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1.
《Applied Geochemistry》1991,6(5):565-574
Natural colloids (1–450 nm) and suspended particles (>450 nm) were characterized in groundwaters of the Whiteshell Research Area of southern Manitoba to evaluate their potential role in radionuclide transport through fractured granite. Data on particle concentrations, size distributions, compositions and natural radionuclide content were collected to predict radionuclide formation and to provide a database for future colloid migration studies. The concentrations of colloids between 10 and 450 nm ranged between 0.04 and 1 mg/l. The concentrations of suspended particles, which require higher groundwater velocities for transport, varied from 0.04 to 14 mg/l. Colloid (10–450 nm) concentrations as low as these observed in Whiteshell Research Area groundwater would have a minimal effect on radionuclide transport, assuming that radionuclide sorption on colloids is reversible. If radiocolloid formation is not reversible, and radionuclide-containing colloids cannot sorb onto fracture walls, the importance of natural colloids in radionuclide transport will depend upon particle migration properties.  相似文献   

2.
Complexation of metal ions by organic matter is frequently considered to play a part in metal ion dissolution in natural waters. A field study of a relatively unperturbed stream, high in organics, associates this with the fraction related to soil organic acids (humic acids). The association might have two origins. The first is complexation. However, well known sequences of complexing tendency do not predict the behaviour. A better theory uses the additional factor of the reducing capacity of dissolved organic matter toward Fe(III) and Mn(IV).  相似文献   

3.
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4.
In the present study, the performance of three moving bed biofilm reactors (MBBRs) has been evaluated in series with anaerobic/anoxic/oxic (A2O) units for simultaneous removal of organic matter and nutrients (nitrogen and phosphorous) from a synthetic wastewater with characteristics similar to those of a typical municipal wastewater. Response surface methodology based on central composite design was used to investigate the effects of nitrate recycle ratio, hydraulic retention time (HRT), and influent chemical oxygen demand (COD) on the organic and nutrient removal and optimization process. The optimized values of influent COD, HRT, and R were 462 mg/L, 10 h, and 3.52, respectively. The predicted and observed values at optimized conditions were 92.8% and 93 ± 1.3%, 84.3% and 84 ± 1.3%, 71.7% and 68 ± 1.6% for COD, TN, and TP removals and 100 and 97 ± 1.2 mL/g for sludge volume index, respectively. After that, the influent COD, TN, and TP were increased to 550, 48, and 12 mg/L, respectively, to partly simulate the organics and nutrient variations of real wastewater treatment plants. The COD, TN, and TP removals were 91 ± 1.3, 82 ± 1.1, and 71 ± 0.8%, respectively. The influent COD, TN, and TP were increased again to 650, 56, and 14 mg/L, respectively. After this phase, the COD, TN, and TP removals were 90 ± 0.8, 80 ± 1.2, and 70 ± 1.0%, respectively. Obtained results indicated the good stability of the optimized system and the ability of MBBRs to remain stable at influent organics and nutrient variations. The ratio of attached volatile solids to mixed liquor volatile suspended solids was 1.90 ± 0.10, 2.07 ± 0.09, and 2.25 ± 0.14 in phases 1, 2, and 3, respectively. These high ratios indicate that the microorganisms had favored the attached growth to the suspended growth within the whole operation time.  相似文献   

5.
The kinetics of radionuclide desorption from bentonite colloids and subsequent sorption onto fracture filling material can influence colloid-facilitated radionuclide migration in ground water. To shed light on the significance of these issues batch-type experiments using a cocktail of strong and weak sorbing radionuclides as well as FEBEX bentonite colloids in the presence of fracture filling material from Grimsel (Switzerland) under Grimsel ground water conditions have been conducted. Results show that tri- and tetravalent radionuclides, 232Th(IV), 242Pu(IV) and 243Am(III) are clearly colloid associated in contrast to 233U(VI), 237Np(V) and 99Tc(VII). Concentrations of colloid-borne 232Th(IV), 242Pu(IV) and 243Am(III) decrease after ∼100 h showing desorption from bentonite colloids while 233U(VI) and 99Tc(VII) concentrations remain constant over the entire experimental time of 7500 h thus showing no interaction either to colloids or to the fracture filling material. 232Th(IV) and 242Pu(IV) data yield a slower dissociation from colloids compared to 243Am(III) indicating stronger RN–colloid interaction. In the case of 237Np(V), a decrease in concentration after ∼300 h is observed which can be explained either by slow reduction to Np(IV) and subsequent sorption to mineral surfaces in accordance with the evolution of pe/pH and/or by a slow sorption onto the fracture filling material. No influence of the different fracture filling material size fractions (0.25–0.5 mm, 0.5–1 mm and 1–2 mm) can be observed implying reaction independence of the mineral surface area and mineralogical composition. The driving force of the observed metal ion desorption from colloids is binding to fracture filling material surfaces being in excess of the available colloid surface area (76:1, 55:1 and 44:1 for the 0.25–0.5 mm, 0.5–1 mm and 1–2 mm size fraction of the FFM, respectively).  相似文献   

6.
Vast amounts of knowledge about the proton- and metal-binding properties of dissolved organic matter (DOM) in natural waters have been obtained in studies on isolated humic and fulvic (hydrophobic) acids. Although macromolecular hydrophilic acids normally make up about one-third of DOM, their proton- and metal-binding properties are poorly known. Here, we investigated the acid-base and Cu-binding properties of the hydrophobic (fulvic) acid fraction and two hydrophilic fractions isolated from a soil solution. Proton titrations revealed a higher total charge for the hydrophilic acid fractions than for the hydrophobic acid fraction. The most hydrophilic fraction appeared to be dominated by weak acid sites, as evidenced by increased slope of the curve of surface charge versus pH at pH values above 6. The titration curves were poorly predicted by both Stockholm Humic Model (SHM) and NICA-Donnan model calculations using generic parameter values, but could be modelled accurately after optimisation of the proton-binding parameters (pH ? 9). Cu-binding isotherms for the three fractions were determined at pH values of 4, 6 and 9. With the optimised proton-binding parameters, the SHM model predictions for Cu binding improved, whereas the NICA-Donnan predictions deteriorated. After optimisation of Cu-binding parameters, both models described the experimental data satisfactorily. Iron(III) and aluminium competed strongly with Cu for binding sites at both pH 4 and pH 6. The SHM model predicted this competition reasonably well, but the NICA-Donnan model underestimated the effects significantly at pH 6. Overall, the Cu-binding behaviour of the two hydrophilic acid fractions was very similar to that of the hydrophobic acid fraction, despite the differences observed in proton-binding characteristics. These results show that for modelling purposes, it is essential to include the hydrophilic acid fraction in the pool of ‘active’ humic substances.  相似文献   

7.
Thirty of the 58 groundwaters sampled in September-October 2000 in the study area (La Spezia Province, Italy) have Mg-HCO3 to Ca-HCO3 composition, undetectable Cr(III) contents, and virtually equal concentrations of total dissolved Cr and Cr(VI). Therefore, dissolved Cr is present in toto as Cr(VI), with concentrations of 5-73 ppb. These values are above the maximum permissible level for drinking waters (5 ppb). Local ophiolites, especially serpentinites and ultramafites, are Cr-rich and represent a Cr source for groundwaters. However, since Cr is present as Cr(III) in rock-forming minerals, its release to the aqueous solution requires oxidation of Cr(III) to Cr(VI). This can be performed by different electron acceptors, including Mn oxides, H2O2, gaseous O2, and perhaps Fe(III) oxyhydroxides. Based on this evidence and due to the absence of anthropogenic Cr sources, the comparatively high Cr(VI) concentrations measured in the waters of the study area are attributed to natural pollution.  相似文献   

8.
《Applied Geochemistry》1996,11(4):555-565
Organic material is present at low concentrations, typically 1–2 mg/l in terms of dissolved organic carbon (DOC), in groundwaters deep in granitic rock. Hydrophobic and hydrophilic acids may complex inorganic contaminants and change their sorption behaviour on geological materials. This report describes a series of experiments performed under aerobic conditions to investigate the effects of fulvic acid over a concentration range of 0–5 mg/I DOC on the sorption of85Sr,137Cs,233U,238Pu and241'Am by crushed granite, biotite, goethite, montmorillonite and quartz. In addition, similar solutions were used to study the effects of dissolved fulvic acid on the sorption of99Tc and125I on each of the above solids except quartz. The fulvic acid was extracted from groundwater collected at a depth of 240 m in the granitic rock of the Underground Research Laboratory near Lac du Bonnet, Manitoba.In all experiments, the sorption of the fulvic acid by the geological materials was in the order goethite montmorillonite > biotite > granite > quartz. No sorption of Tc was observed from any of the solutions on any of the solids. Low sorption of I on montmorillonite occurred in the presence of the dissolved organic material. No sorption of I was observed with the other solids used. Only montmorillonite sorbed any appreciable amount of Sr in this study with the fulvic acid having no effect on this sorption. All the solids except quartz sorbed substantial amounts of Cs, but sorption was not affected by the organic material in solution. Each of the solids sorbed U with no difference in sorption observed due to the dissolved organic. In general, Pu sorption decreased as the concentration of dissolved fulvic acid increased. However, sorption of Pu on quartz remained at approximately the same levels regardless of the concentration of organic in solution. Generally high sorption of Am was found. Lowest sorption of Am on all solids occurred from the solution with the highest concentration of fulvic acid. Sorption of Am on granite decreased as the concentration of the organic in solution increased.This study indicated that, under aerobic conditions, the effect of dissolved organic material on sorption of radioisotopes depends on the radioisotope in question and the concentration of the organic in solution.  相似文献   

9.
The variation of the natural radionuclide concentrations depends on the chemical composition of each site. In this work, two thermal springs in the east of Algeria have been chosen to assess the activity concentration of natural radionuclide, mainly the three natural radioactive series 238U, 235U and 232Th, and 40K. The high-resolution gamma ray spectroscopy was used to determine these concentrations. In these water samples, 235U, 234Th, 210Pb, 226Ra radionuclides are less than the minimum detectable activity. The activity of 238U is dominant. The 238U activity was determined by taking the mean activity of two separate photo-peaks of daughter nuclides 214Pb at 351.92 (37.2%) keV and 214Bi at 609.31 (45%) keV. The measured activity concentrations of 238U in water samples obtained from the concentrations of 214Bi and 214Pb ranged from 0.56 ± 0.20 to 1.13 ± 0.20 Bq/L. The annual effective dose value due to the ingestion of the measured radionuclide 238U in 1 L of water, for an adult, ranged from 9.20 to 18.56 µSv.  相似文献   

10.
《Applied Geochemistry》2004,19(4):519-560
The hydrogeochemistry of the Lac du Bonnet granitic batholith has been determined for the region of the Whiteshell Research Area (WRA) in southeastern Manitoba, Canada. This work forms part of the geosciences studies performed for the Canadian Nuclear Fuel Waste Management Program over the period 1980–1995 by Atomic Energy of Canada Limited (AECL). Knowledge of the variation of groundwater chemistry and its causes is useful in assessing the performance and safety of a nuclear fuel waste vault located at depths of up to 1000 m in a crystalline rock formation of the Canadian Shield. Groundwaters and matrix pore fluids have been obtained by standard sampling methods from shallow piezometers in clay-rich overburden, from packer-isolated borehole zones intersecting fractures or fault zones in the bedrock, and from boreholes in unfractured rock in AECL's Underground Research Laboratory (URL). Eighty-six individual fracture groundwaters have been sampled and analysed from permeable zones in 53 boreholes drilled to depths of up to 1000 m in the Lac du Bonnet batholith. In addition, 28 groundwaters from piezometers in a large wetland area near the URL have been sampled and analysed to determine the influence of clay-rich overburden on the bedrock hydrogeochemistry. Analyses have been made for major and minor ions, pH, Eh, trace metals, and stable and radioactive isotopes, to characterise these groundwaters and relate them to their hydrogeologic regimes. Shallow groundwaters in the fractured bedrock are generally dilute (TDS <0.3 g/l), Ca–Na–HCO3 waters and show little indication of mixing with Ca–Mg–HCO3–SO4 groundwater from overburden sediments. The near-modern levels of 3H and 14C, and a warm-climate 2H/18O signature in these groundwaters, indicates that the upper ∼200 m of fractured bedrock contains an active groundwater circulation system with a residence time of tens to hundreds of years. Deeper fracture groundwaters (200–400 m depth) in recharge areas, are more alkaline, Na–Ca–HCO3 waters and evolve to Na–Ca–HCO3–Cl–SO4 waters with increasing distance along the flow path. Isotopic data indicate the presence of a glacial melt-water component suggesting that the residence times of these waters are 103–105 a. These waters form a transition zone between the upper, advective flow regime and a deeper regime in sparsely fractured rock where groundwater in fractures and fracture zones is largely stagnant. At these depths (> 500 m), Na–Ca–Cl–SO4 waters of increasing salinity (up to 50 g/l) with depth are found and in some fractures the waters have evolved to a Ca–Na–Cl composition. Isotopic data indicate that these waters are warm-climate and pre-glacial in origin, with residence times of over 1 Ma. Pore fluids observed to drain from the unfractured rock matrix in the URL facility are almost pure Ca–Cl in composition, ∼90 g/l salinity, and have a 2H/18O composition displaced well to the left of the global meteoric water line, about which all other WRA groundwaters lie. This information indicates that these pore fluids have undergone prolonged water-rock interaction and have residence times of 101–103 Ma. Most of the deeper fracture groundwaters and pore fluids have low Br/Cl ratios and moderate to high δ34S values of dissolved SO4 which indicates that their salinity could be derived from a marine source such as the basinal sedimentary brines and evaporites to the west of the batholith. These fluids may have entered the batholith during early Paleozoic times when sedimentary rocks were deposited over the granite and were driven by a hydraulic gradient resulting from higher ground in western Canada. The hydrogeochemical data and interpretations show that below ∼500 m in the WRA, fracture-hosted groundwaters are very saline, reducing and old, and are, therefore, indicative of stagnant conditions over the period of concern for nuclear waste disposal (1 Ma). The intact rock matrix at these depths is extremely impermeable as indicated by the presence of pore fluids with unusual geochemical and isotopic characteristics. The pore fluids may represent basinal brines that have evolved geochemically and isotopically to their current composition over periods as long as 103 Ma.  相似文献   

11.
This study examined the interaction between Cr(VI) and a Fe-rich soil in the presence of low-molecular-weight organic acids as a function of pH. Oxalic and tartaric acids were chosen since they existed in soils commonly. Batch experiments showed that adsorption of Cr(VI) by the soil within the pH range examined was inhibited in the presence of oxalic acid, which was more pronounced when the initial ratio of [oxalic acid]/[Cr(VI)] was raised from 1:1 to 2:1. With the addition of tartaric acid, concentration of Cr(VI) in equilibrium solutions was far less than that of single adsorbate system across the pH wide (2.5–5.5), which was noticeable especially at low pH. The results were attributed to Cr(VI) adsorption and, particularly, the soil surface catalyzed reduction of Cr(VI) to Cr(III) by tartaric acid. The data reported in this paper suggested that the mobility, the bioavailability, and the toxicity of Cr(VI) in soil environments might be greatly affected by pH, the presence and nature of low-weight-molecular organic acids (oxalic and tartaric acids).  相似文献   

12.
Hexavalent chromium [Cr(VI)] is used in various industries, but its improper and uncontrolled discharge contaminates the environment. In order to circumvent chromium toxicity, several physicochemical and biological strategies have been employed. Among biological approach, microbes convert toxic Cr(VI) to less soluble Cr(III) form and hence can be used to detoxify/remove Cr(VI) from contaminated environment. Considering these, present study was designed to assess the effect of chromium reductases and antioxidants secreted by Penibacillus species to detoxify Cr(VI) and concurrently to augment soybean growth. Bacterial strains (MAI1 and MAI2) were identified as Penibacillus sp. using 16S rRNA gene. Penibacillus species reduced Cr(VI) significantly at pH 7. Maximum Cr(VI) was reduced at 50 and 100 µg/ml of Cr(VI) concentrations. Penibacillus sp. also reduced Cr(VI) significantly at 25 and 35 °C as well as 1 g sodium alginate in 1 g polyvinyl alcohol. Bacterial strains reduced Cr(VI) into Cr(III) which were detected as 33 ± 1 and 35 ± 1 µg/ml in supernatant and 67 ± 2.5 and 65 ± 1 µg/ml in cell debris, respectively, after 120 h. Chromium reductase found in cell-free extract reduced almost all Cr(VI) compared to those observed in cell debris. Both malondialdehyde and antioxidant levels were increased with gradual increase in Cr(VI) concentration. Penibacillus species inoculated soybean plants had better growth and photosynthetic pigments under Cr(VI) stress.  相似文献   

13.
Tropical peat soils present higher ash content than those generated at temperate climate areas. Therefore, this study evaluated the characteristics of a Brazilian organic soil (OS), commercialized as peat, as well as its capacity in removing Cr(VI) from contaminated waters. The OS is composed of 35.5 wt% of organic matter and 56 wt% of inorganic fraction (ash), which is formed by minerals and phytoliths rich in silica (29.2 wt%) and alumina (23.6 wt%). The Cr(VI) removal tests were carried out in batch and column systems using OS and solutions of Cr(VI) prepared with distilled water and groundwater. Batch tests revealed that the organic substances in the OS caused the reduction of Cr(VI) to Cr(III), with an efficiency depending on solution pH. At pH 5.0 the Cr(VI) removal was 0.45 mg g?1 in 24 h; whereas at pH 2.0, this removal increased to 1.10 mg g?1. Since this redox reaction is very slow, the removal of Cr(VI) at pH 5.0 increased to around 2 mg g?1 after 5 days. The removal of Cr(VI) was more effective in the column tests than in the batch test due to the greater solid/solution ratio, and their half-lives were 4.4 and 26.2 h, respectively. Chemical analysis indicated that Cr(VI) was reduced by the humic substances of OS, followed by the precipitation and/or adsorption of Cr(III) into the organic and inorganic components, as anatase. The presence of Cr(III) increased the stability of anatase structure, avoiding its transformation into rutile, even after being heated at 800 °C/2 h.  相似文献   

14.
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15.
We have examined the effects of aqueous complexation on rates of dissimilatory reductive precipitation of uranium by Shewanella putrefaciens. Uranium(VI) was supplied as sole terminal electron acceptor to Shewanella putrefaciens (strain 200R) in defined laboratory media under strictly anaerobic conditions. Media were amended with different multidentate organic acids, and experiments were performed at different U(VI) and ligand concentrations. Organic acids used as complexing agents were oxalic, malonic, succinic, glutaric, adipic, pimelic, maleic, citric, and nitrilotriacetic acids, tiron, EDTA, and Aldrich humic acid. Reductive precipitation of U(VI), resulting in removal of insoluble amorphous UO2 from solution, was measured as a function of time by determination of total dissolved U. Reductive precipitation was measured, rather than net U(VI) reduction to U(IV), to assess overall U removal rates from solution, which may be used to gauge the influence of chelation on microbial U mineralization. Initial linear rates of U reductive precipitation were found to correlate with stability constants of 1:1 aqueous U(VI):ligand and U(IV):ligand complexes. In the presence of strongly complexing ligands (e.g., NTA, Tiron, EDTA), UO2 precipitation did not occur. Our results are consistent with ligand-retarded precipitation of UO2, which is analogous to ligand-assisted solid phase dissolution but in reverse: ligand exchange with the U4+ aquo cation acts as a rate-limiting reaction moderating coordination of water molecules with U4+, which is a necessary step in UO2 precipitation. Ligand exchange kinetics governing dissociation rates of ligands from U(VI)-organic complexes may also influence overall UO2 production rates, although the magnitude of this effect is unclear relative to the effects of U(IV)-organic complexation. Our results indicate that natural microbial-aqueous systems containing abundant organic matter can inhibit the formation of biogenic amorphous UO2.  相似文献   

16.
Surfactant-enhanced remediation of contaminated soil: a review   总被引：48，自引：0，他引：48  
Extracting aqueous solutions with or without additives are employed to solubilize contaminants in soil. Since water solubility is the controlling removing mechanism, additives are used to enhance efficiencies. These additives can reduce the time to treat a site compared to the use of water alone. Additives must be of low toxicity and biodegradable. The research in this area has focussed mainly on halogenated volatile organic compounds (VOCs) and is still quite limited for metal removal. Additives include surfactants, organic and inorganic acids, sodium hydroxide, which can dissolve organic soil matter, water-soluble solvents such as methanol, displacement of cations with nontoxic ones, complexing agents such as EDTA, acids in combination with complexing agents or oxidizing/reducing agents. Cationic, anionic and nonionic surfactants are particularly used for soil washing or flushing. They contain both hydrophobic and hydrophilic portions, making them ideal for solubilization of hydrophobic compounds. Numerous studies have indicated that surfactants enhance recoveries of non-aqueous phase liquids (NAPLs). There have also been indications that pretreatment of soil with surfactant washing to solubilize hydrophobic compounds such as PAHs enhances biodegradation of these contaminants. A few in situ field studies have been performed with surfactants. Large-scale treatment has been done mostly for organic removal. Soil pH, soil type, cation exchange capacity (CEC), particle size, permeabilities and contaminants all affect removal efficiencies. High clay and organic matter contents are particularly detrimental. Understanding the chemistry of the binding of the contaminant and the hydrogeology of the site are very important. Once the water is pumped from the soil, it must be extracted and then treated to remove the hydrocarbons and metals. Several technologies exist such as sodium hydroxide or sodium sulfide precipitation, ion exchange, activated carbon adsorption, ultrafiltration, reverse osmosis, electrodialysis and biological processes. Recycling of the surfactants is desired to decrease treatment costs.

This paper will provide an overview of the laboratory research, field demonstration and full-scale application of surfactants for the remediation of contaminated soil. The majority of pilot scale in situ flushing tests, particularly in the United States, have involved the use of surfactants and co-solvents. There are only a few full-scale projects however. Recent laboratory scale efforts by the authors concerning the use of biosurfactants, biologically produced surfactants, to enhance the removal of copper, cadmium and zinc from contaminated soils and sediments are discussed. Three types of biosurfactants were evaluated for their effectiveness. They included a lipopeptide called surfactin from Bacillus subtilis, a rhamnolipid from Pseudomonas aeruginosa and a sophorolipid from Torulopsis bombicola. The results indicated the feasibility of removing the metals with the anionic biosurfactants even though the exchangeable fractions were not significant.  相似文献   


17.
Data are presented in this study from laboratory model experiments describing the behaviour of Cu, Pb, Zn and Ni at a simulated sediment-water boundary. The interactions involved are sorption by kaolin and by bentonite, organic complexing in solution by fulvic acid and by humic acid, carbonate reactions, hydrolysis, and desorption of the cations from a clay-bound phase and from their metal hydroxides by the organic acids. The organic acids increase the solubility of Cu, Zn and Ni in the presence of clay. The Pb solubility is variable and can even decrease, particularly at acidic pH, with organic complexing likely due to colloidal coagulation. Both Zn and Ni are influenced by hydrolysis at basic pH. When carbonate was added to the metal-organic acid-clay mixtures, a further decrease in solubility was observed for Ni and, to a lesser extent, for Zn. The organic acids prove capable of remobilizing Cu, Pb, Zn and Ni from the solid phases examined. However, there is a general kinetic hindrance to the desorption particularly at basic pH. Copper desorption appears to be the most kinetically hindered. Conclusions pertinent to the geochemical dispersion of these metals are drawn.  相似文献   

18.
The present study reports on the preliminary investigation of three low-cost natural materials with respect to their chromium(VI) removal efficiency from contaminated water. The tested materials were reed, in milled and chopped form, compost, and dewatered sludge from a municipal wastewater treatment plant. The chromium(VI) removal capacity of the aforementioned materials was investigated by simulating the physicochemical conditions prevailing in a stormwater outfall flowing into the Asopos River in Inofyta, Central Greece. Thus, batch and column experiments were carried out using solutions of 3–5 mg/L chromium(VI) and pH value 8.5 ± 0.5. The results showed that the tested materials were capable of removing 3 mg/L chromium(VI), however by allowing different contact times for each material. The chromium(VI) removal kinetics were studied through batch experiments, and reed was found to be the most efficient material. Therefore, at a second series of batch and up-flow column experiments, the effect of the liquid-to-solid ratio, pH, and contact time on chromium(VI) removal using chopped reed was investigated. Chromium(VI) removal took place through both reduction and adsorption mechanisms, while the released soluble organic matter from reed seemed to favor the reduction mechanism. As a result, reed is a potential biosorbent capable of treating heavily chromium(VI)-contaminated water flows, although a high mass of reed is required for a treatment process, such in the case of the stormwater discharged into Asopos River.  相似文献   

19.
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.  相似文献   

20.
《Applied Geochemistry》2005,20(2):443-451
The influence of water-extractable organic matter from 6 Opalinus Clay (OPA) samples from Mont Terri and Benken (Switzerland) on the sorption of Ni(II), Eu(III) and Th(IV) has been measured using an ion exchange technique. OPA is considered to be one of the potential host rocks for the deep geological disposal of high-level and long-lived intermediate-level radioactive waste in Switzerland. Within the range of estimated uncertainties, no significant differences in sorption were observed in most cases as compared with suitable synthetic waters devoid of organic C. Only in certain individual cases were slight reductions in sorption (less than a factor of 5) for Eu(III) and Ni(II) found. The results of accompanying laser fluorescence spectroscopy experiments did not show any influence of the extracts on Cm(III) speciation. This would suggest that the reduction of sorption occasionally observed in the ion exchange experiments is probably not caused by the formation of complexes between the radionuclides and the organic matter in the extracts, but is rather due to an underestimation of systematic uncertainties. From these findings, and from UV–VIS spectroscopic characterisation of the organic matter in the extracts, it can be concluded that only a negligible fraction of the organic matter present may be in the form of humic or fulvic acids. It is consequently justified to put aside overly conservative assumptions with respect to the complexing behaviour of the organic matter used towards the metal ions investigated and their chemical analogues. In view of the site-specific character of the present study, these conclusions may not be arbitrarily applied to other geological formations considered as possible host rocks for the disposal of radioactive waste.  相似文献   

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