Geochemical discrimination of different magma series and their differentiation products using immobile elements

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

Trace element and isotopic effects of combined wallrock assimilation and fractional crystallization

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

Volcanic eruptions are an important natural cause of climate change on many timescales. A new capability to predict the climatic response to a large tropical eruption for the succeeding 2 years will prove valuable to society. In addition, to detect and attribute anthropogenic influences on climate, including effects of greenhouse gases, aerosols, and ozone-depleting chemicals, it is crucial to quantify the natural fluctuations so as to separate them from anthropogenic fluctuations in the climate record. Studying the responses of climate to volcanic eruptions also helps us to better understand important radiative and dynamical processes that respond in the climate system to both natural and anthropogenic forcings. Furthermore, modeling the effects of volcanic eruptions helps us to improve climate models that are needed to study anthropogenic effects. Large volcanic eruptions inject sulfur gases into the stratosphere, which convert to sulfate aerosols with an e-folding residence time of about 1 year. Large ash particles fall out much quicker. The radiative and chemical effects of this aerosol cloud produce responses in the climate system. By scattering some solar radiation back to space, the aerosols cool the surface, but by absorbing both solar and terrestrial radiation, the aerosol layer heats the stratosphere. For a tropical eruption this heating is larger in the tropics than in the high latitudes, producing an enhanced pole-to-equator temperature gradient, especially in winter. In the Northern Hemisphere winter this enhanced gradient produces a stronger polar vortex, and this stronger jet stream produces a characteristic stationary wave pattern of tropospheric circulation, resulting in winter warming of Northern Hemisphere continents. This indirect advective effect on temperature is stronger than the radiative cooling effect that dominates at lower latitudes and in the summer. The volcanic aerosols also serve as surfaces for heterogeneous chemical reactions that destroy stratospheric ozone, which lowers ultraviolet absorption and reduces the radiative heating in the lower stratosphere, but the net effect is still heating. Because this chemical effect depends on the presence of anthropogenic chlorine, it has only become important in recent decades. For a few days after an eruption the amplitude of the diurnal cycle of surface air temperature is reduced under the cloud. On a much longer timescale, volcanic effects played a large role in interdecadal climate change of the Little Ice Age. There is no perfect index of past volcanism, but more ice cores from Greenland and Antarctica will improve the record. There is no evidence that volcanic eruptions produce El Nino events, but the climatic effects of El Nino and volcanic eruptions must be separated to understand the climatic response to each.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/1998RG000054

Volcanic eruptions and climate

Ultrasonic longitudinal acoustic velocities in oxidized silicate liquids indicate that the pressure derivative of the partial-molar volume of Fe2O3 is the same in iron-rich alkali-, alkaline earth- and natural silicate melt compositions at 1 bar. The dV/dP for multicomponent silicate liquids can be expressed as a linear combination of partial-molar constants plus a positive excess term for Na2O−Al2O3 mixing. Partial-molar properties for FeO and Fe2O3 components allow extension of the empirical expression of Sack et al. (1980) to permit the calculation of Fe-redox equilibrium in a natural silicate liquid as a function of composition, temperature, fo2 and pressure; a more formal thermodynamic expression is presented in the Appendix. The predicted equilibrium fo2 of natural silicate melts, of fixed oxygen content, closely parallels that defined by the metastable assemblage fayalite+magnetite+β-quartz (FMQ), in pressure-temperature space. A silicate melt initially equilibrated at 3 GPa and FMQ, will remain within approximately 0.5 log10 units of FMQ during its closed-system ascent. Thus, for magmas closed to oxygen, iron-redox equilibrium in crystal-poor pristine glassy lavas represents an excellent probe of the relative oxidation state of their source regions.

The compressibility of silicate liquids containing Fe 2 O 3 and the effect of composition, temperature, oxygen fugacity and pressure on their redox states

The co-existing microphenocrysts of magnetite and ilmenite together with the ferromagnesian silicates in salic volcanic rocks have been analysed with the electron microprobe. The temperatures and oxygen fugacities of the oxide equilibration have been estimated from the curves of Buddington and Lindsley (1965). The co-existing ferromagnesian silicate phenocrysts are either iron-rich olivine, or orthopyroxene or biotite and amphibole; for each of these groups of phenocrysts, the oxide equilibration data are specific and fall on three distinct curves, parallel to experimental oxygen buffer curves. Many of the investigated rhyolites were quenched at temperatures near 900°C, which may represent liquidus temperatures for those with sparse phenocrysts, and also the intrusion temperature of water-undersaturated granites. The composition of the biotite phenocrysts, which are Al-poor and Ti-rich, taken in conjunction with the oxide data, suggest that two Lassen dacites precipitated biotite at a water fugacity of approximately 400 bars. The composition of the later crystallizing ferromagnesian silicates, particularly the pyroxenes which show a wide range in Fe/Mg ratio, is strongly influenced by the prior crystallization of the oxide phases. If the biotite phenocrysts are typical of acid liquids, then they are incapable of generating by fractionation a peraluminous residual liquid; rather they would tend to make a liquid peralkaline.

The iron-titanium oxides of salic volcanic rocks and their associated ferromagnesian silicates

Densities of Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-TiO2-SiO2 liquids: New measurements and derived partial molar properties

At present the best estimates of the oxygen fugacity of spinel-lherzolites that could be the source material of basic magmas is about five log units below the Ni−NiO buffer to one above it. However partially glassy basic lavas, ranging from MORBs to minettes, all with olivine on their liquidus, cover a wider range, and may have oxygen fugacities that extend to four log units above NNO. Surprisingly the range of oxygen fugacities observed in silicic lavas and ashflows with quartz phenocrysts is smaller, despite a crustal dominated evolution. The peralkaline silicic lava type pantellerite is the most reduced, equivalent to MORBs, whereas the large volume ashflows with phenocrysts of hornblende and/or sphene are the most oxidised. As the concentration of water in the basic lavas is correlated with increase in their redox state, it would seem that water could be the agent of this increase. That this is unlikely is seen in the behavior of silicic ashflows and lavas, particularly those of Yellowstone. Here the silicic magmas of the last 2Ma contain about 2 wt% FeO(total), and typically phenocrysts of fayalite, quartz and Fe−Ti oxides. Despite extensive exchange of the 18O of the magma with meteoric water after caldera collapse (Hildreth et al. 1984), there is no displacement of the redox equilibria. Thus the thermal dissociation of molecular H2O to H2, and its subsequent diffusive loss to cause oxidation must have been minimal. This could only be so if the activity of water was small, as it would be if H2O reacted with the silicate liquid to form OH groups (Stolper 1982). The conclusion is that silicic magmas with small amounts of iron and large amounts of water do not have their redox states reset, which in turn presumably reflect their generation. By analogy basic magmas with large amounts of iron and far less water are even less likely to have their redox equilibria disturbed, so that their oxygen fugacities will also reflect their source regions. The effect of pressure on the ferric-ferrous equilibrium in basic magmas can be calculated from experimental measurements of the partial molar volumes of FeO and Fe2O3, and their pressure derivatives ϖV/ϖP, in silicate liquids. The effect of pressure is found to be about the same on the liquid as it is for various solid oxygen buffers. Accordingly there should be mantle source regions covering the same range of oxygen fugacity as that found in basic lavas, but so far samples of spinel-lherzolite of equivalent oxygen fugacity to minettes or other potassic lavas have not been found. Whether or not the redox state of phlogopite-pyroxenites is equivalent to these potassic lavas cannot be established without experiment.

Ian S. E. Carmichael

Papers

The compressibility of silicate liquids containing Fe 2 O 3 and the effect of composition, temperature, oxygen fugacity and pressure on their redox states

The iron-titanium oxides of salic volcanic rocks and their associated ferromagnesian silicates

Densities of Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-TiO2-SiO2 liquids: New measurements and derived partial molar properties

The redox states of basic and silicic magmas: a reflection of their source regions?

Oxidation states of mid-ocean ridge basalt glasses