Abstract: Naturally occurring uranium geochemical anomalies, representative of the several thousand recognized in the Portuguese section of the Iberian Massif and outcropping in three target areas with a total of a few thousand square metres, were subjected to a detailed study (1:1000 scale) to evaluate the radiological health-risk on the basis of a dose assessment. To reach this goal some radioactive isotopes from the uranium, thorium and potassium radioactive series were measured in 52 samples taken from different environmental compartments: soils, stream sediments, water, foodstuff (vegetables) and air; external radiation was also measured through a square grid of 10×10m, with a total of 336 measurements. The results show that some radioisotopes have high activities in all the environmental compartments as well as a large variability, namely for those of the uranium decay chain, which is a common situation in the regional geological setting. Isotopic disequilibrium is also common and led to an enrichment of several isotopes in the different pathways, as is the case of 226Ra; maximum values of 1.76BqL−1 (water), 986Bqkg−1 (soils) and 18.9Bqkg−1 (in a turnip sample) were measured. On the basis of a realistic scenario combined with the experimental data, the effective dose from exposure to ionizing radiation for two groups of the population (rural and urban) was calculated; the effective dose is variable between 8.0 and 9.5mSvyear−1, which is 3–4 times higher than the world average. Thus, the radiological health-risk for these populations could be significant and the studied uranium anomalies must be taken into account in the assessment of the geochemical background. The estimated effective dose can also be used as typical of the background of the Beiras uranium metalogenetic province and therefore as a “benchmark” in the remediation of the old uranium mining sites.

Abstract: Unconventional hydrocarbon production has become the target of an intensive environmental debate due to the risks it poses to water resources. Fracking, while enabling the extraction of oil and gas from ultra-low permeability reservoirs, also possesses the risk of polluting water systems through failures from hydraulic fracturing and its associated procedures. The need to foster national industrial development with a transitional energy matrix has led Brazil to discuss the environmental suitability before producing its large unconventional reserves. Many studies have highlighted the need for a robust environmental characterization before the development of the unconventional industry. In this sense, multiple environmental isotopes may work as a proxy for identifying water contamination right from the early stages. Environmental isotopes may also be applied to enhance the understanding of the natural geochemical processes intrinsic to a given area. This study presents an environmental isotopes baseline for the groundwater and riverine water systems within the São Francisco Basin, a proven tight gas reservoir in Brazil, in a pre-operational context. δ18O, δ2H, 3H, δ13C, and Δ14C were evaluated in three different seasons in groundwater and surface water samples, along with other auxiliary parameters such as physical-chemical parameters (in situ), major ions, and d-excess. The δ2H and δ18O in surface water shows an upstream → downstream enrichment trend, with some variations suggesting baseflow interactions in the surface water systems. An evaporation line for the study area was defined as δ2H = 4.6903 δ18O + 10.362. δ13C indicates a mutual dissolution of silicates and carbonates in the groundwater system and suggests a group of samples highly related to the recharge areas. Groundwater dating denotes the Serra da Saudade Formation as a modern fractured aquifer with a strong recharge capacity. These findings support stakeholders in environmental monitoring and management of the unconventional gas industry.

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: The recharge of stream water below the baseflow water table can mobilize groundwater contaminants, particularly redox-sensitive and sorptive metals such as uranium. However, in-situ tracer experiments that simulate the recharge of stream water to uranium-contaminated groundwater are lacking, thus limiting the understanding of the potential mechanisms that control the mobility of uranium at the field scale. In this study, a field tracer test was conducted by injecting 100 gal (379 l) of oxic river water into a nearby suboxic and uranium-contaminated aquifer. The traced river water was monitored for 18 days in the single injection well and in the twelve surrounding observation wells. Mobilization of uranium from the solid to the aqueous phase was not observed during the tracer test despite its pre-test presence being confirmed on the aquifer sediments from lab-based acid leaching. However, strong evidence of oxidative immobilization of iron and manganese was observed during the tracer test and suggested that immobile uranium was likely in its oxidized state as U(VI) on the aquifer sediments; these observations ruled out oxidation of U(IV) to U(VI) as a potential mobilization mechanism. Therefore, desorption of U(VI) appeared to be the predominant potential mobilization mechanism, yet it was clearly not solely dependent on concentration as evident when considering that uranium-poor river water (\textless0.015 mg/L) was recharged to uranium-rich groundwater (≈1 mg/L). It was possible that uranium desorption was limited by the relatively higher pH and lower alkalinity of the river water as compared to the groundwater; both factors favor immobilization. However, it was likely that the immobile uranium was associated with a mineral phase, as opposed to a sorbed phase, thus desorption may not have been possible. The results of this field tracer study successfully ruled out two common mobilization mechanisms of uranium: (1) oxidative dissolution and (2) concentration-dependent desorption and ruled in the importance of advection, dispersion, and the mineral phase of uranium.

Abstract: The uranium (U) concentrations and isotopic composition of waters and sediment cores were used to investigate the transport and accumulation of U in a water system (tailings pond, two lakes, and the Kalix River) receiving mine waters from the Kiruna mine. Concentrations of dissolved U decrease two orders of magnitude between the inflow of mine waters and in the Kalix River, while the concentration of the element bound to particulate matter increases, most likely due to sorption on iron‑manganese hydroxides and organic matter. The vertical distribution of U in the water column differs between two polluted lakes with a potential indication of dissolved U supply from sediment’s pore waters at anoxic conditions. Since the beginning of exposure in the 1950s, U concentrations in lake sediments have increased \textgreater20-fold, reaching concentrations above 50 μg g-1. The distribution of anthropogenic U between the lakes does not follow the distribution of other mine water contaminants, with a higher relative proportion of U accumulating in the sediments of the second lake. Concentrations of redox-sensitive elements in the sediment core as well as Fe isotopic composition were used to re-construct past redox-conditions potentially controlling early diagenesis of U in surface sediments. Two analytical techniques (ICP-SFMS and MC-ICP-MS) were used for the determination of U isotopic composition, providing an extra dimension in the understanding of processes in the system. The (234 U)/(238 U) activity ratio (AR) is rather uniform in the tailings pond but varies considerably in water and lake sediments providing a potential tracer for U transport from the Kiruna mine through the water system, and U immobilization in sediments. The U mass balance in the Rakkurijoki system as well as the amount of anthropogenic U accumulated in lake sediments were evaluated, indicating the immobilization in the two lakes of 170 kg and 285 kg U, respectively.