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.

As one of the most common ways to get rid of municipal waste, landfill leachate, waste with complicated compositions and high levels of contaminants, has become a significant threat to the world's environment. Here, the impact of sewage sludge (SS) and derived-biochar (SSB) amendments on the immobilization and potential mobility of heavy metals in a contaminated soil-plant system was investigated. The sequential fractionation findings showed that using SS-2%, SSB-2%, and SSBC-1% reduced the potential mobility of heavy metals while increasing the residual fraction in polluted soils. The translocation and bioconcentration factors showed that heavy metals were slightly transferred into shoots from roots and lowered accumulation in roots from contaminated soils. Fourier transform infrared (FTIR) and X-ray photoelectron spectrum (XPS) comprehensive characterization results indicated the significant role of applied amendments for heavy metals transformation from the exchangeable-soluble fractions to the least available form by lowering their mobility to confirm the adsorption-based complexes, which results in the surface adsorption of heavy metals with functional groups. The electron paramagnetic resonance (EPR) results indicated the dominance of reactive oxygen species (ROS) in the intracellular formation of hydroxyl radicals (•OH) in maize plant roots and shoots. ROS (•OH) generation plays a critical influence in the interaction between the physiological processes of plants and heavy metals. Moreover, all the amendments increased maize growth and biomass production. Our study suggests that alone and combined application of SS and SSB have great potential to remediate heavy metals contaminated soil for environmental sustainability.

Aging is an important natural process affecting the physiochemical properties of biochar, while mechanistic understanding of its effect on the adsorbed heavy metals is still lacking. After adsorption of Cd²⁺ and Pb²⁺, biochars produced from wheat straw (WS) and maize straw (MS) at 300 and 500 °C (denoted as WS300, WS500, MS300, and MS500, respectively) were subjected to 60 cycles of wet–dry or freeze–thaw aging. The results showed that simulated aging treatment transformed the Cd²⁺ and Pb²⁺ adsorbed on the low-temperature biochars from the readily and potentially bioavailable fractions into the non-bioavailable one, while the fractionation of Cd²⁺ and Pb²⁺ adsorbed on WS500 and Pb²⁺ on MS500 barely changed. Spectroscopic characterization revealed that simulated aging enhanced the complexation of Cd²⁺ and precipitation of Pb²⁺ on the biochars. These findings suggest that heavy metals could be effectively immobilized on low-temperature biochars amended to contaminated soils in the long term.

Exposure to electronic and electrical waste (e-waste) has been related to a few adverse health effects. In this study, sediment samples from an e-waste recycling town in China were collected, and aryl hydrocarbon receptor (AhR) agonists in the samples were identified using an effect-directed analysis (EDA) strategy. The CBG2.8D cell line reporter gene bioassay was used as a toxicity test, while suspect screening against chemical databases was performed for potential AhR agonist identification where both gas chromatography- and liquid chromatography-high resolution mass spectrometry analyses were run. When the original sample extract showed high AhR-mediated activity, sample fractionation was performed, and fractions exhibiting high bioactivity were chemically analyzed again to reveal the corresponding AhR agonists. In total, 23 AhR agonists were identified, including 14 commonly known ones and 9 new ones. Benzo [k]fluoranthene and 6-nitrochrysene were the dominant AhR agonists, covering 16–71% and 2.7–12%, respectively, of the AhR activation effects measured in the parent extracts. The newly identified AhR-active chemicals combined explained 0.13–0.20% of the parent extracts’ effects, with 7,12-dimethylbenz [a]anthracene and 8,9,11-trimethylbenz [a]anthracene being the major contributors. A diagnostic isomer ratio analysis of polycyclic aromatic hydrocarbons suggested that the major source of AhR agonists identified in these e-waste related sediment samples were probably petroleum product combustion and biomass combustion. In the future, for a more comprehensive AhR agonist investigation, in-house chemical synthesis and purification, and, when necessary, a secondary sample fractionation, would be beneficial.

Electronic waste (e-waste) pollution is of great concern due to the release of hazardous chemicals during the improper e-waste disposal. Many chemicals leached from e-waste were reported to pose estrogenic effects. To date, little is known regarding the occurrence and biological effects of estrogenic chemicals in sediments near an e-waste area. In this study, an effect-directed analysis (EDA) is applied to determine the estrogenic chemicals in sediments of four sites collected from a typical e-waste recycling city in China. Following screening with the ER-CALUX assay, the extract of sample with the most potent effect was subjected in fractionation using reverse phase liquid chromatography. Based on a target analysis for the active fractions, four compounds, including estrone, 17β-estradiol, 17α-ethinylestradiol and bisphenol A, were identified, and these contributed to 17% of the total toxic effects in the sample. A further nontarget analysis screened four candidates, namely diethylstilbestrol (DES), hexestrol (HES), nandrolone and durabolin, and the total contribution was found to be 48% from the active sample. Specifically, DES and HES were only detected in the active sample and were found to be the primary drivers of estrogenic effects. An examination of the identified chemicals in the four sites indicated that these estrogenic chemicals may originate from e-waste recycling, livestock excretion and domestic waste. These findings uncovered the estrogenic pollutants in sediments from an e-waste area. Considering single endpoint in biological assay is not abundant to screen chemicals with different toxic effects, further EDA studies with multiple endpoints are required to better understand the occurrence of representative or unknown chemicals in e-waste-polluted areas.

Rare earth elements have been increasingly used in modern societies and soils are likely to be the final destination of several REE-containing (by)products. This study reports REE contents for topsoils (0–20 cm) of 175 locations in reference (n = 68) and cultivated (n = 107) areas in Brazil. Benchmark soil samples were selected accomplishing a variety of environmental conditions, aiming to: i) establishing natural background and anthropogenic concentrations for REE in soils; ii) assessing potential contamination of soils - via application of phosphate fertilizers - with REE; and, iii) predicting soil-REE contents using biomes, soil type, parent material, land use, sand content, and biomes-land use interaction as forecaster variables through generalized least squares multiple regression. Our hypotheses were that the variability of soil-REE contents is influenced by parent material, pedogenic processes, land use, and biomes, as well as that cultivated soils may have been potentially contaminated with REE via input of phosphate fertilizers. The semi-total concentrations of REE were assessed by inductively coupled plasma mass spectrometry (ICP-MS) succeeding a microwave-assisted aqua regia digestion. Analytical procedures followed a rigorous QA/QC protocol. Soil physicochemical composition and total oxides were also determined. Natural background and anthropogenic concentrations for REE were established statistically from the dataset by the median plus two median absolute deviations method. Contamination aspects were assessed by REE-normalized patterns, REE fractionation indices, and Ce and Eu anomalies ratios, as well as enrichment factors. The results indicate that differences in the amounts of REE in cultivated soils can be attributed to land use and agricultural sources (e.g., phosphate-fertilizer inputs), while those in reference soils can be attributed to parent materials, biomes, and pedogenic processes. The biomes, land use, and sand content helped to predict concentrations of light REE in Brazilian soils, with parent material being also of special relevance to predict heavy REE contents in particular.

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.

The annual production of sludges is significant all over the world, and large amounts of sludges have been improperly disposed by random dumping. The contaminants in these sludges may leak into the surrounding soils, surface and groundwater, or be blown into the atmosphere, thereby causing adverse effects to human health. In this study, the (anti-)androgenic activities in organic extracts of sludges produced from both industrial and domestic wastewater treatment plants (WWTPs) were examined using reporter gene assay based on MDA-kb2 cell lines and the potential (anti-)androgenic risks were assessed using hazard index (HI) based on bioassays. Twelve of the 18 samples exhibited androgen receptor (AR) antagonistic activities, with AR antagonistic equivalents ranging from 1.2 × 10² μg flutamide/g sludge to 1.8 × 10⁴ μg flutamide/g sludge; however, no AR agonistic activity was detected in any of the tested samples. These 12 sludges were all from chemical WWTPs; no sludges from domestic WWTPs displayed AR antagonistic activity. Aside from wastewater source, treatment scale and technology could also influence AR antagonistic potencies. The HI values of all the 12 sludges exceeded 1.0, and the highest HI value was above 3.0 × 10³ for children; this indicates that these sludges might cause adverse effects to human health and that children are at a greater risk than adults. The anti-androgenic potencies and risks of the subdivided fractions were also determined, and medium-polar and polar fractions were found to have relatively high detection rates and contribution rates to the AR antagonistic potencies and risks of the raw sample extracts.