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Accessory phases and minor components in minerals are commonly ignored in thermodynamic modelling. Such an approach seems unwarranted, as accessory phases can represent a significant element reservoir and minor components can substantially change their host mineral's stability field. However, a lack of thermodynamic data prohibits assessment of these effects. In this contribution, the polyhedron method is used to estimate the thermodynamic properties of tourmaline, a common and widespread accessory phase, stable over a range of P–T–X conditions. The polyhedron method allows Δ H , S , V , C P and V m ( T , P ) properties to be estimated from a linear stoichiometric summation over the fractional properties of its polyhedron constituents. To allow for estimates of tourmaline, fractional thermodynamic properties for BIII and BIV polyhedra were derived. Mixing contributions to molar volume were evaluated and symmetrical mixing parameters derived for Al-Mg, Al-Fe and Al-Li interaction on tourmaline's Y-site and T-site Al-Si interaction. Evaluation of the estimated properties using experimental and natural equilibria between tourmaline and melts, minerals and hydrothermal fluids, shows that reliable semi-quantitative results are obtained. The boron contents in fluids coexisting with tourmaline are calculated to within an order of magnitude of measured content, and where anchor-points are available, agreement improves to within a factor of 2. Including tourmaline in petrogenetic modelling of metamorphic rocks indicates that its presence leads to disappearance of staurolite and garnet, among others, and modifies the X Mg of coexisting phases, in line with observations on natural rocks. 相似文献
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Thermodynamic calculations in petrology are generally performed at pressures and temperatures beyond the standard state conditions. Accurate prediction of mineral equilibria therefore requires knowledge of the heat capacity, thermal expansion and compressibility for the minerals involved. Unfortunately, such data are not always available. In this contribution we present a data set to estimate the heat capacity, thermal expansion and compressibility of mineral end‐members from their constituent polyhedra, based on the premise that the thermodynamic properties of minerals can be described by a linear combination of the fractional properties of their constituents. As such, only the crystallography of the phase of interest needs to be known. This approach is especially powerful for hypothetical mineral end‐members and for minerals, for which the experimental determination of their thermodynamic properties is difficult. The data set consists of the properties for 35 polyhedra in the system K–Na–Ca–Li–Be–Mg–Mn–Fe–Co–Ni–Zn–Al–Ti–Si–H, determined by multiple linear regression analysis on a data set of 111 published end‐member thermodynamic properties. The large number of polyhedra determined allows calculation of a much larger variety of phases than was previously possible, and the choice of constituents together with the large number of thermodynamic input data results in estimates with associated uncertainty of generally <5%. The quality of the data appears to be sufficiently accurate for thermodynamic modelling as demonstrated by modelling the stability of margarite in the CASH system and the position of the talc–staurolite–chloritoid–pyrope absent invariant point in the KMASH system. In both cases, our results overlap within error with published equivalents. 相似文献
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The thermodynamic properties of silicate minerals can be described as a linear combination of the fractional properties of their constituent polyhedra. In contrast, given the thermodynamic properties of these polyhedra, the thermodynamic properties of minerals can be estimated, where only the crystallography of the mineral needs to be known. Such estimates are especially powerful for hypothetical mineral end‐members or for minerals where experimental determination of their thermodynamic properties is difficult. In this contribution the fractional enthalpy, entropy and molar volume for 35 polyhedra have been determined using weighted multiple linear regression analysis on a data set of published mineral thermodynamic properties. The large number of polyhedra determined, allows calculation of a much larger variety of phases than was previously possible and the larger set of minerals used provides more confident fractional properties. The OH‐bearing minerals have been described by partial and total hydroxide coordinated components, which gives better results than previous models and precludes the need of a S–V term to improve estimates of entropy. However, the fractional thermodynamic properties only give adequate results for silicate minerals and double oxides, and should therefore not be used to estimate the properties of other minerals. The thermodynamic properties of ‘new’ minerals are calculated from a linear stoichiometric combination of their constituent polyhedra, resulting in estimates generally with associated uncertainty of <5%. The quality of such data appears to be of sufficient accuracy for thermodynamic modelling as shown for meta‐bauxites from the Alps and the Aegean, where the effect of Zn on the P–T stability of staurolite can be both qualitatively and quantitatively reproduced. 相似文献
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Post-emplacement serpentinization and related hydrothermal metamorphism in a kimberlite from Venetia, South Africa 总被引：2，自引：0，他引：2
G. R. STRIPP M. FIELD J. C. SCHUMACHER R. S. J. SPARKS G. CRESSEY 《Journal of Metamorphic Geology》2006,24(6):515-534
The common serpentine–diopside matrix assemblage in volcaniclastic kimberlite (VK) at the Venetia Mine, South Africa is ascribed to a secondary origin, because of post‐emplacement serpentinization and associated hydrothermal metamorphism. Volcaniclastic deposits with 20–30% porosity infill kimberlite pipes in the waning stages of kimberlite eruptions. Olivine macrocrysts are typically rimmed by talc and are pseudomorphed by lizardite, with minor magnetite. The fine matrix consists of mixtures of lizardite, chlorite, smectite, brucite, calcite, titanite and andradite, an assemblage which either pseudomorphed microcrysts or in‐filled voids. Locally we recognize microcryst pseudomorphs rich in sub‐microscopic mixtures of lizardite with smectite, and other microcryst pseudomorphs and void‐filling matrix rich in chlorite and lizardite. Interstitial lizardite and associated phyllosilicates (brucite, smectite and chlorite) crystallized progressively from meteoric or hydrothermally derived pore waters, and Si4+ and Mg2+ released into the fluid phase during serpentinization of olivine macrocrysts. Radial‐fibrous fringes of diopside microlites around crystals display void‐filling textures because of unrestricted growth into pore spaces. Secondary diopside is attributed to Si4+, Mg2+ and Ca2+ cations released into the fluid phase by interaction with olivine, calcite and plagioclase in siliceous xenoliths. The paucity of primary, fine‐grained groundmass phases resistant to alteration, for example, perovskite and spinel, precludes an origin for the intergrain matrix as altered interstitial ash, glass or a late‐stage kimberlite melt. Isovolumetric replacement of olivine results in a volume increase of 60% so that pore spaces in the original deposit can be easily filled up with serpentine. The source of Al3+ to form chlorite and smectite is attributed to alteration of plagioclase in xenoliths which comprise 20–30 vol.% of the deposit. Titanite, hydro‐andradite and second‐generation diopside precipitate as hydrothermal minerals from calcium‐bearing serpentinizing fluids in replacement reactions and as void‐filling minerals. Consideration of mineral equilibria in the CaO‐MgO‐SiO2‐H2O‐CO2 system constrains the common matrix assemblage of lizardite and diopside in XCO2)–T space. At 300 bar, the assemblage is stable only at temperatures below 370 °C and XCO2 < 0.01. This upper limit on temperature is well below the plausible solidus of ultrabasic magmas. Furthermore, the requirement of trace CO2 in the fluid phase implies a post‐emplacement external source rather than ‘autometamorphism’ from kimberlite‐derived fluids, because of high PCO2 commonly inferred for kimberlite magmas. 相似文献
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Mineral Chemistry and Metasomatic Growth of Aluminous Enclaves in Gedrite--Cordierite-Gneiss from Southwestern New Hampshire, USA 总被引：2，自引：0，他引：2
The aluminous enclaves occur in gedrite-cordierite-gneissesof the Middle Ordovician Ammonoosuc Volcanics, and are composedof combinations of the aluminous minerals sillimanite (Sill),kyanite, corundum (Cor), staurolite (St), sapphirine (Sa), andspinel (Sp), which are set in a matrix of cordierite (Crd) orplagioclase (Plag). Generally, where plagioclase is present,both it and the aluminous minerals are separated from gedrite(Ged) and rare hornblende (Hbl) by cordierite. The enclavesarc interpreted to have formed near the peak of Acadian (Devonian)metamorphism at sillimanite-staurolite-muscovite grade by reactionsthat were encountered during the pressure decrease which accompaniedthe rise of gneiss domes in the region. The enclaves are divided into two main types: (1) enclaves ofcordierite surrounding aluminous minerals; and (2) enclavesof cordierite and plagioclase surrounding aluminuous minerals.Sapphirine grains contain between 9?2 and 9?3 Al atoms per formulacalculated to 14 cations. Staurolites from the enclaves areMg-rich and have (Fe2++ Mn)/(Fe2++Mn+Mg) ratios of 0-59–0?64. The textures and mineralogy of the enclaves suggest that theserocks originally consisted of Ged+Sill?Qz?Hbl?Sp?Plag. Theseminerals reacted to form Crd+Aluminous Minerals?Plag. The mineralogyof both main types of enclaves can be explained by two analogoussets of continuous Fe-Mg reactions:The structure of the enclavessuggests that the mineral growth by the above reactions wasdiffusion controlled, which would have resulted from oversteppingthe above reactions (i.e. the P change exceeded the reactionrate). Therefore, chemical potential gradients (relative mobilityof diffusing components) between gedrite and sillimanite controlledthe location of mineral growth. The Fe-Mg ratio of the bulkcomposition and the proportions of non-Fe-Mg minerals (quartzand sillimanite) appear to determine which continuous Fe-Mgreactions were encountered. Examples of mineral sequences in the cordierite enclaves are:Sill (core)/St+Crd/Ged (matrix); Cor+Crd (core)/Ged (matrix),and Sill (core)/St+Crd/Sa+Crd/Ged (matrix). Examples of themineral sequences in the cordierite-plagioclase enclaves are:Sill (core)/St+Plag/Plag+Crd/Hbl+Ged (matrix); Cor+Plag (core)/St+Plag/Sa+Plag/Ged+ Hbl (matrix); and St+Plag (core)/Plag+Crd/Ged+Hbl (matrix). P–µFeMg–1 diagrams proved to be an importanttool for understanding and illustrating the development of theenclaves. These diagrams allow one to view simultaneously allthe discontinuous and continuous Fe-Mg reactions along a P–µH2O(or T) rock path. With this information it is possible to determinequalitatively which reactions and what sequence of reactionsmight be encountered by bulk compositions with variable Fe-Mgratios and modal proportions of phases. 相似文献
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High-Temperature Metamorphism and the Role of Magmatic Heat Sources at the Rogaland Anorthosite Complex in Southwestern Norway 总被引：3，自引：0，他引：3
The Rogaland complex covers 相似文献
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