Economic Geology

Vol. 68, 1973, pp. 480-492

The HydrothermalTransportandDepositionof
GalenaandSphaleriteNear 100øC
G. M. ANDERSON

Abstract

Using experimentaldata on the solubility of galena and calculated solubilitiesof

sphalerite,someof the consequences of assumingthat the ore-depositingfluid has the
compositionindicatedby fluid inclusionevidenceare examined. Assumingthat at least
! ppm Pb or Zn must be depositedas sulfidefrom the solutionbeforean ore body can
form, it is concludedthat there is no difficulty in transportingand depositingsufficient
metal and sulfurfrom a slightlyacid, chloride-richbrinewith a fairly low sulfatecontent.
If the reason for sulfide precipitation is cooling, neutralization, or dilution, the ore-
formingbrine will actively dissolvecalciteand dolomiteand the sulfur fugacity is quite
high. This meansthat, amongother things,chalcopyriteis not stableduringdeposition
of PbS and ZnS. If increasein reduced sulfur is the reason for sulfide precipitation,
then calcite,dolomite,and chalcopyritemay or may not be stableduring precipitation,
but it is more difficult to account for zoning of galena and sphalerite.

Introduction the discussionto point out here that under the

conditionsdiscussedthe known H•.S complexesof
IN recent years, the idea that MississippiValley- lead and zinc are quite negligible, so that the
type lead-zincoresare depositedfrom chloride-rich discussionof depositionalprocessesrefers only to
brines at quite shallow depths and at temperatures conditions in which metal-chloride complexesare
not far from 100ø C has gained wide acceptance. dominant.
The evidence from fluid inclusions (e.g., Roedrier,
1960, 1967) indicates that these brines are low in Galena and Sphalerite Solubilities
sulfur and that the sulfur presentis predominantly
sulfate. The chemical problem in this situation Experimental data on the solubility of lead and
zinc sulfidesin aqueoussolutionsat elevated tem-
is to show that it is possible to carry sufficient
quantities of lead and zinc as chloridecomplexes peraturesare quite scarceand have been reviewed
recently by Barnesand Czamanske (1967). Since
at pH valuesnot far from neutral, and that a small
amount of some geologicallyreasonableprocess then the work of Nriagu (1971a, b) and Nriagu and
such as cooling or neutralization will result in Anderson (1971) has provided data on galena
solubilities in chloride solutions and on the lead
precipitation of PbS and ZnS from the predomi-
chloride stability constants.
nantly sulfate brine.
Using these and other data and calculation
Some authors (e.g., Barnes, 1967; Barnes and
Czamanske,1967) have pointed out the difficulties procedures which are outlined in the appendix,
in this situation and have concluded that the ore- galena solubilities in NaCI solutions have been
calculatedup to 150ø C. These calculatedvalues
carrying solutions must have a much higher
content of reduced sulfur • than fluid inclusion were found to be higher than the 25 experimental
evidence would indicate, and that the metals are values of Nriagu (1971b) at temperaturesof 28ø,
60ø, and 90ø C (the temperatures for which pH
carried as bisulfide complexes. However the
values were measured rather than calculated) by a
evidence of Hamann (1973) indicates that the
factor of 2.6 4-0.6 (std dev'n). This factor has
lead bisulfidecomplexis not sufficientlystable to
been used to reduce all calculated galena solu-
provideore quantitiesof lead in brinesnear 100ø C.
Since there are recent conflictingdata on this point bilities to the valueswhich appear in the diagrams.
in the literature (Nriagu, 1971a), we have un- Thus the galena solubilitieson which the conclu-
doubtedlynot heard the last of this proposal,but sions of this paper are based are calculated ones
in thispaperI proposeto acceptHamann'sevidence which check quite well with experimentaldata, at
at face value and to examine the chloride complex- least up to 90ø C.
ing hypothesisin somedetail. It will alsosimplify Stability constants for the zinc chloride com-
plexesup to 65ø C have recentlybeendetermined
• Molality of reducedsulfur=rnsr=
Total sulfur=I•S=(m•+msmi-),q. Other aqueoussulfur by Fedorovet al. (1970)allowingcalculation(again
speciesare negligiblein the solutionsconsideredhere. by the proceduresoutlined in the appendix) of
48O
 TRANSPORT AND DEPOSITION OF GALENA AND SPHALERITE 481

sphalerite solubilities in NaC1 solutions, but there

are insufficient experimental data with which to 60-- o/
check the calculations. Comparison of appropriate
calculations with the data of Hinners (1963) and
with preliminary results from our own laboratory
(Barrett, unpublished data) indicates that the
5o- +Galena ,/•o Sphalerite
(calculated) /
3 m NaCI,pH4.0 •+
calculated sphalerite solubilities are too high.
Galena solubility exceeding that of sphalerite
would agree with Taylor's (1963) prediction based
.

on paragenetic relationships, but is the opposite

of the previouslycalculatedrelationship (Helgeson,
1969; Nriagu, 1971c). The sphalerite solubilities
have not been adjusted, however, and are shown
in Figure 1, together with the galena solubilities,
as a function of temperature at a pH of 4.0.
The remarkable similarity of the solubilities of
the two minerals is purely coincidental and will
disappear when experimental data for sphalerite
o I • I • I • I • ! r I • I
solubility are acquired. Since only the galena 4o ao •o •oo •o ,4o •ao

solubilities are tied solidly to experimental data, Temperature, øC

the other diagrams are drawn for this mineral only. Fro, 1, Solubilities of galena and sphalerite in 3 m NaC1
However there is little doubt that very similar solutionsat a pH of 4.0 as a function of temperature. •olu-
diagrams could be drawn and similar conclusions bilities of both minerals have been calculated but that of
galena has been adjusted to agree with the experimental data
reachedfor sphalerite. of Nriagu (1971b).
Factors Causing Precipitation of PbS and ZnS
metric (mpb(t)= msr) solution. Again, precipi-
For the conditions
considered
in this paper, tation from nonstoichiometric solutions is more
that is, a slightly acid, concentrated NaCI brine complicated and will be consideredlater.
of low reduced sulfur content, several factors will 3. Dilution: Since the heavy metal content of
tend to reducethe solubility of galenaand sphalerite the brines consideredhere is presentalmost entirely
and eventually to causetheir precipitation. These as chloride complexes, isothermal dilution of the
are:
brine will lower the solubility of the sulfides by
1. Changein pH toward neutrality: Both theory lowering the chloride activity. The net effect
and experiment (Nriagu, 1971b; Hinners, 1963) results from a complex interaction of the various
show that pH affects the (logarithm of) solubility equilibria involved, as well as the changein activity
as 1:1 if the solution contains equal amounts of coefficients,and cannot easily be predicted in the
metal and reduced sulfur, and as 1:2 if reduced way that the effect of pH changecan. For galena
sulfur is held constant. In other words, the and sphaleriteat 100ø C, pH 4.0, the stoichiometric
stoichiometric (ml'b(t) = ms,) solubility of galena solubility for NaCI contents of 1, 2, and 3 molal is
in 3 m NaC1 at 100ø C is about 1.47 ppm at pH about 2, 8, and 15 ppm, respectively. For non-
5.0, 14.7 ppm at pH 4.0 (Fig. 1), and 147 ppm at stoichiometric solutionsat 100ø C the change with
pH 3.0. If reducedsulfur content is held constant, NaCI content will be in these proportions.
for example by saturating the solution with H2S, 4. Increase in reducedsulfur: Because of the
moving 1 pH unit toward neutral will lower the solubility product relationship, increasing the re-
solubility by a factor of 100. These relationships duced sulfur content at constant pH reduces the
are illustrated in Figure 2. More realistic cases lead or zinc content of the solution as 1:1. This
in which metal and sulfur contentsare unequal and is also illustrated in Figure 2. In natural brines,
not held constant are more complicated and will be increase in reduced sulfur would result from:
discussedshortly, but pH change is in general a
(a) Sulfate reduction: A number of authors
powerful agent of precipitation.
(e.g., Hinners, 1963; Barton, 1967; Skinner,
2. Cooling: The effect of temperature on solu-
1967) have proposedmethods by which sulfate
bility is seen in Figure 1 to be greater at higher might become reduced to sulfide in the ore zone
temperatures than at lower temperatures, but it causingprecipitation of ore minerals.
has a considerable effect over the whole range. (b) Mixing of two solutions: Increase in
For example, cooling 10ø from 100ø to 90ø C will reduced sulfur could take place if the metal-
result in almost 5 ppm depositionfrom a stoichio- carrying chloride brine encountered another
482 G. M. ANDERSON

T = IO0*C
NaCI = 5.Ore

-2

-4 -- I0 ppmZ n
-- I0 ppm

too little
metal

-6•

-%
-I0 -8 -6 -4 -2_ 0

logms•
F•G.2. Total lead,zinc,andreducedsulfurcontents
of 3 m NaCI solutions
in equilibriumwithgalenaandsphaleriteat 100øC.
The stippledlineat 10ppmPb andthe equivalentamountof sulfurisa generalized cutofffor oreformationbasedon solubility
values. A bettercutoffbasedon amountprecipitatedis presentedin Figures3 and4. Boxedareais enlargedin Figure3.

solution of higher H•.S content. This has been are very helpful in this respect. Chiefly on the
proposedfor example by Lovering (1961) and basis of fluid inclusion evidence, Roedder contends
Jackson and Beales (1967). that ore-forming solutions commonly precipitate
somewherebetween! and 10 ppm of the basemetal
Quantitative Evaluation of Precipitation ore elements, perhaps as much as 100 ppm. He
That the factors listed above would tend to also shows that these amounts of precipitation
precipitate sulfides from acid chloride brines has couldresult in the formation of 108tonsof 1 percent
longbeenknown. What hasnot yet beenevaluated ore in 10,000 years (10 ppm precipitated) or
is just how much galena or sphaleriteprecipitates 100,000 years (1 ppm precipitated) with a reason-
for a given amount of change starting from given able rate of flow. Therefore in the following
conditions. Naturally the precipitatingfactorswill presentation, I assumethat 1 ppm of metal and
not normally act independently;perhapsmost of the equivalent amount of sulfur is the smallest
them are operative simultaneouslyunder natural reasonable amount which is precipitated in the
conditions. Still, a first stepin evaluatingtheir rela- ore-forming environment. This is the amount
tive effectivenessis to considerthem independently. precipitated,and it has quite a variable relationship
In addition to calculating these amounts of to the amount of a metal and sulfur dissolved in or
precipitation, we must choose a threshold value, carried by the solution.
above which the amount precipitated might under
favorable conditions result in an ore body in a Effect of pH change
reasonable length of time, and below which it Figure 2 is a diagram of the type first presented
would not. The observationsof Roedder (1960) by Barnes (1967). It has proved very useful in
 TRANSPORTAND DEPOSITION OF GALENA AND SPH.,'tLERITE 483

-34

T = IO0øC
NaCI= 5.0m

(57)

-:3.8

(21)

-46

...

-50

I I I
-50 -46 -42 -38 -3.4

logms•
FIG. 3. An enlargement of part of figure2. Numbersin parentheses are the ppm Pb in equilibriumwith galenaat those
points. ArrowsjoiningadjacentpH contoursshowthe pathsfollowedby solutions whichincrease their pH by 0.1 unit and
whichin the processdeposit1 ppmor 2 ppmPb as PbS. ArrowfromrandomlychosenpointA to pointB illustratescurved
path followedby solutionchangingby 0.3 pH units. About 7 ppm Pb as PbS are depositedbetweenA and B.

illustrating the differences between the acid, neutral point is pH 6.13, so it will be useful to
chloride-complexand alkaline, bisulfide-complex consideronly pH values above about 4.0.
theories of hydrothermal metal transport. Here Figure 3 is an enlargementof the boxedarea in
we consideronly the low reduced sulfur portion of Figure 2, for PbSonly. The numbersin parentheses
the diagram. For lack of data on amountsprecipi- are the Pb contents in ppm of the solution in
tated by various means, the threshold values of equilibrium with galena at that point. Along the
previous authors have generally been chosensolu- stoichiometricsolubility line (ml.b(t)= msr) the
bility values, and a solubility threshold value of amount of Pb precipitated as PbS for a given pH
10 ppm (Barnesand Czamanske,1967) is illustrated change can be read directly. For example, an
(stippledline) in the diagram. As illustrated, t•he isothermal pH changefrom 4.0 to 4.1 will result
boundary is not only one of metal content but in depositionof about 3 ppm Pb as PbS. At other
also of reduced sulfur content, emphasizing the points on the diagram the amount precipitated by
fact that, for theories which require that metal a pH change of 0.1 units can be calculated by
and reduced sulfur be transported together in the locating on the appropriate pH contour the point
same solution, the problem is not just one of metal which results in an equal amount of change in
transport but of reduced sulfur transport as well. Pb and Sr from the chosenstarting point on the
Many previous authors have concluded that adjacent pH contour. The amounts precipitated
the ore solution is not likely to be more than 2 pH (by 0.1 pH change)have beencontouredas shown.
units on the acid side of neutral. At 100ø C, the Changesin pH of morethan 0.1 unitswill_ofcourse
484 G. M. ANDERSON

pH=4.0
NaCl= 3.0m
ß

iiiiiiii!iii!i
Boundary
ofareawithin
which
I ppm Pb is depositedas PbS
-2- during I0 ø cooling.
Path followed by a particular
solutionin cooling IOøC. Number
is the ppm Pb deposited.
o

o
•o

too I•ttle Lead

-6 -5 -4 -3 -2 -I

log
FIG.4. Total leadandreduced
sulfurcontents
in 3 m NaCl solutions
in equilibrium
with galenaat pH 4.0. Numbered
arrows
show thepathfollowed
bysolutions
whichcoolfrom100
øC to90øC,thenumbers
givetheppmPbdepositedasPbS
during
thisprocess.
Stippled
lineislocus
ofsolution
compositions
which
willdeposit
1ppmPbasPbSwhilecooling
10øC.

result in greateramountsof precipitation,and the andis illustratedby the numberedarrows. Similar

true curved nature of the path followed by a calculationsfor a 10ø drop from other starting
solution precipitatingPbS becomesevident. As temperatures havealsobeenmadeandthestippled
one illustration, a pH changeof 0.3 units starting lineis the "1 ppmdeposited"
contour,withinwhich
from point A will result in about 7 ppmdeposition, morethan 1 ppmwill bedepositedduringa cooling
with the solution ending up at point B. of 10ø. As with pH change,the 10ø changeis
The choice of 0.! pH units is of course quite arbitrarybut usefulin illustratingjust howmueh
arbitrary and the area in which at least 1 ppm is precipitationmight take place.
depositedcouldbe enlargedby choosinga larger
pH interval. That the size of this interval is Effectof dilution
relativelyunimportantto the overallproblemwill The effectsof dilution have not been extensively
be shown later. calculatedor depicted on a separatediagram.
However dilution is similar to cooling and pH
Effect of cooling changeas a precipitating
agentin that bothmetal
Figure 4 is analogousto Figure 3, but with and reduced sulfur are assumedto be carried to the
temperaturerather than pH contoursand at a ore site in the same solution and it will become
fixedpH of 4.0. The amountof PbS precipitated clearshortlythat any suchprocess will be subject
duringa temperaturedrop from 100ø to 90ø C has to the samerequirementand will fall into the same
been calculated for various starting compositions generalarea in Figures5 and 6.
 TRANSPORT AND DEPOSITION OF GALENA AND SPHALERITE 485

-47

-48 T=100øC
NaCI = 3.0m
-- T.S = 0.03m

-49

-5O

•........ Ippm
Pb

-52

-53

-54

3 4 5 6 7

pH
Fro. 5. LeAdAndreducedsulfurcontours
AsAfunctionof oxygenfugAcityAndpH for3 m NACI solutions
in equilibrium
with
gAlenAAt 100øC. NumberedV-shAped contoursrepresentthe ppmPb depositedAsPbSduringcoolingfrom100ø C to 90ø C.
Stippledlineshowsareawithinwhicha solutionin equilibriumwith galenacontains1 ppmor more Pb and the equivalent
amountof St, i.e., the area outsideof whichno amountof changecan precipitate1 ppm Pb as PbS. Total sulfurcontentis
0.03 m, most of which is sulfate.

Effectof increasingreducedsulfur sulfate, 0.45 m calcium, and 0.10 m magnesium,

Once the solution is saturated with galena or aswellas3.51m chloride. UsingthisSO•- molality,
sphalerite, increase in reduced sulfur content will the H2S and HS- molalities at 100 ø C can be
precipitate PbS or ZnS in the 1:1 relationship calculatedas functionsof oxygenfugacity and pH
from the relations
illustratedin Figure2, as notedbefore. The only
additional requirementas far as ore deposition H2S(aq)
q- 202 = 2H+ + SO•-
is concerned is that the solution to which the and
reducedsulfur is addedcontainat least ! ppm Pb
or Zn to begin with. HS- + 202(g)= H + + SO•-.

The Ore Solution Environment

Total reducedsulfur (which is essentiallyequal
to m.2s) has been plotted as a function of logfo2
The compositionalarea of "reasonable" amounts and pH in Figure 5. Using these values of S,, the
of precipitationoutlinedabove can be put into a lead content of the solution in equilibrium with
geologicallymore meaningfulcontextby makinga galena has been calculatedby the proceduresout-
few assumptions about the other componentsin lined in the appendixand plotted in terms of ppm
the solution. For this purposefluid inclusiondata Pb. These "lead solubility" contours are in-
can be used and Roedder's (1967) "typical fluid dependent of pH becausethe effect of decreasing
inclusionanalysis"from sphaleritein the Tri-State pH (which raises the lead content) is exactly
district is convenient. This contains <0.03 m counterbalanced by the increasing reduced sulfur
486 G. M. ANDERSON

-47
T = IO0øC
NoCl=3.Om
-48
0.03 m

-49

-5O I00 ppmPb

I0 ppmPb

I ppmPb

-53

-54
HzS

-55 I I I
3 4 5 Neutral

pH
FIG.6. Mineralandaqueous speciesstabilities
asa function
of oxygenfugacityandpH in 3 m NaC1solutions at 100ø C
containing
0.03m SOd'-,0.45m Ca9'+,
and0.! m Mg9'+.Shaded areaistheranaeof solutions
whichwilldepositat least1 ppm
Pb asPbSwhilecooling
from100øC to 90ø C. Aqueous species
boundaries
arelociof equalmolalities
(notactivities)
of the
species.

content(whichdecreases t). These carrying 1 ppm Pb or more can deposit1 ppm, no

theleadconten,
intersectingPb and Sr contourscan then be usedto amount of coolingor pH changewill push the "1
draw the line for which mpb(t) = ms, and the "ppm ppm deposited"contourbeyondthe "1 ppm in
to this solution" contour, so that the area in Figure 5
Pb deposited"contourscan be transposed
diagram from Figures 3 and 4. The contours in which any amount of coolingor neutralization
shown are the number of ppm depositedduring couldpossiblyresult,in ore formationis outlined
coolingfrom 100ø to 90ø C for solutionssaturated by the stippledline. The main effectof enlarging
with galenaand at the indicatedoxygenfugacities the coolingor pH changeinterval is not to enlarge
and pH values. the area of interest on Figure 5, but to steepen
The area enclosedby the "ppm deposited by the contours within the area. That is, much more
0.1 pH change" contour from Figure 3 covers galenawould be depositedfrom a given solution
almost the same area, but with a nose at about within the area with increasing cooling or pH
pH 4.5. change,but the rangeof pH or fo2valuespossible
The effect of increasingeither the coolingrange for ore formation is not greatly changed.
or thepH changeontheareacoveredby the"1 ppm If the calculatedsphaleritesolubilitiesshown
deposited"contourcan be judged by examining in Figure 1 are anywherenear the correctvalues,
the contoursin Figure 5. Since only a solution then all these diagrams and conclusionswill be
 TR•INSPORT •IND DEPOSITION OF G.4LEN.4 •IND SPH•tLERITE 487

very similar for sphaleritedeposition. The stippled zinc sulfide is stable everywhere on the diagram
area in Figure 5 also delimits the area of possible and galena is stable everywhere below the PbS-
ore deposition by dilution or any other processin PbSO4 boundary. (These statements of course
which metal and sulfur are supplied by the same assume that enough Cu, Fe, Pb, Zn, and Sr is
solution, as mentioned earlier. present to saturate the solution with chalcopyrite,
From Figure 5 we can see that if ore deposition galena, and sphalerite.)
is to result from cooling, neutralization, or dilution, It follows that if we have a MississippiValley-
the solution must be more acid than about pH 5.0 type ore body in which it can be establishedthat
and the fo• range is fairly restricted. However, if chalcopyriteformedcontemporaneously with galena
the principal agent of deposition is addition of and sphalerite, then cooling, pH change, and
reduced sulfur, either by sulfate reduction or by. dilution were not the principal agentsof deposition.
mixing of solutions, the only restriction is that But if chalcopyriteis depositedlater, even directly
conditions (i.e., solution parameters in Figures 5 on crystals of galena or sphalerite, then cooling,
and 6) be above the "1 ppm Pb" contour. pH change,and dilution are not ruled out. It is
important to emphasizethat these conclusionson
Ore Deposition and Mineral Equilibria the relationship between chalcopyrite and galena
It is of interest to determinewhich other pertinent and sphaleritedo not depend at all on the amounts
minerals are stable and which unstable in and of cooling,pH change,or dilution which take place.
around the area outlined in Figure 5. In Figure 6 Quite similar remarks hold for dolomite and
several mineralogical and aqueous species bound- calcitedepositionas well. If, for example,dolomite
aries have been added to Figure 5 to show these is observed to have been deposited contempor-
relationships. The shaded "area of deposition" aneously with galena or sphalerite or if galena or
has been transferred from Figure 5 and represents sphaleriteis depositeddirectly on carbonateswith
the area within which at least 1 ppm is deposited no apparent disequilibrium,then the ore-depositing
on cooling from 100ø to 90ø C. Total sulfur solution was not in the shaded area of Figure 6, as
content has been chosenas 0.03 m, but the positions noted before. However calcite and dolomite could
of the boundaries are not much different for be deposited in the ore body by later, less acid
ZS--0.01 m or other reasonable values. To solutions. There is a great difference, therefore,
calculate the stability limits of calcite and dolomite between carbonates deposited on ore quantities
the calcium and magnesium values (0.45 m and of sulfide and ore quantities of sulfide deposited on
0.10 m, respectively) of Roedder (1967) have been carbonates.
assumedto be the molalities of Ca2+ and Mg 2+ in On the other hand if precipitation takes place
order to give the maximum stability fields. A by an increasein the reducedsulfur content, a much
CO2 pressureof ! atm has been used. wider range of possible starting conditions is
Under these conditions neither calcite nor available. If we assumethat pyrite is stable in the
dolomite is stable at more than one pH unit on the ore zone, then any solutions between the pyrite-
acid side of neutral, and CO• pressuresof several hematite boundary and the stippled ! ppm contour
hundreds of atmospheres would be required to become possible ore-forming solutions. Calcite,
stabilize them to pH values appreciably within dolomite, and chalcopyrite are all stable in parts
the shaded area of deposition. These pressures of this area, so that if any of these minerals is
are out of the question for conditions of typical found to be stable with the precipitating galena
Mississippi Valley-type of ore deposition, so our and sphalerite, then increase of reduced sulfur is
first conclusion is that dolomite and calcite should called for as the ore-precipitating agent.
actively dissolve in any brine that could produce
a galena-sphaleriteore deposit through any com- Additional thoughtson chalcopyrite
bination of cooling, pH change, and dilution. The main conclusions are stated above. With
(Naturally, this does not rule out a dolomitization somewhat greater uncertainty, we may make one
stage precedingthe sulfidedepositionstage.) or two more conclusionsconcerning the conditions
Noting the position of the chalcopyrite = borite under which chalcopyrite is deposited.
q-pyrite boundary, a second conclusion is that The chalcopyritestability field at acid pH values
chalcopyrite is not stable under conditionsin which (below 6.1) lies in a region of very low reduced
galena and sphalerite could form in ore quantities sulfur values (<0.1 ppm St) so that very little
by cooling, pH change, or dilution. This is not chalcopyrite could be precipitated in this region
to say that chalcopyrite and galena or sphalerite (without addition of reduced sulfur) no matter
are not stable together. Although chalcopyrite is how much Cu and Fe was in the solution. It seems
stable only above the cp = bn q- py boundary, therefore that if chalcopyrite is precipitated by
488 G. M. ANDERSON

cooling, pH change, or dilution, it must be from 2. The high fs• values place the shaded "area
solutionswhich are on the alkaline side of neutral, of deposition" in the stability field of covellite,
where reasonable Sr values are achieved within as well as of bornite, and the questionarisesas to
the chalcopyritefield. If precipitation is caused why these minerals are so rare in this type of
by addition of reduced sulfur to an acid solution, deposit. One possibleconclusionis that cooling,
it must be at a fairly slow and controlled rate if pH change,and dilution are uncommonreasonsfor
fs2and Sr values are to be kept within the chalco- precipitation of ore quantities of galena and
pyrite field, becauserapid increaseof the reduced sphalerite. A more likely conclusionis that the
sulfur content would certainly increase S• at least iron activity in ore-forming solutions is generally
locally to values outside (below) the chalcopyrite at a level high enoughto precludeprecipitationof
field and might result in precipitation of bornire, copper sulfides, and also that within the area in
or bornire plus metastablechalcopyrite,or perhaps which bornite is potentially a stable phase, the
metastable copper sulfides as well. copper activity is generally too low to precipitate
If this precipitation (by increaseof S• in an acid bornite. Considerableexperimentalwork is needed
solution) takes place in an ore zone which already to elucidate theserelationships.
contains sphalerite and/or galena, then large 3. Under the conditions considered, solutions
amounts of sphalerite and/or galena will be co- more acid than pH 4.0 in the shadedarea of deposi-
precipitated with the chalcopyrite becauseof the tion are very close to, and could in fact be within,
high Pb and Zn contents in the solution in this the stability field of crystalline sulfur. The occur-
region. Also the field of chalcopyritepluspyrite is renceof native sulfur in or closeto an ore zone might
quite narrow in acid solutionsand onemight expect then indicate that the solutions were at one time
occasionallyto find hematite rather than pyrite. quite acid.
In other words the occurrence of late-stage 4. Precipitation is a nonequilibriumprocess,but
chalcopyriteprecipitated by itself or with carbon- it seems very likely that the various means of
ates on an earlier generation of galena and/or precipitation discussedabove differ greatly in their
sphalerite seems to point to alkaline solution departuresfrom equilibrium. Cooling, pH change,
conditions. At the moment there are no data on and dilution can conceivably take place rather
the solubility of chalcopyritewith which to explore slowlyandgradually overthedistance in whichthe
this idea further. metal-carrying solution passes the site of ore
Some additional conclusions
deposition,and this would allow the differencein
lead and zinc contents of the solution to result in
The relationshipsshown in Figure 6 are nothing sphalerite-galenazonation. On the other hand,
more than an elucidation of the consequencesof mixing of a metal-carrying solution with an H2S-
taking fluid inclusion and solubility data at face bearing solution might result in a rapid precipi-
value, combined with the usual assumption that tation or "dumping" of most of the lead, zinc, and
equilibrium is closelyapproached. The resultslend copperthat was in solution. It alsoseemsunlikely,
support to the idea that at least some Mississippi as discussedpreviously, that this processwould
Valley-type ore bodies could have formed from result in reduced sulfur values consistentlywithin
acidic sulfate solutions. Some additional con- the rather narrow stability field of pyrite phis
clusionsand problems presented by the relation- chalcopyrite,so that evidencesof rapid dumping
shipsin Figure 6 are as follows: of galena and sphalerite (e.g., intimate inter-
1. Sulfur fugacities in the shaded "area of growths, colloform, hopper or dendritic crystals,
deposition" in Figure 6 are quite high--about 10-4 absence of zoning) would be expected to be in-
to 10-•ø arm--and this raisesa coupleof interesting compatiblewith the simultaneousprecipitation of
points. At these sulfur fugacities the iron content chalcopyrite.
of sphalerite coexisting with pyrite at 100ø C The various methods of sulfate reduction prob-
should be almost nil according to extrapolation ably fall somewhere between these two extremes
of the data of Barton and Toulmin (1966). Even in the rate at which they would cause sulfide
closer to the pyrite hematite boundary, the fs2 precipitation, and it seemsimportant to investigate
drops only to about 10-•s arm, which should also their relative effectivenessand rates of production
result in extremely low iron sphalerites. Sphalerites of reduced sulfur under various conditions.
from MississippiValley-Wpe ore bodies are gener- 5. With the compositionschosenfor Figure 6, it
ally low in iron, but not that low, and it seems turns out that for a fco• of 1 atm, anhydrite (or
likely that the lengthy extrapolation to 100ø C gypsum) is stable below a pH of about 5.1, even
from Barton and Toulmin's (1966) higher tempera- if allowances are made for sulfate complexing.
ture data is not warranted. Since anhydrite is a rare epithermal mineral, this
 TRANSPORT AND DEPOSITION OF GALENA AND SPHALERITE 489

might be taken as evidence that the pH of the ore suchasrs2(10-•4 to 10-•ø•tm),fo2(10-•ø to 10-St•tm),
solution does not get much below 5.0. On the other and pH (4 to 5) exist. In a solution having these
hand anhydrite shows quite a marked retrograde parameters in these ranges, calcite and dolomite
solubility effect, that is, it becomes more soluble are unstable (will dissolve), and any precipitation
at lower temperatures (see for example Holland, of copperwill be in the form of bornite (or corellite
1967) and so could easily be dissolved away at if the iron activity is very low). However, once
lower temperatures if deposited earlier at higher deposited,galenaand sphaleriteare stable outside
temperatures. Still one might expect to find it this area and could have the carbonates or chalco-
or some evidence of its former existence occasion- pyrite deposited on them later.
ally and its presencewould be interesting as a If the ore-formingsolution need only supply the
tentative pH indicator. metals, and perhaps the sulfate, with precipitation
6. Any theory calling on ore transport and brought about either by reduction of the sulfate
deposition in a predominantly sulfate brine must or by addition of H2S from another solution, larger
face the problem of the presenceof barite in and ranges of permissibleparameters exist, the only
around the ores. The question is, why does barite requirement for the metal-carrying solution being
precipitate in the immediate vicinity of the ore that it supply at least 1 ppm of metal. Under
rather than at other placesin the plumbing system? these conditions, calcite, dolomite, and chalco-
The question is especially pertinent if increase pyrite might or might not be stable, dependingon
in reduced sulfur is the ore-precipitating agent, the pH. The depositionof appreciableamountsof
since there is no obvious reason why this should chalcopyrite presents a problem and apparently
appreciably affect the solubility of barite. It may can be accomplishedonly from slightly alkaline
be that the transport and deposition of barite is solutions when it appears later than galena and
more complicatedthan the simplesolubility product sphalerite.
relationshipwould suggest. Occurrencesof native sulfur would be expected
occasionallyand gypsum (or anhydrite) would not
Summary and Conclusions be out of place in or around the ore zone. These
The solubilitiesof galenaand sphaleritein NaC1 minerals are sometimes consideredsecondary and
brines at elevated temperaturesmay be similar, attributed to the action of meteoric waters, but
with the solubility of galenabeinggreater than that they might in somecasesbe primary.
of sphalerite. This fact in itself is of limited signifi- There is therefore now no doubt that slightly
cance since as Taylor (1963) has shown, galena- acid chloride-rich brines in which the sulfur content
sphalerite paragenesisor zoning is probably con- is low and predominantly sulfate can transport
trolled at least as much by the relative abundances and deposit galena and sphalerite in ore quantities.
of lead and zinc in the ore-forming solution as it is Nevertheless the details of the depositionalprocess
by solubilities. It follows that the significanceof raise a number of questions which will only be
whether PbS or ZnS precipitates first, or whether answered by close field observation and further
one or the other is virtually absent in a particular experimental work.
district, has to do with the ultimate source of the In a sense these relationships have long been
metals that the solution carries rather than with known by field geologists. For example Heyl and
the reasonsfor, or conditions during, deposition. his co-workers (1959) in their classic description
Assumingthat I ppm or more must be precipi- of the Upper MississippiValley zinc-leadarea very
tated from a solution for an ore body to form in a clearly outline a situation which is compatible in
reasonable length of time, taking fluid inclusion all major aspects discussedabove to deposition
evidence at face value, and assuming that condi- of galena and sphalerite from brines caused by a
tions generally achieve a reasonable approach change in pH, with somecooling anddilution,and
toward equilibrium, a few conclusions may be this is exactly what they have concluded. It would
drawn about mineral stabilities during ore deposi- be of interest to obtain fluid inclusionand para-
tion. (The numbersquoted below are for msol- genetic data from a single deposit, having the
= 0.03 m, NaCI = 3 m, and a temperature of relationships described here in mind, in order to
100ø C, and will be slightly different for other test them in more detail.
conditions.)
For any ore-formingprocessthat calls upon both Acknowledgments
metals and reduced sulfur to be transported to the I am grateful to D. Meyers for supplying a
site of deposition in the same solution and then computer program for calculation of activity coeffi-
deposited (by cooling, pH change, or dilution), cients, which was adapted into the calculations
rather small rangesof possiblesolution parameters describedhere. The manuscripthas benefitedfrom
490 G. M. ANDERSON

the critical commentsof my colleague,S. D. Scott.
Financial support from the National Research
Council of Canada is gratefully acknowledged.
DEPARTMENT OF GEOLOGY
UNIVERSITY OF TORONTO
forming fluids: Internat. Geol. Cong., 21st, Copenhagen,
part XVI, p. 218-229.
1967, Environment of deposition of stratiform
(MississippiValley-type) ore deposits,from studiesof fluid
inclusions,in Symposiumon the genesisof stratiform lead-
zinc-borite-fluorite deposits: EcoN. GEo•.. MoN. 3, p.
326-332.

TORONTO5, ONTARIO, CANADA Schneeberg,E. P., 1973, Sulfur fugacity measurementswith

the electrochemical cell Ag IAgI IAg2+xS,fs2: Ecoa. GEo•..,
v. 68, p. 507-517.
REFERENCES Skinner, B. J., 1967, Precipitation of MississippiValley-type
ores: A possiblemechanism,in Symposiumon the genesis
Barnes, H. L., 1967, Sphalerite solubility in ore solutionsof of stratiform lead-zinc-barite-fluoritedeposits:Ecos. GEOL.
the Illinois-Wisconsin District, in Symposium on the Mo•. 3, p. 363-369.
genesis of stratiform lead-zinc-barite-fluorite deposits: Taylor, H. P., Jr., 1963, Importance of chalcophile element
ECON. GF.o•.. MoN. 3, p. 362-332. abundancesin determining the sequenceof sulfide mineral
-- and Czamanske, G. K., 1967, Solubilities and transport deposition from mono-ascendentore-forming solutions, in
of ore minerals, in Barnes, H. L., ed., Geochemistry of Symposium--Problems of postmagmatic ore deposition:
hydrothermal ore deposits: New York, Holt, Rinehart and Prague, Geol. Survey Czechoslovakia,v. I, p. 267-272.
Winston, Inc., p. 334-381.
Barton, P. B., Jr., 1967, Possiblerole of organic matter in the
precipitation of the Mississippi Valley ores, in Symposium
on the genesis of stratiform lead-zinc-barite-fluorite de- Appendix
posits: ECON.GF.oL. Mo•. 3, p. 371-377.
-- and Skinner, B. J., 1967, Sulfide mineral stabilities, in Equations and Calculation Procedures
Barnes, H. L., ed., Geochemistry oœhydrothermal ore
deposits: New York, Holt, Rinehart and Winston, Inc., Activity coefficients
p. 238-233.
Barton, P. B., Jr., and Toulmin, P., III, 1966, Phase relations To simplify the calculations, the ti parameter in
involving sphalerite in the Fe-Zn-S system: ECON. GEOL., the Debye-Hiickel equation was given a constant
v. 61, p. 815-849. value of 3.8 X 10-8, which meansthat under given
Fedorov, V. A., Chernikova, G. E., and Mironov, V. E., 1970,
Influence of ionic strength and temperature on the forma- conditionsall divalent ions had one activity coeffi-
tion of chloro-complexes of zinc: Russian Jour. Inorg. cient and all univalent ionsanother. Least squares
Chemistry, v. 15, p. 1082-1084. cubic equations in temperature were fitted to the
Hamann, R., 1973, Solubility of galena in alkaline sulfur-rich
NaCI solutions at. 25øC and 90øC: Unpub. M.Sc. thesis, density and dielectric constant values for water
Univ. Toronto. (Helgeson, 1967) and the A and B Debye-Hiickel
Helgeson,H. C., 1967, Solutionchemistryand metamorphism, parameters calculated from these. Another cubic
in Abelson, P. H., ed., Researches in geochemistry, v. 2:
New York, John Wiley & Sons, p. 362-404. equationwasfittedto the 1) function(Helgeson,
• 1969, Thermodynamicsof hydrothermal systemsat ele- 1969, table 2). Then the extended Debye-Hiickel
,vated temperaturesand pressures:Am. Jour. Sci., v. 267,
p. 729-804. equation in the form (Helgeson,1969, equation 43)
Heyl, A. V., Jr., Agnew, A. F., Lyons, E. J., and Behre, C. H.,
Jr., 1959, The geology of the Upper MississippiValley log• = - A.Z•'.II/(1 + •.b. It) + f3-I
zinc-lead district: U.S. Geol. Survey Prof. Paper 309,
310 p. was used to calculate values of •, where Z is 2
Hinners, N. W., 1963, The solubility of sphaleritein aqueous for divalent and I for univalent ions, and I is the
solutionsat 80øC: Unpub. Ph.D. thesis, Princeton Univ.
Holland, H. D., 1967, Gangue minerals in hydrothermal true ionic strength (Helgeson, 1969, table 2).
deposits,in Barnes, H. L., ed., Geochemistryof hydro- The least squaresequations are:
thermal ore deposits: New York, Holt, Rinehart and
Winston Inc., p. 382-436. density = 1.4579 - .0031654T q- 7.9018
Jackson,S. A., and Beales,F. W., 1967,An aspectof sedimen-
tary basin evolution: The concentration of Mississippi X 10 -ø T •'- 8.1461 X 10 -9 T 3
Valley-type oresduring late stagesof diagenesis:Canadian
Petroleum Geology Bull., v. 15, p. 383-433. dielectricconstant= 283.49 - 1.1002T
Lovering,T. S., 1961,Sulfideoresformedfrom sulfide-deficient q- .0016714T •'- 9.6878 X 10 -7 T 3
solutions: EcoN GF.oL., v. 56, p. 68-99.
Nriagu, J. O., 1971a, Studiesin the systemPbS-NaCI-H,.O: f3 = 0.4095- 0.003121Tq- 8.6523X 10-ø T •'
Stability of lead (II) thiocomplexesat 90øC: Chem.
Geology, v. 8, p. 299-310. - 7.772 X 10-9 T a.
1971b, Experimental investigation of a portion of the
systemPbS-NaCI-HC1-Ho.Oat elevated temperatures:Am. Typical activity coefficientsresulting from this
Jour. Sci., v. 271, p. 157-169.
1971c, Expressions for calculating the solubilities of procedureare for I = 3, T --- 100ø C; •'•'+ = 0.072,
metal sulfides in hydrothermal solutions: Canadian Jour. •+ = 0.66.
Earth Sci., v. 8, p. 813-819. For neutral species,the activity coefficientsfor
-- and Anderson, G. M., 1971, Stability of the lead (II)
chloride complexes at elevated temperatures: Chem. CO•. in NaCI solutions (Helgeson, 1969, table 2)
Geology,v. 7, p. 171-183. were fitted with the followingquadratic equations:
Robie, R. A., and Waldbaum, D. R., 1968, Thermodynamic for
propertiesof mineralsand related substancesat 298.15ø K
(25.0ø C) and one atmosphere (1.013 bars) pressureand at m•,c• = 1; •0 = 2.1946 - .004832T
higher temperatures:U.S. Geol. Survey Bull. 1259.
Roedder, E., 1960, Fluid inclusionsas samplesof the ore- q- 5.8091 X 10-6 T 2
 TRANSPORT
AND DEPOSI2•ION
OF GALENAAND SPHALERITE 491
for where Qn is the stability constant of the nth
complexfrom Nriagu and Anderson (1971), T• is
mNaCl • 2; 3.0841 -- .007769T
301.15K, and R is the gas constant in cal/deg mole.
h-8.9647 X 10-6 T •' The regressioncoefficientsa• and as give the
for
best values of the reaction enthalpy and changein
mNaC1----3; 4.7023 -- .01475T heat capacity for the stepwiseformation of the nth
h- 1.8131 X 10-6 T 2. complex, when these are assumed constant over
the temperature interval 28ø to 90ø C. After
These equations give mø values very close to the rearranging terms, the equationsare:
ones listed by Helgeson.
It is likely that a better fit between the log Q• = -14.5143 q- 172.4607/T q- 6.1090 log T,
measured solubility values of Nriagu (1971b) and log Q• = 62.6737 -- 3484.9265/T
calculated solubilities could be achieved by using a
20.24511ogT,
variable a parameter for the different ions.
log Q3 = 39.3918 - 1063.2328/T
Solubility equations 14.32781og T,
Solubilities have been calculated using equations
20 (equivalent to equation 3 of Nriagu, 1971b) log Q4 =
11.3024 -- 1608.1408/T
and 24 (Nriagu, 1971c). Helgeson (1969) pre- 2.489241og T.
viously gave equations which are essentially the The stability constantsare termed Q rather than K
same but which use stoichiometric activity coeffi-
cients which were not used here. In the notation
because they were determined for and are valid
in 3 m NaC1 solutions only. They must be multi-
of this paper, theseequationsare:
plied by factors involving the appropriate activity
for stoichiometric solubility; coefficients when used for solutions of other ionic

s = KMS'qb'aa+S/(m
s+.mo.Kns' K•2s)'•, strengths. They must also be convertedto overall
stability constants (•) before calculating 4,
for sulfur-deficient solutions; where

s = K•s' 4' a-+•/(m s+'mo'Kn2s-St),

1

where s is the solubility (metal content of the then

solution in equilibrium with sphalerite or galena); 4
KMs is the solubility product of the metal sulfide;
4 = • B=(mc•-)=;
an+ is the activity of the hydrogen ion; Kns and 0

Kn, are the ionization constants of HS- and

HsS; Sr is the total reduced sulfur content of the
solution; ms+ and mø are activity coefficients as
defined above, and qOis a term which accounts for
the effect of chloride complexing in the solution
and is defined below. All equilibrium constants are
from Helegeson (1969).
Stability constantsof the metal chloridecomplexes
(a) Lead: The lead chloride stability constants have apparently been rounded, so the stability
were calculated from the data of Nriagu and
Anderson (1971), but using a slightly different
curve fitting and extrapolation procedure than
presented by them. For each stability constant,
the values at 28ø, 40ø, 60ø, and 90ø C were fitted by
a least squaresdouble linear regressionof the form
Z = a0 h- a•X h- asY,
where Z = log Qn
X-- ((l/T)- (1/T•))/2.30259R
Y = (log (T/T•) -- (T- TO /2.30259T) /R,
B0 = ! by definition.
(b) Zinc: Fedorov et al. (1970) give poten-
tiometrically measured stability constants for the
four zinc chloride complexes in 1, 2, 3, and 4
molal NaC1 solutions at several temperatures up
to 65ø C. They claim that log/• vs. 1/T is linear
within the error limits on B, and give /XG, /XH, and
/xS values calculated on this basis. These values
constants from their table I were fitted with a
least squares regressionas log B = a h- b/T(K).
These equations are (for 3 m NaCI):
logfi• = 2.5825 -- 776.07/T
log fis = 4.3534 -- 1312.37/T
log fia = 7.0704- 2020.12/T
log fi4 = 8.8935 -- 2632.23/T.
A more sophisticatedfitting proceduremay well
give better values, but the amount of scatter in
and •4 is disturbing and may precludethis.
492 G. M. ANDERSON
Field boundariesand contours(Figs. 5 and 6)
Appropriate activity coefficientshave been used
in constructing these diagrams, so that field
boundaries between aqueous species are loci of
equal molalities, not equal activities. The equi-
librium constantsfor most of the equilibria have
been taken directly from Helgeson (1969). The
chalcopyrite-bornite-pyrite equilibrium is calcu-
lated using
5CuFeS2 + S= = CusFeS4 q- 4FeS=;
log K•00 = 16.92.
This K value is from the data of Schneeberg(1973)
but is quite similar to that given by Barton and
Skinner (1967). The lowest temperature at which
Schneebergmeasuredthe fs• of this equilibrium
assemblagewas 201ø C, so the position of the
boundary at 100ø C in Figure 6 represents an
extrapolation from the higher temperature data
and could conceivably be in error. A variable
activity of CuFeS2 in chalcopyrite solid solution
will have a small effect on the position of the
boundary in Figure 6, even though• raised to the
5th power.
Equilibrium constantsnot given in thesesources
were calculated from data in Robie and Waldbaum
(1968).