SN W Heinrich

Economic Geology Vol. 85, 1990, pp.
457-481
The Chemistry of Hydrothermal Tin(-Tungsten)Ore Deposition

CHRISTOPH A. HEINRICH
Bureauof Mineral Resources, Geologyand Geophysics, Divisionof Petrology and Geochemistry,

P.O. Box 378, Canberra, A.C.T. 2601, Australia
Abstract
A qualitative modelfor the formation of granite-related mesothermal cassiterite(-wolframite) deposits is derivedfrom a review of geologic evidence andis then testedquantitatively with chemical mass transfercalculations basedon published experimental andthermodynamic data. Laboratory experiments and geologic, mineralogic, fluid inclusion, andstableisotopeobservations indicatethat salinefluidsof magmatic originare involvedin the formation of most tin oresthat occurin veins,breccias, andreplacement bodies of aluminosilicate or carbonate rocks.Transportof the ore fluid from a hot graniticsource into a coolerdepositional environmentprobablyinvolves structural focusing andprevention of completechemical reequilibrationof the fluidwith freshquartzofeldspathic wall rocks. Undertheseconditions, a reduced acidfluid cantransport highconcentrations of Sn(II)-C1 complexes (hundreds of ppmmetal) to a siteof ore deposition at low temperature. Precipitation of cassiterite, Sn(IV)O2,requires oxidationand liberatesacidity, which must be balancedby reductionand acid-consuming reactions involving otherfluidandwall-rock components for cassiterite enrichment to proceed to economicconcentrations. Severalgeologically likely depositionmechanisms have been tested, which differ in efficiencyregardingthe maximumtin ore grade that can be achieved in aluminosilicate hostrocks. By contrast, wolframitecanbe precipitated by cooling of anFeW-bearing fluid without wall-rockreaction. Single-step acidneutralization of magmatic fluidsby feldspar hydrolysis to sheetsilicates (phyllicalteration) probably produces subeconomic greisen mineralization, because the maximum tin ore gradeis severelyconstrained by the high acidcontentof the fluid. Progressive fluid-rockreactionand multistage ore reworkingat an advancing alterationfront, described by a one-dimensional finite-element reactormodelassuming localequilibrium, maybe a more efficientandgeologically realistic process to form tin-richgreisens andbrecciapipes.Lossof H2 froma reduced tin-richfluidby vaporseparation, andsimultaneous reaction with aluminosilicate rocks, isanalternative possibility for the formation of rich greisen-type deposits. Fluid mixingby injectionof minormagmatic fluidinto a coolerenvironment of convecting meteoric fluidscould be a third, particularlyefficient,tin-mineralizing mechanism in vein deposits without extensive wall-rockinteraction.In this caseand in the deposition of cassiterite by carbonate replacement, there are essentially no chemical limitations on tin ore grade,other than dilutionof cassiterite by coprecipitating quartz and sulfides.
Introduction
Bolivia, Sillitoe et al., 1975; Franciset al., 1981), but
A LARGE numberof detailedgeologic,mineralogic, fluid inclusion,and stable isotope studiesof tin(_ tungsten) ore deposits havebeen published in the lasttwo decades (Kelly andTurneaure, 1970; Landis andRye, 1974; Jackson et al., 1977, 1982; Charoy, 1979; Kelly andRye, 1979; Collins,1981; Patterson et al., 1981; Eadington,1983; AndrewandHeinrich, 1984; Campbellet al., 1984; Eadington andPaterson, 1984; Higgins, 1985; Andrew et al., 1986; Ren and
Walshe, 1986; Solomon et al., 1986; Witt, 1988;
the majorityof largetin mines hostcassiterite in veins, breccias,and replacement bodiesformed in moderately shallow plutonicenvironments (seereviewsby Taylor, 1979; Heinrich andEadington,1986; Kwak,
1987; Plimer, 1987; Heinrich et al., 1989; Solomon et al., 1991).
Schwartz andAskury,1989; andothers). Thesedocumenta bewildering rangeof geochemical properties and structural settings but alsopoint out a surprising
number of common features, above all their intimate
association with differentiated felsicmagmatites. Tin

depositsoccur in volcanic and shallow subvolcanic settings(e.g., in Mexico, Huspeni et al., 1984; and
0361-0128/90/1053/457-2553.00
Geochemical aspects of granite-relatedore formationhaverecently beendiscussed by Burnham and Ohmoto(1980), Eugster(1985), EugsterandWilson (1985), andCandela(1990a, b), with the mainfocus on chemicalmechanisms responsible for the generation of metal-richfluidsin magmatic environments at high temperature.Lessquantitativestudieshave focused onmechanisms of cassiterite precipitation and tin enrichmentto form a primary hydrothermal tin or tungstendeposit.The presentpaper attemptsto show,on the basisof publishedexperimental thermodynamic dataandmass balance considerations, that
457
458
the chemistry of cassiteriteprecipitation severely magnetite asthe mainopaque Fe-Ti phase, withfo2 constrains possibilities of forminga tin depositwith below Ni-NiO (NNO) andgenerallynearthe quartzeconomicore grade. fayalite-magnetite(QFM) buffer (Ishihara, 1977;
Based on a review of what are believed to be the
Burnham and Ohmoto, 1980; Shimazaki, 1980;
mostcrucialgeologicobservations common to many Wones, 1981). This may reflect an originof the grantin(___ tungsten) deposits,a number of geologically itesfrom meltingof crustal sources including pelitic reasonable mechanisms of cassiterite and wolframite metasediments which commonly contain organic (for example, Jackson et al., deposition will be testedwith chemical mass transfer matter.Manytin granites calculations, usinga set of thermodynamic data de- 1982; Eugster, 1985; Schwartzand Askury, 1989) of S-typegranitoids in the clasrived from recent experimental studies. The numer- showcharacteristics of ChappellandWhite (1974). MostAusical experiments were designed with the basicidea sification that, amonga range of equally likely geologicpro- tralian examples showmixed S and I characteristics granitoids (Solomon cesses, thoseallowing the highest degrees of chemical but are invariablyilmeniteseries enrichmentof cassiterite in a given mass of rock (i.e., et al., 1991). maximum tin ore grade)canbe predictedasthe most Tin granitesare 2 to 20 (rarely up to 100) times with ordinarygranites, due likely processes to form an economicore deposit enrichedin Sncompared fractionation from sourcemagmas that (as opposedto a subeconomic tin anomaly). For to magmatic this modeling,the softwarepackageCSIRO-SGTE areat most two- to threefoldenriched compared with or average crustalabundance (LehTHERMODATA wasapplied(TurnbullandWadsley, ordinarygranites 1986), makinguseof variousoptions that were orig- mann, 1987; Solomonet al., 1991; Table 1). Tin inally designedfor the optimization of industrial chemical processes. The presentstudyhasbeen undertaken as groundworkfor, and at the sametime TABLE1. Compositionand Mineralogy of a Hypothetical Tin
draws observationsand ideas from, a number of onGranite
goingfield studies of Australian tin andtungsten deposits(Andrew and Heinrich, 1984; Solomon et al., 1986; Higgins et al., 1987). Resultsof mass transfermodelingare dependent on the geologicassumptions upon which they are based. Usingthe same experimental dataandthe same modelingcapabilities, any number of computedresuitsmay be obtaineddepending on what set of assumptions is chosen.Errors in the thermodynamic
data used in the calculations will be reflected in the
Average composition
(wt %) basedon typical analyses in

Solomon et al.
Idealized composition R1 used in

calculations of fluid-
(1991)
SiO2 TiOz 75.74 0.06
rock reaction
77.28
A1203
FeO3
FeO MnO
12.87
0.48
0.46 0.02
12.77
0.41
0.73
accuracy of the model predictions. None of the calculations below reflect absolute constraints on the
MgO
CaO
0.03
0.37
formationof tin-tungsten ores,but they shouldhelp to pointoutthe key chemical andphysical parameters that may control ore-formingprocesses. These parameters should serveasusefulguides for determining the essential ingredients of advanced geneticmodels for mineral exploration. The model calculations will also highlight the likely key problems for furthergeologic and experimentalinvestigations into the formation of tin and tungstendeposits.
GeologicProcesses of Sn-W Vein
and Breccia Mineralization
NaO KO
3.54 4.75
3.62 4.86
P205 HO
CO2 SnO
F
O.11 0.27
0.14 0.005
0.45
0.33
Others
(Rb, Li, SrZr)
0.41
The idealized rock composition R1 has been derived by adjustment to the stoichiometric formula Si.868A12 so8+3 +2 Feo.o.5Feo.o.Na.7K o3.Ho..5703o..56, which hasa formulaweight of 1 kg and is consistentwith the following modal mineralogy: Modal mineralogyof
idealized rock R1
Magmaticcharacteristics of sourcegranitoids
Mosttin deposits are associated with highlydifferentiatedbiotite granitesfree of hornblendeor other calcium silicates(amphiboles,pyroxenes,sphene), whoseabsence may be a prerequisite for the enrichmentof Snasanincompatible elementin the residual melt (Ishihara, 1977; Eugster, 1985). They are reduced and typically contain ilmenite rather than
Mineral
mole/kg rock
Vol %
K feldspar KAISiaOs
Albite
Biotite
NaAISiaOs
0.828
1.170
6.262 0.153
0.051
21
30
41 6
2
Quartz SiO= Muscovite KAIaSi30o(OH)=

KFeaAISiaOo(OOH)
HYDROTHERMAL Sn(-W) CHEMISTRY
459
granites are commonlyenriched in F, Li, and/or B, with topaz, fluorite, lepidolite and tourmaline as magmatic or early subsolidus alteration minerals. Fluorine lowers the solidustemperature of granitic meltsto eutectic temperaturesas low as 650C at 2 kbars, with residual melts enriched in albite and H20 relative to the F-free granite minimum (Manning, 1982; cf. Eadington, 1983; Weidner and Martin, 1987). Thesecomponents alsolower the melt viscosity at a giventemperature, whichmaybe instrumental in the physical separation betweenmelt, crystals, and fluids (Dingwell, 1988). Granitoidsassociated with tungsten-onlydeposits are not aswell characterized astin granites. They are generallyI type, encompass a muchwider compositionalrangefrom granodiorite to alkalifeldspar granites, and contain magnetite rather than ilmenite (Newberry and Swanson, 1986; Kwak, 1987).
rangeof silicateandsulfideassemblages (e.g., Collins, 1981; Pattersonet al., 1981; Eadingtonand Kinealy, 1983; Holyland, 1987; Kwak, 1987). Cassiteritein veins is generally precipitatedtogether with quartz and muscoviteor Li micas,frequentlyassociated with F minerals, biotite, chlorite, arsenopyrite, and/or pyrite. In many compositeor crosscutting veins, this early oxide stageis followed by a sulfide stage comprising chalcopyrite, pyrrhotite, sphalerite, galena,stannite,and other sulfides. Chlorite and carbonates are the dominant gangueminerals associated with the sulfidestage.The mineralogy and the widespread occurrence of CH4 in fluid inclusions (below) suggests a relatively reducing depositional
environment in most aluminosilicate-hosted tin de-
posits(Heinrich and Eadington, 1986).
Stableisotopes and fluid inclusions
Alteration,ore mineralogy,and paragenesis Tin andtungstengranitesshowextensiveand commonly pervasive metasomatic alteration (e.g., Shcherba, 1970; LandisandRye, 1974; Pollard,1983; Jackson and Helgeson, 1985b; Stemprok, 1987) whichstarts at hightemperature wheremagmatic and postmagmatic processes arehardlydistinguishable (cf. Burnham andOhmoto,1980). Earlyhigh-temperature stages includefeldspar metasomatism (albitization or replacementby potassicfeldspar), associated with
Combined stableisotope andfluidinclusion studies providethe mainevidence,besides the closegeologic association, for a geneticrelationof hydrothermal Sn oreswith granites. Oxygenisotopes of quartzprecipitated with cassiterite or wolframite are generally consistent with an isotopically heavy fluid that could have originatedfrom a magmatic source(Landisand Rye, 1974; Kelly and Rye, 1979; Collins, 1981; Patterson et al., 1981; Andrew and Heinrich, 1984;
Campbellet al., 1984; Higgins, 1985; Sun and Eadington, 1987). However, oxygenisotopes alonecanmiarolitic veins or as pervasivealteration zonesnear not generallydifferentiate a true magmatic fluid,prothe roof of intrusions. This is followed by pervasive ducedby exsolution of a crystallizing magma,from a or vein-related (and hence clearly subsolidus) alter- fluid of meteoric origin that was equilibratedwith a ation to greisenconsisting dominantlyof muscovite hot but solidgraniteunderrock-dominated conditions + quartz ___ biotite or chlorite ___ topaz ___ fluorite. Ka- (T > 400-500C, fluid/rock ratio < 0.1). olinitc alterationis generallythe latestand occursat Combination with hydrogenisotopicdatacanprolower temperatures. The main alterationtypes and vide a more sensitive tracer for meteoric fluids, but their relationshipare similar to the alkalic, phyllic, only a smallnumberof detailedstudies of deposits at andargillicalterationtypesassociated with porphyry suitably high palcolatitude or palcotopography have copper deposits(Landisand Rye, 1974; Eadington beenpublished (AndrewandHeinrich, 1984; Campand Giblin, 1979; Pollard, 1983). bell et al., 1984, alsoquotingLandisandRye, 1974, Cassiterite and wolframite mineralization in aluand Kelly and Rye, 1979; Sun and Eadington1987). minosilicate host rocks (granites, felsic volcanics, The data for the Mole Granite (New South Wales; quartzofeldspathic metasediments) is mostly asso- Eadington, 1983; Sun and Eadington, 1987) clearly ciated with phyllic alteration. It occursas low-grade indicatedirect input of salinemagmatic fluids into a disseminations in greisenizedgranite and in higher tin-depositinghydrothermal system.All other exlocal concentration within veins and breccias. Alter-
amples havein common a fluid SO signature consistent with a high-temperature magmatic source, but a lineartrendin D extending to lighterthanmagmatic values.Campbellet al. (1984) interpreted this trend as a result of rock-dominated exchange of meteoric fluid with granite at 400 to 600C. However, the ratio of meteoricfluid to rock requiredto explainthe data of Campbell et al. (1984; 0.1-2 wt %) is substantiallylower than the amountof magmaticfluid that is likely to be exsolved during crystallization of a water-saturatedgranite (5-10 wt %; Burnham, 1979). The interpretationof Campbellet al. (1984)
ationin manyrich vein deposits (particularlythe ones hosted by semipelitic hornfelses) isconfined to narrow selvagesof complete replacementof feldsparsby muscovite(Eadington, 1983; Solomonet al., 1986; Andrew and Heinrich, 1984). This, and vein textures indicating repeated overgrowths of hydrothermal mineralson the vein walls, suggests that chemicalinteraction between vein fluids and feldspathicrocks was commonly inhibited by low wall-rock permeability (Heinrich and Eadington, 1986). Carbonate hostrocksare intenselyalteredto skarns, with a wide
460
thusimpliesthat comparatively large amounts of igneous fluidhavebeenlostfromthe system at anearly stage whichisunrelated to the inferredlaterleaching of the granite and formationof the ore veinsby a smalleramountof meteoricfluid.This seems improbable, sincethe data of Campbellet al. (1984) could be explained equallywell by minoradmixture of meteoricwater to a dominantly magmatic fluid, andreequilibrationof the mixture with graniteat 400 to 600C (at higher total fluid/rock ' 0.15). This ex-
tation at 200 to 300C (Heinrich and Eadington, 1986, table 1). Correlations betweenfillingtemperature andtotal salinityare common, suggesting mixingof a magmatic saline fluidwith cooler,lower salinity meteoric waters at the site of ore deposition(Kelly and Rye, 1979; Eadington, 1983; Davis and Williams-Jones, 1985; Witt, 1988). Meteoricfluids increasingly predominate towardthe paragenetically late stages of mineralization (sulfides, carbonates; e.g., Kelly andRye, 1979; planation ispreferred for a similar 3sO/D trendob- Eadington,1983; Witt, 1988). evidence for boiling,or separation servedat the Sundown tin prospect (SE-Queensland; Fluid inclusion AndrewandHeinrich, 1984). Other explanations for of a CO- (CH4-)-rich gasphase,is recordedfrom slightly reduced D values in magmatic fluids aredis- many tin and tungstendeposits(see Heinrich and et al., in press). cussed by Higgins(1986). Irrespectiveof the ambi- Eadington,1986, table 1; Solomon record coexistence of two fluids,a guity regardingultimatesources of H20, the stable Sometin systems brine or saltmelt anda medium-density isotope datafromnearlyall deposits indicate thattin- high-density and tungsten-mineralizing fluidswere equilibrated vapor, already from an early magmaticstage (e.g., isotopically (andprobablychemically aswell) with a Eadington 1983; Solomonet al., 1986). Where sitrapped liquid- and vapor-richincluhot (y400C) granitic sourcerock, prior to their multaneously havebeen studiedquantitatively, they suggest transport into a cooler(400C) ore deposition site. sions of 200 to 600 bars for the ore depoSulfurisotopes of sulfides associated with cassiterite fluid pressures et al., 1986; Eadington andPatdeposits are generallyconsistent with a reducedig- sitionstage(Solomon 1985; Higneous sulfursource (e.g.,Landis andRye, 1974; Kelly erson, 1984; Davis and Williams-Jones, andRye, 1979; Collins,1981;Patterson et al., 1981). gins, 1985; Rambozet al., 1985; Ren and Walshe, are interpreted Some sulfide-richdepositscontain a secondsulfur 1986). Theserelativelylow pressures in studies where independent escomponentcontributedby sedimentary wall rocks asnear-hydrostatic timatesof overburden are available(e.g., Landisand (e.g., AndrewandHeinrich, 1984). were esFluid inclusions in mosttin deposits are saline(5- Rye, 1974), or where lithostaticpressures (e.g., Kelly and 50 equiv wt % NaC1) and commonlycontain CO2 timatedfrom preore fluid inclusions (Taylor, 1979; Heinrich andEadington,1986; Kwak, Rye, 1979; Eadingtonand Paterson,1984) or from mineralassemblages (Solomon 1987). Limited data are availableon the salt com- contact-metamorphic ponents, but FeCI is probablya major component et al., 1986; Hoffmannet al., 1988). besidesNaC1, KC1, and minor CaCI, MgCI, and Hydrodynamic,thermal, and ZnCI (Eadington, 1983; BottrellandYardley,1988). Interpretation: chemical evolution
Substantialfractionsof CH4 have been observedin
The formation of mesothermaltin(-tungsten)deCO2-richinclusions, suggesting fairly reducedfluids isprobably dominated by fluidprocesses at the in these instances (e.g.,Patterson et al., 1981;Ramboz posits transition, in time and space,from a magmatic lithoet al., 1985; Hoffmannet al., 1988). deposiReportedhomogenization temperatures of fluid staticsourceregime to a cooler hydrostatic inclusions associated with cassiterite mineralization tionalenvironment (Fig. 1). The chemical andisotopic of the ore-formingfluid(s),includinglivary from about 220 to over 500C, but main ore- constitution andoremetalaquisition, isprobably dominated stagefilling temperatures are mostlybetween280 gand of magmatic fluids. and 400C (Haapala and Kinnunen, 1982; Kwak, by a directcontribution Sourceregime--hot geopressured stage:Many tin 1987). Where fluid inclusiondata are availablein containmiaroliticcavitiessuggesting fluid combinationwith paragenetic observations,they granites commonly indicatea sequence of mineraldeposition saturationat near-solidusconditions.Experimental that the aqueous fluid exsolved by a with fallingtemperature(e.g., Kelly andTurneaure, data suggest hydrousgranodiorite at P > I kbar is 1970; Kelly andRye, 1979; Collins,1981; Patterson crystallizing salineandsinglephase(Burnham, 1979), et al., 1981; Andrew and Heinrich, 1984; Solomon moderately and et al., 1986). The early oxidestageof manydeposits but elevatedC1/H in the melt, lower pressure, typicallyprecipitatedat 300 to 400C, i.e., lower higher temperaturestypical for porphyry-copper thanthe temperatures inferredfor the lastrock-dom- stocksfavor two fluids, a low-salinityvapor and a brine, to separate directlyfrom the melt (e.g., inatedoxygen isotope exchange of the orefluids with dense the magmatic source rock.A furthertemperature de- Eastoe,1978, 1982; Bodnaret al., 1985). High-denare observed in some tin systems crease is recordedby the late-stage sulfideprecipi- sitybrine inclusions
HYDROTHERMAL Sn(-W)CHEMISTRY
Rock/Process Fluid Characteristics
461
Fluid Pressure
}t
xx
300C
7'0
Quartzofeldspathic countryrock(granite, volcanics,semipelitic hornfels)

Cassiterite ore vein or
Mostly meteoric:Lowsalinitycool aqueous

solution + CO2/HCO3-
Near-hydrostatic
Mostlymagmatic, or
mixed
Near-hydrostatic
after initial vein formation
,,'
I
D
breccia pipe, restrictedphyllic

alteration
magmatic+meteoric: Medium-salinity aqueous solution+ low-density vapour
Site of initialvein formation (e.g. high

curvature in contact)
Magmatic
Near-lithostatic at hydraulic failure Lithostatic changing to hydrostatic
Pervasiveor vein related phyllic alteration(greisen)_+

disseminated Sn
Mostlymagmatic: Mediumsalinity aqueoussolution
B
,
High-T postmagmatic alteration:dispersed feldspathisation etc. Crystallizing source granite
Magmatic:Residual salt melt+ buoyant medium-salinity

vapour
?Lithostatic
* "1 A
+ + + + + + + + + +l
16-3/276
Magmatic:Mediumsalinity fluid,supercriticalor coexisting

with salt melt
Lithostatic
FIG. l. Schematic cross section through a shallow plutonic tin-mineralizing system. Tin(-tungsten) oresare interpreted to formby ventingof magmatic fluidfroma lithostatic igneous source regimeinto an overlyinghydrostatic ore-depositional environment, where the magmatic fluid coolsand interacts
with wall rocksand/or external fluids.
(e.g., Eadington, 1983; Solomonet al., 1986; Hoff- cipalstress androck strength. Initial hydraulicfailure mannet al., 1988; Witt, 1988) but are not ascommon will be localizedat pointsof stress concentration, for as in porphyry copper deposits,possiblydue to example, the pointof highest curvaturein granitecugreateremplacement depthof mosttin granites and/ polas(Solomon et al., 1986; Fig. 1) andthisprobably or somewhat lower solidus temperatures due to ad- controls the localization andgeometric styleof many ditionalmelt components suchasF (Manning, 1982; tin-tungstendeposits. Weidner and Martin, 1987). On the other hand,the Ore depositional regime--coolerhydrostatic stage: presenceof CO2 extendsthe vapor-brinesolvus at Initial fracturingleadsto fluid loss,decrease in fluid highP andT (Holloway,1976; HenleyandMcNabb, pressure, anda tendencyfor veinsto collapse under 1978; Gehrig,1980) andprobably favored separation the loadof the rockcolumn. The hydrodynamic evoof twofluids fromthe finalmeltin some tin-tungsten lutionafterinitialrupturedepends on the rateof fluid systems (e.g., Aberfoyle;Solomon et al., 1986). lossto the surface(or an overlyinghydrostatic reBurnham (1979) haspointed outthatcrystallization gime), relative to the supplyrate of magmatic fluid reactionsof the type: fromthegranite intothevein,breccia, or replacement body.Well-documented examples of vein andbreccia hydrousgranitoidmelt --* granite deposits record a changewith time from high-temperature lithostaticconditions prior to ore formation, 4- aqueous fluid(s), (1) to near-hydrostatic fluid pressures attending the main
involvea positive volumechange up to several tens stage of tin or tungsten precipitation (Landis andRye, of percent (depending onH20 content andemplace- 1974; Kelly andRye, 1979; Jackson et al., 1982;Eadmentdepth)whichleads to a fluidoverpressure within ington, 1983; EadingtonandPaterson,1984; Ren and the pluton.Failure of early crystallized outer shells Walshe,1986; Solomon et al., 1986). Thesedeposits oftheintrusion (carapace) andoftheintruded country haveprobably not formedby diffusive closed-system rocksby hydraulicfracturing occurs when the fluid ore transportwithin a stagnant ore fluid (which repressure exceeds the lithostatic load pressure (Burn- quiresveinsto be kept openby lithostatic fluid presham,1979) or moreexactly the sumof lowestprin- surefor periodsof 10,000-100,000 yr; e.g., Kigai,
462
1978), but rather by focused fluid advection in a dynamic open environment.
TABLE 2.
Composition of HypotheticalTin Ore-Forming Fluids (concentrations in mole/kg HO)

Rangeusedin additionalcalculations
0.32-1.86 0.10-0.63
There is widespread evidencefor decreasing temperatureswith time during the evolutionof manytin deposits. Theseobservations mightbe explained by generalcoolingof the depositand its igneous fluid sourceasa whole, due to dissipation of heat from an igneous intrusionthroughconduction and convection of meteoricwater (Cathies,1977). However, the interpretation of stable isotope data from many tintungstendeposits implies coolingof the fluid itself betweensourceanddeposition site. Sincethe site of ore formation is likely to be a site of focusedfluid flowthrougha small volumeof rock(below),the heat transferredby the fluid is probablytoo great to be dissipated by local heating of the wall rock (Barton and Toulmin, 1961). The two mosteffectivecooling mechanisms consistent with observations on tin-tungsten deposits are probably, adiabaticexpansion (reversible, or irreversible throttling, with or without vapor separation);and heat transfer between hot magmatic and coolermeteoricfluids,which may or may not include physicalfluid mixing (Barton and Toulmin, 1961). Eadington(1983) andSunandEadington (1987) have presentedconvincing evidence that the tin depositsaroundthe Mole Granite were locatedat an interfacebetweena regimeof high-temperatureigneous brines,anda lower temperature environment of low-salinitymeteoric fluids (at a local scale of hundreds of meters or less).The outer meteoric fluid systemwas probably under hydrostatic pressures andconvecting, thusproviding a mechanism of efficientheat dissipation on a larger scaleof kilometers(Eadington,1983; Hoffmannet al., 1988; see alsoEastoe,1978, 1982; Henley andMcNabb, 1978; and Fig. 1).
Component
NaCI KCI 0.62 0.21
Fluid Fll
FeCI
HCI
0.07
0.02
0.03-0.42
0.002-0.06
0.3
0.03-3.0
CO
HS
0.075-1.0
0.06-0.84
SnCI HWO4
SiO2
0.004 (500 ppm) 0.00055 (100 ppm)

0.04
0.0004-0.012
I Hypothetical fluidcomposition in equilibrium withK feldspar

+ albite + muscovite+ quartz, oxidationpotential buffered by quartz + fayalite + magnetite,at 600C and 1 to 2 kbars;used in calculationof Figures 3 to 8 and 11 2 Additionallyusedin fluidssimilarto F1, for calculation of
Figure 9
and Eugster (1980). A total salinity of 1 m Cltotal, a
temperature of 600C, a lithostatic fluidpressure of 1 to 2 kbars,and at a redoxlevel near QFM wasassumed to derivethe composition of fluid Fl. A wider rangeof total salinities and soluteratiosaswell asa number of additional components (Table 2, right) were usedin various numerical experiments discussed below. Metal ratiosin the samerangeastheseexper-
imental estimateshave been observedby leachate analyses of magmatic brineinclusions fromtin granites (Eadington,1983; Bottrell and Yardley, 1988). Taylor et al. (1984) and Taylor (1988) have measuredthe partitioningof Sn between graniticmelts andsupercritical fluidsof low to intermediate chloride concentration, at controlledoxidation potentials.Tin partitioning in favorof the fluid phase increases with Compositionof MagmaticTin(-Tungsten) increasing fluid salinityandhydrogenfugacity,indiOre Fluids cating the presenceof complexSn(II)-C1 species in The foregoing reviewsuggests thatthe composition the fluid and of Sn(IV) in the coexisting silicatemelt of tin ore fluids,prior to their arrival at the ore de- (e.g., Snfluid/Snmelt = 10-30 at QFM and 1 m Cltotal in positionsite, are primarily controlledby chemical the fluid;Taylor, 1988). Considering that average tin processes in the magmaticenvironment.Even where granitescontaina few tens of ppm Sn (Table 1), a some infiltration of meteoric water into the source concentration of 500 ppm Sn in the modelore fluid area doesoccur, the major element soluteload of tin wasassumed (Table 1). This is probablyat the upper andtungstenore solutions is probablydominated by limit for any tin ore fluid of this salinityarrivingat elementpartitioning betweenfinalmelt andexsolving the site of ore deposition(below). The lessextensive magmatic fluidsandby high-temperature subsolidus dataavailable for tungsten (ManningandHenderson, reequilibrationwith magmatic minerals.Basedon this 1984) suggest that similarly high concentrations of couldbe partitionedfrom graniticmeltsinto assumption, the major elementcomposition of a sim- tungsten plified Fe-Na-K-Si-C1-O-H-bearing model ore fluid exsolving salinefluids.An arbitraryconcentration of (fluid F1, Table 2) has been estimated,usinghigh- 100ppmtungsten (5.5 X 10-4 m asHe, WO4)has been temperatureequilibriaand limits from experimental selectedto illustrate someaspects of wolframite dedata by Hemley (1959), Chou and Eugster(1977), position. A fluid with the bulk composition F1 (Table 2) is Lagacheand Weisbrod (1977), Chou (1978), Burnham (1979), Holland andMalinin (1979) and Gunter supercriticalin its magmaticsourceregion at 600C
463
and1 kbar,but after cooling below 400C anda transitionto hydrostatic conditions at similardepthit represents a subcritical aqueous liquid slightlyaboveits boiling pressure('--300 bars; Bodnar et al., 1985). Sufficientthermodynamic data are now availableto calculate,with someconfidence, manymulticomponent fluid-mineralequilibria at conditions approximatingthe depositional regime of tin deposits, using experimental measurements on various subsystems at the saturation vaporpressure up to 350C (Table 3). For lack of quantitativeexperimental data and geologicinformationon the interveningcoolingand depressurization path of magmatic ore-forming fluids, the masstransfercalculations below will primarily explorethe chemicalconsequences of direct transfer of a hypothetical tin ore fluidfromitsmagmatic source into a coolerlow-pressure depositional environment. Selected Thermodynamic Data for the System
Sn-W-Fe-Na-K-A1-Si-CI-S-C-O-H
ature, T(K), to experimentally determinedequilibrium constants of balanced reactions. A data base of
free energyfunctions for selected aqueous species of

the form:
AG[(T) = A + BT + CT In T,
(2)
wasderivedfrompublished experimental datawithin the restrictedtemperaturerange of 200 to 350C and at the saturation vapor pressure of H.O (Table 3; Appendix). Equation (2) isused merelyforthepurposeof representing equilibrium constant datawithin
quoted experimental uncertainties. It does notimply (although it isformally consistent with)anassumption of constant changes in standard enthalpy,entropy, and heat capacityof formationof the species from
elements,which is clearlynot valid across this temperature range (Helgesonet al., 1981). To minimize errors in the geologicresultsdue to internal inconsistency, the free energiesof species were derived from (or at leastcheckedagainst) publishedequilibrium constants of balancedreactionsof importance to the following calculations (e.g.,feldspar-fluid alkali exchange andhydrolysis equilibria). Estimated P-T conditionsof tin depositionare in manyinstances somewhat above350C and closeto the critical point of the pure solvent,HO, where thermodynamic properties of solutes at infinitedilutionvarysteeply with minorchanges in pressure and temperature(Helgesonet al., 1981). However, tin
The free energy minimizationcode CHEMIX of the CSIRO-SGTETHERMODATA softwarepackage (Turnbull and Wadsley, 1986) was usedfor all calculations presentedin this paper. This packagerequires representationof thermodynamicdata for chemical species in the form of Gibbsfree energies
of formation fromelements, AGp,andprovides routinesfor fittingfree energies asa functionof temper-
TABLE 3.
Sources of ThermodynamicData
Species
Referenceand remarks
CPDMRLDATA, Turnbull and WadsIcy (1986) CPDMRLDATA, Turnbull and WadsIcy (1986) CPDNPLDAT, Turnbull and WadsIcy (1986) Cobble et al. (1982) SOLMIN, M. H. Reed, pers. commun. (1986) Hewitt and Wones (1984, p. 216) Oxyannitecomponent in biotite; free energychosen sothatfo2 near Ni/NiO in intermediateannite-oxyannite solidsolutions Fe chlorite solidsolution,Walshe (1986); enthalpyestimatebasedon James et al. (1976) Ruaya and Seward (1987) Lukashov et al. (1975) Drummond (1981) Cobble et al. (1982) Pabalan(1986)
All elements, CO2(g), CH4(g), SO2(g), HCI(g), HaO(g), HaO(/)

Minerals KAISiaOs, KAIaSiaO0(OH), NaAISiaOs, SiOs, FeS2, FeS, FeaOa,
Fe304, SnOa, FeWO4, FeCOa
FeaSiO4, NiO
Simpleaqueous ionsH +, Na+, K+, Fe+a,OHKC1 , A12SiaOs(OH)4, SiOn, NaA1SiaOo(OH) KFeaAISiaOo(OH)a KFeaAISiaOo(OOH)
FesAlaSiaOo(OH)s, Fe7SiaOo(OH)s
HC1
NaOH , KOH COg, CH, H2S
HCOg, HS-, HSO, SO, Hg
SnCI +, SnCI,SnCI5,SnCI , SnCIa(OH), SnCI(OH), SnCI(OH) 2, Sn(OH)g

FeCl +, FeCl
HaWO], HWO, WO a
Heinrich and Seward(1990; above200C, isocoulombic extrapolation using data from Ruaya and Seward, 1986) Wesolowski(1984), Jairethet al. (1990), and S. Jaireth,pets. commun.
Compounds in the systemSn-W-Fe-Na-K-A1-Si-Ni-CI-S-C-O-H considered in mass transfercalculations; superscripts for charge denote aqueous species; sequence in the list corresponds to the order of sequential fitting in the buildup of the data base
464
ore fluids contain at least 1 m total chloride, which (1985), whoconcluded thatSn(II)-C1 complexes preextends the liquidbehavior of thesesolutions to about dominate at reduced aswell asmoderately oxidized 430C or above(Bodnaret al., 1985) and probably conditions. Pabalan(1986) measured cassiterite sol-
reduces the effectof pressure on fluid-mineral equi- ubility in aqueous chloridesolutions between200 libriain the 350to 400C range. Empirical free en- and350C.Hisdataconfirm thatSn(II)-C1 complexes ergy vs. temperature relationsof equation (2) have predominate at 350Cthroughout theredox stability therefore been tentatively extrapolatedto 400C, fieldof magnetite. Sn(IV)-C1-OH complexes become without explicit consideration of pressure. Empirical relatively moreimportant with decreasing temperaobservations show that supercritical aqueous equilib- tureandincreasingfo2 butdonotallow highsolubilria varyprimarilyasa functionof solvent density(e.g., ities of cassiterite exceptin very acid solutions. This Marshall andMesmer,1981), andextrapolated equi- qualitatively confirms earlier extrapolations of lowlibrium constants are thereforebelievedto approxi- temperature data(Eadington and Giblin, 1979; Patmatethe true values at pressures somewhere between tersonet al., 1981; Jackson and Helgeson,1985a; the liquid-vapor curve of HeO-NaC1 (270 bars at Heinrich and Eadington, 1986) which predicted 400C)andthe isochore ofpurewaterextending from somewhat higher solubilities. Sn-F complexes have 350C/Psaturated to 400C/'500 bars (Vn2o= 1.74 not yet been studied with thermodynamically concm3/g). Although crude, thisassumption isconsistenttrolledhigh-temperature experiments, but extrapowith a recent predictionof Pb speciation in super- lations of low-temperature datasuggest thattheyare criticalfluidsusingmoreadvanced andtheoretically generally less important thanC1complexes, because basedpredictionmethods (Sverjensky, 1987b). The of the strong predominance of C1overF evenin flufree energyof HeO itself wasextrapolated alongthe orite- or topaz-saturated magmatic fluids(Eadington 1.74 cm3/g isochore using datafromBurnham et al. andGiblin,1979;Patterson et al., 1981;Jackson and (1969). Free energydatafor minerals andgases were Helgeson, 1985a,b). Tin solubility is probably domtaken from the file CPDMRLDAT by Turnbull and inatedby equilibriaof the type: Wadsley (1986) and from other sourcesgiven in
Table 3.
Activity coefficients for aqueous ionswere calculated from the b-dot extension of the Debye-Hiickel equationof Helgeson (1969), using ft valuesfrom TruesdellandJones (1974). Electrostatic properties of ricO were extrapolated isochorically to 400C/500 bars(Helgeson andKirkham,1974), consistent with the free energyfunctionof HeO. Activitycoefficients of neutral aqueousspecies were set to 1, exceptfor
Sn(II)Cl$ -x + 2HeO= Sn(IV)Oe (aqueous) (cassiterite)
+ 2H+ + xCl- + H0, (3)

andcassiterite precipitation from a reducedacid solution is favoredby oxidation (He consumption) or acid neutralization(Pabalan,1986). Figure2 (solid contours) indicates the solubility of
cassiterite in a fluid with 2 m total chloride as NaC1
COgwheredatafromDrummond (1981) wereused. + KC1,bufferedwith regardto acidityby the assempotassic feldspar + albite+ muscovite + quartz Fugacity coefficients in the low-densitygas phase blage solubility as Sn(IV) species is were ignoredin boilingcalculations. Biotiteandchlo- (KAbMQ). Cassiterite rite were treated as ideal binary solidsolutions, and very low, and unusually reducingconditions (fo2
in excess of 400C are all other minerals were considered aspure end mem- < Ni/NiO) or temperatures
bers. In all, uncertainties in calculated metal solubil-
requiredto reach Sn(II) solubilities of 10 ppm or
ities are estimated to be on the order of 0.5 log units more. By contrast,100 to 1,000 times higher solu(muscovite up to 350C, but at leastonelog unit in extrapolations bilities are supportedin feldspar-absent to 400C. + quartz+ kaolinitc) assemblages at given T andredox conditions (Fig.2; broken contours). The experiments Hydrothermal Geochemistry of Tin of Eugster andWilson(1985) suggest evenlowersolTin in the earth's crustoccurs mainly in twovalence ubilitiesin the feldspar-excess field, below concenstates. Sn(IV) formsthe mainore mineral,cassiterite, trationsthat are realistically requiredto form an ecosome aqueous complexes, andprobably predominates nomictin deposit below 400C under chemical conin granitic melts(Taylor,1988). Sn(II) complexes are ditionsbufferedby the mineralogy of typical tin probably the most important species in deephydro- granites. Thisindicates that conditions of incomplete thermal fluidsovera widerangeof P-T-X conditions chemicalbufferingof the fluidsby feldspathic host (Eadington and Giblin, 1979; Taylor et al., 1984; rocksare requiredto transporteconomic amounts of Jackson and Helgeson, 1985a;Eugster andWilson, tin to an ore depositional environmentat lessthan 1985; Pabalan, 1986; Taylor, 1988). 400C (see Eugster andWilson,1985, p. 99). IncomCassiteritesolubility in supercriticalH20-HC1- plete wall-rock buffering will occurif the flowof hyNaC1fluidswas measured by Eugsterand Wilson drothermal fluidthrough a confined channel (such as
HYDROTHERMAL Sn(W)CHEMISTRY
465
path.Neitherprocess maybe realized in nature, but

the rock-buffered evolutionis approached by in situ cooling of an igneous fluidin contact with its source
granite, which will typically involve a 10-to 100-fold

A 0
magnetite
-hematite
-4
Sn02
cassiterite
I-
excess of rockoverfluid (by weight;Burnham,1979). The fluid-buffered evolutioncan be approached by quenching of a fluidor anyotherphysical process of fluid focusing, suchthat the amount of fluidrelative to reactivewall rock is sufficiently high to dominate the equilibrium mineralogy of the rock,withoutsignificantmodification of the fluid composition by rock interaction. Figure3 compares thepredicted chemical evolutionof a fluid in the system Sn-W-Fe-Na-K-A1Si-C1-O-H for these two cases. For the rock-buffered evolution of the fluid from
400
250
300
350
Temperature (C)
2 m C/to t
K-feldspar
Albite +
magmatic conditions to 250C (Fig. 3a, calculated for 1-kgF1 in equilibrium with 30-kgmodelgranite
R1; Tables 1 and 2), the initial high concentrations
-- --
2 m Clto t
(K/K + Na) = O.25
Kaolinite Muscovite Quartz
Muscovite
Quartz
FIG. 2. Temperaturevs. redox diagramshowing contours for the solubilityof cassiterite (SnO2)in a 2-m chloridefluid, calcu- 3KA1Si3Os + 2HC1 lated from data referencedin Table 3 includingexperiments by Pabalan(1986). Note that high tin solubilities in fluidsbuffered : KAI3Si30]o(OH), + 6SiOn, + with regardto acidityby muscovite + feldspars + quartz are restrictedto high temperatures and/or very reducingconditions and (solidlines).High solubilitiesextendto muchlower temperatures in moreacidfluidsin equilibrium with muscovite andquartzalone 3NaA1Si3Os 2HC1 + KC1 (limited by the dashedcontoursfor the buffer assemblage mus(feldspars) covite + kaolinitc + quartz).
of acidity(HC1 , H+) in the fluid andits content of the dominant reducing species (H ) dropoff steeply with fallingtemperature. Acidityisconsumed by hydrolysis of feldspars to hydrous silicates (muscovite)' 2KC] (4)
: KA13Si30]o(OH), + 6SiOn, + 3NaC1 . (5)

a vein)is rapidrelativeto the kinetics controlling the (muscovite) (quartz) interactionwith freshwall rocks(for example,the is usedin the reductionof ferric silicatecompodiffusion of aqueous components throughan exhaus- H nents, e.g., in biotite: tively alteredvein selvage; Heinrich, 1986; Heinrich and Eadington,1986; Holyland, 1987).
KFe(II)Fe(III)AiSi30,o(OOH) + 0.SH
(oxy-annite)
Reactionof MagmaticFluids with FeldspathicRocks Fluid-bufferedvs. rock-buffered coolingof magmatic fluid Two limiting cases for the chemicalevolutionof a single-phase magmaticfluid on its coolingand depressurization path fromthe source to the ore deposit are considered first (Fig. 3; Table 4): coolingof the igneous fluid in equilibriumcontactwith excess granitic source rock: i.e., rock-buffered evolution; and
= KFe3(II)A1Si30]0(OH),, (6) (annRe)
orby morecomplex Fe(III)-Fe(II) reactions involving Ti minerals (Wones, 1981).Beduetion andacidneutralization bothpromote reaction (3), andunderrockbufferedconditions 99 percentof the initial Sn content of fluid F1 will be preeipitatedat temperatures above400C. After cooling,low concentrations of eassiterite will be dispersed over a largequantityof slightlyalteredgranite. In the absenceof rock-buffering, the high initial concentrations of HC1 + H + and of H0 ,are maintainedthroughout cooling,andthe acidityandredox level of the fluid are only constrained by equilibria
(7)
coolingin isolation from reactivehostrocks,suchthat fluid speciation is controlledentirely by equilibria amongaqueous species (andpossibly congruent precipitationof minerals):i.e., fluid-bufferedevolution. These two extremes(in contrastto any intermediate cases of partial rock reaction)lead to an equilibrium stateof the fluid at any P and T of a deposi- among aqueous species, i.e.: HCl = H + + C1tionalsitethat is independent of the interveningP-T
466
(a) Granite-buffered fluid cooling (b) Fluid-buffered cooling
-3
-4
'"
'o 200
conditionsit becomesincreasinglyundersaturated with SnO2,because the precipitation reaction(3) is HO....-" counteracted by increasing hydrogen ion concentration anda constant highH concentration. The behaviorof tin indicatedby Figure 3a and b :::: ..... 'i ............. is exhibitedby any reduced,acid,andchloride-rich ....................................... . .... fluidandanyalkalifeldspar-bearing rock.It indicates ,/ H2 quenching of a tin-richore fluid, H2 ///' .... 1000 that neithersimple / $n(tot) ...... norin situcooling of a magmatic fluidin contact with anexcess of quartzofeldspathic rock,islikely to form """ ........................... -1 an economictin depositat the typical temperature rangeof 300 to 400Crecorded by fluidinclusion studies. Figure 3b, however,emphasizes that high concentrations of tin can be transported by a saline fluid to any low-temperature site,providedthat the ,,o0,) fluid is preventedfrom chemicalinteraction with
? ........ '...w(,,,) (t,,t)
20 300 350 400
/,//
200 250 300 350 400

Inp
feldspathic rock duringpartsof its cooling history

IguS fluid
Falling Temm
*C
(Heinrich, 1986). The predicted behavior of tungstenis different.
c. 3. Predicted chemicalevolution of a magmaticfluid (model fluid F1, Table 2) during coolingin equilibriumwith an excess of its graniticsource rock (a, rock-buffered evolution based on modelgraniteR1, Table 1), compared with the evolutionof the samefluid coolingin isolationfrom feldspathic wall rock (b, fluid-buffered evolution).The latter maybe realizedby relatively rapid fluid flow in a confinedchannel (e.g., vein) with limited exposure of freshwall rock.
Wolframite (ferberite)deposition, like that of cassit-
erite,probably liberates acid(H+ or HCl): HWO + FeCI = FeWO4 + 2HCI,

(ferberite)
(9)
but this is outweighed by a steepincrease of the calculated equilibrium constants of reactions of thistype with falling temperature.Wolframite precipitation and proceedsover a relatively narrow cooling interval + = .H2o. (8) through350 to 300C, with or without rock interaction(Jaireth et al., 1990). The 100-ppmW solubility Fluid F1 is close to eassiterite saturation at 400C, limit is indeedslightly extended to lower temperature but with falling temperature under fluid-buffered in the presenceof excess granitebecause of the deTABLE 4. Processes ofTin(-Tungsten) Mineralization Testedwith Mass Transfer Modeling
Results andconclusions for tin(-tungsten) mineralization
100-1,000 ppm Sn partitioned into reduced chloride fluid Tin precipitatedabove400C aslow-gradedissemination
Geologic process (modelfeatures)

Exsolution of magmatic fluid from graniticmelt Rock-buffered coolingof magmatic fluid with excess granite;no fluid focusing Fluid-bufferedcoolingand decompression; ___ muscovite _ quartz but isolatedfrom feldspars
Single-step reaction of magmatic fluidwithfeldspath, ic

rocksat T < 400C (titration)
Progressive fluid-rockreaction(staged equilibrationof fluidsalongone-dimensional flowpath) Vapor separation at T < 400C (single-step boiling) Simultaneous vapor separation and reactionwith quartz
+ muscovite + chlorite or biotite
Presence of additionalCO2 or arsenicin cooling magmaticfluid
Mixing of magmatic fluid with epithermalfluid
No cassiterite saturation; effectivetransportof high Sn concentrations to low temperatures in increasingly acidandreducingfluid; quantitativedepositionof wolframite from W, Fe-rich fluid Cassiterite precipitation by acidneutralization (feldspar --* muscovite + quartz),acidcontentof fluid (including metalprecipitation) restrictsSn enrichmentto subeconomic ore grade;titration model andF/R conceptgeologially unrealistic description of fluid-rock reactionin advectivesystem Chromatographic enrichmentof cassiterite at feldsparhydrolysis front to economicgreisen ore (>1 wt % Sn) Partial precipitationof cassiterite due to oxidationby H loss; relatively inefficienttin mineralizationprocess Economicgreisenmineralization by combinedoxidation(H loss)and acidity control by Fe silicate reactions RedoxequilibriabetweenH and CH] (or As(III) and arsenopyrite) may limit Sn solubility;potential mechanisms for fluid-buffered cassiterite precipitation(insufficient datafor testing) Depositionof cassiterite by cooling,decomplexation, oxidation (CO), and acid neutralization(HCO); efficient Sn mineralization, no chemical limit on grade
HYDROTHERMAL Sn(W) CHEMISTRY
467
piction of the Fe concentration of the fluid by the ing a sufficientquantity of fluid within a restricted formationof Fe silicates (biotite, chlorite)from feld- ore volume,and/or (3) reactionof relatively Ca-Fe(scheelite skarns; Wesospars and muscovite (Fig. 4). This suggests that the poor fluidswith calcareous formation of an economic tungsten deposit primarily lowski, 1984) or iron-rich wall rocks(Jairethet al., depends on (1) high-temperature magmatic processes 1990). Observations on the contrasting distributions of tin leading to generation of highW concentrations in the at the Panasqueira deposit (Polya,1988) fluid (fluid-meltpartioningor subsolidus leaching?; andtungsten Campbell et al., 1984), (2) physical processes of cool- maybe easilyexplained by the differentchemical be-
A
lOO
240C
320C
qtz qtz
400C
qtz
o 80
60
o 40
.- 20
ksp
1 ,
Io
(a)
mu$
(b)
..... '(c)
O
,.J
i i i i
-7
(d)
10
100
1000
.1
10
100
1000
.1
10
100
10
Ratio Fluid F1 / Granite R1 (bywt.)
FIG. 4. Calculatedresultsof single-step isothermal equilibrationof a magmaticfluid (F1, Table 2) with a typical tin granite (R1, Table 1) at three temperatures.The mineralogiccompositionof the resultingaltered rock (row a), the chemicalcomposition of the residualsolution(rowsb and c), and the tin enrichmentin the final rock (row d) are shownasa functionof the bulk fluid to rock ratio (by weight; note that thesecalculations are time and spaceinvariant).LabelsA, B, C, D refer to titration stepsdiscussed in the text. Abbreviations(usedthroughout): alb = albite, bio = biotite, chl -- chlorite, kao -- kaolinite, ksp -- potassium feldspar,mus -- muscovite, qtz -- quartz, tot -- total.
468
multipliedby the numberof O atoms in their formula unit) and normalizedto 100 percent.This approxiqueira becauseit is concentratedwithin thick veins matesthe volumeproportions of the phases (modal (focused fluidflowwith restricted wall-rock contact). mineralogy) in the altered rock, becausethe molar Cassiterite occurs only in minor quantities within the volumeof oxides andsilicates is approximately proveins(mostlywith muscovite at vein walls;Kelly and portionalto the numberof oxygenatomscontained Rye, 1979, p. 175), whereas a muchlargerquantity in onemole(Thompson et al., 1982; 12 +_1 cm3/O of tin (fivetimesthe tonnage of mineable tungsten!) unit). is disseminated in a wide halo of uneconomic veinlets With anincreasing fluid/rock ratio,the mineralogy in the semipeliticschists(dispersedfluid flow with of the alteredrock changes from feldspars + minor intimaterock contact). sheetsilicates (with partialreplacement of albiteby potash feldspar), to quartz + muscovite _ kaolinitc Single-step fluid-rock reaction and variable amounts of ferrous sheet silicates. The The calculations for the two extremecases of pos- predictedmineralogic sequence with increasing desible fluid evolution(Fig. 3) suggest that economic gree of alterationalsovarieswith temperature (see cassiterite mineralization in aluminosilicate host rocks Fig. 4 for abbreviations): couldformby a process in whicha tin-richmagmatic fluid undergoespart of its early evolution above - bio-mus-qtz - mus-qtz at highT, 400C in effectiveisolation from excess feldsparand bio-fsp-mus bio-fsp-mus - chl-mus-qtz at medium T, rockredoxbuffers (rapidquenching andfocused fluid flow),andislaterexposed to renewed rockinteraction bio-fsp-mus - chl-mus-qtz - at somelower temperature(e.g., in a zone of brec- (feldspathic) (phyllicalteration, ciation),leadingto localizedcassiterite precipitation greisen) by acid neutralization and oxidation (Eadington and Giblin, 1979; Jackson andHelgeson,1985b). kao-mus-qtz at low T. The conceptuallyand computationally simplest (argillic) modelfor sucha process includes a stepof fluid-buffered coolingand decompression of a singlebatchof Thisis in broadagreement with geologic observation magmatic fluid, followedby a stepof irreversible re- of biotite-bearingphyllic assemblages in relatively action with an amount of fresh granite at constant high-temperature greisens (commonly early in paratemperature (Fig. 4). Mass transfer calculations of this genetic sequence),the widespreadoccurrenceof type were introducedby Helgesonet al. (1969) and quartz-muscovite-chlorite assemblages at somewhat werefirstapplied to ore-forming systems by Helgeson lower temperature(frequentlyassociated with a later (1970). If it is assumed that the reactionreachesa sulfidestage)and the restrictionof kaolinitcto low state of local equilibrium between fluid and rock at temperatures (generallylate) in manySn-W systems. the deposition site,then the reaction progress in these The natureand amountof the predictediron silicate models canbe simplyexpressed in termsof the ratio phaseis sensitive to smallvariations in the iron conof the inputfluid.DoublingFetotal stabilizes of input fluid to reactiverock.Titrationdiagrams of centration thistype havebeenpresented by Reed(1983), Sverq chlorite relative to biotite up to 400C, and halving jensky (1987a), and others. It shouldbe noted that Fetotal restrictsthe stabilityof ferroussheetsilicates theseplotshaveno spatial dimension or directionand relativeto pure quartz-muscovite greisen. Significant arethereforeat bestqualitatively relatedto alteration iron additionis recordedby mass balancestudiesof geometrysuchasmineral zonation. tin greisens replacinggranite (e.g., Taylor, 1979, p. Calculatedresultsof equilibratingfluid F1 with 176; Charoy, 1979; Adam, 1983; Stemprok, 1987; variableamounts of model graniteR1 at three tem- Schwartz andAskury,1989), but part of thismaybe peraturesare shownin the three columns of Figure incorporated in other mineralsincludingmuscovite in phengitic solid solution), 4, with the weightratioof fluid/rock(F/R) plottedon (FeSiAI_2substitution the horizontal axes. Relative amounts of minerals in zinnwaldite, tourmaline, and iron sulfides(pyrite, the resultingrock, and species concentrations in the pyrrhotite;seebelow). equilibratedfluid, are plotted on the vertical axes. The composition of the fluid resulting from interThe equilibriumstatesalongthe left (low F/R) and actionat an increasing fluid/rockratio displays three the right (highF/R) extremityof eachdiagram cor- to four steps (Fig. 4, rowsc andd andlabels A to D). respond,respectively,to pointson the rock-buffered PointA marksthe exhaustion of the redoxexchange and fluid-buffered coolingpathsshown in Figure 3a capacity of the rock,whichin R1 is givenby its conand b. Amountsof silicates in Figure 4 (row a) are tent of Fe(III) hostedby biotite (eq. 6). For most presented in termsof oxygen units(moles of minerals quartzofeldspathic rocks (andparticularly for Fe(III)framitc is the main economic ore mineral at Panas-
havior of the two elementspredictedabove.Wol-
HYDROTHERMAL Sn (-W) CHEMISTRY
469
andFetotal-poor granitoids typically relatedto tin de- andin chlorite-muscovite assemblages by: posits; Table 1) reacting with reduced(H2-rich)tin + 2KAlaSiaO10(OH)2 + 3SiO + 24HO ore fluids,the redoxexchange capacity of the rock 15FeCl will be exhausted at relatively low fluidto rockratios (muscovite) (quartz) (0.03-1.0), irrespective of the actual Fe(III) mineral. + 2KCI + 28HC1 . (12) Substantially higherfluid/rock ratios will generally = 3FesAlSiaO10(OH)s
be required to consume the acidexchange capacity (chlorite) ofmost feldspathic rocks. This defines thesecond step in thevariation of fluidcomposition in Figure4 (point A fourth step associated with further hydrolysis of B, rowsb andc), whichoccurs wherefeldspars are muscovite to kaolinitc is restrictedto highly fluiddominated conditions andtemperatures below280C (pointD, Fig. 4). Tin solubility(Fig. 4, row c) is very low at a low fluid/rockratio (whollyrock-buffered conditions left of pointA), but somewhat higherconcentrations are of contributions from all dissolved metals that are supported where the redoxexchange capacityof the precipitated asa resultof acidneutralization by re- feldspathic rock is exhausted sothat H in the fluid actions producing H+ or HC1 .Thisincludes tin predominates the redox stateof the system(A to B; 80 cipitationaccording to reaction(3), but the mostim- ppm Sn at m H = 0.3, T -- 400C;10 ppm Sn at portant contribution is from iron, which formsbiotite 30C). Oncefeldspar is exhausted (F/R abovepoint at the expense of feldspars according to reactions of B) andacidityaswell asredoxlevel becomes increasthe type: ingly fluid-dominated, the tin concentration remains at the initial 500 ppm without cassiterite saturation 3FeCI + KA1SiaOs + 4H20 at any temperature. While feldsparremainsin the equilibriumassem(K feldspar) blage,aqueous tin is almost quantitatively extracted = KFeaA1SiaO0(OH)2 + 6HC1 . (10) ascassiterite. The tin ore gradein the rock (Fig. 4, row d) therefore increases nearlyproportionally with (biotite) the fluid/rockratio, to reach a maximum near point B wherefeldspars arejust consumed. The magnitude In the presentcase(F1 with 0.07 m FeC12),and of thismaximum, i.e., the highest ore gradethat can probably in many magmatic fluids reacting with alu- be achievedby the presentmodel process of acid minosilicate rocks, the contribution of reaction (10) neutralization by feldspar hydrolysis, is thereforein(or similar reactions involving plagioclase andother verselyrelated to the total acid contentof the fluid. Fe minerals) to the totalacidbudget substantially exGiven that the latter is dominated by aqueous iron ceeds thecontributions dueto theoriginal HC1 input, species(eq. 10), a reduction of the Fe concentration and thereby,determines the fluid to rock ratio (B) of the incomingfluid would increasethe maximum
completely consumed by reactions (4) and(5). Given the modalcomposition of a feldspathic protolith, the F/R at whichfeldspar exhaustion occurs (pointB) is proportional to the total acid contentof the input fluid.Thisconsists not onlyof H+ andHC1 but also
wherefeldspar isexhausted. Notethatthearguments possible cassiterite enrichment by allowing a higher regarding acidbudget(asH + + HC1 ) derivedfrom F/R for pointB. However,the solubilities of cassiterite equations (3) to (5) and (9) through12 (below)are and of the Fe silicates are coupledat givenacidity an expression of mass andcharge balance only.They andchloride(andH) concentrations. A series of simdo not dependon the actualcoordination numberof ilar calculations usingvariations in input fluid comthe metal chloridecomplexes presentin solution, positions (Table2, right) indicated that maximum tin whichvariesas a functionof temperature and total enrichment cannotbe raisedsubstantially abovethe chloride ligand concentration. Forexample, equation valueof 0.35 wt percentshownin Figure 4d. An al(10) canequally be writtenin termsof3FeC1 + onthe of feldspar-buffered cooling to left and3H+ + 3HC1 ontherightside of thereaction. ternativeassumption, 400C followedby fluid-buffered coolingto some At F/R above the point of feldsparexhaustion, lower temperatureandrenewedfeldspar interaction, acidityis controlled by equilibria betweenaqueous results in evenlower grades of tin enrichment. ironandsheet silicates, i.e., in biotitegreisens by: A maximum tin enrichment of 0.35 wt percentis probably insufficient to produceaneconomic tin ore9FeCl + KAlaSiaO0(OH) + 6SiO + KC1 body,considering that bulk mineable oresare typi(muscovite) (quartz) callyinhomogeneous andare likely to contain a predominant proportion of rockaffected by fluidto rock + 12HO = 3KFeaA1SiaO10(OH) + 20HC1 , (11) ratiosthat were higher or lower than the optimum (biotite) value.Bulk equilibration of a magmatic fluid with a
470
Fluid
feldspathic rock(atleast in thesimple chemical system
Vluid
considered sofar) therefore appears asa ratherunlikely and probably inadequatemodel for the formationof an economic tin deposit.
batches
3
Rock
column,
segments
batch
Progressive fluid-rockreaction at an alterationfront

Progressing
(nearpointB of feldspar exhaustion andmaximum tin enrichmentof 0.35 wt % shownin Fig. 4). This extractsabout 60 percent of the tin contained in fluid batches of fluid, each of which has itself been chem- batch 1. The remaining40 percent (whichwouldbe icallymodified by previous steps of fluid-rock reaction lost in the single-step process, Fig. 4) is deposited (Korzhinskii,1970). Reactionprogress alonga flow almostquantitativelyin rock segment2. After this, line of hydrothermalfluid passing through reactive the metal and acid content of the fluid is exhausted rock hasbeen describedby simultaneous calculation and the fluid composition and mineralogyof the subrock segments passed by fluid batch 1 remain of fluid flow and chemical reaction kinetics (e.g., sequent Lichtner, 1988; andBaumgartner andRumble,1988, unchanged. At a more advanced stageafter passage of the sixth for stable isotope exchange). Similar models havebeen appliedto specific situations of hydrothermal ore for- fluidbatch(Fig. 6b) a largernumberof rocksegments mation, to obtain chemicalpredictionsthat include are exhaustivelyaltered to chlorite q- muscovite time and spaceas explicit variables(e.g., Merino et q- quartz, and tin becomesprogressivelyenriched front of feldspar consumption. This al., 1986; Holyland,1987; AgueandBrimhall,1989). nearthe alteration by dissolution of cassiterite at the backof Time-specific information on in situpermeabilityand is achieved reaction rate constants are difficult to estimate for the ore zone (where the incomingacid fluid is unhigh-temperature magmatic systems. However, even dersaturatedwith cassiterite),a transientincreasein without suchdata, a one-dimensionaladvectionmodel the fiuid'stin concentration, followedby quantitative assuming local equilibriumbetween successive small deposition where the fluid encountersunreacted batches of fluid andsegments of a columnof reactive feldspar-bearing rock. After passage of severalfluid the gradeof cassiterite rock alonga fluid flow line (asindicatedby Fig. 5) batchesthroughthe system, reachesa maximum canbe used,which affords a geologically morereal- enrichmentin one rock segment istic descriptionof hydrothermalalterationthan sin- or plateauvalue after which the ore zone still widens gle-steptitration calculations. but no longer increases in ore grade (Fig. 6c). Figure 6 shows part of the resultsof a one-dimenThe maximumtin enrichment achievedby this sionallocal-equilibriumflow path calculation,based processis still limited by the massbalance between on identicalinput fluid androck compositions asused advectedacidity and the acid exchangecapacityof in the calculation of Figure 4 (centercolumn,320C). the protolith,but it is three to five timeshigherthan A total of 0.2 kg of rock R1 is subdivided into ten the maximumore grade resultingfrom single-step segments alonga linear array. 1 kg of fluid F1 is par- equilibration, at givencompositions of inputfluid and titioned into ten batches,which sequentiallyequili- hostrock. The predictedhigher chemicalefficiency realityof the advection model brate with eachsegment of the rock column.Figure andthe greaterphysical 6 shows the states of eachrock segment after the pas- suggest that thischromatographic enrichment process for the formation sageof one, six, and eight of the ten fluid batches, could be a widespreadmechanism andthe concentration of somecomponents in the fluid of economicgreisen-hosted tin deposits.A similar after each equilibriumcontact. process may alsooccurin extendedbut laterally conReactionof the first batch of fluid with rock seg- finedbrecciapipesdraininga granitepluton.Ore rement1 (Fig. 6a) isidentical to single-step equilibration working may be realized by local reequilibrationof
The titrationcalculations depicted in Figure4 point out general massbalanceand thermodynamic relations and are useful for determiningthe dominant chemicalreactionsin a hypotheticalfluid-rockreaction process.However, the conceptsof fluid/rock ratio andsingle-step equilibration of onebatchof rock with one large batch of fluid clearly do not allow a geologically realisticdescription of hydrothermal ore formationby advectivemasstransfer.Fluid-rock interactionin a dynamic(flow-through) system is progressive, in the sensethat it involvesrepeated overprinting of a rock volume by sequential smaller
alteration
front
FIG. 5. Cartoon showingthe principle of a finite element, local equilibrium model for progressivefluid-rock interaction alonga one-dimensional fluid flow paththrougha permeablerock (see Fig. 6, below). This model probably affordsa geologically morerealisticdescription of anadvancing alteration front (or progressive alterationin a confinedchannelsuchas a breccia pipe) thanthe single-step equilibration(titration) depictedin Figure 4.

(a) 1/10 of 0.2 kg fluid passed
lOO
471
(b) 6/10 of 0.2 kg fluid passed
(c) 8/10 of 0.2 kg fluid passed

[] qtz
[] mu$
[] ksp
[]
[]
alb
bio chl
_
O) -2
t)
=o-3
H+(tot)
Sn(tot) _
''T
.c:
0.5
Cassiterite
0.0
I 2 3 4 5
10
10
10
Distance(rocksegment)
FIG. 6. Progressive alteration and cassiteritemineralizationof a granite by a magmaticfluid of constant input composition, aspredictedby the flow-line model sketched in Figure 5 (calculated with the STAGEoptionof program CHEMIX; TurnbullandWadsley,1986). Ten batches of fluid of identical startingcomposition (F1, Table 2) successively flow from left to right througha columnof graniticrock (R1, Table 1) subdivided into ten segments. The three columns of diagrams showthe stateof all rock segments andcoexisting fluid compositions after passage of the first,sixth,andeighthfluid batch.An advancing alterationfront of feldspars reactingto muscovite q- quartz + chloritedevelops, whichis associated with progressive cassiterite enrichmentby dissolution and reprecipitation.This resultsin tin ore grades that areconsiderably higherthanthe maximum oregradeachieved by a single-step fluidrock reaction (Fig. 4).
the fluidswith previously alteredrocksin the lower 1974), shifts in aciditydue to preferentialloss of weak portions of the pipeor in intensely greisenized apical acids(e.g.,CO2; Giggenbach, 1981; Henley andEllis, portions of the intrusion (Fig. 1). Possible examples 1983), or changes in redox level (lossof C-S-N-O-H include the chlorite- or tourmaline-rich breccia col- gases; Giggenbach, 1980). Ignoringpossible gaseous umns at Ardlethan (Eadingtonand Paterson,1984; speciesof tin (which has been detected in volcanic Ren and Walshe, 1986), in the Herberton district gases; Symonds et al., 1987) effects of boilingon cas(Taylor,1979),or at Zaiplaats (Andrew et al., 1986). siterite solubility in an Sn-Fe-Na-K-Si-C1-O-Hfluid are primarily due to oxidationresulting from preferentialloss of the mainreducingspecies, Hg. Figure Vapor Separation 7 showsthe calculatedcompositional evolutionand Two-phase fluid separation or boilingcaninfluence tin solubilityin modelfluid F1, assuming single-step mineral solubilitiesdue to preferential fractionation closed-system isothermalvapor lossat 380C, and ofcomponents between theliquidandthevapor phase Figure 8 summarizessimilar calculations for other (e.g., Reed and Spycher, 1984; Drummond and temperatures.Two hypotheticalprocesses are conOhmoto,1985; SpycherandReed, 1986). Ore min- sidered. eral deposition mayoccurdue to ligandloss(e.g., S If the magmatic fluid isquenched withoutanyrock in the case of gold bisulfide complexes; Seward, interactionprior to boiling at 380C (open symbols
472
Fluid composition
(tot)
H2(-q)
Fa(lol)
-1
E H*(IOl)
o .2 .J
OO04
10o
Minerals A
a
Ce*,titaritl 4 M% Sn
,in .,,,,, rock c,,,i,;ii; .....................................

0OO0
G.
equilibrium contactwith a greisen assemblage of muscovite + quartz+ chloriteor biotite duringcooling andboiling,its acidityis controlled by equilibria (11) and (12) betweenaqueous iron andferroussilicate. This acidity control (represented in Fig. 4 by the regionat highF/R betweenB andC) isinsufficient by itselfto precipitatecassiterite froma reducedtinrichfluid,but in conjunction with the oxidizing effect of fluidboilingprovides a potentially significant precipitationmechanism for cassiterite. Compared with simpleboiling,the precipitation mechanism of combined vapor separation and wall-rockreactionis effective over a wider temperaturerange,and the efficiencyof tin extraction at any temperature is enhanced (Figs.7 and8b). The process leading to point A in Figure 7 (pointof chloriteexhaustion, and maximum tin extractionafter 40% H20 loss)produces a rock consisting of muscovite + quartz + cassiterite with a tin contentof 4 wt percent.This ore gradeis more than an order of magnitude greaterthan the maximum value(0.35%) that canbe obtained by single-step feldspar titrationof anidentical ore fluidwith the same feldspathic protolith(Fig. 4).
Additional Fluid Components
-- vapor lossfrom a fluid in equilibriumcontactwith muscovite centrations than those of the dominant acid and redox + quartz + an Fe mineral (chlorite or biotite), equivalent to a species of the simplemodelsystem. If the high conhigh F1/R1 ratio 100. The higher efficiency of tin extraction centrations of HC1 andH assumed sofar (Table2) of combined boilingandfluid-rock reaction isdueto acidity control are indeed required for effective tin transport,then by equilibria between aqueousiron and Fe silicate.
The calculations presentedso far are basedon a highly simplified chemical system. Nevertheless, giventhe assumptions and the thermodynamic data Water Loss to Vapor (percent H20) for all compounds in the simplesystem, the results FIG. 7. Isothermal boilingoffiuid F1 at 380C, with andwith- with regard to cassiterite mineralization will not be out simultaneous fluid/rock reaction.Brokenlines and open symaltered significantly by any additional fluid species bols -- evolutionof residualliquid as a functionof single-step theseare presentin comparable or largerconclosed-system vaporloss (in % of initialH20); full linesandsymbols unless
20 40 60
the possibilities for competing components are quite

restricted.
in Figs. 7 and 8a), it will reach cassiterite saturation after 8 percent H20 loss,as a consequence of the oxidizing effectof preferential loss of H2. On further
(a)
(b)
/
/
16o% Fluid bolling without

rockInteraction
Fluid bolling + rack reaction 400 1100 '

36O
boiling,up to one-thirdof the tin in solution is precipitated,but then the tin solubilityincreases again asa consequence of risingconcentrations of total ligand,Cltotal, andacidity,Htotal,due to the lossof solvent. Vapor losswithout concomitant rock reaction is a moderately efficient cassiteriteprecipitation
'3 1
?*C I
,
20
""1
: o.ooo I r
0
340 6O
)
, 3,o
40 60
r/
(qtz+m"+blhl) /
2O
mechanism at 400C where the fluid is alreadyclose to saturation prior to boiling, but with decreasing FIG. 8. Influenceof temperatureonthe two boilingprocesses temperatureit becomes lessefficientbecause of in- comparedin Figure 7. H2 lossdue to fluid boilingalone(a) is only cassiterite if the fluid is alreadycloseto creasing H + activity(eq. 7; Fig. 8a). Simplefluidboil- effectivein precipitating ing thereforedoesnot appearto be an effectivetin- saturation(400C in this case).In the more realisticcase(b) of fluidsreequilibratingwith a greisenassemblage containing an Fe mineralizing process, all the moreasit will generally mineral (chlorite, biotite, or Fe sulfide), the oxidationeffect asbe associated with cooling(adiabatic boiling). sociated with vaporloss contributes to a moreeffective cassiteriteover a wider temperaturerange. Alternatively, if the samestarting fluid remains in precipitatingmechanism
Water Loss to Vapor
(percent H20)

Aluminum and boron
(a)
1
473
mC02
= 1/4 mH2
In all calculations and reactionspresentedabove, aluminumwasassumed to be conserved amongrockformingsilicates. This is not entirelyconsistent with evidencefor at leastsomeAI mobilityduringgreisen-
CH4
' E -2
H2 'C
Sn(tot)
typealteration (e.g.,Taylor,1979;Stemprok, 1987).

-4
At near-solidus temperatures, polymetallicA1-Na-K Temperature C Temperature C hydroxycomplexes are probablypresentin solution (Anderson and Burnham,1983), and species of this FC. 9. Schematic diagram indicating the likely variationof type could potentially neutralize part of the high cassiterite solubilityin COg-bearing fluidsat high temperature, acidity of magmatic fluids during coolingand de- for fluid F1 with additionof (a) 0.075 ra COg and (b) 1 ra COg. compression. However, experiments by Woodland Redox conditions in the absenceof mineral buffers are dominated C-O-H equilibria; the consumption of H2, by reaction with andWalther (1986) suggest that their concentration by COgto CH4, with fallingtemperature mayleadto cassiterite prein the modelore fluid F1 is significantly smaller than cipitationwithoutanyfluid-rockinteraction. its estimated HC1 content. The omission of aqueous aluminumfrom the presentcalculations, for lack of in excess over H;equivalent to thermodynamic data and knowledge of its complex 1 mole/kg(CO Xcog " 0.02; Fig. 9b). The extrapolation above stoichiometry and concentration at high T, should but qualitatively shows the shift thereforenot significantly alter the results discussed 400Cis schematic, sofar. Moreover,the observation of ubiquitous phyllic of equilibrium(13) to the right with fallingtemperof H effectively oxidizes the (acid)alteration associated with tin deposits provides ature.The consumption fluid, and as a consequence, a major fraction of its stronggeologicevidencethat the high initial HC1 ascassiterite, at temcontentof the ore fluidsoutweighs their total content initial tin contentisprecipitated peratures well above 400C,by reactions ofthe type: of alkalinespecies suchasA1hydroxycomplexes.
Boron could influence the acid balance of fluid-
rock interaction in tin deposits, if it ispresentin high concentrations comparable to HC1andFeCb..If tourmalineisrelativelyinsoluble up to hightemperature, its precipitationcoulddepletethe fluid in iron close to the source andtherebyfavorhighertin enrichment by phyllic alterationat lower temperatures (greisen ores). Again,there arenot enough experimental data to test this quantitatively.
Carbonspecies
4SnCI + CO + 6H.O= 4SnO. + CH + 8HC1 ,

(14)
i.e., anHE-balanced combination of equations (3) and
(13). Aswith the case of H loss by vaporseparation (Figs.7 and8), tin solubility asa function of temperaturepasses through a minimum. In presence ofexcess CO, cassiterite precipitation is associated with the
crossover from Hi asthe dominant reducedspecies
at highT, to CH4 at lowerT (Fig. 9b, arrow).The
temperature of thiscrossover is quitesensitive to unRedoxeffects: Many cassiterite-related fluid inclu- certaintiesin the thermodynamic data and activity sionscontain CO. as the main gaseouscomponent, coefficients for the C-O-H species. For the calculation besides comparable or smaller concentrations of CH4. of Figure 9, data for aqueous species derivedfrom At temperatures near the granitesolidus, the C-O-H Henry constant measurements below300 to 400C components of a supercritical fluidare dominated by were extrapolated. This is certainlynot valid up to H.O, CO., and H.. With falling temperature, CO. 500C where the relationswill be stronglypressure and H. react to CH 4 according to: dependent (in a low-density gas withH.O> CO.> H. the crossover is shiftedto lower temperature).Even CO + 4H = CH4 + 2H.O, (13) thoughthe high-temperature solubility of cassiterite to equilibrium (14) cannot be fully evalu(Ohmotoand Kerrick, 1977) down to about250C, according that it may signifibelow which temperaturethe reactionbecomes ki- ated, the availabledata suggest neticallyinhibited(Giggenbach, 1980). Thisequilib- cantly limit hydrothermaltransportof tin in CO.fluids.On the otherhand,reaction rium probably exertsthe mainredoxcontrolin rela- bearingmagmatic mechanism of cassiterite tivelyreduced magmatic fluids, if theycontain a total (14) mightoffer a possible by simple cooling of a single-phase fluid, CO.concentration comparable to or largerthan that precipitation of H. (Burnham andOhmoto, 1980). Figure 9 shows without any wall-rockinteraction,which is not posin the previous the equilibriumevolution(withoutrock interaction) sible in the C-free systemdiscussed of a fluid similar to F1 (Table 2) with additional sections. Acid-base effects: In the lower temperature,lower CO concentrations of 0.075 moles/kg H.O(justbalsysancing the 0.3 m H according to eq. 13; Fig. 9a) or salinity,andlessacidfluidstypicalof geothermal
474
temsandepithermal precious metaldeposits, carbonic HCO in hot, saline, and/or acid fluids even in the acid and bicarbonate ion constitute the dominant acidpresence of highCO concentrations. Figure10 shows basepair in the fluid (Giggenbach, 1980, 1981; Hen- the approximate boundaryin temperatureversus saley andEllis, 1983). They controlsolution acidityby linity space,between the fieldsof dominanceof the the equilibrium: CO-HCO andHCI-C1 - acid-base pairs at a given totalCO concentration. Theboundary was calculated COg+ H20 = H + + HCOg (15) for an Na-K-C1-C-O-Hfluid in equilibriumwith K feldspar q-albite+ muscovite q-quartz,to summarize or by the carbonate-silicate equilibriaof the type: resultsfrom calculations usingmore complexfluids. CO + (anorthite) Upon boiling (after isolation from the minerals) the acidbalance of fluidsoriginating from the HCl-C1 = (calcite)+ (sheetsilicates) + H + (16) field are not significantly affected by CO loss to the (Giggenbach, 1981). In those fluids, vaporseparation vapor, becausethe dominantacid, HCI, doesnot leads to loss ofthe dominant acid(CO )in preference stronglypartition into the vapor phase.In contrast, in the CO-HCO fieldmayexperience a sigoverthebase(HCOS),whichstrongly affects solution fluids of preferential acidity and thereby mineralsolubility(Drummond nificantacidityshiftasa consequence of their dominant acid,CO, unless otheracid/ andOhmoto,1985; Spycher andReed, 1986). How- loss base pairs are present in higher concentration (e.g., ever, the importanceof CO2 for the acid balanceof the typicallymoresaline, hotter,andmoreacidmag- HSO-SO2; cf. Drummond and Ohmoto, 1985, maticfluidsassociated with tin deposits is diminished figs.5-8). Magmatic fluidscapable of retaining hightin confor a combination of reasons (Fig. 10). centrations down to temperatures below 400C have The dominantaciditybuffer within a fluid canbe highly saline oronetotwoorders ofmagconsidered asthatacid-base pairof whichbothspecies tobeeither are presentin concentrations that outweighthe con- nitudemoreacidthanthe KAbMQbuffer(Fig. 4). This further reduces the field of dominance of centrations of any other acid-base pair. In low-temperature, near-neutral, and/or low-salinity CO- CO-HCO5 as an aciditybuffer within the fluid, to a shiftof the curves in Figure10 to the bearingsolutions this is generallythe casefor CO equivalent units.This indicates andHCOS, but with increasing temperature, the dis- left by 1 to 2 log concentration by fluidboilingisnotanimportant prosociation constantof equation(15) becomessmaller thatCO loss moter of cassiterite deposition, but that it could aid (i.e.,CO becomes a veryweakacid)sothattheconof wolframite from a low-salinity COcentration of HCO5 becomes very low. Conversely, precipitation fluid (Higgins, 1985). the dissociation constant of HC1 according to equa- rich magmatic tion (7) ishighat low T, but it decreases with increasSulfur
ing temperature so that HC1 and C1- outweigh
Most tin depositscontainat least minor amounts
450 I ' I
| '.
'.
'-
+ksp HCI/Cl' dominant+alb

acid/base pair
of iron (and/orbasemetal)sulfides. Tracesof pyrite or pyrrhotitealsooccurin mostof their parentgranitoids,but it is uncertain whetherthey represent saturatingsolidus minerals.The initial sulfurcontentof magmatictin ore fluids is therefore difficult to estimate and probablyvariesconsiderably amongindividual systems. Under the reducingconditions that
+ mus
The additionof HS hasa relativelyminor effect on the resultsof calculations similarto the onesprelog mCl(tot) (mol/kg fluid) sentedin Figures3 to 9, exceptthat the iron silicates biotite)arereplaced by pyrrhotiteor pyrite FIG. 10. Diagramof temperature versus totalchloridemolality, (chlorite,
25o /
t- / acid/base pair In fluid 0.1 .

me02
[ c02O/HCO '' E 300 e q dominant .

-2.0 -'.0 010
' 3. I
favorpartitioning of tin intothemagmatic fluid,H2S

is expectedto be the predominantsulfurspecies in
solution.
110
delimiting the two regions whereCO-HCO (eq. 15) andHC1 C1- (eq. 7) are the predominantacid-base pairs in fluidswith 1 m CO,o, (ca. 2 mole % = solidline; 0.1 m and3 m CO indicated by dashed lines), bufferedwith regardto acidityby muscovite, quartz, and feldspars (KAbMQ). Upon CO-1oss by vapor sepa-
under certain conditions. Fluid-rock
titration calcu-
more alkaline,whereas typicaltin-transporting fluidsoriginating ditions are rock buffered:
lationssimilarto Figure 3 with fluidscontaining HS of twice the concentration of FeC12 precipitateiron andsulfuralmost quantitatively aspyrite at very low fluid/rock ratio, where acidity as well as redox conration, fluids originating fromtheCO-HCOregion may become
fromthe HCI-CI - region will notexperience significant changes

in acidity and hencecassiterite solubility.
FeClz + 2H2S : FeSz+ 2HC1 + H . (17)
HYDROTHERMAL Sn (-W) CHEMISTRY
475
(acidsulfatewaters)or possibly in marine-exhalative sulfate)tin ore-forming environments. mediate fluid/rock ratios where acidity is feldspar (seawater In the mesothermal regimeof typicaltin veins and buffered but the fluidremains reduced dueto itshigh H2 concentration: breccias, mixingof magmatic fluid with moderately reduced fluids comparableto thosein deeper parts FeCI + H2S = FeS+ 2HC1 . (18) of active geothermalfields (and epithermalore deposits)is more likely. There is strongevidencethat At temperaturesbelow 350C, pyrrhotite replaces the chemical composition of deeplow-salinity fluids biotite and chlorite throughoutthe range of F/R from the Taupo geothermal fieldsin New Zealand where redox levels are low (compareHeinrich and indeedoriginates fromminoradmixture of magmatic Eadington,1986, Fig. 5a and b). fluid to a large convecting body of surface-derived The precipitationof one mole of iron assulfidelibwaters(Giggenbach, 1981; Henley and Ellis, 1983) erates2 moles of acidity(eq. 17 and 18), just like its and a similarprocess is consistent with observations precipitation asferroussilicate(eq. 10). The acidity from fossil tin systems (e.g., Eadington, 1983). balanceof alterationprocesses andits consequences Comparedwith the magmatic ore fluid, mostgeofor cassiterite ore gradediscussed in previous sections thermalfluidscontainlower concentrations of nearly are thereforenot significantly alteredby additional all speciesconsideredin the previous calculations HS, evenif it is present in highconcentrations. (Henley andEllis, 1983, tableI). Carbonspecies repPreliminarycalculations considering calcium,flu- resent the only componentoccurringin most geoorine, arsenic,and basemetals(Cu, Pb, Zn) indicate thermal fluidsat concentrations comparable to those that none of these additionalcomponents is funda- in the tin ore fluid F1 (Table 2). Carbon speciation mentally likely to alterthe general relations discussed in the deep Taupo fluidsis buffered by carbonateabove.However, they provideadditional constraints silicate equilibria (eq. 16; Giggenbach,1981), and on fluid evolution in individual ore systems where carbonatesaturation is alsotypical for the paragecombined paragenetic information andfluidinclusion netically late, meteoric water-dominated,stagesin dataare available. They mayalsoimpose alternative mesothermal cassiterite deposits (e.g.,Kelly andTuraciditycontrols, e.g., fluoritedeposition in Ca,F-rich neaure, 1970; Kelly and Rye, 1979; Andrew and systems(Jaireth et al., 1990), or redox controls. Heinrich, 1984). Low-salinitygeothermalfluids are Heinrich and Eadington(1986) suggested that co- typicallynear-neutralor slightlyalkaline,sothat the precipitation of arsenopyrite, FeAs(-I)S, fromAs(III)- concentration of HCO5 is significant (Fig. 10). The rich solutions coulddominate the oxidation potential deepfluidof theRotokawa system in theTauporegion and hencecassiterite deposition in certain systems, (KruppandSeward,1987, table2, RK4a)is estimated but insufficient experimental dataare available to test to contain between 3 X 10 -4 m and 2 X 10 -3 m
Pyrrhotite depositionat 400C is restrictedto inter-
HCO5 at depth(calculated, respectively, fromtabulated pH = 5.75 at 320C, or assuming equilibrium with K feldspar+ albite + muscovite + quartz).The Mixing betweenmagmatic and externalfluidsis higherbicarbonate valuewasadoptedfor the calcuwell documented in a numberof tin-depositing sys- lationof Figure 11, whichpredicts the results of mixtems(KellyandRye, 1979;DavisandWilliams-Jones,ing the magmatic CO2-freemodelfluid F1 (600C) 1985; Sun and Eadington, 1987; Witt, 1988) and with variable proportionsof a simplifiedRotokawa could be important in many more. Little is known fluid (in moles/kg H20 at T = 320C):CO -- 0.280, aboutthe chemical composition of the nonmagmatic NaHCO3 = 0.002, CH4 = 0.009, NaC1 = 0.019, and fluid,exceptthat it is coolerandof low salinity(cor- KC1 = 0.003. For comparison, the effect of simple relations betweenfluidinclusion temperature andsa- dilution of themagmatic fluidby purewaterof 320C linity beingthe mainevidence of fluid mixing)and is indicatedby stippledlinesin Figure 11. The temthat its water is largelyof meteoricorigin.Fluidsin peratureof the mixturewasassumed to vary linearly continentalgeothermalsystems, associated with in- with the mixing ratio (Fig. 11a), i.e., differences in termediate to acid volcanics and inferred intrusions heatcapacity of the two fluidsandanyheatexchange at depth, suchasthe Taupo zone (New Zealand)or with rock were ignored (cf. Henley and McNabb, Yellowstone, probablyrepresentthe nearestrecent 1978). The calculations arerestricted to temperatures analogues from which supplementary indications on below 400C, i.e., to mixingratiosof magmatic/methecomposition of external fluids in Sn-Woresystems teoric fluid of lessthan 0.3, which is realisticin light may be inferred. of the observations fromgeothermal fields. The calculations indicate that fluid dilution alone Mixing of granite-derived tin ore fluidswith oxidized sulfate waters would cause a dramatic reduction (stippled;Fig. 11) may lead to substantial precipitaof cassiterite solubility. This mightbe a significant tion of cassiterite, due to loweredacidityand total mechanism of cassiterite deposition in subvolcanic ligand concentration(decomplexation of Sn-C1speFluid Mixing
this further.
476
0600{ 500 t
300 I , , . , ,
cies). However, up to 20 percent of the initial 500 ppm Sn will remainin solutionand be dispersed in the absenceof carbonspecies. By contrast,tin is almostquantitativelydepositedupon mixingwith the feldspar-saturated geothermal fluid containing carbon species in the concentrations above.Thisis partlydue to the oxidizingeffect of CO2 (eq. 14; Fig. 11c) and
(b)
partly due to the acid neutralization of HC1 by

HCO (Fig. 11d; low mixing ratios of magmaticto geothermal fluid).The modelcalculations suggest that minoradmixtureof granitictin ore fluid into the base of a convecting epithermalenvironment shouldbe a very favorablemechanism for the formationof a mesothermalcassiterite ore deposit.
Summary and Conclusions
._x
cl(tot)
0.2
(tot) 0.4 OC 02
(c)
(no C02)
(d)
o.oool I '
,
A review of geologicevidence on mesothermal cassiterite veins,breccias,and greisen-typereplacement bodiesindicatesthat theseores are formed by salinefluids, which are initially equilibratedwith a high-temperature (>400C) granitic source, and which then reactirreversiblywith rocks_ fluidsin a cooler depositionalenvironment. Thermodynamic mass transfercalculations basedon publishedexperimental data show that high tin concentrations (hundreds or possibly thousandsof ppm) can be transportedas Sn(II)-C1 complexes to any low-temperature (<400C) depositionsite, provided that chemical bufferingof the cooling fluidsby feldspathic wall rocksis preventedby relatively rapid fluid flow through a confinedconduit such as a vein. Several
alternative mechanisms to saturate cassiterite,
.,,.
._x ,::
E
.... o
HC03'
0 0000
."'T'"
100
--;
(e)
Cassiterite extraction
Sn(IV)O2, at temperatures below 400C are consistent with geologicevidence,but most of these are subjectto severe thermodynamicand massbalance constraints on the degreeof tin enrichment, andonly a few processes are likely to accumulate economic primary ore grades in aluminosilicate host rocks (Table 4). Acid neutralization by feldspathic host rocks throughhydrolysis to muscovite + quartz _ biotite _ chlorite_ Fe sulfides (phyllicor greisen alteration)
is an effective tin extraction mechanism,but the max-
',
90 (
efficiency
20
40
60
80
100
Percent magmatic fluid in mixture
imum ore grade achievedby this is limited by the acid exchange capacityof the rock (essentially given by its feldsparcontent) relative to the total acidity advectedby the fluid. The latter consists not only of HC1, but includesall metalscontributingacidity by their precipitationreactions, notablyiron deposited
as ferrous sheet silicates or sulfides. Acid neutraliza-
FIG. 11. Predicted resultsof mixinga hot salinetin-rich magmaticfluid (F1, Table 2) with a coolerlow-salinity CO2bicarbonate solution, such as the deep meteoric fluid of the Rotokawageothermal field (Krupp and Seward, 1987). The stippled lines indicate the effect of dilution of the magmaticfluid with pure water of the sametemperature(320C) for comparison. Partial cassiterite precipitation occursby acid dilution and decomplexation of stannous chloride species(stippled), but the oxidizing and acid-
neutralizing effectof COe and HCO, respectively, greatlyenhance the tin extraction efficiency, particularly at low ratios of magmaticto meteoric fluid (full lines).
tion by feldspars may be insufficient to producean economictin deposit, except by multistageenrichment at an advancing(chromatographic) alteration front or in a confined brecciapipe. Fluid-boiling or vaporloss probably haslittle effect on the acidbalanceof a typicaltin ore fluid evenif it
is COe-rich,because HCl/C1 - is the predominant acid-base pair, rather than COe-HCO as in most
4 77
cooler lower salinity geothermal-epithermal fluids. Vapor separationmay neverthelesslead to effective cassiterite mineralization throughthe oxidizingeffect of H2 loss,provided that boiling is associated with simultaneous fluid/rock equilibrationwith a greisen assemblage (e.g., muscovite+ quartz + Fe chlorite or biotite). More than ten timeshigherore gradecan
Acknowledgments
This studyhasbeen stimulated by discussions with Mike Solomon, who hasprovidedimportantideasand has greatly contributed with his broad geological knowledgeof tin and tungstendeposits (but who is not to blamefor any unduegeneralizations). I would alsolike to thankDick Henley, Neville Higgins,Subbe achievedfrom a given fluid and protolith, com- hashJaireth,JeffTaylor, Vic Wall, andJohnWalshe pared with single-step feldsparhydrolysis. for stimulating discussions, helpful comments, and Fluid mixingof smallproportions of magmatic tin access to unpublished information. Particularthanks fluid with coolerlow-salinitymeteoricfluid is an ex- are due to Alan Turnbull for his advice with the use tremely efficient mechanismof tin extraction, es- of the CSIRO-SGTE THERMODATA software. The peciallyif the meteoricwater hasnear-neutral acidity manuscript hasgreatlybenefitedfromthoughtful and andcontains CO2-HCO, like manyactivegeother- detailedEconomicGeologyreviews.Published with mal fluids.Coprecipitation of gangueminerals(e.g., permission of the Director, Bureau of Mineral Requartzin a fissure vein) places the only chemical lim- sources, Geologyand Geophysics. itation on tin ore gradein this case,in contrast to any alternative mechanism of cassiteritedepositionin February 16, November28, 1989 REFERENCES aluminosilicate hostrocks.Dilution by quartz + sulfides is also the main chemical limitation on tin en-
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APPENDIX
Summary of ThermodynamicData
Equilibrium constants of formation fromelements, logKf, at selected temperatures andthe equilibrium vapor pressure of H9O. Extrapolations to 400Caretentative. References andcomments on derivation see
Table 3 and text.
log Kr
Temperature (C)
H20(g) HCI(g) CO2(g) CH4(g ) SOlg )
H20 H H+ OHCINa+ K+ NaCI KC1 NaOH
200
24.3 10.7 43.6 3.9 33.2
23.2 -2.8 0.0 11.7 11.4 30.4 33.4 41.4 43.9 40.4
250
21.7 9.7 39.4 3.1 30.1
20.3 -2.6 0.0 9.0 0.3 27.8 30.7 37.3 39.6 36.9
300
19.6 8.9 36.0 2.3 27.4
17.8 -2.4 0.0 6.6 7.5 25.6 28.4 33.9 36.0 33.9
350
17.8 8.2 33.1 1.7 25.2
15.8 -2.1 0.0 4.4 5.0 23.8 26.5 31.1 33.0 31.5
(400)
(16.3) (7.6) (30.7) (1.2) (23.3)
(14.0) (-1.O) (0.0) (2.5) (4..5) (22.2) (24.9) (28.6) (30.5) (29.4)
HYDROTHERMAL Sn(-W)CHEMISTRY
481
APPENDIX
(Cont.)
log Kt
Temperature (C)
KOH Fe+2
200
43.6 10.1
250
39.8 9.1
300
36.6 8.3
350
34.0 7.6
(400)
(31.7) (7.1)
FeCI+
22.6
20.61
19.41
18.5
(18.1)
FeCI SnCI + SnCI SnCI
32.8 18.8 31.9 43.5
29.11 17.3 28.3 38.3
26.71 16.4 25.8 34.0
25.01 15.8 23.9 30.6
(24.1) (15.4) (22.5) (27.7)
SnCI 2
SnCI(OH) SnCI(OH) SnCI(OH) Sn(OH) HWO
HWO
53.7
79.6 100.9 113.7 107.5 86.8
82.6
46.3
69.3 87.9 97.8 92.9 77.2
73.1
40.0
61.3 77.2 84.8 80.9 69.6
65.7
34.4
55.1 68.2 73.8 70.8 63.7
59.8
(29.5)
(50.2) (60.5) (64.4) (62.2) (59.0)
(55.2)
WO
SiO CO CH HCO H2S HSHSO
KAISiaO8 NaA1SiaO8 KAISiaO1o(OH) NaAlSiaOlo(OH) A12SiOs(OH)4 SiO2 FeS FeS Fe203 FeO4 SnO FeWO4 FeSiO4 FeCO3 KFe3A1Si301o(OH) KFe3A1Si301o(OOH) FesAlSi30o(OH) Fe?SiaOlo(OH)s NiO
77.2
88.6 41.6 1.1 57.5 2.8 -4.4 73.9
397.7 393.7 589.5 584.2 395.0 91.0 16.8 11.2 76.9 105.4 53.5 101.3 174.7 68.9 508.8 508.0 679.7 588.9 21.7
67.0
79.2 37.5 O.6 49.9 2.5 -5.1 64.1
355.9 352.3 526.7 521.8 351.8 81.4 14.9 10.2 68.2 93.7 47.3 89.9 155.9 61.1 454.3 453.7 604.8 522.9 19.1
58.8
71.5 34.2 O.2 43.6 2.3 -5.8 55.9
321.4 318.1 474.9 470.3 316.2 73.5 13.3 9.3 61.0 84.0 42.2 80.6 140.4 54.6 409.3 408.9 543.0 468.6 17.1
52.1
64.9 31.5 -0.1 38.2 2.2 -6.6 49.0
292.4 289.4 431.4 427.2 286.3 66.8 12.0 8.6 55.1 75.9 37.9 72.7 127.3 49.2 371.5 371.3 491.2 422.9 15.3
(46.6)
(59.4) (29.2) (-O.2) (33.6) (2.0) (-7.3) (43.0)
(267.8) (265.0) (394.4) (390.4) (260.8) (61.2) (10.8) (8.0) (50.0) (69.1) (34.3) (66.0) (116.2) (44.7) (339.4) (339.3) (447.2) (384.2) (13.9)
Fittedto logK (Fe+ + C1-) = FeCI +) = 1.1 (200C),2.2 (250C),3.6 (300C),.5.0(350C)andlogK (Fe+ + 2C1-= FeCI)
-0.1 (200C), 1.4 (250C), 3.4 (300C), 5.6 (350C) estimatedfrom isocoulombic extrapolationof data by Heinrich and Seward (1990).

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Economic Geology Vol. 85, 1990, pp.

The Chemistry of Hydrothermal Tin(-Tungsten)Ore Deposition

Bureauof Mineral Resources, Geologyand Geophysics, Divisionof Petrology and Geochemistry,

Bolivia, Sillitoe et al., 1975; Franciset al., 1981), but

association with differentiated felsicmagmatites. Tin

Burnham and Ohmoto, 1980; Shimazaki, 1980;

(wt %) basedon typical analyses in

Idealized composition R1 used in

(Rb, Li, SrZr)

Quartz SiO= Muscovite KAIaSi30o(OH)=

HYDROTHERMAL Sn(-W) CHEMISTRY

posits(Heinrich and Eadington, 1986).

Stableisotopes and fluid inclusions

Quartzofeldspathic countryrock(granite, volcanics,semipelitic hornfels)

Mostly meteoric:Lowsalinitycool aqueous

breccia pipe, restrictedphyllic

magmatic+meteoric: Medium-salinity aqueous solution+ low-density vapour

Site of initialvein formation (e.g. high

Near-lithostatic at hydraulic failure Lithostatic changing to hydrostatic

Pervasiveor vein related phyllic alteration(greisen)_+

Mostlymagmatic: Mediumsalinity aqueoussolution

High-T postmagmatic alteration:dispersed feldspathisation etc. Crystallizing source granite

Magmatic:Residual salt melt+ buoyant medium-salinity

Magmatic:Mediumsalinity fluid,supercriticalor coexisting

1978), but rather by focused fluid advection in a dynamic open environment.

Composition of HypotheticalTin Ore-Forming Fluids (concentrations in mole/kg HO)

0.004 (500 ppm) 0.00055 (100 ppm)

I Hypothetical fluidcomposition in equilibrium withK feldspar

and Eugster (1980). A total salinity of 1 m Cltotal, a

HYDROTHERMAL Sn(-W) CHEMISTRY

ature, T(K), to experimentally determinedequilibrium constants of balanced reactions. A data base of

free energyfunctions for selected aqueous species of

of formation fromelements, AGp,andprovides routinesfor fittingfree energies asa functionof temper-

All elements, CO2(g), CH4(g), SO2(g), HCI(g), HaO(g), HaO(/)

NaOH , KOH COg, CH, H2S

HCOg, HS-, HSO, SO, Hg

SnCI +, SnCI,SnCI5,SnCI , SnCIa(OH), SnCI(OH), SnCI(OH) 2, Sn(OH)g

Sn(II)Cl$ -x + 2HeO= Sn(IV)Oe (aqueous) (cassiterite)

+ 2H+ + xCl- + H0, (3)

requiredto reach Sn(II) solubilities of 10 ppm or

path.Neitherprocess maybe realized in nature, but

granite, which will typically involve a 10-to 100-fold

: KA13Si30]o(OH), + 6SiOn, + 3NaC1 . (5)

= KFe3(II)A1Si30]0(OH),, (6) (annRe)

? ........ '...w(,,,) (t,,t)

20 300 350 400

200 250 300 350 400

feldspathic rock duringpartsof its cooling history

(Heinrich, 1986). The predicted behavior of tungstenis different.

Wolframite (ferberite)deposition, like that of cassit-

erite,probably liberates acid(H+ or HCl): HWO + FeCI = FeWO4 + 2HCI,

Geologic process (modelfeatures)

Single-step reaction of magmatic fluidwithfeldspath, ic

Presence of additionalCO2 or arsenicin cooling magmaticfluid

Mixing of magmatic fluid with epithermalfluid

HYDROTHERMAL Sn(W) CHEMISTRY

Ratio Fluid F1 / Granite R1 (bywt.)

havior of the two elementspredictedabove.Wol-

HYDROTHERMAL Sn (-W) CHEMISTRY

feldspathic rock(atleast in thesimple chemical system

Progressive fluid-rockreaction at an alterationfront

HYDROTHERMAL Sn(W) CHEMISTRY

(b) 6/10 of 0.2 kg fluid passed