The thermodynamic properties of 154 mineral end-members, 13 silicate liquid end-members and 22 aqueous fluid species are presented in a revised and updated data set. The use of a temperature-dependent thermal expansion and bulk modulus, and the use of high-pressure equations of state for solids and fluids, allows calculation of mineral–fluid equilibria to 100 kbar pressure or higher. A pressure-dependent Landau model for order–disorder permits extension of disordering transitions to high pressures, and, in particular, allows the alpha–beta quartz transition to be handled more satisfactorily. Several melt end-members have been included to enable calculation of simple phase equilibria and as a first stage in developing melt mixing models in NCKFMASH. The simple aqueous species density model has been extended to enable speciation calculations and mineral solubility determination involving minerals and aqueous species at high temperatures and pressures. The data set has also been improved by incorporation of many new phase equilibrium constraints, calorimetric studies and new measurements of molar volume, thermal expansion and compressibility. This has led to a significant improvement in the level of agreement with the available experimental phase equilibria, and to greater flexibility in calculation of complex mineral equilibria. It is also shown that there is very good agreement between the data set and the most recent available calorimetric data.

An internally consistent thermodynamic data set for phases of petrological interest

A revised regular solution-type thermodynamic model for twelve-component silicate liquids in the system SiO2-TiO2-Al2O3-Fe2O3-Cr2O3-FeO-MgO-CaO-Na2O-K2O-P2O5-H2O is calibrated. The model is referenced to previously published standard state thermodynamic properties and is derived from a set of internally consistent thermodynamic models for solid solutions of the igneous rock forming minerals, including: (Mg,Fe2+,Ca)-olivines, (Na,Mg,Fe2+,Ca)M2 (Mg,Fe2+, Ti, Fe3+, Al)M1 (Fe3+, Al,Si)2TETO6-pyroxenes, (Na,Ca,K)-feldspars, (Mg,Fe2+) (Fe3+, Al, Cr)2O4-(Mg,Fe2+)2 TiO4 spinels and (Fe2+, Mg, Mn2+)TiO3-Fe2O3 rhombohedral oxides. The calibration utilizes over 2,500 experimentally determined compositions of silicate liquids coexisting at known temperatures, pressures and oxygen fugacities with apatite ±feldspar ±leucite ±olivine ±pyroxene ±quartz ±rhombohedral oxides ±spinel ±whitlockite ±water. The model is applicable to natural magmatic compositions (both hydrous and anhydrous), ranging from potash ankaratrites to rhyolites, over the temperature (T) range 900°–1700°C and pressures (P) up to 4 GPa. The model is implemented as a software package (MELTS) which may be used to simulate igneous processes such as (1) equilibrium or fractional crystallization, (2) isothermal, isenthalpic or isochoric assimilation, and (3) degassing of volatiles. Phase equilibria are predicted using the MELTS package by specifying bulk composition of the system and either (1) T and P, (2) enthalpy (H) and P, (3) entropy (S) and P, or (4) T and volume (V). Phase relations in systems open to oxygen are determined by directly specifying the fo2 or the T-P-fo2 (or equivalently H-P-fo2, S-P-fo2, T-V-fo2) evolution path. Calculations are performed by constrained minimization of the appropriate thermodynamic potential. Compositions and proportions of solids and liquids in the equilibrium assemblage are computed.

Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures

A number of experiments have been conducted in order to study the equilibria between olivine and basaltic liquids and to try and understand the conditions under which olivine will crystallize. These experiments were conducted with several basaltic compositions over a range of temperature (1150-1300 ° C) and oxygen fugacity (10-°.~s-10 -12 arm.) at one atmosphere total pressure. The phases in these experimental runs were analyzed with the electron microprobe and a number of empirical equations relating the composition of olivine and liquid were determined. The distribution coefficient o, (X~o/ (Xreo) K/~- i'~-Liq \ O1 t-XFeoJ (X~go) relating the partioning of iron and magnesium between olivine and liquid is equal to 0.30 and is independent of temperature. This means that the composition of olivine can be used to determine the magnesium to ferrous iron ratio of the liquid from which it crystallized and conversely to predict the olivine composition which would crystallize from a liquid having a particular magnesium to ferrous iron ratio. A model (saturation surface) is presented which can be used to estimate the effective solubility of olivine in basaltic melts as a fune¢ioa of temperature. This model is useful in predicting the temperature at which olivine and a liquid of a particular composition can coexist at equilibrium.

http://www.mantleplumes.org/WebDocuments/RoederEmslie.pdf

Olivine-Liquid Equilibrium

The composition of chromian spinel in alpine-type peridotites has a large reciprocal range of Cr and Al, with increasing Cr# (Cr/(Cr+Al)) reflecting increasing degrees of partial melting in the mantle. Using spinel compositions, alpine-type peridotites can be divided into three groups. Type I peridotites and associated volcanic rocks contain spinels with Cr# 0.60, and Type II peridotites and volcanics are a transitional group and contain spinels spanning the full range of spinel compositions in Type I and Type II peridotites. Spinels in abyssal peridotites lie entirely within the Type I spinel field, making ophiolites with Type I alpine-type peridotites the most likely candidates for sections of ocean lithosphere formed at a midocean ridge. The only modern analogs for Type III peridotites and associated volcanic rocks are found in arc-related volcanic and intrusive rocks, continental intrusive assemblages, and oceanic plateau basalts. We infer a sub-volcanic arc petrogenesis for most Type III alpine-type peridotites. Type II alpine-type peridotites apparently reflect composite origins, such as the formation of an island-arc on ocean crust, resulting in large variations in the degree and provenance of melting over relatively short distances. The essential difference between Type I and Type III peridotites appears to be the presence or absence of diopside in the residue at the end of melting.

Chromian spinel as a petrogenetic indicator in abyssal and alpine-type peridotites and spatially associated lavas

Knowledge of temperature and pressure, however qualitative, has been central to our views of geology since at least the early 19th century. In 1822, for example, Charles Daubeny presented what may be the very first “Geological Thermometer,” comparing temperatures of various geologic processes (Torrens 2006). Daubeny (1835) may even have been the first to measure the temperature of a lava flow, by laying a thermometer on the top of a flow at Vesuvius—albeit several months following the eruption, after intervening rain (his estimate was 390°F). In any case, pressure ( P ) and temperature ( T ) estimation lie at the heart of fundamental questions: How hot is Earth, and at what rate has the planet cooled. Are volcanoes the products of thermally driven mantle plumes? Where are magmas stored, and how are they transported to the surface—and how do storage and transport relate to plate tectonics? Well-calibrated thermometers and barometers are essential tools if we are to fully appreciate the driving forces and inner workings of volcanic systems.

This chapter presents methods to estimate the P-T conditions of volcanic and other igneous processes. The coverage includes a review of existing geothermometers and geobarometers, and a presentation of approximately 30 new models, including a new plagioclase-liquid hygrometer. Our emphasis is on experimentally calibrated “thermobarometers,” based on analytic expressions using P or T as dependent variables. For numerical reasons (touched on below) such expressions will always provide the most accurate means of P-T estimation, and are also most easily employed. Analytical expressions also allow error to be ascertained; in the absence of estimates of error, P-T estimates are nearly meaningless. This chapter is intended to complement the chapters by Anderson et al. (2008), who cover granitic systems, and by Blundy and Cashman (2008) and Hansteen and Klugel (2008), who consider additional methods …

Thermometers and Barometers for Volcanic Systems

Compositional fields for spinels from a wide variety of mafic– a wide range of conditions from mafic and ultramafic ultramafic igneous rock types and tectonic environments have been magmas and, in the case of chromites, are often among determined from a global database of over 26 000 analyses. the first phases to crystallize. They also exhibit a wide These fields are defined using contoured data density plots based range of solid solution, the thermodynamics of which has on the spinel prism, and plots of TiO2 vs ferric iron, for mantle been studied extensively (O’Neill & Wall, 1987; Mattioli xenoliths, ophiolitic rocks, continental layered intrusions, alkalic & Wood, 1988; Wood, 1990; Sack & Ghiorso, 1991; and lamprophyric rocks, tholeiitic basalts, Alaskan ultramafic Poustovetov, 2000). They are relatively refractory and complexes and komatiites. Several trends appear regularly in the resistant to alteration, particularly compared with other various environments: a trend of widely variable Cr/(Cr + Al) high-temperature igneous minerals such as olivine. They at low Fe/(Mg + Fe) (the Cr–Al trend); increasing Fe, occur in a high proportion of terrestrial mafic and ultraFe/(Mg + Fe) and TiO2 at constant Cr/(Cr + Al) mafic rocks, and a very large volume of microprobe data (Fe–Ti trend); a trend found primarily in kimberlites, similar is available on their compositions. to Fe–Ti but at constant Fe/(Mg + Fe); and an unusual Publications on spinels (particularly chromites) have trend of increasing Al found only in layered intrusions. The routinely used compositional fields based on the spinel Cr–Al and Fe–Ti trends are both found to varying degrees in prism to compare populations of analyses. Some of tholeiitic basalts. The Cr–Al trend is prevalent in rocks that these fields have remarkable longevity, particularly those have equilibrated over a range of pressures, whereas the Fe–Ti defined for layered intrusions and Alpine peridotites by trend is dominantly due to low-pressure fractionation. The most Irvine (1967, 1977). Many new data have become availCr-rich chromites found in nature occur in boninites, diamondable in the last 20 years, however, and it has become bearing kimberlites, some komatiites and ophiolitic chromitites. apparent that a new compilation of data is necessary to Exceptionally reduced chromites are found in some komatiites reflect this. The prime purpose of this paper is to analyse and in ophiolitic chromitites. Detrital chromites from the a global database of about 26 000 spinel analyses from Witwatersrand conglomerates are of komatiitic provenance. terrestrial igneous and metamorphosed igneous rocks, and to extract from this database the characteristic compositional fields of spinels from the wide variety of magma types and tectonic environments in which they occur.

https://eps.mcgill.ca/~courses/c186-501/2010/Week10_Readings/Kristal_Leung_Range_Of_Spinel_Compositions_2001.pdf

The Range of Spinel Compositions in Terrestrial Mafic and Ultramafic Rocks

Crystallization of Chromite and Chromium Solubility in Basaltic Melts

The Irvine olivine-spinel geothermometer, as formulated by Jackson (1969), appears to yield magmatic temperatures when applied to plutonic rocks such as the Stillwater Complex but Evans and Wright (1972) have demonstrated that it gives temperatures in excess of 2,000 ° C when applied to volcanic assemblages. A re-evaluation of the geothermometer has shown that more realistic temperatures can be obtained for volcanic rocks by using a different free energy value of FeCr2O4 in the formulation. The revised geothermometer gives temperatures in the range 1,100–1,300 ° C for samples from Kilauea and 500–800 ° C for basic plutonic rocks from layered intrusions, indicating that Mg and Fe2+ have re-equilibrated at subsolidus temperatures in these intrusions as suggested by Irvine (1965). This theory was tested by heating uncrushed natural samples from layered intrusions to magmatic temperatures for periods ranging from two days to four weeks. The result was a marked increase in the Mg/Fe2+ ratio in the spinels and a decrease in the Mg/Fe2+ ratio in the olivines, confirming that considerable subsolidus re-equilibration had taken place in the unheated samples.

A re-evaluation of the olivine-spinel geothermometer

Chromite, spinel and magnetite compositions from a wide range of geological environments have been accumulated from published and unpublished sources in order to better characterize the spinel-group mineral as a function of environment of formation. Approximately 17 000 analyses have been included in a spinel database. The factors that control the crystallization of spinel-group minerals from a basaltic melt are discussed, and their composition is compared for rocks from various terrestrial environments, including mid-ocean-ridge basalts, ocean-island basalts, boninites, ophiolites, mantle xenoliths and kimberlites. The variation in composition of the spinel-group minerals from terrestrial sources are then compared to that in chondritic meteorites. The composition of chromite in unequilibrated chondrites is consistent with crystallization from a chondritic melt, whereas its composition in equilibrated chondrites is consistent with metamorphism at temperatures in the range of 600-800 degrees C.

Peter L. Roeder

Papers

Olivine-Liquid Equilibrium

The Range of Spinel Compositions in Terrestrial Mafic and Ultramafic Rocks

Crystallization of Chromite and Chromium Solubility in Basaltic Melts

A re-evaluation of the olivine-spinel geothermometer

Chromite; from the fiery rain of chondrules to the Kilauea Iki lava lake