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.

Abstract: From 1950 through the early 1980’s New Mexico accounted for roughly half of domestic uranium (U) production for the nuclear power industry and the nation’s weapon programs. Increased interest in nuclear energy has led to proposals for renewed development using both underground mining and uranium in situ recovery (ISR). When feasible, ISR greatly reduces waste generated by the mining and milling processes, however, the ability to restore ground water to acceptable quality after ISR ends is uncertain. This research investigated two methods of stabilizing an aquifer following ISR. Batch and column studies were performed to evaluate chemical and biological methods of stabilization. Columns packed with ore were first leached with an aerated NaHCO3 ground water solution to simulate ISR. Constituents present at elevated concentrations after leaching included molybdenum (Mo), selenium (Se), U, and vanadium (V). Chemical stabilization was studied by passing a phosphate (PO43-) amended solution through the ore to achieve passivation of mineral surfaces by P precipitates. Microbial stabilization was studied by passing a lactate solution through the ore to stimulate growth of anaerobic metal- and sulfate-reducing organisms to reduce U and other elements to less soluble phases. Analyses of the solids from the columns after completion of these experiments by X-ray photo electron spectroscopy (XPS) identified phosphate on samples near the column inlet of the chemically stabilized columns. Microbial populations were characterized by Illumina DNA sequencing and confirmed the presence of metal- and sulfate-reducing organisms. Neither chemical nor microbial stabilization method achieved contaminant immobilization, which is believed due to limited mixing of the stabilization solutions with the contaminated leach solutions. These results emphasize that ground water hydrodynamics, especially mixing, must be considered in aquifer restoration of soluble constituents.

Abstract: The distribution of uranium isotopes (238U and 234U) in groundwaters of the south-western margin of the Great Artesian Basin (GAB), Australia, and underlying Arckaringa Basin were examined using groundwater samples and a sequential extraction of aquifer sediments. Rock weathering, the geochemical environment and α-recoil of daughter products control the 238U and 234U isotope distributions giving rise to large spatial variations. Generally, the shallowest aquifer (J aquifer) contains groundwater with higher 238U activity concentrations and 234U/238U activity ratios close to secular equilibrium. However, the source input of uranium is spatially variable as intermittent recharge from ephemeral rivers passes through rocks that have already undergone extensive weathering and contain low 238U activity concentrations. Other locations in the J aquifer that receive little or no recharge contain higher 238U activity concentrations because uranium from localised uranium-rich rocks have been leached into solution and the geochemical environment allows the uranium to be kept in solution. The geochemical conditions of the deeper aquifers generally result in lower 238U activity concentrations in the groundwater accompanied by higher 234U/238U activity ratios. The sequential extraction of aquifer sediments showed that α-recoil of 234U from the solid mineral phases into the groundwater, rather than dissolution of, or exchange with the groundwater accessible minerals in the aquifer, caused enrichment of groundwater 234U/238U activity ratios in the Boorthanna Formation. Decay of 238U in uranium-rich coatings on J aquifer sediments caused resistant phase 234U/238U activity ratio enrichment. The groundwater 234U/238U activity ratio is dependent on groundwater residence time or flow rate, depending on the flow path trajectory. Thus, uranium isotope variations confirmed earlier groundwater flow interpretations based on other tracers; however, spatial heterogeneity, and the lack of clear regional correlations, made it difficult to identify recharge and inter-aquifer leakage.

Abstract: Secondary uranium encrustations are hosted in thick travertine and calcrete deposits of Pleistocene–Recent age in central Jordan. The central Jordan varicolored marble and travertine are equivalent to the active metamorphic area in Maqarin, north Jordan. More than 100 samples were collected from the outcrops of the varicolored marble, travertine, calcrete, and the yellow uranium encrustations. The secondary yellow encrustations are mainly composed of uranyl vanadate complexes. Tyuyamunite Ca(UO2)2V25+O8·3(H2O)–strelkinite Na2(UO2)2V2O8·6(H2O) solid solution series are the major components and their composition reflects changes in the Ca/Na ratio in solution. Potentially, new vanadium free calcium uranate phases (restricted to the varicolored marble) were identified with CaO:UO3 ratios different from the known mineral vorlanite (CaU6+)O4. Carbon and oxygen isotope data from calcite in the varicolored marble are characterized by Rayleigh-type enrichment in light isotopes associated with release of 13C and 18O enriched CO2 by high temperature decarbonation during combustion of the bituminous marl. Stable isotope results from uranium hosted travertine and calcrete varieties exhibit a wide range in isotopic values, between decarbonated and normal sedimentary carbonate rocks. The depleted δ13C and δ18O values in the travertine are related to the kinetic reaction of atmospheric CO2 with hyperalkaline Ca(OH)2 water. The gradual enrichment of δ13C and δ18O values in the calcrete towards equilibrium with the surrounding environment is related to continuous evaporation during seasonal dry periods. Uranium mineralization in central Jordan resulted from the interplay of tectonic, climatic, hydrologic, and depositional events. The large distribution of surficial uranium occurrences hosted in travertine and calcrete deposits is related to the artesian ascending groundwater that formed extensive lakes along NNW–SSE trending depressions. Fresh groundwater moved upward through the highly fractured phosphate, bituminous marl and varicolored marble to form unusual highly alkaline water (hydroxide–sulfate type) enriched with sensitive redox elements among which were U and V.

Abstract: VNIR-SWIR (400–2500 nm) reflectance measurements were made on the surfaces of various cores, cuttings and sample splits of sedimentary rocks from the Tertiary Jackson Group, and Catahoula, Oakville and Goliad Formations. These rocks vary in composition and texture from mudstone and claystone to sandstone and are known host rocks for roll front uranium occurrences in Karnes and Live Oak Counties, Texas. Spectral reflectance profiles, 569 in total, were reduced to 125 representative spectral signatures, which were analyzed using the U.S. Geological Survey’s (USGS) Material Identification and Characterization Algorithm (MICA). MICA uses an automated continuum-removal procedure together with a least-squares linear regression to determine the fit of observed sample spectral absorption features to those of reference mineral standards in a spectral library. The reference minerals include various clay, mica, carbonate, ferric and ferrous iron minerals and their mixtures. In addition, absorption feature band-depth analysis was done to identify rock surfaces exhibiting absorption features related to uranium and zeolite minerals, which were not included in the command files used to execute MICA. Rocks from each of the four geologic units produced broadly similar spectral signatures as a result of comparable mineral compositions, but there were some notable differences. For example, Ca- and Na-montmorillonite was matched most frequently to the spectral absorption features in 2-μm (∼2000–2500 nm) wavelengths, while goethite occurred often at 1-μm (∼400–1000 nm) wavelengths. The latter is related to limonitic iron-staining in and around oxidized zones of the uranium roll front as described in previous papers. Rocks of the Jackson Group differed from those of the Catahoula, Oakville and Goliad units in that the former exhibited spectral features we interpret as being due to the presence of lignite-bearing mudstone layers. Goliad rocks exhibit spectral features related to dolomite, gypsum, anhydrite, and an unidentified green clay mineral that is possibly glauconite. Jackson Group rocks also exhibit weak but well-resolved absorption features at 964 and 1157 nm related to either or both zeolite minerals clinoptilolite and heulandite. These zeolite minerals and a few spectra exhibiting hydrous silica absorption features are indicative of alteration of volcanic glass in tuffaceous mudstone and claystone layers. A few sample spectra exhibited strong absorption features at around 1135 nm related to the uranium mineral coffinite. Both the 1135 nm coffinite and 1157 nm zeolite absorption features overlap somewhat, potentially making them difficult to distinguish without additional hyperspectral field, laboratory or remote sensing data. The results of this study were compared to mixtures of minerals described for ore, gangue and alteration minerals in deposit models for sandstone-hosted uranium, sedimentary bentonite and sedimentary zeolite. Use of these spectra can help facilitate mapping of both waste materials from the legacy mining of the above commodities, as well as future exploration and resource assessment activities.