American Mineralogist,

Volume 63, pages 641463,

1978

in Phase intervals basalt-andesite-HzO compositions throughcrystallization zonemagmas at 30 kbar with implications subduction for
R. CseRI-ns SrenN rs ia Lamont-D ohe ty Geologi cal Obse ory of Columb Uniue ity r ruat Palisades. New York 10964 eNp PnrsRJ. Wvt-lIr Sciences,Uniuersityof Chicago Departmentof Geophysical Chicago,Illinois 60637

Abstract The melting relationships a gabbro (olivinetholeiite,quartz eclogitecomposition)and of at tonalite (andesite composition)with varying amountsof HrO addedweredetermined 30 and HrO, clinopyroxene garnet With 5 percent kbar pressure usingpiston-cylinder apparatus. the throughout crystallization arethe liquidus minerals the basalt, for and theyoccurtogether at for intervalfrom 1260o 760oC. to With 5 percentHrO, garnetis the liquidusphase andesite occur together 1200'C and it crystallizes alone through l00oC; garnet and clinopyroxene of throughthe rest of the crystallization intervalfrom 1l00o to 740'C. Compositions garnets, microprobeat the followingtemperand weremeasured with electron clinopyroxenes, glasses atures:tonalite, ll75o (Ga,Gl), 1100"(Ga,Cpx,Gl),1000"(Ga,Cpx,Gl),900" (Cpx,Gl); on (Ga,Cpx), gabbro,1200" I100"C(Ga,Cpx). Published databy T. H. Greenand Ringwood combinedwith thesenew data, hydrousand anhydrous calc-alkaline rock compositions, intervals. definecompositional trendsfor mineralsthrough the upper parts of crystallization of From these trends and thermodynamic constraintsfor mineral pairs, the compositions minerals through the completecrystallizationintervals were calculated.Using calculated of the mineralcompositions estimated and mineralproportions, compositions equilibrium intervalsof hydrousand anhydrous liquid paths were calculated through the crystallization liquidsin the crystallizabasalts, basaltic andesite, andesite. and of Compositions quenched well agree microprobe with the electron with 5 percent tion intervalof andesite HrO measured liquid paths.Equilibwith calculated compositions, supportingthe validity of the calculated chemical rium liquid paths for basaltsand andesites 30 kbar divergefrom the average at With variationtrend oftypical calc-alkaline rocks(basalt-andesite-dacite-rhyolite). decreasing temperatureand increasingSiOz content, the liquid paths increasein Cal(Mg*Fe) than for anhydrous. comparedwith the averagetrend, more so for hydrouscompositions With equilibrium partial fusion of quartz eclogite,the first liquids are richer in SiO, than average andesites, significantly if HrO is present. so Liquids with SiO, contentcorresponding positionsuchas a thermalvalley;they aresituatedwithin a to andesites occupyno distinctive oceancrust at 100 continuoussequence liquid compositions. of Partial meltingof subducted km depth producesliquids with a range of intermediate SiOr contents,but thesemust be with chemistry modifiedby fractionationat shallower depthsif they are to reachthe surface to lavas. corresponding average calc-alkaline Introduction Recent andesites and associated calc-alkaline rocks occur above Benioff zones of seismic activity, which mark the position at depth of subductedoceanic crust and lithosphere. The reported petrochemiffi03-004x/78/0708-0641$02.00

to rockstransverse volcanic of cal variations igneous that thereis a to arcshavesuggested many geologists correlation betweenthe chemistryof erupted rocks 1968; zone(Kuno, 1966, and the depthto the seismic 1968,1973;Dickinson and Hatherton, Dickinson, and 1968;Jake5 White,1970;Lopez1967; Sugimura,

641

642

STERI/ AND WYLLIE: PHASE COMPOSITIONS

Escobaret al., 1977).If there is such a correlation, Experimentalapproach the chemicalvariationsreportedshouldbe explicable (1968) In a pioneering study, Greenand Ringwood in termsof the phaserelationships the materials determined phase relationships anhydrous of the of oliprovided involved, that the processes known.Un- vine tholeiite, quartz tholeiite,basalticandesite, are and fortunately,the processes have not beenadequately andesite compositions 18, 27, and 36 kbar. They at defined, havethe phase nor relationships possible measuredthe compositionsof garnetsand clinopyof materialsyet beendetermined sufficient in detail for roxenesin near-liquidusruns, and estimatedtheir critical teststo be madeof competinghypotheses. proportions.From thesedata they calculated equilibThe simplestproposalis that primary intermediate rium pathsofliquids for up to 35 percent crystallizaand acid calc-alkalinemagmasform by differentde- tion. They concludedthat, in the range27-36 kbar, greesof partial meltingof oceanic crust,consisting fractional crystallization basalt,as well as "liquid of (partlymetasoma- fractionates"from quaftzeclogitebulk composition, mostlyof abyssal olivinetholeiite tized and metamorphosed) and siliceoussediments, broadly follow the calc-alkalinetrend, and that the which descended into the mantle in a subduction low-meltingcompositionis andesitic. Experiments zone(Stille,1955; Coats,1962; Greenand Ringwood, with uncontrolledHrO contentsindicatedthat the 1968;Ringwood,1969; Armstrong,1968; Hamilton, low-meltingfraction under hydrous conditionsis 1969a,1969b1, Dickinson, 1970;Oxburgh and Tur- more siliceous. This was confirmedby experiments cotte, 1970;Marsh and Carmichael,1974).The fu- on andesite with 2 perand rhyodacitecompositions sion is presumed occurat depthsbetween and cent,5 percent, to 75 and l0 percentHrO (Greenand Ring350 km, the depth to active Benioff zonesbeneath wood, 1972;Green, 1972). (Dickinson,1971,1973), volcanoes calc-alkaline in We are concerned here with processes 30 kbar, at the presence small proportionsof water carriedin involvinggarnetand clinopyroxene. of Amphiboles of (Raleighand Lee, 1969; hydrousminerals Jake5 and subductedoceanic crust are already dehydratedat White, 1970).Melting may occur in amphibole ec- this pressure (Lambert and Wyllie, 1968, 1972: logite or quartz eclogite,with or without free HrO Wyllie, 1973),so we offer no additionalreview of (Greenand Ringwood, 1968; Boettcher, Wyllie, experiments 1973; relatedto amphibole,nor of the con1973; Ringwood,1975, chapter Allen et al., 1975). troversies 7; concerning effectof HrO on peridotite. the More complexproposals generated In 1971,when Stern beganto study the melting involvemagmas within the overlying mantle peridotite, associated relationships oceanicsediments evaluationof of for with influx of HrO or siliceous meltsfrom the sub- their role in subduction it zones, became evident that ductedoceancrust(Kushiro, 1973; with respect phase Boettcher,1973; the resultsshouldbe considered to Nichollsand Ringwood, 1973). relationships basalt-andesite-rhyolite-HrO (Stern, of Whateverthe sourceand conditionsof generation 1973).This led to extension a generalresearch of of magmas, they may be subjected fractionationat program on the effect of HzO on the rock series to various levels.The minerals involved in fractional gabbro-tonalite-granodiorite-granite a function as crystallization includecombinations garnet, of clino- of P-T-Xrrc,-Xr"o (Wyllie, 1977).Sternet al. (1975) pyroxene,amphibole,and plagioclase, with each summarized the phaserelationships 35 kbar of to combination producing differenteffectsin terms of gabbro, tonalite, and granite with excess HrO, and major and traceelements. chemistry volcanic the HzO-undersaturated The liquidus surfaces. of Sternand rocks suggests that the processes involved are com- Wyllie (1973) outlinedphase relationships 30 kbar at plex rather than simple(Ringwood, 1975,chapter7; for gabbro-tonalite-granite with variable HrO conKay, 1977). tents,and comparedthe resultswith thosefor a peFor evaluation the proposed processes, must lagic red clay. Experimentaldetailsconcerningiron of we know the phaserelationships the observed of and the problem of attainingreversmag- lossto capsules matic products, plutonic and vol- ible equilibrium have been published(Stern and the calc-alkaline canicrock series, of the inferredsource and materials, Wyllie, 1975). mantleperidotiteand oceanic crust,includingsediIn this paper,we present Stern's(1973,1974) exments,throughthe pressure rangeextending from the perimental results on two rocks with varying surfaceto the deep sources. Knowledgeof the com- amountsof HrO at 30 kbar. The rocksare a gabbro positionsof phases through the meltingintervals is (quartzeclogite, olivinetholeiitecomposition) modessential. eling subducted oceancrust and eruptedbasalt,and a

STERIT AND WYLLIE: PHASE COMPOSITIONS

643

tonalitemodelingeruptedandesite. Phases selected in runs with 5 percent HrO were analyzedwith the electronmicroprobe. We have combined the new data for garnet and clinopyroxene with the published data, and extended the resultsof Greenand Ringwood(1968)and Green (1972) through the crystallization intervals. For lower temperatures, where small crystalsand close intergrowths prevent satisfactorymicroprobe measurements, mineral compositions were calculated by extrapolating compositional the trendsand imposing thermodynamic conditions mineralpairs.Liquid for compositions throughthe crystallization intervalsfor basalt, basalticandesite, and andesite, dry and with HrO, werecalculated from mineralcompositions and modes(measured estimated). or Glasscompositions for andesite with 5 percentHrO measured electron by microprobe agreecloselywith the calculatedliquid
Table l. Chemical analyses, Crrw norms,and approximate modes of rocks studied
cabbro onemcaL AWLUseg Si02 Ti0z A120 3 !-e2u 3 Fe0 Mn0 Mqo ca0 Naz 0 Kzo H zo + HzoPz0 s coz DW- I Tonalite IO1

K2o

MgO CoO

FeO

"go

Fig. l. Chemical compositions of calc-alkaline rocks (total Fe calculated as FeO). Compositions plotted are: this study, large s o l i d c i r c l e s ( 1 , g a b b r o D W - l ; 2 , t o n a l i t e l 0 l ; 3 , g r a n i t e 1 0 4 ;s e e Table l, and Stern and Wyllie, 1973); other experimental starting compositions (small solid circles from Green and Ringwood, 1968; solid triangles from Green, 1972); typical compositions of the Taupo volcanic zone, New Zealand (empty circles, Carmichael er al., 1974): representative and average compositions (square, average high-alumina basalt from Kuno, 1960, Table 6; upright triangle, average central type basalt from Nockolds, 1954,p. l02l; upside-down triangle, average calc-alkaline andesite from Taylor and White, 1966; diamond, average Cenozoic andesite, from Chayes, 1969). The line through these points is taken as the average chemical variation trend of calc-alkaline rocks.

4 5 .9 1 0.94 I7.19

59.14 o.79 18.23

o.22 7. 4 4

0.1l 2.50 3.8t 2,19 o.a2 0.04 0. 30 0.01

o. 14 r. 78 t.26 0.04

compositions, indicating that the calculationprocedure providesgood valuesfor successive liquid compositions,with some reservations discussed below. We concludethat the equilibriumliquid paths diverge somewhatfurther from the average andesiteby rhyodacite compositionsthan suggested Green and Ringwood(1968)and Green(1972). Rock startingmaterials The compositions, Crrw norms,and modes the of rocksusedaregivenin Table l. The gabbrois a finegrained,high-alumina olivinetholeiitefrom a sill in Soay,Scotland(Wyllie and Drever, 1963;Table 5, analysis It has low SiOzand high CaO compared 5). to an averageoceanictholeiite (Engel et al., 1965); and low SiOr, NarO and K2O, and high CaO and MgO comparedto typical high-aluminabasalts. The tonalite,from the CentralSierraNevadaBatholith of California, is specimen l0l of Piwinskii (1968a).Piwinskii (1968b) compiled details of its pettology,and field accounts. mineralogy, The tonalite hascompositionsimilarto andesites from Mount Hood (Wise, 1969)and Fiji (Green, 1972),aswell as (Taylor and White, 1966)and other average andesites andesite compositionsused in experimentalstudies (Green and Ringwood, 1968), as shown in Figure l.

CfPV iloms O-z Or Ab An

DI

IL.1 0.83 1 3 .7 8 39.14

26.2

Hy OI Mt I1 Ap Ibdeg Ouartz ArKarr terdspar Plagioclase Augite Biotite Hornblende Olivine Opaque ninerals

9.4 3. 39 o. 7s o.l0

o.7

r.3
41 4-7 L2.5 3 (serp. ) 3

644

STERN AND WYLLIE.'

PHASECOMPOSITIONS

tilled and deionizedwater, within platinum and silver-palladium (Ag.oPdro, AgruPdru) alloy capsules, \ Eoxu piston-cylinderapparatus and reacted single-stage in (Boyd and England, 1960), usinga half-inch diameter \ tungsten carbide pressurechamber with hardened I steelliner. All runs werebroughtto final pressure by c) -our), o the hot piston-out procedure (Boyd et al., 1967); IJ 1l pressure was raised5 to 7 kbar above run pressure, E \? f, the samplewas heatedto run temperature, and the F o o/ pressure was released the run value. No friction to E. -outl Go+KY+L+V uJ correction was applied to the nominal pressure, o/ 3 cor-our which is considered accurate t5 percent. to UJ F Temperaturewas measured with chromel-alumel (7' < 850"C) or ft/Pt l0Rh (Z > 850'C) thermocouples,with no correctionapplied for pressure effects on output emf. Temperatures are preciseto Go+Cpx+Cf+Ky+V t5oC and probably accurateto within tl3oC at pressure 1000'C, 30 kbar pressure, considering ef0r0203040 fects on thermocoupleemf (Getting and Kennedy, T O T A L W i . % H 2 O t N T H E S Y S T E M 197 t). Electronmicroprobeanalysis selected runs was Fig. 2. Isobaric melting relations of tonalite (andesite of composition, Table I ) with varying HrO contents. The position of performed on a 4-spectrometer Anl-Etrx microthe vapor-out curve is uncertain. Abbreviations: Ga-garnet, Cpxprobe. Standards and samples were carbon-coated clinopyroxene, Qz-quartz, Ct-coesite, Ky-kyanite, L-liquid, Vtogether to avoid discrepancies coat thickness. in vapor. were analyzed eight elements: Ti, Al, Samples for Si, The chemistryof andesites other calc-alkaline Fe, Mg, Ca, Na, and K. The standards and usedwerea and associated rocks has been the subjectof many diopsidewith 2 percentTi for Mg and Ti; an anorreviews (see Carmichael et al., 1974, chapter ll; thite, An,oo, Si and Ca; an augitepyroxene Fe; for for Wyllie, 1971, chapter Althoughthe precise 7). chem- an albite for Na; and a sanidinefor K. An acceleraical relationships among the volcanicand plutonic tion voltage l5 kV, a sample of currentof 0.2 microrocks of volcanicislandarcsand continental and counting timesof l0 seconds wereused margins amps, for remainuncertain, line in Figure1A defines Between and l0 point analyses the 5 were what all analyses. is conventionallyacceptedas the averagechemical madeon both standards sample phases. runs and For variation of calc-alkalinerocks (Carmichaelet al., with more than 70 percentglass,an automaticscan1974,Figure l2-2).The pointsplottedincludetypical ning beam was used for analyzingglassin order to volcanic rocks,and compositions havebeenused minimizevolatilization alkalis.For otherruns.the that of in previous experimental studies(Green and Ring- areasof glasswere too small for the scanning beam. wood, 1968). The familiarAFM plot is supplemented Somesamples wereetchedfor ten seconds with conby Figure I B, which showsin addition the variation centrated fluoroboricacid.This createda slightrelief in SiOzand CaOl(MgO+FeO). betweenglassand crystallinephases without changOur experiments have been conductedwith three ing the relative major-elementconcentrationsby rocks which plot as the large circles1,2, and 3 in more than 2 percent(2 to l0 percentfor Na) (AnderFigure l. Theserocks, a gabbro, a tonalite,and a son, 1974). Raw datawereexamined inconsistenfor join through the cies,correctedfor instrumentalfactors(background, granite,represent one composition rock system.Here we are concernedinitially with detectordead-time,beam-current drift) using a prorocks I and2, but the near-coincidence the compo- gram written by L Steele, (abof and for matrix effects sition join (Fig. a) with the average and chemicalvaria- sorption,fluorescence, atomicnumbereffect)ustion (Fig. 1) is usedlater (seeFigs. 14 and l5). ing a programwritten at the Geophysical Laboratory (Boydet al., 1968; Hadidiacos al.,1970). et The accuExperimental methods racyof the microprobe analysis t2 percent is relative The powderedrock samples (passed through 200- for eachelementof greaterthan 5 percentconcentramesh) were sealed,with measuredamounts of dis- tion, and *5 percent for elementsof less than 5 \ TONALITE
l-

STERN AND WYLLIE: PHASE COMPOSITIONS

645

percentconcentration.The detectabilitylevel is 0.5 percent. Platinumand silver-palladium alloysabsorbiron from silicatesamples high temperature at (Yoder and Tilley, 1962;Muan, 1963).Merrill and Wyllie (1973) andSternandWyllie(1975) reviewed problemfor the experiments similar to thoseconducted this study. in Green (1976) discussed ways to minimize or surmount this and other problems rock-HrO experiin ments.For our run timesand temperatures, loss iron affects liquid compositions not mineral composibut tions. Liquid compositions havebeencorrected for iron lossusingtime- and temperature-dependent correction factors determined by Stern and Wyllie (1975).Accordingto Merrill and Wyllie (1975),the oxygenfugacityimposedon the reactants the furby naceassembly slightlybelowthe Ni/NiO buffer. was Phaserelationships

with the electron Table2.Experimental runs analyzed microprobe

RE No, Pres. Kb Tenp. oC Wate! Added wt. I Tine hr.

Capsule

Phases Present*

Ionalite

107 A g 3 9 P d 79 Ag7 5Pdz s Agz sPdz s AgroPdzo Ga, L, v

4t9 420 358

30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30

r000 tr00 I r00 1r00 It00

1100 l10o 1100 1100 900

25 l8 18

1 I 3 I 1Pt 3 3 IO 10 2 I 2 I 6 3 LO 1 I 3 IO

308 30'1 343 329 3r4 3r6 346 344

15 15 15 15 r0

Pt Ag3gPd79 Ag 3 6Pd7 6 Pt Aq3oPclzo AgaoPdzo Ag3oPdTo Ag:oPdzo A g s o P d zo Ag36Pd76 A g 3 9 P d7 e Agg oPd z o Pt Agr oPilz o A g g o P d zo Ag36Pdr o A g 7 5 P d 25 Ag7 sPd2 5 Pt

ca,

CPe, Ky , L

950 1000 l-I25 900 1000 1000 1100 r100 1100 rt00 t1 ?5 r175 1200 1200 1200

lo IO l0

Ga, Cps, Ky , L Ga, C?e, K'!, L

Ga, Cpt, Gq, L Ga, Cpx, Ga, cpx, Ga, L Ga, L Ky, L

L L

Stern(1973)determined rock-HrO diagrams 30 at 362 kbar for the gabbro, tonalite, and graniteplotted in A g 7 s P d 25 1200 30 points l, 2, and 3. Preliminaryresults 406 Figure I as Ga, Cp&, Ky, L Ag7 sPd2 s 408 1100 30 were combined and discussed Stern and Wyllie by A g 7 5 P d 2g Ga, Cpi KA, L tr00 409 30 Gabb"o Dht-1 (1973). Details of the problem of iron loss to capGa, cpx, L I A g 7 s P d 2s 10 414 30 1100 sules,of run durations,and of establishing revers- 4I2 Ga, CPc, L A g 7 5 P d zs 5 I IIOO 30 AgTsPd2s Ga, Cpo, L 5 I L200 ibility of phaseboundaries within narrow temper- 4 1 1 30 ature intervals were reviewedby Stern and Wyllie (1975).We presenthere resultsfor the gabbro and Cpx = Clinopyloxene; v = VaID!; Ga = Garnetr L = Liquidr tonalite,and the liquidusrelationships the series Ky = Kyaniter X = Phase X analyzed. for probasalt-andesite-rhyolite-HzO kbar. These at 30 vide the frameworkfor locationand discussion the of boundary (dashed)with the analyzedphases. of the vapor-saturation liquidus. Andesite-HzO Figure 2 showsphaserelationships the tonalite Basalt-HzO for for Figure 3 showsphaserelationships the gabbro compositionwith varying HzO contentsat 30 kbar. Detailsfor selected runs are listedin Table2. Experi- compositionwith varying H2o contentsat 30 kbar. ments by Green (1972) and Green and Ringwood Details for three runs are listed in Table 2; other The (1968)gavegarnetas the liquidusphasefor one an- detailswerereviewed Sternand Wyllie (1975). by boundariescould hydrous andesite, and clinopyroxene for another. garnet-outand clinopyroxene-out from each other for any H2O The phase boundariesare extrapolatedto the an- not be distinguished and they are drawn coincident.Green and hydrous rock compositionfrom resultsof thesetwo content, as studies.The main differencebetweenthis diagram Ringwood (1968)gaveclinopyroxene the primary (Stern phasefor anhydrousolivine basalt at 27 kbar, with version and an earlier and Wyllie,1973, Fig. l) l0oC belowthe liquidus.At 36 kbar is delineation the field for kyanitealongthe bound- garnetappearing of garnet and clinopyroxeneoccurredtogetheron the ariesmarked. the With increasing HrO content,the phaseboundary liquidus.Considering resultsfor basaltand andefor clinopyroxene-out depressed progressively site, we considerit likely that clinopyroxeneis the is to joined by garnetwithin a few degrees. The sol- liquidusphase, lower temperatures than that for garnet-out. liquid at 30 kbar The field for kyanite doesnot extendto the liquidus ubility of HrO in tonalite(andesite) with a is 22.5 t 2.5 weight percent,as given by intersection as it doesin Figure2.The runs are consistent

310 416 405

646

S7ER/T AND WYLLIE: PHASE COMPOSITIONS

GABBRO 30 Kb o t2oo
IJ E l F

-ourl
al

I I

L+V

.i
o Go+gp1 o
+L+V O

;lrooo UJ
(L

site compositions can be read from Figures3 and 2, respectively. The boundariesmm' and cc' divide the liquidus surfaceinto three fields for the primary crystalliza(and tion of quarlz, of garnet,and of clinopyroxene garnet). With increasingHrO content, the liquidus field for primary garnet, narrow near the dry liqat of uidus, expandsconsiderably the expense both quartzand clinopyroxene. Measuredphasecompositions The Table2 liststhe runsthat wereanalyzed. compositionsof garnets, clinopyroxenes, quenched and liquids (glasses) listedin Tables3, 4, and 5, reare were spectively. Tonalite runs at sometemperatures repeatedfor comparisonof the effectsof different capsule materials,and of differentrun durations(see also Sternand Wyllie, 1975).

F 800

lrJ

Go+Cpx+Ky+L+V

Go+Cpx+Cf+Ky+V

20

30

40

T O T A L W I . % HzO tN THE SYSTEM

Fig. 3. Isobaric .melting relations of gabbro (quartz eclogite, olivine tholeiite composition, Table I ) with varying H,O contents. Note the uncertainty of the dashed phase boundaries for low HrO contents; the vapor-out boundary may be steeper at low temperatures (compare Wyllie, 1971, p, 2O2), which would have the effect of increasing the temperature dependenceof the vaporabsent phase boundaries. Abbreviations, see Fig. 2.

Garnets For eachrun, at leastten individualgarnetgrains wereanalyzed. indicated Reconnaissance that garnets

30Kb
ANOETE SI Liquid

vapor-saturationboundary correspondingto HrO solubility about the sameas for the andesite. Basalt -ande i t e- rhyoI i t e-H rO s Figure4 showsselected phaserelationships the for compositionjoin basalt-andesite-rhyolite with varying amountsof HrO at 30 kbar, constructed deas scribed Sternand Wyllie (1973). by The liquidusfor the dry seriesis basedon the resultsof Green and Ringwood(1968)and Green(1972).They reported the thermalvalleyon the liquidusprofilefor andesitic compositions.We interpret this valley in terms of piercingpoints separating fieldsfor prirnarycrysthe tallization of quartz,garnet,and clinopyroxene. The clinopyroxene field is labeled"Cpx * Ga" because garnet appearsso closeto the liquidus temperature that the distinction is not readily made experimentally. The liquidussurface, contouredby linesof constant HrO content from dry to HrO excess, based is on Figures2 and3 and a similar diagramfor graniteHrO (Stern, 1973).Stern and Wyllie (1973,Fig. 2) illustratedthe phase fieldsintersected this compoby sition join with 5 percentHzO. The liquidus profile corresponds the 5 percentHrO contour in Figure to 4, and the phaseassemblages the basaltand andefor
|flr

o=l F G LrJ

o-l
trJ F

X.{s+L+V

50

60

70

80

s i 0 2 wr . %
Fig. 4. Phase diagram for the composition join basalt-andesiterhyolite, which corresponds closely with the average chemical variation line for calc-alkaline igneous rocks (Fig. l). The isobaric Iiquidus surface for water contents varying from 0 percent to excess,and the crystallization interval with excessHrO. Dry data from Green and Ringwood (1968), with HrO from Stern and Wylf ie (1973). For cross sections see Figs. 2 and 3 (59.14 percent SiO, and 45.91 percent SiOr, respectively,Table l). The solidus is independent of HrO content. Abbreviations, see Fig. 2.

,STERN AND WYLLIE: PHASE COMPOSITIONS

u7

Table 3. Compositions, determined microprobeanalysis, garnets the meltingintervalsof tonaliteand gabbroat 30 kbar in by of
Comrcsition Rm ,+ TemD. oc tH20 capsule * Tine hr. Co-existing Phases r * si02 'lLO2 o1203 Feo l4qo CaO Na20
lbta1 Tonalite 101 Gabbro DW-l

310 416 rt75 1175 5544 1222 ltt5

404 rtoo

409 1100

318 344 1100 ltoo 555 1rl 13r0 CPt 40.3 1.0 2I.4 r7 .6 9.'l 11.6 0.1 40.3 1.0 22.5 7e.2 e.7 tr.3 0.1

353 1100

314 loo0 5 I 3 CPr KY 38.6 2.4 2r.6 2r.6 8.3 9.6 o.2

343 316 1000 looo 5LO I1 102 Cpi Ky 39.0 L.4 27.5 22.7 '1 .O 11.5 0.2 3 9. 2 r.5 2r.r 19.6 1.9 1l.l 0.2 39.7 1.5 2r.6 r7.7 9.8 L2.A

4Il 1200 55 22 Ll CPr 40.4 0.3 22.9 L2.3 13.0 to.4 0.0 99.6

4I2 tl00

4L4 tloo 10 I

Cpx KY 4o.2 O-7 22.5 16.3 l1 .6 IO. 9 0. I 40,2 0.8 22.4 15.6 10.8 8.8 0.1 39.5 r.4 22.3 18.9 8.6 9.9 0.2

Cpr Ky 39.1 L.2 22.4 18.7 8.6 LO.2 0.2

Cpx 40.2 1.0 2L.7 19. r 9.7 9.8 o.2

Cpr 40.2 0.6 22.6 15.5 l1.r rL.2 0.0 10r.6

cpx 40.4 0.3 23.O 13.9 r2.o 11.0 o.o 100.9

o.r
r03.4

ro2,4

98.9
Structural

102. t

ro2.5

ro2.o

103.6
12 Oxygensr*r 2.9I .08 r.A2 .08 .09 J,.32 .77 .92 3.O2

roo.9

Formulae on the Basis of 2.90 .01 1.84 .06 .09 .99 r.O7 .92 2.99 2.97 .o2 1.93 .06 .00 l.l2 .95 .89 2.9'1 2.9A .01 r.88 .06 .05 1.13 1.07 .7A 2.99

sil .,rI rz>r Ar- ,- -..VI TiIe

2.94 .05 r. 88

3 .O l .00 1,98 .o4 .00 .9't I.20 .7r 2.A9

2.96 .04 r.93 .o7 .00 1.18 .96 .80 2.94

2.94 .05 1.93 .o'7 .00 r,r7 .96 .82 2.96

2.A9 .lo l.S0 .13 .05 L.29 .92 .77 2.99

2.96 .03 1.85 .09 ,05 I.l8 .89 .90 2.94

2.97 .02 I .96 .o2 .01 .74 1.43

2.95 ,04 L.92 .03 .o4

ol

2.96 .03 1.95 .0I .o2

al

L Y>-2

.03 .o'7

F.-

Mq

) I

,92 I.26 .85 3.03

l)x?3
t

L.22 .88

1.31 .86 3.01

3.OO

3 .0 2

Mol. Prop. crossular PyroDe Almndine 27.5 40.5 32.O 24,6 4t.6 33.8 2 7. 1 32.7 4 0. 2 2 7. 7 32.6 3 9. 7 2 9. A 3 4. 9 3 5 .3 30.0 3 2. 2 3 7. B 2 5. 7 3 9, 0 25.4 30. 3 44.3 30.6 24.9 44.5 29.4 2 9. 4 40.4 3 1 .I 34.4 2 7. 4 47.5 25.L 28.8 39.9 31.3 2A.5 43.4 2A.r

(I)

Aq3oPd7O, (2) Acr'Pdra. co-exists with all qarnets. conrcsitions of phases in italics have been detemined.

**"1quid ***oltu

= 3-g1; llvr = Al-elrV; icalculated with Fe2+ = tFe,

r,e3+ = 2-(e1Vr+ri)

, F"2+ = Fe-Fe3+.

within experimentallimits imare homogeneous, posed by the small sizeof the grains. Little change was noted from grain to grain in a single run. All garnetshoweda smallNarO contentwhich is not due to contamination from surrounding or included glass, since such contamination would be accompaniedby a detectable KrO content.Garnet analyses with KrO greaterthan 0.1 percentwere considered Total Fe in the garnets and discarded. contaminated is calculated FeO. In the structuralformula of the as garnets(Table3) enoughFe3+ wasassigned analyzed to the Y positionto makeY : 2, but no consistent was apparent.No correctionwas ratio of ps8+/ps2+ testsconfirmed that applied for iron loss, because garnetcompositions with changes in remainconstant

The trendsof run duration(Sternand Wyllie, 1975). garnet compositionsare considered terms of the in ignoring componentsalmandine-pyrope-grossular, TiOr, NarO, and possibleFerOr contentsof the the garnets. garnets Figure 5 showsthe trendsof near-liquidus (within 25'C of the liquidus) in andesite, deteras mined by Green(1972).Figure5A showsthe effectof pressure pressure. and constantHzO With increasing content, the nearJiquidus garnets show slight inin in crease Ca/(Ca + Mg) and decrease FelMg. Our new resultsat 30 kbar (Table3) and Huang'sunpubResultsfor dry lishedresultat l5 kbar areconsistent. andesiteare parallel to those for andesitewith 5 percentHzO.The effectof increasing HrO contentat

648

STERN AND I4/YLLIE PHASE COMPOSITIONS

L I Q U I D U S R N E TN A N D E S I I E S GA I S
ALM 45-PY ALMANDINE A L M4 5 - G R O S S 5

A L M1 5 - P Y GROSSULAR

A L MI 5 - G R O S 5 S PYROPE

A . E f f e c l o f P f o r 0 % H z Oo n d 5 %H z O

i!;i1ifi;;;; o%vo-/
A L MI 5 - P Y GROSSULA R M1 5 - G R O S S 5 PYROPE

&,'lJl,

trendsthrough the crystallization intervalsofbasaltic with HrO aresimilarto thosefor andecompositions site-Hro (Fig. 64). The results Greenand Ringof wood (1968)show little difference between trends the for garnets crystallizing from olivine tholeiite or quaftztholeiiteat27 kbar, although,for similartemperatures,Fe/Mg in garnet from quartz tholeiite is greater than that in olivinetholeiite. Our newdataat 30 kbar with 5 percentand l0 percentHrO for olivine tholeiitedemonstrate largeincrease Cal(Mg + the in Fe) caused additionof HrO to dry liquids(comby pare Fig. 5), and the much smaller produced change by increasing HrO content from 5 percentto l0 percent (seeFigs. 5B and 6A). The phasefieldsintersected 30 kbar are shownin Figure3. at Clinopyroxenes At least ten separateclinopyroxenegrains were analyzed for each experimentalrun. Some large

B . E f f e c t o f H z O C o n t e n lf o r S p e c i f i cp Fig. 5. The compositions near-liquidus garnetsin andesite. of Circlesat 30 kbar are listedin Table 3; the triangleat 15 kbar is from Huang (unpublished); squares 18,2'1, and 36 kbar are at from Green (1972).(A) Trends with increasing pressure conat stant HrO contents;(B) trends with increasing H2O contentsat pressures. point x is for garnetin anhydrous constant The liquid at 30 kbar, as estimated the intersection the jVo H2O trend in by of (A) with the 30 kb trend in (B).

GARNETS ROUGH TH CRYSIALLIZATION INTERVAL

ALMANDINE A L M6 0 - P Y

6 0 - G R o StS 0

i ,iii1ij,*
*o ? ] un t,o,.o
A L M2 5 - P Y L M 2 5 - G R 0 S St 0

a given pressure shown in Figure 5B. Our new is GROSSULAR PYROPE resultsat 30 kbar are consistent A. Andesiles 7 ond 30 Kb with thoseof Green 2 (1972)at 27 and 36 kbar. With increasing HrO content at constantpressure, Ca/(Mg + Fe) increases A L M5 0 - P Y 5 0 - G R 0 SrS 0 significantly. The concomitantslight increase Fel in Mg is due to the decreasing liquidus temperature causedby increasing HrO content,as shownin Figures 2 and 4. Figure 6,4. shows the compositions of garnets i ] o. tto. ,.0 ^o through the crystallization intervalsof andesite with A L MI O - P Y M r0-GRoss t0 5 percentand l0 percentHrO. The phasefieldsinterGROSSU R LA sectedas a function of temperatureat 30 kbar are 8 . B o s o l f s2 7 o n d 3 0 K b shown in Figure 2. Resultsof Green(1972) for 27 kbar showparallel Fig. 6. Garnet compositions through the crystallization intervals trendsfor andesites 5 percent with and l0 percent HrO, with slight separationfor the of andesite and basalt at 27 and 30 kbar. (A) Trends for andesite effect of HrO as indicated by Figure 58. Our new with 5 percent and l0 percent H"O at27 kbar (Green, 1972), and with 5 percent HrO at 30 kbar (Table 3); solid circles represent data at 30 kbar with 5 percentHrO show the same averages for open-circle runs made at the same temperature trend, with slight separation from the 27 kbar-5 per- conditions. (B) Trends for anhydrous olivine basalt (squares) and cent HrO trend for the effectof pressure indicated quartz tholeiite (triangles) at 27 kbar (Green and Ringwood, as 1968). Circles are for garnets from olivine tholeiite with 5 percent by Figure 5,A.With decreasing temperature, FelMg and l0 percent HrO. Points x for olivine tholeiite at 30 kbar are increases significantly, and Cal(Mg + Fe) increases plotted at the intersection of the garnet trends with the estimated very slightly. trend of liquidus garnets with increasing HrO content, based on the Figure 6B shows that the garnet composition a n d e s i t el i n e s i n F i g . 5 B .

: 3: ),'-' It8:

STERN AND WYLLIE: PHASE COMPOSITIONS

649

grains varied in compositioninternally, but smaller grainsappeared be homogeneous, thesewere and to Variation in NarO contentbetween usedfor analyses. grainswas minor comparedwith the variations betweenruns madeat differentconditions.Clinopyroxwith more than 0.I percentKrO were ene analyses No of discarded. correctionwas madefor the effects in clinopyroxenes the melting iron loss.The analyzed interval of tonalite used to establishcompositional trendsoccurredat l000oCor lower,wherethe effects of iron loss are not great(Sternand Wyllie, 1975). Correcting the clinopyroxenecomposition for iron lossin the meltingintervalof the gabbrowould not alter the conclusionsreachedin this study, as discussed below. Extensive development quench clinopyroxene of near the liquidus of the gabbro made microprobe analysis of near-liquidusclinopyroxeneuncertain. Clinopyroxene run 4ll at 1200"C(Table 4) is in considered be a quenchpyroxene, a mixture of to or quenchand primary crystals. has high FeO comIt paredto the clinopyroxene run 412at l100oC.At in I100'C, quench clinopyroxene less a problem. was of Structural formulae of pyroxeneshave been convertedto molecularproportionsby calculating Na all asjadeite,total Al minusthe amountusedin jadeite (equalto Na) aslAlrOr, and total Ca, Mg, and Fe as lwollastonite, |enstatite,and lferrosilite. The TiOz content was neglected, order to simplify calcuin lations. The trendsof clinopyroxene compositions illusare trated in terms of componentsenstatite-wollastonite-ferrosilite, with supplementary diagramsfor jadeite and AlrO, proportions(Figs.7 and 9). Some jadeite and AlrO, data were omitted for clarity. Figure 7 illustratesthe trends reportedby Green and Ringwood(1968) clinopyroxenes for throughthe crystallization interval of anhydrousquartz tholeiite at pressures l8 kbar,27kbar,and 36 kbar. FelMg, of Ca/(ME * Fe), jadeite, and AlrO, all increase with decreasing temperature all pressures. for Trends are similar for the lesscomplete datafor other anhydrous compositions(exceptfor the jadeite content for basaltic andesite, Fig. 7B). Figure 7A showsthat with pressure anhydrousliquids, the clinoincreasing for pyroxene trend line is shiftedtowardshigherMg/Fe. The sameshift is evidentfor trendsat constantpressurefor anhydrous liquids with lower SiO, contents. New data for andesite with 5 percent HrO at 30 kbar (Table4) showa paralleltrendin Figure7A, but with considerable enrichmentof the clinopyroxenes in FelMg, which csuld be due in part to the lower temperatures crystalluation (seeFigs. 2 and 4). of

THRO CLINOPYROXENES UGH INTERVALS CRYSTALLIZATION

ITE WOLLASTON WOLL 0-EN 50-FSO 5

w o L L 0 - E N 2 5 - F2 5 5 S

W O L L 3 5 - E N 6 5 - Fo l0 % H z O , J O K b s 5 eNstlitttr
o o E 0

woLL35-EK5-FS40

o o%rizo,o-rexb,b-z7Kb,c-36KbFERRoslLlrE
_ TE OECREASING MPERATURE
N

42 36 B . t 30 2 4 jug,tt t8
AndesireV o
b x
e

c.
24
0 l iv i n e Tholeiite

o c

o a o 5

o o CL

li. >*
rnn on Qn

o o

r0090

80 70 60

_l 3 6l , | , I
Rn =

Andesile

r00M g/

""=

( M g+ F e )

through the crystallization compositions Fig. 7. Clinopyroxene decreasing liquids.Heavyarrowsindicate intervals calc-alkaline of are Squares for anhydrousliquidsat 18 kbar (a), 27 temperature. kbar (b), and 36 kbar (c) from Green and Ringwood (1968). with 5 percentHzO at 30 kbar (Table4). Circlesare for andesite from compositionol clinopyroxenes The point x is the average differentruns madeat the sameconditions.

with increases The total AlrOs in the clinopyroxenes temperature(Table 4), despitethe fact decreasing in proportion decreases FigAl2O3 that the calculated to ure 7C; the jadeite contentincreases much higher levels than in the anhydrous,less siliceousliquids (Fig.7B). Liquids inthroughthe crystallization Liquid compositions by were determined analyses terval for andesite-HrO with the electron microprobe. of quenchedglasses of For thoserunswith only smallamounts interstitial were not possible.Liqliquid, satisfactoryanalyses extequids from the basalticcompositiondeveloped which precludeduseful sive quench clinopyroxene, liquids commonly analyses.HzO-undersaturated below about l5 at quench to clear glasses pressures varying with liquid compositionand kbar (pressure however, HrO content).For runs at higherpressures, HzO exsolvesduring the quench, expanding and the cracking the glassand increasing densitydifferglasses the stanand between experimental the ences vadards usedin analysis.In addition, the exsolved

SrERl[ AND WYLLIE: PHASE COMPOSITIONS Table4, Compositions, determined microprobe by analysis, clinopyroxenes the meltingintervalof tonaliteand gabbroat 30 kbar; of in with ZFe : FeO
Compos ition Rm .''r' c H20 Caps uJ.e* TiFe hr. lt Tonalite 101 Gabbro DIrt-I

408 1100 4 2 I Ga Ky 5I.2 o.7

lf,.) ? ?

409 llo0 4 2 5 C-a Ktj 50.1 0.7

rb.r ?o

314 lo00 5 1 3 Ga Ky 5 0- 4 o.9 t4.o 9.1 IO.I 12.e 4,3

I01.6 Formul-ae on the 1. 80 .19 .39

3t6 loco 55 1t 106

329 90c

308 900 l0 1

4r2 1100
5 2 I

Co-existing P h a s e s* * si02 Ti02 Ar-0 Fe0 Mgo ca0 Na2O

Total

Ky 5 0 .I o.7 1 3 .7 1.7 1 0 .t I3.8 3.9 I00.6

Basis 1.82 .L'7 .40 .01 of

KY 52.r o.7 1 4 .5 7.7 6.6 r2.2 5.2

99.O 6 Oxvqens

K!, 50.5 0.9 r2.5 10.1 8.1 I2.5 3.8

98.4 46.9 a.J L2.7 4.4 50.9 u.b 7-9 7.5

7.3 I2.A 4-r

aa q

9-6 1-1.9 4.2

oa <

ro.2
L7.9 1.5

t2.'7
L1.9 r.7

9B-9

9 9- 2

Structural

si

1.85 .I4 .51 .cl

1.80 .19 .49 .01 .tl

qt

1.89 .10 .51 .01

-zt

L 87 .13 .4r .o2

,Jr

r.74 .23 .30 .03 .26 .56

L.A7 .L2 .22 .01 .23 .70 .70 .11 t.99

A T I Vf

.o2 . ?,7
.49 .29 2.12

tx+ Y

.22
?q

.35 .53 .27 2.OO .47 . i6 1.96

.44 .49 .2,7 1.96

.49 .2A

.58 .29 2.O2

.7r
. l-1 1.99

Ix + Y
Mol. ProD.***

l. 93

Wollastonite Enstatite Ferrosilite Jadeite

24.O 19.1 r0.8

z t.o 18.3

26.6 23.5 5-4

zo. I t7 .7

Ar^cz5 Atomic ProD.

2 2. 4 24.6 12.4 2 7. 3 t-3.3

24.6 25.1 10. 7 2 5. 4 t4.2

23.2 I7.4 IL-4 35.7 I2.i

24.C 2I.6 15.1 26.0 I3.2

32.7 25.7 11.9

32.I 3I. I 15.0

ro.2 r9.4

r0.8 10.3

M9 Fe

44.6 35.3
?n I

4A.O 42-4
qa

3 7. 7 4r.4 20.9

40.8 41.5 I ' 1. 7

4 4- 7 3 3 .3 22.O

39.5 35.6 24.9

46.5 3 6 .6 16-9

43.2 4 2. 7 14.1

(1) AOaoPdro. (2) Aq75Pd25. I,iquid co-exists A1r0a = (LAIwith al.I clinonyroxenes.
ComDositions of phases in italics have been determined.

Na)/2t,Id = Nai rto = Ca/2i En = Mq/2i Fs = Ee/2.

por may carry dissolved elements, especially alkalis, homogeneous. Oxide totals for analyses 85-95 are from the glass. percent(Table 5). The low totals are caused (l) by Ten individual areas of glass were analyzedfor HrO dissolved the glass, the low density the in (2) of eachrun, usinga scanning beamwherepossible. Re- glasses compared the standards to used, and (3) alkali connaissance studiesindicatedthat the slasses were loss (especially NarO) during microprobeanalysis.

SrtR,V AND WYLLIE: PHASE COMPOSITIONS

651

Table5. Compositions, quenched determined microprobe by analysis, glasses of from themelting interval tonalite 30kbar,with 2Fe of at : FeO
Run tr Temp. oC gHo 2 capsule* Tlme hr. Co-existinq Phases * * 310 318 1175 1100 555555 113111 I Ga. 346 llo0 3I4 1000 316 1000 329 900 306 1125 IO I 1 343 1000 10 11 2I 307 950 10 361 1000 25 1 l

1 Ga

1
(ia

3
(zA

10
tfl

6
(ia

Cne Ky
58.3 0.6 59.4 0.7 16.6 2.5 ( 3 . 2 )* * * nq 4.4 3.0 2.I 90.6

Cpr Ky 63.6 0.6 15.1 0.9 /r ,\**r

Cpr Kv 65.8 0.3 13.1 0.6 /n ?\**t 0.1 2.O 0.9 2.'7

si0 Tio

60.8 o.7 t7.1 0.9

f ? ?l***

62-'7 0.6 14.8 r.2

tt ?)***

5 5 .r 0.8 17.0 4.1,

/( r\***

61.6 0.6 16.5 1.5

/t 7\***

60.9 o.5 16.2

lq

58.3 0.'l I7.I

al

2 olro
FeO

16.9 3.1 (3.9;*** I e

(reo) *** Mqo caO Na20

(1.7)***

(3.9)*t*

1.3 4.3 3.2 2.3 93.3

0.3 2.7 I.I 2.9

46.7 Liquid

0.3 2.4 1.3 2.A a 7. 6

t.9 5.6 2.5 2.2

90.4

0.-l 3.5 3.1 2.5

90.5

o.7
3.2 2.4 2-6 88 . 5

r.2
4.6 3.4 2.I

5.6 3.3 2.I

*2o
Total

93.0

86.0 with

9L.'7

compositions

X oxi<1es = 100.0 76-5 60.9 0.9 15.3 0.8 18.8 5.7 68.1 0,7 \8.2 I.9 6A.9 0.6 18.3 1.9 o.7 63.5 0.8 IA.7 4.2 r.4

sio

62.6 0.9 ra.2 4.2 2.O 6.O

65.6 o.B 18.3 3.5 1.0 4.8

?1

65.1 c.8 18.3 3.4 t.4 4.7 3.4 2.4

7 2. 3 0.7 17.0 1.5 0.4 3.I 1.3 3.4 70.9 22.7 6.4 '?a.r 13.5 a.4 8 2. 4 1,O.2 8.2

Ti02 A1^0FeO Mqo

o.7 r 1. 2 r.4 o.4 2.7

1.5
1?

o'.2 2.4
1.1
?l

2-r
6-2

o.I
3,8

Na2O

3.6 2.3

2.7

3.8 2.3

*2o
Na20+K20 Ee0 Mqo I/4 ca0 Mqo+Feo SrO2

2.4 39.7

2.7 72.A 18.9 8.3 72.O 16.4 11.6

2.9

48. 7 34.6 16.7 56.O 2I .6 2 2. 4 (1) Aq^^Pd-^.

IU IU

55.4 3 4. 4

54.6 31.9 13.5 62.9 18.1 19.0

11,.9 2r .4 1 6. 4 3.9 94.6 10.6 4.8

68.0 23.0 9.0 73-O rq q 11.5

52.O 3 6 .0 t2-o 60.0 tq ? 20.8

43-7 16.6 52.O 2r-2 2 6- 7

r o. 2
63.4 18.9 I7.7 (3) Pt. also iron

Phase (FcO) -

in

ital.ics

analvzed. after correction for iron loSS to caDsules,

ppr.entedF

With decreasing temperature through the crystallization intervalof andesite with 5 percent HrO (Fig. 2), the proportionof liquid decreases, its HrO conand tent thereforeincreases; hencethe oxide totals listed for analyses decrease. All liquid compositions were correctedfor lossof iron from the sampleto the capsule, usingcorrection factorsdetermined Sternand Wyllie (1975), by then

the oxidetotals werenormalized 100.00. norto The malized glass compositions for andesite-HrO are listed in Table 5, and some of them are plotted in Figure13. Calculatedphasecompositions could be analyzed sucGarnetsand clinopyroxenes intervals cessfullyonly through limited temperature

652

STERN AND IVYLLIE: PHASE COMPOSITIONS

-'*cRysTALLrzATroN TNTERVAL
o 27 Kb, O.h HzO o 3 0 K b, 5 % H z O

\,;T;"j
\Oil"in. Thoteiite

PYROPE Fig. 8. Garnet compositions measured and calculated (crosses) through the crystallization intervals of calc-alkaline rock compositions. Squares are for garnets measured by Green and Ringwood (1968) in anhydrous liquids at 27 kbar (Figure 6); circles are for garnets measured in olivine tholeiite and andesite at 30 kbar with 5 percent HzO. The values for hydrous andesite are the solid circles (averages)plotted in Figure 6,{. The temperatures for plotted values through the crystallization intervals of anhydrous liquids are: olivine thoteiite, 1430"-1400"-1375.1350'C; quartz tholeiite, 1420"-1400.-1395._1350.; basaltic a n d e s i t e ,1 3 9 0 " - 1 3 6 0 ' - t 3 2 5 o ; a n d e s i t e s ,1 3 4 0 . - 1 3 2 0 . - 1 3 0 0 o .S e e Table 6 for calculated garnet compositions with 5 percent HrO.

belowthe liquidus.For lowertemperatures, compositions were calculatedin two stages. First, the measuredtrendsof mineral compositions shown in Figures6 and 7 wereextrapolated. Then, the amountof changein mineral compositionsalong thesetrends within a given temperature interval was calculated, basedon (l) the measured compositional differences betweenminerals at known temperatureintervals, and (2) the condition that at a giventemperature the K" : (FelMilc"/(Fe/Mg)cp, of calculatedgarnet pairs equalsthe r(p of natural and and clinopyroxene garnet-pyroxene experimental pairs, at similar temperaturesof final equilibration, as determinedby Mysen and Heier (1972). Glasscompositions weremeasured only for liquids in the andesitecomposition.Liquid compositions through the crystallizationintervalswere calculated from the mineralcompositions (measured calcuand lated), and the proportionsof phases presentat successive temperatures (measured estimated). or Garnets Figure 8 showsthe measured (squares and circles) and calculated (crosses)compositions of garnets

Table 6. Calculated garnet compositions through the melting interval of tonalite and gabbro, with 5 weight percent water at 30 kbar
Conpos i t ion 1 17 5
ProD.

Tonalite

I01

5? H2O

Ga-bbro DW-I

5C H20

1100

1000

9oo

1100

1000

Gross ular Almandine 4I 33

27 33 40
i9.7 22.4 19.0

2A 45 39.2 22.2 2 1. r 7.O IO.2 3 7. 5 I .67 .47 3 .5 6

29 2I 50
38.8 2L.9 2 3. 2 5.4 IO.4

30 I2 58

2A 47 25
40.9 z3.z
LZ. J

29 40 31 4 0 .3

30 35 35
?Qqro( zz.o

3t 29 40

si02 Alzo 3 Feo = IPe Mgo ca0

40.3 2 2. 7 15.9

38.1 2r.6
26.5 3.0 1 0 .6
I7.l 4.83

zz.4

t6.7
IO.7 10.9

18.9 7.6 r1.4 42.O t. 38 .47 2.96

a-7
9.7
llql(Mq+Fe)

1 3 .O 10.4

9.3 IL.2 50.0 1.00 .40 2.50

10.0

lOO

55-4 .800

45.2

29.5 2.ia .70 3 .4 1

65.2
.)J

56.3 .'1A .34 2.29

Fe/I1q (Pe,/i{q) Cpx

.a2
5. 91

.30 r -'17

Oxide

Prop.

Na20+K20 Fe0 MqO I/4 sio

0 59 40 2I 20 57

0 68 31 20 2I 58

0 74 25 2C 27 58

o
8I 18 19 2I 58

o 89 l0 19 2T 59

0 4A 51 22 22 55

0 58 4I 2I
z5

0 64 35 2l 23 55

0 7I 2a 20 23 55

ca0 1490+Ee0

55

STERN AND WYLLIE: PHASE COMPOSITIONS

653

through the crystallizationintervals of four rock compositionsstudied dry at 27 kbar by Green and Ringwood(1968),and of our two rockswith 5 pertrends centHzO at 30 kbar.The mineralcomposition from and extensions the resultsin of are selections and calcuof Figure 6. The temperatures measured latedpoints are shown.The effectof bulk composiFig. 68), but the tion in this rangeis slight(compare effectof adding5 percentHrO to olivinetholeiiteand is andesite larger (compareFigs. 58 and 68). The of oxide percentages the garnetsplotted in Figure 8 from the molecularproportions,and werecalculated with 5 percentHzO arelisted resultsfor the two series in Table6. Clinopyroxenes

THRO CLINOPYROXENES UGH INTERVALS CRYSTALLIZATION

ITE WOLLASTOI'I woLL50-EN25-FS25 ouorlz Bololtl(

30 57.H20, Kb K o ' t " H , / J , 2 7b

CALCULATEO COMPOSITIONS
o o E 0

o
o c o o e o

c.
ouorlz Eosolllc

o
G

o o

Bosclllc ouortz o (circles the and squares) o Figure9 shows measured Thol.iltc\ Andrsil! o(crosses) of compositions clinopyroxand calculated o o 5 enes through the crystallizationintervals of three o o o o rock compositionsstudieddry at 27 kbar by Green = = Ringwood(1968), our two rockswith 5 perof and point for dry + cent HzO at 30 kbar, and a calculated 100 / (Mq Ps; Mq at andesite 30 kbar. The mineral compositiontrends Fig. 9. Clinopyroxene compositions measured and calculated of are selections from and extensions the resultsin (crosses)through the crystallization intervals of calc-alkaline rock variationsin Ca-Mg-Fe compositions. Squares are for clinopyroxenes measured by Green ,Figure 7. The calculated the variation of jadeite and and Ringwood (1968) in anhydrous liquids at 27 kbar (see Fig. 7); determine components circles are for clinopyroxenes measured in olivine tholeiite and AlrO, proportions. andesite at 30 kbar with 5 percent HrO. Jadeite and Al,Ot analysis obtained proportions for the clinopyroxene in hydrous olivine tholeiite at 30 The only reliableclinopyroxene at 30 kbar for olivine tholeiite with 5 percentH2O kbar are low (compare Figs. 78 and C with 98 and C); the trend positionwith respect other for jadeite is constructed parallel to those for clinopyroxene in to plots in a reasonable (Fig. 9A), and the trend is drawn through anhydrous liquids; the AlrO, proportion is assumedto be constant analyses through the crystallization interval as a compromise between the this point parallel to the others.Jadeiteand AlzOa increase for anhydrous liquids and the decrease for hydrous are proportionsfor this clinopyroxene low (Figs. 98 andesite. See Table 7 for calculated clinopyroxene compositions for and 9C), and the trendscalculated this crystalliza- with 5 percent HrO. given in the tion interval are basedon assumptions of legendfor Figure 9, Because the low molecular previouslyreviewedin connectionwith Figures 78 with the other molecular and C. weightof AlzO, compared adoptedhavelittle efthe components, assumptions The oxide percentagesof the clinopyroxenes clinopyroxenes plotted in Figure 9 werecalculated of fect on the compositions calculated from the molecuthrough this melting interval.Changingthesetrends lar proportions, and results for the trends with 5 of percentHrO are given in Table 7. The temperatures would have little effect on the main conclusions this work, which are illustratedin terms of ratios of of points plotted in Figure 9 can be obtained from Theseratiosare not af- corresponding the Ca-Mg-Fe components. points in Figure 8 and data listed in fectedby variationof Na and Al. Tables6 and 7. The effect of bulk compositionon clinopyroxene phases throughcrystallizationinteruals compositions through the crystallization intervals Proportionsof (Fig. 9) is greater Figure l0 showsthe variation of weight percentthan that on garnetcompositions intervalof through the crystallization (Fig. 8). The effectof adding5 percentHrO displaces agesof phases percentHzO at 30 kbar. The curves with 5 the trends slightly in terms of Ca-Mg-Fe. For the andesite andesite composition,the effectof 5 percentHzO on pass through valuesmeasuredfor five samplesby jadeite and AlsOs proportionsis very marked, as point-counting polished run charges(preparedfor

654

SrERt/

AND

IttyLLIE:

PHASE COMPOSITIONS

Table 7. Calculated clinopyroxene compositions through the melting interval of tonalite and gabbro, with 5 weight percent water at 30 kbar
ConEDsition Tonalite I01 5t H20 -

cabbro

DW-I

5t

H2O

1200
Atonic Prop.

rtoo

looo

14g

3 7. 7 4L.4 20.9
Prcp.

44.7 33.3 22,O

4 7. O 30.0 23.0

41.5 45.0 13.5

43.0 42.5 14.5

44.O 40.0 16.o

45.0 37.5 17.5

l4ol.

Wollastoni.te Enstatite Ferros ilite Jadeite A1203 Si0 2 A120 3 Fe0 Mgo Ca0 Na20 l0O Mql(Mg+Fe) Fe/tqq ( F e , / M g )c a

22.4 24.6 L2.4 2 1. 3 1 3 .3 51.3 13.5 4.7 9.7 12.3 4.1

66.5 .47 1.67

23.2 17.4 rr.4 3 5 .7 12.3 51.7 1 5 .r 8.0 6.8 12.7 5.4

60.3 .jO 2.3a

22.7 14.5 ll.o 4 0 .O 11.8 sI.9 15.9 7.7 5.7 L2.4 6.0
56.6 .A2 4.93

32.6 35.3 10.6 10.6 10.7 51.7 7.9 7.3 I3.7 L 7. 6 I .5 76.9 .30 .53 r.77

33.5 33.I 11.3 tr.3 10.7 sr.5 8.0 7.a L2.A l - 8 .0 1.6 74.6 .34 .7A 2.29

34.2 31.I I2.4 r2.o IO.7 5I.3 8.1 8.5 II.9 Ia.2 I.7

34,4 28.6 13.3 12.8 lO.7 5l.r 8.3 9.1 11.0 I8.4 I.9

there is obviously scopefor significanterror in the modesadoptedfor the lower temperatures. The calculated compositions liquids are plotted of in Figures I I and i2, along with the compositions and proportionsofgarnet and clinopyroxene through the crystallization intervals.They are comparedwith the dashed line representing the averagechemical variation trend for calc-alkalinerocks, from Figure l. Errors in estimates modesthrough the crystalliof zationintervalproduceerrorsin the calculated liquid paths,but it will be shown belowthat theseerrorsdo not invalidate the petrological conclusionsdrawn from the liquid paths. Compositionsof anhydrousliquids Figuresl lA and B showthe calculated equilibrium liquid path through the crystallizationinterval for anhydrousolivine tholeiite at 27 kbar, togetherwith garnet and clinopyroxene. coexisting The valuesfor 1430"C(number l) are from Greenand Ringwood (1968,Figure 10, Table 16). Calculated valuesfor 1400"C(number 2) differ from thoseof Green and Ringwood(1968), because theyuseda clinopyroxene compositionfrom the melting intervalof quartztholeiite, and we useda compositioncalculated olifor vinetholeiite (see Fig. 9). Our calculations extend the liquid path to lower temperaturesthan those of Greenand Ringwood. With decreasing temperature, the compositionof

-40 t .00 2.50

.47 I. 38 2.96

5
Oxide Prop.

3.56

3.4r

s.91

Na20+K20 FeO MgO I/4 S!O2 Cao MgO+Feo

18 38 43 29 28 42

26 39 33 31 31 36

31 39 29 33 32 34

'7788 32 60 25 34 40 35 57 25 35 40 38 53 24 35 39 4I 49 24 35 39

microprobeanalysis)under reflected light. Approximately 1200 points were counted for each sample. Volume percentages were then convertedto weight percentages, usingdensities givenin the legend (Table 8). The liquid curve is further constrained the by points at the liquidus and solidustemperatures, de_ termined independently (Fig. 2). The proportionsof mineral phasesthrough the crystallization interval of olivine tholeiitewith 5 percentH2O (Table8) wereestimated examination by of crushedfragments mountedin immersionoils (transmittedlight).The phase assemblages simple are (Fig. 3), but theseestimates, complicated development by of quench clinopyroxenein near-liquidusruns, are much lessreliablethan values plottedin Figure 10. Green and Ringwood (1968) estimated proportions of phasesbelow the liquidi at 27 kbar for anhydrous olivine basalt, quartz tholeiite, basaltic andesite,and andesite.We have extrapolatedthese valuesthrough the crystallization intervals;the temperatureintervalsare about l00oc, contrastedwith 400-500"C 5 percenr if HrO is present (Figs.2 and 3). Despite the narrow temperatureinterval involved.

E-)
(r
f, F lrl

(r
lrJ (L UJ F

20 40 60 80 ro0 WI. % OF CONDENSED PHASES

Fig. 10. The weight percentageofcondensed phasesthrough the melting interval of andesite with 5 percent water at 30 kbar (Fig. 2). Volume percentages determined by point-counting were converted to weight percentages using the following densities: = P*yanrte 3,60; p"o."n = 3.01; psr."" : 2.6; p"o,: 3.40i pe"","t : 4.00. Brackets at 900"C indicate range of error for 1000 counts ( V a n d e r P l a s a n d T o b i , 1 9 6 5 ) .A b b r e v i a t i o n s , s e e F i g . 2 .

STERTTAND WYLLIE: PHASE COMPOSITIONS

relativeto the average EQUILIBRIUM LIQUIDPATHS the remainingliquid changes line, from Fig. I ): Fel calc-alkalinetrend (the dashed + 5O/o ANDESITE HzQ,3OKb Mg increases sharply due to the low FelMg of the (Fig. I lA), and Ca/(ME * Fe) inclinopyroxene isi0, . CALCULATED low Cal(Mg + Fe) of garnet. creases to due o MEASURED is The effectof errorsin modal estimates illustrated by points5 and6 for 1400"C and l375oC, respectively. Thesepoints are calculated bulk mineralcompofor sitionswith a higherproportionof garnet. The proportion is adjustedto reduce FelMg in calculated liquids so that they coincidewith the average calcalkalinetrend. This adjustment increases diverthe genceof the calculatedliquid path from the calcMg0+FeO MgO CoO Nor0 + KrO alkaline trendin termsof Ca/(Mg * Fe),asshownin intervals liquids through the crystallization Figure I lB. Fig. I L Calculated data(olivine at27 kbar. Near-liquidus Figure l lC and D showthe calculated equilibrium ofanhydrouscompositions basaltic quartztholeiite, 1420'-1400'-1385"C; intervalsfor tholeiite,1430"C; liquid paths through the crystallization 1340'C) are from Green andesite,1390"-1360'C;and andesite, quartztholeiite, andesite, an- and Ringwood(1968, and anhydrous basaltic Fig. 10,Tables16,17, and l8). Coexisting data of minerals(Figs.8 and 9 and Tables6 and 7) areconnected tiedesiteat 27 kbar, extending near-liquidus the by trend from Fig. calc-alkaline Greenand Ringwood(1968)to lower temperatures. lines.The dashedline is the average

T a b l e 8 . C a l c u l a t e dl i q u i d c o m p o s i t i o n s ,a n d c o m p o s i t i o n so f b u l k crystal phases,through the melting interval oftonalite and gabbro, with 5 weight percent water at 30 kbar
co@sltion Tenp'C t Liquid te t cpx tKy r ct(qz) TonaLite I0l 5g H20 Gabblo Dw-l 1lo0 60 14 26 5t H20 900 20 2s 50 5

r00o

900

800
24 35

1200 80 r0 10

1000 40 2L 39

liquid pathsfor anhydrous l. (A) and (B) show the equilibrium of olivine tholeiite.The temperatures numberedpoints are: (l) 1430',(2) 1400',(3) 1375',(4) 1350'C.Points5 and 6 at 1400o for liquid compositions are and 1375'C, respectively, calculated (C) and (D) show modes with higher garnet/clinopyroxene. (calculated quartztholeiite equilibriumliquid pathsfor anhydrous (calculated at andesite basaltic at 1420o-1400o-1385"-1350'C), (calculated I 340o-I 320'C). at | 390"- l 360'- I 325 "C), and andesite

92 84 68 50 81612t212 26 14 612t4

Liquid SiO2 AI20 3 Feo = IFe M90 Ca0 Na20 Kzo oxide Prop. 49 58 69 362926163 13 t2 4 55 61 67 Ar 2 7A 62.4 18.3 4.9 r.8 5.7 4.2 2.4 64.6 17.9 3.3 1.3 5.3 4.6 2.6 64.4 15.2 3.0 0.5 4.5 4.8 3.3

conlbsitions 73.4 7-O 0.5 0.7 L.'t 7.O 9.2

76.2 9.r 1.9 0.2 2.9 5.0 4.5

48.4 18.5 10.3 6.4 14.r 0 ,I

48.1 2r.1 lo.l 4.9 t3.r o.2

4A.A 62.3 25.O 22.7 2.3 8.4 2.9 0.2 11.7 1.9 0.3 0.1

Na20+K20 Fe0 Mgo l/4 SiOz

92 4 85

1I L4 57 54 342A203 28 29

20 58 34 33

63 34 59 30

of The temperatures points from Green and RingFig. 10,Tablesl7 and l8) and of points wood (1968, from the mineral data in Figures8 and 9 calculated The liquid pathscorreare listedin the figurelegend. spond fairly closelywith the averagetrend of calcto alkalinerockswith respect FelMg (Fig. I lC), but temperaturethere is a progressive with decreasing ln increase Cal(Mg * Fe) relativeto the rock trend than for less (Fig. I lD), with divergence florandesite basalt. of Compositions hydrousliquids equilibriumliquid Figure l2 showsthe calculated for intervals olivine pathsthroughthe crystallization tholeiite and andesitewith 5 percentHzO at 30 kb of (Figs. 2 and 3), togetherwith the compositions The numerical garnet and clinopyroxene. coexisting data listed in Table 8 incorporatethe modal results modesfor from Figure l0 and estimated for andesite basalt. Numbers identify the coexistingliquids and from 1200'(l) to 900"C (4) at crystals temperatures for the olivine tholeiite in Figures l2A and B, and in from 1175"(l) to 800oC(5) for the andesite Figof uresI 2C and D. The temperatures other pointsare given in the figure legend.

Mgo+FeO

202018L28 24r8L496 ColsDsitions of 45.0 9.7 4.A Bulk

32 32 3837329 crystal 47.6 15.5 12.l

Si0z AlzOs FeO Mqo Ca0 Na 20 Oxide Prop.

40. 3 22.7 11.0 0.0

39.7 19.0 8.7

44.t II.7 6.9

56.5 146.3 7.5 | 14.2 3.1 | 13.4

47.r t5.7 rr -0

44.5 12.L 9.6 15.6 1)

22.4 26.O 23,2 22.4| 15.5 r3.2 ro.0 0.0 9.2 r.8 9.r 2.a 7.4 | 9.8 2.8 | 0.8 1 0 . 3 11. 3 l.t

Na20+K20 Fe0 Mgo L/4 sj,O2

0081620 59 6a 57 33 40 31 2t 20 57 20 21 5S 28 23 48

55 27 32 26 41

55 23 43 23 33

2345 49 54 4'1 42 23 20
5b

56 39 23 23
5J

52 42 22 23
44

23 20
5)

lilgo+Pe0

656

STCRN AND WYLLIE: PHASE COMPOSITIONS

Fe0

: b:li:l

*sio,

o Clinopyroxene o Bulk Cryslols

Mg0+FeO

No2u+K2u

MgO CoO

MgO+FeO

Fig. 12. Calculated liquid compositions through the crystallization intervals of basalt and andesite with 5 percent H,O a t 3 0 k b a r . L i q u i d a n d b u l k c r y s t a l l i n ep h a s ec o m p o s i i i o n sf o r t h e olivine tholeiite and andesite are given in Table 8. Coexisting minerals (from Figs. 8 and 9 and Tables 6 and 7) are connected by tie-lines; coexisting liquids and bulk crystal assemblages are labeled with small integers. The dashed line is the average calcalkaline composition trend (Fig. l). (A) and (B) show the equilibrium liquid paths for an olivine tholeiite and oceanic abyssal b a s a l tw i t h 5 p e r c e n tH , O . L i q u i d s w e r e c a l c u l a t e da t ( l ) 1 2 0 0 . ,( 2 ) 1100', (3) 1000', (4) 900.C. (C) and (D) show the equilibrium liquid path for an andesite with 5 percent H,O. Liquids were c a l c u l a t e da t ( l ) I 1 7 5 o ,( 2 ) I 1 0 0 " , ( 3 ) 1 0 0 0 " ,( 4 ) 9 0 0 . , ( 5 ) 8 0 0 . C .

The liquid path for hydrous olivine tholeiite in Figuresl2A and B (points l-4) follows a trend similar to that for anhydrous olivinetholeiitein Figures I lA and B (pointsl-4), but the increase Cal(Mg in * Fe) is much greaterfor the hydroustholeiite.Consideringapplicationsof theseresults,we may argue that the basalticcompositionused(gabbro DW-I, Table 1) differs from abyssaloceanic basalt, and thereforeis not a usefulmodel for subducted oceanic crust. A liquid path has been calculated subby tracting the same mineral assemblages 1200o, at ll00o, and l000oc (curvesl-3 in Figs. l2A and B) from an average abyssal oceanicbasalt(Engelet al., 1965). Although it is unlikelythat minerals these of exactcompositions would be in equilibrium with liquids through the crystallizationinterval of the oceanic basalt, the equilibrium phase compositions would be in the samerange(Figs.8 and 9).

The calculated liquid path for the hydrousoceanic basaltis closeto the average calc-alkaline rock trend with respectto Fe/Mg, in contrast to the path for hydrousolivinetholeiite (Fig. l2A). It is closer the to average rock trend with respect Cal(Mg * Fe) than to that for the hydroustholeiite,but still it diverges significantly, with increasing Cal(Me * Fe) at lower temperatures (Fig. l28). We noted abovethat corrections iron lossto for the capsule werenot made for clinopyroxenes (Fig. 7).lf a correction had beenapplied, additionof iron to the bulk mineralassemblage Figures in l24 and B would havedecreased iron contentof calculated the liquids,reducingtheir FelMg, and bringingthe liquid path for hydrous olivine tholeiite closer to the calc-alkaline rock trendin Figurel24. However, this correctionwould also lower Ca/(MS + Fe) of the bulk crystalassemblage, increase divergence and the between the calculated liquid path and the average rock trendin Figure l28. The crystallization path for andesite with 5 percent HrO at 30 kbar is morecomplexthanthosereviewed above,as shown by the successive phasefieldsintersected Figure2 (seeFig. l0). Garnet is the only in mineralcrystallizing about l00oC belowthe liqfor uidus. For temperatures I175' and I100.C(points of I and 2, respectively), the high Fe/Mg of garnet maintains liquid composition the close the average to calc-alkaline rock trend in Figure l2C, but the low Ca/(Me + Fe) of garnetdrivesthe liquid path away from the average rock trendin Figure12D.With the appearance clinopyroxene kyanite just below of and I100'C (Figs. 2 and l0), continuedcrystallization causes increase Fe/Mg and constancyof Ca/ an in (Mg + Fe) in the liquids. Figurel2D showsgreatenrichment the remainof ing liquid in SiOr, which may exceed75 percent (Table 8, 1000oand 900'C). Below 900.C quartz crystallizes, followedby coesite (Figs.2 and l0), but the SiO, content of the calculated liquid remains greater than73 percent (Table8, 800.C).Figurel2C showsin additionveryhigh (Na + K)/(Mg * Fe) in the low-temperature liquids for hydrous andesite, compared with liquidsin hydrousbasalts (Fig. l2,{). We detected potassic no minerals the runs,despite in the high KrO contentin calculated liquids(Table8, 4.5percent 900o, percent 800"C). temperat 9.2 at At atures where vaporis present (Fig.2), KrO is strongly partitionedinto the vapor (Boettcherand Wyllie, 1968; Stern,1973). The HrO contents liquidsplotted in Figure 12 of increase from 5 percentat the liquidus to saturation

STERN AND WYLLIE: PHASE COMPOSITIONS

values near 22.5 percent a few degrees above the (Fig. 2) and solidus, that is, about760oC andesite for about 780oCfor tholeiite(Fig. 3). For the andesite, Figure l0 shows that at 900"C there is 50 percent liquid, which must contain l0 percentHzO, and at 800'C the 24 percentliquid must contain about 20 percent H2O. Measuredqnd calculatedliquid compositions (Table 5) and the Figure 13 compares measured (Figs.l2C and D, Table8) liquid composicalculated interval of andesite tions through the crystallization compowith 5 percentHrO at 30 kbar. The measured sitionsagreecloselywith the liquid pathsdefinedby liquids, althoughthere are differences the calculated ratiosat I l00o and 1000'Cin the FAM in elemental diagram,and at 1000oand 900"C in the SiO, diagram. in can The differences be examined detail from the 5 listedin Tables and 8. Thereis normalized analyses good agreement I l75o and I100'C, with disat at from someoxidesbecomingsignificant crepancies the 1000oand 900"C. At all temperatures, NazO glasses are lower than calcucontentsof measured of latedvalues, to volatilization Na duringprobe due by and perhapsenhanced loss of Na*K analysis, from vapor which escapes in dissolved the aqueous The duringquenching. measured the liquid and glass valueat 900'C. If KzO is lower than the calculated correction factors could be applied for NarO lost during microprobe analysis,values for all other would analyses measured in oxides the renormalized but not sufficiently modify to reduced, be sornewhat the followingcomparisons. valuesof total iron drop to about half of Measured and 900oC. The meavalues 1000o at the calculated surementswere corrected for iron loss following Stern and Wyllie (1975),but perhapsthe correction factors applied were too low for thesetemperatures (see SiO, is someTable5). At 1000"Cthe measured CaO is somewhat what higher and the measured values. Measured AlrOr is lower than the calculated valueat 1000o, and slightlyhigherthan thecalculated very much higherat 900oC(15.3percentcompared AlzOgat 800" is with 9.1 percent). The calculated evenlower than that at 900oC(7.0 percent).Sucha in that the modal large discrepancy Al2Ossuggests proportion of kyanite may havebeenoverestimated (Fig. l0). This is the only sequence runsin which of kyanite is significant. in No quenchcrystalswereobserved runs with the of tonalite, but growth of mineralson the surfaces

27 LIQUIDPATHS, KB,DRY EQUILIBRIUM

. Liquid a Gornel o Clinopyroxene o Bulk Cryslols

Nor0+Kr0

MgO CoO

Mg0+FeO

^ U

Quorlz T h o l eiit e

Mg0+Fe0 (closed circles) and measured of Fig. 13.Comparison calculated (open circles) liquid compositionsthrough lhe crystallization with 5 percentHrO at 30 kbar. Calculated interval of andesite from Figs.12Cand l2D and liquidsand liquid path aretransferred glasses listedin Table5. are Table8; measured

primary grains during the quench,althoughdifficult in largechanges the composicould cause to detect, glasses, pointed out by Green as tions of quenched There are no consistent (1973) for clinopyroxene. betweenmeasuredglass and calculated differences that could be causedby the liquid compositions growth of mineralsduring the quench,so we conwith 5 clude that this is not a problem for andesite percent HrO. liquidsfor indicatethat the calculated results These Addireliable. are the othercompositions reasonably tional errors are introducedinto the other calculated of the however,because estimates liquid sequences, phaseproportionsare lesscertain. aPPlications Petrological The calc-alkalineigneousrocks lie in a complex for system,needingten or more major components The linesin FigureI showthe avertheir definition. age chemicalvariation of the rocks in terms of six as The components. linein FigurelB, reproduced the trend in dashedline in Figure 14, showsthe average with SiO, as the main one. terms of three variables, The calc-alkalinerock compositionsstudied by

658

' STERN AND LVYLLIE: PHASE COMPOSITIONS

+ MgO FeO

Fe0

*sloz

Phose + Co0 MgO FeO CoO + MgO FeO Fig. 14.Liquidus phase relations with 5 percent HzOat 30 kbar, and dry at 27 kbar. Dashedlinesshow the average calc-alkaline compositional trendfrom Fig. lB. (A) The calculated equilibrium liquid pathswith 5 percent HzO at 30 kbar from Figs. l28 and D. (B) A schematicpseudoternary liquidus phasediagram with 5 percentHrO at 30 kbar. Pointsz and c are piercingpoints from Fig. 4. For detailsseetext. (C) The calculated equilibriumliquid paths at 27 kbar from Figs. llB and D (anhydrous). (D) A schematicpseudoternary liquidus phase diagram at 27 kbar. Pointsz' and c' arepiercing pointsfrom Fig. 4. For details text. see

Greenand Ringwood(1968,1972)andGreen(1972), and the gabbro-tonalite-granite seriesthat we have (Tablel; Sternand Wyllie,1973), used plot veryclose to this average trend line. We will assume that the join basalt-andesite-rhyolite Figure4 composition of is coincident with the dashed line in Figure 14. Green and Ringwood (1968) and Green (1972) appliedtheir results this composition join in the for range27-36kbar to magmatic processes and above in subducted oceancrust, concluding that liquids derived from partial fusionof quartzeclogite crystalor lization of basalticliquidsbroadly follow the calcalkalinetrend.They discussed sequences crystalliof zation and fusion as if the phase fieldsintersected by their bulk compositions were binary, or nearly so. Sternand Wyllie (1973)pointedout that the basaltjoin andesite-rhyolite of Figure4 is a section through a complexsystem, and they arguedthat, with crystallization,liquid compositions must divergefrom the join. They emphasized needto establish extent the the of this divergence. can now re-examine conWe the clusions with the data in hand.

Equilibrium liquiduspaths andfteld boundaries The calculated equilibrium liquid paths for hydrous compositions havebeentransferred Figure to l44. from Figure 12,andfor anhydrous compositions to Figure l4C from Figure ll. Each liquid path, representing passage a fixed bulk composition the of throughphase fieldssuchasthosein Figures and3, 2 tracesthe composition the liquid across of liquidus surfaces along fieldboundaries. and The phase relationships suchasthoseillustrated in Figures 2,3, and4 canbe represented projections as into a pseudoternary system. liquid pathsin FigThe uresl44 and C are used distinguish to liquidusareas for the primarycrystallization clinopyroxene, of garnet, and quaftz, and the approximatepositions of field boundaries between them,as shownin Figures l48 and D. We are dealing with a hyperdimensional systemprojectedinto a triangle,and the individual liquid paths do not coincide precisely alongternary field boundaries. They occupyzonesthat delineate the patterns shownin Figuresl4B and D. Figure 4 shows liquidusprofilesfor the basaltjoin in the presenceof fixed andesite-rhyolite join, thereare amountsof HzO. For the anhydrous two piercingpoints on the liquidus,c' andm', which have beentransferred Figure l4D. For the join to with 5 percent HrO the liquidusprofileis situated at lower temperatures, and the corresponding piercing points are c and n; thesehave been transferredto Figure l4B. Phaserelationships with 5 percentHrO at 30 kbar. In the presence 5 percent of HrO, Figurel4B shows a clinopyroxene-garnet boundaryand a garnetfield quartz field boundary crossingthe basalt-andesiterhyolitejoin at piercing pointsc andm, respectively. The approximate extentof the garnetliquidusareais shown by the polnt wherethe andesite liquid path (Fig. l4A), whichis where changes direction garnetis joined by clinopyroxene near I 100'C (Fig. 2). The positionof the clinopyroxene-garnet boundary field in Figurel48 is based the liquid path for oceanic on basaltand the portion of the andesite path below I100"C (Fig. laA). In the complexrock system, the clinopyroxene-garnet boundary field wouldoccupya zonein Figure 14, because there are more variables for basalt and clinopyroxene-garnet compositions than can be represented this triangle. in The possible extentof the zone is indicatedby the differentpaths for oceanic basalt and olivinetholeiite Figurel4,{. in The arrangement Figure l48 is probablynearthe in lower limit for the extentof the garnetliquidusfield, with 5 percentHrO. This brings the pseudoternary

STERN AND WYLLIE: PHASE COMPOSITIONS

659

field boundary as close as possibleto the basaltjoin. The crystallizationof accessandesite-rhyolite (see ory kyaniteis not represented Figs.2, 3, and l0). and garnetare With 5 percentHrO, clinopyroxene joined by quartz or coesite 900oCfor the andesite at (Figs.2 and l0) and near800"Cfor the olivinetholeiite (Fig. 3). The position of the garnet-quartzfield boundary, intersectingthe basalt-andesite-rhyolite join at an oblique angle,is basedon the fact that point m at 1050"C contains about 7l percentSiO, (Fig. 4), and point j representing liquid in andesite 5 76 SiO,(Tables and 8). near900"Ccontains percent F PHASE IELDS With continued crystallizationof clinopyroxene* 27-30Kb point),the garnet*quartzQ is not a ternaryreaction liquid is enrichedin Si/(Ca+Mg*Fe) as shown in MgO+ Fe0 Co0 of Figure l48, althoughthe precipitation quartz(or phase diagram showing effect of 5 Fig. 15. Pseudoternary of enrichment liquid in may halt the absolute coesite) (from Figs. l4B and D). SiO, (Table 8). The dominantchangeat the lower percentH,O on liquidusfield boundaries Pointslabelledc, m, c', and m' arefrom Fig' 4. The dashedline is temperatures the enrichmentof liquid in alkalis compositiontrend from Fig. lB' calc-alkaline showsthe average (Figs.l24 and C, Table8), whichis not represented whichis almostcoincident the basalt-andesite-rhyolite of join with in Figure14. Fig. 4. in For initial liquidswith compositions the range the pointT would actuallybe repreandesite-basalt, marking of fromT towardsCaO, with point of intersection the field boundaries sentedby a zoneextending to decreasing temperaturecorresponding the lower the precipitationof quatrz,T',containingmore than (com- 65 percent SiOz. The coprecipitationof quartz at of of temperature appearance quartzor coesite enrichthe absolute below7' reduces the pare Figs.2 and 3). Figure l4B represents most temperatures Si/(Ca+ liquid in SiO', although phasediagramwith respect ment of remaining favorablepseudoternary alongwith alkali enrichto proximity of basalt liquid paths to the basalt- Mg+Fe) may still increase join. ment. andesite-rhyolite phase relationships 27 kbar. Figure at Anhydrous paths of crystallizqtionandfusion l4D representsthe most favorable anhydrous Equilibrium liquidus Figure 15 comparesthe pseudoternary pseudoternary phase to diagramwith respect proximcompositionsfrom liquid pathsto the basalt-andesite-rhyo-surfacesfor calc-alkaline rock ity of basalt liquid paths Figures 14D (anhydrous)and l4B (with 5 percent lite join. It is basedon the calculated is difference not signifiplotted in Figure l4C, which extend the resultsof HzO). The 3 kbar pressure with the effectof 5 percentHzO (Figs. Greenand Ringwood(1968)and Green(1972),and cant compared abovefor con- 5, 6, and 7). None of the equilibriumliquid paths reviewed following the considerations basalt-andecorrespondpreciselywith the average structionof Figure l48. field boundary passing site-rhyolitejoin. Crystallizingliquids are progresThe clinopyroxene-garnet with this join, sivelyenriched Cal(Mg+Fe) compared in through lz' remainscloserto the composition composiis and the garnet field is smaller than in the hydrous join. The divergence smallfor anhydrous in c'm' it Fig. a). This bound- tions, and larger with increasingHzO. The corresystem Figurel4B (see in ary representsthe edge of the zone of hyper- spondingchanges Fe/Me/(Na+K) can be seen of dimensionalfield boundariesin the complexsystem from comparison Figure14with FiguresI I and 12. of the We have considered effects errors in modal rocks,nearest the composito for basiccalc-alkaline and iron correctionfactors,and found that estimates tion join. of with garnetand clino- adjustments theseto bring the liquid paths into liquidscoexisting Calculated with the rock join in one projection(e.9. pyroxene may contain more than 65 percent SiO, coincidence in the (data not tabulated),and the point m' contains63 Fig. l2A) increase path divergence the other (e.g.Fig. l2B). percentSiO, (Fig. 4). Therefore,the garnet-quartz projection Crystallization of anhydrous basalt at |U) km the field boundary intersects join obliquely,with the

660

STERN AND WYLLIE: PHASE COMPOSITIONS

depth. Greenand Ringwood(1968)calculated field boundaryT'c'. Liquids similarto liq- clinopyroxene just uid compositions in producedby equilibriumcrystalli- andesites termsof SiOzcontentrepresent one zationof up to 35 percentof four calc-alkalinerock group in a continuous rangeof compositions. compositions, showed Temperatures requiredto reachthe liquidusof anand that these liquidsbroadly followedthe chemical variation approach 1400"C trendof the Aleutian hydrous andesiticcompositions Islandcalc-alkaline province, plottedon a FAM dia- (Fig. 2 and 4). Thesetemperatures higherthan are gram. They suggested about 50 percent in zoneat 100km depth that crystalli- mostestimates a subduction zationof an anhydrous basaltic liquid would produce (Wyllie,1973). an andesite, Partial melting of hydrousquartzeclogiteat 100 km and concluded that the thermalvalleyin the anhydrousliquidus profile, represented Figure depth. Green and Ringwood (1972) and Green in 4 asc'm', wouldprevent found,consistent with our results Figure4, fractionation liquidsmore (1972) in to SiOr-richthan andesite. This argumentimpliesthat that the thermalvalleyin the liquidusprofilefor the join the thermalminimum is a terminusfor crystallizing basalt-andesite-rhyolite was shiftedfrom andeliquids,as it would be if the composition join werea site(m') to daciteor rhyodacite(m'm) in the presence binary system. of HrO. On this basis, they concluded that daciteor Extension Greenand Ringwood's liquidsmay be produced partial meltof (1968) by calcu- rhyodacite lations beyond 35 percentcrystallization showsthat ing of hydrous quartzeclogiteat 100km depth.This althoughequilibrium would be strictlyvalid only if the compoliquid pathsremainfairly close conclusion to the average sitionjoin approximated binary system. intercalc-alkalinetrend in terms of FAM a We components (Fig. l lC), the liquids are enrichedin pret this thermal valley as a piercingpoint for a Ca/(Me * Fe) compared with the average field boundary,and Figuresl4B and rock trend garnet-quartz (Fig. aC). The lowesttemperature the thermal l5 show that average dacitesand rhyolitesare not in valleyfor the dry profilein Figure4 is about 1390.C; amongliquidsproduced partialfusionof hydrous by quartzeclogite. the soliduswhereequilibriumcrystallization terminatesis lower by 60-70'C, according Figure 3. Figure 4 showsthat the solidustemperature to for Liquidssimilarto andesites termsof SiO, content quartzeclogite the presence HrO is 250"Cbelow in in of just one group in a continuous represent range of the liquidus minimum with 5 percent H2O, and compositions extending liquidswith morethan 65 400"Clowerwith 2 percent to HrO. This is quiteinconpercentSiOr.The compositions near-solidus of liq- sistentwith binary phaserelationships. path of The uids from anhydrousbasaltsare still inadequately equilibrium fusionfor quartzeclogite the presence in determined, enrichment alkalisis anticipated of a fixedamountof HrO can be tracedon Figure3, but in (Greenand Ringwood,1968). with the liquid compositions changing represented as Partial melting of anhydrousquartz eclogiteat 100 in Figures 14 and 15. For 5 percentHrO, melting km depth. Ringwood (1975, p. 269) reviewedthe beginsat a temperaturenear 750"C. Within a few Canberra experimental program, and concluded all that tensof degrees, vapor and coesite dissolve, the and from anhydrousquartz eclogite:"With a moderate liquid passes point corresponding 7 in Figure the to degree partial melting,an andesite of magmacould l4B. At 900"C the liquid contains 62.3percent SiO, be formed.. . . The magmawill not move from the (calculated,Table 8). Kyanite disappearsnear andesite minimumuntil all of the quartzin the paren- l000oC,wherethe liquid contains49 percentSiOr, tal quartz eclogite has been incorporatedinto the andgarnet and clinopyroxene melttogether then with liquid.Then, with greater degree melting,basaltic increasing of temperature. Figure l4'A,showsthat, for a andesite might be formed."Accordingto Greenand quartz eclogite,the point where coesite/quartz disRingwood (1968),40-50 percentmelting produces appearis more enrichedin Cal(Mg+Fe) than the andesitic liquid. pointT in Figure 148. corresponding In fact, thereis no andesite minimum controlling For a more realisticsituation. with a smaller the liquid composition, shown by the paths for amount of HzO, the pseudoternary as phasediagram equilibrium fusion represented schematically Fig- would be intermediate in betweenthe two shown in ures 14D and 15.Melting progresses throughabout Figure15.The pathsfollowedby liquidsduringequi30'C (Fig. 3) along a field boundary for quartz, librium fusionare similarduring the initial stages to clinopyroxene,and garnet until liquid reachesthe those for 5 percent HrO, but they are greatly exj', composition where the last of the quartz dis- tendedin termsof temperature, shownin Figure3 as appears;then fusion continuesalong the garnet- (e.g. quartzremainsto a much higher temperature),

STERN AND WYLLIE: PHASE COMPOSITIONS

661

as and the later statesof fusion approachthosein the productsof equilibriumprocesses, demonstrated (1969). SternandWyllie(1973) for fusionby Presnall system. anhydrous Figure3 shows outlined the effectof fractional fusion on quartz ecbelow I percent, For HzO contents near the solidus,producing logite, dry and with HrO. The effect of fractional that all HzO dissolves of (about 22.5percent H,O). With crystallization a basalticliquid at 100 km depth liquid HzO-saturated liquid compositions liquid would probablytend to change HrO-undersaturated in increase temperature, join for average kyanite, garnet, and further away from the composition persistswith coesite/quartz, becausethe fractionation in increasing amount slowly (with basalt-andesite-rhyolite, clinopyroxene, in decrease HrO content) through a paths shouldcrossthe equilibriumpathsfrom conconcomitant at interval.The temperature which caveto convexsides(Figs. ll,12, and l4). wide temperature critically on the HzO depends all quartz dissolves Conclusions which are not content(and the phaseboundaries, We concludethat partial melting of subducted closely defined). Quartz could persist to 1000o, oceancrust with small amountsof HzO at depths to 1100", 1200"C, a point on an HzO-dependent or convertedto quartz ecto boundarycorresponding jj' (Figs. 14 and l5). At where amphibolitehas been liquidsof broadlyacid or intermediate logiteproduces with garnet the highertemperatures, liquid coexisting from the comliquidsdiverge but (tkyanite) followsthe equivalent compositions, these and clinopyroxene rocks.The prodcalc-alkaline positionsof average of a field boundarybetweenjcandj'c'. fractionationof basalticliquid would of The compositions hydrous liquids coexisting uctsof eclogite from subbe similar. Therefore,liquids generated along the field boundarybelow with quartzeclogite modicrustat this depthmust undergo ductedocean jj' , beforeall quarlzmelts(Fig. 3), arecertainlyricher duringuprisewhich bring themto the calcfications and in SiOzthan andesite, probablygreatlyenriched similar conin alkalis (Fig. l2A) and incompatibleelements alkaline trend. Others have reached and trace-eleof (compare results tonalitein Tables5 and 8). Ac- clusionsfrom consideration majorfor et al.,1977; (Gill, 1974;Lopez-Escobar theyare alsoconsid- mentcontents cordingto Figuresl4A and 15, proposed (1973) with the Kay,1977).Nichollsand Ringwood in erablyenriched Cal(Mg*Fe) compared couldreact from quartzeclogite liquids that siliceous dacites and rhyodacites. average melting pressure. Figures5 and 7A show that, with overlying peridotite, with subsequent Effect of andemantle producingcalc-alkaline in of modified pressuie, Ca/(Mg*Fe) increases with increasing treatment a Kay (1977)presented quantitative Ca/ sites. which would reduce garnetsand clinopyroxenes, and of (Mg+Fe) in liquid pathsif the proportions miner- of a multistagemodel to explain the isotope Mulof chemistry Aleutianvolcanoes. trace-element interval remainedthe als through the crystallization ridgesto subduction from spreading the same.At higher pressures, liquids would then tistageprocesses zonesalso haveappealon the groundsof massbaljoin calc-alkaline the more closely average approach data (Armstrong,1968)' in Figure 14. However, this effect is offset by the anceand isotope haveleaptahead hypotheses As usual,petrogenetic reported with inincreasinggarnet/clinopyroxene data. The resultspreexperimental of quantitative creasingpressurein the crystallizationintervals of among and basaltand andesite, hydrousandesite sentedhere are not definitivediscriminants anhydrous in currently assumed the various complex processes (Greenand Ringwood,1968; Green,1972). the despite urgentneedfelt for the zones, subduction the data in 1971.Nevertheless, resultsconsolidate Fractional crystallization andfusion information neededwhere the magmatic processes Green and Ringwood (1968) and Green (1972) pressure for them begin.We needsimilarresults the total liquid pathsandrelated equilibrium determined of magmageneraand sites the They referred to fractional rangebetween surface to fractional processes. tion. from rocks, and crystallization "liquid fractionates" Acknowledgments and fracequilibrium between without distinguishing Section, was supportedby the Earth Sciences is This research it with solidsolution, tionationpaths.For minerals and EAR 76by Foundation, grantsGSA-29426 with equilibrium National Science not valid to equatefractionation Research in supported part by the M aterials . lt hasalsobeen of paths. Equilibrium fusion is the reverse equilib- 20413 Foundationat the Laboratory Programof the National Science of rium crystallization,but processes fractional fu- Universityof Chicago.We thank A. T. Andersonand R' C' yield products dis- Newton for their critical reviews earlyversions this material, of fractionalcrystallization of sion and tonalite' and tinctly differentfrom eachother, as well as from the and P. C. Bateman F. C. Dodge for the analyzed

662

STERN AND IIYLLIE: PHASE COMPOSITIONS

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Nouember14, 1977; accepted Manuscrtpt receiued, for Publication,March 23, 1978'