The ion-pair constant and other thermodynamic properties of HCl up to 350°C

Solubilities of silver chloride in aqueous hydrochloric acid solutions have been determined from 100 up to 350°C. From these measurements, the ionisation constant of HC1 has been evaluated up to 225°C. Evidence is presented to show that a protonated silver species, HAgCl₂⁰, exists at 275°C and above. Available experimental data up to 200°C have been firted to Pitzer's equation to generate an algorithm to calculate stoichiometric activity and osmotic coefficients of HCl up to 350°C and concentrations up to at least 3.0 m. Using the present results and those of Wrightet al. (1961), Pearsonet al. (1963) and Lukashowet al. (1976), the dissociation constant (K_d) of HCl as a function of temperature is described by the equation log₁₀K = 2136.898 + 1.020349T−4.5045 × 10⁻⁴T²−50396.40/T−901.770 10g₁₀T (Tin °K) which is valid in the range 25–350°C. Calculated enthalpy (ΔH⁰), entropy (ΔS⁰) and heat capacity change (ΔC_p⁰) functions for HCl dissociation have been rationalized in terms of changing solute and solvent characteristics as temperature is raised.     

The stability of chlorozinc(II) complexes in hydrothermal solutions up to 350°C

Solubilities of AgCl in aqueous Zn(II)-HCl solutions have been measured from 100 to 350°C at the saturated vapour pressure. From these measurements, the cumulative equilibrium formation constants of chlorozinc(II) complexes have been evaluated using a nonlinear least squares procedure. At 100°C. all the species ZnCl²⁻ⁿ_n (n = 0 to 4) exist, but as temperature rises, ZnCl⁻₃ concentrations decrease and its stability field vanishes above 200°C. Chlorozinc(II) complex formation is characterized by large positive enthalpy and entropy changes, reflecting the predominantly electrostatic interaction between the acceptor (Zn) and donor (Cl) species. Zinc transport is evaluated in two contrasting geothermal fluids and it is found that Zn chloride complexing is important in low pH, S-deficient hydrothermal solutions (Bacon-Manito, Philippines) of moderate to high salinity but not necessarily in near neutral to alkaline solutions (Broadlands, New Zealand). Sphalerite solubilities in chloride solutions have been calculated using the formation constants obtained in the present study.     

Iodine diagenesis in pelagic deep-sea sediments

Nineteen sediment cores from the Madeira, Seine, Tagus and Nares Abyssal Plains and the Alboran Sea have been used to evaluate the speciation, fluxes and diagenesis of iodine in the deep sea. The sediments have surficial molar I/C ratios of 10–30 × 10⁻⁴ in excess of previous reported values for planktonic material (~1 × 10⁻⁴). Solid phase I contents decrease exponentially with depth corresponding to decomposition rate constants of 5–260 × 10⁻⁶ yr⁻¹ which vary with the carbon accumulation rate.Iodine species in the pore waters follow a vertical sequence of four zones: 1. a zone of I⁻ production where total dissolved iodine (∑I) concentrations initially increase at the seawater-sediment interface; 2. a zone of I⁻ oxidation where interconversion of I⁻ to IO⁻₃ occurs; 3. a zone of IO⁻₃ reduction where interconversion of IO⁻₃ back to I⁻ occurs which corresponds to the suboxic part of the sediment column; and 4. a further zone of I⁻ production which is confined to the lower anoxic part of the sediment column. Benthic ∑I fluxes in the Madeira Abyssal Plain measured from shipboard incubation experiments and calculated from porewater gradients are similar, averaging 0.55 and 0.36 × 10⁻⁸ μmol cm⁻² sec⁻, respectively.In the surface sediment the observed I enrichment results from a quasi-closed cycle for iodine initially involving release of I⁻ from decomposing marine organic matter followed by rapid removal onto organic matter at the sediment-seawater interface where I/C regeneration ratios of up to 200 × 10⁻⁴ are found, lodate reduction occurs during suboxic diagenesis, after denitrification and before MnO₂ reduction, consistent with the sequence of reactions predicted from the free energy yields for organic matter oxidation. There is some further I⁻ production in the anoxic section of sediments but at much smaller rates than occur during the interfacial diagenetic cycling.     

Dissolution kinetics of galena in acid NaCl solutions at 25—75 °C

Experiments on dissolution kinetics of galena were performed in 1 mol l⁻¹ NaCl solutions at pH 0.43–2.45 and 25–75 °C. When the dissolution reaction is far from equilibrium, a linear relation exits between the dissolution rate, r, and the H⁺ ion activity, [H⁺]. The rate law for galena dissolution is given by the following equation: r=k[H⁺]. With respect to H⁺, the dissolution reaction is in the first order. The apparent rate constant, k, has values of 2.34×10⁻⁷ mol m⁻² s⁻¹ at 25 °C, 1.38×10⁻⁶ mol m⁻² s⁻¹ at 50 °C, and 7.08×10⁻⁶ mol m⁻² s⁻¹ at 75 °C. The activation energy of dissolution reaction is 43.54 kJ mol⁻¹. The mechanism of dissolution is suggested to be surface chemical reaction, and the rate determining step is the dissociation of the Pb–S bond of the surface complex, which releases Pb²⁺ into the solution.     

Coal weathering and the geochemical carbon cycle

The weathering rate of sedimentary organic matter in the continental surficial environment is poorly constrained despite its importance to the geochemical carbon cycle. During this weathering, complete oxidation to carbon dioxide is normally assumed, but there is little proof that this actually occurs. Knowledge of the rate and mechanisms of sedimentary organic matter weathering is important because it is one of the major controls on atmospheric oxygen level through geologic time.We have determined the aqueous oxidation rates of pyrite-free bituminous coal at 24° and 50°C by using a dual-cell flow-through method. Coal was used as an example of sedimentary organic matter because of the difficulty in obtaining pyrite-free kerogen for laboratory study. The aqueous oxidation rate obtained in the present study for air-saturated water (270 μM O₂) was found to be on the order of 2 × 10⁻¹² mol O₂/m²/s at 25°C, which is fast compared to other geologic processes such as tectonic uplift and exposure through erosion. The reaction order with respect to oxygen level is 0.5 on a several thousand hour time scale for both 24° and 50°C experiments. Activation energies, determined under 24° and 50°C conditions, were ≈40 kJ/mol O₂ indicating that the oxidation reaction is surface reaction controlled.The oxygen consumption rate obtained in this study is two to three orders of magnitude smaller than that for pyrite oxidation in water, but still rapid on a geologic time scale. Aqueous coal oxidation results in the formation of dissolved CO₂, dissolved organic carbon (DOC), and solid oxidation products, which are all quantitatively significant reaction products.     

Thermal decarboxylation of acetic acid: Implications for origin of natural gas

Laboratory experiments on the thermal decarboxylation of solutions of acetic acid at 200°C and 300°C were carried out in hydrothermal equipment allowing for on-line sampling of both the gas and liquid phases for chemical and stable-carbon-isotope analyses. The solutions had ambient pH values between 2.5 and 7.1; pH values and the concentrations of the various acetate species at the conditions of the experiments were computed using a chemical model.Results show that the concentrations of acetic acid, and not total acetate in solution, control the reaction rates which follow a first order equation based on decreasing concentrations of acetic acid with time. The decarboxylation rates at 200°C (1.81 × 10^?8 per second) and 300°C (8.17 × 10^?8 per second) and the extrapolated rates at lower temperatures are relatively high. The activation energy of decarboxylation is only 8.1 kcal/mole. These high decarboxylation rates, together with the distribution of short-chained aliphatic acid anions in formation waters, support the hypothesis that acid anions are precursors for an important portion of natural gas.Results of the δ¹³C values of CO₂, CH₄, and total acetate show a reasonably constant fractionation factor of about 20 permil between CO₂ and CH₄ at 300°C. The δ¹³C values of CO₂ and CH₄ are initially low and become higher as decarboxylation increases.     

Parameters controlling the partitioning of tributyltin (TBT) in aquatic systems

In the present study the distribution of TBT between solid and water phase as a function of several parameters was determined. Two types of clay minerals (Na-montmorillonite SWy and kaolinite KGa) and quartz sand were used as sorbents in conventional batch experiments. Sorption coefficients (K_d) followed the order montmorillonite (89 l/kg) > kaolinite (51 l/kg) > quartz (25 l/kg), while for sorption coefficients normalized to the surface area (Kd′) an opposite trend was observed, with the lowest value determined for montmorillonite (2.79 × 10⁻³ l/m²) and the highest for quartz sand (8.04 × 10⁻² l/m²). The results demonstrate that numerous environmental parameters influence the adsorption process of TBT, such as solid/solution ratio, clay content and salinity. Another important factor governing TBT adsorption is pH, because it affects both the TBT species in the water phase as well as the surface properties of the mineral phase. The maximum of TBT adsorption onto clays was always around pH 6–7. According to the data, it is evident that the content of organic matter in the solid phase plays an important role on TBT adsorption, either as particulate organic matter (POM) or organic matter adsorbed to mineral particles (AOM). Experiments were carried out with well characterized organic matter and the results showed a linear increase of K_d from 51 up to 2700 l/kg upon the addition of 5% of particulate organic matter to pure phased kaolinite. TBT adsorption onto mineral surfaces, which were previously enriched with adsorbed organic matter, was investigated at different pH. The present study points to the importance of identifying and characterizing sorbents and envrionmental conditions, in order to predict and model TBT distribution in natural systems.     

Dissolution of silica and the development of concentration profiles in freshwater sediments

The dissolution of silica and diffusion of reactive dissolved Si in the porewaters of river sediments are investigated using sediments of different physical and chemical properties. Three sediments are considered: (a) from sectioned cores taken from a river-bed, (b) fine organic-rich surface sediment (<5 cm depth) installed in a fluvarium channel and, (c) coarse river sediment of low organic matter content also installed in a fluvarium channel. Dissolution rates of silica are measured at 10°C using batches of suspended material. The derived dissolution rate constants show large differences between the sediments. The river bed-sediment cores had vertical concentration profiles of dissolved Si that are consistent with the diffusion and dissolution of biogenic silica. Experiments in a fluvarium channel enabled Si fluxes to be calculated from a mass-balance of the overlying solution. The results are consistent with the attainment of a steady-state concentration profile of dissolved Si in the sediment. There are no discernible effects of water velocity over the sediment between 5 and 11 cm s⁻¹. However, at 20 cm s⁻¹, the flux increases as a result of either entrainment of fine particles at the surface or advective effects in the surface sediment. A fluvarium experiment with the fine sediment (<125 μm) over 61 days, produced a concentration profile with the highest concentration of 1025 μmol dm⁻³ at a depth of 4–5 cm in the sediment. A FORTRAN program is used to model the results of the increase in dissolved Si in the overlying water and development of a concentration profile in the porewater. This leads to a sediment diffusion coefficient of 1.21×10⁻⁹ m² s⁻¹ at 8.8°C at the beginning of the experiment and rate constant k=13.1×10⁻⁷ s⁻¹ at pH=7.82 and average temperature of 7.6°C for the entire experiment. Fluxes measured at the sediment–surface interface and calculated assuming steady-state profiles had developed are typically 0.01–0.04 μmol m⁻² (of river bed) s⁻¹. The approach enables the efflux of dissolved Si from bottom-sediments to be estimated from dissolution rates measured using suspensions of bed-sediment.     

Experimental study of the influence of sulfur on gold sorption by bitumen at 200–400°C and 1 kbar Pressure

The effect of sulfur on the sorption of gold by carbonaceous matter (CM) was investigated under hydrothermal conditions (200–400°C and 1 kbar) using the autoclave-ampoule method. The model CM was represented by asphaltenes fractionated from the lignite of the Pavlovskoe coal field. The source of gold was the walls of the Au container, which were dissolved in water under the experimental conditions. Sulfur was added as finely ground pyrite (C-S-Fe-O-H-Au system) or elemental sulfur powder (C-S-O-H-Au system). The contents of Au were measured by atomic absorption spectrometry with electrothermal atomization in quenched aqueous solutions (WF), soluble organic fraction (SF), and insoluble residue (kerogen). The lowest Au concentration was detected in the WF, −8.96 < logmAu < −6.32. The Au concentration is higher in the SF (−5.02 < logmAu < −4.34) and increases by more then an order of magnitude in the kerogen, −3.94 < logmAu < −2.33. The IR spectra of the experimental products showed that sulfur was accumulated in the kerogen, whereas no C-S functional groups were observed in the SF. This is the reason for the negligible influence of sulfur in this system on Au concentration in the SF. The maximum Au concentration was detected in the kerogen in the presence of pyrite, which was transformed into pyrrhotite at 400°C. Thus, iron sulfides promote Au uptake by kerogen from ore-bearing hydrothermal fluids.     

An Experimental Study of Oxygen Isotope Fractionation in the Quartz—Wolframite—Water System

Oxygen isotope fractionation was experimentally studied in the quartz-wolframite-water system from 200 to 420 °C. The starting wolframite was synthesized in aqueous solutions of Na₂WO₄ · 2H₂O + FeCl₂ · 4H₂O or MnCl₂ · 4H₂O. The starting solutions range in salinity from 0 to 10 equivalent wt.% NaCl. Experiments were conducted in a gold-lined stainless steel autoclave, with filling degrees of about 50%. The results showed no significant difference in equilibrium isotope fractionation between water and wolframite, ferberite and huebnerite at the same temperature (310 °C ). The equilibrium oxygen isotope fractionation factors of wolframite and water tend to be equal with increasing temperature above 370 °C, but to increase significantly with decreasing temperature below 370 °C: 1000 ln α_wf-H₂o= 1.03×10⁶T−2-4.91 (370 °C ±200 °C ) 1000 ln α_wf-H₂o = 0.21×10⁶T −2-2.91 (420 °C -370 °C ±) This projects was financially supported by the National Natural Science Foundation of China.     

Celestite (SrSO4(s)) solubility in water,seawater and NaCl solution

Celestite solubility measurements have been conducted in pure water at temperatures from 10 to 90°C. Equilibrium was achieved with respect to a crystalline solid phase from both undersaturated and supersaturated solutions. The measurements show that the solubility undergoes a maximum near 20°C. LogK values for the solubility reaction are adequately described by the following expression over the temperature range 283.15 to 363.15 K: −logK= −35.3106+0.00422837T+318312/T²+14.99586 logT.The following thennodynamic values for the dissolution reaction of SrSO_4(s), at 25°C have been derived: ΔG_R⁰ = 37852 ± 30 Jmol⁻¹ΔH_R⁰ = −1668±920Jmol⁻¹ΔS_R⁰= −132.6±3.2JK^−1mol−1Celestite solubility measurements were also determined in NaCl solutions up to 5 m concentration and from 10 to 40°C. These data are in good agreement with the work of StrÜbel (1966), who reports solubility measurements to temperatures of 100°C.The application of the Pitzer relations and the solubility constants determined in this study to calculate celestite solubility in NaCl solutions yields excellent agreement between predicted values and experimental measurements over the entire range of temperature and NaCl concentration conditions. For the limited number of solubility measurements in seawater-type solutions and mixed-salt brines, the agreement using the Pitzer relations is within three percent of the measured solubility.     

Sorption and desorption of mercury(II) in saline and alkaline soils of Bahía Blanca, Argentina

The objective of this work was to study sorption–desorption and/or precipitation–dissolution processes of Hg(II) compounds considering an eventual contact of soils with Hg-bearing wastes. In addition, this study contributes new data about Hg(II) chemistry in alkaline systems. Saline and alkaline soils with low organic matter (<1 %) and high clay content (60–70 %) were obtained near a chlor-alkali plant. Batch techniques were used to perform the experiments using 0.1 M NaNO₃ solutions. Total Hg(II) concentrations ranged from 6.2 × 10^?8 to 6.3 × 10^?3 M. Sorption of Hg(II) was evaluated at two concentration ranges: (a) 6.2 × 10^?8 to 1.1 × 10^?4 M, and (b) 6.4 × 10^?4 to 6.3 × 10^?3 M. At low Hg(II) concentrations, adsorption occurred with a maximum sorption capacity ranging from 4 to 5 mmol/kg. At high Hg(II) concentrations, sorption–precipitation reactions occurred and maximum sorption capacity ranged from 17 to 31 mmol/kg. The distribution of Hg(II) hydrolysis products showed that Hg(OH)₂ was the predominant species under soil conditions. According to sorption experiments, X-ray diffraction and chemical speciation modelling, the presence of Hg(OH)₂ in the interlayer of the interstratified clay minerals can be proposed. Hg(OH)₂ was partially desorbed by repeated equilibrations in 0.1 M NaNO₃ solution. Desorption ranged from 0.1 to 0.9 mmol/kg for soils treated with 5.8 × 10^?5 M Hg(II), whereas 2.1–3.8 mmol/kg was desorbed from soils treated with 6.3 × 10^?3 M Hg(II). Formation of soluble Hg(II) complexes was limited by low organic matter content, whereas neutral Hg(OH)₂ was retained by adsorption on clay mineral surfaces.     

The concentration of Cu(II), Pb(II) and Zn(II) from aqueous solutions by particulate algal matter

Experimental studies of the reactions of Cu(II), Pb(II), and Zn(II) in aqueous solutions with organic matter derived from fresh samples of the green filamentous algae Ulothrix spp. and the green unicellular algae Chlamydomonas spp. and Chlorella vulgaris show that, under suitable conditions, a significant proportion of the metals is removed from solution by sorption onto the particulate organic matter of the algal suspension.The metal sorption is strongly suppressed by H⁺ but is only marginally influenced by the proportion of whole cells in the suspension and by complexing of metals in solution by the soluble organic matter. The presence of relatively small amounts of the cations Na⁺ and Mg²⁺ in solution reduces the sorption of Zn(II) to near zero, but Pb(II) and Cu(II) sorption occurs to an appreciable extent even in strong brines. This may be a means for the selective precipitation of Pb(II) from brines rich in Pb(II) and Zn(II).Metal “saturation” values indicate that particulate algal matter of the type used in these experiments could sorb sufficient quantities of metal to form an ore deposit if a weight of organic matter of similar order of magnitude to that of the inorganic sediments in the deposits was available. However, the metal sorption is an equilibrium reaction, and the experimentally determined “enrichment factors” suggest that the “saturation” values could be approached only in solutions whose metal contents were initially at least two orders of magnitude above those of normal seawater.     

Adsorption of molybdenum on to anatase from dilute aqueous solutions

Adsorption of Mo on to hydrous TiO₂ (anatase) particles was investigated. Batch experiments were conducted at 19 and 90 °C over a pH range of 2 to 12 and Mo concentrations ranging from approximately 10⁻⁶ to 10⁻⁴ M. The extent of sorption was strongly dependent on pH and surface loading. Maximum sorption was observed in the acidic pH range at low surface loading. Adsorption behavior was described using the empirical Langmuir adsorption model. A constant capacitance surface complexation model was also used to fit the adsorption isotherms using a ligand exchange reaction for a hydroxyl surface site on anatase. Comparison of experimental data at two different temperatures (19 and 90 °C) indicates that Mo sorption in the acidic pH range decreases with increasing temperature.     

Helium measurements of pore fluids obtained from the San Andreas Fault Observatory at Depth (SAFOD, USA) drill cores

⁴He accumulated in fluids is a well established geochemical tracer used to study crustal fluid dynamics. Direct fluid samples are not always collectable; therefore, a method to extract rare gases from matrix fluids of whole rocks by diffusion has been adapted. Helium was measured on matrix fluids extracted from sandstones and mudstones recovered during the San Andreas Fault Observatory at Depth (SAFOD) drilling in California, USA. Samples were typically collected as subcores or from drillcore fragments. Helium concentration and isotope ratios were measured 4?C6 times on each sample, and indicate a bulk ⁴He diffusion coefficient of 3.5?±?1.3?×?10^?C8 cm²?s^?C1 at 21°C, compared to previously published diffusion coefficients of 1.2?×?10^?C18 cm²?s^?C1 (21°C) to 3.0?×?10^?C15 cm²?s^?C1 (150°C) in the sands and clays. Correcting the diffusion coefficient of ⁴He_water for matrix porosity (??3%) and tortuosity (??6?C13) produces effective diffusion coefficients of 1?×?10^?C8 cm^2?s^?C1 (21°C) and 1?×?10^?C7 (120°C), effectively isolating pore fluid ⁴He from the ⁴He contained in the rock matrix. Model calculations indicate that <6% of helium initially dissolved in pore fluids was lost during the sampling process. Complete and quantitative extraction of the pore fluids provide minimum in situ porosity values for sandstones 2.8?±?0.4% (SD, n?=?4) and mudstones 3.1?±?0.8% (SD, n?=?4).     

An empirical method for the determination of single ion hydrogen isotope salt effects in aqueous electrolyte solutions

An empirical method is presented that allows the determination of the individual contributions of anions and cations to the effect of dissolved salts on hydrogen isotope fractionation in aqueous systems (isotope salt effect). The method is solely based on experimental data and does not involve the choice of arbitrary reference values or theoretical assumptions. Plotting experimental liquid–vapor D/H fractionation factors for aqueous solutions of sodium salts vs. O–D stretching frequencies of water molecules in the hydration shells of the anions shows an excellent linear correlation. The distance between this line and the pure water liquid–vapor fractionation data point in the same plot gives the cation contribution to the isotope salt effects. The anion contribution can then simply be derived as the difference between the total salt effect and the cation salt effect. The validity of the concept is demonstrated using precise literature data for the O–D stretching frequencies in the hydration shells of individual ions at 20°C [Bergström, P.A., 1991. Single ion hydration properties in aqueous solution: a quantitative infrared spectroscopic study. PhD Thesis. Uppsala University] and for the liquid–vapor hydrogen isotope fractionation between aqueous solutions and water vapor at the same temperature [Stewart, M.K., Friedman, I., 1975. Deuterium fractionation between aqueous salt solutions and water vapor. Journal of Geophysical Research 80, 3812–3818]. Within the limits of experimental uncertainties, the data set shows internal consistency. Cation salt effects, 1000 ln Γ at 20°C, are (in per mil per mole per liter, using the convention of Horita et al. [Horita, J., Cole, D.R., Wesolowski, D.J., 1993a. The activity–composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: II. Vapor–liquid water equilibration of mixed salt solutions from 50–100°C. Geochimica et Cosmochimica Acta 57, 4703–4711]): Na⁺+0.7; K⁺+0.7; Mg²⁺+6.5; Ca²⁺+1.8; Al³⁺+12. The salt effect of H⁺ cannot be determined unequivocally. The combined effect of the fractionation of H⁺ itself plus its salt effect is +4.9. Anion effects are +1.4 for Cl⁻, +2.7 for Br⁻, +3.5 for I⁻ and −1.4 for SO₄²⁻. Further single anion salt effects are being predicted as −1.8 for F⁻, +4.9 for NO₃⁻, +6.9 for ClO₄⁻ and +5.4 for the triflate ion (CF₃SO₃⁻).     

Effect of confining pressure on the diffusion of HTO, 36Cl− and 125I− in a layered argillaceous rock (Opalinus Clay): diffusion perpendicular to the fabric

The through- and out-diffusion of HTO, ³⁶Cl⁻ and ¹²⁵I⁻ in Opalinus Clay, an argillaceous rock from the northern part of Switzerland, was studied under different confining pressures between 4 and 15 MPa. The direction of diffusion and the confining pressure were perpendicular to the bedding. Confining pressure had only a small effect on diffusion. An increase in pressure from 4 to 15 MPa resulted in a decrease of the effective diffusion coefficient of ∼20%. Diffusion accessible porosities were not measurably affected. The values of the effective diffusion coefficients, D_e, ranged between (5.6±0.4)×10⁻¹² and (6.7±0.4)×10⁻¹² m² s⁻¹ for HTO, (7.1±0.5)×10⁻¹³ and (9.1±0.6)×10⁻¹³ m² s⁻¹ for ³⁶Cl⁻ and (4.5±0.3)×10⁻¹³ and (6.6±0.4)×10⁻¹³ m² s⁻¹ for ¹²⁵I⁻. The rock capacity factors, α, measured were circa 0.14 for HTO, 0.040 for ³⁶Cl⁻ and 0.080 for ¹²⁵I⁻. Because of anion exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than the uncharged HTO. Unlike ³⁶Cl⁻, ¹²⁵I⁻ sorbs weakly on Opalinus Clay resulting in a larger rock capacity factor. The sorption coefficient, K_d, for ¹²⁵I⁻ is of the order of 1–2×10⁻⁵ m³ kg⁻¹. The effective diffusion coefficient for HTO is in good agreement with values measured in other sedimentary rocks and can be related to the porosity using Archie's Law with exponent m=2.5.     

Deformation mechanisms in experimentally deformed single crystals of pyrrhotite,Fe1−xS

Single crystals of hexagonal and monoclinic pyrrhotite, Fe_1?xS, have been experimentally deformed by uniaxial compression at 300 MPa confining pressure, and at a strain rate of 1 × 10^?5 s^?1 in the temperature range from 200° C to 400° C. Very high anisotropy characterizes the mechanical behaviour of the crystal structure. During compression parallel to thec-axis, when no slip system may be activated, the maximum strength is observed. One or two degrees of non-parallelism between [c] and σ₁ results in slip on the basal plane, illustrating the very low resistance of the lattice against shear in this plane. At σ₁ Λ(0001)=45°, i.e. when maximum resolved shear stress is attained on the basal plane, the strength reaches a minimum. Thecritical resolved shear stress (CRSS) increases from less than 4.7 MPa at 400° C to 52 MPa at 200° C. A new slip system, \((10\overline 1 0)\parallel \left\langle {1\overline 2 10} \right\rangle \) prism slip, is described. It is activated only at high angles (>70°) between σ₁ and [c]. The CRSS of the prism slip ranges from 7 MPa (400° C) to 115 MPa (200° C). Twinning on \((10\overline 1 2)[(10\overline 1 2):(1\overline 2 10)]\) , earlier reported by several authors, has been produced only at the highest temperature either as secondary feature during pressure release (compression ‖[c]) or in heterogeneously strained areas (compression ⊥[c]). As twinning and prism slip attain their maximum values of the Schmidt factor under nearly equal stress conditions it is postulated that the former of the two deformation modes has the higher shear resistance.     

Aqueous oxidation of trichloroethene (TCE): a kinetic analysis

An empirical kinetic rate law appropriate for many ground waters (neutral pH, aerobic) has been determined for the aqueous oxidation of trichloroethene (TCE), one of the most volumetrically important chlorinated hydrocarbon pollutants. Mass balances were monitored by measuring both the rate of disappearance of TCE and the rate of appearance of CO₂ and Cl⁻. Dilute buffer solutions were used to fix pH and stoichiometrically sufficient amounts of dissolved O₂ were used to make the reactions pseudo zero-order in O₂. Using a standard chemical kinetic approach, two orders-of-magnitude in initial TCE concentration were spanned and the resulting double-log plot (log concentration vs. log initial rate) was used to determine the rate constant (k=5.77±1.06×10⁻⁷ s⁻¹) and “true” (i.e., with respect to concentration, not time) reaction order (n_c=0.85±0.03) for the rate law. By determining rate constants over the temperature interval 343–373 K, the Arrhenius activation energy (E_a) for the reaction was determined to be 108.0±4.5 kJ/mol. The rate law and derived kinetic parameters may be used in reactive transport simulators in order to account for aqueous oxidation of TCE as a function of temperature.     

Biosorption of cadmium(II), lead(II) and cobalt(II) from aqueous solution by biochar from cones of larch (<Emphasis Type="Italic">Larix decidua</Emphasis> Mill. <Emphasis Type="Italic">subsp. decidua</Emphasis>) and spruce (<Emphasis Type="Italic">Picea abies</Emphasis> L. H. Karst)

Because of their physicochemical properties, biochars can be used as sorption materials for removal of toxic substances. The purpose of the present study was to determine whether biochar obtained from cones of larch (Larix decidua Mill. subsp. decidua) and spruce (Picea abies L. H. Karst) could be used as a sorbent for Cd²⁺, Pb²⁺ and Co²⁺ in aqueous solutions. So far, this feedstock had not been tested in this respect. The material was subjected to pyrolysis at 500 and 600 °C for the duration of 5, 10 and 15 min. The obtained pyrolysates were found to differ in terms of pH and the contents of the essential macroelements. The different values of these parameters were determined for varying temperature, duration of the pyrolysis process and type of feedstock. Sorption capacities of the biochars for removal of Cd²⁺, Pb²⁺ and Co²⁺ were examined using simulated contamination of aqueous solutions with salts of these metals. The findings showed the highest, nearly complete, removal for Pb²⁺ were maximum 99.7%, and almost three times lower value for Cd²⁺ and Co²⁺ (respectively, 35.7 and 24.8%). It was demonstrated that pyrolysis of conifer cones produced optimum sorption capacities when the process was conducted at a temperature of 500 °C for the duration of 5 min. It was shown that products of spruce cone pyrolysis were characterized by better sorption capacity in comparison with products of larch cone pyrolysis. The properties of conifer cone biochar create the possibility of using it as an adsorbent in water and wastewater treatment as well as in production of filters and activated carbon.