Effect of uranium (VI) on two sulphate-reducing bacteria cultures from a uranium mine site

This work was conducted to assess the impact of uranium (VI) on sulphate-reducing bacteria (SRB) communities obtained from environmental samples collected on the Portuguese uranium mining area of Urgeiriça. Culture U was obtained from a sediment, while culture W was obtained from sludge from the wetland of that mine. Temperature gradient gel electrophoresis (TGGE) was used to monitor community changes under uranium stress conditions. TGGE profiles of dsrB gene fragment demonstrated that the initial cultures were composed of SRB species affiliated with Desulfovibrio desulfuricans, Desulfovibrio vulgaris and Desulfomicrobium spp. (sample U), and by species related to D. desulfuricans (sample W). A drastic change in SRB communities was observed as a result of uranium (VI) exposure. Surprisingly, SRB were not detected in the uranium removal communities. Such findings emphasize the need of monitoring the dominant populations during bio-removal studies. TGGE and phylogenetic analysis of the 16S rRNA gene fragment revealed that the uranium removal consortia are composed by strains affiliated to Clostridium genus, Caulobacteraceae and Rhodocyclaceae families. Therefore, these communities can be attractive candidates for environmental biotechnological applications associated to uranium removal.     

Anaerobic bioremediation of hexavalent uranium in groundwater by reductive precipitation with methanogenic granular sludge

Uranium has been responsible for extensive contamination of groundwater due to releases from mill tailings and other uranium processing waste. Past evidence has confirmed that certain bacteria can enzymatically reduce soluble hexavalent uranium (U(VI)) to insoluble tetravalent uranium (U(IV)) under anaerobic conditions in the presence of appropriate electron donors. This paper focuses on the evaluation of anaerobic granular sludge as a source of inoculum for the bioremediation of uranium in water. Batch experiments were performed with several methanogenic anaerobic granular sludge samples and different electron donors. Abiotic controls consisting of heat-killed inoculum and non-inoculated treatments confirmed the biological removal process. In this study, unadapted anaerobic granular sludge immediately reduced U(VI), suggesting an intrinsic capacity of the sludge to support this process. The high biodiversity of anaerobic granular sludge most likely accounts for the presence of specific microorganisms capable of reducing U(VI). Oxidation by O₂ was shown to resolubilize the uranium. This observation combined with X-ray diffraction evidence of uraninite confirmed that the removal during anaerobic treatment was due to reductive precipitation. The anaerobic removal activity could be sustained after several respikes of U(VI). The U(VI) removal was feasible without addition of electron donors, indicating that the decay of endogenous biomass substrates was contributing electron equivalents to the process. Addition of electron donors, such as H₂ stimulated the removal of U(VI) to varying degrees. The stimulation was greater in sludge samples with lower endogenous substrate levels. The present work reveals the potential application of anaerobic granular sludge for continuous bioremediation schemes to treat uranium-contaminated water.     

Biological reduction of uranium in groundwater and subsurface soil

Biological reduction of uranium is one of the techniques currently studied for in situ remediation of groundwater and subsurface soil. We investigated U(VI) reduction in groundwaters and soils of different origin to verify the presence of bacteria capable of U(VI) reduction. The groundwaters originated from mill tailings sites with U concentrations as high as 50 mg/l, and from other sites where uranium is not a contaminant, but was added in the laboratory to reach concentrations up to 11 mg/l. All waters contained nitrate and sulfate. After oxygen and nitrate reduction, U(VI) was reduced by sulfate-reducing bacteria, whose growth was stimulated by ethanol and trimetaphosphate. Uranium precipitated as hydrated uraninite (UO2 x xH2O). In the course of reduction of U(VI), Mn(IV) and Fe(III) from the soil were reduced as well. During uraninite precipitation a comparatively large mass of iron sulfides formed and served as a redox buffer. If the excess of iron sulfide is large enough, uraninite will not be oxidized by oxygenated groundwater. We show that bacteria capable of reducing U(VI) to U(IV) are ubiquitous in nature. The uranium reducers are primarily sulfate reducers and are stimulated by adding nutrients to the groundwater.     

The influence of biofilms on the migration of uranium in acid mine drainage (AMD) waters

The uranium mine in Königstein (Germany) is currently in the process of being flooded. Huge mass of Ferrovum myxofaciens dominated biofilms are growing in the acid mine drainage (AMD) water as macroscopic streamers and as stalactite-like snottites hanging from the ceiling of the galleries. Microsensor measurements were performed in the AMD water as well as in the biofilms from the drainage channel on-site and in the laboratory. The analytical data of the AMD water was used for the thermodynamic calculation of the predominance fields of the aquatic uranium sulfate (UO₂SO₄) and UO₂⁺⁺ speciation as well as of the solid uranium species Uranophane [Ca(UO₂)₂(SiO₃OH)₂?5H₂O] and Coffinite [U(SiO₄)_1 − x(OH)_4x], which are defined in the stability field of pH > 4.8 and Eh < 960 mV and pH > 0 and Eh < 300 mV, respectively. The plotting of the measured redox potential and pH of the AMD water and the biofilm into the calculated pH-Eh diagram showed that an aqueous uranium(VI) sulfate complex exists under the ambient conditions. According to thermodynamic calculations a retention of uranium from the AMD water by forming solid uranium(VI) or uranium(IV) species will be inhibited until the pH will increase to > 4.8. Even analysis by Energy-filtered Transmission Electron Microscopy (EF-TEM) and electron energy loss spectroscopy (EELS) within the biofilms did not provide any microscopic or spectroscopic evidence for the presence of uranium immobilization. In laboratory experiments the first phase of the flooding process was simulated by increasing the pH of the AMD water. The results of the experiments indicated that the F. myxofaciens dominated biofilms may have a substantial impact on the migration of uranium. The AMD water remained acid although it was permanently neutralized with the consequence that the retention of uranium from the aqueous solution by the formation of solid uranium species will be inhibited.     

The effect of groundwater composition on uranium(VI) sorption onto bacteriogenic iron oxides

In this study, we investigated the effect of groundwater composition on the sorption of U(VI) onto bacteriogenic iron oxides (BIOS) and synthetic ferrihydrite (HFO). The concentration of carbonate was found to be the key factor controlling U(VI) sorption onto both BIOS and HFO. However, the efficiency of HFO to adsorb uranium(VI) was higher than that of BIOS at pH 7.0. The pH value also played an important role on the U(VI) sorption onto iron oxides. U(VI) sorption onto BIOS was optimum in the pH range 3-4.5, whereas in the same pH range, the ability of HFO to adsorb U(VI) was very low. HFO was very efficient in adsorbing U(VI) in the pH range 4.5-6.5. Zeta potential measurements have been employed to understand the different removal trends between BIOS and HFO. BIOS had a negative surface charge across the whole pH range examined, in contrast to HFO, which had point of zero charge 7.6. The sorption results have been incorporated in a surface complexation model, which predicted adequately the pH-dependent sorption of U(VI) onto both types of iron oxides.     

Microbial reduction of uranium under iron- and sulfate-reducing conditions: Effect of amended goethite on microbial community composition and dynamics

There is a growing need for a better understanding of the biogeochemical dynamics involved in microbial U(VI) reduction due to an increasing interest in using biostimulation via electron donor addition as a means to remediate uranium contaminated sites. U(VI) reduction has been observed to be maximized during iron-reducing conditions and to decrease upon commencement of sulfate-reducing conditions. There are many unknowns regarding the impact of iron/sulfate biogeochemistry on U(VI) reduction. This includes Fe(III) availability as well as the microbial community changes, including the activity of iron-reducers during the uranium biostimulation period even after sulfate reduction becomes dominant. Column experiments were conducted with Old Rifle site sediments containing Fe-oxides, Fe-clays, and sulfate rich groundwater. Half of the columns had sediment that was augmented with small amounts of Fe(III) in the form of ⁵⁷Fe-goethite, allowing for a detailed tracking of minute changes of this added phase to study the effects of increased Fe(III) levels on the overall biostimulation dynamics. Mössbauer spectroscopy showed that the added ⁵⁷Fe-goethite was bioreduced only during the first thirty days of biostimultuion, after which it remained constant. Augmentation with Fe(III) had a significant effect on the total flux of electrons towards different electron acceptors; it suppressed the degree of sulfate reduction, had no significant impact on Geobacter-type bacterial numbers but decreased the bacterial numbers of sulfate reducers and affected the overall microbial community composition. The addition of Fe(III) had no noticeable effect on the total uranium reduction.     

Uranium reduction and resistance to reoxidation under iron-reducing and sulfate-reducing conditions

Oxidation and mobilization of microbially-generated U(IV) is of great concern for in situ uranium bioremediation. This study investigated the reoxidation of uranium by oxygen and nitrate in a sulfate-reducing enrichment and an iron-reducing enrichment derived from sediment and groundwater from the Field Research Center in Oak Ridge, Tennessee. Both enrichments were capable of reducing U(VI) rapidly. 16S rRNA gene clone libraries of the two enrichments revealed that Desulfovibrio spp. are dominant in the sulfate-reducing enrichment, and Clostridium spp. are dominant in the iron-reducing enrichment. In both the sulfate-reducing enrichment and the iron-reducing enrichment, oxygen reoxidized the previously reduced uranium but to a lesser extent in the iron-reducing enrichment. Moreover, in the iron-reducing enrichment, the reoxidized U(VI) was eventually re-reduced to its previous level. In both, the sulfate-reducing enrichment and the iron-reducing enrichment, uranium reoxidation did not occur in the presence of nitrate. The results indicate that the Clostridium-dominated iron-reducing communities created conditions that were more favorable for uranium stability with respect to reoxidation despite the fact that fewer electron equivalents were added to these systems. The likely reason is that more of the added electrons are present in a form that can reduce oxygen to water and U(VI) back to U(IV).     

Arsenic speciation and uranium concentrations in drinking water supply wells in Northern Greece: correlations with redox indicative parameters and implications for groundwater treatment

The cities in the Aksios and Kalikratia areas in Northern Greece rely on arsenic contaminated groundwater for their municipal water supply. As remedial action strongly depends on arsenic speciation, the presence of other possible contaminants, and on the general water composition, a detailed study with samples from 21 representative locations was undertaken. Arsenic concentrations were typically 10-70 microg/L. In the groundwaters of the Aksios area with lower Eh values (87-172 mV), pH 7.5-8.2 and 4-6 mM HCO(3) alkalinity, As(III) predominated. Manganese concentrations were mostly above the EC standard of 0.05 mg/L (0.1-0.7 mg/L). In groundwaters of the Kalikratia area with higher Eh values (272-352 mV), pH 6.7-7.5 and 6-12 mM HCO(3) alkalinity, As(V) was the main species. Uranium in the groundwaters was also investigated and correlations with total arsenic concentrations and speciation were examined to understand more of the redox chemistry of the examined groundwaters. Uranium concentrations were in the range 0.01-10 microg/L, with the higher concentrations to occur in the oxidizing groundwaters of the Kalikratia area. Uranium and total arsenic concentrations showed no correlation, whereas uranium concentrations correlated strongly with As(III)/As(tot) ratios, depicting their use as a possible indicator of groundwater redox conditions. Finally, boron was found to exceed the EC drinking water standard of 1 mg/L in some wells in the Kalikratia area and its removal should also be considered in the design of a remedial action.     

Biological and chemical interactions with U(VI) during anaerobic enrichment in the presence of iron oxide coated quartz

Microcosm experiments were performed to understand chemical and biological interactions with hexavalent uranium (U(VI)) in the presence of iron oxide bearing minerals and trichloroethylene (TCE) as a co-contaminant. Interactions of U(VI) and hydrous iron oxide moieties on the mineral oxide surfaces were studied during enrichments for dissimilatory iron reducing (DIRB) and sulfate reducing bacteria (SRB). Microbes enriched from groundwater taken from the Test Area North (TAN) site at the Idaho National Laboratory (INL) were able to reduce the U(VI) in the adsorption medium as well as the iron on quartz surfaces. Early in the experiment disappearance of U(VI) from solution was a function of chemical interactions since no microbial activity was evident. Abiotic removal of U(VI) was enhanced in the presence of carbonate. As the experiment proceeded, further removal of U(VI) from solution was associated with the fermentation of lactate to propionate and acetate. During later phases of the experiment when lactate was depleted from the growth medium in the microcosm containing the DIRB enrichments, U(VI) concentrations in the solution phase increased until additional lactate was added. When additional lactate was added and fermentation proceeded, U(VI) concentrations in the liquid phase again returned to near zero. Similar results were shown for the SRB enrichment but lower uranium concentrations were seen in the liquid phase, while in the enrichment with carbonate a similar increase in uranium concentration was not seen. Chemical and biological interactions appear to be important on the mobilization/immobilization of U(VI) in an iron oxide system when TCE is present as a co-contaminant. Interestingly, TCE present in the microcosm experiments was not dechlorinated which was probably an effect of redox conditions that were unsuitable for reductive dechlorination by the microbial culture tested.     

The effects of phosphorus additions on the sedimentation of contaminants in a uranium mine pit-lake

We investigated the usefulness of phytoplankton for the removal of surface water contaminants. Nine large mesocosms (92.2m(3)) were suspended in the flooded DJX uranium pit at Cluff Lake (Saskatchewan, Canada), and filled with highly contaminated mine water. Each mesocosm was fertilized with a different amount of phosphorus throughout the 35 day experiment to stimulate phytoplankton growth, and to create a range in phosphorus load (g) to examine how contaminants may be affected by different nutrient regimes. Algal growth was rapid in fertilized mesocosms (as demonstrated by chlorophyll a profiles). As phosphorus loads increased there were significant declines (p<0.05) in the surface water concentrations of As, Co, Cu, Mn, Ni, and Zn. This decline was near significant for uranium (p=0.065). The surface water concentrations of Ra-226, Mo, and Se showed no relationship to phosphorus load. Contaminant concentrations in sediment traps suspended at the bottom of each mesocosm generally showed the opposite trend to that observed in the surface water, with most contaminants (As, Co, Cu, Mn, Ni, Ra-226, U, and Zn) exhibiting a significant positive relationship (p<0.05) with phosphorus load. Selenium and Mo did not respond to nutrient treatments. Our results suggest that phytoremediation has the potential to lower many surface water contaminants through the sedimentation of phytoplankton. Based on our results, we estimate that the Saskatchewan Surface Water Quality Objectives (SSWQO) for DJX pit would be met in approximately 45 weeks for Co, 65 weeks for Ni, 15 weeks for U, and 5 weeks for Zn.     

Selective removal of dissolved uranium in drinking water by nanofiltration

A procedure for the selective removal of uranium traces dissolved in drinking water has been studied. Plate module membrane filtration equipment was operated to evaluate the performance and selectivity of three different nanofiltration flat-sheet membranes. Experiments were carried out using various commercial mineral waters with distinct physicochemical compositions. The membranes were first discriminating by their ability to reject uranium in the presence of the main cations found in mineral waters, using a 2 mg L(-1) (2000 ppb) concentration of uranium. The rejection of U(VI) was dependent on the uranyl speciation and the ionic strength. Second, removal of uranium traces (0.02 mg L(-1), 20 ppb) was performed using the nanofiltration membrane showing the highest selectivity for uranium toward alkaline and alkaline-earth ions. The results showed a high performance of the nanofiltration membrane, Osmonics DL, for selective uranium rejection at low pressure (1 bar), illustrating the advantage of nanofiltration for the selective removal of uranium from drinking water.     

Treatment of waters containing uranium with saponite clay

The article has investigated sorption of U(VI) on a smectite mineral—saponite from the Tashkinsk deposit in the Khmelnitsk region. The equilibrium in the U(VI)-saponite system sets in within 8 h. The relationship between sorption and the pH has a clear-cut maximum characteristic of uranium sorption on aluminum-silicates at the pH values 5.5–7. The U(VI) sorption isotherm on saponite is described by the Langmuir empirical equation. We have established the influence on the sorption process of complexation reagents (EDTA, carbonate ions, fulvic acids). Based on experimental data the possibility of using the sorption method with the employment of saponite for water treatment containing uranium is shown.     

Airborne emission of enriched uranium at Tokai-mura, Japan

A new strategy for characterisation of airborne uranium contamination based on elemental/isotopic analysis of tree bark is described. Bark samples collected at Tokai-mura (Japan) were subjected to high sensitivity ICP mass spectrometric analysis; for control purposes, samples from the remote Yakushima island (Southern Japan) and central Tokyo were also analysed. The uranium contents of tree bark for Tokyo and Yakushima were of similar magnitude to that at Tokai-mura (U, 0.01-1.0 microg/g - all samples), however, there were marked differences in isotope ratio values between the sites. Whereas natural uranium isotope ratio values (235U/238U, 0.0072) were observed for Yakushima and Tokyo, non-natural and natural signatures (235U/238U, 0.00697-0.01448) were realised at Tokai-mura. These findings are consistent with the release of enriched uranium at Tokai-mura.     

Immobilization of U(VI) from oxic groundwater by Hanford 300 Area sediments and effects of Columbia River water

Regions within the U.S. Department of Energy Hanford 300 Area (300 A) site experience periodic hydrologic influences from the nearby Columbia River as a result of changing river stage, which causes changes in groundwater elevation, flow direction and water chemistry. An important question is the extent to which the mixing of Columbia River water and groundwater impacts the speciation and mobility of uranium (U). In this study, we designed experiments to mimic interactions among U, oxic groundwater or Columbia River water, and 300 A sediments in the subsurface environment of Hanford 300 A. The goals were to investigate mechanisms of: 1) U immobilization in 300 A sediments under bulk oxic conditions and 2) U remobilization from U-immobilized 300 A sediments exposed to oxic Columbia River water. Initially, 300 A sediments in column reactors were fed with U(VI)-containing oxic 1) synthetic groundwater (SGW), 2) organic-amended SGW (OA-SGW), and 3) de-ionized (DI) water to investigate U immobilization processes. After that, the sediments were exposed to oxic Columbia River water for U remobilization studies. The results reveal that U was immobilized by 300 A sediments predominantly through reduction (80-85%) when the column reactor was fed with oxic OA-SGW. However, U was immobilized by 300 A sediments through adsorption (100%) when the column reactors were fed with oxic SGW or DI water. The reduced U in the 300 A sediments fed with OA-SGW was relatively resistant to remobilization by oxic Columbia River water. Oxic Columbia River water resulted in U remobilization (∼7%) through desorption, and most of the U that remained in the 300 A sediments fed with OA-SGW (∼93%) was in the form of uraninite nanoparticles. These results reveal that: 1) the reductive immobilization of U through OA-SGW stimulation of indigenous 300 A sediment microorganisms may be viable in the relatively oxic Hanford 300 A subsurface environments and 2) with the intrusion of Columbia River water, desorption may be the primary process resulting in U remobilization from OA-SGW-stimulated 300 A sediments at the subsurface of the Hanford 300 A site.     

诸广山岩体北部营盘圩地区铀成矿条件浅析

营盘圩地区位于诸广复式岩体北部,地处华夏板块武功—诸广断隆区,区域性北东向桂东—汝城断裂和遂川—热水断裂夹持部位。区内分布营盘圩、茶叶龙、九罗洞3个矿(化)点以及众多异常点。文章在前人勘查和研究工作的基础上分析了工作区铀成矿地质条件,认为该区具有丰富的铀源岩体和富铀地层;北东向小夏—黄坳断裂(桂东—汝城断裂带的一部分)为区内主干断裂,其旁侧次级断裂裂隙为主要控矿、容矿构造;多期次、多阶段蚀变叠加,造成了区内铀富集;晚期中基性脉岩发育,为成矿提供活化剂;地质调查、地面伽玛总量及土壤~(210)Po活度测量成果显示区内具有较好的浅深部铀矿化信息。综合分析认为,营盘圩地区具有较优越的成矿地质条件,值得进一步开展地质找矿工作。     

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H₂, pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H₂ concentrations were heterogeneous at the microscale (<500-1000 μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H₂ under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L_III-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state.     

Evaluation and application of anion exchange resins to measure groundwater uranium flux at a former uranium mill site

Laboratory tests and a field validation experiment were performed to evaluate anion exchange resins for uranium sorption and desorption in order to develop a uranium passive flux meter (PFM). The mass of uranium sorbed to the resin and corresponding masses of alcohol tracers eluted over the duration of groundwater installation are then used to determine the groundwater and uranium contaminant fluxes. Laboratory based batch experiments were performed using Purolite A500, Dowex 21K and 21K XLT, Lewatit S6328 A resins and silver impregnated activated carbon to examine uranium sorption and extraction for each material. The Dowex resins had the highest uranium sorption, followed by Lewatit, Purolite and the activated carbon. Recoveries from all ion exchange resins were in the range of 94-99% for aqueous uranium in the environmentally relevant concentration range studied (0.01-200 ppb). Due to the lower price and well-characterized tracer capacity, Lewatit S6328 A was used for field-testing of PFMs at the DOE UMTRA site in Rifle, CO. The effect on the flux measurements of extractant (nitric acid)/resin ratio, and uranium loading were investigated. Higher cumulative uranium fluxes (as seen with concentrations > 1 ug U/gram resin) yielded more homogeneous resin samples versus lower cumulative fluxes (<1 ug U/gram resin), which caused the PFM to have areas of localized concentration of uranium. Resin homogenization and larger volume extractions yield reproducible results for all levels of uranium fluxes. Although PFM design can be improved to measure flux and groundwater flow direction, the current methodology can be applied to uranium transport studies.     

The influence of the abandoned Kalecik Hg mine on water and stream sediments (Karaburun,Izmir, Turkey)

This study covers the geochemical investigations on water and stream sediments to evaluate the influence from the abandoned Kalecik Hg mine. The groundwater samples (S5, S8, S9, WW10) are neutral, slightly alkaline waters which have pH values varying between 7.3 and 7.5. Electrical conductivity (EC) values of groundwaters for spring samples are low (250-300 microS/cm). However, groundwater obtained from a deep well has a higher EC value of 950 microS/cm. Hg concentrations of groundwater samples vary between 0.01 and 0.13 microg/l. Hg concentrations of other water samples taken from mining area from surface waters and adits are between 0.10 and 0.99 microg/l. Adit water (A4) collected at the mine has the highest Hg content of 0.99 microg/l and a pH of 4.4. Trace element concentrations of mine water samples show variable values. As is observed only in MW1 (310 microg/l). A4 was enriched in Cd, Co and Cr and exceed the Turkish drinking water standards (Türk Standartlari Enstitüsü, 1997). Cu concentrations vary between 6.0 and 150 microg/l and are below the Turkish water standards. Mn concentrations in mine waters are between 0.02 and 4.9 mg/l. Only for sample A4 Mn value (4.9 mg/l) exceeds the standard level. Ni was enriched for all of the mine water samples and exceeds the safe standard level (20 microg/l) for drinking water. Of the major ions SO(4) shows a notable increase in this group reaching 650 mg/l that exceeds the drinking water standards. Stream sediment samples have abnormally high values for especially Hg and As, Sb, Ni, Cr metals. With the exception of sample Ss6 of which Hg concentration is 92 mg/kg, all the other samples have Hg contents of higher than 100 mg/kg. Pollution index values are significantly high and vary between 69 and 82 for stream sediment samples.     

Potential impact of former Zn ore extraction activities on dissolved uranium distribution in the Riou-Mort watershed (France)

The industrial basin of Decazeville (Riou-Mort watershed, South-West France) is well known for its heavy metal pollution and its subsequent environmental effects on the Lot-Garonne River system. The source of this pollution is the Riou-Mort River, which drains smelting waste areas. A first survey after remediation works has revealed elevated dissolved uranium (U(D)) concentrations in the outlet of the Riou-Mort River. The objective of this research is to identify the origin of U(D) in the Riou-Mort watershed and to evaluate the impact of industrial activities on this element. Uranium was measured at 10 water sampling sites, located upstream and downstream the industrial basin, and in three smelting waste deposits. Uranium concentrations in the smelting waste deposits reach up to 14.4 mg kg(-1) and (234U/238U) activity ratios (AR) are near unity. Dissolved U concentrations in the Riou-Mort River and its main tributaries ranges over two orders of magnitude from 0.02 to 6.1 microg L(-1). The highest levels were measured in a site with no anthropogenic pollution, upstream from the industrial area. This observation suggests that U(D) is mainly linked to weathering; the elevated U concentrations originate from the naturally occurring radioactive materials (NORM) located in the Permian bedrock and no significant U pollution exists, at present, in the Riou-Mort watershed. This work demonstrates that spatial monitoring coupled with a long time-series are an essential prerequisite in assessment of spatiotemporal variations of U(D), prior to a diagnostic of pollution in a small watershed.     

Field and laboratory arsenic speciation methods and their application to natural-water analysis

The toxic and carcinogenic properties of inorganic and organic arsenic species make their determination in natural water vitally important. Determination of individual inorganic and organic arsenic species is critical because the toxicology, mobility, and adsorptivity vary substantially. Several methods for the speciation of arsenic in groundwater, surface-water, and acid mine drainage sample matrices using field and laboratory techniques are presented. The methods provide quantitative determination of arsenite [As(III)], arsenate [As(V)], monomethylarsonate (MMA), dimethylarsinate (DMA), and roxarsone in 2-8 min at detection limits of less than 1 microg arsenic per liter (microg As L(-1)). All the methods use anion exchange chromatography to separate the arsenic species and inductively coupled plasma-mass spectrometry as an arsenic-specific detector. Different methods were needed because some sample matrices did not have all arsenic species present or were incompatible with particular high-performance liquid chromatography (HPLC) mobile phases. The bias and variability of the methods were evaluated using total arsenic, As(III), As(V), DMA, and MMA results from more than 100 surface-water, groundwater, and acid mine drainage samples, and reference materials. Concentrations in test samples were as much as 13,000 microg As L(-1) for As(III) and 3700 microg As L(-1) for As(V). Methylated arsenic species were less than 100 microg As L(-1) and were found only in certain surface-water samples, and roxarsone was not detected in any of the water samples tested. The distribution of inorganic arsenic species in the test samples ranged from 0% to 90% As(III). Laboratory-speciation method variability for As(III), As(V), MMA, and DMA in reagent water at 0.5 microg As L(-1) was 8-13% (n=7). Field-speciation method variability for As(III) and As(V) at 1 microg As L(-1) in reagent water was 3-4% (n=3).