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1.
Sorption processes on mineral surfaces are a critical factor in controlling the distribution and accumulation of potentially harmful metals in the environment. This work investigates the effectiveness of gypsum (CaSO4⋅2H2O) to sequester Pb. The interaction of gypsum fragments with Pb-bearing solutions (10, 100 and 1000 mg/L) was monitored by performing macroscopic batch-type experiments conducted at room temperature. The aqueous phase composition was periodically determined by Atomic Absorption Spectrometry (AAS), Ion Chromatography (IC) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP–OES). Regardless of the [Pbaq]initial, a [Pbaq]final < 4 mg/L was always reached. The uptake process was fast (t < 1 h) for [Pbaq]initial ? 100 mg/L and significantly slower (t > 1 week) for [Pbaq]initial = 10 mg/L. Speciation calculations revealed that after a long time of interaction (1 month), all the solutions reached equilibrium with respect to both gypsum and anglesite. For [Pbaq]initial ? 100 mg/L, sorption takes place mainly via the rapid dissolution of gypsum and the simultaneous formation of anglesite both on the gypsum surface and in the bulk solution. In the case of [Pbaq]initial = 10 mg/L, no anglesite precipitation was observed, but surface spectroscopy (proton Rutherford Backscattering Spectroscopy, p-RBS) confirmed the formation of Pb-bearing surface layers on the (0 1 0) gypsum surface in this case also. This study shows that the surface of gypsum can play an important role in the attenuation of Pb in contaminated waters.  相似文献   

2.
79Se is a potentially mobile long-lived fission product, which may make a dominant contribution to the long-term radiation exposure resulting from deep geological disposal of radioactive waste. Its mobility is affected by sorption on minerals. Selenium sorption processes have been studied mainly by considering interaction with a single mineral surface. In the case of multi-component systems (e.g. soils), it is difficult to predict the radioelement behaviour only from the mineral constituents. This study contributes to the understanding of multi-component controls of Se concentrations towards predicting Se behaviour in soils after migration from a disposal site. This goal was approached by measuring selenite sorption on mono and multi-phase systems physically separated by dialysis membranes. To the best of the authors’ knowledge, very few studies have used dialysis membranes to study the sorption competition of selenite between several mineral phases. Other workers have used this method to study the sorption of pesticides on montmorillonite in the presence of dissolved organic matter. Indeed, this method allows measurement of individual Kd in a system composed of several mineral phases. Dialysis membranes allowed (i) determination of the competition of two mineral phases for selenite sorption (ii) and determination of the role of humic acids (HAs) on selenite sorption in oxidising conditions. Experimental results at pH 7.0 show an average Se(IV) sorption distribution coefficient (Kd) of approximately 125 and 9410 L kg−1 for bentonite and goethite, respectively. The average Kd for goethite decreases to 613 L kg−1 or 3215 L kg−1 in the presence of bentonite or HA, respectively. For bentonite, the average Kd decreases slightly in the presence of goethite (60 L kg−1) and remains unchanged in the presence of HA. The experimental data were successfully modelled with a surface complexation model using the PHREEQC geochemical code. The drastic decrease in Se(IV) sorption on goethite in a multi-phase system is attributed to competition with dissolved silica released by bentonite. As with Si the HA compete with Se for sorption sites on goethite.  相似文献   

3.
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 Kd 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 Kd 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 NiCO3,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.  相似文献   

4.
Zinc uptake in suspensions (?3.7 g L−1) of MX80 montmorillonite was investigated at pH 4.0 and 7.3, a total Zn concentration ([Zn]total) of 500 μM, and dissolved Si concentrations ([Si]aq) of ∼70 and ∼500 μM in 0.5 M NaCl, by kinetics experiments and polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Differential thermogravimetric analysis verified the cis-vacant character of the montmorillonite. No Zn uptake occurred at pH 4.0, confirming that cation exchange was hampered by the high ionic strength of the suspension. At pH 7.3 and low [Si]aq (∼70 μM), Zn uptake occurred rapidly during the first hour of reaction, and then leveled off to 50 μmol/g montmorillonite at 168 h. The uptake rate is consistent with Zn sorption on pH-dependent edge sites. At pH 7.3 and high [Si]aq (∼500 μM), the initial sorption rate was similar, but Zn sorption continued, reaching 130 μmol/g at 168 h, and was paralleled by Si uptake with a Si/Zn uptake ratio of 1.51(10), suggesting formation of a Zn (hydrous) silicate. P-EXAFS data indicated that the first oxygen coordination shell of sorbed Zn is split into two subshells at 1.97(2) and 2.08(3)-2.12(2) Å for all EXAFS samples. These two distances are assigned to a mixture of tetrahedral (IVZn) and octahedral (VIZn) Zn complexes. The proportion of IVZn was lower in the high [Si]aq samples and decreased with reaction time. Al low [Si]aq and 216 h of reaction, nearest cationic shells of 0.6(4) Al in the film plane and 0.5(4) Si out of the film plane were detected at 3.00(2) and 3.21(2) Å, respectively, and were interpreted as the formation of IVZn and VIZn mononuclear complexes at the edges of montmorillonite platelets, in structural continuity to the (Al, Mg) octahedral sheets. At high [Si]aq, in-plane Zn and Al and out-of-plane Si neighbors were detected at 4 h, indicating the formation of Zn phyllosilicate nuclei at the layer edges. At 313 h, Zn-Al pairs were no longer detected, and Zn atoms were surrounded on average by 3.4(5) in-plane Zn at 3.10(1) Å and 1.7(9) out-of-plane Si at 3.30(2) Å, supporting the precipitation of a Zn phyllosilicate. Thus, dioctahedral Al phyllosilicate may act as a nucleating surface for the heterogeneous formation of trioctahedral Zn phyllosilicate at [Si]aq relevant to natural systems.  相似文献   

5.
Strontium-90 is a beta emitting radionuclide produced during nuclear fission, and is a problem contaminant at many nuclear facilities. Transport of 90Sr in groundwaters is primarily controlled by sorption reactions with aquifer sediments. The extent of sorption is controlled by the geochemistry of the groundwater and sediment mineralogy. Here, batch sorption experiments were used to examine the sorption behaviour of 90Sr in sediment–water systems representative of the UK Sellafield nuclear site based on groundwater and contaminant fluid compositions. In experiments with low ionic strength groundwaters (<0.01 mol L−1), pH variation is the main control on sorption. The sorption edge for 90Sr was observed between pH 4 and 6 with maximum sorption occurring (Kd ∼ 103 L kg−1) at pH 6–8. At ionic strengths above 10 mmol L−1, and at pH values between 6 and 8, cation exchange processes reduced 90Sr uptake to the sediment. This exchange process explains the lower 90Sr sorption (Kd ∼ 40 L kg−1) in the presence of artificial Magnox tank liquor (IS = 29 mmol L−1). Strontium K-edge EXAFS spectra collected from sediments incubated with Sr2+ in either HCO3-buffered groundwater or artificial Magnox tank liquor, revealed a coordination environment of ∼9 O atoms at 2.58–2.61 Å after 10 days. This is equivalent to the Sr2+ hydration sphere for the aqueous ion and indicates that Sr occurs primarily in outer sphere sorption complexes. No change was observed in the Sr sorption environment with EXAFS analysis after 365 days incubation. Sequential extractions performed on sediments after 365 days also found that ∼80% of solid associated 90Sr was exchangeable with 1 M MgCl2 in all experiments. These results suggest that over long periods, 90Sr in contaminated sediments will remain primarily in weakly bound surface complexes. Therefore, if groundwater ionic strength increases (e.g. by saline intrusion related to sea level rise or by design during site remediation) then substantial remobilisation of 90Sr is to be expected.  相似文献   

6.
The application of stable Fe isotopes as a tracer of the biogeochemical Fe cycle necessitates a mechanistic knowledge of natural fractionation processes. We studied the equilibrium Fe isotope fractionation upon sorption of Fe(II) to aluminum oxide (γ-Al2O3), goethite (α-FeOOH), quartz (α-SiO2), and goethite-loaded quartz in batch experiments, and performed continuous-flow column experiments to study the extent of equilibrium and kinetic Fe isotope fractionation during reactive transport of Fe(II) through pure and goethite-loaded quartz sand. In addition, batch and column experiments were used to quantify the coupled electron transfer-atom exchange between dissolved Fe(II) (Fe(II)aq) and structural Fe(III) of goethite. All experiments were conducted under strictly anoxic conditions at pH 7.2 in 20 mM MOPS (3-(N-morpholino)-propanesulfonic acid) buffer and 23 °C. Iron isotope ratios were measured by high-resolution MC-ICP-MS. Isotope data were analyzed with isotope fractionation models. In batch systems, we observed significant Fe isotope fractionation upon equilibrium sorption of Fe(II) to all sorbents tested, except for aluminum oxide. The equilibrium enrichment factor, , of the Fe(II)sorb-Fe(II)aq couple was 0.85 ± 0.10‰ (±2σ) for quartz and 0.85 ± 0.08‰ (±2σ) for goethite-loaded quartz. In the goethite system, the sorption-induced isotope fractionation was superimposed by atom exchange, leading to a δ56/54Fe shift in solution towards the isotopic composition of the goethite. Without consideration of atom exchange, the equilibrium enrichment factor was 2.01 ± 0.08‰ (±2σ), but decreased to 0.73 ± 0.24‰ (±2σ) when atom exchange was taken into account. The amount of structural Fe in goethite that equilibrated isotopically with Fe(II)aq via atom exchange was equivalent to one atomic Fe layer of the mineral surface (∼3% of goethite-Fe). Column experiments showed significant Fe isotope fractionation with δ56/54Fe(II)aq spanning a range of 1.00‰ and 1.65‰ for pure and goethite-loaded quartz, respectively. Reactive transport of Fe(II) under non-steady state conditions led to complex, non-monotonous Fe isotope trends that could be explained by a combination of kinetic and equilibrium isotope enrichment factors. Our results demonstrate that in abiotic anoxic systems with near-neutral pH, sorption of Fe(II) to mineral surfaces, even to supposedly non-reactive minerals such as quartz, induces significant Fe isotope fractionation. Therefore we expect Fe isotope signatures in natural systems with changing concentration gradients of Fe(II)aq to be affected by sorption.  相似文献   

7.
In this study the physico-chemical, titration and sorption characteristics of Na-illite du Puy (Na-illite) have been measured and modelled. Samples of illite, collected in the region of le Puy-en-Velay, France, were purified and conditioned to the Na-form and physico-chemically characterised. Potentiometric titrations on suspensions of the Na-illite were carried out using a batch backtitration technique in 0.01, 0.1 and 0.5 M NaClO4 background electrolytes from pH∼3 to ∼11.5 in an inert atmosphere glove box. The supernatant solutions from each titration experiment in each series were analysed for K, Mg, Ca, Sr, Si, Al, Fe and Mn. The titration data were modelled in terms of the protolysis of two amphoteric edge sites (SW1OH and SW2OH) without an electrostatic term. Sorption edges (solid/liquid distribution ratios versus pH at trace sorbate concentrations and constant ionic strength) were determined for the transitions metals Ni(II) and Co(II), the lanthanide Eu(III), and the heavy metal Sn(IV) on Na-illite with NaClO4 as the background electrolyte under anoxic conditions (CO2 ? 2 ppm, O2 ? 2 ppm). The study thus encompasses a broad range of metals with different thermodynamic characteristics and with valence states ranging from II to IV. The results from the modelling of the titration data, in combination with a non electrostatic surface complexation and cation exchange sorption model were applied to quantitatively describe the uptake characteristics of the metals listed above on Na-illite. Since sorption edges were measured at trace concentrations, metal uptake was modelled as occurring on strong type sites (SSOH) only. This sorption model, the two site protolysis non electrostatic surface complexation and cation exchange model (2SPNE SC/CE model) had been previously developed and used to describe metal uptake on montmorillonite.  相似文献   

8.
The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6 m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6 m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory.  相似文献   

9.
The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO4 solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10−6 mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni2+, Cs+ and Ln3+ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta69, 4937-4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be AlOEu2+ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the AlOEu2+ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta66, 2325-2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p].  相似文献   

10.
Sorption of U(VI) on Hanford fine sand (HFS) with varying Fe-oxide (especially ferrihydrite) contents showed that U(VI) sorption increased with the incremental addition of synthetic ferrihydrite into HFS, consistent with ferrihydrite being one of the most reactive U(VI) sorbents present in natural sediments. Surface complexation model (SCM) calculations for U(VI) sorption, using only U(VI) surface-reaction constants obtained from U(VI) sorption data on freshly synthesized ferrihydrite at different pHs, were similar to the measured U(VI) sorption results on pure synthetic ferrihydrite and on HFS with high contents of ferrihydrite (5 wt%) added. However, the SCM prediction using only U(VI) sorption reactions and constants for synthetic ferrihydrite overestimated U(VI) sorption on the natural HFS or HFS with addition of low amounts of added ferrihydrite (1 wt% added). Over-predicted U(VI) sorption was attributed to reduced reactivity of natural ferrihydrite present in Hanford Site sediments, compared to freshly prepared synthetic ferrihydrite. Even though the SCM general composite (GC) approach is considered to be a semi-quantitative estimation technique for contaminant sorption, which requires systematic experimental data on the sorbent–sorbate system being studied to obtain credible SCM parameters, the general composite SCM model was still found to be a useful technique for describing U(VI) sorption on natural sediments. Based on U(VI) batch sorption results, two simple U(VI) monodentate surface species, SO_UO2HCO3 and SO_UO2OH on ferrihydrite and phyllosillicate in HFS, respectively, can be successfully used to describe U(VI) sorption onto Hanford Site sediment contacting varying geochemical solutions.  相似文献   

11.
The fate of harmful metals in the Earth crust is importantly affected by sorption processes on mineral surfaces. Here, a study of the ability of anhydrite surfaces to uptake dissolved Pb is presented. Experiments were conducted at room temperature using initial Pb concentration ([Pbaq]0) ranging between 10 and 1000 mg/L and a batch type set-up. Inductively coupled plasma optical emission spectrometry analyses showed that [Pbaq] progressively decreased as the time of interaction increased, to reach a final steady state value of ∼3.0 mg/L, irrespectively of [Pbaq]0. However, the time elapsed before the steady state value was reached strongly depended on [Pbaq]0, with the drop to this final value occurring in less than 1 day interaction when [Pbaq]0 ⩾ 50 mg/L and after 20 days when [Pbaq]0 < 50 mg/L. Scanning Electron Microscopy and X-ray diffraction analyses confirmed the epitactic growth of anglesite (PbSO4) crystals on anhydrite surfaces when [Pbaq]0 ⩾ 50 mg/L. X-ray Absorption Near Edge Structure spectroscopy points to a different sorption mechanisms when [Pbaq]0 < 50 mg/L. The results show that the epitactic growth of anglesite on anhydrite has no significant impact on the ability of anhydrite surfaces to remove Pbaq, which show equal effectiveness as that of gypsum surfaces. The high reactivity of anhydrite surfaces renders this phase potentially important in the control of the fate of dissolved metals in nature.  相似文献   

12.
We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km2 region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce∗]NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu∗]NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce∗]NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu∗]NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO2/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.  相似文献   

13.
Sorption of the 14 rare earth elements (REE) by basaltic rock is investigated as a function of pH, ionic strength and aqueous REE concentrations. The rock sample, originating from a terrestrial basalt flow (Rio Grande do Sul State, Brazil), is composed of plagioclase, pyroxene and cryptocrystalline phases. Small amounts of clay minerals are present, due to rock weathering. Batch sorption experiments are carried out under controlled temperature conditions of 20 °C with the <125 μm fraction of the ground rock in solutions of 0.025 M and 0.5 M NaCl and at pH ranging from 2.7 to 8. All 14 REEs are investigated simultaneously with initial concentrations varying from 10−7 to 10−4 mol/L. Some experiments are repeated with only europium present to evaluate possible competitive effects between REE. Experimental results show the preferential retention of the heavy REEs at high ionic strength and circumneutral pH conditions. Moreover, results show that REE sorption increases strongly with decreasing ionic strength, indicating two types of sorption sites: exchange and specific sites. Sorption data are described by a Generalised Composite (GC) non-electrostatic model: two kinds of surface reactions are treated, i.e. cation exchange at >XNa sites, and surface complexation at >SOH sites. Total site density (>XNa + >SOH) is determined by measuring the cation exchange capacity (CEC = 52 μmol/m2). Specific concentrations of exchange sites and complexation sites are determined by fitting the Langmuir equation to sorption isotherms of REE and phosphate ions. Site densities of 22 ± 5 and 30 ± 5 μmol/m2 are obtained for [>XNa] and [>SOH], respectively. The entire set of REE experimental data is modeled using a single exchange constant (log Kex = 9.7) and a surface complexation constant that progressively increases from log K = −1.15 for La(III) to −0.4 for Lu(III).The model proves to be fairly robust in describing other aluminosilicate systems. Maintaining the same set of sorption constants and only adjusting the site densities, we obtain good agreement with the literature data on REE/kaolinite and REE/smectite sorption. The Generalised Composite non-electrostatic model appears as an easy and efficient tool for describing sorption by complex aluminosilicate mineral assemblages.  相似文献   

14.
Cadmium (Cd) is a toxic trace element and due to human activities soils and waters are contaminated by Cd both on a local and global scale. It is widely accepted that chemical interactions with functional groups of natural organic matter (NOM) is vital for the bioavailability and mobility of trace elements. In this study the binding strength of cadmium (Cd) to soil organic matter (SOM) was determined in an organic (49% organic C) soil as a function of reaction time, pH and Cd concentration. In experiments conducted at native Cd concentrations in soil (0.23 μg g−1 dry soil), halides (Cl, Br) were used as competing ligands to functional groups in SOM. The concentration of Cd in the aqueous phase was determined by isotope-dilution (ID) inductively-coupled-plasma-mass-spectrometry (ICP-MS), and the activity of Cd2+ was calculated from the well-established Cd-halide constants. At higher Cd loading (500-54,000 μg g−1), the Cd2+ activity was directly determined by an ion-selective electrode (ISE). On the basis of results from extended X-ray absorption fine structure (EXAFS) spectroscopy, a model with one thiolate group (RS−) was used to describe the complexation (Cd2+ + RS− ? CdSR+; log KCdSR) at native Cd concentrations. The concentration of thiols (RSH; 0.047 mol kg−1 C) was independently determined by X-ray absorption near-edge structure (XANES) spectroscopy. Log KCdSR values of 11.2-11.6 (pKa for RSH = 9.96), determined in the pH range 3.1-4.6, compare favorably with stability constants for the association between Cd and well-defined thiolates like glutathione. In the concentration range 500-54,000 μg Cd g−1, a model consisting of one thiolate and one carboxylate (RCOO−) gave the best fit to data, indicating an increasing role for RCOOH groups as RSH groups become saturated. The determined log KCdOOCR of 3.2 (Cd2+ +  RCOO− ? CdOOCR+; log KCdOOCR; pKa for RCOOH = 4.5) is in accordance with stability constants determined for the association between Cd and well-defined carboxylates. Given a concentration of reduced sulfur groups of 0.2% or higher in NOM, we conclude that the complexation to organic RSH groups may control the speciation of Cd in soils, and most likely also in surface waters, with a total concentration less than 5 mg Cd g−1 organic C.  相似文献   

15.
Sorption interactions with montmorillonite and other clay minerals in soils, sediments, and rocks are potentially important mechanisms for attenuating the mobility of U(6+) and other radionuclides through the subsurface environment. Batch experiments were conducted (in equilibrium with atmospheric % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% acbiGaiWiG-bfadaWgaaWcbaacbaGaa43qaiaa+9eadaWgaaqaaiaa% +jdaaWqabaaaleqaaaaa!400D!\[P_{CO_2 } \])to determine the effects of varying pH (2 to 9), solid-mass to solution-volume ratio (M/V = 0.028 to 3.2 g/L), and solution concentration (2 × 10?7 and 2 × 10?6 M 233U) on U(6+) sorption on SAz-1 montmorillonite. The study focused on U(6+) surface complexation on hydroxylated edge sites as the sorption mechanism of interest because it is expected to be the predominant sorption mechanism at pHs typical of natural waters (pH ≈6 to ≈9). Thus, the experiments were conducted with a 0.1 M NaNO3 matrix to suppress ion-exchange between U(6+) in solution and interlayer cations. The results show that U(6+) sorption on montmorillonite is a strong function of pH, reaching a maximum at near-neutral pH (≈6 to ≈6.5) and decreasing sharply towards more acidic or more alkaline conditions. A comparison of the pH-dependence of U(6+) sorption with that of U(6+) aqueous speciation indicates a close correspondence between U(6+) sorption and the predominance field of U(6+)-hydroxy complexes. At high pH, sorption is inhibited due to formation of aqueous U(6+)-carbonate complexes. At low pH, the low sorption values indicate that the 0.1 M NaNO3 matrix was effective in suppressing ion-exchange between the uranyl (UO2 2+) species and interlayer cations in montmorillonite. At pH and carbonate concentrations typical of natural waters, sorption of U(6+) on montmorillonite can vary by four orders of magnitude and can become negligible at high pH. The experimental results were used to develop a thermodynamic model based on a surface complexation approach to permit predictions of U(6+) sorption at differing physicochemical conditions. A Diffuse-Layer model (DLM) assuming aluminol (>AlOH?) and silanol (>SiOH?) edge sites and two U(6+) surface complexation reactions per site effectively simulates the complex sorption behavior observed in the U(6+)-H2O-CO2-montmorillonite system at an ionic strength of 0.1 M and pH > 3.5. A comparison of model predictions with data from this study and from published literature shows good agreement and suggests that surface complexation models based on parameters derived from a limited set of data could be useful in extrapolating radionuclide sorption over a range of geochemical conditions. Such an approach could be used to support transport modeling by providing a better alternative to the use of constant K d s in transport calculations.  相似文献   

16.
Sorption of Ni(II) onto chlorite surfaces was studied as a function of pH (5–10), ionic strength (0.01–0.5 M) and Ni concentration (10−8–10−6 M) in an Ar atmosphere using batch sorption with radioactive 63Ni as tracer. Such studies are important since Ni(II) is one of the major activation products in spent nuclear fuel and sorption data on minerals such as chlorite are lacking. The sorption of Ni(II) onto chlorite was dependent on pH but not ionic strength, which indicates that the process primarily comprises sorption by surface complexation. The maximum sorption was at pH ∼ 8 (Kd = ∼10−3 cm3/g). Desorption studies over a period of 1–2 weeks involving replacement of the aqueous solution indicated a low degree of desorption. The acid–base properties of the chlorite mineral were determined by titration and described using a non-electrostatic surface complexation model in FITEQL. A 2-pK NEM model and three surface complexes, Chl_OHNi2+, Chl_OHNi(OH)+ and Chl_OHNi(OH)2, gave the best fit to the sorption results using FITEQL. The high Kd values and low degree of desorption observed indicate that under expected groundwater conditions, a large fraction of Ni(II) that is potentially leachable from spent nuclear fuel may be prevented from migrating by sorption onto chlorite surfaces.  相似文献   

17.
Calcium oxalate monohydrate (CaC2O4·H2O—abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II)aq following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4-10, with initial Sr solution concentrations, [Sr]aq, ranging from 1 × 10−4 to 1 × 10−3 M and ionic strengths ranging of 0.001-0.1 M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sraq for two days, the solution Ca concentration, [Ca]aq, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sraq removed from solution was nearly equal to the total [Ca]aq after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model to account for anharmonic effects in the EXAFS data. For Sr-bearing phases with low to moderate first-shell (Sr-O pair correlation) anharmonicity, the cumulant expansion model is sufficient for EXAFS fitting; however, for higher degrees of anharmonicity, an analytical model is required. Based on batch uptake results and EXAFS analyses of reaction products, we conclude that Sr is dominantly sequestered by a solid phase at the CaOx surface, likely the result of a dissolution-reprecipitation mechanism, to form SrC2O4 of mixed hydration state (i.e. SrOx·nH2O, where n = 0, 1, or 2). Surprisingly, no spectroscopic or XRD evidence was found for a (Sr,Ca)Ox solid solution or for a separate SrCO3 phase. In addition, we found no evidence for Sr(II) inner-sphere sorption complexes on CaOx surfaces based on lack of Sr-Ca second-neighbor pair correlations in the EXAFS spectra, although some type of Sr(II) surface complex (perhaps a type B Sr-oxalate ternary complex or an outer-sphere Sr(II) complex) or some as yet undetected Sr-bearing solid phases are needed to account for approximately 10% of Sr uptake by CaOx. The formation of a hydrated SrOx phase in environments under conditions similar to those of our experiments should retard Sr mobility and could be a significant factor in the biogeochemical cycling of Sr in soils and sediments or in plants and plant litter where CaOx is present.  相似文献   

18.
Co sorption was measured as a function of pH, ionic strength (0.001-0.1 M NaNO3) and sorbate/sorbent ratio on pure quartz, HFO and kaolinite and on binary and ternary mixtures of the three solids. Sorption data measured for the pure solids were used to derive internally-consistent diffuse layer surface complexation model (DLM) stability constants for Co sorption. Co sorption on HFO could be adequately modeled over a broad range of ionic strengths and sorbate/sorbent ratios with a two variable-charge site model. Fits based on a single variable-charge site model were reasonable, but were improved by using ionic-strength dependent stability constants. A single variable-charge site model with an additional permanent ion exchange site produced the best fit to Co edges measured on kaolinite over a range of ionic strength and sorbate/sorbent ratios. These DLM fits were also improved by using ionic-strength dependent stability constants. The DLM approach could not adequately describe the slope of Co sorption edges on quartz. This study demonstrates that for accurate prediction of Co sorption over wide ranges of ionic strength and sorbate/sorbent ratio, the DLM may require ionic-strength dependent stability constants. DLM stability constants for Co sorption derived for the pure solids were used to predict sorption as a function of pH and solid concentration on binary and ternary mixtures of the three solids. Discrepancies between predictions and measurements were quantitatively similar to those observed for the pure mineral systems. Thus, a simple component additivity approach provides useful predictions of metal sorption in the mixed solid systems.  相似文献   

19.
Information on the particle size and reactive surface area of natural samples is essential for the application of surface complexation models (SCM) to predict bioavailability, toxicity, and transport of elements in the natural environment. In addition, this information will be of great help to enlighten views on the formation, stability, and structure of nanoparticle associations of natural organic matter (NOM) and natural oxide particles.Phosphate is proposed as a natively present probe ion to derive the effective reactive surface area of natural samples. In the suggested method, natural samples are equilibrated (?10 days) with 0.5 M NaHCO3 (pH = 8.5) at various solid-solution ratios. This matrix fixes the pH and ionic strength, suppresses the influence of Ca2+ and Mg2+ ions by precipitation these in solid carbonates, and removes NOM due to the addition of activated carbon in excess, collectively leading to the dominance of the PO4-CO3 interaction in the system. The data have been interpreted with the charge distribution (CD) model, calibrated for goethite, and the analysis results in an effective reactive surface area (SA) and a reversibly bound phosphate loading Γ for a series of top soils.The oxidic SA varies between about 3-30 m2/g sample for a large series of representative agricultural top soils. Scaling of our data to the total iron and aluminum oxide content (dithionite-citrate-bicarbonate extractable), results in the specific surface area between about 200-1200 m2/g oxide for most soils, i.e. the oxide particles are nano-sized with an equivalent diameter in the order of ∼1-10 nm if considered as non-porous spheres. For the top soils, the effective surface area and the soil organic carbon fraction are strongly correlated. The oxide particles are embedded in a matrix of organic carbon (OC), equivalent to ∼1.4 ± 0.2 mg OC/m2 oxide for many soils of the collection, forming a NOM-mineral nanoparticle association with an average NOM volume fraction of ∼80%. The average mass density of such a NOM-mineral association is ∼1700 ± 100 kg/m3 (i.e. high-density NOM). The amount of reversibly bound phosphate is rather close to the amount of phosphate that is extractable with oxalate. The phosphate loading varies remarkably (Γ ≈ 1-3 μmol/m2 oxide) in the samples. As discussed in part II of this paper series (Hiemstra et al., 2010), the phosphate loading (Γ) of field samples is suppressed by surface complexation of NOM, where hydrophilic, fulvic, and humic acids act as a competitor for (an)ions via site competition and electrostatic interaction.  相似文献   

20.
This work reports, for the first time, the mineralogical and geochemical characteristics of the Cretaceous sedimentary kaolin deposits in the Red Sea area, Egypt and sheds the light on their source. Mineralogical and geochemical analyses of both bulk deposits and the sand and clay fractions of these deposits indicated that they are composed of kaolinite (average of 75 wt.%) and quartz (average of 22 wt.%). Traces of anatase (average of 1 wt.%) were identified in all kaolin samples, while traces of halite (average of 2 wt.%) and hematite (average of 1 wt.%) were reported in the majority of the analyzed samples. The clay fractions show relatively high contents of TiO2 (average of 2.1%), Ni (average of 103 ppm), Nb (average of 98 ppm), Y (average of 67 ppm), and Zr (average of 630 ppm). Sum of the rare earth elements (ΣREE) in the clay fractions varies between 193 and 352 ppm. Chondrite-normalized REE patterns show enrichment of the light REE relative to the heavy REE ((La/Yb)N = 9) and negative Eu anomaly (Eu*/Eu = 0.67).  相似文献   

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