Canadian Mineralogist Vqr. 13, pp.

2742 (1975)

BINARY AND TERNARY SULPHOSALT ASSEMBLAGES IN THE SYSTEM Cr.uS-AgbS-PbS-As,S*Sb,S,-BinS, PHILIP C. GOODELL
Dept. ol Earth and Planetary Sciences, City CoIIege, City Uni.versity ol New York" N,Y. 10031 New York,

Petersen(1962). This work has the same limitations and qualifications expressed in the preThe Cuz$Agz$Pb$As2Ss-SbaSs-BilSssystem vious studies, plus a few peculiar to sulpbosalt has 18 temary sub-systems which contain sulphosalts. Phasesand natural assemblages reported in mineralogy. Having indicated above the purPose of the ths literature are plotted on ternary composition Tie line variations present work, it is important to note also what diagrams of these sub-systems. provided by extensive solid solutions suggest nu- it will not include. This study is not intended to merous potential geothermometers. Facies changes be a review of sulphosalt mineralogical data nor are also indicated in certain systems by tie line phase relations. The details of mineralogical switches as suggestedfrom natural assemblages. problems within so large a group of minerals is from a deposit have the beyond the scope of this endeavor. The docuSequences assemblages of potential of indicating relative metal and/or semimentation of the consistent or sonflicting patmetal fugacity changes. of sulphosals is, rather, This type of data analysis suffers from the am- terns of assemblages the object of this study. The resulting diagmms biguities inherent in sulphosalt identification. Additionally, detailed analysesof pbaseshaving vari- are useful to investigators of sulphosalt mineraable compositions are atnost completely lacking. logy and geochemistry, and in pointing out sulQualifications concerning the meaning of an as- phosalt systems of potential geochernical insemblage,and tle degree of attainment of equili- terest. As sulphosalts are often found within, or brium are also noted. adjacent to, important ore deposits, knowledge Tho potential interest of detailed investigations of the genesis of this family of minerals can be on sulphosalt assemblages emphasized. is useful in mineral exploration. The most severe limitations encountered when relying on tle literature for sulphosalt assemINt'nonucttox blageo is the question of identification of species. purpose of the present study is to derive Sulphosalt systems commonly have a multipliThe ternary compatibility diagrams lor a large por- city of phases present, and many phases have tion of sulphosalt chemistry using previously- similar properties and appearanc,e.Most studies reported data concerning natural assemblages before 1955 relied solely upon microchemical of sulphosalts. Many sulphosalt compositions and microscopic techniques, which have since can be expressed as combinations of simple proved not diagnostic for many sulphosalts. sulphide components, and the system considered Some studies reported assemblagesof 8 or 10 hero is CueS-AgzS-PbS-As"Sa-SbzSa-BisSa. Phases sulphosalb, with many conflicting tie lines and present in the sulphosalt binaries and ternaries disregard for the PhasE Rule limifalipl on the of this system are listed in Tables I al.d 2, number of possible coexisting phases in a sysrespectively, and phases are plotted on ternary tem. X-ray identifications can generally be recomposition diagrams using all combinations of lled on, but the literature suffers from the scarthese sulphides ,as end-member components of city of such critical studies. The second question raised in the present sulphosalt systoms. Reported natural assemand the reservablages are then indicated as tie lines on the com- study of sulphosalt assemblages, position diagrams. Reference is madE to phase tion shared with the earlier studies of McKinstry equilibriurn studies where they are relevant to and Petersen, is what is meant by an assemblage. or interpretation of natural assemblages, in some The relations between assemblages,associations, cass to fill in where reported assemblagesare and true equilibrium are discussed further by lacking. As such, this study might be considered Barton et al, (1963). In the present wirik the 'associated with' as used an extension of work initiated by McKinstry on terms 'found with' or the Cu:Fe-S-O (McKinstry 1959) andCu-Fe-As-S in the literature are accepted :to mean assem(McKinstry 1963) systems, and continued by blage. Unfortunately, it is all too often left un' AssrRAc"T

28

THE cANADTaN

MINERALOGIST

specified whether these terms mean intimate grain to grain contact, or found together in tle same polished section, hand sample, paragenetic zone, or merely in the same mining district. Ideally, the use of the term assemblageindicates compatibiliry and equilibrium, but as McKinstry (1959) pointed out, two minerals which occur together are not an absolute guarantee of compatibility. Another term used in the literature is 'replacemenf, but this term generally does not indicato an equilibrium assemblage. The textural
TAri.[ l. PHASES PmB{T,toild nE EIMRYSYSTBiS ftr C!?s-A9Zs-pbS-,szS3-Sbt3-BtA I[ SYSIS(se tqt for s*tnl rct6) Blnary 3Ftd h$6 pr6enr tu@ta #ffTltr B l. C!2s-ASZS l. strc@F.lre 2. @ki6tryl& 3. JalFle

,08 narglb, luade h6e A (kke t stt@r 19nl ?. slnnrlb Cu3A9S4 toelAtZs:t C!OAS4S9 aal.92, t..02.4,27 3:l ?tl 3,2

th6e B (*klderlto) (Skinner 6, aZ. 1972) fa@ti nl te 2. dalcosilbl&

&e6&i n 1. ulrtldenl&
2. @lectlte 4. hod6hite 5.'dldberglh' ?

to3Sls3 &BISZ tutoBltfzz C!SBjiZSZ

CuBt.Sa

3;l l: l 5:5 2:3

l:3

k-3r4hadre (xall 1956) l, prcGtlte, xantho@nlte 2, sdi$iG, trcdr@nnlte

Jo-orrrrnFryrrc l. sephadb pymsfftpntb te 2. pyrarydb, 3: niaBrl

Agsks4 AS3BS3 AqAeSZ AgTsbs6 AS.$S,

l:l 5:l l:l

]
6r:totS2j* h,,k,s., h$zss hgkt:SZg 26t7' 2817 211 18:13

4. rahl te 5. hd@rlh 6. liveinl91te 7. sarbfr& (scleroclse)

I . bul aqorl

te

3. 6dsonl& 4. heiarcmrphlh 5. lauroylb 5. plagiorite 7. &blNoniie 8. z1*6nite 9. fuloppile

65$qsil b9$aSZl ht7($,&)l6s4t htt$tZSZg hfsstg Pb2z($,kl26s6t bg$glr bftases fta$tqSa

h:$gStg

5.2 9 t4 l7:8 1116 7.4 At13 5:4 7t6 6,7

3:4

establishmentof replacement versus coprecipitation is, furthermore, a matter of conjecfure in certain cases. The assemblages noted in this study have been obtained from a number of sources. The standard references are Palache et al. (1944), Ramdohr (1969), Schouten (1962), Traill (1970), and Uytenbogaardt (1951). Original sources were sought in instanoes of reported conflicting tie lines, and a review of the pertinent literature for the past twenty yeani wa$ made. Conflicting assemblages are indicated on the diagra,ms by dashed lines. Undoubtedly, some reported assemblages have been misged, and the author would appreciate hearing of any such omissions. In spite of the reservations which have been mentioned abovg and in light of the increasing mineralogic, crystallographic, phase equilibrium, and thermodyn'amic data on sulphosalts that are becoming available, it is strongly felt that we must come to a better understanding of the natural occurrences of these species. In the idea of McKinstry (1963), "Chemistry, however precise, is not geology until natural occlurenceB are correlated and reconciled with it." In addition paragenetic squencesof sulphoto ,assemblages, salts are also noted, as such data are relevant to an understanding of the genesisof the mineralization. In the tables and figures which follow, metalrich phases and sub-systems are listed fint, with progressively more semi-metal-rich phases and sub-systemsfollowing. When more than one meta.l or semi-metal constituent appears in a system, as in the ternaries, each appears in the order of the atomic weights of the metallic or semi-metallic element. Binaries and then ternaries are discussed,and at each successivestep new phases appearing in a system are listed in table form according to the abovedescribed order. The numerical appearance of a phase in these tables is then used for reference in the accompanying composition diagrams, and is indicated in parentheses when a species is referred to in the text. It is hoped that this binary and ternary nu'nerical reference scheme will keep the diagrams relatively uncluttered; however, the interested reader may find ,it useful to write his own abbreviations on the figures. BrNary Sysrrus Table 1 lists the sequence of binaries, and tle formulas and metal/semi-mtal ratios of tlg speciesin each of the 15 binaries. Only tle more important of these .are discussed below. References to the most recent phase equilibrium studies can be found in Craig & Barton (1973), and

lllllanl& l. bu6.i& ?. @sallt! 3. lal#l3dtl&

6381256

3:t

hsBlllt b28t 2s5 bBt 2s4 mll!

ltz

'r. trca-$?!3

BINARY

AND

TERNARY

SULPHOSALT

ASSEMBLAGES

rr

Cu^S-Ag"S-PbS-AscS-SbrSis-BirSg

Cu

Cu

Cu25

Cu25

AsrSa

Ag2S

sb2s3
Cu2S

Asf

Bi2s3

A92S

30

THE CANADIAN

MINERALOGIST

recourse should be made to this work for a list of critical points and stability ranges of binary assemblages.E The natural phases appearing on the CuzSjoins are given in Table 1, A:fg and CusS-SbzSs #4 and $5, along with the synthetic phases which might be recognized in natural assemblages in the future. These two important joins are also arnong the more complicated .ones, in that they necessitatethe projection of compositions from sulphur onto the join of interest. Natural assemblages the Cu-As-S and Cu-Sbin S systems are given in Figures 1 and 2. Sinnerite is the only phase which plots exactly on the Cu"S-As:Ssjoin, so that the tennantite field is projected away from sulphur onto this join. Digenite and djurelite project onto the CuaS position. Enargite and luzonite project onto the tennantite field and also have substitution of As by Sb (Springer 1969a). Their presence indicates high sulphur fugacity conditions, and their coexistence has the possibility of providing geothermometric measurements (Skinner 1960). .{ particularly i.m.Fortant assemblage is that of enargite-realgar, which precludes the coexistence of orpiment with tennantite. These observations are compatible with equilibria studies down to 3@'C (Maske & Skinner 1971), and the assemblagesindicated in Figure 1 are in agreement with their work. Sinnerite has been found with tennantito at ib only natural occurrence, the Lengenbach Quarryo Switzerland. Tennantitechalcocite (digenite) is a not unsommon assemblage. The assemblagesfor the Cu-Sb-S system given in Figure 2 present fewer complications. Digenite and the tetrahedrite field project away from join, and famatinite sulphur onto the CuaS-Sb:Ss projects onto the tetrahedrite field, occurring under higher sulphur fugacity conditions. A recent review of phase relations is in Chen & Chang (L974). Phase B of Skinner et aI. (1972) plots on the Cuz$Sb:,Sa join ,at the point where famatinite and ideal tetrahedrite are projected. Except for Phase B, all two-phase assemblages along the join are found in nature. join Clable l, #6), mineral On the CurS-BirSa #2 (Ifonnorez-Guerstein 1971) falls on the sulphur-rich side of this join. Cuprobismutite, long thought to be dimorphic with emplectite, has been found to have a distinct composition in both synthetic @uhlrnann l97l) aid natural
aReference should also be made to Sulfide Phase Equilibria, chapter 5 in the Short Course on Sulphide Mineralogy given by the Mineratogical Society of America, November, 1974.

(Iaylor et al. 1973) materials. Eichbergite, although thought to be discredited,has been found in synthesis studies in this system (Buhlmann L97l\, and consequently is retained in the present work. The natural assemblageson this join are wittichenite(1)-emplectite(2), and wittichenite(1)-chalcocite,w.ith this latter reported also with enargite(Ramdohr L969, p.711). It would be of interest to investigate this high-sulphur fugacity assemblage for the presen@ of minerul #2. The sequence of phases on the AgaS-As:Ss joins (Table 1, #7&8; Figs. 3&4) and AgzS-SbrSa includes billingsleyite and its antimony analogue, although these phaseslie o: the sulphur-rich side of the poins. All two-phase assemblages adof joining phasesare reported in nature except that (2)-proustite(xanthocoof smithite(trechmanaite) nite)(l). Although smithite was reported @alache et al. 1944) in association with orpiment, later studies (Graeser 1968) do not substantiate this assemblage.The tlree-phase assemblageargentite-stephanite(1) -pyrarryite(2), not uncommon in the literature, is interpreted (Keighin & Honea L969) to represent subsequentprecipitation of stephanite on previously-deposited argentite-pyrargyrite, in one instance. Stephanite is stable below 197'C. join (Iable I, #9; Fig. 5), On the AgzS-Bi,Su all adjoining phases have been observed; matildife-bismuthinite has also been reported (Schouten L962), but this does not agree with phase equilibrium studies of the simple binary. The matildite polymorph stable above 195oC has a solid solution in both directions along the join, and is a potential geothermometer if found with acanthite or pavoaite. joins (fable 1, The PbS-AseSg and PbS-SbrSe Figs. 6&7) sontain a protusion of #fi&lL; phases. The four most arsenic-rich phaoes on the PbS-As:S' join were described from the Lengenbach Quarry, Binnatal, Swiuerland. Dufrenoysite has been reported @alacbe et al. L944) with orpiment, realgar, sphalerite and gypsum. This is probably a low-ternperatur assemblage when compared with the Binnatal deposit. Jordanite(2)-dufrenoysite(3) has been reported from Binnatal, and this assemblage stable beis low approximately 480'C. Gratonite(l) is considered by Roland (1968) to be a low-temperature dimorph of jordanite, which serves to explain the reported coexistence of jordanite and gptonite each with galena. This idea is supported by more detailed chemical analyses of gratonite @urkart-Baumann et al. 1968). Iordanite is the arsenic end-member of the geocronite solid solution, which takes up to 58 atomic Vo Sb replacing As (Roland 1968; Walia

BINARY

AND TERNARY SULPHOSALT ASSEMBLAGES N

CU6.Ag"S.PbS-ASISA'Sb'S'-BiT,S'

3I

& Chang L973). A review of mineralogical and stability relations can be found in Chang & Bever (1973). Numerous mineralogical and phase equilibrium studies have failed to resolve questions as to the nature and stability of phases within the PbS-Sb:$ system. Some of this work is reviewed in Chang & Bever (1973). Reported twophase assemblagescompatible with phase equilibrium studies include galena-boulangerite(1), boulangerite(1)-zinkenite(8) Oelow 3 18 oC, Craig et al. 1973),,and zinkenite(8)-stibnite.Boulangerite(1)-robinsonite(7)-stibnite, semseyite(2)-hete' romorphite(4)-plagionite(6) (Jambor L969), galena-zinkenite(8), and zinkenite(8){uliippite (9), are reported assemblages not compatible with phase equilibrium studies. Arsenic-free geocronite, madocite, and launayite have not been found. Jamesonite and meneghinite lie just off this join, having essential Fe and Cu, respectively. A review of mineralogical and stability studies in the PbS.BLSa system can be found in Chang & Bever (L973). On this join (Iable I, re#t2; Fig. 8), tle two-phase ,assemblages ported are galena-cosatteQ), cosalite(2)-bismugalena-galenobismutite(3), galenobisthinite, mutite(3)-bismuthinite, and cosalite(2)-galenobismutite(3). Only the last two of these are compatible with phase equilibrium studies (Craig 1967). Bursaite(l) and bonchevite(4) aro rare, and giessenite apparently has copper and antimony as essential constituents that causes it to plot off of the join. Heyrovskyite is probably a member of this join Klominsky et al. I97l; Crallg 1967, Phase trI), although a copper- and silver-free membet has not been reported. Trnrenv Svsrsrvls

three phases have been reported are noted especially. In ,many cases solid solutions are present; however, very little data are available concerning coexisting compositions, so tlat tie line distributions given are only schematic. Conflicting tie lines are dashed. The changes of tie line distributions suggest numerous potential geotherrnometers.
IABLr2. nRMRI PXAISlil nt Cu2S"A9ZS"SS-ts2S3-5b25j-9i2sj roatli'r' St:it!, "'r FIGURIS 3-A ' ---- - --b preae;-fo@I; .;cn

l;intt-tai--Fag-

I . e,rs-Aq:ins; - 6u"m 1 r*"a"mo:ffi ;;-"r*

(r1!' 3) Farcelte (lll) (Harris 0':'t.2

J -.t,

i::i"":;q'
larr:rre

2. a6srjMsre,t-"$:lf::-"to.u+-)B?sil z. dt:rgF-$-25.'1.;

r963) ot':2 6 Flybaslte (lll) (Harris ;; rt. 1965) (Agt5.4_-Cuo.6&)$2sil 2. plybdlb(rrodel variable F&'7 ) (rant"

3.-.rt:&t-tl3

(F19.8)

2. rabaryi&
3. lindsbonlle 4. ? (relln 6. alklrlte 1966)

C!6b681to539 CubBlJS6 Cu3&3Bi7St5

3:6:10 I :2:3 3:6:7

7. nuffieldite 8. ?g(&Fll & hkovlcky 7.lll. ql

Cu4PbtOBltOSZg to4h8lsslt

2:10:5 412.5

(Flq. l0)

2. dilphorlte

AS362Sb3Ss &3h$3S, AgetuS$e5tg Agzfr3sb6sl3 Aob$-S.

Ag2hS$AS)A

3. ? {Hoda& ftang 1972)

5, raMhrlte 5. adorlb 7. flrelyl b

3:4r3 3,2t3 1:5r3 I :2:3

I:5:4

,.
(Fis' ll' 23)

Agztb7Bttos24 l:7r5 I 14:3 AStt2Bl3ST 6(roo.68i0.m(A!,cu).04s .Bi2s3 (6):l 4. r ({ed!cnr.t aL. 1913) 0.9&2S.8.5Pbs.1.9812\ 0.9:8.5:4.9 5. Z (ldddl at aL. 1973) 0.5A92S.9.9roS.4.381t3 0.5:9.9:4.3
2. schl6erlh 3, heyrcbtylh

x (ktup-,ioller 1970)

Ternary sulphosalt composition diagrams are considered in the order of two metal -l- one semi-metal sulphide components, followed by one metal + two semi-metal sulphide components. These components are listed according to the increasing atomic weights of their metallic and then semi-metallic elements. This same order of components is listed clockwise around the ternary composition diagrams. Binary phases are referred to by their identification number along a particular join, as listed in Table 1. Ternary phasee are indicated in Table 2, and are noted on the diagrams by their number of appearance in the ternary. Natural assemblages ate shown as tie lines on the composition diagrams. These assemblages are most often only of two phases; cases wherg

(Fls.12) (Fio.l3) = (r1!. lai = = rr. Ag2)-s2)3-5Dt3 (Fia.t5)

lFl..)61 t.1ffi

(Ftg. 18)

2. gleiudl& 3. tul nnih 4. veelie 5. lbrrylb 6. so6yl& 7. @&clte E. bllangol& 9. pi.yfalrite 10. gdctunlh
B (lalla & 01dig l9l3)

b6(Sb,16)lOS21 Pb(sb,l3)2s1 Pbz($,As)Asz 612($,As)los27 Pqr(sb,k)zsm

tu5(sb tbr6(s

6:(5) 1:1 2:(l) tzr(9) l7:(11) l7r (8) 5: (2) I 5 :( 9 ) 5:(l)

2. k4b6lll!q 8. Ebr6l$

32

THE CANADIAN

MINERALOGIST

7.

f
-u-

'rr. \)
-\], ,,

-z'

1.4-$-\r' \7
\-*f .t

4ozs

4ozs

N N
\.\.

\7

Cu25

BTNARy AND TERNARy SULPHosALT ASsEMBLAGESIN CurS-A&S-PbS-AsrSs-Sbr$'8i6,

33

-A g -As a CuzS-A e,S sS and CuerS grS-SbsS " Natural assemblages for these syctems are ghown in Figures 3 and 4. The substitution of silver for copper in tennantite an'd tetrahedrite dominates the copper-rich portion of the diaglams, the latter being the variety freibergite. These solubility limits hane not yet been investigated by phase equilibrium studies; however, in natural material silver substitutes for copper up to 18 wt. Vo n tennantite, and from 3.5 to 23.8 wt. Vo siTverin tetrahedrite from Japan (Shimada & Hirowatari 1972), and 18.4-42.5 wI.Vo silver in tetrahedrite from Mt. Isa, Austmlia @iley 1974). Substitution of copper for silverr in proustite or pyrargyrite appears negligible. The ternary phasesin Table 2, #l & #2, were defined by Frondel (1963) and Harris et aJ. (1965), and substantiated by Hall (1967) in synthesis studies. Frond,el presents analyses of ternary phases coexisting with argentite and pyrargynteQ)n and these have been used as a guide in drawing tle tie lines in Figure 4. The three-phase assemblageargentite-polybasite(2)pyrargyrite(2), which has been reported several times, probably formed above 197oC, below which stephanite(l) is s-*ble. Tho Cur$AgrS-As"S, system (Fig. 3) has no conflicting assemblages except pearceite(l)-tennantite(l) (Palache et al. 1944) with stromeyerite(1)-proustite(1) (Petruk & staff l97I). (Only the former of these is shown in Figure 3). The CUS-Ag#Sb,Ss system (Fig. a) is topologically similar to its arsenic 'analogue in the antimony-deficient portion of the diagram. Rarndohr (1969, p. 654) reports rniargyrite(3) with polybasite(2) and with stephanite(1), which both conflict with th,e common tetrahedrite(1)polybasite(2) assemblages. These conflicting assemblages.may indicate differing primary depoitional conditions, or may result from the difference between primary and secondary environmeints. More study is needed on these assemblages. The ores of the East Tintic District, Utah, have an abundanceof phasesin these systems, as noted by Pape (1971) and Radtke el are al. (L969). Most assemblages applicable only to more complex sulphosalt systems. The distribution of copper and silver between coexisting solid solutions in these systems provides a potential geothermometer. Solid-state diffusion might, however, tesult in low-temperature re-equilibration, negating such measurements (Barton et aI. 1963). The quaternary CuzS-Ag'S-A&Sa-Sb$a system includes the partitioning of copper-silver and arsenic-antimony between coexisting solid solutions, but it does not fall within the limits of this discussion.

CusS-AsbS-Bi"Ss Stromeyerite(1)-wittichenite(1) and copperrich pavonite(2) -matildite( 1) -bismuthinite, both from Cobalt-Gowganda" Ontario (Petruk & staff I97I), are the only assemblagesreported in this system (Fig. 5). Additional tie lines shown in Figure 5 are taken from phase equilibrium studies at 454"C (Chen & Chang t974), so are only meant to be suggestive. Each of the AgrS-tsiaSs phases has extensive solid solutions into the ternary at this temPerature. Phases on the CurS-BirSs join are generally found in copper-rich zones' whereas phases on join are found in lead-rich zones. tho Ag^S-BizSs It may be that the lack of internal natural assemblages results from the geochemical sepalation of copper and lead in hydrothermal condi' tions. Cu"S-PbS-AssSg Seligmannite is a ternary phase @ig. 6). The assemblagesin the porti,on of the diagram more arsenic+ich than tennantite(l) and dufrenoysite(3) are restricted to the Lengenbach Quarry, Binnatal, Switzerland. A significant sequenceof assemblages has been described by Markham (1959) from South West Africa as: 1. jordanite jordanite(2)(2)-tennantite(1)-sphalerite, 2. tennantite(l) -galena, 3. jordanite(2)cnargite-gawas reported as "narlena. The third assemblage row veinlets of galena, frequently accompanied by enargiie, that intersect masses of jordanite, which suggestslater replacement of jordanite by galena-enargite".Jordanite was verified by r-ray diffraction. whereas the other identifications were made by ore microscopy. The changefrom assemblage2 to 3 reflects an increase in sulphur fugacrty if at constant temperature, and the presence of enargite suggsts a temperature greater than 320oC (Skinner 1960). Another tlree-phaseas:emblage @amdohr t969, p.748) 1) is galena-tennantite( -gratonite(1) orystallized from Pb-As-Sb gels or glasses found at Cerro de Pasco, Peru. The glassesare thought to have formed at temperatures of approxirnately 100'C. The glasses show a large chemical variabitrity, and a recent microprobe study (Burkart-Baumann e, al. 1972) of crystalline inclusions gave a composition of PbrAsesn for the lead sulpharsenide phase, somewhat more arsenic-rich than jordanite. The above discussion establishes one gxoup of tie lines on Figure 6, whereas the following presents less carefully substantiated evidence for i conflicting galena-seligmannite(1) tie line. Refsrring to jordanite from Balmat, New York,

THB CANADIAN

MINERALOGIST

Ramdohr (L969, p. 745) states that it ..partly ^seligdecomposes -into myrmekitic aggregatesof mannite, galena, a little tennantite, and native arsenis". Copper, however, is not balanced in yc\ a suggested decomposition. Seligmannite has been observed microscopically as a reaction product between galena and tennintite, with tle reaction zone b,eing porou (Sztrokay 1945). "f-hese apparently conflicting tie lines merit further investigation. Tennantite in these assemblages should be checked for the presence of anrimsrt' alternatively, two primary-facies may be present in the system. Finally, Uytenbogaardt (1951) and Schouten (1962) roport gratonite found with chalcocite, which conflicts with the common assemblage galena-tennantite. This reported association ls apparently taken from Rust (1940) who considen the chalcocite to be supergene. This assemblage has not been indicated in Figu,re 6.

assemblages arsenic-bearing.*Petersen (1962) is resolves these conflicts by suggesting the two different facies ghown in Figure 21 which might represent the ends of a spectrum of.P-T changes. Paragenetic sequences frequently take a path from tetrahedrite to tetrahedrite-bournonite, or tetrahedrite-bournonite-galena to boulangeritegalena, making a series of steps across tle diagram. This sequence, wi'th minor rnineralogical variations, reflects the differentiation of copper and lead. A different lmragenetic sequence has been documented from stibnite veins at Dubrava, Czechoslovakia(Jakos 1963, mainly microscopic observations). The assemblagesare stibnite, to zinkenite(8)-bournonite(1), followed by tarahedrite( 1) -chalcostibite(2). Cugs.PbS.Bi,,Ss

The profusion of ternary phases is listed in Table 2, ff6, and Figure 8. Five phasesplot on CuS-PbS-Sbp,Ss a line colinear with bismuthinite and aikinite (6), with their unif cells being a continuous seThis system contains a number of conflicting (Fig. 7); however, tie lines to tetra- quence of ordered superstructures based on assemblages hedrite(l) must be viewed with caution due ro aikinite (Padera 1955; Welin 1966; Moore its solid solution with tennantite. Although lead L967), These intermediate phases, except rezbanyite(2), have been found only at Gladhamhas been reported in tetrahedrite in subitantial amounts (10 wt. Vo,PalacAe et al. 1944), recent mar, Sweden, and have been subjected to eleselectron microprobe investigations have not tron microprobe verification (Welin 1966). Little is known of their paragenesis, but they found measurable quantities (Shi.mada& Hiromight be used as indicators of bismuth fugacity wataJi 1972i Riley 1974). Bournonite(l) has been reported with most changesand,/or temperature. Aikinite is reported with a number of phases other phases in the system. Its coexistence with in the system.Emplectite(2) is found with cosachalcocite is prevented by the common galenatite(2) and galenobismutite(3) (Uy"tenbogaardt tetrahedrite(l) assemblage. The phases appear- 1951), which would conflict with the phaseson Pg_-gn the galena-stibnitejoin between semseyite(.2) and zinkenite(8), although possibly com- the bismuthinite-aikinite join. Primary facies patible with bournonite, have 6een fourd onlv changes are suggestedfor this system, in agreewith jgqepnite, which lies jusr off this plane ment with its antimony analogue.Berryite (Nuftoward FeS. The three-ph,aseassemblagegalena- field & Harris 1966) and larosite (petruk 1972) tetrahedrite(1)-bournonite(1) is very common are phases which lie off of this composition (standard references; Itrarada Lg73) both in plane, with silver substituting for copper. Finalequigranular textures and as gal,enareplacing te- ly, it is noted that the Cu-Pb-Bi sulphosalt reported by Honnorez-Guerstein (1971) is too trahedrite with a reaction rim of 6ourno-nite (Anderson 1940; Ramdohr 1969). This is in sulphur-rich to plot in this system. conflict with the repeatedly reported tetrahedrite(1)-meneghinite(2) (siandard referenc,es) Agz'S-PbS-AseS" 11d tetrahedrite(1)-bournonite(l)-meneghinite (2) ot Warren Q.946). On the more antimonvNo sclid solutions and comparativeily few asrich portion of the diagram, boulang.erite(l)- semblages are observed (Fig. 9). Marrite (1) tetrahedrite(l) (standard references; Warren & (lable 2, #7) is the only ternary phase, and is Thompson l9M) conflicts with other a:semblages of bournonite. These conflicts are explained if either there is a temperature range *J. Wu & R. Birnie have found arrenic-bearing over which bournonite is unstable, or, more bournoniie, which could also probably, if the tetrahedrite in certain of these flicts, personal communication, explain these cont974.

TN Cu$-AgzS-PbS.ASzSs-Sb'S',Bi,Ss BINARY AND TERNARY sULPHosALT ASSEMBLAGES

35

repolted only from the Lengenbach Quarry, linna,fnl, Switzerland. The only assemblage is that of proustite(l) - jordanite(2) (uytenbogaardt 1951), each of which could contain antimony. Several of the phases on the anenic-rich side of the tie line are found only at Binnatal; several additional phases closely related to this composition plane and found almost exclusively at Binnalal are lengenbachite, which has copper substituting for silver, hatchite with thallium substituting for lead, and hutchinsonite which has both substitutions taking place. Ae"S-PbS-SbeSs The profusi,on of ternary phases in this system (Table 2, #8; Fig. 10) can be better-visualized by considering several colinearities. The galena-miargyrite(3) join appears as a complete solid solution in phase equilibrium studies at 500'C (Hoda & Chang 1972), but is more limited at lower temperatures. Phasesreported here are freieslebenite(1), diaphorite(2), and synthefic AgsPbSbssr(Hoda & Chang 1972). Another oolinearity is a ray from galena to AgSbaSr,with andoritq ramdohrite, and owyheeite. Fizelyite' however, might be considered to plot on a coli(falkmanite') and Agnearity between PbgSbaso (andorite), as suggestedby Karup-Mlller PbSbaSc (1970). Crystallographic, electron microprobe, and phase equilibrium studies would help decipher which substitutional mechanisms are operational. The compilation of reported assemblages in tiis system is complicated (Fig. 10). The association of phases on both the galena-miargyrite (3) and galena-andorite(6) joins with 'pyrargyrite' provides many crossing tie lines. As pyrargyite(2) has a solid solution of arsenic substituting for antimony, it is possible that the phases on the galena-andorite(6) join coexist with a pyrargyrite more arsenic-rich than those on the galena-miargyrite(3) join. Alternatively, the phases on the galena-miargyrite(3) colinearif become unstable below 300oC (the lowest temperaturo of investigation of Hoda & Chang 1972), permitting the association of phases on the galena-andorite(6) join with pyrargyrite(2). A number of additional conflicting tie lines which are reported include argentite-freieslebenite(l) versus the more common galena-pyrargalena-fizelyite(7) versus boulangegyite(Z), rits(1)-owyheeite(4), and stephanite(1)-andorite(6) (Williams 1968) versus several tie lines. Furthermore, tle galena-miargyrite(3) coexistence (Ramdohr 1969, p. 653) can be explained only if all of the intervening phases are unstable over a certain P-7 interval.

Three-phase assemblagesreported are pyrar(Ramefite (2)-miargyrite (3)-owyheeite (4) dohr 1969, p. 736), galena-stephanite(1)+yrargynte(z) (Oelsner 1961, Fig. 58), galena-argortite-freieslebenite (1), galena-pyrargyrite (2)-diaphorite(2), and stephanite( 1) -pyrargyrite (2)'an' dorite(6) (ast tlree from Palache et al. L9M\ This last assemblage was again recognized by Williams (1968) in another study of the same area, Morey, Nevada. Williams describes a complex series of paragenetic changes starting with jamesonite and followed by owyheeite(4) or andorite(6). Andorite is then replaced by stephan' ite(l) and pyrareyrite(2) or by freieslebenite(l) and owyheeite(4), and this in turn is replaced by galenaor pyrargyrite(2). No mention is made oi identification techniques or replacement cri' teria, and the position of stephanite on the composition diagram is misPlaced. Phases and assemblages in this system are complicated and warr'ant further detailed study. The profusion of phases provides for the measurement of subtle changes in the relative fugacities of the components when sequencesof assemblages are documented. Ag"S-PbS-Bi"Ss Six temary phasesare reported (table 2, #9; Fig. 11 & 23). None was found in synthesisstudies down to 4@oC (Craig 1967)' with the implication that they appear at lower temperatures. Craig inferred from his work and from natural assemblagesthe lower temperature compatibilities given in Figure 11, to which the three-phase assemblage galena-cosalite-heyrovskyiie (Klominsky er al. I97I), and tle two-phase assernblages galena-schirmerite and gustavite-pavonite, have been added. A sequence of natural assemblages @ig. 22) with some of these te'rnary phases has been dessriM by Nedachi er alTtgZl), who used an electron microprobe. Fluid inclusion filling temperatures in associatedquq4z have ranges between 87'L42"C and 2W245"C7 a maximum partial pressure of sulphur is apas proximately 10'14-10-15 inferred by e-xtrapolation of higher-temperature data to 225"C, gsven the presence of pyrrhotite and native bismuth. Such detailed studies of sulphosalt assemblages are needed for further understandrng of sulpho' salt systems. The bismuthinite-pavonite(2)-gus197O) and galena-matavite(l) KaruFMlller L973\ tildite(1)-sshirmerite(2) (Karup-Mlller assemblages are not incompatible with these low-temperature assemblages of Nedachi et a/. teur which includes CuaS, but they are beyond the scope of the present studY.

(1e73). sysphases in the quaternary exist Numerous

Cu25

Cu25

BrZSS

AsrSa

Fizss

4oz s

sbzs3

AsaSa

agzs

Bizs3

s b2s3

sb2s3

A s2S3

TN Cu6-Ag:S.PbS-AsISTSbsSs"Bi6a BINARY AND TERNARY sULPHosALT ASSEMBLAGES

37

Cu%l-AsoSrSbz'Se The projection of the tennatrtite-tetrahsdrite solid solution falls on this compositional plane (Fig. 12). Complete exchange of antimony for arsenis takes place above 400oC, but there is some suggestionthat one or.more solvi are present at lower temperatures (!Vu, J., personal communication L972), Tennantite-tetrahedrite compositions also have a significant variation off this plane towards sulphur, being limited by the compositions which coexist with the enargitefamatinite solid solution. Synthesis studies on theso coexisting solid solutions have resulted in a geothermometer which has been applied to (Feiss 1974). Temperature natural assemblages and sulphur fugacity measurements are also potentially available from tennantite-tetrahedrite coexisting with both chalcostibite and stibnite. Detailed analysis of mineral assemblagesin the Cu-As-Sb-S system (Petersen 1962) indisates that this three-phase assemblage is a relatively sulphur-deficient one. It has yet to be adequately documented in natural material. Antimony-rich tetrahedrite is reported (Petruk 1971) coexisting with cobalt arsenidesin an environment deficient in sulphur.

potential geothermometers exist from the compositional variations within the five three-phase assemblages. Phase equilibrium studies of the solid solution of chalcostibite fu1e this ternary are not in agreement with the extreme rarity of this phase, and the relatively more abundant tetrahedrite-bismuthinite. AgzS-AszS.Sbz'Ss

This ternary system is dominated by the proustite-pyrargyrite solid solution which is complete down to at least 3O0oC (Toulmin 1963). Coexisting prou:tite and pyrargyrite have been reported several times, but infor'mation on coexisting compositionsis lacking. Ramdohr (1969, p. 722) states that a miscibility gap exists between 13-97% proustite at room temperature. Reaction rates (Barton et al. 7963) suggestthat high-temperature assemblages including proustite-pyrargyrite may redistribute arsenic and antimony in the solid state at lower temperatures. The tie lines shown in trigure L5 are schematic, and the composition of only one assemblage, argentite-pyrargyrite (Frondel 7963), is reported. Pearceite and As-polybasite lie just off this plane towards chalcocite, and billingsleyite lies toCusS-As$rBitSt wards sulphur. These expanded systemscontain of assemblages potential geochemical interest No ternary phasesare reported (lable 2, #ll; Tho assemblageproustite-stephanite (Petruk Fig. 13) although a maximum of 15.9 wt. Vo 1971) conflicts with the more common argenbismuth in tennantite has been reported (Springer tite-pyrargyrite. L969). The only assemblageis a bhmuthian ten' nantite-wittichenite tie line (Oen er al. 1973). This lack of assemblages,might reflect a geo- Ag'S-AsESrBinS" chemical soparation of arsenic and bismuth in No ternary phasesand no reported compatibi' irondeficient environments, the latter qualifipresent in this system (Fig. 16). of the more common bis- lities are cation added because muthinite-arsenopyrite assemblage. Ag"S-SbeSnBias' CusS-Sbz,S-Bie,Ss Ono ternary phase, aramayoite, has been re' Phase equilibrium studies in this system (Chen ported, and is found with bismuthinite, with py& Chang 1971) suggest a compositional varia- rargyrite(2), and coexisting with both miargytion of wittichenite 'on the Cua$BizSs bina'ry rite(3) and pyrargyrite(2) (Lewis 1964). Synftom 22 tn 27 mole 7a. Substitutiot of. 6O at. Vo thesis studies (Chen & Chang 1971) indicate a Sb for Bi in wittichenite, but with very little con- complete solid solution between matildite(l) verso substitution taking ptrace, was found at and miargyrite(3) at 450oC. At 3o0oC, 56 mole 450'C. Similar semi-metal substitutions provide Vo miargyite is still soluble in matildite. Aramasolid solutions into the ternary io chalcostibite yoite may be an ordered phase cooled from this solid solution, and its compositional variations and 'eichbergite'. Naturally occurring tetrahedrite has been may prove to have geothermometric interest. found to contain 3.1 wt. % bis,muth (Petruk L97lr. A large number of coexisting phaseshas PbS-Asz,SrSbz'Sa been reported (Fig. la) with no conflicting tie In spite of the fact that both of the lead-bearlines. The solid soluti,ons and tie line distributions are only topologically conect as no data ing binaries of this system are characterized by on coexisting compositions are repo.rted. Five a profusion of phases, in all but a very few

38

THE CANADIAN

MINERALOGIST

cases have any coexisting phases in this system been reported. The geological environment in whish the most cornmon of these phases are generally found is in aJfiliation with hydrothermal ore deposits. The several compatibilities frcm this environment are tle jordanite-geocronite solid solution assosiated with galena and semseyite, and with meneghinite which lies just off this plane towards CuaS. In this system are a large number of phases which have been found only in a second, rare environment. Many of the lead sulpharsenideshave been found only in the Lengenbach Quarry, Binnatal, Switzerland, whereas a majority of phases present in the ternary system under discussion have been found only at Madoc, Ontario (Jam-

bor 1967u b, 1968). The suggestedsolid solutions, observed phases, and their associations are seen in Figure 18, based largely on Jambot's work. He reports a paragenetic sequencexhibiting decreasing As/Sb values, and points out one possiblo origin of such a complex mineralogy as the reworking of an original galena, arsenopyrite, sphalerite assemblage by antimony-rich solutions. This conclusion is similar to that of Graeser (1968) with respect to the origin of the complex mineralogy found in the Binnatal. Phase equilibrium studies in the system at 400'C (Walia & Chang 1973) verify the existence of a number of solid solutions. Fifty-eigbt at. Vo antimony can substitute for arsenis in jordanite as the geocronite solid solution, 45 at. Vo

PbS

PbS

Bi2s3

Ast53

Bi2s3
Ag25
N e d q c h ie t . o l . , , t973

sb2s3

22.

Sb253

BTNARY AND TERNARY SULPHOSALT ASSEMBLAGES rN cuaS-AgiaS-PbS-AsrS3-SbzSa'BirS.

39

in dufrenosite towards the Sb end-member veenite, and 3O at. Vo antimony in z.inftsnile can be suhtituted by arsenic. Madocite has compositional ranges in both the As/Sb and Pb/(As* Sb) dimensions.The lsmaining phases of Jambor, except guettardite, wle not found in the phase equilibrium studies down to 400"C. Coexisting solid solutions in this system have potential for geothermometric or semi-metal fugacity measurements, but their extreme rarity Iimits their development and applicability.

tions are extended along them in topological agreement with reported asnemblages.Conflicting tie lines in these ternary systems might be explained by substitutions into quaternary or higher systems. An example of this is pyrargyrite in the Cu*S-AgzS-Sb,$ and ApS-PbS-Sb"$ systems,where arsenic substituting for antimony may resolve conflicting tie lines. Other such substitutions are Cu - Ag, 2Pb - AgSb, 2W AgBi, As-Sb, Sb-Bi, and Pb-Bi (limited), although others occur also. Certain quaternary systems of particular interest resulting from such substitutions are CurS-Ag2S-PbS-BirSs, PbS-AsESsBt2,St and Cu#Ag;$AszSrSbzSg, CuzS-PbS-Asfg-SbzSg, No naturally occurring phaseshave been re- CurS-As^$-SbrS'-BirSg. With the above ideas in mind, and considering ported rn this system, although Walia & Chang the composition diagrams as strictly ternaries, (1973) found two zuch phases (table 2, #I7) at 400oC. No assemblages have been reported. there are certain bivariant assemblages(in terms of pressure and temperature) in which solid solutions may vary enough to make them of poPbS.SbESl..Blds tential geochemical interest. They can be identifields joined Several ternary phases are reported (Table 2, fied on tho figures as three-phase to one or more solid solutions, and they are listed #18; Fig. 20), and antimony substitutesfor bisof these lie in the muth to a small extent in lillianite. Assemblages in Table 3. The fact that many CurS-AgrS-As#r-SbrS" system makes it of parare kobellite(2) with galena, and with bismuthiBarton et al. (L963) point nite, and tintinaite(1) with galena. Solid solu- ticular interest, but as out, trtostdepositional solid-state exchange may tions within the ternary are predicted on the primary compositions. Ideally, basis of the diadochy of antimony and bismuth, occur, modifying .partitioning of these elements between calibration of compositional variations with phyand the parameters can be used to resuch solid solutions is of potential interest. This sico-chemical strict degrees of freedom of natural assemblages system is of the type which will prove more (Barton & Skinner L967). Such studies will be complicated and interesting when it receives particularly useful when other variables can be more detailed studv. fixed by an independent means. Certain other DrscussroN The above study of natural sulphosalt assemblages has resulted in the derivation of 18 ternary sulphosalt composition diagrams. In general only those phases and assemblages which lie strictly on the ternaries have been considered. Exceptions are tennantite and tetrahedrite which havo been projected onto the CuzS-As$s and joins, and digenite which is proCu,S-SbzSa jected to CurS. This limitation prevents the inclusion of certain phases, notably jamesonite, which contains essential iron. In other cases the essentialnafure of a minor element is not known; in these instances a mineral may be mentioned in the text or tables, but is left off the related diagram. Examples of these are neyite and berryite, which have small amounts of silver and conplane. sequently plot off the CusS-PbS,BizSia Reported phasc are plotted as being of endmember composition, in general, as only a few studies have reported assemblages with actual coexisting compositions. Tie lines to solid soluTABLE3 of P and ?) ln whlch Llsted belry are bivarlant asss$lagG (in tem solid solutloE may vary ercugh as to mke tim of potentlal gechemlStudy of certain tf,o-phase assenblages arcng tiese cal inter6t. mlqht also be used to limit ore or bro dtrrees of freedon. These A. are arrived at frcm 4!gD1qg6

Sys ts

Assemblages strcmeyeni te-pearcei tstennanti te Dearcel te-tennantl te-prcus tl te pearcel te-prcustl t*aEenpolyb6l te pearcei te-a6enpolybasl t$argentl te prcus tl te-a6enpolybas i t-argentl te

Cu2s-AS25-As2s3 chal cocl te-s trcneyeri te-tennantl te

Cu2S-AS25-!,b253 coci te-: tmmeyerl te-tetrahedri chal

te s trcmeyeri te-tetrahedri te-antJrcnpearcej te antircnpearcei tepo lybasi t-argenti te polybasl te-argentl ts-s tephani te polybas i te-s tephani te-pyrarqyri te po lybasl t*antlrcnpearcei te-pyrargyr'l te antimnpearcei te-pyrargyr'l te-mlargyri te antlrcnpearcel te-tetrahedrl te-niarqyri te pyrargyri te-mi argyri te-tetrahedri te niargyrl te-tetrahedri te-s tlbni te tetrahedrl te-s tibnl techal os tibl te

te-chal cos tib i te Cu2S-4s253-Sb253 tennati teltetrahedri t*stibnl B Cu2sSb2S3-i 253 chal coci te-tetrahedri te-wi tti cheni te tetrahedri te-vi tticheni t$empl ecti te tetrahedri te-bi snutlti nl techal cos tib i te bismthl nl te-chal @stibl te-s tibni te argenti te-pyrargyri te te-prcustJ te

Ag25-As253-Sb253 argerii te-s tephanl te-pyrargyri

AS2S-Sb253-Bi Ihere are nwercF potential blvarlant asssblage5 2S3 Natural assenlrlag6, hofever, do Pb5-As2s3-sb2s3ln tise systm. not define tlle topolow of the diagrare emugh for pb5-5b2s3-Bi 2s3 thm to be idotified.

40

THE CANADIAN

MINERALOGIST

systems (CulS and FbS with AszSb, Sbs.Sa and BigSsiand AgrS and pbs with sb"ss and Bi"sa); commonly possessing number of ternary phases, a indicate facies changesby tie line switches. Phase equilibrium studies can theoretically deterrnine the pressure and temperature xanges of sulphosalt facies, and such ranges can also be calculated from thermodynamic parameters (Craig & Barton 1973). The study of sulphosalt stability relations in temperature/sulphur-fugacity space has been initiated (Craig & Barton L973; Crug et al, L973), and can prove fruitful rn defining conditions of formation. The present study of natural assemblagesadvances this work. Einally, documentation of sequences of primary assemblagesin a deposit can serve as an indicator of the direction of fugacity changes during deposition. It is emphastzed. that whereas many of the phases mentioned in thi$ study are quite rare, taken as a group these sulphosalts are more significant. A common geologic setting of these species lg rvirhin, or marginal to, base metal deposits, some of great value. Sulphosalt petrology can conceivably be used as a guide to exploration for and development of such deposits; consequently, an understanding of the environments of formation of these minerals is of interest. It is hoped that the present work will stirnulate interest in and further studv of natural assemblages sulphosalts. of AcrNom.ppceMENTs I am grateful to R. Birnie, J. R. Craig R. Kamilli, and U. Petersen, who kindly read early drafts of the manuscript. Their commnts wele helpful, but they are not responsible for remaining deficiencies. REFrnr,Ncss ANDERsoN, J, (1940): Microscopicfeatures of R. ore from the SunshineMine. Econ. Geol. BS, 662-665. p. Banrou, P. ts. Jn., BETIKE,p. M. & Tour,Mrr.r, (1963):Equilibrium in ore deposits. Mineral. Soc. Amer. SpecialPaper L, 171-185. & SrrNlqER, J. (1967): Sulfide mineral B. stabilities. In Geochemistry ol Hydrothermal Ore Deposits(H. L. Barnesed.), 236-333.H:olt, Rhinehart, and Winston, New York. BuHrrvrarrrN, (1971): Untersuchungen E. im System BirSg-Cu2S und geologisch: Schlussfolger ungen. N. lahrb. Mineral. Monat. 3, 137-141. Bunrenr-BluMeNN, I., Orrsr"reNN,J., Nusrn, B. (1968): Gratonit aus der LagerstiitteRio Tinto, Siidspanien. Jahrb. Mineral. Monat. 7, 215N. 224.

& Alrsrrnz, G. C. (1972): The r-ray amorphous s 'tfides from Cerro de Pasco, Peru, and the crystalline inclusions. lf. Jahrb. Mineral, Monat. 433446. CHANc, L. L. Y. & Bnwn, J. E. (1973): Leacl sulphosalt minerals: crystal struc.tures, stability relations, and paragenesis. Minerals Sci, Engng. 5,181-191. CrrEN, T. T. & CueNc, L, L. (1971): Phase relations in the systems Ag*9SbzSg-BiuS, and Cur$, Sbrsa-Birss. Geol. Soc. Amer. Ann. Mtg. Prog. Abstr. 43. Cnerc, J. R. (1967): Phase relations and mineral assemblages in the Ag'Bi-Pb-S system. Mlneralium Deposita L, 278-306. & BenroN, P. B. Jn. (1973): Thermochemical approximations for zulfosaft* Econ, Geol. 68, 493-506. --, CneNc, L. & Lsrs, W. R. (1973): Investigations in the Pb-Sb.S system. Can. Mineral. L2, 199-206. FEIss, P. G. (1974): Reconnaissance of the tetrahedrite-tennantite/enargite-famatinite phase relations as a possible geothermometer, Econ. Geol. 69, 383-390. Fr.usctlrR, M. (1971): Glossary ol Mineral Species. Mineralogical Record Inc., Bowie, Maryland. FnoNonr, C. (1963): Isodimorphism of the polybasite and pearceite series, Amer. Mineral. 48, 565-572. & HoNrr., R. M. (i968): Billingsleyite, a new silver sulfosalt, Amer. Mtneral. 53. l79l1798. Gooorrr., P. (1970) : Zoning and Paragenesi,sin the Julcani District, Peru. Ph.D. Thesis, Harvard University. GnensER, S. (1968): Kurz Be*chreibung der wichtigsten Ingenbacher Mineralien. /z Die Mineralfundstelle Irngenbach in Biunatal. Natarlrist. Mus. der Stadt Bern, Switzerland, Herr, H. T. (1967): The pearceite and polybasite seies. Amer. Mineral. 52, l3ll-1321. (1966): The Systems Ae-Sb-9, Ae-As-S and Ag-Bi-S: Phase Relations and Mi,neralogical Significance. Ph.D. thesis, Brown Univ., Providence, R. I. (1964): Equilibrium relations among some sllver sulfosalts and arsenic sulfides. Trans. Amer. Geophys. Union 45, 122 (Abstr,). Herene, K., Sexevroto, O., Nereo, K. & NecistultA, K. (1970): Bournonite from Daikoku, Chichibu mine, Saitama, Japan. Mineral. l, (Japan) 6, 186-188. HenRrs, D. C. & OwsNs, D. R. (1973): Berryite, a Canadian occurrence. Can. Mincrql, 11, 1016-1018. Nurrrrr,o, E. W. & FronsERc, M. H. (1965): Studies of mineral sulphosalts: XIXselenian polybasite. Can. Mineral. 8, L72-184. Hooe, S. N. & Cnarc, L. L. Y. (1972): Phase relations in the systems AggS-PbS-Sb:Sg aud Ag:S-Pb$BirSs. Geol. Soc, Amer. Progrant Abstr. 4,539-540.

--,

BTNARYAND TERNARv suLpHosALT ASSEMBLAGEsm CUS-Ag"$PbS-AsfrSbrSr-Bin

4l

HoNNomz-Gurnsttnt, B. M. (1971): Betekhtical. N. lahrb. Mineral. Monat, l, 4346. nite and Bisuffosalts from the copper mine of PADERa, (1955): Beitrag zur Revision der MiK" "La I,eolra", Argentina. fuliheralium Deposita neralien aus der Gruppe von Wismutglanz und 6, llL-L2L. Aikinite. Chemte Erde L8, l-14. JAKES,P. (1963): Studies in stibnite veins on P.lrs, L. W. (1971): Geology and mineralogy of qorth-western slope of Nizke Tatry Mts., in the Trump fissure-fault ore body, Trixie Mine, tho area of Dubrava deposiL Acta Univ. CaroEast Tintic District, Utah. Geol. Studies, Briglinae Geol. L59-L78. (Czech with English sumham Young Unlv. t8, ll5-L46. Eary). PAr-acun,C., BErureN, H. & Fnoxoer-, C. (L944): Jeunon, l. L. (1967): New lead sulfantimonides The System o! Mineralogy 1. New York, John from Madoc, Ontario - Part L. Can. IuTineral Wiley & Sons. 9, 7-24, PntrRsaN, U. (1962)z Genesisof Ore Deposits in (I961b): New lead sulfantimonides the Andes of Central Peru. Ph.D. Thesis, Harfrom Madoc, Ontario - Part 2 - Mineral devard Univenity. scriptions. Can. Mineral. I, t7t-2L3. dePrrr.ur, W. & staff (I971)z The silver-arsenide (1968): New lead sulfantimonides posits of the Cobalt-Gowgandaregion, Ontario. from Madog Ontario - Part 3 -=- Syntheses,paraCharacteristics of the sulphides. Can. Mineral. genesis,oigsn. Can. Mineral. 9, 505-521. Ll, 196-231. (1969): Sulphosaltsof the plagionite ReDrrs, A. S., Tevro& C. M. & Monnrs, H. T. groll;p.Mineral, Mag, 37, 4/.2446. (1969): Micromineralogy of galena ores, Burgin Mine, East Tintic Diatrict, Utah, U,S. Geol. Kenw-Mdr.r.rn, S. (1973): New data on schirmerite. Can. Mineral, LL, 952-957. Surv. Prof. Paper 6L4-4, t-I7. (1970): Gustavite,new sulphosaltmin- nmroom, P. (1969): The Ore Minerals and Theb eral from Greenland. Can. Mineral. LA, fi4-790. Intergrowths. Pergamon Fress, New York Kuclilrr, C. W. & HoNne, R. M. (1969): The Rnsl J. F. (1974): The tetrahedrite-freibergite systemAg-Sb-Sfrom 600'C to 200"C. Mineralseries, with reference to the Mount Isa Pb-Znium Deposita 4, 153-171. Ag orebody. Mineraliam Deposita 9, ll7-124. Klol,,frNsKy, J,, Rrcorn, M., Krnnl C. & MRAZ, RoLANo, G. W. (1968): The system Pb-As-S; L. (1971): Heyrovskyite, 6(Pbo.86Bi.o0r(Ag,Cu)- composition and stabilif of jordanite. Mineral. ium Deposlta g, 249-260. 0.04)5 Bir,$ from Hurky, Czechoslovakia,a (1970): Phaserelationsbelow 575"C in new mineral of genetic interest. Minerallurn Deposita 6, 733-147. the system Ag-As-S. Econ. Geol. 65' 24t-252. Kurcx, V. & MAKovrcKy, (1968): Die Kristall- Rusr, G. W. (1940): Geologic occutrenceof graE. structur des Minerals (PbAg,Bi)CuaBioSrr. lV. tonite at Cerro de Pasco, Peru. Amer. Mineral. Jahrb. Mineral. IVIonat.7, 236-237. 25, 266-270. Lnwrs, R. W. Jn. (1964): The Geology, Mineral- ScnorrrBw, C, (L962): Determination Tables tor ogy and Paragenesisof the Castrovineyna PbOre Mlooscopy. Elsevier, New York. Zn-Ag Deposits, Peru. Ph.D. Thesis. Stanford Scott, J. D. (1971): Collecting rare sulfosaltsin Univenity. British Columbia. Mlneralogical Record 2, MenxueM, N. L. (1959): Occurrence jordanite 203-209. of in the Otavi Mountains, South West Africa. Srur,rao.l, N. & I{rnowetenr, F. (1972): ArgenAmer. Mineral. 44, 68L685. tian tetrahedrites from the Taishu-Shigekuma mine, Tsushima Island, Japan. Mineral. J. Mlsrr, S. & SmnlsR, B. J. (1971): Studiesof the (Japan)7,77-87, sulfosalts of copper. I. Phases and phase relations in the system Cu-As-S. Econ. Geol. 66, Srnwrn, B. J. (1960): Assemblage enargite-fama901-918. tinite, a possible geologic thermometer. Geof. McKrNsrnv, H. (1963): Mineral assemblages in Soc. Amer. Abstr. Ann. Mtg. 7t, 7975. sulfide ores: The system Cu-Fe-As-S. Econ. LucB, F. D. & MAKovrcrv, E. (1972)z Geol. 58, 483-505. Studies of the sulfosalts of col4rer III. Phases (1959): Mineral assemblages sulfide in and phase relations in tle system Cu-Sb-S" ores: The system Cu-Fe-S-O.Econ. Geol. 54, Econ. Geol. 67, 924-938. 975-1001. SrnrNcrn, G. (1969a): Compositional variations Moonr, P. B. (1967): A classificationof sulfoin enargite and luzonite. Mineraliam Deposita salt structures derived from the structure of 4, 72-74. aikinite. Amer. Mineral. 52, 1874-1876, (1969b): Naturally occurring composiNrpaclrt, M., Tercucrn, T., Yevreore, K. & tions in the solid solutions series Bis,$-SbeSs. Terincucrr, M. (1973): Bt-Ag-Pb-S minerals Mineral. Mag, 37, 295-296. (1969o): Electronprobeanalysis of tefrom Agenosawamine, Akita Prefecture, Northeastern lapan. Mineral. "/. (Japan) 9, 69-80. trahedrite. N. tahrb. Mineral. Monat. t, 2+32. & Lerr,err,rur,J. H. G. (1971): The sysOrrsNnn, O. (1961): Atlas ol the Most Important tenr Birsg-SbzSa. Can. Mineral. 10, 847-853. Ore Mineral Parageneses Under the Microscope, Pergamon Press, New York, N.Y. beobachSzrs.oKA! K. (1945): Erzmikroskipische OBN,I. S., Bumr, E. A. I. & Krrrr, C. (1973): tungen an erzen von Recsk (Matra Banya) in Bismuthian tennantite from Mangualde,PortuUngarn. N. Jahrb. Mineral. Ab. A79, L0+128.

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TUE CANADIAN MINERALOGIST

Trxr.on, C. M., RADTKB, S. & Cnnrsr, C. L A. tions in the systems Pb$SbrSs-AsrSg and PbS (1973)z New data on cuprobismutite. J. Res. Bi2Ss-Ase$. Can. Iulineral. L2, LL3-LL9. US. Geol. Surv. L, 99-103. Wnr;N, E. (1966): Notes on the mineralogy of Tout rurx, P. 3no. (1963): Proustite-pyrargyrite Sweden. 5. Bismuth-bearing sulfosalts from solid solutions. Amer. Minerul. 48, 725-736. Gladhammar, a revision. Arkiv Mineral. GeoI. fRAIr;L, R. J. (1970): A catalogue of Canadian 4, 377-386. minerals. Geol. Surv. Canada Paper 6945. Wu-lreus, S. A. (1968): Complex silver ores from UyreNBocAARDr, (1951): Tables for lVlitoW. Morey, Nevada. Can. Minerul. 7, 475483. scoplc ldentification of Ore Ml,nerals. Hafner Pub. Co., New York. Manuscript received July 1974, emended October WALIA,D. S. & GraNc, L. L. Y. (1973): Investiga1974