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Purpose of Review The ubiquity of soil contamination by lead (Pb) and arsenic (As) has prompted the development of numerous techniques for its remediation. For human health exposure assessment, oral bioavailability-based methods are the most suitable to assess the efficacy of these treatment strategies, including in vivo relative bioavailability (systemic absorption relative to a toxicity reference) and in vitro bioaccessibility (dissolution in simulated gastrointestinal solutions). This paper provides a critical review of opportunities and challenges associated with the immobilization of Pb and As in contaminated soil. Recent Findings This review identified that the major inorganic and organic amendments used to reduce Pb and As exposure include phosphate, industrial by-products, metal oxides, organic matter, biochar, and treatment with iron sulphate to promote the formation of plumbojarosite in soil. In addition to RBA and IVBA assessment, investigating changes in Pb/As speciation in untreated vs treated soil can provide additional confirmation of treatment efficacy. The results of this review showed that immobilization efficacy may vary depending on amendment type, Pb, and As speciation in soil and the approach used for its assessment. Summary Reducing childhood exposure to Pb and As is a significant challenge, given the variety of contamination sources and treatment strategies. A lines-of-evidence approach using standardized methodologies is recommended for the assessment of immobilization efficacy to ensure exposure and risk reduction Graphical Abstract Bioavailability-based remediation strategies. Popular soil amendments to reduce Pb exposure include phosphate, industrial by-products, metal oxides, organic matter, and biochar; however, these may increase As exposure. The plumbojarosite formation technique has been recently developed to mitigate Pb and As exposure simultaneously. Multiple lines-of-evidence approach is recommended to assess treatment efficacy

To understand the biogeochemistry of nutrients and contaminants in environmental media, their speciation and behavior under different conditions and at multiple scales must be determined. Synchrotron radiation-based X-ray techniques allow scientists to elucidate the underlying mechanisms responsible for nutrient and contaminant mobility, bioavailability, and behavior. The continuous improvement of synchrotron light sources and X-ray beamlines around the world has led to a profound transformation in the field of environmental biogeochemistry and, subsequently, to significant scientific breakthroughs. Following this introductory paper, this special collection includes 10 papers that either present targeted reviews of recent advancements in spectroscopic methods that are applicable to environmental biogeochemistry or describe original research studies conducted on complex environmental samples that have been significantly enhanced by incorporating synchrotron radiation-based X-ray technique(s). We believe that the current focus on improving the speciation of ultra-dilute elements in environmental media through the ongoing optimization of synchrotron technologies (e.g., brighter light sources, improved monochromators, more efficient detectors) will help to significantly push back the frontiers of environmental biogeochemistry research. As many of the relevant techniques produce extremely large datasets, we also identify ongoing improvements in data processing and analysis (e.g., software improvements and harmonization of analytical methods) as a significant requirement for environmental biogeochemists to maximize the information that can be gained using these powerful tools. Refereed/Peer-reviewed

Understanding the molecular-scale complexities and interplay of chemical and biological processes of contaminants at solid, liquid, and gas interfaces is a fundamental and crucial element to enhance our understanding of anthropogenic environmental impacts. The ability to describe the complexity of environmental biogeochemical reaction mechanisms relies on our analytical ability through the application and developmemnt of advanced spectroscopic techniques. Accompanying this introductory article are nine papers that either review advanced in situ spectroscopic methods or present original research utilizing these techniques. This collection of articles summarizes the challenges facing environmental biogeochemistry, highlights the recent advances and scientific gaps, and provides an outlook into future research that may benefit from the use of in situ spectroscopic approaches. The use of synchrotronbased techniques and other methods are discussed in detail, as is the importance to integrate multiple analytical approaches to confirm results of complementary procedures or to fill data gaps. We also argue that future direction in research will be driven, in addition to recent analytical developments, by emerging factors such as the need for risk assessment of new materials (i.e., nanotechnologies) and the realization that biogeochemical processes need to be investigated in situ under environmentally relevant conditions Refereed/Peer-reviewed

The benefits of Mn and Zn fluid fertilizers over conventional granular products in calcareous sandy loam soils have been agronomically demonstrated. We hypothesized that the differences in the effectiveness between granular and fluid Mn and Zn fertilizers is due to different Mn and Zn reaction processes in and around fertilizer granules and fluid fertilizer bands. We used a combination of several synchrotron-based x-ray techniques, namely, spatially resolved micro-x-ray fluorescence (?-XRF), micro-x-ray absorption near edge structure spectroscopy (?-XANES), and bulk-XANES and -extended x-ray absorption fine structure (EXAFS) spectroscopy, along with several laboratory-based x-ray techniques to speciate different fertilizer-derived Mn and Zn species in highly calcareous soils to understand the chemistry underlying the observed differential behavior of fluid and granular micronutrient forms. Micro-XRF mapping of soil-fertilizer reactions zones indicated that the mobility of Mn and Zn from liquid fertilizer was greater than that observed for equivalent granular sources of these micronutrients in soil. After application of these micronutrient fertilizers to soil, Mn and Zn from liquid fertilizers were found to remain in comparatively more soluble solid forms, such as hydrated Mn phosphate-like, Mn calcite-like, adsorbed Zn-like, and Zn silicate-like phases, whereas Mn and Zn from equivalent granular sources tended to transform intomore » comparatively less soluble solid forms such as Mn oxide-like, Mn carbonate-like, and Zn phosphate-like phases.« less