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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 John J. Sammarco

This report (Safety File Guidance 6.0) is the eighth in a nine-part series of recommendations and guidance addressing the functional safety of processor-controlled mining equipment. It is part of a risk-based system safety process encompassing hardware, software, humans, and the operating environment for the equipment’s life cycle. Figure 1 shows a safety framework containing these recommendations. The reports in this series address the various life cycle stages of inception, design, approval and certification, commissioning, operation, maintenance, and decommissioning. These recommendations were developed as a joint project between the National Institute for Occupational Safety and Health and the Mine Safety and Health Administration. They are intended for use by mining companies, original equipment manufacturers, and aftermarket suppliers to these mining companies. Users of these reports are expected to consider the set in total during the design cycle. • 1.0 Safety Introduction (Part 1).—This is an introductory report for the general mining industry. It provides basic system/software safety concepts, discusses the need for mining to address the functional safety of programmable electronics (PE), and includes the benefits of implementing a system/software safety program. • 2.1 System Safety (Part 2) and 2.2 Software Safety (Part 3).—These reports draw heavily from International Electrotechnical Commission (IEC) standard IEC 61508 [IEC 1998a,b,c,d,e,f,g]and other standards. The scope is “surface and underground safety-related mining systems employing embedded, networked, and nonnetworked programmable electronics.” System safety seeks to design safety into all phases of the entire system. Software is a subsystem; thus, software safety is a part of the system’s safety. • 3.0 Safety File (Part 4).—This report contains the documentation that demonstrates the level of safety built into the system and identifies limitations for the system’s use and operation. In essence, it is a “proof of safety” that the system and its operation meet the appropriate level of safety for the intended application. It starts from the beginning of the design, is maintained during the full life cycle of the system, and provides administrative support for the safety program of the full system. • 4.0 Safety Assessment (Part 5).—The independent assessment of the safety file is addressed. It establishes consistent methods to determine the completeness and suitability of safety evidence and justifications. This assessment could be conducted by an independent third party. • Safety Framework Guidance.—It is intended to supplement the safety framework reports with guidance providing users with additional information. The purpose is to assist users in applying the concepts presented. In other words, the safety framework is what needs to be done and the guidance is how it can be done. The guidance information reinforces the concepts, describes various methodologies that can be used, and gives examples and references. It also gives information on the benefits and drawbacks of various methodologies. The guidance reports are not intended to promote a single methodology or to be an exhaustive treatment of the subject material. They provide information and references so that the user can more intelligently choose and implement the appropriate methodologies given the user’s application and capabilities. The guidance reports comprise parts 6 through 9 of the series and are listed below: [5.1System Safety Guidance (Part 6).—This guidance supplements 2.1 System Safety. < 5.2 Software Safety Guidance (Part 7).—This guidance supplements 2.2 Software Safety. < 6.0 Safety File Guidance (Part 8).—This guidance supplements 3.0 Safety File. < 7.0 Independent Functional Safety Assessment Guidance (Part 9).—This guidance supplements 4.0 Independent Functional Safety Assessment.] [ ]

Jan 4, 2006

By Joseph M. Singer

Having established that sodium chloride reduces the incendivity of explosives, the Bureau of Mines studied the effect of sodium nitrate in reducing ignition hazards. Gallery experiments showed that sodium nitrate reduced the incendivity of certain explosives to 8 percent natural gas in air but increased their incendivity to coal dust predispersed in air. Laboratory experiments using hot jets from explosions of stoichiometric mixtures of methane-oxygen-nitrogen showed that both sodium chloride and sodium nitrate reduced the incendivity to methane, to mixtures of coal dust and methane) and to coal dust. The difference between the gallery and laboratory results with respect to coal dust is attributed to temperature-time effects.

Jan 1, 1967

This Part is concerned with the theoretical study of UHF radio communication in coal mines, with particular reference to the rate of loss of signal strength along a tunnel, and from one tunnel to another around a corner. Of prime interest are the nature of the propagation mechanism and the prediction of the radio frequency which propagates with the smallest loss. Our theoretical results are compared with measurements made by Collins Radio Co. This work was conducted as part of the Pittsburgh Mining and Safety Research Center&apos;s investigation of new ways to reach and extend two-way communications to the key individuals that are highly mobile within the sections and haulage ways of coal mines.

Jan 1, 1974

By Martin H. Stanezyk

The Bureau of Mines investigated leaching of selected copper sulfide minerals and a composite of impure flotation concentrates at elevated temperatures and pressures with ammoniacal solutions. Copper 1 (tractions of 96 percent were obtained by leaching chalcopyrite at 75° C under oxidizing conditions for 60 minutes. An extraction of 99 percent of the copper contained in the composite concentrate was obtained by leaching the product for 90 minutes at 75° C. In tests of bornite, chalcocite, and covellite, 90 to 97 percent of the copper was extracted at 20° C provided an 8-hour reaction period was used. At 75° C essentially complete dissolution of the copper from these three minerals was accomplished in 60 minutes. Additions of ammonium sulfate to the leach solutions were required to obtain high-percentage extractions of the copper from bornite, chalcocite, and covellite. Although ammonium sulfate was not required when digesting chalcopyrite, copper extraction was enhanced and less free ammonia was required when ammonium sulfate was added to the leach pulps. The chemistry of leaching copper minerals was studied. It was C, termined that chalcocite altered to covellite as one step in the dissolution When leaching iron-bearing copper sulfides, hydrated iron oxide formed on the mineral surfaces, indicating that a diffusion process prevailed. No evidence of covellite was detected.

Jan 1, 1966

By Arne Landsberg

Experiments were made with a batch reactor to determine the effect of gas pressures, temperature, and gamma radiation intensity on the reaction CO + Ch ? COC12. The equation, [dp = 0.0110 (1 - 0.01t) (PCOI)1/2 PC12] where [dP] is the change of pressure of phosgene with time (atm/hr), t is the temperature (°C), PCO and PC12 are the reactant pressures (atm), and I is the radiation intensity (r/hr), was found to best fit the data. Oxygen and a large ratio of reactor surface to volume retarded the reaction, but inert gases had no effect. A low-temperature reactor system is proposed to take advantage of the conditions which give a high reaction rate with gamma radiation and a simple scheme of product purification.

Jan 1, 1970

By Robert W. Smith

The Bureau of Mines is engaged in a systematic evaluation of the thermodynamic properties of combustion gases. These studies are designed to provide basic thermodynamic information of high accuracy, facilitating the theoretical study of flame and combustion phenomena. This report is the fourth of a series4/ presenting results of the study for particular fuel-oxidant systems. These calculations have as their objective the evaluation of the constant pressure flame temperatures of methane-air, propane-air, and ethylene-air mixtures for a range of pressures.

Jan 1, 1953

By Edward D. Thimons

A remote-actuated stench gas fire-warning system has been designed and tested by the Bureau of Mines. This system makes use of the hard-wire network for the mine&apos;s phone pager system, thus greatly reducing the system cost. By locating stench gas canisters with remote-actuation release capabilities near working sections, the fire-warning time can be greatly reduced. In a test of the system in a Missouri lead mine, the time required to warn miners of a fire at two working faces was reduced from about 20min with the conventional system to less than 4 min with the remote-actuated system.

Jan 1, 1984

By K. K. Kelley, W. W. Weller

The heat capacities of four crystalline silicates of barium ( BaSiO3 , BaSiO4 , Ba Si¸0 , and BaSi₂0 ) and two crystalline silicates of strontium (SrSio and Sr₂Sio ) were measured over the temperature range from 51 ° to 298° K. The results were used to evaluate the entropies at 298.15 ° K. The entropy values were joined with known heats of formation to obtain the free energies of formation of the silicates with respect to their constituent oxides at 298.15 ° K.

Jan 1, 1964

By F. P. Haver

A method to recover copper and elemental sulfur from chalcopyrite concen¬trate, using a ferric chloride leach, CuFeS2 + 3FeCl3 ? CuCl + 4FeCl2 + 2S, was reported by the Federal Bureau of Mines in 1971 (Report of Investigations 7474). Since that time, additional work has been done to improve certain steps in the procedure; that is, the recovery of sulfur from the leach residue, the recovery of copper and iron from the leach solution, and the regeneration of the leach solution. It was determined that over 99 pct of the elemental sulfur in the leach residue could be extracted at ambient temperature with an ammonium sulfide solution. Heating the pregnant solution precipitated crystals of rhombic sulfur (99.5 pct purity) and liberated ammonia and hydrogen sulfide for recycle. Copper with a purity in excess of 99 pct was obtained from the leach solution by electrolysis, using a diaphragm cell, with an energy requirement of less than 0.7 kW-hr/lb. Metal was deposited as a weakly adherent powder that could be easily dislodged from the cathode and withdrawn continuously from the cell in the form of a slurry. During electrolysis, part of the Fe(II) was oxidized to Fe (III) at the anode so there was no chlorine evolution. The leach solution was regenerated by direct oxidation of the spent electrolyte with air or oxygen in a turboaerator at 80° C. This precipitated the iron dissolved during leaching in an easily filterable form, Fe203.xH20, and converted the remaining Fe(II) to Fe(III).

Jan 1, 1975

By John J. Sammarco

This U.S. Bureau of Mines report describes the research effort and results for a computer-assisted appendage control system of a Joy 14CM continuous mining machine. The cutter head (shear), gathering head, conveyor, and stabilizer jack are the appendages. Positional control of each appendage is accomplished by specifying the desired position to the appendage control computer, which uses appendage position sensor data. Appendage movement is actuated until the desired position is attained as determined by control algorithms. A description of the sensors, mechanical and electrical interfaces, data acquisition and control (DAC) system, experimental method to determine appendage response characteristics (range of motion, start and stop delay times, and movement rates), and their application to the position control loop algorithms are presented. Also, the test results for the shear in an unloaded (free space) and loaded (cutting) condition of the shear are presented.

Jan 1, 1991

By L. F. Willmott

Pulverized high-volatile A bituminous coal was gasified with oxygen and superheated steam in a pressure-gasification pilot plant equipped for slurry feeding. The minimum ratio of water to pulverized coal that could be pumped satisfactorily as a slurry was about 1 to 1. Heating this slurry produced a suspension of coal in superheated steam having a steam-to-coal ratio greater than the 0.3 to 1 proportion that is considered optimum for pressure gasification of pulverized coal. A steam separator removed enough steam to provide ratios down to about 0.5 to 1, but a 0.3 to 1 ratio was not achieved. Gasification of Sewickley coal produced a synthesis gas containing about 36 percent H2, 46 percent CO, and 13 percent CO2, Gas output, gas composition, and coal and oxygen requirements were Virtually the same as for a pilot plant equipped for fluidized-coal feeding. Typical results from the slurry-fed plant at 300 psig were carbon gasified, 95 percent; coal requirement, 34 lb/M (thousand) std cu ft CO + H2 produced; oxygen requirement, 365 std cu ft/M std cu ft CO + H2 produced. The results showed that the two feeding methods are equally satisfactory from the standpoint of gasification. A choice between a fluidized-coal gasification process or a slurry gasification process depends on considerations relating to the coal-feeding phase itself, including capital and operating costs, manpower requirements, safety, and flexibility of operation.

Jan 1, 1962

By G. R. Hopkins, E. M. SEELEY

According to reports received by the Bureau of Mines, Department of Commerce, as of Jamary 1, 1930, there were 1,035 natural-gasoline plants in the United States, with a total daily capacity of 10,516,000 gallons. (These data do not include one small plant in Alaska.) The last similar survey, that of Jamary 1, 1928, showed a total of 1,155 plants of 8,048,000 gallons daily capa- city. This in two years time the number of plants has decreased by 120, but the total capacity has increased 2,468,000 gallons or 31 per cent. This is roughly equivalent to the gain in production over the same periodi Over half of the increase in total capacity was registered in California, where the development of flush oil production having a comparatively high gas-oil ratio in such fields as Santa Fe Springs led to construction of some new plants and material enlargement of others. Of the total plants, 999 were operating on Jamary 1, 1930, and 36 were shut down. This compares with 1,060 operating and 95 shut down two years ago, which indicates a tendency to dismantle plants as soon as they become obsolete or umrofitable. The total daily capacity of the plants operating on Jamiary 1, 1930, amounted to 10,278,000 gallons, or 98 per cent of the total, leaving only 238,000 gallons, or 2 per cent, for the shut-down plants. This contrasts with the refining industry, which usually has 5 per cent of its total capacity idle; the difference is due to the relative ease with which a refiner can secure a crude supply as against the difficulty the natural gasoline manufacturer has in reestablishing his gas connections. During 1929 the average total daily capacity of the operating plants was 9,899,000 gallons, while the average daily production amounted to 6,015,000 gallons. This indicates that the plants operated during 1929 at 61 per cent of their capacity. Although over 60 plants were dismantled in Oklahoma during 1929 the State continued to rank first in total mumber. California was second in mumber of plants with 165, and was one of the few States that showed a gain since the

Jul 1, 1930

By James Noll

Total carbon (TC) is sometimes used to measure or characterize diesel particulate matter (DPM) in occupational settings such as underground mines. DPM samples are collected on quartz fiber filters. When using quartz fiber ?lters, adsorption of gas phase organic carbon (OC) has been reported, causing a positive bias in the particulate TC results (adsorption artifact). Most of the data on the sampling artifacts and corrections apply to environmental air sampling, where samples are collected at a much higher filter face velocity and the OC concentrations are generally much lower relative to occupational sampling. In this study, we investigated the effects of adsorption artifact on samples from occupational settings. Samples were collected with and without denuders to determine the amount of gas phase OC collected and the accuracy of certain corrections. In underground stone mines, the adsorption artifact was found to positively bias the particulate TC by greater than 20% for filter loadings below 25 µg/cm2 TC (8-h time weighted average) 262 µg/m3). The tandem ?lter correction reduced the effect of the artifact, as high as 60% of the TC value, to less than 11% for laboratory data. It also significantly reduced the effect of the artifact obtained for field samples.

Jan 1, 2008

By E. F. Foerster

The Bureau of Mines used a diphenyl ether calorimeter to determine the heat contents of natural and synthetic blast-furnace slags. For solid slags, enthalpy (HT-H298) at 1,448° to 1,680° K ranged from 282.1 to 348.5 cal/g (±3 percent); liquid slag values were 400.1 to 514 cal/g (±3 percent) in the temperature range between 1,626° and 1,890° K. Experimental results for liquid slags were 14.3 to 16.2 percent higher than the enthalpies calculated from thermodynamic tables; values for solid slags ranged from 5.3 percent lower to 3.9 percent higher than calculated values. Experimental results for liquid synthetic slags ranged from 14.9 to 24.3 percent higher than the calculated enthalpies; values for solid synthetic slags were from 1.0 to 3.4 percent higher.

Jan 1, 1967

By James E. Mauser

This report deals with the investigation of a continuous process for producing pure zirconium. It covers the construction, operation, and maintenance of the semicontinuous reactor. The report covers a study of test variables, such as reactor temperature and reluctant charge weights, and evaluates the results, such as billet metal hardness, residual billet salt content, and suitability of a purified billet as a consumable electrode for arc melting. The purpose of this project was to develop an inexpensive and continuous process for producing pure zirconium. The process developed, termed the semicontinuous reactor process, produced billets of compacted zirconium sponge. The metal was produced by reducing zirconium tetrachloride with sodium and magnesium beneath molten byproduct salt. Hydraulic rams at each end of a vertical reaction tube compacted the sponge and ejected it as a billet. These billets were purified by heat under vacuum to remove entrapped salt. The goal was to utilize the purified billet directly as a consumable electrode for arc melting.

Jan 1, 1961

By A. Gene Collins

Rapid, sensitive, and precise methods of determing major, minor and trace constituents of oilfield brines are needed. Several methods have been developed or adapted by the Federal Bureau of Mines at the Petroleum Research Center, Bartlesville, Okla. The following methods are described in this report: Spectrophotometric and volumetric for iodides and bromides; potentiometric for pH, alkalinity, acidity, borate boron, total boron, and organic boron; gravimetric for potassium; disodium ethylenediaminetetraacetate (EDTA) volumetric for total hardness, calcium, and magnesium; spectrophotometric for fluorides; and color comparison .for arsenic. Adequate sensitivity, precision, and accuracy were obtained for each method. The Bureau of Mines pioneered in research on the analysis of oilfield waters (2, 46, 47).6 However, several of these early procedures were quite time consuming. Also, they did not include methods for determining trace and minor constituents of brines.

Jan 1, 1961

By Hewitt Wilson

A review is given of the nomenclature, sources, imports, statistics, common methods of preparation, and testing of mineral pigments. A description of the Deer Park-Spokane colored-clay district and the laboratory methods of preparation of these colored clays, others, and siennas follows. The mineral pigments were prepared by washing or grinding the original material as received and by calcination of the yellow ocher and brown sienna with and without manganese dioxide to produce red, brown, and black colors. These prepared powders were tested for fineness, oil absorption, and color as compared with well-known brands of commercial pigments. Similar tests were made with several basalt red clays occurring in the neighborhood of Salem, Oreg., and Kalama, Eatonville, and Clay City, Wash. The color particularly was studied, since this property is the most important commercial characteristic of the minerals. PURPOSE OF INVESTIGATION Since the development of the clay industry in the Pacific Northwest, some curiosity and interest have been aroused by the red and yellow clay or ocherouslike material that has often been found associated with the commercial clay deposits. These include the red and yellow "paint pots" near Deer Park and Spokane in eastern Washington, a red clay at Clay City, another close to Eatonville in western Washington, and red basalt earths near Salem, Oreg., and along the Columbia River near Kalama, Wash. Several companies have been organized to produce pigment colors from two of these deposits but have either discontinued or never started operations.

Jan 1, 1929

By John Nagy

The effect of low percentages of methane (0 to 5 pet.) in an air atmosphere on spark initiated explosions of coal dust was investigated. With low dust concentrations (0.1 to 0.4 oz./cu, ft.), small amounts of methane increase the explosion pressure; with larger dust concentrations (0.5 to 2.0 oz./cu. ft.), small amounts of methane decrease the explosion pressure. The rate of pressure rise of a coal dust explosion increases with increase in methane concentration; about 3 to 4 pct. further addition of methane yields a decrease in the rate of pressure rise. Convection currents created by the air or gas blast used to disperse dust produce an increase in explosion pressure and rate of pressure rise. The minimum explosive concentration of the coal dust decreases about linearly as the concentration of methane increases from 0 to 5 pct. The explosion pressure increases linearly as the initial pressure within the chamber increases. Similarities between coal dust and methane explosions are indicated, INTRODUCTION During coal mining, methane occluded in coal or adjoining strata is liberated into the mine atmosphere,4 Normally, the methane is diluted and swept away by the ventilating air. Under some conditions, through accidental disruption of the ventilation system, sudden outburst, or because insufficient fresh air is supplied to a working place, low percentages of methane may be present during mining operations. If it is permitted to accumulate, methane itself presents an explosion hazard; its limits of explosibility arc approximately 5 and 15 pct. The effect of low percentages of methane on the explosibility of coal dust was studied to provide a broader understanding of the hazards of ignition and explosion and thus to facilitate development of control

Jan 1, 1961

By F. H. Nehl

The U.S. Bureau of Mines investigated the selective electrowinning of Ag and Au from cyanide solutions contaminated with Cu with the goal of decreasing the amount of Cu codeposited. Decreasing Cu codeposited will reduce refinery costs. Direct current was applied to the cell in pulsed and square wave voltages at 0.070 A?h per 150 mL of solution. Times tested for each cycle ranged from 1 to 10,000 ms. Graphite, lead, and stainless steel were evaluated as electrode materials. Square wave electrowinning at 70° C gave the best separation of Ag and Au from Cu. Applying 2.5 V during the duty cycle, 0.0 V the rest of the period, a duty cycle of 10 to 30 pct, and a period of 100 to 1,000 ms gave the following results: Ag concentrations decreased from 34 to 0.1µg/mL, Au concentrations decreased from 54 to 0.2 µg/mL, and Cu concentrations remained almost constant at 560 µg/mL.

Jan 1, 2010