The truth and beauty of chemical potentials

This essay in honour of Mike Brown addresses aspects of chemical equilibrium and equilibration in rocks, with a focus on the role that chemical potentials play. Chemical equilibrium is achieved by diffusive attening of chemical potential gradients. The idea of equilibration volume is developed, and the way equilibration volumes may evolve along a pressure-temperature path is discussed. The effect of the environment of an equilibration volume is key to understanding the evolution of the equilibration volume with changing conditions. The likely behaviour of equilibration volumes is used to suggest why preservation of equilibrium mineral assemblages and mineral compositions from metamorphism tends to occur. This line of logic then provides the conceptual support to conventional equilibrium thermodynamic approaches to studying rocks, using, for example, thermobarometry and pseudosections.PostprintPeer reviewe

Mineral-petrochemical wallrock alteration of rocks in Bericul gold-ore deposit (Kuznetsk Alatau)

The distribution of mineral associations in near-veined zonal propylite-beresite metasomatic columns of mesothermal Bericul gold-ore deposit was analyzed. However, the polymineral composition in the inner (axial and adjacent with it rear) zones is inconsistent to the existing metasomatic column theoretical model. According to Korzhinskii metasomatic zoning theory, implied monomineral (quartz) and binary-mineral (quartz, sericite) compositions are characteristic of axial and rear zones, respectively. In common with above-mentioned facts, the zoning formation of differential component mobility is influenced by two additional factors: counter diffusion of components from fractured fluids into pores and diffusion mechanism of mass transfer it's from pores fluids into fractured of rock-fluid systems

Calculation of the relative metastabilities of proteins using the CHNOSZ software package

<p>Abstract</p> <p>Background</p> <p>Proteins of various compositions are required by organisms inhabiting different environments. The energetic demands for protein formation are a function of the compositions of proteins as well as geochemical variables including temperature, pressure, oxygen fugacity and pH. The purpose of this study was to explore the dependence of metastable equilibrium states of protein systems on changes in the geochemical variables.</p> <p>Results</p> <p>A software package called CHNOSZ implementing the revised Helgeson-Kirkham-Flowers (HKF) equations of state and group additivity for ionized unfolded aqueous proteins was developed. The program can be used to calculate standard molal Gibbs energies and other thermodynamic properties of reactions and to make chemical speciation and predominance diagrams that represent the metastable equilibrium distributions of proteins. The approach takes account of the chemical affinities of reactions in open systems characterized by the chemical potentials of basis species. The thermodynamic database included with the package permits application of the software to mineral and other inorganic systems as well as systems of proteins or other biomolecules.</p> <p>Conclusion</p> <p>Metastable equilibrium activity diagrams were generated for model cell-surface proteins from archaea and bacteria adapted to growth in environments that differ in temperature and chemical conditions. The predicted metastable equilibrium distributions of the proteins can be compared with the optimal growth temperatures of the organisms and with geochemical variables. The results suggest that a thermodynamic assessment of protein metastability may be useful for integrating bio- and geochemical observations.</p

On equilibrium in non-hydrostatic metamorphic systems

Metamorphic geology has accumulated a huge body of observation on mineral assemblages that reveal strong patterns in occurrence, summarized, for example, in the idea of metamorphic facies. On the realization that such patterns needed a simple explanation, there has been considerable a posteriori success from adopting the idea that equilibrium thermodynamics can be used on mineral assemblages to make sense of the patterns in terms of, for example, the pressure and temperature of formation of mineral assemblages. In doing so, a particularly simple implicit assumption is made, that mineral assemblages operate essentially hydrostatically. Structural geologists have studied the same rocks for different ends, but, remarkably, the phenomena they are interested in depend on non-hydrostatic stress. We look at the effect of such behaviour on mineral equilibria. With adoption of some plausible assumptions about how metamorphism in the crust works, the consequence of minerals being non-hydrostatically stressed is commonly second order in equilibrium calculations

Dioctahedral mixed K-Na-micas and paragonite in diagenetic to low-temperature metamorphic terrains: bulk rock chemical, thermodynamic and textural constraints

Abstract Metamorphic mineral assemblages in low-temperature metaclastic rocks often contain paragonite and/or its precursor metastable phase (mixed K-Na-white mica). Relationships between the bulk rock major element chemistries and the formation of paragonite at seven localities from Central and SE-Europe were studied, comparing the bulk chemical characteristics with mineral assemblage, mineral chemical and metamorphic petrological data. Considerable overlaps between the projection fields of bulk chemistries of the Pg-free and Pg-bearing metaclastic rocks indicate significant differences between the actual (as analyzed) and effective bulk chemical compositions. Where inherited, clastic, inert phases/constituents were excluded, it was found that a decrease in Na/(Na+Al*) and in K/(K+Al*) ratios of rocks favors the formation and occurrence of Pg and its precursor phases (Al* denotes here the atomic quantity of aluminum in feldspars, white micas and “pure” hydrous or anhydrous aluminosilicates). In contrast to earlier suggestions, enrichment in Na and/or an increase in Na/K ratio by themselves do not lead to formation of paragonite. Bulk rock chemistries favorable to formation of paragonite and its precursor phases are characterized by enrichment in Al and depletion in Na, K, Ca (and also, Mg and Fe2+). Such bulk rock chemistries are characteristic of chemically “mature” (strongly weathered) source rocks of the pelites and may also be formed by synand post-sedimentary magmatism-related hydrothermal (leaching) activity. What part of the whole rock is active in determining the effective bulk chemistry was investigated by textural examination of diagenetic and anchizone-grade samples. It is hypothesized that although solid phases act as local sources and sinks, transport of elements such as Na through the grain boundaries have much larger communication distances. Sodium-rich white micas nucleate heterogeneously using existing phyllosilicates as templates and are distributed widely on the thin section scale. The results of modeling by THERMOCALC suggest that paragonite preferably forms at higher pressures in low-T metapelites. The stability fields of Pg-bearing assemblages increase, the Pg-in reaction line is shifted towards lower pressures, while the stability field of the Chl-Ms-Ab-Qtz assemblage decreases and is shifted towards higher temperatures with increasing Al* content and decreasing Na/(Na+Al*) and K/(K+Al*) ratios

Order/disorder phase transition in cordierite and its possible relationship to the development of symplectite reaction textures in granulites

Based on a consistent set of empirical interatomic potentials, static structure energy calculations of various Al/Si configurations in the supercell of Mg-cordierite and Monte Carlo simulations the phase transition between the orthorhombic and hexagonal modifications of cordierite (Crd) is predicted at 1623 K. The temperature dependences of the enthalpy, entropy, and free energy of the Al/Si disorder were calculated using the method of thermodynamic integration. The simulations suggest that the commonly observed crystallization of cordierite in the disordered hexagonal form could be related to a tendency of Al to occupy T1 site, which is driven by local charge balance. The increase in the Al fraction in the T1 site over the ratio of 2/3(T1): 1/3(T2), that characterizes the ordered state, precludes formation of the domains of the orthorhombic phase. This intrinsic tendency to the crystallization of the metastable hexagonal phase could have significantly postponed the formation of the association of orthorhombic cordierite and orthopyroxene over the association of quartz and garnet in metapelites subjected to granulite facies metamorphism. The textures of local metasomatic replacement (the formation of Crd + Opx or Spr + Crd symplectites between the grains of garnet and quartz) indicate the thermodynamic instability of the association of Qtz + Grt at the moment of the metasomatic reaction. This instability could have been caused by the difficulty of equilibrium nucleation of orthorhombic cordierite

Solubility of Rock in Steam Atmospheres of Planets

Extensive experimental studies show that all major rock-forming elements (e.g., Si, Mg, Fe, Ca, Al, Na, K) dissolve in steam to a greater or lesser extent. We use these results to compute chemical equilibrium abundances of rocky-element-bearing gases in steam atmospheres equilibrated with silicate magma oceans. Rocky elements partition into steam atmospheres as volatile hydroxide gases (e.g., Si(OH)4, Mg(OH)2, Fe(OH)2, Ni(OH)2, Al(OH)3, Ca(OH)2, NaOH, KOH) and via reaction with HF and HCl as volatile halide gases (e.g., NaCl, KCl, CaFOH, CaClOH, FAl(OH)2) in much larger amounts than expected from their vapor pressures over volatile-free solid or molten rock at high temperatures expected for steam atmospheres on the early Earth and hot rocky exoplanets. We quantitatively compute the extent of fractional vaporization by defining gas/magma distribution coefficients and show that Earth's subsolar Si/Mg ratio may be due to loss of a primordial steam atmosphere. We conclude that hot rocky exoplanets that are undergoing or have undergone escape of steam-bearing atmospheres may experience fractional vaporization and loss of Si, Mg, Fe, Ni, Al, Ca, Na, and K. This loss can modify their bulk composition, density, heat balance, and interior structure

Fenites associated with carbonatite complexes : a review

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record.Carbonatites and alkaline-silicate rocks are the most important sources of rare earth elements (REE) and niobium (Nb), both of which are metals imperative to technological advancement and associated with high risks of supply interruption. Cooling and crystallizing carbonatitic and alkaline melts expel multiple pulses of alkali-rich aqueous fluids which metasomatize the surrounding country rocks, forming fenites during a process called fenitization. These alkalis and volatiles are original constituents of the magma that are not recorded in the carbonatite rock, and therefore fenites should not be dismissed during the description of a carbonatite system. This paper reviews the existing literature, focusing on 17 worldwide carbonatite complexes whose attributes are used to discuss the main features and processes of fenitization. Although many attempts have been made in the literature to categorize and name fenites, it is recommended that the IUGS metamorphic nomenclature be used to describe predominant mineralogy and textures. Complexing anions greatly enhance the solubility of REE and Nb in these fenitizing fluids, mobilizing them into the surrounding country rock, and precipitating REE- and Nb-enriched micro-mineral assemblages. As such, fenites have significant potential to be used as an exploration tool to find mineralized intrusions in a similar way alteration patterns are used in other ore systems, such as porphyry copper deposits. Strong trends have been identified between the presence of more complex veining textures, mineralogy and brecciation in fenites with intermediate stage Nb-enriched and later stage REE enriched magmas. However, compiling this evidence has also highlighted large gaps in the literature relating to fenitization. These need to be addressed before fenite can be used as a comprehensive and effective exploration tool.This research has received funding from the European Union’s Horizon 2020 research and innovation programme under grant No 689909