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A rapid procedure for the determination of thorium, uranium, cadmium and molybdenum in small sediment samples by inductively coupled plasma-mass spectrometry: Application in Chesapeake Bay

This paper describes a rapid procedure that allows precise analysis of Mo, Cd, U and Th in sediment samples as small as 10 mg by using a novel approach that utilizes a "pseudo" isotope dilution for Th and conventional isotope dilution for Mo, Cd and U by ICP-MS. Long-term reproducibility of the method is between 2.5 and 5% with an advantage of rapid analysis on a single digestion of sediment sample and the potential of adding other elements of interest if so desired. Application of this method to two piston cores collected near the mouth of the Patuxent River in Chesapeake Bay showed that the accumulation of authigenic Mo and Cd varied in response to the changing bottom water redox conditions, with anoxia showing consistent oscillations throughout both pre-industrial and industrial times. Accumulation of authigenic U shows consistent oscillations as well, without any apparent increase in productivity related to anoxic trends. Degrees of Mo and Cd enrichment also inversely correlate to halophilic microfaunal assemblages already established as paleoclimate proxies within the bay indicating that bottom water anoxia is driven in part by the amount of freshwater discharge that the area receives. ?? 2002 Elsevier Science Ltd. All rights reserved.

Applied Geochemistry↗

Use of 234U and 238U isotopes to identify fertilizer-derived uranium in the Florida Everglades

Surface water and peat in the northern Everglades have very low natural concentrations of U and are therefore sensitive to the addition of small amounts of U from anthropogenic sources such as fertilizer. Peat samples collected along a nutrient gradient in the northern Everglades have unusually high concentrations of U (> 1 ??g/g, dry basis) and also have a distinctive 234U/238U activity ratio (AR). AR values for U-enriched peat fall in the narrow range of AR values for commercial phosphate fertilizer (1.00 ??0.05) In contrast, AR values for low-U peat from background sites exceed 1.05. The spatial distribution of anomalous U concentration, and of fertilizer-like AR values in peat, parallel a previously documented pattern of P enrichment These results strongly suggest that some of the U in nutrient-impacted peatlands is fertilizer-derived. Agricultural drainage water sampled in the northern Everglades has high concentrations of dissolved U (0.3-2.4 ??g/1) compared to surface water from background sites (<0 1 ??g/1) Measured AR values in drainage water (0.949-0.990) are also permissive of a fertilizer origin for the U and are different from AR values in surface water or peat at background sites (AR > 1.05). Synoptic sampling of surface water along drainage canals indicate that Lake Okeechobee, and some drainage from agricultural fields, are sources of dissolved U, whereas wetlands farther downstream act as sinks for U. Historically cultivated agricultural soft has only a marginally elevated (+0.2 ??g/g) average concentration of U compared to nearby uncultivated soil and incorporates only 20% of the U from an aqueous solution that was slurried with the soil. In contrast, a similar experiment with fresh Everglades peat indicated uptake of 90% of the added U. These experiments support the proposed removal of U from agricultural fields and concentration of U in downstream peatlands. The methodology of this study can be used to describe the behavior of fertilizer-derived U in other low-U environments.

Applied Geochemistry↗

Effect of calcium on the bioavailability of dissolved uranium(VI) in plant roots under circumneutral pH

We integrated field measurements, hydroponic experiments, microscopy, and spectroscopy to investigate the effect of Ca(II) on dissolved U(VI) uptake by plants in 1 mM HCO 3 – solutions at circumneutral pH. The accumulation of U in plants (3.1–21.3 mg kg –1 ) from the stream bank of the Rio Paguate, Jackpile Mine, New Mexico served as a motivation for this study. Brassica juncea was the model plant used for the laboratory experiments conducted over a range of U (30–700 μg L –1 ) and Ca (0–240 mg L –1 ) concentrations. The initial U uptake followed pseudo-second-order kinetics. The initial U uptake rate ( V 0 ) ranged from 4.4 to 62 μg g –1 h –1 in experiments with no added Ca and from 0.73 to 2.07 μg g –1 h –1 in experiments with 12 mg L –1 Ca. No measurable U uptake over time was detected for experiments with 240 mg L –1 Ca. Ternary Ca–U–CO 3 complexes may affect the decrease in U bioavailability observed in this study. Elemental X-ray mapping using scanning transmission electron microscopy–energy-dispersive spectrometry detected U–P-bearing precipitates within root cell walls in water free of Ca. These results suggest that root interactions with Ca and carbonate in solution affect the bioavailability of U in plants. This study contributes relevant information to applications related to U transport and remediation of contaminated sites.

Environmental Science & Technology↗

Uranium and radon in private bedrock well water in Maine: geospatial analysis at two scales

In greater Augusta of central Maine, 53 out of 1093 (4.8%) private bedrock well water samples from 1534 km 2 contained [U] >30 μg/L, the U.S. Environmental Protection Agency’s (EPA) Maximum Contaminant Level (MCL) for drinking water; and 226 out of 786 (29%) samples from 1135 km 2 showed [Rn] >4,000 pCi/L (148 Bq/L), the U.S. EPA’s Alternative MCL. Groundwater pH, calcite dissolution and redox condition are factors controlling the distribution of groundwater U but not Rn due to their divergent chemical and hydrological properties. Groundwater U is associated with incompatible elements (S, As, Mo, F, and Cs) in water samples within granitic intrusions. Elevated [U] and [Rn] are located within 5–10 km distance of granitic intrusions but do not show correlations with metamorphism at intermediate scales (100−101 km). This spatial association is confirmed by a high-density sampling (n = 331, 5–40 samples per km 2 ) at local scales (≤10 –1 km) and the statewide sampling (n = 5857, 1 sample per 16 km 2 ) at regional scales (10 2 –10 3 km). Wells located within 5 km of granitic intrusions are at risk of containing high levels of [U] and [Rn]. Approximately 48 800–63 900 and 324 000 people in Maine are estimated at risk of exposure to U (>30 μg/L) and Rn (>4000 pCi/L) in well water, respectively.

Maine↗

Experimental investigation and modeling of uranium (VI) transport under variable chemical conditions

The transport of adsorbing and complexing metal ions in porous media was investigated with a series of batch and column experiments and with reactive solute transport modeling. Pulses of solutions containing U(VI) were pumped through columns filled with quartz grains, and the breakthrough of U(VI) was studied as a function of variable solution composition ( p H, total U(VI) concentration, total fluoride concentration, and p H-buffering capacity). Decreasing p H and the formation of nonadsorbing aqueous complexes with fluoride increased U(VI) mobility. A transport simulation with surface complexation model (SCM) parameters estimated from batch experiments was able to predict U(VI) retardation in the column experiments within 30%. SCM parameters were also estimated directly from transport data, using the results of three column experiments collected at different p H and U(VI) pulse concentrations. SCM formulations of varying complexity (multiple surface types and reaction stoichiometries) were tested to examine the trade-off between model simplicity and goodness of fit to breakthrough. A two-site model (weak- and strong-binding sites) with three surface complexation reactions fit these transport data well. With this reaction set the model was able to predict (1) the effects of fluoride complexation on U(VI) retardation at two different p H values and (2) the effects of temporal variability of p H on U(VI) transport caused by low p H buffering. The results illustrate the utility of the SCM approach in modeling the transport of adsorbing inorganic solutes under variable chemical conditions.

Water Resources Research↗

Uranium-lead isotopic ages from the Sierra Nevada Batholith, California

This study provides new information on the timing and distribution of Mesozoic magmatic events in the Sierra Nevada batholithic complex chiefly between 36° and 37°N. latitude. U-Pb ages have been determined for 133 zircon and 7 sphene separates from 82 samples of granitoid rocks. Granitoid rocks in this area range in age from 217 to 80 m.y. Triassic intrusions are restricted to the east side of the batholith; Jurassic plutons occur south of the Triassic plutons east of the Sierra Nevada, as isolated masses within the Cretaceous batholith, and in the western foothills of the range; Cretaceous plutons form a continuous belt along the axis of the batholith and occur as isolated masses east of the Sierra Nevada. No granitic intrusions were emplaced for 37 m.y. east of the Sierra Nevada following the end of Jurassic plutonism. However, following emplacement of the eastern Jurassic granitoids, regional extension produced a fracture system at least 350 km long into which the dominantly mafic, calc-alkalic Independence dike swarm was intruded 148 m.y. ago. The dike fractures probably represents a period of regional crustal extension caused by a redistribution of the regional stress pattern accompanying the Nevadan orogeny. Intrusion of Cretaceous granitic plutons began in large volume about 120 m.y. ago in the western Sierra Nevada and migrated steadily eastward for 40 m.y. at a rate of 2.7 mm/y. This slow and constant migration indicates remarkably uniform conditions of subduction with perhaps downward migration of parent magma generation or a slight flattening of the subduction zone. Such steady conditions could be necessary for the production of large batholithic complexes such as the Sierra Nevada. The abrupt termination of plutonism 80 m.y. ago may have resulted from an increased rate of convergence of the American and eastern Pacific plates and dramatic flattening of the subduction zone. U-Pb ages of the Giant Forest-alaskite sequence in Sequoia National Park are all in the range 99±3 m.y., indicating a relatively short period of emplacement and cooling for this nested group of plutons. U-Pb ages of a mafic inclusion and its host granodiorite indicate that both were derived from a common source or that the mafic inclusion was totally equilibrated with the granodioritic magma. Comparison of isotopic ages determined by different methods such as zircon U-Pb, sphene U-Pb, hornblende K-Ar, and biotite K-Ar suggests that zircon U-Pb ages generally approximate the emplacement age of a pluton. However, some plutons probably contain inherited or entrained old zircons, and the zircons of some samples are disturbed by younger thermal and metamorphic events. The ages reported here are consistent with U-Pb age determinations previously made on granitic rocks to the north [Stern et al., 1981], The age distribution of granitic belts determined here is in general agreement with those established by K-Ar dating [Evernden and Kistler, 1970] but does not differentiate the five epochs of plutonism determined in their study.

California↗

Age of the moon: An isotopic study of uranium-thorium-lead systematics of lunar samples

Concentrations of U, Th, and Pb in Apollo 11 samples studied are low (U. 0.16 to 0.87; Th, 0.53 to 3.4; Pb, 0.29 to 1.7, in ppm) but the extremely radiogenic lead in samples allows radiometric dating. The fine dust and the breccia have a concordant age of 4.66 billion years on the basis of 207 Pb/ 206 Pb, 206 Pb/ 238 U, 207 Pb/ 235 U, and 208 Pb/ 232 Th ratios. This age is comparable with the age of meteorites and with the age generally accepted for the earth. Six crystalline and vesicular samples are distinctly younger than the dust and breccia. The 238 U/ 235 U ratio is the same as that in earth rocks, and 234 U is in radioactive equilibrium with parent 238 U.

Science↗

Diatremes and uranium deposits in the Hopi Buttes, Arizona

The Hopi Buttes diatremes erupted in a shallow lake that was filled in as volcanic activity progressed in Pliocene time. At the end of the period of volcanism the landscape included low lava domes capping some of the diatremes, a few flows, and numerous craters of the maar type, surrounded by rims of volcanic debris with gentle exterior slopes that merged with the surrounding plain. Erosion, probably chiefly during early and middle Pleistocene, has exposed the diatremes in varying stages of denudation.

Arizona↗

Approaches to modelling uranium (VI) adsorption on natural mineral assemblages

Component additivity (CA) and generalised composite (GC) approaches to deriving a suitable surface complexation model for description of U(VI) adsorption to natural mineral assemblages are pursued in this paper with good success. A single, ferrihydrite-like component is found to reasonably describe uranyl uptake to a number of kaolinitic iron-rich natural substrates at pH > 4 in the CA approach with previously published information on nature of surface complexes, acid-base properties of surface sites and electrostatic effects used in the model. The GC approach, in which little pre-knowledge about generic surface sites is assumed, gives even better fits and would appear to be a method of particular strength for application in areas such as performance assessment provided the model is developed in a careful, stepwise manner with simplicity and goodness of fit as the major criteria for acceptance.

Radiochimica Acta↗