The adsorption of plutonium IV and V on goethite

The adsorption of Pu(IV) and Pu(V) on goethite (αFeOOH) from NaNO₃ solution shows distinct differences related to the different hydrolytic character of these two oxidation states. Under similar solution conditions, the adsorption edge of the more strongly hydrolyzable Pu(IV) occurs in the pH range 3 to 5 while that for Pu(V) is at pH 5 to 7. The adsorption edge for Pu(V) shifts with time to lower pH values and this appears to be due to the reduction of Pu(V) to Pu(IV) in the presence of the goethite surface. These results suggest that redox transformations may be an important aspect of Pu adsorption chemistry and the resulting scavenging of Pu from natural waters.Increasing ionic strength (from 0.1 M to 3 M NaCl or NaNO₃ and 0.03 M to 0.3 M Na₂SO₄) did not influence Pu(IV) or Pu(V) adsorption. In the presence of dissolved organic carbon (DOC), Pu(V) reduction to Pu(IV) occurred in solution. Pu(IV) adsorption on goethite decreased by 30% in the presence of 240 ppm natural DOC found in Soap Lake, Washington waters. Increasing concentrations of carbonate ligands decreased Pu(IV) and Pu(V) adsorption on goethite, with an alkalinity of 1000 meq/l totally inhibiting adsorption.The Pu-goethite adsorption system provides the data base for developing a thermodynamic model of Pu interaction with an oxide surface and with dissolved ligands, using the MINEQL computer program. From the model calculations we determined equilibrium constants for the adsorption of Pu(IV) hydrolysis species. The model was then applied to Pu adsorption in carbonate media to see how the presence of CO₃^?2 could influence the mobility of Pu. The decrease in adsorption appears to be due to formation of a Pu-CO₃ complex. Model calculations were used to predict what the adsorption curves would look like if Pu-CO₃ complexes formed.     

Characterization and environmental application of a Chilean natural zeolite

The use of natural zeolites for environmental applications is gaining new research interests mainly due to their properties and significant worldwide occurrence. The present work describes the characterization of a natural Chilean zeolite and the results as adsorbent for ammonia from aqueous solutions. The zeolitic-rich tuff sample, mainly composed of clinoptilolite and mordenite, consisted of 13 μm mean volumetric particle diameter, 55 m² g⁻¹ (methylene blue adsorption) and 177 m² g⁻¹ (nitrogen adsorption) of specific surface area. Particles were negatively charged over a broad pH range (with or without ammonia) and 1.02 meq NH₄⁺ g⁻¹ cation-exchange capacity. The ammonia removal appears to proceed through ion-exchange and rapid kinetics (rate constant of 0.3 min⁻¹) at neutral pH value, with removal capacities up to 0.68 meq NH₄⁺ g⁻¹. The Langmuir isotherm model provided excellent equilibrium data fitting (R²=0.97). Results indicate a significant potential for the Chilean natural zeolite as an adsorbent/ion-exchange material for wastewater treatment and water reuse applications.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Carbonate equilibrium in the water of the Razdol’naya River

The paper suggests an accurate approach to studying carbonate equilibrium in the water of the Razdol’naya River. The approach involves measuring pH by Pitzer’s scale, using a cell without liquid junction; measuring the total alkalinity by Bruevich’s technique; and using apparent constants of carbonate equilibrium with regard for the organic alkalinity. The Pitzer technique was employed to calculate the apparent constants of carbonate equilibrium in solution that models the riverine water: Ca(HCO₃)₂–NaCl–H₂O within the range of alkalinity of 0–0.005 mol/kg and temperatures of 0–25°C. Carbonate equilibrium in the water of the Razdol’naya River was sampled for studying at eight sites during all four seasons. Although the contents of biogenic compounds in the water are high, they can merely insignificantly affect the acid–base equilibrium, which is controlled in the riverine water by carbonate equilibrium and the concentrations of humic substances, which play the greater role, the greater the discharge of the river. In addition to the production and destruction of organic matter, carbonate equilibrium in the river is also affected by the supply of humic substances with soil waters and total alkalinity with groundwaters. The fluxes of alkalinity and humic substances annually brought by the Razdol’naya River to Amur Bay are evaluated at 1.33 × 10⁹ mol and 9.9 × 10⁶ kgC, respectively. The carbon dioxide export with the Razdol’naya River is equal to the alkalinity flux and does not depend on the weathering mechanisms.     

Adsorption of uranyl onto ferric oxyhydroxides: Application of the surface complexation site-binding model

Uranyl adsorption was measured from aqueous electrolyte solutions onto well-characterized goethite, amorphous ferric oxyhydroxide, and hematite sols at 25°C. Adsorption was studied at a total uranyl concentration of 10^?5 M, (dissolved uranyl 10^?5 to 10^?8 M) as a function of solution pH, ionic strength and electrolyte concentrations, and of competing cations and carbonate complexing. Solution pHs ranged from 3 to 10 in 0.1 M NaNO₃ solutions containing up to 0.01 M NaHCO₃. All the iron oxide materials strongly adsorbed dissolved uranyl species at pHs above 5 to 6 with adsorption greatest onto amorphous ferric oxyhydroxide and least onto well crystallized specular hematite. The presence of Ca or Mg at the 10^?3 M level did not significantly affect uranyl adsorption. However, uranyl carbonate and hydroxy-carbonate complexing severely inhibited adsorption. The uranyl adsorption data measured in carbonate-free solutions was accurately modeled with the surface complexation-site binding model of Davis et al. (1978), assuming adsorption was chiefly of the UO₂OH⁺ and (UO₂)₃(OH)⁺₅, aqueous complexes. In modeling it was assumed that these complexes formed a monodentate UO₂OH⁺ surface complex, and a monodentate, bidentate or tridentate (UO₂)₃(OH)⁺₅surface complex. Of the latter, the bidentate surface complex is the most likely, based on crystallographic arguments. Modeling was less successful predicting uranyl adsorption in the presence of significant uranyl carbonate and hydroxy-carbonate complexing. It was necessary to slightly vary the intrinsic constants for adsorption of the di- and tricarbonate complexes in order to fit the uranyl adsorption data at total carbonate concentrations of 10^?2 and 10^?3 M.     

The adsorption characteristics of δ-manganese dioxide: a collection of diffuse double layer constants for the adsorption of H+, Cu2+, Ni2+, Zn2+, Cd2+ and Pb2+

Thermodynamic data for all fate-determining processes are needed in order to predict the fate and transport of metals in natural systems. The surface complexation properties of a synthetic MnO₂, δ-MnO₂, have accordingly been investigated using glass electrode potentiometry. Experimental data were interpreted according to the surface complexation model in conjunction with the diffuse double layer model of the solid/solution interface. Adsorption constants were determined using the non-linear optimisation program FITEQL. Surface complexation parameters determined in this way were validated against results obtained from the literature. Best fits of alkalimetric titration data were obtained with a 2-site, 3 surface-species model of the δ-MnO₂ surface. Site concentrations of 2.23×10⁻³ mol g⁻¹ and 7.66×10⁻⁴ mol g⁻¹ were obtained. Corresponding logarithms of formation constants for the postulated surface species are −1.27 (≡XO⁻), −5.99 (≡YO⁻) and 3.52 (≡YOH₂⁺) at I=0.1 M. The surface speciation of δ-MnO₂ is dominated by ≡XO⁻ over the pH range investigated. Metal adsorption was modelled with surface species of the type ≡XOM⁺, ≡XOMOH, ≡YOM⁺, ≡YOMOH (M=Cu, Ni, Zn, Cd and Pb) and ≡XOM₂OH²⁺ (M=Pb). For Cu, Ni and Zn, titration data could be modelled with ≡XOM⁺, ≡XOMOH, ≡YOM⁺ and ≡YOMOH, whereas for Cd, ≡XOM⁺ and ≡YOM⁺ were sufficient. Lead data were best modelled by assuming the dinuclear species ≡XOM₂OH²⁺ to be the only surface species to form. Adsorption constants determined for Ni, Cu and Zn follow the Irving-Williams sequence. The model suggests an adsorption order of (Pb, Cu) > (Ni, Zn) > Cd. The discrepancy between model predictions and published adsorption results is similar to the variability observed in experimental results from different laboratories.     

Benthic fluxes and the cycling of biogenic silica and carbon in two southern California borderland basins

Benthic fluxes in two southern California borderland basins have been estimated by modeling water column property gradients, by modeling pore water gradients and by measuring changes in concentration in a benthic chamber. Results have been used to compare the different methods, to establish budgets for biogenic silica and carbon and to estimate rate constants for models of CaCO₃ dissolution. In San Pedro Basin, a low oxygen, high sedimentation rate area, fluxes of radon-222 (86 ± 8 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.9 ± 0.3 mmol m⁻² d⁻¹) and nitrate (−0.8 ± 0.1 mmol m⁻² d⁻¹) measured in a benthic chamber agree within the measurement uncertainty with fluxes estimated from modeling profiles of nutrients and radon obtained in the water column. The diffusive fluxes of radon, SiO₂ and TCO₂ determined from modeling the sediment and pore water also agree with the other approaches. Approximately 33 ± 13% of the organic carbon and 37 ± 47% of the CaCO₃ arriving at the sea floor are recycled. In San Nicolas Basin, which has larger oxygen concentrations and lower sedimentation rates than San Pedro, the fluxes of radon (490 ± 16 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.7 ± 0.2 mmol m⁻² d⁻¹), oxygen (−0.7 ± 0.1 mmol m⁻² d⁻¹) and nitrate (-0.4 ± 0.1 mmol m⁻² d⁻¹) determined from chamber measurements agree with the water column estimates given the uncertainty of the measurements and model estimates. Diffusion from the sediments matches the lander-measured SiO₂ and PO₄³⁻ (0.017 ± 0.002 mmol m⁻² d⁻¹) fluxes, but is not sufficient to supply the radon or TCO₂ fluxes observed with the lander. In San Nicolas Basin 38 ± 9% of the organic carbon and 43 ± 22% of the CaCO₃ are recycled. Approximately 90% of the biogenic silica arriving at the sea floor in each basin is recycled. The rates of CaCO₃ dissolution determined from chamber flux measurements and material balances for protons and electrons are compared to those predicted by previously published models of CaCO₃ dissolution and this comparison indicates that in situ rates are comparable to those observed in laboratory studies of bulk sediments, but orders of magnitude less than those observed in experiments done with suspended sediments.     

Ra and Th adsorption coefficients in lakes—Lake Kinneret (Sea of Galilee) “natural experiment”

The adsorption rate constants of Ra and Th were estimated from empirical data from a freshwater lake and its feeding saline springs. We utilized the unique setting of Lake Kinneret (Sea of Galilee, northern Israel) in which most of the Ra and Th nuclides are introduced into the lake by saline springs with high ²²⁶Ra activities and a high ²²⁴Ra/²²⁸Ra ratio of 1.5. The mixing of the Ra enriched saline waters and freshwater in the lake causes the ²²⁴Ra/²²⁸Ra ratio to drop down to 0.1 in the Kinneret due to preferential adsorption of ²²⁸Th. These conditions constitute a “natural experiment” for estimating adsorption rates. We developed a simple mass-balance model for the radionuclides in Lake Kinneret that accurately predicted the Ra isotope ratios and the ²²⁶Ra activity in the lake. The model is comprised of simultaneous equations; one for each radionuclide. The equations have one input term: supply of radionuclides from the saline springs; and three output terms: adsorption on particles in the lake, radioactive decay and outflow from the lake. The redundancy in the analytical solutions to the mass balance equations for the relevant nuclides constrained the values of Ra and Th adsorption rate constants to a very narrow range. Our results indicate that the adsorption rate constant for Ra is between 0.005 d⁻¹ and 0.02 d⁻¹. The rate constant for Th is between 0.5 d⁻¹ and 1 d⁻¹, about fifty to a hundred times higher. The estimated desorption rate coefficient for Ra is about 50-100 times larger than its adsorption rate constant. The mass-balance equations show that the residence times of all Ra isotopes (²²⁶Ra, ²²⁸Ra,²²³Ra, ²²⁴Ra) and of ²²⁸Th in the lake are about 95, 92, 14, 6 and 1 d, respectively. These residence times are much shorter than the residence time of water in the lake (about 5.5 y). The steady state activity ratios in Lake Kinneret depend mainly on the adsorption rate constants, decay constants, the outflow rate from the lake and the activity ratios in the saline springs. The activity ratios are independent of the saline springs flow rate.     

Impact of nitrogen fertilizers on the natural weathering-erosion processes and fluvial transport in the Garonne basin

Knowledge of the impact of N-fertilizers on the weathering-erosion processes of soils in intensively cultivated regions is of prime importance. Nitrification of NH₄⁻ fertilizers produces HNO₃ in the basin of the Garonne river, enhancing soil degradation. Their influence on the weathering rates was determined by calculating the consumption rate of atmospheric/soil CO₂ by soil weathering and erosion, and its contribution to the total dissolved riverine HCO₃⁻. This contribution was found to be less than 50% which corresponds normally to a complete carbonate dissolution by carbonic acid, suggesting that part of the alkalinity in the river waters is due to carbonate dissolution by an acid other than carbonic acid, probably HNO₃.     

Hydrogeochemistry of arsenic and other inorganic constituents in groundwaters from La Pampa,Argentina

Groundwaters from Quaternary loess aquifers in northern La Pampa Province of central Argentina have significant quality problems due to high concentrations of potentially harmful elements such as As, F, NO₃-N, B, Mo, Se and U and high salinity. The extent of the problems is not well-defined, but is believed to cover large parts of the Argentine Chaco-Pampean Plain, over an area of perhaps 10⁶ km². Groundwaters from La Pampa have a very large range of chemical compositions and spatial variability is considerable over distances of a few km. Dissolved As spans over 4 orders of magnitude (<4–5300 μg l⁻¹) and concentrations of F have a range of 0.03–29 mg l⁻¹, B of 0.5–14 mg l^−l, V of 0.02–5.4 mg l⁻¹, NO₃–N of <0.2–140 mg l⁻¹, Mo of 2.7–990 μg l⁻¹ and U of 6.2–250 μg l⁻¹. Of the groundwaters investigated, 95% exceed 10 μg As l⁻¹ (the WHO guideline value) and 73% exceed 50 μg As l⁻¹ (the Argentine national standard). In addition, 83% exceed the WHO guideline value for F (1.5 mg l⁻¹), 99% for B (0.5 mg l⁻¹), 47% for NO₃-N (11.3 mg l⁻¹), 39% for Mo (70 μg l⁻¹), 32% for Se (10 μg l⁻¹) and 100% for U (2 μg l⁻¹). Total dissolved solids range between 730 and 11400 mg l⁻¹, the high values resulting mainly from evaporation under ambient semi-arid climatic conditions. The groundwaters are universally oxidising with high dissolved-O₂ concentrations. Groundwater pHs are neutral to alkaline (7.0–8.7). Arsenic is present in solution predominantly as As(V). Groundwater As correlates positively with pH, alkalinity (HCO₃), F and V. Weaker correlations are also observed with B, Mo, U and Be. Desorption of these elements from metal oxides, especially Fe and Mn oxides under the high-pH conditions is considered an important control on their mobilisation. Mutual competition between these elements for sorption sites on oxide minerals may also have enhanced their mobility. Weathering of primary silicate minerals and accessory minerals such as apatite in the loess and incorporated volcanic ash may also have contributed a proportion of the dissolved As and other trace elements. Concentrations of As and other anions and oxyanions appear to be particularly high in groundwaters close to low-lying depressions which act as localised groundwater-discharge zones. Concentrations up to 7500 μg l⁻¹ were found in saturated-zone porewaters extracted from a cored borehole adjacent to one such depression. Concentrations are also relatively high where groundwater is abstracted from close to the water table, presumably because this zone is a location of more active weathering reactions. The development of groundwaters with high pH and alkalinity results from silicate and carbonate reactions, facilitated by the arid climatic conditions. These factors, together with the young age of the loess sediments and slow groundwater flow have enabled the accumulation of the high concentrations of As and other elements in solution without significant opportunity for flushing of the aquifer to enable their removal.     

Comparison of the acid-base behaviour and metal adsorption characteristics of a gram-negative bacterium with other strains

Thermodynamic parameters for proton and metal adsorption onto a gram-negative bacterium from the genus Enterobacteriaceae have been determined and compared with parameters for other strains of bacteria. Potentiometric titrations were used to determine the different types of sites present on bacterial cell walls. Stability constants for adsorption of Pb, Cu and Zn to specific sites were determined from batch adsorption experiments at varying pH with constant metal concentration. Titrations revealed 3 distinct acidic surface sites on the bacterial surface, with pK values of 4.3±0.2, 6.9±0.5 and 8.9±0.5, corresponding to carboxyl, phosphate and hydroxyl/amine groups, with surface densities of 5.0±0.7×10⁻⁴, 2.2±0.6×10⁻⁴ and 5.5±2.2×10⁻⁴ mol/g of dry bacteria. Only carboxyl and phosphate sites are involved in metal uptake, yielding the following intrinsic stability constants: Log K_carboxyl: Zn=3.3±0.1, Pb=3.9±0.8, and Cu=4.4±0.2, Log K_phosphoryl: Zn=5.1±0.1 and Pb=5.0±0.9. The deprotonation constants are similar to those of other strains of bacteria, while site densities are also within an order of magnitude of other strains. The similarities in surface chemistry and metal stability constants suggest that bacteria may be represented by a simple generic thermodynamic model for the purposes of modelling metal transport in natural environments. Comparison with oxide-coated sand shows that bacteria can attenuate some metals to much lower pH values.     

Temperature and pH controls over isotopic fractionation during adsorption of boron on marine clay

The variation of adsorption constants and isotope fractionation with pH and temperature during the adsorption of B from seawater onto marine clay have been examined. The controls over adsorption are similar to those exhibited by pure clay minerals (Bassett, 1976; Keren and Mezuman, 1981). The isotope fractionations are the result of equilibrium processes, not kinetic effects. Variations in the measured fractionation factor with pH arise from the differences between the isotope fractionation associated with adsorption of B(OH)₃ and B(OH)₄⁻ and the pH dependence of B speciation. The implications of these results for the distribution of B isotopes in seawater and sediment porewaters are briefly discussed.     

Combined effects of water pH and alkalinity on the accumulation of lead, cadmium and chromium to Labeo rohita (Hamilton)

Influence of pH (5.5, 7.0 and 8.5) and alkalinity (40 to 200 mg/L as CaCO₃) on the accumulation of Pb (NO₃)₂ CdCl₂, H₂O and K₂Cr₂O₇ to Labeo rohita (Hamilton) was investigated in the laboratory. Highest accumulation of Pb and Cr in whole fish occurred at pH 5.5 and at alkalinity level of 40 to 46 mg/L as CaCO₃ compared to 7.0 and 8.5. In case of Cd maximum accumulation occurred at pH 7.0 and at alkalinity of 100 mg/L as CaCO₃ than that of pH 5.5 and 8.5 and alkalinity 42 and 156 mg/L as CaCO₃. Maximum accumulation of lead and chromium occurred at total alkalinity level of 40 and 46 mg/L as CaCO₃, respectively while maximum accumulation of cadmium occurred at an alkalinity level of 200 mg/L as CaCO₃. A significant (p<0.05) linear relationship was demonstrated between increasing pH/ alkalinity and decreasing accumulation in Pb and Cr treatment at all exposure period while for Cd there was no significant linear relationship established.     

Adsorption of zinc on colloidal (hydr)oxides of Si,Al and Fe in the presence of a fulvic acid

The adsorption of Zn (total concentration 10⁻⁶ M) to colloidal quartz, hydrargillite and goethite (50, 300 and 70 mg/l, respectively) was studied by a batch technique at a constant ionic strength (0.01 M) but with variation of pH (3–10) and fulvic acid (FA) concentration (0, 2 or 20 mg/l). The adsorption had similar pH-dependence in all systems in the absence of FA giving a pH₅₀ (pH of 50% adsorption) of 7.6 under these conditions. The presence of the FA reduced the overall adsorption to quartz (pH₅₀ of 7.9 at 2 mg FA/I and 9.3 at 20 mg/1) and shifted the adsorption curves downwards (pH₅₀ of 6.8) in the hydrargillite and goethite systems at 2 mg FA/l. At 20 mg FA/l, the adsorption in the two latter systems was increased at pH <6.5 and reduced at pH >6.5. The results reflect the affinity of the surfaces for FA as well as the formation of Zn–FA complexes (in solution and on solid surfaces).     

Sorption of Np(V) and Np(IV) onto kaolinite: Effects of pH,ionic strength,carbonate and humic acid

The sorption of Np(V) and Np(IV) onto kaolinite has been studied in the absence and presence of humic acid (HA) in a series of batch equilibrium experiments under different experimental conditions: [Np]₀: 1.0 × 10^-6 or 1.0 × 10^-5 M, [HA]₀: 0 or 50 mg/L, I: 0.01 or 0.1 M NaClO₄, solid to liquid ratio: 4 g/L, pH: 6–11, anaerobic or aerobic conditions, without or with carbonate. The results showed that the Np(V) sorption onto kaolinite is affected by solution pH, ionic strength, Np concentration, presence of carbonate and HA. In the absence of carbonate, the Np(V) uptake increased with pH up to ∼96% at pH 11. HA further increased the Np(V) sorption between pH 6 and 9 but decreased the Np(V) sorption between pH 9 and 11. In the presence of carbonate, the Np(V) sorption increased with pH and reached a maximum of 54% between pH 8.5 and 9. At higher pH values, the Np(V) sorption decreased due to the presence of dissolved neptunyl carbonate species with a higher negative charge that were not sorbed onto the kaolinite surface which is negatively charged in this pH range. HA again decreased the Np(V) uptake in the near-neutral to alkaline pH range due to formation of aqueous neptunyl humate complexes. The decrease of the initial Np(V) concentration from 1.0 × 10⁻⁵ M to 1.0 × 10⁻⁶ M led to a shift of the Np(V) adsorption edge to lower pH values. A higher ionic strength increased the Np(V) uptake onto kaolinite in the presence of carbonate but had no effect on Np(V) uptake in the absence of carbonate.     

西藏纳木错沉积物单水方解石出现前后的环境变化

2005年在西藏纳木错水下60m处钻取一支332cm的湖芯,沉积物皆为灰黑-黑色碳酸盐粘土。对湖芯1cm间隔取样并进行X射线、扫描电镜、Sr/Ca和碳酸盐含量的分析。研究发现,纳木错湖底0～258cm沉积物中出现了单水方解石,扫描电镜下该矿物晶形完好,这是个亚稳定矿物,具有重要环境意义。利用碳酸盐含量（24.12%～54.52%）、Sr/Ca比值（<0.006）、方解石中Mg含量（MgCO₃mol%<3.325%）、石膏、粘土矿物（伊利石和镁绿泥石）、单水方解石成因和沉积速率讨论了单水方解石形成前后湖泊环境的变化。2.1cal.kaB.P.单水方解石开始出现,此时纳木错湖水性质推断为pH>8.6,mol Mg/Ca>6.5,Ca²⁺和SO^2-₄离子浓度足以沉淀少量石膏,演化至现代,表层湖水性质为pH=9.4,mol Mg/Ca=10.03～15.03,SO^2-₄浓度较高,Ca²⁺含量低,不足以沉淀石膏。单水方解石出现之前的3.0～2.1cal.kaB.P.时期,沉积速率低（0.134mm/a）,蒸发作用强度不稳定,湖水温度低,矿化度呈上升趋势。该矿物出现后的2.1～1.7cal.kaB.P.时期,沉积速率快（1.639mm/a）,矿化度稳定,气温低,1.8cal.kaB.P.温度达到最低值,为气候冷事件的表现。较快的沉积速率（>1.168mm/a）是纳木错单水方解石形成的重要原因之一,碳酸盐沉积加快和入湖碎屑物质增加是沉积速率加快的主要原因。     

Modeling transport of arsenic through modified granular natural siderite filters for arsenic removal

Groundwater arsenic(As)contamination is a hot issue,which is severe health concern worldwide.Recently,many Fe-based adsorbents have been used for As removal from solutions.Modified granular natural siderite(MGNS),a special hybrid Fe(II)/Fe(III)system,had higher adsorption capacity for As(III)than As(V),but the feasibility of its application in treating high-As groundwater is still unclear.In combination with transport modeling,laboratory column studies and field pilot tests were performed to reveal both mechanisms and factors controlling As removal by MGNS-filled filters.Results show that weakly acid pH and discontinuous treatment enhanced As(Ⅲ)removal,with a throughput of 8700 bed volumes(BV)of 1.0 mg/L As(Ⅲ)water at breakthrough of 10 μg/L As at pH 6.Influent HCO_3~-inhibited As removal by the filters.Iron mineral species,SEM and XRD patterns of As-loading MGNS show that the important process contributing to high As(Ⅲ)removal was the mineral transformation from siderite to goethite in the filter.The homogeneous surface diffusion modeling(HSDM)shows that competition between As(III)and HCO_3~-with adsorption sites on MGNS was negligible.The inhibition of HCO_3~-on As(Ⅲ)removal was connected to inhibition of siderite dissolution and mineral transformation.Arsenic loadings were lower in field pilot tests than those in the laboratory experiments,showing that high concentrations of coexisting anions(especially HCO_3~-and SiO_4~(4-)),high pH,low EBCT,and low groundwater temperature decreased As removal.It was suggested that acidification and aeration of highAs groundwater and discontinuous treatment would improve the MGNS filter performance of As removal from real high-As groundwater.     

Influence of microbial hydroxamate siderophores on Pb(II) desorption from α-FeOOH

Siderophores are low-molecular weight organic molecules secreted by plants and micro-organisms in response to Fe stress. With stability constants commonly exceeding 10³⁰, siderophores are considered to have higher affinities for Fe(III) than for any other major or trace element dissolved in soil solution. However, several siderophores have affinities for trace metals that approach those for Fe(III), and certain actinides form siderophore complexes of surprisingly high stability. The purpose of this study was to examine the role of hydroxamate siderophores in controlling Pb sorption to an Fe(III) oxide adsorbent. Goethite [α-FeOOH], prepared by standard methods and identified by X-ray diffraction, gave a specific surface of 36 m² g⁻¹ as determined by N₂ multipoint BET analysis. Adsorption experiments were performed aseptically using a batch method with a goethite concentration of 1.0 g l⁻¹ and an ionic strength of 0.01 M NaClO₄. Soluble Pb and Fe were measured between pH 3 and 8 by first adding Pb (10 μM) and then siderophore (10, 20, or 40 μM) to the goethite suspension. Three hydroxamate siderophores were employed: desferrioxamine B (DFB), ferrichrome (FC), and rhodotorulic acid (RA). Following 20 h reaction, Pb and Fe in solution were measured by ICP–MS and ICP–AES, respectively. The efficacy of siderophore-mediated Pb desorption varied with siderophore type and generally increased with pH and siderophore/Pb molar ratio. Desferrioxamine B, at pH 6.5 and a DFB/Pb molar ratio of 4, solubilised nearly 25% of the total sorbed Pb. In the presence of 10 μM FC, Pb adsorption largely mimicked that for the siderophore-free system, whereas significant amounts of Pb were desorbed with 20 μM FC at pH >5.5. The dihydroxamate siderophore, RA, was the least effective Pb chelator, requiring 20 μM to desorb detectable amounts of Pb.