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Paradis, C. J., Hoss, K. N., Meurer, C. E., Hatami, J. L., Dangelmayr, M. A., Tigar, A. D., et al. (2022). Elucidating mobilization mechanisms of uranium during recharge of river water to contaminated groundwater. Journal of Contaminant Hydrology, 251, 104076.
Abstract: The recharge of stream water below the baseflow water table can mobilize groundwater contaminants, particularly redox-sensitive and sorptive metals such as uranium. However, in-situ tracer experiments that simulate the recharge of stream water to uranium-contaminated groundwater are lacking, thus limiting the understanding of the potential mechanisms that control the mobility of uranium at the field scale. In this study, a field tracer test was conducted by injecting 100 gal (379 l) of oxic river water into a nearby suboxic and uranium-contaminated aquifer. The traced river water was monitored for 18 days in the single injection well and in the twelve surrounding observation wells. Mobilization of uranium from the solid to the aqueous phase was not observed during the tracer test despite its pre-test presence being confirmed on the aquifer sediments from lab-based acid leaching. However, strong evidence of oxidative immobilization of iron and manganese was observed during the tracer test and suggested that immobile uranium was likely in its oxidized state as U(VI) on the aquifer sediments; these observations ruled out oxidation of U(IV) to U(VI) as a potential mobilization mechanism. Therefore, desorption of U(VI) appeared to be the predominant potential mobilization mechanism, yet it was clearly not solely dependent on concentration as evident when considering that uranium-poor river water (\textless0.015 mg/L) was recharged to uranium-rich groundwater (≈1 mg/L). It was possible that uranium desorption was limited by the relatively higher pH and lower alkalinity of the river water as compared to the groundwater; both factors favor immobilization. However, it was likely that the immobile uranium was associated with a mineral phase, as opposed to a sorbed phase, thus desorption may not have been possible. The results of this field tracer study successfully ruled out two common mobilization mechanisms of uranium: (1) oxidative dissolution and (2) concentration-dependent desorption and ruled in the importance of advection, dispersion, and the mineral phase of uranium.
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Orloff, K. G., Mistry, K., Charp, P., Metcalf, S., Marino, R., Shelly, T., et al. (2004). Human exposure to uranium in groundwater. Environmental Research, 94(3), 319–326.
Abstract: High concentrations of uranium (mean=620μg/L) were detected in water samples collected from private wells in a residential community. Based on isotopic analyses, the source of the uranium contamination appeared to be from naturally occurring geological deposits. In homes where well water concentrations of uranium exceeded the drinking water standard, the residents were advised to use an alternate water source for potable purposes. Several months after the residents had stopped drinking the water, urine samples were collected and tested for uranium. Elevated concentrations of uranium (mean=0.40μg/g creatinine) were detected in urine samples, and 85 percent of the urine uranium concentrations exceeded the 95th percentile concentration of a national reference population. Urine uranium concentrations were positively correlated with water uranium concentrations, but not with the participants’ ages or how long they had been drinking the water. Six months later, a second urine sample was collected and tested for uranium. Urine uranium concentrations decreased in most (63 percent) of the people. In those people with the highest initial urine uranium concentrations, the urine levels decreased an average of 78 percent. However, urine uranium concentrations remained elevated (mean=0.27μg/g), and 87 percent of the urine uranium concentrations exceeded the 95th percentile concentration of the reference population. The results of this investigation demonstrated that after long-term ingestion of uranium in drinking water, elevated concentrations of uranium in urine could be detected up to 10 months after exposure had stopped.
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Gimeno, M. J., Tullborg, E. - L., Nilsson, A. - C., Auqué, L. F., & Nilsson, L. (2023). Hydrogeochemical characterisation of the groundwater in the crystalline basement of Forsmark, the selected area for the geological nuclear repositories in Sweden. Journal of Hydrology, 624, 129818.
Abstract: Numerous groundwater analyses from the crystalline bedrock in the Forsmark area have been performed between 2002 and 2019, together with thorough geological, geophysical, and hydrogeological studies, within the site investigations carried out by the Swedish Nuclear Fuel and Waste Management Company. The groundwater samples have been taken from boreholes down to ≈ 1000 m and the analysis include major- and trace-elements, stable and radiogenic isotopes, gases and microbes. The chemical and isotopic composition of these groundwaters evidences the presence of non-marine brackish to saline groundwaters with very long residence times (many hundreds of thousands of years) and a series of complex mixing events resulting from the recharge of different waters over time: glacial meltwaters, probably from different glaciations of which the latest culminated some 20,000 years ago, and marine waters from the Baltic starting some 7000 years ago. Later, meteoric water and present Baltic Sea water have recharged in different parts of the upper 100 m. These mixing events have also triggered chemical and microbial reactions that have conditioned some of the important groundwater parameters and, together with the structural complexity of the area, they have promoted a heterogeneous distribution of groundwater compositions in the bedrock. Due to these evident differences in chemistry, residence time and origin of the groundwater, several groundwater types were defined in order to facilitate the visualisation and communication. The differentiation (linked to the paleohydrological history of the area) was based on Cl concentration, Cl/Mg ratio (marine component), and δ18O value (glacial component). The work presented in this paper increases the understanding of the groundwater evolution in fractured and compartmentalised aquifers where mixing processes are the most important mechanisms. The model proposed to characterise the present groundwater system of the Forsmark area will also help to predict the future hydrogeochemical behaviour of the groundwater system after the construction of the repositories for the nuclear wastes.
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Jroundi, F., Povedano-Priego, C., Pinel-Cabello, M., Descostes, M., Grizard, P., Purevsan, B., et al. (2023). Evidence of microbial activity in a uranium roll-front deposit: Unlocking their potential role as bioenhancers of the ore genesis. Science of The Total Environment, 861, 160636.
Abstract: Uranium (U) roll-front deposits constitute a valuable source for an economical extraction by in situ recovery (ISR) mining. Such technology may induce changes in the subsurface microbiota, raising questions about the way their activities could build a functional ecosystem in such extreme environments (i.e.: oligotrophy and high SO4 concentration and salinity). Additionally, more information is needed to dissipate the doubts about the microbial role in the genesis of such U orebodies. A U roll-front deposit hosted in an aquifer driven system (in Zoovch Ovoo, Mongolia), intended for mining by acid ISR, was previously explored and showed to be governed by a complex bacterial diversity, linked to the redox zonation and the geochemical conditions. Here for the first time, transcriptional activities of microorganisms living in such U ore deposits are determined and their metabolic capabilities allocated in the three redox-inherited compartments, naturally defined by the roll-front system. Several genes encoding for crucial metabolic pathways demonstrated a strong biological role controlling the subsurface cycling of many elements including nitrate, sulfate, metals and radionuclides (e.g.: uranium), through oxidation-reduction reactions. Interestingly, the discovered transcriptional behaviour gives important insights into the good microbial adaptation to the geochemical conditions and their active contribution to the stabilization of the U ore deposits. Overall, evidences on the importance of these microbial metabolic activities in the aquifer system are discussed that may clarify the doubts on the microbial role in the genesis of low-temperature U roll-front deposits, along the Zoovch Ovoo mine.
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Jaireth, S., Roach, I. C., Bastrakov, E., & Liu, S. (2016). Basin-related uranium mineral systems in Australia: A review of critical features. Ore Geology Reviews, 76, 360–394.
Abstract: This paper reviews critical features of basin-related uranium mineral systems in Australia. These mineral systems include Proterozoic unconformity-related uranium systems formed predominantly from diagenetic fluids expelled from sandstones overlying the unconformity, sandstone-hosted uranium systems formed from the influx of oxidised groundwaters through sandstone aquifers, and calcrete uranium systems formed from oxidised groundwaters flowing through palaeochannel aquifers (sand and calcrete). The review uses the so-called ‘source-pathway-trap’ paradigm to summarise critical features of fertile mineral systems. However, the scheme is expanded to include information on the geological setting, age and relative timing of mineralisation, and preservation of mineral systems. The critical features are also summarised in three separate tables. These features can provide the basis to conduct mineral potential and prospectivity analysis in an area. Such analysis requires identification of mappable signatures of above-mentioned critical features in geological, geophysical and geochemical datasets. The review of fertile basin-related systems shows that these systems require the presence of at least four ingredients: a source of leachable uranium (and vanadium and potassium for calcrete-uranium deposits); suitable hydrological architecture enabling connection between the source and the sink (site of accumulation); physical and chemical sinks or traps; and a post-mineralisation setting favourable for preservation. The review also discusses factors that may control the efficiency of mineral systems, assuming that world-class deposits result from more efficient mineral systems. The review presents a brief discussion of factors which may have controlled the formation of large deposits in the Lake Frome region in South Australia, the Chu-Sarysu and Syrdarya Basins in Kazakhstan and calcrete uranium deposits in the Yilgarn region, Western Australia.
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Silva, M. L. da, & Bonotto, D. M. (2015). Uranium isotopes in groundwater occurring at Amazonas State, Brazil. Applied Radiation and Isotopes, 97, 24–33.
Abstract: This paper reports the behavior of the dissolved U-isotopes 238U and 234U in groundwater providing from 15 cities in Amazonas State, Brazil. The isotope dilution technique accompanied by alpha spectrometry were utilized for acquiring the U content and 234U/238U activity ratio (AR) data, 0.01–1.4µgL−1 and 1.0–3.5, respectively. These results suggest that the water is circulating in a reducing environment and leaching strata containing minerals with low uranium concentration. A tendency to increasing ARs values following the groundwater flow direction is identified in Manaus city. The AR also increases according to the SW–NE directions: Uarini→Tefé; Manacapuru→Manaus; Presidente Figueiredo→São Sebastião do Uatumã; and Boa Vista do Ramos→Parintins. Such trends are possibly related to several factors, among them the increasing acid character of the waters. The waters analyzed are used for human consumption and the highest dissolved U content is much lower than the maximum established by the World Health Organization. Therefore, in view of this radiological parameter they can be used for drinking purposes.
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Lartigue, J. E., Charrasse, B., Reile, B., & Descostes, M. (2020). Aqueous inorganic uranium speciation in European stream waters from the FOREGS dataset using geochemical modelling and determination of a U bioavailability baseline. Chemosphere, 251, 126302.
Abstract: The concentration of the bioavailable uranium fraction (Ubio) at the European scale was deduced by geochemical modelling considering several definitions found in the literature and the FOREGS European stream waters geochemical atlas dataset to produce a Ubio baseline. A sensitivity analysis was performed using three thermodynamic databases. We also investigated the link between total dissolved uranium (Uaq) concentrations, speciation and global stream water chemistry on the one hand, and the lithology and ages of the surrounding rocks on the other. The more U-enriched the stream sediments or rock type contexts are, which tends to be the case with rocks containing silicates (4.1 mg/kg), the less U-concentrated the stream waters are (0.15 μg/L). Sedimentary rocks lead to slightly higher Uaq concentrations (0.34 μg/L) even if the concentration in sediment (Used) is relatively low (1.6 mg/kg). This trend is reversed for Ubio, with higher concentrations in a crystalline context. The mean estimated Ubio value ranges from 1.5.10−3 to 65.3 ng/L and can fluctuate by 3 orders of magnitude depending on the considered definition as opposed to by 2 orders of magnitude accountable to differences between thermodynamic databases. The classification of the water in relation to the two surrounding rock lithologies makes it possible to reduce the mean variability for the Ubio concentrations. Irrespective of the definition of Ubio considered, in 59% of cases the Ubio fraction represents less than 1% of Uaq. Several threshold values relating to Ubio were proposed, assuming knowledge only of the aqueous concentrations of the major elements and Uaq.
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Mühr-Ebert, E. L., Wagner, F., & Walther, C. (2019). Speciation of uranium: Compilation of a thermodynamic database and its experimental evaluation using different analytical techniques. Applied Geochemistry, 100, 213–222.
Abstract: Environmental hazards are caused by uranium mining legacies and enhanced radioactivity in utilized groundwater and surface water resources. Knowledge of uranium speciation in these waters is essential for predicting radionuclide migration and for installing effective water purification technology. The validity of the thermodynamic data for the environmental media affected by uranium mining legacies is of utmost importance. Therefore, a comprehensive and consistent database was established according to current knowledge. The uranium data included in the database is based on the NEA TDB (Guillaumont et al., 2003) and is modified or supplemented as necessary e.g. for calcium and magnesium uranyl carbonates. The specific ion interaction theory (Brönsted, 1922) is used to estimate activity constants, which is sufficient for the considered low ionic strengths. The success of this approach was evaluated by comparative experimental investigations and model calculations (PHREEQC (Parkhurst and Appelo, 1999)) for several model systems. The waters differ in pH (2.7–9.8), uranium concentration (10−9-10−4 mol/L) and ionic strength (0.002–0.2 mol/L). We used chemical extraction experiments, ESI-Orbitrap-MS and time-resolved laser-induced fluorescence spectroscopy (TRLFS) to measure the uranium speciation. The latter method is nonintrusive and therefore does not change the chemical composition of the investigated waters. This is very important, because any change of the system under study may also change the speciation.
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Lawrinenko, M., Kurwadkar, S., & Wilkin, R. T. (2023). Long-term performance evaluation of zero-valent iron amended permeable reactive barriers for groundwater remediation – A mechanistic approach. Geoscience Frontiers, 14(2), 101494.
Abstract: Permeable reactive barriers (PRBs) are used for groundwater remediation at contaminated sites worldwide. This technology has been efficient at appropriate sites for treating organic and inorganic contaminants using zero-valent iron (ZVI) as a reductant and as a reactive material. Continued development of the technology over the years suggests that a robust understanding of PRB performance and the mechanisms involved is still lacking. Conflicting information in the scientific literature downplays the critical role of ZVI corrosion in the remediation of various organic and inorganic pollutants. Additionally, there is a lack of information on how different mechanisms act in tandem to affect ZVI-groundwater systems through time. In this review paper, we describe the underlying mechanisms of PRB performance and remove isolated misconceptions. We discuss the primary mechanisms of ZVI transformation and aging in PRBs and the role of iron corrosion products. We review numerous sites to reinforce our understanding of the interactions between groundwater contaminants and ZVI and the authigenic minerals that form within PRBs. Our findings show that ZVI corrosion products and mineral precipitates play critical roles in the long-term performance of PRBs by influencing the reactivity of ZVI. Pore occlusion by mineral precipitates occurs at the influent side of PRBs and is enhanced by dissolved oxygen and groundwater rich in dissolved solids and high alkalinity, which negatively impacts hydraulic conductivity, allowing contaminants to potentially bypass the treatment zone. Further development of site characterization tools and models is needed to support effective PRB designs for groundwater remediation.
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Ren, Y., Yang, X., Hu, X., Wei, J., & Tang, C. (2022). Mineralogical and geochemical evidence for biogenic uranium mineralization in northern Songliao Basin, NE China. Ore Geology Reviews, 141, 104556.
Abstract: The sandstone-hosted uranium mineralization areas in the Sanzhao Sag of the northern Songliao Basin have been newly identified. The target stratum is the Upper Cretaceous Sifangtai Formation and the uranium mineralization mainly occurs in the bottom of Sifangtai Formation, corresponding to channel sand bodies in meandering river system, characterized by medium to fine-grained sandstone. This study proposes the uranium metallogenic model through petrographic observation, whole rock geochemistry, mineralogical study of uranium occurrence form (SEM), organic matter rock–eval pyrolysis analysis (REP) and in-situ sulfur isotope determination of different generations of pyrite by LA-MC-ICP-MS. Compared with the sandstones collected in barren reduction and oxidization zones, the mineralized sandstones show obvious increase in the contents of TOC, total sulfur, Y and U. Petrographic observations indicate that organic matters are mainly inherited from land plants. REP data display that the organic matter (OM) disseminated in the sandstone has very low hydrogen index (HI) from around 0 to 21 mg HC/g TOC and varied oxygen index (OI) from 44 to 115 mg CO2/g TOC, corresponding to Type Ⅳ kerogen (degraded kerogen). There are two types of coffinite with different grain size, micro-particles (μm-sized) and large aggregates (generally up to 100 μm) respectively. The coffinite micro spherules exhibit short rod-like or worm-like morphology occurring in clay matrix and cell cavities in degradofusinite or around subidiomorphic-idiomorphic pyrite. The coarse-grained coffinite contains other mineral facies (e.g. pyrite, quartz) and some of large coffinite aggregates display thrombolite-type microbial structures. The irregular pyrite relict particles in coarse-grained colloidal coffinite have light sulfur isotope compositions characterized by δ34S values from –39.96‰ to –49.89‰. The δ34S values of colloidal pyrite in replacement of OM or of the sub-idiomorphic FeS2 cement filling in the cavities of OM range from –52.77‰ to –13.88‰. Some of sub-idiomorphic pyrite cement and idiomorphic crystal have the heavier signature from – 27.06‰ to + 14.23‰. The light sulfur isotope signature suggests that the sulfur originates from bacterial sulfate reduction (BSR). The OM replacement by pyrite and the highest OI values recorded by REP in uranium mineralized samples are lines of evidence of biodegradation. Bacteria use the organic matter as food source and produce isotopically light reduced sulfur species. Oxygenated uranium-bearing waters infiltrated through the denudated windows at Daqing placanticline into the porous reduced sandstones deposited in the Sanzhao Sag. Uranium was indirectly reduced by BSR-derived iron disulfides or directly reduced by sulfate-reducing bacteria.
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