Radioactivity measurements and radiation dose evaluation in tap waters of Central Italy

Consumption of drinking water is very important for human nutrition and its quality must be strictly controlled. A study of radioactivity content in tap water samples collected in the Central Italy was performed in order to check the compliance with recent European regulations. Gross alpha and beta activity, 226Ra, 238U and 234U concentrations were measured. Gross alpha and beta activities were determined by standard ISO 9696 and ISO 9697; for 226Ra determination liquid scintillation was used. 238U and 234U concentrations were determined by alpha spectrometry after separation from matrix by extraction chromatography and electroplating. Recommended WHO guideline activity concentrations for drinking water (0.1 and 1.0 Bq/L for gross alpha and gross beta activity, respectively) are exceeded in two cases for gross alpha activity and are not exceeded in any case for gross beta activity. The concentrations (mBq/L) of 226Ra, 238U and 234U ranged from <1.70 to 15.3, 0.65 to 48.8 and 0.780 to 51.5, respectively. Effective dose due to the uranium isotopes and radium was calculated for children and adults using the dose coefficients reported by EC Directive 96/29 EURATOM and annual water intake. For all class ages, the doses are quite similar and much lower than 0.1 mSv/year.     

Methods for estimating adsorbed uranium(VI) and distribution coefficients of contaminated sediments

Assessing the quantity of U(VI) that participates in sorption/desorption processes in a contaminated aquifer is an important task when investigating U migration behavior. U-contaminated aquifer sediments were obtained from 16 different locations at a former U mill tailings site at Naturita, CO (U.S.A.) and were extracted with an artificial groundwater, a high pH sodium bicarbonate solution, hydroxylamine hydrochloride solution, and concentrated nitric acid. With an isotopic exchange method, both a KD value for the specific experimental conditions as well as the total exchangeable mass of U(VI) was determined. Except for one sample, KD values determined by isotopic exchange with U-contaminated sediments that were in equilibrium with atmospheric CO2 agreed within a factor of 2 with KD values predicted from a nonelectrostatic surface complexation model (NEM) developed from U(VI) adsorption experiments with uncontaminated sediments. The labile fraction of U(VI) and U extracted by the bicarbonate solution were highly correlated (r2 = 0.997), with a slope of 0.96 +/- 0.01. The proximity of the slope to one suggests that both methods likely access the same reservoir of U(VI) associated with the sediments. The results indicate that the bicarbonate extraction method is useful for estimating the mass of labile U(VI) in sediments that do not contain U(IV). In-situ KD values calculated from the measured labile U(VI) and the dissolved U(VI) in the Naturita alluvial aquifer agreed within a factor of 3 with in-situ KD values predicted with the NEM and groundwater chemistry at each well.     

In situ bioreduction of uranium (VI) to submicromolar levels and reoxidation by dissolved oxygen

Groundwater within Area 3 of the U.S. Department of Energy (DOE) Environmental Remediation Sciences Program (ERSP) Field Research Center at Oak Ridge, TN (ORFRC) contains up to 135 microM uranium as U(VI). Through a series of experiments at a pilot scale test facility, we explored the lower limits of groundwater U(VI) that can be achieved by in-situ biostimulation and the effects of dissolved oxygen on immobilized uranium. Weekly 2 day additions of ethanol over a 2-year period stimulated growth of denitrifying, Fe(III)-reducing, and sulfate-reducing bacteria, and immobilization of uranium as U(IV), with dissolved uranium concentrations decreasing to low levels. Following sulfite addition to remove dissolved oxygen, aqueous U(VI) concentrations fell below the U.S. Environmental Protection Agengy maximum contaminant limit (MCL) for drinking water (< 30/microg L(-1) or 0.126 microM). Under anaerobic conditions, these low concentrations were stable, even in the absence of added ethanol. However, when sulfite additions stopped, and dissolved oxygen (4.0-5.5 mg L(-1)) entered the injection well, spatially variable changes in aqueous U(VI) occurred over a 60 day period, with concentrations increasing rapidly from < 0.13 to 2.0 microM at a multilevel sampling (MLS) well located close to the injection well, but changing little at an MLS well located further away. Resumption of ethanol addition restored reduction of Fe(III), sulfate, and U(VI) within 36 h. After 2 years of ethanol addition, X-ray absorption near-edge structure spectroscopy (XANES) analyses indicated that U(IV) comprised 60-80% of the total uranium in sediment samples. Atthe completion of the project (day 1260), U concentrations in MLS wells were less than 0.1 microM. The microbial community at MLS wells with low U(VI) contained bacteria that are known to reduce uranium, including Desulfovibrio spp. and Geobacter spp., in both sediment and groundwater. The dominant Fe(III)-reducing species were Geothrix spp.     

Identifying the sources of subsurface contamination at the Hanford Site in Washington using high-precision uranium isotopic measurements

In the mid-1990s, a groundwater plume of uranium (U) was detected in monitoring wells in the B-BX-BY Waste Management Area at the Hanford Site in Washington. This area has been used since the late 1940s to store high-level radioactive waste and other products of U fuel-rod processing. Using multiple-collector ICP source magnetic sector mass spectrometry, high-precision uranium isotopic analyses were conducted of samples of vadose zone contamination and of groundwater. The isotope ratios 236U/238U, 234U/238U, and 238U/235U are used to distinguish contaminant sources. On the basis of the isotopic data, the source of the groundwater contamination appears to be related to a 1951 overflow event at tank BX-102 that spilled high-level U waste into the vadose zone. The U isotopic variation of the groundwater plume is a result of mixing between contaminant U from this spill and natural background U. Vadose zone U contamination at tank B-110 likely predates the recorded tank leak and can be ruled out as a significant source of groundwater contamination, based on the U isotopic composition. The locus of vadose zone contamination is displaced from the initial locus of groundwater contamination, indicating that lateral migration in the vadose zone was at least 8 times greater than vertical migration. The time evolution of the groundwater plume suggests an average U migration rate of approximately 0.7-0.8 m/day showing slight retardation relative to a groundwater flow of approximately 1 m/day.     

Use of ICP/MS with ultrasonic nebulizer for routine determination of uranium activity ratios in natural water

A method is described that allows precise determination of 234U/238U activity ratios (UAR) in most natural waters using commonly available inductively coupled plasma/mass spectrometry (ICP/MS) instrumentation and accessories. The precision achieved by this technique (+/- 0.5% RSD, 1 sigma) is intermediate between thermal ionization mass spectrometry (+/- 0.25% RSD, 1 sigma) and alpha particle spectrometry (+/- 5% RSD, 1 sigma). It is precise and rapid enough to allow analysis of a large number of samples in a short period of time at low cost using standard, commercially available quadrupole instrumentation with ultrasonic nebulizer and desolvator accessories. UARs have been analyzed successfully in fresh to moderately saline waters with U concentrations of from less than 1 microg/L to nearly 100 microg/L. An example of the uses of these data is shown for a study of surface-water mixing in the North Platte River in western Nebraska. This rapid and easy technique should encourage the wider use of uranium isotopes in surface-water and groundwater investigations, both for qualitative (e.g. identifying sources of water) and quantitative (e.g. determining end-member mixing ratios purposes.     

Microbial reductive transformation of phyllosilicate Fe(III) and U(VI) in fluvial subsurface sediments

The microbial reduction of Fe(III) and U(VI) was investigated in shallow aquifer sediments collected from subsurface flood deposits near the Hanford Reach of the Columbia River in Washington State. Increases in 0.5 N HCl-extractable Fe(II) were observed in incubated sediments and (57)Fe M?ssbauer spectroscopy revealed that Fe(III) associated with phyllosilicates and pyroxene was reduced to Fe(II). Aqueous uranium(VI) concentrations decreased in subsurface sediments incubated in sulfate-containing synthetic groundwater with the rate and extent being greater in sediment amended with organic carbon. X-ray absorption spectroscopy of bioreduced sediments indicated that 67-77% of the U signal was U(VI), probably as an adsorbed species associated with a new or modified reactive mineral phase. Phylotypes within the Deltaproteobacteria were more common in Hanford sediments incubated with U(VI) than without, and in U(VI)-free incubations, members of the Clostridiales were dominant with sulfate-reducing phylotypes more common in the sulfate-amended sediments. These results demonstrate the potential for anaerobic reduction of phyllosilicate Fe(III) and sulfate in Hanford unconfined aquifer sediments and biotransformations involving reduction and adsorption leading to decreased aqueous U concentrations.     

Dissolved organic carbon reduces uranium bioavailability and toxicity. 2. Uranium[VI] speciation and toxicity to three tropical freshwater organisms

The influence of dissolved organic carbon (DOC) on the toxicity of uranium (U) to three Australian tropical freshwater species, the Northern Trout Gudgeon (Mogurnda mogurnda), green hydra (Hydra viridissima) and unicellular green alga (Chlorella sp.) was assessed. Exposures were conducted in synthetic soft water without DOC and with DOC added in the form of standard Suwannee River Fulvic Acid (SRFA). Organisms were exposed to a range of U concentrations at a range of DOC concentrations (0-20 mg L(-1)). U toxicity was up to 20 times less in water containing 20 mg L(-1) DOC, relative to DOC-free test waters. U toxicity was also assessed using natural water from a tropical Australian billabong containing 10 mg L(-1) DOC. U toxicity was up to ten times less in the billabong water, relative to DOC--free test waters. SRFA was twice as effective at reducing U toxicity as the billabong water at equivalent DOC concentrations. Geochemical speciation modeling confirmed the decreased U toxicity that resulted from both DOC sources was primarily due to a decrease in the free uranyl ion (UO2(2+)) through complexation with DOC. A predictive model is presented for each of the organisms that can be used to predict U toxicity at a given U and DOC concentration.     

Molybdenum speciation in uranium mine tailings using X-ray absorption spectroscopy

Uranium (U) mill tailings in northern Saskatchewan, Canada, contain elevated concentrations of molybdenum (Mo). The potential for long-term (>10,000 years) mobilization of Mo from the tailings management facilities to regional groundwater systems is an environmental concern. To assist in characterizing long-term stability, X-ray absorption spectroscopy was used to define the chemical (redox and molecular) speciation of Mo in tailings samples from the Deilmann Tailings Management Facility (DTMF) at the Key Lake operations of Cameco Corporation. Comparison of Mo K near-edge X-ray absorption spectra of tailings samples and reference compounds of known oxidation states indicates Mo exists mainly as molybdate (+6 oxidation state). Principal component analysis of tailings samples spectra followed by linear combination fitting using spectra of reference compounds indicates that various proportions of NiMoO(4) and CaMoO(4) complexes, as well as molybdate adsorbed onto ferrihydrite, are the Mo species present in the U mine tailings. Tailings samples with low Fe/Mo (<708) and high Ni/Mo (>113) molar ratios are dominated by NiMoO(4), whereas those with high Fe/Mo (>708) and low Ni/Mo (<113) molar ratios are dominated by molybdate adsorbed onto ferrihydrite. This suggests that the speciation of Mo in the tailings is dependent in part on the chemistry of the original ore.     

Time scales for sorption-desorption and surface precipitation of uranyl on goethite

The sorption of uranium on mineral surfaces can significantly influence the fate and transport of uranium contamination in soils and groundwater. The rates of uranium adsorption and desorption on a synthetic goethite have been evaluated in batch experiments conducted at constant pH of 6 and ionic strength of 0.1 M. Adsorption and desorption reactions following the perturbation of initial states were complete within minutes to hours. Surface-solution exchange rates as measured by an isotope exchange method occur on an even shorter time scale. Although the uranium desorption rate was unaffected by the aging of uranium-goethite suspensions, the aging process appears to remove a portion of adsorbed uranium from a readily exchangeable pool. The distinction between sorption control and precipitation control of the dissolved uranium concentration was also investigated. In heterogeneous nucleation experiments, the dissolved uranium concentration was ultimately controlled by the solubility of a precipitated uranyl oxide hydrate. The X-ray diffraction pattern of the precipitate is characteristic of the mineral schoepite. Precipitation is kinetically hindered at low degrees of supersaturation. In one experiment, metastable sorption controlled dissolved uranium concentrations in excess of the solubility limit for more than 30 d.     

Isotopic disequilibrium during uptake of atmospheric CO2 into mine process waters: implications for CO2 sequestration

Dypingite, a hydrated Mg-carbonate mineral, was precipitated from high-pH, high salinity solutions to investigate controls on carbon fixation and to identify the isotopic characteristics of mineral sequestration in mine tailings. δ(13)C values of dissolved inorganic carbon content and synthetic dypingite are significantly more negative than those predicted for equilibrium exchange of CO(2) gas between the atmosphere and solution. The measured δ(13)C of aqueous carbonate species is consistent with a kinetic fractionation that results from a slow diffusion of atmospheric CO(2) into solution. During dypingite precipitation, dissolved inorganic carbon concentrations decrease and δ(13)C values become more negative, indicating that the rate of CO(2) uptake into solution was outpaced by the rate of carbon fixation within the precipitate. This implies that CO(2) gas uptake is rate-limiting to CO(2) fixation. δ(13)C of carbonate mineral precipitates in mine tailings and of DIC in mine process waters display similar (13)C-depletions that are inconsistent with equilibrium fractionation. Thus, the rate of carbon fixation in mine tailings may also be limited by supply of CO(2). Carbon sequestration could be accelerated by increasing the partial pressure of CO(2) in tailings ponds or by using chemicals that enhance the uptake of gaseous CO(2) into aqueous solution.     

Water use for Shale-gas production in Texas, U.S

Shale-gas production using hydraulic fracturing of mostly horizontal wells has led to considerable controversy over water-resource and environmental impacts. The study objective was to quantify net water use for shale-gas production using data from Texas, which is the dominant producer of shale gas in the U.S. with a focus on three major plays: the Barnett Shale (~15,000 wells, mid-2011), Texas-Haynesville Shale (390 wells), and Eagle Ford Shale (1040 wells). Past water use was estimated from well-completion data, and future water use was extrapolated from past water use constrained by shale-gas resources. Cumulative water use in the Barnett totaled 145 Mm(3) (2000-mid-2011). Annual water use represents ~9% of water use in Dallas (population 1.3 million). Water use in younger (2008-mid-2011) plays, although less (6.5 Mm(3) Texas-Haynesville, 18 Mm(3) Eagle Ford), is increasing rapidly. Water use for shale gas is <1% of statewide water withdrawals; however, local impacts vary with water availability and competing demands. Projections of cumulative net water use during the next 50 years in all shale plays total ~4350 Mm(3), peaking at 145 Mm(3) in the mid-2020s and decreasing to 23 Mm(3) in 2060. Current freshwater use may shift to brackish water to reduce competition with other users.     

Sedimentological control on Mn, and other trace elements, in groundwater of the Bengal delta

To reveal what controls the concentration and distribution of possibly hazardous (Mn, U, Se, Cd, Bi, Pb) and nonhazardous (Fe, V, Mo, PO(4)) trace elements in groundwater of the Bengal delta, we mapped their concentrations in shallow groundwater (<60 mbgl) across 102 km(2) of West Bengal. Only Mn is a potential threat to health, with 55% of well water exceeding 0.3 mg/L, the current Indian limit for drinking water in the absence of an alternate source, and 75% exceeding the desirable limit of 0.1 mg/L. Concentrations of V are <3 μg/L. Concentrations of U, Se, Pb, Ni, Bi, and Cd, are below WHO guideline values. The distributions of Fe, Mn, As, V, Mo, U, PO(4), and δ(18)O in groundwater reflect subsurface sedimentology and sources of water. Areas of less negative δ(18)O reveal recharge by sources of evaporated water. Concentrations of Fe, As, Mo, and PO(4) are high in palaeo-channel groundwaters and low in palaeo-interfluvial groundwaters. Concentrations of U, V, and Mn, are low in palaeo-channel groundwaters and high in palaeo-interfluvial groundwaters. Concentrations of Fe and Mn are highest (18 and 6 mg/L respectively) at dual reduction-fronts that form strip interfaces at depth around the edges of palaeo-interfluvial aquifers. The fronts form as focused recharge carries dissolved organic carbon into the aquifer margins, which comprise brown, iron-oxide bearing, sand. At the Mn-reduction front, concentrations of V and Mo reach peak concentrations of 3 μg/L. At the Fe-reduction front, concentrations of PO(4) and As reach concentrations 3 mg/L and 150 μg/L respectively. Many groundwaters contain >10 mg/L of Cl, showing that they are contaminated by Cl of anthropogenic origin and that organic matter from in situ sanitation may contribute to driving reduction.     

Impact of natural organic matter on uranium transport through saturated geologic materials: from molecular to column scale

The risk stemming from human exposure to actinides via the groundwater track has motivated numerous studies on the transport of radionuclides within geologic environments; however, the effects of waterborne organic matter on radionuclide mobility are still poorly understood. In this study, we compared the abilities of three humic acids (HAs) (obtained through sequential extraction of a peat soil) to cotransport hexavalent uranium (U) within water-saturated sand columns. Relative breakthrough concentrations of U measured upon elution of 18 pore volumes increased from undetectable levels (<0.001) in an experiment without HAs to 0.17 to 0.55 in experiments with HAs. The strength of the HA effect on U mobility was positively correlated with the hydrophobicity of organic matter and NMR-detected content of alkyl carbon, which indicates the possible importance of hydrophobic organic matter in facilitating U transport. Carbon and uranium elemental maps collected with a scanning transmission X-ray microscope (STXM) revealed uneven microscale distribution of U. Such molecular- and column-scale data provide evidence for a critical role of hydrophobic organic matter in the association and cotransport of U by HAs. Therefore, evaluations of radionuclide transport within subsurface environments should consider the chemical characteristics of waterborne organic substances, especially hydrophobic organic matter.     

Extraction of oxidized and reduced forms of uranium from contaminated soils: effects of carbonate concentration and pH

Uranium may present in soil as precipitated, sorbed, complexed, and reduced forms, which impact its mobility and fate in the subsurface soil environment. In this study, a uranium-contaminated soil was extracted with carbonate/ bicarbonate at varying concentrations (0-1 M), pHs, and redox conditions in an attempt to evaluate their effects on the extraction efficiency and selectivity for various forms of uranium in the soil. Results indicate that at least three differentforms of uranium existed in the contaminated soil: uranium(VI) phosphate minerals, reduced U(IV) phases, and U(VI) complexed with soil organic matter. A small fraction of U(VI) could be sorbed onto soil minerals. The mechanism involved in the leaching of U(VI) by carbonates appears to involve three processes which may act concurrently or independently: the dissolution of uranium(VI) phosphate and other mineral phases, the oxidation-complexation of U(IV) under oxic conditions, and the desorption of U(VI)-organic matter complexes at elevated pH conditions. This study suggests that, depending on site-specific geochemical conditions, the presence of small quantities of carbonate/bicarbonate could result in a rapid and greatly increased leaching and the mobilization of U(VI) from the contaminated soil. Even the reduced U(IV) phases (only sparingly soluble in water) are subjected to rapid oxidation and therefore potential leaching into the environment.     

Kinetics of soluble chromium removal from contaminated water by zerovalent iron media: corrosion inhibition and passive oxide effects

Permeable reactive barriers containing zerovalent iron are being increasingly employed for in situ remediation of groundwater contaminated with redox active metals and chlorinated organic compounds. This research investigated the effect of chromate concentration on its removal from solution by zerovalent iron. Removal rates of aqueous Cr(VI) by iron wires were measured in batch experiments for initial chromium concentrations ranging from 100 to 10 000 microg/L. Chromate removal was also measured in columns packed with zerovalent iron filings over this same concentration range. Electrochemical measurements were made to determine the free corrosion potential and corrosion rate of the iron reactants. In both the batch and column reactors, absolute rates of chromium removal declined with increasing chromate concentration. Corrosion current measurements indicated that the rate of iron corrosion decreased with increasing Cr(VI) concentrations between 0 and 5000 microg/L. At a Cr(VI) concentration of 10 000 microg/L, Tafel polarization diagrams showed that chromium removal was affected by its diffusion rate through a passivating oxide film and by the ability of iron to release Fe2+ at anodic sites. In contrast, water reduction was not mass transfer limited, but chromium did decrease the exchange current for the hydrogen evolution reaction. Even at the most passivating concentration of 10 000 microng/L, effluent Cr(VI) concentrations in the column reactors reached a steady state, indicating that passivation had also reached a steady state. Although chromate contributes to iron surface passivation, the removal rates are still sufficiently fast for in situ iron barriers to be effective for Cr(VI) removal at most environmentally relevant concentrations.     

Early breakthrough of molybdenum and uranium in a permeable reactive barrier

A permeable reactive barrier (PRB) using zerovalent iron (ZVI) was installed at a site near Ca?on City, CO, to treat molybdenum (Mo) and uranium (U) in groundwater. The PRB initially decreased Mo concentrations from about 4.8 to less than 0.1 mg/L; however, Mo concentrations in the ZVI increased to 2.0 mg/L after about 250 days and continued to increase until concentrations in the ZVI were about 4 times higherthan in the influent groundwater. Concentrations of U were reduced from 1.0 to less than 0.02 mg/L during the same period. Investigations of solid-phase samples indicate that (1) calcium carbonate, iron oxide, and sulfide minerals had precipitated in pores of the ZVI; (2) U and Mo were concentrated in the upgradient 5.1 cm of the ZVI; and (3) calcium was present throughout the ZVI accounting for up to 20.5% of the initial porosity. Results of a column test indicated that the ZVI from the PRB was still reactive for removing Mo and that removal rates were dependenton residence time and pH. The chemical evolution of the PRB is explained in four stages that present a progression from porous media flow through preferential flow and, finally, complete bypass of the ZVI.     

Remediation and recovery of uranium from contaminated subsurface environments with electrodes

Previous studies have demonstrated that Geobacter species can effectively remove uranium from contaminated groundwater by reducing soluble U(VI) to the relatively insoluble U(IV) with organic compounds serving as the electron donor. Studies were conducted to determine whether electrodes might serve as an alternative electron donor for U(VI) reduction by a pure culture of Geobacter sulfurreducens and microorganisms in uranium-contaminated sediments. Electrodes poised at -500 mV (vs a Ag/AgCl reference) rapidly removed U(VI) from solution in the absence of cells. However, when the poise at the electrode was removed, all of the U(VI) returned to solution, demonstrating that the electrode did not reduce U(VI). If G. sulfurreducens was present on the electrode, U(VI) did not return to solution until the electrode was exposed to dissolved oxygen. This suggeststhat G. sulfurreducens on the electrode reduced U(VI) to U(IV) which was stably precipitated until reoxidized in the presence of oxygen. When an electrode was placed in uranium-contaminated subsurface sediments, U(VI) was removed and recovered from groundwater using poised electrodes. Electrodes emplaced in flow-through columns of uranium-contaminated sediments readily removed U(VI) from the groundwater, and 87% of the uranium that had been removed was recovered from the electrode surface after the electrode was pulled from the sediments. These results suggest that microorganisms can use electrons derived from electrodes to reduce U(VI) and that it may be possible to remove and recover uranium from contaminated groundwater with poised electrodes.     

Electron microbeam investigation of uranium-contaminated soils from Oak Ridge, TN, USA

Two samples of uranium-contaminated soil from the Department of Energy's Oak Ridge Reservation in Oak Ridge, Tennessee were investigated using electron microprobe analysis and transmission electron microscopy. The objectives of this research were to identify and characterize soil particles and rock chips with high uranium concentrations, to investigate the extent of uranium penetration into chips of parent material, and to identify solid-phase hosts for uranium in the samples. Three distinct solid-phase hosts for uranium have been identified: (1) iron oxyhydroxides, including goethite and ferrihydrite; (2) mixed Mn-Fe oxides; and (3) discrete uranium phosphates. In all three, uranium is associated with phosphorus. The ubiquitous U-P association highlights the influence of phosphate on the environmental fate of uranium. Uranium-bearing phases are found well within chips of weathered shale, as far as 900 microm from fractures and chip edges, indicating that uranium has diffused into the shale matrix.     

Arsenic transformation and mobilization from minerals by the arsenite oxidizing strain WAO

Analysis of arsenic concentrations in New Jersey well water from the Newark Basin showed up to 15% of the wells exceed 10 microg L(-1), with a maximum of 215 microg L(-1). In some geologic settings in the basin, this mobile arsenic could be from the weathering of pyrite (FeS2) found in black shale that contains up to 4% arsenic by weight. We hypothesized that under oxic conditions at circumneutral pH, the microbially mediated oxidation of sulfide in the pyrite lattice would lead to the release of pyrite-bound arsenic. Moreover, the oxidation of aqueous As(III) to As(V) by aerobic microorganisms could further enhance arsenic mobilization from the solid phase. Enrichment cultures under aerobic, As(III)-oxidizing conditions were established under circumneutral pH with weathered black shale from the Newark Basin as the inoculum source. Strain WAO, an autotrophic inorganic-sulfur and As(III)-oxidizer, was isolated and phylogenetically and physiologically characterized. Arsenic mobilization studies from arsenopyrite (FeAsS) mineral, conducted with strain WAO at circumneutral pH, showed microbially enhanced mobilization of arsenic and complete oxidation of released arsenic and sulfur to stoichiometric amounts of arsenate and sulfate. In addition, WAO preferentially colonized pyrite on the surface of arsenic-bearing, black shale thick sections. These findings support the hypothesis that microorganisms can directly mobilize and transform arsenic bound in mineral form at circumneutral pH and suggest that the microbial mobilization of arsenic into groundwater may be important in other arsenic-impacted aquifers.     

Uranium biomineralization as a result of bacterial phosphatase activity: insights from bacterial isolates from a contaminated subsurface

Uranium contamination is an environmental concern at the Department of Energy's Field Research Center in Oak Ridge, Tennessee. In this study, we investigated whether phosphate biomineralization, or the aerobic precipitation of U(VI)-phosphate phases facilitated by the enzymatic activities of microorganisms, offers an alternative to the more extensively studied anaerobic U(VI) bioreduction. Three heterotrophic bacteria isolated from FRC soils were studied for their ability to grow and liberate phosphate in the presence of U(VI) and an organophosphate between pH 4.5 and 7.0. The objectives were to determine whether the strains hydrolyzed sufficient phosphate to precipitate uranium, to determine whether low pH might have an effect on U(VI) precipitation, and to identify the uranium solid phase formed during biomineralization. Two bacterial strains hydrolyzed sufficient organophosphate to precipitate 7395% total uranium after 120 h of incubation in simulated groundwater. The highest rates of uranium precipitation and phosphatase activity were observed between pH 5.0 and 7.0. EXAFS spectra identified the uranyl phosphate precipitate as an autunite/meta-autunite group mineral. The results of this study indicate that aerobic heterotrophic bacteria within a uranium-contaminated environment that can hydrolyze organophosphate, especially in low pH conditions, may play an important role in the bioremediation of uranium.