Abstract: To effectively manage sustainably groundwater bodies, it is essential to establish what the naturally occurring ranges of chemical concentrations in groundwaters are and how they change over time. We defined baseline trends for New Zealand groundwaters using: 1) pattern recognition techniques to deal with inconsistent monitoring suites between the national (110 sites) and the denser regional network (\textgreater1000 sites), and 2) multivariate statistics to identify and remove impacted sites from the enhanced dataset. Rates of changes were calculated for 13 parameters between January 2005 and December 2014 at more than 1000 groundwater quality monitoring sites. The resulting dataset included 262 complete cases (CC), which was enhanced using Machine-Learning (ML) techniques to a total of 607 sites. Hierarchical cluster analysis was used to identify trend clusters that were consistent between the CC, ML-enhanced datasets and a 2006 study based on solely on the national network. The largest cluster (WR) consisted of low magnitude changes across all parameters and was attributed to water-rock interaction processes. The second largest cluster (I) exhibited fast changes particularly for parameters linked to human-induced impact. The third largest cluster (D) comprised decreases of all parameters and was associated with dilution processes. Trend clusters were further refined using groundwater quality state information, enabling the identification of impacted sites outside of Cluster I in the ML-enhanced and CC datasets. Corresponding trend baselines were subsequently derived at unimpacted sites using univariate quantile distribution (5th and 95th percentile thresholds). Finally, we developed classifications combining baselines (state and trend) and natural variability to enhance state of the environment reporting. This allowed the new identification of deteriorating trends at sites where groundwater quality state is not yet affected in addition to trend reversals. These classifications can be adapted to incorporate new knowledge or align with surface water quality reporting.

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.

Abstract: We show evidence that the primary uranium minerals, uraninite and coffinite, from high-grade ore samples (U3O8\textgreater0.3%) in the Wuyiyi, Wuyier, and Wuyisan sandstone-hosted roll-front uranium deposits, Xinjiang, northwestern China were biogenically precipitated and psuedomorphically replace fungi and bacteria. Uranium (VI), which was the sole electron acceptor, was likely to have been enzymically reduced. Post-mortem accumulation of uranium may have also occurred through physio-chemical interaction between uranium and negatively-charged cellular sites, and inorganic adsorption or precipitation reactions. These results suggest that microorganisms may have played a key role in formation of the sandstone- or roll-type uranium deposits, which are among the most economically significant uranium deposits in the world.

Abstract: The Zoovch Ovoo uranium roll-front-type deposit is hosted in the Sainshand Formation, a Late Cretaceous siliciclastic reservoir, which constitutes the upper part of the post-rift infilling of the Mesozoic East Gobi Basin in SE Mongolia. The Sainshand Formation consists of unconsolidated medium-grained sand, silt and clay intervals deposited in fluvial-lacustrine settings. The uranium deposit is confined within a 60–80 m thick siliciclastic sequence inside aquifer-driven systems. The overall system experienced shallow burial and was never subjected to temperatures higher than 40 °C. This study proposes a comprehensive metallogenic model for this uranium deposit. Sedimentological and mineralogical observations from drill core samples to the microscopic scale (optical and Scanning Electron Microscopy) together with in situ geochemistry of late-formed phases (Laser Ablation–Inductively Coupled Plasma Mass Spectrometry, Electron Probe Microanalysis, Fourier Transform–Infrared Spectroscopy) were considered for the reconstruction of the main stages of U trapping. In the mineralized zone, the uranium ore is expressed as Ca–enriched uraninite (UO2) and less commonly as Ca–enriched phospho-coffinite (U, P)SiO4. Trapping mechanisms include i) complexation (i.e. uranyl-carboxyl complexes), ii) adsorption on organic or clay particles) and iii) reduction by pyrite and by bacterial activity to amorphous uraninite. In all cases, the organic matter plays either the role of trap for uranium or nutrient for bacteria that can trap uranium through their metabolism. The shallow burial diagenesis conditions do not allow direct reduction of U(VI) by organic carbon. The δ34S values of the iron disulfide are very diverse, fluctuating in extreme cases between −50 to + 50‰, with an average δ34S value for framboidal pyrite at 2‰, and −20‰ for euhedral pyrite. The positive and negative values reflect close versus open fractionation systems, while bacterial sulphate reduction (BSR) is active during the whole diagenetic history of the deposit as an essential source of reduced sulfur. Therefore, using detrital organic matter as a carbon source, microorganisms play a significant role in uranium trapping, either as a direct reducing agent for uranium or pyrite formation, which will trap uranium through redox driven epigenetic processes.

Abstract: A complete hydrogeological understanding of the deep Upper Jurassic carbonate aquifer in the South German Molasse Basin is essential for the future development of this important drinking water resource and geothermally used system. Water chemistry data, δ13CDIC, 14C of the dissolved inorganic carbon (14CDIC) and stable water isotope (δ18O and δD) measurements have been used to evaluate a promising groundwater dating approach with 14C of dissolved organic carbon (14CDOC). The pre-concentration of dissolved organic matter (DOM) was performed by the easy applicable solid phase extraction (SPE) with a styrene-divinylbenzene copolymer sorbent (PPL). Based on the sampling campaign of seven groundwater wells conducted between 2017 and 2019, it was shown that the groundwater is mainly of Ca–HCO3 type with some evidence of ion exchange between Ca2+ and Na+ at two of the investigated wells. The δD values ranged from −89.4‰ to −70.9‰ while δ18O values varied between −12.5‰ and −9.8‰. The obtained stable water isotope signatures indicated that the groundwater is of meteoric origin and was recharged during warm climate (Holocene), intermediate climate and cold climate (Pleistocene) infiltration conditions. The measured 14CDOC activities varied from 5.7 pmC to 51.1 pmC and the calculated piston-flow water ages (ORAs) ranged from 4200 years to 25,248 years using an initial 14C0DOC of 85 pmC. The calculated ORAs showed a very good correlation to the infiltration temperature-sensitive δ18O values which were affirmed with noble gas infiltration temperatures for two wells after Weise et al. (1991) and were also in good accordance with the atmospheric temperature record of the northern hemisphere from Dokken et al. (2015). The results reflect a consistent hydrogeological picture of the carbonate aquifer, which also supports the applicability of the SPE-PPL method for 14CDOC dating in groundwater with a low DOC content (<1 mg/l). In contrast, 14CDIC activities of 1.4 pmC to 21.3 pmC led to geochemically corrected piston-flow ages between 8057 years and >30,000 years and generally to an overestimation of the apparent water ages. This study gives insights into the promising approach of 14CDOC groundwater dating in carbonate aquifers with low DOC contents and allows future sustainable groundwater resource management of the investigated aquifer system.