A radiotracer study on the kinetics of gold sorption by mineral surfaces

Aqueous solutions with about 10 ppt¹⁹⁵Au and [HCl] of 10^–2.3 and 10^–1.3 m were exposed to solid minerals for several months. The gold uptake with time was observed by time-stepped sampling and radiochemical Au analysis. Sorbants were polished thick sections of quartz, pyrite, pyrrhotite and elemental gold, as well as crushed grains and sawed mineral cubes of quartz and pyrite (all randomly oriented). The kinetics of gold sorption strongly varied with the surface area of the sorbents, the type of mineral and the pH of the solution. Mineral-specific differences in reaction rates were observed only at experimental pH values around 2.3, where sorption on pyrrhotite and elemental gold was much more rapid than by quartz and pyrite. At pH around 1.3 gold sorption was rapid on all minerals. This finding is thought to reflect the gold speciation, i.e. neutral hydroxo-gold complexes above pH 1.5, for which only chemisorption is possible, versus dominantly AuCl ₄ ^– below pH 1.5, where unspecific electrostatic interaction enhances reaction rates with all protonated mineral surfaces.     

Temperature-dependent leaching of chemical elements from mineral water bottle materials

It is well established that minute amounts of chemical elements will leach from bottle materials (glass or PET – polyethylene terephthalate) to water stored in such bottles. This study investigated whether leaching increases with storage temperature. For glass bottles this is clearly the case for a long list of elements: Ag, Al, As, B, Ba, Ca, Co, Cr, Cs, Cu, Fe, Ga, Ge, K, La, Li, Mg, Mo, Na, Ni, Pb, Rb, Sb, Se, Sn, Sr, Ti, U, V, W and Zr. However, for glass bottles drinking water maximum admissible concentration values as defined by European authorities are not exceeded even after 1 week of leaching at 80 °C. The critical temperature limit where leaching substantially increases for many elements appears to be 45 °C. For PET bottles, Sb is the only element where leaching is observed at all temperatures and again leaching strongly increases at 45 °C. For PET bottles Sb concentrations observed in water after 1 week storage at 80 °C reach almost four times the maximum admissible concentration values for drinking water but do not exceed the relevant higher limit for food (including water) packaged in PET.     

北京平原周边基岩水和地表水的水化学及同位素分析

利用北京市平原周边基岩水和地表水样品中的T值和Cl-含量对大气降水的输入进行了定量估计。研究结果表明全部样品均为热核爆炸后的补给输入,Cl-≤6.8mg/L的水样为北京平原区近工业化前(距今约150～200a)的输入值,6.8～20mg/L为北京地区区域大气轻微污染条件下的Cl-输入值。通过对2H和18O同位素的关系研究,认为北京平原区的高程效应远比大陆效应显著,并且提供了一张北京平原区地下水研究用的比对样板。     

河北小寺沟蛇纹石玉的矿物成分和化学成分研究

在野外地质调查的基础上,通过显微薄片观察、电子探针分析、X射线衍射分析、红外光谱分析、X射线荧光光谱分析、微量元素分析、稀土元素分析等现代测试方法对河北小寺沟蛇纹石玉的矿物成分、化学成分进行了研究。结果表明,小寺沟蛇纹石玉为富镁碳酸盐岩蚀变形成的蛇纹岩,其主要矿物成分为利蛇纹石,次要矿物成分有方解石、白云石、透辉石、金云母、磁铁矿、黄铁矿等。蛇纹石玉的稀土元素来源于围岩大理岩,其稀土元素球粒陨石标准化配分图与其围岩大理岩的稀土配分图非常相似,为陡右倾型,具有稀土元素总量较低、富集轻稀土、具δEu负异常的特点。     

扁铲探头贯入干砂的位移特征试验研究

扁铲侧胀试验（DMT）已在国内外岩土工程勘察、地基加固效果评价等领域中得到广泛应用。DMT的测试过程在扁铲探头贯入到测试位置后进行,因此探头的贯入过程对土体造成的扰动在一定程度上将直接影响测试结果。目前关于扁铲探头的贯入机理,以及贯入过程可能引起的土体扰动及其对测试结果的影响尚未研究清楚。通过室内模型试验手段,进行扁铲探头贯入不同初始密实状态下均质干砂的试验研究,分析了探头贯入过程中产生的土体位移场分布特征。试验结果表明：扁铲探头的楔形部和膜片所在的侧胀部贯入产生的挤压作用是引起土体变形扰动的主要原因;探头楔形部的贯入过程表现为向下和向斜侧面挤压土体,竖向位移量很小,产生向两侧扩展为主的扁状位移场,而探头侧胀部的贯入过程主要表现为向两侧面水平向挤压土体,产生半椭圆状水平位移场且分布范围明显更大,同时探头侧面表现为一定的剪切作用而产生较窄范围的竖向位移场。另外,扁铲探头贯入干砂产生的位移场受砂土初始密实状态的影响较小,主要表现为探头楔形部周围的位移场分布范围随密实度增大而扩大。     

Effects of substrate structure and composition on the structure, dynamics, and energetics of water at mineral surfaces: A molecular dynamics modeling study

Molecular dynamics computer simulations of the molecular structure, diffusive dynamics and hydration energetics of water adsorbed on (0 0 1) surfaces of brucite Mg(OH)₂, gibbsite Al(OH)₃, hydrotalcite Mg₂Al(OH)₆Cl · 2H₂O, muscovite KAl₂(Si₃Al)O₁₀(OH)₂, and talc Mg₃Si₄O₁₀(OH)₂ provide new insight into the relationships between the substrate structure and composition and the molecular-scale structure and properties of the interfacial water. For the three hydroxide phases studied here, the differences in the structural charge on the octahedral sheet, cation occupancies and distributions, and the orientations of OH groups all affect the surface water structure. The density profiles of water molecules perpendicular to the surface are very similar, due to the prevalent importance of H-bonding between the surface and the water and to their similar layered crystal structures. However, the predominant orientations of the surface water molecules and the detailed two-dimensional near-surface structure are quite different. The atomic density profiles and other structural characteristics of water at the two sheet silicate surfaces are very different, because the talc (0 0 1) surface is hydrophobic whereas the muscovite (0 0 1) surface is hydrophilic. At the hydrophilic and electrostatically neutral brucite and gibbsite (0 0 1) surfaces, both donating and accepting H-bonds from the H₂O molecules are important for the development of a continuous hydrogen bonding network across the interfacial region. For the hydrophilic but charged hydrotalcite and muscovite (0 0 1) surfaces, only accepting or donating H-bonds from the water molecules contribute to the formation of the H-bonding network at the negatively and positively charged interfaces, respectively. For the hydrophobic talc (0 0 1) surface, H-bonds between water molecules and the surface sites are very weak, and the H-bonds among H₂O molecules dominate the interfacial H-bonding network. For all the systems studied, the orientation of the interfacial water molecules in the first few layers is influenced by both the substrate surface charge and the ability by the surfaces to facilitate H-bond formation. The first layer of water molecules at all surfaces is well ordered in the xy plane (parallel to the surface) and the atomic density distributions reflect the substrate crystal structure. The enhanced ordering of water molecules at the interfaces indicates reduced orientational and translational entropy. In thin films, water molecules are more mobile parallel to the surface than perpendicular to it due to spatial constraints. At neutral, hydrophilic substrates, single-monolayer surface coverage stabilizes the adsorbed water molecules and results in a minimum of the surface hydration energy. In contrast, at the charged and hydrophilic muscovite surface, the hydration energy increases monotonically with increasing water coverage over the range of coverages studied. At the neutral and hydrophobic talc surface, the adsorption of H₂O is unfavorable at all surface coverages, and the hydration energy decreases monotonically with increasing coverage.     

甘肃省锶矿泉水的富集环境及其形成机理研究

甘肃省位于中国四大地理区（北方区、南方区、西北区和青藏高原区）的相接部位,气候类型多样、地质构造活动强烈、地形复杂、地貌形态多样,复杂的地质条件、多样的地理气候环境和水文地质条件,为锶矿泉水的形成提供了有利条件。通过对全省644个水点的样品检测分析,表明锶含量主要集中在0.09~1.00 mg/L,最高值达15.6 mg/L,锶含量≥0.40 mg/L、达到饮用天然矿泉水界限含量的水点共有411个,占全部水点的58.1%,锶是甘肃省地下水中普遍含有并且含量较丰的微量元素之一。经统计分析表明,在水文地质单元上,以山前盆地第四系地下水为主的河西走廊平原区和以白垩系碎屑岩孔隙裂隙水为主的陇东黄土丘陵区地下水中最有利于锶的富集;地下水类型上,以中新生界碎屑岩地下水锶最易富集,而以变质岩为主的基岩裂隙水不利于锶的富集;循环特征上,以具备深循环条件的盆地型地下水系统最有利于锶的富集,而循环路径短、交替条件较强烈的局部水流系统中地下水锶偏贫。围岩中的锶丰度,决定了地下水中锶的含量,白垩系和新近系碎屑岩、古生界碳酸盐岩中锶丰度高,决定了白垩系碎屑岩地下水、新近系碎屑岩地下水和碳酸盐岩岩溶水具备锶矿泉水富集的物质条件;同时锶在地下水中富集,还与地下水所处的构造环境和地下水循环运移特征有关,盆地型的地下水流系统和进行深循环的地下水从补给区到排泄区径流距离远,循环路径长,地下水在含水层的滞留时间长,有利于锶在地下水中的溶解和富集。     

粉质黏土强度指标的水化学敏感性研究

通过对重塑粉质黏土的液、塑限和固结慢速直剪试验,探讨了粉质黏土液限、塑性指数及抗剪强度与不同浓度NaCl孔隙溶液的关系。试验结果表明,随着孔隙溶液浓度增加,液限随之减小,塑性指数表现出粉土的性质;不同竖向正应力下的强度随浓度变化表现出较大的差异,正应力较低时,强度不断减小,而正应力较高时,则强度不断增大,正应力介于二者之间强度则先降后升;内摩擦角随浓度增加而增大,最终趋于稳定;黏聚力先迅速减小后逐渐回升,且均为负值。其性质变化主要是因为扩散双电层、颗粒间作用力以及孔隙比发生了改变。基于Terzaghi的有效应力原理,对饱和粉质黏土固结慢速直剪试验测得的负值黏聚力进行了分析和讨论,认为渗透压力对黏聚力起了非常重要的作用,从而使黏聚力成为负值。     

Adsorption of organic matter at mineral/water interfaces: I. ATR-FTIR spectroscopic and quantum chemical study of oxalate adsorbed at boehmite/water and corundum/water interfaces

The types and structures of adsorption complexes formed by oxalate at boehmite (γ-AlOOH)/water and corundum (α-Al₂O₃)/water interfaces were determined using in situ attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy and quantum chemical simulation methods. At pH 5.1, at least four different oxalate species were found at or near the boehmite/water interface for oxalate surface coverages (Γ_ox) ranging from 0.25 to 16.44 μmol/m². At relatively low coverages (Γ_ox < 2.47), strongly adsorbed inner-sphere oxalate species (IR peaks at 1286, 1418, 1700, and 1720 cm⁻¹) replace weakly adsorbed carbonate species, and a small proportion of oxalate anions are adsorbed in an outer-sphere mode (IR peaks at 1314 and 1591 cm⁻¹). IR peaks indicative of inner-sphere adsorbed oxalate are also observed for oxalate at the corundum/water interface at Γ_ox = 1.4 μmol/m². With increasing oxalate concentration (Γ_ox > 2.47 μmol/m²), the boehmite surface binding sites for inner-sphere adsorbed oxalate become saturated, and excess oxalate ions are present dominantly as aqueous species (IR peaks at 1309 and 1571 cm⁻¹). In addition to these adsorption processes, oxalate-promoted dissolution of boehmite following inner-sphere oxalate adsorption becomes increasingly pronounced with increasing Γ_ox and results in an aqueous Al(III)-oxalate species, as indicated by shifted IR peaks (1286 → 1297 cm⁻¹ and 1418 → 1408 cm⁻¹). At pH 2.5, no outer-sphere adsorbed oxalate or aqueous oxalate species were observed. The similarity of adsorbed oxalate spectral features at pH 2.5 and 5.1 implies that the adsorption mechanism of aqueous HOx⁻ species involves loss of protons from this species during the ligand-exchange reaction. As a consequence, adsorbed inner-sphere oxalate and aqueous Al(III)-oxalate complexes formed at pH 2.5 have coordination geometries very similar to those formed at pH 5.1.The coordination geometry of inner-sphere adsorbed oxalate species was also predicted using quantum chemical geometry optimization and IR vibrational frequency calculations. Geometry-optimized Al₈O₁₂ and Al₁₄O₂₂ clusters with the reactive surface Al site coordinated by three oxygens were used as model substrates for corundum and boehmite surfaces. Among the models considered, calculated IR frequencies based on a bidentate side-on structure with a 5-membered ring agree best with the observed frequencies for boehmite/oxalate/water samples at Γ_ox = 0.25 to 16.44 μmol/m² and pH 2.5 and 5.1, and for a corundum/oxalate/water sample at Γ_ox = 1.4 μmol/m² and pH 5.1. Based on these results, we suggest that oxalate bonding on boehmite and corundum surfaces results in 5-coordinated rather than 4- or 6-coordinated Al surface sites.     

Seasonal water uptake near trees: a numerical and experimental study

Issues related to the numerical simulation of moisture migration patterns in the unsaturated zone and in the vicinity of mature trees are explored in this paper. The research is based on the use of Richard's equation for unsaturated moisture flow incorporating a sink term. A numerical solution has been achieved via the finite-element method for spatial discretization along with a finite-difference time-marching scheme. An axisymmetric solution is developed to represent water uptake near an established tree. The approach adopted utilizes radial symmetry and assumes a linear distribution of water extraction rates with both depth and radius. The model has been validated by direct comparison with field measurements recorded (by others) for a mature lime tree located on a boulder clay subsoil. Non-linear hydraulic properties have been obtained from independent published data. A good correlation between field data and simulated results has been achieved. The simulation covers a full annual cycle starting from field capacity in winter, extending through a full spring–summer drying period and subsequent autumn recharge. It is believed that this is the first attempt to simulate the behaviour of an established tree over such a time-scale. This relatively straightforward approach is thought to be suitable for development and application to a range of geo-engineering problems (e.g. slope stability, shrinkage/heave prediction, etc).     

试论吉林省天然矿泉水资源及其价值

吉林省天然矿泉水资源十分丰富 ,在全国占有重要地位。本文根据大量的实际资料 ,从理论上对矿泉水的形成机制和分布规律进行了探讨。同时从矿泉水的资源属性出发 ,对其价值问题提出了新的认识。     

A computational study of oxygen diffusion in olivine

Atomistic modelling techniques are used to study the rate-determining steps that limit diffusion of oxygen in forsterite. The activation energies for diffusion parallel to all three crystallographic axes by the vacancy and interstitial mechanisms are calculated. The activation energy for extrinsic vacancy diffusion is predicted to be isotropic with a barrier height of 119 kJ mol^–1. Conversely, in the interstitial case it is found to be anisotropic, with extrinsic activation energies that range between 94 and 178 kJ mol^–1. The effect of intrinsic defects and two typical impurities, iron and hydrogen, upon diffusion is also considered. We find that the migration energy is slightly higher in iron-rich fayalite compared with forsterite and that the presence of hydrogen defects will not affect the diffusion mechanism. These observations lead us to reinterpret existing experimental results on oxygen diffusion in natural olivine. We suggest that at low oxygen partial pressure the mechanism observed is a vacancy mechanism, while at high oxygen partial pressure the mechanism is interstitial. We believe that this change in mechanism is mediated by iron redox reactions. Taking this process into account, we derive activation energies in excellent agreement with those found experimentally in natural samples of olivine. The anisotropy of activation barriers and hence the change in diffusion rates with temperature could be used to distinguish between the two mechanisms in future experimental work.     

Comparison on landslide nonlinear displacement analysis and prediction with computational intelligence approaches

Landslide displacement is widely obtained to discover landslide behaviors for purpose of event forecasting. This article aims to present a comparative study on landslide nonlinear displacement analysis and prediction using computational intelligence techniques. Three state-of-art techniques, the support vector machine (SVM), the relevance vector machine (RVM), and the Gaussian process (GP), are comparatively presented briefly for modeling landslide displacement series. The three techniques are discussed comparatively for both fitting and predicting the landslide displacement series. Two landslides, the Baishuihe colluvial landslide in China Three Georges and the Super-Sauze mudslide in the French Alps, are illustrated. The results prove that the computational intelligence approaches are feasible and capable of fitting and predicting landslide nonlinear displacement. The Gaussian process, on the whole, performs better than the support vector machine, relevance vector machine, and simple artificial neural network (ANN) with optimized parameter values in predictive analysis of the landslide displacement.     

A preliminary study on the spatial distribution characteristics and causes of strontium-rich mineral water in the Dushan complex

The mountain rocks in the Dushan Complex are Sr-rich granite with a much higher Sr level than those in other crustal lithospheres in eastern China. That presents a high potential for developing Sr-rich mineral water. In this study, 6 groups of rock samples, together with 30 groups of water samples, were collected. Combining with the existing data, the Sr contents in three different types of underground water were obtained, which are the Quaternary pore water, the meshed bedrock fissure water in weathered zones and the tectonic bedrock fissure water. On the basis of preliminary understanding for the distribution characteristics of Sr-rich mineral water in the Dushan Mountain region, the causes for the Sr-rich mineral water were investigated. Our results showed that the Sr content of the rocks in the studied area ranges from 988 to 1 950 μg/g. In the horizontal direction, those in both the pore water and the meshed bedrock fissure water in weathered zones show high values in the west but low ones in the east, and high ones in the south but low ones in the north. Furthermore, both types of water meet the standard for Sr-rich mineral water in the western areas. In the vertical direction, the Sr content shows the lowest value in pore water(the average value is 0.707 mg/L), middle value in the meshed bedrock fissure water in weathered zones(the average value is 1.415 mg/L) and the highest value in the tectonic bedrock fissure water(the average value is 8.331 mg/L). It was thought that the widely-developed Sr-rich granite in this region provides physical sources for the formation of Sr-rich mineral water. The continuous dissolution of Sr during underground water runoff is the internal mechanism. In addition, the hydraulic interrelations may exist between the three vertical aquifers, leading a continuous accumulation of the Sr level during infiltration.     

Structure and dynamics of the water films confined between edges of pyrophyllite: A first principle study

Edge sites of clay minerals play a key role for pH dependent sorption of ions from solutions of electrolytes. Pyrophyllite, Al₂[Si₄O₁₀](OH)₂, is an important structural prototype for a variety of 2:1 dioctahedral phyllosilicates but in contrast to the other clays has no permanent structural charge. The structure of thin water films confined between most common edges of 1Tc pyrophyllite: (0 1 0), (1 1 0) and (1 0 0), was analyzed by means of ab initio molecular dynamic simulations. The system setup allowed for a full flexibility of the interfaces and a proton exchange between the edges of pyrophyllite and water molecules in solution. The structure of hydrated surfaces is compared with the recent predictions of static geometry optimizations for edge-vacuum interfaces. All surfaces studied reveal a strong hydrophilic character of edge similar to the hydrated silica surface and the facets of simple layered hydroxides. Spontaneous proton transfer between different surface sites were observed in molecular dynamics simulations of the (0 1 0) interface. The proton bound to the SiOH site was found to exchange with the AlOH group by the mechanism . The direction of the proton transfer agrees with the scale of relative proton affinities for surface sites obtained from the static calculations. Alternatively, the proton attached to the AlOH₂ site exchanges with the AlOH group. In both reactions, the protons are transferred through the chains of hydrogen bonds formed between water molecules in the solution and the surface sites. The observed mechanisms might be one of the basic schemes for the surface proton diffusion in compacted clays. Kinetics of the proton transfer at edge sites is limited by the rate of rearrangements of the water molecules near interface.     

王庄油田强水敏油藏粘土矿物危害研究

强水敏油藏指储层遇到外来流体后,渗透率的下降幅度超过70%的油藏.该类油藏由于渗透率的大幅下降,导致注水、注汽等地层能量补充困难,开发效果不理想.目前国内外对储层敏感性机理研究逐渐从试验走向实践,并形成了一套系统的储层敏感性试验研究方法,但敏感性油藏的开发始终未取得较大的突破,其重要原因就是粘土矿物伤害储层.笔者以王庄油田强水敏性油藏为例,对粘土矿物危害进行探讨.     

稀土矿物的综合利用和化学性能

文章介绍了稀土矿物的化学性能和综合利用情况,稀土矿区的矿石和围岩中稀土元素总体特征非常相似,说明围岩和矿石中稀土元素特征是基本一致的。形成于裂陷盆地初期的硅质岩,比古华南残留洋盆和扬子陆块边缘的硅质岩轻稀土元素更加富集;构造拉张期形成的硅质岩为热液成因硅质岩,其稀土配分模式显示出轻稀土相对亏损、Eu正异常特征;构造稳定期形成的硅质岩为沉积成因硅质岩,稀土配分模式显示出轻稀土相对富集、Eu弱负异常征。我国稀土矿产主要集中在华北区的内蒙古白云鄂博铁-铌、稀土矿区,其稀土储量占全国稀土总储量的90%以上,是我国轻稀土主要生产基地。在钢铁冶炼中添加稀土或碱土金属元素使镁基体中形成若干具有耐热性能的金属间化合物,抑制晶界滑移和位错,从而提高钢材的耐热性能。固溶于钢铁中的稀土可提高钢材抗高温氧化性,抑制再结晶、细化晶粒、抑制表面活性元素在晶界的偏析,提高钢材综合机械性能。     

Adsorption and stabilization of organic carbon by mineral surfaces in soils

Soils are the largest carbon reservoir in the terrestrial system. Soils contain about three times more carbon than vegetation and twice as much as that present in the atmosphere. Soil organic matter （SOM） is very complex in composition and structure, formed of heterogeneous substances and generally associated with minerals in soils. SOM is classified as labile and stable fractions on the basis of residence time, determined not only by the chemical composition of SOM, but also by types of protection or bonds within soils. The stable carbon fraction is protected either physically or chemically. To understand the process of SOM stabilization, physicochemical properties of organic-mineral complexes were determined by Fourier transformed infrared （FTIR） with attenuated total reflectance （ATR） and diffuse reflectance （DRIFT）, atomic force microscopy （AFM）, and nuclear magnetic spectroscopy （NMR）. Humic acids and carboxylic acids with relatively short carbon chains were used as sorbates, and goethite, kaolinite, and montmorillonite as adsorbents. Humic acid was fractionated during adsorption on the minerals, which was highly influenced by the characteristics of minerals. For instance, long-chain aliphatic carbon was likely to be adsorbed onto the surface of kaolinite and montmorillonite, while goethite surface attracted carboxylic functional groups of humic acid.     

矿产资源与可持续发展研究

本文从经济发展角度,分析我国矿产资源现状和形势,阐明矿产资源在建设小康社会和实现可持续发展中的地位和作用,指出我国矿产资源发展存在的主要问题,提出解决上述问题的办法和实现小康目标、保障矿产资源可持续发展的基本对策.