Abstract: 81Kr and 36Cl can both be used to date groundwater beyond the dating range of 14C. 81Kr usually provides reliable groundwater ages because it has uniform initial distribution and negligible subsurface generation, while 36Cl is commonly influenced by subsurface sources or “dead” chloride dissolution. Therefore, the combined use of 81Kr and 36Cl could provide clues on the evolution history of groundwater. In the present study, we performed 36Cl and 81Kr dating of geothermal water in Weihe Basin of China and interpreted the possible cause of disagreement. Two distinct water masses were identified with distinctive isotopic signals: groundwater with significant δ18O shifts (up to −2.0‰), dissolved dead Cl and ages < 1.0 Ma (Cluster A), and older water with little δ18O shifts, negligible dissolved Cl and ages >1.0 Ma (Cluster B). The results confirm the eastward flow path of Cluster B to the Ancient Sanmen Lake with an increasing trend of Cl concentration and age. Modern recharge from the mountains flows to the basin center with intense interaction between water and carbonate under respective reservoir temperatures (100 ∼ 130 °C). These waters flow through the saline stratum emerging from the spillover of the Ancient Sanmen Lake, resulting in higher dead Cl dissolution. A significant linear relationship is observed with the older end-member of ∼1.3Ma under the topographically-driven faster circulation effect. 81Kr ages seem to support the hypothesis that the birth of the modern Yellow River was at about 1.0–1.3 Ma. We inferred the drainage reorganization from the Ancient Sanmen Lake to the modern Yellow River since the Mid-Pleistocene Transition induced the change in groundwater dynamics as well as its chemical evolution. The excavation of the Ancient Sanmen Lake and the accentuated incision of the Weihe River induced groundwater gradient, and therefore the recharge from precipitation from both slopes of the Qinling Mountains in the south and the Beishan Mountains in the north. Our results highlight the effects of dead Cl on 36Cl dating and demonstrate the significant impact of catchment reorganization on groundwater dynamics and its chemistry.

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.

Abstract: Complex pyrite textures associated with large changes in isotopic and trace element compositions are routinely assumed to be indicative of multi-faceted processes involving multiple fluid and sulfur sources. We propose that the features of ore-stage pyrite from roll front deposits across the world, revealed in exquisite detail via high-resolution trace element mapping by LA-ICP-MS, reflect the dynamic internal evolution of the biogeochemical processes responsible for sulfate reduction, rather than externally driven changes in fluid or sulfur sources through time. Upon percolation of oxidizing fluids into the reduced host-sandstones, roll front systems become self-organized, with a systematic reset of their activity cycle after each translation stage of the redox interface down dip of the aquifer. Dominantly reducing conditions at the redox interface favor the formation of biogenic framboidal pyrite (δ34S from −30.5 to −12.5‰) by bacterial sulfate reduction and the genesis of the U mineralization. As the oxidation front advances, oxidation of reduced sulfur minerals induces an increased supply of sulfate and metals in solution to the bacterial sulfate reduction zone that has similarly advanced down the flow gradient. Hence, this stage is marked by increased rates of the bacterial sulfate reduction associated with the crystallization of variably As-Co-Ni-Mo-enriched concentric pyrite (up to 10,000′s of ppm total trace contents) with moderately negative δ34S values (from −13.7 to −7.5‰). A final stage of pyrite cement with low trace element contents and heavier δ34S signature (from −6.9 to +18.8‰) marks the end of the roll front activity cycle and the transition from an open to a predominantly closed system behavior (negligible advection of fresh sulfate). Blocky pyrite cement is formed using the remaining sulfate, which now becomes quickly heavy according to a Rayleigh isotope fractionation process. This ends the cycle by depleting the nutrient supplies for the sulfate-reducing bacteria and cementing pore spaces within the host sandstone, effectively restricting fluid infiltration. This internally-driven roll front activity cycle results in systematic, large S isotope and trace element fractionation. Ultimately, the long-time evolution of the basin and fluid sources control the metal endowment and evolution of the system; these events, however, are unlikely to be preserved by the roll front, as a direct result of its hydrodynamic nature.