American Mineralogist, Volume 71, pages 301-316, 1986 Phaserelationshipsof gabbro-tonalite-granite-water at 15 kbar with applicationsto differentiation and anatexis Wuu-LrlNc HuaNc Exxon Production ResearchCompany, Houston, Texas 77001 Pprnn J. Wrr-r-rn Division of Geologicaland Planetary Sciences,California Institute of Technology,Pasadena,California 9 1I 25 Ansrnncr Phase relationships have been determined at 15 kbar with variable HrO contents for three rocks-a gabbro,a tonalite, and a muscovite granite-representing the compositional trend of the calc-alkalinerock series.Experimentswereconductedin 0.5-in. piston-cylinder apparatususing Ag-Pd or Pt capsules.The results obtained are acceptablerepresentations ofthe phaserelationships for elucidation ofpetrological processes.Selectedruns with 5olo HrO were completed using Au capsulesto overcome the problem of iron loss, up to the temperature limit of Au, for reliable electron microprobe analysesof glass,garnet, clinopyroxene, amphibole, and plagioclase.No glassescould be analyzedin the gabbro. The data provide Ko values as a function of temperaturefor pairs of coexisting minerals and liquid. The chemical variations are usedto evaluate(l) the fractionation trends in hydrous magmasat 55 km in thickened continental crust or uppermost mantle and(2) the products ofanatexis ofthe thickened crust. At this depth, fractionation ofhydrous basalt,or anatexis of gabbro and tonalite or their metamorphosedequivalents, appearsto produce liquids diverging from the calc-alkalinetrend. Anatexis ofgranite producesa liquid less siliceous than itself, with some chemical characteristicsof syenite. INrnooucrroN ExpnnrunNTAL One of the major chemical trends in igneouspetrology is given by the calc-alkaline rock seriesgabbro-tonalitegranodiorite-granite(basalt-andesite-rhyolite).The phase relationships of specific rocks in this series have been studied under a variety of conditions by many investigators, commonly with applications to particular petrogeneticproblems related to the specificrocks. The experimental resultsfor three rocks at l5 kbar are presentedin this paper in T-Xrro phase diagrams,together with a set of reliable analysesof minerals and glasses. The more general construction of the phase relationships for the complete rock series,representinga compositional line through the componentsof igneousrocks, hasbeenaddressedby Piwinskii and Wyllie (1968, 1970) and Piwinskii (1968, 1973a, 1973b, 1975) with excess HrO at 2 and l0 kbar, by Green and Ringwood (1968) for the anhydrous seriesat 18,27, and 36 kbar [seealso Green (1972), Green and Ringwood (1972) for the effect of HrO on the liquidus at high pressuresl,by Stern and Wyllie (1973,1978) at 30 kbar with HrO contentsfrom 5oloto excess,and by Green ( I 982) at I 5 and 30 kbar from dry to excessHrO. An important petrogeneticquestion is to what extent the liquid compositions within the crystallization intervals of gabbro and tonalite parallel the calc-alkalinecomposition trend, for a variety of pressures and water contents. 0003{04xi8610304{30I $02.00 METHoDs Starting materials Natural olivine tholeiitic basalt (gabbro), tonalite, and muscovite granite were usedas startingmaterials.The chemicalcompositions,clrw norms, and approximatemodesarelisted in Table l. The tholeiite is from a fino-grained basaltic sill in Scotland (Lambert and Wyllie,1972). The tonalite from the SierraNevada batholith was kindly provided by P. C. Batemanand F. C. Dodge (tonalite 101, or M 127 in Piwinskii, 1973b). Field and petrographic descriptionsofthe tonalite have been given by Bateman et al. (1963). The granite collected from Harney Peak, South Dakota, was kindly provided by T. T. Norton and R. T. McLaughlin of the U.S. GeologicalSurvey(Huangand Wyllie, 1973, 1981). The chemistry of major elements in these rocks corresponds closely to the calc-alkaline trend (although the granite is of S-type). Apparatus and procedures Experimentswere performed in a single-stagepiston-cylinder apparatussimilar to that describedby Boyd and England(1960), using a 0.5-in.-diameterpiston and chamber with hardenedsteel liner. The apparatus was calibrated for pressureand temperature asdescribedby Boettcherand Wyllie (1968).Temperatures,measuredwith chromel-alumel(below 850€) and Pt-PtroRh,o(above 850"C) thermocouples, were precise to +5"C and accurate to + l5'C. Furnaceassemblieswere constructedfrom graphite and talc for mns up to 850'C, but for higher temperatures,the talc rods were replaced by pyrex glass to avoid talc dehydration and 301 HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER AT l5 kbar 302 Table 2. Results of quenchingexperiments for gabbro (DW-l) at l5-kbar pressure Table 1. Chemical analyses,crpw nonns and approximate modes for whole rocks in the present study cabbro, Dw-1 Tonafite I01 cranite L26 (1) Cheni@L a@L!6ea 45-91 o.94 17,19 2.33 Ti02 A 1 2 03 F e 2 O3 Fe0 ho ugo o.22 '7 .4A r3. 54 1.63 0.14 1.78 Na2O Kzo H zo + Pzos cQz 0.04 14-66 0-03 15.55 0.17 o.42 0.07 0.02 o.42 4-29 3.08 0.66 0,04 0.15 o.02 59. 14 o.79 18.23 2.32 0.I1 2.50 5.92 3.81 2. r9 0.82 0.04 0,30 0.01 ( 2) CfPW Mome Quartz orthoclase AIbite horthite Diopside 0.83 13.78 39.14 22.59 5-95 8.55 3. 39 0.78 0.10 olivine Ilmenite Apatite Corudw 1I. 7 12.9 3 2- 2 26.2 0.9 9.4 18.20 36.24 o.98 3.4 1.5 o-7 0.06 4.80 800 825 a25 850 4A4 451 480 4s4 453 452 456 455 451 463 461 46a 470 46I 469 472 476 47r 459 462 30 4-4 30 30 30 23 22 1l 30 40 20 25 25 3014L 4013L 5 1022L 1523L 3072L 458 1200 514L s 488 IOOO 4a6 llOO 485 1150 30 Lpx, rc, I L Cpx, Hb, Hb, I Cpx' Hb' Gt(?) 12 12 Lr 1l I0 cPx, b, I cpx, ft, I cpx, Hb, I CPx, ft, I Cpx, ft, I Cpx, Hb(tr), cpx, Hb(tr), Cpx(tr) + L + L cpx(tr) CPx(tr) + L 14 cpx+r 23-5 34 23 23.5 30 5 900 925 975 1000 rO25 1050 1050 1075 I075 I075 1075 1075 1100 1100 1100 1100 Cpx, Cpx(tr), 5 5 5 1r 3 I 1 + L L I L L CPr' Hb' Ga, L cpx, Hb(?), L Cpx(tr), L 4811200511 (3) App"aeimate l4ade6 Quartz a1 Lal i F-l Ac^:r PIagj-oclase Augite 4'7 41 Horhblende Opaques krnet Apatite 473 ] I "t.t 12.5 9 Biotite Olivine I3 4.5 59 3 3 2 0.1 466 475 411 I l ) 47a 0.9 479 Muscovite 414 465 embrittlement. All runs were brought to final pressure with the "piston-out" proceduresas describedby Boyd et al. (1967).Pressures listed are nominal, incorporate no corrections for friction, and are consideredaccurateto +590. Crystalline rock sampleswere used in the experiments. Oxygen fugacity was not controlled. The oxidation state of the sample during the mn conditions should be close to the Ni-NiO buffer (Allen et al., 1975). Water and (dry) powdered rock sample were weighed into capsules in the required proportions, sealed, and run at 15 kbar and selectedtemperatures.The run tableslist the HrO weighed into the capsules.The actual HrO present in a capsule during a mn was thus the total of HrO stored in the hydrous minerals of the rock, plus the HrO added. Two types of runs were made to determine the phaseboundaries:(l) "singlestage" runs in which the crystalline rock samples were brought directly to the desired temperatures and (2) "two-stage" runs in which the crystalline samples were held above the liquidus until completely melted and then the temperature was reduced to the desired value. The first type was prevalently used in the present study while the secondwas made as a test for equilibrium. Electron-microprobe analyses were performed on quenched charges at two intervals during the present study. Early reconnaissanceanalyseswere made on an ARr-/EMxelectron-microprobe analyzer at 15 kV,0.02 pA sample current, for l0 s per element. The beam size was about 2 pm. The microprobe analyzer was then automated. Most of the analysesfor the present study were performed on the computerized .ornr-/er'.rx analper, using standard procedures for the J. V. Smith laboratory at the University ofChicago. The accuracyofanalyses is -r2% ofthe amount of major elementspresent. 1150 1020 1150 1040 1200 1050 1150 r050 rr50 1050 l]so 1050 1200 1075 r200 40 40 40 40 5 5 15 15 20 20 30 30 5 5 '7 22 7 25 9 25 2r 24 6 Cpx, S(?), cpx, L L cpx, L cpx, Eb(?), L cPx, L 9 24L 11 23L 'l Identification of phases Phasespresent in quenched runs were identified using standard optical and X-ray powder-diffraction techniques, described in previous papers on these rocks. Phases encountered include in the gabbro-watersystem,amphibole, clinopyroxene,garnet,liquid, and vapor deposits; in the tonalite-water system, garnet, clinopyroxene, plagioclase, quartz, biotite, liquid, and vapor deposits; in the granite-water system, quartz, plagioclase, alkalifeldspar, muscovite, kyanite, sillimanite, corundum, garnet, liquid, and vapor deposits. Opaque minerals, although of interest, were too sparsefor confrdent identification. Expnnrlvrmlur, REsULTS AT 15 KBAR One major uncertainty in the interpretation of experimental results is the absorption of iron from samplesby the noble-metal capsules(Merrill and Wyllie, 1973;Sternand Wyllie, 1975;Nehru and Wyllie, 1975). Experimentsfor the gabbro-watersystem were first performed using Pt capsules.In order to test the effect of iron loss on the liquidus boundary, some additional runs with 5% HrO were performed, using AgrrPd25capsulesto determine the liquidus temperature. Most runs for the tonalite-water system capsules.Runs for the low-iron granwere made using Ag3oPd?o ite-water system were performed using Pt capsules. When the phase diagrams had been determined, selected runs lvere com- AT 15 kbar HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER 303 I I t I I I I I ll LI r200 v i Hb-ouT t I CJ cc = 1000 ro I i\o lr r\ O CL = Hb + cpx + lGal + t Hb+Cpx+02+lcal+l+v Hb+Gpx+Pl+(L+lGal Hb+CpxaPl+(lz+lGal+U WATER WT.% Fig. |. Phaserelations of gabbro Oasal| at l5 kbar with varylng HrO contents. For definitive runs and abbreviations, seeTable 2. Squaresindicate runs oflambert and Wyllie (1972). Seetext for other data sources.HrO bound in the original rock is indicated by the arrow. Only for 090 HrO is mineral assemblagedevoid of Hb + Bi. (Ga) indicates garnet, which should be stable, but failed to nucleateexceptin Au capsules(seetext). pleted in Au capsulesfor analysis of minerals and glasseswith minimum iron loss, up to the temperature limit of Au. Phase relationships for gabbrewater Figure I shows the experimental results at 15 kbar for the melting relations of gabbro with 5-400/0HrO added. The H,O structurally bound in the original rock is shown by the arrow. Near-solidus runs with excessHrO are from I-ambert and Wyllie (1972). The definitive mns are listed in Table 2. The liquidus temperature of an anhydrous rock of similar composition was determined by Green and fungwood (1968). The solubility of HrO in gabbro liquid at 15 kbar and 1080"C,which should be given by the change of the slope of liquidus boundary, is not constrained. The subsolidus mineral assemblageat this pressurewith excess water is Ga + Hb + Cpx + Pl + Qz + V according to the results of Lambert and Wyllie (1972). There are three solidus temperatures, depending upon the amount of water present. For a dehydrated rock, the solidus temperature is about 1200€, esti- mated from Green and Ringwood (1968). For a vapor-absent rock, with all HrO stored in amphibole, the solidus corresponds to the reaction temperature of amphibole in this assemblage, extrapolated from runs with HrO added. This temperature was not determined, but it is probably between 1000 and ll00"C. For a rock with a free vapor phase, the solidus is at 635qC. Plagioclaseand quartz disappear, respectively, at I 5 and 40€ above the solidus in the presence of excess water. The upper stability boundaries for plagioclase and quartz are estimated by interpolation between the anhydrous melting relations of similar rock compositions (Green and Ringwood, 1968; Ito and Kennedy, 1968)and the melting boundariesin the presenceof excess H,O. The boundaries fall steeply with increasing HrO in the vapor-absent region. The runs do not define the position of the dashed boundary separating the phase fields with vapor present or absent. Amphibole is present from subsotdus temperature to nearliquidus temperature (1070"C) with excess HrO. In the vaporabsent region, lve expect the upper stability temperature of amphibole to increaseslighfly with decreasingHrO content (Hol- HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER 304 AT 15 kbar 1200 s0u0us oo lllllll llt G .,' G EI G = H Hb+Cpx+Ky+[+v 800 f' Q r\<*, r," (Ga + l[ , , ' - - - H b +c l x+ ( G a ) + B i a K Y +t + v D f i l * C o+ , 0 r * ( G .*] B i+ x y + [ + V [ l Bi H b + G p x+ P l + 0 z + ( G a + tr H b + C p x + P l + 0 z + ( G a ) +B i + V WATER WT % Fig. 2. Phaserelations of tonalite at 15 kbar with varying HrO contents. For definitive runs and abbreviations, see Table 3. Squaresindicate runs from Lambert and Wyllie (1974). Seetext for subsoliduschanges,other data sources,and seelegendfor Figure 1. loway, 1973). No garnet was observedin run products using h and Ag-Pd capsules,except in a single run (#R488) at 1000t with 5% HrO (Ag^Pd.). Yet garnets occur in runs from Au capsuleswith 50/oHrO between 700 and 1000qC(Table 5). The failure ofgarnet to nucleateunder theseconditions is well known and much reviewed (Lambert and Wyllie, 1972, 1974; Green, 1972). The nucleation ofgarnet in Au capsulesmay be due to retention of iron in the sample. (Ga) indicates regions where garnet should be stable, despite its failure to nucleate in Pt and Ag-Pd capsules. Clinopyroxene and garnet are the near-liquidus phasesfor all HrO contents (separate boundaries not distinguished). They are joined by amphibole just below the liquidus with excessHrO. Through more than 350{, liquid coexistswith amphibole, clinopyroxene,and garnet for HrO contents at least down to 5olo. Phase relationships for tonalite-water Figure 2 shows the experimental results at 15 kbar for the melting relations of tonalite with 5-35 wt% HrO added.The HrO structurally bound in the rock is shown by the arrow. Near-solidus runs with excessHrO are from Lambert and Wyllie (1974). The definitive runs are listed in Table 3. The liquidus temperature for anhydrous tonalite is near l250qC as estimatedfrom Green's (1972) study of a rock of similar composition. The liquidus temperature drops to about 1 140"C for the vapor-absent rock (with HrO releasedfrom amphibole and biotite), and down to 940qC with excessH,O. The solubility of H,O in tonalite liquid at 15 kbar and 950qC,which should be grven by the changein slope of the liquidus boundary, is not constrained. Clinopyroxene and amphibole are liquidus or nearJiquidus phaseswith excessHrO. Clinopyroxene occurs only in minor amounts except near the liquidus. In the vapor-absent region, the upper stability temperature of amphibole changes little with decreasing HrO content and thereforedivergesfrom the liquidus. Amphibole is the dominant phase down to the solidus region. The biotite-out curve rises to somewhat higher temperatures in the vapor-absent region. Precisedetermination of rhe amphibole-out and biotite-out curves at low HrO contents is highly desirable, but experimentally difficult. The solidus at 15 kbar is within the garnet stability field and in the region of the reaction of plagioclase to jadeitic pyroxene. 305 15kbar HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATERAT According to Lambert and Wyllie (1974), the subsolidusassemblage with excessHrO is Pl + Qz + Hb + Bi, u.ith a trace of Cpx and possible Ky, and with Ga, which failed to nucleate. Plagioclase should be replaced completely by clinopyroxene and garnet within a short temperature interval below the solidus. This is not indicated in Figure 2, and no nrns were completed to establish this, but the generalpicture is clear (Lambert and Wyllie, 1974, Fig. l). There are three different solidus reactions and temperatures, depending on HrO content, as discussed for gabbro-HrO. Plagioclasedisappearswithin 5'C above the solidus with excess HrO, but is stable to considerably higher temperature, 950eC, with 50/oHrO added, and is stable to almost 1350€ in a dehydrated rock (Green, 1972).For a dehydratedandesite,quartz is stable to about I 150'C, 50'C below the liquidus (Green, 1972), but addition of 50/oHrO is sufrcient to lower its upper stability temperatureto about 775'C. Quartz disappearsabout 50€ above the solidus with excessHrO. The dashed boundary separating vapor-absent from vapor-present fields is only estimated. However, its estimated position constrains the low-temperature ends and the curvaturesofthe plagioclase-outand quartz-out boundaries. The latter boundary has the normal concave-upward curvature (seeFigs. I and 3). The unusual, retrograde shape for the plagioclase-outcurve is a consequenceof the plagioclase-clinopyroxene reaction near the solidus, which can be modeled in the systemNaAlSiO4-SiOr-HrO. In the presenceofexcess vapor, trace amounts ofgarnet were observed at 15 kbar between 725 all.d 875"tCby Lambert and Wyllie (1972). In the presentexperimentswith Ag-Pd capsules, garnetswere observeddown to 850qCwith 5% HrO added. The amount of garnet increaseswith temperature, and near the liquidus, garnet and clinopyroxene become the dominant phases. However, garnet appearsin runs down to 700qCin Au capsules with 50/oHrO (Table 5). The failure of gamet to nucleateat lower temperatures where it should be stable, denoted in Figure 2 by (Ga), was alreadydiscussedin connectionwith the gabbro-water systemand by I-ambert and Wyllie (1972). Phase relationships for granite-water Figure 3 shows the experimental results at 15 kbar for the melting relationships of muscovite-granite with and without water added, and the results are extrapolated toward the anhydrous rock composition (Huang and Wyllie, 1973, l98l). The HrO structurally bound in the muscovite granite is shown by the arrow at0.66o/o. The definitive runs arelisted in Table 4. The subsolidus assemblageat this pressure corresponds to that of the natural rock, two feldspars,quartz, and muscovite, with just a trace of garnet. The phase-boundarybetweenvapor-absentand vapor-present fields is determined by runs in Figure 3, in contrast to Figures 1 and 2, and this gives a better estimate of HrO solubility in the liquid at about 77 5C. ln the vapor-absentregion, upper boundaries for quartz, feldspars, and garnet decreaseconsiderably with increasing HrO content. The muscovite-out temperature increasessomewhat with decreasingHrO content, as anticipated from phase relationships in synthetic mica systems (Yoder and Kushiro, 1969;Huang and Wyllie, 1974).The vapor-absentsolidus for the beginning of reaction of Na-bearing muscovite in this assemblagehas been measured(Huang and Wyllie, 1981). Quartz was the liquidus phase for the biotite-granite studied by Stern and Wyllie (1973, l98l), and the correspondingboundary is shown by the heavy line in Figure 3. For the aluminous granite used in the present study, traces ofcorundum persisted Table 3. Results of quenchingexperimentsfor tonalite (l0l) at l5-kbar Pressure Rm ----:------- 444 441** 4r9 442 4I3 44r 403 422 420 429 404 423 4I2 4L6 421 4L1 402 4r4 445*r 435 410 40a 424 4ra 431 407 405 800 425 850 475 925 925 925 940 94A 950 950 950 975 975 975 1000 1000 1025 rO25 102s to50 rloo Lr25 1150 1150 1150 1200 430 rooo 915 rO50 925 1050 950 1050 96s lO50 975 1100 1000 1100 1025 43A 42a 425 433 432 42r gonet; Hzo Results* Bio, Cpx, PL cpx, P], Bio' cpx, Ca(tr), cpx, @, PI' Pl, cpx, G, cpx, Ga, Pl, KY' cPx(tr), KYr L L Pr, Bio(?)' KY(?), r L KY(tr), L Ky(tr), 5 5 5 5 5 5 33 32.7 f5 9,6 24 9 12 3 13 1l Hb, &, b, S, &, 6, Eb, I 50 20 20 28 5 L4 7 1 20 2l 18.5 1 2I-S L 6(tr), CPx, KY, I b, cpx, KY(tr), L L ft(?). cpx' c, I cpx, I L2I4L 33 5 5 s 5 25 3 3 L cpx, L cpx,@,l cpx, Ga, a 0 05L 0 5lal 5 33 33 339 33 235 23lAL 204 2o,4 13 13 52r 5 5 L 18 A 5 I7 s(tr), 22 Cpx, L 25 L L cpx,l t2 10 35 11 24 KY(?), cpx, r cpx(?), r Cpx' L cPx, r 514L Addi-tional abb?eoiatians: see Table 2 For ahbpetiatian PL = plagioc1'ase; Bio = biotitej 4i = kAmite. 0a = to higher temperatures. Metastable corundum forms from the breakdown ofmuscovite at 15 kbar, instead ofthe anticipated AlrSiO, polymorph. Corundum, once formed metastably, persists indefinitely in this system, as well as in parts of the synthetic muscovite system (Huang and Wyllie, 1974). Phase relationships for gabbretonalite-granite-water Figure 4 comparesand combines the phase relationships for the rock seriesat 15 kbar with 5qoHrO. The phaseboundaries have been drawn through points transferred from Figures 1, 2, and 3. The data of Green and fungwood (1972) on a rhyodacite with 690loSiO, were included in constnrction ofthe diagram. The diagram shows two liquidus piercing points bounding the garnet liquidus between about 60 arrd 700/oSiOr, with lowest liquidus temperaturenear 700/oSiOr. The effectof pressureand HrO content on the liquidus profile for the calc-alkaline rock series has been discussedby Green and Ringwood (1968) and Stern and Wyllie (1973,1978). Test of equilibrium The phase diagrams in Figures l, 2, and 3 are reaction diagrams, with phase boundaries drawn on the basis of single-stage runs using capsulesofPt and AgrrPd' for gabbro, AgroPdrofor tonalite, and Pt for granite. Tests for continuation or completion of reaction and for the attainment of equilibrium include increasingrun duration and making two-stagenrns (also necessarily oflonger duration) to reversethe reactions.The longer durations 306 HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER AT 15 kbar I t I I CJ o I I I I I I I I I 1000 trt CE oc \l ltt 4 = ll,l e\ \% tu o 0z+Ms+L 0z+Ms+[+V Pl+02+Ga+Ms+L+V Pl*0r+02+Ga+Ms+[*V Pl+0r+02+Ga+Ms+V 30 WT % WATER Fig. 3. Phase relations ofgranite at 15 kbar with varying HrO contents. For definitive runs and abbreviations, see Table 4. Modified after Huang and Wyllie (1973). for enhancing the degree of reaction and testing reversibility introduce other problems, such as increased iron loss from the sarnple and contamination of thermocouple junctions, causing drift of temperature. The liquidus boundaries for gabbro-water were determined in three groups of runs: (l) ft capsulesin single-stage,(2) AgrrPd* capsules in single-stage, and (3) Pt capsules in two-stage runs. The definitive runs are listed in Table 2. The liquidus boundary determined by the first group is at 1080.,Cwith excesswater. With 5oloH,O, the liquidus boundary is I l3OC, identical to that from the second group of runs. However, the liquidus boundary determined by two-stageruns is 55"C lower with 590HrO and 30"C lower with excessHrO. For the tonalite-water system, the liquidus boundaries for clinopyroxene were reversed successfrrlly in two-stage runs within a 25 and 50"C bracket, respectively, for 33 and 50/o watercontents;butno amphibole orgarnetcrystallized in these two runs in contrast with their presence in the singlestageruns. The diference between liquidus temperatures determined by single-stage and two-stage runs for both gabbro and tonalite is tentatively attributed to the nucleation problem, but also to the iron loss ofbulk composition from charge to capsules. For the granite-water system, the upper boundary ofquartz was experimentally determined with a 25"C bracket at 15 kbar with excesswater (runs 240 and242 in Table 4) and with 9.5% water addedat 25kbar (runs2l5 and2I7; HuangandWyllie, l98l). The granite-water system is notorious for its sluggish reaction rates. dthough the results in Figures 1, 2, and 3 must be regarded as provisional, for the reasons stated above (similar statements could be made for most published rock-HrO studies), the results with Au capsules (50/oHrO) are broadly consistent (Table 5). Therefore, the diagrams are considered to be acceptable representationsof the phase relationships,with respectto major assemblagesand geometricalsequences. The etrect of iron loss from the sample in changing the phase assemblage,in addition to changingthe compositions of phases, can be seen by comparison of the results listed in Table 4 for selectedruns in Au capsules,with the results plotted in Figures I, 2, and 3. For gabbro with 5% H,O, the use of Au capsules between 700 and l00OC produced garnet where none nucleated with Pt capsules;garnet was also present in the 1000t run using Ag-Pd. A similar difference occurred with tonalite-5% HrO. With Ag-Pd capsules,garnetformed only at 850€ and above,whereas in Au, it occurred down to 700C, the lowest-temperature run. No quartz occurred in the 700qCrun with Au, whereas with AgPd capsules it should be present. No kyanite occurred in runs \4'ith Au, whereasit was presentup to 925qCin Ag-Pd capsules. 307 AT I 5 kbar HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER Table 4. Resultsof quenchingexperimentsfor muscovite granite (L26) at 15-kbar pressure TemDerature Ru H,0 added *at 226 227 600 610 351 660 21r 374 307 3r0 240 I i 23I 242 t | 2a2 299 3a6 301 229 395 293 337 660 700 700 700 425 7oo 725 a25 125 750 750 750 750 150 750 715 715 2r9 303 257 2A3 223 302 306 715 195 800 800 aOO 820 520 2ro 292 38a 2AO 230 390 3€2 289 | { 2ea 219 284 354 425 425 850 850 475 875 475 94O 87s 900 900 925 950 241 269 363 266 265 50r 502 263 296 | + 247 2 5 4| + 249 1000 1000 1000 1050 1100 1125 1175 1200 1315 12OO 1250 1315 r24O 1300 Time hous 29 3a 9 12 9 9 20 16 22 l6 1 5 LO 36.3 36. 3 24 25 40 43 20 46 5 0 l5 5 9 o 45 15 3.2 l4 0 2.7 5 9.5 9.5 9.5 9.5 0 r.6 r.6 o o 0 0 0 0 0 4I 21 6 16 26 6 ls 20 24 l2 22 24 I2 22 22 21 2! 20 23 20 2T 20 22 18 20 25 ro.5 l0 9 11 11 20 9 3 43 5 42 47 23 Qz, 92, Qz, Qz, Qz, Qz, Qz, Qz, Qz, Qz, M, S, Ab, Ab, Ab, re, re' M, Ab, w, 10000c 950.C 900'c 800'c ?oo'c Or, Ms, Ga Or(tr), Ms, e, L re, Co(?), Ga{tr), L re, Ga(tr) , t re, L I I Or, re, G, I b, Ga, I L 5 h 15 h 36 h 3 days 53.5h A93oPd7o 9250C 900'c A930Pd70 Au Au 700.c 40 7OO'c 63h Ar = orthocLase; eoL;'d soLution; Amphibole-out occurredbetween900 and 950"Cin Au capsules, whereasa trace of amphibole may remain in the 975'C run with an Ag-Pd capsule. In the granite-water system, results in Au capsulesbetween650 and 1000{ were the same as those in Pt capsules,probably becauseofthe smaller Fe content ofthe granrte. RUNS Several runs made in Pt and Ag-Pd capsules were originally selected for microprobe analyses. Figure 5A shows the percentage ofiron loss (forglass) quenched from above the liquidus as a function of time. Figure 58 shows the difference in Mg/(Mg + 2Fe) values for coexisting garnet, clinopyroxene, and glass using Ag.oPdro and AgrrPd* capsules under the same conditions. Diferent phases lose iron G+cpx+6+L G+Cpx+b+L Ga+CPx+&+i Ga+cPx+6+L 6+cPx+b+L lAj 445 Ga + CFx + L 4I2 G+cpx+&(?) 609 G+CPx+L +L 44I G+S+cpx+Pl+Ky(t!) 606 fr+&+Cpx+P1+L 442 4a9 +L 6+S+cpx+P1+(Y(?J Ga(tr) +S+cpx+Pl+Bio(?) 444 602 6+Cp*+P1+Bio+Ky+l &+ft+cPx+PI+Blo+L au 603 e+e+CPx+P1+Bio+L au 610 Ga+b+cPx+P]+Bio+L Au Au 506 Qz+Co+L 509 Qz+Co+L 25 h 505 48 h Au Au 507 Qz+co+L re+Pl+Qz+Co+L 700"c 90 h Au 508 Ms+PI+Qz+ Ga+L Au 5to b+P]+Qz+ Ga+L 5 days + 21 h +L A93oPd7o Au t h 7 h 650'c L Dw-1 493 494 4A9 49o 492 Tanalitu 900"c 800"c 9500c Co(tr?) ' I Q z( t ! ) RESULTS FRoM GoLD cApsuLE 15 30 10000c Qz, Co, L Q2, Co, L co, L si(?), co, L Qz, si(?), co(tr), L Qz, FsP, Co, G, L Qz, Fsp, Co, I Qz, co, L 92, Fsp, Ky(tr), Co, L Qz, Kyl?), Co(tr), I Qz, Co, L Co, L Qz, si, L si(tr), Co(tr), Co(tr), I aoo.c a000c kbbro A9!0Pd?0 AgroPdTo a50ec Ga, L(tr) u u u u u 975.C 9 5 00 C e750c Qz, re(tr), ! Qz, re, Co(tr), I Qz, Ms, Co(tr), I 92, re, Co, I co, f, Qz, b(tr), Ky(tr), Co, L Ky(tr), Co, L Qz, Co, L Qz{tr), Co, L Ky, Co, L Ky(tr), Co, L 02, Ab, re, Co, I Qz, Ab, Or, Ms, k Qz, co(tr), L Co(tr), L Qz, Ab, re(?), co, L Qz, Co, L Qz, I$t Ot, re(tr) ' Co(tr), Co(tr), L Qz, Co, L L Qz, t\b, Co, e{?), co, I qz, Fsp, Co, Ga, L e, L Qz, Fsp,6, Qz, Co, L A A A A A AqTsPd2s I025.C QZ, re, L Qz, MS, L Abb\eoiation,: Qz = qu@tz; Ab = albite; lsp = alkaLi-feldepd" Ga = gffiet; Me = Mcaotte; Si = siLlimite' KA = kAnite; Co = cowdn; AN.ql-yrrcAr- Table 5. Selectedruns for microanalysesat l5-kbar pressure and 5oloH"O +Kv+L at different rates. Therefore,theseanalyseswere discarded. Runs using Au capsuleswith 50/oHrO added are listed in Table 5 for gabbro, tonalite, and granite compositions at temperaturesof 650, 700, 800, 900, 950, 1000, and 1025'C. The phase results are broadly consistent with those shown in Figures 1,2, and 3, with the differences described in the preceding section. Electron-microprobe analyseswere performed for l0 elements(Si, Ti, Al, Cr, Fe, Mn, Mg, Ca, Na, and K) for garnet, clinopyroxene, amphibole, plagioclase,muscovite, and glass. For most runs, there is considerablescatter of analysesfrom one mineral grain to another, with less variation from center to margin of individual grains. Rangesof values and averagecompositions are plotted in Figures 6 through 10. Glass compositions plotted are averagesof 4 to l0 analyses.We have eight tablesof analysesthat, unfortunately, cannot be fitted into this paper. Spacelimitations also precludedetailed comparison of our analyseswith related resultsby Green and Ringwood ( 1972),Allen and Boettcher (1978, 1983),Allen et al. (1975), and Stern and Wyllie (l 978). Garnet Garnet analysesare plotted in Figure 64' Note the range ofresults at eachtemperature. Garnet synthesizedat 950qC contains less gtossular component in the center than in the margin. Garnet synthesizedat 800€ exhibits lesszoning. The averagevalues in Figure 68 define a trend showing significant decreasein pyrope component with decreasingtemperaturesfor both gabbro and tonalite. There is also a decreaseof grossular components in garnet as rock composition becomesmore silicic from gabbro to tonalite to rhyodacite. Data for rhyodacite with 50/oHrO at 13.5kbar werereportedby Greenand Ringwood(1972), with garnet compositions located on the upper right-hand side of the tonalite curve in Figure 68. HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER AT 15kbar 308 1400 rSKb 5WT.%r{20 t200 GRANITE TONATITE GABBRO t t I 1000 qt E CE u IL = F 8oo --t--- , t, 600 Hb+ Cpx Pl+ oz Ga*V 40 r, Fsp+ 0z H b + c p r + F s p + o z + c a + M i c av+ IrJ, ! +{i I 50 60 70 80 slucAwT % Fig.4. Phaserelations of the calc-alkalinerock seriesas a function of SiO, at 15 kbar and with 50/oHrO. Rectanglesindicate the temperaturesofphase boundaries from Figures I,2, ald 3. The vapor-out boundary is situated a few degreesabove the solidus. For abbreviations, seeTables 2, 3, and,4. 0 1025c 15Kb,3h 5 W lY o H 2 0 1234 H()URS TIME Ago As$ Pd70 As75Pd25 A9100 % As lN AsPdCAPSUTES Fig. 5. Absorption ofiron by AgroPdroand AgrrPd- capsules.(A) Percentageofiron lossin glassquenchedfrom liquid oftonalite composition as function of time. (B) Comparison of Mgl(Mg + Fe) values for coexistinggarnet, clinopyroxene,and glassquenched from two runs differing only in capsules,AgroPdroand AgrrPdrr. HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER 309 AT 15 kbar GARNET Alm 60 15Kb 5%H,O Alm 20 Py 80 Alm 60 Gr 40; ALMANDINE { + SPESSARTINE) Alm 6 0 \ P y 40 An 6O PLAGIOCLASE (TONALITE} Alm Grt MOLE% GROSSULAR 20 o Py 80 u PYROPE AsPd\\Au P soo Fig. 6. Garnetcompositions from gabbroand tonalite,partially meltedat 15kbarin Au capsules, with 50/o H,O added.(A) Rangeof analyses in eachsample.(B) Trendlinesasa function of temperature shownby average analyses. 15Kb 5 YoH.O u o- = u F 7oo RIM CORE I-----l 600 Clinopyroxene and amphibole Clinopyroxene compositions for each run with gabbro are plotted in Figure 7. There is considerableoverlap of resultsfrom 700 to 1000"c. The averagecompositions for each temperature are closely clustered, with no defined variation as a function of temperature.The averagecomposition of clinopyroxene in tonalite at 1025'C has a somewhatlower Mg/(Mg + ZFe) value than that in gabbro. Average amphibole analysesfor gabbro and tonalite, plotted in Figure 7, are very similar. According to the classificationof kake (1978), the amphiboles lie closeto the boundary between magnesio-hornblendeand tschermakitic hornblende. EXCESSWATER 30 60 40 50 MOLE% AnCONTENT 70 Fig. 8. Plagioclasecompositions from partly melted tonalite and granite with 50/oHrO at 15 kbar. (A) Individual analysesfrom runs in Au capsules.(B) Average analysesfrom tonalite as a function of temperature, compared with the zoned plagioclasein original tonalite. Results of Piwinskii (1968) on the same rock at 2 kbar with excessHrO are shown for comparison. Plagioclase and muscovite Plagioclase analyses for granite and tonalite runs are plotted in Figure 8A. Results for granite at 650 and 700"C remain similar to the 50/oAn in the original plagioclase Ca2Q MsSO MOLE PERCENT Ca2O 'M920 Fe60 Fig. 7. Clinopyroxene and amphibole compositions in partly melted gabbro and tonalite in Au capsules,with 5% HrO at 15 kbar. The closedsymbols indicate the composition of amphibole in gabbro. 310 AT l5 kbar HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER Fe0 r TONAIITE 1sKb5%H,O A GABNET O AMPHIBOIE . GLASS O PTAGIOCTASE 1/4Si02 t\\ ailo"l s00''i I I I O GLASS (AsPd) 9500. i t t2- .."4 I I I a-" gsoo I .{o (!'r*'o " ' 8000 o o MgO+ FeO Ga0 B WETGHTPERCENT Fig. 9. Compositions of glass and crystals quenched from partially melted tonalite at l5 kbar with 50/oHrO added. All runs rvere in Au capsules, except for the open circles for glassesfrom Ag-Pd capsules. The dashed lines show the average calc-alkaline rock trend. Na20+ l(20 A (Huang and Wyllie, 1973). For the tonalite, the average plagioclasecompositions (closeto clusteredanalysesdespite broad ranges)show increaseofAn between900 and 800'C, and decreaseof An between 800 and 700"C (Fig. 8B). This is probably related to changesresulting from proximity to the albite-jadeite reaction and the retrograde curvature ofplagioclase-out in Figure 2. Piwinskii (1968) determined the composition of plagioclasein the same tonalite at 2 kbar with excesswater and found the expected increase of An content with increasing temperature, as shown in Figure 8B. There is a decreaseof l-2o/o An component in plagioclasefrom tonalite run in Ag-Pd capsules,compared with Au capsules. Muscovite was analyzedin two granite nrns. The paragonite componentsat 700 and 650'C were,respectively5.9 and3.7 molo/0,in contrast to 6.7 molo/oparagonite in muscovite of the original granite (Huang and Wyllie, 1973). Glass in tonalite The composition of glassesquenchedfrom the melting interval for the tonalite were measuredat 950, 900, and 800'C, with resultscomparedwith mineral analysesin the AMF and CMS diagramsof Figure 9. The glassesat 800900'C contain 7 1.6-72o/oSiO2, 3.2-4.290NarO, and 2.83.10/oKrO (cf. Table l). The runs in Au capsulesfollow the calc-alkalinecomposition trend quite well in the AMF diagram, but deviate somewhat from this trend in the CMS diagram. The loss of iron from samplesrun in AgPd capsulesis obvious in Figure 9A. Ifthe differencebetweenthe total ofeach analysisand 1000/o is equatedto the dissolved HrO in the glasses,and thus to that dissolved in the original HrO-undersaturated liquid, the results indicate l2-l5o/o HrO between800 and 950"C, compared with an estimated saturation value at 15 kbar of l9o/o(poorly constrained in Fig. 2). r GRANITE 15 Kb 5% H,O . GLASS O MICA O PLAGIOCLASE Na20+ K20 Mgo Ga0 WEIGHT PERCENT Mso Fig. 10. Compositions of glass and crystals quenchedfrom partially melted granite in Au capsulesat 15 kbar with 5% HrO added. The dashed lines show the average calc-alkaline rock trend. AT l5 kbar HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER r GABBBO 3lI 1/4.SiO2 1sKb 5% H,o A GARNET O CI.INOPYROXENE O AMPHIBOTE MgO+ FeO WEIGHTPER CENT B Fig. 11. Compositions of crystals coexisting with liquid in partially melted gabbro in Au capsuleswith 5% HrO at 15 kbar. Gamet compositions at 1000 and 700'C are extrapolated from data measured at other temperatures (Fig. 6). The dashed lines show the average calc-alkaline rock trend. Glass in granite The compositions of glassesquenchedfrom the melting interval for the granite were measuredat six temperatures. The analyseswerepublishedbyHuangandWyllie (1981), and results are plotted in Figure 10. The glasscompositions change fairly regularly with increasing temperature (although the 800'C glassdeparts from the main trend). AlrO, At 650 and 700"C,SiO, is in the range61.4-65.50/0, in the range 22.6-26.70/o(considerablyhigher than in the original granite; Table l), KrO is about twice as high as in the original granite, and NarO is somewhatlower. The glasscomposition has similarities with syenite. Between 700 and 900'C, SiO, increasesto the 750lolevel, and AlrO, and KrO reachgranitic levels.The NarO content increases to the granitic level between 800 and 900"C, where the plagioclasedissolves. If the difference between the total analysesand 1000/ois equated to the HrO content of the glasses,and thus to that of the original HrO-undersaturated liquids, the results indicate that dissolved HrO between650 and 800oC,with changedfrom about I 1-130/o BULKMItrERAL coMx)stTtoN l[61[ * KrO A MgO CaO WEIGHT PER CENT Fig. 12. The dashed lines show the average calc-alkaline rock trend. (A) Ifliquids are assumed to lie on the dashed trend line, the bulk mineral composition must be as shown. (B) From partial modal analyses of partially melted gabbro in Au capsulesat 15 kbar with 50/oadded HrO, the analyzed minerals from Figure 11 yield by calculation the bulk mineral compositions plotted as a function of temperature. The plotted liquid compositions in equilibrium with these calculated mineral assemblagesdiverge significantly from the calc-alkaline trend. 3t2 AT 15kbar HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER 15Kblr 1000 5o/oH.O c- i - - $-TONAL .q?19 o o uJ PLAGIOCLASE 5 eoo ul kE kcc = u E 8oo uJ o- u F 700 o \. AMPHIBOLE TONALITE 1.5 1.O o.5 Log Na/K (ATOMICRATIO) 2.O 1OO Mg/Mg+ Fe (ATOM;C RATTO) Fig. 14. Variationof Na/K for coexisting liquidsandcrystals HrO. The dashedand solid at 15 kbar with 50/o Fig. I 3. Variationof Mil (Me + Fe)for coexistingliquidsand in Au capsules Arresultsfor gabbroand tonalite,respectively. crystalsin Au capsules at l5 kbarwith 5olo HrO.Thedashedlines linesrepresent for rock rows show log(Na/K) the compositions. and solidlinesrepresent resultsfor gabbroand tonalite,respectively.ArrowsshowMg/Mg + Fe)for the rock compositions. used to calculatethe averagemodal percentageof crystals through the melting interval. Finally, these modal percentagesof the crystals and their compositions (Fig. I l) were used to calculatethe liquid compositions plotted in Figure l2B. The results diverge from the calc-alkaline trend in Figure l28. The maximum liquid variation that Liquid in gabbro could be produced from the calculated mineral assemThe presenceof quenchcrystalsprecludedreliable mea- blageslies betweenthe pair of arrows. Similaily, if it was surementof liquid composition for the gabbro.However, assumedthat the liquids lay on the calc-alkalinetrend line a mass-balancecalculation was made to determine if the in Figure I 28, the correspondingcalculation showedthat liquid compositions were close to the averagecalc-alka- the liquids could not lie on the trend in Figure l2A,. Thus, line-rock trend line. The compositions of averagegarnets, althouglr the liquid compositions are not known, it is clinopyroxenes,and amphiboles transferredfrom Figures demonstratedthat the liquid path doesnot follow the calc6 and 7 to Figure I I were used in the calculations. The alkaline trend. first assumptionis that the liquid compositions follow the DrsrnrnurloN oF ELEMENTSAS FUNcrroN oF calc-alkalinetrend in terms of the (NarO + KrOlMgOTEMPERATURE FeO, as illustrated in Figure 12A; then, a seriesof calparameters culations were made to determine whether the same liqTwo chemical of significancein magmatic uids would also follow the trend in terms ofCaO{MgO + history are the Mg-number, representedin Figure 13 as FeOfSiO, in Figure l2B. the atomic ratio Mg/(Mg * Fe), and Na/K, represented The percentagesof liquid producedthrough the melting in Figure 14 as the log of the atomic ratio. Figures 13 and interval were point counted petrographically from the run 14 compare the values of these parametersfor the bulk products. The results are 25, 40, 52, 60, and 800/oby rock compositions of gabbro and tonalite with the values volume with 5olouncertainty, respectively, at 700, 800, derived from the analysesof minerals and glasses(plotted '7, 900, 950, and 1000"C.The percentages ofgarnet, clino- in Figs. 6, 8, and 9) through the melting intervals of pyroxene, and amphiboles could only be roughly esti- gabbro and tonalite. mated from the polished sections.The percentagesof the The Mg-numbersofgarnet (Fig. l3) arelower than those minerals in Figure I I required to keep the liquids on the of coexisting amphibole, clinopyroxene, and liquid, but calc-alkaline trend in Figure l2A, were calculated. The at high temperaturesthey are similar to or slightly lower bulk crystal composition required to yield the liquids fol- than those of the rocks; they decreaserapidly with delowing the trend is indicated by the open circle in Figure creasing temperature in both gabbro and tonalite. The l2A; the shaded area indicates the limited range of the variation of Mg-numbers of clinopyroxene with temperbulk crystal composition when the maximum variation ature is small, but the Mg-numbers are much higher than ofthe trend is taken into account,giving the rangebetween the coexisting garnet and amphibole, and higher than those the pair of arrows. The bulk crystal composition was then ofthe rocks. a decreaseto about 7-80loassociatedwith the increased melting where plagioclaseand muscovite disappear between 800 and 900"C. According to Figure 3, aboul 22o/o HrO is required for saturation of the liquid at 15 kbkar. AT l5 kbar HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER 1100 10 OC TEMPERATURE 900 900 2.5 AC TEMPERATURE 800 30 2.O 5 4 3 JIJ 3.0 20 1.5 t'o tn*o KD2 2.O L nK p KP 0.5 1 0.5 o -.--- GABBRO o.o TONALITE " " " " R & c ( 1 9 7 4 ) -0.5 G R E E (N1 9 7 7 } - . - " - - E & c ( 1 9 7 9 ) 7.O 8.O 10.O 9.0 11.0 1fi oKx10a Fig. 15. The partition coefrcientsof Mg/Febetweencoexistingmineralsand glassas a functionof temperature with 50/o HrO at 15 kbar.The dashedand solidlinesarefor gabbroand tonalitecompositions, respectively. Thedottedanddash{ouble dot lines grve Ko valuesbetweenclinopyroxeneand garnetin anhydroustholeiiteat 15 kbar, interpolatedfrom Raheimand Green(1974)andEllisandGreen(1979).Thedash-dotlinegives Ko valuesbetweenglassand garnetfrom a pelitecomposition (Green,1977). The compositions of amphibole in both gabbro and tonalite are similar in terms of Mg-number, which is close to the value for the gabbro, but higher than that for the tonalite (Fie. l3). Figures13 and 14 also show that amphibole variations in Mg-number and Na/K with temperature are small. The Mg-number of the amphibole appears to be nearly independent of bulk composition, as well as temperature. Na/K ratio, on the contrary, is significantly controlled by bulk composition. The Na/K for amphibole in tonalite is slightly lower than that of the tonalite, whereas amphibole in gabbro changes from slightly lower to slightly higher than that of the gabbro between800 and 700'C. The Na/K ratio of plagioclasein gabbro, considerably higher than that in tonalite, shows little variation with temperature. The Mg-numbers of successiveliquids are lower than the coexisting amphiboles but higher than the coexisting garnet. The Na/K ratio of liquids increasesslightly with degreeof partial melting. Partition coefficientsamong coexisting phases Figure l5 showsthe partition coefficientsof Mg/Fe ratio as a function of temperaturefor gabbro and tonalite compositions. For gabbro, the partition coefficientsof Mg/Fe betweencoexistingclinopyroxene and garnet,K": (M9 Fe)""./(MglFe)o",and betweenclinopyroxene and amphibole decreasewith increasingtemperature. For tonalite, the KD values betweenamphibole and garnet, amphibole and glass,and glassand garnet decreasewith increasing temperature. Raheim and Green (1974) experimentally determined the temperature and pressuredependenceof the Fe-Mg 1.0 0 9.0 9.5 1/T oKxlOo 10.0 10.5 Fig. 16. The partition coefrcieRts of Na/K and CalNa bemineralsandglassasa functionof temperature tweencoexisting with 50/oHrO at 15 kbar. The dashedand solid lines are for gabbroandtonalite,respectively. partition coefrciont (K") for coexisting garnet and clinopyroxene. Our results on basaltic composition for Ko vs. temperatureare in good agreementwith theirs, as shown in Figure 15. Note that the definition of Ko used in our study, (Mg/Fe).o./(Mg/Fe)"",is different from theirs, (Fe/ Mg)""/(Fe/Mg)"o.,but the actualK" value is the same.Ellis and Green (1979) redetermined the coefrcient by taking the effect of Ca on the garnet-clinopyroxeneFe-Mg equilibrium into consideration.They derived a new empirical equation by incorporating the effectofthe Ca component in garnet. When the equation was applied to calculateKo by using the Ca component in garnetsat 800, 900, and 950"C from our experiments, the Ko values are significantly higher than our experimentally determined data. This suggeststhat some other parameter that was not identified by Ellis and Green (1979) may significantly affect the Ko value. These unknown parameterscausethe inconsistencybetweenour data and results calculated from Ellis and Green( I 979). However, we are unableto explain why our data are consistent with those of Raheim and Green(1974). The partition coefficients of Mg/Fe between hydrous glassand garnet of a model pelite composition at l5 kbar (Green, 1977)also show closeagreementwith our tonalite data, in spite of different bulk composition. However, the same coefrcient for Mt. Hood andesite determined by Allen and Boettcher(1983) at 900"Cand 19 kbar is significantlylower (0.8)than ours(1.4 at 900C1andl5 kbar). Figure 16 showsthe partition coefficientsof Na/K and CalNa ratios as a function of temperature. The different partitioning of Na/K and CalNa betweencoexisting plagioclaseand liquid is evident. The Na/K ratio in plagroclase is much higher than that in glass,but the CalNa ratio is lower in plagioclasethan in glass.The K" of Na/K betweenplagioclaseand glassand that of CalNa between glass and plagioclasedecreasewith increasing temperature. In contrast to plagioclase,amphibole in tonalite has 314 HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER AT 15 kbar lower Na/K and higher CalNa than the coexistingliquid. The K" of Na/K betweenamphibole and glassdecreases with increasing temperature whereas the Ko of CalNa between amphibole and glass increaseswith increasing temperature. compositional range,with overall higher Mg-numbers than ours (Fig. l3), and on this basis they concludedthat amphibole fractionation could cause iron-enrichment in magmas. However, this contradiction now appears less pronounced, since the new data of Allen and Boettcher (1983) on the samesamples,with lessiron loss,gives Mg/ Pnrnor,ocrcAr, AppLrcATroNS (Mg + Fe) values for amphibole closer to our results in The generationof magmasby differentiation of a parent Figure 13. or by partial fusion is complex and probably intermediate The variety of amphibole compositions determined in betweenequilibrium and fractional conditions. However, experimental studies, and especially those of Allen and equilibrium experimental results are required as a starting Boettcher(1978, 1983)under a variety of experimental point. Our experimentally determined phase diagrams, conditions, implies that many factors including pressure, although not representingperfect equilibrium, neverthe- water content, noble-metal capsule,and oxygenfugacity, lessdefinethe phaserelationshipswell enoughto elucidate as well as liquid composition and temperature,may affect processes.The resultson liquid compositionsand the dis- amphibole composition. Similarly, many factors will intribution of elementsbetweencoexistingcrystalsand liq- fluence amphibole composition in natural magmas. In uids are reliable, having beenmeasuredfor runs complete order to evaluate the actual role of amphibole fractionin Au capsules.They provide some basis for prediction ation during magma differentiation, a detailed and sysof the differentiation trends of hydrous basaltic and an- tematic experimental program for determination of amdesitic magmas in the deep crust or uppermost mantle phibole composition as a function of the variables is and for the products of anatexis of deep crustal rocks required. composedof gabbro, tonalite, and granite or their metamorphic equivalents.A pressureof l5 kbar is attained at Magma differentiation at 55-km depth a depth of about 55 km in thickened crust of orogenic Although fractionation of amphibole from basaltic belts. magmamay be capableofproducing differentiatedliquids with Mg/Fe correspondingto those of the calc-alkaline Amphibole fractionation at 55-km depth trend at leastduring the early stagesofdifferentiation, our It has been suggestedthat amphibole fractionation ex- results indicate that it is not the dominant process in erts a major control on the formation and differentiation hydrous basalts at 55-km depth. Fractionation of clinoof the calc-alkalinerock suite (e.g.,Boettcher, 1973;C,aw- pyroxene and garnet togetheris the main processcausing thorn and O'Hara, 1976).Figure l3 showsthat Mg-num- changesin composition ofhydrous basalt, becausethese bers of amphibole in gabbro (basalt)and tonalite (andes- two minerals are the liquidus phases,with subordinate ite) lie in a small range from 56 to 60 and are nearly amphibole joining them below the liquidus; these three independent of temperature and bulk composition. The minerals are coprecipitated through several hundred deamphiboles have Mg-numbers close to those of basalt, grees (Fig. l). The analysesand calculations plotted in but much higher than those of andesite,as well as of the Figures I I and I 2 confirm that the differentiating hydrous liquids in the crystallization interval of andesite. These basalticliquid doesnot follow the calc-alkalinetrend. The Mg-numbers are in good agreementwith the values be- crystallization of clinopyroxene with high Mg-numbers tween 59 and 62 reported by Holloway and Burnham averaging70 tends to produce a liquid with high Fe/Mg, (1972) for amphibole in basalt of similar composition at but this effect is offset at least at the lower temperatures 5 and 8 kbar. by the low Mg-numbers of garnet(Fig. l3). Crystallization Ringwood (1974) usedthe data of Holloway and Burn- of amphibole controls Na/K in liquids until the low temham (1972) to support his proposal that fractionation of peratureswhere plagioclasebegins to crystallize. amphibole from basaltic magmas may not cause ironGarnet and subordinateclinopyroxeneare also the liqenrichment in diferentiating basalt.Our resultsfor gabbro uidus minerals in crystallization of hydrous andesite(Fig. are consistentwith this conclusionasillustrated in Figures 2), joined within a small temperatureinterval by amphiI lA and 13. However, our data demonstratein addition bole and plagioclase,with biotite and quartz appearingat that precipitation of amphibole from hydrous andesitic lower temperatures.Precipitation of clinopyroxene and magma at this depth may contribute to iron-enrichment amphibole, with Mg-numbers much higher than that of of liquids (Fig. l3). The latter conclusion is contradicted the liquids, tends to causeiron-enrichment of the liquids, by the data reported by Green (1972) on amphiboles in but garnetoperatesin the other direction (Fig. 9), asshown andesite(Mg-number: 48) with 2o/otolDo/oHrObetween by values of K" for Hb/glass and glass/Gain Figure 15. 5 and 15 kbar. He reported Mg-numbers for amphibole The glassanalysesplotted in Figure 9 indicate that liquid lower than thoseplotted in Figure 13. Allen et al. (1975) compositions in the middle-temperature range approxiand Allen and Boettcher (1978) also reported amphibole mate the calc-alkalinetrend, with slight divergencetoward analysesfrom basaltsand andesitesthrough pressureranges higher CaOl(MgO + FeO) with decreasingtemperature. including 15 kbar with H,O-CO, mixtures giving varia- The Na/K is mainly controlled by the relative amount of tions in X"ro. Their amphibole analysescovered a wide amphibole and plagioclaseprecipitating. Becauseof the AT 15kbar HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATER very high K" for PVglass(Fig. 16), we expectthe effect of plagioclaseto dominate, causingdecreaseof Na/K in the liquid with decreasingtemperature, which is consistent with the glassanalysesin Figure 14. We do not expect to find granite or rhyolite magma differentiating at a depth of 55 km, but Figures 3 and l0 illustrate the controls on suchbehavior. Hydrous rhyolite liquid would precipitatequartz alone (excludingthe metastablecorundum) through 100"Cor more, causingdepletion of the liquid in SiOr, as illustrated by the glasscompositions plotted in Figure l0B. With subsequent coprecipitation of plagioclase,the depletion of the liquid in SiO, continues,with the formation of liquid similar in composition to syenite (Huang and Wyllie, 198l). Anatexis of lower crust, thickened to 60 km It is generallyassumedthat the baseof the continental crust is composeddominantly of the metamorphic equivalentsofgabbro and tonalite, hydrated to greateror lesser extent. At compressiveplate boundaries with thickened crust, or during the Archean when localized subduction might have been more prevalent, we consider also the prospect that granitic rocks could be carried as deep as for theserocks at 5555-60 km. The mineral assemblages km depth are given in the subsolidusregions ofFigures 1,2,3, and, in combination,in Figure 4. Wyllie (1977) reviewed the conditions for anatexisof the samerangeof rock compositions at l0 kbar, correspondingto crustal thickness of 35-40 km, concluding that HrO-undersaturated granite or rhyolite magma was the normal product of progressive metamorphism of many crustal rocks at moderate depths and that the generationof magmasless siliceous required the addition of heat or magmatic material or both from the underlying mantle. The mineralogy in a thickened crust differs from that in the normal crust by the addition of the high-pressure minerals garnet and clinopyroxene in the gabbro and tonalite, but the muscovite granite retains essentially the same mineral assemblage.Wyllie (1977) reviewed the conditions for partial fusion of the rocks both with pore fluid and without. In this paper, we consider only the anatexisofthe rocks in the presenceofaqueouspore fluid, using compositions of glassesmeasuredin runs with 50/o HrO as a possible guide to liquid paths. Unfortunately, we have no glasscompositions for the gabbro, and it was difficult to obtain reliable glass measurementsnear the solidus with small fractions of melting. Anatexis ofgabbro and tonalite under theseconditions involves similar minerals, with a quartz field-boundary controlling the composition of the first liquid. The first liquids developedfrom either rock are thereforesiliceous, and probably similar in composition. Successiveliquids, however, will follow different paths becausequartz and plagioclase(with biotite) remain among the residual minerals through a wider temperature in the progressivefusion oftonalite than ofgabbro. The analysesand calculations based on Figures I I and 12 indicate that partial fusion of hydrous gabbro at this depth does not yield a 315 seriesof liquids with chemical variation correspondingto the calc-alkalinerock series.The glassanalysesfrom partially melted tonalite indicate a liquid trend with CaO/ (MgO + FeO) somewhat higher than the calc-alkaline trend. At 900'C, with a generousallowance of 50/oHrO, the residual mineral assemblageHb + Ga + Cpx + Pl NarO, and coexistswith liquid containingT2o/oSiOr, 4.2010 3.10/oKrO. Despite its high SiO, content, this does not correspondto a granite becausegranite under these conditions would precipitate only quartz through a wide temperature interval below its hydrous liquidus (seeFig. 3). The evidence indicates that if magmas are generatedby partial fusion of gabbro and tonalite in thickened continental crust, they do not correspond to the rocks composing the calc-alkaline batholiths, nor do they give rise to the batholiths by fractional crystallization. The partial melting of deep granite proceedsalong a path quite different from that for tonalite and gabbro.The alkali feldspar dissolves first, yielding a potassic liquid, and subsequentfusion is controlled essentially by the quartz-plagioclaseboundary. The quartz volume expands considerablyat high water pressures,and the liquid compositions coexistingwith quartz and feldspar arethus forced to lower SiO, contents (Huang and Wyllie, 1975).This is indicated in Figure l0B. The relatively low-SiOr, highKrO liquids at 650 and 700'C have some characteristics of syenite. Trondhjemite is an important component of Archean igneous activity and of some more recent calc-alkaline batholiths. The data in this paperdo not provide evidence for the conditions ofgeneration oftrondhjemites, but they do demonstratesome conditions unsuitable for their formation. Na/K ratios as high as 2-4 are characteristicof trondhjemites. None of the hydrous glassesanalyzed in the tonalite (Fig. la) or granite approachedthis value, and extrapolation from the analyzedglassesthrough other parts of the determined phaserelationships (Figs. 2 and 3) suggest that trondhjemites are not simply related to either granites or tonalites at 15 kbar. We have no analysesof glassesfrom the gabbro,but within the phaserelationships at 15 kbar (Fig. l), there appearsto be a prospect that liquids of appropriate composition might be found at moderate HrO contents near the plagioclase-out and quartz-out boundaries. Holloway and Burnham (1972) and Helz (1976) analyzedglassesfrom partially melted hydrous basaltsat lower pressures,reporting trondhjemitic to tonalitic compositions with l5-300/omelting, 850 to 1000'C. AcxNowr,nocMENTS This researchwas supportedby the Earth ScienceSectionof the National ScienceFoundation,NSF grant EAR 84-07115. Companycontributedto manuscript ExxonProductionResearch preparationcosts. RnrnnrNcns Allen, J.C.,and Boettcher,A.L. (1978)Amphibolesin andesite andbasalt:II. Stabilityasa functionof P-T-f',o-for. American Mineralogist,63, 1074-1087. 316 - HUANG AND WYLLIE: GABBRO-TONALITE-GRANITE-WATERAT 15kbar (1983) The stability of amphibole in andesiteand basalt at high pressures.American Mineralogist, 68, 307-314. Allen, J.C.,Boettcher,A.L., and Marland,G. (1975)Amphiboles in andesite and basalt: I. Stability as a function of P-T-fo,. American Mineralogist,60, 1069-1085. Bateman,P.C., Clark, L., Huber, N.K., Moore, J.G., and Rhinehart, C.D. (1963) The Sierra Nevada batholith, a synthesisof recent work across the central part. U.S. Geological Survey ProfessionalPaper,414-D, Dl-D46. Boettcher,A.L. 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