Nitrate-Stimulated Release of Naturally Occurring Sedimentary Uranium.

Groundwater uranium (U) concentrations have been measured above the U.S. EPA maximum contaminant level (30 µg/L) in many U.S. aquifers, including in areas not associated with anthropogenic contamination by milling or mining. In addition to carbonate, nitrate has been correlated to uranium groundwater concentrations in two major U.S. aquifers. However, to date, direct evidence that nitrate mobilizes naturally occurring U from aquifer sediments has not been presented. Here, we demonstrate that the influx of high-nitrate porewater through High Plains alluvial aquifer silt sediments bearing naturally occurring U(IV) can stimulate a nitrate-reducing microbial community capable of catalyzing the oxidation and mobilization of U into the porewater. Microbial reduction of nitrate yielded nitrite, a reactive intermediate, which was further demonstrated to abiotically mobilize U from the reduced alluvial aquifer sediments. These results indicate that microbial activity, specifically nitrate reduction to nitrite, is one mechanism driving U mobilization from aquifer sediments in addition to previously described bicarbonate-driven desorption from mineral surfaces, such as Fe(III) oxides.

Ferrihydrite enrichment in the rhizosphere of unsaturated soil improves nutrient retention while limiting arsenic and uranium plant uptake.

Improvement of nutrient use efficiency and limiting trace elements such as arsenic and uranium bioavailability is critical for sustainable agriculture and food safety. Arsenic and uranium possess different properties and mobility in soils, which complicates the effort to reduce their uptake by plants. Here, we postulate that unsaturated soil amended with ferrihydrite nanominerals leads to improved nutrient retention and helps reduce uptake of these geogenic contaminants. Unsaturated soil is primarily oxic and can provide a stable environment for ferrihydrite nanominerals. To demonstrate the utility of ferrihydrite soil amendment, maize was grown in an unsaturated agricultural soil that is known to contain geogenic arsenic and uranium. The soil was maintained at a gravimetric moisture content of 15.1 ± 2.5%, typical of periodically irrigated soils of the US Corn Belt. Synthetic 2-line ferrihydrite was used in low doses as a soil amendment at three levels (0.00% w/w (control), 0.05% w/w and 0.10% w/w). Further, the irrigation water was fortified (~50 µg L-1 each) with elevated arsenic and uranium levels. Plant dry biomass at maturity was ~13.5% higher than that grown in soil not receiving ferrihydrite, indicating positive impact of ferrihydrite on plant growth. Arsenic and uranium concentrations in maize crops (root, shoot and grain combined) were ~ 20% lower in amended soils than that in control soils. Our findings suggest that the addition of low doses of iron nanomineral soil amendment can positively influence rhizosphere geochemical processes, enhancing nutrient plant availability and reduce trace contaminants plant uptake in sprinkler irrigated agroecosystem, which is 55% of total irrigated area in the United States.

Ferrihydrite Reduction Increases Arsenic and Uranium Bioavailability in Unsaturated Soil.

Redox driven mobilization and plant uptake of contaminants under transiently saturated soil conditions need to be clarified to ensure food and water quality across different irrigation systems. We postulate that solid-phase iron reduction in anoxic microsites present in the rhizosphere of unsaturated soil is a key driver for mobilization and bioavailability of contaminants under nonflooded irrigation. To clarify this, two major crops, corn and soybean differing in iron uptake strategies, were grown in irrigated synthetic soil under semiarid conditions with gravimetric moisture content ∼12.5 ± 2.4%. 2-line ferrihydrite, which was coprecipitated with uranium and arsenic, served as the only iron source in soil. Irrespective of crop type, reduced iron was detected in pore water and postexperiment rhizosphere soil confirming ferrihydrite reduction. These results support the presence of localized anoxic microsites in the otherwise aerobic porous bulk soil causing reduction of ferrihydrite and concomitant increase in plant uptake of comobilized contaminants. Our findings indicate that reactive iron minerals undergo reductive dissolution inside anoxic microsites of primarily unsaturated soil, which may have implications on the mobility of trace element contaminants such as arsenic and uranium in irrigated unsaturated soils, accounting for 55% of the irrigated area in the US.

Occurrence and removal of pharmaceutical compounds and steroids at four wastewater treatment plants in Hawai'i and their environmental fate.

The occurrence of pharmaceutical and steroid compounds in groundwater due to wastewater reuse has been reported and is of concern in tropical islands which primarily rely on groundwater. The objective of this study was to investigate the occurrence and removal of 43 pharmaceutical and steroid compounds detected in wastewater at four different wastewater treatment plants (WWTPs) in Hawai'i and to understand their environmental behavior through tropical soils as the treated effluents are used in landscapes for irrigation. Eight soil sampling locations, collected at three different depths, representing the most common soil types in Hawai'i and four WWTPs located across the major Hawaiian Islands were used. Disturbed soil samples were used to conduct the soil sorption and degradation studies and to estimate the leaching risk associated to the identified compounds. Quantification of selected compounds was conducted using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Among the investigated compounds, only ten were detected in the treated effluents at concentrations ranging from 0.004 to 0.900 µg L-1. Caffeine (64 µg L-1) and ibuprofen (96.5 µg L-1) showed the highest concentration in raw samples, while diphenhydramine (0.9 µg L-1) showed the highest concentration in treated effluent samples. Sulfamethoxazole showed the lowest removal (0-75%). Several pharmaceuticals showed consistently higher sorption capacity and longer persistency compared with steroids regardless of soil types and depths. Poamoho (Oxisol soil) and Waimanalo (Mollisol soil) showed the highest sorption capacity, while Waimea (Entisol soil) showed the lowest sorption capacity. Soil physico-chemical properties (i.e., clay content, level of organic carbon, and presence of metal oxide) and soil depth highly impacted the sorption behavior of the selected pharmaceutical compounds. In particular, the sorption capacity decreased with soil depth due to the higher level of organic carbon present in the first 30 cm compared with the deeper depths (60-90 cm).

Evaluation of Fecal Indicators and Pathogens in a Beef Cattle Feedlot Vegetative Treatment System.

Runoff from open-lot animal feeding areas contains microorganisms that may adversely affect human and animal health if not properly managed. One alternative to full manure containment systems is a vegetative treatment system (VTS) that collects runoff in a sediment basin and then applies it to a perennial vegetation (grass) treatment area that is harvested for hay. Little is known regarding the efficacy of large-scale commercial VTSs for the removal of microbial contaminants. In this study, an active, pump-based VTS designed and built for a 1200-head beef cattle feedlot operation was examined to determine the effects of repeated feedlot runoff application on fecal indicator microorganisms and pathogens over short-term (2 wk) and long-term (3 yr) operations and whether fecal bacteria were infiltrating into deeper soils within the treatment area. In a short-term study, fecal bacteria and pathogen numbers declined over time in soil. Measurements of total coliforms and Enterococcus counts taken on control soils were not effective as fecal indicators. The repeated application of manure-impacted runoff as irrigation water did not enrich the pathogens or fecal indicators in the soil, and no evidence was seen to indicate that pathogens were moving into the deeper soil at this site. These results indicate that large-scale, active VTSs reduce the potential for environmental contamination by manure-associated bacteria. Also, this study has implications to full-containment systems that apply runoff water to land application areas (cropland) and the fate of pathogens in the soils of land application sites.

Effect of growth promotants on the occurrence of endogenous and synthetic steroid hormones on feedlot soils and in runoff from beef cattle feeding operations.

Supplements and growth promotants containing steroid hormones are routinely administered to beef cattle to improve feeding efficiency, reduce behavioral problems, and enhance production. As a result, beef cattle manure will contain both synthetic steroids as well as a range of endogenous steroids including androgens, estrogens, and progestogens. A two-year controlled study was conducted in which beef cattle were administered steroid hormones via subcutaneous implants and feed additives and the occurrence of 16 endogenous and synthetic steroid hormones and metabolites was evaluated in runoff from beef cattle feedlots and in manure and soil collected from feedlot surfaces. Samples were extracted and analyzed using liquid chromatography tandem mass spectrometryfor metabolites of the synthetic androgen trenbolone acetate, 17α-trenbolone, 17ß-trenbolone, for the nonsteroidal semisynthetic estrogen agonist, α-zearalanol, and the synthetic progesterone melengesterol acetate, as well as a wide range of endogeneous estrogens, androgens, and fusarium metabolites. Synthetic steroids including trenbolone metabolites and melengestrol acetate were detected in fresh manure and in feedlot surface soils from cattle administered synthetic steroids at concentrations up to 55 ± 22 ng/g dry weight (dw) (17α-trenbolone) and 6.5 ± 0.4 ng/g dw (melengesterol acetate). Melengesterol acetate was detected in 6% of runoff samples from feedlots holding cattle administered synthetic steroids at concentrations ranging up to 115 ng/L. The presence of melengesterol acetate in runoff from beef cattle feeding operations has not been previously reported. Synthetic steroids were not detected in manure or runoff from control cattle. A wide range of endogenous hormones were detected in runoff and feedlot surface soils and manure from cattle given synthetic steroids and from control cattle, with no statistically significant differences in concentration. These results indicate that runoff from confined animal production facilities is of environmental and public health concern regardless of the use of growth promotants.

In vitro and in vivo safety assessment of edible blue-green algae, Nostoc commune var. sphaeroides Kützing and Spirulina plantensis.

Blue-green algae (BGA) have been consumed as food and herbal medicine for centuries. However, safety for their consumption has not been well investigated. This study was undertaken to evaluate in vitro and in vivo toxicity of cultivated Nostoc commune var. sphaeroides Kützing (NO) and Spirulina platensis (SP). Neither NO nor SP contained detectable levels of microcystin (MC)-LA, MC-RR, MC-LW and MC-LR by LC/MS/MS. Cell viability remained ∼70-80% when HepG2 cells were incubated with 0-500 µg/ml of hexane, chloroform, methanol and water-extractable fractions of NO and SP. Four-week-old male and female C57BL/6J mice were fed an AIN-93G/M diet supplemented with 0%, 2.5% or 5% of NO and SP (wt/wt) for 6 months. For both genders, BGA-rich diets did not induce noticeable abnormality in weight gain and plasma alanine aminotransferase (ALT) and aspartate aminotransferase concentrations except a significant increase in plasma ALT levels by 2.5% NO supplementation in male mice at 6 month. Histopathological analysis of livers, however, indicated that BGA did not cause significant liver damage compared with controls. In conclusion, our results suggest that NO and SP are free of MC and the long-term dietary supplementation of up to 5% of the BGA may be consumed without evident toxic side-effects.

Distribution of selenium, mercury, and methylmercury in surficial Missouri River sediments.

Sediment deposition into Lewis and Clark Lake, an impoundment of the Missouri River, has caused substantial storage capacity reductions. Current proposals to hydrologically flush sediment would disturb river and reservoir sediment that may contain heavy metals. We quantified existing concentrations of selenium (Se), mercury (Hg), and methylmercury (MeHg) in surficial sediments upstream of and in Lewis and Clark Lake. We found elevated levels of Se (range 0.12-9.62 microg/g) and Hg (range 0.021.55 microg/g) at several sites throughout the study area; however, few sites contained levels of MeHg above detection limits. Sites with highest MeHg concentrations were found in Lewis and Clark Lake and ranged from below detection limit to 0.79 ng/g. We conclude that further investigation of sediment-sequestered contaminants in Lewis and Clark Lake should be conducted.