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Occurrence of Uranium and 222Radon in Glacial and Bedrock Aquifers in the Northern United States, 1993-2003

Water-quality data collected from 1,426 wells during 1993-2003 as part of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) program were evaluated to characterize the water quality in glacial and bedrock aquifers of the northern United States. One of the goals of the NAWQA program is to synthesize data from individual studies across the United States to gain regional- and national-scale information about the behavior of contaminants. This study focused on the regional occurrence and distribution of uranium and 222radon in ground water in the glacial aquifer system of the United States as well as in the Cambrian-Ordovician and the New York and New England crystalline aquifer systems that underlie the glacial aquifer system. The occurrence of uranium and 222radon in ground water has long been a concern throughout the United States. In the glacial aquifers, as well as the Cambrian-Ordovician and the New York and New England crystalline aquifer systems of the United States, concentrations of uranium and 222radon were highly variable. High concentrations of uranium and 222radon affect ground water used for drinking water and for agriculture. A combination of information or data on (1) national-scale ground-water regions, (2) regional-scale glacial depositional models, (3) regional-scale geology, and (4) national-scale terrestrial gamma-ray emissions were used to confirm and(or) refine the regions used in the analysis of the water-chemistry data. Significant differences in the occurrence of uranium and 222radon, based primarily on geologic information were observed and used in this report. In general, uranium was highest in the Columbia Plateau glacial, West-Central glacial, and the New York and New England crystalline aquifer groups (75th percentile concentrations of 22.3, 7.7, and 2.9 micrograms per liter (ug/L), respectively). In the Columbia Plateau glacial and the West-Central glacial aquifer groups, more than 10 percent of wells sampled had concentrations of uranium that exceeded the U.S. Environmental Protection Agency (USEPA) Maximum Contaminant Level of 30 ug/L; in the New York and New England crystalline aquifer group, 4 percent exceeded 30 ug/L. Ground-water samples with high concentrations of uranium were commonly linked to geologic sources rich in uranium. In eight of nine aquifer groups defined for this study, concentrations of uranium correlated significantly with concentrations of sulfate in ground water (Spearman's rho = 0.20 to 0.56; p < 0.05). In the Columbia Plateau, glacial aquifers were derived in part from basaltic lava flows, some felsic volcanic rocks, and some paleo-lake bed materials that may be rich in uranium. In the Columbia Plateau and West-Central glacial aquifer groups, uranium correlated with total dissolved solids, bicarbonate, boron, lithium, selenium, and strontium. In the West-Central glacial aquifer group, rocks such as Cretaceous marine shales, which are abundant in uranium, probably contribute to the high concentrations in ground water; in the southern part of this group, which extends into Nebraska, the glacial or glacial-related sediment may be interbedded with uranium-rich materials that originated to the north and west and in the Rocky Mountains. In New England, crystalline bedrock that is granitic, such as two-mica granites, as well as other high-grade metamorphic rocks, has abundant uranium that is soluble in the predominantly oxic to sub-oxic geochemical conditions. This appears to contribute to high uranium concentrations in ground water. The highest 222radon concentrations were present in samples from wells completed in the New York and New England crystalline aquifer group; the median value (2,122 picocurries per liter (pCi/L)) was about 10 times the median values of all other aquifer groups. More than 25 percent of the samples from the New York and New England crystalline aquifer group wells had 222radon concentrations that exceeded the USEPA Alternative

Scientific Investigations Report

Arsenic, chromium, uranium, and vanadium in rock, alluvium, and groundwater, Mojave River and Morongo Areas, western Mojave Desert, southern California

Trace elements within groundwater that originate from aquifer materials and pose potential public-health hazards if consumed are known as geogenic contaminants. The geogenic contaminants arsenic, chromium, and vanadium can form negatively charged ions with oxygen known as oxyanions. Uranium complexes with bicarbonate and carbonate to form negatively charged ions having aqueous chemistry similar to oxyanions. The concentrations of arsenic, chromium, uranium, and vanadium in groundwater result from the combined effects of (1) geologic abundance within aquifer materials; (2) the fraction of these elements that have weathered from and sorbed to the surfaces of mineral grains and are potentially available to groundwater; and (3) the aqueous chemistry of dissolved oxyanions in groundwater during different redox conditions and pH, both of which are affected by hydrogeology, including the length of time groundwater has been in contact with aquifer materials. Concentrations of arsenic, chromium, uranium, and vanadium were measured in samples of (1) rock, surficial alluvium, and drill cuttings using portable (handheld) X-ray fluorescence (pXRF); (2) operationally defined fractions extractable from these materials; and (3) water from wells sampled between 2000 and 2018 within the 3,500 square mile Mojave River area and Morongo area of the western Mojave Desert, southern California. Regionally, rock and surficial alluvium in the Mojave River and Morongo areas are high in arsenic, low in chromium and uranium, and near the average bulk continental crust concentration for vanadium. Locally, high chromium concentrations are present in mafic rock within the San Gabriel Mountains; high uranium concentrations are present in felsic rock within the San Bernardino Mountains; and high arsenic, uranium, and vanadium concentrations are present in extrusive (volcanic) felsic rock within uplands surrounding groundwater basins along the Mojave River downstream from Barstow, California. Elemental assemblages identified using principal component analyses (PCA) of pXRF data were used to characterize felsic, mafic, and felsic volcanic source terranes in rock, surficial alluvium, and in geologic material penetrated by selected monitoring wells drilled between 1994 and 2018. Highly felsic alluvium associated with recent deposition from the Mojave River was identified along the 90-mile length of the floodplain aquifer along the river. The thickness of these highly felsic alluvial deposits ranged from 200 feet (ft) near Victorville and near Barstow to a thin veneer about 30 ft thick downstream from Victorville and downstream portions of the floodplain aquifer within the Mojave Valley. Groundwater in the Mojave River and Morongo areas was generally oxic and alkaline (pH≥7.5). Maximum concentrations of arsenic, hexavalent chromium [Cr(VI)], uranium, and vanadium in water from as many as 498 wells sampled between 2000 and 2018 were 360, 140, 1,470, and 690 micrograms per liter (μg/L), respectively. Water from 22 percent of sampled wells exceeded the U.S. Environmental Protection Agency (EPA) maximum contaminant level (MCL) for arsenic of 10 μg/L, with arsenic concentrations commonly exceeding the MCL in water from wells east of Barstow, deep wells in the Victorville fan, and in suboxic or reduced groundwater within the floodplain aquifer. Water from about 1 percent of sampled wells had Cr(VI) concentrations greater than the California MCL for total chromium of 50 μg/L, whereas 13 percent of sampled wells had Cr(VI) concentrations greater than the former California MCL of 10 μg/L. Hexavalent chromium concentrations were highest in water from wells in the Sheep Creek alluvial fan, eroded from mafic rock in the San Gabriel Mountains, although Cr(VI) concentrations greater than the former California MCL also were present elsewhere in the study area where mafic materials or older groundwater were present. Water from about 9 percent of sampled wells exceeded the EPA MCL for uranium of 30 μg/L, with concentrations exceeding the MCL commonly associated with irrigation return from agricultural land overlying the floodplain aquifer. Water from about 7 percent of sampled wells had vanadium concentrations greater than the California notification level of 50 μg/L; most of these wells were in the Victorville fan within the Mojave River area. In general, arsenic concentrations were higher in suboxic or reduced water; chromium concentrations were higher in oxic, alkaline (pH≥7.5) water; uranium concentrations were higher in circumneutral to slightly alkaline water (pH≤7.4); and vanadium concentrations were higher in highly alkaline (pH≥8.0) water, independent of redox status. Concentrations within geologic source terranes are not the sole factor controlling the concentrations of geogenic elements in groundwater. Differences in mineral weathering, pH-dependent sorption to surface-exchange sites on mineral grains, and aqueous geochemistry (especially redox status and pH) affect geogenic element concentrations in groundwater. Consequently, the relative abundances of arsenic, Cr(VI), uranium, and vanadium in groundwater differ from their relative abundances in the average bulk continental crust and their regional abundances in rock and surficial alluvium within groundwater basins of the western Mojave Desert. Processes that control the concentrations of arsenic, chromium, uranium, and vanadium in groundwater operate at the mineral-grain and aquifer scale. At the mineral-grain scale, sequential chemical extraction data show arsenic and uranium are more available to groundwater (under specific geochemical conditions) than chromium or vanadium, which largely are unavailable within unweathered mineral grains. Additionally, chromium and vanadium form few aqueous complexes and bind tightly with iron minerals within surface coatings on mineral grains making them less available to groundwater, whereas complexation with other dissolved ions enhances the solubility of uranium and, to a lesser extent, arsenic. Complexation also increases the valence (less negative charge) and increases the size of dissolved oxyanions and uranium complexes with bicarbonate and carbonate making them less readily sorbed to aquifer materials. At the aquifer scale, hydrogeology (including isolation of water in aquifers from surface sources of recharge, older groundwater age, and long contact times between groundwater and aquifer materials) combined with geochemical processes (such as silicate weathering) to produce alkaline groundwater. Desorption from sorption sites on the surfaces of mineral grains with increasing pH increases arsenic, chromium, and vanadium concentrations in water from wells and increases Cr(VI) concentrations as long as water remains oxic. Aqueous geochemistry and concentrations of geogenic contaminants also are affected by anthropogenic activities including (1) discharge of treated municipal wastewater, which may change the redox status of groundwater; (2) return from irrigated agriculture, which may alter the chemistry of groundwater and increase the solubility of trace elements such as uranium; and (3) groundwater pumping and subsequent water-level declines, which may change the source of water yielded by wells. The quality of water imported from northern California and infiltrated from ponds for groundwater recharge may be altered by naturally present trace elements, especially uranium in areas of agricultural land use or chromium within mafic alluvium.

California

Critical analysis of world uranium resources

The U.S. Department of Energy, Energy Information Administration (EIA) joined with the U.S. Department of the Interior, U.S. Geological Survey (USGS) to analyze the world uranium supply and demand balance. To evaluate short-term primary supply (0–15 years), the analysis focused on Reasonably Assured Resources (RAR), which are resources projected with a high degree of geologic assurance and considered to be economically feasible to mine. Such resources include uranium resources from mines currently in production as well as resources that are in the stages of feasibility or of being permitted. Sources of secondary supply for uranium, such as stockpiles and reprocessed fuel, were also examined. To evaluate long-term primary supply, estimates of uranium from unconventional and from undiscovered resources were analyzed. At 2010 rates of consumption, uranium resources identified in operating or developing mines would fuel the world nuclear fleet for about 30 years. However, projections currently predict an increase in uranium requirements tied to expansion of nuclear energy worldwide. Under a low-demand scenario, requirements through the period ending in 2035 are about 2.1 million tU. In the low demand case, uranium identified in existing and developing mines is adequate to supply requirements. However, whether or not these identified resources will be developed rapidly enough to provide an uninterrupted fuel supply to expanded nuclear facilities could not be determined. On the basis of a scenario of high demand through 2035, 2.6 million tU is required and identified resources in operating or developing mines is inadequate. Beyond 2035, when requirements could exceed resources in these developing properties, other sources will need to be developed from less well-assured resources, deposits not yet at the prefeasibility stage, resources that are currently subeconomic, secondary sources, undiscovered conventional resources, and unconventional uranium supplies. This report’s analysis of 141 mines that are operating or are being actively developed identifies 2.7 million tU of in-situ uranium resources worldwide, approximately 2.1 million tU recoverable after mining and milling losses were deducted. Sixty-four operating mines report a total of 1.4 million tU of in-situ RAR (about 1 million tU recoverable). Seventy-seven developing mines/production centers report 1.3 million tU in-situ Reasonably Assured Resources (RAR) (about 1.1 million tU recoverable), which have a reasonable chance of producing uranium within 5 years. Most of the production is projected to come from conventional underground or open pit mines as opposed to in-situ leach mines. Production capacity in operating mines is about 76,000 tU/yr, and in developing mines is estimated at greater than 52,000 tU/yr. Production capacity in operating mines should be considered a maximum as mines seldom produce up to licensed capacity due to operational difficulties. In 2010, worldwide mines operated at 70 percent of licensed capacity, and production has never exceeded 89 percent of capacity. The capacity in developing mines is not always reported. In this study 35 percent of developing mines did not report a target licensed capacity, so estimates of future capacity may be too low. The Organisation for Economic Co-operation and Development’s Nuclear Energy Agency (NEA) and International Atomic Energy Agency (IAEA) estimate an additional 1.4 million tU economically recoverable resources, beyond that identified in operating or developing mines identified in this report. As well, 0.5 million tU in subeconomic resources, and 2.3 million tU in the geologically less certain inferred category are identified worldwide. These agencies estimate 2.2 million tU in secondary sources such as government and commercial stockpiles and re-enriched uranium tails. They also estimate that unconventional uranium supplies (uraniferous phosphate and black shale deposits) may contain up to 7.6 million tU. Although unconventional resources are currently subeconomic, the improvement of extraction techniques or the production of coproducts may make extraction of uranium from these types of deposits profitable. A large undiscovered resource base is reported by these agencies, however this class of resource should be considered speculative and will require intensive exploration programs to adequately define them as mineable. These resources may all contribute to uranium supply that would fuel the world nuclear fleet well beyond that calculated in this report. Production of resources in both operating and developing uranium mines is subject to uncertainties caused by technical, legal, regulatory, and financial challenges that combined to create long timelines between deposit discovery and mine production. This analysis indicates that mine development is proceeding too slowly to fully meet requirements for an expanded nuclear power reactor fleet in the near future (to 2035), and unless adequate secondary or unconventional resources can be identified, imbalances in supply and demand may occur.

Scientific Investigations Report

Uranium in surface waters and sediments affected by historical mining in the Denver West 1:100,000 Quadrangle, Colorado

Geochemical sampling of 82 stream waters and 87 stream sediments within mountainous areas immediately west of Denver, Colorado, was conducted by the U.S. Geological Survey in October 1994. The primary purpose was to evaluate regionally the effects of geology and past mining on the concentration and distribution of uranium. The study area contains uranium- and thorium-rich bedrock, numerous noneconomic occurrences of uranium minerals, and several uranium deposits of variable size and production history. During the sampling period, local streams had low discharge and were more susceptible to uranium-bearing acid drainage originating from historical mines of base- and precious-metal sulfides. Results indicated that the spatial distribution of Precambrian granites and metamorphic rocks strongly influences the concentration of uranium in stream sediments. Within-stream transport increases the dispersion of uranium- and thorium rich mineral grains derived primarily from granitic source rocks. Dissolved uranium occurs predominantly as uranyl carbonate complexes, and concentrations ranged from less than 1 to 65 micrograms per liter. Most values were less than 5 micrograms per liter, which is less than the current drinking water standard of 30 micrograms per liter and much less than locally applied aquatic-life toxicity standards of several hundred micrograms per liter. In local streams that are affected by uranium-bearing acid mine drainage, dissolved uranium is moderated by dilution and sorptive uptake by stream sediments. Sorbents include mineral alteration products and chemical precipitates of iron- and aluminum-oxyhydroxides, which form where acid drainage enters streams and is neutralized. Suspended uranium is relatively abundant in some stream segments affected by nearby acid drainage, which likely represents mobilization of these chemical precipitates. The 234U/238U activity ratio of acid drainage (0.95-1.0) is distinct from that of local surface waters (more than 1.05), and this distinctive isotopic composition may be preserved in iron-oxyhydroxide precipitates of acid drainage origin. The study area includes a particularly large vein-type uranium deposit (Schwartzwalder mine) with past uranium production. Stream water and sediment collected downstream from the mine's surface operations have locally anomalous concentrations of uranium. Fine-grained sediments downstream from the mine contain rare minute particles (10-20 micrometers) of uraninite, which is unstable in a stream environment and thus probably of recent origin related to mining. Additional rare particles of very fine grained (less than 5 micrometer) barite likely entered the stream as discharge from settling ponds in which barite precipitation was formerly used to scavenge dissolved radium from mine effluent.

Colorado

Uranium-bearing lignite in southwestern North Dakota

Uranium-bearing lignite was mapped and sampled in the Bullion Butte, Sentinel Butte, HT Butte, and Chalky Buttes areas in southwestern North Dakota. The uraniferous lignite occurs at several stratigraphic positions in the Sentinel Butte member of the Fort Union formation of Paleocene age. A total of 261 samples were collected for uranium analysis from 85 localities, Lignite contained as much as 0.045 percent uranium, 10.0 percent ash, and 0.45 percent uranium in the ash was found although the average is lower. Inferred reserves for the four areas examined are estimated to be about 27 million tons of lignite in beds about 2 feet thick and containing more than 3000 tons of uranium. The lignite in beds about 2 feet thick and containing more than 3000 tons of uranium. The lignite averages more than 30 percent ash in the surface samples. The principal factor that seems to influence the uranium content of lignite beds is their stratigraphic position below the overlying rocks of the White River group of Oligocene age. All of the uranium-bearing beds closely underlie the base of the White River group. Although this relationship seems to be the controlling factor, the relative concentration of uranium may be modified by other conditions. Beds enclosed in permeable rocks are more uraniferous than beds in impermeable rocks, and thin beds have higher content of uranium than thick beds. In addition, thick lignite beds commonly have a top=preferential distribution of uranium. These and other factors suggest that the uranium is secondary and this it was introduced by ground water which had leached uranium from volcanic ash in the overlying rocks of the White River group. It is thought that the uranium is held in the lignite as part of a metallo-organic compound.

Montana;North Dakota;South Dakota

Uranium-bearing coal in the central part of the Great Divide basin, Sweetwater County, Wyoming

Field work leading to this report was done by the U.S. Geological Survey for the Division of Raw Materials of the U.S. Atomic Energy Commission. Nearly 24 townships were mapped in the central part of the Great Divide Basin, Sweetwater County, Wyoming. Fourteen of these townships contain outcrops of uranium-bearing coal. Thirty coal beds were mapped, but only seven of them have uranium-bearing coal reserves as defined in this report. Coal beds 2.5 or more feet thick are considered in calculating coal reserves, and of these, only beds containing 0.003 or more percent uranium are considered in calculating reserves of uranium in coal. Reserves of uranium in coal ash include those beds 2.5 or more feet thick that contain 0.015 or more percent uranium in coal ash. Measured and indicated coal reserves total about 700,000,000 short tons which contain about 2,600 short tons of uranium in the coal, or about 2,400 short tons of uranium in the coal ash. Strippable reserves, defined as reserves in beds beneath 60 or less feet of overburden, are about 250,000,000 short tons of coal containing about 1,100 short tons of uranium in coal, or about 600 tons of uranium in coal ash. The thickest coal beds underlie a relatively narrow belt that trends northwest and coincides approximately with the axis of the Red Desert syncline. The coal beds contain the most uranium on the east flank of the syncline near the southwesternmost edge of the Battle Spring formation (new). This formation is of early and middle Eocene age and consists predominantly of very coarse-grained arkosic sandstone which is highly permeable. It intertongues southwestward with the Tess permeable Green River and Wasatch formations. The Green River formation consists from youngest to oldest of the Morrow Creek and Laney shale members and the Tipton and Luman (new) tongues. The Wasatch formation interfingers with the Green River formation and consists from youngest to oldest of the Cathedral Bluffs, Niland, and Red Desert tongues. The latter two are here recognized for the first time and contain all the coal beds in the Wasatch formation. The Morrow Creek member of the Green River formation is of middle Eocene age. The Laney member and Cathedral Bluffs tongue of the Green River and Wasatch formation, respectively intertongue and are in part equivalent, and are of early or middle Eocene age. The other units are of early Eocene age. A broad gentle arch which is either the eastern extension of the Wamsutter arch, or a separate arch en echelon to it, separates the Washakie Basin the southeastern part of the map area from the Red Desert syncline in the northeastern part. The Red Desert syncline plunges gently northwest into the nearly circular structural Niland basin. The south flank of the Wamsutter(?) arch dips southeastward at an average rate of about 230 feet per mile. The northern flank of the arch dips northeastward at an average rate of about 140 feet per mile. North of the Niland basin, the structure is more complex and is dominated by a northwestwardtrending graben which parallels and includes the Cyclone Rim in the northern part of die map area. Schroeckingerite deposits in the northeastern part of the map area lie within this graben in a sequence of arkosic sandstone and clay shale stratigraphically equivalent to the lower part of the Cathedral Bluffs tongue of the Wasatch formation and to the uppermost part of the Tipton tongue of the Green River formation. Weakly radioactive tuffaceous sandstone beds of the Browns Park formation that probably once blanketed the entire Great Divide Basin are preserved a short distance north and northwest of the schroeckingerite deposits. The geologic settings of the schroeckingerite and uranium-bearing coal are similar and their source of uranium is probably the same. The uranium probably was leached from tuffaceous beds in the Browns Park formation and carried to its present site of deposition by groundwater whose circulation was guided by structure and changes in facies.

Wyoming

Uranium Sequestration During Biostimulated Reduction and In Response to the Return of Oxic Conditions In Shallow Aquifers

A proposed approach for groundwater remediation of uranium contamination is to generate reducing conditions by stimulating the growth of microbial populations through injection of electron donor compounds into the subsurface. Sufficiently reducing conditions will result in reduction of soluble hexavalent uranium, U(VI), and precipitation of the less soluble +4 oxidation state uranium, U(IV). This process is termed biostimulated reduction. A key issue in the remediation of uranium (U) contamination in aquifers by biostimulated reduction is the long term stability of the sequestered uranium. Three flow-through column experiments using aquifer sediment were used to evaluate the remobilization of bioreduced U sequestered under conditions in which biostimulation extended well into sulfate reduction to enhance precipitation of reduced sulfur phases such as iron sulfides. One column received added ferrous iron, Fe(II), increasing production of iron sulfides, to test their effect on remobilization of the sequestered uranium, either by serving as a redox buffer by competing for dissolved oxygen, or by armoring the reduced uranium. During biostimulation of the ambient microbial population with acetate, dissolved uranium was lowered by a factor of 2.5 or more with continued removal for over 110 days of biostimulation, well after the onset of sulfate reduction at ~30 days. Sequestered uranium was essentially all U(IV) resulting from the formation of nano-particulate uraninite that coated sediment grains to a thickness of a few 10’s of microns, sometimes in association with S and Fe. A multicomponent biogeochemical reactive transport model simulation of column effluents during biostimulation was generally able to describe the acetate oxidation, iron, sulfate, and uranium reduction for all three columns using parameters derived from simulations of field scale biostimulation experiments. Columns were eluted with artificial groundwater at equilibrium with atmospheric oxygen to simulate the upper limit of dissolved oxygen in recharge water. Overall about 9% of total uranium removed from solution during biostimulation was remobilized. Release of U during oxic elution was a continuous process over 140 days with dissolved uranium concentrations about 0.2 and 0.8 aM for columns with and without ferrous iron addition, respectively. Uranium remaining on the sediment was in the reduced form. The prolonged period of biostimulation and concomitant sulfate reduction appears to limit the rate of U(IV) oxidative remobilization in contrast to a large release observed for columns in previous studies that did not undergo sulfate reduction. Although continued sulfate reduction may cause decreased permeability from precipitation of iron sulfide, the greater apparent stability of the sequestered U(IV) provided by the sustained biostimulation should be considered in design of field scale remediation efforts. Remobilization of uranium following biostimulated reduction should be tested further at the field scale.

Report

Factors controlling localization of uranium deposits in the Dakota Sandstone, Gallup and Ambrosia Lake mining districts, McKinley County, New Mexico

Geologic studies were made at all of the uranium mines and prospects in the Dakota Sandstone of Early(?) and Late Cretaceous age in the Gallup mining district, McKinley County, New Mexico. Dakota mines in the adjacent Ambrosia Lake mining district were visited briefly for comparative purposes. Mines in the eastern part of the Gallup district, and in the Ambrosia Lake district, are on the Chaco slope of the southern San Juan Basin in strata which dip gently northward toward the central part of the basin. Mines in the western part of the Gallup district are along the Gallup hogback (Nutria monocline) in strata which dip steeply westward into the Gallup sag. Geologic factors which controlled formation of the uranium deposits in the Dakota Sandstone are: (1) a source of uranium, believed to be uranium deposits of the underlying Morrison Formation of Late Jurassic age; (2) the accessibility to the Dakota of uranium-bearing solutions from the Morrison; (3) the presence in the Dakota of permeable sandstone beds overlain by impermeable carbonaceous shale beds; and (4) the occurrence within the permeable Dakota sandstone beds of carbonaceous reducing material as bedding-plane laminae, or as pockets of carbonaceous trash. Most of the Dakota uranium deposits are found in the lower part of the formation in marginal-marine distributary-channel sandstones which were deposited in the backshore environment. However, the Hogback no. 4 (Hyde) Mine (Gallup district) occurs in sandy paludal shale of the backshore environment, and another deposit, the Silver Spur (Ambrosia Lake district), is found in what is interpreted to be a massive beach or barrier-bar sandstone of the foreshore environment in the upper part of the Dakota. The sedimentary depositional environment most favorable for the accumulation of uranium is that of backshore areas lateral to main distributary channels, where levee, splay, and some distributary-channel sandstones intertongue with gray carbonaceous shales and siltstones of the well-drained swamp environment. Deposits of black carbonaceous shale which were formed in the poorly drained swamp deposits of the interfluve area are not favorable host rocks for uranium. The depositional energy levels of the various environments in which the sandstone and shale beds of the Dakota were deposited govern the relative favorability of the strata as uranium host rocks. In the report area, uranium usually occurs in carbonaceous sandstone deposited under low- to medium-energy fluvial conditions within distributary channels. A prerequisite, however, is that such sandstone be overlain by impermeable carbonaceous shale beds. Low- to medium-energy fluvial conditions result in the deposition of sandstone beds having detrital carbonaceous material distributed in laminae or in trash pockets on bedding planes. The carbonaceous laminae and trash pockets provide the necessary reductant to cause precipitation of uranium from solution. High-energy fluvial conditions result in the deposition of sandstones having little or no carbonaceous material included to provide a reductant. Very low energy swampy conditions result in carbonaceous shale deposits, which are generally barren of uranium because of their relative impermeability to migrating uranium-bearing solutions.

Open-File Report

The discovery and character of Pleistocene calcrete uranium deposits in the Southern High Plains of west Texas, United States

This report describes the discovery and geology of two near-surface uranium deposits within calcareous lacustrine strata of Pleistocene age in west Texas, United States. Calcrete uranium deposits have not been previously reported in the United States. The west Texas uranium deposits share characteristics with some calcrete uranium deposits in Western Australia—uranium-vanadium minerals hosted by nonpedogenic calcretes deposited in saline lacustrine environments. In the mid-1970s, Kerr-McGee Corporation conducted a regional uranium exploration program in the Southern High Plains province of the United States, which led to the discovery of two shallow uranium deposits (that were not publicly reported). With extensive drilling, Kerr-McGee delineated one deposit of about 2.1 million metric tons of ore with an average grade of 0.037 percent U 3 O 8 and another deposit of about 0.93 million metric tons of ore averaging 0.047 percent U 3 O 8 . The west-Texas calcrete uranium-vanadium deposits occur in calcareous, fine-grained sediments interpreted to be deposited in saline lakes formed during dry interglacial periods of the Pleistocene. The lakes were associated with drainages upstream of a large Pleistocene lake. Age determinations of tephra in strata adjacent to one deposit indicate the host strata is middle Pleistocene in age. Examination of the uranium-vanadium mineralization by scanning-electron microscopy indicated at least two generations of uranium-vanadium deposition in the lacustrine strata identified as carnotite and a strontium-uranium-vanadium mineral. Preliminary uranium-series results indicate a two-component system in the host calcrete, with early lacustrine carbonate that was deposited (or recrystallized) about 190 kilo-annum, followed much later by carnotite-rich crusts and strontium-uranium-vanadium mineralization in the Holocene (about 5 kilo-annum). Differences in initial 234 U/ 238 U activity ratios indicate two separate, distinct fluid sources.

Texas

The roles of organic matter in the formation of uranium deposits in sedimentary rocks

Because reduced uranium species have a much smaller solubility than oxidized uranium species and because of the strong association of organic matter (a powerful reductant) with many uranium ores, reduction has long been considered to be the precipitation mechanism for many types of uranium deposits. Organic matter may also be involved in the alterations in and around tabular uranium deposits, including dolomite precipitation, formation of silicified layers, iron-titanium oxide destruction, dissolution of quartz grains, and precipitation of clay minerals. The diagenetic processes that produced these alterations also consumed organic matter. Consequently, those tabular deposits that underwent the more advanced stages of diagenesis, including methanogenesis and organic acid generation, display the greatest range of alterations and contain the smallest amount of organic matter. Because of certain similarities between tabular uranium deposits and Precambrian unconformity-related deposits, some of the same processes might have been involved in the genesis of Precambrian unconformity-related deposits. Hydrologic studies place important constraints on genetic models of various types of uranium deposits. In roll-front deposits, oxidized waters carried uranium to reductants (organic matter and pyrite derived from sulfate reduction by organic matter). After these reductants were oxidized at any point in the host sandstone, uranium minerals were reoxidized and transported further down the flow path to react with additional reductants. In this manner, the uranium ore migrated through the sandstone at a rate slower than the mineralizing ground water. In the case of tabular uranium deposits, the recharge of surface water into the ground water during flooding of lakes carried soluble humic material to the water table or to an interface where humate precipitated in tabular layers. These humate layers then established the chemical conditions for mineralization and related alterations. In the case of Precambrian unconformity-related deposits, free thermal convection in the thick sandstones overlying the basement rocks carried uranium to concentrations of organic matter in the basement rocks.

Ore Geology Reviews

Uraniferous opal, Virgin Valley, Nevada: Conditions of formation and implications for uranium exploration

Uraniferous, fluorescent opal, which occurs in tuffaceous sedimentary rocks at Virgin Valley, Nevada, records the temperature and composition of uranium-rich solutions as well as the time of uranium-silica coprecipitation. Results are integrated with previous geologic and geochronologic data for the area to produce a model for uranium mobility that may be used to explore for uranium deposits in similar geologic settings. Uraniferous opal occurs as replacements of diatomite, or silicic air-fall ash layers in tuffaceous lakebeds of the Virgin Valley Formation (Miocene) of Merriam (1907). Fission-track radiography shows uranium to be homogeneously dispersed throughout the opal structure, suggesting coprecipitation of dissolved uranium and silica gel. Fluid inclusions preserved within opal replacements of diatomite have homogenization temperatures in the epithermal range and are of low salinity. Four samples of opal from one locality all have U-Pb apparent ages which suggest uraniferous opal precipitation in late Pliocene time. These ages correspond to a period of local, normal faulting, and highangle faults may have served as vertical conduits for transport of deep, thermalized ground water to shallower levels. Lateral migration of rising solutions occurred at intersections of faults with permeable strata. Silica and some uranium were dissolved from silica-rich host strata of 5–20 ppm original uranium content and reprecipitated as the solutions cooled. The model predicts that in similar geologic settings, ore-grade concentrations of uranium will occur in permeable strata that intersect high-angle faults and that contain uranium source rocks as well as efficient reductant traps for uranium. In the absence of sufficient quantities of reductant materials, uranium will be flushed from the system or will accumulate in low-grade disseminated hosts such as uraniferous opal.

Nevada

Uranium(VI) attenuation in a carbonate-bearing oxic alluvial aquifer

Uranium minerals are commonly found in soils and sediment across the United States at an average concentration of 2–4 mg/kg. Uranium occurs in the environment primarily in two forms, the oxidized, mostly soluble uranium(VI) form, or the reduced, sparingly soluble reduced uranium(IV) form. Here we describe subsurface geochemical conditions that result in low uranium concentrations in an alluvial aquifer with naturally occurring uranium in soils and sediments in the presence of complexing ligands under oxidizing conditions. Groundwater was saturated with respect to calcite and contained calcium (78–90 mg/L) with elevated levels of carbonate alkalinity (291–416 mg/L as HCO 3 − ). X-ray adsorption near edge structure (XANES) spectroscopy identified that sediment-associated uranium was oxidized as a uranium(VI) form (85%). Calcite was the predominant mineral by mass in the ultrafine fraction in uranium-bearing sediments (>16 mg/kg). Groundwater geochemical modeling indicated calcite and/or a calcium-uranyl-carbonate mineral such as liebigite in equilibrium with groundwater. The δ 13 C (0.57‰ ± 0.15‰) was indicative of abiotic carbonate deposition. Thus, solid-phase uranium(VI) associated with carbonate is likely maintaining uranium(VI) groundwater levels below the maximum contaminant level (MCL; 30 µg/L), presenting a deposition mechanism for uranium attenuation rather than solely a means of mobilization.

Nebraska

Reconnaissance of uranium and copper deposits in parts of New Mexico, Colorado, Utah, Idaho, and Wyoming

Because of the common association of uranium and copper in several of the commercial uranium deposits in the Colorado Plateau Province, a reconnaissance was made of several known deposits of copper disseminated through sandstone to determine whether they might be a source of uranium. In order to obtain more information regarding the relationship between copper, uranium and carbonaceous materials, some of the uraniferious asphaltrite deposits in the Shinarump conglomerate along the west flank of the San Rafael Swell were also investigated briefly. During this reconnaissance 18 deposits were examined in New Mexico, eight in Utah, two in Idaho, and one each in Wyoming and Colorado. No uranium deposits of commercial grade are associated with the copper deposits that were examined. The uraniferous asphaltites in the Shinarump conglomerate of Triassic age on the west flank of the San Rafael Swell, however, are promising from the standpoint of commercial uranium production. Spectrographic analyses of crude oil, asphalt, and bituminous shales show a rather consistent suite of trace metals including vanadium, nickel, copper, cobalt, chromium, lead zinc, and molybdenum. The similarity of the metal assemblage, including uranium of the San Rafael Swell asphaltites, to the metal assemblage in crude oil and other bituminous materials suggests that these metals were concentrated in the asphaltites from petroleum. However, the hypothesis that uranium minerals were already present before the hydrocarbons were introduced and that some sort of replacement or uranium minerals by carbon compounds was effected after the petroleum migrated into the uranium deposit should not be disregarded. The widespread association of uranium with asphaltic material suggests that it also may have been concentrated by some agency connected with the formation of petroleum. The problem of the association of uranium and other trace metals with hydrocarbons should be studied further both in the field and in the laboratory.

Colorado;Idaho;New Mexico;Utah;Wyoming

The copper and uranium deposits of the Coyote district, Mora County, New Mexico

The copper and uranium-vanadium deposits of the Coyote district, Mora County, N. Mec, are confined to the lower 2,000 feet of the Sangre de Gristo formation of Pennsylvanian and Permian age. A narrow belt of deposits in steeply dipping or overturned rocks extends for 7 miles along Coyote Creek south of Guadalupita. Earlier studies showed that the copper deposits contained uranium, but both the reserves and the uranium content of the copper-bearing shale are too low to permit the recovery of uranium. However, small, commercial grade uranium deposits have been discovered in sandstone. Small lenses of copper-bearing carbonaceous shale, siltstone, limestone or sandstone, interbedded with predominantly red rocks, are present at intervals at 12 or more stratigraphic levels. The better deposits, in carbonaceous shale, average about 2 percent copper. The copper content of the other rocks is usually lower, but small concentrations may contain 6 percent copper. The principal copper minerals are chalcocite and malachite. Chalcocite replaces wood and forms nodules that contain small, variable amounts of pyrite, bornite, covellite, and rarely, uraninite. The uranium deposits occur as small closely spaced pockets that are commonly localized by sedimentary structures within one or more fluviatile arkosic sandstone beds near the middle of the formation, particularly" where carbonized wood, clay galls, and rock fragments are abundant. The uraniferous sandstone is commonly stained pink by hematite that probably was introduced with the uranium. The color increases in intensity with the radioactivity. The outcrops of the uranium deposits are typically inconspicuous, but close inspection shows they contain malachite, chalcopyrite, black vanadium minerals of micaceous habit, metatyuyamunite and microscopic grains of an unidentified black uraniferous substance. The proportion of copper, uranium, and vanadium is variable and any metal may be dominant. The metals probably were derived from pre-Cambrian granitic rocks. Copper and minor amounts of uranium were deposited in local stagnant basins by reaction with hydrogen sulfide. and decaying organic material. The uraniferous shales and the copper deposits are believed to be syngenetic, or nearly so, but the uranium deposits in sandstone are epigenetic and probably were deposited from ground waters with a possible hydrothermal admixture. The uranium and vanadium may have been reconcentrated from earlier, low-grade, syngenetic deposits.

New Mexico

Distribution of uranium in the Florida phosphate field

Land-pebble phosphate, hard-rock phosphate, and river-pebble phosphate are the three types of phosphatic rock found in Florida. This report is concerned primarily with the land-pebble deposits, the only type which contains a significant amount of uranium. The most productive part of the land-pebble district is in Polk and Hillsborough Counties, in the west-central part of the Florida peninsula. Phosphate occurs in both the Hawthorn formation of lower middle Miocene age and the Bone Valley formation of Pliocene age. The phosphate in the Bone Valley is generally of higher grade, probably as the result of mechanical reworking and further precipitation during submergence in Pliocene time. In a few places, leached parts of the Hawthorn formation are also of minable grade. , Pleistocene terrace deposits and beach sands unconformably overlie the Bone Valley. In Polk and Hillsborough Counties, the high-grade part of the land-pebble phosphate district, uranium occurs principally in the Bone Valley formation and is concentrated in the upper part of the formation, which has been leached by ground water. The maximum tenor found to date is 0.1 percent uranium. The basal member of the Bone Valley has a maximum grade of .02 percent uranium, and averages about .01 percent uranium. Fresh, unweathered Hawthorn formation has little or no uranium, but leached Hawthorn, rich in P 2 O 5 , contains a maximum of 0.01 percent uranium. The Pleistocene sands have no uranium except where they contain reworked phosphatic material from the Bone Valley formation. South of the high- grade district, in Manatee and Hardee Counties, the Bone Valley, Hawthorn, and Pleistocene formations contain only very minor amounts of uranium. The uranium in the land-pebble deposits was probably syngenetic in origin. Subsequent leaching of soluble material has resulted in residual enrichment of uranium. The uranium seems to be associated with the phosphate mineral.

Florida

Transport and speciation of uranium in groundwater-surface water systems impacted by legacy milling operations

Growing worldwide concern over uranium contamination of groundwater resources has placed an emphasis on understanding uranium transport dynamics and potential toxicity in groundwater-surface water systems. In this study, we utilized novel in-situ sampling methods to establish the location and magnitude of contaminated groundwater entry into a receiving surface water environment, and to investigate the speciation and potential bioavailability of uranium in groundwater and surface water. Streambed temperature mapping successfully identified the location of groundwater entry to the Little Wind River, downgradient from the former Riverton uranium mill site, Wyoming, USA. Diffusive equilibrium in thin-film (DET) samplers further constrained the groundwater plume and established sediment pore water solute concentrations and patterns. In this system, evidence is presented for attenuation of uranium-rich groundwater in the shallow sediments where surface water and groundwater interaction occurs. Surface water grab and DET sampling successfully detected an increase in river uranium concentrations where the groundwater plume enters the Little Wind River; however, concentrations remained below environmental guideline levels. Uranium speciation was investigated using diffusive gradients in thin-film (DGT) samplers and geochemical speciation modelling. Together, these investigations indicate uranium may have limited bioavailability to organisms in the Little Wind River and, possibly, in other similar sites in the western U.S.A. This could be due to ion competition effects or the presence of non- or partially labile uranium complexes. Development of methods to establish the location of contaminated (uranium) groundwater entry to surface water environments, and the potential effects on ecosystems, is crucial to develop both site-specific and general conceptual models of uranium behavior and potential toxicity in affected ground and surface water environments.

Wyoming

Uranium(VI) interactions with mackinawite in the presence and absence of bicarbonate and oxygen

Mackinawite, Fe(II)S, samples loaded with uranium (10 -5 , 10 -4 , and 10 -3 mol U/g FeS) at pH 5, 7, and 9, were characterized using X-ray absorption spectroscopy and X-ray diffraction to determine the effects of pH, bicarbonate, and oxidation on uptake. Under anoxic conditions, a 5 g/L suspension of mackinawite lowered 5 × 10 -5 M uranium(VI) to below 30 ppb (1.26 × 10 -7 M) U. Between 82 and 88% of the uranium removed from solution by mackinawite was U(IV) and was nearly completely reduced to U(IV) when 0.012 M bicarbonate was added. Near-neighbor coordination consisting of uranium–oxygen and uranium-uranium distances indicates the formation of uraninite in the presence and absence of bicarbonate, suggesting reductive precipitation as the dominant removal mechanism. Following equilibration in air, mackinawite was oxidized to mainly goethite and sulfur and about 76% of U(IV) was reoxidized to U(VI) with coordination of uranium to axial and equatorial oxygen, similar to uranyl. Additionally, uranium-iron distances, typical of coprecipitation of uranium with iron oxides, and uranium-sulfur distances indicating bidentate coordination of U(VI) to sulfate were evident. The affinity of mackinawite and its oxidation products for U(VI) provides impetus for further study of mackinawite as a potential reactive medium for remediation of uranium-contaminated water.

Environmental Science & Technology

Isotopic fractionation of uranium in sandstone

Relatively unoxidized black uranium ores from sandstone deposits in the western United States show deviations in the uranium-235 to uranium-234 ratio throughout a range from 40 percent excess uranium-234 to 40 percent deficient uranium-234 with respect to a reference uranium-235 to uranium-234 ratio. The deficient uranium-234 is leached preferentially to uranium-238 and the excess uranium-234 is believed to result from deposition of uranium-234 enriched in solutions from leached deposits.

Science