Uranium Concentrations In Groundwater Research Articles

Establishing the Origin of Elevated Uranium Concentrations in Groundwater near the Central Ogcheon Metamorphic Belt, Korea

We examined the origin of the U-enriched groundwater in Daejeon, near the Ogcheon U zone in Korea. For this study, groundwater ionic species and C, S, and Sr isotopic compositions were analyzed. The U-enriched groundwater occurred only in the Daejeon granite region, while all the groundwater in the Ogcheon Supergroup showed very low U concentrations. In the granite region, the pedospheric or atmospheric origin of dissolved C and S means that the aquifer has been well connected to the oxidized surface environment. The Sr/Sr ratios indicated a lithospheric origin of Sr. Groundwater isotopic compositions in the Ogcheon belt varied greatly, indicating their complex sources. In this region, dissolved C originated from graphite-rich slate and limestone. The broad range of δS suggested that the composite sources included atmospheric SO for most groundwater, lithogenic SO for mine drainage and quarry water, and anthropogenic SO for polluted groundwater. This study indicates that the U-enriched groundwater is not related to the present U ores in the Ogcheon belt but is genetically associated with the granite body itself. The varying but considerable U contents within the granite body can be present as isolated groups. We infer that locally high U contents in the Daejeon granite might inherently be due to assimilation of the Ogcheon U-mineralized zone into granitic melt during the Mesozoic; however, the pH and Eh conditions except aquifer geology were very important factors in developing highly enriched U groundwater in the Daejeon granite region. Thermodynamic modeling highlights the importance of dissolved Ca and (bi-)carbonate in U geochemistry.

Occurrence of uranium in groundwater of a shallow granitic aquifer and its suitability for domestic use in southern India

Groundwater used for domestic purpose without proper treatment should be free from chemical and biological contaminants. This study was carried out to assess the groundwater quality with respect to uranium in a part of Nalgonda district, Andhra Pradesh, India. Groundwater was regularly monitored for uranium concentration by collection of samples once every two months from March 2008 to November 2009 from 44 wells. The concentration of uranium in groundwater ranged from 0.2 to 118.4 ppb. Groundwater is unsuitable for domestic use in 2 % of this area based on the limit of 60 ppb prescribed by the Atomic Energy Regulatory Board of India. However, due the wide variation in limit suggested by different organizations and countries, the no-observed-adverse-effect level and lowest-observed-adverse-effect level (in mg/kg day) was used to understand the dosage of uranium that reaches the people through drinking water pathway. This level varied from 0 to 0.02 mg/kg day and 0 to 0.08 mg/kg day based on an uncertainty factor of 10 and 50 respectively for the mean uranium concentration in groundwater in each well. With an uncertainty factor of 50, 5 groundwater samples had uranium above 0.06 mg/kg day which is the lowest-observed-adverse-effect level. This study showed that with the presence of present level of uranium concentration in groundwater of this area there is no major threat to humans through the drinking water pathway.

Activity concentration of uranium in groundwater from uranium mineralized areas and its neighborhood

Uranium mineralization in parts of northeastern Nigeria necessitated its exploration during early eighties by the Nigeria Uranium Mining Company (NUMCO) which was later abandoned. During their course of decay, uranium isotopes pass through radioactive decay stage and eventually into stable isotope of lead. The course of concern for soluble uranium in groundwater especially from the mineralized areas include ionizing radiation, chemical toxicity and reproductive defects for which ingested uranium has been implicated to have caused. This study is aimed at assessing the levels of concentration of uranium in groundwater to ascertain its compliance with the World Health Organization’s (WHO) and the United State Environmental Protection Agency’s (EPA) guideline for uranium in drinking water. Thirty five groundwater samples were collected using EPA’s groundwater sampling protocol and analyzed at the Department of Geology, University of Cape Town using an Inductively Coupled Plasma Mass Spectrometric (ICP-MS) technique. Significant finding of this work was that there is radiological contamination of groundwater in the area. There is also an indication that the extent of radiological contamination is not much within the mineralized zones, therefore, there is likelihood that groundwater has acted as a medium of transporting and enhancing uranium in groundwater in an environment away from that of origin. About 5.7 % of the samples studied had uranium concentration above WHO and EPA’s maximum contaminant level of 30 μg/L which is a major concern for inhabitants of the area. It was also apparent that radiological contamination at the southwestern part of the study area extends into the adjacent sheet (sheet 152). Uranium concentration above set standards in those areas might have originated from rocks around established mineralized zones but was transported to those contaminated areas by groundwater that leaches across the host rock and subsequently mobilizing soluble uranium along with it.

Study of uranium isotopic composition in groundwater and deviation from secular equilibrium condition

Uranium concentration in groundwater reflect both redox conditions and uranium content in host rock. In the present study an attempt has been made to study the uranium concentration and activity ratios of uranium isotopes to present the geochemical conditions of the groundwater in Malwa region of Punjab state, India and the reason for high uranium levels and variation of activity ratios from secular equilibrium conditions. Uranium concentration in groundwater samples was found to be in the range of 13.9 ± 1.2 to 172.8 ± 12.3 μg/l with an average value of 72.9 μg/l which is higher than the national and international guideline values. On the basis of uranium concentration, the groundwater of the study region may be classified as oxidized aquifer on normal uranium content strata (20 %) or oxidized aquifer on enhanced uranium content strata (80 %). The 238U, 235U and 234U isotopic concentration in groundwater samples was found to be in the range of 89.2–1534.5, 4.4–68.5, and 76.4–1386.2 mBq/l, respectively. Activity ratios of 234U/238U varies from 0.94 to 1.85 with a mean value of 1.11 which is close to unity that shows secular equilibrium condition. High value of 234U isotope than 238U may be due to alpha recoil phenomenon. The plot of AR of 234U/238U against the total uranium content in log scale reveals that the groundwaters of the study region either belongs to stable accumulation or normal oxidized aquifer.

Assessing Migration of Uranium through Chalk Substrate: Field Study and Reactive Transport Modelling

The migration of uranium from polluted soil has been investigated in the field, and through modelling of thermodynamics and kinetics of uranium-water-rock interactions. Field monitoring following surface contamination by uranium deposits revealed up to 5 m deep uranium migration in soil and chalk substrate, as well as uranium concentrations in groundwater significantly higher than the geochemical background. Such observations can hardly be explained by a pure reactive transport dominated by reversible adsorption of uranium onto mineral phases. Therefore, a reactive transport model using the HYTEC code has been developed to better assess uranium migration through soil to the carbonate aquifer. Reactive transport modelling shows that adsorption of U (VI) at equilibrium on goethite at pH 7 is responsible for strong immobilization of uranium in the soil and carbonate matrix, matching uranium concentration profiles observed in boreholes. Simulations considering highly mobile ternary complex Ca2UO2(CO3)3(aq) in the aqueous phase cannot account alone for the rapid migration of uranium through the unsaturated zone. Without a mobile colloidal phase, the model clearly underestimates the concentration of aqueous U(VI) that reached groundwater underneath polluted soils.

지역별 지하수중 우라늄과 라돈의 함량 분포 특성

In order to figure out the characteristics of radionuclides concentrations of nine provinces, we analyzed uranium and radon in 681 samples of groundwater. Most of uranium concentrations in each province were less than <TEX>$10{\mu}g/L$</TEX>, and Gyeongnam, Jeonnam, Jeju provinces did not have groundwaters exceeding the US EPA drinking water MCL (<TEX>$30{\mu}g/L$</TEX>) of uranium. The ratio of radon values exceeding US EPA drinking water AMCL (4,000 pCi/L) was 22.6% (154/681) and Gyeongnam and Jeju provinces had no groundwaters exceeding the AMCL (alternative maximum contaminant level). Uranium and radon concentrations in groundwaters of Gyeonggi, Chungbuk, Jeonbuk, Chungnam mainly composed of the Mesozoic granite and the Precambrian gneiss were relatively high, but the concentrations of Gyeongnam and Jeju widely comprised of the sedimentary rock and the volcanic rock were relatively low. A week correlation between uranium and radon values showed in Gangwon, Chungbuk, Gyeonggi provinces.

Occurrence of uranium in Swiss drinking water

The results of a nationwide survey of uranium in Swiss drinking water are reported. Elevated concentrations of uranium in groundwater are found mainly in the alpine regions and can be traced back to the geology of the bedrock. Water sources were systematically surveyed and analysed for the presence of Li, B, Si, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Sn, Sb, Ba, Tl, Pb and U and the results were analysed to determine if any correlation with uranium concentration was apparent. No correlation was found. The results are interpreted in relation to the current WHO guideline and those of other countries with a view to determining which areas would be affected if a maximum value were to be adopted and which areas require further investigation. Uranium content varied considerably, from below the limit of detection to almost 100 μg L −1. Of the 5548 data samples, 98% are below the 2004 WHO provisional guideline value of 15 μg L −1 and 99.7% below the revised (2011) value of 30 μg L −1.

Spatial and temporal variation of uranium in a shallow weathered rock aquifer in southern India

Uranium occurs naturally in groundwater and surface water. The objective of this study is to understand the causes for the occurrence of uranium and its spatio-temporal variation in groundwater in a part of Nalgonda district, Andhra Pradesh, south India. Uranium deposits occur in the southeastern part of this area. Groundwater samples were collected from 44 wells every two months from March 2008 to January 2009. The samples were analyzed for pH, ORP and uranium concentration. The uranium concentration in groundwater varies from 0.2 ppb to a maximum of 68 ppb with a mean of 18.5 ppb. About 21.6% of the samples were above the drinking water limit of 30 ppb set by USEPA. The uranium concentration varied with fluctuation in groundwater level, pH and ORP. Uranium concentration in groundwater changes depending on lithology, degree of weathering and rainfall recharge.

Acetate Availability and its Influence on Sustainable Bioremediation of Uranium-Contaminated Groundwater

Field biostimulation experiments at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, have demonstrated that uranium concentrations in groundwater can be decreased to levels below the U.S. Environmental Protection Agency's (EPA) drinking water standard (0.126 μM). During successive summer experiments – referred to as “Winchester” (2007) and “Big Rusty” (2008) - acetate was added to the aquifer to stimulate the activity of indigenous dissimilatory metal-reducing bacteria capable of reductively immobilizing uranium. The two experiments differed in the length of injection (31 vs. 110 days), the maximum concentration of acetate (5 vs. 30 mM), and the extent to which iron reduction (“Winchester”) or sulfate reduction (“Big Rusty”) was the predominant metabolic process. In both cases, rapid removal of U(VI) from groundwater occurred at calcium concentrations (6 mM) and carbonate alkalinities (8 meq/L) where Ca-UO2-CO3 ternary complexes constitute >90% of uranyl species in groundwater. Complete consumption of acetate and increased alkalinity (>30 meq/L) accompanying the onset of sulfate reduction corresponded to temporary increases in U(VI); however, by increasing acetate concentrations in excess of available sulfate (10 mM), low U(VI) concentrations (0.1–0.05 μM) were achieved for extended periods of time (>140 days). Uniform delivery of acetate during “Big Rusty” was impeded due to decreases in injection well permeability, likely resulting from biomass accumulation and carbonate and sulfide mineral precipitation. Such decreases were not observed during the short-duration “Winchester” experiment. Terminal restriction fragment length polymorphism (TRFLP) analysis of 16S rRNA genes demonstrated that Geobacter sp. and Geobacter-like strains dominated the groundwater community profile during iron reduction, with 13C stable isotope probing (SIP) results confirming these strains were actively utilizing acetate to replicate their genome during the period of optimal U(VI) removal. Gene transcript levels during “Big Rusty” were quantified for Geobacter-specific citrate synthase (gltA), with ongoing transcription during sulfate reduction indicating that members of the Geobacteraceae were still active and likely contributing to U(VI) removal. The persistence of reducible Fe(III) in sediments recovered from an area of prolonged (110-day) sulfate reduction is consistent with this conclusion. These results indicate that acetate availability and its ability to sustain the activity of iron- and uranyl-respiring Geobacter strains during sulfate reduction exerts a primary control on optimized U(VI) removal from groundwater at the Rifle IFRC site over extended time scales (>50 days).

Groundwater uranium and cancer incidence in South Carolina

This ecologic study tested the hypothesis that census tracts with elevated groundwater uranium and more frequent groundwater use have increased cancer incidence. Data sources included: incident total, leukemia, prostate, breast, colorectal, lung, kidney, and bladder cancers (1996-2005, SC Central Cancer Registry); demographic and groundwater use (1990 US Census); and groundwater uranium concentrations (n=4,600, from existing federal and state databases). Kriging was used to predict average uranium concentrations within tracts. The relationship between uranium and standardized cancer incidence ratios was modeled among tracts with substantial groundwater use via linear or semiparametric regression, with and without stratification by the proportion of African Americans in each area. A total of 134,685 cancer cases were evaluated. Tracts with ≥50% groundwater use and uranium concentrations in the upper quartile had increased risks for colorectal, breast, kidney, prostate, and total cancer compared to referent tracts. Some of these relationships were more likely to be observed among tracts populated primarily by African Americans. SC regions with elevated groundwater uranium and more groundwater use may have an increased incidence of certain cancers, although additional research is needed since the design precluded adjustment for race or other predictive factors at the individual level.

Effects of Groundwater Development on Uranium: Central Valley, California, USA

Uranium (U) concentrations in groundwater in several parts of the eastern San Joaquin Valley, California, have exceeded federal and state drinking water standards during the last 20 years. The San Joaquin Valley is located within the Central Valley of California and is one of the most productive agricultural areas in the world. Increased irrigation and pumping associated with agricultural and urban development during the last 100 years have changed the chemistry and magnitude of groundwater recharge, and increased the rate of downward groundwater movement. Strong correlations between U and bicarbonate suggest that U is leached from shallow sediments by high bicarbonate water, consistent with findings of previous work in Modesto, California. Summer irrigation of crops in agricultural areas and, to lesser extent, of landscape plants and grasses in urban areas, has increased Pco(2) concentrations in the soil zone and caused higher temperature and salinity of groundwater recharge. Coupled with groundwater pumping, this process, as evidenced by increasing bicarbonate concentrations in groundwater over the last 100 years, has caused shallow, young groundwater with high U concentrations to migrate to deeper parts of the groundwater system that are tapped by public-supply wells. Continued downward migration of U-affected groundwater and expansion of urban centers into agricultural areas will likely be associated with increased U concentrations in public-supply wells. The results from this study illustrate the potential long-term effects of groundwater development and irrigation-supported agriculture on water quality in arid and semiarid regions around the world.

Significant Association between Sulfate-Reducing Bacteria and Uranium-Reducing Microbial Communities as Revealed by a Combined Massively Parallel Sequencing-Indicator Species Approach

Massively parallel sequencing has provided a more affordable and high-throughput method to study microbial communities, although it has mostly been used in an exploratory fashion. We combined pyrosequencing with a strict indicator species statistical analysis to test if bacteria specifically responded to ethanol injection that successfully promoted dissimilatory uranium(VI) reduction in the subsurface of a uranium contamination plume at the Oak Ridge Field Research Center in Tennessee. Remediation was achieved with a hydraulic flow control consisting of an inner loop, where ethanol was injected, and an outer loop for flow-field protection. This strategy reduced uranium concentrations in groundwater to levels below 0.126 μM and created geochemical gradients in electron donors from the inner-loop injection well toward the outer loop and downgradient flow path. Our analysis with 15 sediment samples from the entire test area found significant indicator species that showed a high degree of adaptation to the three different hydrochemical-created conditions. Castellaniella and Rhodanobacter characterized areas with low pH, heavy metals, and low bioactivity, while sulfate-, Fe(III)-, and U(VI)-reducing bacteria (Desulfovibrio, Anaeromyxobacter, and Desulfosporosinus) were indicators of areas where U(VI) reduction occurred. The abundance of these bacteria, as well as the Fe(III) and U(VI) reducer Geobacter, correlated with the hydraulic connectivity to the substrate injection site, suggesting that the selected populations were a direct response to electron donor addition by the groundwater flow path. A false-discovery-rate approach was implemented to discard false-positive results by chance, given the large amount of data compared.

COMPARISON BETWEEN EXPERIMENTALLY MEASURED AND THERMODYNAMICALLY CALCULATED SOLUBILITIES OF UO2AND THO2IN KURT GROUND WATER

Solubility of a radionuclide is important for defining the release source term of a radioactive waste in the safety and performance assessments of a radioactive waste repository. When the pH and redox potential of the KURT groundwater were changed by an electrical method, the concentrations of uranium and thorium released from <TEX>$UO_2$</TEX>(cr) and <TEX>$ThO_2$</TEX>(cr) at alkali pH(8.1 <TEX>${\sim}$</TEX> 11.4) and reducing potential (Eh < -0.2 V) conditions were less than <TEX>$10^{-7}mole/L$</TEX>. Unexpectedly, the concentration of tetravalent thorium is slightly higher than that of uranium at pH = 8.1 and Eh= -0.2 V conditions, and this difference may be due to the formation of hydroxide-carbonate complex ions. When <TEX>$UO_2$</TEX>(s) and <TEX>$UO_2$</TEX>(am, hyd.), and <TEX>$ThO_2$</TEX>(s) and <TEX>$Th(OH)_4(am)$</TEX> were assumed as solubility limiting solid phases, the concentrations of uranium and thorium in the KURT groundwater calculated by the PHREEQC code were comparable to the experimental results. The dominating aqueous species of uranium and thorium were presumed as <TEX>$UO_2(CO_3)_3^{4-}$</TEX> and <TEX>$Th(OH)_3CO_3^-$</TEX> at pH = 8.1 <TEX>${\sim}$</TEX> 9.8, and <TEX>$UO_2(OH)_3^-$</TEX> and <TEX>$Th(OH)_4(aq)$</TEX> at pH = 11.4.

EVALUATION OF TOTAL EFFECTIVE DOSE DUE TO CERTAIN ENVIRONMENTALLY PLACED NATURALLY OCCURRING RADIOACTIVE MATERIALS USING A PROCEDURAL ADAPTATION OF RESRAD CODE

Due to a recent upward trend in the price of uranium and subsequent increased interest in uranium mining, accurate modeling of baseline dose from environmental sources of radioactivity is of increasing interest. Residual radioactivity model and code (RESRAD) is a program used to model environmental movement and calculate the dose due to the inhalation, ingestion, and exposure to radioactive materials following a placement. This paper presents a novel use of RESRAD for the calculation of dose from non-enhanced, or ancient, naturally occurring radioactive material (NORM). In order to use RESRAD to calculate the total effective dose (TED) due to ancient NORM, a procedural adaptation was developed to negate the effects of time progressive distribution of radioactive materials. A dose due to United States' average concentrations of uranium, actinium, and thorium series radionuclides was then calculated. For adults exposed in a residential setting and assumed to eat significant amounts of food grown in NORM concentrated areas, the annual dose due to national average NORM concentrations was 0.935 mSv y(-1). A set of environmental dose factors were calculated for simple estimation of dose from uranium, thorium, and actinium series radionuclides for various age groups and exposure scenarios as a function of elemental uranium and thorium activity concentrations in groundwater and soil. The values of these factors for uranium were lowest for an adult exposed in an industrial setting: 0.00476 microSv kg Bq(-1) y(-1) for soil and 0.00596 microSv m(3) Bq(-1) y(-1) for water (assuming a 1:1 234U:238U activity ratio in water). The uranium factors were highest for infants exposed in a residential setting and assumed to ingest food grown onsite: 34.8 microSv kg Bq(-1) y(-1) in soil and 13.0 microSv m(3) Bq(-1) y(-1) in water.

Uranium in the Groundwater of Permo-Triassic Aquifers of the Visok Region, Stara Planina, Eastern Serbia

An elevated concentration of uranium in the water of some springs in the Permo-Triassic sedimentary rocks of the Visok region, south-eastern slopes of the Stara Planina, eastern Serbia, is interpreted based on geological, hydrogeological and hydrochemical data. Uranium concentration in groundwater was first examined whilst exploring for uranium minerals as an energy resource. The purpose of a later hydrogeological investigation was assessment of a safe drinking water supply to a planned ski-centre hotel. The maximum contaminant level for uranium, recommended by the World Health Organization (WHO), is 15 μg/L. This work reviews and interprets the naturally elevated uranium in springs from the Permo-Triassic sediments of Visok, focusing on geological, hydrogeological, hydrogeochemical and other factors of uranium contamination. Uranium distribution in groundwater from Permo-Triassic aquifers was studied by taking groundwater, spring sediment and rock samples. The varied mobility of uranium depends largely on lithology, which also controls the chemistry of groundwater. The investigation results have shown that sulfate-calcium groundwater is a suitable facilitator of uranium mobility with a high migration coefficient of 0.77. Uranium concentrations in this water were up to 41 μg/L, with a Sa/Sr mass ratio of around 20, and a mineral content of about 0.5 g/L. The hydrochemistry was characteristically transitional Eh and pH neutral. Elevated uranium in groundwater has been reported globally and may be compared.

Sorption and binary exchange of nitrate, sulfate, and uranium on an anion-exchange resin.

Competitive ion-exchange reactions were studied on a strong-base anion-exchange resin to remove NO3- and uranium from a contaminated groundwater containing high levels of NO3- (approximately 140 mM), SO4(2-) (approximately 10 mM), and U(VI) (approximately 0.2 mM). Results indicate that although SO4(2-) carries divalent negative charges, it showed the least selectivity for sorption by the Purolite A-520E resin, which is functionalized with triethylamine exchange sites. Nitrate was the most strongly sorbed. Sorption selectivity followed the order of NO3- > Cl- > SO4(2-) under the experimental conditions. Nitrate competitively sorbed and displaced previously sorbed SO4(2-) in a column flow-through experiment and resulted in a high elution front of SO4(2-) in the effluent. Although the concentration of uranium in groundwater is orders of magnitude lower than that of NO3- or SO4(2-), it was found to be strongly sorbed by the anion-exchange resin. Because the most stable uranium species in oxic and suboxic environments is the UO2(2+) cation, its strong sorption by anion-exchange resins is hypothesized to be the result of the co-ion effect of NO3- by forming anionic UO2(NO3)3- complexes in the resin matrix. These observations point out a potential alternative remediation strategy that uses strong-base anion-exchange resins to remove uranium from this site-specific groundwater, which has a low pH and a relatively high NO3- concentration.

Uranium isotopic evidence for groundwater chemical evolution and flow patterns in the eastern Snake River Plain aquifer, Idaho

The isotopic composition and concentration of uranium and strontium in groundwater, combined with solute concentration data, provide important details regarding groundwater geochemical evolution and flow-pathways in the eastern Snake River Plain aquifer. The study was conducted in the vicinity of the Idaho National Engineering and Environmental Laboratory (INEEL), Idaho, which has a long history of storing and disposing of radioactive waste, some of which has entered the aquifer. Uranium concentrations in INEEL groundwater range from 0.3 to 3.6 ppb, and 234 U/ 238 U atomic ratios range between 0.000085 and 0.000168 (activity ratios of 1.5 to 3.1). All of the samples have natural 235 U/ 238 U ratios, and 236 U was not detected; thus, the trends delineated by the 234 U/ 238 U ratios reflect natural variations in the aquifer. Groundwater nearest the valleys that provides focused recharge to the Snake River Plain aquifer from the northwest has high 234 U/ 238 U ratios when compared to values of regional groundwater flowing southwestward in the aquifer. Mixing of these water masses can account for the intermediate uranium isotope ratios of some of the samples; however, water-rock interaction must also be invoked to account for the observed trends in isotopic data. Uranium and 87 Sr/ 86 Sr isotope ratios are positively correlated and define a trend toward isotope ratios of the aquifer host rock. These relations indicate that dissolution and/or ion exchange are more important than alpha recoil or selective leaching in controlling 234 U/ 238 U ratios. As a result, 234 U/ 238 U ratios decrease along flow pathways toward the secular equilibrium values of the aquifer host rock. Uranium and strontium isotopic modification can be explained by incongruent dissolution of the host basalt. Lateral distributions of 234 U/ 238 U ratios indicate elongate zones of high 234 U/ 238 U ratios extending southward from the mouths of Birch Creek and the Little Lost River. These elongate zones are interpreted as preferential flow paths. Two isolated pockets of groundwater located in the central and western parts of the study area have lower 234 U/ 238 U ratios than the adjacent aquifer water. Both of these zones are interpreted to contain stagnant waters that are relatively isolated from flow in the regional aquifer due to lower permeability. Physical and chemical evidence strongly suggests that the stagnant zones are dominated by water from the Big Lost River that infiltrated via flood control ponds (spreading areas), playas, and the riverbed.

Oxidative dissolution of uraninite precipitated on Navajo sandstone

Column and batch experiments were conducted with sandstone and ground water samples to investigate oxidation of uraninite precipitated by microbially mediated reduction of U(VI), a contaminant in ground water beneath a uranium mill tailings site near Tuba City, AZ, USA. Uraninite precipitated together with mackinawite (FeS 0.9) because Fe(III) from the sandstone and sulfate, another contaminant in the water were reduced together with U(VI). After completion of U(VI) reduction, experiments were conducted to find out whether uraninite is protected by mackinawite against reoxidation. Uncontaminated ground water from the same site, containing 7 mg/l of dissolved oxygen, was passed through the columns or mixed with sandstone in batch experiments. The results showed that small masses of uraninite, 0.1 μg/g of sandstone, are protected by mackinawite from reoxidation. Uraninite masses on the order of 0.1 μg/g correspond to U(VI) concentrations of 0.5 mg/l, typically encountered in uranium contaminated ground waters. Mackinawite is an effective buffer and is formed in sufficient quantity to provide long-term protection of uraninite. Uranium concentrations in ground water passed through the columns are too low (4 μg/l) to distinguish between dissolution and oxidative dissolution of uraninite. However, batch experiments showed that uraninite oxidation takes place.

Groundwater geochemistry in the Koongarra ore deposit, Australia (I): Implications for uranium migration.

Groundwater geochemistry at the Koongarra uranium ore deposit was investigated in order to gain a detailed understanding of the migration of uranium in a highly weathered water-rock system. Koongarra groundwaters are quite dilute with the total dissolved solids usually below 200 mg/l. The pH is slightly acidic or neutral, and the major chemical characteristics are dominated by magnesium and bicarbonate. Partial pressures of CO2 in the deeper groundwaters are substantially elevated relative to those of surface waters. Groundwater in the mineralized zones exhibits elevated levels of uranium up to three orders of magnitude above background levels. Total organic carbon levels are generally low, suggesting that uranium complexation by organic species plays a minor role. Due to the high bicarbonate concentration, uranium appears to be mobile in the weathered zone as uranyl carbonate complexes. Other inorganic uranium complexants are not present at levels sufficient to influence uranium speciation, with the possible exception of phosphate. On the basis of chemical and isotopic evidence, there are two major inputs of groundwater to the system. The first of these is flows from the vicinity of the Koongarra fault into the Cahill formation, which hosts the uranium mineralization. A second major source is infiltrating waters which permeate downward from the surface, and cause a gradual mixing and dilution of the characteristics of groundwaters from the mineralized zone. The migration of uranium in groundwater is not only perpendicular to the fault, but includes a component at an angle to it. In the vicinity of borehole C1 (due south of the ore zone), uranium concentrations are comparatively high, given the distance from the orebody. Moving away from the ore zone to the south-east, there is a gradual decrease of groundwater uranium concentrations to background levels over approximately 200 meters, which coincides with the uranium distribution in the solid phase. Therefore, at Koongarra, uranium seems to have migrated over distances of approximately 200 m toward the south-east over a time period estimated to be 1 to 1.5 million years.

Interaction between aqueous uranium (VI) and sulfide minerals: Spectroscopic evidence for sorption and reduction

The interaction of aqueous U(VI) with galena and pyrite surfaces under anoxic conditions has been studied by solution analysis and by spectroscopic methods. The solution data indicate that uranyl uptake is strongly dependent on pH; maximum uptake (>98%) occurs above a pH range of between 4.8 and 5.5, depending on experimental conditions. Increasing the sorbate/sorbent ratio results in a relative decrease in uptake of uranyl and in slower sorption kinetics. Auger electron spectroscopy (AES) analysis indicates an inhomogeneous distribution of sorbed uranium at the surface. In the case of galena, formation of small precipitates (~40 nm wide needles) of a uranium oxide compound are found. Pyrite shows a patchy distribution of uranium, mainly associated with oxidized surface species of sulfur and iron. X-ray photoelectron spectroscopy (XPS) yields insight into possible redox processes indicating, for both sulfides, the concomitant formation of polysulfides and a uranium oxide compound with a mixed oxidation state at a U(VI)/U(IV) ratio of ~2. Furthermore, in the case of pyrite, at pH above 6 increased oxidation of sulfur and iron and higher relative amounts of unreduced surface-uranyl are observed. Fourier Transformed Infrared (FTIR) analysis of surface-bound uranyl shows a significant shift of the asymmetric stretching frequency to lower wavenumbers which is consistent with the formation of a U 3O 8-type compound and thus, independently, confirms the partial reduction of uranyl at the sulfide surface. The combination of AES, XPS, and FTIR provides a powerful approach for identifying mechanisms that govern the interaction of redox sensitive compounds in aqueous systems. Our overall results indicate that sulfide minerals are efficient scavengers of soluble uranyl. Comparing our results with recent field observations, we suggest that thermodynamically metastable U 3O 8 controls uranium concentrations in many anoxic groundwaters.