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By N. S. Dalal, X. Shi

"Electron spin resonance (ESR) spectroscopy has been employed to· examine the role of tetraperoxochromate( V) ions (Cro:-) and other Cr(V) species in the generation of hydroxyl (OH) radicals in the reaction of Cr(VI) with H2O 2 in biological media. In contrast to earlier suggestions, the present ESR studies using crystalline K3CrO8 as a source of Cro:- show that decomposition of Cro:- in water or in H2O 2 does not generate significant amounts of OH radicals. Addition of NADH to a solution containing Cro:- yields a Cr(V)-NADH complex, which readily reacts with H2O 2 to generate OH radicals. Similar results obtained from several other biological reductants, including vitamin B2 , indicate that a vacant coordination site on a Cr(V) complex facilitates its reaction with H2O 2 to generate ""OH radicals. We thus suggest that in biological media, reaction [3] instead of [1] or [2] is the major pathway for the OH radical generation: While the carcinogenic potential of Cr(Vl)-based compounds has been well established via epidemiologic and animal studies (1), the underlying biochemical mechanism is still not well understood (2). In a recent development, however, Kawanishi et al. (3) have reported that hydroxyl (OH)2 radicals might be the key species in the mechanism of Cr(VI) toxicity. As to the mechanism of the ""OH radical formation they suggest that Cr(VI) reacts with cellular hydrogen peroxide (H2O 2) to form the tetraperoxochromate(V) (Crog-) ions, which decompose to produce hydroxyl radicals. It was also suggested (3) that the ""OH radicals thus produced cause genotoxicity via DNA base modification and deoxyribose phosphate backbone alterations. More recently Aiyar et al. (4) reported the detection of OH radicals in the reaction of Cr(VI) with H2O 2 in biological media, including the reaction of ""OH radicals with deoxyguanosine to generate 8-hydroxydeoxyguanosine adducts, confirming that ""OH radicals could indeed play a significant role in the mechanism of Cr(VI) toxicity. However, the mechanism for the ""OH generation was not clarified, although the role of Crog- ions as possible precursors was mentioned, somewhat along the lines suggested by Kawanishi et al. (3). The possibility of the participation of Crog- in the ""OH generation has also been indicated by Sugiyama et al. (5), since they mention that vitamin B2 enhances the formation of""OH radicals in the reaction of Cr(VI) with H2O 2 because of the generation of Crog- in the reaction."

Jan 1, 1990

By J. E. Conley

[Available statistics show that the demands of the American chemical industry for sodium sulphate have been increasing slightly in recent years. The supply from domestic sources, particularly in the form of byproduct salt cake from the acid manufacturers, has been tending to decease due to the growing manufacture of synthetic acid. Both hydrochloric and nitric acids are being synthesized from their elements. The natural result has been that a smaller amount of salt cake is available. Simultaneously, the expansion of the Kraft-paper industry, especially in Lie South, has brought about greater demand for sodium sulphate in that section. This demand is being met by domestic byproduct salt cake, by imported German sodium sulphate made from potash waste liquors, and by favorably situated domestic deposits of Glauber salts and tile anhydrous salt, thenardite. No shortage of natural sodium sulphate exists in the United States, but usually such deposits occur in semiarid regions far re¬moved from transportation facilities and from markets. Moreover, the major portion of the natural deposits is Glauber salt or mirabilite (Na2SO4?10H20), which must be dried or dehydrated in order to most consumer requirements. The waters of hydration represents, roughly, 55 percent of tae total weight of the crude salts and therefore has a very important influence on transportation costs. In marry instances the cost of getting even the dehydrated product to market is the deciding economic factor. Therefore, the recovery or production of anhydrous sodium sulphate from plant-waste liquors or from natural brines of suitable composition might be economically feasible.]

Jan 1, 1936

By D. J. Bauer

The Bureau of Mines demonstrated the feasibility of fractionating lanthanide nitrates with a tertiary amine on lanthanum-cerium and thulium-ytterbium pairs. Optimum values were determined for pH, phase concentration, and percent chelation of metal ions in the aqueous phase. Percent extraction is markedly dependent on the concentration of lithium nitrate in the aqueous phase. Selective masking of the heavier element in each extraction system with DTPA or EDTA aqueous-phase chelating agents resulted in lanthanum-cerium separation factors of 8.5 and thulium-ytterbium separation factors of 3.4.

Jan 1, 1966

By E. Morrice

This report of the Federal Bureau of Mines presents a laboratory procedure, with the requisite equipment, for electrowinning ingot (liquid) cerium metal from a fused-fluoride bath, the metal purity being about 99.9 percent. Physicochemical studies, including bath properties and electrochemistry, are included, with a speculative model of the mechanisms involved. An historical review of the methods used for electrowinning misch metals and yttrim-group metals, as well as individual rare-earth metals, is presented. The electrolytic preparation of metal from fused salt and nonaqueous media is summarized, along with the unsuccessful attempts at depositing the metals from aqueous solutions.

Jan 1, 1961

By Northcutt Ely

This volume- summarizes mining and petroleum legislation in 18 European jurisdictions. Within these jurisdictions, primary attention is given to requirements that must be met in each country for acquisition of rights to permit development of mineral resources. Coverage includes: First, identitication of the controlling laws or statutes governing minerals acquisition and reference to the administrative authority; second, analysis; of the laws governing mines and quarries and their products; third, analysis of laws applicable to natural gas, petroleum, and related materials; and fourth, mention of laws regulating offshore operations. Where pertinent, sections dealing with historical background or administration have been added in countries where minerals are subject to control of States or Provinces, those areas are considered separately from the central government.

Jan 1, 1974

By R. A. Franks, G. F. Friel, J. C. Edwards, L. Yuan

Two mine-fire experiments were conducted in the National Institute for Occupational Safety and Health's (NIOSH) Safety Research Coal Mine (SRCM) at the Pittsburgh Research Laboratory (PRL) which demonstrated that smoke from diesel-fuel fires of 500 kW and 660 kW heat-release rates in a return airway can develop, without causing a complete air flow reversal, into a roof layer that can migrate upwind forming a counter flow to the primary airflow in a crosscut. Subsequently, smoke can penetrate into an intake airway and create a hazardous atmosphere in the intake airway upwind from the fire. Visibility conditions less than 13 m were created by the smoke in the intake airway downwind from the crosscut. Modeling of the event with a three-dimensional, time-dependent, computational fluid dynamics (CFD) program correctly represented the smoke movement.

By J. R. Cobble

Dissolution of chalcopyrite with acidified ferric sulfate produces a sulfur layer on the unreacted chalcopyrite surface that interferes with further dissolution. The U.S. Bureau of Mines has developed a process to improve the leaching kinetics of these types of diffusion-controlled systems. The system features the Bureau-developed turbomill, an attrition grinder that scrubs the reaction product coating away from the unreacted mineral grains during leaching. The system can be operated continuously at any temperature up to the boiling point of the leaching agent. This method is a hydrometallurgical alternative to chalcopyrite smelter technology and eliminates sulfur dioxide emission problems with its associated costs. Batch testing at 900 C with the chalcopyrite-ferric sulfate system resulted in copper extraction exceeding 99 pct. At an optimal energy consumption of 1,520 kW· hjst, 95 pct of the copper was extracted. The pregnant liquor was clarified and tested for typical solvent-extraction recovery of the copper. Two-stage extraction and two-stage stripping recovered 96 pct of the copper in an electrolyte suitable for copper electrowinning.

Jan 1, 1993

By M. J. Ferrante

The Bureau of Mines recovered rhenium powder from scrap tungsten alloy containing approximately 25 percent rhenium. Oxidation of the scrap at 950° C separated volatile rhenium heptoxide from tungsten trioxide. Minor amounts of tungsten, iron, and nickel were removed by selective precipitation from a rhenium solution from which was recovered crystalline ammonium perrhenate. Experimentation showed that hydrogen reduction of minus 325-mesh ammonium perrhenate at 1,000° C produced rhenium powder averaging 2.1 microns in size (Fisher Sub-Sieve method). The powder contained <50 ppm of total metallic impurities and 1,070 ppm of total interstitial impurities. Sintered compacts had a density of 95 percent of theoretical. Approximately 96 percent of the rhenium contained in the scrap alloy was recovered.

Jan 1, 1969

By M. B. Shirts

Numerous alternative processes have been proposed as being potentially more economical or less polluting than the traditional smelting of copper sulfide concentrates. One such process as recently developed in the laboratory by the Bureau of Mines is composed of a two-stage fluid-bed, oxidation-reduction roasting followed by ammoniacal leaching, solvent extraction, and electrowinning. A copper-leaching recovery of 97.4 percent was obtained, and electrolysis of the acid strip solution deposited metal assaying 99.99 percent copper. The roaster gases contain over 95 percent of the sulfur at a concentration of 12 percent which is better suited for acid making or elemental sulfur production than conventional smelter gas. When considering byproduct recovery, a preliminary estimate indicates copper production costs are com-parable to the conventional smelters.

Jan 1, 1975

By J. H. East, D. Harrington

"INTRODUCTION The tremendous expansion of industry during the war and the unprecedented demands for metals and minerals are reflected in the production and use of explosives during that period. The increased use of explosives brought added safety problems to industry because of the necessity of using men as blasters who were not entirely familiar with and some who were totally unfamiliar with the characteristics of some or all of the various explosives. A discussion of the characteristics of the ordinary types of explosives used in: industry should assist in giving a better understanding of the hazards attending their use. Explosives are compounded so they may be used with reasonable safety provided the user understands and follows the procedure recognized as standard safety practice. Short cuts and the failure to understand and use recognized safe practices, as well as the selection of explosives unstited for the work at hand, are all part of the safety problem,The extent to which explosives are used in the United States is shown by a study of the statistics compiled by the Bureau of Mines 4/ regarding them. Some of these statistics are shown below and serve as an indicator of the tremendous number of men engaged in the transportation, storage, and use of explosives. Theme men are exposed to the inherent hazards attending this occupation and they should be familiar with the recognized safe practices relative to explosives."

Sep 1, 1946

By W. W. Adams

The first full year of the second World War for the United States presented a picture of the metal-and nonmetal-mining 4 industry which, without proper analysis and explanation, would convey a distorted view of achievements during 1942, especially because employment at gold and silver (lode and placer) mines-the largest group-declined to such an extent that the over-all totals for the country were reduced even though increases were made at mines producing copper, lead-zinc, iron, miscellaneous metals, and non-metals. A complete panorama of the metal-and nonmetal-mining industry, exclusive of coal mining, reveals a decrease in the number of men employed, the man-hours of employment, and the accident-frequency rates. Were the gold and silver (lode and placer) mines to be considered as a separate category; it would be seen that the number of men employed at all the other groups of mines increased appreciably over 1941. These other increases must be considered important, since these mines produced the vital war minerals that made valuable contributions to the military successes of the United States and its Allies during the year. A separate analysis of each of the various groups of mines may be found elsewhere in this bulletin. For the purpose of maintaining continuity in this series of bulletins, however, the discussion in this introduction will be confined to the entire metal-and nonmetal-mining industry (excluding coal mining, for which a separate bulletin, No. 462, has been published).

Jan 1, 1945

By R. E. Coleman

The molecular species occurring at the mineral-reagent interface of the galena-aqueous potassium ethyl xanthate system was studied by developing a technique for using an attenuated reflection method in conjunction with standard infrared spectroscopy procedures. Lead ethyl xanthate was detected from the infrared spectra of all galena surfaces treated in the pH range of 7 to 11. At pH 8.5, lead ethyl xanthate formed as a film chemically bonded to the galena surface. A solvent extraction sampling method was employed with infrared spectroscopy to obtain quantitative data on the lead ethyl xanthate removed from the galena surface. The data showed that between pH 7 and 11 thy quantity of lead ethyl xanthate physically adsorbed decreased as the pH was decreased; in the same pH range, the quantity of free lad ethyl xanthate in the aqueous medium remained constant, and the amount of unreacted xanthate varied.

Jan 1, 1966

By W. W. Simpson

During cyanidation of mercury-bearing gold-silver ores, significant amounts of mercury are extracted. The presence of mercury decreases. gold loading and increases mercury stripping time on activated carbon, complicates fire refining of the gold cathodes, and creates a potential health hazard. Addition of calcium sulfide (CaS) to the cyanide leach slurry precipitates the solubilized mercury but also some silver. The Bureau of Mines investigated silver loss during CaS precipitation of mercury. Addition of 0.1 lb CaS per short ton ore to a mercury-bearing gold-silver ore precipitated both mercury and silver. However, if copper was added with CaS, or if the ore contained copper, much of the sil-ver loss was prevented. Addition of 235 ppm Cu with 0.1 lb/st CaS, prior to carbon-in-pulp adsorption, resulted in 89-to 97-pct, 80-to 91-pct, and O-pct adsorption of the solubilized gold, silver, and mer-cury, respectively, on the activated carbon.

Jan 1, 1986

By J. A. Rowland

Manganese-copper alloys containing 60 percent or more electrolytic manganese exhibit an unusual combination of high vibration damping capacity with good strength properties. Properties of the pure alloys were first studied in the laboratories of the Federal Bureau of Mines and have been described in a series of technical papers1/ published from 1941-49. The unusual characteristics of these manganese-copper alloys attracted the attention of research metallurgists and several additional investigations have also been reported in the literature.2/ The engineer, also, was attracted by the combination of high strength and high vibrational damping capacity possessed by these alloys. A wide field of application in structural and machine design was obvious. However, serious difficulties encountered in commercial fabrication of structural or machine components from the alloys retarded attempts at their practical utilization. For this reason the Federal Bureau of Mines, in cooperation with the United States Navy, Bureau of Ships, undertook a program designed to develop practical methods for fabricating a selected group of the high-damping alloys. It is the purpose of this paper to summarize a part of that investigation in a form suitable for use by the metallurgist interested in commercial fabrication of the alloys.

Jan 1, 1955

The accompanying supply/demand flow diagrams and 10-year tables for mineral and fuel commodities present essential data required by government, industry, and others to formulate policies and programs that can help assure an adequate and continuing supply of mineral raw materials. The 10-year data base terminates with 1974 figures because adequate world information was not available beyond that date. The selected mineral supply/demand tables and flow diagrams comprise but one "output" from the massive body of information and data collected and com-piled by the Bureau of Mines on a continuing basis covering mineral production, consumption, prices, shipments, imports, exports, and stocks, as well as industry activities in all States and abroad.

Jan 1, 2012

By L. A. Neumeier

A refinement of the tungsten-cobalt phase diagram is presented for compositions to 85 at. pct cobalt and for temperatures to the solidus. Preparation of alloys by powder metallurgy methods is described, and the results of studies made by a combination of techniques involving microscopy, X-ray diffraction, thermal analysis, and dilatometry are discussed. The existence of u-W6Co7 is confirmed (rhombohedral D85 structure). The W6Co7 phase forms periectically at 1,685&apos;115° C by reaction of liquid with primary W; the peritectic melt is at 71 at. pct cobalt. The homogeneity range of u-W6Co7 extends to both sides of the ideal stoichiometric ratio, through a compositional range of about 5 at. pct. The compositional limits for u-W6Co7 vary slightly below 1,471°±5° C, the temperature of the eutectic reaction forming u-W6Co7 plus a. The eutectic composition is at 79 at, pct cobalt. The existence of WCo3 is confirmed (hexagonal D019 structure). WCo3 forms peritectoidally at 1,093°±5° C by reaction between a and u-W6Co7 and exists over a narrow homogeneity range of 0.5 to 0.6 at. pct. The solid solubility of cobalt in tungsten is low (maximum 0,9 at, pct cobalt) and results in contraction of the tungsten lattice. Tungsten is extensively soluble in a-Co at higher temperatures; the a-Co lattice is expanded by the presence of tungsten in solid solution. There was no indication of the formation of a o-phase nor of any intermediate phases other than WeCo7 and WCo3. The WeCo7 and WCo3 phases are compared with similar phases in other systems.

Jan 1, 1967

By J. L. Eakin

The Bureau of Mines determined agents that are effective in foaming heavy brines and oil from gas wells in severe concentrations of sodium chloride, in severe concentrations of calcium chloride, or in moderate oil-brine mixtures. Dynamic foam tests were designed to select the more effective foaming agents. Numerous foaming agents were tested in concentrated simulated brines, in oilfield brines having varied concentrations of ions, in heavy natural brines, and in a commercial brine generally used as a reservoir pressure-balancing fluid. Several agents were detected that could perform efficiently in the field under the most severe saline conditions. Agents that promote foaming in oil-brine mixtures were also determined.

Jan 1, 1965

By A. Y. Lee

Prior work at the Bureau of Mines resulted in the successful development of a bench-scale, combination electrorefining-electrowinning method for recycling the lead from scrap batteries using waste fluosilicic acid (H2SiF6) as electrolyte. This paper describes larger scale experiments. Anodes cast from scrap battery lead were electrorefined in a 20-L multielectrode cell for 3 to 7 days. The anodes, containing 2 to 2.5 pct antimony, were ideal for obtaining firm and adherent slime blankets. Cathode deposits, assaying 99.99 pct Pb, were obtained, with current efficiencies near 99 pct. Sludge leaching was done in 100-L tanks followed by filtering in 61 cm square vacuum pan filtersu Lead of greater than 99.99-pct purity was recovered from the filtrate by electrowinning in a 20-L multielectrode cell using insoluble Pb02-Ti (lead dioxide-coated titanium) anodes and pure lead cathodes. The fluo-silicic acid electrolyte depleted in lead was repeatedly recycled to leach more sludge, and there was no problem with impurity buildup. The amount of Pb02 formed on the anodes during electrowinning was less than 1 pct of the total lead deposited on the cathodes, as long as the phosphorus concentration in the electrolyte was greater than 1.3 giL. Emissions of lead in air were less than 10 ~g/m3, well below the proposed OSHA limit of 50 ~g/m3.

Jan 1, 1984

By Allan M. Johnson

Case histories were used to document and evaluate deficiencies in underground mine closures which have resulted in post-operation problems such as subsidence shaft failures, acid or toxic water drainage and others. Three different underground mining districts in the United States were investigated; 1) an iron mining district in Michigan 2) coal mining districts in eastern Ohio and southern Illinois and 3) three metal mining districts in central Colorado. Previous work in the Michigan district on problems with subsidence and acid water drainage provided the background from which the concept for this project was developed Student investigators working towards their MS degrees in Mining Engineering did the work on the eastern coal and western metal districts. The combined studies show that problems from acid water drainage, subsidence and inadequately protected mine shafts are the most severe and widespread. Suggestions of a technical nature are presented as partial solutions to some of these problems. It was determined that pre-closure evaluations could result in the identification of some potential problems that may occur after the mine is closed. Early recognition of these problems would be an advantage for at this time more options are available to the mine operator to either prevent them or to plan for their occurrence. Mine closure and reclamation should be considered as a part of mining and be incorporated in the mining plan. This would result in reduced environmental impact and would be achieved at a lower overall cost to the mining companies and to society. The role of water in the occurrence of several types of subsidence during mine flooding was significant at some mines in the Michigan district. These mechanisms which involve, friction reduction, gravity loading, overburden transport and hydraulic forces in a flooded mine probably have a broader effect than is currently recognized. Control of these processes may offer some interesting options during mine closure. It is recognized that technical solutions alone cannot provide all of the answers to problems associated with underground mines. Education, modified attitudes on the part of regulators and operators, and a more realistic perception of the importance and value of mining by the general public are also needed.

Jan 1, 1983

By William K. Cunningham

The investigation described in this report was begun as part of the Bureau of Mines progress to develop acid processes for the extraction of alumina from low-grade bauxite and. clays. A domestic shortage of high-grade bauxite sui table for treatment by the Bayer process became acute as a result of&apos; World War II; an intensive search for a practical acid process using lower-grade alumina-bearing raw materials was therefore warranted. The laboratory development was described in a preceding Bureau of Mines publication wherein the basic theory for the design and erection of a pilot plant maybe found. A 2-ton-per-day continuous pilot plant was constructed and successfully operated at College Park, Md., which demonstrated conclusively the chemical and mechanical feasibility of a solvent purification process for aluminum sulfate. The estimated production cost of $38.64 indicates that under present market conditions the process would not be economically feasible.

Jan 1, 1948