Structure and dynamics of water on Li-, Na-, K-, Cs-, H3O-exchanged muscovite surfaces: A molecular dynamics study

The distribution and dynamics of water molecules and monovalent cations (Li⁺, Na⁺, K⁺, Cs⁺, and H₃O⁺) on muscovite surfaces were investigated by molecular dynamics (MD) simulations. The direct comparison of calculated X-ray reflectivity profiles and electron density profiles with experiments revealed the precise structure at the aqueous monovalent electrolyte solutions/muscovite interface. To explain the experimentally observed electron density profiles for the CsCl solution-muscovite interface, the co-adsorption of Cs⁺ and Cl⁻ ion pairs would be necessary. Two types of inner-sphere complexes and one type of outer-sphere complex were observed for hydrated Li⁺ ions near the muscovite surface. For Na⁺, K⁺, Cs⁺, and H₃O⁺ ions, the inner-sphere complexes were stable on the muscovite surface. The density oscillation of water molecules was observed to approximately 1.5 nm from the muscovite surface. The number of peaks and the locations for the density of water oxygen atoms were almost similar among the water molecules coordinated to Li⁺, Na⁺, K⁺, and H₃O⁺ ions adsorbed on the muscovite surfaces. The water molecules around Cs⁺ ions that were adsorbed to muscovite surfaces seemed to avoid coordinating with Cs⁺ ions on the surface, and the density of water oxygen near the muscovite surface decreased relative to that in a bulk state. There was no significant difference in self-diffusion, viscosity, retention time, and reorientation time of water molecules among different cations adsorbed to muscovite surfaces. These translational and rotational motions of water molecules located at less than 1 nm from the muscovite surfaces were slower than those in a bulk state. A significant difference was observed for the exchange times of water molecules around monovalent cations. The exchange time of water molecules was long around Li⁺ ions and decreased with an increase in the ionic radius.     

Dissolution of silica from montmorillonite: effect of solution chemistry

The rate of silica removal from two montmorillonites (Chambers and Polkville) has been measured as a function of time, temperature, solution composition, and exchange ion on the clay. Silica removal rate increased with temperature from 200 to 350°C, decreased with time, and could be approximated initially by a parabolic rate law. Solution composition influenced silica removal rate by determining the exchange population of the clay; silica removal is most rapid when K-exchange ions are present. Thus increasing the concentration of K⁺ accelerated silica removal, whereas increasing the concentration of Na⁺, Ca²⁺, and Mg²⁺ inhibited silica removal. Activation energies for silica removal range from 5 to 10 kcal/mol. The largest values are associated with the largest concentrations of inhibitor ions in solution. Activation energies of this magnitude suggest that the rate-limiting step for silica removal is transport through a hydrated, expanded interlayer space. Application of experimental results to diagenesis in moderately to deeply buried sediments suggests that K⁺ uptake by montmorillonite may precede and accelerate illite formation.     

Varietals differences in agronomic performance of six wheat varieties grown under saline field environment

Six wheat varieties (SARC-1, SARC-2, SARC-3, SARC-4, LU26S and Punjab-85) were planted in the field to evaluate their comparative performance under saline conditions. LU26S appeared the most salt-tolerant variety and gave the highest grain weight due to its low Na⁺ uptake, high K⁺/Na⁺ ratio, higher dry weight of shoots and spikes and better grain development. Better exclusion of Na⁺ and other ions from the leaves of salt-tolerant variety LU2 6S could also be a reason for its ability to maintain a higher grain weight in the saline soil. Punjab-85 appeared the most saltsensitive variety as its dry weight of main shoots and spikes were also found to be the lowest. High Na⁺ uptake, lower K⁺/Na⁺ ratio, lower dry weight of main shoots and spikes and lower 100 grain weight were the main reasons for saltsensitivity in Punjab-85. Dry weight of shoots, spikes and grain weight of SARC-3 under saline soil conditions was almost similar to the salt-sensitive variety Punjab-85 and could be classified as salt-sensitive. Flag leaf area decreased drastically due to salt stress in all the varieties and this could be a major cause for low yield. There was however, a very low linear correlation between the flag leaf area and the grain weight in pooled data for all the six wheat varieties.     

Solute distribution in porous rhyolite as evaluated by sequential centrifugation

Pore water in a porous rhyolite, having a porosity of 27% and pore radii ranging from >25 μm to 0.008 μm, was centrifugally extracted stepwise with increasing centrifugal speed to examine the potential variations of the compositions of pore water and their relationships to reaction and transport occurring in the rock. The rock was soaked for from 1 h to 7 days in an aqueous solution prior to centrifugation. To evaluate the effect of adsorption under minimum effect of dissolution, Li⁺ and Br⁻ were added to the solution as tracer ions. As centrifugal speed increased, water was extracted in order of large to small pores and the thickness of residual water film became thinner. The concentrations of ions dissolving from the rock (Na⁺, K⁺, Ca²⁺, etc.) after 7 days of immersion were relatively constant in pores of 1-10 μm radii and exponentially increased by 3-100 fold with decreasing pore radius to 0.1 μm. These ions are dissolved from the rock and transported toward the exterior of the rock by diffusion. The calculation using a reactive-transport equation showed that the observed concentration changes reflect the change in solute distribution profile with pore size. The concentration of Si after 7 days of immersion was approximately constant or slightly decreased with increasing centrifugal speed, which appears to be controlled by the solubility. The concentration of Li⁺ decreased with increasing centrifugal speed after 1 h of immersion but the trend changed after 7 days of reaction. Initial behavior of Li⁺ is explained by adsorption on pore walls, and the change of trend is explained by desorption of that previously adsorbed, slight amounts of dissolution, and inflow from the outside of the rock. The change in concentration of Br⁻ with increasing centrifugal speed was small, probably because Br⁻ was not adsorbed on the surfaces. The sequential centrifugation thus provides information on the solute distribution associated with reaction and transport occurring in rock pores.     

Cation-exchange characteristics of Amazon River suspended sediment and its reaction with seawater

The cation-exchange characteristics of Amazon River suspended sediment have been studied in order to determine the contribution of exchangeable cations to the geochemical fluxes from the river. Sediment samples were obtained throughout most of the Amazon Basin. The range of exchangeable cation compositions is very narrow in the river and in seawater as well. In river water, the exchangeable cation complement (equivalent basis, exclusive of H⁺) is 80% Ca²⁺, 17% Mg²⁺, 3% Na⁺ plus K⁺. In seawater Na⁺ and Mg²⁺ are about equal (38%) while Ca²⁺ ~ 15% and K⁺ ~ 9%.On reaction with seawater, river suspended sediment took up an amount of Na⁺ equal to nearly one-third of the dissolved river load, as well as amounts corresponding to 15–20% of the dissolved fluvial K⁺ and Mg²⁺. These estimates reflect an unusually high suspended-sediment:dissolved-solids ratio of 6.4 at the time of sampling. At a more representative world average ratio of four, the uptake of Na⁺ would be 20% of the dissolved fluvial load, and that for K⁺ and Mg²⁺ about 10%. Over the annual cycle of the Amazon, it is estimated that ion exchange has a still smaller effect, as a consequence of the low average suspended-solids:dissolved-solids ratio of 1.7.Variations in the ratio $\text{X}{}_{\mathrm{Ca}}\text{X}{}_{\mathrm{Mg}}$, the equivalent fraction of exchangeable Ca²⁺ and Mg²⁺, throughout the river, can be described by a single isotherm. This same isotherm accurately describes the distribution of exchangeable Ca²⁺ and Mg²⁺ on sediment equilibrated with seawater, despite that a high proportion of exchange sites is occupied by Na⁺ and K⁺.     

Hydrogeochemical responses to rainfall inputs in a small rainforest basin: Rio de Janeiro,Brazil

This work provides basic information about hydrogeochemical contributions to different pathways of water in a small tropical rainforest catchment (3.5 km²) in Rio de Janeiro, Brazil. Precipitation and discharge measurements were conducted at the basin outlet, and at five other stream sites that were selected according to their hydrological behaviour and lithology. Precipitation and streamflow samples were collected weekly, over seven months, and continuously during one storm event. These streamflow samples were analyzed for Ca²⁺, Mg²⁺ Na⁺, K⁺ and SiO₂. Precipitation, throughfall and topsoil water samples were also collected after various storm events, over six months, within a small sub-catchment and were analysed for Ca²⁺, Mg²⁺, K⁺, Na⁺ and pH. Results from this research showed that rainfall was acid, with low cation content. Throughfall was neutral and cations enriched. Analysis of topsoil water indicated that litter was an important source of Ca²⁺ and K⁺ by means of saturation overland flow. In relation to throughfall, streamflow output was characterized by lower concentrations of K⁺, Ca²⁺, and Mg²⁺. Biotite gneiss weathering was the main source of Mg2+ to streamflow. During stormflow periods SiO₂ and Na⁺ concentrations decreased due to Hortonian overland flow contributions to the stream channel. The increasing concentrations of Ca²⁺ and K⁺ were due to litter leaching, especially in the zones producing saturation overland flow. Streamflow hydrogeochemistry was not only a product of weathering processes, but also of biotic processes.     

离子色谱法同时测定铀矿浸出液中的阳离子

对铬铁矿中亚铁的测定方法进行了探讨。首先对已有方法进行了验证和筛选,然后对Li2SO4助熔剂的助溶作用及其反应机理进行了研究,从而推荐了H2SO4-H3PO4-V2O5-V(Ⅳ)-Li2SO4和H2SO4-H3PO4-Ce(SO4)2-Li2SO4两种改进型的溶剂体系用于铬铁矿试样中亚铁的测定,所得结果具有良好的重现性。     

Sorption of Cs to micaceous subsurface sediments from the Hanford site, USA

The sorption of Cs⁺ was investigated over a large concentration range (10⁻⁹−10⁻² mol/L) on subsurface sediments from a United States nuclear materials site (Hanford) where high-level nuclear wastes (HLW) have been accidentally released to the vadose zone. The sediment sorbs large amounts of radiocesium, but expedited migration has been observed when HLW (a NaNO₃ brine) is the carrier. Cs⁺ sorption was measured on homoionic sediments (Na⁺, K⁺, Ca²⁺) with electrolyte concentrations ranging from 0.01 to 1.0 mol/L. In Na⁺ electrolyte, concentrations were extended to near saturation with NaNO_3(s) (7.0 mol/L). The sediment contained nonexpansible (biotite, muscovite) and expansible (vermiculite, smectite) phyllosilicates. The sorption data were interpreted according to the frayed edge-planar site conceptual model. A four-parameter, two-site (high- and low-affinity) numeric ion exchange model was effective in describing the sorption data. The high-affinity sites were ascribed to wedge zones on the micas where particle edges have partially expanded due to the removal of interlayer cations during weathering, and the low-affinity ones to planar sites on the expansible clays. The electrolyte cations competed with Cs⁺ for both high- and low-affinity sites according to the trend K⁺ >> Na⁺ ≥ Ca²⁺. At high salt concentration, Cs⁺ adsorption occurred only on high-affinity sites. Na⁺ was an effective competitor for the high-affinity sites at high salt concentrations. In select experiments, silver-thiourea (AgTU) was used as a blocking agent to further isolate and characterize the high-affinity sites, but the method was found to be problematic. Mica particles were handpicked from the sediment, contacted with Cs⁺_(aq), and analyzed by electron microprobe to identify phases and features important to Cs⁺ sorption. The microprobe study implied that biotite was the primary contributor of high-affinity sites because of its weathered periphery. The poly-phase sediment exhibited close similarity in ion selectivity to illite, which has been well studied, although its proportion of high-affinity sites relative to the cation exchange capacity (CEC) was lower than that of illite. Important insights are provided on how Na⁺ in HLW and indigenous K⁺ displaced from the sediments may act to expedite the migration of strongly sorbing Cs⁺ in subsurface environments.     

Nature of Co-bearing ferromanganese crusts of the Magellan Seamounts (Pacific Ocean): Communication 2. Ion exchange properties of ore minerals

The results of experimental studies of ion exchange properties of Co-bearing ferromanganese crusts in the Magellan Seamounts (Pacific Ocean) are discussed. Maximum reactivity in reactions with the participation of manganese minerals (Fe-vernadite, vernadite) is typical of Na⁺, K⁺, and Ca²⁺ cations, whereas minimum activity is recorded for cations Pb²⁺ and Co²⁺. The exchange complex of ore minerals in crusts is composed of Na⁺, K⁺, Ca²⁺, Mg²⁺, and Mn²⁺ cations. The exchange capacity of manganese minerals increases from the alkali metal cations to rare and heavy metal cations. Peculiarities of the affiliation of Co²⁺, Mn²⁺, and Mg²⁺ cations in manganese minerals of crusts are discussed. In manganese minerals, Co occurs as Co²⁺ and Co³⁺ cations. Metal cations in manganese minerals occur in different chemical forms: sorbed (Na⁺, K⁺, Ca²⁺, Mn²⁺, Co²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺); sorbed and chemically bound (Mg²⁺, Ni²⁺, Y³⁺, La³⁺, and Mo⁶⁺); and only chemically bound (Co³⁺). It is shown that the age of crust, its preservation time in the air-dry state, and type of host substrate do not affect the ion exchange indicators of manganese minerals. It has been established that alkali metal cations are characterized by completely reversible equivalent sorption, whereas heavy metal cations are sorbed by a complex mechanism: equivalent ion exchange for all metal cations; superequivalent, partly reversible sorption for Ba²⁺, Pb²⁺, Co²⁺, and Cu²⁺ cations, relative to exchange cations of manganese minerals. The obtained results refine the role of ion exchange processes during the hydrogenic formation of Co-bearing ferromanganese crusts.     

Hydrochemical assessment of pond and stream water near abandoned barite mine sites in parts of Oban massif and Mamfe Embayment,Southeastern Nigeria

Hydrochemical studies were carried out in parts of Oban Massif and Mamfe Embayment, Southeastern Nigeria to examine the contributions of barite mining activities on water quality. Pond and stream water samples were collected from six abandoned barite mines and adjoining streams areas during dry and wet seasons. These samples were analysed for physicochemical parameters using standard techniques. The results showed that the quality of water samples in the vicinity of barite mine sites was characterized by low pH, low mineralization, high suspended solids and deep colour. Sodium (Na⁺) and calcium (Ca²⁺) are the dominant cations and bicarbonate (HCO₃ ^?) and sulphate (SO₄ ^2?) the dominant anions. The low concentration of dissolved silica, relatively high concentrations of Na⁺, HCO₃ ^? and SO₄ ^2? suggest a combined influence of silicate, carbonate and weathering of mine spoils. The total dissolved solids, total suspended solids, electrical conductivity and major ions (except Na⁺ and K⁺) are higher for water draining barite mines from Cretaceous sediments, while Na⁺, K⁺, Ba²⁺ are higher in basement rock areas. Correlation and factor analyses suggest that the main components of the water samples are related to anthropogenic, geogenic, mineralization and environmental controls, while Gibbs diagram plots indicate weathering as the main process controlling the chemistry of water. Computed values of hardness and some irrigational parameters showed that the pond and stream water samples are generally soft and can be used for irrigation. Generally, the water quality satisfied the WHO (2008) and NIS (2007) standards for domestic, agriculture and industrial. However, there is the need to assess the impact of the pollution on the ecosystem and human health while remediation measures are being considered.     

Ion balance,acid-base regulation,and chloride cell function in the common killifish,Fundulus heteroclitus—a euryhaline estuarine teleost

The common killifish,Fundulus heteroclitus, is a euryhaline teleost common throughout estuaries of eastern North America. This symposium paper reviews the important contributions of the killifish to our present understanding of ionoregulation in seawater (SW) fish and their mechanisms of euryhalinity, and presents new data developing the killifish as a freshwater (FW) model system. Experiments on killifish have characterized (i) drinking in SW and its reduction in FW; (ii) the adaptive roles of the kidney to SW and FW conditions; (iii) the instantaneous (Phase I) and delayed (Phase II) reductions in Na⁺ outflux that occur upon transfer from SW to FW; (iv) the importance of prolactin secretion in the Phase II effect; (v) the cortisol-stimulated induction of branchial Na⁺, K⁺-ATPase that occurs upon transfer from FW to SW; (vi) the accompanying changes in morphology of the mitochondria-rich (MR) or “chloride cells” on the gills; (vii) the localization of this Na⁺, K⁺-ATPase activity to the basolateral membrane of chloride cells; and (viii) the NaCl-secretory function of these cells in SW. The opercular epithelium, which is rich in chloride cells, has been used as an in vitro model to characterize the mechanisms and control of NaCl secretion in SW fish. Much less is known about gill function in fresh water (inward NaCl transport), primarily due to the absence of a comparable freshwater model. Here we show that killifish acclimated to dilute FW ([NaCl] = 1 mmol I^?1) possess large numbers of MR cells on the opercular epithelium. When mounted in vitro with FW on the outside, the preparation develops a large inside negative transepithelial potential (TEP) that is a Na⁺ diffusion potential. By the Ussing flux ratio criterion, Na⁺ fluxes are passive, but a small active influx of Cl^? occurs, an observation that supports the involvement of MR cells in active Cl^? uptake. This FW opercular epithelium if bathed with isotonic saline on both sides does not secrete Cl^?, indicating that the MR cells indeed are of the FW type. In vivo, the fish exhibits a high rate of Na⁺ influx and outflux; Cl^? outflux is much lower, and there is no detectable Cl^? influx. Experimental variation of FW [NaCl] reveals a saturable, low affinity Na⁺ uptake mechanism, a Cl^? influx mechanism that is activated only at much higher concentrations, and no evidence of exchange diffusion. Acid-base disturbance appears to be corrected by differential regulation of the outflux components only. Hence, the FW killifish ionoregulates somewhat differently from the few other FW teleosts that have been examined, and its opercular epithelium will serve as a very useful model system.     

K-Na exchange in phlogopite on the scale of a single layer

Hydrothermal atomic force microscopy (HAFM) was used to investigate K⁺-Na⁺ ion exchange in phlogopite in-situ. The exchange of K⁺ for Na⁺ caused the interlayer distance to swell by approximately 5 Å. A distinct reaction front could be resolved between the K⁺-areas and the swollen (hydrated) Na⁺-areas, indicating a single reaction step mechanism. Although the fronts revealed kinematic variability due to inhomogeneities, the data indicate a diffusion mechanism within the interlayers. Diffusion coefficients ranged between 2 × 10⁻⁸ and 35 × 10⁻⁸ cm²/s, depending on the depth of the interlayer, the solution composition, and temperature. An activation energy of 15 kJ/mol was calculated from the temperature dependence of the diffusion coefficients. In addition to the regular 5 Å swelling, bulge-shaped irregular swelling of up to 200 nm could be observed. This irregular swelling might be an initial stage of delamination.Reducing the Na⁺-concentration in the solution at a constant K⁺-concentration was found to reduce the exchange rate. The exchange ceases completely when the equilibrium ratio r(K⁺/Na⁺) of the solution is reached. The measured r(K⁺/Na⁺) of 0.013 indicates a lower K⁺-selectivity for interlayers that are closer to the surface. This lower selectivity is most likely related to a lower strain energy associated with the expansion of interlayers close to the surface.Reversing the exchange reaction caused the interlayers to shrink to their original height. The kinematics of the front of the reverse reaction were significantly enhanced. In parts, swollen Na⁺-areas were engulfed and trapped by the shrunken K⁺-areas. No morphological indications of remnant alterations other than these trapped islands and the irregular swelling were observed.     

Geochemical assessment of groundwater around Macherla-Karempudi area,Guntur district,Andhra Pradesh

Groundwater in Palnad sub-basin is alkaline in nature and Na⁺-Cl⁻-HCO₃⁻ type around Macherla-Karempudi area in Guntur district, Andhra Pradesh. Total dissolved solids (TDS) show strong positive correlation with Cl⁻, Na⁺, Ca²⁺ and Mg²⁺, and positive correlation with SO₄²⁻, K⁺ and HCO₃⁻. Calcareous Narji Formation is the dominant aquifer lithology, and water-rock interaction controls the groundwater chemistry of the area. Chloro-alkaline indices (CAI) are positive at Miriyala, Adigopula, Mutukuru, Macherla and Durgi suggesting replacement of Na⁺ and K⁺ ions from water by Mg⁺⁺ and Ca⁺⁺ ions from country rock through base exchange reactions. Negative CAI values are recorded at Terala, Rayavaram and Nehrunagar, which indicate exchange of Na⁺ and K⁺ from the rock as cation-anion exchange reaction (chloro-alkaline disequilibrium). TDS range from 91 to 7100 ppm (Avg. 835 ppm) and exceed the prescribed limit of drinking water around Mutukuru, Durgi, Rayavaram, Khambampadu and Ammanizamalmadaka areas. Scanty rainfall and insufficient groundwater recharge are the prime factors responsible for high salinity in the area. Fluoride content ranges from <1 to 3.8 ppm and contaminated areas were identified around Macherla (1 sq km; 3.8ppm), Mandadi (1 sq km, 2.1ppm) and Adigopula (2 sq km, <1 to 3.7 ppm). The % Na⁺ content varies from 17 to 85 with the mean value of 57, and eighty (80) samples showed higher %Na⁺ in comparison to the prescribed limit of 60 for irrigation water. Sodium Adsorption Ratio (SAR) and % Na⁺ in relation to total salt concentration indicate that groundwater (51%) mostly falls under doubtful to poor quality for irrigation purpose. Groundwater of Adigopula village is fluoride contaminated and remedial measures are suggested to improve the water quality.     

城市小型河流水动力弥散和潜流交换过程

为研究城市小型河流中污染物的物理迁移过程规律,分析基流条件下流动水体与暂态存储区之间的滞留交互作用,采用溴化锂(LiBr)作为保守性示踪剂进行野外现场示踪试验,结合一维溶质运移存储模型(One-dimensional Transport with Inflow and Storage model, OTIS)定量解析潜流交换特性,估算纵向弥散系数(D)、潜流交换面积(A_s)、主河道断面面积(A)和潜流交换系数(α).模型度量指标D_aI值和均方根误差值结果表征参数模拟结果可靠性高,拟合效果理想.由泵入点O至下游1 300 m设置的A、B、C、D 4处监测点的模拟结果表明,水文参数D、A_s、A和α均随水文条件而变,OB河段(0~600 m)潜流交换能力较弱,主要以对流弥散过程为主;BD河段(600~1 300 m)具有较强的暂态存储能力,对溶质的滞留时间长;BC(600~1 000 m)和CD(1 000~1 300 m)河段交换系数分别为(3.42×10-6±0.65×10-6)s-1和(2.87×10-6±0.81×10-6 )s-1;河段BC存在2.2×10-5m3/(s·m)的侧向补给流量.4个河段对比发现,城市河流渠道化、河床沉积物贫瘠等特征导致潜流交换能力弱化.     

Influence of streambed hydraulic conductivity on solute exchange with the hyporheic zone

A conservative solute tracer experiment was conducted in Indian Creek, a small urban stream in Philadelphia, Pennsylvania to investigate the role of subsurface properties on the exchange between streamwater and the hyporheic zone (subsurface surrounding the stream). Sodium Bromide (NaBr) was used as a conservative tracer, and it was monitored in the surface water at two stations and in the upper bed sediments (shallow hyporheic zone extending from 7.5 to 10 cm below the streambed). The hydraulic conductivity (K) of the upper bed sediments and the lower bed sediments (10–12.5 cm below the streambed) was measured in situ. High tracer concentrations were observed in the upper layer at locations where the hydraulic conductivity of the upper layer was larger than that of the lower layer. Low concentrations in the upper layer were observed in the converse case. A statistically significant relationship between the mass retained in the upper layer and the difference of K values between layers was observed.     

多种矿物流体包裹体中液相阴阳离子的同时测定

地质流体研究是地球科学领域的研究热点,矿物流体包裹体中成分是认识地质流体的关键。群体包裹体液相成分分析的传统方法大多采用单通道离子色谱分析阴离子,原子吸收光谱或电感耦合等离子体原子发射光谱分析阳离子,分析方法适用矿物种类少,单矿物需要量大（3g以上）。本文使用双通道离子色谱仪,经过大量条件实验,优化了样品爆裂、提取等前处理分析条件,确认了不同矿物可检测的离子,并采用富集方法将样品需要量由常规的3.00g减少到300mg,实现了石英、方解石、萤石、闪锌矿、石榴子石、磁铁矿和黄铁矿等多种矿物流体包裹体液相成分中Li⁺、Na⁺、K⁺、Mg²⁺、Ca²⁺、F^-、Cl^-、Br^-、NO₂^-、NO₃^-、SO₄^2-等阴阳离子的同时分析。所建立的离子色谱同时分析矿物流体包裹体液相微量成分分析方法简便、快速,成本低,用样量少,扩大了矿物种类的分析范围,为成矿流体研究提供了更加直接、有效的信息。     

Modelling Zn(II) sorption onto clayey sediments using a multi-site ion-exchange model

In environmental studies, it is necessary to be able to predict the behaviour of contaminants in more or less complex physico-chemical contexts. The improvement of this prediction partly depends on establishing thermodynamic models that can describe the behaviour of these contaminants and, in particular, the sorption reactions on mineral surfaces. In this way, based on the mass action law, it is possible to use surface complexation models and ion exchange models. Therefore, the aim of this study is (i) to develop an ion-exchange model able to describe the sorption of transition metal onto pure clay minerals and (ii) to test the ability of this approach to predict the sorption of these elements onto natural materials containing clay minerals (i.e. soils/sediments) under various chemical conditions. This study is focused on the behaviour of Zn(II) in the presence of clayey sediments. Considering that clay minerals are cation exchangers containing multiple sorption sites, it is possible to interpret the sorption of Zn(II), as well as competitor cations, by ion-exchange equilibria with the clay minerals. This approach is applied with success to interpret the experimental data obtained previously in the Zn(II)–H⁺–Na⁺–montmorillonite system. The authors’ research team has already studied the behaviour of Na⁺, K⁺, Ca²⁺ and Mg²⁺ versus pH in terms of ion exchange onto pure montmorillonite, leading to the development of a thermodynamic database including the exchange site concentrations associated with montmorillonite and the selectivity coefficients of Na⁺, K⁺, Ca²⁺, Mg²⁺, and Zn²⁺ versus H⁺.     

Reversible ion-exchange fixation of cesium-137 leading to mobilization from reservoir sediments

The radioactive fission product, ¹³⁷Cs, has been observed to mobilize from bottom sediments of two South Carolina reservoirs during summer thermal stratification and hypolimnetic anoxia. Mobilization is attributed to ion-exchange displacement of ¹³⁷Cs from sediments by cations such as NH⁺₄, Fe⁺² and Mn⁺² released under anaerobic conditions.Three types of ¹³⁷Cs binding sites to sediment clay minerals are identified: 1) surface and planar sites from which ¹³⁷Cs is generally exchangeable by all cations studied (Na⁺, NH⁺₄, H⁺, Cs⁺, Ca⁺², Mg⁺², Fe⁺², and Mn⁺²); 2) wedge sites where ¹³⁷Cs exchange is sterically limited to cations of similar size and charge (NH⁺₄, Cs⁺, K⁺, and perhaps H₃O⁺); 3) interlayer sites from which ¹³⁷Cs is not readily exchanged. More than 15 years after final ¹³⁷Cs inputs, the reservoir sediments we studied showed the following percentage distribution of sites: 2 to 9% surface sites, 6 to 13% wedge sites, and 78 to 85% interlayer sites. In contrast, lake and stream sediments near Oak Ridge, Tennessee receiving ¹³⁷Cs inputs more than 20 years earlier had greater than 99% of their ¹³⁷Cs associated with non-exchangeable interlayer sites. The difference is attributed to the paucity in the South Carolina sediments of weathered micaceous clay minerals with their abundant interlayer sites. Such interlayer deficient clays are dominant in the Atlantic and Gulf coastal plains of the United States and elsewhere. This suggests that ¹³⁷Cs will be physically and chemically more mobile in such areas as well as more biologically available. Mobility will be enhanced in regimes where cation inputs favoring ¹³⁷Cs exchange occur. Subsurface waste disposal sites where anaerobic conditions develop with NH⁺₄ production and Fe⁺² and Mn⁺² release might be such a regime.     

Correlative and comparative characterization of main ion concentrations in laterite groundwater in semi-arid northern Burkina Faso

About 24 samples from hand-dug wells and boreholes were used to characterize concentrations of the main inorganic ions in a laterite environment under semi-arid climatic conditions in Tikaré, northern Burkina Faso. It was found that the most represented groundwater anion in groundwater was HCO₃ ⁻ with average levels of 49.1 mg/L in the dry season and 33.5 mg/L in the rainy season. The most represented cation was Ca²⁺ with mean concentrations of 13.7 and 9.5 mg/L, respectively. The main processes, which influence the concentrations of these ions, are evaporation (dry season), local enrichment of recharge water in some elements, ion exchange and fixation by clay minerals (in case of K⁺). The best correlations were found between Ca²⁺ and Mg²⁺ (r = 0.95), Cl⁻ and Na⁺ (r = 0.95), HCO₃ ⁻ and Mg²⁺ (r = 0.89), HCO₃ ⁻ and Ca²⁺ (r = 0.89), and between HCO₃ ⁻ and Na⁺ (r = 0.80). In general, the quality of the groundwater from the different wells sampled for this study was good enough to serve as drinking water. However, there were situations where the quality of water was polluted because of anthropogenic contaminants (mainly NO₃ ⁻, K⁺, Cl⁻) from septic tanks and manure pits located in the vicinity of some sampled wells. In addition, application of fertilizers also represents a potential anthropogenic contamination source with regard to SO₄ ²⁻, Ca²⁺, K⁺, Na⁺, and Mg²⁺. Considering the high concentrations of SO₄ ²⁻, Mg²⁺, Na⁺ and Ca²⁺ found in one borehole, the deeper, fractured aquifers were also likely to be enriched in these elements. In contrast, the shallow aquifers are likely to be contaminated with Cl⁻, NO₃ ⁻ and K⁺. Cl⁻ and K⁺ seem to be locally present in recharge water as shown by their relative higher mean concentrations in the rainy season samples.