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).     

Effects of dry density and exchangeable cations on the diffusion process of sodium ions in compacted montmorillonite

As a part of the safety assessment of the geological disposal of high-level radioactive waste, the effects of dry density and exchangeable cations on the diffusion process of Na⁺ ions in compacted bentonite were studied from the viewpoint of the activation energy for diffusion. The apparent self-diffusion coefficients of Na⁺ ions in compacted Na-montmorillonite and in a Na- and Ca-montmorillonite mixture were determined by one-dimensional, non-steady diffusion experiments at different temperatures and dry densities. A unique change in activation energy as a function of dry density was found for the Na⁺ ions in compacted Na-montmorillonite. The activation energy suddenly decreased from 18.1 to 14.1 kJ mol^− 1 as the dry density increased from 0.9 to 1.0 Mg m^− 3, whereas it increased to 24.7 kJ mol^− 1 as the dry density increased to 1.8 Mg m^− 3. Examination of the effect of exchangeable cations on the activation energies determined that the activation energies were almost constant, approximately 25 kJ mol^− 1, for the montmorillonite specimens at a dry density of 1.8 Mg m^− 3. However, three different activation energy values were obtained at a dry density of 1.0 Mg m^− 3. These findings cannot be explained by the conventional diffusion model (the pore water diffusion model), which suggests that the predominant diffusion process alternates among pore water diffusion, interlayer diffusion, and external surface diffusion.     

A comparative study on the dissolution and solubility of hydroxylapatite and fluorapatite at 25 °C and 45 °C

Dissolution of the synthetic hydroxylapatite (HAP) and fluorapatite (FAP) in pure water was studied at 25 °C and 45 °C in a series of batch experiments. The XRD, FT-IR and SEM analyses indicated that the synthetic, microcrystalline HAP and FAP with apatite structure used in the experiments were found to have no obvious variation after dissolution except that the existence of OH groups in FT-IR spectra for FAP after 2880 h dissolution was observed. During the HAP dissolution (0–4320 h), the aqueous calcium and phosphate concentrations reached the maxima after 120 h and then decreased slowly with time. For the FAP dissolution in pure water, after a transient time of 1440 h (< 60 d), element concentrations and pH became constant suggesting attainment of a steady-state between the solution and solid. During early stages of the FAP dissolution reaction (< 72–120 h), mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P, Ca:F and P:F being lower than mineral stoichiometric ratios of Ca₅(PO₄)₃F, i.e., 1.67, 5.0 and 3.0, respectively. This indicated that F were preferentially released compared to Ca from the mineral structure. The mean K_sp values were calculated by using PHREEQC for HAP of 10^− 53.28 (10^− 53.02–10^− 53.51) and for FAP of 10^− 55.71 (10^− 55.18–10^− 56.13) at 25 °C, the free energies of formation ΔG_f^o[HAP] and ΔG_f^o[FAP] were calculated to be − 6282.82 kJ/mol and − 6415.87 kJ/mol, respectively.     

Reduced sulfur and iron species in anoxic water column of meromictic crater Lake Pavin (Massif Central, France)

The vertical distribution of reduced sulfur species (RSS including H₂S/HS⁻, S⁰, electroactive FeS) and dissolved Fe(II) was studied in the anoxic water column of meromictic Lake Pavin. Sulfide concentrations were determined by two different analytical techniques, i.e. spectophotometry (methylene blue technique) and voltammetry (HMDE electrode). Total sulfide concentrations determined with methylene blue method (∑H₂S_MBRS) were in the range from 0.6 µM to 16.7 µM and were substantially higher than total reduced sulfur species (RSS_V) concentrations determined by voltammetry, which ranged from 0.1 to 5.6 μM. The observed difference in the sulfide concentrations between the two methods can be assigned to the presence of FeS colloidal species.Dissolved Fe was high (> 1000 µM), whereas dissolved Mn was only 25 µM, in the anoxic water column. This indicates that Fe is the dominant metal involved in sulfur redox cycling and precipitation. Consequently, in the anoxic deep layer of Lake Pavin, “free” sulfide, H₂S/HS⁻, was low; and about 80% of total sulfide detected was in the electroactive FeS colloidal form. IAP calculations showed that the Lake Pavin water column is saturated with respect to FeS_am phase. The upper part of monimolimnion layer is characterized by higher concentrations of S(0) (up to 3.4 µM) in comparison to the bottom of the lake. This behavior is probably influenced by sulfide oxidation with Fe(III) oxyhydroxide species.     

Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: C/C and O/O implications for cleat origin and coalbed methane generation

Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO₂ were evaluated in combination with measured values and published estimates of δ¹⁸O of coalbed paleowaters that had been present at the time of mineralization. δ¹⁸O_mineral and δ¹⁸O_water values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272 Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600 m at  78 ± 5 °C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between  500 to  1300 m at a lower temperature of 43 ± 6 °C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a δ¹⁸O_water  − 1.25‰ versus VSMOW. Inoculation of coalbeds with methanogenic CO₂-reducing microbes occurred at an even later time, because modern microbially influenced ¹³C-enriched coalbed CO₂ (i.e., the isotopically fractionated residue of microbial CO₂ reduction) is out of isotopic equilibrium with ¹³C-depleted calcite in cleats.     

Europium retention onto clay minerals from 25 to 150 °C: Experimental measurements, spectroscopic features and sorption modelling

The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO₄ solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10⁻⁶ mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni²⁺, Cs⁺ and Ln³⁺ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta69, 4937-4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be AlOEu²⁺ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the AlOEu²⁺ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta66, 2325-2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p].     

Diffusion of lead in plagioclase and K-feldspar: an investigation using Rutherford Backscattering and Resonant Nuclear Reaction Analysis

Chemical diffusion of Pb has been measured in K-feldspar (Or₉₃) and plagioclase of 4 compositions ranging from An₂₃ to An₉₃ under anhydrous, 0.101 MPa conditions. The source of diffusant for the experiments was a mixture of PbS powder and ground feldspar of the same composition as the sample. Rutherford Backscattering (RBS) was used to measure Pb diffusion profiles. Over the temperature range 700–1050°C, the following Arrhenius relations were obtained (diffusivities in m²s^-1):Oligoclase (An₂₃): Diffusion normal to (001): log D = ( – 6.84 ± 0.59) – [(261 ± 13 kJ mol ^–1)/2.303RT]Diffusion normal to (010): log D = ( – 3.40 ± 0.50) – [(335 ± 11 kJ mol ^–1)/2.303RT]Andesine (An₄₃): Diffusion normal to (001): log D = ( – 6.73 ± 0.54) – [(266 ± 12 kJ mol ^–1)/2.303RT] Diffusion normal to (010) appears to be only slightly slower than diffusion normal to (001) in andesine.Labradorite (An₆₇): Diffusion normal to (001): log D = ( – 7.16 ± 0.61) – [(267 ± 13 kJ mol ^–1)/2.303RT] Diffusion normal to (010) is slower by 0.7 log units on average.Anorthite Diffusion normal to (010): log D = ( – 5.43 ± 0.48) – [(327 ± 11 kJ mol ^–1)/2.303RT]K-feldspar (Or₉₃): Diffusion normal to (001): log D = ( – 4.74 ± 0.52) – [(309 ± 16 kJ mol ^–1)/2.303RT] Diffusion normal to (010): log D = ( – 5.99 ± 0.51) – [(302 ± 11 kJ mol ^–1)/2.303RT]In calcic plagioclase, Pb uptake is correlated with a reduction of Ca, indicating the involvement of PbCa exchange in chemical diffusion. Decreases of Na and K concentrations in sodic plagioclase and K-feldspar, respectively, are correlated with Pb uptake and increase in Al concentration (measured by resonant nuclear reaction analysis), suggesting a coupled process for Pb exchange in these feldspars. These results have important implications for common Pb corrections and Pb isotope systematics. Pb diffusion in apatite is faster than in the investigated feldspar compositions, and Pb diffusion rates in titanite are comparable to both K-feldspar and labradorite. Given these diffusion data and typical effective diffusion radii for feldspars and accessory minerals, we may conclude that feldspars used in common Pb corrections are in general less inclined to experience diffusion-controlled Pb isotope exchange than minerals used in U-Pb dating that require a common Pb correction.     

Kinetics of leaching of oxidized and reduced ilmenite in dilute hydrochloric acid solutions

Ilmenite separated from beach sands of Bangladesh was oxidized for 1 h at 950 °C and then reduced in charcoal for 4 h at 1050 °C. This was followed by leaching in 5% to 15% hydrochloric acid solution in temperature range of 30 to 75 °C for periods of up to 2 h. The results were compared with those obtained by leaching of ilmenite reduced without oxidizing. Oxidation prior to reduction of the ilmenite was found to increase both the extent and the rate of leaching. The residual iron contents after leaching were also found to be lower than that obtained for non-oxidized samples. The kinetic data of leaching of ilmenite reduced after oxidation was found to follow first order reaction model, i.e., G(α) = − ln(1 − α) up to an α value of 0.5 (i.e. up to 50% reduction) and then changed to spherical model, i.e., G(α) = [1 − (1 − α)]³. On the other hand, leaching of ilmenite reduced without oxidizing was found to follow the Ginstling-Brounshtein reaction, i.e., G(α) = 1 − (2/3)α − (1 − α)^2/3 throughout the leaching process. Oxidation of ilmenite prior to reduction was also found to have decreased the activation energy of leaching from 43 kJ/mol, found for samples leached after reduction without oxidizing, to 30 kJ/mol.     

Solution mechanisms of silicate in aqueous fluid and H2O in coexisting silicate melts determined in-situ at high pressure and high temperature

The structure of H₂O-saturated silicate melts, coexisting silicate-saturated aqueous solutions, and supercritical silicate liquids in the system Na₂O·4SiO₂–H₂O has been characterized with the sample at high temperature and pressure in a hydrothermal diamond anvil cell (HDAC). Structural information was obtained with confocal microRaman and with FTIR microscopy. Fluids and melts were examined along pressure-temperature trajectories defined by the isochores of H₂O at nominal densities, ρ_fluid, (from EOS of pure H₂O) of 0.90 and 0.78 g/cm³. With ρ_fluid = 0.78 g/cm³, water-saturated melt and silicate-saturated aqueous fluid coexist to the highest temperature (800 °C) and pressure (677 MPa), whereas with ρ_fluid = 0.90 g/cm³, a homogeneous single-phase liquid phase exists through the temperature and pressure range (25–800 °C, 0.1–1033 MPa). Less than 5 vol% quartz precipitates near 650 °C in both experimental series, thus driving Na/Si-ratios of melt + fluid phase assemblages to higher values than that of the Na₂O·4SiO₂ starting material.Molecular H₂O (H₂O°) and structurally bonded OH groups were observed in coexisting melts and fluids as well as in supercritical liquids. Their OH/(H₂O)-ratio is positively correlated with temperature. The OH/(H₂O)° in melts is greater than in coexisting fluids. Structural units of Q³, Q², Q¹, and Q⁰ type are observed in all phases under all conditions. An expression of the form, 12Q³ + 13H₂O2Q² + 6Q¹ + 4Q⁰, describes the equilibrium among those structural units. This equilibrium shifts to the right with increasing pressure and temperature with a ΔH of the reaction near 425 kJ/mol.     

Age constraints on the formation and emplacement of Neoproterozoic ophiolites along the Allaqi–Heiani Suture, South Eastern Desert of Egypt

Ophiolites are key components of the Neoproterozoic Arabian–Nubian Shield (ANS). Understanding when they formed and were emplaced is crucial for understanding the evolution of the ANS because their ages tell when seafloor spreading and terrane accretion occurred. The Yanbu–Onib–Sol Hamed–Gerf–Allaqi–Heiani (YOSHGAH) suture and ophiolite belt can be traced  600 km across the Nubian and Arabian shields. We report five new SHRIMP U–Pb zircon ages from igneous rocks along the Allaqi segment of the YOSHGAH suture in southernmost Egypt and use these data in conjunction with other age constraints to evaluate YOSHGAH suture evolution. Ophiolitic layered gabbro gave a concordia age of 730 ± 6 Ma, and a metadacite from overlying arc-type metavolcanic rocks yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 733 ± 7 Ma, indicating ophiolite formation at  730 Ma. Ophiolite emplacement is also constrained by intrusive bodies: a gabbro yielded a concordia age of 697 ± 5 Ma, and a quartz-diorite yielded a concordia age of 709 ± 4 Ma. Cessation of deformation is constrained by syn- to post-tectonic granite with a concordia age of 629 ± 5 Ma. These new data, combined with published zircon ages for ophiolites and stitching plutons from the YOSHGAH suture zone, suggest a 2-stage evolution for the YOSHGAH ophiolite belt ( 810–780 Ma and  730–750 Ma) and indicate that accretion between the Gabgaba–Gebeit–Hijaz terranes to the south and the SE Desert–Midyan terranes to the north occurred as early as 730 Ma and no later than 709 ± 4 Ma.     

Diffusive transport of water in porous feldspars from granitic saprolites: In situ experiments using FTIR spectroscopy

A novel experimental cell was developed for in situ measurements of transport phenomena in porous media using Fourier-Transform Infrared (FTIR) Spectroscopy. The technique was employed at ambient pressure in the temperatures range of 11–44 °C to study the H₂O → D₂O exchange between water-saturated weathered feldspars (bulk porosity of 5–19 vol% for feldspar) from granitic saprolites and a surrounding aqueous liquid. Such measurements are an important step for understanding internal weathering reactions of feldspars in soils and aquifers. Effective diffusion coefficients D_eff for water in water-saturated porous feldspars were determined assuming one-dimensional diffusion in a quasi-homogeneous medium. The values of D_eff vary from 7.2 × 10⁻¹⁰ to 1.9 × 10⁻¹¹ m²/s and are 1–2 orders of magnitude lower than the diffusion coefficients (D) of protons and molecular H₂O in liquid water. The activation energy for the H₂O → D₂O exchange process in porous feldspars ranges from 7.8 to 18.8 kJ/mol.The results imply that the effective diffusivity of water is mainly controlled by physical properties of the feldspars like porosity, pore connectivity, pore geometry and distribution. Perthitic feldspars with homogeneous pore distribution in the albitic lamellas have diffusional tortuosity factors X = D/D_eff between 3 and 10 while alkali feldspars with inhomogeneously distributed and disconnected pores have much higher X values up to 129. Diffusion anisotropy has been verified for a vein perthite with diffusion perpendicular to the lamellas being faster by 0.3–0.5 log units than within the lamellas. It has to be emphasized that the study is based only on few selected feldspars, including perthitic feldspar, and additional work on samples with different weathering stages is needed to test the importance of the different parameters controlling diffusive transport in the pore system.     

Glide systems of hematite single crystals in deformation experiments

The critical resolved shear stresses (CRSSs) of hematite crystals were determined in compression tests for r-twinning, c-twinning and {a}<m>-slip in the temperature range 25 °C to 400 °C, at 400 MPa confining pressure, and a strain rate of 10^− 5 s^− 1 by Hennig-Michaeli, Ch., Siemes, H., 1982. Experimental deformation of hematile crstals betwen 25 °C and 400 °C at 400 MPa confining pressure. In: Schreyer, W. (Ed.) High Pressure Research in Geoscience, Schweizerbart'sche Verlagsbuchhandlung, Stuttgart, p. 133–150. In the present contribution newly performed experiments on hematite single crystals at temperatures up to 800 °C at strain rates of 10^− 5 s^− 1 and 300 MPa confining pressure extends the knowledge about the CRSS of twin and slip modes. Optical observations, neutron diffraction goniometry, SEM forescatter electron images and electron backscatter diffraction are applied in order to identify the glide modes. Both twinning systems and {a}<m>-slip were confirmed by these methods. Besides the known glide systems the existence of the (c)<a>-slip system could be stated. Mechanical data establish that the CRSS of r-twinning decreases from 140 MPa at 25 °C to  5 MPa at 800 °C and for {a}<m>-slip from > 560 MPa at 25 °C to  40 MPa at 700 °C. At room temperature the CRSS for c-twinning is around 90 MPa and at 600 °C  60 MPa. The data indicate that the CRSSs above 200 °C seem to be between the values for r-twinning and {a}<m>-slip. For (c)<a>-slip only the CRSS at 600 °C could be evaluated to  60 MPa. Exact values are difficult to determine because other glide systems are always simultaneously activated.     

Les argiles bleues du Cambrien inférieur de Saint-Pétersbourg et leur fissuration. Implications pour des stockages souterrains

The Lower Cambrian Saint Petersburg blue clays are composed of predominant illite and chlorite, sometimes accompanied by kaolinite. The <0.1 μm fraction has a high content of illite–smectite mixed layers. Particle-size distribution is more than 50% of clay particles and about 30% of silts. These blue clays correspond to plastic (and soft) clays; they may be compared to the Callovian clays of Bure (France), where storage of natural waste is envisaged. To cite this article: M. Arnould et al., C. R. Geoscience 334 (2002) 1135–1140.

Résumé

Les « argiles bleues » du Cambrien Inférieur de Saint-Pétersbourg sont constituées d'illite dominante et de chlorite, avec parfois présence de kaolinite. Des interstratifiés illite/montmorillonite sont très abondants dans la phase <0,1 μm. Du point de vue granulométrique, outre plus de 50% de particules argileuses, il existe une phase silteuse de l'ordre de 30%. Du point de vue pétrophysique, ce sont des argiles plastiques, de consistance molle. Elles sont subhorizontales et ont jusqu'à 116 m d'épaisseur. Outre l'absence de métamorphisme, malgré leur âge, leur caractère le plus remarquable est leur réseau de fracturation, bien observable en carrière. Les joints sont nets, sans remplissage ni cimentation. Les plans verticaux sont particulièrement développés. Le volume unitaire des blocs de matrice ne dépasse guère 1 m³. Des traces d'oxydation témoignent de circulations d'eau. Ces argiles silteuses anciennes peuvent aider à mieux connaı̂tre et comprendre les argilites silteuses épigénétiques calloviennes du site de Bure (Haute-Marne, France), où un stockage souterrain de déchets nucléaires est envisagé. Pour citer cet article : M. Arnould et al., C. R. Geoscience 334 (2002) 1135–1140.     

A new view on gold speciation in sulfur-bearing hydrothermal fluids from in situ X-ray absorption spectroscopy and quantum-chemical modeling

Despite the common belief that Au^I complexes with hydrogen sulfide ligands (H₂S/HS⁻) are the major carriers of gold in natural hydrothermal fluids, their identity, structure and stability are still subjects of debate. Here we present the first in situ measurement, using X-ray absorption fine structure (XAFS) spectroscopy, of the stability and structure of aqueous Au^I–S complexes at temperatures and pressures (T–P) typical of natural sulfur-rich ore-forming fluids. The solubility of native gold and the local atomic structure around the dissolved metal in S–NaOH–Na₂SO₄–H₂SO₄ aqueous solutions were characterized at temperatures 200–450 °C and pressures 300–600 bar using an X-ray cell that allows simultaneous measurement of the absolute concentration of the absorbing atom (Au) and its local atomic environment in the fluid phase. Structural and solubility data obtained from XAFS spectra, combined with quantum-chemical calculations of species geometries, show that gold bis(hydrogensulfide) Au(HS)₂⁻ is the dominant Au species in neutral-to-basic solutions (5.5  pH  8.5; H₂O–S–NaOH) over a wide range of sulfur concentrations (0.2 < ΣS < 3.6 mol/kg), in agreement with previous solubility studies. Our results provide the first direct determination of this species structure, in which two sulfur atoms are in a linear geometry around Au^I at an average distance of 2.29 ± 0.01 Å. At acidic conditions (1.5  pH  5.0; H₂O–S–Na₂SO₄–H₂SO₄), the Au atomic environment determined by XAFS is similar to that in neutral solutions. These findings, together with measured high Au solubilities, are inconsistent with the predominance of the gold hydrogensulfide Au(HS)⁰ complex suggested by recent solubility studies. Our spectroscopic data and quantum-chemical calculations imply the formation of species composed of linear S–Au–S moieties, like the neutral [H₂S–Au–SH] complex. This species may account for the elevated Au solubilities in acidic fluids and vapors with H₂S concentrations higher than 0.1–0.2 mol/kg. However, because of the complex sulfur speciation in acidic solutions that involves sulfite, thiosulfate and polysulfide species, the formation of Au^I complexes with these ligands (e.g., AuHS(SO₂)⁰, Au(HS₂O₃)₂⁻, Au(HS_n)₂⁻) cannot be ruled out. The existence of such species may significantly enhance Au transport by high T–P acidic ore-forming fluids and vapors, responsible for the formation of a major part of the gold resources on Earth.     

Loch Lomond Stadial glaciers in North Harris, Outer Hebrides, North-West Scotland: glacier reconstruction and palaeoclimatic implications

Geomorphological mapping of North Harris provides evidence for the former existence of 10 glaciers with a total area of ca 35 km². A Loch Lomond (Younger Dryas) Stadial age (ca 12.9–11.5 kyr BP) for this glacial episode is inferred from glacier configuration, landsystems dominated by hummocky recessional moraines, and relationships with Lateglacial periglacial phenomena. Equilibrium line altitudes (ELAs) of 150–289 m were calculated for individual glaciers. ELA variability mainly reflects differences in snow-contributing area. The area-weighted mean ELA (204 m) is consistent with a northwards decline in ELAs along the western seaboard of the British Isles of 69.5 m (100 km)⁻¹, equivalent to a northwards ablation-season temperature decrease of 0.42 °C (100 km)⁻¹. This latitudinal temperature gradient implies a mean July sea-level temperature of ca 7.2 °C for the coldest part of the stade, roughly 6 °C lower than at present. Sea-level precipitation at the time of the LLS glacial maximum is inferred to have been between ca 1970±200 and 2350±200 mm yr⁻¹, implying that LLS precipitation was up to 25% greater than now. Patterns of recessional moraines indicate that the glaciers remained close to climatic equilibrium as they retreated to their sources, though moraine belts implying near-stationary or readvancing ice margins on flat valley floors are separated by moraine-free zones indicating uninterrupted retreat. Calculation of ELAs for ‘residual’ glaciers in former source areas suggests that summer warming of 1.0 °C would have resulted in shrinkage of the glaciers to their sources.     

Control of As and Ni releases from a uranium mill tailings neutralization circuit: Solution chemistry, mineralogy and geochemical modeling of laboratory study results

Processing U ores in the JEB Mill of the McClean Lake Operation in northern Saskatchewan produces spent leaching solutions (raffinates) with pH  1.5, and As and Ni concentrations up to 6800 and 5200 mg L⁻¹, respectively. Bench-scale neutralization experiments (pH 2–8) were performed to help optimize the design of mill processes for reducing As and Ni concentrations in tailings and raffinates to 1 mg L⁻¹ prior to their disposal. Precipitate mineralogy determined by chemical analysis, XRD, SEM, EM, XM and EXAFS methods, included gypsum (the dominant precipitate), poorly crystalline scorodite (precipitated esp. from pH 2–4), annabergite, hydrobasaluminite, ferrihydrite, green rust II and theophrastite. The As was mostly in scorodite with smaller amounts in annabergite and trace As adsorbed and/or co-precipitated, probably by ferrihydrite. Geochemical modeling indicated that above pH 2, the ion activity product (IAP) of scorodite lies between the solubility products of amorphous and crystalline phases (log K_sp = −23.0 and −25.83, respectively). The IAP decreases with increasing pH, suggesting that the crystallinity of the scorodite increases with pH. Forward geochemical models support the assumption that during neutralization, particles of added base produce sharp local pH gradients and disequilibrium with bulk solutions, facilitating annabergite and theophrastite precipitation.     

Age and kinematics of ductile deformation in the Cerro Durazno area, NW Argentina: Significance for orogenic processes operating at the western margin of Gondwana during Ordovician – Silurian times

The Cerro Durazno Pluton belongs to a suite of Paleozoic granitoid intrusions in NW-Argentina, that are central for understanding the tectonic setting of the western margin of Gondwana in Ordovician and Silurian times. The pluton and its host rocks were tectonically overprinted by metamorphic mineral shape fabrics formed under middle greenschist-facies metamorphic conditions and associated with the nearby Agua Rosada Shear Zone. Kinematic analysis of the shear zone based on the geometric relationship between individual segments of the shear plane and principal axes of mineral fabric ellipsoids indicates reverse-sense of shear with a minor component of left-lateral displacement. This is compatible with the kinematics of other ductile deformation zones in this area, collectively forming a network, which accomplished orogen-parallel extension in addition to vertical thickening. Using the Rb–Sr isotopic system, an undeformed pegmatite dike of the Cerro Durazno Pluton was dated at 455.8 ± 3.6 Ma and mineral fabrics of the Agua Rosada Shear Zone formed at middle greenschist-facies metamorphism gave deformation ages of 437.0 ± 3.8 Ma and 428.4 ± 4.5 Ma. Thus, tectonic overprint at low metamorphic grade occurred about 20–30 Ma after terminal magmatism in the Cerro Durazno area. Our data from the Cerro Durazno area and regional considerations suggest that the western margin of Gondwana was characterized by orogen-parallel extension in addition to crustal thickening as well as episodes of magmatism and ductile deformation that varied greatly in time and space.     

Source parameters of the ML 4.1 earthquake of November 08, 2006, southeast Beni-Suef, northern Egypt

In the early morning hours on Wednesday November 08, 2006 at 04:32:10(GMT) a small earthquake of M_L 4.1 has occurred at southeast Beni-Suef, approximately 160 km SEE of Cairo, northern Egypt. The quake has been felt as far as Cairo and its surroundings while no casualties were reported. The instrumental epicentre is located at 28.57°N and 31.55°E. Seismic moment is 1.76 E14 Nm, corresponding to a moment magnitude M_w 3.5. Following a Brune model, the source radius is 0.3 km with an average dislocation of 1.8 cm and a 2.4 MPa stress drop. The source mechanism from a first motion fault plane solution shows a left-lateral strike-slip mechanism with a minor dip-slip component along fault NNW striking at 161°, dipping 52° to the west and rake −5°. Trend and plunging of the maximum and minimum principle axes P/T are 125°, 28°, 21°, and 23°, respectively. A comparison with the mechanism of the October, 1999 event shows similarities in faulting type and orientation of nodal planes.Eight small earthquakes (3.0  M_L < 5.0) were also recorded by the Egyptian National Seismological Network (ENSN) from the same region. We estimate the source parameters and fault mechanism solutions (FMS) for these earthquakes using displacement spectra and P-wave polarities, respectively. The obtained source parameters including seismic moments of 4.9 × 10¹²–5.04 × 10¹⁵ Nm, stress drops of 0.2–4.9 MPa and relative displacement of 0.1–9.1 cm. The azimuths of T-axes determined from FMS are oriented in NNE–SSW direction. This direction is consistent with the present-day stress field in Egypt and the last phase of stress field changes in the Late Pleistocene, as well as with recent GPS measurements.     

Kaolinite and smectite dissolution rate in high molar KOH solutions at 35° and 80°C

Experiments measuring kaolinite and smectite dissolution rates were carried out using batch reactors at 35° and 80°C. No potential catalysts or inhibitors were present in solution. Each reactor was charged with 1 g of clay of the ≤2 μm fraction and 80, 160 or 240 ml of 0.1–4 M KOH solution. An untreated but sized kaolinite from St. Austell and two treated industrial smectites were used in the experiments. One smectite is a nearly pure montmorillonite, while the second has a significant component of beidellitic charge (35%). The change in solution composition and mineralogy was monitored as a function of time. Initially, the 3 clays dissolved congruently. No new formed phases were observed by XRD and SEM during the pure dissolution stage. The kaolinite dissolution is characterized by a linear release of silica and Al as a function of the log of time. This relationship can be explained by a reaction affinity effect which is controlled by the octahedral layer dissolution. Far from equilibrium, dissolution rates are proportional to a^0.56±0.12_OH⁻ at 35°C and to a^0.81±0.12_OH⁻ at 80°C. The activation energy of kaolinite dissolution increases from 33±8 kJ/mol in 0.1 M KOH solutions to 51±8 kJ/mol in 3 M KOH solutions. In contrast to kaolinite, the smectites dissolve at much lower rates and independently of the aqueous silica or Al concentrations. The proportionality of the smectite dissolution rate constant at 35 and 80°C was a^0.15±0.06_OH⁻. The activation energy of dissolution appears to be independent of pH for smectite and is found to be 52±4 kJ/mol. The differences in behavior between the two kinds of minerals can be explained by structural differences. The hydrolysis of the tetrahedral and the octahedral layer appears as parallel reactions for kaolinite dissolution and as serial reactions for smectite dissolution. The rate limiting step is the dissolution of the octahedral layer in the case of kaolinite, and the tetrahedral layer in the case of smectite.     

Magnesite growth rates as a function of temperature and saturation state

Magnesite growth rates and step velocities have been measured systematically as a function of temperature from 80 to 105 °C and saturation state in 0.1 M NaCl solutions using hydrothermal atomic force microscopy (HAFM). The observations indicate that at these conditions magnesite precipitation is dominated by the coupling of step generation via spiral growth at screw dislocations and step advancement away from these dislocations. As these two processes occur in series the slowest of these dominates precipitation rates. At 100 °C magnesite growth rates (r) determined by HAFM are consistent with

r=k(Ω-1)²,