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At least 487 records · Page 27Linked to original sources

Uranium(VI) release from contaminated vadose zone sediments: Estimation of potential contributions from dissolution and desorption

A key difficulty in developing accurate, science-based conceptual models for remediation of contaminated field sites is the proper accounting of multiple coupled geochemical and hydrologic processes. An example of such a difficulty is the separation of desorption and dissolution processes in releasing contaminants from sediments to groundwaters; very few studies are found in the literature that attempt to quantify contaminant release by these two processes. In this study, the results from several extraction techniques, isotopic exchange experiments, and published spectroscopic studies were combined to estimate the contributions of desorption and dissolution to U(VI) release from contaminated sediments collected from the vadose zone beneath former waste disposal ponds in the Hanford 300-Area (Washington State). Vertical profiles of sediments were collected at four locations from secondary pond surfaces down to, and slightly below, the water table. In three of the four profiles, uraniumconcentration gradients were observed in the sediments, with the highest U concentrations at the top of the profile. One of the vertical profiles contained sediments with U concentrations up to 4.2×10 −7 mol g −1 (100 ppm). U(VI) release to artificial groundwater solutions (AGWs) and extracts from these high-U concentration sediments occurred primarily from dissolution of precipitated U(VI) minerals, including the mineral metatorbernite, [Cu(UO 2 PO 4 ) 2 ·8H 2 O]. At the bottom of this profile, beneath the water table, and in all three of the other profiles, U concentrations were <5.88×10 −8 mol g −1 (14 ppm), and U(VI) release to AGWs occurred primarily due to desorption of U(VI). When reacted in batch experiments with AGWs with compositions representative of the range of chemical conditions in the underlying aquifer, all samples released U(VI) at concentrations greater than regulatory limits within few hours. A semi-mechanistic surface complexation model was developed to describe U(VI) adsorption on sediments collected from near the water table, as a function of pH, alkalinity, and Ca and U(VI) concentrations, using ranges in these variables relevant to groundwater conditions in the aquifer. Dilute (bi)carbonate solution extractions and uranium isotopic exchange methods were capable of estimating adsorbed U(VI) in samples where U(VI) release was predominantly due to U(VI) desorption; these techniques were not effective at estimating adsorbed U(VI) where U(VI) release was affected by dissolution of U(VI) minerals. The combination of extraction and isotopic exchange results, spectroscopic studies, and surface complexation modeling allow an adequate understanding for the development of a geochemical conceptual model for U(VI) release to the aquifer. The overall approach has generic value for evaluating the potential for release of metals and radionuclides from sediments that contain both precipitated and adsorbed contaminant speciation.

Book chapter↗

Weathering of the meade peak phosphatic shale member, phosphoria formation: Observations based on uranium and its decay products

Variably weathered outcrop samples of the Meade Peak Phosphatic Shale Member of the Phosphoria Formation have 5-10% of the contained uranium (U) in a form readily extractable by 0.1 M sodium bicarbonate. Fission track radiography of outcrop samples and other less-weathered channel and core samples indicate that this mobile fraction of U is likely hosted by organic matter, secondary iron oxides and clay minerals, trace uraninite, and very fine-grained apatite cement. During weathering, this extractable U fraction is especially susceptible to redistribution, which produces small but measurable departures (1-15%) from radioactive (secular) equilibrium in the 238 U decay-series. The most weath- ered samples show the strongest isotopic evidence for redistribution of U during the last 350 ka, but sequestration of U by alteration products limits open-system losses of U at the whole-rock scale. In less-weathered samples, isotopic evidence for minor U loss (or gain) over longer time periods (1 Ma) is consistent with relatively non-aggressive attack of phosphatic rock during weathering. Comparative extractability of selenium (Se) suggests that a larger fraction of Se (19%) is readily available for mobilization during the earliest stages of weathering.

Book chapter↗

Climate-driven mid- to late Holocene hydrologic evolution of arid wetlands documented by strontium, uranium, and oxygen isotopes from Lower Pahranagat Lake, southern Nevada, USA

Lacustrine carbonates in a 12.4-m-long core from Lower Pahranagat Lake (LPAH), southern Nevada, indicate that radiogenic isotopes of Sr and U ( 87 Sr/ 86 Sr and 234 U/ 238 U) preserve evidence of past variations in water sources and evolving hydrologic conditions. Sr and U isotope compositions in LPAH carbonates fall within the range defined by the three primary groundwater sources in Pahranagat Valley and reflect variable mixtures of those sources since the mid-Holocene. Compositions in the oldest sample (5.78 ka) closely match modern compositions of modern discharge from nearby springs, indicating that LPAH water was derived almost exclusively from the local volcanic aquifer. By ca. 5.3–5.2 ka, LPAH water compositions shifted sharply towards isotopic compositions observed in groundwater from the regional carbonate aquifer, indicating a marked increase in surface flow from high-volume springs discharging from the carbonate aquifer to the north. Sediments deposited between 3.08–1.06 ka indicate reduced contributions from the regional aquifer. A comparison of uranium- and oxygen-isotope values in LPAH carbonates suggests that wetter climate conditions favor increased supply from deeper, regional carbonate aquifers compared to drier conditions when contributions from shallower, local volcanic aquifers were more important.

Nevada↗

Determination of lead, uranium, thorium, and thallium in silicate glass standard materials by isotope dilution mass spectrometry

A set of four standard glasses has been prepared which have been doped with 61 different elements at the 500-, 50-, 1-, and 0.02-ppm level. The concentrations of lead, uranium, thorium, and thallium have been determined by isotope dilution mass spectrometry at a number of points in each of the glasses. The results obtained from independent determinations in two laboratories demonstrate the homogeneity of the samples and that precision of the order of 0.5% (95% L.E.) may be obtained by the method even at the 20-ppb level for these elements. The chemical and mass spectrometric procedures necessary are presented.

Analytical Chemistry↗

Uranium bioaccumulation dynamics in the mayfly Neocloeon triangulifer and application to site-specific prediction

Little is known about the underlying mechanisms governing the bioaccumulation of uranium (U) in aquatic insects. We experimentally parameterized conditional rate constants for aqueous U uptake, dietary U uptake, and U elimination for the aquatic baetid mayfly Neocloeon triangulifer . Results showed that this species accumulates U from both the surrounding water and diet, with waterborne uptake prevailing. Elevated dietary U concentrations decreased feeding rates, presumably by altering food palatability or impairing the mayfly’s digestive processes, or both. Nearly 90% of the accumulated U was eliminated within 24 h after the waterborne exposure ceased, reflecting the desorption of weakly bound U from the insect’s integument. To examine whether the experimentally derived rate constants for N. triangulifer could be generalized to baetid mayflies, mayfly U concentrations were predicted using the water chemistry and U measured in periphyton from springs in Grand Canyon (United States) and were compared to U concentrations in spring-dwelling mayflies. Predicted and observed mayfly U concentrations were in good agreement. Under the modeled site-specific conditions, waterborne U uptake accounted for 52–93% of the bioaccumulated U. U accumulation was limited in these wild populations due to a combination of factors including low concentrations of bioavailable dissolved U species, slow U uptake rates from food, and fast U elimination.

Environmental Science & Technology↗

Use of ICP/MS with ultrasonic nebulizer for routine determination of uranium activity ratios in natural water

A method is described that allows precise determination of 234 U/ 238 U activity ratios (UAR) in most natural waters using commonly available inductively coupled plasma/mass spectrometry (ICP/MS) instrumentation and accessories. The precision achieved by this technique (±0.5% RSD, 1 sigma) is intermediate between thermal ionization mass spectrometry (±0.25% RSD, 1 sigma) and alpha particle spectrometry (±5% RSD, 1 sigma). It is precise and rapid enough to allow analysis of a large number of samples in a short period of time at low cost using standard, commercially available quadrupole instrumentation with ultrasonic nebulizer and desolvator accessories. UARs have been analyzed successfully in fresh to moderately saline waters with U concentrations of from less than 1 μg/L to nearly 100 μg/L. An example of the uses of these data is shown for a study of surface-water mixing in the North Platte River in western Nebraska. This rapid and easy technique should encourage the wider use of uranium isotopes in surface-water and groundwater investigations, both for qualitative (e.g. identifying sources of water) and quantitative (e.g. determining end-member mixing ratios purposes.

Environmental Science & Technology↗

Spectroscopic evidence for uranium bearing precipitates in vadose zone sediments at the Hanford 300-area site

Uranium (U) solid-state speciation in vadose zone sediments collected beneath the former North Process Pond (NPP) in the 300 Area of the Hanford site (Washington) was investigated using multi-scale techniques. In 30 day batch experiments, only a small fraction of total U (???7.4%) was released to artificial groundwater solutions equilibrated with 1% pCO2. Synchrotron-based micro-X-ray fluorescence spectroscopy analyses showed that U was distributed among at least two types of species: (i) U discrete grains associated with Cu and (ii) areas with intermediate U concentrations on grains and grain coatings. Metatorbernite (Cu[UO2]2[PO 4]2??8H2O) and uranophane (Ca[UO 2]2[SiO3(OH)]2?? 5H 2O) at some U discrete grains, and muscovite at U intermediate concentration areas, were identified in synchrotron-based micro-X-ray diffraction. Scanning electron microscopy/energy dispersive X-ray analyses revealed 8-10 ??m size metatorbernite particles that were embedded in C-, Al-, and Si-rich coatings on quartz and albite grains. In ??- and bulk-X-ray absorption structure (??-XAS and XAS) spectroscopy analyses, the structure of metatorbernite with additional U-C and U-U coordination environments was consistently observed at U discrete grains with high U concentrations. The consistency of the ??- and bulk-XAS analyses suggests that metatorbernite may comprise a significant fraction of the total U in the sample. The entrapped, micrometer-sized metatorbernite particles in C-, Al-, and Si-rich coatings, along with the more soluble precipitated uranyl carbonates and uranophane, likely control the long-term release of U to water associated with the vadose zone sediments. ?? 2007 American Chemical Society.

Environmental Science & Technology↗

Use of electrical imaging and distributed temperature sensing methods to characterize surface water–groundwater exchange regulating uranium transport at the Hanford 300 Area, Washington

We explored the use of continuous waterborne electrical imaging (CWEI), in conjunction with fiber‐optic distributed temperature sensor (FO‐DTS) monitoring, to improve the conceptual model for uranium transport within the Columbia River corridor at the Hanford 300 Area, Washington. We first inverted resistivity and induced polarization CWEI data sets for distributions of electrical resistivity and polarizability, from which the spatial complexity of the primary hydrogeologic units was reconstructed. Variations in the depth to the interface between the overlying coarse‐grained, high‐permeability Hanford Formation and the underlying finer‐grained, less permeable Ringold Formation, an important contact that limits vertical migration of contaminants, were resolved along ∼3 km of the river corridor centered on the 300 Area. Polarizability images were translated into lithologic images using established relationships between polarizability and surface area normalized to pore volume ( S por ). The FO‐DTS data recorded along 1.5 km of cable with a 1 m spatial resolution and 5 min sampling interval revealed subreaches showing (1) temperature anomalies (relatively warm in winter and cool in summer) and (2) a strong correlation between temperature and river stage (negative in winter and positive in summer), both indicative of reaches of enhanced surface water–groundwater exchange. The FO‐DTS data sets confirm the hydrologic significance of the variability identified in the CWEI and reveal a pattern of highly focused exchange, concentrated at springs where the Hanford Formation is thickest. Our findings illustrate how the combination of CWEI and FO‐DTS technologies can characterize surface water–groundwater exchange in a complex, coupled river‐aquifer system.

Washington↗

Uranium redox and deposition transitions embedded in deep-time geochemical models and mineral chemistry networks

Uranium (U) is an important global energy resource and a redox sensitive trace element that reflects changing environmental conditions and geochemical cycling. The redox evolution of U mineral chemistry can be interrogated to understand the formation and distribution of U deposits and the redox processes involved in U geochemistry throughout Earth history. In this study, geochemical modeling using thermodynamic data, and mineral chemistry network analysis are used to investigate U geochemistry and deposition through time. The number of U 6+ mineral localities surpasses the number of U 4+ mineral localities in the Paleoproterozoic. Moreover, the number of sedimentary U 6+ mineral localities increases earlier in the Phanerozoic than the number of U 4+ sedimentary mineral localities, likely due to the necessity of sufficient sedimentary organic matter to reduce U 6+ –U 4+ . Indeed, modeling calculations indicate that increased oxidative weathering due to surface oxygenation limited U 4+ uraninite (UO 2 ) formation from weathered granite and basalt. Louvain network community detection shows that U 6+ forms minerals with many more shared elements and redox states than U 4+ . The range of weighted Mineral Element Electronegativity Coefficient of Variation (wMEE CV ) values of U 6+ minerals increases through time, particularly during the Phanerozoic. Conversely, the range of wMEE CV values of U 4+ minerals is consistent through time due to the relative abundance of uraninite, coffinite, and brannerite. The late oxidation and formation of U 6+ minerals compared to S 6+ minerals illustrates the importance of the development of land plants, organic matter deposition, and redox-controlled U deposition from ground water in continental sediments during this time-period.

Geochemistry, Geophysics, Geosystems↗

Radiogenic strontium- and uranium-isotope tracers of water-rock interactions and hydrothermal flow in the Upper Geyser Basin, Yellowstone Plateau Volcanic Field, USA

Natural radiogenic isotopes (primarily 87 Sr/ 86 Sr) from hot springs in the Upper Geyser Basin of the Yellowstone Plateau volcanic field and associated rocks were used to evaluate groundwater flow patterns, water-rock reactions, and the extent of mixing between various groundwater sources. Thermal waters have very low uranium concentrations and 234 U/ 238 U activity ratios near 1.0, which limit their utility as tracers in this reducing setting. Thermal waters have higher Sr concentrations (<22 ng/g) and a wide range of 87 Sr/ 86 Sr values that vary both temporally at individual discharge sites and between adjacent springs, indicating that conduits tap different subsurface reservoirs to varying degrees. Sr from local rhyolites have 87 Sr/ 86 Sr compositions that bound the range of values observed in groundwater throughout the basin. Non-boiling springs on the west flank of the basin discharge water with low 87 Sr/ 86 Sr consistent with flow through young volcanic rocks exposed at the surface. Boiling springs in the central basin have higher 87 Sr/ 86 Sr values reflecting interactions with older, more radiogenic volcanic rocks. Variability in upwelling thermal waters requires mixing with a low 87 Sr/ 86 Sr component derived from young lava or glacial sediments, or more likely, from deeper sources of hot groundwater circulating through buried Lava Creek Tuff having intermediate 87 Sr/ 86 Sr. Isotope data constrain basin-wide output of thermal water to 110–140 kg·s −1 . Results underscore the utility of radiogenic Sr isotopes as valuable tracers of hydrothermal flow patterns and improve the understanding of temperature-dependent water-rock reactions in one of the largest continental hydrothermal systems on Earth.

Wyoming↗

Dating a medieval tsunami with uranium-series techniques on Caribbean corals

Uranium-series dates from coral boulders constrain the timing of a medieval tsunami from the Puerto Rico Trench. Previously reported evidence for this tsunami includes hundreds of coral boulders that came to rest hundreds of meters inland on Anegada, British Virgin Islands. New U-series dates on these coral boulders provide limiting dates for the tsunami. The narrowest limits were by dating interior bands of a coral that retains the hemispherical form of a living coral colony, and which include adjustments for the number of annual density band couplets between the dated samples and the boulder exteriors. By those limits, the tsunami dates between 1381 and 1391 CE, and likely occurred during summer or fall. The tsunami is important as the only reported sign that the eastern Puerto Rico Trench has produced a great earthquake. The dating may aid in defining the earthquake source and in communicating tsunami hazards.

British Virgin Islands, Puerto Rico↗

Uranium-series dating of the Mousterian occupation at Abric Romani, Spain

The precise evolutionary position of the Neanderthal people continues to be a major uncertainty in human evolution. Their origin and their relationship to anatomically modern people are unclear and are clouded by poor chronology. Lithic artefacts of the Mousterian type, found throughout Europe and the Mediterranean Basin, are believed to be the tool kit of the Neanderthals, but dates within Mousterian-bearing deposits are extremely rare. We report here on 20 high-quality uranium-series dates from Mousterian beds at Abric Romani, a rock shelter near Barcelona, Spain. The dates range from 39 to 60 kyr before present ( BP ) in an orderly stratigraphic succession and provide precise chronological control on an important Mousterian archaeological site.

Nature↗

Organic matter and containment of uranium and fissiogenic isotopes at the Oklo natural reactors

Some of the Precambrian natural fission reactors at Oklo in Gabon contain abundant organic matter 1,2 , part of which was liquefied at the time of criticality and subsequently converted to a graphitic solid 3,4 . The liquid organic matter helps to reduce U(VI) to U(IV) from aqueous solutions, resulting in the precipitation of uraninite 5 . It is known that in the prevailing reactor environments, precipitated uraninite grains incorporated fission products. We report here observations which show that these uraninite crystals were held immobile within the resolidified, graphitic bitumen. Unlike water-soluble (humic) organic matter, the graphitic bituminous organics at Oklo thus enhanced radionuclide containment. Uraninite encased in solid graphitic matter in the organic-rich reactor zones lost virtually no fissiogenic lanthanide isotopes. The first major episode of uranium and lead migration was caused by the intrusion of a swarm of adjacent dolerite dykes about 1,100 Myr after the reactors went critical. Our results from Oklo imply that the use of organic, hydrophobic solids such as graphitic bitumen as a means of immobilizing radionuclides in pretreated nuclear waste warrants further investigation.

Nature↗

Effects of depleted uranium on survival, growth, and metamorphosis in the african clawed frog (Xenopus laevis)

Embryos (stage 8-47, Nieuwkoop and Faber) of the African clawed frog (Xenopus laevis) were subjected to water-borne depleted uranium (DU) concentrations that ranged from 4.8 to 77.7 mg/Lusing an acute 96-h frog embryo teratogenesis assay-Xenopus (FETAX). In a chronic 64-d assay, X. laevis (from embryo through metamorphosis; stages 8-66) were subjected to concentrations of DU that ranged from 6.2 to 54.3 mg/L Our results indicate DU is a non teratogenic metal. No effects on mortality, malformations, or growth were observed in the 96-h FETAX with concentrations of DU that ranged from 4.8 to 77.7 mg/L From stage 8 to stage 47, X. laevis tadpoles do not actively feed and the gills are not well developed. Thus, uptake of DU was reduced despite exposure to elevated concentrations. The 64-d assay resulted in no concentration response for either mortality or malformations; however, a delay in metamorphosis was observed in tadpoles subjected to elevated DU concentrations (from 13.1 to 54.3 mg/L) compared to tadpoles in both the well-water control and reference. The delay in metamorphosis was likely due to increasing body burden of DU that ranged from 0.98 to 2.82 mg/kg. Copyright?? Taylor & Francis Inc.

Conference Paper↗

Predicted uranium and radon concentrations in New Hampshire (USA) groundwater—Using Multi Order Hydrologic Position as predictors

Two radioactive elements, uranium (U) and radon (Rn), which are of potential concern in New Hampshire (NH) groundwater, are investigated. Exceedance probability maps are tools to highlight locations where the concentrations of undesirable substances in the groundwater may be elevated. Two forms of statistical analysis are used to create exceedance probability maps for U and Rn in NH groundwater. The first, Boosted Regression Tree (BRT), was selected for estimating U exceedance values. It computes exceedance values directly using the Bernoulli distribution function. The second method of statistical analysis used for Rn to determine exceedance probabilities is ordinary least squares (OLS) regression. In the process of determining exceedance probabilities for U and Rn, the utility of a new dataset is investigated. That new predictor dataset is the Multi-Order Hydrologic Position (MOHP) dataset. MOHP raster datasets have been produced nationally for the conterminous United States at a 30-m resolution. The concept behind MOHP is that, for any given point on the earth's surface, there is the potential for a longer groundwater flow path as one goes deeper beneath the land surface. MOHP predictors were tested in both models. Three MOHP predictors were found useful in the BRT model and two in the OLS model. MOHP data were found useful as predictors along with other site characteristics in predicting U and Rn exceedance probabilities in New Hampshire groundwater.

New Hampshire↗

Effects of Groundwater Development on Uranium: Central Valley, California, USA

Uranium (U) concentrations in groundwater in several parts of the eastern San Joaquin Valley, California, have exceeded federal and state drinking water standards during the last 20 years. The San Joaquin Valley is located within the Central Valley of California and is one of the most productive agricultural areas in the world. Increased irrigation and pumping associated with agricultural and urban development during the last 100 years have changed the chemistry and magnitude of groundwater recharge, and increased the rate of downward groundwater movement. Strong correlations between U and bicarbonate suggest that U is leached from shallow sediments by high bicarbonate water, consistent with findings of previous work in Modesto, California. Summer irrigation of crops in agricultural areas and, to lesser extent, of landscape plants and grasses in urban areas, has increased Pco2 concentrations in the soil zone and caused higher temperature and salinity of groundwater recharge. Coupled with groundwater pumping, this process, as evidenced by increasing bicarbonate concentrations in groundwater over the last 100 years, has caused shallow, young groundwater with high U concentrations to migrate to deeper parts of the groundwater system that are tapped by public-supply wells. Continued downward migration of U-affected groundwater and expansion of urban centers into agricultural areas will likely be associated with increased U concentrations in public-supply wells. The results from this study illustrate the potential longterm effects of groundwater development and irrigation-supported agriculture on water quality in arid and semiarid regions around the world.

California↗

Alternative approaches to dryland reclamation enhance vegetation cover and soil stability at a former uranium mine

Introduction Conventional reclamation methods to recover dryland ecosystems after mineral extraction often have low success. Alternative reclamation techniques may help overcome the many challenges to establishing persistent native vegetation and stable soils. Objectives Compare conventional reclamation approaches that focus primarily on soil stabilization to alternative approaches that may improve native ecosystem restoration at the Kanab North Mine in northern Arizona. Methods In a fully crossed experiment, conventional seed mix (native and non-native species) and seeding methods (drill-seeding) were compared to alternative practices, including a native-only seed mix, connectivity modifiers (ConMods) with hand seeding, and a biocrust inoculation. Restoration metrics like plant establishment, species composition, soil surface cover and stability, biocrust establishment, and near-surface wind-driven sediment were monitored over the first 5 years post-reclamation. Results While all restoration metrics improved with time, compared to traditional methods, ConMods increased total, graminoid, and native plant species cover, and the native-only seed mix increased woody, native, and perennial species cover. Biocrust inoculation increased late-successional biocrust development, but biocrusts only persisted over 5 years in combination with ConMods. Soil stability increased in all treatments, but both ConMods and biocrust inoculation increased stability compared to traditional practices. Conclusion Overall, alternative approaches to reclamation tested here (ConMods, native seed, and biocrust inoculation) were more effective than traditional practices at increasing total plant cover, facilitating biocrust establishment, and promoting soil stability after uranium mine reclamation.

Arizona↗

Potassium, rubidium, strontium, thorium, uranium, and the ratio of strontium-87 to strontium-86 in oceanic tholeiitic basalt

The average concentrations of potassium, rubidium, strontium, thorium, and uranium in oceanic tholeiitic basalt are (in parts per million) K, 1400; Rb, 1.2; Sr, 120; Th, 0.2; and U, 0.1. The ratio Sr 87 to Sr 86 is about 0.702, that of K to U is 1.4 x 10 4 , and of Th to U is 1.8. These amounts of K, Th, U, and radiogenic Sr 87 are less than in other common igneous rocks. The ratios of Th to U and Sr 87 to Sr 86 suggest that the source region of the oceanic tholeiites was differentiated from the original mantle material some time in the geologic past.

Science↗