Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2 {+/-} K2O at 1{middle dot}1 GPa

The compositions of multiply saturated partial melts are valuablefor the thermodynamic information that they contain, but aredifficult to determine experimentally because they exist onlyover a narrow temperature range at a given pressure. Here wetry a new approach for determining the composition of the partialmelt in equilibrium with olivine, orthopyroxene, clinopyroxeneand spinel (Ol + Opx + Cpx + Sp + Melt) in the system CaO–MgO–Al₂O₃–SiO₂(CMAS) at 1·1 GPa: various amounts of K₂O are added tothe system, and the resulting melt compositions and temperatureare extrapolated to zero K₂O. The ‘sandwich’ experimentalmethod was used to minimize problems caused by quench modification,and Opx and Cpx were previously synthesized at conditions nearthose of the melting experiments to ensure they had appropriatecompositions. Results were then checked by reversal crystallizationexperiments. The results are in good agreement with previouswork, and establish the anhydrous solidus in CMAS to be at 1320± 10°C at 1·1 GPa. The effect of K₂O is todepress the solidus by 5·8°C/wt %, while the meltcomposition becomes increasingly enriched in SiO₂, being quartz-normativeabove 4 wt % K₂O. Compared with Na₂O, K₂O has a stronger effectin depressing the solidus and modifying melt compositions. Theisobaric invariant point in the system CMAS–K₂O at whichOl + Opx + Cpx + Sp + Melt is joined by sanidine (San) is at1240 ± 10°C. During the course of the study severalother isobaric invariant points were identified and their crystaland melt compositions determined in unreversed experiments:Opx + Cpx + Sp + An + Melt in the system CMAS at 1315 ±10°C; in CMAS–K₂O, Opx + Cpx + Sp + An + San + Meltat 1230 ± 10°C and Opx + Sp + An + San + Sapph +Melt at 1230 ± 10°C, where An is anorthite and Sapphis sapphirine. Coexisting San plus An in three experiments helpdefine the An–San solvus at 1230–1250°C. KEY WORDS: feldspar solvus; igneous sapphirine; mantle solidus; partial melting; systems CMAS and CMAS–K₂O     

The Effect of Cr2O3 on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2-Cr2O3 at 1{middle dot}1 GPa

Chromium as Cr³⁺ substitutes for octahedrally coordinated Alin upper-mantle minerals, thereby reducing the activity of Al₂O₃in the system and hence the concentration of Al₂O₃ in partialmelts. The effect of Cr₂O₃ on melt compositions multiply saturatedwith the spinel lherzolite phase assemblage has been quantifiedin the system CaO–MgO–Al₂O₃–SiO₂–Cr₂O₃at 1·1 GPa as a function of 100 Cr/(Cr + Al) in the spinel(Cr#_sp). The decrease of Al₂O₃ in the melt with increasing Cr#_spis accompanied by increasing MgO and SiO₂, whereas CaO remainsalmost constant. Consequently, the CaO/Al₂O₃ ratio of the meltincreases with Cr#_sp, and the melt becomes richer in normativediopside, hypersthene and quartz. The effect may explain certainmantle melts with unusually high CaO/Al₂O₃ ratios. The concentrationof Cr₂O₃ in the melt remains low even at high Cr#_sp, which meansthat the strong effect of Cr₂O₃ on partial melting equilibriais not readily apparent from its concentration in the melt itself.The existence of a highly refractory major component such asCr₂O₃ nullifies simplified conclusions from the ‘inverseapproach’ in the experimental study of basalt petrogenesis,as there is insufficient information in the composition of thepartial melt to reconstruct the conditions of melting. KEY WORDS: basalt petrogenesis; partial melting; reversal experiment; spinel lherzolite; system CMAS–Cr₂O₃; CaO/Al₂O₃ of melt; effect of Cr₂O₃     

The Effects of Small Amounts of H2O, CO2 and Na2O on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2 {+/-} H2O {+/-} CO2 {+/-} Na2O at 1{middle dot}1 GPa

The effects of small amounts of H₂O (<4 wt % in the melt)on the multiply saturated partial melting of spinel lherzolitein the system CaO–MgO–Al₂O₃–SiO₂ ±Na₂O ± CO₂ have been determined at 1·1 GPa inthe piston-cylinder apparatus. Electron microprobe analysisand Fourier transform infrared spectroscopy were used to analysethe experimental products. The effects of H₂O are to decreasethe melting temperature by 45°C per wt % H₂O in the melt,to increase the Al₂O₃ of the melts, decrease MgO and CaO, andleave SiO₂ approximately constant, with melts changing fromolivine- to quartz-normative. The effects of CO₂ are insignificantat zero H₂O, but become noticeable as H₂O increases, tendingto counteract the H₂O. The interaction between H₂O and CO₂ causesthe solubility of CO₂ at vapour saturation to increase withincreasing H₂O, for small amounts of H₂O. Neglect of the influenceof CO₂ in some previous studies on the hydrous partial meltingof natural peridotite may explain apparent inconsistencies betweenthe results. The effect of small amounts of H₂O on multiplysaturated melt compositions at 1·1 GPa is similar tothat of K₂O, i.e. increasing H₂O or K₂O leads to quartz-normativecompositions, but increasing Na₂O produces an almost oppositetrend, towards nepheline-normative compositions. KEY WORDS: H₂O; CO₂; FTIR; hydrous partial melting; mantle melting; spinel lherzolite; system CaO–MgO–Al₂O₃–SiO₂ ± H₂O ± CO₂ ± Na₂O     

Liquidus Phase Relations in the System CaO-MgO-Al2O3-SiO2 at 2{middle dot}0 GPa: Applications to Basalt Fractionation, Eclogites, and Igneous Sapphirine

To model magmatic crystallization processes for mafic to intermediatecompositions at high pressure, liquidus phase relations in theforsterite–anorthite–diopside–silica (FADS)tetrahedron within the CaO–MgO–Al₂O₃–SiO₂system have been determined at 2·0 GPa. Compositionsof five liquidus invariant points have been determined and theapproximate compositions of five others have been inferred.These involve primary phase volumes for forsterite (fo), enstatite(en), diopside (di), high quartz (qz), spinel (sp), sapphirine(sa), garnet (gt), anorthite (an), and corundum (cor). The determined(with wt % coefficients) and inferred reactions (without coefficients)that define each isobaric invariant point are as follows: 23 en + 68 di + 9 sp = 84 liq + 16 fo 37 di + 63 sa = 47 liq + 40 sp + 13 en 100 gt = 21 liq + 27 sa + 55 en + 18 di 1 di + 59 en + 41 an = 43 liq + 57 gt 18 di + 21 qz + 15 en + 47 an = 100 liq di + an + gt = liq + sa an + gt = liq + sa + en sa + an + di = liq + sp sa + an = liq + cor + sp di + cor = liq + an + sp. These phase relations provide a diverse range of constraintson igneous processes at pressures near 2 GPa. They show thatfractional crystallization of a model basalt gives a residualliquid strongly enriched in SiO₂, strongly depleted in MgO,and mildly enriched in Al₂O₃. Such a trend is consistent withthe calc-alkaline fractionation trend observed at subductionzones, but is in disagreement with suggestions that fractionationof tholeiitic basalt in this pressure range yields an alkalicbasalt. Both trends may occur for natural basalts dependingon the Na₂O content of the parental magma. Also, the data showthat the minimum pressure for the formation of cumulate eclogitesand garnet pyroxenites is about 1·8–1·9GPa. The lower limit of pressure at which sapphirine can crystallizefrom a liquid in the FADS tetrahedron is estimated to be 1·1–1·5GPa and the upper limit is >3 GPa. Sapphirine crystallizesfrom magmas intermediate in composition between basalt and andesite.Probable igneous sapphirine in mafic associations is rare, butit occurs as part of a pyroxenite xenolith from Delegate, Australia,that we suggest is a cumulate assemblage and in a sapphirinenorite at Wilson Lake, Labrador, Canada. KEY WORDS: basalt; eclogite; sapphirine; fractional crystallization     

Melting Behavior of Simplified Lherzolite in the System CaO-MgO-Al2O3-SiO2-Na2O from 7 to 35 kbar

Phase equilibrium data have been collected for isobaricallyunivariant melting of simplified Iherzolite compositions inthe system CaO-MgO-Al₂O₃ SiO₂-Na₂O over a pressure range of7–35 kbar. These data permit the melting behavior of awide variety of model lherzolite compositions to be determinedquantitatively by algebraic methods. Two P-T univariant meltingreactions, corresponding to plagioclase to spinel lherzoliteand spinel to garnet lherzolite, are identified as peritectic-typetransitions and have positive Clapeyron slopes. The univariantcurves move to higher pressures and temperatures with increasingNa₂O in the liquid. The effect of the univariant curves on meltingis to produce low-temperature regions and isobarically invariantmelting intervals along lherzolite solidi. In the plagioclaselherzolite stability field, melting of four-phase model lherzoliteis pseudo-invariant, occurring over small temperature intervals(5C) and producing liquids that are quartz tholeiites at <8kbar and olivine tholeiites at >8 kbar. Calculated equilibriumconstants for plagioclase-liquid equilibria show both temperatureand pressure dependence. Plagioclase with anorthite content(AN) >90 mol%, as observed in some oceanic basalts, can crystallizefrom liquids with <1% Na₂O. Melting of spinel lherzoliteis not pseudo-invariant but occurs over large temperature intervals(15–60 C), producing a wide range in liquid compositions,from alkali basalts and alkali picrites at low to moderate degreesof melting (<1–10%) to olivine tholeiites and picritesat higher degrees of melting (>10%). On the basis of limiteddata in the garnet Iherzolite field, melts from garnet lherzoliteare more silica rich for a given degree of melting than meltsfrom spinel lherzolite, and liquid compositions trend towardenstatite with increase in pressure. Source fertility (especiallyNa₂O content) has a strong control on the temperature of meltingand liquid composition. Less fertile sources produce smalleramounts of liquids richer in normative silica. For certain bulkcompositions (high SiO₂ and low Al₂O₃), spinel is not a stablephase along the lherzolite solidus.     

The Fluid-absent Partial Melting of a Zoisite-bearing Quartz Eclogite from 1{middle dot}0 to 3{middle dot}2 GPa; Implications for Melting in Thickened Continental Crust and for Subduction-zone Processes

Fluid-absent melting experiments on a zoisite- and phengite-bearingeclogite (omphacite, garnet, quartz, kyanite, zoisite, phengiteand rutile) were performed to constrain the melting relationsof these hydrous phases in natural assemblages, as well as themelt and mineral compositions produced by their breakdown. From1·0 to 3·2 GPa the solidus slopes positively from1·5 GPa at 850°C to 2·7 GPa at 1025°C,but bends back at higher pressures to 975°C at 3·2GPa. The melt fraction is always low and the melt compositionsalways felsic and become increasingly so with increasing pressure.The normative Ab–An–Or compositions of the initialmelts vary from tonalites at 1·0 GPa to tonalite–trondhjemitesat 1·5 GPa, adamellites at 2·1 and 2·7GPa, and to true granites at 3·2 GPa. At pressures <     

Melting of Refractory Mantle at 1{middle dot}5, 2 and 2{middle dot}5 GPa under Anhydrous and H2O-undersaturated Conditions: Implications for the Petrogenesis of High-Ca Boninites and the Influence of Subduction Components on Mantle Melting

Boninites are an important ‘end-member’ supra-subductionzone magmatic suite as they have the highest H₂O contents andrequire the most refractory of mantle wedge sources. The pressure–temperatureconditions of boninite origins in the mantle wedge are importantto understanding subduction zone initiation and subsequent evolution.Reaction experiments at 1·5 GPa (1350–1530°C),2 GPa (1400–1600°C) and 2·5 GPa (1450–1530°C)between a model primary high-Ca boninite magma composition anda refractory harzburgite under anhydrous and H₂O-undersaturatedconditions (2–3 wt % H₂O in the melt) have been completed.The boninite composition was modelled on melt inclusions occurringin the most magnesian olivine phenocrysts in high-Ca boninitesfrom the Northern Tongan forearc and the Upper Pillow Lavasof the Troodos ophiolite. Direct melting experiments on a modelrefractory lherzolite and a harzburgite composition at 1·5GPa under anhydrous conditions (1400–1600°C) havealso been completed. Experiments establish a P, T ‘meltinggrid’ for refractory harzburgite at 1·5, 2 and2·5 GPa and in the presence of 2–3 wt % H₂O. Theeffect of 2–3 wt % dissolved H₂O produces a liquidus depressionin primary boninite of     

Melting Relations in Part of the System CaO-MgO-Al2O3-SiO2-Na2O-H2O under 5kb Pressure

In the system CaO-MgO-Al₂O₃-SiO₂-Na₂O-H₂O under 5 kb pressurethe invariant equilibrium forsterite-orthopyroxene-Ca-rich clinopyroxene-amphibole-plagioclase-liquid-vapourhas been identified at 960?12 ?C. A similar invariant assemblagewith spinel replacing Ca-rich clinopyroxene exists at 950?8?C. The liquid in the former equilibrium contains 16.5 per cent(wt.) normative quartz and 3 per cent Na₂O; the plagioclaseis more calcic than An₈₇; the pyroxenes contain about 3 percent Al₂O₃ and the amphibole is hypersthene-normative. Two anhydrousthermal maxima, the olivine-Ca-rich clinopyroxene-plagioclaseand the orthopyroxene-Ca-rich clinopyroxene-plagioclase dividezones are not encountered in this system, and nepheline-normativeliquids may crystallize amphibole?olivine?Ca-rich clinopyroxeneto produce quartz-normative residual liquids of andesite-typecomposition. A thermal maximum involving amphibole-olivine-Ca-richclinopyroxene-liquid-vapour exists for liquids containing approximately11 per cent normative nepheline and liquids more undersaturatedthan this will crystallize these phases to produce extremelynephelinitic liquids. Phase diagrams are presented which facilitate the predictionof crystallization sequences and liquid evolution paths forany basic or intermediate composition under the conditions employedhere.     

Carbonatitic melts along the solidus of model lherzolite in the system CaO-MgO-Al2O3-SiO2-CO2 from 3 to 7 GPa

We have experimentally determined the solidus position of model lherzolite in the system CaO-MgO-Al₂O₃-SiO₂-CO₂ (CMAS.CO₂) from 3 to 7 GPa by locating isobaric invariant points where liquid coexists with olivine, orthopyroxene, clinopyroxene, garnet and carbonate. The intersection of two subsolidus reactions at the solidus involving carbonate generates two invariant points, I_1A and I_2A, which mark the transition from CO₂-bearing to dolomite-bearing and dolomite-bearing to magnesite-bearing lherzolite respectively. In CMAS.CO₂, we find I_1A at 2.6 GPa/1230 °C and I_2A at 4.8 GPa/1320 °C. The variation of all phase compositions along the solidus has also been determined. In the pressure range investigated, solidus melts are carbonatitic with SiO₂ contents of <6 wt%, CO₂ contents of ˜45 wt%, and Ca/(Ca+Mg) ratios that range from 0.59 (3 GPa) to 0.45 (7 GPa); compositionally they resemble natural magnesiocarbonatites. Volcanic magnesiocarbonatites may well be an example of the eruption of such melts directly from their mantle source region as evidenced by their diatremic style of activity and lack of associated silicate magmas. Our data in the CMAS.CO₂ system show that in a carbonate-bearing mantle, solidus and near-solidus melts will be CO₂-rich and silica poor. The widespread evidence for the presence of CO₂ in both the oceanic and continental upper mantle implies that such low degree SiO₂-poor carbonatitic melts are common in the mantle, despite the rarity of carbonatites themselves at the Earth's surface. Received: 9 April 1997 / Accepted: 25 November 1997     

Equilibrium and Fractional Crystallization Experiments at 0{middle dot}7 GPa; the Effect of Pressure on Phase Relations and Liquid Compositions of Tholeiitic Magmas

Two series of anhydrous experiments have been performed in anend-loaded piston cylinder apparatus on a primitive, mantle-derivedtholeiitic basalt at 0·7 GPa pressure and temperaturesin the range 1060–1270°C. The first series are equilibriumcrystallization experiments on a single basaltic bulk composition;the second series are fractionation experiments where near-perfectfractional crystallization was approached in a stepwise mannerusing 30°C temperature increments and starting compositionscorresponding to that of the previous, higher temperature glass.At 0·7 GPa liquidus temperatures are lowered and thestability of olivine and plagioclase is enhanced with respectto clinopyroxene compared with phase equilibria of the samecomposition at 1·0 GPa. The residual solid assemblagesof fractional crystallization experiments at 0·7 GPaevolve from dunites, followed by wehrlites, gabbronorites, andgabbros, to diorites and ilmenite-bearing diorites. In equilibriumcrystallization experiments at 0·7 GPa dunites are followedby plagioclase-bearing websterites and gabbronorites. In contrastto low-pressure fractionation of tholeiitic liquids (1 bar–0·5GPa), where early plagioclase saturation leads to the productionof troctolites followed by (olivine) gabbros at an early stageof differentiation, pyroxene still crystallizes before or withplagioclase at 0·7 GPa. The liquids formed by fractionalcrystallization at 0·7 GPa evolve through limited silicaincrease with rather strong iron enrichment following the typicaltholeiitic differentiation path from basalts to ferro-basalts.Silica enrichment and a decrease in absolute iron and titaniumconcentrations are observed in the last fractionation step afterilmenite starts to crystallize, resulting in the productionof an andesitic liquid. Liquids generated by equilibrium crystallizationexperiments at 0·7 GPa evolve through constant SiO₂ increaseand only limited FeO enrichment as a consequence of spinel crystallizationand closed-system behaviour. Empirical calculations of the (dry)liquid densities along the liquid lines of descent at 0·7and 1·0 GPa reveal that only differentiation at the baseof the crust (1·0 GPa) results in liquids that can ascendthrough the crust and that will ultimately form granitoid plutonicand/or dacitic to rhyodacitic sub-volcanic to volcanic complexes;at 0·7 GPa the liquid density increases with increasingdifferentiation as a result of pronounced Fe enrichment, renderingit rather unlikely that such differentiated melt will reachshallow crustal levels. KEY WORDS: tholeiitic magmas; experimental petrology; equilibrium crystallization; fractional crystallization     

Experimental Investigation and Optimization of Thermodynamic Properties and Phase Diagrams in the Systems CaO-SiO2, MgO-SiO2, CaMgSi2O6-SiO2 and CaMgSi2O6-Mg2SiO4 to 1{middle dot}0 GPa

Using experimental results at 1·0 GPa for the systemsCaO–SiO₂, MgO–SiO₂, CaMgSi₂O₆–SiO₂ and CaMgSi₂O₆–Mg₂SiO₄,and all the currently available phase equilibria and thermodynamicdata at 1 bar, we have optimized the thermodynamic propertiesof the liquid phase at 1·0 GPa. The new optimized thermodynamicparameters indicate that pressure has little effect on the topologyof the CaO–SiO₂, CaMgSi₂O₆–SiO₂, and CaMgSi₂O₆–Mg₂SiO₄systems but a pronounced one on the MgO–SiO₂ binary. Themost striking change concerns passage of the MgSiO₃ phase fromperitectic melting at 1 bar to eutectic melting at 1·0GPa. This transition is estimated to occur at 0·41 GPa.For the CaMgSi₂O₆–SiO₂ and CaMgSi₂O₆–Mg₂SiO₄ pseudo-binaries,the size of the field clinopyroxene + liquid increases withincreasing pressure. This change is related to the shift ofthe piercing points clinopyroxene + silica + liquid (from 0·375mol fraction SiO₂ at 1 bar to 0·414 at 1·0 GPa)and clinopyroxene + olivine + liquid (from 0·191 molfraction SiO₂ at 1 bar to 0·331 at 1·0 GPa) thatbound the clinopyroxene + liquid field in the CaMgSi₂O₆·SiO₂and CaMgSi₂O₆·Mg₂SiO₄ pseudo-binaries, respectively. KEY WORDS: CaO–SiO₂; CaMgSi₂O₆–Mg₂SiO₄; CaMgSi₂O₆–SiO₂; experiments; MgO–SiO₂     

An Experimental Study of the Sulfur Content in Basaltic Melts Saturated with Immiscible Sulfide or Sulfate Liquids at 1300{degrees}C and 1{middle dot}0 GPa

The sulfur content in basaltic melts coexisting with eithersulfide or sulfate melts was determined experimentally. Theexperimental conditions were in the range of 1300–1355°Cand 1·0–1·6 GPa, conditions appropriatefor the melting of the upper mantle above subduction zones.Under these conditions, both sulfide and sulfate were presentas immiscible liquids, as inferred from the round geometriesof the quenched sulfide and sulfate phases. The measured S contentin basaltic melts saturated with sulfate liquids ([S] = 1·5± 0·2 wt %) was 10 times higher than the S contentin basaltic melts saturated with sulfide liquids ([S] = 0·14± 0·02 wt %). In our experiments, sulfate liquidswere stable at fO₂ as low as FMQ = +1·85 [FMQ = log (fO₂)_sample– log (fO₂)_FMQ, where FMQ is the fayalite–magnetite–quartzoxygen buffer], and evidence from other sources indicates thatsulfates will be stable at lower fO₂ in melts with lower activitiesof silica. Because chalcophile and highly siderophile elements,such as Cu, Ni, Au, and Pd, are partitioned preferentially intosulfide phases, melting of sufficiently oxidized sources, inwhich sulfides are not stable, would favor incorporation ofthese elements into the silicate melt produced. Such melts wouldhave a higher potential to generate ore deposits. This studyshows that the high sulfur contents of such oxidized basaltsalso means that relatively small amounts of such magmas canprovide significant amounts of sulfur to exsolving volatilephases and account for the bulk of the sulfur expelled in somevolcanic eruptions, such the 1991 eruption of Mount Pinatubo. KEY WORDS: basalt; mantle; oxidation state; sulfate; sulfur     

黑云母片麻岩—H2O系统在0.1—0.2GPa压力下的熔融实验

本文提出了冀东黑云母片麻岩—H2O系统在0.1一0.2GPa压力下熔融买验的相关系。其固相线温度分別为0.1GPa时762℃,0.2GPa时712℃。黑云母消失的温度分別为0.1GPa时787℃,0.2GPa时737℃,石英消失的温度分别为0.1GPa时837.℃,0.2GPa时787.℃。采用Burn-ham模型计算的在液相线温度下岩浆饱和水的含量分別为0.1GPa时3.8%与0.2GPa时5.8%。根据实验结果以及早前寒武纪时冀东陆壳的古地温可知,该区早前寒武纪角阿岩相岩石分布的地区广泛出现的混合岩化作用应主要归因于陆壳岩石(黑云母片麻岩等)的局部熔融作用。由实验结果以及现代冀东陆壳的地温可推知,壳内低速层可能不是由岩石局部熔融所引起,而是由岩石中含有隙间水流体引起。     

An Internally Consistent Thermodynamic Model for the System CaO-MgO-Al2O3-SiO2 Derived Primarily from Phase Equilibrium Data

An internally consistent thermodynamic model for the subsolidus system CaO-MgO-Al2O3-SiO2 (CMAS) was developed and refined using primarily data from phase equilibrium experiments. The solution properties of pyroxenes and garnet were approximated with an ionic model, with independent mixing on adjacent crystallographic sites. This approach simplified the calculation of phase relations by allowing sequential calculation of the site occupancies. Enthalpy, entropy, and volume differences, nominally at 970 K, were derived for all participating phases by matching as closely as possible the experimentally observed phase relations. Although thermochemical measurements were not used directly in the refinement, the results were continuously monitored and compared with the thermochemical data to achieve a close match. The new model can be used to calculate phase diagrams for the CMAS system and its subsystems in the whole pressure range of the upper mantle. Simple empirical corrections for the effects of Na, Fe, Cr, etc., could potentially be introduced to make the model applicable to the thermobarometry of chemically complex mantle materials. Application of the new model to garnet lherzolite xenoliths from northern Lesotho and garnet peridotites from Norway supports the proposals for higher temperatures of the continental lithosphere.     

Synthesis of Ca-tourmaline in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl

Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)₂ and CaCl₂-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between oxy-uvite, CaMg₃- Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, and oxy-Mg-foitite, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration in the starting mixture. No hydroxy-uvite, CaMg₃(MgAl₅)(Si₆O₁₈)(BO₃)₃(OH)₃(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70 with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al₂□Mg₋₂Ca₋₁ and AlMg₋₁H₋₁. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline. Other phases are chlorite, tremolite, enstatite or cordierite. Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation (whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca²⁺ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as an indicator for the fluid composition.

---

Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al ₂ O ₃ -SiO ₂ -B ₂ O ₃ -H ₂ O-HCl Im System CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)₂ and CaCl₂-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, und Oxy-Mg-Foitit, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg₃(MgAl₅) (Si₆O₁₈)(BO₃)₃(OH)₃(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al₂□Mg₋₂Ca₋₁ und AlMg₋₁H₋₁. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca²⁺ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.

---

---

Received July 24, 1998;/revised version accepted October 21, 1999     

Two-pyroxene thermobarometry with new experimental data in the system CaO-MgO-Al2O3-SiO2

In the system CaO-MgO-Al₂O₃-SiO₂ (CMAS), equilibrium alumina contents of orthopyroxene and clinopyroxene, both coexisting with spinel + forsterite or spinel + anorthite, have been reversed in 16 runs at 1,300–1,400°C and 10.2–20.8 kbar, using PbO flux. The present data and the data of Perkins and Newton (1980) have been modeled using the Redlich-Kister equation. The resulting model satisfies most of the reversed data in the CMAS system, agrees very well with thermochemical measurements, and is consistent with the model for the enstatite-diopside join of Lindsley et al. (1981) and with the system MgO-Al₂O₃-SiO₂ of Gasparik and Newton (1984). The present data, however, do not confirm the negative slopes of Al-isopleths in the spinel lherzolite field suggested by Dixon and Presnall (1980). The new model has been used to calculate a graphical two-pyroxene thermobarometer applicable to natural two-pyroxene assemblages closely approaching in composition the CMAS system.     

The Liquid Line of Descent of Anhydrous, Mantle-Derived, Tholeiitic Liquids by Fractional and Equilibrium Crystallization--an Experimental Study at 1{middle dot}0 GPa

Two series of anhydrous experiments have been performed in anend-loaded piston cylinder apparatus on a primitive, mantle-derivedtholeiitic basalt at 1·0 GPa pressure and temperaturesin the range 1060–1330°C. The experimental data provideconstraints on phase equilibria, and solid and liquid compositionsalong the liquid line of descent of primary basaltic magmasdifferentiating in storage reservoirs located at the base ofthe continental crust. The first series are equilibrium crystallizationexperiments on a single basaltic bulk composition; the secondseries are fractionation experiments where near-perfect fractionalcrystallization was approached in a stepwise manner using 30°Ctemperature steps and starting compositions corresponding tothe liquid composition of the previous, higher-temperature glasscomposition. Liquids in the fractional crystallization experimentsevolve with progressive SiO₂ increase from basalts to dacites,whereas the liquids in the equilibrium crystallization experimentsremain basaltic and display only a moderate SiO₂ increase accompaniedby more pronounced Al₂O₃ enrichment. The principal phase equilibriacontrols responsible for these contrasting trends are suppressionof the peritectic olivine + liquid = opx reaction and earlierplagioclase saturation in the fractionation experiments comparedwith the equilibrium experiments. Both crystallization processeslead to the formation of large volumes of ultramafic cumulatesrelated to the suppression of plagioclase crystallization relativeto pyroxenes at high pressures. This is in contrast to low-pressurefractionation of tholeiitic liquids, where early plagioclasesaturation leads to the production of troctolites followed by(olivine-) gabbros at an early stage of differentiation. KEY WORDS: liquid line of descent; tholeiitic magmas; equilibrium crystallization; fractional crystallization     

X-ray determination and equilibrium composition of clinopyroxenes in the system CaO-MgO-Al2O3-SiO2

Ternary clinopyroxenes have been synthesized in the plane Di-CaTs-En. The variation of their crystallographic parameters has allowed the development of three determinative grids, which utilize b-, 2 _22¯1–2 ₃₁₀ and 2 ₃₃₀ –2 ₂₀₂ respectively. These grids show significant differences in comparison with the previously proposed ones. Present results have been used to review some data on clinopyroxenes equilibria in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS) (Biggar 1969; Bruno and Facchinelli 1978; Herzberg 1978; O'Hara and Schairer 1963; Boyd 1969). In particular the petrogenic grid correlating P, T and CaTs content of clinopyroxenes in spinel-lherzolite assemblage (Herzberg 1978) has been revised, and consequently equilibrium temperatures rise by one hundred degrees.     

The Composition of Near-solidus Partial Melts of Fertile Peridotite at 1 and 1{middle dot}5 GPa: Implications for the Petrogenesis of MORB

We have determined the near-solidus melt compositions for peridotiteMM-3, a suitable composition for the production of mid-oceanridge basalt (MORB) by decompression partial melting, at 1 and1·5 GPa. At 1 GPa the MM-3 composition has a subsolidusplagioclase-bearing spinel lherzolite assemblage, and a solidusat 1270°C. At only 5°C above the solidus, 4% meltis present as a result of almost complete melting of plagioclase.This melting behaviour in plagioclase lherzolite is predictedfrom simple systems and previous experimental work. The persistenceof plagioclase to > 0·8 GPa is strongly dependenton bulk-rock CaO/Na₂O and normative plagioclase content in theperidotite. At 1·5 GPa the MM-3 composition has a subsolidusspinel lherzolite assemblage, and a solidus at 1350°C.We have determined a near-solidus melt composition at 2% meltingwithin 10°C of the solidus. Near-solidus melts at both 1and 1·5 GPa are nepheline normative, and have low normativediopside contents; also they have the highest TiO₂, Al₂O₃ andNa₂O, and the lowest FeO and Cr₂O₃ contents compared with higherdegree partial melts. Comparison of these near-solidus meltswith primitive MORB glasses, which lie in the olivine-only fieldof crystallization at low pressure, indicate that petrogeneticmodels involving aggregation of near-fractional melts formedduring melting at pressures of 1·5 GPa or less are unlikelyto be correct. In this study we use an experimental approachthat utilizes sintered oxide mix starting materials and peridotitereaction experiments. We also examine some recent studies usingan alternative approach of melt migration into, and entrapmentwithin ‘melt traps’ (olivine, diamond, vitreouscarbon) and discuss optimal procedures for this method. KEY WORDS: experimental petrology; mantle melting; near-solidus; fertile peridotite; MORB     

Solid-Fluid Equilibria in the System KAlSi3O8-NaAlSi3O8-Al2SiO5-SiO2-H2O-HCl

Activity diagrams in the system KAlSi₃O₈-NaAlSi₃O₈-Al₂SiO₅-SiO₂-H₂O-HClhave been calculated in terms of a_K+/a_H+ and a_N+/a_H+ from existingexperimental data. They show the effect of temperature, pressure,and a_H2O on the stability fields of the alkali feldspars, micas,and aluminium silicate. These activity diagrams are useful in revealing the bufferingcapacity of mineral assemblages and the chemical potential gradientsestablished by changes in T, P, a_H2O, and mineral assemblage.An analysis of mineral paragenesis in terms of these diagramssuggests that mosaic equilibrium, allowing limited metasomatismand internal buffering of chemical potentials, best describemetamorphic systems. Thus the dehydration reaction: muscovite+quartz=K-feldspar+Al₂SiO₅+H₂O which is most important in closed systems, probably fails todescribe in detail the mechanism of natural muscovite decomposition.Rather the decomposition of muscovite is more likely representedby ionic reactions. The replacement of muscovite by feldspar: muscovite+6 SiO₂+2 K⁺=3 K-feldspar+2 H⁺ muscovite+6 SiO₂+3 Na⁺=3 Albite+K⁺+2 H⁺ is favored at high temperature and low pressure, and may accountfor the crystallization of some feldspars in metamorphic rocks.The reaction involving aluminium silicate replacement of muscovite: 2 muscovite+2 H⁺=3 Al₂SiO₅+3 SiO₂+3 H₂O+2 K⁺ is favored at high temperature and pressure and low a_H2O, andcould contribute to the development of the aluminium silicates.It is concluded that both activity diagrams and AKNa projectionsshould be used together to more completely evaluate mineralparagenesis in terms of mosaic equilibria.