Structure cristalline d'une ménéghinite naturelle pauvre en cuivre,Cu0,58Pb12,72(Sb7,04Bi0,24)S24Crystal structure of a Cu-poor natural meneghinite,Cu0.58Pb12.72(Sb7.04Bi0.24)S24

Cu-poor meneghinite from La Lauzière Massif (Savoy, France) has the composition (electron microprobe) (in wt%): Pb 59.50, Sb 20.33, Bi 1.19, Cu 0.87, Ag 0.05, Fe 0.03, S 17.62, Se 0.05, Total 99.64. Its crystal structure (X-ray on a single crystal) was solved with R1=0.0506, wR2=0.1026, with an orthorhombic symmetry, space group Pnma, and a=24.080(5) Å, b=4.1276(8) Å, c=11.369(2) Å, V=1130.0(4) Å³, Z=4. Relatively to the model of Euler and Hellner (1960), this structure shows a significantly lower site occupancy factor for the tetrahedral Cu site (0.146 against 0.25). Among the five other metallic sites, Bi appears in the one with predominant Sb. Developed structural formula: Cu_0.15Pb₂(Pb_0.53Sb_0.47)(Pb_0.46Sb_0.54)(Sb_0.75Pb_0.19Bi_0.06)S₆; the reduced one: Cu_0.58Pb_12.72(Sb_7.04Bi_0.24)S₂₄. The formation of such a Cu-poor variety seems to be related to specific paragenetic conditions (absence of coexisting galena), or to crystallochemical constraints (minor Bi). To cite this article: Y. Moëlo et al., C. R. Geoscience 334 (2002) 529–536.     

Molecular modeling of the 10-Å phase at subduction zone conditions

Molecular dynamics (MD) modeling of the 10-Å phase, Mg₃Si₄O₁₀(OH)₂·xH₂O, with x=2/3, 1.0 and 2.0 shows complex structural changes with pressure, temperature and water content and provides new insight into the structures and stabilization of these phases under subduction zone conditions. The structure(s) of this phase and its role as a reservoir of water in the mantle have been controversial, and these calculations provide specific predictions that can be tested by in situ diffraction studies. At ambient conditions, the computed structures of talc (x=0) and the 10-Å phases with x=2/3 and 1.0 are stable over the 350-ps period of the MD simulations. Under these conditions, the 10-Å phases show phlogopite-like layer stacking in good agreement with previously published structures based on powder X-ray diffraction data for samples quenched from high-pressure and high-temperature experiments. The calculations show that the 10-Å phase with x=2.0 is unstable at ambient conditions. The computed structures at P=5.5 GPa and T=750 K, well within the known stability field of the 10-Å phase, change significantly with water content, reflecting changing H-bonding configurations. For x=2/3, the layer stacking is talc-like, and for x=1.0, it is phlogopite-like. The calculations show that transformation between these two stackings occurs readily, and that the talc-like stacking for the x=2/3 composition is unlikely to be quenchable to ambient conditions. For x=2.0, the layer stacking at P=5.5 GPa and T=750 K is different than any previously proposed structure for a 10-Å phase. In this structure, the neighboring basal oxygens of adjacent magnesium silicate layers are displaced by b/3 (about 3 Å) resulting in the Si atoms of one siloxane sheet being located above the center of the six-member ring across the interlayer. The water molecules are located 1.2 Å above the center of all six-member rings and accept H-bonds from the OH groups located below the rings. The b/3-displaced structure does not readily transform to either the talc-like or phlogopite-like structure, because neither of these stackings can accommodate two water molecules per formula unit. There is likely to be a compositional discontinuity and phase transition between the b/3-displaced phase and the phase with phlogopite-like stacking. The simulations reported here are the first to use the recently developed CLAYFF force field to calculate mineral structures at elevated pressures and temperatures.     

内蒙古镁铁质-超镁铁质岩型铜镍矿床成矿条件与找矿远景分析

按构造环境控岩控矿特点,划分区内铜镍型矿成矿(岩)带,分析成矿条件,研究了与该类矿床成矿有关的镁铁质岩、超镁铁质岩分布规律及铜镍硫化物成矿特征,提出了找矿方向和建议.     

Improved Platinum-Group Element Extraction by NiS Fire Assay from Chromitite Ore Samples Using a Flux Containing Sodium Metaphosphate

Many chromite-rich rocks contain relatively high concentrations of the platinum-group elements (PGE). In many cases, the phases carrying PGE occur as either platinum-group minerals (PGM) or as base metal sulfides in solid solution in sulfides. In some cases, such as the UG-2 unit of the Bushveld Complex, the PGM are occluded inside chromite grains. Chromites are notably difficult to dissolve in most fluxes and if the chromite contains some PGM the possibility exists that not all the PGE will be recovered during fusion. In this work, shortcomings in published methods of analysis based on the nickel sulfide fire assay procedure were investigated and a new procedure developed based on the addition of sodium metaphosphate to the fusion mixture. Optimum composition of the fusion mixture was found to be 10 g sodium metaphosphate and 9 g silica to 10 g sample, 15 g sodium carbonate, 30 g lithium tetraborate, 7.5 g nickel and 4.5 g sulfur to achieve complete dissolution of chromite grains. The new flux mixture was evaluated by the analysis of reference material CHR-Pt+ (which is known to contain PGM inside chromite grains) and no undissolved chromite grains were found in the glassy slag. Analysis of the nickel sulfide beads from this fire assay using neutron activation analysis showed similar results for Rh and Ru when compared with published conventional true (or accepted) values, while Au, Ir, Os, Pd and Pt values determined here were 10 to 30% higher than the corresponding published conventional true values. It was concluded that the addition of sodium metaphosphate improved chromite dissolution in the flux and appears to improve PGE recovery.     

地质勘探过程中煤层气联测氢气方法

瓦斯的危害和煤层气的利用,不断在推进着瓦斯地质理论、煤层气开发利用技术的进步和发展。在以往的诸多研究中,不论是防治瓦斯的危害还是着眼于煤层气的利用,甲烷都是研究的重点。但是,除甲烷之外,还有没有其它影响或控制瓦斯危害和煤层气利用的组分或因素呢？煤层气（瓦斯）联测氢气的方法和应用研究,就是循着这一思路而做的探索性工作。     

Differing controls on river‐ and lake‐water hydrogen and oxygen isotopic values in the western United States

Surface water oxygen and hydrogen isotopic values are commonly used as proxies of precipitation isotopic values to track modern hydrologic processes while proxies of water isotopic values preserved in lake and river sediments are used for paleoclimate and paleoaltimetry studies. Previous work has been able to explain variability in USA river‐water and meteoric‐precipitation oxygen isotope variability with geographic variables. These studies show that in the western United States, river‐water isotopic values are depleted relative to precipitation values. In comparison, the controls on lake‐water isotopic values are not well constrained. It has been documented that western United States lake‐water input values, unlike river water, reflect the monthly weighted mean isotopic value of precipitation. To understand the differing controls on lake‐ and river‐water isotopic values in the western United States, we examine the seasonal distribution of precipitation, evaporation and snowmelt across a range of seasonality regimes. We generate new predictive equations based on easily measured factors for western United States lake‐water, which are able to explain 69–63% of the variability in lake‐water hydrogen and oxygen isotopic values. In addition to the geographic factors that can explain river and precipitation values, lake‐water isotopic values need factors related to local hydrologic and climatic characteristics to explain variability. Study results suggest that the spring snowmelt runs off the landscape via rivers and streams, depleting river and stream‐water isotopic values. By contrast, lakes receive seasonal contributions of precipitation in proportion to the seasonal fraction of total annual precipitation within their watershed. Climate change may alter the ratio of snow to rain fall, affecting water resource partitioning between rivers and lakes and by implication of groundwater. Paleolimnological studies must account for the multiple drivers of water isotopic values; likewise, studies based on the isotopic composition of fossil material need to distinguish between species that are associated with rivers versus lakes. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrogen sulfide measurements in air by passive/diffusive samplers and high-frequency analyzer: A critical comparison

In this study, hydrogen sulfide (H₂S) measurements in air carried out using (a) passive/diffusive samplers (Radiello^® traps) and (b) a high-frequency (60 s) real-time analyzer (Thermo^® 450i) were compared in order to evaluate advantages and limitations of the two techniques. Four different sites in urban environments (Florence, Italy) and two volcanic areas characterized by intense degassing of H₂S-rich fluids (Campi Flegrei and Vulcano Island, Italy) were selected for such measurements. The concentrations of H₂S generally varied over 5 orders of magnitude (from 10⁻¹–10³ μg/m³), the H₂S values measured with the Radiello^® traps (H₂S_R) being significantly higher than the average values measured by the Thermo^® 450i during the trap exposure (H₂S_Ta), especially when H₂S was <30 μg/m³. To test the reproducibility of the Radiello^® traps, 8 passive/diffusive samplers were contemporaneously deployed within an 0.2 m² area in an H₂S-contaminated site at Mt. Amiata (Tuscany, Italy), revealing that the precision of the H₂S_R values was ±49%. This large uncertainty, whose cause was not recognizable, is to be added to that related to the environmental conditions (wind speed and direction, humidity, temperature), which are known to strongly affect passive measurements. The Thermo^® 450i analyzer measurements highlighted the occurrence of short-term temporal variations of the H₂S concentrations, with peak values (up to 5732 μg/m³) potentially harmful to the human health. The Radiello^® traps were not able to detect such temporal variability due to their large exposure time. The disagreement between the H₂S_R and H₂S_Ta values poses severe concerns for the selection of an appropriate methodological approach aimed to provide an accurate measurement of this highly toxic air pollutant in compliance with the WHO air quality guidelines. Although passive samplers may offer the opportunity to carry out low-cost preliminary surveys, the use of the high-frequency H₂S analyzer is preferred when an accurate assessment of air quality is required. In fact, the latter provides precise real-time measurements for a reliable estimation of the effective exposure to hazardous H₂S concentrations, giving insights into the mechanisms regulating the dispersion of this air pollutant in relation to the meteorological parameters.     

金川铜镍矿床中新生代抬升冷却过程：来自裂变径迹的证据

本文基于热年代学理论,利用锆石和磷灰石裂变径迹测年数据及对磷灰石热史的模拟,分析探讨金川铜镍矿床在中新生代的抬升冷却过程,认为金川超基性岩体自中生代以来一直处于持续的冷却抬升阶段,且在中侏罗世和晚白垩世早期经历了两期快速的抬升冷却事件,推断此事件与青藏高原后期活动时间相对应,证明金川岩体受到该事件的远程效应波及,致使该矿床遭受了一定的改造。     

Dimethylsulfide production in Sargasso Sea eddies

Lagrangian time series of dimethylsulfide (DMS) concentrations from a cyclonic and an anticyclonic eddy in the Sargasso Sea were used in conjunction with measured DMS loss rates and a model of vertical mixing to estimate gross DMS production in the upper 60 m during summer 2004. Loss terms included biological consumption, photolysis, and ventilation to the atmosphere. The time- and depth (0–60 m)-averaged gross DMS production was estimated to be 0.73±0.09 nM d⁻¹ in the cyclonic eddy and 0.90±0.15 nM d⁻¹ in the anticyclonic eddy, with respective DMS replacement times of 5±1 and 6±1 d. The higher estimated rate of gross production and lower measured loss rate constants in the anticyclonic eddy were equally responsible for this eddy's 50% higher DMS inventory (0–60 m). When normalized to chlorophyll and total dimethylsulfoniopropionate (DMSP), estimated gross production in the anticyclonic eddy was about twice that in the cyclonic eddy, consistent with the greater fraction of phytoplankton that were DMSP producers in the anticyclonic eddy. Higher rates of gross production were estimated below the mixed layer, contributing to the subsurface DMS maximum found in both eddies. In both eddies, gas exchange, microbial consumption, and photolysis were roughly equal DMS loss terms in the surface mixed layer (0.2–0.4 nM d⁻¹). Vertical mixing was a substantial source of DMS to the surface mixed layer in both eddies (0.2–0.3 nM d⁻¹) owing to the relatively high DMS concentrations below the mixed layer. Estimated net biological DMS production rates (gross production minus microbial consumption) in the mixed layer were substantially lower (by almost a factor of 3) than those estimated in a previous study of the Sargasso Sea, which may explain the relatively low mixed-layer DMS concentrations found here during July 2004 (3 nM) compared to previous summers (4–6 nM).     

中子活化分析在铼—锇法年龄测定中的应用

同位素稀释中子活化分析铼与感耦等离子体质谱法测定锇相结合，应用于辉钼矿及铜＿镍硫化物矿物的铼＿锇年龄测定，取得了满意的结果，扩大了铼＿锇测年法的应用范围。