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By N. S. Dalal, Xianglin Shi

"Electron spin resonance (ESR) measurements provide direct evidence for the involvement of Cr(V) in the reduction of Cr(VI)· by NAD(P)H. Addition of hydrogen peroxide (H2 O 2) to NAD(P)H-Cr(VI) reaction mixtures suppresses the Cr(V) signal and generates hydroxyl (·OH) radicals (as detected via spin trapping), suggesting that Cr(V) reacts with H2O 2 to generate the ·OH radicals. Reaction between H2O 2 and a Cr(V)·glutathione complex, and between H2O 2 and several Cr(V)-carboxylato complexes also produces ·OH radicals. These results suggest that Cr(V) complexes catalyze the generation of ·OH radicals from H2O 2, and that ·OH radicals might play a significant role in the mechanism of Cr(VI) cytotoxicity. KEY WORDS: ESR. spin trapping, Cr(VI) reduction, Cr(V), hydrogen peroxide, free radicals.INTRODUCTIONThis communication reports an ESR spin trapping detection of hydroxyl ( OH) radicals.in reactions between some Cr(V) complexes containing biologically important ligands and hydrogen peroxide (H2O 2 ). This work was undertaken because while the reduction of Cr(VI) to lower oxidation states has been suggested as a key step in the mechanism of Cr(VI) toxicity, the reaction· mechanism is not yet clear. 1 Mutagencity has been well documented for Cr(VI) via various bacterial assays, while Cr(III) has been shown not to be mutagenic.2 • 3 Since it has been reported that compounds containing Cr(VI) do not react with isolated DNA,4 the reduction of Cr(VI) by other cellular constituents has been thought to be important in the mechanism of Cr(VI) induced DNA alteration.1·4 • 5 For cellular systems earlier studies include those on the reduction of C~(VI) by microsomes,6-8 rat liver DT-diaphorase,9 and aldehyde oxidase. 10 Regarding the reduction mechanism, Jennette used ESR spectroscopy to show that a long-lived Cr(V) complex is formed as an intermediate in the microsomal reduction of Cr(VI) in the presence of NADPH.8 She postulated that Cr(V) is the ""ultimate"" carcinogenic form of chromium compounds. This conclusion has led to many further investigations of the formation of Cr(V) in the reduction of Cr(VI) under biologically relevant conditions.11 - 19 More recently, however, it has been suggested that oxygen-derived radicals generated during the Cr(VI) reduction are the species responsible for the DNA alteration.20.2• To the best of our knowledge, however, no information is available on the generation of such radicals in the reduction of Cr(VI) under biologically relevant conditions, except some preliminary results on the glutathionyl (GS·) radical formation in the reduction of Cr(VI) by glutathione (GSH). 11 - 19 We, therefore, undertook a systematic investigation of the reaction of Cr(VI) with NAD(P)H, GSH, ix-hydroxycarboxylic acids, and H2O 2 • NADPH was chosen as a model reductant because of its ubiquitous existence inside the cells, its critical role in the enzymatic Cr(VI) reduction,1·6-9 its representation of important cellular Cr(VI) reductants, and its ability to reduce other metal ions.22 GSH was chosen as another model Cr(VI) reductant because GSH also exists inside cells, it represents another important category of cellular Cr(VI) reductants, the thiols, and it also plays an important role in the Cr(VI) toxicity .1• 1 ""- 19.i3.i4 For further clarification, we also studied the reaction of Cr(VI) with several '1'.-hydroxycarboxylic acids in the presence of H2O 2 since these acids are definitively known to reduce Cr(VJ) to form stable, isolable Cr(V).25 .2 6 The results obtained indicate that Cr(V) complexes, produced in the reduction of Cr(VJ) by cellular reductants, react with H2 O 2 to generate ·OH radicals, which might be the initiators of primary events in Cr(VI) carcinogenicity."

Jan 1, 1990

By M. J. Kirwan

[There have been large increases in the oil production and casing-head gas production of certain wells on the Quinn dome (northern part of the Lyons-Quinn field of Oklahoma) caused by large volumes of gas under high pressure entering Vie productive oil sand, The oil production of sore of the leases in this part of the field temporarily increased over 100 per cent within a few days after gas entered the oil sand among the leases that had the greatest increases in oil production wore those on which no gas wells were drilled but which were located up-elope on the structure in reference to gas wells on adjoining properties. It is conservatively estimated that 1,444,000,000, cubic feet of gas entered the productive oil sand and, up to January 1, 1924, caused an increase of about 950,000 barrels of oil from this sand. The casing-held gas volumes of a number of wells producing between 25,000 and 75,000 cubic feet of gas per day increased to several hundred thousand cubic feet and a few walls increased to nearly two million cubic feet per day after extraneous gas entered the oil sand from which the wells were producing.]

Jan 1, 1924

By W. H. Young

MOST OF THE key items in the bituminous-coal and Lignite industry declined in 1954 compared with 1953. Production, consumption, exports, average value per ton, men working, and days worked all declined; however, in the field of mechanization, the percentages mechanically loaded, mechanically cleaned, mined by auger, and mined by stripping all increased, as did production per men per day. Production.-The output of soft coal in 1954-391.7 million tons- was 14 percent less than the 457.3 million tons produced in 1953. The lower production in 1954 was due largely to a sharp reduction in consumption in the United States and to a drop in exports.

Jan 1, 1958

By Richard D. Miller

This publication contains routine analyses and related source data for 350 natural gas samples from 19 States collected during calendar year 1362 as part of a continuous survey of the United States for occurrences of helium in natural gas. This survey has been conducted by the Helium Activity of the Bureau of Mines since 1917. The analyses published herein were made by mass spectrometer and a special helium analysis apparatus. Four previous publications have been made to present the results of 5,648 gas analyses made by the Bureau of Mines, Helium Activity, prior to 1962. The first, Bulletin 486, 3/ contains analyses and data on 2,195 gas samples collected during the period 1917-47. Bulletin 576, 4/ the second publication, includes data and analyses for 1,575 samples collected from 1947 through May 1956. The third bulletin contains 1,444 analyses and source data of samples obtained from May 1956 to January 1, 1961.

Jan 1, 1964

By Sidney A. Suhler

A field operable, breadboard model, borehole radar was developed for the detection of hazardous geological anomalies in and above a coal seam in advance of mining. A four-inch diameter downhole probe was fabricated and tested in several environments. The radar transmitter was also employed in a cross-hole or through transmission mode to determine natural geotechnical and man-made conditions between boreholes. Sensitivity to underground conditions in both modes of operation were indicated.

Jan 1, 1978

By R. F. Abernethy

Recent investigations in the United States and in other countries have produced considerable information on the nature and occurrence of minor elements in coal. The possibility of recovering certain elements, particularly germanium and uranium, from coal ash and other coal products has received considerable attention. Some flue dusts are potential sources of germanium, and certain lignite deposits are potential sources of uranium, but industrial recovery of these elements has been limited to small quantities for technical and economic reasons. Considering the large amount of coal mined annually, a small percentage of a rare element may have industrial significance if an economical method of recovery can be developed. In 1944 information on the occurrence of rare elements in coal was reviewed in Bureau of Mines Technical Paper 669 (46).3 This report is a revision of that paper with the view of summarizing published information available for United States coals, and pertinent information concerning coals of other countries. Selected references from the original paper are retained. New references do not include all preliminary reports when more permanent literature describing complete projects is available. Consequently, the list of references should not be considered complete.

Jan 1, 1963

By L. D. Schmidt, H. G. Graham

Several processes for the production of ultra-clean coal for electrode carbon were developed in Germany prior to and during World War II . These processes have been investigated since the end of the war by the British and U. S. Government missions . As the reports of the investigations are not readily available to the public , it is the purpose of this paper to present the information which has been obtained regarding the methods by which ultraclean coal was produced . Almost all the ultra-clean coal was used in the manufacture of electrodes for the production of aluminum and magnesium . Standard raw materials for making these electrodes are pitch coke and petroleum coke , which are nearly ashless . The inclusion of ash in the electrode carbon results in lowered efficiency and impure metal from the reduction process . Petroleum coke and pitch coke were in very short supply in Germany during the war , so that it was necessary to augment the supply with carbon produced from coal . In the emergency , methods were developed to clean coal which had never before been economically feasible . However , a demand for nearly ash-free coal might develop in the United States if a shortage of petroleum coke were to occur at the same time as a strong demand for light metals . Other uses of ultraclean coal are in direct hydrogenation of coal , in production of activated carbon, and for special fuels . Specifications for electrode carbon are rather severe owing to the necessity for producing pure metal . Maximum amounts of impurities allowable in American practice are as follows : Total ash , 1.0 percent ( in finished coke , 0.7 percent ) Silica , 0.08 percent Ca or Na, or their sum , 0.12 percent Sulfur , 2.0 percent Ba , Ni , Cr , Mn , Co , and V are objectionable in very small amounts . The most important process for ultra cleaning of coal in Germany was froth flotation . Froth flotation had been used widely there to process washery -water sludges and to recover coking coal from high - ash fines . Its use was indicated , therefore , when the demand for ultra low-ash coal arose . In two plants the coal cleaned by froth flotation was treated with acid or caustic to lower further the ash content . Another process used on an industrial scale was that of dissolving the coal substance in the middle oil from direct hydrogenation of coal under controlled pressure and temperature . The resulting paste was heated, filtered , and the oil distilled off . The residue was a low-ash organic material that could be carbonized for electrode carbon or could be hydrogenated directly . Several other processes had been developed to the laboratory or pilot - plant stage but had never been used on a commercial scale . These processes included cleaning by centrifugal action , cleaning by electrostatic action , and cleaning by forming a paste with oil in water . The coal-preparation plants at the Carl Alexander mine , Augusta Viktoria mine , and Kőenigin Elisabeth mine are described in Bureau of Mines Information Circular 7389 : " Coal Preparation Practice in Western Germany" , by Thomas . Fraser and M. G. Driessen . Most of the special equipment used at these plants is described in the above publication .

Oct 1, 1948

By M. Kanda, W. D. Bensema, J. W. Adams

Two different techniques were used to make measurements of the absolute value of electromagnetic noise in and above an operating coal mine, McElroy Mine, located near Moundsville, Nest Virginia. The electromagnetic environment created by 300 volt dc and 480 volt ac machinery was measured. In one technique noise was measured over the entire electromagnetic spectrum of interest for brief time periods. The noise was recorded using broadband analog magnetic tape. The noise data was later transformed to give spectral plots. In the other technique, noise amplitudes were recorded at several discrete frequencies for a sufficient length of time to provide amplitude probability distributions. The specific, measured results are given in a number of spectral plots and amplitude probability distribution plots.

Jan 6, 1974

By Graham W. Marks, Clyde A. Bridger

"INTRODUCTION An electrolytic process for the preparation of metallic cobalt has been developed recently in the Bureau of Mines Experimental Station at Boulder City, Nev. Chemical analysis shows this cobalt to contain impurities in small percentages, chief of which is nickel. It is desirable to be able to determine these impurities spectrographically. This report is concerned with a procedure for the spectrochemical determination of nickel in cobalt.Previous spectrographic work on cobalt was done by Breckpot and Mevis,/ who used the method of homologous pairs of lines. However, it was felt that a more detailed investigation was needed, employing the method of internal standards.ACKNOWLEDGMENTWe are indebted to B. G. Knickerbockor and his staff at the Boulder City, Nev., station of the Federal Bureau of Mines for their cooperation, and particularly to Richard W. Lewis and Robert G. Sanderson, who prepared nickel-free electrolytic cobalt for us."

Feb 1, 1948

By B. W. Madsen

The Bureau of Mines conducted a large-scale (6.4 t), long-term (2,165 days) test to gain a better understanding of the leaching characteristics of chalcopyritic ores. An ore sample containing 0.77 pct Cu was leached in a fiberglass column by downward percolation of acidified ferric sulfate solutions. Three sets of leaching conditions were investigated: (1) ambient temperature leaching, (2) elevated temperature (50° to 60° C) leaching, and (3) elevated temperature leaching after inoculation with thermophilic bacteria. Leaching at ambient temperature resulted in a copper extraction rate of 0.44 pct per 100 days. Increasing the temperature to 50° to 60° C resulted in decreased activity of natural mesophilic bacteria, and the leaching rate decreased to 0.22 pct per 100 days. The pH was lowered from 2.0 to 1.6, and nutrient solutions that contained thermophilic bacteria were added. This procedure resulted in an increase in the ferric-to-ferrous iron ratio and an increase in the copper leaching rate. However, the increased leaching rate was not sustained, and 120 days after inoculation the bacterial activity declined, the ferrous iron content increased, and the copper leaching rate decreased.

Jan 1, 1983

By M. Orchin

THIS PAPER is concerned with two aspects of the behavior of coal: (1) Dispersion by solvents atmospheric pressure and high temperature and (2) the destruction and regeneration of the coking properties of coal. Several pure polycyclic compounds and a coal-tar fraction were found to extract 95 percent of the organic material of a bituminous coal. About 20 percent of the extract was soluble in benzene, and this fraction contained the ?coking principle? of the coal. From an extensive chemical spectroscopic, and x-ray study of the benzene-soluble material, some conclusions could be drawn concerning the composition and structure of this fraction of coal. A possible commercial application of the extraction technique is in the preparation of low-ash carbonaceous material for the manufacture of electrode carbon.

Jan 1, 1951

By Arthur B. Johnson

The Bureau of Mines investigated the concentration characteristics of high-clay sylvinite ores from four potash companies operating in the Permian Basin near Carlsbad, N. Mex. These ores, containing 13 to 22 percent K20 and 3 to 7 percent clay slimes, cannot be effectively processed by current commercial flotation methods because of their high slime content. A solution to this problem was shown to be the use of two-stage moderate scrubbing conditions and washing of the ore as opposed to strenuous attritioning. Bench-scale physical beneficiation techniques for recovering potash minerals and the development of ore-dressing systems by flotation resulted in obtaining acceptable product grades and recoveries. By using a coarse grind, emphasis was placed on production of premium granular and coarse products. Flotation results showed that concentrates of 58.7 to 60.4 percent K20 with recoveries of 71.0 to 83.4 percent 0f the K20 values can be obtained.

Jan 1, 1971

By Oliver C. Fursman

This work was conducted to determine the feasibility of producing aluminum-silicon alloys in a pit-type, three-phase electric-arc furnace. Two carbon-lined furnaces were used in the tests. The power input ranged from 120 to 240 kw. in the small furnace and from 420 to 460 kw. in the large furnace. Energy consumption ranged from 5.3 to 11.5 kw.-hr. per pound of alloy produced and electrode consumption, from 240 to 510 pounds per ton of alloy produced. A wide range of crude aluminum-silicon alloys was produced by direct smelting of clays or similar aluminum silicate raw materials, using hogged fuel or wood chips as the major source of carbon in the furnace charge, and silicon of high grade was produced by smelting quartz. The aluminum content of the aluminum-silicon alloys ranged from 15 to 55 percent. Alloys produced from a white opaline-silicate clay were relatively free of iron, titanium, and other impurities. Those produced from western fire clays and kyanite, although richer in aluminum, contained considerable amounts of impurities. The purity of the alloys depended largely on the composition of the raw materials.

Jan 1, 1960

By William D. Monaghan

The U.S. Bureau of Mines evaluated a teleoperated continuous mining machine for deep mining in thin-seam applications as low as 1 m. Teleoperation increases the safety of mining machine operators because it removes the operator from the face, an area of immediate hazards to safer outby locations. By using teleoperation, the miner can avoid many including unexpected roof falls that can maim or kill miners instantly, methane and coal dust explosions that can be ignited with just a small spark or flame, adverse health effects from miners breathing coal and silica dust, adverse long-term inner ear damage from loud noise pollution, and other hazards related to heavy mining equipment moving about in confined underground roadways. This report presents the surface evaluation results of a teleoperated control system.

Jan 1, 1994

By Richard V. Ageton, Harry E. Tufft, E. A. Holbrook

When an underground excavation is made, the rock surrounding the sides and top of the opening is deprived of its natural support and tends to fall. Whenever caving takes place, the time and extent of the caving depend on the character and condition of the rock. In strong homogenous rock, such as solid granite, even a large chamber may stand indefinitely, whereas a soft material, such as clay or a loose material like unconsolidated sand, falls immediately if not supported. Weaknesses in the rocks induced by structural features, such as joints, :fissures, bedding and cleavage planes, and fractures produced by blasting, will cause the falling of insecure blocks or slabs unless means are provided to support these in place. In an unsupported mine opening, as a tunnel, the first slight settling or adjusting movement of the rocks (the "initial creep" or "set") is caused by the great weight of overlying material pressing down the rock masses above and around the roof and sides of the opening until they key together in roughly the form of an arch. The rock, after it has adjusted itself to this shape, becomes. selfsupporting. Timbering is necessa.ry in all mining only to support, therefore, those comparatively small blocks or pieces of rock which tend to loosen from the top and sides of the opening during or after the formation 'of the natural rock arch, and which lie between this natural rock arch and the opening. This statement, of course, has its limitations. For example; a layer of strong rock, like limestone, may act as a beam; then only the material under the limestone will need support. Timbering is not, as is commonly supposed by the layman, used to supp!ort the huge mass of rock between the back (roof) of an underground opening and the surface. It would be impossible to place enough timbers in a:ny underground opening to support such a mass. This fact is not'·perceived by all miners.

Jan 1, 1923

By George H. Holmes

This paper is one of a series being prepared by the Minerals Division of the Bureau of Mines on mining and milling methods and practices at various mines in the United States. It describes such methods at the Caselton mine of the Combined Metals Reduction Co. The Caselton mine and mill are in secs. 28 and 29, T. 1 N., R. 67 E., M. D. B. & M., Lincoln County, Nev., about 10 miles by paved highway south- west of Pioche, Nev. (fig. 1). the history of the district and company This circular summarizos operations, describes physical features, labor and living conditions, the geology, ore deposits, and the ore. Prospecting and exploration methods are outlined, and shaft sinking, drifting and crosscutting, and raising are covered under development methods. In the soction on mining mothods, stoping and slushing are discussed, following which are descriptions of underground transportation, hoisting, ventilation, drainage and sampling, and surveying. The surface and crushing plants are described, and milling practices are presented in dotail with explanation of the filter plant and assay office. Safoty practices and the company organization are described in the concluding sections of the circular.

Nov 1, 1950

By B. D. Sartwell

The formation of alloyed regions near the surface of metals using ion implantation is being investigated by the Bureau of Mines as a means of providing corrosion resistance using much smaller amounts of the strategic alloying metals. Two ion implantation systems that can implant low-energy chromium, nickel, or aluminum ions into low-cost substrate materials such as iron or carbon steel have been designed and constructed. The development of the ion source, ion beam acceleration stage, mass analysis system, and target chamber are described in detail. The ion-implanted alloys have been characterized using proton-induced x-ray emission to give the total number of atoms implanted and to determine the extent of any surface contamination introduced by the ion implantation process. Research conducted at other laboratories on metallurgical applications of ion implantation is given.

Jan 1, 1980

By O. C. Blade

Consumption of Diesel fuel oil in the United States has increased very rapidly during recent years. At the present time approximately 5 percent of the crude oil refined in this country is said to be processed for this purpose. This figure represents approximately 20 percent of the total distillate-type fuel oils now being produced in the United States. One factor contributing greatly to the recent increase in consumption of Diesel fuel oil has been the conversion from steam locomotives to Diesel engines by a number of railroads. Other contributing factors are greFl.ter use of Diesel engine8 in buses, trucks, tractors, water craft, and stationary power plants. The growing importance of Diesel fuel oil has resulted in a need by the petroleum industry, engine manufacturers, and consumers for more information regarding the types and quality of Diesel fuels currently being marketed. To supply this information, the American Petroleum Institute and the Bureau of Mines, United states Department of the Interior, under a cooperative agreement, have conducted a survey of Diesel fuel all produced in refineries in this country during 1950. Under the agreements, samples of Diesel fuel oil, representative of actual shipments, were analyzed by the manufacturers in accordance with instructions issued by the Fuel Survey Panel of the Automotive Research Committee of the American Petroleum Institute. Results of the analyses were transmitted to the Bureau of Mines, and that agency has studied the data and compiled them by groups in comparable form as shown in the tables of this report.

Jan 1, 1950

By H. L. Riley

This report describes the methods and equipment used by the Watauga Stone Co. to drill and blast limestone in a two-level quarry, and to crush, screen, blend, and load this stone. Power requirements per ton of stone produced are reported. The personnel requirements for individual phases of the operation are tabulated in man-hours per ton of stone produced.

Jan 1, 1963

By John R. Benham

In 1979 and 1980, the U.S. Bureau of Mines and U.S. Geological Survey conducted a mineral survey of the 20,500 acre Black Butte RARE II area (No. 5102) in the Los Padres National Forest (fig. 1). The work by the Bureau of Mines indicates that the potential tor mineral resources in the area is low. Samples of outcrops and stream channels contained no economic minerals. A mercury deposit near a granodiorite-sedimentary rock contact occurs 2 mi northeast of the study area, but similar deposits have not been discovered within the area. Geothermal potential exists near Tassajara Hot Springs, but no thermal springs occur in the area; nor have oil, gas, or coal resources been found.

Jan 1, 1982