Se Isotopes as Groundwater Redox Indicators:Detecting Natural Attenuation of Se at an in Situ Recovery U Mine

One of the major ecological concerns associated with the in situ recovery (ISR) of uranium (U) is the environmental release of soluble, toxic selenium (Se) oxyanions generated by mining. Post-mining natural attenuation by the residual reductants in the ore body and reduced down-gradient sediments should mitigate the risk of Se contamination in groundwater. In this work, we investigate the Se concentrations and Se isotope systematics of groundwater and of U ore bearing sediments from an ISR site at Rosita, TX, USA. Our results show that selenate (Se­(VI)) is the dominant Se species in Rosita groundwater, and while several up-gradient wells have elevated Se­(VI), the majority of the ore zone and down-gradient wells have little or no Se oxyanions. In addition, the δ⁸²Se_VI of Rosita groundwater is generally elevated relative to the U ore up to +6.14‰, with the most enriched values observed in the ore-zone wells. Increasing δ⁸²Se with decreasing Se­(VI) conforms to a Rayleigh type distillation model with an ε of −2.25‰ ± 0.61‰, suggesting natural Se­(VI) reduction occurring along the hydraulic gradient at the Rosita ISR site. Furthermore, our results show that Se isotopes are excellent sensors for detecting and monitoring post-mining natural attenuation of Se oxyanions at ISR sites

Chlorine-36 abundance in natural and synthetic perchlorate

Perchlorate (ClO{sub 4}{sup -}) is ubiquitous in the environment. It occurs naturally as a product of atmospheric photochemical reactions, and is synthesized for military, aerospace, and industrial applications. Nitrate-enriched soils of the Atacama Desert (Chile) contain high concentrations of natural ClO{sub 4}{sup -}; nitrate produced from these soils has been exported worldwide since the mid-1800's for use in agriculture. The widespread introduction of synthetic and agricultural ClO{sub 4}{sup -} into the environment has complicated attempts to understand the geochemical cycle of ClO{sub 4}{sup -}. Natural ClO{sub 4}{sup -} samples from the southwestern United States have relatively high {sup 36}Cl abundances ({sup 36}Cl/Cl = 3,100 x 10{sup -15} to 28,800 x 10{sup -15}), compared with samples of synthetic ({sup 36}Cl/Cl = 0.0 x 10{sup -15} to 40 x 10{sup -15}) and Atacama Desert ({sup 36}Cl/Cl = 0.9 x 10{sup -15} to 590 x 10{sup -15}) ClO{sub 4}{sup -}. These data give a lower limit for the initial {sup 36}Cl abundance of natural ClO{sub 4}{sup -} and provide temporal and other constraints on its geochemical cycle

蓮華寺池と西湖 : 石野雲嶺の風景

The potential for increased drought frequency and severity linked to anthropogenic climate change in the semi-arid regions of the southwestern United States (US) is a serious concern1. Multi-year droughts during the instrumental period2 and decadal-length droughts of the past two millennia1, 3 were shorter and climatically different from the future permanent, ‘dust-bowl-like’ megadrought conditions, lasting decades to a century, that are predicted as a consequence of warming4. So far, it has been unclear whether or not such megadroughts occurred in the southwestern US, and, if so, with what regularity and intensity. Here we show that periods of aridity lasting centuries to millennia occurred in the southwestern US during mid-Pleistocene interglacials. Using molecular palaeotemperature proxies5 to reconstruct the mean annual temperature (MAT) in mid-Pleistocene lacustrine sediment from the Valles Caldera, New Mexico, we found that the driest conditions occurred during the warmest phases of interglacials, when the MAT was comparable to or higher than the modern MAT. A collapse of drought-tolerant C4 plant communities during these warm, dry intervals indicates a significant reduction in summer precipitation, possibly in response to a poleward migration of the subtropical dry zone. Three MAT cycles ~2 °C in amplitude occurred within Marine Isotope Stage (MIS) 11 and seem to correspond to the muted precessional cycles within this interglacial. In comparison with MIS 11, MIS 13 experienced higher precessional-cycle amplitudes, larger variations in MAT (4–6 °C) and a longer period of extended warmth, suggesting that local insolation variations were important to interglacial climatic variability in the southwestern US. Comparison of the early MIS 11 climate record with the Holocene record shows many similarities and implies that, in the absence of anthropogenic forcing, the region should be entering a cooler and wetter phase

Uranium isotope composition of waters from South Texas uranium ore deposits

Redox conditions and associated changes in mobility of uranium (U) are tightly linked to a multitude of challenges connected with U mining in sandstone-hosted deposits and new methods that directly measure reduction or oxidation of U can inform on these questions. A novel proxy for understanding U redox chemistry has recently emerged, the volume dependent isotopic fractionation of uranium-238 (²³⁸U) from uranium-235 (²³⁵U). Novel measurements of ²³⁸U/²³⁵U isotopic ratio are combined with measurements of the more commonly utilized uranium-234/uranium-238 activity [(²³⁴U/²³⁸U)] ratio, as both isotopic ratios can be measured simultaneously. However, application of both U isotopic ratios in the contexts of exploration and environmental remediation of U ores requires characterization of these isotopic ratios across a variety of redox settings. Here, ²³⁸U/²³⁵U and (²³⁴U/²³⁸U) ratios are examined from eight transects in two U ore bodies (the Rosita and Kingsville Dome deposits) in South Texas; these sites are classic roll front deposits and exhibit a wide variety of both natural and altered redox conditions. Across all transects it is observed that (²³⁴U/²³⁸U) ratios decrease systematically towards the ore body from both the oxidizing and reducing sides, irrespective of whether the site has been mined or not. This pattern reflects geologically recent and significant U leaching and mobility and is characteristic of active roll fronts. Overall δ²³⁸U values in these transects decrease systematically towards the reducing zone. A simple Rayleigh fractionation model, where U ore is deposited from an increasingly isotopically depleted reservoir of dissolved U best explains the overall trend; very negative δ²³⁸U values likely reflect multiple cycles of U deposition and dissolution. The South Texas data set indicates that both (²³⁴U/²³⁸U) ratios and δ²³⁸U values can be variable at an individual mine site. However, overall low (²³⁴U/²³⁸U) ratios and negative δ²³⁸U values are characteristic of active roll front deposits. The comprehensive U isotopic composition of both ores and well waters represents a powerful new tool in prospecting of sandstone-hosted U ore and in environmental remediation following extraction of U ore

Coral microbial communities, zooxanthellae and mucus along gradients of seawater depth and coastal pollution

The high incidence of coral disease in shallow coastal marine environments suggests seawater depth and coastal pollution have an impact on the microbial communities inhabiting healthy coral tissues. A study was undertaken to determine how bacterial communities inhabiting tissues of the coral Montastraea annularis change at 5 m, 10 m and 20 m water depth in varying proximity to the urban centre and seaport of Willemstad, Curaçao, Netherlands Antilles. Analyses of terminal restriction fragment length polymorphisms (TRFLP) of 16S rRNA gene sequences show significant differences in bacterial communities of polluted and control localities only at the shallowest seawater depth. Furthermore, distinct differences in bacterial communities were found with increasing water depth. Comparisons of TRFLP peaks with sequenced clone libraries indicate the black band disease cyanobacterium clone CD1C11 is common and most abundant on healthy corals in less than 10 m water depth. Similarly, sequences belonging to a previously unrecognized group of likely phototrophic bacteria, herein referred to as CAB-I, were also more common in shallow water. To assess the influence of environmental and physiologic factors on bacterial community structure, canonical correspondence analysis was performed using explanatory variables associated with: (i) light availability; (ii) seawater pollution; (iii) coral mucus composition; (iv) the community structure of symbiotic algae; and (v) the photosynthetic activity of symbiotic algae. Eleven per cent of the variation in bacterial communities was accounted for by covariation with these variables; the most important being photosynthetically active radiation (sunlight) and the coral uptake of sewage-derived compounds as recorded by the delta(15)N of coral tissue

Vadose Zone Transport of Tritium and Nitrate under Ponded Water Conditions

Vadose zone transport of tritium and nitrate can be important considerations at radioactive waste sites, landfills, or areas with industrial impacts. These contaminants are of particular concern because they typically have a relatively higher mobility in the subsurface compared to other compounds. Here, we describe a semiarid site with tritium and nitrate contamination involving a manmade ponded water source above a thick unsaturated zone at Los Alamos National Laboratory in New Mexico, USA. This study demonstrates the value of vadose zone flow and transport modeling for the development of field investigation plans (i.e., identifying optimal borehole locations and depths for contaminant characterization), and how a combination of modeling with isotope and geochemical measurements can provide insight into how tritium and nitrate transport in the vadose zone in semiarid environments. Modeling results suggest that at this location, tritium transport is well predicted by classical multiphase theory. Our work expands the demonstrated usefulness of a standard tritium conceptual model to sites with ponded surface conditions and agrees with previous results where a standard model was able to explain the evolution of a tritium plume at an arid waste disposal site. In addition, depth-based analyses of δ18O and δ2H of pore waters helped confirm the extent of pond infiltration into the vadose zone, and the δ15N of nitrate showed that the contaminant release history of the site was different than originally assumed

Se Isotopes as Groundwater Redox Indicators: Detecting Natural Attenuation of Se at an in Situ Recovery U Mine.

One of the major ecological concerns associated with the in situ recovery (ISR) of uranium (U) is the environmental release of soluble, toxic selenium (Se) oxyanions generated by mining. Post-mining natural attenuation by the residual reductants in the ore body and reduced down-gradient sediments should mitigate the risk of Se contamination in groundwater. In this work, we investigate the Se concentrations and Se isotope systematics of groundwater and of U ore bearing sediments from an ISR site at Rosita, TX, USA. Our results show that selenate (Se(VI)) is the dominant Se species in Rosita groundwater, and while several up-gradient wells have elevated Se(VI), the majority of the ore zone and down-gradient wells have little or no Se oxyanions. In addition, the δ82SeVI of Rosita groundwater is generally elevated relative to the U ore up to +6.14‰, with the most enriched values observed in the ore-zone wells. Increasing δ82Se with decreasing Se(VI) conforms to a Rayleigh type distillation model with an ε of -2.25‰ ± 0.61‰, suggesting natural Se(VI) reduction occurring along the hydraulic gradient at the Rosita ISR site. Furthermore, our results show that Se isotopes are excellent sensors for detecting and monitoring post-mining natural attenuation of Se oxyanions at ISR sites