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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 W. W. Stephens

As part of the Bureau of Mines program directed toward more effective utilization of the mineral resources of the United States, a number of processes for production of sponge iron have been investigated. The use of sponge iron as a raw material for production of steels and other ferrous alloys offers several possible advantages over the conventional pig-iron and scrap process, especially for utilization of the smeller, widely distributed iron-ore deposits of the western United States. Although considerable information has been made available on various processes for production of sponge iron, little information 118.6 been published heretofore on the problems and costs involved in melting the sponge iron for production of steel. The present Paper reports the results of tests conducted at the Bureau of Nines pilot plant at Redding, Calif. in which several different types of sponge iron Were used as charge material for production of steel in a 4-ton-capacity basic arc furnace.

Jan 1, 1949

The first metal-mine accident-prevention course was prepared and published in 1942-45 as a series of seven miners' circulars (Nos. 51-57). The course has been broadened in scope, revised, and brought up to date and is being published as a similar series of seven miners' circulars (Nos. 51-57, revised) on accident prevention in metal and non-metallic mines. These circulars are as follows: Injury Statistics (Miners' Circular 51), dealing with general statistics on injuries from accidents at metal and nonmetallic mines, including causes, costs, and the use of investigations and reports of all injuries.

Jan 1, 1960

By R. W. Hiteshue, R. W. Fridy, W. Kawa

A study of the production of coronene , a high - melting ( 440 ° C ) , highboiling ( 525 ° C) , polynuclear hydrocarbon , was made by the Bureau of Mines to determine the maximum yield obtainable by the hydrogenation of coal and coalderived materials . Experiments were made with anthracite and bituminous coals and with asphaltenes and centrifuged residue obtained from heavy oil produced in a pilot plant by the hydrogenation of a bituminous coal at 2,000 psi and 480 ° C. With anthracite , yields of coronene of 0.5 to 0.7 wt pct of moistureand ash - free coal were obtained at 6,000 to 8,000 psi , 700 ° to 750 ° C , and a residence time of 30 minutes . With bituminous coal , yields averaging 0.4 wt pct of maf coal were obtained at 6,000 psi , 800 ° C , and 30 minutes ' residence time . With asphaltene and centrifuged residue , yields of less than 0.02 wt pct of maf coal were obtained at 6,000 psi , 700 ° C , and 60 minutes ' residence time .

Jan 1, 1964

By W. Bruce Montgomery

Manganese oxides occur, with some iron oxides, in small scattered lenses on property controlled by the Columbia Manganese Co. (1943) near Evington, Campbell County, Va. The company mined some manganese ore during 1917 and 1918. A preliminary examination in May 1942 indicated the possibility of finding additional ore. On August 21, 1942, the Bureau of Mines began prospecting to verify the continuity of the ore exposures. Work on this project continued until February 5, 1943. Prospecting and development work included shaft sinking, crosscutting, drifting, trenching, and test-pitting in six separate areas indicating two types of deposits. The most predominant type is a wide brecciated area in which occur lenses or pockets of nodular manganese oxides. The other type is characterized by more of a vein structure, including thin layers of manganese oxides.

Jan 1, 1949

By G. M. Potter

During the investigation of the occurrence of manganese deposits in the western United States, examining engineers of the Bureau of Mines collected samples from four properties in Siskiyou and Mendocino Counties northern California. As the ores were too low-grade to be acceptable to manufacturers of ferromanganese, beneficiation studies were made between 1941 and 1945 to determine the amenability of the ores to concentration. The Johnson and Reynolds properties are near Fort Jones Siskiyou County. The ore occurs in a number of small lenses in that area. Samples were taken for testing for amenability to treatment in a small custom-gravity plant, tentatively planned. by the Waiter Johnson interests of San Francisco. A 2-ton representative sample was obtained from numerous exposed portions of an outcrop on the property of the Mayland Mining Co. The Mayland mine is about 8 miles from Sawyers Bar in Siskiyou County. The ore body consists of stringers and irregular masses of oxide, and. silicate ore scattered through quartz, which these minerals have replaced.

Jan 1, 1952

By HOWARD I. OSHRY, James W. Ballard, H. H. Schrenk

Photometric instruments were designed and built for use with X- ray and spectrographic apparatus for the investigation and analysis of a variety of materials of hygienic interest . The instruments are simple in design , may be constructed economically , and have a number of features that make them stable and easy to operate . They are readily adaptable for measurement of either X - ray diffraction patterns or spectrographic films or plates . Because of these features and the interest shown in the instruments , they are described in detail , and reference is made to their application in the laboratory .

Apr 1, 1942

By Victor Spironello

The Bureau of Mines is studying cupola ironmel technology with the objectives of conserving high-quality raw materials through substitution and productivity. In the research re-ported here, a ize was modified by a gas-fired melting and/or ing chamber into the stack above the level of the coke bed, for study as a prototype for a coal-fired melting chamber. The modified cupola, in which natural gas was used to partially replace foundry coke, was evaluated in several trial runs. Data were obtained on furnace performance, metal and slag chemistry, and scrubber waters as particulates. Results of the modified ion were compared to those of conventional cupola operation. Although this research was preliminary--since the ultimate goal is to use pulverized coal instead of yielded ample evidence that the melting rate of a cupola can be icantly increased with less than a increase in energy input. Other evidence suggests that melting of low-density scrap can be enhanced and that scrap containing undesirable and/or oxidizable elements can be appreciably upgraded. This work is continuing and will include the use of pulverized coal of low rank to assist in melting.

Jan 1, 1984

By H. R. Babitzke

To develop alloys suitable for use at elevated temperatures, columbium and tantalum were combined with tungsten, hafnium, vanadium, zirconium, and titanium, and the resulting alloys were evaluated with respect to fabricability, hardness, Electrical resistivity, strength at elevated temperatures, oxidation resistance, and bend transition. Of the 23 compositions tested, Cb-2OHf-5W-10Ti exhibited superior high-temperature properties. A recrystallized sample of this alloy was fabricable at room temperature, had a strength of 44,000 psi at 1,200° C, and had an oxidation rate of only 7.7 mg/cm2/hr at 1,000° C.

Jan 1, 1966

By Raymond B. Lucas

"Distinction between Tripoli and Diatomaceous EarthMuch confusion exists both in the literature and in the trade as to the proper use of the terms tripoli, tripolite diatomeceons or infusoriai earth, and kieseigunr. All of these terms are often used synonymously by the trade and even in mineralogists and other reference books. Actually, tripoli is a ma- is a material of definite and distinct physical and chemical properties and all of the other terms belong to a different material with just as definite and distinct properties.Originally the term tripolite (loosely called tripole) was given to a diatomaceous cart from Tripoli in Northern Africa. Dena (J.D. Dana, A System of Mineralogy 6th Ed.) calls this material tripolite and gives no authority for the use of the terms tripoli. Between 1880 and 1890 the deposits near Missouri, were opened and the material placed on the market as ""Tripoli"" no doubt due to its resemblance in some respect to the original tripolite or diatomaceous worth from Tripoli. Since that time the term tripoli has with increasing definitenesss been reserved for the Seneca material and other siliceous of similar origin and physical properties, while all siliceous material of organic origin, containing dilators, has been called diatomaceous earth (or its synonyms infusorial earth, kiselguhr, etc.). Rottenstone is sometimes classed with tripoli."

Nov 1, 1920

By T. A. Clancy

Since many new mineral processing systems under development can impose severe corrosive conditions on construction materials, the Bureau of Mines reviewed and assessed the literature on corrosion resistance of ceramic materials. Corrosive conditions were categorized as: (1) acids and aqueous solutions, (2) glass and slag/metal melts, and (3) gases. Information on the corrosion resistance of ceramic materials, generally, is disseminated by many sources, each of which is interested in specific corrosive environments. Based on this survey, it was noted that (I) the development of standardized tests is needed to study solution-type corrosion of ceramics, (2) slag/melt corrosion data are the most comprehensive of the available data, and (3) better definition of corrosion mechanisms In gaseous environments is needed.

Jan 1, 1980

By R. R. Sayers

Carbon monoxide poisoning, as usually encountered, is an acute condition resulting from breathing atmospheres containing that gas. It is characterized clinically by headache, dizziness, weakness in the legs, increased respiration at first which later becomes irregular and depressed, collapse, unconciousness, and death; anatomically it is characterized by temporary changes in the red blood cells due to the combination of carbon monoxide with hemoglobin, and, in prolonged severe exposures, degenerative changes in various tissues of the body, especially those of the central nervous system. No race or nationality is immune or has a, special tolerance for carbon monoxide. From data at hand, it is known that both sexes are about equally susceptible. All ages are affected, but small percentages seem to have a more deleterious effect upon young animals and this is possibly true of children. Exercise, high temperature and humidity, and low oxygen content of en atmosphere increase the degree of poisoning for a certain concentration of carbon monoxide. Anything that lowers the physical fitness of a man, such as illness, overwork, or excesses of any kind, exaggerates the effects. More cases of poisoning from carbon monoxide occur in coal mines in the cold months of the year, because explosions take place more frequently during that period, also in homes where gas is used for beating purposes, and in garages from accumulation of automobile exhaust gases due to poor ventilation.

Jan 1, 1923

By Maria I. De Rosa

Table 1 and figure 1 show the number of fires and fire injuries that occurred in underground metal/nonmetal and stone mines by state during 1990-2001. Table 1 also shows the injury risk rates, employees' working hours, and lost workdays. Overall, 65 fires occurred in 20 states; these include 2 fires and no injuries for contractors. Six of the fires caused nine injuries. The yearly average was 5.4 fires and 0.75 injury. Forty-one fires with 2 injuries occurred in metal mines, 14 fires with 7 injuries occurred in nonmetal mines, and 10 fires with no injuries occurred in stone mines. The underground mine fires required 25 mine rescue team interventions and 30 mine/section evacuations. The Ewhr value was 260 x 10° hr (Irr = 0.007), and the LWD value was 83. Idaho had the most fires (eight fires and no injuries), followed by Louisiana (seven fires and two injuries), Michigan (six fires and six injuries), and Missouri (six fires and no injuries). Of these states, Michigan had the highest injury risk rate value (Irr = 0.146). Table 2, partly illustrated in figure 2, shows the number of fires, fire injuries, risk rates, employees' working hours, and lost workdays by time period. The number of fires during the six time periods show an increase during the fourth period followed by a sharp decrease during the fifth period and a sharp increase in the last period. The number of fire injuries show an increase followed by a decrease during most of the periods, accompanied by a decline in employees' working hours during most of the periods; an increase is seen during the third and fourth periods. The In values follow patterns similar to those shown by the injury values. Tables 3-8 show the number of fires by ignition source, method of detection and suppression, equipment involved, location, and burning material by time period. Figure 3 shows the major variables related to fires for 1990-2001. Table 9 shows the number of fire injuries per number of fires causing injuries and total fires by year, ignition source, equipment involved, and location.

Jan 1, 2004

By D. N. Nilsen

A mathematical modeling method was developed by the Bureau of Mines for the prediction of the principal equilibrium species in the solvent extraction of copper. The use of models for predicting the amount of metal extracted can reduce the amount of experimental work required to characterize a system for purposes such as optimization studies. Models were developed for the extraction of copper from ammoniacal sulfate and carbonate solutions with commercially available extract ants commonly used by industry. Results from laboratory shakeout tests compared well with predictions of the equilibrium concentrations of copper and pH values. For example, the loading of copper onto the solvent was predicted for most cases within ±S pct of the measured values, and the pH to with-in ±O.l pH unit in sulfate systems and ±O.2 pH unit in carbonate systems. Both mechanistic and empirical extraction equations were developed from laboratory data for copper and ammonia. The empirical-based models were slightly more accurate than were the mechanistic-based mod-els. Industrial level concentrations of the aqueous and organic constituents were used in this work. Independent variables included copper concentration, ionic strength, and initial pH of the aqueous phase; extractants, diluents, and their concentration in the organic phase; and temperature.

Jan 1, 1988

By Robert L. Grayson, Syd S. Peng

"An airborne dust study was undertaken at a Southwestern Pennsylvania underground bituminous coal mine by the Pennsylvania Department of Mines and Mineral Industries in 1964 for the purpose of making recommendations and requirements regarding compliance with health and safety aspects of The Bituminous Coal Mining Laws of Pennsylvania, approved by the legislature on July 17, 1961. The study was designed to accurately represent the airborne dust conditions of the subject mine. Sampling by midget impinger of specific worker locations throughout the mine was accomplished. Sample analyses yielded dust concentrations to mppcf, particle size determinations in cumulative per cent less than specified cut-off diameters, and determinations of free silica percentages in total dust samples. The data from this study is further analyzed, and the results are presented.INTRODUCTIONThe Bituminous Coal Mining Laws of Pennsylvania, enacted in 1961, prompted a study of respirable coal mine dust by the Department of Mines and Minerals Industry in 1964. In recognition of their obligation for ensuring the health and safety of bituminous coal miners, the department set out to characterize the airborne dust of mines throughout the commonwealth. The purpose of the studies was to make recommendations and requirements for compliance with the law and for control of airborne coal mine dust in Pennsylvania mines.One such study was undertaken at an underground bituminous coal mine operating in the Pittsburgh Seam in Southwestern Pennsylvania. The study was desig11ed to sample specific worker locations throughout the mine site and characterize the respirable dust relative to each of them. A midget impinger was used to gather respirable range dust samples during an 8-hour shift. Continuous miner operator, roof bolter, stoper bolter, loading machine operator, shuttle car operator, gathering motorman, mainline motorman, and rotary dumper jobs were sampled underground. In addition, barge mover, coal sampler, fine coal operator, heavy media operator, and boiler room attendant occupations were sampled on the surface. The surface sampling was over a 71-hour shift because of UMWA contract provisions."

Jan 1, 1988

By Martin J. Gavin

The oil- shale studies of the Bureau of Mines , conducted in cooperation with the State of Colorado and the University of Utah , have for their primary purpose the determination of retorting and refining conditions most favorable for obtaining the highest yields of most satisfactory products . Oil shales , typical of the deposits in several States , are retorted in carefully controlled retorts of differe types , the conditions being varied in successive runs as the results indicate that improvement in the yield and quality of the products most desired may be expected . Each shale presents a somewhat different problem , for it has been found that different shales treated under similar conditions yield products of different natures , and also that the same shale will yield products of different natures when retorted under different conditions . Some shales apparently can not be made to yield , under any set of conditions , products of so high an order as are yielded by other shales . This indicates that the oil -yielding materials of certain shales differ in constitution and in their manner of breaking down when undergoing destructive distillation . Other shales appear to contain oil - yielding materials that resemble each other closely as regards chemical constitution , yet they require some. what different conditions of treatment , if products of similar nature are to be produced from each . In such cases the controlling factors seem to be the richness of the shale that is , its content of oil -yielding material and the physical and chemical nature of its mineral parts .

Mar 1, 1922

By C. H. Riggs, Kenneth H. Johnston

The application of modern secondary-recovery methods has made possible the the extraction of more than 13 million barrels of crude petroleum from the eastern part of the Delaware-Childers field Nowata County, Okla., over and above the production that might have :been expected by continuing primary production methods, including the use of vacuum. Foremost among the secondary-recovery methods used in this foil was the repressuring of the Bartlesville sand with air and gas through injection wells spaced on sym-metrical patterns. Between 1925 and 1945, about 51 billion cubic feet of air and gas were injected into the producing formation, and the total recovery was increased from, 25 million to about 40 million barrels of oil. To produce as much as possible of the 28 million barrels of recoverable oil remaining in the sand will require the initiation of systematic water-flooding projects on many properties and the continuation of air and gas injection on others.

Dec 1, 1946

By Forrest T. Moyer, Nina L. Jones, Mary B. McNair, Virginia C. Berté

To keep the mineral and allied industries informed of trends in the causes of accidents, and to point out the need for corrective measures, the Bueau of Mines collects, analyzes, and periodically publishes health and safety statistics. This report includes data for 1963 on injury experience, with related employment statistics, at coal mines in the United States. These data are presented in tabular form under the following headings:

Aug 1, 1965

By Michael J. Friedel

As part of an investigation aimed at mitigating the hazards caused by abandoned mine openings, the Bureau of Mines conducted a series of electromagnetic surveys in the Galena, KS, area of the Tri-State mining district. The application of monostatic ground-penetrating radar (OPR) and inductive electromagnetic methods for detecting and delineating hazardous mine openings and attendant features was demonstrated to be feasible for shallow mine workings (i.e., less than 35 ft) occurring below flat-lying areas. Accurate determinations of depth to a mine roof appeared to be limited to roughly 20 ft using the GPR method. Features such as mine voids, fractures, and zones of subsidence were located beneath the Mainstreet (State Highway 26) site using the GPR system. Both the GPR and inductive electromagnetic techniques satisfactorily located mine openings and pillars at the Hell's Half Acre site. Geophysical interpretations were supported by exploratory drilling and mine maps.

Jan 1, 1990

By Gergely Markos

Uranium mill tailings represent a potential threat to the human habitat by containing large amounts of radioactive and chemically toxic substances in high concentrations. These: undesired components enter the human habitat in various pathways such as by erosion and water or air transport. The main objective of this investigation was to evaluate the actual movement and model the potential movement of contaminants by seepage of water from the tailings into the subtailings soil. This report represents various models of the movement of contaminants using both theoretical approaches and empirical evaluation of data available from other investigations. The data consist of field measurements and laboratory determi¬nations of major and trace cations, the dominant anions, pH, and Eh of moist solids, extracts, and waters from the tailings and surroundings. Evaluation and interpre¬tation of data were accomplished by using Eh-pH diagrams, various statistical methods and the WATEQFC computer program. Data analyses show that the critical area of investigating movement- is the interfaces between tailings and the external environment. The chemical differences at interfaces seem to result in a sink system for contaminants. The tailings-soil¬-water system shows extreme complexities because of chemical and physical hetero¬geneity of the system preventing the use of a single comprehensive model to represent real conditions. The validity of the simplifying assumption used has been shown and increasing complexity has been built into the models. Analogs of these models can be used for evaluation of similar systems.

Jan 1, 1981