Soil Weathering as an Engine for Manganese Contamination of Well Water.

Manganese (Mn) contamination of well water is recognized as an environmental health concern. In the southeastern Piedmont region of the United States, well water Mn concentrations can be >2 orders of magnitude above health limits, but the specific sources and causes of elevated Mn in groundwater are generally unknown. Here, using field, laboratory, spectroscopic, and geospatial analyses, we propose that natural pedogenetic and hydrogeochemical processes couple to export Mn from the near-surface to fractured-bedrock aquifers within the Piedmont. Dissolved Mn concentrations are greatest just below the water table and decrease with depth. Solid-phase concentration, chemical extraction, and X-ray absorption spectroscopy data show that secondary Mn oxides accumulate near the water table within the chemically weathering saprolite, whereas less-reactive, primary Mn-bearing minerals dominate Mn speciation within the physically weathered transition zone and bedrock. Mass-balance calculations indicate soil weathering has depleted over 40% of the original solid-phase Mn from the near-surface, and hydrologic gradients provide a driving force for downward delivery of Mn. Overall, we estimate that >1 million people in the southeastern Piedmont consume well water containing Mn at concentrations exceeding recommended standards, and collectively, these results suggest that integrated soil-bedrock-system analyses are needed to predict and manage Mn in drinking-water wells.

The Structure of Natural Biogenic Iron (Oxyhydr)oxides Formed in Circumneutral pH Environments.

Biogenic iron (Fe) (oxyhydr)oxides (BIOS) partially control the cycling of organic matter, nutrients, and pollutants in soils and water via sorption and redox reactions. Although recent studies have shown that the structure of BIOS resembles that of two-line ferrihydrite (2LFh), we lack detailed knowledge of the BIOS local coordination environment and structure required to understand the drivers of BIOS reactivity in redox active environments. Therefore, we used a combination of microscopy, scattering, and spectroscopic methods to elucidate the structure of BIOS sampled from a groundwater seep in North Carolina and compare them to 2LFh. We also simulated the effects of wet-dry cycles by varying sample preparation (e.g., freezing, flash freezing with freeze drying, freezing with freeze drying and oven drying). In general, the results show that both the long- and short-range ordering in BIOS are structurally distinct and notably more disordered than 2LFh. Our structure analysis, which utilized Fe K-edge X-ray absorption spectroscopy, Mössbauer spectroscopy, X-ray diffraction, and pair distribution function analyses, showed that the BIOS samples were more poorly ordered than 2LFh and intimately mixed with organic matter. Furthermore, pair distribution function analyses resulted in coherent scattering domains for the BIOS samples ranging from 12-18 Å, smaller than those of 2LFh (21-27 Å), consistent with reduced ordering. Additionally, Fe L-edge XAS indicated that the local coordination environment of 2LFh samples consisted of minor amounts of tetrahedral Fe(III), whereas BIOS were dominated by octahedral Fe(III), consistent with depletion of the sites due to small domain size and incorporation of impurities (e.g., organic C, Al, Si, P). Within sample sets, the frozen freeze dried and oven dried sample preparation increased the crystallinity of the 2LFh samples when compared to the frozen treatment, whereas the BIOS samples remained more poorly crystalline under all sample preparations. This research shows that BIOS formed in circumneutral pH waters are poorly ordered and more environmentally stable than 2LFh.

Assessment of trace element impacts on agricultural use of water from the Dan River following the Eden coal ash release.

Catastrophic events require rapid, scientifically sound decision making to mitigate impacts on human welfare and the environment. The objective of this study was to analyze potential impacts of coal ash-derived trace elements on agriculture following a 35,000-tonne release of coal ash into the Dan River at the Duke Energy Steam Station in Eden, North Carolina. We performed scenario calculations to assess the potential for excessive trace element loading to soils via irrigation and flooding with Dan River water, uptake of trace elements by crops, and livestock consumption of trace elements via drinking water. Concentrations of 13 trace elements measured in Dan River water samples within 4 km of the release site declined sharply after the release and were equivalent within 5 d to measurements taken upriver. Mass-balance calculations based on estimates of soil trace-element concentrations and the nominal river water concentrations indicated that irrigation or flooding with 25 cm of Dan River water would increase soil concentrations of all trace elements by less than 0.5%. Calculations of potential increases of trace elements in corn grain and silage, fescue, and tobacco leaves suggested that As, Cr, Se, Sr, and V were elements of most concern. Concentrations of trace elements measured in river water following the ash release never exceeded adopted standards for livestock drinking water. Based on our analyses, we present guidelines for safe usage of Dan River water to diminish negative impacts of trace elements on soils and crop production. In general, the approach we describe here may serve as a basis for rapid assessment of environmental and agricultural risks associated with any similar types of releases that arise in the future.