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By X. Shi, N. S. Dala, V. Vallaythan

"Cellular damage induced by silica dust is known to be associated with increased fragility and destabilization or destruction of the cell membranes. The mechanism by which silica dust effects biological membranes is still unknown. Using the ESR spin-trap methodology, we find that hydroxyl radicals are generated in aqueous suspensions of freshly ground silica. The amount of the radicals generated depends on the extent of grinding and ""freshness"" of the dust. Using linoleic acid as a model lipid, we show that the silica dust causes lipid peroxidation via ·OH, 02-, or linoleic acid related radicals as intermediates. Catalase and superoxide dismutase inhibit the formation of these radicals. The results suggest that free radicals associated with freshly ground silica and the related lipid peroxidation of the memberanes may be the starting point of the silicotic processes.INTRODUCTIONDespite considerable-effort over the years, the mechanism by which the quartz particles exert their toxic action on cells and the process(es) by which these actions progress to fibrosis are still not fully understood (1,2). It is generally thought, nevertheless, that the interaction of the quartz particles with the cell membranes is the starting point of the silicotic process (3). We felt that the mechanism of the membrane damage by quartz might involve oxygenated free radicals because (a) a suspension of quartz particles in contact with alveolar macrophages has been reported.(4,5) to initiate an enhancement of lipid peroxidation, defined broadly as the ;oxidative deterioration of polyunsaturated components of lipids, and (b) hydroxyl (·OH) radicals are known to be capable of peroxidation by abstracting hydrogen atoms from cell-membrane lipids (6) and initiating lipid peroxidation in lysosomal membranes (7). Moreover it is known that exposure of cell membranes, fatty acids and unsaturated food oils to ionizing radiation, which generates ·OH. radicals, causes rapid peroxidation (6). Earlier studies o~ the aqueous chemistry of quartz suspensions have reported detection of HzOz (8), implicating the formation of ·OH radicals as transient species, but, we are not aware of any report of the detection of ·OH radicals in quartz suspensions and this provided the motivation for the present undertaking. Since it is known that, because of their high reactivity (hence short life time) in aqueous media, the ·OH radicals cannot be detected via electron spin resonance (ESR) directly (9,10), we have used ESR combined with the spin-trap methodology (9) for studying the •OH formation."

Jan 1, 1988

By A. L. Engel

Included in the program of the Rare and Precious Metals Station, Metallurgical Division, Bureau of Mines at Reno, Nev., are investigations of treatment methods for ores representative of various mining districts throughout the country. The samples received for this work may come from areas only recently explored or from newly discovered ore deposits in older mining districts. The present investigation deals with a case of the latter type, the. ample having come from a section that has a past record of considerable precious. metals production. The application of current treatment methods to this type of ore seems to offer excellent possibilities of satisfactory economic results. Definite identification of the silver mineral in this ore asthe chloride cerargyrite, AgCl, adds considerable interest to, the investigation, as in many cases where silver occurs in comparatively small amounts in an ore it is not possible to identify the particular mineral carrying the silver or else it is contained in or combined with other more common minerals. Cerargyrite is the "horn silver" of the bananza period and is mentioned in many accounts of pioneer mining of high-grade ores The occurrence of this mineral in finely disseminated form it a low-grade ore is believed to be unusual. The sample investigated was obtained from the' Bullfrog District neat Beatty, southwest Nye County, Nevada. The ore contained 16.7 ounces of silver per ton of ore, 0.007 ounce gold, and 0.32 percent copper in a silicious gangue, with accessory minerals, including iron oxides and scorodite; the hydrous iron arsenate.

Jan 1, 1949

By W. T. Millar

Magnetite mines in the Sterling tract, Orange County, N. Y., were operated almost continuously from pre-Revolutionary days until 1923. The Red-Back mine, one of several in this tract, was discovered in 1780; operated briefly in 1880; and abandoned, presumably because the iron ore contained considerable sulfur. The mine is in rough, mountainous country, with altitudes ranging from 500 to 1,100 feet. The magnetite deposit occurs in complex metamorphosed pre-Cambrian formation and is thought to be a replacement of limestone by magnetite. A dip-needle survey, completed in 1916, traced magnetic anomalies for a mile along the outcrop. A preliminary examination of the Red-Back mine was made by W. T. Millar, Bureau of Mines engineer, in December 1942. The Bureau of Mines bored seven diamond-drill holes aggregating 2,727.6 feet during the winter of 1943-44. A zone of magnetite mineralization was intersected in each of the holes.

Jan 1, 1949

By Peter Krause

This report provides an overview of the worldwide photographic industry and of the applications of photography. It also covers important technological and market trends, with special emphasis on those factors which may affect the consumption of silver in the future. The text is divided into the following eight sections: 1. Principal manufacturers of silver-based photographic products 2. Major product sectors 3. Structure of the international market for silver-based photographic products 4. Silver-bearing raw materials for the manufacture of photographic products 5. Processing of photographic products: recovery of silver and recycling 6. Methods for estimating the use of silver in photographic products 7. Basic function of silver in photography and alternate image capture and recording systems 8. Brief history of photography Silver- based photographic materials are made for many applications that require different photochemical and physical response characteristics and a wide variety of formats and sizes. All of these products are laminates consisting of a surface-treated support and bonded gelatin layers. Two basic types predominate - films and papers. Films have transparent or translucent plastic supports (mostly cellulose tri-acetate and polyester), while papers have mostly a paper core coated with polyethylene resin layers on both sides (RC type). The front layer contains white titanium dioxide to provide high reflectivity and the back layer a matting agent. However, a few so-called fiber base papers are still supplied. These have a high quality paper base coated with a baryta layer ; i.e. a gelatin layer containing white barium sulfate. The manufacture of photographic film and paper supports requires special procedures and equipment, because of the severe requirements for chemical purity, optical integrity and uniformity (see Table 1 on page 10 for a list of the principal makers of film and paper supports).

Jan 1, 1992

By J. A. Herdlick

"INTRODUCTION The BeVan quartz crystal prospect in the Indian Creek mining district of Lemhi County, west-central Idaho, was examined by an engineer of the Bureau of Mines 3/ on July 9, 1943. As quartz crystals possessing peizoelectric properties were on the critical list of strategic war minerals, further exploration of the deposit was recommended. The Bureau of Mines exploration began in December 1943 and continued through January 1944. Additional trenching was completed during May and June 1944. This report presents the data obtained by this exploration.ACKNOWLEDGMENTSIn its program of exploration of mineral deposits, the Bureau of Mines has as its primary objective the more effective utilization of our mineral resources to the end that they make the greatest possible contribution to national security and economy. The Mining Division, Lowell B. Moon, chief, conducts preliminary examinations, does the actual exploratoiy work, and prepares the final report. The Metallurgical Division, O. C. Ralston, chief, analyses samples and makes beneficiation tests.The quartz crystals found during the exploration were examined and classified at the Bureau of Mines College Park, Md., laboratory and checked at the National Bureau of Standards, Washington, D. C.Fred BeVan, of North Fork, Idaho, and Edward F. Cenis, of the Montana Coal & Iron Company, Spoane, Wash., provided much information on the history and past production of the property."

Mar 1, 1948

By Vernon C. Davis

"INTRODUCTION This report describes the work done and presents the data obtained from limited diamond drilling at the lead-zinc deposits cf the Belle Eldridge Gold Mines, Inc., in Lawrence County, S. Dak. during the summer and fall of 1943. The work was undertaken in an effort to increase reserves and step-up production of zinc and lead so vitally important to the war program.The geology, topography and existing mine workings were mapped and studied. Subsequently, six vertical core-drill holes were put down from surface sites.ACKNOWLEDGMENTSIn its program of investigation of mineral deposits, the Bureau of Mines has as its primary objective the more effective utilization of our natural resources to the end that they make the greatest possible contribution to national security and economy. The Mining Division, Lowell B. Moon, chief, conducts preliminary examinations, does the actual investigative work, and prepares the final report. The Metallurgical Division, Oliver C. Ralston, chief, analyzes samples and makes beneficiation tests, if such are necessary.Special acknowledgment is made to John Paul Gries, geologist, South Dakota School of Mines, for mapping and interpretation of geology and topography, logging of cores obtained, and his assistance in guiding the drilling."

Mar 1, 1948

Rock mass classification is widely used throughout the underground mining industry—in both coal and hard-rock mines. The technique has been successful because it— • Uses simple measurements to rate rock mass strength. • Helps mine planners to make the best use of geologic information in mine design. • Makes it possible to compare ground control experiences between mines, even when the geologic conditions are very different.

Jul 1, 2007

By N. S. Dalal, B. Jafari, X. Shi, M. M. Suryan

"It is well known that prevalence and severity of coal worker's pneumoconiosis (CWP) differ markedly in different regions and mines despite comparable exposures. These variations in the pathogenicity of different coal mine dusts can only partially be explained by the mineral composition of the coal mine dust and the rank of coal. Laboratory studies also do not correlate with the human experience. One major difference between human exposure and laboratory studies is that the coal miner breathes dust from freshly broken coal, while the animals or cells are exposed to stale dust. In an effort to find biochemical clues for resolving this apparent paradox, we have carried experiments to detect differences in chemical reactivities of fresh versus stale coal dust from several U.S. coal mines. Electron spin resonance (ESR) was used as a technique for the direct detection of the concentration and reactivity of free radicals. ESR measurements of freshly ground coal dusts of different ranks and composition showed significant differences in the amount and reactivities of the organic free radicals produced. The half-lives and reactivity patterns of these newly formed species of free radicals seem to correlate with the expected toxicity and pathogenicity of the dust, thereby, providing new clues to the biochemical mechanisms and pathogenesis of CWP. Similar detection of free radicals in freshly crushed quartz suggest that free radicals might play a significant role in the pathogenicity of quartz in causing fibrosis and eventually silicosis.IntroductionThe pathogenesis of coal workers' pneumoconiosis (CWP) has been an important topic of concern for decades, but the mechanism of CWP is still not understood. It is well known, for example, that the prevalence and severity of CWP differ markedly in different regions and mines despite com¬parable exposure'(1,2) but these observations can only par¬tially be explained by differences in mineral composition and rank of coal (3-5) Specifically, while epidemiological studies of coal miners indicate (1,2) that the effectiveness of coal in producing CWP correlates roughly with the rank (i.e. %,carbon content) of coal, such correlation has not been established via biological studies.(4-6)"

Mar 1, 1989

By R. V. Lundquist

The Bureau of Mines made a laboratory study of the amenability of anorthosite rock ( from the San Gabriel Mountains , Los Angeles County , Calif . ) to treatment by the lime soda sinter process for the extraction of alumina . The study was done under a cooperative agreement with the California Division of Mines and Geology . This report presents the results of the investigation , and it includes a review of the geology of the deposit ( 7 ) by Dr. Gordon B. Oakeshott . Interest in the recovery of alumina from submarginal aluminum silicate ores is stimulated by the fact that the domestic aluminum industry depends on imports of bauxite for its alumina requirements . Of the 8.0 million long dry tons of high - grade bauxite consumed in 1961 for producing metallurgicalgrade alumina , only 0.9 million long tons , or 11 percent , was mined in this country . During past years many organizations have carried out research programs to determine if alumina could be extracted economically from such domestic ores as clays ( 3 , 4 ) , anorthosite ( 8 ) , and other silicate sources . Successful alumina extraction is the ultimate objective of the Bureau of Mines program.

Jan 1, 1963

By R. D. Leitch

Beside many other damaging effects of acid mine drainage, corrosion of pipe lines and pumps frequently adds much to mine operating costs. Not only is it often necessary to install special and relatively costly acid-resistant materials, but even these may require frequent replacements. It is not unusual for ordinary steel pipe to last only a few days in some highly acid waters, while other common materials, though more resistant, frequently last only a few weeks. In the spring of 1935, local PWA authorities offered to assign a number of persons to various problems under the direction of regular employees of the Bureau of Mines. It was believed that at least some simple tests on as many different kinds of acid-resistant pipes as could readily be obtained might produce interesting and valuable information for the mining industry. This paper describes the tests and some results that have since been noted.

Jan 1, 1938

By G. W. Jones, R. E. Kennedy

Most gasolines and naphthas are mixtures of paraffin- series hydrocarbons and comprise such substances as pentane , hexane , heptane , octane , and others up to perhaps dodecane . Many of these hydrocarbons , when mixed with the proper proportions of air and ignited , are highly explosive . It is due to this characteristic that gasoline has become so important as a fuel in internal -combustion engines . Gasoline and naphtha also are used in the industry as solvents and cleaning agents . Because of their explosive properties they are dangerous to use unless the composition is so chosen that the vapor pressure of the mixture is not high enough to produce explosive mixtures with air at the temperature at which they are used . Hydrocarbon mixtures may be made less hazardous by adding some incombustible liquid , such as carbon tetrachloride . Barrier reports the amount of carbon tetrachloride that must be added to different naphthas to render such mixtures free from fire and explosion hazards . He found that the amount of carbon tetrachloride that must be present in the final mixture of naphtha and carbon tetrachloride varied with the density of the naphtha . Of the naphthas tested the amount of carbon tetrachloride necessary to render such mixtures free from fire and explosion hazards ranged from 30 to 70 percent . .. Determination of the fire and explosion hazards of carbon tetrachloridehydrocarbon mixtures would be easy if the boiling points and vapor pressures of the two were the same at any given temperature . The fact that carbon tetrachloride boils at 76° C. while the boiling points of the hydrocarbons found in gasoline and naphtha may range from 37° , the boiling point of pentane ,

Nov 1, 1934

By L. J. E. Hofer, J. L. Snyder, J. N. Barn, J. E. Chilton, W. E. Thomas

Various silicone materials have been proposed for use in mining environments. The catalytic methane sensors now employed are poisoned by silicone vapors. Activated charcoal and carbon cloth adsorbents will increase the sensor lifetimes in an environment containing significant silicone vapor concentrations. The results of a study of catalytic methane sensor operation with adsorbent materials in hexamethyldisiloxane-air mixtures are reported. Sampling techniques developed for measuring silicone vapor content of mine atmospheres are described.

By N. S. Dalal, X. Shi, V. Vallyathan

"Correlated spectroscopic and cytotoxicity measurements were made on newly crushed silica to find whether the fracture-induced, silicon related (Si-0· or Si· type) free radicals play a direct role in the mechanism of hemolysis by silica particles. The free radical content of the silica particles was controlled through the radical decay, thermal annealing, and boiling processes, and was followed with electron spin resonance spectroscopy. Portions of the same sample were evaluated for their hemolytic potential, employing sheep erthyrocyte and optical absorption techniques. The results indicate little, if any, correlation between the amount of the silicon-based radicals and the hemolytic potential of the fresh dusts, but these or related radical sites might be contributors to silica cytoxicity and fibrogenicity via peroxidative pathways .INTRODUCTIONIn an earlier convnunication (1.) from our laboratory it was reported that mechanical crushing of coal and quartz under normal air atmosphere generates free rad;cals on the particle surfaces, and that these radicals decay with time, hence pointing to a higher toxicity of fresh dusts in relationship to pneumoconiosis and silicosis. More recently Fubin; et al.(2) have also reported the detection by electron spin resonance (ESR) of the formation of SiO· and Si·-type of radicals from quartz particles crushed under atmospheric conditions. In agreement with earlier ESR studies on single crystals of quartz crushed under high vacuum (10-10 torr) (3) and subsequent exposure to air (3), and to other gases (4), these radicals were identified (2) as being formed by the hemolytic cleavage of the Si-0-Si bonds and the reactions of the Si· and SiO· ,radical with atmosphere. Fubin; et al. (2) also suggested that these radicals might be involved in the mechanism of the fibrotic action by silica, either by transforming the particle surface into a selective oxidating agent or as an initiator of a sequence of reactions leading to fibrosis. Earlier Gabor and Anea (5) had reported that lipid peroxidation caused by free radicals on the silica surface might be involved in the red blood cell membrane damage. Thus far, however, no parallel cytotoxicity, fibrogenicity, and free radical studies on a given Quartz dust sample have been reported, except for some earlier work from our laboratory (1,6,7). We now present more recent results obtained from parallel cytotoxicity, fibrogenicity, and free radical measurements on a freshly made quartz dust. The dust’s free radical content was measured using ESR spectroscopy while its cytotoxicity poteni1al was estimated via hemolysis. Hemolysis was employed as the tox1c1ty test because it 1s a widely used method for estimating the potential of a dust for disrupting the cell membrane (8). The f1brotic potential was followed.by measuring the dust-induced lipid perox1dat1on. us1ng linole1c ac1d as a model lipid. As discussed below, the results obtained suggest new clues.to the mechanism of the Quartz-related cytotoxicity and fibrogenicity."

Jan 1, 1988

By Nar S. Dalal, Xianglin Shi, Val Vallyathan

"INTRODOCTIONIn an earlier communication 1 from our laboratory it was reported that mechanical crushing of coal and quartz under normal air atmosphere generates of free radicals on the particle surfaces, and that these radicals decay with time, hence pointing to a higher toxicity of fresh dusts in relationship to pneumoconiosis and silicosis. More recently Fubini et al.2 have also reported the detection by electron spin resonance (ESR) of the formation of SiO. and Si-type of radicals from quartz particles crushed under atmospheric conditions. In agreement with earlier ESR studies on single crystals of quartz crushed under high vacuum ( -10-10 torr>3 and subsequent exposure to air,3 and to other gases,4 these radicals were identified2 as being formed by the homolytic cleavage of the Si-0-Si bonds and the reactions of the Si• and SiO- radical with atmosphere. Fubini et al.2 also suggested that these radicals might be involved in the mechanism of the fibrotic action by silica, either by transforming the particle surface into a selective oxidating agent or as an initiator of a sequence of reactions leading to fibrosis. Earlier Gabor and Anca5 bad reported that lipid ·peroxidation caused by free radicals on the silica surface might be involved in the red blood cell membrane damage. Thus far, however, no parallel cytotoxicity, fibrogenicity, and free radica1 studies on a given quartz dust sample have been reported, except for some earlier work from our laboratory.1·6·7 We now present more recent results obtained from parallel cytotoxicity, fibrogenicity, and free radica1 measurements on a freshly made quartz dust. The dust's free radica1 content was measured using ESR spectroscopy while its cytotoxicity potential was estimated via hemolysis. Hemolysis was employed as the toxicity test because it is a widely used method for estimating the potential of a dust for disrupting the cell membrane. 8 The fibrotic potential was followed by measuring the dust-induced lipid peroxidation, using linoleic acid as a model lipid. As discussed below, the results obtained suggest new clues to the mechanism of the quartzrelated cytotoxicity and fibrogenicity. MATERIALS AND METHODSReagentsCrystalline quartz particles with a size range of 0.2-2.5 mm were obtained from the Generic Respirable Dust Technology Center, Pennsylvania State University, University Park, Pennsylvania. These particles were crushed in air to obtain quartz dust samples with particle sizes smaller than 20 microns. We chose to work with a dust with mixed particle sizes, rather than a specific range, as an effort to simulate the mining atmosphere. An agate mortar-pestle arrangement was used for the crushing and grinding because of the close similarity of the structure of agate to that of quartz. Diethylenetriaminepentaacetic acid (DETAPAC) were purchased from Sigma. All other chemica1s were purchased from Fisher or Aldrich.Hemolysls ExperimentsHemolytic activity of silica was measured, following an established procedure,9 as the amount of hemoglobin released from a 2 % suspension of sheep erythrocytes after incubation with 10 mg of silica dust for one hour at 37 °C. The hemoglobin release was estimated via the absorbance at 540 nm using a Gioford spectrophotometer. The procedure was calibrated by substituting the silica dust by a phosphate buffer solution as a negative control (background) and O.S % Triton-X-100 as a positive control (100% hemolysis). The percentage of hemolysis was calculated as follows:"

Jan 1, 1990

By N. S. Dalal, B. Jafari, F. H. Y. Green, M. M. Suryan, V. Vallyathan

"Freshly ground and aged anthracite and bituminous coal samples were investigated by electron spin resonance (ESR) spectroscopy to detect the presence, concentration and reactivity of free radicals. Freshly ground anthracite coal produced greater concentration of free radicals than the bituminous coal, and the radical reactivity was also greater for the anthracite. The reactivity of the newly produced free radicals in the anthracite dust correlated with the dust's toxicity. Furthermore similar coal-based free radicals were detected in the lung tissue of autopsied coal miners, suggestive of persistent reactivity by the embedded coal dust leading to the progressive disease process. Results of the studies on the severity of coal workers' pneumoconiosis (CWP) and free radical concentration m lung tissue support this hypothesis.INTRODUCTIONCOAL WORKERS' PNEUMOCONIOSIS (CWP) has been an important topic of concern to miners, mining engineers, epidemiologists and medical researchers for decades. It is well known that the prevalence and severity of CWP differ markedly between different regions and mines despite comparable exposures to respirable dust (REISNER and RoBOCK, 1977; HURLEY et al., 1979). These variations in pathogenicity of coal mine dusts can only partially be explained by differences in the mineral composition and by rank of coal (CHRISTIAN and NELSON, 1978; CHRISTIAN et al., 1979; HATCH et al., 1980). Cytotoxity studies on mammalian cells do not correspond well with the human disease pattern (CHRISTIAN and NELSON, 1978; CHRISTIAN et al., 1979; HATCH et al.,1980; VALL YA THAN et al., 1988). For example, while epidemiological studies of coal miners (REISNER and ROBECK, 1977; HURLEY et al., 1979) indicate that the prevalence of CWP correlates roughly with the rank of coal, such correlation has not yet been established in biological studies, despite considerable effort (CHRISTIAN and NELSON, 1978; CHRISTIAN et al., 1979; HATCH et al., 1980). In order to help resolve this apparent paradox we have undertaken a systematic study to evaluate whether any correlation exists between the concentration of free radicals present in fresh or aged coal dusts from two well-characterized U.S. coals. This study was also prompted in part by observations reported in the literature that organic free radicals can be formed on the surface of freshly fractured coals (LEBEDEV et al., 1978; DULIBA and CLARKSON, 1984). In particular, ARTEMOV and REZNIK (1980) noted that the decay lifetimes and, hence, the reactivity of the organic free radicals formed on crushing Russian coals, .depended"

Jan 1, 1989

By B. R. Mohal, F. F. Aplan, S. Chander

"The wetting behavior of coal has been determined in the presence of nonyl and octyl series of nonionic surfactants containing polyethoxy groups of different sizes. The wetting behavior was determined by a modified Walker technique and contact angle measurements. The results show that the wetting rate of coal varies with coal rank, structure of the hydrocarbon chain and number of ethoxy groups in the hydrophilic group of the surfactant. A close relationship has been observed between the wetting rates and the short-time advancing contact angles.INTRODUCTIONNonionic surfactants are used in many applications to improve wettability of solids. They can be used as dispersing agents [ 1 ] or dust suppressants [ 2-5] and to control the flotation, flocculation, filtration and flowability of particulates. This study was undertaken to study the effect of a series of nonionic surfactants on the wetting behavior of coal. Two series of surfactants, namely, ethoxylated nonyl and octyl phenols were used. The nonyl phenol series contains a linear hydrocarbon chain containing nine carbon atoms ( CH3 ( CH2 ) 8-C6H4-( OC2H4 )""' where n is the number of ethoxy groups). The octyl phenol series contains a branched hydrocarbon chain containing eight carbon atoms ( ( CH3 ) 3CCH2C ( CH3 ) 2-C6H4-( OC2H4)"").Initial wetting rates - modified Walker techniqueWalker et al. [ 6] developed a sink test to determine the wettability of coal particles. In this technique, coal particles are dropped individually onto the surface of surfactant solutions of different concentrations, and the most dilute concentration in which coal would sink ""instantaneously"" is determined. This technique is a variation of a procedure initially developed by Draves and Clarkson [ 7] to determine the effect of surfactants on wettability of cotton fibers."

Jan 1, 1989

By Joseph A. Hrabik

The Bureau of Mines compared the feasibility of mining deep phosphate deposits by a borehole mining system with mining by proven conventional techniques. An economic comparison of the borehole mining system with conventional dragline and bucket wheel excavator mining systems was completed at various mining depths and production rates. Hypothetical phosphate deposits, with various overburden thicknesses and reserve tonnages, were defined. Geologic conditions necessary for the application of the borehole system were identified. Discounted cash flow analyses based on derived capital and operating costs were used to generate rates of return and product prices. Borehole mining was found to be more economical where overburden thickness was 150 ft or greater; however, at 50- and 100-ft thicknesses, conventional surface mining was more economical. Overburden thickness has a great effect on the economic feasiblity of the conventional mining systems but less effect on the economics of borehole mining. Economies of scale are only realized in conventional mining, since larger equipment is employed to achieve greater production, whereas increased production from borehole mining is achieved using additional equipment units. A comparison of the environmental effects of borehole and conventional surface mining systems showed that borehole mining is environmentally more desirable.

Jan 1, 1983

By X. Shi, V. Vallyathan, N. S. Dalai

"Using. ESR spin trapping methodology, evidence was obtained that fresh quartz dust in a cell-free aqueous medium generated hydroxyl - and possibly superoxide radicals. The hydroxyl radical generation potential decreases on storing of fresh quartz dust in ambient air and on the addition of either catalase, superoxide dismutase, desferoxamine, or DMSO. The role of quartz related radicals in the biochemical mechanism of acute silicosis is suggested from these findings.IntroductionThis report summarizes our electron spin resonance (ESR) detection of oxygenated radical formation by freshly crushed quartz particles in a cell-free aqueous medium, and its inihibition by radical scavengers. This study was undertaken with to elucidate the primary biochemical mechanism involved in the development of silicosis (Farber, 1983; Reiser and Last, 1979; Silicosis and Silicate Disease Committee, 1988). In particular the mechanism by which the quartz particles exert their toxic action on cells and the process(es) by which these actions progress to fibrogenesis are still not well understood (Farber. 1983; Reiser and Last, 1979;). It is generally believed that the action of quartz particles on the cell membrane is the starting point of the silicotic process (Farber, 1983; Parazzi et al., 1968). Thus the surface characteristics of the quartz particles have been the subject of several recent studies (Bolls et al.. 1983; Dalai et al., 1986; Fubini et al., 1987). Recently, We reported that mechanical crushing of quartz under normal atmosphere generates free radicals which decay with time, and that these free radicals are associated with a higher cytotoxicity of fresh quartz dust as compared to aged dust from the same stock (Dalai et al., 1986; Vallyathan et al.. 1988). The formation of Si• and. SiO--type of radicals from quartz particles crushed under atmospheric conditions has also been reported by Fubini et al. (1987). In addition, Gulumian and van Wyk (1987) have reported that quartz particles react with hydrogen peroxide (H202) to generates hydroxyl radicals (•OH) and suggested that this process might contribute to quartz's pathogenicity. However, these authors did not report the effects of metal chelators, so it was not clear as to whether the detected -OH radicals simply resulted from the Fenton reaction involving exogenous metal ion contaminants. Earlier, Marasas and Harington (1960) reported that quartz particles could function as an oxidant in a number of in vitro oxidations, including the hydroxylation of proline and lysine. They postulated that silica dusts, on reacting with water, could release H2O2 which might have the potential to react with various biological constituents and thus cause tissue damage. In fact, Gabor and coworkers (Gabor and Anca, 1974; Gabor et al., 1975) suggested that the cytotoxicity of quartz particles might be associated with the generation of some 'factor or factors possessing the properties of a free radicals capable of promoting the peroxidative chain cleavage of polyunsaturated fatty acid moieties of the phospholipids in the cell membrane. More recently Weitzman and Graceffa (1984) reported that asbestos is able to catalyze the generation of • OH radicals from H2O2. Their later work indicated that lipid peroxidation may be one of the mechanism by which asbestos produces tissue injury (Weitzman and Weitberg, 1985). This is significant because • OH radicals are capable of causing peroxidation by abstracting hydrogen atoms from cell-membrane lipids and initiating lipid peroxidation in lysosomal membrane (Fong et al., 1973). In fact, the formation of oxygenated species in reactions involving quartz was suspected since Kolbanev et al. (1980) reported the detection of H2O2 in the reaction of fresh quartz particle with aqueous medium. The present work was thus undertaken to detect the anticipated formation of some oxygenated, radical species by reactions of quartz in a cell-free media and its inhibition by radical"

Jan 1, 1988

By Michael E. Henderson

Presented in this report are the experimental results of coarse coal slurry degradation data obtained from the Hydraulic Transport Research Facility (HTRF) at the Pittsburgh Research Center (PRC), Bruceton, PA. The facility is operated by Boeing Services International, under Bureau of Mines Contract No. J0333956. Presented in this report are the experimental results of coarse coal slurry degradation data obtained from the Hydraulic Transport Research Facility (HTRF) at the Pittsburgh Research Center (PRC), Bruceton, PA. The facility is operated by Boeing Services International, under Bureau of Mines Contract No. J0333956. This particle degradation report is a summary of the particle distribution data obtained at the HTRF for the period 26 November 1982 to 1 October 1983. The testing covered herein is for coarse Pittsburgh Seam coal in the 6-in (150 mm) and 12-in (300 mm) pipelines, at velocities ranging from 5 to 18 ft/s (1.5 to 5.5 m/s), and at concentrations by weight ranging from 15 to 55 pet. Particle size distribution samples were taken systematically throughout the testing.

Jan 1, 1985

By N. S. Dalal, X. Shi, V. Vallyathan

"Electron spin resonance (ESRJ spectrum of the hydroxyl (· OH) radical spin adduct with .the spin trap 5,5-dimethyl-1-pyrrolintt-N-oxide has been obtained in suspensions of freshly ground quartz particles. The concentration of the spin adduct (and hence of the • OH radicals) increases with the amount of grinding. The dust's potential for the generation of the· OH radicals is maximum when fresh (i.e., immediately after grinding) and decreases to 50% in about a day on storage in air. Studies involving metal chelates .indicate that the • OH radical formation involves mainly the silica surface and H20 rather than the Fenton reaction. The results suggest that hydroxyl radical reaction(s) could be important in the lipid peroxidation and fibrogenicity by quartz dust, particularly .in acute silicosis. INTRODUCTIONIn this paper we report on our electron spin resonance (ESR) detection of the formation of hydroxyl (·OH) radicals in aqueous suspensions of freshly crushed quartz particles. This work was undertaken with a view to find possible clues to the role of free radicals in the pathogenesis of quartz-induced fibrogenicity, commonly known as silicosis. We noted that while silicosis is one of the major health hazards in coal and mineral industries, the mechanism by which the quartz particles exert their toxic action on cells and the process(es) by which these actions progress to fibrogenesis are still poorly ·understood (Reiser and Last, 1979; Singh and .Rahman, 1987). It is generally thought, nevertheless, that the action of quartz particles on the biological membranes is the starting point of the silicotic process (Parazzi et - al., 1968). A possible clue to the mechanism of the membrane damage by quartz particles, in terms of the role of oxygenated free radicals, is suggested by the following observations. A suspension of quartz particles in contact with alveolar macrophages has been reported (Gabor et al., 1975; Koike et al., 1982) to initiate an enhancement of lipid peroxidation, defined broadly as the oxidative deterioration of polyunsaturated components of lipids. Hydroxyl (· OH) radicals are known to be capable of peroxidation by abstracting hydrogen atoms from cell-membrane lipids (Halliwell and Gutteridge, 1985) and of initiating lipid peroxidation in lysosomal membranes. (Fong et al., 1973). Arong other lines, it is known that exposure of cell membranes, fatty acids, and unsaturated food oils to ionizing radiation, which generates· OH radicals, causes rapid peroxidation (Halliwell and Gutteridge, 1985). Thus • OH radicals (and also other oxygenated species such as Oi, 10 2, and H20 2) might be expected to play a role in the toxicity of quartz. Earlier studies of the aqueous chemistry of quartz suspensions have reported detection of H2O 2 (Kalbanev et al., 1980), implicating the formation of ·OH radicals as transient species. However, we are not aware of any report of the detection of • OH radicals in quartz reactions, and thus the present study was undertaken. Since it-is known that, because of their high reactivity (hence short lifetime) in aqueous media, the • OH radicals cannot be detected via ESR directly (Finkelstein et al., 1980; Buettner, 1982) we have used .ESR combined with the spin-trap methodology (Finkelstein et al., 1980) for studying the· OH formation. The results show that· OH radicals are indeed formed in aqueous suspensions of freshly ground quartz; thus pointing to ·a possible new clue to the cytotoxicity of freshly formed quartz particles and thereby to silica fibrogenicity."

Jan 1, 1988