First-Order Chemistry in the Surface-Flux Layer

We have discussed the behavior of a non-conserved scalar in the stationary, horizontally homogeneous, neutral surface-flux layer and, on the basis of conventional second-order closure, derived analytic expressions for flux and for mean concentration of a gas, subjected to a first-order removal process. The analytic flux solution showed a clear deviation from the constant flux, characterizing a conserved scalar in the surface-flux layer. It decreases with height and is reduced by an order of magnitude of the surface flux at a height equal to about the typical mean distance a molecule can travel before destruction. The predicted mean concentration profile, however, shows only a small deviation from the logarithmic behavior of a conserved scalar. The solution is consistent with assuming a flux-gradient relationship with a turbulent diffusivity corrected by the Damköhler ratio, the ratio of a characteristic turbulent time scale and the scalar mean lifetime. We show that if we use only first-order closure and neglect the effect of the Damköhler ratio on the turbulent diffusivity we obtain another analytic solution for the profiles of the flux and the mean concentration which, from an experimental point of view, is indistinguishable from the first analytic solution. We have discussed two cases where the model should apply, namely NO which, by night, is irreversibly destroyed by interaction with mainly O₃ and the radioactive ²²⁰Rn. Only in the last case was it possible to find data to shed light on the validity of our predictions. The agreement seemed such that a falsification of our model was impossible. It is shown how the model can be used to predict the surface flux of ²²⁰Rn from measured concentration profiles.     

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.     

Genesis of Kanggur Gold Deposit in Eastern Tianshan Orogenic Belt, NW China: Fluid Inclusion and Oxygen and Hydrogen Isotope Constraints

Abstract. Primary fluid inclusions in quartz and carbonates from the Kanggur gold deposit are dominated by aqueous inclusions, with subsidiary CO₂-H₂O inclusions that have a constant range in CO₂ content (10–20 vol %). Microthermometric results indicate that total homogenization temperatures have a wide but similar range for both aqueous inclusions (120 to 310C) and CO₂-H₂O inclusions (140 to 340C). Estimates of fluid salinity for CO₂-H₂O inclusions are quite restricted (5.9∼10.3 equiv. wt% NaCl), whereas aqueous inclusions show much wider salinity ranging from 2.2 to 15.6 equivalent wt %NaCl.
The 6D values of fluid inclusions in carbonates vary from -45 to -61 %, in well accord with the published δD values of fluid inclusions in quartz (-46 to -66 %). Most of the δ¹⁸O and δD values of the ore-forming fluids can be achieved by exchanged meteoric water after isotopic equilibration with wall rock by fluid/rock interaction at a low water/rock ratio. However, the exchanged meteoric water alone cannot explain the full range of δ¹⁸O and δD values, magmatic and/or meta-morphic water should also be involved. The wide salinity in aqueous inclusions may also result from mixing of meteoric water and magmatic and/or metamorphic water.     

Isotopic evidence of TSR origin for natural gas bearing high H_2S contents within the Feixianguan Formation of the northeastern Sichuan Basin, southwestern China

Isotopic evidence of TSR origin for natural gas bearing high H2S contents 1961 As the hazardous component of natural gas, the ex-istence of H2S, due to its extremely strong toxicity and corrosivity, not only decreases the percentage of hy-drocarbon gas within natural gas and reduces its in-dustrial value, it also threatens each aspect of drilling and exploitation. It frequently causes serious safety accidents[1] and leads to the E&P cost and risk of natural gas with higher H2S contents be…     

Vertical variations and transport mechanism of soil moisture in response to vegetation restoration on the Loess Plateau of China

Soil moisture is essential for vegetation restoration in arid and semi-arid regions. Ascertaining the vertical distribution and transportation of soil moisture under different vegetation types has a profound effect on the ecological construction. In this study, the soil moisture at a depth of 500 cm for four typical vegetation types, including Robinia pseudoacacia, Caragana korshinskii, Stipa bungeana, and corn, were investigated and compared in the Zhifanggou watershed of the Loess plateau. Additionally, hydrogen and oxygen stable isotopes were detected to identify the transport mechanism of soil moisture. The results showed vertical distribution and transportation of soil moisture were different under different vegetation types. Depth-averaged soil moisture under S. bungeana and corn generally increased along the profile, while C. korshinskii and R. pseudoacacia showed weakly increasing and relatively stable after an obvious decreasing trend (0–40 cm). The soil moisture under R. pseudoacacia was lower than that under other vegetation types, especially in deep layer. However, the effect of R. pseudoacacia on soil moisture in the topsoil (< 30 cm) could be positive. For R. pseudoacacia (160–500 cm), C. korshinskii (0–500 cm), and S. bungeana (0–100 cm), the soil moisture declined with increased in vegetation age. Planting arbor species such as R. pseudoacacia intensified the decline of soil moisture on the Loess Plateau. The capacity of evaporation fractionation of soil moisture followed the sequence: corn > S. bungeana > R. pseudoacacia > C. korshinskii. The δ¹⁸O values in soil water fluctuated across the profile. The δ¹⁸O values changed sharply in upper layer and generally remained stable in deep layer. However, in middle layer, the vertical distribution characteristics of the δ¹⁸O values were different under different vegetation types. We estimated that piston flow was the main mode of precipitation infiltration, and the occurrence of preferential flow was related to vegetation types. These results were helpful to improve the understanding of the response of deep soil moisture to vegetation restoration and inform practices for sustainable water management.     

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.     

The behavior of a multilayered porous thermo-elastic medium with anisotropic thermal diffusivity and permeability

With the aid of integral transform techniques, this paper presents an extended precise integration solution for thermal consolidation problems of a multilayered porous thermo-elastic medium with anisotropic thermal diffusivity and permeability due to a heat source. From the fundamental governing equations, ordinary differential equations are derived by employing Laplace–Hankel transforms. By applying the extended precise integration method, equations in the transformed domain can be solved, and the actual solutions are further obtained by adopting a numerical inverse transformation. The accuracy and feasibility of the proposed theory is demonstrated by contrastive analysis with existing studies. Finally, several examples are carried out to investigate the influence of heat source’s type, axial distance, burial depth of heat source, ratio of thermo-permeability, permeability anisotropy, thermal diffusivity anisotropy and stratification on the thermal consolidation process.     

广西栗木钨锡铌钽矿区流体包裹体及氢氧同位素研究

本文通过对广西栗木矿区金竹源矿床和水溪庙矿床的流体包裹体研究,得出该矿区流体包裹体主要有两相H_2O-NaCl和H_2O-NaCl-CO_2两种类型。显微测温结果表明:两相H_2O-NaCl型流体包裹体均一温度主要集中于181.9~258.8℃,盐度w(Na Cleq)主要集中于4.01%~6.87%,密度0.690~0.988 g/cm3;H_2O-NaCl-CO_2型流体包裹体均一温度为178.5~331.1℃,主要集中在两个温度段,分别为高-中温段(265.3~315.5℃)和中-低温段(202.3~264.1℃),盐度w(NaCleq)主要集中在0.21%~5.05%,密度为0.678~0.886 g/cm3。栗木矿区成矿流体有两个温度集中段,且具有低盐度、低密度的特征。氢氧同位素研究结果表明:金竹源矿床钨锡铌钽矿化花岗岩石英δD值为-73.6‰~-62.8‰,δ~(18)OV-SMOW值为7.5‰~8.9‰,计算得δ~(18)OH2O值为6.00‰~7.40‰;水溪庙矿床钨锡铌钽矿化花岗岩石英δD值为-73.8‰~-58.3‰,δ~(18)OV-SMOW值为11.0‰~13.2‰,计算得δ~(18)OH2O值为9.50‰~11.70‰,水溪庙矿床含钨锡石英脉石英δD值为-75.3‰~-56.6‰,δ~(18)OV-SMOW值为11.8‰~14.1‰,计算得δ~(18)OH2O值为2.20‰~4.50‰。栗木矿区钨锡铌钽矿化花岗岩成矿流体来源于岩浆水,含钨锡石英脉成矿流体来源于岩浆水和大气降水的混合流体。     

从平衡-封闭-静态转向非平衡-开放-动力学研究-热液矿床成因的若干新概念概述

热液金属矿床成因研究过程中,观测与实验始终是密切结合的。上世纪70年代,平衡热力学的实验数据的快速积累,使人们用热力学理论计算可以预测和反演矿石和岩石的成因。但是,没有矿物-水溶液的反应速率数据,又没有与流体力学的结合,搞清楚矿石成因是困难的。七、八十年代,开始研究矿物与水溶液的反应动力学实验。科学家们开始瞄准了从平衡-封闭-静态转向非平衡-开放-动力学研究的这个大方向。1992年我们建立地球化学动力学开放研究实验室。研究高温高压矿物与水反应速率,发现固液的开放体系的自组织现象。实验发现温度影响矿物的各个元素反应速率改变,发现在跨越水临界态时矿物与水反应速率涨落、在近临界的气-液两相不混溶区一些金属进入气相、超临界流体的氧化作用及特别的溶剂性能影响矿物溶解性质。实验证实:临界态区流体与矿石成因有关。水岩相互作用的反应动力学实验温度从低温到550度,揭示矿石的金属来源、迁移、金属与蚀变分带机制。一大批大于300度的矿物与水反应动力学实验在国际界是少有报道的。九十年代,超高压的科学发展,与同步辐射光源的技术进步的结合,使固体地球科学又迈向了地球深内部。我们发展了高温高压流体性质的原位直测(测量850℃水溶液)红外谱,发现深部流体的新性质:气液两相流体的新结构,在临界温度区(300~400℃),水分子氢键网络的破坏受压力影响不大(23MPa~3GPa),同时,出现水的高电导率。研发新仪器为开放-流动-非平衡的反应动力学实验与极端条件下物质性质的直接观测结合,在科学前沿领域开辟了创新道路。