Arsenic (As) is carcinogenic and of major concern in groundwater. We collected sediment material from a contaminated anoxic aquifer in Sweden and investigated the immobilization of As by four commercial zero-valent iron (ZVI) particles. Solid-phase As and Fe speciation was assessed using X-ray absorption spectroscopy (XAS) and solution-phase As speciation using chromatographic separation. Without ZVI addition, arsenite dominated in solution and As(V) species in the solid phase. Adding ZVI caused a sharp increase in solution pH (9.3-9.8), favoring As oxidation despite a lowered redox potential. ZVI greatly improved As retention by complex binding of arsenate to the Fe(III) (hydr)oxides formed by ZVI corrosion. Uncoated ZVI, both in nano- and microscale, performed better than their sulfidated counterparts, partly due to occlusion of As by the Fe(III) (hydr)oxides formed. The effect of particle size (micro vs. nano ZVI) on As immobilization was small, likely because immobilization was related to the corrosion products formed, rather than the initial size of the particles. Our results provide a strong geochemical background for the application of ZVI particles to remove As in contaminated aquifers under anoxic conditions and illustrate that immobilization mechanisms can differ between ZVI in As spiked solutions and sediment suspensions. ENVIRONMENTAL IMPLICATION: Arsenic ranks first on the list by the US ATSDR of substances posing a threat to human health and the WHO considers groundwater the riskiest source for human intake of As. However, dealing with As contamination remains a scientific challenge. We studied the immobilization of groundwater As by commercially available ZVI particles at field-realistic conditions. Arsenic immobilization was highly efficient in most cases, and the results suggest this is a promising in situ strategy with long-term performance. Our results provide a strong geochemical background for using ZVI to remove As in contaminated anoxic aquifers.

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. Abstract A standardized batch test evaluated by a simplified biotic ligand model approach could provide a useful tool to improve site specific assessment of metal ecotoxicity in soil. EC50 = median effective concentration.

The effectiveness of biochar amendment for remediation purposes depends on many factors related to the biochar and the contaminated site. Therefore, each application must be evaluated site-specifically. To facilitate full-scale implementation, more information from field studies on biochar-amended contaminated sites, as well as cost-effective approaches to evaluate the remediation efficacy of specific biochar materials are needed. We studied the effects of biochar and peat on metal solubility and bioavailability in a contaminated soil in a fully factorial field trial. The biochar was produced from wood via gasification in a floating fixed-bed reactor at 750 °C. Soil solutions from field-installed lysimeters, grass (Lolium perenne L), and earthworms (Eisenia fetida) were analyzed. In addition, a standardized batch leaching test (ISO 21268-2:2019) was performed to evaluate its feasibility to mimic soil solution concentrations. The results showed that biochar generally reduced the solubility and uptake of cationic metals. In situ solubility of Cu and Hg was reduced more than 80%, and Zn up to 70%. Soil solution concentrations of Cr increased in biochar-amended soils, but this effect was reduced by peat. Peat had small effects on in situ solubility of other metals. For cations, the batch test showed the same trends as the soil solution, with biochar decreasing solubility. However, mobilization of colloids during shaking in the batch test induced artefacts, leading to an overestimation of the solubility of some metals, especially Pb and Hg, an effect that was enhanced by peat applications.