Concentration of Platinum-Group Elements by Magmatic Fluids in Layered Intrusionss

Economic Geology
Vol. 87, 1992, pp. 1830-1848
Concentration Platinum-Group of Elements Magmatic by Fluids in Layered Intrusions

A. E. BOUDREAU
Department Geology, of DukeUniversity, Durham, NorthCarolina 27706

AND I. S. MCCALLUM
Department Geological of Sciences, AJ-20,University Washington, of Seattle, Washington 98195

Abstract
Evidenceleadingto a model which supports formationof Pt-Pd reefs in a layered the intrusionby the actionof magmaticfluidsis presented,as well as someof the constraints imposed such model.The Stillwater on a Complex usedasanexample thismodel.Within is of the StillwaterComplex,no laterallycontinuous sulfide-enriched cumulates occurabovethe lowermost partsof the Ultramaficseriesuntil one reaches platiniferous the J-M reef. This sulfide-poor stratigraphic intervalbeneath J-M reef ischaracterized unusually the by Cl-rich apatite.Althoughreported sulfidemodesand whole-rocksulfurcontents the cumulates in belowthe J-M reef are approximately orderof magnitude an lowerthanthat expected a for sulfide-saturated magma; sulfide saturation priorto the formation theJ-M reefissuggested of by relatively highPd andPt concentrations reportedin the eumulates belowthe J-M reef as well asby the presence sulfideasinclusions silicateandoxidecumulus of in minerals. Hence it is suggested the footwallcumulates the J-M reef were originallysulfidesaturated that to but later lost sulfurto a fluid phaseexsolving from inter-cumulus liquid. Sporadic sulfidebearingpegmatoids someof theserocksare additionalevidencefor late lossof sulfur. in Theseobservations, well asthe association the J-M reef at the first significant as of stratigraphic breakin the CI/(C1+ F) ratioof apatite the relatively and highsolubility Pt andPd of asaqueous complexes, consistent CI are with the formationof the J-M reef by exsolution of C1-andvolatile-rich fluids fromfootwall intercumulus liquids whichleached transported and ore components (both the PGE and S) upwardto the level of the reef. Usingpublished whole-rock platinum-group element(PGE)concentrations the Ultrafor maficandLower Bandedseries, cumulates the belowthe J-M reef musthavebeen enriched by a factorof, at most,1.24 for Pt and 1.75 for Pd if theserocks were to be the source the for metalsin the J-M reef. Model Raleighfractionation calculations suggest that the cumulates beneath J-M reef couldhavehadthe requiredmetalconcentrations duringthe crystalthe if, lizationof a parentmagma containing morethan 15 ppb of eithermetal,the average no bulk solid/liquiddistributioncoefficients Pt and Pd were no more than 5; these valuesare for consistent with assumption sulfide of saturation prior to the formation the J-M reef. of During solidification intercumulus of liquid, the separation lossof a Cl-rich fluid will and depletethe residualassemblage S and PGE. If 0.1 to 0.5 wt percentfluid containing of 5 percent S evolvedduring solidification the footwalleumulates of (the amountof fluid expectedto be exsolved the crystallization approximately to 10 percentfluid-saturated by of 2 intercumulus liquid),the fluid/liquiddistribution coefficients Pt andPd wouldneedto be for almost largeasthe (sulfide as liquid)/(silicate liquid)distribution coefficients remove to significant amounts of Pt and Pd. Much smaller distribution coefficients are needed if sulfide is
completely to fluidduringdegassing. latter possibility consistent the low S lost The is with contents the footwall of cumulates beneath J-M reef. Numerical the models the degassing of of intercumulus liquidssuggest that thick cumulus sequences act as chromatographic can columns separate PGE andS duringthe degassing intercumulus to the of silicate liquids,the PGEbeingenriched a sulfide-dissolution asupwardmigrating at front sulfide-undersaturated fluidsresorbcumulus sulfides. Zonesof PGE andS enrichment occurwhere degassing can frontsencounter stratigraphic physical-chemical discontinuities suchaschanges the fluid in saturation temperature the intercumulus of silicate liquids.
Introduction
Stillwaterand BushveldComplexes must have involvedthe interaction a volatile-rich of fluidphase at
IT HaS become increasingly apparent thepetro- some that point theirformation. thispaper, term in (In the genesis platinum-group of element(PGE)-enriehed "liquid"is used denote silicate to a liquidor magma sulfide deposits large in layered intrusions asthe and"fluid"to denote high-temperature such the volatile0361-0128/92/139.5/1830-1953.00 1830
PGE CONCENTRATION IN LAYERED INTRUSIONS
1831
rich fluid phasethat exsolvesfrom a silicate liquid.
wall rocks.On encountering stratigraphically higher,
Similarly,"sulfide"and "sulfideliquid" are usedto denotean immiscible sulfideliquid exsolved from a silicate magma.) Features indicative the action a of of fluid include pegmatitictextures,graphiticassemblages,and the high-temperature, Cl-rich hydrous minerals that are associated with thesedeposits. Earlier models, suchasthat of Campbellet al. (1983), proposedthat PGE enrichmentoccurredduring a magma-mixing event that led to immiscible sulfide liquid saturation. settling thisimmiscible The of sulfide liquid through a thick (severalkilometers)column of liquid scavenged PGE from the silicate the liquid, a process madepossible the large (sulfide by liquid)/(silicate liquid) partitioning coefficients for the PGE. In thesemodels, interaction volatile any of
fluids into the ore zone would be a later event that occurred after the initial sulfide accumulation and
hotterintercumulus liquids whichwere not yet fluid saturated, upward-percolating redissolved. the fluid
This redissolution of the fluid added both sulfur and
wouldactto obscure magmatic the originof the deposits (e.g.,Barnes andCampbell,1988).

More recently, Boudreau and McCallurn (1989) haveproposed high-temperature, that Cl-richhydrothermalfluidsare responsible the formationof for PGE-bearing zonesin theselayeredintrusions. This model,whichwe wishto developfurtherhere, suggests that strata-bound zonesmay developby a ore zone-refiningor chromatographic processbroadly analogous the formation roll-fronturaniumdeto of posits(Fig. 1). We suggest that Cl-rich fluids, exsolvedfrom the cumulatepile beneath the stratigraphic location of the reefs, migrated upward throughthe cumulatesequence remobilizedthe and minoramounts sulfurandPGEpresent the footof in
PGE to the silicateliquid, and owingto the limited solubility sulfideand the PGE in silicateliquid, of caused sulfide precipitation. thismodel,the metal In "front" iscontinuously moving upwardasthe system coolsand the fluid saturation front movesupward with time. Any earlier magmatic mixingevent may form a stratigraphic discontinuity which the ore at fluids trapped,andtherefore, are control location the of the ore zone.However,the magmatic eventwould not be the primaryore-forming event. While there havebeennumerous studies regarding the possible role of fluidsin the generation the of platiniferous reef of the StillwaterComplexor J-M the UG-2 andMerensky reefsof the Bushveld Complex,there hasbeenlittle positive discussion the of geochemical mass and balanceconstraints required for a fluid transport petrogeneticmodel. In this paper, we summarizeobservations which suggest that there hasbeen significant transportof the ore components from the cumulate section belowthe JM reef of the StillwaterComplex,and we highlight
the importance chlorinein the transport the of of PGE. We alsodiscuss someof the requirements for the formationof strata-bound PGE depositsin the Stillwater Complex the action magmatic by of fluids, includingnecessary fluid/liquiddistribution coefficientsand the mass balance requirements the cuif mulate sequence below the ore zone is to be the source. the ore elements of seenin the reef. Finally,
Magma
Vapor
saturation front
CI/F
FiG. 1. The roll fronturanium deposit analogue the formation PGE-enriched for of zones a layered in intrusion. The solidification interstitialliquid deep within the cumulatepile leadsto saturation a of in fluidphase. exsolution, fluidmigrates On this upwardandcarries with it the fluid-compatible elements whichwere originally concentrated a minorcumulate in sulfide fraction,e.g.,S,PGE,Cu, Ni, As,Te. The upward migrationof fluid is limited at any time to the level at which the interstitialliquid is fluid saturated; fluidmigrating above thislevel mustredissolve the hotter,fiuid-undersaturated in liquidsand precipitate sulfide whichis relativelyinsoluble silicate in liquids. the crystal As pile continues grow, to the fluid saturation boundary moves upward.Upwardmigration maybe limitedby (1) encountering a stratigraphic discontinuity, mightoccurat the level at whicha freshinjectionof primitivemagma as occurred, complete (2) degassing the footwall, of resulting the sulfide in frontbecoming frozenat some level within the cumulate pile, or (3) reactionof the fluidwith the crystal+ liquid assemblage.
1832
BOUDREA AND McCALL U UM
numerical models the separation thePGEandS for of by chromatographic processes duringthe solidification anddegassing intercumulus of liquidsare presented whichillustrate someof the phenomena involvedin fluid transport models.
Zones
Stratigraphic Trendsof SulfideMineralization
andtheHalogens the Stillwater in Complex

In Figure'2areplottedtheC1/C1 F ratios inter+ of stitialapatite(Boudreau and McCallurn,1989) and
Mlnerallzatlon
Meters
Gabbronorite III
(GN lid
6,000
Olivine-BearingV
(OB V)
Picket I Pin DepasitI
5,000
Anodhosite II
(AN II)
(oa S IV)
Olivine-Bearing III
Anodhosite I
- Olivine-Bearing IV
S
S
4,000
r
--
'
(AN I)
Oilvine-Bearing II
3,000II)I S (GN IOlivine-eing

Noritii)-
Gabbronorite II
I (OB - [J-M I) Reef

O, Norite I, I(N I)
[ Pegtol
Pt+Pal-rich
2,000
[Garoronorite I, t Pegmatoicl
Bronzitite
Zone (BZ)
K D
1,000 .... ,
_ Zone(PZ)
Discordant , ,
platiniferous
r*l H
E
B Peridotite IG
J
J
Cl/(CI+F) of apatite
dunite, I ' B chromitlte A C Basal Series disseminated

Massive &
sulfides
02
04,
0605
1D
FIG. 9.. Stratigraphic distribution sulfide-bearing of rocks andvariations the C1/(C1 F) ratio in in + intercumulus apatite (afterMcCallum al., 1980;Toddet al., 1982;Raedeke McCallum, et and 1984;Page et al., 1985;Boudreau McCallum, and 1989). On the stratigraphic column, denotes "S" sulfide-enriched zone;A-K denotethe A throughK chromitites. Note that only the sulfidemineralization the Basal of series, J-Mreef,andthePicket sulfide the Pin zone thetopofAN II have at beenshown havesignificant to lateralcontinuity; column the should viewedasindicative the typesof mineralization occurin be of that the different zones the Stillwater of Complex discussed the text. as in
1833
the distribution sulfide-bearing of rocksas summa- thoughto date only oneof thesezonesabovethe J-M rizedby Pageet al. (1985) andToddet al. (1982) asa reef, the platiniferous PicketPin sulfidezone at the function stratigraphic of position. (Stratigraphic sub- top of AN II, isknown be laterallyextensive to across divisions nomenclatureare after McCallurnet al., the exposed and portionof the intrusion(Boudreau and 1980; Raedekeand McCallurn, 1984; and Zientek et McCallurn, 1986). The increase sulfide in aboveOB I al., 1985.) Apatite is usedasan indicatorof the rela- is reflectedby an increase whole-rocksulfurconin tive halogen concentrations because apatiteis stable tent in average cumulate rocks across zoneaswell the at magmatic temperatures is the mostubiquitous (Toddet al., 1982; Keays al., 1991). The presence and et halogen-bearing mineralin the StillwaterComplex. of the J-M reef at the firstmajorchange the haloin In addition, halogen the exchange idealat magma- gen geochemistry sulfideabundance is and abovethe tic temperatures apatitedoes readilyreequil- baseof the Stillwater and not Complex suggests the two that ibrate on cooling(e.g., Boudreau and McCallum, are morethanfortuitously related. 1989; TackerandStormer,1989). Although average the cumulate within the chloraThe stratigraphic trend of the halogens charac- patitc-bearing is stratigraphic section beneaththe J-M this terizedby an initial increase the C1/(C1 F) ratio reef is notably poor in sulfidemineralization, in +
of apatitein the Basalseriesand into the lowermost chlorine-rich zone does contain sulfide- and PGEpart of the Ultramaficseries. the uppermost In two- rich pegmatoids. Thesepegmatoidal bodiesare assothirds of the Ultramafic series and into the lower half
ciated with the G chromitite in the Ultramafic zone
developed beneaththe J-M reef of the LowerBanded series, apatitegenerally con- andare sporadically tains>90 mole percentchlorapatite component and and alongthe Ultramaficseries-Banded seriesconlocallynomeasurable fluorine. With the exception of tact. Discordant (late-forming) bodiesof Pt- andPdthe rocks of the Critical zone of the Bushveld Comenriched dunitc also occur within the Ultramafic se-
plex (Boudreau al., 1986; Boudreau Kruger, et and 1990), suchstratigraphically extensive Cl-rich aparite compositions have not been reported in other layeredintrusions. significant No variation apatite in
ries(Page al., 1985). Elsewhere, et discordant, and SPGE-enriched bodiesonly againbecomeprominent immediatelybelow the Picket Pin Pt-Pd depositof AN II (Boudreau McCallum,1986). Thesebodies and composition observeduntil OB I, the hostzone of suggest at leastsome the PGE andsulfurin the is that of the J-M reef,whereapatite compositions strati- surrounding show rocks wereremobilized during solidificagraphic variability betweenchlorapatite moreF- tion. and richcompositions, latterhaving the compositions simDiscussion ilar to thoseobserved sills,dikes,andcumulates in at Todd et al. (1982), notingthe lower sulfurconcenthe bottomof the complex. belowthe J-M reef relativeto those Sulfidemineralization the StillwaterComplex trationsin rocks in that the magmawas undersatushows broad, a inverse correlation withtheC1/Fratio aboveit, suggested of apatite. Sulfideis mostabundantin the Basalse- rated with sulfurprior to the formationof the reef. ries, where large tonnages (>150 million tons) of However, there are several lines of evidence that this rockwith an average gradeof about0.25 wt percent suggest wasnot the case.First, sulfideminerals phase polyphase and grains) foundas are copperand0.35 wt percentnickelhavebeen identi- (bothsingle
fied(Page al., 1985).Apatite et compositions within

the Basal series characteristicallyrich. In conare F
trast, within the Cl-rich section of the Ultramafic se-
inclusions in silicate and chromite cumulus minerals in the Ultramafic and Lower Banded series beneath
the J-M reef (e.g.,Page,1971; Talkington andLipin, 1986; Fooseand Nicholson, 1990; PageandMoring, and are fides generally withtheexception sulfides 1990). Second, moresignificant, the highPt are rare of associated with sporadically developed pegmatoidal and Pd concentrations in the cumulates beneath the valuesof bodies (discussed below).Measured sulfide modes in J-M reef. Pageet al. (1972) report average otherthanthe nonpegmatoidal cumulates from this Cl-rich section 26 ppbPt and49 ppbPd for cumulates
ries and lower half of the Lower Bandedseries,sul-
typicallyrangefrom 0.001 to 0.016 percent(e.g.,

content of the cumulates is reflected in the low
chromitites of the Peridotitc zone of the Ultramafic
and Page,1971; PageandMoring,1990). The low sulfide series, 21 ppbPt and12 ppbPd in the Bronzitite
zone. For the chromitites of the Peridotitc zone, the
whole-rock sulfurcontent,typicallylessthan 100 ppmS for the LowerBanded series beneath J-M the reef (Boudreau, unpub. data; Page and Moring, 1990; Keayset al., 1991). Sulfides becomemore
abundant in the Lower Banded series at and above
valuescan be higherby an order of magnitude or more. The major cumulatetypes(noritesand gabbronorites) the LowerBanded of series belowthe JM reef contain average concentrations ranging from 21 to 23 ppb Pt and 6.5 to 7.5 ppb Pd (Pageand
the levelof theJ-Mreefin OBI. Above J-Mreef, Moring, 1990). the the Banded series contains at least ten sulfideTo the degree thatthe sillanddikecompositions of enrichedintervalsin the ContactMountain area, al- theBasal series theStillwater of Complex (e.g.,Zien-
1834
BO UDREA U AND McCALL UM
tek et al., 1986) andthoseof the marginal rocksand sillsof the Bushveld Complex(e.g.,DaviesandTredoux,1985) areindicative the magmas formed of that theseintrusions, parent magmas the probablycontainedno morethanabout10 to 20 ppb eachof Pt and Pd. As notedby Campbellet al. (1983), if the Stillwater magma were not sulfide saturated prior to the formation the J-M reef, andsincesilicate of mineralsdo not hostsignificant amounts the Pt andPd of (seebelow),then the PGE concentrations the cuin mulates wouldbe controlled only by the amountof trappedintercumulus liquid.Therefore,if the original liquid had approximately ppb eachof Pt and 15 Pd andassuming cumulates the initiallycontained no morethan10 to 30 percent trapped intercumulus liquid, thenthe rocks belowthe J-M reef should haveno morethan 1.5 to 4.5 ppb eachof Pt andPd. If this were indeedthe case, then cumulates belowthe J-M reef could not be a significant sourcefor the PGE
contained in the reef.
It is worth notingthat a comparison reasonable of Pt and Pd abundance the parent liquid composiin tionswith the higherabundance observed the cuin mulatesection beneaththe J-M reef suggests the that cumulate section a potentially is bettersource the for PGEthanwasthe proposed parentmagma. The relativelyfertile character the cumulates evenmore of is
remarkable since some of the PGE must have been
lost to form the PGE-rich bodies noted above and, as
suggested here,mayhavegoneintothe formation of the J-M reef duringdegassing intercumulus of liquid.

Hence, the PGE concentrations the cumulatesiniof
tially may have been even higher than is now observed.
The assumption the magma that wassulfide saturatedprior to the formation the J-M reef apparof ently conflicts with the low observed whole-rock sulfur content and modal sulfide mineral concentrations
in theserocks.Let usconsider magma a whichis sulfide saturated a constant wt percentsulfide at 0.1 (or In fact, however, the observedPt valuesare much about400 ppm S) throughout crystallization its hishigherthantheseestimates. the Ultramafic In series, tory.If we crystallize some proportion it, thenthe of the Pt and Pd concentrations are at least an order of precipitated assemblage always will contain 400 ppm liquid. Because precipithe magnitude higherthan wouldbe expected their S, aswill the remaining if concentrations resulted had fromtrappedliquidcon- tated assemblage mustcontainthe sameamountof centrations alone. While the Pd values of the Lower sulfurasthe liquid,the whole-rock abundance sulof Banded series approach thesetrapped liquidconcen- fur in the cumulate rocks(or equivalently, modal the trations,theserocksare texturallythe mostadcumu- abundance sulfide) of should reflectthe sulfur-saturalateof therocks beneath J-Mreef (asseen the qualita- tion level in the magma. Thiswouldbe true whether orthocumulates adcumuor tively by the low modalabundance postcumulus or notonewasobserving of minerals suchasapatitein the Lower Bandedseries latesbecause both the cumulus assemblage the and ascompared with the Peridotitczoneof the Ultrama- intercumulus liquid mustcontainthe samebulk sulAlso, settling mayredistribfic series). most The readyexplanation these for high fur abundances. although Pt andPd contents thatthe magma sulfide is was satu- ute the sulfide the cumulate in pile to somedegree, ratedthroughout crystallization its history. Whereas on averagethe massbalancemust be maintained. one cannotrule out that Pt andPd perhaps behaved Naldrett and yon Gruenwaldt(1989) have summacompatibly duringcrystallization silicate of minerals rized the variationin the solubilityof iron sulfide of chilledmarginsamor precipitated nativemetals, presence sul- with fractionation a Bushveld as the of fide inclusions silicate in cumulus minerals supports ple, whichhasthe crystallization sequence olivine-- the inference that the magma wassulfidesaturated lowCa pyroxene plagioclase low Ca pyroxene -- + + duringcrystallization. chalcophile The natureof Pt clinopyroxene. Assuming similaritywith the StillandPd andthe lack of any evidence that theseele- watermagma, thenthe Stillwater liquids should have ments behavecompatibly with common silicate min- startedto saturate sulfide about0.4 wt percent in at eralswouldsuggest that they are not incorporated sulfide about1,600 ppmS) at the base the Ul(or of into silicatestructures (e.g., Westland,1981). Fur- tramarieseries,decreasing about 0.1 wt percent to thermore,the manystudies the Ultramaficseries sulfide about400 ppmS)whenthe LowerBanded of (or and Lower Banded series cumulates confirm that Pt seriesrockscrystallized. The rocksformed from andPd are largelyhosted minorPGE-bearing in sul- thesesulfur-saturated liquids should thuscontain befidephases notasdiscrete and nativemetals alloys tween 0.1 to 0.4 wt percentsulfide(or 400-1,600 or (seethe summary Pageet al., 1985). By whatever ppmS).Thisis considerably by morethanthe reported path one might imagine,however,the conclusion is modal abundance 0.001 to 0.016 percent of sulfide. the same:the cumulatesare much more strongly The apparent contradiction betweenthe high Ptand can if enriched Pt andPd thanwouldbe expected in from Pd contents lowS abundance be explained trappedliquidconcentrations alone.It isfurthercon- sulfurwaspreferentially fromthe cumulate lost pile cluded that the Pt-Pd enrichment is a result of sulfide duringdegassing a sulfur-bearing phase of fluid dursaturation throughout crystallization the Still- ing solidification intercumulus the of of liquid. The occurrence of discordant,PGl,-enriched sulfide-bearing water magma.
1835
below.
bodies scattered throughout cumulate the sequence Consider the case for Pd, where we will assumean belowtheJ-Mreefisconsistent themigration initial concentration 10 ppb in the parentliquid. with of of thesecomponents. Although remobilization loss Assumiug (sulfideliquid)/(silicate and a liquid) distribuof bothsulfurandPGEcouldbe achieved either tion eoeffleient of 104anda modalabundance by (D) of dissolution a migrating in interstitial silicate liquidor sulfideof 0.1 percentof the eumulate assemblage, a volatile~rich fluid,the lowsolubility sulfur liq- then the bulk distribution eoeffleient would be on the of in uid relativeto a fluid (lowerby at leastone to two order of 10. That is, the cumulatescould contain as orders magnitude, below) wellasthepegma- muchas100 ppb Pd. Thisvaluewouldbe the maxiof see as titletexture these of bodies suggests volatile-rich mum,because that variations the silicate in liquid/sulfide fluids the most are likelyagent formthesefeatures. liquid mass to ratio (the R factor) may causeit to be Also,anintercumulus liquidalready saturated sul- lower(Campbell al., 1983). Considering in et variations fidewould be effective removing not in cumulus sulin R, the concentration of Pt in the bulk eumulates fide;instead, sulfide would continue precipitate wouldbe givenby to as temperature dropsand the crystallization sulfurof Ccumulate s = Csulfide Wsulfide , (1) free minerals wouldkeepthe liquidsaturated sulin fide. Finally, if the liquid were sulfidesaturated where Ccumulatebulk-rock concentrationof Pd, = throughout crystallization its history,then the PGE Ws,lm& weightfraction sulfide, C,,l.i&= con= of and content the intercumulus of liquidwouldhavebeen centration of Pd in the sulfide fraction. The concenstrongly depleted hence and wouldnotproduce the tration of Pd in the sulfidefractionis givenby the observedPGE-enriehed pegmatoids. contrast, formulation Campbell al. (1983): In of et fluids separating anevolved from intercumulus liquid cancarrysignificant amounts sulfur, inducing of thus Csnlfid a+r) +1)' e: Cliqnid' D-(R a significant of sulfur eausing resorption loss and the of sulfide (e.g.,Whitney,1984). Further,such fluids liquid/sulfide liquidmass ratioand mayremove some thePGE,asdiscussed fully whereR = silicate of more
Cliqidconcentration = ofelement liquid. in

Footwall Cumulates
Formationof the RequiredEnrichments the in
base metals), verylittle stratigraphic thickness re- value will increaseto 10,000 and the bulk distribuis
quired to accountfor the abundance these eleof ments. the PGE,however, For verylowabundance in the footwallsequence high enrichments the and in ore zoneplacestrong constraints mass on balance.
TABLE Abundance S, Pt, andPd Requiredin Cumulates 1. of belowthe J-M ReefIf All MaterialCamefromthe Footwall
Cumulate Section
The J-M reef averages, roundnumbers, in 2,000 Cliquid , would onthe orderof 0.9 andPd would be ppm S, 8 ppm Pt, and28 ppm Pd if considered over behave a weakly as incompatible traceelement. Howan average thickness 1 m, based the typical ever, the Stillwatercumulates typicallymesocuof on are grades reported Conn(1979). Table 1 shows by how mulates to adcumulates and become more adcumumuchmetalandsulfurmust present different late asthe J-M reef is approached be in from below.This thicknessesof eumulate sectionsbelow an ore zone in requiresthe cumulates have equilibrated to with a orderto support mass the balance requirements largervolume magma. givenmass rockequilito of Ifa of formtheJ-Mreef.For sulfur (andby inference, the bratedwith 10 timesits mass magma,then the R of
tion coefficient would be on the order of 5. In this
For a liquid precipitating vt percentsulfide, 0.1 the minimum valuewouldbe 1,000; e.g., the effecR tive bulk distributioncoefficient Pd, Cc,m,ats/ for
easePd wouldbehaveas a compatible element.In

other words, cumulates rocks which are to some de-
gree adeumulatemay have their Pd content increased a factorof up to 10 timesthe parentliquid by

concentrations.
Approximate stratigraphic
source
Above GN I
Above Ultramarie Above Basal series Series
Thicknessof
cumulate
source
40 m
400 m
1,600 m
Simple Raleigh fractionation mass and balance calculations maybe usedto estimate average the bulk distributioncoefficients required for a magmato have precipitatedsuffleient metal concentration in the footwallsequence (Fig. 3). Mass balance requires thatthe Pt andPd concentration originally contained in the eumulate sequence belowthe reef musthave
been suffleient both to form the ore horizon and to
Amount of element
required in
source
S Pt Pd
50 ppm '200ppb 7,50ppb
,5ppm `20ppb 75 ppb
1 ppm ,5ppb 19 ppb
leavethe presently observed metalconcentrations as "residue"in the footwallsequence. (The PGE-rieh pegmatoids beneath reef should be included the also
in the mass balance calculations as well. However,
the tonnage and grades the PGE-enriehed of bodies
1836
BOUDREAUAND McCALLUM
6O
P
Pt
[;(calc.
D--5
[;(calc. - obs.) = 28.3 ppm
Co -15 ppb
about2.5 for Pt and 5 for Pd. This impliesthat the firstprecipitating cumulates should contain ppb 42 Pt and 75 ppb Pd. Theseconcentrations not unare usualfor the cumulates the lowermost in part of the
4O
20
observed
Total obs. = 37.6 ppm
Co = 14 ppb
- obs.)
30
rnD 2.5 -observed

--
Ultramafic series (e.g.,Pageet al., 1972). Also,because observed the averages havea sizable standard deviation (e.g., the standard deviation Pt -- 35 for ppbfor38 LowerBanded series analyses reported by Page Moring,1990),themodeled and concentrations should viewedas approximate be only. Note, however,that Pd shows stronger a decrease observed in abundance relativeto Pt up through cumulate the sequence beneath reef andis the metalthatis the the moreenriched withinthe J-M reef. The calculations shown Figure3 suggest the in that cumulates below the J-M reef wouldneed to have contained 1.24 timesthe presently observed conPt
centrations and 1.75 timesmore Pd if they were to
lO
Total -- 32.8 obs. ppm

Peridotite zone I Bronzitite I zone
I i I I I I t t i i i
J-M r Reef
Lower Banded
Series
I I t i
provide these metals formthe J-M reef.Thisindito cates these that cumulates 19 percent the origilost of nalPt and43 percentof the original to formthe Pd J-M reef if they were the sourceof thesemetals.
Since these calculations are based on the minimum
500
1OOO
15OO
observedthicknessof the cumulatesbelow the reef,

Stratigraphic height (m)
FIG.3. The required (top)andPt (bottom) Pd budgetrequired of the cumulates beneaththe J-M reef if they are to be the source forthese elements thereef,assumingrelatively in a thinUltramafic section is seenin the ChromeMountainarea(e.g.,Raedeke as and McCallurn,1984). Straightsolidlines ("observed")are the observed bulk average andPt concentrations the predominant Pd in silicatecumulaterock types below the J-M reef, from sources notedin the text.Smooth curves ("calculated") the calculated are PdandPt values derivedfroma simple Raleigh fractionation model for thisstratigraphic section. the model, istakenthatthe cuIn it mulate sectionbelow the reef represents percent crystalliza25 tionof a magma hadthe initialliquidconcentrations of 15 that (Co) ppb for Pd and14 ppb for Pt andaverage bulk distribution coefficients of 5 forPdand2.5 forPt.The "totalobs."values the (D) are
total amount of observed Pt and Pd that would be concentrated
they represent maximum the enrichment valuesrequiredto formthe J-M reef. Because thesecalculations be complicated can by several factors, theyshould considered onlyesbe as timates. For example, manyfreshmagma the additionsthat probablyoccurred duringthe crystallizationof the Peridotitezone(andpossibly the Bronzin itite zone and Lower Bandedseriesas well) would haveprevented rapiddepletion the PGEin the reof sidualliquid and hencewouldhave led to overall smaller required values theinitialliquidPGEconfor centrations the average or bulk distribution coefficients.We concludethat, for sulfide-saturated liquidsfor whichthe average bulk distribution coeffiformthe J-M reef.
into anore zone1 m thickusingthe total metalcontentnowpres- cients for Pt and Pd are about 2 to 5, the footwall ent in the cumulates beneaththe J-M reef. The cross-ruled areas cumulates could have been a suitable source rock to and the "Y(calc.-obs.)" valuesare the differencebetween the
model-calculated Pd and Pt concentrations and the observed Pd and Pt values for the whole of the cumulate section below the reef
andrepresent integrated the excess andPt available forma Pd to reef 1 m thick.TheseY(calc.-obs.) values compare closely with the observed reef average J-M grades 8 ppmPt and28 ppmPdover of 1 m asreportedby Corm(1979). are not known but are considered to be minor and are
Fluid Transport the Ore Elements of and the Importanceof Chlorine A fluidexsolving froma sulfide-saturated intercu-
mulus liquidhas Sconcentration byequilibthe fixed

rium with sulfide,which we will consider fixedfor as
long as sulfideremains part of the residual assemHowever, estimates the sulfur of contents of ignoredin the followingmass balance calculations.) blage. For thesecalculations, usea liquid containing we 14 igneous fluids varywidely. fluid/liquid For distribufor equalto 40 (Brimhall and ppb Pt and 15 ppb Pd. The calculation assumes tioncoefficients sulfur also that thatthecumulate section beneath J-M reefrepre- Crerar,1987),andassuming theliquidat sulfide the contains to 1,000 ppmS,the fluidwill 400 sents percent 25 crystallization theoriginal of magma saturation from 1.6 to 4 percentS. The highervalue without any additionof more primitivemagma.In contain thiscase, average the bulk distribution coefficient re- agrees withanestimate 5 percent Mathez al. of by et fluids. Holloway (1987)has calquiredto account the metalcontentin the J-M (1989)forStillwater for reef and in the cumulates below it would need to be culatedthat a C-O-H-S fluid in equilibriumwith
18 3 7
grains mayremainisolated fromthe degassing pyrrhotite and with carbonactivity fixed at 0.1 will sulfide containasmuchas0.1 to 0.2 molefractionH2S+ SO2 because they occurasinclusions cumulus in minerals. (equivalentto about 18-30 wt % S) at 850C, the These isolated sulfides will reduce the amount of to which amounts eachspecies of beinga function fo. fluidthat mustseparate removethat sulfide of Carroll andRutherford(1985) havecalculated that remains equilibrium in with the intercumulus liquid. an H-O-S fluid in equilibriumwith a sulfide-and In anyevent,the continued presence sulfide the of in water-saturated dacitic liquidwill contain about0.06 cumulates over an extensive degassing intervalhas molefractionH2S(or about10% S) at 2 kbarstotal consequences the transport metals discussed for of as
The solubility the PGE in an igneous of fluid isthe subjectof somedebate.Currentlythere is little exingfs butthatit also 2, increases rather sharply z perimentalevidenceon the solubilityof the PGE in forfo aqueous solutions magmatictemat belowthe QFM buffer.Finally,Barnes Campbell Cl-complexing and (mostthermodynamic is tabulatedat data (1988) havecalculated H2Swill be the predomi- peratures that solubilities elevated at temperanantsulfurspecies anaqueous in fluidin equilibrium 25C)andcalculated and with olivine,pyrrhotite,andmagnetite 900Cand turestendto varywidely(e.g.,Mountain Wood, at and with a water fugacityequalto 2 kbars,and that its 1988; Sassani Shock,1990). The highersolubilfugacity be about100bars. will Thisisthe equivalent ity estimatesat temperaturesto 750C by Sassani that to about10 wt percentS.Theynotethatthiswill be a and Shock(1990) suggest Pd(II) chloridecomplexesare the major dissolved species Pd in C1of maximum sulfurconcentration, any reduction as of fluidsandthat the solubility these of water fugacity will reducethe H2Sfugacity through bearingaqueous the reaction: species likely to be considerable is (ppm levelsand higher),especially underlow pH conditions. These H20 + S2 = H2S + 02. (3) relativelyhigh solubilities supported the exare by of to They suggest igneous that fluids,if C1rich, will have periments Pd solubilityin chloridesolutions that, a lowerwater fugacityandhencethe fluid will con- 700C of Hsu et al. (1991). One mightexpect liquids exsolvingCl-richfluidattemperaa tain very little sulfur.However,theoreticaland ex- forsilicate turesin excess 1,000C,the solubility Pdcould of of perimentalestimates the C1-OH exchange of betweenapatiteandaqueous fluidsdemonstrate that, at be evenhigher. FollowingHolland (1972), we discuss here the magmatic temperatures, fluidsin equilibriumwith of Cl-richapatites be predominantly may aqueous (e.g., partitioning chlorineand a divalentmetal cation silicate liquid Korzhinskiy,1981; Boudreau al., 1986; Zhu and suchasPd+2betweenan intercumulus et Sverjensky, 1991). This is further supported the and a Cl-bearingvolatilefluid. In this case,chlorine by partitionintothe fluidphase, with NaC1 OH-rich natureof the Stillwaterintercumulus phlo- will strongly aqueous chloridecomplex.Hence gopite and amphibolewhich locally accompany as the dominant exchange minor of chlorapatite (Boudreau al., 1986; Pageand Zien- NaC1will controlthe fluid-liquid et involving tracemetals. plausible A exchange tek, 1987):micas amphiboles and cannot incorporate species muchC1for structural reasons (e.g.,Volfingeret al., reactionfor Pd betweenfluid and liquid couldbe 1985),hence presence hydroxyphlogopite the of and written as follows: hydroxyamphibole wouldmilitateagainst unusually Pd+2+ 2NaC1= PdC12 2Na+. + (4) lowwater fugacities hence and unusually PH2s. low liquid fluid fluid liquid If we assume the fluid separating that from a sulfide-saturated intercumulus liquidcontains wt per- For thisexchange 5 reaction, equilibrium the constant cent S as a low estimate,then degassing 0.8 wt canbe expressed of as: percentfluidfroma crystal intercumulus + liquidast/fluid / liquid 2 semblage containing wt percentsulfide(or 400 0.1 Pac' -Na+ (5) ppmS)will resultin the totalresorption all sulfide. of K= a2fl-fluid ' \ttNaCl \2 ] In other words,if a silicateliquid is fluid saturated whenthe liquidcontains percentH20, then16 per- The Na content intercumulus 5 of liquidislikelyto recentfluid-saturated intercumulus liquidmust crystal- main approximately constant owingto the presence lize to evolve amount fluidrequired(0.8 wt %) of plagioelase a cumulusor intercumulus the of as phase. to completely remove0.1 wt percentcumulus sul- Thus,the concentration Pd in the fluid (asPdC12) of fide.Actually, because degassinga consequence will be proportional the squareof the C1concenis of to solidification, slightly morefluidmustbe evolved to tration (as NaC1),if all other activitiesremainconaccount the additional for sulfide precipitated during stant; doubling the chlorinecontentof the fluid a of
fluidpressure 1,027C at andfs2 -1.60 andatfo =

definedby the QFM buffer.They indicatethat the
amount of S in the fluid will decrease with a decreas-
in more detail below.
solidification the intercumulus of liquid.Thisis dis-
means that the fluid will be able to contain four times
cussed the calculations in below. In addition,some more Pd.
1838
BO UDREAU AND McCALLUM
Boudreauand McCallurn (1989) have calculated that the C1/F ratio of the intercumulus liquid would havebeen30 to 40 timesabove typicalmagmatic values to accountfor the high C1/F observed the in chlorapatite from the Ultramaficseriesand Lower Bandedseries.Because the exponential of relationshipbetweenC1concentration metal solubility, and the partitioning Pdbetweenfluidandliquidcanbe of asmuchasthree ordersof magnitude morein the or Cl-richcumulates belowthe J-M reef ascompared to the moretypical,low C1concentration fluidspresent in mostmagmatic systems. Therefore,it is suggested that the presenceof an economic PGE zone above
the Cl-rich sections in the Stillwater is the result of
lent to fractional melting,the concentration a trace of elementremaining a degassing of cumulates in pile relativeto itsinitialbulk composition the crystal in + sulfideliquid + silicateliquid assemblage a funcas tionof the mass fluidlostis givenby the following of relationship (Shaw,1970):
Co
Cr (1- Fvap) _
(6)
more efficientlossof Pt and Pd to exsolving fluids compared with other intrusions.

Partitioningof ChalcophileElements betweenLiquid, Fluid, and Sulfide
for which, Cr = residualconcentration trace eleof ment in rock, Co = concentration startingsolid+ in liquidassemblage, Fvap= and weightfraction fluid of evolved. the bulk (solid+ liquid)/fluiddistribuD, tion coefficient, calculated the following: is by
D=(X'iquia/+ Xsulfide'
where Xliquid Xsumae and = weight fraction liquidand sulfide, respectively, Kf/ Ks/ distribution and and =
coefficient between fluid/liquid sulfide/liquid, and respeetively. (Notethatthe silicate solids neednotbe included, the solid/fluid as distribution coefficient is assumed equalto zero.) Lossof elements duringfractional vaporization is calculated iteration. by The metalandsulfur durlost ingeach1 percent solidification interval calculated is and then subtracted from the originalassemblage,
new bulk distribution coefficients are determined,
In the followingdiscussion examine partiwe the tioningbehavior Pd andCu. Theseelements of have stronglycontrasting (sulfideliquid)/(silicate liquid) partitioncoefficients are both not significantly and heldin anyothertypicalcumulus crystals. Fluid/sulfide and fluid/liquiddistribution coefficients Pd for arenotknown maficmagmatic in systems, asdisbut cussed above,are inferred to be exponential functionsof chlorideabundance. Althoughnot known, their requiredmagnitude be estimated these can if metals werepartitioned fromasulfide-bearing assemblageandtransported a fluidphase. the followin In ing,Pd andCu aretreatedastraceelements displayingNernst partitioning behavior. reality,theabunIn danceof Cu in sulfideis high and hence the Cu content a separating of fluidmaydeviate fromNernst behavior longassulfide present. as is Starting witha crystallizing assemblage bulk which initially consists 0.1 percentsulfide,25 percent of intercumulus liquid, and74.9 percentsilicatecumulates,we calculate how muchof the crystallizing liquid must have been fluid saturated and what values of
and the process repeated.Sulfurcontentof the is fluidis fixedat 5 percentaslongassulfide remains in the assemblage; sulfide beencompletely after has resorbed,the fluid/liquid distributioncoefficient for
sulfuris assumed be 40. The instantaneous to compositionof the fluid phase,Cr, separating any given at
point relativeto the starting bulk concentration is givenby:
Co'Co'
Ct= 1 Cr
(S)
fluid/liquidpartition coefficients were needed to transport metals. ore The liquid at fluid saturation is assumed be saturated a constant percentfluid to at 5 components; is, crystallization i percentliqthat of uid resultsin the exsolution 0.05 percent fluid of which contains 5 percent sulfur. The (sulfide liquid)/(silicate liquid) distributioncoefficients for
Cu andPd are takenas250 and 10,000, respectively. Neither elementis assumed partitioninto silicate to
crystals; the startof fluidsaturation, the Pd and at all

Cu residein either the sulfideliquid or the silicate
liquid.The liquidis assumed be saturated sulto in fideat 400 ppmS, anestimate based thestudy on by are less Naldrett and von Gruenewaldt(1989) for Lower liquid partitioncoefficients considerably thanthe sulfide/liquid distribution coefficient 250 of Banded series-equivalent liquid compositions. If fractional vaporization considered beequiva- for Cu and10,000forPd,thenverylittle ofthemetal is to
Shown plottedin Figure4 is the amount Cu, Pd, of and S remainingin the eumulateassemblage a as functionof the weight fractionfluid evolved.The partitioning Cu andPdintofluidisshown fluid of for solubility ranging froma solubility equalto 10 times to 10,000times solubility theliquid.Asfluidis the in evolved, sulfurin liquidis lostto the exsolving fluid phase, whichresults dissolution sulfide in of liquid into silicateliquid to preserveequilibrium.In general, Pd is retainedmuch more stronglyin sulfide thanisCu owing itslargerpartition to coefficient into thesulfide phase. Notethat,evenforlowsolubility in fluid,Pdcanbe readily if enough lost fluidisevolved to removethe cumulus sulfidecompletely. fluid/ If
PGECONCENTRATION LAYERED IN INTRUSIONS

Weight fraction intercumulus melt crystallized
o.1 I '
I I
1839
.2 I
Pd -100 --.
1.0
Pd -10
, 1.5
E
,
'"
1.o
Pd-
metal-
enriched
0.8
O3
I
-1enriched
0.008 0,012
0.2
0,004
Weight fraction water evolved
Fig. 5. Metal/sulfur ratioin residual cumulate assemblagea as function theweight of fraction fluidevolved of fromintercumulus Details fortheprevious as figure. FIc. 4. Plotof the amount S,Pd,andCu remaining a crystal liquid. of in
0.004
0,008
0,012
+ liquid assemblage, normalized startingconcentration, a to as function theweightfraction fluidevolved of of during crystallizationofintercumulus liquid.Theinitialassemblage consists 25 wt of percentliquid,0.1 wt percentsulfide, and 74.9 wt percentsili- 1989),thePGEmay leached enriched residbe or in cates. Pd andCu, the curves calculated For are assuming ele- ualsulfides different the at times during degassing the of menthas fluid/liquid a distribution coefficient labeled. as Sulfide- the cumulus pile. out = pointat whichcumulus sulfide completely is resorbed by Figure6 shows concentration the metals the of in exsolving fluid.Seetextfor additional discussion the details of of the fluid relative to the initial bulk concentrations. the calculation.
Except the case for wherePd is onlyslightly preferred in the fluid relative to the liquid, the metal is transported the fluid, unless in enoughfluid is concentration the fluidis higherthanin the origiin evolved cause complete of a separate to the loss sul- nalbulkrock;it is onlybecause relativelysmall volfide phase. the fluid/liquidpartitioncoefficientsumesof fluid are exsolved Pd is prevented If that from are higher (on the order of 100 for both elements), then Cu will be readilylostto the fluid,but Pd will still not be significantly depleteduntil all the sulfide is dissolved. the fluid/liquiddistribution If coefficientsare very large, i.e., approaching (sulfide the liquid)/(silicate liquid) distribution coefficients, then the presence sulfide of becomes much less important in termsof preventing lossof ore metalsto an the exsolving fluid.In contrast Pd,Cuisnotasstrongly to affected loss sulfide by of because liquidserves the as a significant reserveof Cu. Figure 5 shows how the metal/sulfurratio of the Cu-10 residualassemblage changes a functionof fluid as evolved. those For cases whichthe metals only in are modestly moresoluble fluidrelativeto liquid,sulin fur is lostin preference the metal,whichsuggests to
that if large amounts fluid are exsolved, of metal alloysmaybe left asa residual phase. contrast, the In if metalsstronglyprefer the solution,they can be leachedfrom the residualsulfide.Because fluid/liquid partitioning likely to be a strong is function C1 of
concentrations as noted above, and because fluid
0.004 0.008 0.012
compositional evolutionduringcrystallization inof trusions likely to be complex is (e.g.,Mathezet al.,
FIG. 6. Log of the concentration metalin fluidnormalized of to concentration the originalcrystal+ liquid assemblage the in at onsetof degassing, plottedasa function the weightfractionof of fluidevolved fromtheintercumulus liquid.Detailsasfor Figure4.
18 4 0
BOUDREAU AND McCALLUM
being rapidly depleted from the cumulate assem- ported duringthe lossof sulfideduringdegassing, blage.For metalswhich are only weakly or moder- that is more fully modeled below as a ehromatoately partitionedinto the fluid, the highestfluid con- graphicseparation process.
centrations of the metals occur when the last residual
sulfidesare resorbed. In contrast,the metal content
is highestin the first exsolving fluids for the ease wherePd is strongly partitioned into fluid.For a rock originallycontaining to 50 ppb Pd, the highest 10 fluid concentrations would be about 1 to 5 ppm.
These values are consistent with Pd solubilities in C1-
NumericalModelsof Chromatographic Separation of PGE and S duringDegassing Intercumulus of SilicateLiquids
bearingfluidsnotedpreviously. Figure 6 alsoshows that metalconcentrations tend to change only moderately duringmuchof the early stages fluid loss.During this time the presence of of sulfidecontrols metalbudget.However,one exthe ceptionisthe ease wherePd isassumed be strongly to partitionedinto the fluid. Here, the presence sulof
fide exerts much less control on the metal content of the fluid.
The trendsshown Figures4 and 6 suggest in that the removalof significant by degassing Pd requires either that the silicate/liquid partitioncoefficient be approximately largeas(sulfide as liquid)/(silieate liquid) distribution coefficients that degassing exor is tensiveenough dissolve cumulus to the sulfidefraetion completely. 0.1 to 0.5 wt percentfluid conIf taining5 percentS evolvedduringsolidification of the footwalleumulates amount fluidexpected (the of to be exsolved the crystallization approximately by of 2 to 10 percentfluid-saturated intercumulus liquid), the fluid/liquid distribution coefficients Pt andPd for
would need to be on the order of 1,000 to 10,000 to
In a moreformalattemptto modelthe migration of sulfurandthe PGE duringthe degassing intercuof mulusliquid, we assume that the exsolution fluid of fromintercumulus liquidoccurs some at depthin the cumulate pile beneath the advancingnucleation front, or floor, of the magmachamber.That is, as shown Figure 1, there is a zoneof solidification in anddegassing thatboththe nucleation such frontand the fluid saturation front moveupwardasthe entire magmaticsystemcrystallizes, with the nucleation frontalways beingahead the fluidsaturation of front. One can qualitatively justify this by notingthat the upwardgrowthof the cumulus is caused the pile by lossof heat out of the top of the magmachamber aided by convectionwithin the magmachamber, whereas solidification trappedintercumulus of liquid
would be the result of downward heat loss out of the
removesignificant amounts Pt and Pd while still of leavingsomesulfidein the source. Whether or not distribution coefficients high are possible not this is known.However,a comparison the calculated of Pd solubility low pH, Cl-riehfluidsat 700Cthat ap- comesfluid saturated at somelater time, we can simin aspects the situation ignoring of by proachhundreds ppm (e.g., Sassani Shock, plify the physical of and growth thecrystal andassume of pile that 1990) with the solubilityof Pt andPd in basaltic liq- theupward stratigraphic assemblage cumuof uids fo,2 at equivalent QFMontheorder 500ppb wehavea uniform to of and liquid.In otherwords, to a few ppm (Amosse al., 1986, in Naldrett and lusminerals intercumulus et intercumulus liquidsare conBarnes, 1986; Capobianeo al., 1992) suggests et that asfar asthe degassing that the fluid/liquid distributioncoefficients least on the cerned, it doesnot matter if one assumes at order of 100 are not unreasonable. The low modal initial cumulus assemblage formingjust aheadof is front or if the entire stratigraphic sulfideabundance noted previously the eumu- the degassing for of phases intercumulus + liquid latesbelowthe J-M reef are aboutanorderof magni- thickness cumulus tude lower than expectedfrom sulfide saturation forms first and then degasses some later time. at studies notedabove,andat leastpart of thisexisting Hence, in the first three of the four casesdiscussed sulfide fraction present inclusions othercumu- below,it is assumed onehasan initiallyuniform is as in that lus phases and henceis protectedagainst lossto a crystal+ liquid assemblage throughout the entire separating fluid. This evidenceis consistent with stratigraphic intervalunderconsideration. should It PGE transport havingrequiredthe completelossof be noted,however,that in the real system initial the sulfide fromthe eumulates beneaththe J-M reef dur- cumulate assemblage actually is formedat somedising the loss volatilefluidsexcept, of perhaps, sul- tanceabovethe degassing for front and that the stratifide inclusion cumulus in silicates sulfidegrains graphicdistance or betweenthe floor of the chamber that are otherwise isolated from equilibrating with and the solidus the cumulates of may be relatively
the fluid. It is this ease, in which the PGE are transnarrow.
crystalpile largelyby thermaldiffusion. Hence, although upward the growthof the crystal maybe pile ratherrapid,the finalsolidification thetrapped of liquid maybe considerably delayed. As a first approximation, assume we that either crystalsettlingor in situ cotecticnucleation and growthof the cumulus phases (including sulfide) at the floorof the magma chamber produces initially an uniformassemblage consisting cumulus of minerals and intercumulus liquid. Because are interested we in what happens when the intercumulus liquid be-
1841
Figures7 to 9 showthe results numerical of models movesthroughthe pile as a fluid is eventuallyexof the evolution fluidandthe transport Pd andS solved of of from solidifying intercumulus liquids.Case3: duringcrystallization intercumulus of silicate liquid. The entire crystal+ liquid pile is againinitially fluid Details of the modelsare given in the appendix. undersaturated, a stratigraphic but discontinuity exBriefly, in the simulation, startwith a model"cuwe mulatepile" consisting 69.9 percentsilicate of crystals, 30 percentsilicateliquid, and 0.1 wt percent sulfide liquid (whichis itselfcomposed 40 wt % of sulfur).The intercumulus liquid crystallizes the as crystalpile is cooledby diffusive heat lossthrough thebottom. Crystallization results aheatofcrystalin lizationthat alsomustbe lostby thermaldiffusion. Fluid is evolved fromthe crystallizing silicate liquid such thatthe volatilecontent the liquid,oncesatuof ratedin fluid, remains 5 wt percent.Sulfuris asat sumedto partitionbetweensulfide,silicateliquid andfluidaspreviously described, the sulfurconi.e., tent of the fluidis takenas5 wt percent aslongas S sulfide present is andthe silicate liquidsaturates in Pd _ Pd ists at the 500-m level suchthat liquidsbelow this heightarefluidsaturated 1,245Cwhereas liqat the uidsabove heightarefluidsaturated 1,200C. this at
This mimics the case in which the influx of a more
primitivemagmainto the chamberproduces stratia graphic discontinuity the fluid saturation in behavior of the intercumulus liquid. Case4: A stratigraphic discontinuity present is betweenthe crystal+ liquid pile anda supernatant magma--the magma remains continuously fluid undersaturated. Thesefour cases are discussed separately below.
Case 1
The initial solid+ liquid assemblage fluid satuis rated throughoutthe stratigraphic section(Fig. 7a the prosulfide 400ppm Dfluid/liqui and at S. d- 100 Dsulfide/liquib). Figure 7a shows initial stratigraphic d and = 10,000. Temperatures are initially uniform at files for Pd concentration,sulfide concentration,tem1,250Cthroughout system, the exceptat the base perature, theweightfraction and solidified. Notethe where the temperature is allowed to cool from logarithmic scale the Pd concentration the linon and
1,200 to 700Coverthe first500 yr of cooling. Oncea fluidisevolved fromthecrystallizing intercumulus liquid at anystratigraphic level, it migrates upward through crystal the pile,remaining equilibin riumwith the assemblagesit passes as through them.
ear scale on the sulfide concentration. Also, the sul-
fideconcentration the amount sulfide is of liquidpresent and not the whole-rock sulfur concentration. The
assemblageallowed coolandcrystallize diffuis to by siveheatlossthroughthe base.
Solidification results in additional fluid evolution The upwardmigrationcontinues until the fluid is either lostout the top of the crystal pile or the fluid which results in resorptionof sulfide; Figure 7b encounters intercumulus liquid that is not fluid satu- shows the loss of sulfide from the lower 700 m of the rated. In the latter case, the fluid redissolves the section in whichhasoccurred after 600 yr asa resultof intercumulus liquid; the added sulfur causesaddi- solidification degassing intercumulus and of liquids tional sulfideprecipitation. The additionof volatile near the base. Because the exsolution of fluid results components hotter, fiuid-undersaturated to liquid + in the completeresorptionof sulfideprior to the solidassemblages causes partialmeltingaswell; the complete solidificationof the rock, significant
heatofmelting supplied thesolid liquidassem- amounts of fluid that are undersaturated in sulfide is by + blage.Hence the degassing intercumulus of liquid are evolved late in the solidification of the rock. The canresultin boththeredistribution sulfur per- upward migration of these sulfide-undersaturated of and turbations the thermalprofileandin the amounts fluidscauses in sulfide dissolution alonga sharpsulfide of solidandliquidpresent. all cases, For calculations resorptionfront. Becauseof the relatively large are doneusingstratigraphic steps 5 m and time quantityof fluid evolved,the sulfideresorption of front steps 145 days. of Finally,a relatively largeamount advances faster than the thermal front; the leading of intercumulus silicate liquidis usedsothatthe ef- edgeof the thermalfront hasadvanced about300 to fectsof degassing especially migration and fluid are m, andonly the lowermost175 m of the crystalpile enhanced. Results, however, wouldbe qualitatively hassolidified completely, whereas sulfide the resorpsimilar smaller for volumes intercumulus of liquid(or tion front hasadvanced about700 m after 600 yr. to even an externalsource fluid) aslong as enough As discussed of previously, stronglychalcophile a elefluidis exsolved resorb original to the sulfide. mentsuch Pd shows as onlymodest mobilityuntil the We lookat four degassing cases. Case1:The entire sulfide completely is resorbed. andbelowthe sulAt crystal+ liquid pile is initiallyfluid saturated the fideresorption at front,Pdistransported upward the to startof the.simulation; additionalfluid evolvedfrom level at which sulfideis again encountered. With the pile is allowedto movethrough andremainin time, Pd becomes progressively enriched the sulat equilibrium with the crystal liquidassemblage + but fide resorption front, producing Pd enrichment a doesnot encounter fiuid-undersaturated any silicate front that becomes progressively richer in Pd asthe liquids. Case The entirecrystal liquidpileisini- sulfidedissolution 2: + front movesupward.In other tially fluidundersaturated a fluidsaturation and front words, all the Pd from the cumulatesbeneath the sul-
1842
BOUDREA AND McCALL U UM

fide dissolution front is concentrated at the sulfide
1000
dissolution duringdegassing. front

Case 2
The intercumulus liquidisassumed be fluidsatuto
500
0
i i
ratedonlyat temperatures below1,245C (Fig.7c). In thiscase, again we start withahomogeneous assemblageasshown Figure7a, but in thisinstance in the entireassemblagenotfluidsaturated is initially. This
results in a fluid saturation front which advances
lOOO
aheadof the sulfidedissolution front. Figure 7c shows how the system evolvedafter 200 (solid has lines)and600 yr (dashed lines).Asfor case the Pd 1, enrichment frontis again coincident with the sulfide
dissolutionfront, which follows well below the fluid
saturation front.
Pd front
500
Asthe fluids whichexsolved in the crystal low pile

migrateupwardandencounter hotter,fiuid-undersat-
front
500
--:'-:::
....
uratedliquid + solidassemblages, fluidis redisthe solved into the silicate liquid.The redissolution resuitsin three effects: the sulfurcarriedby the (1) fluidandredissolved the intercumulus in silicate liquidresults anincrease theScontent theliquid in in of abovethe 400 ppm saturation level, which leadsto additional sulfideprecipitation just abovethe fluid saturation front; (2) the additionof volatilecomponents a liquid+ solidassemblage is above to that the fluidsaturation temperature results partial in melting of the solids just abovethe fluid saturation front; in
effect, the addition of fluid to a fiuid-undersaturated
tionanddegassing ofintercumu]us liquids. co]umns, ]eft The from
assemblage changes bulk composition the suchthat the amount liquid mustincrease of (seeAppendix); c in Log 'Pd Co Wt.%sulfide Temperature Fsolid and (3) the increase liquidmustbe accomplished (C) by the melting cumulates above fluidsatuof just the FIo.?. ]Numerical models Sand transport of ?d during solidifica- rationfront. The heat of meltingis supplied from
0 I
o'.2 oI,
J-
115o ,5o 0.7 0.9
I I
to right,show concentration Pdnormalized initialconcenthe of to
both within and around the fluid saturation front and
in temperature dropto the fluidsatutration(logarithmic sca]e), weightpercent the sulfide (linear results a modest scale), temperature, theweight the and fraction (Fsolid) a ration temperature.The net result is that a modest solid as function stratigraphic and different of height at times. = liquid, stratigraphic 1, S jump in the thermalprofileandin the
= solid.(a). Initial conditions cases to $ asdiscussed the for ] in
text. (b). Case ] (the intercumulus liquid is fluid saturated migration the fluid saturation of front. throughout stratigraphic the section) showing changes asolidafter ification timeof 600 yr. Degassing resulted loss sulfide Case 3 has in of
from the ]owermost 700 m of cumu]ates so]idification as releases
amounts solid, of liquid,andsulfide accompanies the
additional which fluid absorbs cumulus sulfide. sharp enrichA Pd Themigrating fluids encounterstratigraphic a fluid mentfrontfollows sulfide the dissolution front.(c). Case (the 2 saturation discontinuity 8). Again,the starting (Fig. intercumulus isfluidsaturated at temperatures liquid only below are in the 1,245C) showing changes solidification of 200 yr conditions asfor Figure7a,except thiscase after times
(solid lines) 600 yr (dashed and lines). thiscase, In fluidreleased
intercumulus liquid below the 500-m height be-
modest increasetheamount liquid, aconsequent in of and tempera- marked fluid saturation difference in the intercumuturedrop, thefluidsaturation moves as front through crystal the the has in pile.ThePdenrichment isagain front coincident thesulfide lusliquidacross discontinuity resulted relawith
dissolution front and is well below the fluid saturationfront. See
text for additional details.
cumulus liquid abovethe 500-m height becomes fluid saturated 1,200C.After 100 yr, solidificaat saturation front (whichhasmigrated upwardto almost 1,000 m part pile proafter200 yr) asthefluidsaturation moves front through se- tionof thelowermost of thecrystal has the quence. Addition fluid thefiuid-undersaturated + solid duced fluidsaturation of to liquid a frontwhich migrated has upassemblage abovethe fluid saturation just front hasalsocaused a wardto just pastthe level of the discontinuity. The
suitsin a modestincreasein the amountof sulfideat the fluid
higher hotter and liquids arenotyetfluidsaturated. rethat This
during solidification base redissolved stratigraphically atthe is into comesfluid saturatedat 1,245C whereasthe inter-
tivelyabundant sulfide precipitation theboundary at but not above (Fig. 8a). Thisoccurs it because more

i i
1843
lOOO
level, producinga zone enrichedin both sulfideand Pd (Fig. 8c); the fluid saturation front at this later
time has reached about the 800-m level. With contin-
Fluid front
5oo
Pd front
I I I
ued degassing intercumulus of liquidsbelowthe discontinuity,the zone of S and Pd enrichmentat the levelof the discontinuity eventually displaced will be upward.However, because the large amountof of sulfide precipitated thislevel,it ispossible the at that footwallmay solidifycompletely before all the sulfideisresorbed fluids by migrating through zone. the
Case 4
s
lOOO
b)'' [' ' ' '

ol
I i I I I I
__ _ Fluid Front
' ''
L
5oo
/
S
The degassing frontis allowedto reachthe floorof the magma chamber(Fig. 9). In cases and3, it was 2 seenthat a fluidsaturation frontmayadvance rapidly through cumulate the pile,much faster thanthesolidification front. In case4, the fluid saturationfront is allowedto reach the top of the crystalpile. Within
Pd front
o
I I I
I I I
I
c
0.4
0.8
115o
125o
0.7
o.9
Log ' Pd oo
Wt. sulfide % Temperature Fsolid (C)
the crystalpile, conditions the beginningof the at simulation (Fig. 9a) are asfor case i.e., the intercu2, mulus liquidreaches fluidsaturation 1,245C.The at top of the crystalpile is at 500 m. All liquid in the
a) l i i i i i i i i i i i i i
L
FIG. 8. Case3 (the migrating fluidsencounter stratigraphic a fluidsaturation discontinuity). Starting conditions asforFigure are 7a, exceptthe intercumulus liquidbelowthe 500-m heightbecomes fluidsaturated 1,245C at whereas intercumulus the liquid above 500-mheight the becomes saturated 1,200C. fluid at (a). After100yr, fluids evolved from lowermost of thecrystal the part pilehavereached levelof thediscontinuity, the wheretheyhave redissolved precipitated and sulfide produce sulfide-enriched to a horizon. Melting,whichaccompanies fluidredissolution the the at 500-mlevel,causesmarked a lowering thetemperature in profile
500
__
o
b)l , i , i i t i i
Fluid front
i iL i i
and changestheamountsboth in of solid liquid and present the 5oo in E

cumulates across 500-mboundary. the Lower thecrystal a in pile,
Pd enrichmentfront followsthe sulfidedissolution front similarto
cases and2. (b).After450vr,thePdfronthas 1 reached disconthe , tinuityat the 500-mlevel,producing zoneenriched bothsula in
fide and Pd. The fluid saturation front has advanced to about the o
500
Pd front
800-mlevelby thistime.Seetextfor additional discussion.

500 L
fluid, andhenceS, canbe addedto the rocks just abovethe discontinuity beforethe rockcools its to fluidsaturation temperature. Melting, whichaccompaniesthe fluid redissolution the 500-m level, at
causes moremarkedloweringin the temperature a as the heat of meltingcomes fromthe eumulates and in
I
c
0.4
0.8
115o
125o
0.7
0.9
Log ' Pd oo
Wt.%sulfide Temperature Fsolid (C)
Ftc. 9. Case (thedegassing front to reach topof the around the discontinuityand more significant thecrystal 4(a).Conditions theisallowedofthesimulation: pile). at beginning changes the amounts bothsolid liquidpres- thecrystal liquidassemblage up the lower500 m of the in of and + makes section andfor whichthe initial conditions asfor are ent thanis seenin ease'2.Thisstrong cooling that stratigraphic liquid reaches fluid saturation at develops thediscontinuity cools overlying case2 (i.e., the intercumulus at also the 1,245C). intervalabove500 eumulates such that they reach fluid saturation mains All liquid in the solid-absent simulation. m refluidundersaturated throughout the (b). After sooner than if the discontinuity were not present; 200yr,thefluidsaturation has front reached topofthecrystal the hence,the high sulfideconcentration occurs that at pile,andredissolutionfluidintothesupernatant of magma results sulfide precipitation. for theprevious As figures, the the originaldiscontinuity doesnot migrateupward in additional front, which with the fluidsaturation front.Lowerin the crystal Pd enrichmentfront followsthe sulfidedissolution
to a after200 yr. (c).After500 pile, a Pd enrichment front followsthe sulfidedisso- hasmigrated about 100-mheight
lutionfront, similar eases and2. After450 yr, the point,virtually thePdandS fromthecumulus isnowconto 1 all pile Pd fronthasreached discontinuity the 500-m centrated at the 500-m level. See text for additional discussion. the at
yr, the Pd fronthasreached top of the crystal the pile.At this
1844
BOUDREAU AND McCALLUM
magma above500 m is constrained remainfluid rock sulfide abundance which is well above the exto undersaturated throughout the simulation. That is, pected modal proportionssulfide if wereprecipitatthe mass magma largeenough asto absorb of is so any ingaspartof a cotectic assemblage. However, these may to disvolatile components degassed the crystalpile firsttwocases be applicable the recently by withoutbecoming fluid saturated. Duringsolidifica- covered PGE-Au zone in the Skaergaard,where are tion, the top of the crystal pile is not allowedto con- marked metal enrichments broadly associated increase sulfide in abundance to tinueto advance crystallization cumulates by of from with a stratigraphic cotectic proportions do not apbut the supernatant magma, assumption maybe approximately an that defendedon the grounds that volatile components pearto be associated eitherzones magma with of or abundance sulfide of (Birdet al., addedto the magma will inhibit crystallization. The mixing anexcess evolution the system of after 200 yr is shown Fig- 1991). in ure 9b. At this point,the fluid saturation front has Cases3 and 4, however,illustratethat the presdiscontinuities, as may such reached top of the crystal the pile andredissolution ence of stratigraphic additions haveocof fluidintothe supernatant magma results sulfide format levelswherenew magma in sulfide precipitation durprecipitation. for the previous As figures, Pd en- curred,mayleadto excess the
richment front follows the sulfide dissolutionfront,
ingdegassing. sulfide then This may becomesignifia
trap frontas whichhasmigratedto abouta 100-m heightafter cantstratigraphic for thePdenrichment 200 yr. After 500 yr, the Pd fronthasreached top it arrives at some later time. Once formed, the Pdthe of the crystal pile (Fig. 9c). At thispointessentially and S-enriched zone will remain at the level of the except thecase which for in enough volall Pd andS fromthe cumulus is concentrated discontinuity pile at the 500-m level. No lossof S or Pd wouldbe possible atile material still present the footwall comis in to fromthe top of the crystal pile, asthe fluidfrontcan- pletely resorb abundant the additional sulfide precipitatedat the discontinuity. However,in the case of not migrate pastthe top of the pile. We cansummarize several importantpointsfrom onlypartialresorption, continued degassing the of
footwall preferentially will resorb sulfide thebase at of the sulfur-enriched leaving PGEpreferzone, the enriched relative Sat thebase. to Such proa pected coincide to with whatwouldnormally de- entially be may for, enhance, offsets PGE scribedas the stratigraphic level in which sulfide cess account or at least
these four cases. First, Pd will be concentratedat the sulfidedissolution front. That is, Pd enrichment is ex-
wouldfirst occurasa cumulus phase.Second, fluids such as occur in the Main Sulfide zone of the Great
exsolved from the section below the Pd front are not
Dyke (e.g.,WilsonandTredoux, 1990),whereit is observed PGE concentrations highest the that are at baseof the sulfide zoneprior to maximum enrichalthough is not shown Figures to 9, fluidsexit in 7 solving from the sulfide-absent assemblages below ment in sulfur and the base metals. Oneshould noteseveral possible problems comor the Pd enrichment front containvery little Pd (and in with chromatoS),andthePdconcentration onlymarginally is higher plications connection the simple separation model presented as here.For exin thesefluidsoncethey migrateabovethe Pd zone. graphic it that from crystalIt is onlyasthe fluidsmigratepastthe Pd frontthat ample, isassumed allfluidcomes of liquid,whereas some fluidmaybe theydissolve some the S andPd asthey attemptto lization trapped of into fromthe country rock. remainin equilibrium with the changing mineralas- migrating the intrusion that fluidswill move unisemblage. Once the fluidsreach equilibriumwith Also, it hasbeen assumed upward arenotinhibited adcumulate and by sulfide, Pd is recaptured the sulfide. is only formly the by It of The asthe sulfide dissolution front migrates upwardthat layers lowor nopermeability. ideathatfluids beneath "impermeable" layers must the Pd front migrates upwardaswell. Also,the fluid maybe trapped saturation front need not be coincident with the minbe considered something anidealization, rocks of as eralization front; instead the fluid saturation front arerarely100percent adcumulate, furthermore, and permeability is seen as by may advanceupward ahead of the mineralization evensolidrockhassome front. the fact that there is no free fluid phase foundbelayers.Fluid migration may be Finall-y, casesand2, thePdenrichment is neath adcumulate in 1 front associated with the dissolution of sulfide and hence slowed through zones wherethereis some decrease and henceenjoy a temporary the highest concentrations seenin rocksin in the permeability Pd are which the sulfideabundance actuallydecreasing buildupbeneaththe zone,but this doesnot mean is pass through. Furtherwith time. That is,Pd enrichment highest is immedi- that theywill not eventually rocksmay form relativelylate in atelypriorto thestratigraphic occurrence rocks more, adcumulate of in which the modal abundance of sulfide increases to thecrystallization thecumulates such of by processes accompanying compacthe expected cumulus abundance. These simple as infiltration metasomatism two Irvine,1980),bywhich timethechromatomodels thusdo not explain J-M reef, since the PGE tion(e.g., frontmayhavemoved through. enrichment accompanies a marked increase whole- graphic in
the sourcefor the ore metals in the Pd front. Indeed,
1845
Thechromatographic presented repro- would tend to channel some amount of fluid and ore model here
duces manyof the first-order effects whichcharacter- elementsout toward the thinner stratigraphic sec-
ize these deposits, particular orders magni- tionsasfluidmoves in the of laterallyalongmorepermeable

tude enrichment in Pd and the association with
layers.
Conclusions
changes the stratigraphic in abundance sulfur.Alof thoughonemayimagine several observations which maysupport chromatographic the process preferin ence to conventional models,we presentbut two. First, in the chromatographic model, PGE sulfide zones wouldbe expected develop to onlywithinthe thick pile of cumulates the floor of an intrusion on
It is suggestedthat PGE-enriched horizons in
andnotin the marginal rocks crystallizing along the

wall or roof of the intrusion, becausethe rock se-
layered intrusions formduringthe separation can and migration Cl-bearing of fluids mobilized comthat ore ponents originallyheld in sulfideprecipitated part a of a cotectic cumulus assemblage. highPt andPd The concentrations (higherthancanbe accounted by for trappedliquid concentrations alone)and the pres-
quences thin in the marginal are rocks, andfluid mi- ence of sulfide as inclusions in cumulus oxides and gration,at leastalongthe walls,need not be normal silicates the cumulates in beneaththe J-M reef of the Complex interpreted consistent are as with to the crystallization front.In contrast, a magmatic Stillwater if sulfide saturation event occurred midway thecrys- the precipitationof sulfideasa hostfor the PGE as in assemblage. low sulfurconThe tallization a magma of chamber conventionallypart of the cumulus as of and proposed, it should recorded the marginal centrations the footwallcumulates the presthen be in rocks well asat the floor.One wouldexpect as that enceof PGE-andS-enriched pegmatoids beneath the J-M reef are consistent with the later lossof some the convection magma these of past sulfide-bearing fluid.Mass balance calculamarginal rockswouldlead to somedegreeof PGE PGEandSto a separating enrichment the sidewallto produce mineralized tionssuggest enrichments Pd andPt required in a that in zoneequivalentto the mineralization formedon the of a cumulates source readilyattainable sulfide are if floor.Marginal rocks whichformed growing by on precipitates part of the cumulus as assemblage. a If the sideor roofof the Stillwater magma chamber are 0.1- to 0.5-wt percentfluidwere evolved duringsonot exposed the Stillwatercomplex. in However,in lidification the footwallcumulate of sequence (the by of thoseintrusions wherethere are exposed marginal amountof fluid exsolved the crystallization rocks whichnominally record compressed sequences from 2 to 10% fluid-saturated intercumulus liquid) of the cumulates formed on the floor of the intrusion without completelyresorbingthe cumulussulfide (e.g.,asis seen the Skaergaard in intrusion in the fraction,the fluid/(silicate and liquid) distribution coeffiGreat Dyke of Zimbabwe), there are no reported cients Pt andPd wouldneedto be approximately for PGE-richsulfidezonesequivalent thosein the aslargeasthe (sulfide to liquid)/(silicate liquid) distrifloor cumulates these intrusions. in Second,it is bution coefficients order to removesignificant in notedthatin the Bushveld intrusion platiniferous amounts Pt andPd.Considerably the of smaller fluid/liqare reefsdo not lap ontothe country rocks whichwere uid distributioncoefficients required if enough locallypart of the chamber floorwhenthe ore zones fluid is evolved to remove the cumulus sulfide comofthatintrusion wereforming figs. and2 ofVon pletely.Isolation somesulfidefrom the fluid, by (of. 1 of Gruenewaldtet al., 1985). If the ore zoneshad trapping cumulate in minerals example, for wouldreless formed the settling sulfide by of through relatively quire proportionally fluid and alsoallow some to thickcolumns magma, of thenthe sulfide should set- ore components remain in the sourcecumulates. presented here for the enrichment Pd of tle indiscriminately exposed on country rockaswell The models processes suggest some of as on the cumulates the floor of the magma andSby chromatographic on that the chamber, whereas formation orezones the the complexity mightaccompany solidificathe of by chromatographic mechanism described here would tion anddegassing intercumulus of liquid. be produced entirelywithin the floor cumulate seMuchof thedebate overthe originofPGEdeposits quenceonly. in layeredintrusions involves which "Maxwell'sdeFinally, a possible test of the chromatographic mon" one findsmostplausible: fluid transport promodel would tosee there along-strike be if is variabil- cesses the effects volatilecomponents the and of on ity in PGEgradethat mightcorrelate with the thick- crystallization magmas, magma of or mixing andsulnessof underlying cumulates. However,one must fide precipitation processes. The collectionof the note that fluid migrationand sulfide dissolution PGEby directmagmatic sulfide precipitation remay fronts have horizontal may a component: thefronts quire sulfideequilibration as with as muchas 7 km of moveupward theymayalso movelaterally. Thislat- magma with closeto !00 percentremovalof Pt and eral movement wouldbe enhanced the factthat Pd (Naldrett al., 1986).A fluidtransport by et interprelayering layered in intrusions generally inward tationrequires dips that the PGE are preconcentrated in toward the thickest sectionsof cumulates,which footwallcumulates the precipitation cumulus by of
1846
BOUDREAUAND lVlcCALLUM
crystal growth thethermal and regime cooling of magmas: Jour. sulfide. The unusually Cl-rich assemblages the cuin Geophys. v. sec.B12, p. mulatesbeneaththe J-M reef may be fortuitousor Brimhall, Research, 89,D. A., 1987,10161-10177. G. H, andCrerar, Ore fluids: Magmatic to they mayindicate Cl-richenvironment the necessary supergene: Mineralogy,v. 17, p. 235-322. Rev. for the efficienttransportof Pt and Pd. The anoma- Campbell, H., Naldrett,A. J., andBarnes, J., 1983, A model I. S.
lous PGE- and S-rich bodies that occur below the for the originof the platinum-rich sulfide horizons the Bushin
veld andStillwater complexes: Jour.Petrology, 24, p. 133v. level of the J-M reef, but not immediately abovethe 165. reef,maybe considered evidence thelatetrans- Capobianco, J.,Hervig,R. L., andAmelin,A. A., 1992,Effectof as for C. port of ore elements the fluid transportmodel. by oxygen fugacity meltcomposition PGEsilicate soluand on melt
The excess modal sulfide concentrations observed in
bilities [abs.]: Geophys. Am. Union Trans., 73, Spring v. Meeting

Supp., p. 344.
the J-M reef wouldrequireeither sulfide saturation alone during magmamixingor someother mechanismto producethe concentrations sulfideabove of expected maximum cotectic proportions about0.1 of wt percent. contrast, addition a sulfur-bearIn the of ingfluidto a fiuid-undersaturated canresultin liquid excess sulfideprecipitation. We do not think that the "silver bullet" has yet beenfoundwhichcankill offeitherof thesehypothewhich could be made both in other intrusions and in
Carroll,M. R., andRutherford, J., 1985, Sulfideand sulfate M. saturation hydrous in silicate melts: Jour.Geophys. Research, v. 90 (supp.),p. C601-C612. Corm,H. K., 1979, The Johns-Manville platinum-palladium prospect, StillwaterComplex,Montana,USA: Canadian Mineralogist, v. 17, p. 463-469.
Davies,G., andTredoux, M., 1985, The platinum-group element andgoldcontents the marginal of rocks sills the Bushveld and of Complex: ECON. GEOL., 80, p. 838-848. v.
Foose,M.P., and Nicholson, W., 1990, Sulfideinclusions S. within
the B chromitite, Stillwater Complex, Montana: U.S.Geol.Surses.However, the observations calculations and prevey Bull. 1674, 22 p. sented here suggestmany possibleobservations Holland,H. D., 1972,Granites, solutions base and metaldeposits:
experimentalsituationswhich might further con- Holloway,J. R., 1987, Igneous fluids: Rev. Mineralogy, 17, p. v. 211-234. strainthe petrogenesis PGE zones layeredintruof in
sions.
ECON.GEOL.,v. 67, p. 281-301.
Acknowledgments 422-427. Thisworkwasfunded NationalScience by Founda- Irvine, T. N., 1980, Magmaticinfiltrationmetasomatism, double diffusive fractional crystallization, adcumulus and growthin the tiongrants EAR 8803340 andEAR 9017069. Critical Muskoxintrusion and other layeredintrusions, Hargraves, in comments S. J. Barnes by andthree Economic GeolR. B., ed., Physics magmatic of processes: Princeton, Princeton ogyreviewers haveresulted a muchimproved in preUniv. Press,p. 325-383. sentation are very muchappreciated. and Keays,R. R., Hamlyn, P. R., and Shane,J. R., 1991, Platinum
Hsu,L. C., Lechler,P. J., andNelson,J. H., 1991, Hydrothermal solubility of palladium in chloride solutionsfrom 300 to 700C:Preliminary experimental results: ECON. GEOL., 86, p. v.
October 1990;April 21, 1992 24,

REFERENCES
Amosse, Allibert, M., Fisher,W., andPiboule,M., 1986, Etude J., exp6rimentalde la diffrenciationdes platinoidesdans un Internat., no. 3, p. 45-60. magma silicate ultra-basique. R6sultats pr61iminaires [abs.]: PIR- Kushiro,I., Yoder, H. S., and Nishikawa,M., 1968, Effect of water SEM Convention,1986, Montpellier,Abstracts 19. p. on the meltingof enstatite: Geol. Soc.America Bull., v. 79, p. Barnes,S. J., and Campbell,I. H., 1988, Role of late magmatic 1685-1692. fluidsin Merensky-type platinumdeposits: discussion: A GeolMathez,E. A., Dietrich,V. J.,Holloway, A., andBoudreau, E., J. A. ogy, v. 16, p. 488-491. 1989, Carbon distribution the Stillwater in Complex evoluand Bird, D. K., Brooks, C. K., Gannicott, R. A., and Turner, P. A., tion of fluid duringcrystallization Stillwaterand Bushveld of 1991, A gold-bearing horizonin the Skaergaard intrusion,east magmas: Jour.Petrology, 30, p. 153-173. v. Greenland: Eco. GEOL., 86 p. 1083-1092. v. McCallum, I. S., Raedeke,L. D., and Mathez, E. A., 1980, InvestiBoudreau, E., 1992, Volatile fluid overpressure layered inA. in gations the Stillwater of Complex. I. Stratigraphy strucPart and trusions and the formationof potholes: Australian Jour.Earth ture of the Banded zone:Am. Jour.Sci.,v. 280A, p. 59-87. Sci., v. 39, p. 277-287. B. andtransport Boudreau, E., andKruger,F. J., 1990, Variationin the composi- Mountain, W., andWood, S. A., 1988, Solubility A. of theplatinum-group elements hydrothermal in solutions: Thertion of apatitethrough Merensky the cyclicunit in the western modynamicand physical chemical constraints,in Prichard, Bushveld Complex: ECON.GEOL., 85, p. 737-745. v. H. M., Potts,P. J., Bowles, F. W., and Cribbs,S. J., eds.GeoJ. Boudreau, E., andMcCallum, S., 1986, Iuvestigations the A. I. of Platinum New York,Elsivier,p. 57-82. 87: Stillwater Complex:III. The Picket Pin Pt/Pd deposit:ECON. Naldrett,A. J., andBarnes, S.-J.,1986, The behavior platinum of GEOL.,v. 81, p. 1953-1975. group elementsduring fractionalcrystallization partial and -- 1989, Investigations the Stillwater of Complex: PartV. Apameltingwith special reference the composition magmatic to of titesasindicators evolving of fluidcomposition: Contr.Mineralsulfide ores: Fortschr. Mineralogle, 64, p. 113-133. v. ogyPetrology, 102, p. 138-153. v. Naldrett,A. J., andvonGruenewaldt, 1989, The association G., of Boudreau,A. E., Mathez, E. A., and McCallum, I. S., 1986, The PGE with chromititein layered intrusions and ophiolite comhalogengeochemistry the Stillwater and BushveldComof plexes: ECON.GEOL., 84, p. 180-187. v. plexes: Evidencefor the transportof the platinum-group eleNaldrett, A. J., Cameron,G., yon Gruenewaldt, and Sharpe, G., ments Cl-rich fluids: by Jour.Petrology, 27, p. 967-986. v. M.R., 1986, The formation of stratiformPGE depositsin Brandeis, Jaupart,C., and Allegre, C. J., 1984, Nucleation, G.,
groupelementbehavior throughout 5.3 km stratigraphic a section of the StillwaterComplex,Montana/abs.]: Internat. PlatinumSymposium, Perth,Australia, 6th, July8-11, Program and Abstracts, 27-28. p. Korzhinskiy, A., 1981, Apatite solidsolutions indicators M. as of the fugacity HC1andHF in hydrothermal of fluids: Geochem.
PGE CONCENTRATIONIN LAYERED INTRUSIONS
1847
layeredintrusions, Parsons, ed., Originsof igneous in I., layering:Boston, Reidel,p. 313-398. D. Page,N. J, 1971, Sulfide minerals the G andH chromitite in zones of the StillwaterComplex, Montana: U.S. Geol. SurveyProf.
cumulus liquidasthe crystal pile solidifies a result as of heat loss of the bottomof the crystalpile. Folout lowingBoudreau (1992), crystallization governed is by the evolution temperature of with time whichis Paper 694, 20 p. Page,N. J, andMoring,B.C., 1990, Petrology the noriticand taken to be controlledby two parameters: of thermal gabbronoritic rocksbelowthe J-M reef in the Mountain View diffusion, and thermalchanges involving latent the area, StillwaterComplex,Montana: U.S. Geol. SurveyBull. heatof crystallization. Makinga simplifying assump1674-C, 47 p. tion that the heat capacities densities the liqand of Page, J,andZientek,M. L., 1987,Composition primary N. of postcumulus amphibole phlogopite and withinan olivinecumulate uid andsolid phases equal(andignoring small are the in the StillwaterComplex,Montana: U.S. Geol. SurveyBull. heat capacity contribution any fluid phase),these of 1674-A, 35 p. effects be expressed a numerical can by analogue to Page,N. J, Riley, L. B., andHaffty,J., 1972, Verticalandlateral the followingone-dimensional transport heat reacvariationof platinum,palladium, andrhodiumin the Stillwater
Complex, Montana: EGOS. GEOL., 67, p. 915-923. v. Page,N. J, Zientek, M. L., Czamanske, K., and Foose,M. P., G. 1985, Sulfidemineralizationin the Stillwater Complexand underlying rocks: Montana Bur. MinesGeology Spec. Pub.92, p.
93-96.
tion equation:
aT
at - K
O2T AHem, st
pcp -- ' dt
(al)
Raedeke, D., and McCallum, S., 1984, Investigations the L. I. of StillwaterComplex: Part II. Petrology andpetrogenesis the of Ultramafic series: Jour.Petrology, 25, p. 395-420. v. Sassani, D.C., andShock, L., 1990, Speciation solubility E. and of palladium aqueous in magmatic-hydrothermal solutions: Geology, v. 18, p. 925-928.
wheret is time, x is the one (vertical)dimension, is K
thethermal diffusivity, iStheheat cp capacity, AHcryst

is the latentheatof crystallization, is the temperaT
ture,is density, is rate change p the and the of of
Shaw, M., 1970,Traceelement D. fractionation duringanatexis: the mass crystalline of material unit volume per with Geochim. Cosmochim. et Acta,v. 34, p. 237-243. time. Tacker,R. C., andStormer, C., 1989, A thermodynamic J. model Heat lossfrom the eumulate+ liquid assemblage for apatite solidsolutions, applicable hightemperature to geologicproblems: Mineralogist, 74, p. 877-888. Am. v. will resultin crystallization. Hencethe change the in Talkington, W., andLipin, B. R., 1986, Platinum-group R. min- amount crystalline of materialcanbe expressed a as eralsin chromiteseams the StillwaterComplex,Montana: function the gainor loss heat,q, with time: of of of
ECON.GEOL.,v. 81, p. 1179-1186. Todd, S. G., Keith, D. W., LeRoy, L. W., Schissel, J., Mann, D. E. L., andIrvine,T. N., 1982,The J-M platinum-palladium reef of the Stillwater Complex, Montana: Stratigraphy petroI. and logy:ECON. GEOL., 71, p. 1270-1298. v. Volfinger,M., Robert,J. L., Vielzeuf,D., and Neiva, A.M. R., 1985, Structural controlof the chlorinecontentof OH-bearing silicates (micas amphiboles): and Geochim. Cosmochim. et Acta,
v. 49, p. 37-48.
at
Oq at'
whereis mass the crystallizedheat per unit loss
and the transferfrom difO heat resulting is thermal

fusion.In the followingexamples, is assumed it that anassemblage, originally consisting 30 percent of interstitial liquid,will solidify uniformly overa temperaturerangeof 100C.Thusone candefinethe thermal requirement solidification for as
O
--
Von Gruenewaldt, Sharpe,M. R., andHatton, C. J., 1985, The G., Bushveld Complex: Introductionand review: ECON.GEOL., v.
80, p. 803-812.
Westland, A.D., 1981, Inorganic chemistry the platinum of group elements: Canadian Inst. Mining MetallurgySpec.Vol. 23, p.
5-18.
Whitney,J. A., 1984, Fugacities sulfurous of gases pyrrhotitein bearing silicic magmas: Mineralogist, 69, p. 69-78. Am. v.
Wilson, A. H., andTredoux, M., 1990, Lateral and vertical distri-
0.3
In the numericalexperiments, coolingis through the base only,whichiscooled uniformly from1,200 GEOL.,v. 85, p. 556-584. to 700C overthe first500 yr of the simulation: this Zhu, C., and Sverjensky, A., 1991, Partitioning F-C1-OH D. of severe overstepping the solidus of nearthe between minerals hydrothermal and fluids: Geochim. Cosmo- prevents et
chim. Acta,v. 55, p. 1837-1858. Zientek, M. L., Czamanske, K., and Irvine, T. N., 1985, StratiG. graphyandnomenclature the StillwaterComplex: of Montana
bution platinum-group of elements petrogenetic and controls on the sulfide mineralization the P1 pyroxenite in layer of the Darwendalesubchamber the Great Dyke, Zimbabwe:ECON. of
Oq(0.3Hcryst ' +100Cp) (A3)
base. Values constants = 10- em s-1; = for are . ep 1 j.g-1. oc-; Hst = 350 J.g-; Pliquid 2.7 =
g. cm (e.g.,Brandeis al., 1984).The space is -a et step takenas500 cm andthe time stepis takenas
Bur. MinesGeology Spec.Pub.92, p. 21-32. Zientek,M. L., Foose,M.P., andMei, L., 1986, Palladium, platinumandrhodium contents rocks of nearthe lowermargin the of StillwaterComplex,Montana: ECON.GEOL., 81, p. 1169v.
1178.
time =0.5 step) (A4) step (space
= 145 days. The following section addresses separation the of Degassing duringcrystallization assumed be is to fluid asit evolves duringcrystallization the inter- suchthat the HO contentin the liquid remains a of at
APPENDIX
1848
BOUDREAUAND McCALL UM
constant percent.Metal andsulfurpartitioning 5 are throughB shows that the bulk solidscomposition takento be asdiscussed Figures4 to 6, with the will migrateto point S and (asfoundby the lever for distribution coefficient for Pd between fluid and sili- rule) impliesthat liquid is now more abundant than cateliquid, d, equal 100.Thetemperature are solids. system coolerbecause heat of K[/ to is The is the assumed be initiallyuniformat 1,250Cthrough- melting to mustcomefromthe rockitselfif thereis no out the system; fluidis assumed beginto exsolve outsidesourceof heat. The liquid at point L is asto once system cooled the has belowsome arbitrary tem- sumedto becomefluid saturatedat 5 wt percent perature which is different in the severalcases stud- water. Alternatively,this impliesthat the ratio of ied (seebelow). Any fluid which doesexsolve as- mass melt produced a givenvolumeof water is of for sumed risethrough cumulate to the pile, maintaining added to a fluid-undersaturated liquid is 20/1. Fiequilibrium with the bulk assemblage it migrates nally, the temperatureat which fluid saturation as ocupward, and redissolveonce it reaches a level at cursmayvary in eachof the simulations. which the temperatureis abovethe fluid saturation Once a fluid is exsolved, is allowed to migrate it temperature. upwardbut mustremainin equilibrium with the asThe behavior of volatile elements is taken to be as semblages eachstratigraphic at level.If the fluidmishown schematically FigureA1 for a three-compo- grates in through interval an whichisalready fluidsatunent system definedby two solidsilicatephases (A rated,the mass fluiddoes change, the Sand of not but andB) andwater. Considera fluid-undersaturated as- Pd contentmustremain in equilibrium.Hence, for semblage consisting A andB andsilicate of liquid(L1) Pd,thetotalmass Pd at anygiven Mtotal, of interval, Pd at 1,250C.For a bulk solids composition the whenthe fluid first entersthe intervalis givenby: of S1, bulkcomposition anassemblage is70 percent for that pd = Pd d- Pd Mtota Mfiuid Msolids+liquids (A5) I , solid be at pointB. At thistemperature bulk will and pd Pd composition, fluidphase a cannot present be andany whereMfluid mass = Pdm the flmdandMsolids+liquids fluidadded the system dissolve the liquid. = mass in the silicatesolids,silicateliquids,and to will into Pd This results a migration the bulk composition the sulfideliquid assemblage. new equilibrium in of The alongthe dotted"fluid mixingline," in thisease,to concentration the fluid, irafluid, is constrained in s,'d by pointB2.The tie line connecting solids the composi- the bulk distributioncoefficient(found by application and the liquid composition mustpass through tion of eq. 7) between fluid and the liquid + solid thisnewbulk composition. Additionof enough fluid assemblage follows: as suchthat all four phases B, liquid, and fluid) are (A, M, Pd fluid presentwill constrain liquid composition mithe to M fluid grate to point L2. A line from L and extending (A6)
--
PdI - [/lfPd ' (mtota l,Xfluid ! M solid +liquid
H20
where d= mass fluidandMsolid+liquid of Mflui of = mass

silicate solids,silicate liquids, and sulfide liquid. Rearranging equations (AS)and(A6), onecalculates the Pd concentration after equilibrationwith the
solid+ liquid assemblage:
l/,Pd
= M + D.Msolid+liqui *xfluidfluid d
Mfluid ' Mtotal
pd
(A7)
The differencebetweenthe concentration Pd (and of
similarly S)in the fluidbeforeandafterequilibrafor tion with the solid+ liquid assemblage that mass is whichis eithergained lostfromthe interval. or For any fluidsencountering fiuid-undersaturated liquids, fluidisassumed dissolve the to completely as
A s s B
discussed above and the Pd and S concentrations are
FIG.AI. Schematic phase diagram the solids andB, plus for A water.Dashed linesare isotherms temperatures at noted.Simplified afterthe forsteritc-quartz-water system (e.g.,Kushiro al., et 1968). Seetext for additional discussion.
addedto the bulk liquid + solidconcentrations. Any
sulfurover the 400-ppmsulfidesaturation limit of thesilicate liquidisassumed precipitate sulfide to as whichis composed 40 wt percentsulfur. of

Concentration of Platinum-Group Elements by Magmatic Fluids in Layered Intrusionss

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Concentration of Platinum-Group Elements by Magmatic Fluids in Layered Intrusionss

Uploaded by

Copyright:

Available Formats

Economic Geology

Vol. 87, 1992, pp. 1830-1848

Concentration Platinum-Group of Elements Magmatic by Fluids in Layered Intrusions

Department Geology, of DukeUniversity, Durham, NorthCarolina 27706

Department Geological of Sciences, AJ-20,University Washington, of Seattle, Washington 98195

Stillwaterand BushveldComplexes must have involvedthe interaction a volatile-rich of fluidphase at

PGE CONCENTRATION IN LAYERED INTRUSIONS

rich fluid phasethat exsolvesfrom a silicate liquid.

wall rocks.On encountering stratigraphically higher,

wouldactto obscure magmatic the originof the deposits (e.g.,Barnes andCampbell,1988).

BOUDREA AND McCALL U UM

Stratigraphic Trendsof SulfideMineralization

andtheHalogens the Stillwater in Complex

Picket I Pin DepasitI

3,000II)I S (GN IOlivine-eing

I (OB - [J-M I) Reef

dunite, I ' B chromitlte A C Basal Series disseminated

PGE CONCENTRATION IN LAYERED INTRUSIONS

ciated with the G chromitite in the Ultramafic zone

fied(Page al., 1985).Apatite et compositions within

typicallyrangefrom 0.001 to 0.016 percent(e.g.,

chromitites of the Peridotitc zone of the Ultramafic

BO UDREA U AND McCALL UM

lost to form the PGE-rich bodies noted above and, as

suggested here,mayhavegoneintothe formation of the J-M reef duringdegassing intercumulus of liquid.

tially may have been even higher than is now observed.

PGE CONCENTRATION IN LAYERED INTRUSIONS

Cliqidconcentration = ofelement liquid. in

Formationof the RequiredEnrichments the in

easePd wouldbehaveas a compatible element.In

gree adeumulatemay have their Pd content increased a factorof up to 10 timesthe parentliquid by

Above Ultramarie Above Basal series Series

50 ppm '200ppb 7,50ppb

,5ppm `20ppb 75 ppb

1 ppm ,5ppb 19 ppb

the tonnage and grades the PGE-enriehed of bodies

[;(calc. - obs.) = 28.3 ppm

rnD 2.5 -observed

Total -- 32.8 obs. ppm

observedthicknessof the cumulatesbelow the reef,

mulus liquidhas Sconcentration byequilibthe fixed

PGE CONCENTRATION IN LAYERED INTRUSIONS

fluidpressure 1,027C at andfs2 -1.60 andatfo =

in more detail below.

solidification the intercumulus of liquid.Thisis dis-

means that the fluid will be able to contain four times

cussed the calculations in below. In addition,some more Pd.

BO UDREAU AND McCALLUM

more efficientlossof Pt and Pd to exsolving fluids compared with other intrusions.

point relativeto the starting bulk concentration is givenby:

crystals; the startof fluidsaturation, the Pd and at all

PGECONCENTRATION LAYERED IN INTRUSIONS

Weight fraction water evolved

Weight fraction water evolved

compositional evolutionduringcrystallization inof trusions likely to be complex is (e.g.,Mathezet al.,

BOUDREAU AND McCALLUM

sulfidesare resorbed. In contrast,the metal content

NumericalModelsof Chromatographic Separation of PGE and S duringDegassing Intercumulus of SilicateLiquids

PGE CONCENTRATION IN LAYERED INTRUSIONS

ear scale on the sulfide concentration. Also, the sul-

assemblageallowed coolandcrystallize diffuis to by siveheatlossthroughthe base.

BOUDREA AND McCALL U UM

dissolution duringdegassing. front