Adsorption of As on hydroxy-Fe-montmorillonite complexes

DOI: 10.1360/03yd0553 Arsenic, a toxic element, is ubiquitous in the earth’s crust and may lead to health risks for humans. This may come about as a result of oxidative weathering and dissolution of As-containing minerals, use of ar-senical pesticides, excess use of some fertilizers and from mine drainage, smelter wastes and agricultural drainage water from certain arid regions. The dis-solved inorganic arsenic is transported in surface or2156 Science in China Ser. D Earth Sciences groun…     

离子色谱法测定温泉水中多种阴阳离子

在用离子色谱法测定温泉水样中F~-、Cl~-、Br~-、NO_2~-、NO_3~-、SO_4~(2-)、PO_4~(2-)等阴离子和Li~+、Na~+、K~+、Mg~(2+)、Ca~(2+)等阳离子过程中,研究了用油泵超声波池内脱气法处理H_2CO_3过饱和水样以排除HCO_3~-对阴离子检测干扰的方法.研究采用青岛普仁仪器有限公司生产的PIC-8型离子色谱仪,分离柱为TSK-GEL SuperIC-CationColumn(150 mm×4.5 mm)离子分离柱,以1.9 mmol/L碳酸钠-1.8mmol/L碳酸氢钠作为阴离子淋洗液,流量为1.5 Ml/min;以2 mmol/L HNO_3为阳离子淋洗液,流量为1.0 ml/min,测定了腾冲火山区叠水河、大滚锅两个温泉水中的阴阳离子的含量.研究结果表明:该方法简便、快速、准确可靠,可在火山和地震监测中推广使用.     

Sorption of Eu~(3+) onto nano-size silica-water interfaces

A large amount of nuclear wastes has been pro-duced due to nuclear weapon development and nuclear electricity generation. One possible resolution for the disposal of the nuclear wastes is to seal them in an underground repository, which requires detailed knowledge on the mobility, chemical behavior and immobilization of radionuclides in underground water. In addition, toxic heavy metals are extensively present in ground and underground water, how to immobilize and remedy these toxic heavy meta…     

气体受激增温的实验研究

试验结果基本证明了热红外温度异常与太阳照射、大气电场、大气成分密切相关。非极性气体如CO2 、CH4 的含量越高, 增温越大。而极性气体, 如水蒸气则相反, 含量越高, 增温越小。CO2 、CH4 含量高的大气, 其增温远远超过单纯由温室效应引起的增温, 其幅度可达10℃,而水蒸气引起的增温还没有单纯由其温室效应引起的高。     

封管法制备有机碳同位素质谱分析样

本文介绍了在分析有机质中稳定碳同位素时制备CO_2的一种简单方法。该方法可用于湖泊沉积物样品及各种物态的石油分馏物,并且对其它有机化合物有很好的潜力。有机物样品在高温中灼烧生成CO_2和H_2O,然后进行分离转移。该方法所需材料极其便宜,设备简单,并且在8h内可制备近30个样品,适合我国一些中小实验室。     

Adsorption of Cadmium Ions from Aqueous Solution Using Granular Activated Carbon and Activated Clay

The present study was aimed at removing cadmium ions from aqueous solution through batch studies using adsorbents, such as, granular activated carbon (GAC) and activated clay (A‐clay). GAC was of commercial grade where as the A‐clay was prepared by acid treatment of clay with 1 mol/L of H₂SO₄. Bulk densities of A‐clay and GAC were 1132 and 599 kg/m³, respectively. The surface areas were 358 m²/g for GAC and 90 m²/g for A‐clay. The adsorption studies were carried out to optimize the process parameters, such as, pH, adsorbent dosage, and contact time. The results obtained were analyzed for kinetics and adsorption isotherm studies. The pH value was optimized at pH 6 giving maximum Cd removal of 84 and 75.2% with GAC and A‐clay, respectively. The adsorbent dosage was optimized and was found to be 5 g/L for GAC and 10 g/L for A‐clay. Batch adsorption studies were carried out with initial adsorbate (Cd) concentration of 100 mg/L and adsorbent dosage of 10 g/L at pH 6. The optimum contact time was found to be 5 h for both the adsorbents. Kinetic studies showed Cd removal a pseudo second order process. The isotherm studies revealed Langmuir isotherm to better fit the data than Freundlich isotherm.     

Direct scanning tunneling microscope (STM) observation of Cr(III) complexes on hematite (001) surfaces

Scanning tunneling microscopy (STM) is used to observe, at the atomic scale, Cr(III) adsorbed to hematite (001) surfaces from aqueous solution. The Cr(III) adsorbates are relatively immobile, but estimated activation energies for surface self-diffusion are lower than those for water or hydroxyl substitution in aqueous Cr(III). Possible causes are effects of STM imaging (artifacts), high ligand-substitution rates for adsorbed species, or participation of substrate Fe (III) ligand exchange. STM imaging of suitable aqueous surface complexes is shown to be feasible, and constitutes a new way to study the relationships between microscopic and macroscopic chemical behavior of adsorbed species in aqueous systems.     

The significance of surface complexation reactions in hydrologic systems: a geochemist's perspective

Complexation reactions at the mineral–water interface affect the transport and transformation of metals and organic contaminants, nutrient availability in soils, formation of ore deposits, acidification of watersheds and the global cycling of elements. Such reactions can be understood by quantifying speciation reactions in homogeneous aqueous solutions, characterizing reactive sites at mineral surfaces and developing models of the interactions between aqueous species at solid surfaces. In this paper, the application of thermodynamic principles to quantify aqueous complexation reactions is described. This is followed by a brief overview of a few of the methods that have been used to characterize reactive sites on mineral surfaces. Next, the application of empirical and semi-empirical models of adsorption at the mineral–water interface, including distribution coefficients, simple ion exchange models, and Langmuir and Freundlich isotherms is discussed. Emphasis is placed on the limitations of such models in providing an adequate representation of adsorption in hydrological systems. These limitations arise because isotherms do not account for the structure of adsorbed species, nor do they account for the development of surface charge with adsorption. This is contrasted with more sophisticated models of adsorption, termed ‘surface complexation models’, which include the constant capacitance model, the diffuse layer model, the triple layer model and the MUSIC model. In these models, speciation reactions between surface functional groups and dissolved species control the variable surface charge build-up and the specific adsorption properties of minerals in aqueous solutions. Next, the influence of mineral surface speciation on the reactivity of adsorbed species and on far from equilibrium dissolution rates of minerals is discussed. Finally, the applicability of microscopic models of surface complexation to field-scale systems is explored and the need to integrate sophisticated surface chemical and hydrological modeling approaches is stressed.     

Gold solubility in silicate melts and fluids: Advances from high-pressure and high-temperature experiments

The solubility of Au in silicate melts and fluids governs the enrichment and migration of Au during the formation of magmatic-hydrothermal Au deposits. Large Au deposits require vast amounts of Au to migrate from the upper mantle-lower crust to the shallow crust, and high Au solubility in magma and hydrothermal fluid facilitates the formation of Au-rich magma and fluid in the crust and mantle source and efficient transport. This paper reviews recent high-pressure and high-temperature experimental studies on Au species in magmas and hydrothermal fluids, the partitioning behavior of Au between silicate melts and fluids, and the effects of temperature, pressure, oxygen fugacity, sulfur fugacity, silicate melt composition, and volatiles(H_2O, CO_2, chlorine, and sulfur) on the solubility of Au in magma. We show that the solubility of Au in magma is largely controlled by the volatiles in the magma: the higher the content of reduced sulfur(S~(2-) and HS~-) in the magma, the higher the solubility of Au. Under high-temperature, high-pressure, H_2O-rich, and intermediate oxygen fugacity conditions, magma can dissolve more reduced sulfur species, thus enhancing the ability of the magma to transport Au. If the ore-forming elements of the Au deposits in the North China Craton originate from mantle-derived magmas and fluids, we can conclude, in terms of massive Au migration, that these deep Au-rich magmas might have been generated under H2 O-rich and moderately oxidized conditions(S~(2-) coexists with S~(6+)). The big mantle wedge beneath East Asia was metasomatized by melts and fluids from the dehydration of the Early Cretaceous paleo-Pacific stagnant slab, which not only caused thinning of the North China Craton, but also created physicochemical conditions favorable for massive Au migration.     

Adsorption characteristics of copper ion on nanoporous silica

Adsorption by nanoporous media is critically involved in many fundamental geological and geochemical processes including chemical weathering,element migration and enrichment,environmental pollution,etc.Yet,the adsorption behavior of metal ions on nanoporous materials has not been systematically investigated.In this study,MCM-41 material with a monodisperse pore size(4.4 nm)and a large BET specific surface area(839 m^2/g)was hydrothermally prepared and used as a model silica adsorbent to study the adsorption characteristics of Cu^2+as a representative metal ion.The Cu^2+adsorption capacity was found to increase with increasing suspension pH in the range from 3 to 5 and to decrease in the presence of NaNO3.At 25℃,pH=5,and a solid-to-liquid ratio of 5 g/L,the adsorption capacity was determined to be 0.29 mg/g,which can be converted to a dimensionless partition coefficient of 45,indicating a strong enriching effect of nanoporous silica.The adsorption isotherm and kinetic data were fitted to several commonly used thermodynamic,kinetic,and diffusion models.The adsorption mechanism was also studied by Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy and synchrotron-based X-ray absorption spectroscopy.The results suggest that Cu2+ion adsorption is an entropy-driven endothermal process,possibly involving both outer-sphere and inner-sphere complexes.     

A three-scale model for ionic solute transport in swelling clays incorporating ion–ion correlation effects

A new three-scale model is proposed to describe the movement of ionic species of different valences in swelling clays characterized by three separate length scales (nano, micro, and macro) and two levels of porosity (nano- and micropores). At the finest (nano) scale the medium is treated as charged clay particles saturated by aqueous electrolyte solution containing monovalent and divalent ions forming the electrical double layer. A new constitutive law is constructed for the disjoining pressure based on the numerical resolution of non-local problem at the nanoscale which, in contrast to the Poisson–Boltzmann theory for point charge ions, is capable of capturing the short-range interactions between the ions due to their finite size. At the intermediate scale (microscale), the two-phase homogenized particle/electrolyte solution system is represented by swollen clay clusters (or aggregates) with the nanoscale disjoining pressure incorporated in a modified form of Terzaghi’s effective principle. At the macroscale, the electro-chemical–mechanical couplings within clay clusters is homogenized with the ion transport in the bulk fluid lying in the micro pores. The resultant macroscopic picture is governed by a three-scale model wherein ion transport takes place in the bulk solution strongly coupled with the mechanics of the clay clusters which play the role of sources/sinks of mass to the bulk fluid associated with ion adsorption/desorption in the electrical double layer at the nanoscale. Within the context of the quasi-steady version of the multiscale model, wherein the electrolyte solution in the nanopores is assumed at instantaneous thermodynamic equilibrium with the bulk fluid in the micropores, we build-up numerically the ion-adsorption isotherms along with the constitutive law of the retardation coefficients of monovalent and divalent ions. In addition, the constitutive law for the macroscopic swelling pressure is reconstructed numerically showing patterns of attractive forces between particles for bivalent ions for particular ranges of bulk concentrations. The three-scale model is applied to numerically simulate ion diffusion in a compacted clay liner underneath a sanitary landfill. Owing to the distinct constitutive behavior of the swelling pressure and partition coefficient for each ionic species, different compaction regimes and diffusion/adsorption patterns, with totally different characteristic time scales, are observed for sodium and calcium migration in the clay liner.     

Improved method to determine the molar volume and compositions of the NaCl-H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript> system inclusion

On the basis of Parry’s method (1986), an improved method was established to determine the molar volume (Vm) and compositions (X) of the NaCl-H2O-CO2 (NHC) system inclusion. To use this method, the determination of Vm-X only requires three microthermometric data of a NHC inclusion: partial homog-enization temperature (Th ,CO2), salinity (S) and total homogenization temperature (Th). Theoretically, four associated equations are needed containing four unknown parameters: X CO2, XNaCl, Vm and F (volume fraction of CO2 phase in total inclusion when occurring partial homogenization). When they are released, the Vm-X are determined. The former three equations, only correlated with Th ,CO2, S and F, have simplified expressions:XCO2=f1(Th,CO2,S,F),XNaCl=f2(Th,CO2,S,F),Vm=f3(Th,CO2,S,F). The last one is the thermodynamic relationship of X CO2, XNaCl, Vm and Th:f4(XCO2,XNaCl,Vm,Th)=0.Since the above four associated equations are complicated, it is necessary to adopt iterative technique to release them. The technique can be described by:(i) Freely input a F value (0≤F≤1),with Th ,CO2 and S, into the former three equations. As a result,X CO 2,XNaCl and the molar volume value recorded as Vm1 are derived. (ii) Input the X CO2 and XNaCl gotten in the step above into the last equation, and another molar volume value recorded as Vm2 is determined. (iii) If Vm1 is unequal to Vm2, the calculation will be restarted from “(i)”. The iteration is completed until Vm1 is equal to Vm2, which means that the four associated equations are released. Compared to Parry’s (1986) solution method, the improved method is more convenient to use, as well as more accurate to determine X CO 2. It is available for a NHC inlusion whose partial homogenization temperature is higher than clatherate melting temperature and there are no solid salt crystals in the inclusion at parital homogenization.     

Hydrated cluster ion formation rates and winter anomaly

Expressions for the effective cluster formation rates are written in terms of neutral densities and recent laboratory data on reaction rate coefficients. At D-region heights these parameters show seasonal variations due to mesospheric temperature changes. Reduction in cluster formation rates for winter months would result in a decrease in the concentration of hydrated ions and hence reduced effective recombination coefficient for electrons. The results show latitude and seasonal variations which are similar to that of a normal winter anomaly in radio wave absorption.     

Determining CO_2 consumption from elemental change in soil profiles developed on carbonate and silicate rocks

To further understand the roles of carbonate and silicate rocks in regulating the atmosphere/soil CO_2level,the flux of CO_2 consumed by the chemical weathering of silicate and carbonate rocks was determined from the elemental change in soil profiles.Results showed that the chemical weathering of carbonate rocks mainly occurred at the rock-regolith interface,and that the further weathering of the residua soil on the carbonate rocks was similar to that of the granite profile.Chemical weathering of the silicate rocks occurred through the whole profiles.Therefore,CO_2 consumed per volume by the silicate profiles[M_(sr)(CO_2)]and the residues on carbonate rocks[M_(cr)(CO2)]were calculated based on the elemental weathering gradients.CO_2 consumed by carbonate protolith[M_(cp)(CO_2)]was calculated from the elemental change at the rock-regolith interface.The M_(sr)(CO_2) were about tens to thousands orders of magnitude greater than M_(cr)(CO_2).Even so,this demonstrated that the residues on carbonate rocks could be a sink of CO2_ on long-term scales.The M_(cp)(CO_2) was about four times larger than M_(sr)(CO_2),which demonstrated that carbonate rocks played a more important role in regulating the CO_2 level than the silicate rocks did during the pedogenic process of the profiles.     

Research on preservation and enrichment mechanisms of organic matter in muddy sediment and mudstone

Using multidiscipline methodologies, the differences in preservation and enrichment mechanisms of organic matter (OM) in muddy sediment and mudstone are investigated. In clay fractions, concentra- tions of TOC and chloroform bitumen “A” are significantly higher than those in coarser fractions. This indicates that clay minerals (CM) play an important role in enriching OM. The content of chloroform bitumen “A” increases obviously in the clay fraction, which reveals that dissolvable OM is the main composition of coalesce with clay minerals. Furthermore, TG and DTA data show that OM enrichment mechanisms and preservation forms have multiplicity. Several exothermic peaks in the DTA curves demonstrate that muddy sediment and mudstone contain a number of bioclasts and amorphous OM besides dissolvable OM. Through analyzing with XRD and DTA after mudstone samples were pretreated, the conclusions can be arrived at. Firstly, CM interlayer space of XRD curves and exothermic peaks of DTA curves both change as temperature increases. Secondly, the changes of CM interlayer space and exothermic peaks are concordant and stable around 350℃. All these are the features that OM enters CM interlayers to form stable organo-clay complexes. Therefore, the combination format of OM with CM is not only surface adsorption, partial OM enters CM interlayers to form stable organo-clay complexes. Finally, through the research on OM preservation forms and enrichment mechanisms in muddy sedi- ment and mudstone, the hydrocarbon-generation processes and the global carbon cycle and budget can be explained.     

Evaluation of selected cobalt-60 complexes as tracers of groundwater

A series of Co-60 compounds, considered as potentially useful tracers of groundwater movement, were prepared and evaluated in soil column and batch studies. The compounds were: potassium hexacyanocobaltate (III), K₃Co(CN)₆; potassium ethylenediamminetetraacetato-cobaltate (III), KCo(EDTA); ammonium 12-tungstodicobaltoate (III), (NH₄)₈[Co(II)Co(II)W₁₂O₄₂] · 20 H₂O; chloraquotetrammine cobalt (III) chloride, [Co(NH₃)₄(H₂O)Cl]Cl₂; and sodium hexanitrocobaltate (III), Na₃Co(NO₂)₆. The performance of K₃ ⁶⁰Co(CN)₆ and K ⁶⁰Co EDTA were dependent on their environment and more especially on the type and amount of clay present. The EDTA cobalt complex cannot be used in soils that are basic or where a large fraction of the clay is saturated with Na⁺ and/or Ca⁺⁺. Of the other radioactive tracers tested, none were suitable for groundwater tracing because of instability in aqueous solution (Na₃Co(NO₂)₆), variable anionic structure under acid conditions ((NH₃)₈[Co(II)Co(II)W₁₂O₄₂] · 20 H₂O), or preferential uptake by the clay fraction ([Co(NH₃)₄(H₂O)Cl]Cl₂).     

1950年以来青藏高原兹格塘错碳酸盐稳定碳同位素变化及其原因

兹格塘错是青藏高原中部一个典型的半混合型咸水湖泊。本文在~(210)Pb和~(137)Cs定年的基础上,研究了兹格塘错重力岩芯(ZGTC A-1)小于38.5μm细颗粒组分碳酸盐稳定碳同位素1950年以来的变化及其影响因素。对冬夏季湖水水化学特征的分析表明,夏季湖水溶解CO_2呈逸出状态,冬季湖水钙离子浓度是夏季湖水的10倍,据此可以得出兹格塘错碳酸盐矿物主要在夏季沉淀。通过与那曲气象站气象记录对比发现,1950年以来A-1岩芯碳酸盐碳同位素变化与年均温度有很好的相关性,表现出年均温度高时碳同位素偏重,而年均温度低时碳同位素偏轻的特征。兹格塘错1950年以来自生碳酸盐碳同位素的变化是由湖区及水体碳循环(如碳酸盐沉淀,有机质的沉淀与分解,有机碳和无机碳的转化等)的变化引起的,但各种因素的相互作用非常复杂。碳酸盐含量也与温度有关,温度越高,碳酸盐含量越高,同时降水量与碳酸盐含量也存在明显的相关关系。1950年以来有机质含量与温度呈反相关,可能与湖泊生产力的下降有关。     

The removal of aqueous silica from dilute aqueous solution

The adsorption characteristics of orthosilicate on hydrous γ-Al₂O₃ from dilute aqueous solution (10^?4 to 10^?3 M) at constant ionic strength (0.1M NaCl) was investigated in the laboratory.The extent of adsorption is affected by pH, concentration of silicate, or the relative concentration of silicate and oxide surface. With short reaction time (24 hours), adsorption is the major interfacial reaction and follows an S-type adsorption isotherm. The steepness of the S-curve isotherm is influenced by the degree of equilibrium. The slower the adsorption reaction is, the flatter the S-curve becomes.Two steps, an initial fast followed by a second slow, of silicate removal were observed. The first fast step, which lasts for about one to two hours, depends greatly on pH and has the following expressions: ?d[Si]/dt = 1.3 × 10^?3 [A]²[H⁺]^?0.5[Si]^1.5; pH < 9 and ?d[Si]/dt = 4.0 × 10¹⁰ [A]²[H⁺][Si]^1.5; pH > 9. The second slow step is a first-order form with respect to the concentration of silicate. The specific rate constant depends on pH, concentration of silicate and surface area.Specific chemical energy contributes significantly to the adsorption of silicate and a value of ??12RT was found.     

Migration and enrichment of trace elements of Lower Palaeozoic carbonate rock strata in Beijing

Analyses of trace elements of the Lower Palaeozoic carbonate rock strata in Beijing show that the contents of As, Hg, F increase from primary carbonate rocks to weathered carbonate rocks and from primary carbonate rocks to the soil coexisting with carbonate rocks, but the distribution regularity of S is not obvious. In the whole weathered stages, the sorption of As is mainly affected by Fe2O3. In soil Fe2O3 is also the main affecting factor of Hg enrichment. The main existing forms of Hg in primary carbonate rocks should simply be physical adsorption, coprecipitation and false isomorphous form between surface of carbonate rock and Hg. In soil the enrichment of F has little relationship with sul-fides and Fe2O3. In primary carbonate rocks, F is mainly absorbed by sulfides and clay minerals, etc. Weathered samples have closer genetic relationships with primary carbonate rocks. This also implies that weathered carbonate rocks have the close existing forms to that of primary carbonate rocks. In primary carbonate rocks FeS2 and FeS are the main forms of S, and sulfides have fixation effect on some heavy metals, whereas in weathered carbonate rocks and soil the fixation effect is weakened.     

西安市地裂缝CO2异常特征及异常机理初步研究

本文论述了西安地裂缝0.5m和2.0m深处CO_2异常特征,并对其异常机理进行了初步探讨。结果表明,0.5m深处CO_2异常范围较大,与地裂缝造成的破坏范围基本一致,其CO_2主要来源于生物作用;2.0m深处CO_2异常范围窄,与主地裂缝的位置有很好的对应关系,其CO_2主要来源于断裂活动造成的碳酸盐岩破裂释气。