Rosen, M. R., Burow, K. R., & Fram, M. S. (2019). Anthropogenic and geologic causes of anomalously high uranium concentrations in groundwater used for drinking water supply in the southeastern San Joaquin Valley, CA. Journal of Hydrology, 577, 124009.
Abstract: Concentrations of uranium (U) \textgreater30 µg/L in groundwater are relatively uncommon in drinking water in the United States but can be of concern in those areas where complex interactions of aquifer materials and anthropogenic alterations of the natural flow regime mobilize U. High concentrations (\textgreater30 µg/L) of U in the southeastern San Joaquin Valley, California, USA, have been detected in 24 percent of 257 domestic, irrigation, and public-supply wells sampled across an approximately 110,000 km2 area. In this study we evaluated mechanisms for mobilization of U in the San Joaquin Valley proposed in previous studies, confirming mobilization by HCO3 and refuting mobilization by NO3 and we refined our understanding of the geologic sources of U to the scale of individual alluvial fans. The location of high concentrations depends on the interactions of geological U sources from fluvial fans that originate in the Sierra Nevada to the east and seepage of irrigation water that contains high concentrations of HCO3 that leaches U from the sediments. In addition, interactions with PO4 from fertilized irrigated fields may sequester U in the aquifer. Principal component analysis of the data demonstrates that HCO3 and ions associated with high total dissolved solids in the aquifer and the percentage of agriculture near the well sampled are associated with high U concentrations. Nitrate concentrations do not appear to control release of U to the aquifer. Age dating of the groundwater and generally increasing U concentrations of the past 25 years in resampled wells where irrigation is prevalent suggests that high U concentrations are associated with younger water, indicating that irrigation of fields over the past 100 years has significantly contributed to increasing concentrations and mobilizing U. In some places, the groundwater is supersaturated with uranyl-containing minerals, as would be expected in roll front deposits. In general, the interaction of natural geological sources high in U, the anthropogenically driven addition of HCO3 and possibly phosphate fertilizer, control the location and concentration of U in each individual fluvial fan, but the addition of nitrate in fertilizer does not appear control the location of high U. These geochemical interactions are complex but can be used to determine controls on anomalously high U in alluvial aquifers.
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Belz, L., Schüller, I., Wehrmann, A., Köster, J., & Wilkes, H. (2020). The leaf wax biomarker record of a Namibian salt pan reveals enhanced summer rainfall during the Last Glacial-Interglacial Transition. Palaeogeography, Palaeoclimatology, Palaeoecology, 543, 109561.
Abstract: Conventional continental geoarchives are rarely available in arid southern Africa. Therefore, palaeoclimate data in this area are still patchy and late Quaternary climate development is only poorly understood. In the western Kalahari, salt pans (playas, ephemeral lakes) are common and can feature quasi-continuous sedimentation. This study presents the first climate-related biomarker record using sediments from the Omongwa Pan, a Kalahari salt pan located in eastern Namibia. Our approach to reconstruct vegetation and hydrology focuses on biogeochemical bulk parameters and plant wax-derived lipid biomarkers (n-alkanes, n-alkanols, and fatty acids) and their compound-specific carbon and hydrogen isotopic compositions. The presented record reaches back to 27 ka. During the glacial, rather low δ2H values of n-alkanes and low sediment input exclude a strong influence of winter rainfall. n-Alkane and n-alkanol distributions and δ13C values of n-hentriacontane (n-C31) indicate a shift to a vegetation with a higher proportion of C4 plants at the end of the Last Glacial Maximum until the end of Heinrich Stadial I (ca. 18–14.8 ka), which we interpret to indicate an abrupt excursion to a short wetter period likely to be caused by a temporary southward shift of the Intertropical Convergence Zone. Shifts in δ2H values of n-C31 and plant wax parameters give evidence for changes to drier conditions during early Holocene. Comparison of this dataset with representative continental records from the region points to a major influence of summer rainfall at Omongwa Pan during the regarded time span and demonstrates the potential of southern African salt pans as archives for biomarker-based climate proxies.
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Milena-Pérez, A., Piñero-García, F., Benavente, J., Expósito-Suárez, V. M., Vacas-Arquero, P., & Ferro-García, M. A. (2021). Uranium content and uranium isotopic disequilibria as a tool to identify hydrogeochemical processes. Journal of Environmental Radioactivity, 227, 106503.
Abstract: This paper studies the uranium content and uranium isotopic disequilibria as a tool to identify hydrogeochemical processes from 52 groundwater samples in the province of Granada (Betic Cordillera, southeastern Spain). According to the geological complexity of the zone, three groups of samples have been considered. In Group 1 (thermal waters; longest residence time), the average uranium content was 2.63 ± 0.16 μg/L, and 234U/238U activity ratios (AR) were the highest of all samples, averaging 1.92 ± 0.30. In Group 2 (mainly springs from carbonate aquifers; intermediate residence time), dissolved uranium presented an average value of 1.34 ± 0.13 μg/L, while AR average value was 1.38 ± 0.25. Group 3 comes from pumping wells in a highly anthropized alluvial aquifer. In this group, where the residence time of the groundwater is the shortest of the three, average uranium content was 5.28 ± 0.26 μg/L, and average AR is the lowest (1.17 ± 0.12). In addition, the high dissolved uranium value and the low AR brought to light the contribution of fertilizers (Group 3). In the three groups, 235U/238U activity ratios were similar to the natural value of 0.046. Therefore, 235U detected in the samples comes from natural sources. This study is completed with the determination of major ions and physicochemical parameters in the groundwater samples and the statistical analysis of the data by using the Principal Component Analysis. This calculation indicates the correlation between uranium isotopes and bicarbonate and nitrate anions.
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Christofi, C., Bruggeman, A., Külls, C., & Constantinou, C. (2020). Hydrochemical evolution of groundwater in gabbro of the Troodos Fractured Aquifer. A comprehensive approach. Applied Geochemistry, 114, 104524.
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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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