International audience | The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn2+, Soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K-d) for Zn ranged from 17 to 13, 100 L kg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn2+ varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn2+, dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils. (C) 2007 Elsevier Ltd. All rights reserved.

International audience | Mining areas and in particular those containing massive sulfides have left a heavy environmental legacy with soils and hydrographic networks highly contaminated with metals and metalloids as for example in the Iberian Pyrite Belt (Huelva, Spain). Here, we present new data on copper (Cu) isotopic composition of waters and solids collected along a continuum Mine (Tharsis)-River (Meca)-Lake (Sancho) in the Iberian Pyrite Belt. Our results show that the isotopic signature of pit lakes is spatially variable, but remains stable over the seasons; this signature seems to be controlled by water-rock interaction processes. The data obtained on the Meca River imply a number of attenuation processes such as decrease in the metal concentration by precipitation of secondary minerals. This is accompanied by preferential retention of the heavy isotope (Cu-65) with a possibility of living organisms (e.g., algae) participation. The terminal Sancho lake demonstrated constant isotopic signature over the entire depth of the water column despite sizable variations in Cu concentrations, which can be tentatively explained by a superposition of counter-interacting biotic and abiotic processes of Cu fractionation. Overall, the understanding of the isotopic variations along the hydrological continuum is useful for a better understanding of metal element transfer within mining environments and surrounding surface waters.

In this study, a novel approach was employed for the remediation of cationic and anionic metals/metalloids co-contaminated soil by tetrapolyphosphate enhanced soil washing coupled with ferrous sulfide treatment. Tetrapolyphosphate could simultaneously enhance the desorption of cationic metals (Pb and Zn) and anionic metal/metalloid (Cr and As) from the contaminated soil in the whole tested pH range of 2–10. With addition of 0.15 mol/L tetrapolyphosphate at pH 7.0, the removal ratio of Pb, Zn, As and Cr could achieve 83.1%, 70.4%, 75.7% and 66.4% respectively. The fractionation analysis of heavy metals/metalloids demonstrated the release of exchangeable and Fe/Mn bound forms contributed to most desorption of Pb and Zn. The decreases of non-specifically sorbed form and amorphous and poorly-crystalline hydrous oxides of Fe and Al bound form were responsible for most removal of As. The comparison with other common washing agents (EDTA, oxalate and phosphate) under their respective optimal dosage could confirm that tetrapolyphosphate was superior to simultaneously desorb the cationic and anionic metals/metalloids with higher efficiency. After 12 h, applying 150 mg/L FeS at pH 3.5 could totally remove Pb, Zn, As and Cr from the washing effluent by sulfide precipitation, reduction and adsorption processes. Higher pH would inhibit the removal of As and Cr by FeS. Meanwhile, the residual of tetrapolyphosphate could be totally recovered from the washing effluent by employing anion exchange resin. This study suggests tetrapolyphosphate enhanced soil washing coupled with ferrous sulfide treatment is a promising approach for remediation of cationic and anionic metals/metalloids co-contaminated soil in view of its high efficiency and simple operation.

Identifying the bioavailability and release-desorption mechanism of heavy metals (HMs) in soil is critical to understand the release risk of HMs. Simultaneously, the mechanistic investigation of affecting the bioavailability of HMs in soil is necessary, such as the grain-size distribution and soil mineralogy. Herein, the bioavailability of HMs (Cu, Cd, Ni, Pb, and Zn) in different area soils near a typical copper-smelter was evaluated by the sequential extraction technique (BCR), diffusive gradients in thin-films (DGT), and DGT-induced fluxes in sediments (DIFS) model. Results showed that the HMs proportion of the residual fraction in all soils was the highest. The average bioavailability concentration (CDGT) of Cu and Cd in industrial soil was the highest, with 45.12 μg· L⁻¹ and 9.06 μg· L⁻¹. The result of DIFS model revealed that the decreased order of the mean value of desorption rate constant (K₋₁) was Cd > Zn > Ni > Cu > Pb, 5.91 × 10⁻⁵, 4.96 × 10⁻⁵, 2.89 × 10⁻⁵, 9.64 × 10⁻⁶, and 8.69 × 10⁻⁶, respectively. According to the spatial distribution of release potential (R-value), the release potential of labile-Cu in agricultural soil was the highest, which was mainly attributed to fertilizer application in farmland. Simultaneously, the reduced hydroxyl was also related to the agricultural activities, resulting in the weakened adsorption capacity of HMs by soil. Redundancy analysis (RDA) results showed that the bioavailability of Cd, Ni, and Zn was mainly driven by soil pH, while the bioavailability of Cu and Pb was primarily driven by dissolved organic carbon (DOC). Meanwhile, carbonate minerals had a positive correlation with the bioavailability of Cd, Ni, and Zn, which could promote the release of HMs in mining soil as chemical weathering progresses. In conclusion, this study provides a structured method which can be used as a standard approach for similar scenarios to determine the geochemical fractionation, bioavailability, and release kinetics of heavy metals in soils.

Abnormally high concentrations of metals including nickel (Ni) in soils result from high geochemical background (HB) or anthropogenic contamination (AC). Metal bioaccessibility in AC-soils has been extensively explored, but studies in HB-soils are limited. This study examined the Ni bioaccessibility in basalt and black shale derived HB-soils, with AC-soils and soils without contamination (CT) being used for comparison. Although HB- and AC-soils had similar Ni levels (123 ± 43.0 vs 155 ± 84.7 mg kg⁻¹), their Ni bioaccessibility based on the gastric phase of the Solubility Bioaccessibility Research Consortium (SBRC) in vitro assay was different. Nickel bioaccessibility in HB-soils was 6.42 ± 3.78%, 2-times lower than the CT-soils (12.0 ± 9.71%) and 6-times lower than that in AC-soils (42.6 ± 16.3%). Based on the sequential extraction, a much higher residual Ni fractionation in HB-soils than that in CT- and AC-soils was observed (81.9 ± 9.52% vs 68.6 ± 9.46% and 38.7 ± 16.0%). Further, correlation analysis indicate that the available Ni (exchangeable + carbonate-bound + Fe/Mn hydroxide-bound) was highly correlated with Ni bioaccessibility, which was also related to the organic carbon content in soils. The difference in co-localization between Ni and other elements (Fe, Mn and Ca) from high-resolution NanoSIMS analysis provided additional explanation for Ni bioaccessibility. In short, based on the large difference in Ni bioaccessibility in geochemical background and anthropogenic contaminated soils, it is important to base contamination sources for proper risk assessment of Ni-contaminated soils.

The contamination of paddy soils is of great concern since it links to human health via food supply. Limited knowledge is available on PCB residue characteristics and the associated health risks in paddy soils under various environmental conditions. In this study, a soil sampling campaign was conducted in three typical paddy fields, i.e., Sanjiang Plain (SP), Taihu Plain (TP) and Hani Terrace (HT), crossing a transect of 4000 km in China. The concentrations of 29 quantified PCBs varied from 58.6 to 1930 pg/g in paddy soils, with samples at TP showing the highest burden. Tri-CBs were the major homologue group at SP and HT, whereas hexa-CBs at TP. Altitude, temperature, soil organic matter content and soil conductivity well explained the variations in PCB concentrations among sites. The homologue profiles of soil PCBs followed the fractionation theory. In addition, soil conductivity was found to be negatively correlated to low-chlorinated PCBs and positively to high-chlorinated congeners. Furthermore, the toxicities of soil PCBs and the exposure risks through rice intake were estimated. Higher toxicity equivalent quantities and hazard indexes were found at SP than TP and HT, with over one third of the samples displaying health risks. The results of this work highlight the necessity to better understand the occurrence characteristics and the associated health risks of PCBs in soils of rice-growing regions.

Overuse of phosphorus (P) fertilizer and the resulting soil P accumulation in vegetable production increases the risk of P runoff and leaching. However, P transformations under continuous fertilization and their effects on environmental risk are unclear. The current study examined the effects of long-term P fertilizer application on P fractions in different soil layers, and assessed the correlations between P fractions and environmental risks in intensive vegetable production in a subtropical region. A total of 32 fields were studied, including 8 uncultivated fields and 24 fields continuously used for vegetable production for 1–3, 4–9, or 10–15 years. The results showed that excessive P fertilizer input caused soil P surpluses ranging from 204.6 to 252.4 kg ha⁻¹ yr⁻¹. Compared to uncultivated fields, vegetable fields contained higher levels of labile P, moderately labile P, sparingly labile P, and non-labile P. The combined percentage of labile P and moderately labile P increased from 55.2% in fields cultivated for 0–3 year to 65.5% in fields cultivated for 10–15 years. The concentrations of soil P fractions were higher at 0–20 cm soil depth than at 20–40 and 40–60 cm soil depth. Soil available P was positively correlated with all soil P fractions except diluted HCl-Pᵢ or concentrated HCl-Pₒ. Long-term vegetable production increased CaCl₂–P downward movement, which was positively correlated with levels of labile and moderately labile P. The P index indicated a high risk of P losses from the vegetable fields. The P index was on average 3.27-fold higher in the vegetable fields than in uncultivated fields, and was significantly correlated with soil available P and organic and inorganic P fertilizer input. The environmental risk caused by P in vegetable production should be reduced by reducing P fertilizer input so as to maintain soil available P within an optimal range for vegetable production.

Agricultural products from seleniferous areas commonly face problems associated with substantial variation in selenium (Se) concentration, which is mainly caused by the heterogeneity of Se bioavailability in soil. Many studies have assessed the bioavailability of Se and its influencing factors using soil samples treated with exogenous Se. Given the distinctly different characteristics of Se-spiked soils and naturally seleniferous soils, exploring Se bioavailability in naturally seleniferous soils is crucial to the stable production of Se-enriched agricultural products. In this study, we used the classical sequential extraction method to determine the Se fractionation and then applied the diffusive gradients in thin-films (DGT) technique to assess the Se bioavailability in naturally seleniferous soils. The results indicated that soluble and exchangeable Se fractions with high bioavailability accounted for only 0.7% and 5.1% of total Se, respectively. Both soluble and exchangeable Se concentrations were significantly positively correlated with soil pH (r = 0.329 and 0.262, respectively; P < 0.01). Se mainly exists in Fe–Mn oxide-bound, organic matter-bound, and residual Se fractions with low mobility (94.2% of total Se), among which organic matter-bound Se was the predominant fraction (49.5% of total Se). A significant positive correlation was found between total Se and soil organic matter (r = 0.539; P < 0.01). Multiple regression analysis revealed that the DGT-determined Se was mostly derived from soluble and exchangeable Se. The high correlation between the DGT-determined Se fraction and Se uptake by rice (r = 0.91; P < 0.01) confirmed that DGT can accurately assess Se bioavailability in naturally seleniferous soils in Enshi and other similar environmental settings.

Biochar has been widely used in the mitigation of soil potentially toxic metals due to its high efficiency and low cost. Crayfish shell biochar (CSBC) was prepared at 300, 500, and 700 °C (referred to as CS300, CS500, and CS700, respectively) and the performance and mechanism of CSBC for mitigating Pb polluted water and soil was investigated. The results indicated that CSBC prepared at higher temperatures possessed higher pH value and ash content, more abundant pore structure, and higher stability. Pb²⁺ adsorption onto CSBC fitted well with the pseudo second order and intraparticle diffusion models. The maximum adsorption capacity of Pb²⁺ increased with the pyrolysis temperature, being 599.70, 1114.53, and 1166.44 mg·g⁻¹ for CS300, CS500 and CS700, respectively. Compared with the control soil samples, the content of available Pb after applying 0.05%–5% CSBC was reduced by 1.87%–16.48% in acidic soils and 1.00%–11.09% in alkaline soils. Moreover, the fractionation of exchangeable Pb was converted to stable organic matter bound, Fe-Mn oxide bound, and residue fractions. XRD, SEM-EDS, and FTIR analysis showed that ion exchange, complexation, precipitation, and C−π interaction are the dominant interaction mechanisms. Therefore, CSBC can employ as an effective immobilizing agent for the mitigation of Pb contaminated water and soil.

It is highly likely that the toxicity of water accommodated fractions (WAF) will influence marine microalgae, and consequently lead to potential risk for the marine ecological environment. However, it was often neglected whether WAF can influence the transformation of relative compounds in organisms. The metabolism of amino acids (AAs) can be used to track physiological changes in microalgae because amino acids are the basis of proteins and enzymes. In this study, using marine Chlorophyta Platymonas helgolandica as the test organism, the effects of different concentrations of WAF on AA compositions and stable carbon isotope ratios (δ¹³C) of individual AAs of Platymonas helgolandica were investigated. The results showed that the WAF of #180 fuel oil had an obvious suppressing effect on the growth and chlorophyll a content of microalgae. The growth inhibitory rate at 96 h was 80.66% at a WAF concentration of 0.50 mg L⁻¹ compared with the control. Furthermore, seven among the 16 AAs, including alanine, cysteine, proline, aspartic acid, lysine, histidine and tyrosine, had relatively high abundance. Under the glycolysis pathway, the cysteine abundance was higher than control, meaning that the biosynthesized pathway of alanine through cysteine as a precursor could be damaged. Phosphoenolpyruvate (PEP) was an important synthesis precursor of alanine (leucine) and aromatic AA family (Phenylalanine and tyrosine), and played an important role in δ¹³CAAₛ fractionation under the WAF stress. Under the TCA pathway, to protect cell metabolism activities under WAF stress, the δ¹³C value of threonine and proline abundance in microalgae with the increase in WAF stress. Therefore, δ¹³CAAₛ fractionation can be used as a novel method for toxicity evaluation of WAF on future.