NOMENCLATURE OF THE ALUNITE SUPERGROUP

1323
The Canarlian Mineralogist
V o l . 3 7 .p p . 1 3 2 3 - 1 3 4t1I 9 9 9 )
NOMENCLATURE
OFTHEALUNITE
SUPERGROUP
JOHN L. JAMBORS
Depat'tment
of Earth and OceanSciences,
Universityof British Columbia,Vancouver,
British ColumbiaV6TlZ4, Canadn
Aesrnlcr
The alunite supergroupconsistsof 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 recommended 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, several inconsistencies
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, several other 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 concordance sont relevds; d titre d'exemple, la beaverite et 1'osarizawaite, auxquelles on attribue couramment les formules
Pb(Cu,Fe)3(SOa)2(OH)6
et 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 aussiOtrevariable. 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, compos1t10ns.structures.
E E-mail address:jlj @wimsey com
t324
THE CANADIAN MINERALOGIST
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 previgroups 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 numthat 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 incorin_(7Oa)2is 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) prothe 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)2representsone 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 propacan 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 comMineralogy (Palache et al. I95l), wherein the alunite plex and promisesto be increasingly so if the CNMMNgroup 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 beenrecognizedto
etc." , andtheplumbogummite group is equivalent to the occur within the supergroup. In the following discuscurrent 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 crysevident 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
sensustrictohaveSO3contentsof 12.30and 74.82wt%a, equal fields (Fig. 1, left), which is in accord with curwhereas the appropriate value is 11.24 wt%o for
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,thesecompositions 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 speTun, 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 substiINrnooucrroN
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).
1325
NOMENCLATURE OF THE ALUNITE SUPERGROUP
TABLE I MINERALS OF IIIE ALIINITE GROTJP(CURRENI USAGE)
jrosite
aluite
KFq(soa),(olD5
KAls(S0rl(0rr)6
mlrojao$te
mtroaluite
N&Fe3(SOJdOH)6
NaAL(s01),(0l{)6
moniojuosite
monioaluite
(NHr)Fq(soXoH)6
hydronim jrcsite
Gr.O)re(so.)doH)6
ilgentojmsite
AeFq(so.),(OH)"
doEllchtrite
rlFq(soa),(oH).
b@vqite
Pb(Fe,cu[SO,),(OH,H,O)"
plMbojilosit€*
PbFe(SOJr(oII)o
(NlI4)Aq(SO1L(Orr)5
schlossmcherite
(H'o,ca)Al'(so.)"(ol0"
oseiawaite
Pb(Al,Cu)3(SO4)r(OEII2O)6
minuiite*
(NaCa,K),AUsoa)a(olo'
humgite*
CaAl6(Sq)4(OI{)n
ualthisite+
BaAL(SO)(oII)u
* Length of c unit-cell pdameter is double that of the other members of the group
tution may be substantial, and these minerals a"rediscussed separately.In the synthetic alunite-jarosite series, Fe-for-Al solid solution is complete (Brophy et al.
1962, Hartig et al. 1984); although natural members
with intermediate compositions are known (Palache er
al. 1951, van Tassel 1958), the degree of Fe-for-Al
substitution in most occuffences is limited, and compositions are close to those of either the Fe or Al end-members.
Solid solution involving K+, Na+, and (H3O)+is extensive in both alunite andjarosite (Brophy et al. 1962,
Parker 1962, Brophy & Sheridan 1965, Kubisz 1960,
1970, Stoffregen & Cygan 1990,Liet al. 1992). Substitution involving K+ and Pb2* has been shown by Scott
(1987) to be extensive in alunite, and by de Oliveira et
al. (1996) and Roca et al. (1999) to be equally extensive in jarosite. The incorporation of NHa in ammonioalunite (Altaner et al. 1988) and ammoniojarosite
(Odum er al. 1982) seemsto be mainly at the expense
of K+ and (H:O)*. Apparent deficiencies in K + Na +
NH+ D-site occupancy are generally attributed to
(Hso)*.
unchanged:
iarosite
natrojarosite
hydroniumjarosite
ammoniojarosite
argentojarosite
dorallcharite
soo
K:jarosite
Na: natrojarosite
HrO: hydroniumjarosite
Fe>Al
NHo: ammoniojarosite
Ag: argentojarosite
Tl: dorallcharite
AsOo
Al >Fe
geo:
minamiite
Na: natroalunite,
alunite
HrO: schlossmacherite
SO,
N H o :a m m o n i o a l u n i t e
SOo
minamiite
natroalunite,
schlossmacherite
.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 endmember composition, although in synthetic systemsthe
solid solution between Ag-Pb (t H3O) and Ag-K
(+ H:O) has been shown to be complete (Ildefonse el
al. 1986, Dutrizac & Jambor 1984). The Tl+ member,
dorallcharite, is known only from one locality, and the
mean occupancy of the D site is (TlosrKole) (Bali6
Zuntd et al. 1994).The remaining membersof the alunite
group, except minamiite and schlossmacherite,contain
a predominance of divalent D-site cations. As these
minerals present some difficulties in nomenclature,the
speciesare discussedindividually.
Minamiite
regardedminamiite to be compositionally equivalent to
calcian natroalunite, but with the c axis doubled in
minamiite. A plot by Matsubara et al. (1998) of Na + K
(alunite-natroalunite) versus Ca (huangite) does not
show significant compositional gapsto be presentin the
series.Becauseof small grain-size,however, X-ray data
have not been obtained for all compositions. Thus, if
ordering of Ca is assumedto be the sole cause for the
doubling of c, the lower limit to trigger the change has
not been established.
B eaverite and osarizaw aite
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 (Nasa6K01eCa6
1atr6r+):os:Al: l1(SO4)2(OH)5
70 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 (Na636K0tCaoztloz)>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 valcanciesthat 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, Breidensteinet 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 anaminamiite 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 beaveriteCa-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 = 0:100 to 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 retution 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 nomenGiuseppetti & Tadini (1980) solved the structure of
clature of the existing species.The three divalent ele- osarizawaite of composition Pb(Alr 62Cu6esFes3s
ments predominating at the D site in the alunite-group Zn6s2)23ss(SO+)z(OH)o
in 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 plumboboth minerals show an 11 A diffraction effect, indicar
jarosite-beaverite,however, doubled cells appearedraning 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
t327
NOMENCLATURE OF THE ALUNITE SUPERGROUP
In terms of composition, beaverite is a Cu-rich
plumbojarosite. All occurrences of natural plumbojarosite have so far been reported to have a doubled c
axis, but in synthetic hydronium-b-earing plumbojarosite, the c may be either 17 or 34 A, apparently depending on whether Pb is ordered or disordered. The
degreeof order can be variable, and this is readily indicated by variations in the intensity ofthe 11 A diffraction line or peak in the X-ray pattern.
Schlossmacherite
TABLE 2 MINERALS OF TIIE BEUDANTITE GROIJP(CIJRRENTUSAGE)
corkite
b@dutite
PbFe[(P,S)OJ,(OH,H,o)6
rbre3[(As,S)OJdOH,HTO)5
hinsdalite
hidalgoite
PbAl3(As,S)O4],(OH,n
kenmlitzite
PbAl3t@,s)orl,(orlE
0)6
srAl,lG,s)O-l,(oEH'o)"
(sr,ce)Al.t(nqs)oJloH,Eo)6
woodhouwite
CaAl3[(P, S)O.],(OH,II'o).
gallobeudmtite
PbGa3(As, S)O4]2(OH,H,O)6
Either As or S my be predominaot in (A5,S)O4, ud
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). Recalculation of the only analytical data available (Schmetzer
et al. 1980) gives [(H3O)6:zno zsCao26Na667K6.05
516s1Ba6sll;1 oo (Alz eaFe602Cu606)>302 [(SO+)rsr
(AsO+)0.+ql(OH)s
zo on the basis of TOa = 2 and after
reassignmentof Cu from the D to the G position. The
formula conforms with that generalizedby the authors
(Schmetzer et al. 1980). The ratio of SOa:AsO+is
75.6:24.4,thus placing schlossmacheritein the SOaAsOa-dominant field in Figure 2. The mineral is therefore the Al-dominant analogue of hydronium jarosite.
Cell dimensions ate a = 6.998, c = 16.67 A.
Tue CneNoallrrE GRoUP
The minerals of the crandallite group are listed in
Table 3. Nine of the members have Ba. Sr. or Ca domi-
0)6
srubqgite
eiths
P or S may be
nant in D (threemembersfor eachofthese cations),four
members have Pb dominant, and the remainder has REE,
Ca, or Th dominant. As in the alunite group, a primary
distinction rests on whether the proportion of Fe is
greater than that of Al or vice versa.
Ba predominance
The Ba-dominant member of the alunite group is
walthierite BaosAI3(SO4)2(OH)0,and its relationship to
other Ba-dominant members of the alunite supergroup
is shown in Figure 3. AlthoughLiet al. (1992) obtained
a = 7.08, c = 1'7.18A by electron-diffraction study of
walthiedte, X-ray powder pattemsof bulk samplesshow
an ll A diffraction peak, requiring that the length of c
be doubled. The inconsistency was attributed to disorder induced by the electron-diffraction beam.
TABLE 3. MINERALS OF THE CRANDALLITE GROI.]P (CTJRRENTUSAGE)
Fe>Al
Al>Fe
gorceixite
BaAlj(Po1)eq.orD(oII)6
qmdallite
CaAl3[PO3(O1D(OI'rJ],(OID6
goyuite
STALIPO3(On(OH)rrl,(OH)6
plMbogwite
PbAl3@o4)'(oH,r{'o)6
florencit€-(Ce)
CeAIr(POo)r(OHL
florscite-(La)
LaA[(PO1)b(OFD6
floretrcite-(Nd)
NdAteo4)'(or{)6
waylmdite
(Bi, Ca)AL@Or,SiO,),(OH)e
rsnogor@ixite
BaAL(AsO{XASO3.OID(OlI)6
reocmdallite
CaAl3[AsO j(On(OID;)]r(OIt6
dmogoyete
SrAl[AsO.(O,"(OH)'J]
{0II)6
philipsbomite
PbAl3(AsO4XOH,IIP)6
trsofloretrcite-(Ce)
CeAl(AsO'),(OtI)c
"dsoflorflcits(La)"*
LaA13(As04),(OlD5
"usmoflorscite-(Nd)"*
NdAl3(A504)2(0II)6
"ilsrcwylmdite"f
@i,Ca)Al (AsOo),(OH,IlO).
dusrertite
BaFes(AsOJdOH)6
b@uite
Srre(PO,),(OH,H,O)6
kintorcite
pbpe@o.),(oEEo)6
wEnitite
zakite
BiFeeoXoH).
e'.lsttssite
Othes
(ThPb)ALeO4,SiO4)'(oIr)6
springcr@kite
BaV3eOaL(OH,ILO)6
* not CNMMN-approved, but included here for completeness.
PbFq(.csoaXOH,ILo)6
t328
THE CANADIAN MINERALOGIST
soo
soo
Fe > A l
dussertite
AsOo
Poo
sorceixite
POo
arsenogorceixiter/
arsenogorceixite
\
walthierite
AI
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 substitution atthe T site; for walthierite, such substitution
was not detected (Li et al. 1992). Likewise, compositions of gorceixite are typically close to, or at, the POa
end-member. For arsenogorceixite,however, the type
material shows AsOa:POq = 74:26 (Walenta & Dunn
1993).The AsOa (arsenogorceixite)and PO4(gorceixite)
end-membershave been synthesizedby Schwab et al.
(1990,1991).
"Weilerite" is included as a valid species in some
modern compilations (Clark 1993, Gaines er al. 1997),
but the mineral was discredited by the CNMMN (IMA
1968). As no quantitative chemical data had been published for the mineral (Fleischer 1962, 1967), the posrtion on the AsO+-SO+join is uncertain, and the mineral
may have been identical to the more recently described
arsenogorceixite.The removal of "weilerite" from the
system is appropriate, thus leaving a gap between
gorceixite-arsenogorceixite and walthierite (Fig. 3).
Dussertite is the only known member with Fe > A1,
thus theoretically allowing six additional names to be
introduced in the left diagram of Figure 3. In a ternary
system, the potential six are reduced to two.
Ca predominance
All Ca-dominant minerals in the alunite supergroup
are also Al-dominant (Fig. a). Numerous compositions
of crandallite are near that of the POa end-member.but
substitution of S for P is extensive, and compositions
extend well into the current field for woodhouseite
(Stoffregen & Alpers 1987, Spcitl 1990, Li et al. 1992),
including compositions with formula SO+> PO+ (Wise
1975). For arsenocrandallite(Walenta 1981), the type
material contains substantial Si in the Z position:
(Aso qqPozsSioz6).The As:P ratio is 57:43, which is well
within the field for arsenocrandallite.
Adoption of a temary system for the Ca-Al-dominant minerals would pose the problem of whether
woodhouseite or huangite is to be used to designatethe
SOa end-member. Type woodhouseite has POa:SOa=
54:46 (Lemmon 1937), but it has long been accepted
that either formula S or P can be predominant. The only
composition given by Palache et al. (1951) has P > S,
but more modern analyses,by electron microprobe, of
woodhouseite from the type locality have shown both
formula P > S and S > P (Wise 1975). Moreover. the
1329
NOMENCLATURE OF THE ALUNITE SUPERGROUP
Soo
AsO, POo
c r a n d al l i t e
arsenocrandallite
crandallite
a r s e n o c r a n d aIli t e
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
composition of woodhouseite well into the SOa-dominant field (Fig. a). Accordingly, woodhouseitehas been
adopted to designatethe field with S > P in the ternary
system (Fig. 4).
Sr predominance
The minerals with Sr predominant in the D site are
shown in Figure 5. The two minerals with Fe > A1 are
benauite and an associatedunnamed mineral richer in
SOa (Walenta et al. 1996). The empirical formula for
benauite is (Sre67Ba616Pbse7Ca661Koot):,0sz (Fezgo
Alo o:):z s: [(PO+)r+s(SO+)o
as(AsO4)0
04](OH,H2O)8
3,
which was simplified by Walenta et al. (1996) as
SrFe3(POa)2(OH,HzO)0.
The proportion of atoms in the
T site, however,is P:S:As = 74:24:2, which placesthe
mineral just beyond the boundary designatedby the simplified formula, and into the field of the unnamed SOaricher mineral (Fig. 5). The rangein compositions(wt7o)
reported by Walenta et al. (1996) is PzOs l'1 .98-19.93
(mean 18.53usedto calculatethe formula), As2O50.640.94 (mean0.78), SO36.24-:7.37(mean6.79),and thus
the compositions probably straddle the aforementioned
boundary. The formula of the unnamed mineral rs
(SrzsrBaooo)Fe:r:(PO+)r:s(SO+)oos(OH,H2O),,which
places the mineral well beyond the field of benauite. If
Scott's (1987) nomenclature systemis to be adheredto,
benauiterequiresredefinition as ideally SrFe3[e,S)O4]2
(OH,H2O)6.The field shown Bboccupied by benauitein
Figure 5 would therefore remain vaguint.
For the Al-dominant group. (Fig. 5), goyazite and
svanbergitehave long beenusedto indicate the POa and
PO+-SO+ minerals, respectively. For svanbergite, the
compositions listed in Palache et al. (1951) have formula P > S, but compositions with S > P also are known
(Wise 1975); the CNMMN-approved system accepts
that either S or P may predominate (Fig. 5). Type
arsenogoyazite(Walenta & Dunn 1984) has AsOa:PO+
= 64:36, but the pure end-member has also been described (Zhang et al. 1987). Kemmlitzite (Hak et al.
1969) was regardedby Fleischer (1970) to be the arsenate analogue of svanbergite; analysis of type material,
however, gave [(AsO+)oes@Oa)6a2(SOa)s3e(SiOa)s1e]
11e3,which places kemmlitzite in the field of arsenogoyazite(Fig. 5). Re-examinationof the holotype speci-
1330
THE CANADIAN MINERALOGIST
soo
soo
Fe
/
a"n^uit
a
Poo
covazite
AsOo PO,
^"tloo'o'^'n"/
arsenogoyazrte
\
AI
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 inhomogeneous (Novdk et al. 1994). Kemmlitzite predates
arsenogoyazite,and the latter was specifically defined
as occupying the AsOa-dominant field because adoption of the current (Scott) system of nomenclature had
the effect of entrenching kemmlitzite as representative
of SOa-richcompositions(Fig. 5). Such a SOa-richcomposition has been reported by Nov6k et al. (1997). ln
view of the reported zoning and lack of homogeneity in
type kemmlitzite, retention of the name arsenogoyazite
would seem,arguably, to be preferred. In a ternary system, therefore, the most appropriate names are considered to be goyazite, arsenogoyazite,and svanbergitefor
the Al-dominant members, and benauite for the Fedominant mineral with POa greater than AsOa or SOa
(Fie.s).
Bi predominance
Minerals with Bi predominant in D are shown in
Figure 6. Analyses of waylandite (Clark et al. 1986i)and
zairite (van Wambeke 1975) are within the designated
compositional fields. "Arsenowaylandite" is an unofficial name (Scharm et al.1994) that has not been submitted to the CNMMN for approval. The anhydrous
composition for ZOa = 2 vaies from (Bi68esr005
Caoos)>os7 (Al2 e6Fe610)[(AsOa)1or(SO+)o
zz@O+)o
rr]
to (Bi6 eeSrs65)116a(A12
e6Fe6
ea)[(AsO+)r sr(SO+)ors,.
Pb predominance
Figure 7 is illustrative of the profusion of mineral
names possible as the compositional fields within the
alunite supergroup are frlled. For Fe-dominant minerals, plumbojarosite, corkite, and beudantite have been
in use for many years, and corkite and beudantite occupy the bulk ofthe field. Segnitite (Birch et al. 1992)
and kintoreite (Pring et al. 1995) occupy the SOa-poor
fields that opened only as a consequenceof the adoption of the current CNMMN-approved system of nomenclature.For Al-dominant minerals,plumbogummite
and hinsdalitehave beenknown for many years(Palache
r33r
NOMENCLATURE OF THE ATUNITE SUPERGROUP
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
= 59:47, and the mineral was specifically named as the
arsenate analogue of hinsdalite (Smith er al. 1953).
Philipsbornite (Walenta et al. 1982) is somewhat
unusual in its high Cr content in TO+, for which
= 76:19 5. The small freld at the SO+
AsOa:CrOa:SO+
apex (Figs. 7, 8) has beenreferred to as "plumboalunite"
(Novrik et al. 1994) and "plumbian alunite" (Sejkora er
al. 1998). However, if it is acceptedthat (Cu + Zn) substitution is non-essential,then the Pb-Al sulfate in this
field is osarizawaite.
Adoption of a ternary system for the Pb-dominant
members would pose some difficulties. In the system
with Fe predominant in G, corkite and beudantite have
priority, thereby requiring the abandonment of the recently named kintoreite and segnitite.In the systemwith
Al predominant in G, plumbogummite and hinsdalite
have priority. Osarizawaite was named as the Al analogue ofbeaverite, but the requirement, as will be discussed, is that neither be retained as a mineral name.
Plumbogummite and hinsdalite thus occupy the PO+-
SO+join as shown in Figure 7. The consequenceis that
the field for hidalgoite, which includes the composition
oftype hidalgoite, would be overlappedby the new field
for hinsdalite. Therefore, as was done for arsenogoyazite,philipsbornite would be retained to designate
the As-dominant member.
REE predominance
The REE-bearing minerals are characterized by a
predominanceof trivalent cations in D, and it has been
suggested(Scott 1987) that such minerals be classified
as the florencite group. Accepted minerals within the
group (Fig. 9) are florencite-(Ce), florencite-(La),
fl orencite-(Nd), and arsenoflorencite-(Ce). Compositions corresponding to the La and Nd analogues of
arsenoflorencite-(Ce)have been reported by Scharm er
al. (1991,1994), but the new nameshave not been submitted to the CNMMN for approval. Adoption of a ternary system for the REE-dominant members would not
affect the current nomenclature.
1332
THE CANADIAN MINERALOGIST
soo
soo
rmbojarosite
plumbojarosite
/
kintor"it"
segnitite
beudantite
soo Po.
Poo
ohilivsbornite
\lumbogummite
AI
,/
plumbogummite philipsbornite
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 osarizawaite if it is acceptedthat Cu is non-essential.Compositions are shown by Sejkora
et al. (1998) as extending into this field, which has been named 'plumboalunite" 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 member of the crandallite group, with P as the main cation in
70+ (Table 3). Hqryever, the calculated formulas also
incorporate substantiai(H+O+)in ZOa,and show excessive Al (>3.5 mol) for G (Van Wambeke 1972). Such a
G-cation excess is untenable for an alunite-type mineral, and eylettersite is considered to need restudy.
Gallobeudantitewas defined ashaving subequalvalues of AsOa and SO+, and a predominance of Ga in G
(Jambor et al. 1996). However, ZO4 compositions extend into the fields encompassedby Ga analogues of
segnitite, corkite, and kintoreite, thus permitting the introduction of three additional new names for the Gadominant minerals. The distribution of 7Oa values in
the Ga minerals is such that adoption of a ternary system would not reduce the number of potential new
names.Also presentwith gallobeudantiteis the Ga analogue of arsenocrandallite.
Numerous members of the alunite supergroup have
been synthesized.Among those not known as minerals
are the Rb* and Hg2+ analogues of jarosite; the Hgdominant and Pb-dominant phases described by
Dutizac & Kaiman (1976) and Dutrizac et al. (1980)
are indexed with c = 33 A, but no diffraction line at 11
A was reported. Mumme & Scott (1966) also noted that
the 11 A line is absent from their synthetic plumbojarosite.
Tananaevet al. (1961) preparedanalogueswith Na,
K, Rb, H3O, and NHa in D, and Ga in G. Only small
amounts of various divalent metals other than Cu2+and
Znz* have been reported to be taken up by the alunite
supergroup. The In3+, V3*, and Cr3* analogues have
been synthesized (Dutrizac 1982, Dt;trizac & Dinardo
1983,T,engauer
et al. 1994):up to 0.6 mol V3* and 0.18
mol Crr* have beenreportedin natural gorceixite (Johan
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 discussedto this point hasbeenmainly chemical, and structural aspects have 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 plumbojarosite were first determinedby Hendricks (1937), who
a
-^
n)\-/4
concluded that becausealunite andjarosite show strong
pyroelectric properties, their spacegroup must be R3m
plumbojarosite was deterrather than R3m. In co_ntrast,
mined 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, severalstudies 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
The basic structural motif of the supergroupconsists
field, asin Figure7, illustratingtheextensiverangeof ZOa
solid solution Solidcircles:abridgeddatafrom Sejkoraer of TOa tetrahedra and variably distorted R-cation octafrom Rattrayel hedra, the latter corner-shared to form sheets perpenal. (1998);opensquaresarecompositions
al. (1996\.
dicular to the c axis. Substitutionsinvolving G therefore
mainly affect the a dimension, and a increasesas Fefor-Al substitutionincreases.The ZO+tetrahedra,which
are aligned along [001], occur as two crystallographispringcreekite (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 another pointing downward. The oxygen and hydroxyl
documentedby Kolitsch et al. (1999b).
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.
Symmetry changes arise principally becauseof orhave been synthesized,and substantial Cr has been reder-disorder relationships among the 7Oa tetrahedra,or
ported in the Z site in philipsbornite (Walenta et al.
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+AsO+ tetrahedra must be disordered; ordering, as has
or as amorphous SiO2. Other substitutions, such as Nb
(Lottermoser 1990) and CO3, are possible but generally been found in corkite and gallobeudantite, reduces the
not significant; analysesshowing percentagequantities symmetry to R3m.
A second principal effect is related to the presence
of CO2 (e.9., Frirtsch 1967) predatethe widespreaduse
ofthe electron microprobe, and the high valuesreported of a divalent cation in D. In such a case, the standard
jarosite-typeformula D*G3*3(SOa)2(OH)6
becomeseither
in a few older analysesmay be the result of inclusions -7|+162+
of carbonateminerals.
3(Soa)2
t(soo)r(og)ul, (ordered) or, D2* 112G3*
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 electroneutralstitution 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 thesevacanciesproducesa supercell,which is manifested as a doubling of the c axis to 33-34 A.
al. 1984\.
r334
THE CANADIAN MINERALOGIST
soo
Soo
fe>Al
Fe)Al
AsOu
AsOo PO,
arsenoflorencite
{Ce)
florencite-(Ce) arsenoflorencite-(Ce)
_(Nd)*
-(La)*
Al >Fe
Al )Fe
sou
500
Soo
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
ZOa group. Where ZOa is POa or AsOa rather than SOa,
an extra proton is required to maintain charge balance.
In crandallite, Blount (1974) concluded that the formula
takes the form CaAl3[PO30 1p(OH) 1p]2(OH)6, thereby
achieving compensation by having partial substitution
of hydroxyl for oxygen of the PO+ tetrahedron.
Radoslovich (1982), however, determined that such a
configuration would not be permitted in gorceixite because of the larger size of Ba. He therefore concluded
that the formula of gorceixite is best represented by
BaAl3eO4)(PO3.OHXOH)6.
It is possible, therefore, that order may exist without
the necessity of having the 7 site occupied by different
elements (As, P, S). Furthermore, the crystal-structure
determination (R = 0.0195) of unnamed PbFe3GO4)2
(OH,H2O)6 by J.T. Szymanski (Table 4) revealed that
distortion at the Pb sites leads to two indeoendent Pb
atoms in the structure. Thus, a ruperstru.ture is formed
in this mineral without the necessiw of havine D-site
vacancres.
Szymafiski (1985) has pointed out additional aspects
relevant to the crystal chemistry of the alunite supergroup. Among these is the report by Loiacono et al.
(1982) that the space group of their natural alunite is
R3m. For hydronium jarosite - schlossmacherite,
Szymafiski(1985) pointed out that "... the hydronium
ion, whether it remains in its original H3O+ form or
whether it is reduced to water, cannot have a centre of
symmetry and cannot be located at a centre of symmetry. Any hydronium-for-cation substitution will destroy
the symmetry, and reduce the space group to R3m or
lower. This is not to say that the hydrogen atoms of the
hydronium ion or the water molecule cannot be statistically distributed or dynamically disordered, and hence
give the structure the overall appearanceof having a
centre of symmetry."
As with hydronium, the NHa ion cannot be accommodated within R3m (Arkhipenko et al. 1985, Sema et
al. 1986).However, as discussedby Szymahski (1985),
in the absenceofincontrovertible sfuctural data,the space
group of alunite minerals should be consideredas R3m.
I 335
NOMENCLATURE OF THE ALUNITE SUPERGROUP
TABLE 4 SINGLB-CRYSTALX-RAY STRUCTURESTTIDIESOF MINERALS IN TIIE ALUMTE SUPERGROTJP
a,L
Compositio4oments
alunite
natroalsite
mimiite
JilOSrte
@mpo$uoDnor grvm
(Nao,slqrJAls(SO),(OH)6
(Nao*Ig rCa".rrtrnr)Alr(Sq)r(O$.
not givq; synthetic
not giv€n;mtural
gorccixite
qmdallite
woodhouseite
goyuite
svmbergite
os@awilte
plmbojaosite
bfldatite
corkite
hin$datite
galobildantite
plmbogwite
kirio!eite
du$ertite
nnnnrBed
florencite-(Ce)
[email protected](OID6
Cao"At*P,*; CaAlrlPO3(O@(OIDdlr(OID6
not givm; CaAI,(PO*)(SO4XOID5
not givm; SrAI3[PO3(O,"(OID,J]2(OI06
rot givs; SrAL(POa)(SO4XOID6
Pb(Al, .rCuo,rFeo,lq d(SO1)r(OH)5
trot givd; structurefomula u below
PboJq *So*; Pb[Fe(sOJr(o]D51,
Pboe(FqsCuo@zrboilSO).lAsOJ.'(0II)6d
Pb,*(Fe,"Alo*)(AsOJr odsO4te(OEHp)6
Pb,.(FerorAlorr)(AsO,)rB(SO)0'(OH,ILO)6
Pbo*(Fer"Cuo *)(PO4)I.6(SOJ0*(Asq)o ml(OH)6q
PbALleo,), 3r(so{Lcl(orr,H,o)5
Pbl u(Gal fAli laFeo
szno ilGei 6XAsO{)r&(SQI *(OIO"
"
PbALI(PoJ, s(Aso)o,J(oI!H,o).
PbFq(POJ',(AsOn)ur(SO4)03(OII,Hp)6
Ba(Fd.' s4sb*o,b)3(Aso"),(ollHp).
PbooFq n,@Oo),
,,(SOn)o,(OI1I4O)' ,,
(CeoalrorNdo,rSmo*Car*)A1r(PO,l(OlD.
c, A spaegroup Ref.
17 27
6970
16095
6 990
33 490
6 981
l7 l9O
1 305
17268
7304
monoclinic
monoclinic*
16192
7 005
6 993
16386
? 015
16558
16567
6992
70'15
17 I
33 60
720
7 3055 33 675
1 339
17 034
7 3l5l
I7 0355
triclinic**
7 ZaO
16821
16789
7 029
1703
7 225
16761
7 039
't
331,0 16885
l'l 484
7 410
7 28A5 33 680
6912
16-261
Rim
Bm
R3m
Rlm
Rim
Cm
Rlm
Bm
Rlm
Rim
Rlm
Rim
Em
R1m
Rlm
R3m
Rim
R3m
Bm
Bm
Rlm
R3m
Bm
1
2
3
4
5
6
7
8
9
10
5
1l
12
13
14
15
15
16
f'l
18
17
'19
20
21
22
* a 12 195,b 7 o4o,c ? 055A 0 125 l0' S@slroBlEnchdd(1989)
* * q 7 3r9, b 7 309,c 17032A, a 90 004,p 90 022,y 119974"
Referenes:7 Wngetdl.(1965),2 Okedaetal0982), 3 O$ska"t4l. (1982),4 Mf,chetti&Sabeli(1976), 5 Kato
E Blout(1974),9 Kato097l, 1977)' l0 Ksto
? Radostovich(1982),
&M{m(1977),6 Radoslovich&Slade(1980),
(1971,198?),1I Giuseppetti
(1937),who alsogavereflrltsfor aluite edjeositq 13 Szf& Tadini(1980),12 Hendricks
& Tadini(1987), 17Kolitsh
miski (1985), 14 Giuseppelti
& Tadini(1989), 15 SzJmiski (1988), 16 Giuseppetti
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
formulas of minerals in the alunite supergroup.Among
the most common are normalization to 14 oxygen atoms, or to TO4 = 2. Some authors (e.g., Scharm et al.
1991, Novrik & Jansa1997, Sejkoraet al. 1998)have
used G3(IOa)2 = 5. Use of TOa - 2 is preferred here
becausenonstoichiometry in both D and G is common,
particularly in synthetic samples. To paraphrase
Szymafrski(1985), use of ZO4 = 2 has a sound structural basisbecause"... it is inconceivableto visualizea
stablejarosite structure with vacanciesin the [TOa] layers as well."
A second difficulty in formula calculations is that
hydronium cannot be determineddirectly. This problem
is not significant for most of the minerals in the supergroup, but it doesemphasizethe precarious statusof the
sole composition available for schlossmacherite, for
which D is [(H:O)o :zno z8ca026].Ia0
07Kos5Sr6slBaos1l.
Regardless of symmetry variations (Table 4), the
topology of the unit cell of all minerals in the family
can be related to a rhombohedral cell that has hexagonal dimensions of a x 7, c N l7 A. The development of
a supercell with c = 2 X l7 A can arise becauseof ordering ofD-site cations, regardlessof whether D contains vacanciesor is filled completely. Moreover, order
does not require the presence of a combination of
monovalent and divalent cationsin D, but can take place
solely with monovalent ions (Dutrizac & Jambor 1984).
Many rapidly crystallized syntheticproducts show signs
of an ordered structure,and it is inconceivablethat some
of the commonly more slowly crystallized natural minerals would not be ordered.On the other hand, synthetic
Pb-H3O systemsshow various degreesof disorder, and
synthetic plumbojarosite without detectablediffraction
effects due to a superstructureis well known. At the
opposite extreme, in their X-ray structure studies both
r336
THE CANADIAN MINERALOGIST
Hendricks (1937) and Szymairski (1985) used plumbojarosite from the Tintic Standardmine, Utah, for which
an exceptionally high degreeof order was found; in the
case of the latter author at least, the material was selected specifically becauseX-ray powder patterns had
previously indicated an exceptionally high degree of
order to be present.
If minerals in the alunite supergroup are to be named
simply on the presenceor absenceof the c-axis superstructure, the potential for the introduction of "trivial"
names will increase enormously. I believe that detection of the superstructurewill become more common
once there is an increasedawarenessof the sisnificance
of the I I A powder-diffraction line or peak.
Recol,rlr,rewoauoNsoN Noprexcr-erunE
If the proliferation of mineral names in the alunite
supergroup is to be avoided, two properties or factors
must be addressed:(a) crystallographic, and (b) chemical. In some casesthese factors are independent,as for
example minamiite and as-yet-unnamedmineral IMA
No. 93-039, both of which are distinguished from
previously named minerals solely on the presence of
standard cell versus supercell relationships. The fundamental topology of the alunite structure remains the
same regardlessof space group or symmetry changes.
The fundamental cell is rhombohedral, space group
R3m, with a x 7 and c = 17 A as expressedwitli hexagonal parameters.Slight distortion of this cell can lead
to orthorhombic (Jambor & Dutrizac 1983), monoclinic
(Radoslovich 1982),or triclinic (Szymairski 1988)polymorphs, and patterns of order of various kinds can lead
to a doubling of c.
Crystallographic aspects
Various systems have been used to accommodate
structural changeswithin a mineral group while maintaining a comprehensible nomenclature. For example,
Pring et al. (1990) used the CNMMN-approved name
baumhauerite-2a to designate a silver-bearing mineral
having a superstructurederived from a baunihauerite-
like structure.For minerals of the alunite supergroup,a
similarly simplified system of nomenclature system
could be adopted such that: (a) no modifier accompany
the mineral name if the unit cell has not been determined, or if only one structure type is known; (b) if there
is a need to distinguish between the conventional cell
and the supercell, the former should be designated lc,
and the latter 2c, each followed by the standard
(CNMMN-approved) abbreviation for the unircell type
[1: hexagonal,rt: rhombohedral, M: monoclinic, A: triclinic (anorthic), erc.l. Note that it is important to retain
the c to avoid confusion with the nomenclature designations for polytypes. Thus, for example, rhombohedral
plumbojarositelacking a superstructurewould be named
plumbojarosite-lcR, and that with a superstructure
would be plumbojarosite-2cR. Monoclinic gorceixite
remains as gorceixite, but if a doubled c axis for the
monoclinic cell were to be found, the nomenclature
would distinguish gorceixite-7cM and gorceixite-2cM.
It has not yet been proved that gorceixite with a conventional rhombohedral cell exists, but such a mineral
would simply be designatedas gorceixite-lcR.
Adoption of such a system would involve the following nomenclature
changesor revisionsin:
1. Minamiite, which is fundamentally different from
natroalunite only in order-disorder relationships, is
natroalunite-2cR.
2. Monoclinic gorceixite, assuming that the rhombohedral form also exists, would not be entitled to a
trivial name.
3. Triclinic crandallite, reported by Cowgill et al.
(1963), ifverified, would be designatedcrandallite-lcA.
4. Triclinic beudantite reported by Szymafiski
(1988) would be designatedwith the suffix lcA.
5. Unnamed rhombohedral mineral IMA No. 93039 would likewise adopt the appropriate already established name, together with the suffix 2cR.
6. Beaverite is cuprian plumbojarosite without superstructure reflections. Beaverite is therefore cuprian
plumbojarosite-1cR.
7. Orthorhombic jarosite with the doubled c and
composition K6e6Fe2qo(SO+)z(OH)6
16 (Jambor &
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
b@vqite
cupriu
corkite2cR
jtosite-2co
kintoreite
@rkite
plufi$ojdositelcR
segilwe
bodmtite
hidalgoite
hinsdalite
osrizawaite
hinsdalite
orthorhombic juosite
r337
NOMENCLATURE OF THE ALUNITE SUPERGROUP
Compositional aspects
Two approachesare used, namely, (a) an evaluation
in terms of the existing (Scott 1987) system of nomenclature, and (b) an evaluation on the basis of a ternary
compositional system.Neither systemtakesinto account
possible miscibility gaps, which have not been proved
to exist within the alunite supergroup, although such a
possibility is highly likely. For example, Stoffregen &
Cygan (1990) have argued that a miscibility gap may
exist on the simple alunite-natroalunite binary join if
theseminerals crystallize under equilibrium conditions.
Under nonequilibrium conditions, however, a gap is not
evident.Numerous proposalsfor miscibility gapsamong
minerals other than the alunite supergroupcan be found
in the literature, but in many casesthe purported gaps
simply reflect plots of existing chemical data, without
good evidencethat the gapscannot be breached.For the
alunite supergroup,it is likely that it will be many years
before miscibility gaps can be incontrovertibly demonstrated to exist. This aspect,therefore, is not taken into
considerationin this review of nomenclature;nevertheless, it is evident that, over the long term, the multicompaftment systemin current use for alunite nomenclature
would fare less well in terms of avoiding complexity
than would a ternary system.
If a ternary system of nomenclature,combined with
the superstructure-symmetrynotation, were adoptedfor
the alunite supergroup,the following would result:
1. Alunite group with monovalent ions in D: removal of minamiite, beaverite, and osarizawaite, and
expansion of the compositional fields as shown in Figure 2 (right).
2. Ba predominant in D (Fig. 3): the compositional
field available for a "weilerite"-t1pe mineral disappears.
3. Ca predominant in D (Fig. 4): huangite is
woodhouseite-2cR.
4. Sr predominant in D (Fig. 5): kemmlitzite is no
longer retained.
5. Bi predominant in D (Fig. 6): no change other
than expansion of the compositional fields.
6. Pb predominant in D (Fig. 7): for Fe > A1, corkite
and beudantite have priority, so that kintoreite and
segnititeare no longer retained.Similarly, hinsdalite has
priority over hidalgoite, and the latter is no longer retained.
7. REE predominant in D (Fig. 8): no change other
than expansion of the compositional fields.
The nomenclature changes are summarized rn
Table 5.
CoNcrusroNs
Independentof any new nomenclatureproposals,the
following minerals and namesrequire reappraisal:
(a) Beaverite: Cu:(Fe,Al) is not 1:2, and Fe is predominant.
(b) Osarizawaite:Cu:(Al,Fe) is not 1:2, and Al rs
predominant.
(c) Minamiite is compositionally equivalent to
natroalunite. but has c ! 33 A. Mineral IMA No. 93039 (Table 4) could be given a trivial name on identical
grounds.
(d) Benauite: the compositional field doesnot coincide with that of the ideal formula.
(e) Eylettersite requiresre-examination becausethe
formula(s) exceed acceptablelimits for minerals of the
alunite supergroup.
(f) The possible triclinic analogue of crandallite
(Cowgill et al. 1963, Blount 1974) requires re-examination both with respectto composition and symmetry;
no single-crystal X-ray study has been done, and the
formula deviates significantly from that of the alunite
supergroup.
(g) Orpheite, a Pb-Al phosphate-sulfate, is variously classified as in (Gaines et al. 1997) or out
(Mandarino 1999) of the alunite supergroup.Fleischer
(in Fleischer et al. 7976) concluded that orpheite is
hinsdalite, but orpheite has retained speciesstatus.
AcrNowrsocrvsrvrs
The initial version of the manuscript was examined
by, among others,J.E. Dutrizac, J.D. Grice, U. Kolitsch,
J.A. Mandarino, E.H. Nickel, and A.C. Roberts. I am
grateful for their comments and, in some cases, their
strong encouragementto continue to pursue the nomenclature issues.I am also thankful to W.D. Birch for his
appreciable input during the formative stages of this
review, to P. Bayliss for incisive and useful refereecomments, and to R.F. Martin both for editorial comments
and for acceptingthat this review of nomenclaturemerited airing. Acknowledgement is not intended to imply
agreementwith the views that have been expressed.
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ReceivedJune I 1, 1999, reyised mnnuscript acceptedNovember 12,1999.