Growth kinetics of enstatite reaction rims studied on nano-scale,Part I: Methodology,microscopic observations and the role of water

The kinetics of (Mg, Fe)SiO₃ pyroxene layer growth within silicate thin films with total thickness <1 μm was studied experimentally at 0.1 MPa total pressure, controlled fO₂ and temperatures from 1,000 to 1,300°C. The starting samples were produced by pulsed laser deposition. Layer thickness before and after the experiments and layer composition as well as microstructures, grain size and shape of the interfaces were determined by Rutherford back scattering and transmission electron microscopy assisted by focused ion beam milling. Due to the miniaturization of the starting samples and the use of high resolution analytical methods the experimentally accessible temperature range for rim growth experiments was extended by about 300°C towards lower temperatures. The thickness of the layers at a given temperature increases proprotional to the square root of time, indicating a diffusion-controlled growth mechanism. The temperature dependence of rim growth yields an apparent activation energy of 426 ± 34 kJ/mol. The small grain size in the orthopyroxene rims implies a significant contribution of grain boundary diffusion to the bulk diffusion properties of the polycrystalline rims. Based on microstructural observations diffusion scenarios are discussed for which the SiO₂ component behaves immobile relative to the MgO component. Volume diffusion data for Mg in orthopyroxene from the literature indicate that the measured diffusivity is probably controlled by the mobility of oxygen. The observed reaction rates are consistent with earlier results from dry high-temperature experiments on orthopyroxene rim growth. Compared to high pressure experiments at 1,000°C and low water fugacities, reaction rates are 3–4 orders of magnitude smaller. This observation is taken as direct evidence for a strong effect of small amounts of water on diffusion in silicate polycrystals. In particular SiO₂ changes from an immobile component at dry conditions to an extremely mobile component even at very low water fugacities.     

Experimental determination of the Raman CH4 symmetric stretching (ν1) band position from 1-650 bar and 0.3-22 °C: Application to fluid inclusion studies

The position of the Raman methane (CH₄) symmetric stretching band (ν₁) over the range 1-650 bar and 0.3-22 °C has been determined using a high-pressure optical cell mounted on a Raman microprobe. Two neon emission lines that closely bracket the CH₄ band were collected simultaneously with each CH₄ spectrum. The peak position was determined after least squares fitting using a summed Gaussian-Lorentzian method, resulting in a precision of ≈±0.02 cm⁻¹ in peak position determination. The CH₄ν₁ band position shifts to lower wave number with increasing pressure. At a given pressure, the band shifts to lower wave number with decreasing temperature, and the magnitude of the temperature shift increases with increasing pressure. The relationship between the Raman CH₄ν₁ band position and temperature and pressure determined here may be used to estimate the internal pressure in natural or synthetic CH₄-bearing fluid inclusions. This information, in turn, may be used to determine the density of pure CH₄ fluid inclusions and the salinity of CH₄-bearing aqueous inclusions.     

Stratospheric Photolysis Frequencies: Impact of an Improved Numerical Solution of the Radiative Transfer Equation

Numerical schemes for the calculation of photolysis rates are usually employed in simulations of stratospheric chemistry. Here, we present an improvement of the treatment of the diffuse actinic flux in a widely used stratospheric photolysis scheme (Lary and Pyle, 1991). We discuss both the consequences of this improvement and the correction of an error present in earlier applications of this scheme on the calculation of stratospheric photolysis frequencies. The strongest impact of both changes to the scheme is for small solar zenith angles. The effect of the improved treatment of the diffuse flux is most pronounced in the lower stratosphere and in the troposphere. Overall, the change in the calculated photolysis frequencies in the region of interest in the stratosphere is below about 20%, although larger deviations are found for H₂O, O₂, NO, N₂O, and HCl.     

深海火山堆积期间从海底火山作用到富含硫化物石英脉型金成矿作用的演化

富含硫化物石英脉型金矿是加拿大太古宙金矿类型中重要的一种.关于它的成因仍是个谜.象Copper Rand和Geant Dormant这样一些金矿,其中的富硫化物含金石英脉的形成早于区域韧性变形,因而排除了变质成因的可能.Geant Do rmant金矿尤其适合于阐述金矿成因问题,因为其中的含金石英脉产于一层序关系保存完好的弱形变火山沉积序列中.本文论述了与该矿床有关的火山堆积及其热液系统的演化.从野外、岩相学与地球化学资料确定了火山演变及其形成的水下环境.热液事件则从野外分布特征、硫化物以及蚀变矿物组合和蚀变围岩的质量平衡计算等方面加以讨论.在分析火山与热液事件年代学和几何学关系基础上,认为含金石英脉是在火山成因热液系统的最后阶段形成的,该热液系统包括在深水火山堆积期间从贫金海底火山作用演变成富金矿脉型成矿作用的整个过程.本文探讨了在这种环境中含金石英脉的形成和金的富集机制以及所提出的金矿成因模式在勘探中的意义.     

Short-time induction of oxidative stress in hepatocytes of the European flounder (Platichthys flesus).

Oxidative stress induced by xenobiotic compounds has been studied using primary hepatocytes of juvenile European flounder (Platichthys flesus L.) caught in a low polluted area of the German Bight, Tiefe Rinne (Landwüst et al., 1996.). Cells were exposed to known oxidative stressors such as hydrogen peroxide and benzo[a]pyrene (B[a]p) in various concentrations (50 and 100 microM) up to 6 days. Cell mortality was determined using fluorescent ethidium homodimer-1 and calcein AM. Oxidative stress response was measured by image analysis using dihydrorhodamine 123, which is converted to fluorescent rhodamine 123 in the presence of intracellular ROS. Oxyradical formation was initiated already after 2 h of exposure to low concentrations of B[a]p and hydrogen peroxide. Probably due to a membrane stabilising effect of the serum factors the addition of fetal bovine serum to the culture medium had a protecting influence on the hepatocytes and resulted in (1) an increased cell viability and (2) reduced formation of intracellular ROS during exposure. In conclusion, the assay is a sensitive tool for testing the potential of various xenobiotics to induce oxidative stress in living hepatocytes.     

Organochlorine and mecury concetrations in eggs of grey plovers (Pluvialis squatarola) breeding in the Lena Dlta, north-east Sibveria, 1997

Seven eggs from four clutches of grey plovers ( Pluvialis squatarola ) breeding in the Lena Delta, Sakha Republic, Yakutia, in 1997 were analysed for persistent organochlorines and mercury. Contamination levels were low and within the same range as found in eggs from waders (Charadriiformes) breeding in north-west Europe. One exception was ∑HCH, averaging 99.2 ng g⁻¹ fresh egg mass, a level about ten times higher than in wader eggs from north-west Europe. β-HCH accounted for 98% of the total HCH concentration. There are indications that the pesticide levels may reflect former local use. ∑PCB level (57.0 ng g⁻¹, 62 congeners) and mercury concentration (68.7 ng g⁻¹) can be considered low.     

Electrochemical gold precipitation to explain extensive vertical and lateral mineralization in the world‐class Poderosa‐Pataz district,Peru

The world‐class Poderosa‐Pataz district is famous for its gold endowment in vertically and laterally extensive quartz‐sulphide veins. Precipitating mechanisms are investigated to determine why gold is so laterally and vertically distributed. Micro‐XRF and LA‐ICP‐MS element mapping of pyrites surrounding gold grains reveals systematic enrichment of As around or near visible gold accumulations. These As‐enriched zones define discordant rims and corridors overprinting pyrites. LA‐ICP‐MS spot analyses performed within and outside the As enrichment zones indicate that As is enriched on average by two orders of magnitude in association with gold. Secondary pyrite transformation by hydrothermal fluids with elevated As‐Au induced a change in the semiconducting properties of pyrite grains, resulting in the precipitation of visible gold particles at the interfaces of As‐enriched zones. The electrochemical precipitation mechanism acted as a filter to extract gold in solution regardless of variations in pressure and temperature, hence explaining the vertically and laterally extensive gold mineralization.     

Silicon and iron isotopes in components of enstatite chondrites: Implications for metal–silicate–sulfide fractionation in the solar nebula

Silicon and iron isotope compositions of different physically separated components of enstatite chondrites (EC) were determined in this study to understand the role of nebular and planetary scale events in fractionating Si and Fe isotopes of the terrestrial planet-forming region. We found that the metal–sulfide nodules of EC are strongly enriched in light Si isotopes (δ³⁰Si ≥ −5.61 ± 0.12‰, 2SD), whereas the δ³⁰Si values of angular metal grains, magnetic, slightly magnetic, and non-magnetic fractions become progressively heavier, correlating with their Mg# (Mg/(Mg+Fe)). White mineral phases, composed primarily of SiO₂ polymorphs, display the heaviest δ³⁰Si of up to +0.23 ± 0.10‰. The data indicate a key role of metal–silicate partitioning on the Si isotope composition of EC. The overall lighter δ³⁰Si of bulk EC compared to other planetary materials can be explained by the enrichment of light Si isotopes in EC metals along with the loss of isotopically heavier forsterite-rich silicates from the EC-forming region. In contrast to the large Si isotope heterogeneity, the average Fe isotope composition (δ⁵⁶Fe) of EC components was found to vary from −0.30 ± 0.08‰ to +0.20 ± 0.04‰. A positive correlation between δ⁵⁶Fe and Ni/S in the components suggests that the metals are enriched in heavy Fe isotopes whereas sulfides are the principal hosts of light Fe isotopes in the non-magnetic fractions of EC. Our combined Si and Fe isotope data in different EC components reflect an inverse correlation between δ³⁰Si and δ⁵⁶Fe, which illustrates that partitioning of Si and Fe among metal, silicate, and sulfidic phases has significantly fractionated Si and Fe isotopes under reduced conditions. Such isotope partitioning must have occurred before the diverse components were mixed to form the EC parent body. Evaluation of diffusion coefficients of Si and Fe in the metal and non-metallic phases suggests that the Si isotope compositions of the silicate fractions of EC largely preserve information of their nebular processing. On the other hand, the Fe isotopes might have undergone partial or complete re-equilibration during parent body metamorphism. The relatively uniform δ⁵⁶Fe among different types of bulk chondrites and the Earth, despite Fe isotope differences among their components, demonstrates that the chondrite parent bodies were not formed by random mixing of chondritic components from different locations in the disk. Instead, the chondrite components mostly originated in the same nebular reservoir and Si and Fe isotopes were fractionated either due to gas–solid interactions and associated changes in physicochemical environment of the nebular reservoir and/or during parent body processing. The heavier Si isotope composition of the bulk silicate Earth may require accretion of chondritic and/or isotopically heavier EC silicates along with cumulation of refractory forsterite-rich heavier silicates lost from the EC-forming region to form the silicate reservoir of the Earth.     

Chronology of latest Pleistocene mountain glaciation in the western Wasatch Mountains, Utah, U.S.A.

Understanding the timing of mountain glacier and paleolake expansion and retraction in the Great Basin region of the western United States has important implications for regional-scale climate change during the last Pleistocene glaciation. The relative timing of mountain glacier maxima and the well-studied Lake Bonneville highstand has been unclear, however, owing to poor chronological limits on glacial deposits. Here, this problem is addressed by applying terrestrial cosmogenic ¹⁰Be exposure dating to a classic set of terminal moraines in Little Cottonwood and American Fork Canyons in the western Wasatch Mountains. The exposure ages indicate that the main phase of deglaciation began at 15.7 ± 1.3 ka in both canyons. This update to the glacial chronology of the western Wasatch Mountains can be reconciled with previous stratigraphic observations of glacial and paleolake deposits in this area, and indicates that the start of deglaciation occurred during or at the end of the Lake Bonneville hydrologic maximum. The glacial chronology reported here is consistent with the growing body of data suggesting that mountain glaciers in the western U.S. began retreating as many as 4 ka after the start of northern hemisphere deglaciation (at ca. 19 ka).     

Connectivity clues from short-term variability in settlement and geochemical tags of mytilid mussels

The use of geochemical tags in calcified structures of fish and invertebrates is an exciting tool for investigating larval population connectivity. Tag evaluation over relatively short intervals (weeks) may detect environmental and ecological variability at a temporal scale highly relevant to larval transport and settlement. We collected newly settled mussels (Mytilus californianus and M. galloprovincialis) weekly during winter/spring of 2002 along the coast of San Diego, CA, USA, at sites on the exposed coast (SIO) and in a protected coastal bay (HI), to investigate temporal patterns of geochemical tags in mussel shells. Analyses of post-settlement shell via LA-ICP-MS revealed statistically significant temporal variability for all elements we examined (Mg, Mn, Cu, Sr, Cd, Ba, Pb and U). Despite this, our ability to distinguish multielemental signatures between sites was largely conserved. Throughout our 13-week study, SIO and HI mussels could be chemically distinguished from one another in 78–87% of all cases. Settlement varied between 2 and 27 settlers gram-byssus^?1 week^?1 at SIO and HI, and both sites were characterized by 2–3 weeks with “high” settlement. Geochemical tags recorded in early larval shell of newly settled mussels differed between “high” and “low” settlement weeks at both sites (MANOVA), driven by Mg and Sr at SIO (p = 0.013) and Sr, Cd, Ba and Pb at HI (p < 0.001). These data imply that shifts in larval sources or transport corridors were responsible for observed settlement variation, rather than increased larval production. In particular, increased settlement at HI was observed concurrent with the appearance of geochemical tags (e.g., elevated Cd), suggesting that those larvae were retained in upwelled water near the mouth of the bay. Such shifts may reflect short-term changes in connectivity among sites due to altered transport corridors, and influence the demography of local populations.