Melting Behaviour of Model Lherzolite in the System CaO-MgO-Al2O3-SiO2-FeO at 0{middle dot}7-2{middle dot}8 GPa

Fe–Mg exchange is the most important solid solution involvedin partial melting of spinel lherzolite, and the system CaO–MgO–Al₂O₃–SiO₂–FeO(CMASF) is ideally suited to explore this type of exchange duringmantle melting. Also, if primary mid-ocean ridge basalts arelargely generated in the spinel lherzolite stability field bynear-fractional fusion, then Na and other highly incompatibleelements will early on become depleted in the source, and themelting behaviour of mantle lherzolite should resemble the meltingbehaviour of simplified lherzolite in the CMASF system. We havedetermined the isobarically univariant melting relations ofthe lherzolite phase assemblage in the CMASF system in the 0·7–2·8GPa pressure range. Isobarically, for every 1 wt % increasein the FeO content of the melt in equilibrium with the lherzolitephase assemblage, the equilibrium temperature is lower by about3–5°C. Relative to the solidus of model lherzolitein the CaO–MgO–Al₂O₃–SiO₂ system, melt compositionsin the CMASF system are displaced slightly towards the alkalicside of the basalt tetrahedron. The transition on the solidusfrom spinel to plagioclase lherzolite has a positive Clapeyronslope with the spinel lherzolite assemblage on the high-temperatureside, and has an almost identical position in P–T spaceto the comparable transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O(CMASN) system. When the compositions of all phases are describedmathematically and used to model the generation of primary basalts,temperature and melt composition changes are small as percentmelting increases. More specifically, 10% melting takes placeover 1·5–2°C, melt compositions are relativelyinsensitive to the degree of melting and bulk composition, andequilibrium and near-fractional melting yield similar melt compositions.FeO and MgO are the oxides that exhibit the greatest changein the melt with degree of melting and bulk composition. Theamount of FeO decreases with increasing degree of melting, whereasthe amount of MgO increases. The coefficients for Fe–Mgexchange between the coexisting crystalline phases and melt,K_dFe–Mg^xl–liq, show a relatively simple and predictablebehaviour with pressure and temperature: the coefficients forolivine and spinel do not show significant dependence on temperature,whereas the coefficients for orthopyroxene and clinopyroxeneincrease with pressure and temperature. When melting of lherzoliteis modeled in the CMASF system, a strong linear correlationis observed between the mg-number of the lherzolite and themg-number of the near-solidus melts. Comparison with meltingin the CMASN system indicates that Na₂O has a strong effecton lherzolite melting behaviour only at small degrees of melting. KEY WORDS: CMASF; lherzolite solidus; mantle melting     

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     

Calculated Phase Relations in the System Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O with Applications to UHP Eclogites and Whiteschists

Pressure–temperature grids in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O and its subsystems have been calculatedin the range 15–45 kbar and 550–900°C, usingan internally consistent thermodynamic dataset and new thermodynamicmodels for amphibole, white mica, and clinopyroxene, with thesoftware THERMOCALC. Minerals considered for the grids includegarnet, omphacite, diopside, jadeite, hornblende, actinolite,glaucophane, zoisite, lawsonite, kyanite, coesite, quartz, talc,muscovite, paragonite, biotite, chlorite, and plagioclase. Compatibilitydiagrams are used to illustrate the phase relationships in thegrids. Coesite-bearing eclogites and a whiteschist from Chinaare used to demonstrate the ability of pseudosections to modelphase relationships in natural ultrahigh-pressure metamorphicrocks. Under water-saturated conditions, chlorite-bearing assemblagesin Mg- and Al-rich eclogites are stable at lower temperaturesthan in Fe-rich eclogites. The relative temperature stabilityof the three amphiboles is hornblende > actinolite > glaucophane(amphibole names used sensu lato). Talc-bearing assemblagesare stable only at low temperature and high pressure in Mg-and Al-rich eclogites. For most eclogite compositions, talccoexists with lawsonite, but not zoisite, in the stability fieldof coesite. Water content contouring of pressure–temperaturepseudosections, along with appropriate geotherms, provides newconstraints concerning dehydration of such rocks in subductingslabs. Chlorite and lawsonite are two important H₂O-carriersin subducting slabs. Depending on bulk composition and pressure–temperaturepath, amphibole may or may not be a major H₂O-carrier to depth.In most cases, dehydration to make ultrahigh-pressure eclogitestakes place gradually, with H₂O content controlled by divariantor higher variance assemblages. Therefore, fluid fluxes in subductionzones are likely to be continuous, with the rate of dehydrationchanging with changing pressure and temperature. Further, eclogitesof different bulk compositions dehydrate differently. Dehydrationof Fe-rich eclogite is nearly complete at relatively shallowdepth, whereas Mg- and Al-rich eclogites dehydrate continuouslydown to greater depth. KEY WORDS: dehydration; eclogites; phase relations; THERMOCALC; UHP metamorphism; whiteschists     

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     

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     

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 <     

Experimentally Determined Phase Relations in Hydrous Peridotites to 6{middle dot}5 GPa and their Consequences on the Dynamics of Subduction Zones

Fluid-saturated subsolidus experiments from 2·0 to 6·5GPa, and from 680 to 800°C have been performed on threemodel peridotites in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O(NCFMASH). Amphibole and chlorite coexist up to 2·4 GPa,700°C. Chlorite persists to 4·2 GPa at 680°C.Starting from 4·8 GPa, 680°C a 10 Å phase structurereplaces chlorite in all compositions. The 10 Å phasestructure contains significant Al₂O₃ (up to 10·53 wt%) deviating from the MgO–SiO₂–H₂O 10 Å phase(MSH 10 Å phase). A mixed layered structure (chlorite–MSH10 Å phase) is proposed to account for aluminium observed.In the Tinaquillo lherzolite amphibole breakdown occurs viathe reaction Thermal stabilityof chlorite (chlorite + orthopyroxene = forsterite + garnet+ H₂O) is shifted towards lower temperatures, compared withthe system MASH. Furthermore, the chlorite thermal breakdownis also related to the degenerate reaction Chlorite and the Al-10 Å phase structurecontribute significantly to the water budget in subduction zonesin the depth range relevant for arc magmatism, whereas amphibole-relatedfluid release is restricted to the forearc region. Chloriteand Al-10 Å phase breakdowns might explain the occurrenceof a double seismic zone by dehydration embrittlement. KEY WORDS: amphibole; chlorite; high pressure; peridotites; subduction zones     

Thermochemical Data on Mineral Phases: The System CaO-MgO-Al2O3-SiO2

Thermochemical data on several phases forming in the systemCaO-MgO-Al₂O₃-SiO₂ have been tested for consistency in reproducingexperimental phase equilibrium relationships. Calorimetric dataon enthalpy, entropy and heat capacity have been adjusted withinexperimental errors and new data on some phases have been estimatedusing phase equilibrium data. The consistency of the data inreproducing phase equilibrium relations in the multicomponent-multiphasesystems has been tested by computing phase diagrams using themethod of minimization of total Gibbs free energy. The recentcalorimetric data on most phases can be used without any significantchange except for phases that show cation disorder. Disordercorrections have been added to the heat capacity data on gehlenite,anorthite, spinel and Ca-Tschermak.     

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.     

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     

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     

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     

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     

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.     

Phase Relations and Melting of Anhydrous K-bearing Eclogite from 1200 to 1600{degrees}C and 3 to 5 GPa

To investigate eclogite melting under mantle conditions, wehave performed a series of piston-cylinder experiments usinga homogeneous synthetic starting material (GA2) that is representativeof altered mid-ocean ridge basalt. Experiments were conductedat pressures of 3·0, 4·0 and 5·0 GPa andover a temperature range of 1200–1600°C. The subsolidusmineralogy of GA2 consists of garnet and clinopyroxene withminor quartz–coesite, rutile and feldspar. Solidus temperaturesare located at 1230°C at 3·0 GPa and 1300°C at5·0 GPa, giving a steep solidus slope of 30–40°C/GPa.Melting intervals are in excess of 200°C and increase withpressure up to 5·0 GPa. At 3·0 GPa feldspar, rutileand quartz are residual phases up to 40°C above the solidus,whereas at higher pressures feldspar and rutile are rapidlymelted out above the solidus. Garnet and clinopyroxene are theonly residual phases once melt fractions exceed 20% and garnetis the sole liquidus phase over the investigated pressure range.With increasing melt fraction garnet and clinopyroxene becomeprogressively more Mg-rich, whereas coexisting melts vary fromK-rich dacites at low degrees of melting to basaltic andesitesat high melt fractions. Increasing pressure tends to increasethe jadeite and Ca-eskolaite components in clinopyroxene andenhance the modal proportion of garnet at low melt fractions,which effects a marked reduction in the Al₂O₃ and Na₂O contentof the melt with pressure. In contrast, the TiO₂ and K₂O contentsof the low-degree melts increase with increasing pressure; thusNa₂O and K₂O behave in a contrasted manner as a function ofpressure. Altered oceanic basalt is an important component ofcrust returned to the mantle via plate subduction, so GA2 maybe representative of one of many different mafic lithologiespresent in the upper mantle. During upwelling of heterogeneousmantle domains, these mafic rock-types may undergo extensivemelting at great depths, because of their low solidus temperaturescompared with mantle peridotite. Melt batches may be highlyvariable in composition depending on the composition and degreeof melting of the source, the depth of melting, and the degreeof magma mixing. Some of the eclogite-derived melts may alsoreact with and refertilize surrounding peridotite, which itselfmay partially melt with further upwelling. Such complex magma-genesisconditions may partly explain the wide spectrum of primitivemagma compositions found within oceanic basalt suites. KEY WORDS: eclogite; experimental petrology; mafic magmatism; mantle melting; oceanic basalts     

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.     

Adakitic Dacites Formed by Intracrustal Crystal Fractionation of Water-rich Parent Magmas at Nevado de Longavi Volcano (36{middle dot}2{degrees}S; Andean Southern Volcanic Zone, Central Chile)

The mid-Holocene eruptive products of Nevado de Longavívolcano (36·2°S, Chile) are the only reported occurrenceof adakitic volcanic rocks in the Quaternary Andean SouthernVolcanic Zone (33–46°S). Dacites of this volcano arechemically distinct from other evolved magmas of the regionin that they have high La/Yb (15–20) and Sr/Y (60–90)ratios and systematically lower incompatible element contents.An origin by partial melting of high-pressure crustal sourcesseems unlikely from isotopic and trace element considerations.Mafic enclaves quenched into one of the dacites, on the otherhand, constitute plausible parental magmas. Dacites and maficenclaves share several characteristics such as mineral chemistry,whole-rock isotope and trace element ratios, highly oxidizingconditions (NNO + 1·5 to >NNO + 2, where NNO is thenickel–nickel oxide buffer), and elevated boron contents.A two-stage mass-balance crystal fractionation model that matchesboth major and trace elements is proposed to explain magmaticevolution from the least evolved mafic enclave to the dacites.Amphibole is the main ferromagnesian phase in both stages ofthis model, in agreement with the mineralogy of the magmas.We also describe cumulate-textured xenoliths that correspondvery closely to the solid assemblages predicted by the model.We conclude that Nevado de Longaví adakitic dacites arethe products of polybaric fractional crystallization from exceptionallywater-rich parent magmas. These basaltic magmas are inferredto be related to an exceptionally high, but transient inputof slab-derived fluids released from serpentinite bodies hostedin the oceanic Mocha Fracture Zone, which projects beneath Nevadode Longaví. Fractional crystallization that is modallydominated by amphibole, with very minor garnet extraction, isa mechanism for generating adakitic magmas in cold subductionzones where a high flux of slab-derived fluids is present. KEY WORDS: adakite; amphibole; Andes; differentiation; Southern Volcanic Zone     

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