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By B. L. Razzaboni, P. Bolsaitis

"The formation of reactive oxygen species resulting from the interaction of silica dust particles with red blood cell membranes was investigated; particularly, the effect of surface hydroxyl (silanol) group concentration on the rate of formation of such reactive oxygen species was investigated. The rate of formation was measured indirectly through the effect of catalase, a hemoprotein peroxidase, on silica-induced hemolysis. It was found that the addition of exogenous catalase to erythrocytes markedly reduces the hemolysis caused by silica particles. Furthermore, the amount of catalase required for deactivation of silica per unit area of particle surface is lower for fumed silica particles and calcined crystalline particles than for uncalcined, crystalline silica, suggesting a correlation between the concentration of OH groups at the silica particle surface and its potential for generation of H2O 2• The addition of albumin, a copper chelator, also decreases hemolysis. These results suggest that the hemolysis caused by silica particles is at least partly related to the formation of H2O2 at the particle surface and its subsequent reaction with Cu+ ions. The relationship between the concentration of surface silanol groups on the silica surface and the amount of catalase required to decrease hemolysis may also provide a method for testing potential fibrogenicity of respirable dusts. IntroductionReactive hydroxyl groups on silica surfaces are known to be cytotoxic and are believed to play a major role in silicosis (1-9). It has been proposed that this cytotoxicity results from hydrogen bonding to cell membranes and a resulting increase in membrane fluidity and permeability (4). Surface hydroxyl groups on silica surfaces have also been shown to interact with carbonyl oxygens in cell membranes (1,5). An extensive study by Nolan et al. (6) of the relationship between the negative surface charge resulting from ionized silanol groups and the hemolytic activity of crystalline a-quartz (Min-U-Sil) has shown a positive correlation between hemolytic activity and the surface concentration of silanol groups. These authors demonstrated that the hydrogen bonding of polyvinyl-N-oxide (PVPNO) with silanol groups, as well as the bonding of metal cations to the ionized sm- groups, results in significant decreases in hemolytic activity. Furthermore, it has been found that the complete removal of surface hydroxyl groups from the surface of respirable silica particles nearly eliminates the hemolytic potential of silica (7), suggesting that hydroxyl groups might be involved in other cytotoxic processes associated with silica-induced lung injury. Reactive oxygen species have been .implicated in cellular damage caused by respirable silica particles. Evidence for the presence .of oxygen radical species (02, OH°, H2O2) generated by silica, especially on freshly formed surfaces, has been produced by various investigators. Kalbanev et al. (8) detected H2O 2 in aqueous suspensions of quartz. Electron spin resonance and spin trapping by Shi et al. (9) confirmed the presence of OH"" radicals in aqueous suspensions of quartz, and Gulumian and van Wyk (10) suggested that both glass and quartz produce hydroxyl radicals in the presence of H2O 2 • Gabor et al. (11) detected the presence of malondialdehydereactive lipid peroxides (i.e., lipid-0°) in cultures of macrophages and respirable silica particles using the thiobarbituric acid (TBA) reaction test. Will (12), however, reported that iron enhances the TBA value of peroxidized lipids, and Scheulen and Kappus (19) found that catalase augmented malondialdehyde formation, thereby increasing the TBA values."

Jan 1, 1990

By Leslie D. Marrus

This project and final report represent an effort to collect, analyze, and verify reliability and performance data on currently available medium -to-high seam models of continuous miners being used in underground coal mining. The analysis determined availability, mean time and tons between failures, amounts of down time associated with various failures, labor and part costs required to correct failures, and various indices of maintainability. Machine performance and reliability are discussed relative to cumulative tons (machine age) produced and production rates (machine loading). It was determined that performance can be significantly improved given preventive maintenance programs that will increase machine availability.

Jan 1, 1976

By Michael G. Zabetakis, Glenn H. Damon, Joseph A. Herickes

The flammability and explosibility of unsymmetrical dimethylhydrazine ( UDMH ) were investigated by the Federal Bureau of Mines to evaluate hazards associated with commercial application of this material as a missile fuel . This program included the following determinations : 1. Temperature limits of flammability in air at one atmosphere pressure ; 2. limits of flammability at selected elevated temperatures and pressures ; 3. 4 . 5. spontaneous ignition temperature in air at one atmosphere and at 200 pressure per square inch gage ( p.s.i.g. ) initial pressure ; spontaneous decomposition temperatures in nitrogen at one atmosphere and at 200 p.s.i.g .; shock sensitivity over a temperature range from about ( ca. ) 25 ° to 50 ° C .; 6. shock sensitivity of reference propellants ( hydrazine , nitromethane , methyl acetylene , etc. ) ; 7 . shock sensitivity of UDMH plus small amounts of selected metal catalysts . Part of the corresponding data was obtained for a mixture of unsymmetrical - dimethylhydrazine and diethylenetriamine ( U - DETA) .

Jul 1, 1960

By Theodore Kessler

The purpose of this Bureau of Mines investigation was to determine what new organic compounds or high concentrations of a particular organic species can be formed by exposure of coal derivatives to ultrasonic energy. Tetralin, l-methylnaphthalene, and pyridine were used as model compounds. Gaseous and solid reaction products resulting from the ultrasonic irradiation of these coal derivatives were determined using mass spectrometry. Products from the irradiation of tetralin were studied as a function of time, atmosphere, and sample size. The sonolysis (chemical reactions produced by ultrasonic energy) of tetralin and l-methylnaphthalene produced C2H2, HCN, CH4, H2, CO, and CO2, depending upon the experimental conditions. The ultrasonic irradiation of tetralin also produced diacetylene under certain experimental conditions. The cleavage of organic chemical bonds by ultrasonic cavitation in the absence of water was also observed in this study.

Jan 1, 1967

By H. E. Perlee

Autoignition temperatures and limits of flammability of nine halogenated hydrocarbons in atmospheres of air, oxygen, and nitrogen tetroxide were measured in a modified standard autoignition apparatus and limit-of-flammability apparatus previously developed at the Bureau of Nines. Of the nine halogenated hydrocarbons investigates--bromochloromethane, bromotrifluoromethane, bromochlorodifluoromethane, 1,1,2-trichlorotrifluoroethane, 1-bromo-l-chloro-2,2,2-trifluoroethane, dibromodifluoromethane, l,2-dibromo-1,1,2,2-tetrafluoro-ethane, 1,1,1,3,3-pentachlorotrifluoropropane, and l-bromo-2,4-dichloro-1,1,2, 3,3,4-hexafluorobutane--two formed flammable mixtures with nitrogen tetroxide and six with oxygen; none formed flammable mixtures with air. Three of the halogenated hydrocarbons formed no flammable zones with any of the three oxidizing atmospheres. For those halogenated hydrocarbons that supported combustion in oxygen atmospheres, explosion pressures developed during constant-volume burning of mixtures near the middle of the flammable zone were observed to range from about 6 psig for dibromodifluoromethane to 158 psig for 1-bromo-1-chloro-2,2,2-trifluoroethane. In all cases, the calculated burning velocities of these mixtures were less than 8 in/sec.

Jan 1, 1966

By Margaret E. Egan

Reliable fire detection is essential for both safe evacuation and containment or extinguishment. In order to increase reliability by reducing the number of nuisance fire alarms in underground mines that use diesel-powered equipment, the U.S. Bureau of Mines has developed a diesel-discriminating fire detector (DDD). It was designed to discriminate between smoke produced by a fire and the smoke-laden exhaust of a diesel engine. Experiments were conducted by the Bureau to compare the smoke detection capabilities of the DDD with those of conventional fire detectors in response to smoldering coal and conveyor belting. A comparison was made among the alarm times of a carbon monoxide (CO) detector with an alarm threshold of 5 ppm, a smoke detector with an optical density alarm threshold of 0.044 of', and the DDD with an alarm threshold of 0.025 V. The results show that the DDD will reliably detect developing coal and conveyor belt fires. The average time delay separating the DDD alarm from the first detector to alarm was 76 s for smoldering conveyor belt and 65 s for smoldering coal. The longest time delay between the response of the DDD and the first detector to alarm was approximately 120 s.

Jan 1, 1993

By J. E. Chilton

The Bureau of Mines has developed a portable flammable gas detecting system for estimating the flammable gas concentrations in a mine containing one or more combustible gases at concentrations up to 100 vol pct. With this portable detecting system, mine rescue or recovery personnel can quickly determine if they are working in a potentially explosive gas atmosphere and either leave the area or make appropriate changes in the fresh air ventilation of the mine to render the area safe. The detecting system uses a commercial, intrinsically safe, flammable gas detector with a range from 0 to 5 vol pct methane (CH4). The flammable gas detector has a catalytic heat-of-combustion sensor that can detect all flammable gases that would be encountered in a mine including methane (CH4), ethane (C2H6), carbon monoxide (CO), and hydrogen (H2). To determine the mine gas concentration, the rescue worker dilutes a sample with fresh air carried within the detecting system. The concentration of the diluted sample is then measured with the permissable flammable gas detector. The actual mine gas concentration is calculated from the product of the indicated diluted gas concentration and the system dilution ratio using a pocket calculator or the nomograph on the side of the unit.

Jan 1, 1987

By J. A. McAllister, H. G. Iverson, K. C. Dean

"INTRODUCTION During the course of the investigation of the occurrence of manganese deposits in the western United States, laboratory studies of concentration were conducted at the Salt Lake City station on a sample of ore from the Lake Valley mines of the Newalpitt Fluorspar Corp. of Deming, N. Mex. The ore was reported to be representative of the type that would be mined for mill feed. The sample tested was found to be amenable to beneficiation by ore-dressing methods for the production of products that, when sintered, assayed over 44 percent Mn.At the beginning of the investigation of manganese-ore beneficiation in December 1940, the only product marketable to Metals Reserve Company was ferrograde manganese grade B, the requirements for which follow: Mn, min., 48 percent; Fe, max., 7 percent; Si02, max., 10 percent; P, max., 0.18 percent; Al203, max., 6 percent; Zn, max., 1 percent, Al2O3,Later the specifications were modified gradually. As of May 15, 1943, manganese products were acceptable if they contained over 35 percent manganese and less than 3 percent zinc and 1 percent phosphorus. Prices were based upon material containing 48 percent manganese, 6.0 percent iron, and 11 percent silica plus alumina. Premiums were paid for manganese content in excess of 48 percent and iron content below 6 percent, penalties being imposed upon products containing less than 43 percent -manganese, or more than 6 percent iron, or more than 11 percent silica plus alumina. The specifications for commercial manganese further required that maximum particle size be 12 inches and that, 75 percent of the product be coarser than 20-mesh. Therefore, fine material such as table and flotation concentrates had to be nodulized or sintered. In addition, oarbcnate manganese ores were not acceptable unless calcined."

Feb 1, 1948

By A. B. Hooker, L. C. IlsLey

"The last previous Bureau of Mines publication relative to details of permissible electric mine lamps is Bulletin 332, which describes 16 lamps approved prior to May 1930. Some of the lamps have become obsolete through the development of improved models which, with several new types, make it desirable to supplement the Bureau's published data relative to permissible electric mine lamps.In the following descriptions, lamps approved since May 1930 and prior to July 1, 1935, are placed in the three following groups: (1) Electric cap lamps, (2) electric hand lamps, and (3) lamps for miscellaneous applications,ELECTRIC CAP LAMPS APPROVED UNDER SCHEDULE 6B1. Edison model J lamp, approval no. 24. - The features that distinguish this lamp from earlier models of Edison electric cap lamps are:(a) The battery consists of two F-2 cells of square cross section and about 1-1/4 inches higher than M-14 cells in the model H lamp, making the battery narrower and higher than any of the earlier models of Edison cap lamps.(b) The cells are insulated from each other and the Monel-metal casing by enclosure in vulcanized-rubber baglike enclosures. Both cell terminals are insulated from the cell jar.(c) The battery is equipped with rubber-tube Bunsen-valve-type gas vents.(d) The battery casing is secured by a new-type magnetic lock.(e.) The battery and cover terminal clips have been redesigned to give a wiping contact."

Jun 1, 1936

By R. E. Lindstrom

Electrooxidation techniques were investigated on a bench scale by the Bureau of Mines to determine the applicability of the process for extracting molybdenum and rhenium from low-grade molybdenite concentrates. Parameters affecting the extraction, such as pulp density, power consumption, reagent requirements for pH control, and electrolytic cell configuration, were studied. Molybdenum and rhenium extractions of 98 to 99 percent were achieved from several concentrates containing 4.76 to 28.6 percent molybdenum and 180 ppm to 1,000 ppm rhenium. Optimum results were obtained by maintaining pH values between 5.5 and 7.0 during electrolysis and allowing the final pH to rise to about 8.2. Reagent consumption was 4 to 6 pounds of sodium carbonate per pound of molybdenum extracted. The power consumption declined from a range of 12 to 25 kilowatt hours per pound of molybdenum extracted with immersion electrodes to 9.7 kilowatt hours with a bipolar flow-through cell; however, molybdenum extraction was independent of cell configuration.

Jan 1, 1973

By Martin Hertzberg

The concept of limit burning velocities is used to formulate a quantitative theory of flammability limits. Competing processes dissipate power from a combustion wave and quench propagation at some characteristically low limit velocity. There are four competing processes and one complication: (a) Free, buoyant convection, (b) conductive-convective wall losses, (c) radiation, (d) selective, diffusional demixing (the complication), and (e) flow gradient effects (flame stretch). These complexities are unraveled by creating an idealization that is initially freed from these competing processes. The ideal serves as a standard, and its burning velocity (Su), ideal is a unique function of the initial thermodynamic variables of state. By adding each process individually, it is possible to evaluate their significance, quantitatively, in terms of a limit velocity (Su)a , b , c , or e , and to explore the nature of their cooperative interactions. The larger the limit velocity, the more significant the process. The apparently diverse observations of flammability behavior are readily unified within this simple, conceptual framework.

Jan 1, 1976

By A. R. Taylor

Using solution calorimetry, the following heats of reaction were determined: (1) NaCN(c) + 1/Cu20(c) + 129H20(l) ? CuCN(c) + NaOH?128.5H2O ?H = -13.44±0.10 kcal/mole, (2) HCN(2) + NaOH?128.5H20 ? NaCN(c) + 129.5H20(l) ? = -2.52±0.02 kcal/mole. From these reactions, the heats of formation for CuCN(c) and HCN(2) were calculated to be 22.7±0.4 kcal/mole and 24.9±0.4 kcal/mole, respectively. Reaction 2 was made to check the consistency of literature values for heats of formation of HCN and NaCN. Adiabatic calorimetric measurements between 10° and 400° K showed the entropy and heat capacity of CuCN(c) to be 21.51±0.06 eu and 14.58±0.04 cal/mole deg, respectively, at 298° K. A broad anomaly in the heat capacity was found in the temperature range 285°-320° K. The heat of transition associated with this anomaly was less than 1 cal/mole, the sensitivity of the measurements.

Jan 1, 1971

By G. W. Jones

The Bureau of Mines has advocated the use of stenches as warning agents in metal mines and in gas-distribution systems since 1920 A considerable amount of research has been conducted on ethyl mercaptan and other compounds to determine their effectiveness when used for this purpose.4/5/6/7/8/9/10/11/12/13/ Miners are warned of danger by a stench injected, in measured quantity, into a compressed-air line through which it is rapidly carried to the working faces, where it escapes from the compressed-air equipment and imparts a characteristic odor to the air. This method is not applicable to mines where only a limited number of com-pressed-air lines are used, as for example, many coal mines; the ventilation currents available in these mines may be too slow for warning purposes.14/

Jan 1, 1954

By V. Castranova, T-M. Ong, V. Vallyathan, M. J. Keane, W. E. Wallace Jr.

"Inhalation of certain forms of silica, asbestos and some other respirable dusts can result in pulmonary fibrosis, characterized by destruction of the surfaces of alveoli and respiratory bronchioles. Fibrous thickening of the alveolar septa decreases the lung's capacity for gas exchange.Pulmonary macrophage damage by respired dust may initiate the fibrotic response.In one proposed mechanism, dust particles interact with the plasma membrane of a macrophage. This damages the cell or induces some hyperactivity of the cell, resulting in excessive release of lysosomal enzymes and reactive forms of oxygen (1). These reactive enzymes or radicals then damage the alveolar surface epithelial cells. A second mechanism has also been pro¬posed (2,3) in which dust damage to the macrophage causes the release of mediator substances which induce pulmonary fibroblast cell proliferation and increased collagen synthesis. This produces fibrous tissue in the terminal air spaces (4,5).Mineral surface interactions with plasma membrane lipoproteins have been proposed as a mechanism of lytic damage of pulmonary cells by silica dust in numerous models (6,7). The significance of dust surface proper¬ties has been further revealed in studies showing significant changes in dust induced cytotoxicity as a function of dust surface crystallinity and organic or inorganic contamination or coating of mineral surfaces (8,9). Such modification of the mineral surface might interfere with surface sites responsible for the toxicity of dusts for pulmonary macrophages, thus interrupting the early stages of the process of fibrosis.In vitro cellular assay systems using erythrocyte hemolysis or the release of macrophage cytosolic or lysosomal enzymes following dust challenge, have been used to analyze the initial mechanism of dust damage to cells. However the ability of these assays to predict the pulmonary disease producing potential of various dusts is imperfect owing to some ""false positive"" results. These assays as performed are therefore questionable models for the initial lesion in pneumoconiosis or silicosis. In particular, kaolin frequently is found to have comparable biological activity to silica quartz in these assays (10,11).Silica and kaolin have distinctly different fibrogenic potentials. Silica is highly fibrogenic, resulting in both acute and chronic silicosis (12). Some epidemiological data and animal experimentation data have indicated that long term exposure to kaolin can result in pneumoconiosis; however, kaolin is relatively benign as compared to silica (13-18). Kaolin is also of interest because it is one of the major mineral inclusions in Eastern U.S. bituminous coals. We have observed that exposing respirable sized native silica or kaolin for two hours to pulmonary macrophages results in a greater enzyme release for kaolin exposures, on a dust mass basis. Exposure of erythrocytes to the dusts also results in greater levels of hemolysis by kaolin for equal mass respirable dust doses. Therefore, these results do not correlate positively with known disease inducing potentials of the two dusts.Characterization of physical and chemical surface properties of dusts involved in occupational exposures, and characterization of the alteration of those surface properties which are likely to occur upon deposition of the dust in the lung, should improve the identification of respiratory disease hazards.Inhaled dust particles deposited in the lower respiratory tract will come in contact with pulmonary surfactant. This surfactant forms a surface film on and emulsion in the liquid hypophase coating of the alveoli and respiratory bronchioles. The primary constituent of this pulmonary surfactant is the lipid diacyl glycerophosphorylcholine, lecithin (19). Because this lipid is also a major component of cell membranes, it is possible that surfactant can interact with mineral dust to alter its Interaction with macrophages and other pulmonary cells and, thus, it"

Jan 1, 1988

By Guy A. Johnson

To improve productivity and cut costs, modern underground mining operations have become more mechanized. This mechanization has increased the usage of fuels, hydraulics, and electrical equipment associated with diesel-powered vehicles, thereby also increasing the hazards of underground mine fires. The Bureau of Mines evaluated the fire hazard problem and assembled prototype components for a system that would automatically sense and extinguish fires on mobile underground equipment. The prototype system and alternative designs were in-mine-tested and proved effective. This report summarizes this technology, which can cost effectively help solve the problem of fire hazards on underground vehicles.

Jan 1, 1983

By L. H. Adami

The heats of formation of anhydrous cadmium sulfate, cobalt sulfate, copper sulfate, nickel sulfate, and zinc sulfate were determined by hydrochloric acid solution calorimetry. The values at 298.15° K for formation from the metal, rhombic sulfur, and oxygen gas follow (cal/mole): CdS04J -222.0 ± 0.3; CoS04, -212.0 ± 0.4; CuS04) -183.4 ± 0.6; NiS04, -208.1 ± 0.2; and ZnS04, -233.1 ± 0.2. Corresponding heats of decomposition to form the metal oxide, sulfur dioxide, and oxygen were derived from these results; heats of decomposition to form the metal oxide and sulfur trioxide were also derived.

Jan 1, 1965

This NIOSH Toolbox Training program contains 52 different modules designed to stimulate safety discussions among your employees. Each module is intended to be completed in roughly 10 or 15 minutes, so a Toolbox Training session can be conducted once a week for the entire year. Each session counts toward your employee’s 8-hour annual MSHA refresher training, thus saving an entire day of work.. The modules are used to refresh employees on the procedures, policies, and practices of working safely at a specific mine site and can easily be tailored to fit conditions and situations found on your property. Every module follows the same format, so that as the weeks pass, miners will start to approach every safety situation in the same way. A typical Toolbox Training session contains five basic steps that cover all the information in the module. 1. Identification of the hazard and discussions about the types of injuries typically associated with the hazard. 2. Discussions of some of the causes of the hazard. The MSHA example included with each module should be referenced. 3. After the hazard and accident has been explained and understood, discussions about best practices and tips for avoiding a similar accident. 4. Review of similar conditions or near misses from your mine site using the leading questions on the form to start a discussion. Specific examples of equipment or structures on the site that could lead to the same accident should be discussed. The blank space on the module is used to add your own remarks and questions to supplement the given information. 5. Miners fill out the training record on the back of the form with name, initials, and date of training session. The modules are designed to be kept in a standard three-ring binder and easily photocopied. This way, the same set of modules can be used for years to come. A blank form is included that can be used to create more Toolbox Training modules. The key component of Toolbox Training is to start a discussion among employees that will allow them to see the hazards around them every day and respond to these hazards in a safe and consistent manner. To start a discussion, ask questions that need more than a one-word response. Get the miners to talk about similar situations from their own experiences and give suggestions about how to fix the hazards around them. Toolbox Training is a quick and effective way to cover specific mining hazards, but it only works if miners are involved in the discussion.

Jan 1, 2004

By Edward F. Divers

This Bureau of Mines report describes a new type of scrubber (dust collector) and ventilation system built into the auger support frame (boom) of a Jeffrey 120L continuous mining machine. With this twin scrubber arrangement, one scrubber is mounted into each side of the boom. Each scrubber includes a 2,500-cfm fan, a flooded fibrous-bed scrubber panel, and a water droplet eliminator. The system was designed for minimum size and adds only a few inches to machine height. Exhaust duct design allows flexibility with various airflow configurations to suit both blowing and exhaust fare ventilation systems and brattice distances ranging up to 20 feet. Full-scale tests with exhaust ventilation were conducted at a Mine Safety and Health Administration surface facility at Bruceton, Pa., to determine the scrubbers' methane dilution capability. Several configurations of the twin scrubber-ventilation system produced striking improvements in face methane dilution when compared with conventional systems.

Jan 1, 1981

By Jos. R. Guiteras

This paper is one of a series describing; mining and milling methods and costs being published by the Bureau of Mines. It deals with the mineral resources of western South Dakota and describes the mining and milling of tantalite and associated amblygonite by the Black Hills Tin Co. and the Fansteel Mining Corporation. ACKNOWLEDMENTS Acknowledgment is made to Earl C. Schultz and Arthur I. Johnson, respectively superintendent and engineer for both the Black Hills Tin Co. and the Fansteel Mining Corporation, who contributed the information on mining and milling operations.

Jan 1, 1939

By F. E. Brantley

Blister copper was successfully deoxidized with any of a variety of reducing gases; lancing techniques or a vertical-column furnace were used to contact the copper and gases. Of the gases tested, butane, when used to lance molten copper at about 1,200° C, reaction temperature, was slightly more effective than propane, natural gas, carbon monoxide, or reformed gas for deoxidizing copper from about 1.0 to less than 0.1 percent oxygen content, Laboratory-scale tests revealed that the vertical furnace, composed of a heated column packed with silicon carbide chips or hollow carbon cylinders, was significantly faster and more efficient than the lancing technique for deoxidizing molten copper with any of the gases tested. Comparison of the gaseous-reduction method with the conventional poling method suggests that the gaseous method has important technical and economic advantages for deoxidizing blister copper to any readily controlled amount of residual oxygen content.

Jan 1, 1962