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Boiling Hydrothermal Systems: Chemical Evolution and Mineral 'Deposition in
Boiling Hydrothermal Systems: Chemical Evolution and Mineral 'Deposition in
AND H. OHMOTO
Departmentof Geosciences,
The PennsylvaniaStateUniversity,UniversityPark, Pennsylvania16802
Abstract
0361-0128•85•381/126-2252.50 126
BOILING HYDROTHERMAL SYSTEMS 127
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
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
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
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
-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
-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.
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
[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"/
./,';'.. --
-8
solutions with 10 -3 m Ca. When all of these restric-
tionsare consideredtogether,the rangeof chemical ISOENTHALPICT,-=20_•0øC-•
- '-""""--""' --"--
-
conditionsconduciveto increasedpH duringboiling -7
C1, CO2, SO4, and H2S, metals) boiling systems. FIC. 10. Percent boiling/IH+] paths for open and closed
Figures 9 and 10 help illustrate the influence of isoenthalpic boiling solutions with the initial composition as
temperature, heat budget, and physicalconstraints given for Figure 9. Temperaturesprior to boiling are indicated.
on typicalpH-boilingpaths.Severalsignificanttrends
are obviousin these figures,but perhapsthe most
notableone is the abrupt pH increasein the initial Qw/Q systematically decreases with decreasingtem-
stageof boiling followed by smalleror negligible perature. Even though the 200 ø, 250 ø, and 300øC
changes.Initially [H+] respondsrapidly to COe exso- isoenthalpicboiling solutionscool by 140ø, 130ø,
lution such that there is essentiallya one to one and 110øC, respectively,in the first 25 percent
relationshipbetween [H+] and [COe] for solutions boiling, heat budgeteffectson the pH-boilingpaths
with excessbase. However, after either [COe] or are relatively minor. The general tendencyis for
[HCO•] becomeslessthan [OH-], [H+] is buffered larger pH increasesin isoenthalpicsystemssince
more by the dissociationof water than by the the volatility ratio and liquid to vapor partitioning
carbonateequilibria,with the net result being that of COe increaseswith decreasingtemperature.This
the [H+] decreases at a continuallydiminishingrate. effect is mostapparentfor closedand high-temper-
These trends are most exaggeratedfor both open ature systemswhere the solutionscool appreciably
and low-temperaturesolutionsand resultsfrom the before most of the COe is exsolved.
rapid separationof COe from these solutionsin the It is clear that dramaticchangesare possiblewhen
initial stagesof boiling (Figs. 3 and 4). This pH- a hydrothermalsolutionlosesonly a few percent of
increasingmechanism is moreprotractedandgradual its massto the vaporphaseby boiling.The conditions
for closedand high-temperaturesystems.Increases that are conduciveto thesechangesand the magni-
in pH are summarilylarger for openboilingsystems tude of thesechangesare definedabove.Resultsof
reflectingthe lower ultimate CO2 concentrationin this analysisare very usefulin determiningthe role
an open boiling system.Low-temperaturesolutions of the boiling processas a mechanismfor mineral-
undergo the greatestpH increasesfor both open ization in the complex hydrothermal systemsthat
and closedsystems.This sametendencyis illustrated form ore deposits.Consequently,the discussion will
in Figure 6 and predicted by equation (17) since be directed toward that ultimate goal.
Mineral Depositionfrom Boiling
-8
I I I I
Hydrothermal Solutions
ISOTHERMAL 200øC • • • General discussion
ß-.-"- • 250
-7 The efficiencyof a mineralizing processis indi-
/ 300 catedmostdirectly by monitoringthe changein the
metal concentrationsas the processproceeds.For
250 _
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
-4
0 systems. Represented withinthisgroupof five metals
% BOLLING are the mostimportantmetaloxidationstates,mineral
groups,and aqueouscomplexesof ore components.
FIG. 9. Percent boiling/IH+] paths for open and closed
isothermalboiling solutionswith initial molalitiesof H + = ]0 -4 s
Under the conditions considered here, silver is
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-". (Seward,1976) and is depositedas either the metal
BOILING HYDROTHERMALSYSTEMS 139
+H]6Ol
I I
(todd) õOl
(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 boiling is insignificantsince most of the metal is
Figures 11 and 12 result from similar changesin depositedin the initial stagesof boiling before the
IH+], mineralphasetransitions(Table 1), or in the solutioncoolsmore than a few degrees.Increased
caseof gold,a changebetweenbisulfideandchloride salinityis associated
with lessseverelimits(asdefined
complexing.Modelingresultsfor isoenthalpic boiling in eqs. 13, 17, and 19 above) on the threshold
or for solutionswith ionic strengthsother than I m concentrationsof CO2, ZSO4, and H + in the initial
resemblethose shownin Figures 11 and 12. The solution(Fig. 7) and therefore enhancesthe depo-
similaritiesin the pH-boiling trends between iso- sitionof mostmetalsduringboiling.Salinityeffects
thermal and enthalpicboiling (e.g., Figs. 8 and 9) are otherwiserelatively minor and predictablefrom
indicate that the most important differencesin the Figures 3, 4, and 6.
percentboiling-metalconcentrationpathsbetween Decreases in metal and proton concentrations
isothermaland isoenthalpicboilingare not associated range from severalorders of magnitudein the first
with [H+] trendsbut are attributableto the generally one percent vaporizationfor low-temperature,high
lower solubilitiesof chloride-complexedmetals at ZCO2, low ZSO4, open systemsto lessthan a tenth
lower temperatures.This cooling effect generally of a log unit after 50 percent boiling in high-
resultsin morenegativeslopesin the percentboiling- temperature,low ZCO2, high ZSO4 closedsystems.
metal concentration curves and somewhat more ef- For any given condition, the concentrationof each
fective mineral depositionthan is shownin Figures metal hasa characteristicresponseto boiling that is
11 and 12. This is particularlytrue for high-temper- dictatedby the stabilitiesand stoichiometriesof the
ature solutionsthat depositmetal sluggishlyduring mineralsand aqueouscomplexesof each metal. Just
isothermalboiling. In most caseswhere isothermal as H2S lossduring boiling destabilizessulfides,the
boilingis effectivein depositingmetalfromsolution, associated oxidation stabilizes oxides, destabilizes
the effect of coolingon metal depositionduring native metals, and dependingon the oxidationstate
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
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
with
3. Typicallythe mostsignificantchemicalchanges the mineralsbefore boiling.
(e.g.,pH, fo•, Y,COe, Y,HeS,etc.) in the liquid phase 12. Carbonatesand quartz are likely to be the
occurby the time the vapor phasehasexpandedto preponderant ganguemineralsassociatedwith boil-
a volume equal to the liquid. This occursat about ing-derivedores.Boilingnaturallyproducesa greater
1, 2, 5, and 10 percentboilingat 200 ø, 250 ø, 300 ø, ratio of ore minerals to silica than most other de-
and 350øC, respectively. positionalmechanisms.
4. Within the confinesof the amountof vapori- Conclusions
zationthat is both chemicallysignificantand physi-
cally reasonable,isoenthalpiccooling has a minor Given the proper circumstances, boiling can be a
effecton chemicalevolutionand mineraldeposition very powerful depositionalmechanism.These cir-
below about 300øC. cumstances are commonbut not universalin hydro-
5. Open boiling systemsexsolvegasesmore effi- thermal systems.Distinctionsbetween boiling and
ciently than closed systems, resulting in larger other ore depositionalmechanismsare possibleon
chemicalchangesand more effectivemineral depo- the basisof severallines of physicaland chemical
sition in open systems. evidence.Now that the systematicsof the boiling
6. For a given amount of water vaporization, processare defined and the effectson mineral pre-
considerablymore gasis partitioned into the vapor cipitation are well understood,a rigorousanalysis
phase at the lower temperatures. This effect is canandshouldbe madeof eachtype of hydrothermal
reflectedin the relatively sluggishdecreasesin the systempurported to have depositedminerals as a
concentrationsof metals and protons in high-tem- consequenceof boiling. It is certain that the mineral
perature boiling solutions. zoning and paragenesis,the amountsof metals de-
7. The net effect of higher mineral solubilitiesat posited, and the physical and chemical constraints
elevatedtemperatures,and more vigorousdecreases on the systemwill be compatiblewith the charac-
in these solubilities at lower temperatures, is that teristicsof the boiling depositionalmechanismfor
saturatedboiling solutionswith initial temperatures many systemsand incongruousfor others.
around 300øC deposit the greatest mass of most
types of ore minerals. Solutionswith the highest Acknowledgments
initial CO2 concentrationwill tend to deposit these This studybenefitedgreatlyfrom discussions with
ore mineralsover the greatestvertical distance. D. R. Cole and D. Wesolowskiduringthe formative
8. The chemicalconditionspermitting apprecia- stagesof the original manuscriptand from their
ble changesin the proton concentration(i.e., thresh- perceptive review of later drafts. The research for
old conditions)upon devolatilizationof a hydrother- this paper was supportedby the National Science
mal solutionare largely definedby a few equilibria Foundation under the geochemistry program at
in the H20-CO•-SO4-NaC1 system. Solutionswith PennsylvaniaState University through grant EAR-
the highest[COe]/IH+l and IcOel/Y,IS04] ratiosbe- 76-03724, under the petrology program through
fore boilingwill decrease[H+] mostmarkedlyduring grant EAR-80-07839, as well as by the Division of
boiling. Engineering,Mathematicaland Geosciences,Office
9. The range of chemicalconditionsamenableto of Basic Energy Sciences, U.S. Department of
significantprotonconcentration changesuponboiling Energy, under contract DE-AC05-840R21400 with
are more restricted at high temperatures and low the Martin Marietta Energy Systems,Inc.
ionic strengths.
10. Generally, conditionsamenableto decreased November2, 1983; June 26, 1984
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