Atomistic simulation of the mechanisms of noble gas incorporation in minerals

Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1⁺, 2⁺, 3⁺ and 4⁺ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces.     

Metallographic cooling rates and origin of IVA iron meteorites

We have determined the metallographic cooling rates for 13 IVA irons using the most recent and most accurate metallographic cooling rate model. Group IVA irons have cooling rates that vary from 6600 °C/Myr at the low-Ni end of the group to 100 °C/Myr at the high-Ni end of the group. This large cooling rate range is totally incompatible with cooling in a mantled core which should have a uniform cooling rate. Thermal and fractional crystallization models have been used to describe the cooling and solidification of the IVA asteroid. The thermal model indicates that a metallic body of 150 ± 50 km in radius with less than 1 km of silicate on the outside of the body has a range of cooling rates that match the metallographic cooling rates in IVA irons in the temperature range 700-400 °C where the Widmanstätten pattern formed. The fractional crystallization model for Ni with initial S contents between 3 and 9 wt% is consistent with the measured variation of cooling rate with bulk Ni and the thermal model. New models for impacts in the early solar system and the evolution of the primordial asteroid belt allow us to propose that the IVA irons crystallized and cooled in a metallic body that was derived from a differentiated protoplanet during a grazing impact. Other large magmatic iron groups, IIAB, IIIAB, and IVB, also show significant cooling rate ranges and are very likely to share a similar history.     

Surface evolution of dissolving minerals investigated with a kinetic Ising model

In natural weathering systems, both the chemistry and the topography of mineral surfaces change as rocks and minerals equilibrate to surface conditions. Most geochemical research has focused on changes in solution chemistry over time; however, temporal changes in surface topography may also yield information about rates and mechanisms of dissolution. We use stochastic dissolution simulations of a regular 2-D lattice with reaction mechanisms defined in terms of nearest neighbor interactions to elucidate how the surface area and reactivity of a crystal evolve during dissolution. Despite the simplicity of the model, it reproduces key features observed or inferred for mineral dissolution. Our model results indicate that: (i) dissolving surfaces reach a steady-state conformation after sufficient dissolution time, (ii) linear defects cause surface area and dissolution rate to vary in concert with one another, (iii) sigmoidal and non-sigmoidal rate vs. free-energy of reaction (ΔG_rxn) behavior can be rationalized in terms of the multiple steps occurring during dissolution, and (iv) surface roughness as a function of ΔG_rxn is highly sensitive to the reaction mechanism. When simulated times to reach steady-state are compared to published time series rate data using suitable scaling, good agreement is found for silicate minerals while the model significantly over-predicts the duration of the transient for Fe and Al oxides. The implication of our simple model is that many aspects of mineral dissolution behavior, including approach to steady-state, sigmoidal vs. non-sigmoidal rate vs. ΔG_rxn behavior, and development of rougher surfaces in conditions further from equilibrium can be explained by nearest neighbor interactions and simple Kossel-type models where reactivity of a surface is defined in terms of perfect surface, step, and kink sites.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.     

Geochronology of Pliocene volcanism in the Dzhavakheti Highland (the Lesser Caucasus). Part 1: Western part of the Dzhavakheti Highland

Isotopic-geochronological study of the Pliocene magmatic activity in western part of the Dzhavakheti Highland (northwestern region of the Lesser Caucasus) is carried out. The results obtained imply that the Pliocene magmatic activity lasted in this part of the highland approximately 2 million years from 3.75 to 1.75–1.55 Ma. As is established, the studied volcanic rocks correspond in composition mostly to K-Na subalkaline and more abundant normal basalts. Time constraints of main phases in development of basic volcanism within the study region are figured out. We assume that individual pulses of silicic to moderately silicic volcanism presumably took place in the Dzhavakheti Highland about 3.2 and 2.5 Ma ago.     

Background concentrations of elements in surface soils and their changes as affected by agriculture use in the desert-oasis ecotone in the middle of Heihe River Basin,North-west China

The concentrations of twenty four chemical elements in the surface layer of natural desert soils and the cultivated farmland soils were measured at a desert-oasis ecotone in the middle of Heihe river basin, north-west China. Background values were estimated for (a) major elements (Si 335.3 g kg^− 1, Al 49.4 g kg^− 1, Fe 19.1 g kg^− 1, Ca 29.4 g kg^− 1, Mg 8.9 g kg^− 1, K 20.1 g kg^− 1, Na 17.5 g kg^− 1 and P 0.338 g kg^− 1), (b) heavy metals and non-metals (Cr 55.8 mg kg^− 1, Mn 404.8 mg kg^− 1, Ni 17.7 mg kg^− 1, Cu 5.1 mg kg^− 1, Zn 33.7 mg kg^− 1, Pb 15.5 mg kg^− 1 and As 5.2 mg kg^− 1) and (c) other trace elements (Ti 2.0 mg kg^− 1, V 55.3 mg kg^− 1, Co 5.7 mg kg^− 1, Rb 82.4 mg kg^− 1, Sr 232.9 mg kg^− 1, Y 14.7 mg kg^− 1, Zr 194.9 mg kg^− 1, Nb 7.8 mg kg^− 1 and Ba 720.6 mg kg^− 1). After natural desert soil was cultivated for agricultural use, significant changes in element concentrations occurred under tillage, irrigation and fertilisation management. Compared to natural soil, the for the levels of Si, K, Na, Sr, Zr and Ba decreased, and no changes were observed for Rb, while the values of the other 17 elements increase in agricultural soil from 1.2 to 3.5 times. However, their absolute concentrations are still low, suggesting that the arable soil in this region remains comparatively a clean soil. The increased silt, clay and organic carbon content, under long-term irrigation, enriched the fine-grained materials, and application of fertilisers and manure contributed to the accumulation of most elements in arable soil. The accumulation of elements in agricultural soil increased with increasing cultivation years and extent of soil development.     

碳酸盐岩裂缝与岩溶作用研究

从构造与非构造作用角度出发,突出研究断层对裂缝的控制作用、断裂与岩溶的关系和裂缝与岩溶之间的关系,揭示碳酸盐岩裂缝与岩溶的发育规律。研究表明：构造裂缝为岩溶发育提供岩溶作用进行的有利通道,非构造裂缝则可以加速溶蚀作用的进行,促进岩溶的发育;裂缝与岩溶之间的关系始终是相辅相成、相互促进的关系。     

长春季节性冻土地区土体微观结构与水分迁移的关系

利用扫描电子显微镜(SEM)技术,从土体微观结构特征出发,对长春—吉林公路某路段季节冻土的粒度成分、结构单元体成分、孔隙特征及结构特征进行了定量分析,并对其与水分迁移的关系进行了讨论。从SEM图像定量分析中可以看出,研究路段的土体,其微观颗粒——结构单元体、孔隙的定向性均较差,粒内微小孔隙发育,土体尽管在粘粒含量较高的情况下,也表现出孔隙主要在1~2μm内分布,即毛细孔隙极发育,说明样品具有各向同性的特点,即在外界条件相同的情况下水分迁移的通道在水平和垂直方向上具有相同的性质。     

天津地面沉降区土水比论述

天津市地面沉降分布广,沉降速率大。本文针对当前地面沉降研究和防治过程中所遇到的勘查资料严重缺乏、禁采难以全面实现等难题,提出了土水比指标量。通过概念分析和对多年数据的分析,认为土水比可以检验地下水开采量数据的统计精度,指示地下水资源补给及土层释水条件,并表明沉降的严重程度,反映地下水资源的保障程度。建议在沉降防治工作中,以土水比作为指标,通过相关分析模型来制定压采量。     

基于分布式水文模拟的三峡区间洪水预报(Ⅰ)——模型构建及验证

长江三峡区间因暴雨形成的洪水峰高量大,对三峡水库的防洪安全和运行调度的影响很大.本论文依据三峡地区的地形地貌特征,采用基于GIS的机理性分布式水文模型,来模拟三峡区间入库洪水,以尽量减少洪水预报中的不确定性.利用近期建成的78个自动雨量站网监测的小时降雨信息作为模型的输入,对模型参数进行了率定和验证,结果表明:大多数洪水过程的模拟精度较好,但也有的模拟结果较差,其中降雨信息缺失是洪水预报不确定性的主要来源.