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.

Abstract: The long-lived radio-krypton isotope 81Kr (t1/2 = 2.29 × 105 yr) is an ideal tracer for old groundwater age dating in the range of 105–106 years which goes beyond the reach of radio-carbon (14C) age dating. Analytical breakthrough made over the last two decades in Atom Trap Trace Analysis (ATTA) has enabled the use of this isotope with extremely low abundance (81Kr/Kr = 6 × 10−13) to be used as a practical dating tool for very old groundwater. The International Atomic Energy Agency aims to provide this new isotope tool for better groundwater resource management of Member States and developed a field sampling device to collect dissolved gas samples from groundwater and a system to separate and purify trace amounts of krypton from the gas samples for the ATTA analysis. The design, setup and performances of our sampling and purification systems are described here. Our system can produce a high purity aliquot of about 5 μL of krypton from 5 L of air sample (recovery yield of >90%). The samples made by our system were confirmed to be acceptable for the ATTA analysis.