The effects of FeO on the system CMAS at low pressure and implications for basalt crystallization processes

The common occurrence of olivine, clinopyroxene and plagioclase in natural basalts may suggest that crystallization of these phases exerts important controls on the evolution of natural basalts at low pressure. In order to understand the effects of such an assemblage on the evolution of basalt, an experimental study of the divariant assemblage 1+an+cpx+ol in the system CMAS + FeO was undertaken at 1 bar and under very reducing conditions. Experiments have been performed along three isothernal sections. Detailed electron microprobe data have been collected on all the coexisting phases. Combining these data with available data in the system CMAS, the compositions of all the coexisting phases have been described as functions of temperature and CaO content in the melt by applying a multiple linear regression method. This allows a quantitative characterization of the divariant assemblage 1+an+epx+ol in the system CMAS + FeO, from 1275°C to 1160°C, with liquid compositions ranging from mg#=1 to mg#=0.28. Knowing the composition-temperature relationships, the basic T-X configuration of the assemblage 1+an+cpx+ol has been analysed, and mass balance calculations have been performed to examine the FeO effect on different crystallization processes. Addition of FeO to the system CMAS transforms the thermal divide in the assemblage 1+an+cpx+ol to a thermal ridge, and shifts the spine of the thermal ridge towards SiO₂-poor compositions with decreasing temperature. This indicates that tholeiitic basalts can be relatively silica-poor, and evolve towards slightly more silica-poor compositions. With increasing FeO content, pigeonite replaces ortheonstatite as a crystallizing phase along the silica-rich boundary of the assemblage 1+an+cpx+ol. In some iron, and silica rich composition, olivine possibly terminates its crystallization or even starts resorption prior to pigeonite precipitation; this suppresses silica enrichment in the melt. Crystallization paths of the assemblage 1+an+cpx+ol are determined by the detailed T-X relations of the thermal ridge with the melt evolving away from the spine. The liquid evolution trend depends strongly on the initial compositions. A tholeiitic liquid can follow a moderate silica enrichment path at the same very reducing condition of there is a high modal proportion of olivine. ‘A Fenner mechanism therefore is at work at the same place as a Bowen mechanism’.     

Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

The stability of cordierite and garnet relative to their anhydrous breakdown products, i.e. hypersthene, sapphirine, olivine, spinel, sillimanite and quartz, has been studied experimentally in model pelitic compositions (system MgO-FeO-Al₂O₃-CaO-K₂O-SiO₂). Below 1000° C cordierite breaks down according to the divariant reaction cordierite garnet+sillimanite+quartz (1) for most values of the MgO/MgO + FeO ratio (X). At very high values of X (ca. X0.9) garnet in reaction (1) is replaced by hypersthene. The position and width of the divariant field (in terms of pressure and temperature) in which cordierite and garnet coexist, is a function of the MgO/MgO + FeO ratio. If this ratio is increased then the stability field of garnet is reduced and that of cordierite extended towards higher pressure. Compositions of coexisting cordierite and garnet in divariant equilibrium have been analysed by electron probe micro-analyser. These compositions are unique functions of pressure and temperature. Above ca. 1000° C the breakdown of cordierite involves the phases sapphirine and hercynite-rich spinel in Mg-rich and Fe-rich compositions respectively.     

Low-Pressure Phase Relationships in the System Na2O--CaO--FeO--MgO--Al2O3--SiO2 at 1100C, with Implications for the Differentiation of Basaltic Magmas

Experiments were performed on the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂at 1100C, with the interest focused on the assemblage Liq+Aug+Pl+Oland its boundaries. Glass synthesized in a very reducing atmospherewas used as starting material. To avoid sodium loss during theexperiment, the starting material was loaded into iron capsules,and the experiments were carried out in evacuated silica glasstubes. All phases in the products were identified and analysedwith an electron microprobe. The probe analyses indicate thatthe assemblage Liq+Aug+Pl+Ol is stable over a wide range ofcompositions, and is bounded by the appearance of pigeonitein the silica-rich compositions. In the silica-poor compositions,the assemblage is successively bounded by the appearance ofkirschsteinite, melilite, and nepheline with increasing sodiumcontent. Owing to the isothermal and ‘isobaric’divariant nature of the assemblage Liq+Aug+Pl+Ol in the studiedsystem, a numerical method has been used to describe the phasecompositions with Si and Na contents in the liquid as two arbitrarilychosen independent variables. This procedure results in quantitativecharacterization of the assemblage Liq+Aug+Pl+Ol over a rangeof compositions. ^*Present address: Geochemistry Group, Geology Dept., Beijing University, Beijing, 100871, P.R. China.     

Petrology of the zoned calcalkaline magma chamber of Mount Mazama,Crater Lake,Oregon

Evolution of the magma chamber at Mount Mazama involved repeated recharge by two types of andesite (high-Sr and low-Sr), crystal fractionation, crystal accumulation, assimilation, and magma mixing (Bacon and Druitt 1988). This paper addresses the modal compositions, textures, mineral chemistry and magmatic temperatures of (i) products of the 6845±50 BP climactic eruption, (ii) blocks of partially fused granitoid wallrock found in the ejecta, and (iii) preclimactic rhyodacitic lavas leaked from the chamber in late Pleistocene and early Holocene time. Immediately prior to the climactic eruption the chamber contained ≳ 40 km³ of rhyodacite (10 vol% plag + opx + aug + hb + mt + ilm, ∼880° C) overlying high-Sr andesite and cumulus-crystal mush (28–51 vol% plag + hb ± opx ± aug + mt ± ilm, 880° to ≥950° C), which in turn overlay low-Sr crystal mush (50–66 vol% plag + opx + aug ± hb ± ol + mt + ilm, 890° to ≥950† C). Despite the well known compositional gap in the ejecta, no thermal discontinuity existed in the chamber. Pre-eruptive water contents of pore liquids in most high-Sr and low-Sr mushes were 4–6 wt%, but on average the high-Sr mushes were slightly richer in water. Although parental magmas of the crystal mushes were andesitic, xenocrysts of bytownite and Ni-rich magnesian olivine in some scoriae record the one-time injection of basalt into the chamber. Textures in ol-bearing scoriae preserve evidence for the reactions ol + liq = opx and ol + aug + liq(+ plag?) = hb, which occurred in andesitic liquids at Mount Mazama. Strontium abundances in plagioclase phenocrysts constrain the petrogenesis of preclimactic and climactic rhyodacites. Phenocryst cores derived from high-Sr and low-Sr magmas have different Sr contents which can be resolved by microprobe. Partition coefficients for plagioclase in andesitic to rhyolitic glasses range from 2 to 7, and increase as glass %SiO₂ increases. Evolved Pleistocene rhyodacites (∼30–25,000 BP) and rhyodacites of the Holocene Llao Rock center (7015±45 BP) contain Sr-poor plagioclase and are derivatives from low-Sr magma. Rhyodacites of the Pleistocene Sharp Peak domes, Holocene Cleetwood flow (∼6850 BP), and climactic ejecta contain discrete Sr-rich and Sr-poor plagioclase phenocryst populations and are hybrids produced by mixing low-Sr rhyodacite (containing Sr-poor plag + opx + aug) with a more mafic high-Sr magma (with Sr-rich plag [ + hb?]). The data reinforce the conclusions of crystal-liquid mixing calculations (Bacon and Druitt 1988), and suggest some important refinements to the magma chamber model.     

Experimental study of phase relations involving osumilite in the system K2O-FeO-MgO-Al2O3-SiO2-H2O at high pressure and temperature

Abstract Phase relations and mineral chemistry for garnet (Grt), orthopyroxene (Opx), sapphirine (Spr), water-undersaturated cordierite (Crd), osumilite (Osu), sillimanite (Sil), K-feldspar (Kfs), quartz (Qtz) and a water-undersaturated liquid (Liq) have been determined experimentally in the system KFMASH (K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O) under low P_H2O and f_O2 conditions. Four compositions have been studied with 100 [Mg/(Mg + Fe)] ranging from 65.6 to 89.7. Based on our experimental data, a P-T grid is derived for the KFMASH system in the presence of quartz, orthopyroxene and liquid. Osumilite has been found in various mineral assemblages from 950 to 1100°C and 7.5 to 11 kbar. In the temperature range 1000-1100°C, the pair Os-Grt is stable over a pressure range of about 3kbar. The divariant reaction Os + Opx = Grt + Kfs + Qtz runs to the right with increasing pressure. Because osumilite is the most magnesian phase it is restricted to Mg-rich compositions at high pressure. The reaction defining the upper pressure stability limit of Os-Grt is located around 11 kbar with a nearly flat dP/dT slope over the temperature range 950–100°C. Over the entire temperature range investigated osumilite is not stable beyond 12 kbar. The data imply a restricted pressure range between 11 and 12 kbar for the stability of the assemblage Os-Opx-Sil-Kfs-Qtz. At 1050°C and above, osumilite occurs in various mineral assemblages together with the high-T pair Spr-Qtz. When coexisting with garnet, orthopyroxene or sapphirine, osumilite is always the most magnesian phase. At 1050 and 1100°C, liquid is invariably the most Fe-rich phase in the run product. Our data support a theoretical P-T grid for the KFMAS system in which osumilite is stable outside the field of the high-T assemblage Spr-Qtz. Moreover, our grid indicates that Os-Opx-Sil-Kfs-Qtz has a more restricted pressure and compositional stability domain than Os-Grt, in agreement with natural occurrences. Osumilite is stable over a large pressure range, such that in Mg-rich rocks, and at high temperature, it can occur at any depth in normal thickness continental crust.     

Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

The stability of cordierite and garnet has been studied experimentally in complex, silica oversaturated compositions (in the systems MgO-FeO-Al₂O-CaO₃-Na₂O-K₂OSiO₂) in which the molecular ratio Al₂O₃/FeO+MgO<1. Compositions with 100 Mg/Mg+Fe²⁺ ratios (X) of 0, 30, 50, 70 and 100 have been used to investigate the role of this ratio in determining phase assemblages and P, T coordinates of reactions. The minimum pressure for appearance of garnet at a given temperature is strongly dependent on X _{total rock}.The X-values of co-existing phases (chiefly garnet, cordierite, hypersthene) in divariant equilibrium are a function of temperature and pressure and have been experimentally determined at 900° C, 1000° C and 1100° C. At high temperature (>1050° C) the phases sapphirine and spinel are stable with quartz in Mg-rich and Fe-rich compositions respectively. Experiments in the system MgO-FeO-Al₂O₃-SiO₂ show that for a given X-value and temperature the pressure required to produce Ca-free garnet from hypersthene-cordierite assemblages is 1–2 kb greater than that required to produce garnet containing 6±2 mol percent grossular solid solution in the more complex Ca-bearing system.     

Experimental study of chloritoid stability at high pressure and various fO2 conditions

The reaction chloritoid (ctd)=almandine (alm)+diaspore+H₂O (CAD) has been reversed using Fe³⁺-free synthetic chloritoid and almandine, under fO₂ conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO₂ conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO₂ conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH₂O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H₂O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H₂O bracketed on the Fe/FeO buffer and under unbuffered fO₂ conditions. For fO₂ buffered by the assemblage Fe/FeO, aH₂O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO₂ buffered by the assemblage Ni/NiO, aH₂O=1. The aH₂O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H₂O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H ^o f,ctd and S ^octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and K_D=(Fe³⁺/Al)ctd/(Fe³⁺/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe³⁺ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl₂SiO₅(OH)₂ formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe³⁺ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H₂O (CQGK), calculated for intermediate Fe–Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65<(XFe)gt<0.8, CQKG calculated from FASH and MASH overlap for K_D=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the K_D values reported from chloritoid+garnet+quartz+kyanite natural assemblages.     

Thermodynamic modelling of the reaction muscovite+cordierite→Al2SiO5+biotite+quartz+ H2O: constraints from natural assemblages and implications for the metapelitic petrogenetic grid

The reaction muscovite+cordierite→biotite+Al₂SiO₅ +quartz+H₂O is of considerable importance in the low pressure metamorphism of pelitic rocks: (1) its operation is implied in the widespread assemblage Ms + Crd +And± Sil + Bt + Qtz, a common mineral assemblage in contact aureoles and low pressure regional terranes; (2) it is potentially an important equilibrium for pressure estimation in low pressure assemblages lacking garnet; and (3) it has been used to distinguish between clockwise and anticlockwise P–T paths in low pressure metamorphic settings. Experiments and thermodynamic databases provide conflicting constraints on the slope and position of the reaction, with most thermodynamic databases predicting a positive slope for the reaction. Evidence from mineral assemblages and microtextures from a large number of natural prograde sequences, in particular contact aureoles, is most consistent with a negative slope (andalusite and/or sillimanite occurs upgrade of, and may show evidence for replacement of, cordierite). Mineral compositional trends as a function of grade are variable but taken as a whole are more consistent with a negative slope than a positive slope. Thermodynamic modelling of reaction 1 and associated equilibria results in a low pressure metapelitic petrogenetic grid in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH) which satisfies most of the natural and experimental constraints. Contouring of the Fe–Mg divariant interval represented by reaction 1 allows for pressure estimation in garnet‐absent andalusite+cordierite‐bearing schists and hornfelses. The revised topology of reaction 1 allows for improved analysis of P–T paths from mineral assemblage sequences and microtextures in the same rocks.     

Major element evolution of basaltic magmas: a comparison of the information in CMAS and ALFE projections

Basalt petrologists disagree as to whether the commonly used projection, forsterite-diopside-silica, in the system CMAS (CaO-MgO-Al₂O₃-SiO₂), can adequately resolve differences in basaltic glass compositions for purposes of petrogenetic modelling. Here, we suggest than an analogous plot, the aluminium-factor diagram (ALFE) of Nesbitt and Cramer (1981), has greater diagnostic value than Fo-Di-Sil. A plot of molar (Al₂O₂-CaO-Na₂O-K₂O)/(FeO + MgO) vs FeO/(FeO + MgO), it produces more coherent patterns both for experimental basalt glasses, and for natural lavas. It is, like Fo-Di-Sil, a projection through plagioclase, but has the advantage that it monitors changes in Fe/(Fe + Mg) in melts and associated crystalline phases, and is particularly useful in assessing the timing of clinopyroxene crystallization in a suite of lavas. The diagram owes its greater resolving power to the fact that the computation of its coordinates is less sensitive to analytical uncertainty than for Fo-Di-Sil. In the latter diagram, normative quartz is calculated as a residual and thus manifests the uncertainties in all the major elements.     

Actinolite-forming reaction at low pressure and the role of Fe2+-Mg substitution

The 6km-thick Karmutsen metabasites, exposed over much of Vancouver Island, were thermally metamorphosed by intrusions of Jurassic granodiorite and granite. Observation of about 800 thin sections shows that the metabasites provide a complete succession of mineral assemblages ranging from the zeolite to pyroxene hornfels facies around the intrusion. The reaction leading to the appearance of actinolite, which is the facies boundary between prehnite-pumpellyite and prehnite-actinolite facies, was examined using calcite-free Karmutsen metabasites collected from the route along the Elk river. In the prehnite-pumpellyite facies, X _Fe3+[Fe³⁺/(Fe³⁺+Al)] in prehnite, pumpellyite and epidote buffered by the four-phase assemblage prehnite+pumpellyite+epidote+chlorite systematically decreases with increasing metamorphic grade. Such a trend is the reverse of that proposed by Cho et al. (1986); this may be related to the higher in the Mt. Menzies area. The actinolite-forming reaction depends on the value of X ^Fe3+ in pumpellyite. If using a low value of ^Fe3+, 3.89 Pr(0.06)+0.48 Ep(0.26)+0.60 Chl+H₂O=2.10 Pm (0.08)+0.17 Act+0.88 Qz is delineated. The number in parentheses stands for the X _Fe3+value in Ca-Al silicates. On the other hand, replacing the X _Fe3+ of 0.08 in pumpellyite with a higher X _Fe3+ value (0.24) changes the reaction to 0.41 Pm+0.02 Chl+0.42 Qz=0.11 Pr+0.62 Ep+0.10 Act+H₂O. The first (hydration) reaction forms pumpellyite and actinolite on the high-temperature side, whereas the second (dehydration) reaction consumes pumpellyite to form prehnite, epidote and actinolite. The former reaction seems to explain the textural relationship of Ca-Al silicates in the study area. However, actinolite-forming reaction changes to a different reaction depending on the compositions of the participating minerals, although in the other area even physical conditions may be similar to those in the study area. Chemographic analysis of phase relations in the PrA facies indicates that the appearance of prehnite depends strongly on the bulk FeO/MgO ratio: this may explain the rarity of prehnite in common metabasites in spite of the expected dominant occurrence in the conventional pseudo-quaternary (Ca-Al-Fe³⁺-FM) system. An increasing FeO/MgO ratio stabilizes the Pr+Act assemblage and reduces the stability of the Pm+Act one. Therefore, the definition of pumpellyite-actinolite facies should include not only Pm+Act but also the absence of Pr+Act assemblages. In addition to the possible role of high (Cho and Liou 1987) and/or high to mask the appearance of prehnite, the effect of the FeO/MgO ratio is emphasized.     

The stability of merwinite in the system CaO-MgO-SiO2-H2O-CO2 with CO2-poor fluids

The stability of merwinite (Mw) and its equivalent assemblages, akermanite (Ak)+calcite (Cc), diopside (Di)+calcite, and wollastonite (Wo)+monticellite (Mc)+calcite was determined at T=500–900° C and P _f=0.5–2.0 kbar under H₂O–CO₂ fluid conditions with X _{CO 2}=0.5, 0.1, 0.05, and 0.02. Merwinite is stable at P _f=0.5 kbar with T>700° C and X _{CO 2}<0.1. At P _f=2.0 kbar, the assemblage Di+Cc replaces merwinite at all T and X _{CO 2} conditions. At intermediate P _f=1 kbar, the assemblage Ak+Cc is stable above 707° C and Wo+Mc+Cc is stable below 707° C. The univariant curve for the reaction Di+Cc=Wo+Mc+CO₂ is almost parallel to the T axis and shifts to low P _f with increasing X _{CO 2}, with the assemblage Di+Cc on the high-P _f side. The implications of the experimental results in regard to contact metamorphism of limestone are discussed using the aureole at Crestmore, California as an example.     

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     

Lunar surface geochemistry: Global concentrations of Th, K, and FeO as derived from lunar prospector and Clementine data

Accurate estimates of global concentrations of Th, K, and FeO have an important bearing on understanding the bulk chemistry and geologic evolution of the Moon. We present empirical ground-truth calibrations (transformations) for Lunar Prospector gamma-ray spectrometer data (K and Th) and a modified algorithm for deriving FeO concentrations from Clementine spectral reflectance data that incorporates an adjustment for TiO₂ content. The average composition of soil samples for individual landing sites is used as ground-truth for remotely sensed data. Among the Apollo and Luna sites, Apollo 12 and 14 provide controls for the incompatible-element-rich compositions, Apollo 16 and Luna 20 provide controls for the feldspathic and incompatible-element-poor compositions, and Apollo 11, 15, and 17, and Luna 16 and 24 provide controls for Fe-rich compositions. In addition to these Apollo and Luna sample data we include the composition of the feldspathic lunar meteorites as a proxy for the northern farside highlands to extend the range of the calibration points, thus providing an additional anorthositic end-member composition. These empirical ground-truth calibrations for Lunar Prospector Th and K provide self consistency between the existing derived data and lunar-sample data. Clementine spectral-reflectance data are used to construct a TiO₂-sensitive FeO calibration that yields higher FeO concentrations in areas of high-Fe, low-Ti, mare-basalt-rich surfaces than previous FeO algorithms. The data set so derived is consistent with known sample compositions and regolith mixing relationships.     

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     

Phase equilibria involving humite minerals in impure dolomitic limestones

The natural occurrence of critical assemblages among the phases clinohumite, chondrodite, norbergite, tremolite, forsterite, brucite, periclase, diopside, calcite and dolomite, together with experimental and thermochemical data, permits the calculation of phase equilibria governing the stability of the humite group minerals in impure dolomitic limestones. The phase relations are described by 29 divariant (OH-F) continuous reactions, and 11 univariant discontinuous reactions. The equilibrium conditions for these reactions have been calculated and plotted in isobaricT-X(OH-F) andT- phase diagrams. Continuous reactions govern the compositions of (OH-F) solid solutions and the consequent movement of three-phase triangles on the chemographic diagram. Discontinuous reactions result in the appearance or disappearance of a distinct phase assemblage. The pure OH-humite minerals are metastable relative to forsterite+brucite. With increasing fluorine content, clinohumite, followed in turn by chondrodite and norbergite, becomes stable. The stability fields for the individual humite minerals expand to more CO₂-rich fluid compositions with increasing fluorine content and decreasing total pressure. At 1,000 bars, clinohumite can contain a maximum of 58 mole percent fluorine before reacting discontinuously to form chondrodite (X _F=0.61) and forsterite. The stability field for clinohumite+calcite is restricted to fluids with <0.40. At temperatures less than 700°C, the minimum fluorine mole fractions required to stabilize chondrodite and norbergite are 0.31 and 0.62 respectively. At the same conditions, chondrodite can contain a maximum of approximately 85 mole % F. The calculated phase equilibrium boundaries, the range of stable humite compositions and the compositions of coexisting (OH-F) phases are in good overall agreement with natural assemblages. Owing to steepdT/d slopes for several of the humite continuous reactions, the F/(F+OH) ratio of a given humite mineral is a useful indicator of the CO₂/H₂O ratio of the fluid phase.     

The effect of sodium and titanium on crystal-melt partitioning of trace elements

Eclogite of recycled slab origin has often been invoked in the source region of mid-ocean ridge and ocean-island basalts. Melts of this eclogitic material are expected to be enriched in incompatible elements including major elements such as Na and Ti. In order to investigate the controls on trace element chemistry of a melt from such a recycled component we have performed trace element partitioning experiments in the simple systems CMAS (CaO-MgO-Al₂O₃-SiO₂), NCMAS (Na₂O-CMAS) and Ti-CMAS (TiO₂-CMAS) at 3 GPa and 1298-1500°C using analogue eclogitic compositions.We show that sodium has a profound effect on clinopyroxene-melt partition coefficients. NCMAS is characterized by elevated partition coefficients, relative to CMAS for all elements except Li. The increase is more pronounced for more highly charged cations, resulting in negative partitioning anomalies for Li, Sr, Ba and Pb. In contrast to sodium, titanium has very little effect on trace element partitioning for all elements except Nb and Ta, which are retained by the rutile that is saturated in this run.     

Constraints on phase diagram topology for the system CaO−MgO−SiO2−CO2−H2O

Published phase diagrams for the siliceous carbonate system CaO–MgO–SiO₂–CO₂–H₂O are contradictory because of different estimates of the relative stability of magnesite. Experimental data on magnesite are too ambiguous to determine the validity of these estimates. Therefore, field evidence is used to select the correct phase diagram topology for siliceous carbonate and carbonate ultramafic rocks at pressures of about 2–5 kbar. The primary selection criterion is provided by the existence of the stable assemblage talc+dolomite+forsterite+tremolite+antigorite, which occurs in the Bergell contact aureole and Swiss Central Alps. Field evidence also is used to argue that the reaction magnesite+quartz=enstatite must occur at lower temperature than the reaction dolomite+quartz=diopside. T-X _{CO 2} and P _{CO 2}-T phase diagrams consistent with these observations are calculated from experimental and thermo-dynamic data. For antigorite ophicarbonate rocks, remarkable agreement is obtained between the spatial distribution of low variance mineral assemblages and the calculated diagrams.     

Partial melting and phase relations in high-grade metapelites: an experimental petrogenetic grid in the KFMASH system

Petrogenetic grids are a powerful tool for understanding metamorphic terrains and many theoretical grids have been suggested for the process of granulite formation in metapelitic rocks, via fluid-absent biotite melting reactions. However, application of these grids has been difficult due to the lack of suitable experimental constraints. We present here an experimentally determined and tightly constrained petrogenetic grid for KFMASH system metapelites which extends from 840–1000°C and 5.0–12.5 kbar. Sixty four experiments on three KFMASH, mineral-mix, bulk compositions (X _Mg=0.62, 0.74, 0.86) provide phase composition and assemblage data from which a grid can be derived and constrained. Reversal experiments and consideration of the phase composition data show the experiments to be close to equilibrium. The KFMASH univariant fluid-absent biotite melting reactions occur between 850 and 870°C at 5 kbar and between 900 and 915°C at 10 kbar. These reactions are connected to equilibria beyond the stability of biotite to develop a fixed framework within which the phase assemblage evolution of metapelitic rocks can be interpreted. The effect of minor components on phase equilibria is evaluated using the experimentally determined grid as a simple-system reference. The temperature at which melting occurs in metapelites is strongly controlled by the concentrations of titanium and fluorine in biotite. Pressure-temperature pseudosections presented for each of the experimental compositions show both the univariant and divariant reactions available to a particular bulk composition, clearly illustrating the possible evolution of the phase assemblage. The pseudosections also constrain the stability limits of     

Stability of sapphirine + quartz in the oxidized rocks of the Wilson Lake terrane,Labrador: calculated equilibria in NCKFMASHTO

The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al₂O₃–SiO₂ (FMAS) system. However, the potential for sapphirine to contain significant Fe³⁺ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al₂O₃–SiO₂–TiO₂–O (FMASTO), expansion into K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H₂O and O contents to use in the modelled compositions are investigated using T–M_H2O and T–M_O pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.