EconomicGeology

Vol. 80, 1985, pp. 126-147

Chemical Evolution and Mineral 'Depositionin

Boiling Hydrothermal Systems
S. E. DRUMMOND

ChemistryDivision,Oak RidgeNational Laboratory,Oak Ridge, Tennessee

37831

AND H. OHMOTO

Departmentof Geosciences,
The PennsylvaniaStateUniversity,UniversityPark, Pennsylvania16802

Abstract

A thermodynamic modelof boilinghydrothermalsolutions is developedandappliedover

a wide rangeof physicaland chemicalconditions.Within the rangeof conditionsobserved
in naturalboilinghydrothermalsystemsthe processes of liquid-vaporpartitioningand the
resultanteffects on mineral solubilitiesare highly varied and complex.Metals that are
complexed by chloridearedeposited largelyasa resultof the decreasing protonconcentration
associated with CO2 exsolutionduringboiling. Metal bisulfidecomplexesare destabilized
mostwhen the decreasein proton concentrationis sluggishrelative to the lossof H2S.
Vaporizationof only a few percent of a solutioncan decreasethe proton concentration
by severalordersof magnitudewhen the CO2/H+ and CO2/Y•SO4concentrationratiosare
initially high. The relationshipbetweenthe proton, CO•, and Y•SO4concentrations prior to
boiling to the proton concentrationafter boiling is defined explicitly by a few simple
equations.These equationsalongwith the solubilitiesof calcite and anhydriteconstitute
the chemicalboundaryconditionsfor significantmineral depositionby boiling. Typical
hydrothermalfluidslosemostof their volatilecomponentsto the vaporphaseand mostof
their metalsto mineral phasesby the time boiling has proceededto the point where the
volumesof the vaporand liquid phasesare equal.
Physicalvariablessuchasthe heatbudgetandthe restrictions on the partitioningof mass
between liquid and vapor, although significant,are subordinateto the compositional
variablesin determiningthe chemicalevolutionof a boilinghydrothermalsolution.Mineral
depositionis mostvigorouswhen the volatilecomponents partitionfrom the solutionto the
vaporphasein a mannerresemblingperfectfractional(Rayleigh)distillation.As temperature
decreases,
the efficiency
of boilingfor ,depositing
metalsfrom solutionincreases,
andthe
amountof metalsin solutiontypicallydecreases
suchthat the net effectof boilingis most
favorablefor ore formationat temperaturesaround300øC. Mineral and metal complex
stoichiometriesin combination with the relative volatilities of CO• and H•S determine the
generalsequenceof mineraldepositionduringboiling.These major variables,many other
minor variables,and the multiple interactionsthereof are accountedfor rigorously.The
amountandparagenesis of ore andganguemineralsdepositedby boilingare presentedfor
numerous hypothetical
hydrothermal systems.Analysisof theseresultssuggeststhat boiling
is perhaps the most generally effective ore depositionalmechanismat the conditions
operativein manyboiling hydrothermalsystems.

Introduction neaure, 1970), silver-gold veins (Kamilli and

IN the past twenty years a sufficientvolume of
evidencehasaccumulated in the geologicalliterature
to suggestthat many ancient hydrothermal ore-
formingsystemshavemaintaineda two-phaseliquid-
vapor fluid. Undoubtedly,the mostoften cited evi-
dence of these liquid-vaporconditionsis the occur-
renceof adjacentfluidinclusions with highlyvariable
liquid/vaporratios(Roedder,1968-1979).
Liquid-vapor conditionshave been documented
in numerousdepositsincluding most notably the
porphyry copper-molybdenum deposits(Cunning-
ham, 1978), tin-tungstendeposits(Kelly and Tur-
Ohmoto,1977), andpolymetallicsulfideveins(Bar-
ton et al., 1977). Commonly,the boiling horizon is
associated with the zone of most intense mineraliza-
tion.This type of spatialassociation
betweenliquid-
vapor conditionsand ore depositionhas prompted
these and many investigators to suggestthat there
is a geneticrelationshipbetween boiling and min-
eralization.
Although the fluid inclusiondata, paragenetic
evidence,and field relationshipspresentedby these
investigators
are compelling,no one hasdeveloped
a convincingquantitativeargumentdemonstrating
that the chemicaleffectsattendantwith boiling are

0361-0128•85•381/126-2252.50 126
 BOILING HYDROTHERMAL SYSTEMS 127

conduciveto mineralization.Most investigatorshave into the complexities of the boilingprocessat other

reasonedthat separatinga vapor phase from the conditions.
liquidphasewouldremoveacidvolatilespeciessuch
Heat budget:Isothermalvs. isoenthalpic
as CO2 and H2S from the aqueoussolution,thereby
raisingthe pH and depositingoxides,sulfides,car- Toulmin and Clark (1967), amongothers, have
bonates, native metals, and other ore minerals. The shownthatheatconduction throughrockis a sluggish
commonoccurrenceof pervasivesericitizationof processand is not an effectiveheat sourceor sink
acidleachingabovethe boilinghorizon(e.g., Barton for hydrothermalfluidsunlessthe temperaturegra-
et al., 1977; Slack, 1980) appearsto support this dient is large,the contactbetweenrock and fluid is
contention. intimate,or fluid residencetimes are long. In some
Few have recognized,however, that the devola- limited casesthe surroundinghot rock may provide
tilization associatedwith boiling is not necessarily enoughheatto balancethe heatof vaporization and
associatedwith large increasesin solutionpH, de- maintain essentiallyisothermalboiling. However,
pending on the prevailing chemical and physical this is likely to be the exceptionrather than the
conditions,but alwayscausessignificantdecreases rule, especiallywhendecompression andboilingof
in the concentrationsof aqueoussulfideand carbon- the fluid is rapid. Consequently,mostboiling epi-
ate and increasedsalinity.Of all these effectsonly sodesare likely to be isoenthalpicrather than iso-
increasingpH is generally favorable for, but not thermal. In other words, heat is conservedsuchthat
necessarilysufficientfor, mineral deposition.These the enthalpyof the liquid and vaporafter boilingis
multiple and opposingeffectsof boiling on mineral equalto the enthalpyof the liquid beforeboiling.
solubilitiescomplicatethe issue considerably,re- Accordingly, the solutionwill loseheat to the vapor
suiting in no easily predictable consequencefor phaseand cool asboilingproceeds.
mineraldeposition.Clearly, an understandingof the The molalenthalpyof H•O in the vaporis greater
interrelationbetweenboilingand mineraldeposition thanin the associated liquid.Thisenthalpydifference
in natural hydrothermalsystemsrequiresa rigorous causescoolingof the solutionasit losesH•O to the
quantitativeapproachthat accountsfor the complex vapor. The AH of vaporizationand consequently
chemicalinteractionsassociatedwith a dynamicliq- the amount of cooling associatedwith boiling is
uid-vaporsystem.In this studythe pivotalphysical relatively constantover a wide range of salinities
and chemicalparametersare definedand discussed (Haas,1976) but decreases from about45 kJ to nil
and, with a computer program developedfor the asthe temperatureincreases from0øC to the critical
purpose,are integrated into a model that gives a pointof the solution.For example,100ø and 300øC
detailedexplanationof the role of boiling in hydro- aqueousNaC1 solutionscool about 8ø and 3øC,
thermal mineralization. respectively,when 1 percentof the H•O in solution
is vaporizedby boiling.The enthalpiesof exsolution
Basic Concepts of other dissolvedvolatile components(e.g., CO•)
In addition to such intensive properties as tem- are smalland have negligibleeffectson the cooling
perature and the concentrationof each component pathsof typicalboiling solutions.
in the initial solution,severalother importantphys-
ical and chemical conditions must be defined in Physicalconstraintson volatile partitioning
order to model the chemicalevolution of a boiling betweenliquid and vapor
hydrothermal solution. Defining the appropriate The degreeof interactionbetweenthe liquid and
conditions and constraintsfor the boiling process vaporphasesis paramountin determiningthe chem-
requires decisionsby the modeler in five basic ical evolution of a boiling hydrothermal solution.
categories:(1) heat budget; (2) physicalconstraints The most dramatic chemical effects on a boiling
on the partitioningof volatilesbetween the liquid aqueoussolutionare associated with the partitioning
and vapor phases;(3) chemical kinetic constraints of volatile components(CO2, H•S, CH4, SO•, H•)
on oxidation-reductionequilibria; (4) physicaland into the vapor phase. These gasesparticipate in
chemicalconstraintson mineral-solutionequilibria; oxidation-reduction and/or acid-baseequilibria and
and (5) definition and modeling of the chemical thereby constitutethe mostchemicallyactive com-
system.Each of these categoriesare consideredin ponentsin boiling hydrothermalsystems.The rate
some detail in this section, and the constraints and of volatile partitioning from a boiling solution is
intensive properties most relevant to natural ore- stronglydependenton whetherboilingoccursasan
forming systemsare chosenjudiciouslyin order to open or closedprocess.Accordingly,the open or
Ultimately closedtissueis crucial to formulating a quantitative
limit the bewilderingarrayof possibilities.
in later sectionsthe modelingresultsare presented chemicalmodel of the boiling process.
in a sufficientlygeneralized manner so that the In closedboiling the liquid is vaporized under
reader can understandand develop some insight conditionssuchthat no massescapesfrom the system
128 $. E. DRUMMONDAND H. OHMOTO

and all the vapor produced is in equilibrium with not, must consideroxidation-reductionequilibria in
the remainingliquid.The conditions of closedboiling the systemsulfur, carbon,oxygen,and hydrogenin
are analogousto a container that can expand to order to determine the stabilities of minerals that
accommodatevaporization and still maintain the are dependenton the oxidationstate of the system
integrityof the closedsystem.The mechanicalprop- (e.g., oxides,native metals, pyrite, etc.). The pre-
ertiesof rock precludelarge dilationwithout failing dominantredoxequilibriain solutions•< 350øC are
and thereby breachingthe closedsystem.Because, givenby the followingmassactionequations:
asexplainedin a later section,chemicallysignificant
amountsof boiling require the fluid volume to H2S + 202 • HSO• + H +, (1)
approximatelydouble,boiling will not appreciably
alter the chemistryof a solutionunlessthe system CH4 -{- 202 • 2H20 + CO2, (2)
is at leastpartially open to mass. 2H2 + O2 • 2H20. (3)
In a boiling systemtotally open to mass,the
liquid is vaporized progressivelysuch that each For equilibrium systemsthe ratios of these redox
increment of vapor is removed from contact with pairs are likely to control the oxidationstate of the
the liquid immediately as it is formed. Although boiling fluid and the associatedredox-dependent
each increment of vapor is in equilibrium with the mineral equilibria. Open boiling systemsmay be
liquid asit is formed,the averagecomposition of all particularly responsiveto such equilibria since the
the vapor produced is not constrainedto be in concentrationsand ratios of these redox pairs are
equilibriumwith the remainingliquid. Openboiling constantlychanging.In closed systems,gas ratios
is synonymous with perfect fractional,or Rayleigh, are fixed so that there is little redox shift associated
distillation. with the boiling process.As shownin a following
Natural boiling systemsmay be more analogous sectionH2S, CH4, and H2 are less soluble than their
to open rather than closedboiling. However, it is oxidizedcounterparis.Consequently,open boiling
difficultto imaginethat in a natural settingliquid will tend to increasethe oxygenfugacitygoverned
and vaporseparatecleanlyinto suchclearlydefined by all of the reactions indicated in equations (1)
and mutually exclusivedomainsas required by a to (3).
totally open system.In most natural casesboiling At equilibrium,the oxygenfugacitywill be largely
occursas the fluid flowsdown a pressuregradient. controlledby the mostabundantredox pair and the
Fluid flow principlessuggestthat, upon boiling, other pairswill adjusttheir ratiosaccordingly.How-
liquid and vapor separateand travel the samepath ever, equilibrationof the oxidation-reductionreac-
at the sameor differentrates(Cathies,1981). Along tions suggestedby equations(1) and (2) has been
the path, vapor no doubt mixes and reacts with questionedby severalinvestigators andthe reaction
liquid and may in some cases condense and be of equation(3) is notoriouslyslowat 25øC. Ohmoto
reincorporatedinto the liquid phase.Even though and Lasaga(1982) showthat sulfurisotopeexchange
naturalboiling systemsare partially open to mass, between sulfide and sulfate between 200 ø to 300øC
there is likely to be an intimateinteractionbetween at typicalpH andtotal sulfurvaluesfor hydrothermal
liquid and vapor not allowedby the definitionof a solutions (pH = 4-7 andY•S= 10-2 m), is 90 percent
totally open system.In this sensenaturalboiling complete in less than 100 years and they suggest
systems are hybridsof totallyopenandtotallyclosed that these isotopic exchangerates are identical to
systems.Althoughneither of thesetwo end members the chemicaloxidation-reductionequilibrationrates.
satisfactorily describesnaturalsystems,they do de- Sackettand Chung(1979) confirmeddisequilibrium
fine limits for the physicalconstraints on boiling. isotopic fractionation between carbon dioxide and
This is convenientsincethe physicalrequirements methane below 500øC. Ziegenbein and Johannes
of both totally open and totally closedboiling are (1980) report disequilibriumproportionsof the gases
easyto visualizeconceptuallyand alsobecausethe CO2, CH4, CO, H2, and H20 in the systemC-H-O
principlesof chemicalpartitioningin suchsystems after runs up to 100 daysand at temperaturesup to
are well defined.Accordingly,in a subsequentsec- 700øC. Perhapsthe most definitive work of this
tion both open and closedboilingwill be discussed type for carbonis the experimentalstudyof Harting
in detailandthe definitiveequationswill be derived and Maass(1980) on the 12C--13C exchangerates
so that open and closedboiling can be contrasted between CO2 and CH4 in the range 500 ø to 700øC.
quantitatively. This work indicatesthat 90 percent carbonisotope
Chemical kinetic constraints on oxidation-
exchangeis attainedin approximatelyl0 ll to l0 s
yearsbetween 200ø to 350øC. As it is highly likely
reductionequilibria that the mechanisms and ratesfor isotopicexchange
Any seriousattempt to model the chemical evo- and chemical reaction (eq. 2) are synonymous
lution of naturalhydrothermalsolutions,boiling or (Ohmoto and Lasaga, 1982), the unavoidablecon-
 BOILING HYDROTHERMALSYSTEMS 129

clusionis that equilibriainvolvingsulfideand sulfate and carbonate to the mineral phase but is not
are considerablymore importantin establishingthe allowedto gain thesecomponents
by redissolving
redox state of typical boiling hydrothermalfluids minerals.This featureis not inherentto the program
than is the extremelysluggishreactionbetweenCO2 itself but merely representswhat perhapsis the
and CH4. In very reduced systems,particularly at most typical scenarioduring the evolutionof a
high temperatures,the H2 concentrationof the packetof boilinghydrothermalsolution.
solution can exceed the sulfate concentration. It is The interactionof boiling solutionswith wall-
likely that, under these conditions,the reaction of rock silicateassemblages (e.g., potassiumfeldspar-
equation(3) ratherthanequation(1) woulddominate muscovite-quartz) may effectivelybuffer solution
the redoxequilibriaof a boilinghydrothermalfluid. pH andconstitutes anothertype of mineral-solution
Becauseof the extremelyhigh volatility of H• this equilibriathatshouldbe considered. The equilibrium
redoxcontrolwould be manifestasa relativelyrapid effects of these silicate reactions on the boiling
oxidizing event limited to the earliest stagesof solutionchemistryare easily modeled and simply
boilingbefore the H• concentrationis depleted.At constitute another mass action constraint for the
somestageduringboilingthe concentrations of H•S, system.However, the rates of these silicate-water
CH4, and H• will all be too low to exert any reactionsare not instantaneous
at hydrothermalcon-
influence on the oxidation state of the fluid. In ditions but depend on temperature,the relative
general, the concentrationof the redox pair for massesof water and rock, surface area, rock com-
equation(1) will be depleted more slowlythan for position,andsolutionchemistry,amongotherphys-
equations(2) and (3) thereby giving the sulfide- ical and chemicalparameters(Cole et al., 1983).
sulfate equilibria more persistencein controlling Thesecomplications in the aqueoussolution-silicate
oxygen fugacity throughout the boiling episode. mineral equilibria imply that time is an important
Accordingly,the oxidationstateof the boiling solu- variable. Unfortunately,the effects of the above
tions consideredin the calculationspresentedhere physicaland chemicalconditionson silicate-water
isdeterminedby equation(1) andhenceisdependent reaction rates are not completely understood.
on the volatility of H2S. In keeping with their Therefore, it is presentlyimpossibleto evaluate
unreactive nature, CO• and CH4 concentrationsand quantitativelythe effectsof silicate-waterreactions
ratiosin solutionsare not governedby equation (2) on solutionchemistryduring a boiling episode.In
but are allowedto vary solelyas a functionof their manycases,however,thesereactionsare likely to
normal boiling evolution, independent of the fo• proceedmoreslowlyandinvolvelessmasstransfer
given by equation(1). thanthe liquid-vaporreactionsassociated with acid
volatile partitioningduring boiling and therefore
Physicaland chemicalconstraintson mineral- will be ineffective pH buffers during boiling. A
solutionequilibria typical silicate reaction involvingprotonsis the
An equallyimportantquestionconcernsthe extent K-feldspar-muscovite-silica equilibria 3KA1Si308
of mineral-solution interactionduringthe evolution + 2H+ • KAI• (A1Si3Oi0)(OH)• + 6SiO• + 2K+.
of a boilinghydrothermalsolution.For the modeling For this reaction to counter the effect of boiling on
resultspresentedhere, the initial metal (Ag, Au, Ba, pH requiresthe kineticallycomplicated processof
Cu, Fe, Pb, Zn, W, etc.) concentrationsare arbitrarily muscovitedissolutioncoupledwith K-feldsparre-
fixed at levels exactly saturatedwith respectto the precipitation.Not only are the kineticsof these
most stablemineral phaseof each metal. If, upon reactions(i.e., feldsparformedat the expenseof a
boiling, the solutionbecomessupersaturatedwith phyllosilicate)somewhatcumbersome,but there
any of the metal-bearingminerals, the metal con- seems to be little evidence for them in natural
centrationis lowered suchthat the thermodynamic hydrothermalsystems.
In addition,the veinswhich
solubility of each phase is satisfiedand that the serveasconduitsfor naturalhydrothermalsolutions
numberof phasespresentdoesnot violatethe phase are commonlyisolatedfrom a silicatebuffer assem-
rule. Likewise, if the solution becomes saturated blageby previously formedminerals(mostcommonly
with respectto either calcite or anhydrite, calcium by quartz).In thesecases,
the solutions
areessentially
and either carbonate or sulfate are removed from isolated from wall-rock chemical reactions. Conse-
solutionin equal proportionsand the aqueousspe- quently,the interactionof naturalboiling solutions
ciation is recalculated in an iterative fashion until with wall-rock silicates is not likely to alter the
the solubilityproduct of the saturatedmineral is solutionchemistrysignificantlyduring boiling and
satisfied.In addition, the model considersthe hy- is ignoredhere.
drothermal systemas a flow-through regime such
that the solutionis not constrainedto be in equilib- Definingand modelingthe chemicalsystem
rium with previouslyprecipitatedminerals.In other The conceptsoutlined above are incorporated
words the solution can lose metal, sulfate, sulfide, within a computermodelof the chemicalevolution
130 S. E. DRUMMOND AND H. OHMOTO

of boiling hydrothermalsolutions.Figure i is a flow INPUT /

chartillustratingthe essentiallogicand computations TEMPERATURE,
[H+]. Z[Na],Z[K],
T.[Ca],T.[mg]
,'r[CO21
,Z[H2S]
,
performed by the program. Methods for handling SO4]
, OPEN
ORCLOSEO,
ISOTHERMAL
the heat budget, the physicalconstraintson volatile ORISOENTHALPIC,
X=1,INC,
LIMIT/
partitioning, oxidation-reductionequilibria, and
mineral-solutionequilibria are addressedin the pre- EQUILIBRIUM CONSTANTS
= f(T)

ceding discussion.A discussionof the treatment of

activity coefficients,gasvolatilities, and the quanti-
fication of the liquid-vaporpartitioningof gasesis
in the following section.The choice of input param-
ACTIVITY
COEFFICIENTS
I
= f(SOLUTION COMPOSITION)

eters, the values of these parameters,and the prin-

ciples and methods for satisfyingthe equilibrium

SATISFY
MASS
BALANCE,
MASS ACTION ANO
CHARGE BALANCE (VIA
massbalance,chargebalance,and massaction con- CI ) FOR THE SOLUTION
BY SUCCESSIVE ITERATION
straints are discussed in this section.
The compositionalrange of natural hydrothermal
fluidsbelow 400øC hasbeen documentedby direct REDUCE CONCENTRATIONS OF
Ca,CO3 ANO/ORSO4 UNTIL THE
analysisof geothermalfluids and oil well brines as SUPE RSATURATED PHASE(S)
ARE SATURATED WITH
well as fluid inclusionanalysesand mineral stability RESPECT TO THE SOLUTION

data from a variety of mineral deposits(Ellis, 1979;

Hanor, 1979; Weissberget al., 1979). Althoughthe COMPUTE
fO2 (FROMH2S/SO
4) ANDMETAL
compositions vary widely, the major dissolvedcom- (Ag, Au, Ba, Cu, Fe, Pb, Sn, W, Zn) SPECIATION
AND CONCENTRATIONS AT SATURATI DN
ponentsof mostnatural solutionsare Na, K, Ca, Mg, WITH THE STABLE MINERAL ASSEMBLAGE
FOR THESE METALS
C1, silica, carbonate, sulfate, sulfide, and methane.
Molecularhydrogenand SO2 are usuallylessabun-
dant but in some casescan be appreciable. Metals
COMPUTE SOLUTION
other than Na, K, Ca, and Mg occasionallyexceed SPECIATION AND

10-2 m but are normallymuchless,rarelycomprising MINERAL SATURATION

INDICES

more than a minor portion of the dissolvedcontent

of the fluid (Barnes, 1979). Solution pH nearly
alwaysfalls within two units of neutral. Most ore-
forming fluids tend to be somewhatacidic while IPARTITION
ASMALL
FRACTION
(INC) OF THE LIQUlOWATER
THE VAPOR PHASE
TO
X = X - INC

manygeothermalwatersare slightlyalkaline(Barnes,
1979). Fluid oxidationstagesrange more than ten
ordersof magnitudefrom a Y.SO4/H2Sratio as low STOP
)
as10-16 (CO2/CH4-• 10-4) up to a Y•SO4/H2S
ratio
= !04 (CO2/CH4• 1016).Other components such
as fluoride, arsenic,boron, phosphorous,and nitro-

COMPUTE
NEW
CONCENTRATI
I
OF RESIDUAL COMPONENTS IN
gen play an important role in some hydrothermal SOLUTION =
(INITIAL CONCENTRATION)/X
solutionsbut are excludedin this investigationbe-
cause they occur in only trace quantities in most
natural fluids. In an effort to minimize the possible BALANCE HEAT BETWEEN

combinationsof concentrationsof the major aqueous LIQUID

RESULT
AND VAPOR:
- SOLUTION COOLS

componentsand select representative values for

these concentrations,as well as vary the concentra-
tions of the componentsmost important in deter-
miningthe chemicalpath of a boiling hydrothermal
solution, the following initial compositionswere
I COMPUTE
CO2' VR(EQ
H2S' 5)
SO2' FOR
H2 I
CH4' I

chosenfor the modeling calculationsthat are pre-

sented here: ZCO2 = 3.0 and 0.03 m, ZSO4 = 3 I COMPUTE
NEW
CONCENTRATIONS
OF GASES IN SOLUTION

X 10-s and 3 X 10-9 m, H + = 10-4"5m, ZNa = 0.9 OPEN-EQll

CLOSED-EO
7
m, ZK = 0.1 m, ZCa = 3 X 10-3 m, ZMg = 1 FIG. 1. Flow chart of the computerprogramusedto deter-
X 10-3 m, ZH2S = 3 X 10-3 m, and ZC1 • 1.0 m. mine the chemicalevolutionand mineralprecipitationassociated
Accordingto the phaserule, in order to define with boilinghydrothermalsolutions.
Refer to text for notation
thermodynamicallya chemical systemC - P q- 2 and discussion.
- R = 0 where, C = number of chemical compo-
nents, P = number of phases,and R = number of K, Mg, C1), two-phasesystem,R -- 9. These nine
restrictingequationsneeded to define the system. equationscanbe anycombinationof uniqueintensive
For example, in a nine-component(O, H, S, C, Na, variablerestrictionson the systembeingconsidered.
 BOILING HYDROTHERMAL SYSTEMS 131

A convenientchoicefor this systemis temperature, a massdistributioncoefficientfor the partitioningof

H +, XH2S, XSO4, XCO2, XNa, XK, ZCa, and ZMg. a volatile speciesbetween the two phasesof a
Obviouslythe initial conditionsof a solution must hydrothermalfluid and is definedhere as:
be adequatelydefinedaccordingto the phaserule
VR = mV/m, (4)
before,its chemicalevolutionduringboiling can be
modeled. Simultaneous numerical solution of the where mVand m indicatethe molality of the volatile
appropriate massbalance (dictated by the phase gasspeciesin the vapor and liquid phases,respec-
rule), massaction(fixedfor a giventemperatureand tively. The ratio is a relative measureof the affinity
ionic medium), and charge balance (required by of a gasfor the vaporphasein a liquid-vaporsystem
electroneutrality for an electrolyte solution) con- and canbe related to the Henry's law constantratio
straintsis required to determine equilibrium con- of pressure/molalityfor the volatile species(Kn) by
centrationsfor the individualspeciescomprisingthe
nine major components.Total chloride for the initial = IC.. V,/ZRT, (5)
solutionis determinedfrom this equilibriumspecia- where V•wis the specificvolume of water vapor and
tion via the chargebalancerestriction.After boiling Z, R, and T are the compressibilityfactor (PV/nRT)
proceedsthere is no independentrestrictionon H +. for the gasin the vaporphase,the gasconstant,and
However, volatile component concentrations(H•S, absolutetemperature,respectively.The gassolubility
CO•, CH4, etc.) are determinedfromgas-partitioning data required to compute the volatility ratio for
equations (see next section), and XC1, XNa, ZK, CO2, H•S, CH4, H•, and SO• in aqueousNaC1
ZCa, ZMg, and ZSO4 are calculatedin terms of the solutionsare available in Drummond (1981) and
original totals and the amount of water removed Drummond and Ohmoto (in prep.). These sources
from solution,so that after boiling proceedsthe representnew experimentalsolubilitydata for CO•
systemis still definedby the minimumnumber of and H2S, a compilationof previousdata for CH4,
restrictingequationsand H + is calculable.All of the H•, and SO•, and theoretical extensions of low-
appropriatemassbalance,chargebalance,and mass temperaturedata for SO2. The uncertaintyin the
action equationsare solved simultaneouslyby suc- gas solubilitydata at elevated temperaturesis gen-
cessiveiterationfor eachboiling increment. erally •>10 percent, thereby makingthe compressi-
bility factorcorrectionfor the nonidealityof the gas
Chemical Evolution of Boiling
Hydrothermal Solutions
in the vapor phase(usually<10%) practicallyneg-
ligible. Valuesof the volatility ratio for thesegases
Unquestionably, the singlemostsignificant change in pure water are shownin Figure 2. Considering
in mineral solubilitiesduring boiling results from the fact that K, goesthrougha maximumbetween
the proton consumptiongenerally associatedwith 25 ø and 350øC for all of these gases,the linear
exsolutionof gases,particularly CO•. This is true relationshipin Figure 2 is remarkable. Ellis and
becausepH is predominantlycontrolledby fluid Fyfe (1957) noted a similar line• relationshipbe-
equilibriarather than mineral-fluidequilibria,be-
causethe concentrationsof metals in equilibrium 5 I L
with mostgroupsof mineralsincreasewith increasing
[H+] and because[H+] increaseswith increasing
[CO•] over muchof the compositionrangeof natural 4
hydrothermal solutions(notethat [] denotesmolality). H2
In fact, with the exception of metals stabilized
predominantlyas bisulfide complexesin solution, CH4
boilingis an effectivedepositionalmechanismonly
whenit isaccompanied by a significant[H+] decrease. log VR
Consequently a fundamental understanding of boiling
as a depositionalmechanismfor ore requiresquan- 2 -

tiffcationof the liquid-vaporpartitioningof gases

during boiling and definition of those conditions
conduciveto diminishingprotonconcentrations dur-
ing the gasevolutionattendantwith boiling.
Liquid-vaporpartitioningof gasesduringboiling
0
Definitiveequationsfor openand closedboiling: o •oo 200 5oo

The extentof volatilepartitioningbetweena liquid T (oc)

and vapor phaseduring boiling can be related to FIG. 2. Temperature dependenceof the volatility ratios of
one parameter, the volatility ratio (VR), for both common hydrothermal gasesin water (data from Drummond,
openandclosedboiling.The volatilityratiois simply 1981).
132 $. E. DRUMMOND AND H. OHMOTO
tween the mass distribution coefficient and the rel-
ative densitiesof water in the vapor and liquid
phases.KH and •w both increasewith salinitysuch
that logVR increases
by about0.1 to 0.2 (depending
on the temperatureand the gas)for each molal unit
increase in NaC1 concentration.
For closedboiling,both the gassoluteand water
are conservedwithin the system so that the total
masses boiling Equation(11) strictlyimpliesthat the volatility ratio
of eachbeforeboilingandthroughout
are the same.For a systemreferenced to one kilo-
gram of water in the initial liquid phaseand no changes.The ratio can changewith decreasingtem-
vaporphaseprior to boiling,this massconservation perature and increasingsalinity during the course
is expressed
by the followingrelationship: of boiling and cannot be assumedconstant over
m, = X-m + (1 - X)mv, (6)
where mi = initial molalityof the volatilegasspecies
in the liquid phasebefore boiling and X = fraction
of the i kg of water remainingin the liquid phase
after boiling. Substitutingfor VR and rearranging
then gives:
m = mi/(X + VR(1 - X)). (7)
So the molality of gas in solutionat any stage of
closed systemboiling can be calculated from the
total moles of gas in the system, the extent of
boiling, and the volatility ratio for the volatile gas
speciesat systemconditions.It is significantto note
that the ratio of final to initial gas molalities can
neverbe lessthan 1/VR in a closedboilingsystem.
For open boiling as well, the changein solution
compositioncan be calculatedquantitativelyif the
volatility ratio is known. Again consideran initial
solutionwith i kg of water and a volatilegasspecies
of concentration mi. Because X is the number of
kilogramsof H20 in the liquid, the number of moles
of gasspeciesin the liquid at any point is given by
Xm. If a differential amount of water, -dX, is
transferredto a vapor phase of composition(mv)
under suchconditionsthat the vapor is continually
removedfrom the system(i.e., there is no transfer
of massfrom vapor to liquid) then the number of
kilogramsof H20 instantaneouslyenteringthe vapor
is dX and the number of moles of gas species
simultaneously
enteringthe vaporis mvdX.Therefore
by massbalance:
-mvdX = -d(Xm) = -Xdm - mdX
or Xdm/dX = mv - m (8)
and
dX/X = In X = dm/(mv - m). (9)
i
Equation(9) wasdevelopedby Rayleigh(1902) and
is oftentermedthe Rayleighdistillationequation.A
more familiar form of the Rayleighequationcan be
derived by integratingequation (9) (Robinsonand
Gilliland, 1950). Substitutingfor VR gives:
In X = dm/(m(VR - 1))
i
= In(m/m,)/(VR- 1) (10)
or, after clearingof logarithmsand rearranging:
rn = mi.X (va- 1) (11)
remains constant over the boiling interval as X
large boiling intervals.In suchcases,equation(11)
is applied successively over small (dX < 0.01 kg)
concentrationand temperature rangesto integrate
satisfactorilythe changesin the volatility ratio into
the calculation(Fig. 2). Therefore, the partitioning
of gasesbetween liquid and vapor for the open as
well as closed systemscan be determined via a
simplefunctionof VR.
Gas dissolutionpaths of boiling hydrothermal
solutions: Equations(7) and (11) were usedto cal-
culate the dissolvedgascontentof 350 ø, 250 ø, and
150øC isothermal (pure water and initially 3 m
NaC1) and isoenthalpic(initially 3 m NaC1) boiling
solutions.Resultsof these calculationsfor CO•, H•S,
CH4, SO•, and H• are illustratedin Figure 3 where
percent boiling [definedas 100 (1 - X)] is plotted
againstthe logarithm of the ratio of gas molality
before and after boiling (m/rni). Note the distinct
differencesbetween open and closedboiling in all
nine diagrams(Fig. 3). In open boiling, gasesare
removedfrom solutionat variable exponentialrates
so asto producemarkedchangesin gascontentand
ratiosafter only a few percent boiling. However, in
closedboiling gas depletion from solutionsis com-
parativelyslow and tendsto level off after the first
few percent boiling because the gas content in
solutionis essentiallybufferedby the gascontentin
the associatedvapor phase. Consequently,open
boiling is much more effectivein perturbing the gas
content and gas ratios in solutionand, as will be
shown later, is associatedwith more significant
changesin pH, fo•, sulfur and carbon speciation,
etc., than closedboiling.
Gas evolution from closedboiling solutionscan,
however,be appreciableinitially. The upper left-
hand cornersof Figures 3b, e, and h are expanded
to show the details of gas depletion in the early
stagesof boiling. Figure 3 showsclearly that the
gasespartition from solutionat variableratesin the
initial stagesof closedboiling. Soonafter the incep-
tion of closed boiling, gas ratios in solution are
essentiallyfixedasthe gasesexsolveat parallelrates.
Within these early stages of closed boiling, gas
concentrationscan decreaseby a factor of 10 to
 BOILING HYDROTHERMAL SYSTEMS 133

350'C 250'C 150'C

-10
CH4

0 20 40 0 10 20 0 2 4
*/, BOILING
FIC. 3. Dissolutionpathsfor H•, CH4, CO•, H•S, and SO• from 350ø (a, b, c), 250ø (d, e, f),
and 150øC (g, h, i) boiling solutions.Lines are for open boiling systems;the shadedarea indicates
the zone of all the closedboiling dissolutionpaths;(mime)representsthe ratio of the gasmolality at
anystageof boilingto the gasmolalityat the inceptionof boiling.(a), (d), and (g) are for isothermal
pure water solutions;(b), (e), and (h) for isothermal3 m solutions;and (c), (•, and (i) for isoenthalpic
3 m NaC1 solutions.The dotted rectanglesin the upper left-hand corners of b, e, and h (b', e', and
h') are expandedin Figure 4.

100 dependingon the volatility ratios. After the sultingeffectis apparentwhencontrasting 3 m NaC1
earlystages,however,closedboilinghasa diminish- and pure water isothermalsolutionsin Figure 3.
ing effect on the gascontentand overall chemistry Gaspartitioningratesare initially much greaterin
of the solution. salt solutions than in salt-free solutions. Thus, as
The rate of liquid to vapor partitioningfor the boilingproceeds,both the salinityand gas-partition-
gasesproceedsin the sameorder as the increasing ing ratescontinuallyincrease.The heat budgetcan
volatility ratio: Hg > CH4 > COg • HgS • SOg also drasticallyaffect the rate of volatile evolution
(Figs.3 and 4). Volatility ratiosfor all gasesdecrease from solutionduring boiling (Fig. 3). Becausethe
with increasingtemperatureand convergeto a value volatilityratioincreases rapidlyasthe solutioncools,
of 1 at the criticaltemperatures of the solution(Fig. gasespartitionfrom isoenthalpicboilingsolutionsat
2). This is reflectedin Figures3 and 4 where the a faster and continuallyincreasingrate than from
rates and variability of volatile evolution decrease isothermalboiling solutions.
with increasing temperature. In other words, at In summary,liquid-vaporpartitioningof a gascan
lower temperatures,lessboiling is required to pro- be adequatelyexpressedin terms of the relative
ducethe samegasconcentrationchangesin solution volatility of the gas-solventcombination(VR) for
for both open and closedsystems.Volatility ratios both open and closedsystems.Volatility ratiosfor
decreasewith increasingwater-vaporpressureand eachgasare a complexfunctionof temperatureand
gas solubilitiesand increasewith salinity. The re- salinityand may increaseby more than an order of
134 $. E. DRUMMOND AND H. OHMOTO

350'C 250'C 150'C

0

-I

log 2
(m/mi)
3-

4-
- CLOSED
5
0 5 I0 15 0 2 4 0 4 8

BOILING

FIG. 4. Gas dissolutionpaths in the initial stagesof boiling for isoenthalpic,3 m NaCI solutions
(expanded from Fig. 3b, e, and h). Heavy and thin lines represent open and closed systems,
respectively.

magnitudeduring isoenthalpicboiling. The interac- (Debye-Hiickelextensions) with a consideration of

tion of all thesesystempropertiescan be quantified all possiblecombinationsof ion pairs(e.g., Helgeson,
to determine the behavior of gasesin a dynamic 1969). In the absenceof reliable stoichiometric
two-phasesystem.In general,boiling is mosteffec- activitycoefficients
at the conditionsof interest,this
tive in strippinggasesfrom solutionwhen the system hasbeen the favoredapproachof mostgeochemists
is open to mass,isoenthalpic,and saline and has a for estimatingthe bulk effectsof ionic media on
low temperature. hydrothermalequilibriafor decades.In the pastten
years, a sufficientbody of stoichiometricactivity
Chemicalsystematics
for pH increases coefficient data has become available to render this
during boiling method of estimatingactivity coefficientsunneces-
Treatment of activity coejficients:The ensuing sarily cumbersomeand inaccuratefor most hydro-
discussionof the principal mass action equilibria thermal solutions to 350øC. For any given ionic
involved in determiningthe pH changesfor com- mediasuchas NaC1,only 13 independentpiecesof
positionallysimpleanalogsof naturalboilinghydro- stoichiometricactivitycoefficientdata are required
thermal solutionsshouldbe prefaced with a short to describethe effectsof the media on any reaction
involvingcombinationsof the 14 speciesabove.
discussionof the treatment of activity coefficients
used herein since the notation, conventions, andExperimentaldata from isopiestic,calorimetry,sol-
datasourcesmaybe unfamiliarto manygeochemists. ubility, and emf studiescurrentlyprovide us with
The compositionof most natural hydrothermal mostof thesequantities(Blountand Dickson,1969;
solutionsfall predominantlywithin the H20-Na-K- BuseyandMesmer,1976, 1978; ChenandMarshall,
Ca-Mg-C1-CO2-SO4-H•S-SiO• system.Of these ten 1982; Drummond, 1981; Ellis, 1963; Holmes et al.,
components,four participate significantlyin one 1978, 1979; Holmes and Mesmer, 1981, 1983;
acid dissociation
reactionwithin the interestingrange Pattersonet al., 1982; Pitzer et al., 1984).
of protonconcentrations (within 2 log unitsof neu- Presentlythe data basefor stoichiometricactivity
tral). Consequently,at least 14 species(H•O, CO•, coefficientsin NaC1media at elevated temperatures
H2S, H+, CI-, Na+, K+, Ca+•, Mg+•, OH-, HCO•, is lackinginformationfor HSO• and HS- which are
HS-, HSO•. SO••) are requiredto describeall mass consideredanalogousto HCO• in this study. One
balance,chargebalance,andequilibriummassaction caveatthat mustbe mentionedregardingthe use of
constraintsin this system.In order to evaluatethe stoichiometricactivity coefficientsfrom experimen-
effect of an ionic medium on the position of any talssystems containingNaC1-t-H•O -t-oneadditional
equilibriait is necessaryto know the activity coef- electrolyte in modeling a ten-componentsystemis
ficient quotientsfor the speciesinvolved.For ionic that specificstronginteractionsbetweencomponents
species,the historicalapproachof mostgeochemists that do not occurtogetherin any of the experimental
for computingactivity coefficientshas involvedan systems representingthe databasefor the stoichio-
iterative couplingof a semitheoreticalestimationof metric activity coefficientsmust be consideredex-
the activity coefficientsof the free ionic species plicitly, usuallythrough an additionalmassaction
 BOILING HYDROTHERMALSYSTEMS 135

equation.For example,with the current data base siondemonstrates this simplicityin order to provide
for the stoichiometricactivity coefficientsin NaC1 a conceptualbasisfor understandingthe modeling
media, there is no provisionfor Mg+g.SO•g or results which are presented subsequentlyfor the
Mg+g.OH- interactions and consequentlythesein- ten-component systems.
teractionsare considered
independently
via ion-pair The most significantprotolytic equilibriumin a
formationconstants.Metal complexes(e.g., FeC1+, boilingsolutionis depictedby the followingreaction:
etc.) are handled in this way as well. With these
COg + HgO • HCO• + H +. (12)
exceptions,however,all other interactionsare either
sufficientlyweak or unspecificsoasto be analogous The second dissociationof aqueous COg can be
to and properly modeled as an interaction with ignored for solutionswithin two log [H+] units of
NaC1. Since these interactions are now well known, neutral.Thereforefor simplicitythe followingequa-
virtually all equilibria within the ten-component tionswere derivedon the basisthat CO• g is negli-
systemat any given salinitycan be expressedjust as gible. In the specialcasewhen the acidity of the
well in terms of concentrationquotientsas activity solution is determined solely by the reaction of
quotients.For example,the equilibrium expression equation (12), [HCO•I = [H+] = (Q' [COg]) •/gwhere
for the ionizationof water (HgO • H + + OH-) at Q is the equilibrium quotient for equation (12). In
any given salinitycan be written either in terms of relation to solutionswith IHCO•] = [H+], solutions
a activities:Kw =aH +'aOH-/aHgO = [H+][OH-] ß with [H+] > [HCO•] have an excessacid concentra-
•I•*•oI•-/•o, or in terms of concentrations:Qw tion (IH+le) equal to [H+] - (Q. [COd/[H+l) and so-
= [H+I[OH-I -- where [ l lutions with [H+] < [HCO•] have an excessbase
denotes stoichiometric concentrations and concentration([OH-le) equal to (Q.[COd/[H+I)
•om/ •o representsthe stoichiometricactivity - [H+]. According to these definitionsthe excess
coefficientquotient which is a well known quantity acid or baseconcentrationis equivalentto the con-
(Buseyand Mesmer, 1978). Hence the availability centrationof HC1or NaOH, respectively,that would
of suchdata over a wide range of salinitiesjustifies have to be addedto a solutionwith [HCO•] = [H+]
the lessconventionalbut more convenientpractice initially, in order to attain the actual distribution of
of using solely concentrationto describeequilibria [HCO•] and [H+] in the solutionwith excessacid or
in the followingdiscussion. For further explanation base. If the quantity n is defined in terms of the
of the use of stoichiometricactivity coefficientsin proton and COg concentrationin the initial solution
compositionallycomplex aqueouselectrolyte solu- beforeCOgexsolution(denotedby i):
tions refer to Harvie et al. (1983), Millero (1983), n = [H+]•/(Q-[COg]i)= [H+MHCO•Ii, (13)
and Drummondet al. (in prep.).
Principal massaction equilibria: It is worthwhile then for solutions with n > 1
to realize that, within the range of compositions of IH+I• = [H+]i(1 - (l/n)) (14)
naturalhydrothermalsolutions,the predominantho- and for solutions with n < 1
mogeneous acidøbaseequilibriaare presentedin the
COg-HgO-NaCI-SO4system.This is because:the [OH-]• = [H+]i((1/n)- 1). (15)
hydrolysesof HgSand COg are remarkablysimilar; Since,for solutionswith excessacid,the final proton
COg is more volatile and far more abundant than concentration after removalof all COg (i.e., [H+]e)is
HgS in mosthydrothermalsystems;NaC1 is a rea- equal to the excessacid concentration([H+]•), the
sonableanalogfor the ionic media effectsof KC1, relationshipbetweenthe initial protonconcentration
CaClg, MgClg, etc.; and sulfate is the only other ([H+]i) and [H+]eis expressed:
protolyticcomponentwhoseabundanceis sufficient
[H+]• = [H+]i(1 - (i/n)). (16)
to alter appreciablythe net changein proton con-
centrationduring devolatilization.This simplicityis Likewise for solutions with excess base, the final
convenientbecauseit allowsthe changein proton hydroxide concentrationafter removal of all COg
concentration associated with devolatilization to be (IOH-]•) is equal to the excessbase concentration
defined explicitly in terms of three equilibria: the ([OH-]•). The parallel to equation(16) for the rela-
first dissociationof COg, the dissociationof water, tionship between [H+]f and [H+]i in solutionswith
and the second dissociationof sulfuric acid. In fact, excessbase (n < 1) can be derived by substituting
armed with equilibrium quotientsfor these three IOH-I = [OH-I = Qw/[H+]r (where Qw is the ion-
reactions(Pattersonet al., 1982; BuseyandMesmer, izationproductfor water) into equation(15) to give:
1978; Marshall and Jones, 1966), the equations [H+]t= Qw/([H+]i((1/n)- 1)). (17)
outlined below, and a hand calculator, it is easily
possibleto determineif and how muchthe proton For example,a solutionwith n = 3 (eq. 16) would
concentrationof a hydrothermalsolutionultimately result in [H+]f = 2/3[H+1•,or a shift of only 0.176
changesasa result of boiling.The followingdiscus- log [H+] units.In order for solutionsto undergoa
136 $. E. DRUMMOND AND H. OHMOTO

changeof onelog [H+] unit uponcompletionof CO2

degassing, n would have to be 1.11. Accordinglya
practical limiting relationshipbetween [H+]i and
[CO2]ithat is permissiveof significant(i.e., one log
unit) decreasesin [H+] during boiling is given by
equation (13) where n •< 1 (excess base). This
threshold(n = 1) relationshipis illustratedin Figure
5 andshowsthat the [H+]i/[CO2]iratio at the bound-
ary between excessacid and excessbase increases
with decreasingtemperature.Sincethe ratio of Qw/
Q rangesfrom 10-3 to 10-9 dependingon the
temperature(0-300øC) and salinity(0-5.0 m NaC1) o
-3 -2 -t 0 t
(Buseyand Mesmer, 1978; Pattersonet al., 1982),
log[C02]
'
the pH increaseduring CO2 exsolutioncan be sub-
stantial even for solutionswith low CO2 concentra- FIG. 6. The relationshipbetween the magnitudeof the pH
tions if the solution has excess base as defined in changeand CO2 molality (eq. 17) for CO2-H•O-NaCI solutions
with excessbase (eq. 13, n < 1). I refers to NaC1 molality.
equation(15). Figure 16 illustratesthe magnitude
of the ultimate decreasein [H+] upon total CO2 loss
for solutionswith [H+] below the threshold(n •< 1).
These trendsshowthat A log[H+] can be enormous ity, will have a secondarybut supplementaryeffect
for solutionswith high [CO2]iand is enhancedfor to CO2 on the increasingpH of a boiling solution.
In some natural solutions total sulfate is 10 -2 m or
solutionswith the lowesttemperaturesand highest
salinities. more. At most temperature-pH conditionsbelow
It is clear from Figure 3 that boiling is very 300øCsulfateexistsdominantlyasSO•2 ratherthan
effective in removing CO2 from solutionand from HSO•. However, fairly low HSO; levels can signif-
the abovediscussionthat for simpleCO2-H20-NaC1 icantly dampenthe pH rise of a boiling solution.If
solutionsthis processcan decreasethe proton con- the excessbase is lessthan the HSO• concentration,
centrationin the solutionby severalordersof mag- the excessbase liberated during boiling will be
nitude (when n •< 1). To a large extent, natural consumedin the conversionof a portion of the
solutionswill mimic the behavior of this relatively HSO; to SO•2 and the pH rise will be small(i.e.,
simplifiedchemical analog. However, there are a •[HSO•]/([HSO•I - [OH-]•))in the initial solution)
few additionalimportantconstraintsfor the natural unless the sulfate in the initial solution exists domi-
systemsthat can limit the scopeof the pH increase nantly as HSO; rather than SO•2. For solutions
during boiling. Other componentsinvolvingproto- within two log[H+] units of neutral, with •10 m
lytic equilibria suchas sulfideand sulfateshouldbe CO2 (mostnaturalsolutions),with excessbase(i.e.,
consideredin this analysis.As mentioned above, havingan inherent capabilityto increasepH during
H2S is volatile, has a first acid dissociationconstant CO2 exsolution),andwith [OH-]• • [H+]•(otherwise
the excess base would be used to consume a fraction
similar to CO2, is the dominant form of sulfide in
hydrothermalsolutions,and due to its lower volatil- of the protons),the [HSO•[/[SO•2[ratiois lessthan
about 10 and usually much less than 1. In the
extremecaseof [HSO;[/[SO•2] = 10 and [OH-I•
= •[HSO;], the decrease
in log[H+[wouldbe about
• -• I
EXCESS
ACID
0oC one unit. In mostcaseswhere [HSO;]/SO•2] • 10
and [OH-]• • [HSO•I, the decreasein log[H+l will
• -4 -- be less than one unit. In other words, the excess
\ baseof the solutionmustbe approximatelyequal to
or greater than [HSO•] in order to increasethe pH
appreciably(i.e., morethan one unit) by boiling.If
-5
the acid dissociation
quotientfor HSO• is expressed
-5 -2 -t 0 asQ,so• = [SO;21[H+I/[HSOI,it canbe shownthat
Io•[co2], [HSO;I = 2[SO41'[H+I/([H+] + Quso0. It follows
FIG. 5. Threshold relationshipbetween the proton and CO2 from this and the requirement[HSO;] •< [OH-]• that
concentrationsin the initial solution (eq. 12, n = 1; salinity favorable conditionsfor a pH increaseby boiling
= 1 m NaCI). Solutions above these lines have excess acid are met when:
(n > 1) and cannot increase pH appreciably upon CO2 loss
duringboiling. Solutionsbelow theselineshave excessbase(n (l/n)- 1 •> •[SO4]/([H+]i q- Quso•). (18)
< 1) and,uponCO2 lossduringboiling,increasepH substantially
(see Fig. 6). For valuesof n ,• 1, (l/n) - 1 • 1/n so that the
 BOILING HYDROTHERMAL SYSTEMS 137

final approximationfor the conditionsamenable to I I/ ,,I

pH increasesduringboilingof sulfate-bearing
solu- 250øC
(c)
tionsafter substitutingfor n (eq. 13) is: 300ø0,l'w

[COd,
•[SO4•
> Q([H+],
+Qao4)
' (19) -00øC
/?ttt•
,L /'7'
-
The [CO2],/X[SO41 ratios required to satisfythis
conditionat different [H+]i are depictedin Figure
7. It is evident that these conditionspose the most
-2 --
L"/
./,';'.. --

severe restrictionson decreasesin the proton con-

centration at high temperatures and in low ionic -3
I i i i i i
strengthsolutions. -7 -6 -5 -4 -3-7 -6 -5 -4 -3-7 -6 -5 -4 -3

It has been shownthat, from the standpointof log[H+],

boththe thresholdconditions for pH increases (Figs. FIG. 8. Summaryof the chemicalboundary conditionsfor
5 and 7) and the magnitudeof the increases(Fig. significant changes in the proton concentration during the
6), solutions
with high [CO2]/[H+] ratiosare the best boiling processfor 1 m NaC1isothermalsolutionsin the system
candidatesfor large pH increasesupon boiling. CO•-H•O-Ca-NaC1-SO4. The heavy slanted lines marked by
However, the chemicalrange of these solutionsis trianglesare defined by equation (13) (n = 1) and representthe
threshold[CO2]i/[H+]i
relationship
depictedin Figure5. Solutions
limited by the solubilityof calcite and anhydrite, to the left of these lines have excessbase and can undergo
and if the solutionbecomessaturatedwith respect significantpH increasesupon CO• exsolution during boiling.
to these minerals, the chemical evolution of the The heavy horizontal lines marked by trianglescorrespondto
solution will also be limited. The chemical restrictions conditiouswhere log ([W]dW,l,)=-1 •rom equation(16).
Above these lines the initial solution has sufficient CO• to
associated
with calcite and/or anhydritesaturation undergo a pH increaseof more than 1 unit upon complete CO2
are such that the presenceof these minerals tends exsolution.In effect, CO• losscan significantlyincreasethe pH
to buffer CO2/HCO5 and HSO•/SO•2 ratios and of a CO.2-H•O-NaC1solution only at conditions within the
hencereducethe pH increasesthat would otherwise stippledareadefinedby thesetriangle-markedlines.The slanted
resultfromboiling.Thesesolubilitylimitsfor calcite dashedlines are defined by equation(19) for XSO4 = 0.01 m.
and anhydritealong with the other limits defined Only solutionsto the left (indicated by arrows) of these lines
are unbuffered by the sulfate equilibria and are capable of
abovein equations(13), (17), and (19) are shown increasingpH by one unit or more during boiling. The slanted
in Figure 8 for 200 ø, 250 ø, and 300øC solutions dash-dot lines correspondto conditionsof both calcite and
with a formal ionic strength(i.e., NaC1 molality) anhydrite saturationat XSO4 = 0.01 m and XCa = 0.0036 m
of 1.0. (a), 0.001 m (b), and 0.0004 m (c). For these arbitrary values
of ZSO• and XCa, solutionsto the right (indicatedby arrows)
of these lines are thermodynamicallycompatiblewith the dis-
solutionof calcite and anhydrite.

A E[SO4]valueof 10-2 waschosenarbitrarilyto

definethe dashedline of equation(19) in Figure 8.
L
2

The XCa level for the calcite-anhydrite-saturated

line is fixed by the X[SO4] concentrationand is
variablewith temperature.In Figure 8 the positions
of the line from equation (19) and the calcite-
/7 00 anhydrite-saturatedline will shift dependingon the
X[SO4]concentration,but the separationbetween
-2 ! 7100
-- theselinesis independentof X[SO4].In other words,
if the •[SO4] is reduced, the XCa concentration
required to saturatethe solutionwith anhydrite is
greaterand the corresponding
[COd/[H+]2 ratio is
proportionatelyless.If the solutionis saturatedwith
respectto both calciteand anhydrite,the favorable
FIG. 7. Threshold relationshipbetween protou, CO•, and rangefor increasedpH during boiling is limited to
XSO4 concentrationsin the initial solution (eq. 19) for three the narrow[CO2],- [H+]•rangebetweenthe arrowed
NaC1 molalities (I = 0, 1, 5). Solutions above these lines have
enough excessbase to overcome the buffering effect of the
linesin Figure 8. In reducedsolutionswhere sulfate
sulfateequilibria and increasepH significantlyupon CO• loss is very low, for any given [CO2],, the [H+I• range
duringboiling.The pH of solutions belowthisline is effectively permitted by calcite solubility and equation (13)
bufferedby sulfate. (for n •< 1) is lessthan 2 log unitsfor 200 ø to 300øC
138
solutions with 10 -3 m Ca. When all of these restric-
tionsare consideredtogether,the rangeof chemical
conditionsconduciveto increasedpH duringboiling
seemsvery narrowand at the sametime very similar
to the conditionsoperativein naturalhydrothermal
systems.
pH-boiling paths:Now that the major variables
controllingthe thresholdsand magnitudesof pH
changesduring boiling have been discussed,it is
appropriate to look (via the computer model) in
somedetailat the evolutionof pH asboilingproceeds
in more complexmulticomponent(Na, K, Ca, Mg,
C1, CO2, SO4, and H2S, metals) boiling systems.
Figures 9 and 10 help illustrate the influence of
temperature, heat budget, and physicalconstraints
on typicalpH-boilingpaths.Severalsignificanttrends
are obviousin these figures,but perhapsthe most
notableone is the abrupt pH increasein the initial
stageof boiling followed by smalleror negligible
changes.Initially [H+] respondsrapidly to COe exso-
lution such that there is essentiallya one to one
relationshipbetween [H+] and [COe] for solutions
with excessbase. However, after either [COe] or
[HCO•] becomeslessthan [OH-], [H+] is buffered
more by the dissociationof water than by the
carbonateequilibria,with the net result being that
the [H+] decreases at a continuallydiminishingrate.
These trends are most exaggeratedfor both open
and low-temperaturesolutionsand resultsfrom the
rapid separationof COe from these solutionsin the
initial stagesof boiling (Figs. 3 and 4). This pH-
increasingmechanism is moreprotractedandgradual
for closedand high-temperaturesystems.Increases
in pH are summarilylarger for openboilingsystems
reflectingthe lower ultimate CO2 concentrationin
an open boiling system.Low-temperaturesolutions
undergo the greatestpH increasesfor both open
and closedsystems.This sametendencyis illustrated
in Figure 6 and predicted by equation (17) since
-8
I I
ISOTHERMAL 200øC
ß-.-"- • 250
-7
/ 300
250
-4
0 systems. Represented withinthisgroupof five metals
% BOLLING
FIG. 9. Percent boiling/IH+] paths for open and closed
isothermalboiling solutionswith initial molalitiesof H + = ]0 -4 s
ZCI • 1.0,ZNa• 0.9, ZK -- 0.1, ZCa-- 0.003,Y•M• transportedin the +1 state as a chloride complex
-- 0.001, ZCO2 -- 0.3, ZH2S -- 0.003, and ZSO4 = 3 X 10-".
$. E. DRUMMONDAND H. OHMOTO
-8
ISOENTHALPICT,-=20_•0øC-•
- '-""""--""' --"--
-
-7
-5
I I I I
-4
0 5 tO t5 20 25
% BOLLING
FIC. 10. Percent boiling/IH+] paths for open and closed
isoenthalpic boiling solutions with the initial composition as
given for Figure 9. Temperaturesprior to boiling are indicated.
Qw/Q systematically decreases with decreasingtem-
perature. Even though the 200 ø, 250 ø, and 300øC
isoenthalpicboiling solutionscool by 140ø, 130ø,
and 110øC, respectively,in the first 25 percent
boiling, heat budgeteffectson the pH-boilingpaths
are relatively minor. The general tendencyis for
larger pH increasesin isoenthalpicsystemssince
the volatility ratio and liquid to vapor partitioning
of COe increaseswith decreasingtemperature.This
effect is mostapparentfor closedand high-temper-
ature systemswhere the solutionscool appreciably
before most of the COe is exsolved.
It is clear that dramaticchangesare possiblewhen
a hydrothermalsolutionlosesonly a few percent of
its massto the vaporphaseby boiling.The conditions
that are conduciveto thesechangesand the magni-
tude of thesechangesare definedabove.Resultsof
this analysisare very usefulin determiningthe role
of the boiling processas a mechanismfor mineral-
ization in the complex hydrothermal systemsthat
form ore deposits.Consequently,the discussion will
be directed toward that ultimate goal.
Mineral Depositionfrom Boiling
I I
Hydrothermal Solutions
• • • General discussion
The efficiencyof a mineralizing processis indi-
catedmostdirectly by monitoringthe changein the
metal concentrationsas the processproceeds.For
_
the purposeof illustratingthe efficiencyof boiling,
XAg, XAu, XCu, XFe, XZn, and H + concentrations
I I OPEN -- are plotted versusthe extent of boiling for a range
• CLOSED of solutiontemperaturesand compositionsand for
both open (Fig. 11) and closed(Fig. 12) isothermal
are the mostimportantmetaloxidationstates,mineral
groups,and aqueouscomplexesof ore components.
Under the conditions considered here, silver is
(Seward,1976) and is depositedas either the metal
 BOILING HYDROTHERMALSYSTEMS 139

+H]6Ol

I I

(todd) õOl

œ_0Lx•=OS.'•' 6_0Lxl:=t'OS.'•' 6_0Lxl:=t'OS.'•

'
'0'•=•OO• '0'•=•OO• •:_0Lxl;:
=•OO•
140 S. E. DRUMMOND AND H. OHMOTO

(tudd) õOl
 BOILING HYDROTHERMAL SYSTEMS 141

or in the +1 state as Ag2S;gold is transportedin •SO 4 ratio. In this sense,Figures 11 and 12 are
the +1 stateaseither a chlorideor bisulfidecomplex biased toward those initial conditions that are at
(Casadevalland Ohmoto, 1977; Seward, 1973) and least somewhatfavorableto mineral depositionby
is depositedas the metal;copperis transportedas a boiling and excludemuch of the range of hydro-
cuprouschloridecomplex(Crerar andBarnes,1976) thermal solutioncompositionswhere boiling is an
and is depositedas either CuFeS2or Cu.sFeS4'iron impotent mineralizing process.
is in solutionas ferrouschloridecomplexes(Crerar The one trend that is most consistentin Figures
et al., 1978) and is depositedprimarily as sulfides 11 and 12 is the sympatheticdecreasein the metal
(FeS•, FeS, CuFeS•, CusFeS4) or oxides (Fe.304, and proton concentrations with increasedboiling.
Fe•Os) that have variable valence states of sulfur Thisis not surprisingsincethe solubilitiesof oxides,
and iron; zinc (a good analogfor lead) is dissolved native metals, and sulfidesare directly dependent
in the +2 state as a chloride complex, except in on the proton concentrationwhen the metals in
high pH, low-temperaturesolutionswhere bisulfide solutionare stabilizedby chloride complexesand
complexescan contribute (Bourcier, 1983), and is when all other intensive variables such as oxygen
depositedas ZnS. fugacityand total sulfurconcentrationare constant.
The hydrothermalsolubilitiesof both silver and Even thoughthesevariablesmay changealongwith
zinc are relativelywell characterized(Seward,1976; protonconcentration, there is nonethelessa marked
Bourcier, 1983) and hence are good choicesfor a dependency of metal concentration on protons
thermodynamicanalysisof the effect of boiling on throughoutboiling at any condition.This demon-
mineral solubilities since the actual levels of these stratesunequivocallythat, as suggestedin the pre-
metalsin solutioncan be computedreliably. Gold, vious discussion,the changein the proton concen-
copper, and iron solubilitiesare lesswell character- tration is an overriding factor in determiningthe
ized. However, gold is an importantcompanionto fate of metalsin boiling hydrothermalsystems.
silver and is economicallysignificant;copper is an However, when a metal in solution is stabilized
important ore commodity and can determine the by bisulfide complexes,solubility increaseswith
level of iron in solution via the Cu-Fe sulfides; and decreasingproton concentration(within the pH
iron is ubiquitousin a variety of mineralsfound in rangewhereinHsS dominatesover HS-) according
ore-formingsystems,formsphaseswith many other to a reactionsimilarto the followingone for gold:
metals, and at high temperaturesits concentration
in solution can exceed that of all other metals Auø + 15/8HsS+ 1/8SO•s •
combined.Consequently, thesefivemetalsarelogical
choicesfor illustratingboth the general effect of Au(HS)• + 1/2HSO+ 6/SH+. (20)
boiling on the depositionof the full range of ore
mineralsand the specificeffect on the precipitation In boilingsolutions there are the simultaneous and
of someeconomicallyimportantmetals. competingeffectsof diminishingproton and H•S
As discussedabove and illustrated in Figures 5 to concentrations as boiling proceeds.This tradeoff
7, the protonconcentrationchangeduringboiling between protonsand HsS is responsiblefor the
at any temperaturedependsprimarilyon the [COs]/ sluggishdepositionaltrend for gold in the 200øC
[H+I and [co]/[zso41 ratiosin the initial solution. solutions in Figures11 and12. Sinceultimately,for
Within that contextthe systematics of the chemical solutionswith excessbase,the changein the log of
evolutionof a boiling solutionand the extent of the protonconcentration is approximately propor-
mineralprecipitationcanbe investigatedby varying tionalto the changein the log of CO• concentration,
the concentrationof any two of these three initial the net effect of boiling on the reactionin equation
solution chemistry compositionalparameters. For (20) dependson the relativevolatilitiesof H•S and
the presentpurposes,the [H+] wasfixedat a reason- COs. For boiling solutionswith excessbase, the
ablevaluefor hydrothermal solutions(10-4"5, slightly valueof A log[H+l/AloglH2S]at the inceptionof
acidic) and the ZCO2 and ZSO4 concentrations boilingvariesbetweenabout1.5 and3.0 depending
were varied widely (Y,CO• = 3.0 and 0.03 m and on the conditions. This ratio is highest in open
Y,SO4= 3 X 10-0 and3 X 10-"m) to demonstrate systems
andat lowtemperatures
wherethe volatility
the dramatic effects of these two major solution ratiosof CO• and H•S are mostdifferentfrom each
componentson the fate of metalsin a boilingsolution. other. When this ratio is less than 2.5 (15/6), the
It should be noted that the combination, ECOs equilibriumin equation(20) is suchthat gold is
= 0.03 m and ZSO4 = 0.003 m, is not shown in deposited.As a result,goldcomplexedasAu(HS)•
Figures11 and 12 because,aspredictedby equation will tend to be depositedfrom many but not all
(19) and shownin Figure 7, neither [H+1 nor the boilingsolutions
withexcessbaseandwill universally
concentrationsof mostmetalsare changedapprecia- tendto depositfromboilingsolutionswithoutexcess
bly by boiling a solutionwith such a low ZC02/ base.
142 $. E. DRUMMOND AND H. OHMOTO

Abrupt changesin the slopesof the curves in
Figures 11 and 12 result from similar changesin
IH+], mineralphasetransitions(Table 1), or in the
caseof gold,a changebetweenbisulfideandchloride
complexing.Modelingresultsfor isoenthalpic boiling
or for solutionswith ionic strengthsother than I m
resemblethose shownin Figures 11 and 12. The
similaritiesin the pH-boiling trends between iso-
thermal and enthalpicboiling (e.g., Figs. 8 and 9)
indicate that the most important differencesin the
percentboiling-metalconcentrationpathsbetween
isothermaland isoenthalpicboilingare not associated
with [H+] trendsbut are attributableto the generally
lower solubilitiesof chloride-complexedmetals at
lower temperatures.This cooling effect generally
resultsin morenegativeslopesin the percentboiling-
metal concentration curves and somewhat more ef-
fective mineral depositionthan is shownin Figures
11 and 12. This is particularlytrue for high-temper-
ature solutionsthat depositmetal sluggishlyduring
isothermalboiling. In most caseswhere isothermal
boilingis effectivein depositingmetalfromsolution, associated oxidation stabilizes oxides, destabilizes
the effect of coolingon metal depositionduring native metals, and dependingon the oxidationstate
boiling is insignificantsince most of the metal is
depositedin the initial stagesof boiling before the
solutioncoolsmore than a few degrees.Increased
salinityis associated
with lessseverelimits(asdefined
in eqs. 13, 17, and 19 above) on the threshold
concentrationsof CO2, ZSO4, and H + in the initial
solution(Fig. 7) and therefore enhancesthe depo-
sitionof mostmetalsduringboiling.Salinityeffects
are otherwiserelatively minor and predictablefrom
Figures 3, 4, and 6.
Decreases in metal and proton concentrations
range from severalorders of magnitudein the first
one percent vaporizationfor low-temperature,high
ZCO2, low ZSO4, open systemsto lessthan a tenth
of a log unit after 50 percent boiling in high-
temperature,low ZCO2, high ZSO4 closedsystems.
For any given condition, the concentrationof each
metal hasa characteristicresponseto boiling that is
dictatedby the stabilitiesand stoichiometriesof the
mineralsand aqueouscomplexesof each metal. Just
as H2S lossduring boiling destabilizessulfides,the

TABLE1. Mineral Paragenesesfor Figures 11 and 12

Figure 11
Age + Au + CuFeSe+ FeSe+ ZnS - FeS2(i)+ CaCOa(0.2) - CuFeS2(0.4)- ZnS(1.8)
b Age + Au + CuFeSe+ ZnS - FeS,2(i)+ CaCOa(0.8) - CuFeS,2(0.8)- ZnS(5.2) - Ag,2S(5.2)+ Ag(5.2)
c Ages + Au + CuFeSe+ FeSe+ ZnS - FeS,2(i)+ CaCO3(1.6) + CASO4(1.6)- CASO4(2.4)- CuFeS,2(10.4)
+ Fe,304(10.4) - Ag,2S(14.4)+ Ag(14.4) - CACO3(14.4)
d Age + Au + CuFeSe+ Fea04 + ZnS - CuFeS2(i) + CaCOa(6.4) - ZnS(35.2) - Ag2S(35.2) + Ag(35.2)
Ages + Au + CuFeSe+ FeSe+ ZnS + CaCOa(0.2) - FeS,2(0.4)+ FeS(0.4) - FeS(1.2) + Fe•O4(1.2)
- CuFeS2(1.2) - Ag2S(1.2) + Ag(1.2) - ZnS(1.8)
Age + Au + CuFeSe+ FeSe+ ZnS + CaCOa(0.8) - FeS2(1.6) + FeS(1.6) - FeS(2.0) + Fe•O4(2.0) -
CuFeS,2(2.0)- Ag2S(2.8) + Ag(2.8) - ZnS(5.2)
Ages + Au + CuFeSe+ FeSe+ ZnS - FeS,2(i)+ Fe•O4(i) + CaCOa(1.6) - CuFeS,2(1.6)- Ag,2S(5.6)+ Ag(5.6)
- CaCOa(15.2) - ZnS(15.2)
Ag + Au + CuFeS2+ Fea04 + ZnS - CuFeS,2(i)+ CaC0•(6.4) - CaC03(32.0) - ZnS(36.8)
Age + Au + CuFeSe+ FeSe+ ZnS - FeS,2(0.4)+ FeS(0.4) - CuFeS,2(2.0)- Ag,2S(3.6)+ Ag(3.6) - ZnS(4.8)
- Ag(•0.0)
J Ages+ Au + CuFeSe+ FeSe+ ZnS - FeS2(1.6) + FeaO4(1.6) - CuFeS2(2.0) - Ag,2S(3.6)+ Ag(3.6) - ZnS(4.8)
- Ag(10.0)
Age + Au + CuFeSe+ FeS.2+ ZnS - FeS.2(i)+ FeaO4(i) - CuFeS,2(1.6) - Ag,2S(6.4)+ Ag(6.4) - ZnS(8.0)
- Ag(14.4) - Au(14.4)
Ag + Au + CuFeSe+ Fea04 + ZnS - CuFeSa(i) - ZnS(i)
Figure 12
Age + Au + CuFeSe+ FeSe+ ZnS - FeSe(i) + CaCO3(0.2) - CuFeS,2(0.4)
b Age + Au + CuFeSe+ FeSe+ ZnS - FeSe(i) + CaCO3(0.8)
Age + Au + CuFeSe+ FeSe+ ZnS - FeS2(i) + CASO4(1.6) + CaCO3(2.4) - CASO4(3.2)
d Age + Au + CuFeSe+ Fea04 + ZnS - CuFeS,2(i)+ CaCO•(9.6)
Ages + Au + CuFeSe+ FeSe+ ZnS + CaCOa(0.2) - FeS,2(0.6) + FeS(0.6) - CuFeSe(2.2)
f Ages + Au + CuFeS• + FeSe+ ZnS + CACO3(0.8) - FES,2(2.4)+ Fe•O4(2.8) - CuFeS•(3.2)
g Age + Au + CuFeSe+ FeSe+ ZnS - FeS,2(i)+ Fe304(i) - CaCO•(1.6) - CuFeS,2(1.6)- AgeS(13.6) + Ag(13.6)
h Ag + Au + CuFeSe+ Fea04 + ZnS - CuFeS,2(i)+ CaCO3(11.2)
i Ages + Au + CuFeSe+ FeSe+ ZnS - FeS,2(0.6) + FeS(0.6) - CuFeS,2(1.8)
J Age + Au + CuFeSe+ FeSe+ ZnS - FeS•(2.8) + FeaO4(2.8) - CuFeS,2(3.2)
k Ages + Au + CuFeSe+ FeSe+ ZnS - FeS,2(i)+ Fe•O4(i) - CuFeS,2(i)- Ag,2S(16.0)+ Ag(16.0) - ZnS(16.0)
1 Ag + Au + CuFeSe+ Fea04 + ZnS - CuFeS,2(i)- ZnS(i)

Italicized phasesrepresentthe stableassemblage before boiling;minusand plus signsindicatethe end and onsetof deposition,
respectively,for the indicatedphases;numbersin parenthesessignifythe percent boiling correspondingto the phasetransition;
i indicatesthat the transitionstartedwith the inceptionof boiling
 BOILING HYDROTHERMAL SYSTEMS 143

of the fluid, hasvarying effectson the stabilitiesof with isoenthalpicboiling can have a dominanteffect
sulfideswith intermediatesulfurvalence(e.g.,FeS•,). on mineralprecipitationabove300øC if the amount
The copper minerals, chalcopyrite and bornitc, are of boiling is substantial(•10%). Under these cir-
often destabilizedby the scavengingof iron from cumstancesisoenthalpic boiling solutions above
solutionduring the active stagesof pyrrhotite or 300øC can deposita greater massof mineralsof all
magnetiteprecipitation.All of these major interac- classes than solutions below 300øC if the solutions
tions and many other minor onescontribute to the are initially saturated.
complexityof the boiling processand are accounted When the initial solution is not saturated with
for here. respect to the most stable phase of each metal the
consequences of boiling on mineral depositionare
Amountof metalsdeposited muchmore conditionaland varied. Whereasin Fig-
ures 11 and 12 eachmetal is shownto haveprecip-
Althoughthe trajectoriesof the metal concentra- itated from the onsetof boiling, a solutionwith only
tionsin Figures 11 and 12 are markedly dependent one tenth the saturated value for a metal would not
on the physical and chemical conditions,the mass precipitate that metal until boiling increasedthe
of eachmetaldepositedduringboilingfrom a solu- saturationindex of the most stable solid phase of
tion initially saturatedwith the moststablephaseof that metal by one log unit. This is perhaps an
thesemetalsis dependenton the temperaturebut extreme example becausefor most conditionsand
remarkablyindependentof the initial solutionchem- metals (particularlyat the lowest temperatures)a
istry (within the range outlined by the threshold solutionwith only one-tenththe metalconcentration
criteria established above)or whetherthe systemis needed in order to be saturatedmay not have
open or closed (Fig. 13). At or below 300øC, the sufficientmetalto be a potentialore-formingsolution.
firstfive percentboilingis capableof precipitating In addition, there are virtually no circumstances
mostof the metalfromsaturated solutionsat virtually under which closedisothermalboiling would cause
all conditions within the threshold constraints. Con- precipitationof as much as half of any metal from a
sequentlythe amountof metal depositedfrom a solutionthat is initially one order of magnitude
saturatedsolutionduringboilinggenerallyincreases undersaturatedwith the most stablephaseof each
with increasingtemperatureover the range from metal (Fig. 12). The variety and amount of metals
200ø to 300øC. Theseobservations clearlyindicate depositedfrom 350øC solutionsduringopenboiling
that, within this temperaturerange, the massof would also be very limited (Fig. 11). At lower
metalprecipitatedfrom a saturatedsolutionis limited temperaturesopen boiling is adequateto overcome
moreby the amountin solution thanby the efficiency the initial deficit of being an order of magnitude
of the boilingdepositional mechanism. Above300øC, undersaturatedand still depositmost of the metals
substantially morevaporization is requiredto pre- in solution. At these temperatures, however, the
cipitatethe bulk of the metal in solutionexceptat amount of metal is meager for ore formation. This
the mostfavorableconditions. Typicallyfor saturated analysissuggests,with perhapsthe exceptionof
solutions,less metal is depositedas sulfidesand preciousmetal deposits,that ore depositsformed
more as oxidesat 350ø than at 300øC (Table 1). by boilingare generatedprincipallyfrom solutions
The amountof nativemetal depositedis relatively less than one order of magnitude undersaturated
insensitiveto temperature. The cooling associated with respect to the metal of interest.

o Ag o

-- -1 • .- •.... " -1

-2 -2
200 250 500 200 250 500 200 250 500 550
TøC
FIG. 13. Amountof metaldepositedafterboilingfive percentof solutionsinitiallysaturatedwith
respectto the moststablephasesof silver,gold,iron, and zinc (samenotationas for Figs. 11 and
12). (a) corresponds
to Figure1le-h (open,Y•CO•-- 3.0 m andY•SO4= 3 X 10-9m); (b) corresponds
to Figure11i-I (open,Y•CO•= 3 X 10-• m, Y•SO4 -- 3 X 10-9m); (c) corresponds to Figure12i-I
(closedY•CO•= 3 X 10-• m, Y•S04= 3 X 10-9 m).
144 s. E. DRUMMOND AND H. OHMOTO

In consideringthe conditionsmost favorablefor FeSa+ 3/2H + + HaO •

creatinghigh ore gradesit is importantto identify
not only the chemicalconditionsmostconduciveto Fe+a+ 7/4H2S+ 1/4SO•a, (25)
the depositionof the greatestmassof metal but also and
thoseconditions that causethe metalto be deposited 1/2AgaS+ H + • Ag+ + 1/2HAS. (26)
within a small volume of rock. In an ascending
hydrothermalsolutionthat is boilingand depositing Equations(21) to (26) are generallyin the order of
mineralsalong its path, the vertical extent of the decreasingtendency to precipitate during boiling.
depositwill be proportionalto the amountof COa The ambiguityof this ordering increasesfrom equa-
exsolvedduring ascentbecauseCO2 exsolutionis a tions(21) to (26) as the net result of the competing
consequence of pressurereductionduringascension, effectsof decreasingproton and HaS concentrations
as well as the chemicaldriving force for the depo- are dependent on the conditions of boiling. For
sition of most minerals(HS--complexedmetalsex- solutionsmeetingthe thresholdconditionsof equa-
cepted).For pressuregradientsthat rangebetween tion (19), the reaction in equation(20) is lesslikely
hydrostaticand lithostatic and CO2 concentrations to cause deposition than any of the reactions in
ranging between several molal and several hun- equations(21) to (26) and is the reason for the
dredths molal, the vertical ascensionrequired to sluggishdepositionaltrend for gold duringthe initial
exsolve99 percent of the CO• (and hencd deposit stagesof boiling in Figures 11a, e, i and 12a, e, i.
mostof the metals)rangesfrom severalmetersto in Of course for solutionsnot increasingpH during
excess of one kilometer in the 150 ø to 350øC boiling,bisulfide-complexed metalsare highly likely
temperaturerange. Hence, the role of COa in form- to precipitate whereas the depositionof chloride-
ing ore by boiling is paradoxicalbecause mineral complexedmetalsis precluded.Changesin the log
deposition,but not necessarilyhigh ore grade, is of the HaS concentrationduring the initial stagesof
favoredby solutionswith the highestCOa concen- boiling vary between one-third and two-thirds of
trations. the changein the log of the proton concentration.
This variability can causethe rate of changein the
Mineral paragenesis degree of saturationof either pyrite or argentireto
be greatest.
Unlike saturatedsolutions,which candepositone
In the latter stagesof boiling it is common for
or more mineralsof eachmetal simultaneously from
the [H+] to be sufficiently low such that [HS-]
the inception of boiling, undersaturatedsolutions
> /HaSI. In these casesthe equilibria in equations
commence the precipitationof mineralssequentially.
The sequenceof mineral depositiondependson the (20) to (26) are more appropriatelyexpressedin
terms of HS-. Under these conditions, because HS-
relative rates of reduction in the extent of undersat-
is nonvolatile, E[sulfidel reduction due to HaS dis-
uration as boiling proceedsand is such that the
solution is far less than when HaS is the dominant
metalswith the largest negative slopesin Figures
sulfide species.As a consequence,boiling rarely
10 and 11 are depositedfirst. The corresponding
paragenetic sequencesof minerals deposited are
decreasesE lsulfidelmore than two orders of mag-
summarized in Table 1. nitude in solutionsmeetingthe thresholdconditions
of equation(19) for pH increases.
The shapesof the differentpercentboiling-metal
In Figures 11 and 12 and Table 1 there are
concentration curves in Figures 10 and 11 are
several casesof magnetite deposition preempting
controlledby the changesin solutionchemistry
duringboilingandthe stoichiometry of the solubility chalcopyrite depositionby scavengingiron from
equationsfor the respectiveminerals.The equilibria solution(e.g., d, h, 1 in Figs. 11 and 12). In other
casesthere is insufficientiron in solutionto deposit
pertinent to the metals in Figures 11 to 13 and to
metalswith mineralsof similarstoichiometryare: significantamountsof copperaseither chalcopyrite
or bornitc even though they are the most stable
copper minerals.The net result in many instances
1/3FeaO4+ 11/6H + + 1/12HAS • is that copper depositionby boiling can occur only
Fe+a+ 1/12SO•a + HaO, (21) when there is sufficientiron, and when magnetite
or pyrrhotiteare not stable,asboth of theseminerals
ZnS+ 2H+ • Zn+a+ HaS, (22) are depositedmore vigorouslythan chalcopyrite.
Accordingto the abovediscussion, if FeaO4, FeS,
Auø + 5/4H + + 1/8SO•a ,• ZnS,Auø, Agø, CuFeSa,FeSa,andAgaSare equally
Au+ + 1/SIlaS + 1/2HaO, (23) undersaturatedprior to boiling, the mineral para-
genesisproducedby boiling a solutionmeetingthe
1/2CuFeSa+ 11/SH+ + 1/4HaO • 1/2Cu+ threshold conditions of equation (19) would be
Fe304 • ZnS • Agø + Auø (if chloride com-
+ 1/2Fe+a+ 15/16HAS+ 1/16SO•a, (24) plexed) • CuFeSa (if Y,Cu > EFe) -• Auø (if
 BOILING HYDROTHERMALSYSTEMS 145

bisulfidecomplexed).Note that FeS,FeS2,andAg2S about 10 times more silica with the same amount of
can be depositedby boiling only if they are more ore metals.
stable than Fe304 and Agø, respectively, in the For solutions that meet the threshold criteria
initial solution.Statedsomewhatdifferently,boiling cited above, the tendency of calcite to deposit
will never causedepositionof a metal sulfide after duringboilingvirtually parallelsthe proton concen-
depositionof an oxide or native metal of the same tration trend in the early stages.In thesecalculations
metal. The subordinate role of sulfides, relative to it is not uncommonfor boiling to remove several
oxides and native metals, is not the only reason hundredppm Ca ascalcitewithin the spanof a few
somesulfidesare unlikely to be depositedafter the percentboiling.The depositionalpatternsfor car-
initial stagesof boiling. Sulfideslike AgeS, FeS2, bonates,oxides,sulfides,and nativemetalsare very
and CuFeS•, where the stoicbiometricsof the solu- similar,all being primarily dependenton decreases
bility equations(eqs. 26, 25, 24, respectively)are in the proton concentrationand strongestin the
suchthat the value of the coefficientfor the protons early stagesof boiling.This suggests that calcitewill
minus half the coefficient for H•S is less than about be an abundantganguemineral in many mineral
one• can only be deposited early in the boiling depositsderivedby boilingwhenthe initial solutions
process.It is only in this early stagethat the driving are within 1 to 2 log units of calcite saturation
force for deposition(Figs. 9 and 10) is sufficientto (Table 1). In general,calcite will be contempora-
override the concomitanteffect of H2S loss. Conse- neous with the bulk of the oxides, sulfides, and
quently,depositionof thesesulfidesis possibleonly native metalsif the initial solutionis within one log
if the initial solutionis near saturationwith respect unit of calcite saturation and will occur after these
to these phases, if the metal sulfide is the most ore mineralsif depositedfrom less saturatedsolu-
stablephaseof the metal,and only in the beginning tions.
of the boiling process.Sphalerite(and galena)de- Accordingto the model, anhydrite, and sulfates
positionis less subject to these limitations,and is in general,will not be commondepositional products
possiblebeyondthe early stagesof boiling, partic- of boiling. For the temperatures and com-
ularly when [HS-] > [H•S] suchthat the reduction positions of most hydrothermal solutions the
in E[sulfide] due to H2S exsolution is diminished. HSO•/SO•2 equilibriumlies in or near the SOj2
Open boiling is more dynamicthan closedboiling dominantfield. Under these conditionsboiling can
and accordinglyis associated with more phasetran- have only a minimaleffect on the stabilityof sulfate
sitions and a more complex mineral paragenesis minerals. In relatively dilute and slightly acidic
(Table 1). solutionsabove about 250øC HSO• is the dominant
form of sulfate. For these limited eases the decrease
Ganguedeposition in proton concentrationassociated
with boiling can
generate significantamountsof SO•• and cause
Quartz, calcite, and anhydrite are perhaps the sulfate mineralsto deposit. As a result, sulfate de-
three most prevalent primary gangue phases in positionis not necessarilylimited to the early stages
hydrothermalore deposits.As silicaoccurspredom- of boiling but may occur whenever the proton
inantlyassilicicacidin mosthydrothermalsolutions, concentrationis decreasing.
the effect of boiling on silica depositionis quite
simple.Assumingthat there are no kinetic barriers Summary
to precipitation and that the initial solution is satu-
The principlesoutlinedin thispaperare applicable
rated with respect to quartz, the amount of silica
to the many different types of hydrothermal ore-
depositedby isothermal boilingis simplythe product
forming and geothermalsystemsthat boil. A com-
of the saturationsolubilityand the fractionof water
plete discussionof any one of these systemsis
removed.Hence,the behaviorof silicaduringboiling
beyondthe practicalrangehere and mustbe left to
differsmarkedlyfrom that of the ore mineralswhich
subsequentpapers.However, severalof the more
are largelydepositedin the firstfew percentboiling generallyusefulresultsof this studyare summarized
at 300øC andbelowandin the first 10 to 20 percent below:
boiling at higher temperatures.This indicatesthat
duringthe early and mostactivestageof ore depo- 1. For the purposesof modeling the chemical
sition only a fraction of the total silica in solution changesof a boiling hydrothermalsolution,several
can be deposited. The resulting weight ratio of physicaland chemicalconditionsmust be defined:
quartz/metals in the ore horizon would increase heat budget, physicalconstraintson vaporization;
with decreasingtemperaturefrom about 1 at 350øC controlling redox equilibria, constraintson mass
where the ratio of metal/silicain a saturatedsolution transferbetween the liquid and solid phases,and
is greatest,to about 30 at 200øC. In this respect, the intensivepropertiesof the system.
below 300øC, the boiling depositionalmechanism 2. The most significanteffect of boiling on the
isclearlydifferentfromcooling,whichwoulddeposit chemistryof a hydrothermalsolutionis associated
146 S. E. DRUMMOND AND H. OHMOTO
with the exsolutionof CO2 and H2S. COe exsolution sulfates(e.g.,CaSO4,BaSO4).Thisis alsothe general
causesdramaticchangesin pH while HeS exsolution order of first to last in a depositionalsequencefrom
destabilizessulfidesandperturbsthe oxidationstate. a boilingsolutionthat is equallyundersaturated
3. Typicallythe mostsignificantchemicalchanges
(e.g.,pH, fo•, Y,COe, Y,HeS,etc.) in the liquid phase
occurby the time the vapor phasehasexpandedto
a volume equal to the liquid. This occursat about
1, 2, 5, and 10 percentboilingat 200 ø, 250 ø, 300 ø,
and 350øC, respectively.
4. Within the confinesof the amountof vapori-
zationthat is both chemicallysignificantand physi-
cally reasonable,isoenthalpiccooling has a minor
effecton chemicalevolutionand mineraldeposition
below about 300øC.
5. Open boiling systemsexsolvegasesmore effi-
ciently than closed systems, resulting in larger
chemicalchangesand more effectivemineral depo-
sition in open systems.
6. For a given amount of water vaporization,
considerablymore gasis partitioned into the vapor
phase at the lower temperatures. This effect is
reflectedin the relatively sluggishdecreasesin the
concentrationsof metals and protons in high-tem-
perature boiling solutions.
7. The net effect of higher mineral solubilitiesat
elevatedtemperatures,and more vigorousdecreases
in these solubilities at lower temperatures, is that
saturatedboiling solutionswith initial temperatures
around 300øC deposit the greatest mass of most
types of ore minerals. Solutionswith the highest
initial CO2 concentrationwill tend to deposit these
ore mineralsover the greatestvertical distance.
8. The chemicalconditionspermitting apprecia-
ble changesin the proton concentration(i.e., thresh-
old conditions)upon devolatilizationof a hydrother-
mal solutionare largely definedby a few equilibria
in the H20-CO•-SO4-NaC1 system. Solutionswith
the highest[COe]/IH+l and IcOel/Y,IS04] ratiosbe-
fore boilingwill decrease[H+] mostmarkedlyduring
boiling.
9. The range of chemicalconditionsamenableto
significantprotonconcentration changesuponboiling
are more restricted at high temperatures and low
ionic strengths.
10. Generally, conditionsamenableto decreased
proton concentrationsin solutionduring boiling are
synonymouswith conditionsthat are favorable for
mineral deposition.Bisulfide-complexedmetals are
an exceptionto this rule.
11. Listed in the order of mostto least likely to
depositfromboilinghydrothermalsolutionsmeeting
the thresholdcriteria for pH increases,the sequence
is: oxides(e.g., Fe304, SnO•), simple metal sulfides
(e.g., ZnS, AgS), native metals(chloridescomplexed,
e.g., Agø andAuø), carbonates(e.g., CaCO3),sulfides
with intermediate sulfur valence (e.g., CuFeS2,
FeS•), sulfidesof the Me•S class(e.g., AgeS,Cu•S),
native metals (bisulfidecomplexed,e.g., Auø), and
with
the mineralsbefore boiling.
12. Carbonatesand quartz are likely to be the
preponderant ganguemineralsassociatedwith boil-
ing-derivedores.Boilingnaturallyproducesa greater
ratio of ore minerals to silica than most other de-
positionalmechanisms.
Conclusions
Given the proper circumstances, boiling can be a
very powerful depositionalmechanism.These cir-
cumstances are commonbut not universalin hydro-
thermal systems.Distinctionsbetween boiling and
other ore depositionalmechanismsare possibleon
the basisof severallines of physicaland chemical
evidence.Now that the systematicsof the boiling
processare defined and the effectson mineral pre-
cipitation are well understood,a rigorousanalysis
canandshouldbe madeof eachtype of hydrothermal
systempurported to have depositedminerals as a
consequenceof boiling. It is certain that the mineral
zoning and paragenesis,the amountsof metals de-
posited, and the physical and chemical constraints
on the systemwill be compatiblewith the charac-
teristicsof the boiling depositionalmechanismfor
many systemsand incongruousfor others.
Acknowledgments
This studybenefitedgreatlyfrom discussions with
D. R. Cole and D. Wesolowskiduringthe formative
stagesof the original manuscriptand from their
perceptive review of later drafts. The research for
this paper was supportedby the National Science
Foundation under the geochemistry program at
PennsylvaniaState University through grant EAR-
76-03724, under the petrology program through
grant EAR-80-07839, as well as by the Division of
Engineering,Mathematicaland Geosciences,Office
of Basic Energy Sciences, U.S. Department of
Energy, under contract DE-AC05-840R21400 with
the Martin Marietta Energy Systems,Inc.
November2, 1983; June 26, 1984
REFERENCES
Barnes, H. L., 1979, Solubilities of ore minerals, in Barnes,
H. L., ed., Geochemistryof hydrothermal ore deposits:New
York, John Wiley and Sons,p. 404-460.
Barton, P. B., Bethke, P.M., and Roedder, E., 1977, Environment
of ore deposition in the Creede mining district, San Juan
Mountains, Colorado: Pt. III. Progresstoward interpretation
of the chemistry of the ore-forming fluid for the OH vein:
ECON. GEOL., v. 72, p. 1-24.
Blount, C. W., and Dickson, F. W., 1969, The solubility of
anhydrite(CaSO•) in NaCI-H•O from 100 to 450øC: Geochim.
et Cosmochim.Acta, v. 33, p. 227-245.
Bourcier, W. L., 1983, Stabilities of chloride and bisulfide
complexesof zinc in hydrothermalsolutions:Unpub. Ph.D.
thesis,The PennsylvaniaState Univ., 179 p.
 BOILING HYDROTHERMAL SYSTEMS 147

Busey,R. H., and Mesmer, R. E., 1976, The ionizationof water -- 1983, Thermodynamicpropertiesof aqueoussolutionsof
in NaC1 media to 300øC: Jour. Solution Chemistry, v. 5, p. the alkali metal chlorides to 250øC: Jour. Phys. Chemistry,
147-152. v. 87, p. 1242.
1978, Thermodynamicquantities for the ionization of Holmes, H. F., Baes, C. F., and Mesmer, R. E., 1978, Isopiestic
water in sodium chloride media to 300øC: Jour. Chem. Eng. studiesof aqueoussolutionsat elevatedtemperatures.I. KCI,
Data, v. 23, p. 175-176. CaCI•, MgC12:Jour. Chem. Thermodynamics,v. 10, p. 983-
Casadevall,T., and Ohmoto, H., 1977, Sunnysidemine, Eureka 996.
mining district, SanJuanCounty, Colorado:Geochemistryof -- 1979, Isopiesticstudiesof aqueoussolutionsat elevated
gold and basemetal ore depositionin a volcanicenvironment: temperatures.II. NaC1 + KC1 mixtures:Jour. Chem. Ther-
ECON. GEOL., v. 72, p. 1285-1320. modynamics,v. 11, p. 1035-1050.
Cathies, L. M., 1981, Fluid flow and genesisof hydrothermal Kamilli,R. J., and Ohmoto,H., 1977, Paragenesis,
zoning,fluid
ore deposits:ECON. GEOL. 75th ANNIV. VOL., p. 424-457. inclusion,and isotopicstudiesof the Finlandia vein, Colqui
Chen, C. T., and Marshall, W. L., 1982, Amorphous silica district, central Peru: ECON. GEOL., v. 72, p. 950-982.
solubilitiesIV. Behavior in pure water and aqueoussodium Kelly, W. C., andTurneaure,F. S., 1970, Mineralogy,paragenesis
chloride, sodiumsulfate,magnesiumchloride, and magnesium and geothermometry of the tin and tungstendepositsof the
sulfatesolutionsup to 350øC: Geochim.et Cosmochim.Acta, eastern Andes, Bolivia: ECON. GEOL., v. 65, p. 609-680.
v. 46, p. 279-287. Marshall, W. L., and Jones,E. V., 1966, Second dissociation
Cole, D. R., Ohmoto, H., and Lasaga, A. C., 1983, Isotopic constantof sulfuric acid solutions:Jour. Phys. Chemistry, v.
exchangein mineral-fluid systems.I. Theoretical evaluation 70, p. 4028-4040.
of oxygenisotopicexchangeaccompanyingsurfacereactions Millero, F. J., 1983, The estimation of the pK•^ of acids in
and diffusion:Geochim. et Cosmochim.Acta, v. 47, p. 1681- seawaterusingthe Pitzer equations:Geochim.et Cosmochim.
1693. Acta, v. 47, p. 2121-2129.
Crerar, D. A., and Barnes, H. L., 1976, Ore solution chemistry Ohmoto,H., and Lasaga,A., 1982, Kineticsof reactionsbetween
V. Solubilitiesof chalcopyrite and chalcocite assemblagesin aqueoussulfatesand sulfidesin hydrothermalsystems:Geo-
hydrothermal solution at 200 ø to 350øC: ECON. GEOL., v. chim. et Cosmochim. Acta, v. 46, p. 1727-1745.
71, p. 772-794. Patterson, C. S., Slocum, G. H., Busey, R. H., and Mesmer,
Crerar, D. A., Susak, H. J., Borcsik, M., and Schwartz, S., R. E., 1982, Carbonate equilibria in hydrothermal systems:
1978, Solubilityof the buffer assemblage pyrite + pyrrhotite First ionization of carbonic acid in NaC1 media to 300øC:
+ magnetitein NaC1solutionsfrom 200 ø to 300øC: Geochim. Geochim. et Cosmochim. Acta, v. 46, p. 1653-1663.
et Cosmochim. Acta, v. 42, p. 1427-1439. Pitzer, K. S., Peiper, J. C., and Busey,R. H., 1984, Thermody-
Cunningham,C. G., 1978, Pressuregradients and boiling as namicpropertiesof aqueoussodiumchloridesolutions:Jour.
mechanismsfor localizing ore in porphyry systems:U.S. Phys.Chemistry,Ref. Data, v. 13, p. 1-102.
Geol. Survey Jour. Research, v. 6, p. 745-754. Rayleigh, O. M., F. R. S., 1902, On the distillation of binary
Drummond, S. E., 1981, Boiling and mixing of hydrothermal mixtures:Phil. Mag., 6th ser., v. IV, p. 521-537.
fluids: Chemical effects on mineral precipitation: Unpub. Robinson,C. S., and Gilliland, E. R., 1950, Elements of fractional
Ph.D. thesis,The PennsylvaniaState Univ., 380 p. distillation: New York, McGraw-Hill, 492 p.
Ellis, A. J., 1963, The solubility of calcite in sodium chloride Roedder,E., 1968-1979, Fluid InclusionResearch,Proceedings
solutionsat high temperatures: Am. Jour. Sci., v. 261,, p. of COFFI, v. 1-12: Ann Arbor, Univ. Michigan Press.
259-267. Sackett,W. M., and Chung, H. M., 1979, Experimentalconfir-
Ellis, A. J., and Fyfe, W. S., 1957, Hydrothermal chemistry: mation of the lack of carbon isotope exchange between
Rev. Pure Appl. Chemistry (Austria), v. 7, p. 261-316. methane and carbon oxides at high temperatures:Geochim.
Ellis, A. J., 1979, Explored geothermal systems,in Barnes, et Cosmochim.Acta, v. 43, p. 273-276.
H. L., ed., Geochemistryof hydrothermal ore deposits:New Seward, T. M., 1973, Thiocomplexesof gold and the transport
York, JohnWiley and Sons,p. 632-683. of goldin hydrothermalore solutions:
Geochim.et Cosmochim.
Haas, J. L., 1976, Physicalproperties of the coexistingphases Acta, v. 37, p. 379-399.
and thermochemical properties of the H20 component in 1976, The stability of chloride complexes of silver in
boiling NaC1 solutions:U.S. Geol. Survey Bull. 1421-A, hydrothermalsolutionsup to 350øC: Geochim.et Cosmochim.
73 p. Acta, v. 40, p. 1329-1341.
Hanor, J. S., 1979, The sedimentarygenesisof hydrothermal Slack,J. F., 1980, Multistagevein oresof the Lake City district,
fluids, in Barnes, H. L., ed., Geochemistry of hydrothermal western San Juan Mountains, Colorado: ECON. GEOL., v. 75,
ore deposits:New York, JohnWiley and Sons,p. 137-172. p. 963-991.
Harting, P., and Maass,I., 1980, Neue Ergebnissezum Kohlen- Toulmin, P., and Clark, S. P., 1967, Thermal aspects of ore
stoff Isotopenaustausch im System CH4-CO2: Isotop in der
formation,in Barnes,H. L., ed., Geochemistryof hydrothermal
Natur Conference,2nd, Leipzig, November 1979, v. 2b, p.
13-14.
ore deposits:New York, JohnWiley and Sons,p. 437-464.
Harvie, C. S., Muller, N., and Weare, J. H., 1983, The prediction Walshe, J. L., and Solomon,M., 1981, An investigationinto the
of mineral solubilities in natural waters: The Na-K-Mg-Ca- environment of formation of the volcanic-hostedMt. Lyell
H-CI-SO4-OH-HCOa-COa-CO•-H•O systems to high ionic copper depositsusing geology, mineralogy, stable isotopes,
strengthsat 25øC: Geochim. et Cosmochim.Acta, v. 48, p. and a six-component chlorite solid solution model: ECON.
723-751. GEOL., v. 76, p. 246-284.
Helgeson,H. C., 1969, Thermodynamics of hydrothermalsystems Weissberg,B. G., Browne, P. R. L., and Seward, T. M., 1979,
at elevated temperatures and pressures:Am. Jour. Sci., v. Ore metals in active geothermal systems,in Barnes, H. L.,
267, p. 729-804. ed., Geochemistryof hydrothermal ore deposits:New York,
Henley, R. W., 1973, Solubilityof goldin hydrothermalchloride JohnWiley and Sons,p. 738-780.
solutions:Chem. Geology, v. 11, p. 73-87. Ziegenbein, D., and Johannes,W., 1980, Graphite in C-H-O
Holmes, H. F., and Mesmer, R. E., 1981, Isopiestic studiesof fluids:An unsuitablecompoundto buffer fluid compositionat
aqueoussolutionsat elevatedtemperatures.III. ((1 - y)NaC1 temperaturesup to 700øC: NeuesJahrb.MineralogieMonatsh.,
+ CaCI•): Jour.Chem.Thermodynamics, v. 13, p. 101-113. v. 7, p. 283-305.