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238U-234U-230Th disequilibrium in hydrogenous oceanic Fe-Mn crusts: Palaeoceanographic record or diagenetic alteration?

A detailed TIMS study of ( 234 U exc / 238 U), ( 230 Th/ 232 Th), and Th/U ratios have been performed on the outermost margin of ten hydrogenous Fe Mn crusts from the equatorial Pacific Ocean and west-central Indian Ocean.Th/U concentration ratios generally decrease from the crust's surface down to 0.5-1 mm depth and growth rates estimated by uranium and thorium isotope ratios are significantly different in Fe Mn crusts from the Peru Basin and the west-central Indian Ocean. Fe Mn crusts from the same geographical area define a single trend in plots of Ln( 234 U exc / 238 U) vs. Ln( 230 Th/ 232 Th) and Th/U ratios vs. age of the analysed fractions. Results suggest that (l) hydrogenous Fe Mn crusts remain closed-systems after formation, and consequently (2) the discrepancy observed between the 230 Th and 234U chronometers in Fe Mn crusts, and the variations of the Th/U ratios through the margin of FeMn crusts, are not due to redistribution of uranium and thorium isotopes after oxyhydroxide precipitation, but rather to temporal variations of both Th/U and initial thorium activity ratios recorded by the Fe Mn layers. Implications of these observations for determination of Fe Mn crust growth-rates are discussed. Variations of both Th/U and initial Th activity ratios in Fe Mn crusts might be related to changes in particle input to seawater and/or changes in ocean circulation during the last 150 ka.

Geochimica et Cosmochimica Acta↗

222Rn transport in a fractured crystalline rock aquifer: Results from numerical simulations

Dissolved 222Rn concentrations in ground water from a small wellfield underlain by fractured Middle Proterozoic Pikes Peak Granite southwest of Denver, Colorado range from 124 to 840 kBq m-3 (3360-22700 pCi L-1). Numerical simulations of flow and transport between two wells show that differences in equivalent hydraulic aperture of transmissive fractures, assuming a simplified two-fracture system and the parallel-plate model, can account for the different 222Rn concentrations in each well under steady-state conditions. Transient flow and transport simulations show that 222Rn concentrations along the fracture profile are influenced by 222Rn concentrations in the adjoining fracture and depend on boundary conditions, proximity of the pumping well to the fracture intersection, transmissivity of the conductive fractures, and pumping rate. Non-homogeneous distribution (point sources) of 222Rn parent radionuclides, uranium and 226Ra, can strongly perturb the dissolved 222Rn concentrations in a fracture system. Without detailed information on the geometry and hydraulic properties of the connected fracture system, it may be impossible to distinguish the influence of factors controlling 222Rn distribution or to determine location of 222Rn point sources in the field in areas where ground water exhibits moderate 222Rn concentrations. Flow and transport simulations of a hypothetical multifracture system consisting of ten connected fractures, each 10 m in length with fracture apertures ranging from 0.1 to 1.0 mm, show that 222Rn concentrations at the pumping well can vary significantly over time. Assuming parallel-plate flow, transmissivities of the hypothetical system vary over four orders of magnitude because transmissivity varies with the cube of fracture aperture. The extreme hydraulic heterogeneity of the simple hypothetical system leads to widely ranging 222Rn values, even assuming homogeneous distribution of uranium and 226Ra along fracture walls. Consequently, it is concluded that 222Rn concentrations vary, not only with the geometric and stress factors noted above, but also according to local fracture aperture distribution, local groundwater residence time, and flux of 222Rn from parent radionuclides along fracture walls.

Journal of Hydrology↗

Optical dating of tufa via in situ aeolian sand grains: A case example from the Southern High Plains, USA

Precipitated carbonates (commonly termed tufas or travertines) maybe of considerable utility for palaeoenvironmental reconstruction. Their potential, however, for such reconstruction is commonly limited by difficulties associated with their absolute age control. Attempts to date such deposits via uranium series techniques have been complicated by their chemically open behaviour. Here we describe an alternative approach to date tufa deposits associated with ephemeral saline lake basins from the Southern High Plains, USA. We have optically dated sand grains of a mixed aeolian/fluvial (spring fed) origin as the integrating dosimeter. We assume that the grains are fully resetting prior to their incorporation into the tufa deposits and employ a time-dependent disequilibrium dosimetric model to account for the build-up of uranium series daughter products. The approach was applied to a set of four samples with known stratigraphic association. We obtained stratigraphically sensible optical ages ranging from 78??8 to 56??4ka. These data are consistent with existing palaeoenvironmental models of regional recharge. ?? 2003 Elsevier Science Ltd. All rights reserved.

Conference Paper↗

Quantitative radiochemical method for determination of major sources of natural radioactivity in ores and minerals

When an ore sample contains radioactivity other than that attributable to the uranium series in equilibrium, a quantitative analysis of the other emitters must be made in order to determine the source of this activity. Thorium-232, radon-222, and lead-210 have been determined by isolation and subsequent activity analysis of some of their short-lived daughter products. The sulfides of bismuth and polonium are precipitated out of solutions of thorium or uranium ores, and the α -particle activity of polonium-214, polonium-212, and polonium-210 is determined by scintillation-counting techniques. Polonium-214 activity is used to determine radon-222, polonium-212 activity for thorium-232, and polonium-210 for lead-210. The development of these methods of radiochemical analysis will facilitate the rapid determination of some of the major sources of natural radioactivity.

Analytical Chemistry↗

Decadal trends and occurrence of geogenic constituents and mixtures in groundwater across the continental United States

Worldwide, about 50% of the population is served by groundwater-sourced drinking water. Numerous groundwater quality assessments have found that geogenic constituents are among the most common contaminants in drinking-water aquifers. Documenting changing groundwater quality is a crucial aspect of water availability assessments. We assess trends and occurrence of geogenic constituent concentrations in groundwater across the continental United States using 3 decades of data from the U.S. Geological Survey’s National Water Quality Network. Thousands of groundwater wells were grouped into agricultural, urban, or domestic supply network types. Although most networks and constituents had no statistically significant change in concentration, many had increasing concentration trends, elevated concentrations, or both. Lithium, sodium, radium, sulfate, and uranium had increasing trends in more than 10% of the study networks. Urban and domestic well networks had increasing lithium and sodium trends more often than agricultural networks. Manganese most commonly increased in domestic well networks; uranium more commonly increased in agricultural and urban networks. Elevated concentration mixtures were widespread, and mixture complexities appeared to increase over time. Our results indicate that more than 2.3 million domestic-well users may be affected by elevated concentrations of one or more geogenic constituents.

continental United States↗

Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10 -8 to 10 -5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10 -3 to 6.0 ?? 10 -3 M in [Ca 2+ ], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Evaluation of weights of evidence to predict epithermal-gold deposits in the Great Basin of the western United States

The weights-of-evidence method provides a simple approach to the integration of diverse geologic information. The application addressed is to construct a model that predicts the locations of epithermal-gold mineral deposits in the Great Basin of the western United States. Weights of evidence is a data-driven method requiring known deposits and occurrences that are used as training sites in the evaluated area. Four hundred and fifteen known hot spring gold–silver, Comstock vein, hot spring mercury, epithermal manganese, and volcanogenic uranium deposits and occurrences in Nevada were used to define an area of 327.4 km 2 as training sites to develop the model. The model consists of nine weighted-map patterns that are combined to produce a favorability map predicting the distribution of epithermal-gold deposits. Using a measure of the association of training sites with predictor features (or patterns), the patterns can be ranked from best to worst predictors. Based on proximity analysis, the strongest predictor is the area within 8 km of volcanic rocks younger than 43 Ma. Being close to volcanic rocks is not highly weighted, but being far from volcanic rocks causes a strong negative weight. These weights suggest that proximity to volcanic rocks define where deposits do not occur. The second best pattern is the area within 1 km of hydrothermally altered areas. The next best pattern is the area within 1 km of known placer-gold sites. The proximity analysis for gold placers weights this pattern as useful when close to known placer sites, but unimportant where placers do not exist. The remaining patterns are significantly weaker predictors. In order of decreasing correlation, they are: proximity to volcanic vents, proximity to east-west to northwest faults, elevated airborne radiometric uranium, proximity to northwest to west and north-northwest linear features, elevated aeromagnetics, and anomalous geochemistry. This ordering of the patterns is a function of the quality, applicability, and use of the data. The nine-pattern favorability map can be evaluated by comparison with the USGS National Assessment for hot spring gold–silver deposits. The Spearman's ranked correlation coefficient between the favorability and the National Assessment permissive tracts is 0.5. Tabulations of the areas of agreement and disagreement between the two maps show 74% agreement for the Great Basin. The posterior probabilities for 51 significant deposits in the Great Basin, both used and not used in the model, show the following: 26 classified as favorable; 25 classified as permissive; and 1, Florida Canyon, classified as nonpermissive.The Florida Canyon deposit has a low favorability because there are no volcanic rocks near the deposit on the Nevada geologic map used. The largest areas of disagreement are caused by the USGS National Assessment team concluding that volcanic rocks older than 27 Ma in Nevada are not permissive, which was not assumed in this model. The weights-of-evidence model is evaluated as reasonable and delineates permissive areas for epithermal deposits comparable to expert's delineation. The weights-of-evidence model has the additional characteristics that it is well defined, reproducible, objective, and provides a quantitative measure of confidence.

California, Nevada↗

Pedologic and climatic controls on Rn-222 concentrations in soil gas, Denver, Colorado

Soil-gas radon concentrations are controlled seasonally by factors of climate and pedology. In a swelling soil of the semiarid Western United States, soil-gas radon concentrations at 100 cm depth increase in winter and spring due to increased emanation with higher soil moisture and the capping effect of surface water or ice. Increased soil moisture results from a combination of higher winter and spring precipitation and decreased insolation in fall and winter, lowering soil temperatures so that water infiltrates deeper and evaporates more slowly. Radon concentrations in soil drop markedly through the summer and fall. The increased insolation of spring and summer warms and dries the soil, limiting the amount of water that reaches 100 cm. As the soil dries, radon emanation decreases, and deep soil cracks develop. These cracks aid convective transport of soil gas, increase radon's flux into the atmosphere, and lower its concentration in soil gas. Probable controls on the distribution of uranium within the soil column include its downward leaching, its precipitation or adsorption onto B-horizon clays, concretions, or cement, and the uranium content and mineralogy of the soil's granitic and gneissic precursors.

Geophysical Research Letters↗

Age estimates and uplift rates for late Pleistocene marine terraces: Southern Oregon portion of the Cascadia forearc

Interest in the Cascadia subduction zone has increased because recent investigations have suggested that slip along plates at certain types of convergent margins is characteristically accompanied by large earthquakes. In addition, other investigations have suggested that convergent margins can be broadly classified by the magnitude of their uplift rates. The authors generated new uranium series, amino acid, and stable isotope data for southern Oregon marine terrace fossils. These data, along with terrace elevations and two alternative estimates of sea level at the time of terrace formation, allow one to determine terrace ages and uplift rates. Uranium series analysis of fossil coral yields an age of 83 {plus minus} 5 ka for the Whisky Run terrace at Coquille Point in Bandon, Oregon. A combination of amino acid and oxygen isotope data suggest ages of about 80 and 105 ka for the lowest two terraces at Cape Blanco. These ages indicate uplift rates of 0.45-1.05 and 0.81-1.49 m/kyr for Coquille Point and Cape Blanco, respectively. In order to assess the utility of the southern Oregon uplift rates for predicting the behavior of the Cascadia subduction zone, the authors compared late Quaternary uplift rates derived from terrace data from subduction zones around the world. On the basis of this comparison the southern Oregon rates of vertical deformation are not usually high or low. Furthermore, late Quaternary uplift rates show little relationship to the type of convergent margin. In the case of the southern Oregon coast, variability in uplift rate probably reflects local structures in the overriding plate, and the rate of uplift cannot be used as a simple index of the potential for great earthquakes along the southern Cascadia subduction zone.

California, Oregon↗

Rapidly-formed ferromanganese deposit from the eastern Pacific Hess Deep

A thick ferromanganese deposit encrusting fresh basaltic glass has been dredged from the Hess Deep in the eastern Pacific. Contiguous layers within the Fe-Mn crust have been analysed for uranium-series isotopes and metal contents. The rate of accumulation of the deposit, based on the decline of uranium-unsupported 230Th, is calculated to be approximately 50 mm per 106 yr. Based on hydration-rind dating of the underlying glass and an 'exposure age' calculation, this rate is concluded to be too slow, and an accretion rate on the order of 1 mm per 103 yr is more consistent with our data. ?? 1977 Nature Publishing Group.

Nature↗

Radiometric dating of sediments using fission tracks in conodonts

Conodonts are microfossils which are commonly found in marine rocks of Cambrian to Triassic age. Although their biological affinities are difficult to assess, conodonts are valuable stratigraphical indices for much of their geological range1. Recent work has also established that conodont colour alteration indices (CAI) are useful guides to diagenetic temperatures and hence burial depth2. Fission tracks3 in conodonts allow measurement of uranium concentrations and estimates of 'age' to be made using isotopic methods4. We report here that fission tracks counted in irradiated, thermally unaltered (as indicated by CAI) middle Palaeozoic conodonts indicate typical uranium concentrations of ???1 part in 10 9, with some samples higher. A single specimen of Siphonodella from the Lower Mississippian yielded an age estimate of 380??140 Myr consistent with conventional interpolations. This method may also allow the unroofing of deeply buried sediments to be dated. ?? 1980 Nature Publishing Group.

Nature↗

Arsenic and other geogenic contaminants in global groundwater

Geogenic groundwater contaminants (GGCs) affect drinking-water availability and safety, with up to 60% of groundwater sources in some regions contaminated by more than recommended concentrations. As a result, an estimated 300–500 million people are at risk of severe health impacts and premature mortality. In this Review, we discuss the sources, occurrences and cycling of arsenic, fluoride, selenium and uranium, which are GGCs with widespread distribution and/or high toxicity. The global distribution of GGCs is controlled by basin geology and tectonics, with GGC enrichment in both orogenic systems and cratonic basement rocks. This regional distribution is broadly influenced by climate, geomorphology and hydrogeochemical evolution along groundwater flow paths. GGC distribution is locally heterogeneous and affected by in situ lithology, groundwater flow and water–rock interactions. Local biogeochemical cycling also determines GGC concentrations, as arsenic, selenium and uranium mobilizations are strongly redox-dependent. Increasing groundwater extraction and land-use changes are likely to modify GGC distribution and extent, potentially exacerbating human exposure to GGCs, but the net impact of these activities is unknown. Integration of science, policy, community involvement programmes and technological interventions is needed to manage GGC-enriched groundwater and ensure equitable access to clean water.

Nature Reviews Earth & Environment↗

Antiferromagnetism of UO2⋅2H2O

Magnetic susceptibility measurements have been made on UO 2 · x H 2 O for x =1.78 to x =2.13, and from 77° to 375°K. As the value of x decreased the susceptibility increased. Both these data and structural arguments imply that the formula of this compound is U(OH) 4 rather than the dihydrate form. Based on this concept the data have been corrected for diamagnetism and also small amounts of UO 2 and H 2 O which were present. The molar susceptibility of U 4+ in U(OH) 4 is nearly an order of magnitude less than in other uranium compounds, and it is suggested that this is probably due to superexchange between adjacent uranium atoms through intervening oxygen atoms.

Journal of Chemical Physics↗

Igneous rocks of the East Pacific Rise

The apical parts of large volcanoes along the East Pacific Rise (islands and seamounts) are encrusted with rocks of the alkali volcanic suite (alkali basalt, andesine- and oligoclase-andesite, and trachyte). In contrast, the more submerged parts of the Rise are largely composed of a tholeiitic basalt which has low concentrations of K, P, U, Th, Pb, and Ti. This tholeiitic basalt is either the predominant or the only magma generated in the earth's mantle under oceanic ridges and rises. It is at least 1000-fold more abundant than the alkali suite, which is probably derived from tholeiitic basalt by magmatic differentiation in and immediately below the larger volcanoes. Distinction of oceanic tholeiites from almost all continental tholeiites is possible on the simple basis of total potassium content, with the discontinuity at 0.3 to 0.5 percent K 2 O by weight. Oceanic tholeiites also are readily distinguished from some 19 out of 20 basalts of oceanic islands and seamount cappings by having less than 0.3 percent K 2 O by weight and more than 48 percent SiO 2 . Deep drilling into oceanic volcanoes should, however, core basalts transitional between the oceanic tholeiites and the presumed derivative alkali basalts. The composition of the oceanic tholeiites suggests that the mantle under the East Pacific Rise contains less than 0.10 percent potassium oxide by weight; 0.1 part per million of uranium and 0.4 part of thorium; a potassium: rubidium ratio of about 1200 and a potassium: uranium ratio of about 10 4 .

Science↗

Excess lead in "rusty rock" 66095 and implications for an early lunar differentiation

Apollo 16 breccia 66095 contains a remarkably high amount of lead (15 parts per million), 85 percent of which is not supported by uranium and thorium in the rock. An acid leach experiment coupled with separate analyses of the whole rock and mineral fractions for uranium, thorium, and lead indicate that the excess lead has a lunar source and was apparently introduced about 4.0 × 10 9 years ago. The data also suggest that a major lunar crustal differentiation occurred about 4.47 × 10 9 years ago.

Science↗

Ages and stable-isotope compositions of secondary calcite and opal in drill cores from Tertiary volcanic rocks of the Yucca Mountain area, Nevada

Stable-isotope compositions of fracture-and cavity-filling calcite from the unsaturated zone of three drill cores at Yucca Mountain Tertiary volcanic complex indicate that the water from which the minerals precipitated was probably meteoric in origin. A decrease in 18 O in the calcite with depth is interpreted as being due to the increase in temperature in drill holes corresponding to an estimated average geothermal gradient of 34° per kilometer. A few of the calcite samples and all of the opal samples yielded uranium-series ages older than 400,000 yr, although most of the calcite samples yielded ages between 26,000 and 310,000 yr. The stable-isotope and uranium- series dates from precipitated calcite and opal of this reconnaissance study suggest a complex history of fluid movement through the volcanic pile, and episodes of fracture filling predominantly from meteoric water during at least the past 400,000 yr.

Nevada↗

Conditions and processes affecting radionuclide transport

Characteristics of host rocks, secondary minerals, and fluids would affect the transport of radionuclides from a previously proposed repository at Yucca Mountain, Nevada. Minerals in the Yucca Mountain tuffs that are important for retarding radionuclides include clinoptilolite and mordenite (zeolites), clay minerals, and iron and manganese oxides and hydroxides. Water compositions along flow paths beneath Yucca Mountain are controlled by dissolution reactions, silica and calcite precipitation, and ion-exchange reactions. Radionuclide concentrations along flow paths from a repository could be limited by (1) low waste-form dissolution rates, (2) low radionuclide solubility, and (3) radionuclide sorption onto geological media. The chief sources of radioactivity in spent nuclear fuel are americium, plutonium, and neptunium. Therefore, studies have concentrated on their geochemical mobility. Uranium-233, uranium-234, iodine-129, technetium-99, and other radionuclides also have been included in some experiments. Solubilities were determined experimentally in representative Yucca Mountain waters. Sorption coefficients were determined using water, rock, and pure mineral samples from Yucca Mountain. Batch experiments were performed at several pH levels and oxidizing conditions. Dynamic transport-column experiments, diffusion experiments, and solid-rock beaker experiments also were conducted. The batch tests gave slightly lower retardation factors than those derived from column-breakthrough experiments. This finding indicates that using batch-sorption coefficients to predict radionuclide transport will yield conservative results in a performance assessment. Understanding of unsaturated-zone transport is based on laboratory and field-scale experiments. Fractures provide advective transport pathways. Sorption and matrix diffusion may contribute to retardation of radionuclides. Conversely, sorption onto mobile colloids may enhance radionuclide transport.

GSA Memoirs↗

Pleistocene lakes and paleohydrologic environments of the Tecopa basin, California: Constraints on the drainage integration of the Amargosa River

The Tecopa basin in eastern California was a terminal basin that episodically held lakes during most of the Quaternary until the basin and its modern stream, the Amargosa River, became tributary to Death Valley. Although long studied for its sedimentology, diagenesis, and paleomagnetism, the basin’s lacustrine and paleoclimate history has not been well understood, and conflicting interpretations exist concerning the relations of Tecopa basin to the Amargosa River and to pluvial Lake Manly in Death Valley. Previous studies also did not recognize basinwide tectonic effects on lake-level history. In this study, we focused on: (1) establishing a chronology of shoreline deposits, as the primary indicator of lake-level history, utilizing well-known ash beds and new uranium-series and luminescence dating; (2) using ostracodes as indicators of water chemistry and water source(s); and (3) correlating lake transgressions to well-preserved fluvial-deltaic sequences. During the early Pleistocene, the Tecopa basin hosted small shallow lakes primarily fed by low-alkalinity water sourced mainly from runoff and (or) a groundwater source chemically unlike the modern springs. The first lake that filled the basin occurred just prior and up to the eruption of the 765 ka Bishop ash during marine isotope stage (MIS) 19; this lake heralded the arrival of the Amargosa River, delivering high-alkalinity water. Two subsequent lake cycles, coeval with MIS 16 (leading up to eruption of 631 ka Lava Creek B ash) and MIS 14 and (or) MIS 12, are marked by prominent accumulations of nearshore and beach deposits. The timing of the youngest of these three lakes, the High lake, is constrained by a uranium-series age of ca. 580 ± 120 ka on tufa-cemented beach gravel and by estimates from sedimentation rates. Highstand deposits of the Lava Creek and High lakes at the north end of the basin are stratigraphically tied to distinct sequences of fluvial-deltaic deposits fed by alkaline waters of the Amargosa River. The High lake reached the highest level achieved in the Tecopa basin, and it may have briefly discharged southward but did not significantly erode its threshold. The High lake was followed by a long hiatus of as much as 300 k.y., during which there is evidence for alluvial, eolian, and groundwater-discharge deposition, but no lakes. We attribute this hiatus, as have others, to blockage of the Amargosa River by an alluvial fan upstream near Eagle Mountain. A final lake, the Terminal lake, formed when the river once again flowed south into Tecopa basin, but it was likely short-lived due to rapid incision of the former threshold south of Tecopa. Deposits of the Terminal lake are inset below, and are locally unconformable on, deposits of the High lake and the nonlacustrine deposits of the hiatus. The Terminal lake reached its highstand at ca. 185 ± 21 ka, as dated by infrared-stimulated luminescence on feldspar in beach sand, a time coincident with perennial lake mud and alkaline-tolerant ostracodes in the Badwater core of Lake Manly during MIS 6. A period of stillstand occurred as the Terminal lake drained when the incising river encountered resistant Stirling Quartzite near the head of present-day Amargosa Canyon. Our studies significantly revise the lacustrine and drainage history of the Tecopa basin, show that the MIS 6 highstand was not the largest lake in the basin as previously published (with implications for potential nuclear waste storage at Yucca Mountain, Nevada), and provide evidence from shoreline elevations for ∼20 m of tectonic uplift in the northern part of the basin across an ENE-trending monoclinal flexure.

California↗