 Different mine materials have statistically dissimilar As bioaccessibility values  As bioaccessibility is dependent on As and Fe speciation and particle size  As:Amorphous Fe molar ratio describes As bioaccessibility in calcinated materials  Default RBA values may not be appropriate for different mine-impacted materials Manuscript word count: 4625

Biochars produced from meat and bonemeal (MBM) waste materials contain large amounts of calcium phosphate and are potentially useful sorbents for the remediation of metals. Because the reactivity of biochars depends strongly upon the conditions used in their production, the objective of this study was to evaluate the rates and mechanisms of Zn sorption onto a commercially supplied MBM biochar prior to its application in a field-scale revegetation project. Sorption experiments varying pH, time, and Zn concentration found that, above pH 6.1, Zn adsorbed to MBM biochar quickly (within 5 h) with a maximum adsorption capacity of 0.65 mmol Zn g(-1). Synchrotron-based Zn K-edge extended X-ray absorption fine structure spectroscopy was consistent with a tetrahedral Zn bound to phosphate groups in a monodentate inner-sphere surface complex for all conditions tested. With an acidification pretreatment and at more acidic pH, MBM biochar causes precipitation of a ZnPO4 phase. On the basis of these results, this MBM biochar has a high capacity to rapidly adsorb Zn in adsorption experiments and can be considered a promising sorbent for Zn remediation of contaminated soils.

Permafrost contains a large (1700 Pg C) terrestrial pool of organic matter (OM) that is susceptible to degradation as global temperatures increase. Of particular importance is syngenetic Yedoma permafrost containing high OM content. Reactive iron phases promote stabilizing interactions between OM and soil minerals and this stabilization may be of increasing importance in permafrost as the thawed surface region (“active layer”) deepens. However, there is limited understanding of Fe and other soil mineral phase associations with OM carbon (C) moieties in permafrost soils. To elucidate the elemental associations involved in organomineral complexation within permafrost systems, soil cores spanning a Pleistocene permafrost chronosequence (19,000, 27,000, and 36,000 years old) were collected from an underground tunnel near Fairbanks, Alaska. Subsamples were analyzed via scanning transmission X-ray microscopy–near edge X-ray absorption fine structure spectroscopy at the nano- to microscale. Amino acid-rich moieties decreased in abundance across the chronosequence. Strong correlations between C and Fe with discrete Fe­(III) or Fe­(II) regions selectively associated with specific OM moieties were observed. Additionally, Ca coassociated with C through potential cation bridging mechanisms. Results indicate Fe­(III), Fe­(II), and mixed valence phases associated with OM throughout diverse permafrost environments, suggesting that organomineral complexation is crucial to predict C stability as permafrost systems warm.

In this study, the in vitro bioaccessibility (IVBA) of lead (Pb) in phosphate-amended Pb-contaminated soil was assessed using a variety of IVBA assays with an overarching aim of determining whether changes in Pb IVBA were congruent to those observed for Pb relative bioavailability (RBA) determined using an in vivo mouse assay. Amending soil with phosphoric acid or rock phosphate resulted in changes in Pb speciation, however, varying Pb IVBA results were obtained depending on the methodology utilized. In addition, IVBA assays influenced Pb speciation as a consequence of interactions between dissolved Pb and unreacted phosphate arising from the amendment or from assay constituents. When the relationship between Pb RBA and IVBA was assessed, a comparison of treatment effect ratios (Pb RBA or IVBA in treated soil divided by Pb RBA or IVBA for untreated soil) provided the best in vivo-in vitro correlation particular for SBRC (r = 0.83) and IVG (r = 0.89) intestinal extraction. For these assays, the slope of the lines of best fit were close to 1 (1.12, 0.82; SBRC, IVG intestinal extraction respectively) with small y-intercepts (0.09, 0.08 respectively) indicating that the efficacy of phosphate amendments for reducing Pb RBA may be predicted using IVBA assays.