Jason W. Stuckey

Sea level rise induced arsenic release from historically contaminated coastal soils

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions. We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.

Highly charged swelling mica reduces Cu bioavailability in Cu-contaminated soils.

This is the first test of a highly charged swelling micas (Na-2-mica) ability to reduce the plant-absorbed Cu in Cu-contaminated soils from Chile. Perennial ryegrass (Lolium perenne L.) was grown in two acid soils (Sector 2: pH 4.2, total Cu = 172 mg Cu kg(-1) and Sector 3: pH 4.2, total Cu = 112 mg Cu kg(-1)) amended with 0.5% and 1% (w/w) mica, and 1% (w/w) montmorillonite. At 10 weeks of growth, both mica treatments decreased the shoot Cu of ryegrass grown in Sector 2 producing shoot Cu concentrations above 21-22 mg Cu kg(-1) (the phytotoxicity threshold for that species), yet the mica treatments did not reduce shoot Cu concentrations when grown in Sector 3, which were at a typical level. The mica treatments improved shoot growth in Sector 3 by reducing free and extractable Cu to low enough levels where other nutrients could compete for plant absorption and translocation. In addition, the mica treatments improved root growth in both soils, and the 1% mica treatment reduced root Cu in both soils. This swelling mica warrants further testing of its ability to assist re-vegetation and reduce Cu bioavailability in Cu-contaminated surface soils.

Advances in Scanning Transmission X-Ray Microscopy for Elucidating Soil Biogeochemical Processes at the Submicron Scale

Organic matter, minerals, and microorganisms are spatially associated in complex organo-mineral assemblages within soils. A mechanistic understanding of processes occurring within organo-mineral assemblages requires noninvasive techniques that minimize any disturbance to the physical and chemical integrity of the sample. Synchrotron-based soft (50-2200 eV) X-ray spectromicroscopic techniques, including scanning transmission X-ray microscopy (STXM), transmission X-ray microscopy (TXM), X-ray photoemission electron microscopy (X-PEEM), and scanning photoelectron microscopy (SPEM), coupled with microspectroscopy (e.g., near-edge X-ray absorption fine structure; NEXAFS) allow for determining the spatial association and speciation of most elements found in soils while maintaining sample integrity. This review highlights application of the four spectromicroscopic techniques mentioned above to soil biogeochemical research, with particular emphasis on STXM-NEXAFS, which has contributed to the greatest set of advancements in the understanding of soil organo-mineral interactions, including mineral control on organic carbon cycling and the mechanisms of biomineral formation.

The synergistic effect of calcium on organic carbon sequestration to ferrihydrite

Sequestration of organic carbon (OC) in environmental systems is critical to mitigating climate change. Organo-mineral associations, especially those with iron (Fe) oxides, drive the chemistry of OC sequestration and stability in soils. Short-range-ordered Fe oxides, such as ferrihydrite, demonstrate a high affinity for OC in binary systems. Calcium commonly co-associates with OC and Fe oxides in soils, though the bonding mechanism (e.g., cation bridging) and implications of the co-association for OC sequestration remain unresolved. We explored the effect of calcium (Ca2+) on the sorption of dissolved OC to 2-line ferrihydrite. Sorption experiments were conducted between leaf litter-extractable OC and ferrihydrite at pH 4 to 9 with different initial C/Fe molar ratios and Ca2+ concentrations. The extent of OC sorption to ferrihydrite in the presence of Ca2+ increased across all tested pH values, especially at pH ≥xa07. Sorbed OC concentration at pH 9 increased from 8.72xa0±xa00.16 to 13.3xa0±xa00.20xa0mmol OC g−1 ferrihydrite between treatments of no added Ca2+ and 30xa0mM Ca2+ addition. Batch experiments were paired with spectroscopic studies to probe the speciation of sorbed OC and elucidate the sorption mechanism. ATR-FTIR spectroscopy analysis revealed that carboxylic functional moieties were the primary sorbed OC species that were preferentially bound to ferrihydrite and suggested an increase in Fe-carboxylate ligand exchange in the presence of Ca at pH 9. Results from batch to spectroscopic experiments provide significant evidence for the enhancement of dissolved OC sequestration to 2-line ferrihydrite and suggest the formation of Fe–Ca-OC ternary complexes. Findings of this research will inform modeling of environmental C cycling and have the potential to influence strategies for managing land to minimize OM stabilization.

Impacts of hydrous manganese oxide on the retention and lability of dissolved organic matter

Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides—collectively referred to as “oxides” hereafter—are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO2, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite Oi, Oe, and Oa horizon leachate (“O horizon leachate” hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy–near-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (rxa0=xa00.78, Pxa0<xa00.0006) on the DOM–HMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2xa0×xa0102xa0μgxa0Cxa0m−2), DOM desorption—assessed by 0.1xa0M NaH2PO4 extraction—is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4xa0×xa0102xa0μgxa0Cxa0m−2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOM–HMO complexes may be more vulnerable to reductive dissolution than DOM–goethite complexes.