Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).     

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

A review and analysis of silicate mineral dissolution experiments in natural silicate melts

We present a database and a graphical analysis of published experimental results for dissolution rates of olivine, quartz plagioclase, clinopyroxene, orthopyroxene, spinel, and garnet in basaltic and andesitic melts covering a range of experimental temperatures (1100–1500°C) and pressures (10⁵ Pa-3.0 GPa). The published datasets of Donaldson (1985, 1990) and Brearly and Scarfe (1986) are the most complete. Experimental dissolution rates from all datasets are recalculated and normalized to a constant oxygen basis to allow for direct comparison of dissolution rates between different minerals. Dissolution rates (ν) range from 5·10⁻¹⁰ oxygen equivalent moles (o.e.m.) cm⁻² s⁻¹ for olivine in a basaltic melt to 1.3·10⁻⁵ o.e.m. cm⁻² s⁻¹ for garnet in a basaltic melt. Values of ln ν are Arthenian for the experiments examined and activation energies range from 118 to 1800 kJ/o.e.m. for quartz and clinopyroxene, respectively.

The relationship between calculated A/RT for the dissolution reactions, where A is the thermodynamic potential affinity, and values of ν is linear for olivine, plagioclase, and quartz. We interpret this as strong evidence in support of using calculated A as a predictor of ν for, at least, superliquidus melt conditions.     

Dissolution kinetics of experimentally shocked silicate minerals

The effect of lattice strain on mineral dissolution rates was examined by comparing the dissolution rates of shocked and unshocked minerals. Labradorite, oligoclase and hornblende were explosively shocked at mean pressures ranging from 4 to 22 GPa. The labradorite was examined with transmission electron microscopy to estimate the density of dislocations produced by the shock-loading experiment. Subsamples of the labradorite were then thermally annealed to remove some of the dislocations, and to evaluate the importance of such thermal pre-treatment in preparing mineral surfaces for experiments. The dissolution rates of these minerals were measured in batch experiments at pH-values of 2.7 and 4.0.

Shock-loading did not produce extremely high dislocation densities in the labradorite. The density of dislocations in the unshocked labradorite is ≤ 10¹⁰ m⁻². After shocking, the density increases to 10¹²-10¹³ m⁻². The distribution of dislocations is heterogeneous, and the amount of deformation does not increase substantially with shock pressure. These results are highly atypical of shock-modified minerals, where relatively low shock pressures usually induce high ( 10¹⁵ m⁻²) densities of dislocations. Thermal annealing for 1 hr. at 900°C in a dry furnace removes many dislocations from the shocked labradorite.

The difference in observed dissolution rates between shocked and unshocked minerals appears to have a weak correlation with the increase in the density of dislocations on the mineral surface. The unshocked and shocked oligoclase and hornblende samples exhibit limited dissolution enhancement at pH 4.0. Increasing the density of dislocations by several orders of magnitude with shock-loading causes a relatively small increase in dissolution rates for these silicate minerals. These results suggest that the surface dislocations produced by the shock treatment are not the primary sites for dissolution reactions.     

Gum rosin (colophony): A suitable material for thermomechanical modelling of the lithosphere

We investigate the use of a ductile material with temperature-sensitive viscosity for thermomechanical modelling of the lithosphere. First, we consider the scaling of mechanical and thermal properties. For a normal field of gravity, the balance of stresses and body forces sets the stress scale, in proportion to the linear dimensions and the densities. The equation of thermal conduction sets the time scale. The activation enthalpy for creep sets the temperature scale; but the thermal expansivity provides an additional constraint on this temperature scale.

Gum rosin appears to be a suitable material for lithospheric modelling. We have measured its flow properties, at various temperatures, in a specially designed rotary viscometer with unusually low machine friction. The rosin is almost Newtonian. Strain rate depends upon stress to the power n, where 1.0 <n < 1.14. The viscosity varies over 5 orders of magnitude, from about 10² Pa s at 80°C, to about 10⁷ Pa s at 40°C. The activation enthalphy is thus about 250 kJ/mol. Measured with a needle probe, the thermal conductivity is 0.113 ± 0.001 W m⁻¹K⁻¹; the thermal diffusivity, (6±3) ×10⁻⁷ m² s⁻¹. Calculated from X-ray profiles, the thermal expansivity is about 3 × 10⁻⁴ K⁻¹. These thermal and mechanical properties make gum rosin suitable for thermomechanical models, where linear dimensions scale down by a factor of 10⁶; time, by 10¹¹; viscosity, by 10¹⁷; and temperature change, by 10¹.     

An experimental study of calcite dissolution rates at acidic conditions and 25 °C in the presence of NaPO3 and MgCl2

Dissolution rates of single calcite crystals were determined from sample weight loss using free-drift rotating disk techniques. Experiments were performed at 25 °C in aqueous HCl solutions over the bulk solution pH range −1 to 3 and in the presence of trace concentrations of aqueous NaPO₃ and MgCl₂. These salts were chosen for this study because aqueous magnesium and phosphate are known to strongly inhibit calcite dissolution at neutral to basic pH. Reactive solutions were undersaturated with respect to possible secondary phases. Neither an inhibition or enhancement of calcite dissolution rates was observed in the presence of aqueous MgCl₂ at pH 1 and 3. The presence of trace quantities of NaPO₃, which dissociates in solution to Na⁺ and H₂PO₄⁻, decreased the overall calcite dissolution rate at pH≤2. This contrasting behavior could be attributed to the different adsorption behavior of these dissolved species. As calcite surfaces are positively charged in acidic solutions, aqueous Mg²⁺ may not adsorb, whereas aqueous phosphate, present as either the anion H₂PO₄⁻ or the neutral species H₃PO₄⁰, readily adsorbs on calcite surfaces leading to significant dissolution inhibition.     

Equilibria in the system Au–Ag–S–fluid: computed and experimental data

We present results of computations on the interaction of solid-phase electrum–argentite–pyrite (weight ratios 210⁻⁵/ 210⁻³/1 and 210⁻⁵/410⁻²/1) association with Cl-containing aqueous moderately acid solutions (0.5m NaCl, pH = 3.08) at 300 °C and 500 bars. These data are a physicochemical basis for predicting the geochemical behavior of Au and Ag during the hydrothermal-metasomatic transformation of Au-Ag-pyrite. We also propose a technique of study of this process based on the phase equilibria of the subsystem Au–Ag–S with the aqueous solution at different liquid/solid (l/s) ratios, with the use of new graphic diagrams. The relationship of the composition of the solid-phase association with l/s ratio in real boundary conditions (Au = 17 ppm, mAu/mAg = 10^–3.57–10^–2.28) is shown. The maximum l/s values for complete leaching of gold and silver (l/smax = 200–800) are estimated. It has been established that argentite is the first to dissolve when mAu/mAg(s) > mAu/mAg(sol), and electrum, when mAu/mAg(s) < mAu/mAg(sol).

The experimental results showed that at 300 °C, the conversion of electrum (N_Au = 300‰) nonequilibrated with pyrite into an Au-richer form (N_Au = 730‰) and argentite follows an intricate kinetic scheme. Using the Pilling-Bedwords kinetic equation for processing data yielded the process rate constant K = 2.8(±0.5)10⁻⁵ g²cm⁻⁴day⁻¹. With this equation, the time of the complete conversion of 200 μm thick flat gold grains is 604 days. These data evidence a significant role of kinetic factors in hydrothermal-metasomatic processes involving native gold, which requires combination of thermodynamic and kinetic approaches on the construction of geologo-genetic models for hydrothermal sulfide formation.     

Upper Mississippi embayment shallow seismic velocities measured in situ

Vertical seismic compressional- and shear-wave (P-and S-wave) profiles were collected from three shallow boreholes in sediment of the upper Mississippi embayment. The site of the 60-m hole at Shelby Forest, Tennessee, is on bluffs forming the eastern edge of the Mississippi alluvial plain. The bluffs are composed of Pleistocene loess, Pliocene-Pleistocene alluvial clay and sand deposits, and Tertiary deltaic-marine sediment. The 36-m hole at Marked Tree, Arkansas, and the 27-m hole at Risco, Missouri, are in Holocene Mississippi river floodplain sand, silt, and gravel deposits. At each site, impulsive P- and S-waves were generated by man-made sources at the surface while a three-component geophone was locked downhole at 0.91-m intervals.

Consistent with their very similar geology, the two floodplain locations have nearly identical S-wave velocity (V_S) profiles. The lowest V_S values are about 130 m s⁻¹, and the highest values are about 300 m s⁻¹ at these sites. The shear-wave velocity profile at Shelby Forest is very similar within the Pleistocene loess (12 m thick); in deeper, older material, V_S exceeds 400 m s⁻¹.

At Marked Tree, and at Risco, the compressional-wave velocity (V_P) values above the water table are as low as about 230 m s⁻¹, and rise to about 1.9 km s⁻¹ below the water table. At Shelby Forest, V_P values in the unsaturated loess are as low as 302 m s⁻¹. V_P values below the water table are about 1.8 km s⁻¹. For the two floodplain sites, the V_P/V_S ratio increases rapidly across the water table depth. For the Shelby Forest site, the largest increase in the V_P/V_S ratio occurs at 20-m depth, the boundary between the Pliocene-Pleistocene clay and sand deposits and the Eocene shallow-marine clay and silt deposits.

Until recently, seismic velocity data for the embayment basin came from eartquake studies, crustal-scale seismic refraction and reflection profiles, sonic logs, and from analysis of dispersed earthquake surface waves. Since 1991, seismic data for shallow sediment obtained from reflection, refraction, crosshole and downhole techniques have been obtained for sites at the northern end of the embayment basin. The present borehole data, however, are measured from sites representative of large areas in the Mississippi embayment. Therefore, they fill a gap in information needed for modeling the response of the embayment to destructive seismic shaking.     

Determining mineral weathering rates based on solid and solute weathering gradients and velocities: application to biotite weathering in saprolites

Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area.

Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6×10⁻¹⁷ mol m⁻² s⁻¹ for biotite. Faster weathering rates of 1.8 to 3.6×10⁻¹⁶ mol m⁻² s⁻¹ are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering.     

Antimony in hydrothermal processes: solubility, conditions of transfer, and metal-bearing capacity of solutions

Based on data on the composition of ore-bearing hydrothermal solutions and parameters of ore-forming processes at various antimony and antimony-bearing deposits, which were obtained in studies of fluid inclusions in ore minerals, we investigated the behavior of Sb(III) in the system Sb–Cl–H₂S–H₂O describing the formation of these deposits.

We also performed thermodynamic modeling of native-antimony and stibnite dissolution in sulfide (m_HS⁻ = 0.0001−0.1) and chloride (m_Cl⁻ = 0.1−5) solutions and the joint dissolution of Sb_(s)⁰ and Sb₂S_3(s) in sulfide-chloride solution (m_HS⁻ = 0.01; m_Cl⁻ = 1) depending on Eh, pH, and temperature. All thermodynamic calculations were carried out using the Chiller computer program. Under the above conditions, stibnite precipitates in acid, weakly acid to neutral, and medium redox solutions, whereas native antimony precipitates before stibnite under more reducing conditions in neutral to alkaline solutions.

The metal-bearing capacity of hydrothermal solutions (200–250 °C) of different compositions and origins has been predicted. We have established that the highest capacity is specific for acid (pH = 2–3) high-chloride solutions poor in sulfide sulfur and alkaline (pH = 7–8) low-chloride low-sulfide solutions.     

Water-enhanced dynamic recrystallization and solution transfer in experimentally deformed carnallite

Cylindrical samples of polycrystalline carnallite (KMgCl₃, 6H₂O) were deformed in a triaxial apparatus at 60°C, at confining pressures between 0.1 and 31 MPa and at strain rates between 10⁻⁴ and 10⁻⁸ s⁻¹. In a number of cases, small amounts of saturated carnallite brine were added. Samples without added brine deform by intracrystalline slip, mechanical twinning, cracking, and by frictional sliding on crack surfaces. Stress-strain curves of these samples are strongly dependent on confining pressure. Addition of brine has a dramatic effect on both microstructural development and mechanical properties. Grain-boundary migration is strongly enhanced. At lower strain rates, additional intracrystalline effects start to appear, together with the onset of solution transfer. Rapid compaction in samples deformed with added brine causes high fluid pressures to develop. At higher strain rates addition of brine results in a decrease of the flow stress by a factor of two. This weakening will increase even further at strain rates below about 10⁻⁹ s⁻¹, when solution transfer becomes rate controlling. It is argued that deformation of carnallite in nature is adequately described by the flow law found for samples deformed with added brine.     

Strain rate effect on the compressive strength of frozen sand

Cylindrical specimens of fine Ottawa sand (A.S.T.M. designation C-109), compacted at the optimum moisture content and saturated before unidirectional freezing, have been tested in uniaxial compression at a cold room temperature of —5.5°C and strain rates between 10⁻⁷ and 10⁻² s⁻¹. The results agree with an extrapolation of data obtained by Sayles and Epanchin [1], but are much higher than those obtained by both Goughnour and Andersland [2] and Perkins and Ruedrich [3] at strain rates below 10⁻⁵ s⁻¹. There is evidence that this may be due to variation in total moisture (ice) content, the conditions under which the specimens were frozen (closed system or an open system) and to the end effects at the platen—specimen interface.     

藏南扎西康铅锌多金属矿床成因——硫化物原位硫同位素证据

藏南扎西康铅锌多金属矿床是特提斯喜马拉雅构造带（TH）东段发现的首个大型铅锌矿床,但其成因备受争议。本文在详细研究矿床地质特征的基础上,对矿硐内具有"同心环带"或"热水蛋"构造的铅锌矿石中的黄铁矿、方铅矿和闪锌矿进行了原位微区硫同位素分析。结果显示：铅锌矿石硫同位素组成变化范围在8.88‰~11.83‰之间,平均为10.50‰,总硫同位素组成（δ³⁴S_∑S）约为10.07‰。其中：7个黄铁矿（Py）测点的δ³⁴S_Py值为10.29‰~11.14‰,平均为10.70‰;6个闪锌矿（Sp）测点的δ³⁴S_Sp值为10.78‰~11.83‰,平均为11.49‰;5个方铅矿（Gn）测点的δ³⁴S_Gn值为8.88‰~9.18‰,平均为9.04‰。总体表现为δ³⁴S_Sp > δ³⁴S_Py > δ³⁴S_Gn,指示硫同位素未达到分馏平衡。利用方铅矿与闪锌矿矿物对硫同位素温度计计算可得,铅锌成矿温度介于224~280℃之间,平均值为259℃。结合前人研究成果,进一步得出扎西康铅锌多金属矿床主成矿期硫源主要来自日当组（J₁r）围岩地层,并可能有少量岩浆硫的混入,属受控于地层-构造-岩浆热液作用的中温热液矿床。     

Multisite surface reaction versus transport control during the hydrolysis of a complex oxide

Dissolution experiments of a tholeiite basalt glass carried out at different pH and T (up to 300°C) using a rotatingdisc apparatus show that, depending on pH and T, dissolution can be controlled by one of the following steps: (1) surface reaction; (2) transport of reactants in solution; and (3) mixed reaction. The activation energies of these different processes were found to be 60, 9 and 15–50 kJ mol⁻¹, respectively. Taking account of these results, it appears likely that surface reactions are not rate limiting for the hydrolysis of most crystalline silicate minerals in hydrothermal and metamorphic processes, and that caution should be exercised when predicting rate of reactions at high temperatures solely on the basis of activation energies measured at low temperatures.

Comparison of experimental and theoretical potentiometric titrations of the basalt glass and its constituent oxides indicates that the adsorption of H⁺ and OH⁻ ions at the basalt surface is metal cation specific and that the net adsorption can be predicted from the sole knowledge of the acidity constants of the network-forming constituent oxides. We found that in the acidic pH region dissolution is promoted by the adsorption of H⁺ on al and Fe surface sites while in the basic region, dissolution is promoted by the adsorption of OH⁻ on Si sites. The combination of the two distinct types of surface sites, Al and Fe on the one hand, and Si on the other hand, results in a dissolution rate minimum at a pH-value between the pH_zpc of the two groups of oxide components. Linear regressions with a slope n=3.8 are observed both in acid and alkaline solutions in logarithmic plots of the rate of dissolution vs. the surface charge. The value of n, which represents the number of protonation or hydroxylation steps prior to metal detachment, has been found equal to the mean valence of the network-forming metals.

Combining concepts of surface coordination chemistry with transition state theory afforded characterisation of the activated complexes involved in basalt dissolution processes. From the values obtained for the thermodynamic properties of activation for basalt dissolution it is assumed that the activated complexes formed during the H₂O-promoted dissolution of the basalt glass are more tightly bonded than those formed during H⁺- or OH⁻-promoted dissolution.     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Evolution of mineral–fluid interfaces studied at pressure with synchrotron X-ray techniques

In situ measurements of mineral surface evolution during the process of pressure solution are possible with the high brightness of synchrotron X-ray sources. This capability has been explored through the use of newly developed reaction vessels that allow transmission of the incident and scattered X-ray beam through a low atomic weight piston. Several new vessels are described, along with details of computational algorithms that are used to simulate X-ray scattering in this unconventional geometry. Results using calcite (CaCO₃) and halite (NaCl) as reactant crystals are presented and compared to other atomic-scale measurements of surface dissolution processes. Calcite was reacted with an unsaturated fluid at 30 bars of pressure for approximately 24 h. During reaction the root mean square surface roughness (σ) evolved from 13.7 Å (± 0.5 Å) to 19.5 Å (± 1.0 Å), giving a roughening rate of: dσ/dt = +6.3 × 10^− 5 Å s^− 1. This is consistent with other measurements made with free calcite surfaces and is driven almost entirely by chemical disequilibrium. Analysis of the surface ex situ post-reaction gives an identical σ value, showing that the in situ measurements are well-constrained. Experiments also at 30 bars but in a saturated solution indicate that the calcite surface does not significantly roughen, giving the result that pressure solution of calcite at this pressure cannot be monitored in experiments of several days duration. Experiments with halite, a much more reactive phase, in saturated solutions showed the reflectivity profile to be dynamic on a time scale of hours. This experiment was left to reach equilibrium over 108 days and then re-analyzed, showing that σ had increased from 34 Å (± 2 Å) to 41 Å (± 2 Å), giving a roughening rate of: dσ/dt ≤ +6.4 × 10^− 7 Å s^− 1. This is two orders of magnitude smaller than the calcite roughening rate caused by chemical disequilibrium and provides the first direct in situ atomic-scale measurement of the rate of surface roughening due to pressure solution.     

Gas pressures and redox reactions in geothermal fluids in Iceland

The gas and redox chemistry of 100–300 °C geothermal fluids in Iceland has been studied as a function of fluid temperature and fluid composition. The partial pressures of CO₂ in dilute (mCl<500 ppm) and saline (mCl>500 ppm) geothermal fluids above 200 °C are controlled by the mineral buffer clinozoisite+prehnite+calcite+quartz. Two buffers are considered to control the H₂S and H₂ partial pressures above 200 °C depending on fluid salinity, epidote+prehnite+pyrite+pyrrhotite for dilute fluids and pyrite+prehnite+quartz+magnetite+anhydrite+clinozoisite+quartz for saline fluids. Below 200 °C, the partial pressures of CO₂, H₂S and H₂ also seem to be buffered but other minerals must be involved. Zeolites are expected to replace prehnite and epidote. Redox potential calculated on the assumption of equilibrium for the H⁺/H₂ redox couple decreases in dilute geothermal fluids with increasing temperature from about −0.5 V at 100 °C to −0.8 V at 300 °C, whereas saline geothermal fluids at 250 °C display a redox potential of about −0.45 V. A systematic discrepancy between redox couples of about 0.05–0.09 V is observed in the redox potential for the dilute geothermal fluids, whereas redox potentials agree within 0.02–0.04 V for saline geothermal waters. The discrepancies in the calculated redox potential for dilute geothermal fluids are thought to be due to a general lack of equilibrium between CH₄, CO₂ and H₂ and between H₂S, SO₄ and H₂. It is, accordingly, concluded that an overall equilibrium among redox species has not been reached for dilute geothermal fluids whereas it appears to be more closely approached for the saline geothermal fluids. The latter conclusion is based on limited database and should be treated with care. Since the various redox components are not in an overall equilibrium in geothermal fluids in Iceland these fluids cannot be characterised by a unique hydrogen fugacity, oxygen fugacity or redox potential at a given temperature and pressure.     

Strontium diffusion in sanidine and albite, and general comments on strontium diffusion in alkali feldspars

Strontium chemical diffusion has been measured in albite and sanidine under dry, 1 atm, and QFM buffered conditions. Strontium oxide-aluminosilicate powdered sources were used to introduce the diffusant and Rutherford Backscattering Spectroscopy (RBS) used to measure diffusion profiles. For the 1 atm experiments, the following Arrhenius relations were obtained:

Sanidine (Or₆₁), temperature range 725–1075°C, diffusion normal to (001): D=8.4 exp(−450±13 kJ mol⁻¹/RT) m²s⁻¹. Albite (Or₁), temperature range 675–1025°C, diffusion normal to (001): D=2.9 × exp(−224±11 kJ mol⁻¹/RT) m²s⁻¹.

The alkali feldspars in this and earlier work display a broad range of activation energies for Sr diffusion, which may be a consequence of the thermodynamic non-ideality of the alkali feldspar system and/or the mixed alkali effect.     

Geothermal studies in the Hyderabad granitic region and the crustal thermal structure of the Southern Indian Shield

Based on temperature measurements in three boreholes (one specially drilled for the purpose) and thermal conductivity determinations, heat flow density values were determined for three sites in the Archaean Hyderabad granitic batholith. A mean heat flow density value of 40± 1 (s.d.) mW m⁻² has been obtained. The heat generation in its rocks (5.57 μW m⁻³) is significantly higher than in average crustal rocks. It has been proposed that the Hyderabad batholith has a layered structure with a thin ( ≈ 1 km) surface layer of high radioactivity. These results together with the already reported data have been used to estimate the conductive steady-state temperature within and at the base of the crust of the Southern Indian Shield, yielding values of the same order as found in the Western Australian Shield.