Canadian MineralogistVqr. 13, pp. 2742 (1975)

AssrRAc"T

The Cuz$Agz$Pb$As2Ss-SbaSs-BilSs systemhas 18 temary sub-systems which contain sulpho-salts. Phases and natural assemblages reported inths literature are plotted on ternary compositiondiagrams of these sub-systems. Tie line variationsprovided by extensive solid solutions suggest nu-merous potential geothermometers. Facies changesare also indicated in certain systems by tie lineswitches as suggested from natural assemblages.Sequences of assemblages from a deposit have thepotential of indicating relative metal and/or semi-metal fugacity changes.

This type of data analysis suffers from the am-biguities inherent in sulphosalt identification. Ad-ditionally, detailed analyses of pbases having vari-able compositions are atnost completely lacking.Qualifications concerning the meaning of an as-semblage, and tle degree of attainment of equili-brium are also noted.

Tho potential interest of detailed investigationson sulphosalt assemblages is emphasized.

INt'nonucttox

The purpose of the present study is to deriveternary compatibility diagrams lor a large por-tion of sulphosalt chemistry using previously-reported data concerning natural assemblagesof sulphosalts. Many sulphosalt compositionscan be expressed as combinations of simplesulphide components, and the system consideredhero is CueS-AgzS-PbS-As"Sa-SbzSa-BisSa. Phasespresent in the sulphosalt binaries and ternariesof this system are listed in Tables I al.d 2,respectively, and phases are plotted on ternarycomposition diagrams using all combinations ofthese sulphides ,as end-member components ofsulphosalt systoms. Reported natural assem-blages are then indicated as tie lines on the com-position diagrams. Reference is madE to phaseequilibriurn studies where they are relevant tointerpretation of natural assemblages, or in somecas€s to fill in where reported assemblages arelacking. As such, this study might be consideredan extension of work initiated by McKinstry onthe Cu:Fe-S-O (McKinstry 1959) andCu-Fe-As-S(McKinstry 1963) systems, and continued by

BINARY AND TERNARY SULPHOSALT ASSEMBLAGES IN THECr.uS-AgbS-PbS-As,S*Sb,S,-BinS, SYSTEM

PHILIP C. GOODELLDept. ol Earth and Planetary Sciences, City CoIIege, City Uni.versity ol New York,

New York" N,Y. 10031

Petersen (1962). This work has the same limita-tions and qualifications expressed in the pre-vious studies, plus a few peculiar to sulpbosaltmineralogy.

Having indicated above the purPose of thepresent work, it is important to note also whatit will not include. This study is not intended tobe a review of sulphosalt mineralogical data norphase relations. The details of mineralogicalproblems within so large a group of minerals isbeyond the scope of this endeavor. The docu-mentation of the consistent or sonflicting pat-terns of assemblages of sulphosals is, rather,the object of this study. The resulting diagmmsare useful to investigators of sulphosalt minera-logy and geochemistry, and in pointing out sul-phosalt systems of potential geochernical in-terest. As sulphosalts are often found within, oradjacent to, important ore deposits, knowledgeof the genesis of this family of minerals can beuseful in mineral exploration.

The most severe limitations encountered whenrelying on tle literature for sulphosalt assem-blageo is the question of identification of species.Sulphosalt systems commonly have a multipli-city of phases present, and many phases havesimilar properties and appearanc,e. Most studiesbefore 1955 relied solely upon microchemicaland microscopic techniques, which have sinceproved not diagnostic for many sulphosalts.Some studies reported assemblages of 8 or 10sulphosalb, with many conflicting tie lines anddisregard for the PhasE Rule limifalipl on thenumber of possible coexisting phases in a sys-tem. X-ray identifications can generally be re-lled on, but the literature suffers from the scar-city of such critical studies.

The second question raised in the presentstudy of sulphosalt assemblages, and the reserva-tion shared with the earlier studies of McKinstryand Petersen, is what is meant by an assemblage.The relations between assemblages, associations,and true equilibrium are discussed further byBarton et al, (1963). In the present wirik theterms 'found with' or 'associated with' as usedin the literature are accepted :to mean assem-blage. Unfortunately, it is all too often left un'

n

28 THE cANADTaN

specified whether these terms mean intimategrain to grain contact, or found together in tlesame polished section, hand sample, parageneticzone, or merely in the same mining district.Ideally, the use of the term assemblage indicatescompatibiliry and equilibrium, but as McKinstry(1959) pointed out, two minerals which occurtogether are not an absolute guarantee of compa-tibility. Another term used in the literature is 're-placemenf, but this term generally does not in-dicato an equilibrium assemblage. The textural

TAri.[ l. PHASES PmB{T,toild nE EIMRY SYSTBiS I[ ftr C!?s-A9Zs-pbS-,szS3-Sbt3-BtASYSIS (se tqt for s*tnl rct6)

Blnary 3Ftd h$6 pr6enr tu@ta #ffTltr B

€narglb, luade Cu3A9S4 3:lh6e A (kke t st t@r 19nl toelAtZs:t ?t l

?. slnn€rlb C!OAS4S9 3,2

MINERALOGIST

establishment of replacement versus coprecipita-tion is, furthermore, a matter of conjecfure incertain cases.

The assemblages noted in this study have beenobtained from a number of sources. The stand-ard references are Palache et al. (1944), Ram-dohr (1969), Schouten (1962), Traill (1970), andUytenbogaardt (1951). Original sources weresought in instanoes of reported conflicting tielines, and a review of the pertinent literature forthe past twenty yeani wa$ made. Conflicting as-semblages are indicated on the diagra,ms bydashed lines. Undoubtedly, some reported as-semblages have been misged, and the authorwould appreciate hearing of any such omissions.

In spite of the reservations which have beenmentioned abovg and in light of the increasingmineralogic, crystallographic, phase equilibrium,and thermodyn'amic data on sulphosalts that arebecoming available, it is strongly felt that wemust come to a better understanding of the na-tural occurrences of these species. In the ideaof McKinstry (1963), "Chemistry, however pre-cise, is not geology until natural occlurenceB arecorrelated and reconciled with it." In additionto ,assemblages, paragenetic s€quences of sulpho-salts are also noted, as such data are relevant toan understanding of the genesis of the mineraliz-ation.

In the tables and figures which follow, metal-rich phases and sub-systems are listed fint,with progressively more semi-metal-rich phasesand sub-systems following. When more than onemeta.l or semi-metal constituent appears in asystem, as in the ternaries, each appears in theorder of the atomic weights of the metallic orsemi-metallic element. Binaries and then ter-naries are discussed, and at each successive stepnew phases appearing in a system are listed intable form according to the abovedescribedorder. The numerical appearance of a phase inthese tables is then used for reference in the ac-companying composition diagrams, and is indi-cated in parentheses when a species is referredto in the text. It is hoped that this binary andternary nu'nerical reference scheme will keepthe diagrams relatively uncluttered; however, theinterested reader may find ,it useful to writehis own abbreviations on the figures.

BrNary Sysrrus

Table 1 lists the sequence of binaries, and tleformulas and metal/semi-m€tal ratios of tlgspecies in each of the 15 binaries. Only tle moreimportant of these .are discussed below. Refer-ences to the most recent phase equilibrium stu-dies can be found in Craig & Barton (1973), and

l. C!2s-ASZS l. strc@F.lre2. @ki6tryl&3. JalFle

aal.92, t..02.4,27th6e B (*klderlto)(Sk inner 6 , aZ. 1972)

fa@ti nl te

2 . da lcos i lb l&

&e6&i n1. ulr t ldenl&2. @lec t l te

4 . hod6h i te

5 . ' d l d b e r g l h ' C u B t . S a l : 3?

l : l

Jo-or r r rnFr€yr rc

l . sephadb

2. pyrarydb, pymsf f tpn tb

3: niaBrl te

]

k-3r4hadre (xall 1956) Agsks4l, prcGtlte, xantho@nlte AS3BS32, sdi$iG, trcdr@nnlte AqAeSZ

AgTsbs6AS.$S, 5 : l

l : l

4 . rah l te

5 . hd@r lh

6 . l i v e i n l 9 1 t e

7 . sarb f r& (sc le roc lse)

65$qsil 5.2b9$aSZl 9 t4ht7($,&)l6s4t l7:8htt$tZSZg 1116hfsstg 7.4Pb2z($,kl26s6t At13bg$glr 5:4bftases 7t6fta$tqSa 6,7

9. fuloppile h:$gStg 3:4

l l l l l an l& 6381256 3 : t

I . bul aqorl te

3 . 6dson l&

4. heiarcmrphlh

5. lauroylb

5 . p lag io r i te

7. &blNoniie

8. z1*6nite

l . bu6. i&

?. @sallt!

3 . la l# l3d t l&

hsBllltb28t 2s5bBt 2s4

,08

to3Sls3 3;l&BISZ l : ltutoBlt fzz 5:5C!SBj iZSZ 2:3

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

'r . t rca-$?!3mll ! l tz

BINARY AND TERNARY SULPHOSALT ASSEMBLAGES

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

Cu

Cu25 Cu25

AsrSa Ag2S sb2s3 Asf

Cu2S

NBi2s3 A92S

30 THE CANADIAN MINERALOGIST

recourse should be made to this work for a listof critical points and stability ranges of binaryassemblages.E

The natural phases appearing on the CuzS-A:fg and CusS-SbzSs joins are given in Table 1,#4 and $5, along with the synthetic phaseswhich might be recognized in natural assem-blages in the future. These two important joinsare also arnong the more complicated .ones, inthat they necessitate the projection of composi-tions from sulphur onto the join of interest.Natural assemblages in the Cu-As-S and Cu-Sb-S systems are given in Figures 1 and 2. Sinne-rite is the only phase which plots exactly on theCu"S-As:Ss join, so that the tennantite field isprojected away from sulphur onto this join. Di-genite and djurelite project onto the CuaS posi-tion. Enargite and luzonite project onto the ten-nantite field and also have substitution of Asby Sb (Springer 1969a). Their presence indicateshigh sulphur fugacity conditions, and their co-existence has the possibility of providing geo-thermometric measurements (Skinner 1960). .{particularly i.m.Fortant assemblage is that ofenargite-realgar, which precludes the coexist-ence of orpiment with tennantite. These observa-tions are compatible with equilibria studies downto 3@'C (Maske & Skinner 1971), and the as-semblages indicated in Figure 1 are in agreementwith their work. Sinnerite has been found withtennantito at ib only natural occurrence, theLengenbach Quarryo Switzerland. Tennantite-chalcocite (digenite) is a not unsommon assem-blage.

The assemblages for the Cu-Sb-S system givenin Figure 2 present fewer complications. Dige-nite and the tetrahedrite field project away fromsulphur onto the CuaS-Sb:Ss join, and famatiniteprojects onto the tetrahedrite field, occurringunder higher sulphur fugacity conditions. Arecent 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 wherefamatinite and ideal tetrahedrite are projected.Except for Phase B, all two-phase assemblagesalong the join are found in nature.

On the CurS-BirSa join Clable l, #6), mineral#2 (Ifonnorez-Guerstein 1971) falls on the sul-phur-rich side of this join. Cuprobismutite, longthought to be dimorphic with emplectite, hasbeen found to have a distinct composition inboth synthetic @uhlrnann l97l) aid natural

aReference should also be made to Sulfide PhaseEquilibria, chapter 5 in the Short Course on Sul-phide Mineralogy given by the Mineratogical So-ciety of America, November, 1974.

(Iaylor et al. 1973) materials. Eichbergite, al-though thought to be discredited, has been foundin synthesis studies in this system (BuhlmannL97l\, and consequently is retained in the pre-sent work. The natural assemblages on this joinare wittichenite(1)-emplectite(2), and wittiche-nite(1)-chalcocite, w.ith this latter reported alsowith enargite (Ramdohr L969, p.711). It wouldbe of interest to investigate this high-sulphurfugacity assemblage for the presen@ of min-erul #2.

The sequence of phases on the AgaS-As:Ssand AgzS-SbrSa joins (Table 1, #7&8; Figs. 3&4)includes billingsleyite and its antimony analogue,although these phases lie o: the sulphur-rich sideof the poins. All two-phase assemblages of ad-joining phases are reported in nature except thatof smithite(trechmanaite) (2)-proustite(xanthoco-nite)(l). Although smithite was reported @ala-che et al. 1944) in association with orpiment,later studies (Graeser 1968) do not substantiatethis assemblage. The tlree-phase assemblage ar-gentite-stephanite(1 ) -pyrarryite(2), not uncom-mon in the literature, is interpreted (Keighin &Honea L969) to represent subsequent precipita-tion of stephanite on previously-deposited argen-tite-pyrargyrite, in one instance. Stephanite isstable below 197'C.

On the AgzS-Bi,Su join (Iable I, #9; Fig. 5),all adjoining phases have been observed; matil-dife-bismuthinite has also been reported (Schou-ten L962), but this does not agree with phaseequilibrium studies of the simple binary. Thematildite polymorph stable above 195oC has asolid solution in both directions along the join,and is a potential geothermometer if found withacanthite or pavoaite.

The PbS-AseSg and PbS-SbrSe joins (fable 1,#fi&lL; Figs. 6&7) sontain a protusion ofphases. The four most arsenic-rich phaoes onthe PbS-As:S' join were described from theLengenbach Quarry, Binnatal, Swiuerland.Dufrenoysite has been reported @alacbe et al.L944) with orpiment, realgar, sphalerite and gyp-sum. This is probably a low-ternperatur€ assem-blage when compared with the Binnatal deposit.Jordanite(2)-dufrenoysite(3) has been reportedfrom Binnatal, and this assemblage is stable be-low approximately 480'C. Gratonite(l) is con-sidered by Roland (1968) to be a low-temper-ature dimorph of jordanite, which serves to ex-plain the reported coexistence of jordanite andgptonite each with galena. This idea is sup-ported by more detailed chemical analyses ofgratonite @urkart-Baumann et al. 1968). Ior-danite is the arsenic end-member of the geo-cronite solid solution, which takes up to 58atomic 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 andstability relations can be found in Chang &Bever (1973).

Numerous mineralogical and phase equili-brium studies have failed to resolve questionsas to the nature and stability of phases withinthe PbS-Sb:$ system. Some of this work is re-viewed in Chang & Bever (1973). Reported two-phase assemblages compatible with phase equi-librium studies include galena-boulangerite(1),boulangerite(1)-zinkenite(8) Oelow 3 1 8 o C, Craiget al. 1973),,and zinkenite(8)-stibnite. Boulange-rite(1)-robinsonite(7)-stibnite, semseyite(2)-hete'romorphite(4)-plagionite(6) (Jambor L969), ga-lena-zinkenite(8), and zinkenite(8){uliippite(9), are reported assemblages not compatiblewith phase equilibrium studies. Arsenic-freegeocronite, madocite, and launayite have notbeen found. Jamesonite and meneghinite liejust off this join, having essential Fe and Cu,respectively.

A review of mineralogical and stability stu-dies in the PbS.BLSa system can be found inChang & Bever (L973). On this join (Iable I,#t2; Fig. 8), tle two-phase ,assemblages re-ported are galena-cosatteQ), cosalite(2)-bismu-thinite, galena-galenobismutite(3), galenobis-mutite(3)-bismuthinite, and cosalite(2)-gale-nobismutite(3). Only the last two of these arecompatible with phase equilibrium studies(Craig 1967). Bursaite(l) and bonchevite(4)aro rare, and giessenite apparently has cop-per and antimony as essential constituents thatcauses it to plot off of the join. Heyrovskyiteis probably a member of this join Klominskyet al. I97l; Crallg 1967, Phase trI), althougha copper- and silver-free membet has not beenreported.

Trnrenv Svsrsrvls

Ternary sulphosalt composition diagrams areconsidered in the order of two metal -l- onesemi-metal sulphide components, followed byone metal + two semi-metal sulphide compo-nents. These components are listed accordingto the increasing atomic weights of their metal-lic and then semi-metallic elements. This sameorder of components is listed clockwise aroundthe ternary composition diagrams. Binaryphases are referred to by their identificationnumber along a particular join, as listed inTable 1. Ternary phasee are indicated in Ta-ble 2, and are noted on the diagrams by theirnumber of appearance in the ternary. Naturalassemblages ate shown as tie lines on thecomposition diagrams. These assemblages aremost often only of two phases; cases wherg

three phases have been reported are notedespecially. In ,many cases solid solutions arepresent; however, very little data are availableconcerning coexisting compositions, so tlat tieline distributions given are only schematic.Conflicting tie lines are dashed. The changes oftie line distributions suggest numerous poten-tial geotherrnometers.

IABLr 2. nRMRI PXAIS l i l nt Cu2S"A9ZS"SS-ts2S3-5b25j-9i2sj St: i t ! , roat l i ' r ' " ' rFIGURIS 3-A

l;intt-tai--Fag- preae;-- - fo@I;

' ---- - - --b .;cn

I . e,rs-Aq:ins; - 6u"m 1 r*"a" mo:ffi ;;-"r* J -.t, i::i"":;q'( r1 ! ' 3 )

Farce l te ( l l l ) (Har r is 0 ' : ' t .2

2. a6srjMsre,t-"- $:lf::-"to.u+-)B?sil

larr:rre

z. dt:rgF-$-25.'1.;r 9 6 3 )

Flybaslte ( l l l ) (Harr is ot ' :2 6; ; r t . 1 9 6 5 )

2. plybdlb(rrodel (Agt5.4_-Cuo.6&)$2si l var iable

3.-.rt:&t-tl-

3

(F19. 8) 2. rabaryi& 3 : 6 : 1 0I : 2 : 33 : 6 : 7

6 . a l k l r l t e

7. nuff ie ldi te Cu4PbtOBltOSZg 2:10:58. ?g(&Fl l & hkovlcky to4h8lssl t 412.5

7 . -l l l . q l

(F lq . l0 ) 2 . d i lphor l te

C!6b681to539

AS362Sb3Ss3. ? {Hoda & ftang 1972) &3h$3S,

AgetuS$e5tgAgzfr3sb6sl3Aob$-S.

AStt2Bl3ST

5, raMhrlte

5 . ador lb

7 . f l r e l y l b A g 2 h S $ A S ) A I : 5 : 4

, .(Fis ' l l ' 23) x (ktup-, iol ler 1970) Agztb7Bttos24 l : 7 r 5

I 1 4 : 32. sch l6er lh

3, heyrcbtylh 6(roo.68i0.m(A!,cu).04s. B i 2 s 3 ( 6 ) : l

4. r ({ed!cnr . t aL. 1913) 0.9&2S.8.5Pbs.1.9812\ 0.9:8.5:4.95. Z ( ldddl at aL. 1973) 0.5A92S.9.9roS.4.381t3 0.5:9.9:4.3

( F l s . 1 2 )

( F i o . l 3 )

= ( r 1 ! . l a i = =rr. Ag2)-s2)3-5Dt3( F i a . t 5 )

l F l . . ) 6 1

t .1 f f i

(Ftg. 18) 2. gleiudl&

3. tul nni h4. veel ie5. lbrrylb6. so6yl&7. @&clteE. bl langol&9. pi .yfalr i te

10. gdctunlh

3 : 4 r 33 , 2 t 31 : 5 r 3

I : 2 : 3

b6(Sb,16)lOS21 6:(5)Pb(sb, l3)2s1 1:1Pbz($,As)Asz 2:( l )612($,As)los27 tzr(9)Pqr(sb,k)zsm l7:(11)

tu5(sbtbr6(s

l7r (8)5: (2)

I 5 : ( 9 )5 : ( l )

B (lalla & 01dig l9l3)

2 . k4b6 l l l !q

8. Ebr6l$

) (rant" F&'7

3. l indsbon l le CubBlJS6

4. ? ( re l ln 1966) Cu3&3Bi7St5

32

7.

THE CANADIAN MINERALOGIST

f 'rr.

\)

- - u -

- -

\ ] , , ,

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

4ozs 4ozs

NN\.\.

\7

Cu25

BTNARy AND TERNARy SULPHosALT ASsEMBLAGES IN CurS-A&S-PbS-AsrSs-Sbr$'8i6, 33

C uzS-A g e,S - As sS a and C uerS -A g rS - S b sS "

Natural assemblages for these syctems areghown in Figures 3 and 4. The substitution ofsilver for copper in tennantite an'd tetrahedritedominates the copper-rich portion of the dia-glams, the latter being the variety freibergite.These solubility limits hane not yet been in-vestigated by phase equilibrium studies; how-ever, in natural material silver substitutes forcopper up to 18 wt. Vo n tennantite, and from3.5 to 23.8 wt. Vo siTver in tetrahedrite fromJapan (Shimada & Hirowatari 1972), and18.4-42.5 wI.Vo silver in tetrahedrite fromMt. Isa, Austmlia @iley 1974). Substitution ofcopper for silverr in proustite or pyrargyrite ap-pears negligible.

The ternary phases in Table 2, #l & #2, weredefined by Frondel (1963) and Harris et aJ.(1965), and substantiated by Hall (1967) insynthesis studies. Frond,el presents analyses ofternary phases coexisting with argentite and py-rargynteQ)n and these have been used as aguide in drawing tle tie lines in Figure 4. Thethree-phase assemblage argentite-polybasite(2)-pyrargyrite(2), which has been reported severaltimes, probably formed above 197oC, belowwhich stephanite(l) is s-*ble.

Tho Cur$AgrS-As"S, system (Fig. 3) has noconflicting assemblages except pearceite( l)-ten-nantite(l) (Palache et al. 1944) with stromey-erite(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 topo-logically similar to its arsenic 'analogue in theantimony-deficient portion of the diagram. Rarn-dohr (1969, p. 654) reports rniargyrite(3) withpolybasite(2) and with stephanite(1), whichboth conflict with th,e common tetrahedrite(1)-polybasite(2) assemblages. These conflictingassemblages .may indicate differing primary de-poitional conditions, or may result from thedifference between primary and secondary en-vironmeints. More study is needed on these as-semblages. The ores of the East Tintic District,Utah, have an abundance of phases in these sys-tems, as noted by Pape (1971) and Radtke elal. (L969). Most assemblages are applicable onlyto more complex sulphosalt systems.

The distribution of copper and silver betweencoexisting solid solutions in these systems pro-vides a potential geothermometer. Solid-statediffusion might, however, tesult in low-temper-ature re-equilibration, negating such measure-ments (Barton et aI. 1963). The quaternaryCuzS-Ag'S-A&Sa-Sb$a system includes the par-titioning of copper-silver and arsenic-antimonybetween coexisting solid solutions, but it doesnot fall within the limits of this discussion.

CusS-AsbS-Bi"Ss

Stromeyerite(1)-wittichenite(1) and copper-rich pavonite(2) -matildite( 1) -bismuthinite, bothfrom Cobalt-Gowganda" Ontario (Petruk & staffI97I), are the only assemblages reported in thissystem (Fig. 5). Additional tie lines shown inFigure 5 are taken from phase equilibrium stu-dies at 454"C (Chen & Chang t974), so are onlymeant to be suggestive. Each of the AgrS-tsiaSsphases has extensive solid solutions into the ter-nary at this temPerature.

Phases on the CurS-BirSs join are generallyfound in copper-rich zones' whereas phases ontho Ag^S-BizSs join are found in lead-rich zones.It may be that the lack of internal natural as-semblages results from the geochemical sepala-tion of copper and lead in hydrothermal condi'tions.

Cu"S-PbS-AssSg

Seligmannite is a ternary phase @ig. 6). Theassemblages in the porti,on of the diagram morearsenic+ich than tennantite(l) and dufrenoy-site(3) are restricted to the Lengenbach Quarry,Binnatal, Switzerland. A significant sequence ofassemblages has been described by Markham(1959) from South West Africa as: 1. jordanite(2)-tennantite(1)-sphalerite, 2. jordanite(2)-tennantite(l) -galena, 3. jordanite(2)cnargite-ga-lena. The third assemblage was reported as "nar-row veinlets of galena, frequently accompaniedby enargiie, that intersect masses of jordanite,which suggests later replacement of jordanite bygalena-enargite". Jordanite was verified by r-raydiffraction. whereas the other identificationswere made by ore microscopy. The change fromassemblage 2 to 3 reflects an increase in sulphurfugacrty if at constant temperature, and thepresence of enargite sugg€sts a temperaturegreater than 320oC (Skinner 1960). Anothertlree-phase as:emblage @amdohr t969, p.748)is galena-tennantite( 1) -gratonite( 1) orystallizedfrom Pb-As-Sb gels or glasses found at Cerrode Pasco, Peru. The glasses are thought to haveformed at temperatures of approxirnately 100'C.The glasses show a large chemical variabitrity,and a recent microprobe study (Burkart-Bau-mann e, al. 1972) of crystalline inclusions gavea composition of PbrAsesn for the lead sulphar-senide phase, somewhat more arsenic-rich thanjordanite.

The above discussion establishes one gxoupof tie lines on Figure 6, whereas the followingpresents less carefully substantiated evidence fori conflicting galena-seligmannite(1) tie line.Refsrring to jordanite from Balmat, New York,

THB CANADIAN MINERALOGIST

Ramdohr (L969, p. 745) states that it ..partlydecomposes -into myrmekitic aggregates of

^selig-

mannite, galena, a little tennantite, and nativearsenis". Copper, however, is not balanced inyc\ a suggested decomposition. Seligmannitehas been observed microscopically as a reactionproduct between galena and tennintite, with tlereaction zone b,eing porou (Sztrokay 1945)."f-hese apparently conflicting tie lines meritfurther investigation. Tennantite in these assem-blages should be checked for the presence ofanrimsrt' alternatively, two primary-facies maybe present in the system.

Finally, Uytenbogaardt (1951) and Schouten(1962) roport gratonite found with chalcocite,which conflicts with the common assemblagegalena-tennantite. This reported association lsapparently taken from Rust (1940) who consi-den the chalcocite to be supergene. This assem-blage has not been indicated in Figu,re 6.

CuS-PbS-Sbp,Ss

This system contains a number of conflictingassemblages (Fig. 7); however, tie lines to tetra-hedrite(l) must be viewed with caution due roits solid solution with tennantite. Although leadhas been reported in tetrahedrite in subitantialamounts (10 wt. Vo,PalacAe et al. 1944), recentelectron microprobe investigations have notfound measurable quantities (Shi.mada & Hiro-wataJi 1972i Riley 1974).

Bournonite(l) has been reported with mostother phases in the system. Its coexistence withchalcocite is prevented by the common galena-tetrahedrite(l) assemblage. The phases appear-Pg_-gn the galena-stibnite join between semsey-ite(.2) and zinkenite(8), although possibly com-patible with bournonite, have 6een fourd onlvwith jgqepnite, which lies jusr off this planetoward FeS. The three-ph,ase assemblage galena-tetrahedrite(1)-bournonite(1) is very common(standard references; Itrarada Lg73) both inequigranular textures and as gal,ena replacing te-trahedrite with a reaction rim of 6ourno-nite(Anderson 1940; Ramdohr 1969). This is inconflict with the repeatedly reported tetrahe-drite(1)-meneghinite(2) (siandard referenc,es)11d tetrahedrite(1)-bournonite(l)-meneghinite(2) ot Warren Q.946). On the more antimonv-rich portion of the diagram, boulang.erite(l)-tetrahedrite(l) (standard references; Warren &Thompson l9M) conflicts with other a:sem-blages of bournonite. These conflicts are ex-plained if either there is a temperature rangeover which bournonite is unstable, or, moreprobably, if the tetrahedrite in certain of these

assemblages is arsenic-bearing.* Petersen (1962)resolves these conflicts by suggesting the twodifferent facies ghown in Figure 21 which mightrepresent the ends of a spectrum of. P-T changes.

Paragenetic sequences frequently take a pathfrom tetrahedrite to tetrahedrite-bournonite, ortetrahedrite-bournonite-galena to boulangerite-galena, making a series of steps across tle dia-gram. This sequence, wi'th minor rnineralogicalvariations, reflects the differentiation of copperand lead.

A different lmragenetic sequence has beendocumented from stibnite veins at Dubrava,Czechoslovakia (Jakos 1963, mainly microscopicobservations). The assemblages are stibnite, tozinkenite(8)-bournonite(1), followed by tara-hedrite( 1 ) -chalcostibite(2).

Cugs.PbS.Bi,,Ss

The profusion of ternary phases is listed inTable 2, ff6, and Figure 8. Five phases plot ona line colinear with bismuthinite and aikinite(6), with their unif cells being a continuous se-quence of ordered superstructures based onaikinite (Padera 1955; Welin 1966; MooreL967), These intermediate phases, except rez-banyite(2), have been found only at Gladham-mar, Sweden, and have been subjected to eles-tron microprobe verification (Welin 1966).Little is known of their paragenesis, but theymight be used as indicators of bismuth fugacitychanges and,/or temperature.

Aikinite is reported with a number of phasesin the system. Emplectite(2) is found with cosa-tite(2) and galenobismutite(3) (Uy"tenbogaardt1951), which would conflict with the phases onthe bismuthinite-aikinite join. Primary facieschanges are suggested for this system, in agree-ment with its antimony analogue. Berryite (Nuf-field & Harris 1966) and larosite (petruk 1972)are phases which lie off of this compositionplane, with silver substituting for copper. Final-ly, it is noted that the Cu-Pb-Bi sulphosalt re-ported by Honnorez-Guerstein (1971) is toosulphur-rich to plot in this system.

Agz'S-PbS-AseS"

No sclid solutions and comparativeily few as-semblages are observed (Fig. 9). Marrite (1)(lable 2, #7) is the only ternary phase, and is

*J. Wu & R. Birnie have found arrenic-bearingbournoniie, which could also explain these con-flicts, personal communication, t974.

BINARY AND TERNARY sULPHosALT ASSEMBLAGES TN Cu$-AgzS-PbS.ASzSs-Sb'S',Bi,Ss 35

repolted only from the Lengenbach Quarry,linna,fnl, Switzerland. The only assemblage isthat of proustite(l) - jordanite(2) (uytenboga-ardt 1951), each of which could contain anti-mony. Several of the phases on the anenic-richside of the tie line are found only at Binnatal;several additional phases closely related to thiscomposition plane and found almost exclusivelyat Binnalal are lengenbachite, which has coppersubstituting for silver, hatchite with thalliumsubstituting for lead, and hutchinsonite whichhas both substitutions taking place.

Ae"S-PbS-SbeSs

The profusi,on of ternary phases in this sys-tem (Table 2, #8; Fig. 10) can be better-visual-ized by considering several colinearities. The ga-lena-miargyrite(3) join appears as a completesolid solution in phase equilibrium studies at500'C (Hoda & Chang 1972), but is more lim-ited at lower temperatures. Phases reported hereare freieslebenite(1), diaphorite(2), and synthe-fic AgsPbSbssr (Hoda & Chang 1972). Anotheroolinearity is a ray from galena to AgSbaSr, withandoritq ramdohrite, and owyheeite. Fizelyite'however, might be considered to plot on a coli-nearity between PbgSbaso (falkmanite') and Ag-PbSbaSc (andorite), as suggested by Karup-Mlller(1970). Crystallographic, electron microprobe,and phase equilibrium studies would help de-cipher which substitutional mechanisms areoperational.

The compilation of reported assemblages intiis system is complicated (Fig. 10). The asso-ciation of phases on both the galena-miargyrite(3) and galena-andorite(6) joins with 'pyrargy-

rite' provides many crossing tie lines. As pyrar-gyite(2) has a solid solution of arsenic substi-tuting for antimony, it is possible that the phaseson the galena-andorite(6) join coexist with apyrargyrite more arsenic-rich than those on thegalena-miargyrite(3) join. Alternatively, thephases on the galena-miargyrite(3) colinearifbecome unstable below 300oC (the lowest tem-peraturo of investigation of Hoda & Chang1972), permitting the association of phases onthe galena-andorite(6) join with pyrargyrite(2).A number of additional conflicting tie lineswhich are reported include argentite-freieslebe-nite(l) versus the more common galena-pyrar-gyite(Z), galena-fizelyite(7) versus boulange-rits(1)-owyheeite(4), and stephanite(1)-ando-rite(6) (Williams 1968) versus several tie lines.Furthermore, tle galena-miargyrite(3) coexis-tence (Ramdohr 1969, p. 653) can be explainedonly if all of the intervening phases are unstableover a certain P-7 interval.

Three-phase assemblages reported are pyrar-

efite (2)-miargyrite (3)-owyheeite (4) (Ram-dohr 1969, p. 736), galena-stephanite(1)+yrar-gynte(z) (Oelsner 1961, Fig. 58), galena-argor-tite-freieslebenite (1), galena-pyrargyrite (2)-dia-phorite(2), and stephanite ( 1 ) -pyrargyrite (2)'an'dorite(6) (ast tlree from Palache et al. L9M\This last assemblage was again recognized byWilliams (1968) in another study of the samearea, Morey, Nevada. Williams describes a com-plex series of paragenetic changes starting withjamesonite and followed by owyheeite(4) or an-dorite(6). Andorite is then replaced by stephan'ite(l) and pyrareyrite(2) or by freieslebenite(l)and owyheeite(4), and this in turn is replacedby galena or pyrargyrite(2). No mention is madeoi identification techniques or replacement cri'teria, and the position of stephanite on the com-position diagram is misPlaced.

Phases and assemblages in this system arecomplicated and warr'ant further detailed study.The profusion of phases provides for the meas-urement of subtle changes in the relative fuga-cities of the components when sequences of as-semblages are documented.

Ag"S-PbS-Bi"Ss

Six temary phases are reported (table 2, #9;Fig. 11 & 23). None was found in synthesis stu-dies down to 4@oC (Craig 1967)' with the im-plication that they appear at lower temperatures.Craig inferred from his work and from naturalassemblages the lower temperature compatibili-ties given in Figure 11, to which the three-phaseassemblage galena-cosalite-heyrovskyiie (Klom-insky er al. I97I), and tle two-phase assern-blages galena-schirmerite and gustavite-pavonite,have been added. A sequence of natural assem-blages @ig. 22) with some of these te'rnaryphases has been dessriM by Nedachi er al-

TtgZl), who used an electron microprobe. Fluidinclusion filling temperatures in associated quq4zhave ranges between 87'L42"C and 2W245"C7a maximum partial pressure of sulphur is ap-proximately 10'14-10-15 as inferred by e-xtrapola-tion of higher-temperature data to 225"C, gsventhe presence of pyrrhotite and native bismuth.Such detailed studies of sulphosalt assemblagesare needed for further understandrng of sulpho'salt systems. The bismuthinite-pavonite(2)-gus-tavite(l) KaruFMlller 197O) and galena-ma-tildite(1)-sshirmerite(2) (Karup-Mlller L973\assemblages are not incompatible with theselow-temperature assemblages of Nedachi et a/.(1e73) .

Numerous phases exist in the quaternary sys-teur which includes CuaS, but they are beyondthe scope of the present studY.

Cu25

BrZSS

Cu25

Fi zss

sbzs3

AsrSa

AsaSa

4oz s

agzs

Bizs3 s b2s3 sb2s3 A s2S3

BINARY AND TERNARY sULPHosALT ASSEMBLAGES TN Cu6-Ag:S.PbS-AsISTSbsSs"Bi6a 37

Cu%l-AsoSrSbz'Se

The projection of the tennatrtite-tetrahsdritesolid solution falls on this compositional plane(Fig. 12). Complete exchange of antimony forarsenis takes place above 400oC, but there issome suggestion that one or.more solvi are pre-sent at lower temperatures (!Vu, J., personalcommunication L972), Tennantite-tetrahedritecompositions also have a significant variation offthis plane towards sulphur, being limited by thecompositions which coexist with the enargite-famatinite solid solution. Synthesis studies ontheso coexisting solid solutions have resulted ina geothermometer which has been applied tonatural assemblages (Feiss 1974). Temperatureand sulphur fugacity measurements are also po-tentially available from tennantite-tetrahedritecoexisting with both chalcostibite and stibnite.Detailed analysis of mineral assemblages in theCu-As-Sb-S system (Petersen 1962) indisatesthat this three-phase assemblage is a relativelysulphur-deficient one. It has yet to be adequatelydocumented in natural material. Antimony-richtetrahedrite is reported (Petruk 1971) coexist-ing with cobalt arsenides in an environment de-ficient in sulphur.

CusS-As$rBitSt

No ternary phases are reported (lable 2, #ll;Fig. 13) although a maximum of 15.9 wt. Vobismuth in tennantite has been reported (SpringerL969). The only assemblage is a bhmuthian ten'nantite-wittichenite tie line (Oen er al. 1973).This lack of assemblages ,might reflect a geo-chemical soparation of arsenic and bismuth inirondeficient environments, the latter qualifi-cation added because of the more common bis-muthinite-arsenopyrite assemblage.

CusS-Sbz,S-Bie,Ss

Phase equilibrium studies in this system (Chen& Chang 1971) suggest a compositional varia-tion of wittichenite 'on the Cua$BizSs bina'ryftom 22 tn 27 mole 7a. Substitutiot of. 6O at. VoSb for Bi in wittichenite, but with very little con-verso substitution taking ptrace, was found at450'C. Similar semi-metal substitutions providesolid solutions into the ternary io chalcostibiteand 'eichbergite'.

Naturally occurring tetrahedrite has beenfound to contain 3.1 wt. % bis,muth (PetrukL97lr. A large number of coexisting phases hasbeen reported (Fig. la) with no conflicting tielines. The solid soluti,ons and tie line distribu-tions are only topologically conect as no dataon coexisting compositions are repo.rted. Five

potential geothermometers exist from the com-positional variations within the five three-phaseassemblages.

Phase equilibrium studies of the solid solutionof chalcostibite fu1e this ternary are not in agree-ment with the extreme rarity of this phase, andthe relatively more abundant tetrahedrite-bis-muthinite.

AgzS-AszS.Sbz'Ss

This ternary system is dominated by theproustite-pyrargyrite solid solution which is com-plete down to at least 3O0oC (Toulmin 1963).Coexisting prou:tite and pyrargyrite have beenreported several times, but infor'mation on co-existing compositions is lacking. Ramdohr (1969,p. 722) states that a miscibility gap exists be-tween 13-97% proustite at room temperature.Reaction rates (Barton et al. 7963) suggest thathigh-temperature assemblages including prous-tite-pyrargyrite may redistribute arsenic and anti-mony 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 planetowards chalcocite, and billingsleyite lies to-wards sulphur. These expanded systems containassemblages of potential geochemical interest

Tho assemblage proustite-stephanite (Petruk1971) conflicts with the more common argen-tite-pyrargyrite.

Ag'S-AsESrBinS"

No ternary phases and no reported compatibi'lities are present in this system (Fig. 16).

Ag"S-SbeSnBias'

Ono ternary phase, aramayoite, has been re'ported, and is found with bismuthinite, with py-rargyrite(2), and coexisting with both miargy-rite(3) and pyrargyrite(2) (Lewis 1964). Syn-thesis studies (Chen & Chang 1971) indicate acomplete solid solution between matildite(l)and miargyrite(3) at 450oC. At 3o0oC, 56 moleVo miargyite is still soluble in matildite. Arama-yoite may be an ordered phase cooled from thissolid solution, and its compositional variationsmay prove to have geothermometric interest.

PbS-Asz,SrSbz'Sa

In spite of the fact that both of the lead-bear-ing binaries of this system are characterized bya profusion of phases, in all but a very few

38 THE CANADIAN MINERALOGIST

cases have any coexisting phases in this systembeen reported. The geological environment inwhish the most cornmon of these phases aregenerally found is in aJfiliation with hydro-thermal ore deposits. The several compatibilitiesfrcm this environment are tle jordanite-geocro-nite solid solution assosiated with galena andsemseyite, and with meneghinite which lies justoff this plane towards CuaS.

In this system are a large number of phaseswhich have been found only in a second, rare en-vironment. Many of the lead sulpharsenides havebeen found only in the Lengenbach Quarry, Bin-natal, Switzerland, whereas a majority of phasespresent in the ternary system under discussionhave been found only at Madoc, Ontario (Jam-

Bi2s3 Ast53

bor 1967u b, 1968). The suggested solid solu-tions, observed phases, and their associations areseen in Figure 18, based largely on Jambot'swork. He reports a paragenetic sequenc€ exhibit-ing decreasing As/Sb values, and points out onepossiblo origin of such a complex mineralogy asthe reworking of an original galena, arsenopy-rite, sphalerite assemblage by antimony-richsolutions. This conclusion is similar to that ofGraeser (1968) with respect to the origin ofthe complex mineralogy found in the Binnatal.

Phase equilibrium studies in the system at400'C (Walia & Chang 1973) verify the exist-ence of a number of solid solutions. Fifty-eigbtat. Vo antimony can substitute for arsenis in jor-danite as the geocronite solid solution, 45 at. Vo

Ag25

PbS PbS

B i2s3 sb2s3

22.Nedqch i , e t . o l . ,t 973

Sb253

BTNARY AND TERNARY SULPHOSALT ASSEMBLAGES rN cuaS-AgiaS-PbS-AsrS3-SbzSa'BirS. 39

in dufrenosite towards the Sb end-member veen-ite, and 3O at. Vo antimony in z.inftsnile can besuhtituted by arsenic. Madocite has composi-tional ranges in both the As/Sb and Pb/(As*Sb) dimensions. The lsmaining phases of Jam-bor, except guettardite, w€le not found in thephase equilibrium studies down to 400"C.

Coexisting solid solutions in this system havepotential for geothermometric or semi-metalfugacity measurements, but their extreme rarityIimits their development and applicability.

PbS-AsESsBt2,St

No naturally occurring phases have been re-ported rn this system, although Walia & Chang(1973) found two zuch phases (table 2, #I7)at 400oC. No assemblages have been reported.

PbS.SbESl..Blds

Several ternary phases are reported (Table 2,#18; Fig. 20), and antimony substitutes for bis-muth to a small extent in lillianite. Assemblagesare kobellite(2) with galena, and with bismuthi-nite, and tintinaite(1) with galena. Solid solu-tions within the ternary are predicted on thebasis of the diadochy of antimony and bismuth,and the .partitioning of these elements betweensuch solid solutions is of potential interest. Thissystem is of the type which will prove morecomplicated and interesting when it receivesmore detailed studv.

DrscussroN

The above study of natural sulphosalt assem-blages has resulted in the derivation of 18 ter-nary sulphosalt composition diagrams. In gen-eral only those phases and assemblages whichlie strictly on the ternaries have been considered.Exceptions are tennantite and tetrahedrite whichhavo been projected onto the CuzS-As$s andCu,S-SbzSa joins, and digenite which is pro-jected to CurS. This limitation prevents the in-clusion of certain phases, notably jamesonite,which contains essential iron. In other cases theessential nafure of a minor element is not known;in these instances a mineral may be mentionedin the text or tables, but is left off the relateddiagram. Examples of these are neyite and berry-ite, which have small amounts of silver and con-sequently plot off the CusS-PbS,BizSia plane.

Reported phasc are plotted as being of end-member composition, in general, as only a fewstudies have reported assemblages with actualcoexisting compositions. Tie lines to solid solu-

tions are extended along them in topologicalagreement with reported asnemblages. Conflict-ing tie lines in these ternary systems might beexplained by substitutions into quaternary orhigher systems. An example of this is pyrargy-rite in the Cu*S-AgzS-Sb,$ and ApS-PbS-Sb"$systems, where arsenic substituting for antimonymay resolve conflicting tie lines. Other suchsubstitutions are Cu - Ag, 2Pb - AgSb, 2W -AgBi, As-Sb, Sb-Bi, and Pb-Bi (l imited),although others occur also. Certain quaternarysystems of particular interest resulting fromsuch substitutions are CurS-Ag2S-PbS-BirSs,Cu#Ag;$AszSrSbzSg, CuzS-PbS-Asfg-SbzSg, andCurS-As^$-SbrS'-BirSg.

With the above ideas in mind, and consideringthe composition diagrams as strictly ternaries,there are certain bivariant assemblages (in termsof pressure and temperature) in which solidsolutions may vary enough to make them of po-tential geochemical interest. They can be identi-fied on tho figures as three-phase fields joinedto one or more solid solutions, and they are listedin Table 3. The fact that many of these lie in theCurS-AgrS-As#r-SbrS" system makes it of par-ticular interest, but as Barton et al. (L963) pointout, trtostdepositional solid-state exchange mayoccur, modifying primary compositions. Ideally,calibration of compositional variations with phy-sico-chemical parameters can be used to re-strict degrees of freedom of natural assemblages(Barton & Skinner L967). Such studies will beparticularly useful when other variables can befixed by an independent means. Certain other

TABLE 3Llsted belry are bivar lant asss$lagG ( in tem of P and ?) ln whlchsol id solut loE may vary ercugh as to mke t im of potent lal gecheml-cal inter6t. Study of certain t f ,o-phase assenblages arcng t iesemlqht also be used to l imit ore or bro dtrrees of f reedon. These

4!gD1qg6 are arr ived at f rcm A. -

Sys ts Assembl ages

Cu2s-AS25-As2s3

Cu2S-AS25-!,b253

Cu2S-4s253-Sb253Cu2s- Sb2S3- B i 253

Ag25-As253-Sb253

AS2S-Sb253-Bi 2S3Pb5-As2s3-sb2s3pb5-5b2s3-Bi

2s3

chal cocl te-s trcneyeri te-tennantl testrcmeyeni te-pearcei tstennanti teDearcel te-tennantl te-prcus tl tepearcel te-prcustl t*aEenpolyb6l tepearcei te-a6enpolybasl t$argentl teprcus tl te-a6enpolybas i t€-argentl te

chal coci te-: tmmeyerl te-tetrahedri tes trcmeyeri te-tetrahedri te-antJrcnpearcej teantircnpearcei tepo lybasi t€-argenti tepolybasl te-argentl ts-s tephani tepolybas i te-s tephani te-pyrarqyri tepo lybasl t*antlrcnpearcei te-pyrargyr'l teantimnpearcei te-pyrargyr'l te-mlargyri teantlrcnpearcel te-tetrahedrl te-niarqyri tepyrargyri te-mi argyri te-tetrahedri teniargyrl te-tetrahedri te-s tlbni tetetrahedrl te-s tibnl techal os tibl te

tennati teltetrahedri t*stibnl te-chal cos tib i te

chal coci te-tetrahedri te-wi tti cheni tetetrahedri te-vi tticheni t$empl ecti tetetrahedri te-bi snutlti nl techal cos tib i tebismthl nl te-chal @stibl te-s t ibni te

argerii te-s tephanl te-pyrargyri teargenti te-pyrargyri te-prcustJ te

Ihere are nwercF potent ial blvar lant asssblage5ln t ise systm. Natural assenlr lag6, hofever, donot define tlle topolow of the diagrare emugh forthm to be idot i f ied.

40 THE CANADIAN MINERALOGIST

systems (CulS and FbS with AszSb, Sbs.Sa andBigSsi and AgrS and pbs with sb"ss and Bi"sa);commonly possessing a number of ternary phases,indicate facies changes by tie line switches.

Phase equilibrium studies can theoreticallydeterrnine the pressure and temperature xangesof sulphosalt facies, and such ranges can alsobe calculated from thermodynamic parameters(Craig & Barton 1973). The study of sulphosaltstability relations in temperature/sulphur-fuga-city space has been initiated (Craig & BartonL973; Crug et al, L973), and can prove fruitfulrn defining conditions of formation. The pre-sent study of natural assemblages advances thiswork. Einally, documentation of sequences ofprimary assemblages in a deposit can serve asan indicator of the direction of fugacity changesduring deposition.

It is emphastzed. that whereas many of thephases mentioned in thi$ study are quite rare,taken as a group these sulphosalts are moresignificant. A common geologic setting of thesespecies lg rvirhin, or marginal to, base metaldeposits, some of great value. Sulphosalt petro-logy can conceivably be used as a guide to ex-ploration for and development of such deposits;consequently, an understanding of the environ-ments of formation of these minerals is of in-terest. It is hoped that the present work will sti-rnulate interest in and further studv of naturalassemblages of sulphosalts.

AcrNom.ppceMENTs

I am grateful to R. Birnie, J. R. Craig R.Kamilli, and U. Petersen, who kindly read earlydrafts of the manuscript. Their comm€nts welehelpful, but they are not responsible for remain-ing deficiencies.

REFrnr,Ncss

ANDERsoN, R. J, (1940): Microscopic features ofore from the Sunshine Mine. Econ. Geol. BS,662-665.

Banrou, P. ts. Jn., BETIKE, p. M. & Tour,Mrr.r, p.(1963): Equilibrium in ore deposits. Mineral. Soc.Amer. Special Paper L, 171-185.

& SrrNlqER, B. J. (1967): Sulfide mineralstabilities. In Geochemistry ol HydrothermalOre Deposits (H. L. Barnes ed.), 236-333. H:olt,Rhinehart, and Winston, New York.

BuHrrvrarrrN, E. (1971): Untersuchungen im Sys-tem BirSg-Cu2S und geologisch: Schlussfolgerungen. N. lahrb. Mineral. Monat. 3, 137-141.

Bunrenr-BluMeNN, I., Orrsr"reNN, J., Nusrn, B.(1968): Gratonit aus der Lagerstiitte Rio Tinto,Siidspanien. N. Jahrb. Mineral. Monat. 7, 215-224.

--, & Alrsrrnz, G. C. (1972):The r-ray amorphous s 'tfides from Cerro dePasco, Peru, and the crystalline inclusions. lf.Jahrb. Mineral, Monat. 433446.

CHANc, L. L. Y. & Bnwn, J. E. (1973): Leacl sul-phosalt minerals: crystal struc.tures, stabilityrelations, and paragenesis. Minerals Sci, Engng.5 , 1 8 1 - 1 9 1 .

CrrEN, T. T. & CueNc, L, L. (1971): Phase rela-tions 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 mineralassemblages in the Ag'Bi-Pb-S system. Mlneral-ium Deposita L, 278-306.

& BenroN, P. B. Jn. (1973): Thermo-chemical approximations for zulfosaft* Econ,Geol. 68, 493-506.

--, CneNc, L. & Lsrs, W. R. (1973): In-vestigations in the Pb-Sb.S system. Can. Min-eral. L2, 199-206.

FEIss, P. G. (1974): Reconnaissance of the tetra-hedrite-tennantite/enargite-famatinite phase rela-tions as a possible geothermometer, Econ. Geol.69, 383-390.

Fr.usctlrR, M. (1971): Glossary ol Mineral Spe-cies. Mineralogical Record Inc., Bowie, Mary-land.

FnoNonr, C. (1963): Isodimorphism of the poly-basite and pearceite series, Amer. Mineral. 48,565-572.

& HoNrr., R. M. (i968): Billingsleyite,a new silver sulfosalt, Amer. Mtneral. 53. l79l-1798.

Gooorrr., P. (1970) : Zoning and Paragenesi,s inthe Julcani District, Peru. Ph.D. Thesis, Har-vard University.

GnensER, S. (1968): Kurz Be*chreibung der wich-tigsten I€ngenbacher Mineralien. /z Die Mine-ralfundstelle Irngenbach in Biunatal. Natar-lrist. Mus. der Stadt Bern, Switzerland,

Herr, H. T. (1967): The pearceite and polybasiteseies. Amer. Mineral. 52, l3ll-1321.

(1966): The Systems Ae-Sb-9, Ae-As-Sand Ag-Bi-S: Phase Relations and Mi,neralog-

ical Significance. Ph.D. thesis, Brown Univ.,Providence, R. I.

(1964): Equilibrium relations amongsome sllver sulfosalts and arsenic sulfides.Trans. Amer. Geophys. Union 45, 122 (Abstr,).

Herene, K., Sexevroto, O., Nereo, K. & Neci-stultA, 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: XIX-selenian polybasite. Can. Mineral. 8, L72-184.

Hooe, S. N. & Cnarc, L. L. Y. (1972): Phaserelations in the systems AggS-PbS-Sb:Sg audAg:S-Pb$BirSs. Geol. Soc, Amer. PrograntAbstr. 4,539-540.

BTNARY AND TERNARv suLpHosALT ASSEMBLAGEs m CUS-Ag"$PbS-AsfrSbrSr-Bin 4 l

HoNNomz-Gurnsttnt, B. M. (1971): Betekhti-nite and Bisuffosalts from the copper mine of"La I,eolra", Argentina. fuliheralium Deposita6, llL-L2L.

JAKES, P. (1963): Studies in stibnite veins onqorth-western slope of Nizke Tatry Mts., intho area of Dubrava deposiL Acta Univ. Caro-linae Geol. L59-L78. (Czech with English sum-Eary).

Jeunon, l. L. (1967): New lead sulfantimonidesfrom Madoc, Ontario - Part L. Can. IuTineral9, 7-24,

(I961b): New lead sulfantimonidesfrom Madoc, Ontario - Part 2 - Mineral de-scriptions. Can. Mineral. I, t7t-2L3.

(1968): New lead sulfantimonides fromMadog Ontario - Part 3 -=- Syntheses, para-genesis, oigsn. Can. Mineral. 9, 505-521.

(1969): Sulphosalts of the plagionitegroll;p. Mineral, Mag, 37, 4/.2446.

Kenw-Mdr.r.rn, S. (1973): New data on schir-merite. Can. Mineral, LL, 952-957.

(1970): Gustavite, new sulphosalt min-eral from Greenland. Can. Mineral. LA, fi4-790.

Kuclilrr, C. W. & HoNne, R. M. (1969): Thesystem Ag-Sb-S from 600'C to 200"C. Mineral-ium Deposita 4, 153-171.

Klol,,frNsKy, J,, Rrcorn, M., Krnnl C. & MRAZ,L. (1971): Heyrovskyite, 6(Pbo.86Bi.o0r(Ag,Cu)-0.04)5 . Bir,$ from Hurky, Czechoslovakia, anew mineral of genetic interest. MinerallurnDeposita 6, 733-147.

Kurcx, V. & MAKovrcKy, E. (1968): Die Kristall-structur des Minerals (PbAg,Bi)CuaBioSrr. lV.Jahrb. Mineral. IVIonat. 7, 236-237.

Lnwrs, R. W. Jn. (1964): The Geology, Mineral-ogy and Paragenesis of the Castrovineyna Pb-Zn-Ag Deposits, Peru. Ph.D. Thesis. StanfordUnivenity.

MenxueM, N. L. (1959): Occurrence of jordanitein the Otavi Mountains, South West Africa.Amer. Mineral. 44, 68L685.

Mlsrr, S. & SmnlsR, B. J. (1971): Studies of thesulfosalts of copper. I. Phases and phase rela-tions in the system Cu-As-S. Econ. Geol. 66,901-918.

McKrNsrnv, H. (1963): Mineral assemblages insulfide ores: The system Cu-Fe-As-S. Econ.Geol. 58, 483-505.

(1959): Mineral assemblages in sulfideores: The system Cu-Fe-S-O. Econ. Geol. 54,975-1001.

Moonr, P. B. (1967): A classification of sulfo-salt structures derived from the structure ofaikinite. Amer. Mineral. 52, 1874-1876,

Nrpaclrt, M., Tercucrn, T., Yevreore, K. &Terincucrr, M. (1973): Bt-Ag-Pb-S mineralsfrom Agenosawa mine, Akita Prefecture, North-eastern lapan. Mineral. "/. (Japan) 9, 69-80.

OrrsNnn, O. (1961): Atlas ol the Most ImportantOre Mineral Parageneses Under the Microscope,Pergamon Press, New York, N.Y.

OBN, I. S., Bumr, E. A. I. & Krrrr, C. (1973):Bismuthian tennantite from Mangualde, Portu-

cal. N. lahrb. Mineral. Monat, l, 4346.PADERa, K" (1955): Beitrag zur Revision der Mi-

neralien aus der Gruppe von Wismutglanz undAikinite. Chemte Erde L8, l-14.

P.lrs, L. W. (1971): Geology and mineralogy ofthe Trump fissure-fault ore body, Trixie Mine,East Tintic District, Utah. Geol. Studies, Brig-ham Young Unlv. t8, ll5-L46.

PAr-acun, C., BErureN, H. & Fnoxoer-, C. (L944):The System o! Mineralogy 1. New York, JohnWiley & Sons.

PntrRsaN, U. (1962)z Genesis of Ore Deposits inthe Andes of Central Peru. Ph.D. Thesis, Har-vard Univenity.

Prrr.ur, W. & staff (I971)z The silver-arsenide de-posits of the Cobalt-Gowganda region, Ontario.Characteristics of the sulphides. Can. Mineral.Ll, 196-231.

ReDrrs, A. S., Tevro& C. M. & Monnrs, H. T.(1969): Micromineralogy of galena ores, Bur-gin Mine, East Tintic Diatrict, Utah, U,S. Geol.Surv. Prof. Paper 6L4-4, t-I7.

nmroom, P. (1969): The Ore Minerals and ThebIntergrowths. Pergamon Fress, New York

Rnsl J. F. (1974): The tetrahedrite-freibergiteseries, with reference to the Mount Isa Pb-Zn-Ag orebody. Mineraliam Deposita 9, ll7-124.

RoLANo, G. W. (1968): The system Pb-As-S;composition and stabilif of jordanite. Mineral-ium Deposlta g, 249-260.

(1970): Phase relations below 575"C inthe system Ag-As-S. Econ. Geol. 65' 24t-252.

Rusr, G. W. (1940): Geologic occutrence of gra-tonite at Cerro de Pasco, Peru. Amer. Mineral.25, 266-270.

ScnorrrBw, C, (L962): Determination Tables torOre Mlooscopy. Elsevier, New York.

Scott, J. D. (1971): Collecting rare sulfosalts inBritish Columbia. Mlneralogical Record 2,203-209.

Srur,rao.l, N. & I{rnowetenr, F. (1972): Argen-tian tetrahedrites from the Taishu-Shigekumamine, Tsushima Island, Japan. Mineral. J.(Japan) 7,77-87,

Srnwrn, B. J. (1960): Assemblage enargite-fama-tinite, a possible geologic thermometer. Geof.Soc. Amer. Abstr. Ann. Mtg. 7t, 7975.

LucB, F. D. & MAKovrcrv, E. (1972)zStudies of the sulfosalts of col4rer III. Phasesand phase relations in tle system Cu-Sb-S"Econ. Geol. 67, 924-938.

SrnrNcrn, G. (1969a): Compositional variationsin enargite and luzonite. Mineraliam Deposita4, 72-74.

(1969b): Naturally occurring composi-tions in the solid solutions series Bis,$-SbeSs.Mineral. Mag, 37, 295-296.

(1969o): Electronprobe analysis of te-trahedrite. N. tahrb. Mineral. Monat. t, 2+32.

& Lerr,err,rur, J. H. G. (1971): The sys-tenr Birsg-SbzSa. Can. Mineral. 10, 847-853.

Szrs.oKA! K. (1945) : Erzmikroskipische beobach-tungen an erzen von Recsk (Matra Banya) inUngarn. N. Jahrb. Mineral. Ab. A79, L0+128.

42 TUE CANADIAN MINERALOGIST

Trxr.on, C. M., RADTKB, A. S. & Cnnrsr, C. L(1973)z New data on cuprobismutite. J. Res.US. Geol. Surv. L, 99-103.

Tout rurx, P. 3no. (1963): Proustite-pyrargyritesolid solutions. Amer. Minerul. 48, 725-736.

fRAIr;L, R. J. (1970): A catalogue of Canadianminerals. Geol. Surv. Canada Paper 6945.

UyreNBocAARDr, W. (1951): Tables for lVlito-scoplc ldentification of Ore Ml,nerals. HafnerPub. Co., New York.

WALIA, D. S. & GraNc, L. L. Y. (1973): Investiga-

tions in the systems Pb$SbrSs-AsrSg and PbSBi2Ss-Ase$. Can. Iulineral. L2, LL3-LL9.

Wnr;N, E. (1966): Notes on the mineralogy ofSweden. 5. Bismuth-bearing sulfosalts fromGladhammar, a revision. Arkiv Mineral. GeoI.4, 377-386.

Wu-lreus, S. A. (1968): Complex silver ores fromMorey, Nevada. Can. Minerul. 7, 475483.

Manuscript received July 1974, emended October1974