Abstract: This study refines the hydrogeological conceptual model of an area with three interconnected aquifers, namely the Crystalline Aquifer System (CAS – igneous and metamorphic rocks), which is in contact with the Tubarão Aquifer System (TAS – sedimentary rocks) and the Diabase Aquifer System (DAS – diabase rocks). The detailed investigation involved geophysical logging and hydraulic and hydrodynamic characterization with straddle packers in a local tubular well, in which groundwater presents high uranium concentrations. Hydrogeochemical and isotope (δ2H, δ18O, 3H, δ13C, 14C) analysis in this well and in other three neighboring wells, with lower U concentrations, showed that ancient and modern waters (3H from <0.8 to 1.12 TU, 14C from 69.43 to 78.72 pMC) mix within the aquifer. During groundwater pumping, vertical fractures in the diabase aquifer possibly induce water mixing and recharge of the deeper levels of the aquifers from shallow layers. The high [U] are related to ancient waters from a confined aquifer hosted in CAS that reaches the wells through hydraulically active fractures located deeper than 159 m depth. Groundwater apparent ages do not increase systematically with depth, revealing a complex circulation model for CAS. The results obtained from the other wells, which are all located on drainage lineaments, reveal that one extracts modern water from DAS and TAS, another one extracts modern and ancient water from DAS and CAS, and the third extracts only ancient water from CAS, confirming the complexity of the local hydrogeology. Regarding regional groundwater management, the study revealed the need to characterize the sources of groundwater in each well, in order to protect modern waters from anthropogenic contamination and to protect ancient groundwater from overexploitation, as CAS hosts groundwaters recharged thousands of years ago or more.

Abstract: Generic hydrochemical modelling of a grantoid-groundwater system, using the Russian software “HydroGeo”, has been carried out with an emphasis on simulating the accumulation of uranium in the aqueous phase. The baseline model run simulates shallow granitoid aquifers (U content 5 ppm) under conditions broadly representative of southern Norway and southwestern Siberia: i.e. temperature 10 °C, equilibrated with a soil gas partial CO2 pressure (PCO2, open system) of 10−2.5 atm. and a mildly oxidising redox environment (Eh = +50 mV). Modelling indicates that aqueous uranium accumulates in parallel with total dissolved solids (or groundwater mineralisation M – regarded as an indicator of degree of hydrochemical evolution), accumulating most rapidly when M = 550–1000 mg L−1. Accumulation slows at the onset of saturation and precipitation of secondary uranium minerals at M = c. 1000 mg L−1 (which, under baseline modelling conditions, also corresponds approximately to calcite saturation and transition to Na-HCO3 hydrofacies). The secondary minerals are typically “black” uranium oxides of mixed oxidation state (e.g. U3O7 and U4O9). For rock U content of 5–50 ppm, it is possible to generate a wide variety of aqueous uranium concentrations, up to a maximum of just over 1 mg L−1, but with typical concentrations of up to 10 μg L−1 for modest degrees of hydrochemical maturity (as indicated by M). These observations correspond extremely well with real groundwater analyses from the Altai-Sayan region of Russia and Norwegian crystalline bedrock aquifers. The timing (with respect to M) and degree of aqueous uranium accumulation are also sensitive to Eh (greater mobilisation at higher Eh), uranium content of rocks (aqueous concentration increases as rock content increases) and PCO2 (low PCO2 favours higher pH, rapid accumulation of aqueous U and earlier saturation with respect to uranium minerals).

Abstract: Most of the World’s germanium (Ge) is mined from Ge-rich lignite, where it is commonly associated with elevated arsenic (As), tungsten (W) and beryllium (Be) contents. Over the past decade, new evidence showing that World-class Ge deposits result from the interaction of hydrothermal fluids with organic matter in coal seams has emerged. Yet, the chemical state of Ge and associated metals in lignite remains poorly understood. We used Mega-pixel Synchrotron X-ray Fluorescence (MSXRF), X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) to characterize the oxidation states and chemical bonding environment of Ge, As, and W in two world-class Mesozoic Ge-in-lignite deposits (Lincang, Yunnan, southwestern China; Wulantuga, Inner Mongolia, northeastern China); in lignite-bearing uranium (U) ores from the Beverley deposit (South Australia) hosted in Eocene sandstones; and in lignite and preserved wood in late Oligocene-Miocene fluviatile sediments (Gore, Southland, New Zealand). The aim was to improve our understanding of the enrichment mechanism of Ge in lignite and better evaluate the environmental mobility of Ge and some of the associated metals (specifically As and W) in lignite ores. In all samples, chemical maps show that Ge is distributed homogeneously (down to 2μm) within the organic matter. XANES and EXAFS data show that Ge exists in the tetravalent oxidation state and in a distorted octahedral coordination with O, consistent with complexing of Ge by organic ligands. In some pyrite-bearing samples, a minor fraction of Ge is also present as Ge(IV) in association with pyrite. In contrast, As displays a more complex speciation pattern, sometimes even in a single sample, including As(III), As(V), and As(−I/+II) in solid solution in sulfides. Arsenic in sulfides occurs in anionic and cationic forms, i.e., it shows both the common substitution for S22− and the substitution for Fe recently discovered in some hydrothermal pyrites. Tungsten was present as W(VI) in distorted octahedral (3+3) coordination. The EXAFS data confirm the absence or minor contribution of individual W-rich minerals such as scheelite or ferberite to W mass balance in the studied samples. These data show that Ge, W, and probably some As are scavenged via formation of insoluble, oxygen-bridged metal organic complexes in lignite. Destruction of the organic ligands responsible for fixing Ge and W (As) in these lignites is required for liberating the metals, e.g. from waste materials. Geochemical modelling suggests that Ge, W, Be and As all can be extracted from granitic rocks by dilute, low temperature hydrothermal fluids. Germanium is transported mainly as the tetrahedral Ge(OH)4(aq) complex, but fixed as an octahedral oxy-bridged organic complex. The same situation is valid for W, which is transported at the tetrahedral tungstate ion, but most likely scavenged via formation of a 6-coordinated metal-organic species. The Ge-Be-W±As association in Ge-rich coals reflects the source of the metals as well as related scavenging mechanisms.

Abstract: Carbon dioxide (CO2) enhanced oil recovery (EOR) provides a pathway for economic reuse and storage of CO2, a greenhouse gas. One challenge with this practice is ensuring CO2 injection does not result in target reservoir fluids migrating into overlying shallow (\textless1000 m) groundwater formations. Effective monitoring for leakage from storage formations could involve measuring sensitive chemical indicators in overlying groundwater units and within the producing formation itself for evidence of deviation from an initial state. In this study, produced waters and overlying groundwaters were monitored over a five-year period to evaluate which geochemical signals may be useful to ensure that oilfield produced waters did not impact overlying groundwaters. During this five-year period, a mature carbonate oil reservoir in the Permian Basin transitioned from a waterflooding operation to a water-alternating-gas injection (WAG), in which the formation was flooded with CO2 and various mixtures of produced water. Significant increases in dissolved inorganic constituents [alkalinity, TDS, Na+, Cl−, SO42−] were observed in produced waters following CO2 injection; however, carbonate reservoir dissolution-precipitation reactions appear to be minimal and injected CO2 appears to be stored via solubility trapping. Although there are statistically significant geochemical variations following CO2 injection, applying isometric log-ratios to certain parameters establishes a narrow range for post-CO2 injection produced waters. This narrow range can be considered a baseline for post-CO2 injection produced waters; this baseline can be utilized to monitor overlying local groundwaters for produced water intrusion. Additionally, certain parameters [Na+, Ca2+, K+, Cl−, alkalinity, and TDS] display large concentration disparities between produced water and overlying groundwaters; these parameters would be sensitive indicators of produced water intrusion into overlying groundwaters.