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Simultaneous estimation of local-scale and flow path-scale dual-domain mass transfer parameters using geoelectrical monitoring

Anomalous solute transport, modeled as rate-limited mass transfer, has an observable geoelectrical signature that can be exploited to infer the controlling parameters. Previous experiments indicate the combination of time-lapse geoelectrical and fluid conductivity measurements collected during ionic tracer experiments provides valuable insight into the exchange of solute between mobile and immobile porosity. Here, we use geoelectrical measurements to monitor tracer experiments at a former uranium mill tailings site in Naturita, Colorado. We use nonlinear regression to calibrate dual-domain mass transfer solute-transport models to field data. This method differs from previous approaches by calibrating the model simultaneously to observed fluid conductivity and geoelectrical tracer signals using two parameter scales: effective parameters for the flow path upgradient of the monitoring point and the parameters local to the monitoring point. We use regression statistics to rigorously evaluate the information content and sensitivity of fluid conductivity and geophysical data, demonstrating multiple scales of mass transfer parameters can simultaneously be estimated. Our results show, for the first time, field-scale spatial variability of mass transfer parameters (i.e., exchange-rate coefficient, porosity) between local and upgradient effective parameters; hence our approach provides insight into spatial variability and scaling behavior. Additional synthetic modeling is used to evaluate the scope of applicability of our approach, indicating greater range than earlier work using temporal moments and a Lagrangian-based Damköhler number. The introduced Eulerian-based Damköhler is useful for estimating tracer injection duration needed to evaluate mass transfer exchange rates that range over several orders of magnitude.

Water Resources Research↗

Effects of error covariance structure on estimation of model averaging weights and predictive performance

When conducting model averaging for assessing groundwater conceptual model uncertainty, the averaging weights are often evaluated using model selection criteria such as AIC, AICc, BIC, and KIC (Akaike Information Criterion, Corrected Akaike Information Criterion, Bayesian Information Criterion, and Kashyap Information Criterion, respectively). However, this method often leads to an unrealistic situation in which the best model receives overwhelmingly large averaging weight (close to 100%), which cannot be justified by available data and knowledge. It was found in this study that this problem was caused by using the covariance matrix, C E , of measurement errors for estimating the negative log likelihood function common to all the model selection criteria. This problem can be resolved by using the covariance matrix, C ek , of total errors (including model errors and measurement errors) to account for the correlation between the total errors. An iterative two-stage method was developed in the context of maximum likelihood inverse modeling to iteratively infer the unknown C ek from the residuals during model calibration. The inferred C ek was then used in the evaluation of model selection criteria and model averaging weights. While this method was limited to serial data using time series techniques in this study, it can be extended to spatial data using geostatistical techniques. The method was first evaluated in a synthetic study and then applied to an experimental study, in which alternative surface complexation models were developed to simulate column experiments of uranium reactive transport. It was found that the total errors of the alternative models were temporally correlated due to the model errors. The iterative two-stage method using C ek resolved the problem that the best model receives 100% model averaging weight, and the resulting model averaging weights were supported by the calibration results and physical understanding of the alternative models. Using C ek obtained from the iterative two-stage method also improved predictive performance of the individual models and model averaging in both synthetic and experimental studies.

Water Resources Research↗

The Sima de los Huesos hominids date to beyond U/Th equilibrium (>350 kyr) and perhaps to 400-500 kyr: New radiometric dates

The Sima de los Huesos site of the Atapuerca complex near Burgos, Spain contains the skeletal remains of at least 28 individuals in a mud breccia underlying an accumulation of the Middle Pleistocene cave bear (U. deningeri). Earlier dating estimates of 200 to 320 kyr were based on U-series and ESR methods applied to bones, made inaccurate by unquantifiable uranium cycling. We report here on a new discovery within the Sima de los Huesos of human bones stratigraphically underlying an in situ speleothem. U-series analyses of the speleothem shows the lower part to be at isotopic U/Th equilibrium, translating to a firm lower limit of 350 kyr for the SH hominids. Finite dates on the upper part suggest a speleothem growth rate of c. 1 cm/32 kyr. This rate, along with paleontological constraints, place the likely age of the hominids in the interval of 400 to 600 kyr. ?? 2002 Elsevier Science Ltd. All rights reserved.

Journal of Archaeological Science↗

Paleoclimatic Inferences from a 120,000-Yr Calcite Record of Water-Table Fluctuation in Browns Room of Devils Hole, Nevada

The petrographic and morphologic differences between calcite precipitated below, at, or above the present water table and uranium-series dating were used to reconstruct a chronology of water-table fluctuation for the past 120,000 yr in Browns Room, a subterranean air-filled chamber of Devils Hole fissure adjacent to the discharge area of the large Ash Meadows groundwater flow system in southern Nevada. The water table was more than 5 m above present level between about 116,000 and 53,000 yr ago, fluctuated between about +5 and +9 m during the period between about 44,000 and 20,000 yr ago, and declined rapidly from +9 to its present level during the past 20,000 yr. Because the Ash Meadows groundwater basin is greater than 12,000 km2 in extent, these documented water-table fluctuations are likely to be of regional significance. Although different in detail, water-level fluctuation recorded by Browns Room calcites generally correlate with other Great Basin proxy palcoclimatic data.

Quaternary Research↗

Duration and structure of the past four interglaciations

Reanalysis and additional dating of the Devils Hole ??18O paleotemperature record confirm that the last interglaciation in the Great Basin (the continental analog of marine isotopic substage 5e) lasted ???22,000 yr, consistent with the Vostok paleotemperature record which suggests a duration of ???19,000 yr for this event in Antarctica. The three preceding interglaciations in the Devils Hole record (analogs of marine isotopic substages 7e, 9c, and 11c) range from 20,000 to 26,000 yr in duration. A ???20,000-yr duration for the last interglaciation is consistent with TIMS uranium-series dated sea-level high stands. Thus, the widely held view that interglaciations were of 11,000-to 13,000-yr duration and constituted only about 10% of mid-to-late Pleistocene climatic cycles needs reexamination. The warmest portion of each interglaciation in the Devils Hole time series is marked by a ??18O plateau, signifying apparent climatic stability for periods of 10,000-to 15,000-yr duration. ?? 1997 University of Washington.

Quaternary Research↗

Last interglacial climates

The last interglacial, commonly understood as an interval with climate as warm or warmer than today, is represented by marine isotope stage (MIS) 5e, which is a proxy record of low global ice volume and high sea level. It is arbitrarily dated to begin at approximately 130,000 yr B.P. and end at 116,000 yr B.P. with the onset of the early glacial unit MIS 5d. The age of the stage is determined by correlation to uranium-thorium dates of raised coral reefs. The most detailed proxy record of interglacial climate is found in the Vostok ice core where the temperature reached current levels 132,000 yr ago and continued rising for another two millennia. Approximately 127,000 yr ago the Eemian mixed forests were established in Europe. They developed through a characteristic succession of tree species, probably surviving well into the early glacial stage in southern parts of Europe. After ca. 115,000 yr ago, open vegetation replaced forests in northwestern Europe and the proportion of conifers increased significantly farther south. Air temperature at Vostok dropped sharply. Pulses of cold water affected the northern North Atlantic already in late MIS 5e, but the central North Atlantic remained warm throughout most of MIS 5d. Model results show that the sea surface in the eastern tropical Pacific warmed when the ice grew and sea level dropped. The essentially interglacial conditions in southwestern Europe remained unaffected by ice buildup until late MIS 5d when the forests disappeared abruptly and cold water invaded the central North Atlantic ca. 107,000 yr ago. ?? 2002 University of Washington.

Quaternary Research↗

Application of molluscan analyses to the reconstruction of past environmental conditions in estuaries

Molluscs possess a number of attributes that make them an excellent source of past environmental conditions in estuaries: they are common in estuarine environments; they typically have hard shells and are usually well preserved in sediments; they are relatively easy to detect in the environment; they have limited mobility as adults; they grow by incremental addition of layers to their shells; and they are found in all the major environments surrounding estuaries—terrestrial, freshwater, brackish, and marine waters. Analysis of molluscan assemblages can contribute information about past changes in sea level, climate, land use patterns, anthropogenic alterations, salinity, and other parameters of the benthic habitat and water chemistry within the estuary. High-resolution (from less than a day to annual) records of changes in environmental parameters can be obtained by analyzing the incremental growth layers in mollusc shells (sclerochronology). The shell layers retain information on changes in water temperature, salinity, seasonality, climate, river discharge, productivity, pollution and human activity. Isotopic analyses of mollusc shell growth layers can be problematic in estuaries where water temperatures and isotopic ratios can vary simultaneously; however, methods are being developed to overcome these problems. In addition to sclerochronology, molluscs are important to Holocene and Pleistocene estuarine palaeoenvironmental studies because of their use in the development of age models through radiocarbon dating, amino acid racemization, uranium-thorium series dating, and electron spin resonance (ESR) dating.

Book chapter↗

Toxicity of inorganic contaminants, individually and in environmental mixtures, to three endangered fishes (Colorado squawfish, bonytail, and razorback sucker)

Two life stages of three federally-listed endangered fishes, Colorado squawfish ( Ptychocheilus lucius ), bonytail ( Gila elegans ), and razorback sucker ( Xyrauchen texanus ) were exposed to copper, selenate, selenite, and zinc individually, and to mixtures of nine inorganics in a reconstituted water that simulated the water quality of the middle Green River, Utah. The mixtures simulated environmental ratios of arsenate, boron, copper, molybdenum, selenate, selenite, uranium, vanadium, and zinc in two tributaries, Ashley Creek and Stewart Lake outlet, of the middle Green River. The rank order of toxicity of the individual inorganics, from most to least toxic, was: copper > zinc > selenite > selenate. Colorado squawfish larvae were more sensitive to all four inorganics and the two mixtures than the juveniles, whereas there was no consistent response between the two life stages for the other two species. There was no consistent difference in sensitivity to the inorganics among the three endangered fishes. Both mixtures exhibited either additive or greater than additive toxicity to these fishes. The primary toxic components in the mixtures, based on toxic units, were copper and zinc. Acute toxicity values were compared to measured environmental concentrations in the two tributaries to derive margins of uncertainty. Margins of uncertainty were low for both mixtures (9–22 for the Stewart Lake outlet mixture, and 12–32 for the Ashley Creek mixture), indicating that mixtures of inorganics derived from irrigation activities may pose a hazard to endangered fishes in the Green River.

Archives of Environmental Contamination and Toxico↗

Lead and strontium isotopes in rocks of the Absaroka volcanic field, Wyoming

The Absaroka volcanic field is comprised of predominant andesitic volcaniclastic rocks and less abundant potassium-rich mafic lavas (shoshonites and absarokites). Strontium and lead isotopic variations preclude a simple derivation from an isotopically uniform source: Sr 87 /Sr 86 , 0.7042 to 0.7090; Pb 206 /Pb 204 , 16.31 to 17.30; Pb 208 /Pb 204 , 36.82 to 37.64. We postulate that these rocks were derived from a lower crust or upper mantle which underwent a preferential loss of uranium relative to lead approximately 2800±200 m.y. ago. Variations in lead and strontium isotopic compositions are thought to reflect small inhomogeneities in U/Pb and Rb/Sr ratios in the source.

Wyoming↗

Tholeiitic basalt magmatism of Kilauea and Mauna Loa volcanoes of Hawaii

The primitive magmas of Kilauca and Mauna Loa are generated by partial melting of mantle peridotite at depths of −60 km or more. Results of high-pressure melting experiments indicate that the primitive melt must contain at least 20% MgO in order to have olivine as a liquidus mineral. The least fractionated lavas of both volcanoes have olivine (Fa 13 ) on the liquidus at 1 atmosphere, suggesting that the only substance lost from the primitive melt, during a rather rapid ascent to the surface, is olivine. This relation allows the primitive composition to be computed by adding olivine to the composition of an erupted lava until total MgO is at least 20 percent. Although roughly similar, historic lavas of the two volcanoes show a consistent difference in composition. The primitive melt of Mauna Loa contains 20% more dissolved orthopyroxene, a high-temperature melting phase in the mantle, and is deficient in elements such as potassium, uranium, and niobium, which presumably occur in minor low-melting phases. Mauna Loa appears to be the older volcano, deriving its magma at higher temperature and greater depth from a more depleted source rock.

Hawaii↗

Relative inactivity during the last 140,000 years of a portion of the La Paz fault, southern Baja California Sur, Mexico

Uranium-series dating of corals overlying the undeformed Punta Coyote gravels indicates that the underlying La Paz fault zone has been relatively inactive in this part of the Baja California peninsula during the last 140,000 years, and possibly for a significantly longer period. However, Holocene seismic activities along extensions of the fault zone north of Cabo San Lucas suggest potential seismic hazards for the city of La Paz (population 200,000), which lies about 6 km from the fault. ?? 1990 Springer-Verlag New York Inc.

Environmental Geology and Water Sciences↗

One-level prediction-A numerical method for estimating undiscovered metal endowment

One-level prediction has been developed as a numerical method for estimating undiscovered metal endowment within large areas. The method is based on a presumed relationship between a numerical measure of geologic favorability and the spatial distribution of metal endowment. Metal endowment within an unexplored area for which the favorability measure is greater than a favorability threshold level is estimated to be proportional to the area of that unexplored portion. The constant of proportionality is the ratio of the discovered endowment found within a suitably chosen control region, which has been explored, to the area of that explored region. In addition to the estimate of undiscovered endowment, a measure of the error of the estimate is also calculated. One-level prediction has been used to estimate the undiscovered uranium endowment in the San Juan basin, New Mexico, U.S.A. A subroutine to perform the necessary calculations is included. ?? 1992 Oxford University Press.

Nonrenewable Resources↗

INAA determination of major and trace elements in loess, paleosol and precipitation layers in a pleistocene Loess Section, China

Instrumental neutron activation analysis was used for the determination of 31 major and trace elements in 32 samples from the Xinji Loess Section, Shaanxi Province, China. Interferences, including those from uranium fission products, were evaluated and corrections applied where necessary. The 39.7-meter deep section comprises of Lishi Loess of the middle Pleistocene (Q2) and Malan Loess of the late Pleistocene (Q3). The section is characterized by the presence of 5 layers of paleosol, and each paleosol is underlain by a precipitation layer. When the elemental abundances are converted to a carbonate-free basis, there is little compositional difference among the carbonate-free fractions of loess, paleosol and precipitation layers. This indicates that dissolution of carbonate minerals by downward-moving surface water was an important process in paleosol formation while other minerals were not severely weathered and elemental fractionation was minimal. The parent materials of the paleosol and precipitation layers closely resemble the loess layers in their elemental abundances, which suggests that all layers in the section have a compositionally similar source. ?? 1987 Akade??miai Kiado??.

Journal of Radioanalytical and Nuclear Chemistry A↗

Summary of the mineral- and energy-resource endowment, BLM roswell resource area, east-central New Mexico

In this summary of two comprehensive resource reports produced by the U.S. Bureau of Mines and the U.S. Geological Survey for the U.S. Bureau of Land Management, we discuss the mineral- and energyresource endowment of the 14-millon-acre Roswell Resource Area, New Mexico, managed by the Bureau of Land Management. The Bureau and Survey reports result from separate studies that are compilations of published and unpublished data and integrate new findings on the geology, geochemistry, geophysics, mineral, industrial, and energy commodities, and resources for the seven-county area. The reports have been used by the Bureau of Land Management in preparation of the Roswell Resource Area Resource Management Plan, and will have future use in nationwide mineral- and energy-resource inventories and assessments, as reference and training documents, and as public-information tools. In the Roswell Resource Area, many metals, industrial mineral commodities, and energy resources are being, or have been, produced or prospected. These include metals and high-technology materials, such as copper, gold, silver, thorium, uranium and/or vanadium, rare-earth element minerals, iron, manganese, tungsten, lead, zinc, and molybdenum; industrial mineral resources, including barite, limestone/dolomite, caliche, clay, fluorspar, gypsum, scoria, aggregate, and sand and gravel; and fuels and associated resources, such as oil, gas, tar sand and heavy oil, coal, and gases associated with hydrocarbons. Other commodities that have yet to be identified in economic concentrations include potash, halite, polyhalite, anhydrite, sulfur, feldspar, building stone and decorative rock, brines, various gases associated with oil and gas exploration, and carbon dioxide. ?? 1993 Oxford University Press.

Nonrenewable Resources↗

Chemical characterization of gas- and oil-bearing shales by instrumental neutron activation analysis

The concentration of As, Ba, Ca, Co, Cr, Cs, Dy, Eu, Fe, Ga, Hf, K, La, Lu, Mn, Mo, Na, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, U, Yb, and Zn were determined by instrumental neutron activation analysis in block shale samples of the New Albany Group (Devonian-Mississippian) in the in the Illinois Basin. Uranium content of the samples was as high as 75 ppm and interfered in the determination of samarium, molybdenum, barium and cerium. In the determination of selenium a correction was made for interference from tantalum. U, As, Co, Mo, Ni and Sb as well as Cu, V and pyritic sulphur which were determined by other methods, were found to correlate positively with the organic carbon content of the samples. ?? 1982 Akade??miai Kiado??.

Journal of Radioanalytical Chemistry↗

Factors influencing the biogeochemistry of sedimentary carbon and phosphorus in the Sacramento-San Joaquin Delta

This study characterizes organic carbon (C organic ) and phosphorus (P) geochemistry in surface sediments of the Sacramento-San Joaquin Delta, California. Sediment cores were collected from five sites on a sample transect from the edge of the San Francisco Bay eastward to the freshwater Consumnes River. The top 8 cm of each core were analyzed (in 1-cm intervals) for C organic , four P fractions, and redox-sensitive trace metals (uranium and manganese). Sedimentary C organic concentrations and C organic : P ratios, decreased, while reactive P concentrations increased moving inland in the Delta. The fraction of total P represented by organic P increased inland, while that of authigenic P was higher bayward than inland reflecting increased diagenetic alteration of organic matter toward the bayward end of the transect. The redox indicator metals are consistent with decreasing sedimentary suboxia inland. The distribution of P fractions and C:P ratios, reflect the presence of relatively labile organic matter in upstream surface sediments. Sediment C and P geochemistry is influenced by site-specific particulate organic matter sources, the sorptive power of the sedimentary material present, physical forcing, and early diagenetic transformations presumably driven by C organic oxidation.

California↗

Insights into the metamorphic history and origin of flake graphite mineralization at the Graphite Creek graphite deposit, Seward Peninsula, Alaska, USA

Graphite Creek is an unusual flake graphite deposit located on the Seward Peninsula, Alaska, USA. We present field observations, uranium-lead (U–Pb) monazite and titanite geochronology, carbon (C) and sulfur (S) stable isotope geochemistry, and graphite Raman spectroscopy data from this deposit that support a new model of flake graphite ore genesis in high-grade metamorphic environments. The Graphite Creek deposit is within the second sillimanite metamorphic zone of the Kigluaik Mountains gneiss dome. Flake graphite, hosted in sillimanite-gneiss and quartz-biotite paragneiss, occurs as disseminations and in sets of very high grade (up to 50 wt.% graphite), semi-massive to massive graphite lenses 0.2 to 1 m wide containing quartz, sillimanite, inclusions of garnet porphyroblasts, K-feldspar, and tourmaline. Restitic garnet, sillimanite, graphite, and biotite accumulations indicate a high degree of anatexis and melt loss. Strong yttrium depletion in monazite, high europium ratios (Eu/Eu*), and excursions of high strontium and thorium concentrations are consistent with biotite dehydration melting. Monazite and titanite U–Pb ages record peak metamorphism from ~ 97 to 92 million years ago (Ma) and a retrograde event at ~ 85 Ma. Raman spectroscopy confirms the presence of carbonaceous material and highly ordered, crystalline graphite. Graphite δ 13 C VPDB values of − 30 to − 12‰ and pyrrhotite δ 34 S VCDT values of − 14 to 10‰ are consistent with derivation from organic carbon and sulfur in sedimentary rocks, respectively. These data collectively suggest that formation of massive graphite lenses occurred approximately synchronously with high-temperature metamorphism and anatexis of a highly carbonaceous pelitic protolith. Melt extraction and fluid release associated with anatexis were likely crucial for concentrating graphite. High-temperature, graphitic migmatite sequences within high-strain shear zones may be favorable for the occurrence of high-grade flake graphite deposits.

Alaska↗

Polyphase stratabound scheelite-ferberite mineralization at Mallnock, Eastern Alps, Austria

A peculiar type of stratabound tungsten mineralization in metacarbonate rocks was discovered and explored at Mallnock (Austria) during the late 1980s. It is the only tungsten occurrence in the Eastern Alps in which scheelite is associated with wolframite (96 mol% ferberite). The tungsten prospect is located in the Austroalpine Drauzug-Gurktal Nappe System recording polyphase low-grade regional metamorphism. Raman spectroscopy of carbonaceous material yield maximum metamorphic temperatures of 296 ± 27 °C and 258 ± 27 °C, which are assigned to Variscan and Eoalpine metamorphism, respectively. Scheelite and ferberite occur as polyphase stockwork-like mineralization in Fe-rich magnesite in the northern ore zone (Mallnock North), whereas in the western ore zone (Mallnock West), scheelite-quartz veinlets are exclusively hosted in dolomitic marbles. LA-ICP-MS analyses of scheelite and ferberite yield low contents of Mo, Nb, Ta, and rare earth elements, but high contents of Na and Sr. Uranium is particularly high in scheelite (up to 200 µg/g) and makes this mineral a suitable target for U–Pb dating. In situ U–Pb dating of scheelite yielded an early Permian age (294 ± 8 Ma) for Mallnock West and a Middle Triassic age (239 ± 3 Ma) for Mallnock North. A monzodioritic dike close to Mallnock yielded a U–Pb apatite date of 282 ± 9 Ma and supports the polyphase formation of this mineralization. The U–Pb scheelite ages indicate that a model for tungsten metallogeny in the Eastern Alps must also consider remobilization of tungsten by metamorphic fluids. In the Alps, the Permian to Triassic period (ca. 290–225 Ma) is characterized by an overall extensional geodynamic setting related to the breakup of Pangea. Lithospheric thinning caused higher heat flow, low-P metamorphism, and anatexis in the lower crust, which led to enhanced crustal fluid flow in the upper crust. These processes were not only responsible for the formation of metasomatic hydrothermal magnesite and siderite deposits in the Eastern Alps but also for this unique magnesite-ferberite-scheelite mineralization at Mallnock.

Mount Mallock↗