Bismuth(III) Forms Exceptionally Strong Complexes with Natural Organic Matter.

The use of bismuth in the society has steadily increased during the last decades, both as a substitute for lead in hunting ammunition and various metallurgical applications, as well as in a range of consumer products. At the same time, the environmental behavior of bismuth is largely unknown. Here, the binding of bismuth(III) to organic soil material was investigated using extended X-ray absorption spectroscopy (EXAFS) and batch experiments. Moreover, the capacity of suwannee river fulvic acid (SRFA) to enhance the solubility of metallic bismuth was studied in a long-term (2 years) equilibration experiment. Bismuth(III) formed exceptionally strong complexes with the organic soil material, where >99% of the added bismuth(III) was bound by the solid phase, even at pH 1.2. EXAFS data suggest that bismuth(III) was bound to soil organic matter as a dimeric Bi3+ complex where one carboxylate bridges two Bi3+ ions, resulting in a unique structural stability. The strong binding to natural organic matter was verified for SRFA, dissolving 16.5 mmol Bi per gram carbon, which largely exceeds the carboxylic acid group density of this compound. Our study shows that bismuth(III) will most likely be associated with natural organic matter in soils, sediments, and waters.

The Adsorption of Per- and Polyfluoroalkyl Substances (PFASs) onto Ferrihydrite Is Governed by Surface Charge.

An improved quantitative and qualitative understanding of the interaction of per- and polyfluoroalkyl substances (PFASs) and short-range ordered Fe (hydr)oxides is crucial for environmental risk assessment in environments low in natural organic matter. Here, we present data on the pH-dependent sorption behavior of 12 PFASs onto ferrihydrite. The nature of the binding mechanisms was investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and by phosphate competition experiments. Sulfur K-edge XANES spectroscopy showed that the sulfur atom of the head group of the sulfonated PFASs retained an oxidation state of +V after adsorption. Furthermore, the XANES spectra did not indicate any involvement of inner-sphere surface complexes in the sorption process. Adsorption was inversely related to pH (p < 0.05) for all PFASs (i.e., C3-C5 and C7-C9 perfluorocarboxylates, C4, C6, and C8 perfluorosulfonates, perfluorooctane sulfonamide, and 6:2 and 8:2 fluorotelomer sulfonates). This was attributed to the pH-dependent charge of the ferrihydrite surface, as reflected in the decrease of surface ζ-potential with increasing pH. The importance of surface charge for PFAS adsorption was further corroborated by the observation that the adsorption of PFASs decreased upon phosphate adsorption in a way that was consistent with the decrease in ferrihydrite ζ-potential. The results show that ferrihydrite can be an important sorbent for PFASs with six or more perfluorinated carbons in acid environments (pH ≤ 5), particularly when phosphate and other competitors are present in relatively low concentrations.

Anaerobic Respiration in the Unsaturated Zone of Agricultural Soil Mobilizes Phosphorus and Manganese.

Anaerobic conditions mobilize phosphorus (P) in soils and sediments. The role of anaerobic microsites in well-drained soil on P migration is unknown. This study aimed to identify mechanisms that control field-scale vertical P mobility as affected by organic fertilizers that may trigger variable redox conditions. Soils were sampled at different depths in a well-drained Luvisol after 19 years of application of organic fertilizers. The concentrations of P and manganese (Mn) in 0.45-µm-filtered extracts (10-3 M CaCl2) of field-moist soil samples were strongly correlated (r = + 0.95), and both peaked in and below the compacted plough pan, suggesting that reductive processes mobilize P. Waterlogged soil incubations confirmed that anaerobic respiration comobilizes Mn and P and that this leads to the release of colloidal P and iron (Fe). The long-term applications of farmyard manure and immature compost enhanced the concentrations of Mn, Fe, and aluminum (Al) in the soil solution of subsurface samples, whereas less such effect was found under the application of more stable organic fertilizers. Farmyard manure application significantly enhanced soil P stocks below the plough layer despite a small P input. Overall, multiple lines of evidence confirm that anaerobic respiration, sparked by labile organic matter, mobilizes P in this seemingly well-drained soil.

Complexation of Arsenite, Arsenate, and Monothioarsenate with Oxygen-Containing Functional Groups of Natural Organic Matter: An XAS Study.

Arsenic (As) is reported to be effectively sorbed onto natural organic matter (NOM) via thiol coordination and polyvalent metal cation-bridged ternary complexation. However, the extent of sorption via complexation with oxygen-containing functional groups of NOM is poorly understood. By equilibrating arsenite, arsenate, and monothioarsenate with purified model-peat, followed by As K-edge X-ray absorption spectroscopic analysis, this study shows that complexation with oxygen-containing functional groups can be an additional or alternative mode of As sorption to NOM. The extent of complexation was highest for arsenite, followed by monothioarsenate and arsenate. Complexation was higher at pH 7.0 compared to 4.5 for arsenite and arsenate and vice versa for monothioarsenate because of partial transformation to arsenite at pH 4.5. Modeling of the As K-edge extended X-ray absorption fine structure data revealed that As···C interatomic distances were relatively longer in arsenate- (2.83 ± 0.01 Å) and monothioarsenate-treated peat (2.80 ± 0.02 Å) compared to arsenite treatments (2.73 ± 0.01 Å). This study suggests that arsenite was predominantly complexed with carboxylic groups, whereas arsenate and monothioarsenate were complexed with alcoholic groups of the peat. This study further implies that in systems, where NOM is the major sorbent, arsenate and monothioarsenate can have higher mobility than arsenite.

Copper Mobilization and Immobilization along an Organic Matter and Redox Gradient-Insights from a Mofette Site.

Mofettes (natural geogenic CO2 exhalations) represent excellent sites to study the behavior of Cu in soils and the co-occurrence of different mobilization and immobilization processes since they exhibit both a gradient in redox conditions (oxic to permanently anoxic) and in soil organic matter (SOM; low to high contents). Soil and pore water samples from an 18 m-transect over a mofette showed a complex behavior of Cu, with highest mobility in the transition between oxic and anoxic conditions. Cu(II) sorption experiments on SOM-rich topsoil revealed that Cu mobility under oxic conditions was confined by adsorption to SOM while in the oxygen-free mofette center reduction and precipitation of sulfides was the dominating Cu-sequestering process. In transition areas with low amounts of oxygen (<10%), there was no mineral precipitation, instead high dissolved-to-soil organic carbon ratios strongly increased Cu mobility. Our results show that low stability of SOM formed under oxygen-limited conditions leads to increased Cu mobility unless sulfur-reducing conditions cause Cu sequestration by sulfide precipitation. The interplay of these (im)mobilization processes and especially the unexpectedly high mobility under suboxic conditions have to be considered when assessing Cu mobility along spatial or temporal redox gradients, e.g., at contamination sites or periodically flooded soils.

Monothioarsenate Transformation Kinetics Determining Arsenic Sequestration by Sulfhydryl Groups of Peat.

In peatlands, arsenite was reported to be effectively sequestered by sulfhydryl groups of natural organic matter. To which extent porewater arsenite can react with reduced sulfur to form thioarsenates and how this affects arsenic sequestration in peatlands is unknown. Here, we show that, in the naturally arsenic-enriched peatland Gola di Lago, Switzerland, up to 93% of all arsenic species in surface and porewaters were thioarsenates. The dominant species, monothioarsenate, likely formed from arsenite and zerovalent sulfur-containing species. Laboratory incubations with sulfide-reacted, purified model peat showed increasing total arsenic sorption with decreasing pH from 8.5 to 4.5 for both, monothioarsenate and arsenite. However, X-ray absorption spectroscopy revealed no binding of monothioarsenate via sulfhydryl groups. The sorption observed at pH 4.5 was acid-catalyzed dissociation of monothioarsenate, forming arsenite. The lower the pH and the more sulfhydryl sites, the more arsenite sorbed which in turn shifted equilibrium toward further dissociation of monothioarsenate. At pH 8.5, monothioarsenate was stable over 41 days. In conclusion, arsenic can be effectively sequestered by sulfhydryl groups in anoxic, slightly acidic environments where arsenite is the only arsenic species. At neutral to slightly alkaline pH, monothioarsenate can form and its slow transformation into arsenite and low affinity to sulfhydryl groups suggest that this species is mobile in such environments.

Silver(I) Binding Properties of Organic Soil Materials Are Different from Those of Isolated Humic Substances.

The solubility of silver(I) in many soils is controlled by complexation reactions with organic matter. In this work we have compared the ability of isolated humic and fulvic acids to bind silver(I) with that of mor and peat materials. One new data set for Suwannee River Fulvic Acid was produced, which was consistent with published data sets for isolated fulvic and humic acids. The ability of soil materials to bind silver(I) was studied as a function of pH in the range 2.5-5.0, at a wide range of silver(I)-to-soil ratios (10(-4.2) - 10(-1.9) mol kg(-1)). By calibrating the Stockholm Humic Model on the humic and fulvic acids data sets, we showed that binding of silver(I) to both types of soil materials was much stronger (up to 2 orders of magnitude) than predicted from the silver(I) binding properties of the isolated humic materials. Thus, the approach taken for many other metals, that is, to model solubility in soils by using metal and proton binding parameters derived from isolated humic and fulvic acids, cannot be used for silver(I). One possible explanation for the discrepancy could be that silver(I) predominately interacted with various biomolecules in the soil samples, instead of humic- and fulvic-acid type materials.

Chromium(III) complexation to natural organic matter: mechanisms and modeling.

Chromium is a common soil contaminant, and it often exists as chromium(III). However, limited information exists on the coordination chemistry and stability of chromium(III) complexes with natural organic matter (NOM). Here, the complexation of chromium(III) to mor layer material and to Suwannee River Fulvic Acid (SRFA) was investigated using EXAFS spectroscopy and batch experiments. The EXAFS results showed a predominance of monomeric chromium(III)-NOM complexes at low pH (<5), in which only Cr···C and Cr-O-C interactions were observed in the second coordination shell. At pH > 5 there were polynuclear chromium(III)-NOM complexes with Cr···Cr interactions at 2.98 Å and for SRFA also at 3.57 Å, indicating the presence of dimers (soil) and tetramers (SRFA). The complexation of chromium(III) to NOM was intermediate between that of iron(III) and aluminum(III). Chromium(III) complexation was slow at pH < 4: three months or longer were required to reach equilibrium. The results were used to constrain chromium-NOM complexation in the Stockholm Humic Model (SHM): a monomeric complex dominated at pH < 5, whereas a dimeric complex dominated at higher pH. The optimized constant for the monomeric chromium(III) complex was in between those of the iron(III) and aluminum(III) NOM complexes. Our study suggests that chromium(III)-NOM complexes are important for chromium speciation in many environments.

Effect of pH, surface charge and soil properties on the solid-solution partitioning of perfluoroalkyl substances (PFASs) in a wide range of temperate soils.

The pH-dependent soil-water partitioning of six perfluoroalkyl substances (PFASs) of environmental concern (PFOA, PFDA, PFUnDA, PFHxS, PFOS and FOSA), was investigated for 11 temperate mineral soils and related to soil properties such as organic carbon content (0.2-3%), concentrations of Fe and Al (hydr)oxides, and texture. PFAS sorption was positively related to the perfluorocarbon chain length of the molecule, and inversely related to solution pH for all substances. The negative slope between log Kd and pH became steeper with increasing perfluorocarbon chain length of the PFAS (r2 = 0.75, p ≤ 0.05). Organic carbon (OC) alone was a poor predictor of the partitioning for all PFASs, except for FOSA (r2 = 0.71), and the OC-normalized PFAS partitioning, as derived from organic soil materials, underestimated PFAS sorption to the soils. Multiple linear regression suggested sorption contributions (p ≤ 0.05) from OC for perfluorooctane sulfonate (PFOS) and FOSA, and Fe/Al (hydr)oxides for PFOS, FOSA, and perfluorodecanoate (PFDA). FOSA was the only substance under study for which there was a statistically significant correlation between its binding and soil texture (silt + clay). To predict PFAS sorption, the surface net charge of the soil organic matter fraction of all soils was calculated using the Stockholm Humic Model. When calibrated against charge-dependent PFAS sorption to a peat (Oe) material, the derived model significantly underestimated the measured Kd values for 10 out of 11 soils. To conclude, additional sorbents, possibly including silicate minerals, contribute to the binding of PFASs in soil. More research is needed to develop geochemical models that can accurately predict PFAS sorption in soils.

Combining a Standardized Batch Test with the Biotic Ligand Model to Predict Copper and Zinc Ecotoxicity in Soils.

Extraction of soil samples with dilute CaCl2 solution in a routinely performed batch test has potential to be used in site-specific assessment of ecotoxicological risks at metal-contaminated sites. Soil extracts could potentially give a measure of the concentration of bioavailable metals in the soil solution, thereby including effects of soil properties and contaminant "aging." We explored the possibility of using a 0.001 M CaCl2 batch test combined with biotic ligand models (BLMs) for assessment of ecotoxicity in soils. Concentrations of Cu2+ and Zn2+ in soil extracts were linked to responses in ecotoxicity tests (microbial processes, plants, and invertebrates) previously performed on metal-spiked soils. The batch test data for soils were obtained by spiking archived soil materials using the same protocol as in the original studies. Effective concentration values based on free metal concentrations in soil extracts were related to pH by linear regressions. Finally, field-contaminated soils were used to validate model performance. Our results indicate a strong pH-dependent toxicity of the free metal ions in the soil extracts, with R2 values ranging from 0.54 to 0.93 (median 0.84), among tests and metals. Using pH-adjusted Cu2+ and Zn2+ concentrations in soil extracts, the toxic responses in spiked soils and field-contaminated soils were similar, indicating a potential for the calibrated models to assess toxic effects in field-contaminated soils, accounting for differences in soil properties and effects of contaminant "aging." Consequently, evaluation of a standardized 0.001 M CaCl2 batch test with a simplified BLM can provide the basis for an easy-to-use tool for site-specific risk assessment of metal toxicity to soil organisms. Environ Toxicol Chem 2022;41:1540-1554. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Binding of per- and polyfluoroalkyl substances (PFASs) by organic soil materials with different structural composition - Charge- and concentration-dependent sorption behavior.

The charge- and concentration-dependent sorption behavior of a range of per- and polyfluoroalkyl substances (PFASs) was studied for three organic soil samples with different organic matter quality, one Spodosol Oe horizon (Mor Oe) and two Sphagnum peats with different degrees of decomposition (Peat Oi and Peat Oe). Sorption to the two peat materials was, on average, four times stronger compared to that onto the Mor Oe material. In particular, longer-chained PFASs were more strongly bound by the two peats as compared to the Mor Oe sample. The combined results of batch sorption experiments and 13C NMR spectroscopy suggested sorption to be positively related to the content of carbohydrates (i.e., O-alkyl carbon). Sorption of all PFAS subclasses was inversely related to the pH value in all soils, with the largest pH effects being observed for perfluoroalkyl carboxylates (PFCAs) with C10 and C11 perfluorocarbon chain lengths. Experimentally determined sorption isotherms onto the poorly humified Peat Oi did not deviate significantly from linearity for most substances, while for the Mor Oe horizon, sorption nonlinearity was generally more pronounced. This work should prove useful in assessing PFAS sorption and leaching in organic soil horizons within environmental risk assessment.

Micro and nano sized particles in leachates from agricultural soils: Phosphorus and sulfur speciation by X-ray micro-spectroscopy.

Colloids and nanoparticles leached from agricultural land are major carriers of potentially bioavailable nutrients with high mobility in the environment. Despite significant research efforts, accurate knowledge of macronutrients in colloids and nanoparticles is limited. We used multi-elemental synchrotron X-ray fluorescence (XRF) microscopy with multivariate spatial analysis and X-ray atomic absorption near-edge structure (XANES) spectroscopy at the P and S K-edges, to study the speciation of P and S in two fractions of leached particles, >0.45 and <0.45 µm respectively, collected from four tile-drained agricultural sites in Sweden. P K-edge XANES showed that organic P, followed by P adsorbed to surfaces of aluminum-bearing particles were the most common forms of leached P. Iron-bound P (Fe-P) forms were generally less abundant (0-30 % of the total P). S K-edge XANES showed that S was predominantly organic, and a relatively high abundance of reduced S species suggests that redox conditions were adverse to the persistence of P bound to Fe-bearing colloids in the leachates. Acid ammonium-oxalate extractions suggested that P associated with Al and Fe (Al-P and Fe-P) in most cases could be explained by the adsorption capacity of non-crystalline (oxalate-extractable) oxides of Al and Fe. These results improve our understanding of particulate P and S speciation in the vadose zone and helps in developing effective technologies for mitigating colloidal driven eutrophication of water bodies near agricultural land.

Chemical equilibrium modeling of organic acids, pH, aluminum, and iron in Swedish surface waters.

A consistent chemical equilibrium model that calculates pH from charge balance constraints and aluminum and iron speciation in the presence of natural organic matter is presented. The model requires input data for total aluminum, iron, organic carbon, fluoride, sulfate, and charge balance ANC. The model is calibrated to pH measurements (n = 322) by adjusting the fraction of active organic matter only, which results in an error of pH prediction on average below 0.2 pH units. The small systematic discrepancy between the analytical results for the monomeric aluminum fractionation and the model results is corrected for separately for two different fractionation techniques (n = 499) and validated on a large number (n = 3419) of geographically widely spread samples all over Sweden. The resulting average error for inorganic monomeric aluminum is around 1 µM. In its present form the model is the first internally consistent modeling approach for Sweden and may now be used as a tool for environmental quality management. Soil gibbsite with a log *Ks of 8.29 at 25°C together with a pH dependent loading function that uses molar Al/C ratios describes the amount of aluminum in solution in the presence of organic matter if the pH is roughly above 6.0.

Phosphate competition with arsenate on poorly crystalline iron and aluminum (hydr)oxide mixtures.

Phosphate competes with arsenate for sorption sites on poorly crystalline iron and aluminum (hydr)oxides. The competition has implications e.g. for the management of arsenic-contaminated soil and water. Phosphate competition with arsenate on mixed phases containing both iron and aluminum (hydr)oxides has rarely been investigated. Here, the phosphate competition with arsenate on mixtures of poorly crystalline aluminum hydroxide (Alhox) and ferrihydrite (Fh), was investigated in batch experiments at pH 6.5. X-ray absorption spectroscopy (XAS) was performed on the phosphorus and arsenic K edges, which offered a unique insight in the partitioning of arsenate and phosphate on mixed Alhox-Fh sorbents. Under the studied conditions the sorption capacity of the mixed sorbents (per mol Al or Fe) increased at higher Alhox to Fh ratios. The XAS measurements provided direct evidence that phosphate competed more effectively with arsenate for sorption sites on Alhox than on Fh. For example, in a mixture with 50% of both sorbents and with similar additions of arsenate and phosphate, 71% of the oxyanions adsorbed on Fh and 46% on Alhox were arsenate. Consequently, phosphate may mobilize arsenate more easily from mixed iron-aluminum matrices that are rich in aluminum.

Hydrogeochemical controls on the mobility of arsenic, fluoride and other geogenic co-contaminants in the shallow aquifers of northeastern La Pampa Province in Argentina.

Elevated Arsenic (As) and Fluoride (F) concentrations in groundwater have been studied in the shallow aquifers of northeastern of La Pampa province, in the Chaco-Pampean plain, Argentina. The source of As and co-contaminants is mainly geogenic, from the weathering of volcanic ash and loess (rhyolitic glass) that erupted from the Andean volcanic range. In this study we have assessed the groundwater quality in two semi-arid areas of La Pampa. We have also identified the spatial distribution of As and co-contaminants in groundwater and determined the major factors controlling the mobilization of As in the shallow aquifers. The groundwater samples were circum-neutral to alkaline (7.4 to 9.2), oxidizing (Eh ~0.24 V) and characterized by high salinity (EC = 456-11,400 µS/cm) and Na+-HCO3- water types in recharge areas. Carbonate concretions ("tosca") were abundant in the upper layers of the shallow aquifer. The concentration of total As (5.6 to 535 µg/L) and F (0.5 to 14.2 mg/L) were heterogeneous and exceeded the recommended WHO Guidelines and the Argentine Standards for drinking water. The predominant As species were arsenate As(V) oxyanions, determined by thermodynamic calculations. Arsenic was positively correlated with bicarbonate (HCO3-), fluoride (F), boron (B) and vanadium (V), but negatively correlated with iron (Fe), aluminium (Al), and manganese (Mn), which were present in low concentrations. The highest amount of As in sediments was from the surface of the dry lake. The mechanisms for As mobilization are associated with multiple factors: geochemical reactions, hydrogeological characteristics of the local aquifer and climatic factors. Desorption of As(V) at high pH, and ion competition for adsorption sites are considered the principal mechanisms for As mobilization in the shallow aquifers. In addition, the long-term consumption of the groundwater could pose a threat for the health of the local community and low cost remediation techniques are required to improve the drinking water quality.

Evaluating the ability of standardised leaching tests to predict metal(loid) leaching from intact soil columns using size-based elemental fractionation.

Laboratory-based leaching tests are frequently used for in situ risk assessments of contaminant leaching to groundwater and surface waters. This study evaluated the ability of three standardised leaching tests to assess leaching of lead (Pb), zinc (Zn), arsenic (As) and antimony (Sb) from four intact soil profiles, by considering particulate (0.45-8 µm; percolation test), colloidal (10 kDa-0.45 µm) and truly dissolved (<10 kDa) fractions of these elements. Deionised water was used as the percolation test leachant, while either deionised water or 1 mM CaCl2 was used in batch tests. Data from an irrigation experiment were used as reference. The results indicated that in percolation tests, leachate should be collected at a liquid:solid ratio (L/S) range of 2-10, instead of 0-0.5 or 0.5-2. Even at L/S = 2-10, the percolation test overestimated total Pb concentration, mainly because of greater mobilisation of particle-bound Pb, but appeared suitable for categorising soils into high/low risk with respect to mobilisation of particulate and colloidal contaminants. The batch test performed better with CaCl2 than with deionised water when standard membrane filtration (0.45 µm) was used, as the high Ca2+ concentration reduced colloidal mobilisation, avoiding overestimation of concentrations of elements such as Pb. However, the higher Ca2+ concentration and lower pH could result in overestimated concentrations of weakly sorbed elements, e.g. Zn.

Redox chemistry of vanadium in soils and sediments: Interactions with colloidal materials, mobilization, speciation, and relevant environmental implications- A review.

Vanadium (V), although serving as an important component of industrial activities, has bioinorganic implications to pose highly toxic hazards to humans and animals. Soils and sediments throughout the world exhibit wide ranges of vanadium concentrations. Although vanadium toxicity varies between different species, it is mainly controlled by soil redox potential (EH). Nonetheless, knowledge of the redox geochemistry of vanadium lags in comparison to what is known about other potentially toxic elements (PTEs). In particular, the redox-induced speciation and mobilization of vanadium in soils and sediments and the associated risks to the environment have not been reviewed to date. Therefore, this review aims to address 1) the content and geochemical fate of vanadium in soils and sediments, 2) its redox-induced release dynamics, 3) redox-mediated chemical reactions between vanadium and soil organic and inorganic colloidal materials in soil solution, 4) its speciation in soil solution and soil-sediments, and 5) the use of advanced geochemical and spectroscopic techniques to investigate these complex systems. Vanadium (+5) is the most mobile and toxic form of its species while being the thermodynamically stable valence state in oxic environments, while vanadium (+3) might be expected to be predominant under euxinic (anoxic and sulfidic) conditions. Vanadium can react variably in response to changing soil EH: under anoxic conditions, the mobilization of vanadium can decrease because vanadium (+5) can be reduced to relatively less soluble vanadium (+4) via inorganic reactions such as with H2S and organic matter and by metal-reducing microorganisms. On the other hand, dissolved concentrations of vanadium can increase at low EH in many soils to reveal a similar pattern to that of Fe, which may be due to the reductive dissolution of Fe(hydr)oxides and the release of the associated vanadium. Those differences in vanadium release dynamics might occur as a result of the direct impact of EH on vanadium speciation in soil solution and soil sediments, and/or because of the EH-dependent changes in soil pH, chemistry of (Fe)(hydr)oxides, and complexation with soil organic carbon. Release dynamics of vanadium in soils may also be affected positively by soil pH and the release of aromatic organic compounds. X-ray absorption spectroscopy (XAS) is a powerful tool to investigate the speciation of vanadium present in soil. X-ray absorption near edge structure (XANES) is often used to constrain the average valence state of vanadium in soils and sediments, and in limited cases extended X-ray absorption fine structure (EXAFS) analysis has been used to determine the average molecular coordination environment of vanadium in soil components. In conclusion, this review presents the state of the art about the redox geochemistry of vanadium and thus contributes to a better understanding of the speciation, potential mobilization, and environmental hazards of vanadium in the near-surface environment of uplands, wetlands, and agricultural ecosystems as affected by various colloidal particles. Further research is needed to elucidate the geochemistry and speciation of vanadium in the dissolved, colloidal, and soil sediments phases, including the determination of factors that control the redox geochemistry of vanadium.

Phosphate removal by mineral-based sorbents used in filters for small-scale wastewater treatment.

The mineral-based sorbents Filtra P, Polonite, natural wollastonite and water-cooled blast furnace slag (WCBFS) were studied in terms of their PO(4) removal performance. Results from a long-term column experiment showed that both Filtra P and Polonite removed >95% of PO(4) from the applied synthetic solution, and that the used filter materials had accumulated several (1.9-19) g kg(-1)P. Phosphorus was removed also by natural wollastonite and WCBFS, but these materials were less efficient. Batch experiments on the used materials showed that the solubility PO(4) was considerably larger than the one expected for crystalline Ca phosphates such as hydroxyapatite, and results from investigations with attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) on the Filtra P material showed that the formed P phase was not crystalline. These evidence suggest that a soluble amorphous tricalcium phosphate (ATCP) was formed in the mineral-based sorbents; the apparent solubility constant on dissolution was estimated to log K(s)=-27.94 (+/-0.31) at 21 degrees C. However, since only up to 18% of the accumulated PO(4) was readily dissolved in the experiments, it cannot be excluded that part of the phosphorus had crystallized to slightly less soluble phases. In conclusion, Filtra P and Polonite are two promising mineral-based sorbents for phosphorus removal, and at least part of the accumulated phosphorus is present in a soluble form, readily available to plants.

Modeling of metal binding in tropical Fluvisols and Acrisols treated with biosolids and wastewater.

There is growing concern about the accumulation of metals in tropical agricultural soils. In this study, experimental results from batch studies were used to test whether multi-surface geochemical models could describe metal binding in selected Vietnamese soils. The multi-surface models considered metal binding to iron hydroxides (using the diffuse layer model), organic matter (Stockholm Humic model and NICA-Donnan model), and phyllosilicate clay (Gaines-Thomas equation) as well as complexation to dissolved organic and inorganic ligands in the solution phase. We found that for total dissolved Cd, Cu and Zn the two multi-surface models being tested provided very good model fits for all soils, as evidenced by low root-mean square errors between model predictions and observations. These results suggest that organic matter is an important sorbent for many metals in these soils. However, poor fits were obtained for Cr(III), Mn and Pb for all soils. The study also suggests that the pH is the main factor that controls the solubility of metals in tropical Fluvisols and Acrisols subjected to application of biosolids and wastewater, and that advanced multi-surface models can be used to simulate the binding and release of many trace metals.

Metal sorption to Spodosol Bs horizons: Organic matter complexes predominate.

While metal sorption mechanisms have been studied extensively for soil surface horizons, little information exists for subsoils, for example Spodosol Bs horizons. Here the sorption of cadmium(II), copper(II) and lead(II) to seven Bs horizons from five sites was studied. Extended X-ray absorption fine structure (EXAFS) spectroscopy showed that cadmium(II) and lead(II) were bound as inner-sphere complexes to organic matter. Addition of o-phosphate (to 1 µmol l-1) did not result in any significant enhancement of metal sorption, nor did it influence EXAFS speciation. An assemblage model using the SHM and CD-MUSIC models overestimated metal sorption for six out of seven soil samples. To agree with experimental results, substantial decreases (up to 8-fold) had to be made for the fraction 'active organic matter', fHS, while the point-of-zero charge (PZC) of ferrihydrite had to be increased. The largest decreases of fHS were found for the soils with the lowest ratio of pyrophosphate-to oxalate-extractable Al (Alpyp/Alox), suggesting that in these soils, humic and fulvic acids were to a large extent inaccessible for metal sorption. The low reactivity of ferrihydrite towards lead(II) can be explained by potential spillover effects from co-existing allophane, but other factors such as ferrihydrite crystallisation could not be ruled out. In conclusion, organic matter was the predominant sorbent for cadmium(II), copper(II) and lead(II). However, for lead(II) the optimised model suggests additional, but minor, contributions from Fe (hydr)oxide surface complexes. These results will be important to correctly model metal sorption in spodic materials.