Mobilization of As, Fe, and Mn from Contaminated Sediment in Aerobic and Anaerobic Conditions: Chemical or Microbiological Triggers?

We integrated aqueous chemistry, spectroscopy, and microbiology techniques to identify chemical and microbial processes affecting the release of arsenic (As), iron (Fe), and manganese (Mn) from contaminated sediments exposed to aerobic and anaerobic conditions. The sediments were collected from Cheyenne River Sioux Tribal lands in South Dakota, which has dealt with mining legacy for several decades. The range of concentrations of total As measured from contaminated sediments was 96 to 259 mg kg-1, which co-occurs with Fe (21 000-22 005 mg kg-1) and Mn (682-703 mg kg-1). The transition from aerobic to anaerobic redox conditions yielded the highest microbial diversity, and the release of the highest concentrations of As, Fe, and Mn in batch experiments reacted with an exogenous electron donor (glucose). The reduction of As was confirmed by XANES analyses when transitioning from aerobic to anaerobic conditions. In contrast, the releases of As, Fe and Mn after a reaction with phosphate was at least 1 order of magnitude lower compared with experiments amended with glucose. Our results indicate that mine waste sediments amended with an exogenous electron donor trigger microbial reductive dissolution caused by anaerobic respiration. These dissolution processes can affect metal mobilization in systems transitioning from aerobic to anaerobic conditions in redox gradients. Our results are relevant for natural systems, for surface and groundwater exchange, or other systems in which metal cycling is influenced by chemical and biological processes.

Arsenic Accumulation in Hydroponically Grown Schizachyrium scoparium (Little Bluestem) Amended with Root-Colonizing Endophytes.

We integrated microscopy, spectroscopy, culturing and molecular biology, and aqueous chemistry techniques to evaluate arsenic (As) accumulation in hydroponically grown Schizachyrium scoparium inoculated with endophytic fungi. Schizachyrium scoparium grows in historically contaminated sediment in the Cheyenne River Watershed and was used for laboratory experiments with As(V) ranging from 0 to 2.5 mg L-1 at circumneutral pH. Arsenic accumulation in regional plants has been a community concern for several decades, yet mechanisms affecting As accumulation in plants associated with endophytic fungi remain poorly understood. Colonization of roots by endophytic fungi supported better external and vascular cellular structure, increased biomass production, increased root lengths and increased P uptake, compared to noninoculated plants (p value <0.05). After exposure to As(V), an 80% decrease of As was detected in solution and accumulated mainly in the roots (0.82-13.44 mg kg-1) of noninoculated plants. Endophytic fungi mediated intracellular uptake into root cells and translocation of As. Electron microprobe X-ray mapping analyses detected Ca-P and Mg-P minerals with As on the root surface of exposed plants, suggesting that these minerals could lead to As adsorption on the root surface through surface complexation or coprecipitation. Our findings provide new insights regarding biological and physical-chemical processes affecting As accumulation in plants for risk assessment applications and bioremediation strategies.

Emerging investigator series: entrapment of uranium-phosphorus nanocrystals inside root cells of Tamarix plants from a mine waste site.

We investigated the mechanisms of uranium (U) uptake by Tamarix (salt cedars) growing along the Rio Paguate, which flows throughout the Jackpile mine near Pueblo de Laguna, New Mexico. Tamarix were selected for this study due to the detection of U in the roots and shoots of field collected plants (0.6-58.9 mg kg-1), presenting an average bioconcentration factor greater than 1. Synchrotron-based micro X-ray fluorescence analyses of plant roots collected from the field indicate that the accumulation of U occurs in the cortex of the root. The mechanisms for U accumulation in the roots of Tamarix were further investigated in controlled-laboratory experiments where living roots of field plants were macerated for 24 h or 2 weeks in a solution containing 100 µM U. The U concentration in the solution decreased 36-59% after 24 h, and 49-65% in two weeks. Microscopic and spectroscopic analyses detected U precipitation in the root cell walls near the xylems of the roots, confirming the initial results from the field samples. High-resolution TEM was used to study the U fate inside the root cells, and needle-like U-P nanocrystals, with diameter <7 nm, were found entrapped inside vacuoles in cells. EXAFS shell-by-shell fitting suggest that U is associated with carbon functional groups. The preferable binding of U to the root cell walls may explain the U retention in the roots of Tamarix, followed by U-P crystal precipitation, and pinocytotic active transport and cellular entrapment. This process resulted in a limited translocation of U to the shoots in Tamarix plants. This study contributes to better understanding of the physicochemical mechanisms affecting the U uptake and accumulation by plants growing near contaminated sites.

Effect of bicarbonate and phosphate on arsenic release from mining-impacted sediments in the Cheyenne River watershed, South Dakota, USA.

The mobilization of arsenic (As) from riverbank sediments affected by the gold mining legacy in north-central South Dakota was examined using aqueous speciation chemistry, spectroscopy, and diffraction analyses. Gold mining resulted in the discharge of approximately 109 metric tons of mine waste into Whitewood Creek (WW) near the Homestake Mine and Cheyenne River at Deal Ranch (DR), 241 km downstream. The highest concentrations of acid-extractable As measured from solid samples was 2020 mg kg-1 at WW and 385 mg kg-1 at DR. Similar sediment mineralogy between WW and DR was identified using XRD, with the predominance of alumino-silicate and iron-bearing minerals. Alkalinity measured in surface water at both sites ranged from 1000 to 2450 mg L-1 as CaCO3 (10-20 mM HCO3- at pH 7). Batch laboratory experiments were conducted under oxidizing conditions to evaluate the effects of NaHCO3 (0.2 mM and 20 mM) and NaH2PO3 (0.1 and 10 mM) on the mobilization of As. These ions are relevant for the site due to the alkaline nature of the river and nutrient mobilization from the ranch. The range of As(v) release with the NaHCO3 treatment was 17-240 µg L-1. However, the highest release (6234 µg L-1) occurred with 10 mM NaH2PO3, suggesting that As release is favored by competitive ion displacement with PO43- compared to HCO3-. Although higher total As was detected in WW solids, the As(v) present in DR solids was labile when reacted with NaHCO3 and NaH2PO3, which is a relevant finding for communities living close to the river bank. The results from this study aid in a better understanding of As mobility in surface water sites affected by the mining legacy.