Uranium sequestration in sediment at an iron-rich contaminated site at Oak Ridge, Tennessee via. bioreduction followed by reoxidation.

This study evaluated uranium sequestration performance in iron-rich (30 g/kg) sediment via bioreduction followed by reoxidation. Field tests (1383 days) at Oak Ridge, Tennessee demonstrated that uranium contents in sediments increased after bioreduced sediments were re-exposed to nitrate and oxygen in contaminated groundwater. Bioreduction of contaminated sediments (1200 mg/kg U) with ethanol in microcosm reduced aqueous U from 0.37 to 0.023 mg/L. Aliquots of the bioreduced sediment were reoxidized with O2, H2O2, and NaNO3, respectively, over 285 days, resulting in aqueous U of 0.024, 1.58 and 14.4 mg/L at pH 6.30, 6.63 and 7.62, respectively. The source- and the three reoxidized sediments showed different desorption and adsorption behaviors of U, but all fit a Freundlich model. The adsorption capacities increased sharply at pH 4.5 to 5.5, plateaued at pH 5.5 to 7.0, then decreased sharply as pH increased from 7.0 to 8.0. The O2-reoxidized sediment retained a lower desorption efficiency at pH over 6.0. The NO3--reoxidized sediment exhibited higher adsorption capacity at pH 5.5 to 6.0. The pH-dependent adsorption onto Fe(III) oxides and formation of U coated particles and precipitates resulted in U sequestration, and bioreduction followed by reoxidation can enhance the U sequestration in sediment.

Arsenic and fluoride removal from contaminated drinking water with Haix-Fe-Zr and Haix-Zr resin beads.

The objective of the study was to carry-out batch tests to examine the effectiveness of Haix-Fe-Zr and Haix-Zr resin beads in the removal of As(III), As(V) and F- from groundwater with a similar geochemistry to a site where a community-based drinking water plant has been installed in West Bengal, India. The groundwater was spiked separately with ∼200 µg/L As(III) and As(V) and 5 mg/L F-. Haix-Zr resin beads were more effective than Haix-Fe-Zr resin beads in removing As(III) and As(V). Haix-Zr resin beads showed higher removal of As(V) compared to As(III). Haix-Zr resin beads removed As(V) below the WHO (10 µg/L) drinking water standards at 8.79 µg/L after 4 h of shaking, while As(III) was reduced to 7.72 µg/L after 8 h of shaking. Haix-Fe-Zr resin beads were more effective in removing F- from the spiked groundwater compared to Haix-Zr resin beads. Concentrations of F- decreased from 6.27 mg/L to 1.26 mg/L, which is below the WHO drinking water standards (1.5 mg/L) for F-, after 15 min of shaking with Haix-Fe-Zr resin beads. After 20 min of shaking in groundwater treated with Haix-Zr resin beads, F- concentrations decreased from 6.27 mg/L to 1.43 mg/L. In the removal of As(III), As(V), and F- from the groundwater, Haix-Fe-Zr and Haix-Zr resin beads fit the parabolic diffusion equation (PDE) suggesting that adsorption of these contaminants was consistent with inter-particle diffusion.

Formation of Soluble Mercury Oxide Coatings: Transformation of Elemental Mercury in Soils.

The impact of mercury (Hg) on human and ecological health has been known for decades. Although a treaty signed in 2013 by 147 nations regulates future large-scale mercury emissions, legacy Hg contamination exists worldwide and small-scale releases will continue. The fate of elemental mercury, Hg(0), lost to the subsurface and its potential chemical transformation that can lead to changes in speciation and mobility are poorly understood. Here, we show that Hg(0) beads interact with soil or manganese oxide solids and X-ray spectroscopic analysis indicates that the soluble mercury coatings are HgO. Dissolution studies show that, after reacting with a composite soil, >20 times more Hg is released into water from the coated beads than from a pure liquid mercury bead. An even larger, >700 times, release occurs from coated Hg(0) beads that have been reacted with manganese oxide, suggesting that manganese oxides are involved in the transformation of the Hg(0) beads and creation of the soluble mercury coatings. Although the coatings may inhibit Hg(0) evaporation, the high solubility of the coatings can enhance Hg(II) migration away from the Hg(0)-spill site and result in potential changes in mercury speciation in the soil and increased mercury mobility.

Reducing SCADA System Nuisance Alarms in the Water Industry in Northern Ireland.

The advancement of telemetry control for the water industry has increased the difficulty of managing large volumes of nuisance alarms (i.e., alarms that do not require a response). The aim of this study was to identify and reduce the number of nuisance alarms that occur for Northern Ireland (NI) Water by carrying out alarm duration analysis to determine the appropriate length of persistence (an advanced alarm management tool) that could be applied. All data were extracted from TelemWeb (NI Water's telemetry monitoring system) and analyzed in Excel. Over a 6-week period, an average of 40 000 alarms occurred per week. The alarm duration analysis, which has never been implemented before by NI Water, found that an average of 57% of NI Water alarms had a duration of <5 minutes. Applying 5-minute persistence, therefore, could prevent an average 26 816 nuisance alarms per week. Most of these alarms were from wastewater assets.

Retrospective assessment of dryland soil stability in relation to grazing and climate change.

Accelerated soil erosion is an aspect of dryland degradation that is affected by repeated intense drought events and land management activities such as commercial livestock grazing. A soil stability index (SSI) that detects the erosion status and susceptibility of a landscape at the pixel level, i.e., stable, erosional, or depositional pixels, was derived from the spectral properties of an archived time series (from 1972 to 1997) of Landsat satellite data of a commercial ranch in northeastern Utah. The SSI was retrospectively validated with contemporary field measures of soil organic matter and erosion status that was surveyed by US federal land management agencies. Catastrophe theory provided the conceptual framework for retrospective assessment of the impact of commercial grazing and soil water availability on the SSI. The overall SSI trend was from an eroding landscape in the early drier 1970s towards stable conditions in the wetter mid-1980s and late 1990s. The landscape catastrophically shifted towards an extreme eroding state that was coincident with the "The Great North American Drought of 1988". Periods of landscape stability and trajectories toward stability were coincident with extremely wet El Niño events. Commercial grazing had less correlation with soil stability than drought conditions. However, the landscape became more susceptible to erosion events under multiple droughts and grazing. Land managers now have nearly a year warning of El Niño and La Niña events and can adjust their management decisions according to predicted landscape erosion conditions.

Ubiquity of polystyrene digestion and biodegradation within yellow mealworms, larvae of Tenebrio molitor Linnaeus (Coleoptera: Tenebrionidae).

Academics researchers and "citizen scientists" from 22 countries confirmed that yellow mealworms, the larvae of Tenebrio molitor Linnaeus, can survive by eating polystyrene (PS) foam. More detailed assessments of this capability for mealworms were carried out by12 sources: five from the USA, six from China, and one from Northern Ireland. All of these mealworms digested PS foam. PS mass decreased and depolymerization was observed, with appearance of lower molecular weight residuals and functional groups indicative of oxidative transformations in extracts from the frass (insect excrement). An addition of gentamycin (30 mg g-1), a bactericidal antibiotic, inhibited depolymerization, implicating the gut microbiome in the biodegradation process. Microbial community analyses demonstrated significant taxonomic shifts for mealworms fed diets of PS plus bran and PS alone. The results indicate that mealworms from diverse locations eat and metabolize PS and support the hypothesis that this capacity is independent of the geographic origin of the mealworms, and is likely ubiquitous to members of this species.

Physicochemical and mineralogical characterization of soil-saprolite cores from a field research site, Tennessee.

Site characterization is an essential initial step in determining the feasibility of remedial alternatives at hazardous waste sites. Physicochemical and mineralogical characterization of U-contaminated soils in deeply weathered saprolite at Area 2 of the DOE Field Research Center (FRC) site, Oak Ridge, TN, was accomplished to examine the feasibility of bioremediation. Concentrations of U in soil-saprolite (up to 291 mg kg(-1) in oxalate-extractable U(o)) were closely related to low pH (ca. 4-5), high effective cation exchange capacity without Ca (64.7-83.2 cmol(c) kg(-1)), amorphous Mn content (up to 9910 mg kg(-1)), and the decreased presence of relative clay mineral contents in the bulk samples (i.e., illite 2.5-12 wt. %, average 32 wt. %). The pH of the fill material ranged from 7.0 to 10.5, whereas the pH of the saprolite ranged from 4.5 to 8. Uranium concentration was highest (about 300 mg kg(-1)) at around 6 m below land surface near the saprolite-fill interface. The pH of ground water at Area 2 tended to be between 6 and 7 with U concentrations of about 0.9 to 1.7 mg L(-1). These site specific characteristics of Area 2, which has lower U and nitrate contamination levels and more neutral ground water pH compared with FRC Areas 1 and 3 (ca. 5.5 and <4, respectively), indicate that with appropriate addition of electron donors and nutrients bioremediation of U by metal reducing microorganisms may be possible.

Distribution of arsenic and risk assessment of activities on a golf course fertilised with arsenic-containing Ascophyllum nodosum seaweed.

The use of seaweed fertilisers in sports green maintenance has become a common practice across the globe due to its image as an "eco-friendly" alternative to chemical fertilisers. The aim of this study was to characterise the risk of human exposure to arsenic (As), via dermal absorption, from golfing activities on a private golf course in the UK, where As contaminated seaweed fertiliser (~100mg/kg d.wt.) is applied. This was fulfilled by, 1) determining As concentrations in shallow soils with GIS geo-statistical analysis, 2) measuring As concentrations from an on-site borehole groundwater well, and (3) developing a risk assessment calculation for golfing activities based on field and questionnaire data. Total As concentrations in shallow soils were less than the UK threshold for domestic soils, however, frequent and sustained dermal contact between site-users and surface soil attributed to a maximum carcinogenic risk value of 2.75×10(-4), which is in the upper limit of the acceptable risk range. Arsenic concentrations in underlying groundwater exceeded the WHO's permissible drinking water standard, demonstrating the risk of groundwater contamination following the application of seaweed fertiliser to golf course soils. This is the first risk study on dermal As absorption via the application of a seaweed fertiliser.

Removal of natural hormones in dairy farm wastewater using reactive and sorptive materials.

The objective of this study was to examine the oestrogen and androgen hormone removal efficiency of reactive (Connelly zero-valent iron (ZVI), Gotthart Maier ZVI) and sorptive (AquaSorb 101 granular activated carbon (GAC) and OrganoLoc PM-100 organoclay (OC)) materials from HPLC grade water and constructed wetland system (CWS) treated dairy farm wastewater. Batch test studies were performed and hormone concentration analysis carried out using highly sensitive reporter gene assays (RGAs). The results showed that hormonal interaction with these materials is selective for individual classes of hormones. Connelly ZVI and AquaSorb 101 GAC were more efficient in removing testosterone (Te) than 17ß-estradiol (E2) and showed faster removal rates of oestrogen and androgen than the other materials. Gotthart Maier ZVI was more efficient in removing E2 than Te. OrganoLoc PM-100 OC achieved the lowest final concentration of E2 equivalent (EEQ) and provided maximum removal of both oestrogens and androgens.

Treatment of estrogens and androgens in dairy wastewater by a constructed wetland system.

Constructed wetland systems (CWS) have been used as a low cost bio-filtration system to treat farm wastewater. While studies have shown that CWS are efficient in removing organic compounds and pathogens, there is limited data on the presence of hormones in this type of treatment system. The objective of this study was to evaluate the ability of the CWS to reduce estrogenic and androgenic hormone concentration in dairy wastewater. This was achieved through a year long study on dairy wastewater samples obtained from a surface flow CWS. Analysis of hormonal levels was performed using a solid phase extraction (SPE) sample clean-up method, combined with reporter gene assays (RGAs) which incorporate relevant receptors capable of measuring total estrogenic or androgenic concentrations as low as 0.24 ng L(-1) and 6.9 ng L(-1) respectively. Monthly analysis showed a mean removal efficiency for estrogens of 95.2%, corresponding to an average residual concentration of 3.2 ng L(-1) 17ß-estradiol equivalent (EEQ), below the proposed lowest observable effect concentration (LOEC) of 10 ng L(-1). However, for one month a peak EEQ concentration of 115 ng L(-1) was only reduced to 18.8 ng L(-1). The mean androgenic activity peaked at 360 ng L(-1) and a removal efficiency of 92.1% left an average residual concentration of 32.3 ng L(-1) testosterone equivalent (TEQ). The results obtained demonstrate that this type of CWS is an efficient system for the treatment of hormones in dairy wastewater. However, additional design improvements may be required to further enhance removal efficiency of peak hormone concentrations.

Uranium deposition in a weathered fractured saprolite/shale.

Chemical analysis and scanning electron microscopy (SEM) microanalysis were carried out on cores of contaminated geological material collected around four closed waste disposal ponds to examine the extent of nitric acid extractable U (U(NA)) association with P, S, and extractable Fe, Al, and Mn oxides within deeply weathered fractured shale. The solid phase in many regimes on the site has been exposed to highly buffered acidic (< 3.5) groundwater and has been aggressively weathered. Higher correlations occur between U(NA) and total P and S (r2 = 0.76, 0.69, respectively), citrate bicarbonate dithionite extractable Fe (Fed) and Al (Ald) (r2 = 0.87, 0.80, respectively), and acid oxalate extractable or amorphous/poorly crystalline Fe (Feo) (r2 = 0.63) in core material from a field plot known as Area 1 compared to core material from another field plot known as Area 3. In Area 3 core material, linear regression analysis of U(NA) and total P and S, and Fed, Ald and Feo gave r2 values of 0.67, 0.4, 0.06, 0.24, and 0.45, respectively. These results showed similar relationships with SEM-wavelength dispersive spectroscopy (WDS) mapping of this material. It is noteworthy that Area 1 geological material has not been as aggressively weathered as Area 3 material due to its physical location from the waste source. In all of the cores, most of the Fe and Al oxides were crystalline, while most of the Mn oxides were amorphous. The greater adsorption and/or fixation of anion complexes of P-U (uranium phosphate) and S onto Fe and Al oxides from Area 1 cores compared to Area 3 core material is probably due to a higher amount of crystalline Fe and Al oxides compared to amorphous Fe and Al oxides and higher Al substitution in Fe oxides in Area 1. This unique study illustrates the relationships between U(NA), total P and S, and Al, Fe and Mn oxides in fractured shale under field conditions which can be used in planning remediation of this site and other similar sites.

Microbiological characteristics in a zero-valent iron reactive barrier.

Zero-valent iron (Fe0)-based permeable reactive barrier treatment has been generating great interest for passive groundwater remediation, yet few studies have paid particular attention to the microbial activity and characteristics within and in the vicinity of the Fe0-barrier matrix. The present study was undertaken to evaluate the microbial population and community composition in the reducing zone of influence by Fe0 corrosion in the barrier at the Oak Ridge Y-12 Plant site. Both phospholipid fatty acids and DNA analyses were used to determine the total microbial population and microbial functional groups, including sulfate-reducing bacteria, denitrifying bacteria, and methanogens, in groundwater and soil/iron core samples. A diverse microbial community was identified in the strongly reducing Fe0 environment despite a relatively high pH condition within the Fe0 barrier (up to pH approximately 10). In comparison with those found in the background soil/groundwater samples, the enhanced microbial population ranged from approximately 1 to 3 orders of magnitude and appeared to increase from upgradient of the barrier to downgradient soil. In addition, microbial community composition appeared to change over time, and the bacterial types of microorganisms increased consistently as the barrier aged. DNA analysis indicated the presence of sulfate-reducing and denitrifying bacteria in the barrier and its surrounding soil. However, the activity of methanogens was found to be relatively low, presumably as a result of the competition by sulfate/metal-reducing bacteria and denitrifying bacteria because of the unlimited availability of sulfate and nitrate in the site groundwater. Results of this study provide evidence of a diverse microbial population within and in the vicinity of the iron barrier, although the important roles of microbial activity, either beneficially or detrimentally, on the longevity and enduring efficiency of the Fe0 barriers are yet to be evaluated.