Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ¹⁸O_H2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O₂ and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε¹⁸O_SO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent ε_SO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O₂ into sulfate. δ³⁴S_SO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ³⁴S_SO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.     

Dissolution kinetics of diopside as a function of solution saturation state: Macroscopic measurements and implications for modeling of geological storage of CO2

Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔG_r) in a continuously stirred flow-through reactor at 90 °C and pH_90 °C = 5.05. The overall relation between r and ΔG_r was determined over a free energy range of −130.9 < ΔG_r < −47.0 kJ mo1⁻¹. The data define a highly non-linear, sigmoidal relation between r and ΔG_r. At far-from-equilibrium conditions (ΔG_r ? −76.2 kJ mo1⁻¹), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔG_r. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔG_r region defined by −76.2 < ΔG_r ? −61.5 kJ mo1⁻¹. Dissolution closer to equilibrium (ΔG_r > −61.5 kJ mo1⁻¹) is characterised by a much weaker inverse dependence of the rates on ΔG_r. Modeling the experimental r-ΔG_r data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔG_r relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO₂ over long time spans. In order to take into account the actual experimental r-ΔG_r relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO₂ interactions performed with classical geochemical codes should be evaluated with great caution.     

The Budget of Turbulent Kinetic Energy in the Urban Roughness Sublayer

Full-scale observations from two urban sites in Basel, Switzerland were analysed to identify the magnitude of different processes that create, relocate, and dissipate turbulent kinetic energy (TKE) in the urban atmosphere. Two towers equipped with a profile of six ultrasonic anemometers each sampled the flow in the urban roughness sublayer, i.e. from street canyon base up to roughly 2.5 times the mean building height. This observational study suggests a conceptual division of the urban roughness sublayer into three layers: (1) the layer above the highest roofs, where local buoyancy production and local shear production of TKE are counterbalanced by local viscous dissipation rate and scaled turbulence statistics are close to to surface-layer values; (2) the layer around mean building height with a distinct inflexional mean wind profile, a strong shear and wake production of TKE, a more efficient turbulent exchange of momentum, and a notable export of TKE by transport processes; (3) the lower street canyon with imported TKE by transport processes and negligible local production. Averaged integral velocity variances vary significantly with height in the urban roughness sublayer and reflect the driving processes that create or relocate TKE at a particular height. The observed profiles of the terms of the TKE budget and the velocity variances show many similarities to observations within and above vegetation canopies.     

Iodine Chemistry and its Role in Halogen Activation and Ozone Loss in the Marine Boundary Layer: A Model Study

A detailed set of reactions treating the gas and aqueous phase chemistry of the most important iodine species in the marine boundary layer (MBL) has been added to a box model which describes Br and Cl chemistry in the MBL. While Br and Cl originate from seasalt, the I compounds are largely derived photochemically from several biogenic alkyl iodides, in particular CH2I2, CH2ClI, C2H5I, C3H7I, or CH3I which are released from the sea. Their photodissociation produces some inorganic iodine gases which can rapidly react in the gas and aqueous phase with other halogen compounds. Scavenging of the iodine species HI, HOI, INO2, and IONO2 by aerosol particles is not a permanent sink as assumed in previous modeling studies. Aqueous-phase chemical reactions can produce the compounds IBr, ICl, and I2, which will be released back into the gas phase due to their low solubility. Our study, although highly theoretical, suggests that almost all particulate iodine is in the chemical form of IO-3. Other aqueous-phase species are only temporary reservoirs and can be re-activated to yield gas phase iodine. Assuming release rates of the organic iodine compounds which yield atmospheric concentrations similar to some measurements, we calculate significant concentrations of reactive halogen gases. The addition of iodine chemistry to our reaction scheme has the effect of accelerating photochemical Br and Cl release from the seasalt. This causes an enhancement in ozone destruction rates in the MBL over that arising from the well established reactions O(1D) + H2O 2OH, HO2 + O3 OH + 2O2, and OH + O3 HO2 + O2. The given reaction scheme accounts for the formation of particulate iodine which is preferably accumulated in the smaller sulfate aerosol particles.     

纤磷钙铝石类化合物:来自地球具工艺用途的材料(英文)

纤磷钙铝石类化合物系由自纤磷钙铝石CaAl3 (OH) 6(HPO4) (PO4)本身、经磷钙铝石CaAl3 (OH) 6(SO4) (PO4)到钾明矾石KAl3 (OH ) 6(SO4) 2 等的天然矿物族所组成的。它们表现出具有很大范围的阳离子置换系列 ,其中以Sr2 +和Ba2 +置换Ca2 +,REEs3 +置换Ca2 +和H+,As5 +置换P5 +,S6+/Se6+置换H+P5 +最为重要。随着置换的进行 ,其热动力学稳定性也逐渐增加。由此 ,纤磷钙铝石类化合物成为很能抗风化的矿物 ,在红土中尤其如此。厚的纤磷钙铝石层形成在闪长岩 (富Sr) ,碳酸盐岩 (富REEs)和含金石英脉 (富As)之上 ,从而保护整个磷酸盐红土 ,使之免受风化。以此方式 ,形成了桌状山脉或岛屿 ,他们具有未受覆盖的表面。这些“纤磷钙铝”石化合物为上述及其它元素形成一有效的地球化学障。“纤磷钙铝石”的这种天然地球化学固定作用可以用适当的母体或人工合成晶体来进行模拟 ,即通过金属阳离子交换或就地反应来模拟。这种固定作用还可用于处理天然和人造的放射性裂变产物、有毒的重金属元素、砷酸盐和硒酸盐、硫酸盐等。     

Pressure–temperature evolution of lawsonite eclogite in Sivrihisar; Tavşanlı Zone–Turkey

The Cretaceous blueschist belt, Tavşanlı Zone, representing the subducted and exhumed northern continental margin of the Anatolide–Tauride platform is exposed in Western Anatolia. The Sivrihisar area east of Tavşanlı is made up of tectonic units consisting of i) metaclastics and conformably overlying massive marbles (coherent blueschist unit), ii) blueschist-eclogite unit, iii) marble–calcschist intercalation and iv) metaperidotite slab. The metaclastics are composed of jadeite–lawsonite–glaucophane and jadeite–glaucophane–chloritoid schists, phengite phyllites, and calcschists with glaucophane–lawsonite metabasite layers. The blueschist-eclogite unit representing strongly sheared, deeply buried and imbricated tectonic slices of accreted uppermost levels of the oceanic crust with minor metamorphosed serpentinite bodies consists of lawsonite-bearing eclogitic metabasites (approximately 90% of the field), lawsonite eclogites, metagabbros, serpentinites, pelagic marbles, omphacite–glaucophane–lawsonite metapelites and metacherts. The mineral assemblage of the lawsonite eclogite (garnet + omphacite > 70%) is omphacite, garnet, lawsonite, glaucophane, phengite and rutile. Lawsonite eclogite lenses are enclosed by garnet–lawsonite blueschist envelopes.Textural evidence from lawsonite eclogites and country rocks reveals that they did not leave the stability field of lawsonite during subduction and exhumation. The widespread preservation of lawsonite in eclogitic metabasites and eclogites can be attributed to rapid subduction and subsequent exhumation in a low geothermal gradient of the oceanic crust material without experiencing a thermal relaxation. Peak P–T conditions of lawsonite eclogites are estimated at 24 ± 1 kbar and 460 ± 25 °C. These P–T conditions indicate a remarkably low geotherm of 6.2 °C/km corresponding to a burial depth of 74 km.