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A preliminary report on the rapid fluorimetric determination of uranium in low-grade ores

A simple and very rapid fluorimetric procedure is described for the determination of uranium in low-grade shale and phosphate ores. The best working range is from 0.001 to about 0.04 percent U. The procedure employs batch extraction of uranium nitrate by ethyl acetate, using aluminum nitrate as the salting agent, prior to the visual fluorimetric estimation. The procedure is especially designed to save reagents; only 9.5 g of aluminum nitrate and 10 ml of ethyl acetate being used for one analysis. The solution of the sample by means of a fusion with NaOH-NaNO 3 flux is rapid. After fusion the sample is immediately extracted without removing silica and other hydrolytic precipitates. Aluminum nitrate very effectively ties up fluoride and phosphate, thus eliminating steps required for their removal.

Trace Elements Investigations

Uranium deposits at Shinarump Mesa and some adjacent areas in the Temple Mountain district, Emery County, Utah

Deposits of uraniferous hydrocarbons are associated with carnotite in the Shinarump conglomerate of Triassic age at Shinarump Mesa and adjacent areas of the Temple Mountain district in the San Rafael Swell of Emery County, Utah. The irregular ore bodies of carnotite-bearing sandstone are genetically related to lenticular uraniferous ore bodies containing disseminated asphaltitic and humic hydrocarbon in permeable sandstones and were localized indirectly by sedimentary controls. Nearly non-uraniferous bitumen commonly permeates the sandstones in the Shinarump conglomerate and the underlying Moekopi formation in the area. The ore deposits at Temple Mountain have been altered locally by hydrothermal solutions, and in other deposits throughout the area carnotite has been transported by ground and surface water. Uraniferous asphaltite is thought to be the non-volatile residue of an original weakly uraniferous crude oil that migrated into the San Rafael anticline; the ore metals concentrated in the asphaltite as the oil was devolatilized and polymerized. Carnotite is thought to have formed from the asphaltite by ground water leaching. It is concluded that additional study of the genesis of the asphaltitic uranium ores in the San Rafael Swell, of the processes by which the hydrocarbons interact and are modified (such as heat, polymerization, and hydrogenation under the influence of alpha-ray bombardment), of petroleum source beds, and of volcanic intrusive rocks of Tertiary age are of fundamental importance in the continuing study of the uranium deposits on the Colorado Plateau.

Utah

Uranium minerals in Oligocene gypsum near Chadron, Dawes County, Nebraska

Carnotite, sabugalite [HAI(UO 2 ) 4 (PO 4 ) 4 • 16H 2 O] and autunite occur in the basal 25 feet of a 270-foot sequence of nonmarine bedded gypsum and gypsiferous clay in the Brule formation of Oligocene age about 12 miles northeast of Chadron in northeastern Dawes County, Nebraska. Uranium minerals are visible at only two localities and are associated with carbonaceous matter. Elsewhere the basal 25 feet of the gypsum sequence is interbedded with carbonate rocks and is weakly but persistently uraniferous. Uranium probably was emplaced from above by uranyl solutions rich in sulfate.

Nebraska

Machine for preparing phosphors for the fluorimetric determination of uranium

The time saved by use of a machine for preparing many phosphors at one time increases the rate of productivity of the fluorimetric method for determining uranium. The machine prepares 18 phosphors at a time and eliminates the tedious and time-consuming step of preparing them by hand, while improving the precision of the method in some localities. The machine consists of a ring burner over which the platinum dishes, containing uranium and flux, are rotated. By placing the machine in an inclined position the molten flux comes into contact with all surfaces within th dish as the dishes rotate over the flame. Precision is improved because the heating and cooling conditions are the same for each of the 18 phosphors in one run as well as for successive runs.

Trace Elements Investigations

Behavior of Colorado Plateau uranium minerals during oxidation

Uranium occurs as U(VI) and U(IV) in minerals of the Colorado Plateau ores. The number of species containing U(VI) is large, but only two U(IV) minerals are known from the Plateau: uraninite, and oxide, and coffinite, a hydroxy-silicate. These oxidize to yield U(VI) before reacting significantly with other mineral constituents. Crystal-structure analysis has shown that U(VI) invariable occurs as uranyl ion, UO 2 +2 . Uranyl ion may form complex carbonate or sulfate ions with resulting soluble compounds, but only in the absence of quinquevalent vanadium, arsenic, or phosphorous. In the presence of these elements in the +5 valence state, the uranyl ion is fixed in insoluble layer compounds formed by union of uranyl ion with orthovanadate, orthophosphate, or orthoarsenate. Under favorable conditions UO 2 +2 may react to form the relatively insoluble rutherfordine, UO 2 CO 3 , or hydrated uranyl hydroxides. These are rarely found on the Colorado Plateau as opposed to their excellent development in other uraniferous areas, a condition which is apparently related to the semiarid climate and low water table of the Plateau. Uranium may also be fixed as uranyl silicate, but little is known about minerals of this kind. In the present study emphasis has been placed on a detailing of the chemical and crystal structural changes which occur in the oxidation paragenetic sequence.

Utah

Summary of reconnaissance for uranium in Alaska, 1955

Reconnaissance for uranium in Alaska during 1955 included airborne radiometric traverses, examination of radioactivity anomalies found during the airborne traverses, examination of prospector leads, and examination of areas that seems geologically favorable for the occurrence of uranium. The airborne radiometric traverses in central Alaska revealed 33 anomalies considered worth examining. The ground examinations of a few of these anomalies indicated that they were due to radiation of from accessory minerals in intrusive granitic rocks. The examination of prospector leads revealed several radioactivity anomalies of interest and one, near Bokan Mountain on prince of Wales Island, of possible commercial importance.

Alaska

Results of reconnaissance for uranium in nonmarine carbonaceous rocks in parts of California, Idaho, Nevada, Oregon, Utah, and Washington during 1951 and 1952

Nonmarine carbonaceous rocks, including shales, coal, and peat, were tested at about 3 localities in California, Idaho, Nevada, Oregon, Utah, and Washington. Rocks ranging in age from Carboniferous to Quaternary were examine, although the principal attention was given middle and late Tertiary lignites of the northern part of the Great Basin. Most carbonaceous rocks examined contained essentially no uranium, but lignitic shales in the Goose Creek district, Idaho, a thin carbonaceous shale near Hagerman, Idaho, and a small peat deposit in Davis County, Utah contained more than 0.003 percent uranium.

California;Idaho;Nevada;Oregon;Utah;Washington

Uranium-Bearing Carbonaceous Nodules of Southwestern Oklahoma

Uranium-bearing carbonaceous nodules have been found along the north flank of the Wichita uplift in southwestern Oklahoma. The carbonaceous nodules are black, hard, and predominantly nodular shaped. One specimen, by analyses, was found to contain approximately 42 percent carbon and 3 percent hydrogen. The uranium, vanadium, cobalt, arsenic, nickel, lead and iron contents each range between 1 and 10 percent. It is concluded that the carbonaceous nodules are epigenetic and that the organic and inorganic constituents were derived from, mobile soluttons.

Trace Elements Memorandum

Hydrology and water-quality monitoring considerations, Jackpile uranium mine, northwestern New Mexico

The Jackpile Uranium Mine, which is on the Pueblo of Laguna in northwestern New Mexico, was operated from 1953 to 1980. The mine and facilities have affected 3,141 acres of land, and about 2,656 acres were yet to be reclaimed by late 1980. The intended use of the restored land is stock grazing. Fractured Dakota Sandstone and Mancos Shale of Cretaceous age overlie the Jackpile sandstone and a 200-ft-thick tight mudstone unit of the Brushy Basin Member underlies the Jackpile. The hydraulic conductivity of the Jackpile sandstone probably is about 0.3 ft/day. The small storage coefficients determined from three aquifer tests indicate that the Jackpile sandstone is a confined hydrologic system throughout much of the mine area. Sediment from the Rio Paguate has nearly filled the Paguate Reservoir near Laguna since its construction in 1940. The mean concentrations of uranium, Ra-226, and other trace elements generally were less than permissible limits established in national drinking water regulations or New Mexico State groundwater regulations. No individual surface water samples collected upstream from the mine contained concentrations of Ra-226 in excess of the permissible limits. Ra-226 concentrations in many individual samples collected from the Rio Paguate from near the mouth of the Rio Moquino to the sampling sites along the downstream reach of the Rio Paguate, however, exceeded the recommended permissible concentration of Ra-226 for public drinking water supplies. Concentrations in surface water apparently are changed by groundwater inflow near the confluence of the two streams. The altitude of the water tables in the backfill of the pits will be controlled partly by the water level in the Rio Paguate. Other factors controlling the altitudes of the water tables are the recharge rate to the backfill and the hydraulic conductivities of the backfill, alluvium, Jackpile sandstone, and mudstone unit of the Brushy Basin Member. After reclamation, most of the shallow groundwater probably will discharge to the natural stream channels draining the mine area. Groundwater quality may be monitored as: (1) ' Limited monitoring, ' in which only the change in water quality is determined as the groundwater flows from the mine; or (2) ' thorough monitoring, ' in which specific sources of possible contaminants are described. (Author 's Abstract)

Water-Resources Investigations Report

Geoenvironmental model for roll-type uranium deposits in the Texas Gulf Coast

Geoenvironmental models were formulated by the U.S. Geological Survey in the 1990s to describe potential environmental effects of extracting different types of ore deposits in different geologic and climatic regions. This paper presents a geoenvironmental model for roll-front (roll-type) uranium deposits in the Texas Coastal Plain. The model reviews descriptive and quantitative information derived from environmental studies and existing databases to depict existing conditions and potential environmental concerns associated with mining this deposit type. This geoenvironmental model describes how features of the deposits including host rock; ore and gangue mineralogy; geologic, hydrologic, and climatic settings; and mining methods (legacy open-pit and in situ recovery [ISR]) influence potential environmental effects from mining. Element concentrations in soil and water are compared to regulatory thresholds to depict ambient surface water and groundwater conditions. Although most open-pit operations in this region have been reclaimed, concerns remain about groundwater quality at three of the four former mills that supported former open-pit mines and are undergoing closure activities. The primary environmental concerns with ISR mining are (1) radon gas at active ISR operations, (2) radiation or contaminant leakage during production and transport of ISR resin or yellowcake, (3) uranium excursions into groundwater surrounding active ISR operations, and (4) contamination of groundwater after ISR mining. Although existing regulations attempt to address these concerns, some problems remain. Researchers suggest that reactive transport modeling and a better understanding of geology, stratigraphy, and geochemistry of ISR production areas could minimize excursions into surrounding aquifers and improve results of groundwater restoration.

Texas

Mapping abandoned uranium mine features using Worldview-3 imagery in portions of Karnes, Atascosa and Live Oak Counties, Texas

Worldview-3 (WV3) 16-band multispectral data were used to map exposed bedrock and mine waste piles associated with legacy open-pit mining of sandstone-hosted roll-front uranium deposits along the South Texas Coastal Plain. We used the “spectral hourglass” approach to extract spectral endmembers representative of these features from the image. This approach first requires calibrating the imagery to reflectance, then masking for vegetation, followed by spatial and spectral data reduction using a principal component analysis-based procedure that reduces noise and identifies homogeneous targets which are “pure” enough to be considered spectral endmembers. In this case, we used a single WV3 image which covered an ~11.5 km by ~19.5 km area of Karnes, Atascosa and Live Oak Counties, underlain by mined rocks from the Jackson Group and Catahoula Formation. Up to 58 spectral endmembers were identified using a further multi-dimensional class segregation method and were used as inputs for spectral angle mapper (SAM) classification. SAM classification resulted in the identification of at least 117 mine- and mine waste-related features, most of which were previously unknown. Class similarity was further evaluated, and the dominant minerals in each class were identified by comparison to spectral libraries and measured samples of actual Jackson Group uranium host rocks. Redundant classes were eliminated, and SAM was run a second time using a reduced set of 23 endmembers, which were found to map these same features as effectively as using the full 58 set of endmembers, but with significantly reduced noise and spectral outliers. Our classification results were validated by evaluating detailed scale mapping of three known mine sites (Esse-Spoonamore, Wright-McCrady and Garbysch-Thane) with published ground truth information about the vegetation cover, extent of erosion and exposure of waste pile materials and/or geologic information about host lithology and mineralization. Despite successful demonstration of the utility of WV3 data for inventorying mine features, additional landscape features such as bare agricultural fields and oil and gas drill pads were also identified. The elimination of such features will require combining the spectral classification maps presented in this study with high-quality topographic data. Also, the spectral endmembers identified during the course of this study could be useful for larger-scale mapping efforts using additional well-calibrated WV3 images beyond the coverage of our initial study area.

Texas

Margaritasite: a new mineral of hydrothermal origin from the Pena Blanca uranium district, Mexico.

Margaritasite, (Cs,K,H3O)2(UO2)2V2O8.nH2O (where Cs > K, H3O and n approx 1), a 10.514, b 8.425, c 7.25 A, beta 106.01o, P21/a, Z = 2, is a newly recognized uranium ore mineral named for the Margaritas deposit, Pena Blanca uranium district, Chihuahua, Mexico, at which it was discovered. A Cs-rich analogue of carnotite, margaritasite is the natural equivalent of synthetic Cs-uranyl vanadate (A.M. 43- 799, 50-825). A fine-grained yellow mineral, it is most easily distinguished from carnotite by XRD; X-ray powder patterns (CuKalpha radiation) show that the (001) reflection of margaritasite lies at 12.7o (2theta ), while that of carnotite is found at 13.8o (2theta ). The shift of the (001) reflection in margaritasite reflects the structural changes caused when Cs occupies the sites filled by K in carnotite. Synthesis experiments indicate that margaritasite also differs from carnotite in a higher-T hydrothermal origin. Chemical analyses and XRD data for margaritasite and synthetic Cs- carnotite, and chemical analyses for rocks from Sierra Pena Blanca and vicinity, are tabulated.-J.A.Z.

American Mineralogist

Chloritization and associated alteration at the Jabiluka unconformity-type uranium deposit, Northern Territory, Australia

Jabiluka is the largest of four known uncomformity-type uranium deposits that are hosted by brecciated and altered metasedimentary rocks in the Pine Creek geosyncline, Northern Territory, Australia. The alteration zone at Jabiluka is dominated by chlorite, but also contains white mica, tourmaline and apatite; hematite is present, but only in minor amounts. Added quartz is mainly restricted to fractures and breccias. Chlorite, which formed during episodic fluid movement, partly to totally replaced all pre-existing minerals. Chloritized rocks are enriched in Mg, and depleted in K, Ca, Na and Si. Five types of chlorite are optically and chemically distinguishable in the rocks at Jabiluka. Chloritization is proposed as a mechanism that lowered the pH of the circulating fluid, and also caused significant loss of silica from the altered rocks. The proposed constraints on alteration, and presumably on at least part of the uranium mineralization, neither require nor preclude the existence of the unconformity as necessary for the formation of ore.

Canadian Mineralogist

Uranium-series dating of secondary carbonates near Yucca Mountain, Nevada. Applications to tectonic, paleoclimatic, and paleohydrologic problems

Near-surface accumulations of secondary carbonates are common in the soils and sediments of the Yucca Mountain area. These carbonates contain small amounts of uranium that allow dating by the uranium-series disequilibrium method. Preliminary results from the Yucca Mountain area indicate that the U-series methods can (1) identify multiple episodes of tectonic fracturing, (2) provide a chronologic framework for paleoclimatically significant eolian deposits, and (3) place constraints on the probable source of waters from which the carbonates precipitated.

Conference Paper

The chemical evolution and paragenesis of uranium minerals from the ruggles and palermo granitic pegmatites, New Hampshire

A study of the chemical evolution and paragenesis of the uranium minerals at the Palermo No. 1 and Ruggles granitic pegmatites, Grafton County, New Hampshire, revealed four stages of secondary mineralization. A total of eight uranium minerals were identified in the four stages. The first stage is a mixture of uranyl oxide hydroxide-hydrates represented by mineral "A", which surrounds and replaces a uraninite core. The second stage is a carbonate stage found only at the Palermo No. 1 pegmatite, and is represented by rutherfordine. The third stage is represented by uranyl silicates. At the Palermo No. 1 pegmatite, this stage consists of ??-uranophane, and at the Ruggles pegmatite, it consists of soddyite and ??-uranophane. A final fourth stage is a phosphate stage represented by phosphuranylite and meta-autunite I. The first three stages of mineralization developed from hydrothermal and meteoric processes. With dropping temperatures, hydrothermal fluids reached meteoric temperatures and acquired the characteristics of meteoric water. The pH shifted from acidic (pH less than about 6 at 100??C) to alkaline (pH > 7 at 25??C). Since mineral "A" contains hydroxyl and a low amount of molecular water, it probably formed at a temperature greater than 100??C in the acidic environment. After the first stage, the hydrothermal fluids likely reached the temperatures of meteoric water. The initial pH of the meteoric water was acidic (pH less than about 6 at 25??C) and then slowly shifted to alkaline. The mineralizing fluids became oversaturated in CO3, Ca, K, and Si. Uraninite and mineral "A" became unstable and were replaced by rutherfordine and uranyl silicates. The fourth or phosphate stage developed from the introduction of groundwater. The uranyl phosphate minerals precipitated from an acidic fluid (pH < 7 at 25??C) that was oversaturated with Ca, K, U, and P.

Canadian Mineralogist

Resource potential for commodities in addition to Uranium in sandstone-hosted deposits

Sandstone-hosted deposits mined primarily for their uranium content also have been a source of vanadium and modest amounts of copper. Processing of these ores has also recovered small amounts of molybdenum, rhenium, rare earth elements, scandium, and selenium. These deposits share a generally common origin, but variations in the source of metals, composition of ore-forming solutions, and geologic history result in complex variability in deposit composition. This heterogeneity is evident regionally within the same host rock, as well as within districts. Future recovery of elements associated with uranium in these deposits will be strongly dependent on mining and ore-processing methods.

Reviews in Economic Geology

Geology of the Brysch uranium mine, Karnes County, Texas

Approximately 13,700 tons (12,400 tonnes) of oxidized uranium ore, averaging about 0.1 percent U 2 O 8 , was mined during 1966 and 1967 from the lower unit of the Deweesville Sandstone Member of the upper Eocene Whitsett Formation, from depths of 75 to 90 feet (23-27 m). The mine is in the Karnes County uranium area, 3 miles (5 km) east of Falls City, Tex. Meta-autunite, Ca(UO 2 ) 2 (PO 4 ) 2 2-6H 2 O, and meta-tyuyamunite, Ca(UO 2 ) 2 (PO 4 ) 2 3-5H 2 O, were identified in samples of the ore. The host rock is light-colored, medium-grained, well-sorted feldspathic sandstone that contains fossil wood and Ophiomorpha . It also contains clinoptilolite, cristobalite, and montmorillonite that probably formed as alteration products of volcanic grains in the original sediment. The host rock was deposited in a beach environment near or on a delta formed at the mouth of a stream channel oriented roughly normal to the beach. The Deweesville can be traced for many miles on the surface and represents in general the point of maximum transgression in a transgressive-regressive cycle. The upper unit of the Deweesville, which overlies the host rock, is now exposed in the mine and contains, in ascending order, storm-beach, shoreface, beach, and tidal-flat facies. The shape of the ore body suggests that it originated as an unoxidized ore roll. The ore-bearing fluids may have entered through porous fluvial rock extending updip. Plant material, abundant in the original host sediment, probably supplied reductant necessary for the roll formation.

Texas

Pleistocene apparent ages by U-Pb isotope and U-series methods for uranium ore in Dakota Sandstone near Gallup, New Mexico

Radiometric dates of a high-grade uranium ore from the Hogback No. 4 mine in Dakota Sandstone near Gallup, N. Mex., indicate a late Pleistocene age of mineralization. The 206 Pb/ 238 U and 207 Pb/ 235 U apparent ages of about 70 000 yr and 100000 yr, respectively, are discordant, but are in broad agreement with the discordant 230 Th/ 238 U and 231 Pa/ 235 U apparent ages of 130000 yr and 78000 yr, respectively. Although it is not clear how the analyzed sample relates to the main period of mineralization at this mine, these dates are consistent with previous age limits suggested for Dakota Sandstone uranium-ores.

New Mexico