Modelling the sorption of Zn and Ni on Ca-montmorillonite

In some previous work titration and Ni/Zn sorption edge/isotherm measurements carried out under a wide variety of experimental conditions on purified Na-montmorillonite were modelled in terms of cation exchange and surface complexation mass action equations. A major objective of the experimental/modelling programme is to understand and predict sorption in commercial bentonite systems. Since montmorillonite is the dominant clay mineral in bentonite and is often present in a mixed Na/Ca form, a natural extension to the previous investigations was to study Ni/Zn sorption on a conditioned Ca-montmorillonite. An important open question was whether the same basic parameters such as site types, site capacities, and acidity constants could be used for both materials and to see to what extent the Ni and Zn surface complexation constants were influenced by the form of the montmorillonite. Sorption edges for Ni and Zn at different Ca(NO₃)₂ background electrolyte concentrations, together with sorption isotherms measured over a range of pH values, are presented and modelled using the MINSORB code. The parameters characterising the sorption of Ni and Zn on Na- and Ca-montmorillonite systems are compared. Finally, examples are given that illustrate how the modelling can provide insight into the sorption processes.     

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X⁻ and Y⁻), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions.Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.     

Experimental measurements and modeling of sorption competition on montmorillonite

The source terms arising from radioactive/toxic metal waste repositories will contain a multitude of dissolved metal species, as do natural systems. The influence of sorption competition on the uptake of safety-relevant metals, and the effects this may have on transport rates to the biosphere, is an important repository performance assessment issue which has not, as yet, been resolved. The main aim of this work was to quantify the influence of competition between metals in different valence states on their individual sorption characteristics under conditions dominated by pH-dependent sorption. The sorption experiments were carried out on Na- and Ca-montmorillonites using various combinations and concentrations of Co(II), Ni(II), Zn(II), Eu(III), Nd(III), Am(III), Th(IV), and U(VI). For metals sorbing at trace concentrations in a background electrolyte containing a competing metal up to mmolar concentrations, and pH values generally greater than 6, all of the experimental results were consistent with the observation that metals with similar chemistries (valence state, hydrolysis behavior) compete with one another, but metals with dissimilar chemistries do not compete, i.e., competition is selective. For example Eu, Nd, and Am exhibit unambiguous sorption competition effects, as do Ni, Co, and Zn. On the basis of the above preliminary criteria, competition between divalent transition metals and trivalent lanthanides, Th(IV), and U(VI) and between Th (IV) and U(VI) would not be expected, and this is found experimentally. In general, neither single-fixed-site capacity models nor two-site (strong/weak) models with fixed capacities, whether with or without electrostatic terms, are capable of modeling the spectrum of experimental results presented here. To explain the competitive effects observed it is proposed that multiple sets of strong sites exist as subsets of the 40 mmol kg⁻¹ of weak sites present in the montmorillonite conceptual model. It is shown that if the 2SPNE SC/CE sorption model is extended to include multiple strong sites, and the average site capacity and protolysis constant values defined in previous publications are assigned to each of the sets of strong sites, then the model can be used to reproduce all of the experimental data, provided it can be specified which groups of metals are competitive and which are not.     

Lead sorption efficiencies of natural and synthetic Mn and Fe-oxides

Lead sorption efficiencies (sorption per specific surface area) were measured for a number of natural and synthetic Mn and Fe-oxides using a flow-through reactor. The Mn-oxide phases examined included synthetic birnessite, natural and synthetic cryptomelane, and natural and synthetic pyrolusite; the Fe-oxides studied were synthetic akaganéite, synthetic ferrihydrite, natural and synthetic goethite, and natural and synthetic hematite. The sorption flow study experiments were conducted with 10 ppm Pb with an ionic strength of either 0.01 M NaNO₃ or 0.01 M KNO₃, both at pH 5.5. The experimental effluent solution was analyzed using aqueous spectroscopic methods and the reacted solids were analyzed using microscopy (field emission scanning electron microscopy, FE-SEM), structure analysis (powder X-ray diffraction, XRD), bulk chemical spectroscopy (energy dispersive spectroscopy, EDS), and surface sensitive spectroscopy (X-ray photoelectron spectroscopy, XPS). Overall and under these conditions, the synthetic Mn-oxides have higher sorption efficiencies than the natural Mn-oxides, which in turn are higher than the natural and synthetic Fe-oxides. Only natural pyrolusite had a sorption efficiency as low as the Fe-oxides. Most of the natural and synthetic Fe-oxides examined in this study removed about the same amount of Pb from solution once normalized to BET N₂ surface area, although synthetic akaganéite and hematite were significantly less reactive than the rest.It is suggested that the observed efficiency of Mn-oxides for Pb sorption is directly related to internal reactive sites in the structures that contain them (birnessite and cryptomelane, in the case of this study). Comparisons of solution data to XPS data indicated that Pb went into the interlayer of the birnessite, which was supported by XRD; similarly some Pb may go into the tunnels of the cryptomelane structure. Layer structures such as birnessite have the highest Pb sorption efficiency, while the 2 × 2 tunnel structure of cryptomelane has lower efficiencies than birnessite, but higher efficiencies than other Mn- or Fe-oxide structures without internal reactive sites.     

Cs and Cl NMR spectroscopy and molecular dynamics modeling of Cs and Cl complexation with natural organic matter

Interaction of dissolved aqueous species with natural organic matter (NOM) is thought to be important in sequestering some species and enhancing the transport of others, but little is known about these interactions on a molecular scale. This paper describes a combined experimental ¹³³Cs and ³⁵Cl nuclear magnetic resonance (NMR) and computational molecular dynamics (MD) modeling study of the interaction of Cs⁺ and Cl⁻ with Suwannee River NOM. The results provide a detailed picture of the molecular-scale structure and dynamics of these interactions. Individual NOM molecules are typically hundreds to thousands of Daltons in weight, and on the molecular scale their interaction with small dissolved species can be investigated in ways similar to those used to study the interaction of dissolved aqueous species with mineral surfaces. As for such surface interactions, understanding both the structural environments and the dynamics over a wide range of frequencies is essential. The NMR results show that Cs⁺ is associated with NOM at pH values from 3.4 ± 0.5 (unbuffered Suwannee River NOM solution) to 9.0 ± 0.5. The extent of interaction increases with decreasing CsCl concentration at constant pH. It also decreases with increasing pH at constant CsCl concentration due to pH-dependent negative structural charge development on the NOM caused by progressive deprotonation of carboxylic and phenolic groups. The presence of NOM has little effect on the ¹³³Cs chemical shifts, demonstrating that its local coordination environment does not change significantly due to interaction with the NOM. Narrow, solution-like line widths indicate rapid exchange of Cs⁺ between the NOM and bulk solution at frequencies of >10² Hz. The MD simulations support these results and show that Cs⁺ is associated with the NOM principally as outer sphere complexes and that this interaction does not reduce the Cs⁺ diffusion coefficient sufficiently to cause NMR line broadening. The ³⁵Cl NMR data and the MD results are consistent in demonstrating that there is no significant complexation between Cl⁻ and NOM in the pH range investigated, consistent with negative structural charge on the NOM.     

考虑各向异性的软黏土扰动状态本构模型

以大量试验结果为依据,运用物理意义明确、获取简便快捷、经济实用的土电阻率结构指标进行软黏土扰动变量的表征和测定。以三轴试验与电阻率测试结果为基础,进行了扰动函数的构建。在软黏土扰动状态描述中,引入旋转硬化因子,用以考虑应力诱发各向异性,进而构建了考虑各向异性的软黏土扰动状态概念本构模型。模型从一定程度上克服了传统扰动变量获取方法的弊端,克服了传统借用数学演绎手段建立扰动函数的不足,提高了模型应用的适用性。在模型构建中,融入初始应力各向异性的影响,从而使模型能更好地反映软土实际工程情况。三轴排水剪切试验验证结果表明,该模型可较好反映软黏土受荷下的结构变化情况和受力特性。     

Modeling of Cs+ diffusion and retention in the DI-A2 experiment (Mont Terri). Uncertainties in sorption and diffusion parameters

In the DI-A2 experiment several non-reactive and reactive tracers were injected as a pulse in a packed-off borehole in the Opalinus Clay. Unlike the previous DI-A1 test, the design of the Teflon filter in the injection borehole forced the water to flow through the filter and the open space between the filter and the borehole wall (the filter itself did not act as a diffusion barrier between the circulating solution and the rock). The decrease in tracer concentration in the liquid phase was monitored during a period of a year. Afterwards, the borehole section was overcored and the tracer profiles in the rock were analyzed. A main interest of this experiment was to understand the chemical behavior of sorbing tracers: Cs⁺ (stable), ⁸⁵Sr²⁺, ⁶⁰Co²⁺ and Eu³⁺ (stable). The complete dataset (except for Eu³⁺ because of strong sorption to experimental equipment) was analyzed in a previous study with a 2D diffusion–reaction model and the derived diffusion and sorption parameters were compared with laboratory data. As in DI-A1, a difference by a factor of about 2 for sorption (magnitude of the Freundlich isotherm) was obtained between in situ and laboratory batch sorption experiments.Recent experimental and modeling studies have shown equivalent Cs⁺ sorption on intact and disaggregated Opalinus Clay samples. In view of these developments, new modeling of Cs⁺ diffusion and retention in the DI-A2 experiment has been performed using CrunchFlow. The calculations include transport by diffusion and a multisite cation exchange model to account for the retention of Cs⁺. The new results show that upscaling of Cs⁺ sorption from laboratory to field is no longer required. However, a difference in sorption by a factor of about 2 is still explained by the use of different versions of the same cation exchange model (a small difference in the selectivity coefficient for one type of site). This uncertainty in sorption leads to an uncertainty in the effective diffusion coefficient (D_e) for Cs⁺, also by a factor of 2 (2–4 × 10⁻¹⁰ m²/s). Clearly, the values of D_e obtained are correlated with the strength of sorption in the model, with stronger sorption leading to larger D_e values. Discrimination between the two versions of the exchange model is not possible when using only the results of the in situ test. Additionally, during early times (t < 10 days) the drop in Cs⁺ concentration in the circulation system is slower than expected. Due to the experimental setup, this slow decrease in concentration cannot be caused by the filter in the contact between borehole and rock. Poor mixing in the circulation system could explain this effect.     

Experimental sorption of Ni, Cs and Ln onto a montmorillonite up to 150°C

The effect of temperature on the sorption of cations onto a dioctahedral smectite was investigated by running batch experiments at 25, 40, 80 and 150°C. We measured the distribution coefficient (Kd) of Cs⁺, Ni²⁺ and 14 lanthanides (Ln³⁺) between solutions and the montmorillonite fraction of the MX80 bentonite at various pH and ionic strengths. Up to 80°C we used a conventional experimental protocol derived from Coppin et al. (2002). At 150°C, the experiments were conducted in a PTFE reactor equipped with an internal filter allowing the sampling of clear aliquots of solution.The results show a weak but measurable influence of the temperature on the elements sorption. Kd’s for Ni²⁺ and Ln³⁺ increase by a factor 2 to 5 whereas temperature raises from 25 to 150°C. This effect seems higher at high ionic strength. The estimated apparent endothermic sorption enthalpies are 33 ± 10 kJ.mol⁻¹ and 39 ± 15 kJ.mol⁻¹ for Ni²⁺ and Eu³⁺, respectively. On the other hand, the temperature effect on Cs⁺ sorption is only evidenced at low ionic strength and under neutral conditions where the Kd decreases by a factor 3 between 25 and 150°C. Apparent exothermic sorption enthalpy for Cs⁺ on the montmorillonite is −19 ± 5 kJ.mol⁻¹.Experiments conducted at the four temperatures with the coexistence of all of the cations in the reacting solution (100 ppb of each element in the starting solution) or only one of them, produced similar values of Kd. This suggests the absence of competition between the sorbed cations, and consequently a low degree of saturation of the available sites. A fractionation of the lanthanides spectrum is also observed at high pH and high ionic strength whatever the temperature.The conclusion of this study is that the temperature dependence on sorption reflects, as the fractionation of REE or the pH and ionic strength effects, the chemical process which controls the overall reaction. In the case of an exchange dominated reaction (low pH and low ionic strength), the temperature effect is negligible. In the case of surface complexation (high pH and high ionic strength), the observed increase of Kd with temperature reflects either an increase of the sorption equilibrium constant with temperature or an endothermic property for reactions describing the montmorillonite surface chemistry.     

Impact of highly basic solutions on sorption of Cs to subsurface sediments from the Hanford site, USA

The effect of caustic NaNO₃ solutions on the sorption of ¹³⁷Cs to a Hanford site micaceous subsurface sediment was investigated as a function of base exposure time (up to 168 d), temperature (10°C or 50°C), and NaOH concentration (0.1 mol/L to 3 mol/L). At 10°C and 0.1 M NaOH, the slow evolution of [Al]_aq was in stark contrast to the rapid increase and subsequent loss of [Al]_aq observed at 50°C (regardless of base concentration). Exposure to 0.1 M NaOH at 10°C for up to 168 d exhibited little if any measurable effect on sediment mineralogy, Cs⁺ sorption, or Cs⁺ selectivity; sorption was well described with a two-site ion exchange model modified to include enthalpy effects. At 50°C, dissolution of phyllosilicate minerals increased with [OH]. A zeolite (tetranatrolite; Na₂Al₂Si₃O₁₀·2H₂O) precipitated in 0.1 M NaOH after about 7 days, while an unnamed mineral phase (Na₁₄Al₁₂Si₁₃O₅₁·6H₂O) precipitated after 4 and 2 days of exposure to 1 M and 3 M NaOH solutions, respectively. Short-term (16 h) Cs⁺ sorption isotherms (10⁻⁹-10⁻² mol/L) were measured on sediment after exposure to 0.1 M NaOH for 56, 112, and 168 days at 50°C. There was a trend toward slightly lower conditional equilibrium exchange constants (Δlog _Na^CsK_c ∼ 0.25) over the entire range of surface coverage, and a slight loss of high affinity sites (15%) after 168 days of pretreatment with 0.1 M base solution. Cs⁺ sorption to sediment over longer times was also measured at 50°C in the presence of NaOH (0.1 M, 1 M, and 3 M NaOH) at Cs⁺ concentrations selected to probe a range of adsorption densities. Model simulations of Cs⁺ sorption to the sediment in the presence of 0.1 M NaOH for 112 days slightly under-predicted sorption at the lower Cs⁺ adsorption densities. At the higher adsorption densities, model simulations under-predicted sorption by 57%. This under-prediction was surmised to be the result of tetranatrolite precipitation, and subsequent slow Na → Cs exchange. At higher OH concentrations, Cs⁺ sorption in the presence of base for 112 days was unexpectedly equal to, or greater than that expected for pristine sediment. The precipitation of secondary phases, coupled with the fairly unique mica distribution and quantity across all size-fractions in the Hanford sediment, appears to mitigate the impact of base dissolution on Cs⁺ sorption.     

On the effects of petrographic composition on coalbed methane sorption

The effect of petrographic composition on the methane sorption capacity has been determined for a suite of coals and organic-rich shales. Subbituminous and bituminous coals were separated into bright and dull lithotypes by hand-picking. The methane sorption capacities range between 0.5 and 23.9 cm³/g at a pressure of 6 MPa. The low volatile bituminous Canmore coal and the anthracite sample have the highest capacities with the “natural coke” having the lowest. For low-rank coals there is no significant difference between bright and dull samples except for one coal with the dull sample having a greater sorption capacity than its bright equivalent. For higher-rank coals, the bright samples have a greater methane capacity than the dull samples and the difference between sample pairs increases with rank. The boghead coal samples have the highest sorption capacities in the liptinite-rich coals suite and are higher than subbituminous to medium volatile bituminous samples. Pore size distribution indicates that methane is held as solution gas in liptinite-rich coals and by physical sorption in micropores in liptinite-poor coals. These contrasting processes illustrate that liptinite-rich samples need to be independently assessed. The positive relationship between reactive inertinite content and methane sorption capacity occurs within the subbituminous to medium volatile bituminous coals because the reactive inertinite is structurally similar to vitrinite and have a higher microporosity than non-reactive inertinite. Reactivity of inertinite should be assessed in CBM studies of dull coals to provide a better understanding of petrographic composition effects on methane capacity.     

Ba isotopic signature for early differentiation between Cs and Ba in natural fission reactors

Ba isotopic studies of the Oklo and Bangombé natural fission reactors in east Gabon provide information on the geochemical behavior of radioactive Cs (¹³⁵Cs and ¹³⁷Cs) in a geological medium. Large isotopic deviations derived from fissiogenic Ba were found in chemical leachates of the reactor uraninites. The fissiogenic Ba isotopic patterns calculated by subtracting the non-fissiogenic component are classified into three types that show different magnifications of chemical fractionation between Cs and Ba. In addition, the isotopic signatures of fissiogenic ¹³⁵Ba, ¹³⁷Ba and ¹³⁸Ba suggest an early differentiation between Cs and Ba of less than 20 years after the production of fissiogenic Cs and Ba. On the other hand, only small excesses of ¹³⁵Ba (ε < +1.8) and/or ¹³⁷Ba (ε < +1.3) were identified in some clay samples, which might have resulted from selective adsorption of ¹³⁵Cs and ¹³⁷Cs that migrated from the reactors by differentiation.     

Europium sorption to sediments in the presence of natural organic matter: A laboratory and modeling study

Cellulosic materials, such as wood, paper products and cardboard that have been co-disposed with low-level nuclear waste have been shown to produce leachate with natural organic matter (NOM) concentrations of hundreds of mg/L C and, as such, have the potential to influence the fate and transport of radionuclides in the subsurface environment. The objective of this study was to examine the influence of NOM on the sorption of Eu (an analogue for trivalent radionuclides) to two coastal plain sediments from the US Department of Energy’s Savannah River Site. Particular attention was directed at quantifying Eu interactions with NOM sorbed to sediments (NOM_sed) in laboratory experiments and developing conditional stability constants for that interaction using the thermodynamic equilibrium speciation model MINTEQA2. Europium sorption to the two sediments systematically increased as pH increased from 3.9 to 6.7. With increasing additions of NOM to the aqueous phase from 0 to 222 mg/L C, Eu sorption initially increased to a maximum at 10 mg/L C NOM_aq and then decreased with increasing NOM_aq concentrations. Increases in Eu sorption at low NOM additions was attributed to the sorption of NOM to the sediment surface increasing the number of sorption sites on the low cation-exchange capacity sediments and/or increasing the association constant (log K) for the Eu-sediment surface reaction. Decreases in Eu sorption at higher NOM levels was attributed to Eu_aq complexation to NOM_aq being more favored than Eu sorption to the solid phase. A component additivity model was developed to describe the Eu–NOM-sediment system by the additive effects of the three binary system models: Eu–NOM, Eu-sediment and NOM-sediment. The model generally captured the data trends in the ternary system. Conditional stability constants developed from the experimental data for the complexation of Eu to NOM_sed were as much as four orders of magnitude greater than Eu complexation with NOM_aq, presumably due to the NOM_sed deriving additional negative (attractive) charge from the sediment surface. At high initial NOM_aq levels, >99 mg/L C, the model captured the trend of reduced Eu sorption but tended to over-estimate Eu sorption. The additivity approach of combining binary models to form a ternary model was only successful when the unique complexation properties of the NOM_sed were properly calculated.     

Trend and mechanisms of transformation of natural sorption barriers in acid soils under phosphate loading

The current status of studies on chemisorption of phosphate anions on soil aluminum(iron)-bearing sorbents has been analyzed. The theoretical possibility of the formation of soluble phosphorus compounds during chemisorption was supported by experiments. It was shown that a decrease in efficiency of aluminum (iron)-bearing mineral and humus-mineral sorbents is related to the peculiar transformation of their phosphatized surfaces with formation of soluble metallophosphate anionic complexes. Mechanisms of the decrease in the efficiency of soil sorbents and their destruction are considered.     

Formation and sorption behavior of the palladium thiosulfate complexes under natural conditions (model experiments)

The formation of significant amounts of thiosulfate ion (up to 42 mg/L) was established in experiments on the interaction of sulfide-bearing rocks with water. The possibility of the formation of palladium compounds with thiosulfate ion [Pd(S₂O₃)₂]^2– was demonstrated. The stability constant of the complex is 3.7 × 10⁹, which may provide intense migration of this palladium species in ecosystem. The study of the behavior of palladium thiosulfates during interaction with inorganic and organic components of geochemical barriers showed that around 50–55% of thiosulfate-bound palladium is extracted by humic acid in the pH range typical of natural waters. Under these conditions, ferrihydrite sorbes palladium quantitatively, and may serve as efficient barrier to the interaction of palladium compounds with particulate matters of waters and bottom sediments.     

Diffusion and sorption of Cs, I and HTO in samples of the argillaceous Wakkanai Formation from the Horonobe URL, Japan: Clay-based modeling approach

Diffusion and sorption behaviors of cationic Cs⁺, anionic I⁻ and neutral HTO in samples of the Wakkanai Formation from the Horonobe underground research laboratory (URL), Japan, were investigated as a function of ionic strength (I) of synthetic groundwater by through-diffusion and batch sorption experiments and mechanistic modeling. The effective diffusivities (D_e) measured by through-diffusion experiments showed cation excess and anion exclusion effects, which were strongly dependent on I; D_e for Cs⁺ decreased as I increased, D_e for I⁻ showed the opposite dependency and D_e for HTO showed no dependence. The sorption of Cs⁺ measured by through-diffusion and batch sorption experiments were described by Freundlich isotherms with consistent parameters and decreased with I as a result of competitive ion exchange.Diffusion and sorption behaviors were interpreted by assuming the clay components of illite and smectite control diffusion and sorption mechanisms. The component additive (CA) sorption model, which includes illite and smectite contents and their ion exchange constants, provided a reasonable account of the Cs⁺ sorption trends measured as functions of I and Cs concentration. The diffusion model was developed by coupling the electrical double layer (EDL) model, describing the change of ionic concentrations (cation excess and anion deficit) and viscoelectric effects caused by electrostatic interaction at negatively charged clay surfaces, and a simplified pore model assuming one type of pore shape and includes their size distribution. When averaging the electrostatic effects by using the pore surface area distribution, the model could predict the cation excess and anion exclusion effects, and its dependence on I reasonably well. This result implies the nanoscale pores dominating the pore surface area can strongly impact on ionic diffusion in argillaceous rocks. The clay-based modeling approach described here provides a useful tool to predict ionic diffusion and sorption in argillaceous rocks.     

Modelling natural attenuation of heavy-metal groundwater contamination in the Selebi-Phikwe mining area,Botswana

Seepage from a tailings dam is the major source of groundwater pollution in the Selebi-Phikwe area, where mining of sulphidic nickel–copper–cobalt ore started in 1973 and will continue until 2014. The seepage water has a pH in the range of 1.7–2.8 and is strongly enriched in SO₄ ²⁻ (5,680 g/L) and heavy metals (6,230 μg/L Ni, 1,860 μg/L Cu and 410 μg/L Co). The fracture aquifer affected by pollution from the dam exhibits a remarkable capacity of heavy-metal sorption. Most of the Ni, Cu and Co is scavenged at less than 500 m distance downgradient from the polluting source, whereas SO₄ ²⁻ is not immobilized significantly. The heavy-metal sorption process is assumed to be due to surface complexation, which is supported by a relatively high groundwater pH (in the range of 6.2–7.8 at >200 m distance from the tailings dam). The objective of this study is to demonstrate that the sorption process can be incorporated into a realistic three-dimensional reactive-transport groundwater model that is implicitly charge-balanced. The simulations are performed with the PHAST1.2 program, which is based on the HST3D flow and transport code and the hydrochemical PHREEQC2.12 code.     

The influence of Fe(II) competition on the sorption and migration of Ni(II) in MX-80 bentonite

The results from batch sorption experiments on montmorillonite systems have demonstrated that bivalent transition metals compete with one another for sorption sites. For safety analysis studies of high level radioactive waste repositories with compacted bentonite near fields, the importance of competitive sorption on the migration of radionuclides needs to be evaluated. Under reducing conditions, the bentonite porewater chosen has a Fe(II) concentration of ∼5.3 × 10⁻⁵ M through saturation with siderite. The purpose of this paper is to assess the influence of such high Fe(II) concentrations on the transport of Ni(II) through compacted bentonite, Ni(II) was chosen as an example of a bivalent transition metal. The one-dimensional calculations were carried out at different Ni(II) equilibrium concentrations at the boundary (Ni(II)_EQBM) with the reactive transport code MCOTAC incorporating the two site protolysis non electrostatic surface complexation/cation exchange sorption model, MCOTAC-sorb. At a Ni(II)_EQBM level of 10⁻⁷ M without Fe(II) competition, the reactive transport calculations using a constant K_d approach and the MCOTAC-sorb calculation yielded the same breakthrough curves. At higher Ni(II)_EQBM (10⁻⁵ M), the model calculations with MCOTAC-sorb indicated a breakthrough which was shifted to later times by a factor of ∼5 compared with the use of the constant K_d approach.When sorption competition was included in the calculations, the magnitude of the influence depended on the sorption characteristics of the two competing sorbates and their respective concentrations. At background Fe(II) concentrations of 5.3 × 10⁻⁵ M, and a Ni(II)_EQBM level of 10⁻⁷ M, the Ni(II) breakthrough time was ∼15 times earlier than in the absence of competition. At such Fe(II) concentrations the Ni(II) breakthrough curves at all source concentrations less than 3.5 × 10⁻⁵ M (fixed by the NiCO_3,S solubility limit) are the same i.e. Ni(II) exhibits linear (low) sorption.Competitive sorption effects can have significant influences on the transport of radionuclides through compacted bentonite i.e. reduce the migration rates. Since, for the case considered here, the Fe(II) concentration in the near field of a high-level radioactive waste repository may change in time and space, the transport of bivalent transition metal radionuclides can only be properly modelled using a multi-species reactive transport code which includes a sorption model.     

Modelling the economic vulnerability of households in the Phang-Nga Province (Thailand) to natural disasters

The 2004 tsunami devastated large areas in the southern part of Thailand. This paper takes a particular look at the circumstances of vulnerability and the process of recovery in the area of Khao Lak and its surrounding villages, which constitute a booming tourist hotspot at the centre of a region that is still dominated by agriculture. A quantitative vulnerability model was developed, integrating a quantitative household survey and remote sensing data. This model describes and specifies the circumstances of vulnerability and the factors leading to a recovery of the area. Indirect effects on the livelihood of households in particular, such as the disruption of infrastructure or the loss of income, show a negative effect on the recovery time. External help received by the households even shows an extending influence on the duration of their recovery period.