高温高压下黄铁矿热力学性质的第一性原理研究

黄铁矿是自然界中分布最为广泛的硫化物矿物,同时也是重要的造矿矿物,在金属矿床、沉积岩、变质岩、花岗岩、基性-超基性岩浆岩、以及地幔岩中都有大量出现。因此,研究黄铁矿在不同温度压力下的热力学性质可以为深入探讨与黄铁矿有关的成岩、成矿、成藏问题提供有用的矿物学依据。本文利用基于密度泛函微扰理论的第一性原理方法,采用准谐近似计算了黄铁矿在高温高压下的热力学性质。我们计算的黄铁矿的晶格常数、零压下的体积模量及其对压力的导数与前人的实验及理论计算结果吻合得很好,零压下等压热容和熵随温度的变化与实验结果有很好的一致性。尤其是,本文计算了直至2500K、100GPa的高温高压下黄铁矿的等温体积模量、热膨胀系数、热容和熵等热力学性质。这为在有硫参与的情况下,人们开展下地壳-岩石圈地幔深度的地球动力学模拟和建立地球物理模型提供了有用的信息。     

Kinetics and thermochemistry of amyl xanthate adsorption by pyrite and marcasite

The kinetics and thermochemistry of the xanthate adsorption reaction on pyrite and marcasite were evaluated with respect to the existing theory. The rate of xanthate adsorption was studied in a stirred reactor and the xanthate concentration was determined by UV spectrophotometry as a function of time. The heat of the adsorption reaction was measured with a microcalorimeter. The results from both experiments indicate that xanthate adsorption by pyrite or marcasite involves the formation of dixanthogen by an electrochemical reaction at the solid surface which supports the conclusions of other investigators:

$\text{1}\text{2}\text{O}{}_2\text{(aq) =}\text{1}\text{2}\text{O}{}_2\text{(ad) 2X + 2H}{}^{\mathrm{+}}\text{+}\text{1}\text{2}\text{O}{}_2\text{→ X}{}_2\text{(ad) + H}{}_2\text{O}$

The rate of the adsorption reaction was found to be approximately one-half order with respect to the xanthate concentration and to have an activation energy of 7.5 kcal/mole. Additionally, the rate was found to have a slight dependence on pH under certain conditions. In view of these results, it appears that the adsorption reaction is controlled by electrochemical discharge at the pyrite surface. Analysis of the data in terms of an electrochemical kinetic model successfully explained the observed rate phenomena.The measured heat of the adsorption reaction at low pH was found to be between ?63 and ?56 kcal/mole of adsorbed dixanthogen and independent of surface coverage. These experimental heats of adsorption agree with the value of ?57 kcal/mole of dixanthogen calculated for the oxidation of xanthate by oxygen from thermodynamic data reported in the literature.     

The thermodynamic properties of pyrrhotite and pyrite: A re-evaluation

On a plot of log sulfur activity versus inverse absolute temperature, the variation in published pyrite/pyrrhotite curves below 500°C is larger than expected from the precision of the measurements. The precise data by Rau (1976) fall between interpretations by Scott and Barnes (1971) and by Toulmin and Barton (1964) and are recommended.Scott and Barnes calibrated sulfur fugacities in the system Fe-Zn-S, against the data of Toulmin and Barton, but this involved a double extrapolation of empirical relationships, to and from a region where fugacities in pyrrhotite are unmeasured. Regular-solution models offer no improvement. An apparent interruption in the properties of the high-temperature pyrrhotite solid solution, at the composition Fe₇S₈ (Powell, 1983) is probably due to the inclusion of metastable microdomains of monoclinic pyrrhotite in some of Rau's experimental runs, rather than to an equilibrium change of structure. Hence, the uncertainties of extrapolation are unlikely to account for the displacement of the pyrite/pyrrhotite curve of Scott and Barnes. There may be a systematic error in the composition of pyrrhotite inferred by Scott and Barnes from X-ray lattice spacings, due to the effects of preparation-dependent ordering.Other influences on pyrrhotite thermodynamics are discussed. There is a maximum in the pyrrhotite fundamental unit-cell parameter, “a,” as composition is changed. This maximum shifts towards the Fe-rich boundary of pyrrhotite as temperature is increased, so it suggests a contribution from intrinsic defects, even at low temperatures. The thermodynamic effects of pressure need recalculating to suit these unit-cell data.     

Constraints on the thermodynamic mixing properties of plagioclase feldspars

Taking account of the Cˉ1/Iˉ1 (Al/Si order/disorder) transformation at high temperatures in the albite-anorthite solid solution leads to a simple model for the mixing properties of the high structural state plagioclase feldspars. The disordered (Cˉ1) solid solution can be treated as ideal (constant activity coefficient) and, for anorthite-rich compositions, deviations from ideality can be ascribed to cation ordering. Values of the activity coefficient for anorthite in the Cˉ1 solid solution (γ _An ^Cˉ1 ) are then controlled by the free energy difference between Cˉ1 and Iˉ1 anorthite at the temperature (T) of interest according to the relation: ΔˉG _ord ^Iˉ1 ⇌Cˉ1 =RT ln γ _An ^Cˉ1 . If the Iˉ1⇌Cˉ1 transformation in pure anorthite is treated, to a first approximation, as first order and the enthalpy and entropy of ordering are taken as 3.7±0.6 kcal/mole (extrapolated from calorimetric data) and 1.4–2.2 cal/mole (using an equilibrium order/disorder temperature for An₁₀₀ of 2,000–2,250 K), a crude estimate of γ _An ^Cˉ1 for all temperatures can be made. The activity coefficient of albite in the Cˉ1 solid solution (γ _Ab ^Cˉ1 ) can be taken as 1.0. The possible importance of this model lies in its identification of the principal constraints on the mixing properties rather than in the actual values of γ _An ^Cˉ1 and γ _Ab ^Cˉ1 obtained. In particular it is recognised that γ _An ^Cˉ1 depends critically on ordering in anorthite as well as, at lower temperatures, any ordering in the Cˉ1 solid solution. A brief review of activity-composition data, from published experiments involving ranges of plagioclase compositions and from the combined heats of mixing plus Al-avoidance entropy model (Newton et al. 1980), reveals some inconsistencies. The values of γ _An ^Cˉ1 calculated using the approach of Newton et al. (1980), although consistent with Orville's (1972) ion exchange data, are slightly lower than values derived from experiments by Windom and Boettcher (1976) and Goldsmith (1982) or from ion-exchange experiments of Kotel'nikov et al. (1981). Based on the Cˉ1/Iˉ1 transformation model, values of γ _An ^Cˉ1 <1.0 are unlikely. Discrepancies between the experimental data sets are attributed to incomplete (non-equilibrium) Al/Si order attained during the experiments. It is suggested that the choice of activity coefficients remains somewhat subjective. The development of accurate mixing models would be greatly assisted by better thermodynamic data for ordering in pure anorthite and by more thorough characterisation of the state of order in plagioclase crystals used for phase equilibrium experiments.     

Fluid-mineral equilibria and thermodynamic mixing properties of fluid systems

The paper presents a review of an experimental method to quantitatively constrain thermodynamic mixing properties of fluid systems at high temperature T and pressure P. The method is based on bracketing equilibrium parameters of simple fluid-mineral reactions. Experimental data obtained with this technique for the H₂O-CO₂, H₂O-N₂, and H₂O-H₂ binary systems were utilized to calculate mixing parameters corresponding to the simplified van Laar model W ₁₂ ^VL , according to which the equation for the integral excess Gibbs free energy of a binary mixture G ^ex is G ^ex =X ₁ X ₂ W ₁₂ ^VL /(X ₁ V ₁ ⁰ + X ₂ V ₂ ⁰ ), where X _i is the mole fractions of the components, and V _i ⁰ are pure species molar volumes at given P and T (in cm³). The W ₁₂ ^VL for the three mixtures correspond to 202, 219, and 331 kJ cm³/mol. The empirical correlation $W_{H_2 O - X}^{VL}$ (kJ cm³/mol) = 887.012 Q _X ? 16.674, where Q = P _c (critical pressure, bar)/T _c (critical temperature, K) for gas X (where X = CH₄, CO, H₂S, O₂, Ar, and NH₃) is used to evaluate the van Laar parameters for a number of petrologically important water-gas mixtures. The H₂O-H₂ system is characterized by the greatest positive deviation from the ideal mixing and can thus decompose into two immiscible fluid phases under the P-T parameters typical of deep lithospheric zones. The exsolution of the H₂O-CO₂ and H₂O-N₂ systems is expected to occur only under high pressure and low temperature. This combination of parameters may be expected only in the environments of cold subduction. Salts (highly soluble simple salts and/or silicates) should significantly expand the exsolution regions in petrologically important fluids.     

Rates of reaction of pyrite and marcasite with ferric iron at pH 2

The relative reactivities of pulverized samples (100–200 mesh) of 3 marcasite and 7 pyrite specimens from various sources were determined at 25°C and pH 2.0 in ferric chloride solutions with initial ferric iron concentrations of 10^?3 molal. The rate of the reaction:

$\text{FeS}{}_2\text{+ 14}\text{Fe}{}^{\mathrm{3+}}\text{+ 8}\text{H}{}_2\text{O}\text{= 15}\text{Fe}{}^{\mathrm{2+}}\text{+ 2}\text{SO}{}^{\mathrm{2?}}{}_4\text{+ 16}\text{H}{}^{\mathrm{+}}$

was determined by calculating the rate of reduction of aqueous ferric ion from measured oxidation-reduction potentials. The reaction follows the rate law:

where m_Fe³⁺ is the molal concentration of uncomplexed ferric iron, k is the rate constant and $\text{A}\text{M}$ is the surface area of reacting solid to mass of solution ratio. The measured rate constants, k, range from 1.0 × 10^?4 to 2.7 × 10^?4 sec^?1 ± 5%, with lower-temperature/early diagenetic pyrite having the smallest rate constants, marcasite intermediate, and pyrite of higher-temperature hydrothermal and metamorphic origin having the greatest rate constants. Geologically, these small relative differences between the rate constants are not significant, so the fundamental reactivities of marcasite and pyrite are not appreciably different.The activation energy of the reaction for a hydrothermal pyrite in the temperature interval of 25 to 50°C is 92 kJ mol^?1. This relatively high activation energy indicates that a surface reaction controls the rate over this temperature range. The BET-measured specific surface area for lower-temperature/early diagenetic pyrite is an order of magnitude greater than that for pyrite of higher-temperature origin. Consequently, since the lower-temperature types have a much greater $\text{A}\text{M}$ ratio, they appear to be more reactive per unit mass than the higher temperature types.     

Arsenic incorporation into authigenic pyrite, Bengal Basin sediment, Bangladesh

Sediment from two deep boreholes (∼400 m) approximately 90 km apart in southern Bangladesh was analyzed by X-ray absorption spectroscopy (XAS), total chemical analyses, chemical extractions, and electron probe microanalysis to establish the importance of authigenic pyrite as a sink for arsenic in the Bengal Basin. Authigenic framboidal and massive pyrite (median values 1500 and 3200 ppm As, respectively), is the principal arsenic residence in sediment from both boreholes. Although pyrite is dominant, ferric oxyhydroxides and secondary iron phases contain a large fraction of the sediment-bound arsenic between approximately 20 and 100 m, which is the depth range of wells containing the greatest amount of dissolved arsenic. The lack of pyrite in this interval is attributed to rapid sediment deposition and a low sulfur flux from riverine and atmospheric sources. The ability of deeper aquifers (>150 m) to produce ground water with low dissolved arsenic in southern Bangladesh reflects adequate sulfur supplies and sufficient time to redistribute the arsenic into pyrite during diagenesis.     

Scaling of thermodynamic mixing properties in garnet solid solutions

 The volumes and enthalpies of mixing, ΔV ^Mix and ΔH ^Mix, of binary solid-solution aluminosilicate garnets have been studied by computer simulation. The use of “average atoms” to simulate solid solution was found to give results that are considerably different from those obtained by calculating and averaging over many configurations of cations at a given composition. Although we expect mineral properties calculated from model calculations to be correct only on a qualitative rather than a quantitative scale, fair agreement with experiment was obtained where carefully tested potential parameters were used. The results show that mixing behaviour in these materials is controlled by local strain and relaxation effects resulting from the atomic size mismatch of the mixing divalent cations. In particular, ΔV ^Mix and ΔH ^Mix are shown to scale quadratically with the volume difference between the end members, and to vary essentially symmetrically with composition, with a moderate dependence on the degree and nature of cation order. We conclude that computer modelling should be useful in providing detailed qualitative information about the mixing properties of solid solutions, which can help to better constrain and interpret experimental results. Received: 8 March 2000 / Accepted: 1 October 2000     

Some constraints on the thermodynamic mixing properties of Fe-Mg orthopyroxenes and olivines

Existing data on the temperature and composition dependence of the Fe²⁺-Mg²⁺ distribution between Fe-Mg olivine and orthopyroxene, the intra-crystalline distribution of Fe²⁺ and Mg²⁺ between M1 and M2 sites in orthopyroxene, and macroscopic activity-composition relations in olivine and orthopyroxene are shown to be inconsistent with generally accepted thermodynamic formulations which assume that the non-configurational Gibbs energy of orthopyroxene is independent of the degree of long-range ordering of Fe²⁺ and Mg⁺ between M1 and M2 sites. These data are interpreted in terms of the constraints they provide on the size of Bragg-Williams type energy, entropy, and volume terms for olivine and orthopyroxene. The apparent equilibrium constant for Fe-Mg exchange between olivine and orthopyroxene is shown to be a potentially useful ‘geothermometer’ for olivine-orthopyroxene assemblages with olivines with mole fraction of Fe₂SiO₄ component less than 0.2 or greater than 0.6. A provisional calibration of this ‘geothermometer’ is presented.     

Molecular simulations of interfacial and thermodynamic mixing properties of grossular–andradite garnets

Experimental observations using transmission electron microscopy (TEM) indicate that Fe³⁺-rich grossular–andradite solid solutions with oscillatory zoning tend to occur as separate lamellae of andradite and intermediate compositions (Hirai and Nakazawa 1986; Pollok et?al. 2001). From one lamella to the next, the Fe³⁺ concentration can change significantly within a few nm. In order to understand the Fe³⁺ and Al content of each phase and the thermodynamics, chemistry, structure, and stability at the interfaces, Monte Carlo simulations were performed. According to our calculations, there is an ordered structure with a 1:1 ratio of Al and Fe³⁺ with alternating Al and Fe octahedra along the main cubic crystallographic axes. Even though this ordered grandite is more energetically favorable than a 1:1 mixture of the end members grossular and andradite [by ≈1.6?kJ (mol exchangeable cations)^?1], this structure is stable only at temperatures below ≈500?K. Enthalpies, free energies, configurational and vibrational entropies of mixing, and the long-range order parameter are influenced by the formation of ordered grandite below 500?K. These data also explain why interfaces are stable only between grossular and grandite or between andradite and grandite but not between the end members. The interface energies between the end members and ordered grandite are comparably low [0.16?meV?Å^?2∥(1?0?0), 0.55?meV?Å^?2∥(1?1?0), 0.63?meV?Å^?2∥(1?1?1)] and, therefore, do not hinder the formation of lamellae. Our calculations on the free energies of mixing indicate that there are miscibility gaps between grossular and grandite and between grandite and andradite only below ≈430?K. Since most of these solid solutions are formed at higher temperatures for which we did not find evidence of a miscibility gap, the formation of compositional oscillations is probably due to kinetic hindering of thermodynamically stable complete solid solutions. ?A new methodological aspect is the incorporation of zero-point energies of vibrations and the vibrational entropies into the calculation of the free energy of mixing. In case of the grossular–andradite solid solution, these vibrational effects change the free energy of mixing by only a few percent.     

The 57Fe Mössbauer parameters of pyrite and marcasite with different provenances

Eighteen pyrite and twelve marcasite samples which have different provenances have been investigated to determine the systematics of the influence of mineralogical and geological factors on the ⁵⁷Fe Mössbauer spectra at 298 K. The following results have been obtained: there is no ambiguity in distinguishing single phase pyrite from single phase marcasite by means of ⁵⁷Fe Mössbauer spectroscopy at 298 K. At 298 K the average electric quadrupole splitting, 〈ΔE_Q〉, and average isomer shift, 〈δ〉, with respect to Fe metal, are 0.6110 ± 0.0030 mm s^?1 and 0.313 ± 0.008 mm s^?1, respectively, for the 18 pyrites; 〈ΔE_Q〉 = 0.5030 ± 0.0070 mm s^?1 and 〈δ〉 = 0.2770 ± 0.0020 mm s^?1 for the 12 marcasites. At 77 K, ΔE_Q is 0.624 mm s^?1 for pyrite and 0.508 mm s^?1 for marcasite. In distinguishing pyrites from marcasites, spectra obtained at 77 K are not warranted.The Mössbauer parameters of pyrite and marcasite exhibit appreciable variations, which bear no simple relationship to the geological environment in which they occur but appear to be selectively influenced by impurities, especially arsenic, in the pyrite lattice. Quantitative and qualitative determinations of pyrite/marcasite mechanical mixtures are straightforward at 298 K and 77 K but do require least-squares computer fittings and are limited to accuracies ranging from ±5 to ±15 per cent by uncertainties in the parameter values of the pure phases. The methodology and results of this investigation are directly applicable to coals for which the presence and relative amounts of pyrite and marcasite could be of considerable genetic significance.     

Simulation of thermodynamic mixing properties of garnet solid solutions at high temperatures and pressures

We present results of high temperature, high pressure atomistic simulations aimed at determining the thermodynamic mixing properties of key binary garnet solid solutions. Computations cover the pressure range 0–15 GPa and the temperature range 0–2000 K. Through a combination of Monte-Carlo and lattice-dynamics calculations, we derive thermodynamic mixing properties for garnets with compositions along the pyrope–almandine and pyrope–grossular joins, and compare these with existing experimental data. Across the pressure–temperature range considered, simulations show virtually ideal mixing behaviour in garnet on the pyrope–almandine join, while large excess volumes and enthalpies of mixing are predicted for garnet along the pyrope–grossular join. Excess heat capacities and entropies are also examined. These simulations shed additional light on the link between the behaviour at the atomic level and macroscopic thermodynamic properties: we illustrate the importance of certain atomistic Ca–Mg contacts in the pyrope–grossular solid solutions. For simulation techniques of this type to become sufficiently accurate for direct use in geological applications such as geothermobarometry, there is an urgent need for improved experimental determinations of several key quantities, such as the enthalpies of mixing along both joins.     

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As−1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O₂), hypoxic (2% O₂, 98% N₂), and anoxic (5% H₂, 95% N₂) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (−1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.     

Arsenic incorporation into FeS2 pyrite and its influence on dissolution: A DFT study

FeS₂ pyrite can incorporate large amounts of arsenic (up to ca. 10 wt%) and hence has a strong impact on the mobility of this toxic metalloid. Focussing on the lowest arsenic concentrations for which the incorporation occurs in solid solution, the substitution mechanisms involved have been investigated by assuming simple incorporation reactions in both oxidising and reducing conditions. The solution energies were calculated by Density Functional Theory (DFT) calculations and we predict that the formation of AsS dianion groups is the most energetically favourable mechanism. The results also suggest that the presence of arsenic will accelerate the dissolution and thus the generation of acid drainage, when the crystal dissolves in oxidising conditions.     

Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO₄ and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O₂) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O₂) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO₄ and water was observed over a pH range of 0–2 only at 50 °C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 °C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T  25 °C, pH  3) for decades.Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O₂ to pyrite surface sites. The sorption of molecular O₂ is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO₄. The calculated bulk contribution of atmospheric O₂ in the dissolved SO₄ reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O₂ in the early-formed sulfates, chemisorption and electron transfer of molecular O₂ on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction of hydroxyls from water with S at the anodic S pyrite surface site. Then, the role of molecular O₂ is as proposed in previous studies: acting as electron acceptor only at the cathodic Fe pyrite surface site for oxidation of Fe(II) to Fe(III).     

含Cu硫化物中S、Fe同位素分馏系数的第一性原理计算

Cu在自然界主要以硫化物的形式存在,目前只确定了几种含Cu硫化物的S同位素分馏系数以及黄铜矿的Fe同位素分馏系数,而且不同研究者确定的系数有很大的差别,使得S、Fe同位素在研究铜矿床的形成、演化等方面不能很好地发挥示踪作用。因此,本文基于第一性原理计算确定了0~1 000℃温度范围内主要含Cu硫化物的S同位素简约配分函数比（10³lnβ_34-32）,以及Cu-Fe硫化物的Fe同位素简约配分函数比（10³lnβ_57-54）。重S同位素在这些含Cu硫化物中的富集顺序为铜蓝>方黄铜矿>黄铜矿≈黑硫铜镍矿>斑铜矿>辉铜矿,重Fe同位素在Cu-Fe硫化物中的富集顺序为方黄铜矿≈黄铜矿>低温斑铜矿>高温斑铜矿>中温斑铜矿>Cu₈Fe₄S₈（中温斑铜矿的可能变体）。含Cu硫化物的10³lnβ_34-32与S原子的配位数、金属-S平均键长、S原子形成的所有化学键的平均键长没有明显的相关性,而Cu-Fe硫化物的10³lnβ_57-54与Fe—S平均键长基本成线性负相关关系。辉铜矿相变引起的S同位素分馏特别大,而斑铜矿相变时产生的S同位素分馏却可以忽略不计。本文的计算结果将会为探讨斑岩铜矿及其它类型的硫化物矿床的成因提供支持。     

Phase diagram and thermodynamic properties of AIPO<Subscript>4</Subscript> based on first-principles calculations and the quasiharmonic approximation

We calculated the phase diagram of \(\hbox {AlPO}_{4}\) up to 15 GPa and 2,000 K and investigated the thermodynamic properties of the high-pressure phases. The investigated phases include the berlinite, moganite-like, \(\hbox {AlVO}_{4},\, P2_1/c\), and \(\hbox {CrVO}_{4}\) phases. The computational methods used include density functional theory, density functional perturbation theory, and the quasiharmonic approximation. The investigated thermodynamic properties include the thermal equation of state, isothermal bulk modulus, thermal expansivity, and heat capacity. With increasing pressure, the ambient phase berlinite transforms to the moganite-like phase, and then to the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases, and further to the \(\hbox {CrVO}_{4}\) phase. The stability fields of the \(\hbox {AlVO}_{4}\) and \(P2_1/c\) phases are similar in pressure but different in temperature, as the \(\hbox {AlVO}_{4}\) phase is stable at low temperatures, whereas the \(P2_1/c\) phase is stable at high temperatures. All of the phase relationships agree well with those obtained by quench experiments, and they support the stabilities of the moganite-like, \(\hbox {AlVO}_{4}\), and \(P2_1/c\) phases, which were not observed in room-temperature compression experiments.     

The thermodynamic properties of radium

The enthalpy, Gibbs free energy, and entropies of aqueous radium species and radium solids have been evaluated from empirical data, or estimated when necessary for 25°C and 1 bar. Estimates were based on such approaches as extrapolation of the thermodynamic properties of Ca, Sr, and Ba complexes and solids plotted against cationic radii and charge to radius functions, and the use of the Fuoss or electrostatic mathematical models of ion pair formation (Langmuir, 1979). Resultant log K (assoc) and ΔH⁰ (assoc) (kcal/mol) values are: for RaOH⁺ 0.5 and 1.1; RaCl⁺ ?0.10 and 0.50; RaCO⁰₃ 2.5 and 1.07; and RaSO⁰₄ 2.75 and 1.3. Log Ksp and ΔH⁰ (dissoc) (kcal/mol) values for RaCO₃(c) and RaSO₄(c) are ?8.3 and ?2.8, and ?10.26 and ?9.4, respectively.Trace Ra solid solution in salts of Pb and of the lighter alkaline earths, has been appraised based on published distribution coefficient (D) data, where D ～- (mM²⁺)(N_RaX)/(mRa²⁺)(N_MX) (m and N are the aqueous molality and mole fraction of Ra and cation M in salt X, respectively. The empirical solid solution data have been used to derive both enthalpies and Gibbs free energies of solid solution of trace Ra in sulfate and carbonate minerals up to 100°C. Results show that in every case D values decrease with increasing temperature. Among the sulfate and carbonate minerals, D values decrease for the following minerals in the order: anhydrite > celestite > anglesite > barite > aragonite > strontianite > witherite > cerussite.     

Mobilization and speciation of arsenic from hydrothermally altered rock containing calcite and pyrite under anoxic conditions

The effects of water residence time and anoxic conditions on the mobilization and speciation of As in a calcite- and pyrite-bearing altered rock excavated during a road-tunnel project has been evaluated using batch and column laboratory experiments. Higher infiltration rates (i.e., shorter water residence times) enhanced the leaching of As due to the higher pH values of the effluents and more rapid transport of dissolved As through the columns. The concentration of As in the effluent also increased under anoxic conditions regardless of the water residence time. This enhanced leaching of As under anoxic conditions could be attributed to a significant pH increase and decreased Fe oxyhydroxide/oxide precipitation compared to similar experiments done under ambient conditions. Processes that controlled the evolution of pH and the temporal release mechanisms of As under anoxic conditions were identical to those previously observed under ambient conditions: the dissolution of soluble phases, pyrite oxidation, co-precipitation and/or adsorption/desorption reactions. Speciation of As in the column experiments could partly be attributed to the pH-dependent adsorption of As species onto Fe oxyhydroxide/oxide precipitates. Moreover, apparent equilibrium of the total As and As[III] concentrations was delayed under anoxic conditions in both batch and column experiments.