Arsenic (As) is one of the most widespread, toxic elements in the environment, and human activities have resulted in a large number of contaminated areas. However abundant, the potential of As toxicity from exposure to contaminated soils is limited to the fraction that will dissolve in the gastrointestinal system and be absorbed into systemic circulation or bioavailable species. In part, the release of As from contaminated soil to gastrointestinal fluid depends on the form of solid phase As, also termed “As speciation”. In this study, 27 As-contaminated soils and solid wastes were analyzed using X-ray absorption spectroscopy (XAS) and results were compared to in vivo bioavailability values determined using the adult mouse and juvenile swine bioassays. Arsenic bioavailability was lowest for soils that contained large amounts of arsenopyrite and highest for materials that contained large amounts of ferric arsenates. Soil and solid waste type and properties rather than the contamination source had the greatest influence on As speciation. Principal component analysis determined that As(V) adsorbed and ferric arsenates were the dominant species that control As speciation in the selected materials. Multiple linear regression (MLR) was used to determine the ability of As speciation to predict bioavailability. Arsenic speciation was predictive of 27% and 16% of Relative Bioavailable (RBA) As determined using the juvenile swine and adult mouse models, respectively. Arsenic speciation can provide a conservative estimate of RBA As using MLR for the juvenile swine and adult mouse bioassays at 55% and 53%, respectively.

Mine lands contaminted with heavy metals pose environmental risks, and thus reclamation is paramount for improving soil, plant, animal, and ecosystem health. A metal-contaminated alluvial mine tailing, devoid of vegetation, received 224 Mg ha⁻¹ of both lime and biosolids in 1998, and long-term reclamation success was quantified in 2019 with respect to soils, plants, and linkages to animals. Reclamation success was quantified using the Soil Management Assessment Framework (SMAF), in conjunction with bioavailable (0.01 M CaCl₂ extractable) and plant-available (Mehlich-3 extractable) soil metal concentrations, X-ray absorption spectroscopy, plant metal concentrations, and plant quality characteristics. Results showed that all soil indicators were improved in successfully-reclaimed areas as compared to on-site degraded areas, including increases in soil aggregate stability, pH, plant-available P and K, soil organic C, potentially-mineralizable N, microbial biomass C and β-glucosidase activity and decreases in soil bulk density and electrical conductivity. Of indicators, unitless soil health scores were assigned based on the SMAF, with data suggesting that bulk density, wet aggregate stability, potentially-mineralizable N, microbial biomass C, pH, and electrical conductivity should be monitored in the future. The long-term effects of lime and biosolids application have improved soil physical, biological, and overall soil health. Plant metal concentrations have decreased by an order of magnitude since early reclamation, with most plant metal concentrations being tolerable for domestic livestock consumption. From an animal health perspective, feeding grasses from this site during latter parts of a growing season may need supplemental feed to provide greater protein and energy content, and to reduce potentially-harmful Cd concentrations from food chain bioaccumulation. However, a health concern exists based on soil bioavailable Cd and Zn concentrations that exceed ecological soil screening levels. Still, plants have stabilized the soil and acidity remains neutralized, leading to long-term improvements in soil health, with overall improved ecosystem health.

Interest in improved understanding of relationships among soil properties and arsenic (As) bioaccessibility has motivated the use of regression models for As bioaccessibility prediction. However, limits in the numbers and types of soils included in previous studies restrict the usefulness of these models beyond the range of soil conditions evaluated, as evidenced by reduced predictive performance when applied to new data. In response, hierarchical models that consider variability in relationships among soil properties and As bioaccessibility across geographic locations and contaminant sources were developed to predict As bioaccessibility in 139 soils on both a mass fraction (mg/kg) and % basis. The hierarchical approach improved the estimation of As bioaccessibility in studied soils. In addition, the number of soil elements identified as statistically significant explanatory variables increased when compared to previous investigations. Specifically, total soil Fe, P, Ca, Co, and V were significant explanatory variables in both models, while total As, Cd, Cu, Ni, and Zn were also significant in the mass fraction model and Mg was significant in the % model. This developed hierarchical approach provides a novel tool to (1) explore relationships between soil properties and As bioaccessibility across a broad range of soil types and As contaminant sources encountered in the environment and (2) identify areas of future mechanistic research to better understand the complexity of interactions between soil properties and As bioaccessibility.

Lead (Pb) is one of the most common heavy metal urban soil contaminants with well-known toxicity to humans. This incubation study (2-159 d) compared the ability of bone meal (BM), potassium hydrogen phosphate (KP), and triple superphosphate (TSP), at phosphorus:lead (P:Pb) molar ratios of 7.5:1, 15:1, and 22.5:1, to reduce bioaccessible Pb in soil contaminated by Pb-based paint relative to control soil to which no P amendment was added. Soil pH and Mehlich 3 bioaccessible Pb and P were measured as a function of incubation time and amount and type of P amendment. XAS assessed Pb speciation after 30 and 159 d of incubation. The greatest reductions in bioaccessible Pb at 159 d were measured for TSP at the 7.5:1 and 15:1 P:Pb molar ratios. The 7.5:1 KP treatment was the only other treatment with significant reductions in bioaccessible Pb compared to the control soil. It is unclear why greater reductions of bioaccessible Pb occurred with lower P additions, but it strongly suggests that the amount of P added was not a controlling factor in reducing bioaccessible Pb. This was further supported because Pb-phosphates were not detected in any samples using XAS. The most notable difference in the effect of TSP versus other amendments was the reduction in pH. However, the relationship between increasing TSP additions, resulting in decreasing pH and decreasing Pb bioaccessibility was not consistent. The 22.5:1 P:Pb TSP treatment had the lowest pH but did not significantly reduce bioaccessible Pb compared to the control soil. The 7.5:1 and 15:1 P:Pb TSP treatments significantly reduced bioaccessible Pb relative to the control and had significantly higher pH than the 22.5:1 P:Pb treatment. Clearly, impacts of P additions and soil pH on Pb bioaccessibility require further investigation to decipher mechanisms governing Pb speciation in Pb-based paint contaminated soils.