MI NE RAL OGI CAL MAGAZI NE, DECEMBER 1983, VOL. 47, PP.

427 35
Chemical behaviour of sphalerite and arsenopyrite
in hydrothermal and metamorphic environments*
S. D. SCOTT
Department of Geology, University of Toronto, Toronto, Ontario M5S 1A1, Canada
ABSTRACT. Examples of application of equilibria in the
systems Fe-Zn-S, Cu-Fe-Zn-S, Fe-As-S, and Fe- Zn-
As-S are drawn from modern sulphide-forming hydro-
thermal vents on the East Pacific Rise, from ancient vein
deposits and from metamorphosed sulphide ores. The
ZnS content (1.2 and 1.3 mole 9/o) of Cu-Fe-S intermediate
solid solution (iss) from the sea-floor deposits gives
temperatures of equilibration of 331 ~ and 335 ~ from
experimental curves, in excellent agreement with the
350 ~ expected from actual measurement of the hot
springs. Heterogeneities in sphalerite in these deposits do
not necessarily represent disequilibrium during deposition
but can be explained simply by small fluctuations in as2.
Diagrams of log as2 vs. 1000/T,K for sphalerite and
arsenopyrite are useful for estimating temperature and
activity of sulphur in hydrothermal or metamorphosed
deposits provided that equilibrium can be demonstrated
and the systems are properly buffered.
The sphalerite geobarometer has had wide applications,
some successful (mostly vein deposits) and some not
(particularly metamorphosed ores in which chalcopyrite
is in contact with sphalerite). Compositions of sphalerites
which are totally enclosed within metablastic pyrites
represent preserved high P - T equilibria which have
been isolated from further reaction during subsequent
retrograde conditions by the inert encapsulating pyrite
and may provide more reliable estimates of pressure.
ATTEMPTS t o use sul phi de mi neral equi l i bri a for
est i mat i ng t emperat ure, pressure, and activities of
component s duri ng ore f or mat i on or subsequent
met amor phi sm have met wi t h onl y par t i al success,
t he mai n pr obl em bei ng changes in composi t i ons
dur i ng cooling. Most sul phi des easily under go
r et r ogr ade react i ons and onl y the most refract ory
can pr ovi de rel i abl e i nf or mat i on from high P and T.
Among t he common sulphides, sphal eri t e and
ar senopyr i t e are t he best under st ood and most
useful. Equi l i bri um composi t i ons of these t wo
mi neral s are usual l y preserved from hydr ot her mal
vein deposits which cool relatively rapidly. However,
equi l i bri um may not always be preserved, part i cu-
l arl y for sphalerite, from regi onal l y met amor phosed
sulphides which can cool very slowly.
*Invited contribution.
t~] Copyright the Mineralogical Society
Thi s paper surveys recent experi ment al studies
i nvol vi ng sphal eri t e and arsenopyri t e, and gives
exampl es of how these dat a may be appl i ed for
est i mat i ng t emperat ures, sul phur activities (as2)
and pressures. Exampl es are dr awn from hydr o-
t hermal deposi t s in which quenchi ng was rel at i vel y
rapi d, such as t he recent l y di scovered sul phi de
chimneys formi ng on t he sea-floor of the East
Pacific Rise and anci ent vein deposits, as well as
from met amor phosed base met al deposi t s where,
despite slow cooling, some geobaromet ri cal l y useful
equi l i bri a are preserved.
F e - Z n - S syst em
Lo w pressure. Phase rel at i ons i nvol vi ng sulphides
under condi t i ons where pressure is not an i mpor t ant
vari abl e are most conveni ent l y di spl ayed on l og as2
(or l og f s) - 1000/ T, K di agrams. Such a di agr am for
t he F e - Zn - S system is shown as fig, 1. Sphal eri t e
has a maxi mum FeS cont ent when in equi l i bri um
wi t h t roi l i t e ( Fe- FeS buffer). The FeS cont ent
decreases gr adual l y wi t h i ncreasi ng as~ across t he
pyrrhot i ne field until at the pyr r hot i ne- pyr i t e buffer
the sphal eri t e cont ai ns 20.6 mol e ~o FeS bel ow
600 ~ or slightly less FeS at hi gher t emperat ures.
Wi t hi n the pyri t e field the decrease in FeS cont ent
of sphal eri t e with i ncreasi ng as2 is much great er
resul t i ng in a close spaci ng of i sopl et hs near t he
pyr i t e- pyr r hot i ne buffer and in very low FeS
cont ent s in sphal eri t e at high as2. The effect of
pressure on t he di agr am is t o raise all buffer curves
t o hi gher values of as2 and all isopleths to even
higher values (e.g. resul t i ng in l ower FeS cont ent
in sphal eri t e al ong t he pyr i t e- pyr r hot i ne buffer).
Below a ki l obar these effects are very small,
pr oduci ng a shift of onl y a few hundr edt hs of a l og
as~ uni t per 100 bars. I n a qual i t at i ve sense, it is
commonl y found t hat sphal eri t es formed at high
as~ such as in equi l i bri um wi t h bor ni t e + pyri t e +
chal copyri t e (fig. 1) have a honey yellow t o l i ght
brown col our consistent with their low FeS contents
whereas t hose formed at l ower as2 within the pyri t e
S. D. SCOTT
1 0 0 0 / m ( K -1 )
+1
0
- 1
- 2
- 3
- 4
- 5
o
- 7
o
- - - 8
- 9
- 1 0
- 1 1
- 1 2
- 1 3
- 1 4
- 1 5
428
3 0 0 4 0 0 5 0 0 6 0 0 7 0 0
Temperature ( ~
FIG. 1. Phase relationships for the Fe Zn-S system at 1 bar compiled from Barton and Toulmin (1966), Scott and
Barnes (1971) and Czamanske (1974). Isopleths are mole ~o FeS in sphalerite coexisting with pyrrhotine or pyrite.
Abbreviations: bn, bornite; cpy, chalcopyrite (or intermediate solid solution); po, pyrrhotine; py, pyrite; Sz,
liquid sulphur; So, sulphur vapour.
field or at any ass within t he pyr r hot i ne field are
dar k br own t o black. The assembl age sphal eri t e +
bor ni t e + pyri t e + chal copyri t e, which is not un-
common in por phyr y copper ores and in some
copper vein deposits, is a pot ent i al geot her momet er
(Czamanske, 1974). However, the shal l ow i nt er-
section of sphal eri t e i sopl et hs with the buffer curve,
coupl ed with t he usual preci si on of el ect ron mi cr o-
pr obe anal yses of onl y a few tenths mol e ~ FeS
precludes accurat e est i mat i on of t emperat ure. The
FeS-ri ch i sopl et hs at l ower as2 woul d be mor e
useful for geot hermomet ry provi ded an equilibrium
buffer assembl age was present which cuts t he
i sopl et hs at a steep angle. The pyr i t e- pyr r hot i ne
assembl age is not a conveni ent buffer except above
600 ~ because it is paral l el or near l y so to the
sphal eri t e isopleths. I will r et ur n t o these geo-
t her momet r i c discussions below.
Fig. 1 may be mor e sui t abl e for est i mat i ng
as2 t han t emperat ure. St yrt et al. (1981) and
Heki ni an et al . (1980) have r epor t ed mi cr opr obe
anal yses of zinc sul phi de (wurtzite and sphalerite)
from hydr ot her mal vents at 2l ~ N. on t he East
Pacific Rise (water dept h 2600 m, confining pressure
260 bars, maxi mum T of vented fluids 350 ~ Their
anal yses show a wide scat t er but when viewed in t he
cont ext of vari at i ons in sphal eri t e composi t i ons
wi t h ass in fig. 1, t he scat t er is not unexpected. Fo r
example, Heki ni an et al. (1980) found t hat most
sphal eri t es coexi st i ng wi t h pyr i t e in inactive vents
SPHALERI TE AND ARSENOPYRI TE 429
(CYAMEX area) contain 14-20 mole % FeS and
those included within pyrite 15-25 ~. Inactive vent
material analysed by Styrt et al. (1981) gave 6-21
mole ~ FeS. For a reasonably constant temperature
of precipitation of zinc sulphide, all of Styrt et aL's
(1981) analyses lie within a remarkabl y small range
of one order-of-magnitude in as2 (i.e. 10 -1~ to
10 -11 for 300 ~ within the pyrite stability field
immediately adjacent t o the pyrrhotine field. The
zinc sulphide compositions more FeS-rich t han 21
mole ~o found by Hekinian et al. (1980) and by Styrt
et al. (1981) (up t o 33 ~ in active vents) are probabl y
a consequence of periodic excursions ofas~ i nt o the
pyrrhotine stability fi dd and is consistent with the
observation by Haymon and Kast ner (1981) t hat
the iron sulphide precipitating in the ' black smoke'
issuing from the vents is hexagonal pyrrhotine.
Similar variations in composi t i on of zinc sulphides
are seen in active vents at 21 ~ N. where tempera-
tures of venting are accurately known. Samples of
wurtzite coexisting with pyrite, barite, and anhydrite
from two active vents whose temperatures were
measured to be 273 and 295 ~ cont ai n 9.5-16.2
and 12.0-16.8 mole ~o FeS, respectively (Marjorie
Styrt, pers. comm., 1981). Despite the rather wide
range of FeS contents and assuming t hat fig. 1
applies equally well t o wurtzite as t o sphalerite and
t hat the depositional temperature was the same as
was measured in the vent fluids, these samples give
very similar values for logas2 of 11. 4+0. 3 and
10.5+0.2, respectively. The reason for the small
variation in l og as~ over a wide range of sphalerite
composition coexisting with pyrite is, of course,
the close spacing of the sphalerite isopleths near
the pyrrhotine stability field in fig. 1. I n fact,
compositionally zoned sphalerites should be ex-
pect ed from hydrot hermal ores formed under
comparable condi t ons of as2 and temperature
within the pyrite stability field because as2 is
unlikely ever t o be buffered so precisely t o give
const ant compositions. Such buffering is possible,
however, t hrough long term annealing during
metamorphism.
Hi gh pressure (sphalerite geobarometry). The
variation of FeS content in sphalerite as a function
of pressure when buffered by pyrite and hexagonal
pyrrhotine is independent of temperature over a
considerable range (fig. 2) and has given rise to
the concept of the sphalerite geobarometer (Barton
and Toulmin, 1966; Scott and Barnes, 1971; Scott,
1973, 1976; Hut chi son and Scott, 1981). The geo-
baromet er has received wide applications, some
successful and some not. Most of the successes have
been with hydrot hermal mineralization in which
cooling was reasonably fast such as skarns (e.g.
Shimizu and Shimazaki, 1981) and veins (e.g.
Hudson Bay Mount ai n area; Hut chi son and Scott,
700
ta 600
o
i._
500
o_
E
4 o 0
300
I
22 20 18 16 14 12 10
Mol e % FeS in Sphal er i t e
FIG. 2. Temperature-composition section along the
ZnS-FeS join of the system ZnS-FeS-S of sphalerite+
pyrite +hexagonal pyrrhotine equilibria as a function of
pressure (in kbar). Temperature-independent portion of
the isobars is shaded. Drawn from the data of Boorman
(1967), Scott and Barnes (1971), Scott and Kissin (1973),
Scott (1973), Lusk and Ford (1978), and Hutchison and
Scott (1981). From Hutchison and Scott (1980).
1981). Met amorphosed deposits which have cooled
very much more slowly, on the ot her hand,
commonl y show evidence of extensive retrograde
changes in sphalerite composition, particularly in
Cu-rich environments (Hutchison and Scott, 1981).
The resulting sphalerites are considerably depleted
in FeS relative t o t hat expected from the high
P and T of met amorphi sm and, indeed, are more
consistent with compositions expected from a low-
temperature assemblage of spbat er i t e+pyr i t e+
monoclinic pyrrhotine (Scott and Kissin, 1973). I n
order t o avoid the problems attending retrogression
and the very real but not underst ood interference
by copper, sphalerite inclusions, and particularly
those with accompanyi ng pyrrhotine as in fig. 3,
that are totally encapsulated in pyrite should be
sought and analysed. Presumably, such poikilo-
blastic inclusions were equilibrated during or near
peak met amorphi c conditions. They display the
requisite buffer assemblage and would have been
protected from hydrot hermal l y enhanced retro-
gression by the inert encapsulating pyrite. Such
inclusions are not uncommon in met amorphosed
ores and their analysis from a wide variety of
deposits is now required in order t o test their
usefulness for geobarometry.
430 S.D. SCOTT
i 84184 ~ ~
@" 'i
t
o ; py
500pm l
r
i lOOpm
sp
B pv
FIG. 3. (A) Poikiloblastic pyrite from the Ducktown
Cu Zn metamorphosed massive sulphide deposit,
Tennessee. One inclusion containing both sphalerite and
pyrrhotine (circled) and suitable for sphalerite geo-
barometry is enlarged in (B). Some inclusions in {A) are
transected by fractures so may have been accessed by
fluids during retrograde metamorphism and are unsuitable
for geobarometry.
Cu- Fe- Zn- S system
A texture commonly seen in hydrothermal Cu-Zn
sulphide ores is an emulsion of tiny (1 to 20 #m)
chalcopyrite inclusions in sphalerite. The texture
has been named ' chalcopyrite disease' by Barton
(1970, 1978) who has described examples from vein
deposits at Creede, Col orado and from the Kuroko
massive sulphide deposits (fig. 4). Chalcopyrite
disease is also found in zinc sulphides from hydro-
thermal vents of the East Pacific Rise at 21 ~ N.
(Oudin, 1981; F6vrier, 1981) and of Guaymas Basin
in the Gulf of California (Scott et al., 1983).
Traditionally, the texture has been described as an
exsolution of chalcopyrite from sphalerite. However,
Barton (1970, 1978) and Kalogeropoulos (1982)
have convincing evidence that ' chalcopyrite disease'
is a ' cancerous' replacement produced by Cu in
aqueous solution reacting with FeS in sphalerite.
Their arguments are borne out by the experimental
FIG. 4. Small blebs of chalcopyrite in sphalerite ('chalco-
pyrite disease') from the Uwamuki no. 2 Kuroko deposit,
Kosaka mine, Japan. (Upper) reflected light; (lower)
transmitted light. The conCentration ofchalcopyrite at the
top of each photomicrograph is so high as to render the
normally translucent sphalerite opaque in transmitted
light. From Farr (1980).
dat a of Hutchison and Scott (1981) who have
shown that at high as2, such as those encountered
in the above examples, the solubility of CuS in
sphalerite is very low, less that 1 mole % below
600 ~ The cited examples formed at far below
600 ~ (200-400 ~ where the equilibrium solubility
of Cu in sphalerite must be in the range of tens or
hundreds of ppm which, together with the fact that
the samples from the East Pacific Rise were
quenched rapidly in ambient 3 ~ seawater, rules
out the possibility of exsolution being an explana-
tion for ' chalcopyrite disease'. Nevertheless, this
texture can easily be confused with exsolution and
it is not difficult to envisage how such chalcopyrite
might be redistributed during recrystalization to
produce a texture which would be indistinguishable
from true exsolution.
ZnS solubility in Cu- Fe sulphide intermediate
solid solution (iss) is another possible geothermo-
meter (fig. 5) although its use is restricted to
SPHALERI TE AND ARSENOPYRI TE
t hose rare nat ur al occurrences where i s s has been
preserved and has not i nvert ed t o ot her Cu- Fe
sul phi de phases. The composi t i on of i ss which
coexists with sphalerite + pyrite + pyrrhot i ne is near
CuFezS 3 (Hut chi son and Scott, 1981). For t unat el y,
this is t he por t i on of the extensive i s s field which can
be quenched and i ss is found in sampl es from
I O
8
6
$
N
4
Z 3
ILl
U
I=-
"1-
o
.7. 1. 0
9 O . 8
0 . 6
0 . 5
l O 0 0 / r , K - I
1 . 7 1 . 6 1 . 5 1 . 4 1 . 3 1 . 2 1 . 1 1 . 0
' 1 1 I ' I r I ' 1 ' 1
_- ~ . 1.0
- 0 . 8 0
- - 0 . 6
- / / A
7 V , I , I , , I , I , I , I - - 1 . 0 . 2
3 0 0 3 5 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0
T E M P E R A T U R E , OC
FIG. 5. Solubility of ZnS in intermediate solid solution
(iss) coexisting with pyrite and pyrrhotine in the Cu-Fe
Zn-S system as a function of temperature and pressure
(1 bar, 5 kbar). Experimental data are from Hutchison and
Scott (1981). Triangles are analyses of ZnS in iss by Oudin
(1981) from sulphide chimneys at 21 ~ N. of the East Pacific
Rise. Confining pressure here is about 260 bars.
hydr ot her mal vents at 21 ~ N. (Styrt e t al . , 1981;
Haymon and Kast ner, 1981; Oudi n, 1981; F6vri er
1981) and Guaymas Basin (Scott, unpubl.). Two i s s
samples anal ysed by Oudi n (1981) cont ai n 1.2 and
1.3 mol e % ZnS from which fig. 5 provides estimated
t emperat ures of equi l i brat i on of 331 and 335 ~
respectively. These are very close t o the 350 ~
maxi mum t emper at ur e of t he 21~ vents and
suggest t hat equi l i bri um may have prevailed.
Analyses by A. J. Br ackmann (unpubl.) give a range
of 1.4 t o 3.2 mol e % ZnS in i s s cor r espondi ng t o
343 to 440 ~ I n maki ng these t emper at ur e esti-
mat es from i s s analyses I have assumed t hat t he
experi ment al l y det ermi ned curves of Hut chi son
and Scot t (1981) in fig. 5 can be r easonabl y
l i nearl y ext r apol at ed to l ower t emperat ures and
t hat t he smal l increase in as2 above the pyr i t e +
pyr r hot i ne solvus as was deduced from fig. 1 is
uni mpor t ant .
431
F e - A s - S s y s t e m
The Fe - As - S system (figs. 6 and 7) det ermi ned by
Kr et schmar and Scot t (1976) has had modest
success in est i mat i ng as2 dur i ng tin mi neral i za-
tion at Reni son Bell, Tasmani a ( Pat t er son e t al . ,
1981) and as a geot her momet er in met amor phosed
massive sul phi de deposi t s of the Skellefte di st ri ct in
Sweden (Berglund and Ekst rom, 1978), an Archaean
banded i r on f or mat i on from West er n Aust r al i a
(Gole, 1980), a silver vein deposi t from Nevada,
USA (Vikre, 1981), and t opaz greisen veins in
Mi ssouri (Lowell and Gaspar r i ni , 1982). However,
as present l y const i t ut ed, t he ar senopyr i t e geo-
t her momet er is useful onl y when t he uni vari ant
buffer assembl ages in figs. 6 and 7 are operative.
Ar senopyr i t e may be a common mi neral in ores
but the buffering phases 1611ingite, arsenic, and
As- S l i qui d (solidified t o or pi ment and realgar)
are not. I n or der t o make full use of t he arseno-
pyri t e i sopl et hs of fig. 6 an appr opr i at e ass sliding
scale buffer is requi red which occurs commonl y
with arsenopyri t e, does not form a sol i d sol ut i on
with ar senopyr i t e and whose i sopl et hs cut t hose of
ar senopyr i t e at a st eep angle. Sphal eri t e coexisting
with pyri t e or pyr r hot i ne (or bot h) meets these
criteria.
F e - Z n - A s - S s y s t e m
Phase relations for the Fe - Zn - As - S system (fig. 8)
were obt ai ned by si mpl y combi ni ng figs. 1 and 6.
(See also Bart on, 1970, Fig. 8). Secondary react i ons
which may occur between sphal eri t e and As
phases have been i gnored and are assumed t o be
uni mpor t ant because Zn - As - S mi neral s are not
found in ores, whereas coexi st i ng sphal eri t e and
arsenopyri t e are ubi qui t ous under a wide range of
pressure and t emper at ur e condi t i ons. The i sopl et hs
for sphal eri t e and ar senopyr i t e in an assembl age
with pyrite and/ or pyrrhot i ne intersect at sufficiently
l arge angles in fig. 8 t o const i t ut e a useful geo-
t hermomet er. Fur t her mor e, because each i sopl et h
is uni var i ant at fixed pressure, t hei r intersections
are i nvar i ant and define a uni que as~ as well as
t emperat ure.
The ar ea of super posi t i on of ar senopyr i t e and
sphal eri t e composi t i ons covers t hat in which
many ore deposi t s are formed or met amor phosed.
However, t he di agr am is r at her cl ut t ered and
awkwar d t o use. For geot her momet r i c purposes,
the same dat a are bet t er di spl ayed on t emperat ure-
composi t i on axes (fig. 9). This di agr am is dr awn
for 1 kbar pressure, which is appr opr i at e for
many hydr ot her mal veins, by appl yi ng t he pressure
correct i ons for Zn - F e - S equi l i bri a det ermi ned
experi ment al l y by Scot t (1973) and Hut chi son and
432 S.D. SCOTT
- 2
- 3
,,,,,,
- 4 - -
i
- 5 - -
o
- 9
- I 0
- I I
- 1 2
- 1 3
- 1 4
- | 5
3 0 0
1.7 1.6 1 5
I
I O0 0 / T ( K - I )
1.4 1.5 1.2
' 1
491"C
I.I
I
6
38. 5 af %,4s
1.0
a s p + 16 + L
363' %
400 500
Temper ai ur e (*C)
j
~
6 0 0 7 0 0
FIG. 6. Phase relations for the Fe-As-S system in equilibrium with vapour. Isopleths are atomic % As in arsenopyrite.
Abbreviations as in fig. I plus the following: asp, arsenopyrite; L, As-S, liquid; 16,1611ingite. From Kretschmar and Scott
(1976).
Scott (1981) and assuming no effect by pressure on
Fe- As - S equilibria as concluded by Kret schmar
and Scott (1976). The effects of confining pressure
on estimated temperature for an arsenopyrite-
sphalerite pair is very small, approximately 4 ~
at 1 kbar.
As an example of an application of fig. 9,
Ki rkham (1969) and Kret schmar (1973) have
analysed two coexisting sphalerites and arseno-
pyrites occurring with pyrite in base metal veins
surroundi ng the cogenetic Hudson Bay Mount ai n
porphyry mol ybdenum deposit in British Columbia.
Sphalerite geobarometry (fig. 2) indicates a confining
pressure of 1. 5+0. 5 kbar (Hutchison and Scott,
1981) so fig. 9 is applicable. The coexisting arseno-
pyrite and sphalerite compositions (31 atomic % As
and 20 mole % FeS; 31.8 atomic % As and 18
mole % FeS) give estimated temperatures of 360
and 425 ~ respectively. Li qui d+vapour fluid
inclusions analysed by Bl oom (1981) from the
central molybdenite deposit homogenize over a
temperature range of 300-440 ~ but their relation-
ship t o the surroundi ng base metal veins is not
known.
Fig. 9 can also be used t o detect obvious
disequilibria between sphalerite and arsenopyrite.
For example, sphalerite coexisting with arseno-
pyrite and pyrite must contain about 10 or more
mole % FeS. Sphalerites in this assemblage from the
Rosebery massive sulphide deposit in Tasmani a
S P H A L E R I T E A N D A R S E N O P Y R I T E 4 3 3
0
o
v
::3
700
650
6 0 0
550
= 702
- - 6 8 8
i i i i i p o + i l 6 + 12 i
Thi s s t udy :
0 9 a s p + p o + L i o s p + p y + As below
3600C and 32 at . % As
-t- a s p + l S + L
asp + L
" 0 - a s p + 18+po
r'1'l asp + p y + L
0 a s p +1 6 +As
0 , 0 osp + py + po
Cl ar k ( 1 9 6 0 a ) :
9 a s p + I S+ As
9 a s p + p o + L i a s p + p y + L
below 491~
asp+16
O
I I
i
i
0-
50O - # t l 0 9 9 _
[] asp+l~+po
4 s ~ a s p + p y + L / / n T / "
~ I ~ 7 1 I ~ I +
l / I / h ~
400 - ~ , - - ~1 4 9 - 0 - -
W//
- ~o o d ~i o / I
sso - ,~ I ,~]o l /
a s p + ~ < " " ~ # ' ~ . / /
PY+ + / ~ / i I
~'~ IL,W~s,.,~ . , / Fe,~a '/,. ~ e A , , . , S o . ~ , , ~ , A , , . , ~ S o . , , 0 , 1
, i i l d _ ~ I J I
28 29 :30 51 32 53 - * - 54 35 36 37 58 :39 4 0
At omi c % Ar seni c in Ar senopyr i t e
FIG. 7. Pseudo-bi narycondensed T-Xsect i on along t he pyrite-16llingitejoin of the Fe- As- S system (from Kret schmar
and Scott, 1976). Abbrevi at i ons are as in fig. 6.
1.9
+1
S. D. SCOTT
I O 0 0 / / T ( K - ' )
1.8 1.7 1.6 1.5 1.4 1.3
-1
- 2
- 3
- 4
- 5
,",-6
0
- 7
0
- 9
-10
-11
-12
-13
-14
434
1.2 1.1 1.0
-15
300 400 500 600 700
TEMPERATURE ( * C)
FIG. 8. Compositions of coexisting sphalerite and arsenopyrite at low pressure for the Fe-Zn As-S system obtained by
superimposing figs. 1 and 6. The small difference in pressure between the two figures (1 bar vs. vapour pressure) is
insig~aificant. Isopleths are in mole ~ FeS for sphalerite and atomic ~o As for arsenopyrite.
contain less t han 5 mole ~ FeS and Green e t al .
(1981) correctly concluded t hat the minerals were
not in equilibrium.
C o n c l u s i o n s
Diagrams of logas2 vs. 1000/T,K for sphalerite
and arsenopyrite can provide reliable estimates of
temperature and as2 during ore format i on provided
the samples are cooled sufficiently rapidly t o avoid
retrograde reactions. Many hydrot hermal vein
deposits and, particularly, the mineral mounds and
chimneys presently forming from hot springs on the
deep ocean floor at various sites along the East
Pacific Rise satisfy this constraint. Heterogeneities
in sphalerite compositions from the sea-floor
deposits are readily explained by surprisingly small
fluctuations in as2 and is the preferred explanation
for compositionally zoned sphalerites from ancient
vein deposits as well. Emulsions of chalcopyrite
inclusions in sphalerite seen bot h in sea-floor and
vein deposits can be explained onl y by replace-
ment in the light of textural observations and
experimental dat a on the solubility of Cu in
sphalerite.
Arsenopyrite, which is even more refractory
t han sphalerite, has been applied successfully for
estimations of either ass or temperature. However,
with the exception of pyr i t e+pyr r hot i ne, the
essential buffered assemblages are uncommon. By
combining sphalerite solid-solution equilibria with
arsenopyrite compositions in the presence of pyrite
S P HAL E R I T E AND AR S E NOP YR I T E 435
! ! : j
. . 0 b ,J/
400 1 2 - - - - - ~- - -
* I p , ,,e l , . e " / " / A ~ , Y e / , , Q - / ~ ' o
Atomic % As in arsenopyri te - - ~
FIG. 9 Compositions of sphalerite and arsenopyrite co-
existing together with pyrite and/or pyrrhotine at 1 kbar
confining pressure. Contours are mole % FeS in sphalerite.
or pyr r hot i ne, uni que val ues of bot h as2 and
t emper at ur e can be obt ai ned.
The pr essur e dependence of sphal er i t e compos i -
t i on i n t he F e - Z n - S syst em is r eas onabl y wel l
known for all asFbuf f er ed assembl ages. However ,
f ur t her exper i ment al wor k is needed t o el uci dat e
t he effect of pr essur e on ar s enopyr i t e equl i br i a so
t hat di agr ams for c ombi ne d sphal er i t e and ar seno-
pyr i t e syst ems can be pr epar ed over a r ange of
pressures per t i nent t o all or e- f or mi ng a nd met a-
mor phi c condi t i ons.
Acknowledgements. My continuing work on sulphides is
supported by the Natural Sciences and Engineering
Research Council of Canada through Operating Grant
A7069. I thank M. N. Hutchison and J. E. Farr for the
photomicrographs of figs. 3 and 4, respectively. The
manuscript has had the benefit of careful scrutiny by P. B.
Barton, Jr. and D. J. Vaughan. I thank Vaughan and both
the Mineralogical and Geological Societies for making it
possible for me to attend the 1983 Mineralogical Society
Anniversary Meeting in London where this paper was
presented.
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[Revised manuscript received 6 July 1983]