Hydrologic Control on Arsenic Cycling at the Groundwater-Surface Water Interface of a Tidal Channel.

Historical industrial activities have resulted in soil contamination at sites globally. Many of these sites are located along coastlines, making them vulnerable to hydrologic and biogeochemical alterations due to climate change and sea-level rise. However, the impact of hydrologic dynamics on contaminant mobility in tidal environments has not been well studied. Here, we collected data from pressure transducers in wells, multi-level redox sensors, and porewater samplers at an As-contaminated site adjacent to a freshwater tidal channel. Results indicate that sharp redox gradients exist and that redox conditions vary on tidal to seasonal timescales due to sub-daily water level fluctuations in the channel and seasonal groundwater-surface water interactions. The As and Fe2+ concentrations decreased during seasonal periods of net discharge to the channel. The seasonal changes were greater than tidal variations in both Eh and As concentrations, indicating that impacts of the seasonal mechanism are stronger than those of sub-daily water table fluctuations. A conceptual model describing tidal and seasonal hydro-biogeochemical coupling is presented. These findings have broad implications for understanding the impacts of sea-level rise on the mobility of natural and anthropogenic coastal solutes.

Chilean regulations on metal-polluted soils: The need to advance from adapting foreign laws towards developing sovereign legislation.

Chile as a major international Cu producer faces serious soil contamination issues in mining areas. Currently Chile does not have any specific law governing the maximum permissible concentrations of metals in soils to protect ecosystems and human health. Chile heavily relies on the use of environmental laws of 14 foreign countries; the choice of the country depends on the similarity of its environmental conditions with those in Chile. In this study, we used an online database to compare the similarity of Chilean rocks to those in foreign countries. Likewise, we performed soil sampling and determined the background concentrations of Cu, As, Pb, and Zn in soils of the Aconcagua basin, the largest river basin in the Valparaiso Region of central Chile. The results showed that geochemical patterns in Chile have the greatest resemblance to New Zealand, Mexico, and Italy. The background Cu concentration in the Aconcagua basin (134 mg kg-1) exceeded the legislated limits of New Zealand (100 mg kg-1) and Italy (120 mg kg-1), whereas the background Zn concentration (200 mg kg-1) exceeded the legislated limit of Italy (150 mg kg-1). Due to the elevated natural abundance of Cu and Zn in Chile, international laws should not be applied in Chile for the assessment of soil contamination. In addition, we assessed ecological risk using the results of our previous studies obtained by analyzing native field-contaminated soils of the Valparaiso region. In the Aconcagua basin, Cu posed high risk for plants in 11% of the samples, whereas As posed high risk for earthworms in 48% of the samples. We suggest that future studies are required to search for other organisms that can serve as biomarkers of metal toxicity because our previous studies were limited to plants and earthworms. Importantly, As posed high risk to human health in 25% of the samples in our study. There is a need for future studies to demonstrate empirically an association between soil As and children's blood As in order to establish the national threshold values of soil As to protect human health. We conclude that there is an urgent need in Chile to advance from the current approach of adapting foreign laws to developing Chilean sovereign environmental legislation.

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 ≥ 7. Sorbed OC concentration at pH 9 increased from 8.72 ± 0.16 to 13.3 ± 0.20 mmol OC g-1 ferrihydrite between treatments of no added Ca2+ and 30 mM 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 (r = 0.78, P < 0.0006) 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 (2 × 102 µg C m-2), DOM desorption-assessed by 0.1 M NaH2PO4 extraction-is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 × 102 µg C m-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.

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.

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.

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

This is the first test of a highly charged swelling mica's (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.

Highly charged swelling mica reduces free and extractable Cu levels in Cu-contaminated soils.

Smelting of copper (Cu) results in the atmospheric deposition of Cu onto surrounding soils. Excess concentrations of Cu in soils can be absorbed by soil biota to toxic levels or leached into the groundwater, threatening the entire ecosystem. A means to restrict Cu mobility and uptake by plants is to remove it from the aqueous phase by applying an adsorptive material. A synthetic clay (highly charged swelling mica) was tested for its ability to decrease the levels of free and 0.1 M KNO3-extractable Cu in 15 surface soils from three different Cu mining areas in central Chile. The soils contained excessive total Cu levels (112-2790 mg Cu (kg soil)(-1)), while extractable Cu ranged from 0.3 to 22.9 mg Cu L(-1). The mica was applied to each soil at rates of 0.1%, 1%, and 2% (w/w). A 2% sodium-montmorillonite treatment and the nonamended soil served as controls. The order of treatment efficacy in reducing extractable Cu and free Cu2+ for low pH soils ( 1% mica > 2% montmorillonite > 0.1% mica. At 120 days, the 2% mica treatment maintained reductions of up to 93% in the free Cu2+ activity and up to 75% in the extractable Cu concentration upon acidification to the original soil pH value. In addition, Cu retention in mica-treated soils was more resistant to acidification than in lime-treated soils. This mica has promise for the remediation of acidic soils with metal contamination at the surface.