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Thorium reacts with morin in solutions at a pH of 2.0 to yield a single complex that has a thorium:morin ratio of 1:2. The yellow complex has a maximum absorbance at 410 m and is stable for at least 7 hours. The sensitivity of the reaction is such that as little as about 0.2 microgram of ThO 2 in 50 ml can be determined using a light path of 5 cm. An average apparent equilibrium constant of approximately l x 10 6 was found for the reaction. The effects of acidity, alcohol content, morin content, time, age of the morin reagent and temperature of the reaction have been studied as have the effect of some other ions. Zirconium and aluminum interfere seriously and must be absent. The interference from ferric iron is also serious but the effect may be appreciably decreased if hydroxylamine is added to the solution. Relatively large amounts of calcium and lanthanum may be present without causing interference, and these ions can be used as carriers in separations of thorium from other ions. Morin is a suitable reagent for the determination of thorium in pure solutions. If appropriate separations are found for the separation of thorium from other ions, the reaction will be useful for the determination of trace amounts of thorium in complex materials. The information presented in this paper is fundamental to any specific adaptation of the reaction to the analysis of complex materials.
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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.
Reconnaissance examinations for uranium in 22 formations containing black shale were conducted in parts of Montana, North Dakota, Utah, Idaho, and Oregon during 1953. About 150 samples from 80 outcrop localities and 5 oil and gas wells were submitted for uranium determinations. Most of the black shale deposits examined contain less than 0.003 percent uranium; however, thin beds of black shale at the base of the Mississippian system contain 0.005 percent uranium at 2 outcrop localities in southwestern Montana and as much as 0.007 percent uranium in a well in northeastern Montana. An eight-foot bed of phosphatic black shale at the base of the Brazer limestone of Late Mississippian age in Rich County, Utah, contains as much as 0.009 percent uranium. Commercial gamma ray logs of oil and gas wells drilled in Montana and adjacent parts of the Dakotas indicate that locally the Heath shale of Late Mississippian age contains as much as 0.01 percent equivalent uranium, and black shales of Late Cretaceous age contain as much as 0.008 percent equivalent uranium.
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In northwestern South Dakota and adjacent areas uranium-bearing lignite beds occur at many horizons in the Hell Creek formation of late Cretaceous age and the overlying Ludlow, Tongue River, and Sentinel Butte members of the Fort Union formation of Paleocene age. Uranium analyses of 275 surface and auger samples and about 1,000 core samples show that many of the lignite beds contain 0. 005 to 0. 02 percent uranium with concentrations of 0. 05 to 0.10 percent uranium in the lignite ash. Analytical data indicate that the region contains an aggregate of at least 47,500, 000 tons of lignite with an average grade of slightly more than .0. 008 percent containing 3, 900 tons of uranium. Almost a fifth of the estimated reserves are adapted to strip mining and are in beds averaging about 4 feet in thickness. Uranium concentrations of this magnitude in lignite indicate that these deposits upon the development of proper utilization techniques and processes may be an important future source of uranium. Recent discoveries of ore-grade deposits of autunite-bearing lignite and secondary uranium minerals in carbonaceous sandstone at Cave Hills and Slim Buttes indicate that northwestern South Dakota and adjacent areas may containimportant reserves of uranium-ore. The stratigraphic units containing the uraniferous lignite beds have a combined thickness of about 1, 500 feet and are unconformably overlapped by 300 feet or more of tuffaceous sandstone and bentonitic claystone of the White River and Arikaree formations of Oligocene and Miocene age. The stratigraphically highest lignite beds in the local sequence have the greatest concentration of uranium,, and the uranium content is greatest at the top of thick lignite beds, diminishing progressively downward to a vanishing point in their lower parts. Variations in permeability of the rock overlying the mineralized lignite beds seem to be reflected in the intensity of uranium mineralization. Most of the known uranium-bearing lignite deposits in the region are closely overlain by the White River and Arikaree formations. Field evidence indicates that the uranium in the lignite is independent of the age of the formation in which the lignite occurs and that the uranium has been concentrated by downward and laterally moving ground water from the overlying mildly radioactive, tuffaceous rocks. The White River and Arikaree formations have about 1.2 times more uranium than the average sedimentary rock. The uranium content of spring water from these formations is 30 times as great or greater than that of normal ground water. Field relations suggest that the uranium is of secondary origin and has been introduced subsequent to the accumulation and marked regional warping of the lignite beds and associated rocks. During the transportation of the uranium-bearing volcanic materials from their place of origin to the site of deposition in South Dakota, the uranium is believed to have been held as a finely disseminated constituent in volcanic ash. Subsequent release or displacement of the uranium is thought to have resulted from weathering and chemical breakdown, thus freeing and allowing the transportation of the uranium, probably in ionic form, to the lignite by downward and laterally moving groundwaters 0 Gar bonaceous material in the path of these uranium-bearing waters is believed to have acted as a receptor that extracted the uranium as a result of an ion exchange mechanism or by the formation of organo-metallic compounds Geologic factors that seem most significant in controlling the distribution and concentration of uranium in Dakota lignites are as follows: 1) stratlgraphic proximity of the lignite to the base of the White River formation; 2) permeability of the rocks overlying the lignites; 3) adsorptive properties and porosities of the lignitic constituents; 4) present and past position of the groundwater table; and 5) the amount of uranium in the original White River and Arikaree sediments. Individual maps showing the extent, thickness, and variations in mineral content of the important deposits in the Table Mountain, Cave Hills, Slim Buttes, Lodgepole, and Medicine Pole areas are included. Conditions controlling the concentration of uranium are described and their application as guides to finding additional reserves by the presently held concepts are explained and illustrated.
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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.
A botanical sampling program has been completed by the U.S. Geological Survey on La Ventana Mesa, Sandoval County, N. Mex. A uranium-bearing coal in the Allison-Gibson members of the Cretaceous Mesaverde formation crops out in erosional remnants of the mesa.The coal is capped by a well-fractured 65-foot sandstone bed through which roots of a pinyon-juniper forest penetrate. Samples of several hundred branches of trees growing on top of the mesa were collected and analyzed for uranium. The assays ranged from 0.1 part per million to 2.3 ppm uranium in the wood ash. Dead branches, which were found to contain more uranium in the ash than live branches, were sampled where possible. The results have been contoured to indicated probable areas of mineralized coal. Parts of the north butte are recommended as favorable for physical exploration.
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