Bor.{NIN,A. & CaILLer, P. (1980): (OH)6, its crystal structure, tetrahedral site disordering and Etudes cnstallographiques et infrarouges d'hydroxychro- scatteredPb distribttion. NeuesJahrb. Mineral, Monatsh., mates de fer et d'aluminium de structure de I'alunite. Rev. z t-JJ. Chimie Mindrale l7, 158-167. Har, J., JourN, 2., Kvabsr, M. & LrssscHsn, W. (1969): DE BRUryN,H., VAN DERWESTHUTzEN, W A., BBurBs, G.J. & Kemmlitzite, a new mineral of the woodhouseite group. Mrvnn, T.Q (1990): Corkite from Aggeneys, Bushman- Neues Jahrb. M ineral., M onatsh., 2O1-212. land, South Africa. Mineral Mag. 54,603-608. HARTrc. C.. BneNo, P. & BoHMHAMunr, K. (1984): Fe-Al- Ds OLrvBrRA,S.M.B., BLor, A., INTnERNIoN,R.A.L. & MAGAT, isomorphie und Strukturwasser in Kristallen vom Jarosit- P. (1996): Jarositae plumbojarosita nos gossansdo distrito Alunite-Typ. Z. Anorg. AIlg. Chem.508, 159-164. mineiro de Canoas (PR). Rev Bras GeociAnc.26,3-I2 HENDRTcKS,S.B. (1937): The crystal structure of alunite and Durnrzac, J.E. (1982): The behavior of impurities during the jarosites.Am. Mineral. 22,773- 784. jarosite precipitalion. In Hydrometallurgical ProcessFun- damentals (R.G Bautista, ed.). Plenum Press, New York, IlnsroNsn, J.P , LB Toulr-Bc, C. & PBnnorel, V. (1986): About N Y. (125-169). the synthetic lead-silverjarosite solid solutions Int. Symp on Experimental Mineralogy and Geochemistry (Nancy), & DrNanoo,O. (1983):The co-precipitationofcop- Abstr.Vol..12-'73. per and zinc with lead jarosite. Hydrometall l1., 6l-78. IMA ( I 968): International Mineralogical Association: Com- & KArNrAr'r,S. (1980): Factors affecting mission on New Minerals and Mineral Names. Mineral' lead j arosite formation. Hy dr ometall. 5, 3O5-324. Mag.36,131-136. NOMENCLATURE OF THE ALUNITE SUPERGROUP 1339

Jlrvreon,J.L & Durnrzlc, J.E. (1983): Beaverite-plumbo- and structure refinement by the Rietveld technique and a jarositesolid solutions.Can. Mineral.21, 101-113. compilation of alunite-type compounds. Powder Dffiac- tion 9.265-217 & _ (1985): The synthesisof beaverite Can. Mineral.23,47-5L LI, GEJrNc,Psacon, D.R, EssrNe,E.J., BnosNeruN, D R. & Bs,Alre,R E. (1992): Walthierite, Ba65n65A13(SOa)2 OwtNs, D.R , Gntce, J D. & FsrNcr-os, M.D. (OH)6, and huangite, CaosEosAl:(SO+)z(OH)0, two new (1996): Gallobeudantite,PbGa:[(AsO+),(SO+)]z(OH)e, a minerals of the alunite group from the Coquimbo region, new mineral species from Tsumeb, Namibia, and assocr- Ch1le.Am. Mineral. TT, l2'15-1284 ated new gallium analoguesof the alunite-jarosite family. Can. Mineral 34, 1305-1315. LorecoNo, GM., KosrEcKy, G. & Wmrp, J.S., Jn. (1982): Resolution of space group ambiguities in minerals. An JonnN, 2., JoHAN, V., Scuenu, H. & Pouea, Z. (1995): Mineral. 67. 846-847. Mindralogie et gdochimie des tenes rareset du chrome dans les cherts prot6rozoiques de Kok5in, Rdpublique tchbque. Lorrnnrraospn,B.G. (1990): Rare-earthelement mineralisation C.R. Acad. Sci. Paris 321, Sdr. IIa, lI27-1138. within the Mt. Weld carbonatitelaterite, Westem Australia Lithos 24, 15I-167. K,rro, T (1971): The crystal structures of goyazite and woodhouseite N eue s J ahrb. M ineral., M onats h.. 241-247 MeNrenrNo, J.A. (1999): Fleischer's Glossary of Mineral Spe- clas Mineralogical Record, Tucson, Arizona. (1977): Further refinement of the woodhouseite structure. Neues Jahrb. Mineral., Monatsh, 54-58 Marsuslnl, S , Kero, A., MarsuyAlral, F & Krvorn, K. (1998): Huangite ftom Okumanza, Gumma Prefecture,Ja- _ (1987): Further refinement of the goyazite structure. pan. Mineral J. 20, 1-8 (in Japanese). Mineral. J. 13,390-396 MENcHErl, S. & SansLLr,C. (1976): Crystal chemistry of the (1990): The crystal structure of fTorcncite.Neues alunite series: crystal structure refinement of alunite and Jahrb. Mine ral., M onatsh.. 227-23 L synthetic jarosite. Neues Jahrb. Mineral , Monatsh.,4O6- 4t7. & Mniu, Y (1977): The crystal structures of jarosite and svanbergite.Mineral. J. 8,419- 430. Munrr.tn,W G. & Scorr, T R. (1966): The relationship between basic ferric sulfate and plumbojarosite. Am. Mineral. 51, KnenrsuN, Teyr-oR,M.R., BEvAN,D.J.M. & PnrNc,A. (1997): 443-453. The crystal structureof kintoreire, PbFe3(POa)2(OH,H2O)". Mineral Mag. 61, 123-129. NICKEL,E.H. (1992): Solid solutions in mineral nomenclature Can. M ineral. 30, 231-234. Kot-rrscH, U , PrrNc, A., TeyloR, M.R. & Far-r-oN,G (1999a): Springcreekite,B a(V3*,Fe)3(pO4)2(OH,H2O)6,a new mem- NovAr, F. & JeNsA.,J. (1997): Minerals of the crandallite and ber of the crandallite group from the Spring Creek mine, kemmlitzite group from Upper Carboniferous sedimentsat South Australia: the first natural V3+ member of the alunite Bbl6 and Libbtdt in the Krkonobe piedmont basin, northem family and its crystal structure. Neues Jahrb Mineral., Bohemia. Vbstnik aesk6ho geol. ristava 72,361-3'77 (in Monatsh.. 529-544. Czech).

Suor, P.G, Trcrrxr, E.R.& PnrNc,A. (1999b): & PnacHe[. | (199$: Classification The structue of antimonian dussertite and the role of anti- and nomenclature of alunite-iarosite and related mineral mony in oxysalt minerals. Mineral. Mag 63, 17-26. groups V?srnikteskdho geol ilsrava 69.51-57.

TTEKTNK,E.R.T., Srnor, P.G., TAyLoR, M.R_ & Paur-rS,P. & JANSA,J (1998): Crandallite, PnrNc, A. (1999c): Hinsdalite and plumbogummite, their gorceixite, goyazite and kemmlitzite from pyrope-gravels atomic arrangementsand disorderedlead sites.Ear. J. Min- of the Cesk6 stiedohoff Mts. VEstnik Ceskiho seol. rtstuva eral. ll,513-520. 73.r01-trl.

KuBISz,J. (1960): Hydroniumjarosite- (H3O)Fe3(SOa)2(OH)6. & MoRAVEc.B. (1997): Minerals of the Bull. Acad. Polon. Sci.,Sir. Sci. Gdol. G6ogr. E, 95-99. goyazite - svanbergite series and kemmlitzite from the Vestiev pyrope deposit near Hastinn6, northern Bohemia. (1970): Studies of synthetic alkali-hydronium VEstnik Ceskdhogeol. itstava 72, 3'13-380(in Czech). jarosites. I. Synthesesof jarosite and natrojarosite.Mine ral. Polonica l,47-57. Oouu, J.K., Heupp,P.L. & Fernow, R.A. (1982): A new oc- cunence of ammoniojarosite in Buffalo, Wyoming Can. LBunoN, D.M. (1937): Woodhouseite, a new mineral of the Mineral. 20,9l-95. beudantite grotp. Am Mineral 22, 939-948. Or.toa, K., Hrnaney,rsHr, J & Oss,q.r,q,,J (1982): Crystal LsNcausn, C.L., GrBsrrn, G & Inn.lN, E. (1994): KCr3(SOa)2 structureofnatroalunite and crystal chemistry of the alunite (OH)6: synthesis,characterization, powder diffraction data, group Neues Jahrb. Mineral., Monatsh,534-540 1340 THE CANADIAN MINERALOGIST

Soce,H., Ossere,J. & Orsur-q,N. (1987):Syn- (Nd) from the uranium district in northern Bohemia, thesis of minamiite type compounds, Mo sAl:(SO+)z(OH)o Czechoslovakia. easopis mineral. geol. 36, 103-113. with M = Sr2*, Pb2* and Ba2+ Neues Jahrb. Mineral., Monatsh.,64-70. Scruprzrn. K., OrrsN{eNN, J & BeNr, H (1980): Schloss- macherite, (H:O,Ca)At:[(OH)o | ((S,As)O+)2],ein neues Ossere, J., HrnasavasHr, J.-I., Or.qo.A,K. & KosavesHr, R. Mineral der Alunit-Jarosit-R eihe. N eue s J ahrb. M ineral., (1982): Crystal structure of minamiite, a new mineral of Monatsh.,2l5-222. the alunite group. Am. Mineral. 67, ll4-119. Scrwes, R.G., Gorz, C., Honolo, H. & hNro DEOLIvsrRA, N. Orsure, N, HrnAslvesHr, J., Orala, K. & SocA, (1991): Compounds of the crandallite type: synthesis and H. (1987): Synthesisof minamiite, CaosAl:(SO+)z(OH)0. properties of pure (Ca,Sr,Ba,Pb,La,Ceto Eu)-arsenocran- Neues Jahrb Mineral., Monatsh., 49-63. dalIites.Neues Jahrb. Mineral , Monatsh.,97-172.

PAAR, W H., BuRGsrALr-Bn,J. & CHSN, T.T. (1980): & PrNro ne Orrvsrnl, N. Osarizawaite-beaverite intergrowths from Sierra Gorda, (1990): Compounds of the crandallite type: synthesis and Chlle.Mineral. Rec.ll. 101-104. properties of pure goyazite, gorceixite, and plumbogummite. N eue s J ahrb. M ineral., M ondtsh., 113 - 126. Per-ecnn, C., BBru.raN,H. & Fnor.,nBI-,C. (1951): The System (1987): of, of Mineralogy (seventh ed.) 2. John Wiley & Sons, New Scorr. KM. Solid solution in, and classification York, N Y. gossan-derived members of the alunite-jarosite family, northwestQueensland, Australia. A m. Mineral. 72, 1'18-187. PARKER,R.L (1962): Isomorphous substitution in natural and V., NovolNA, M. & EDERovA,J. synthetic al:unrte.Am. Mineral 47,127-136. SEJKoRA,J.,6rrxa, J.,SnBN, (1998): Minerals of the plumbogummite-philipsbomite deposit, Kru5nd Hory Mts., Czech Pownns, D.A., Rossrr,raN,G.R., Scuucln, H J & Gnav, H.B. series from Moldava Mineral., Monatsh (1976): Magnetic behaviour and infrared specffaofjarosite, Republic. Neues Jahrb. ,145-163. basic iron sulphate, and their chromate analogs. l. Solid C.J.. Pauol ConrINl, C. & Gencn Reuos, J.V.G. StateChem.13, 1-13. SenNa. (1986): Infrared and Raman study of alunite-jarosite com- powds. Spectrochim Acta 42I^, 129-734. PnrNc,A., BrncH, W.D., DAwE, J., T.r.vlon, M., DuENs, M. & WALeNrn, K. (1995): Kintoreite, PbFe3(PO4)2(OH,H2O)6, SlnrH, D.K., RoBERrs,A.C., BAvrrss,P. & Lmseu, F. (1998): a new mineral of the jarosite-alunite family, and lusungite A systematic approach to general and structure-type for- discredited. Mineral. Mag 59, 143-148. mulas for minerals and other inorganic phases.Am. Mm' eral. 83, 126-132. SBwnrr, D., GRAESER,S., ErsNHAnrrn, A. & Cnroors, A. (1990): Baumhauerite-2a: a silver-bear- SvnH, R.L., Snr,roNS,F.S. & Vlrsnrs, A C. (1953):Hidalgoite, ing mineral with a baumhauerite-like supercell from a new mineral. Am. Mineral 38, 1218-1224. Lengenbach, Switzerland Am. Mineral. 75, 915-922. Sporl, C (1990): Authigenic aluminium phosphate-sulphates Reooslovrcn, E.W (1982): Refinement of the gorceixite in sandstonesof the Mitterberg Formation, northern Cal- structure in Cm. Neues Jahrb. Mineral., Monatsh., 446- careousAlps, Atstrra. Se diment o Io gy 37, 837-845. 464. SroprnscsN, R.E & ALPERS,C.N. (1987): Woodhouseite and & Shos, P.G. (1980): Pseudo-trigonal symmetry svanbergitein hydrothermal ore deposits: products of apa- of gorceixite. Neues Jahrb. Mineral., and the structure tite destruction during advanced arglllic allerutton. Can Monatsh.,l5'7-170. Mineral. 25,201- 211.

Rerrn-Av, K.J., Tevlon, M.R., BBvlN, D.J.M. & PRTNG,A. & Cvc.lN, G.L. (1990): An experimental study of (1996): Compositional segregationand solid solution in the Na-K exchangebetween alunite and aqueoussulfate solu- lead-dominant alunite-type minerals from Broken Hill, tions. Am. Mineral 75,209-220. N.S.W. Mineral. Mag. 60, 779-785. Szwe(rsxr, J.T. (1985): The crystal structureof plumbojarosite RocA, A., VNar-s, J., Annmz, M. & Car-Bno,J. (1999): Char- PblFe:(SO+)z(OH)alz.Can. Mineral. 23, 659-668. acterization and alkaline decompositiorVcyanidation of beudantite -jarosite materials from Rio Tinto gossanores. (1988): The crystal structure of beudantite, Can. Metall. Quart. 38, 93-103. Pb(Fe,Al):[(As,S)O4]2(OH)6. Can. Mineral. 26, 923-932'

Scnanru, B., ScHanrraovA,M. & KUNDRAT,M. (1994): TAGUCHI,Y. (1961): On osarizawaite, a new mineral of the Crandallite group minerals in the uranium ore district of alunite group, from the Osarizawa mine,Japan. Mineral. J. northem Bohemia (CzechRepublicl. Vb srnik a eskd h o geol. 3, 181-194 fistava69,'79-85. TANANAEV,I.V., KuzNErsov, V.G & Bol'sHerove, N.K. Surovsri, P. & KUuN,P. (1991) (1967): Basic gallium salts of the alunite type. Russian J. Philipsbornite, arsenoflorencite-(La),and arsenoflorencite- Inorg. Chem. 12,28-30. NOMENCLATURE OF THE ALUNITE SUPERGROUP 134l

TAyLoR, M , SunH, R W. & Anr-pn, B.A. (1984): Gorceixite & Duuu, P.J. (1984): Arsenogoyazit, ein neuesMin- in topaz greisen assemblages,Silvermine area, Missourr. eral der Crandallitgruppe aus dem Schwarzwald. Schweiz. Am. Minerol. 69, 984-986. Mineral. PetroBr. Mitt. 64, 7l-19

TsvnteNova, I. (1995): Corkite from Brussevtzi deposit, East & _(1993): Arsenogorceixit von der Grube Rhodope massif, Bulgaria. DokI Bulg. Akad. Nauk 48,47- Clara im mittleren Schwarzwald. A ufschluss 44, 250-254. 50. ZwTENER,M. & DuNr,r,P.J. (1982): Philipsbornit, TuDo, J., LAILACE,G, Tecsez, M. & THEosaLo,F. (19731: ein neues Mineral der Crandallitreihe von Dundas auf Sur l'hydroxysulfate VOHSO4. C.R. Acad. Sci.Paris 277, Tasmanien.Neues Jahrb. Mineral.. Monatsh.. 1-5. Sdr. C,767-'17O. WaNc, R., BRADLEv,W.F & SrrrNpnrr, H. (1965): The crys- VAN TASSEL,R (1958): Jarosite, natrojarosite, beaverite, tal stfucture of alunite. Acta Crystallogr. 18, 249-252 leonhardtite et hexahydrite du Congo belge. BuIl Inst. royal Sci. naturelles Belge 34, l-12. Wrsr, W.S. (1975): Solid solution between alunite, woodhouseite,and crandallite mineral series.Neaes Jahrb. Mtn- VeN Wnvstrr, L (1972): Eylettersite, un nouveau phosphate eral., Monatsh., 540-545. de thorium appartenant i la sdrie de la crandallite. Billl. Soc fr. Mindral. Cristallogr. 95, 98-105. YerHoNrovl, L K., DvUREcHENSKAyA,S.S., SlNno- rr,rrnsxav,t,N.E., SBncBrva, N.E. & PALCrilK,N.A. (1988): (1975):La za:rite, un nouveau mindral appartenant Sulfates from the cryogenic hypergenesiszone. New find- d la sdrie de la crandallite. BulI. Soc. fr. Mindral. ings Nomenclature problems. Mineral. Zh 10,3-15 (rn Cristallogr. 98, 351-353. Russ.).

Wer-BNrlr, K. (1981): Mineralien der Beudantit-Crandallit- ZneNc Ruso, Y,qNc Nr,lNznpN, YI SHUANGTTNc& Du gruppe aus dem Schwarzwald: Arsenocrandallit und CnoNcI-IlNc (1987): Arsenogoyazite discovered in sulfatfreier Weilerit. Schweiz. Mineral Petrogr. Mitt. 61, Xinjiang, China. Acta Mineral Sinica 7, 313-316 (in Chr- 23-35. nese).

BIRCH,W.D. & Dt,.l+N,P.J (1996): Benauite, a new mineral of the crandallite group from the Clara mine in the ReceivedJune I 1, 1999, reyised mnnuscript acceptedNovem- central Black Forest, Germany. Chem. Erde 56, l7I-1i6. ber 12,1999.