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By William E. Wallace, S. J. Page, B. L. Razzaboni, C. A. Hill, Pamela Mike, P. Bolsaitis, M. J. Keane, Val Vallyathan

"Respirable quartz cytotoxicity, as measured by erythrocyte hemolysis and pulmonary macrophage release of lactate dehydrogenase in vitro, is neutralized by boiling in water in glass test tubes for 10 to 40 minutes. The cytotoxicity is reduced to near zero by boiling l to IO mg quartz per milliliter water. For greater concentrations of quartz in water the hemolytic potential after 40 minutes of boiling approaches that of native quartz. Replacing the medium with fresh water midway through boiling results in full detoxification through 20 mg quartz per milliliter water. Pre-boiling the medium with silica reduces the detoxification effect. Detoxification persists after mild drying at l 10°C for 8 hours, and persists after three days of resuspension in water at room temperature.INTRODCJCTIONResearch underway to determine interactions of quartz and other mineral dust surfaces with pulmonary fluids and alveolar macrophages in culture led to the observation that when dusts were autoclaved in aqueous suspension, their cytotoxic effects on macrophages were suppressed, in some cases fully and even after several days incubation with the cells. This finding was in direct contradiction to earlier results from both short term macrophage lysosmal enzyme release assays, as well as longer term cytotoxicity assays from macrophages in culture; in those studies, dusts were steam autoclaved at 121°C with no liquid water but with steam present. 1.2 However detoxification under boiling conditions has been reported in other research. 3 It was decided to use the hemolysis assay to further investigate these findings, because of its sensitivity simplicity and cost.RESCULTS AND DISCCISSIONRespirable quartz dust used in this study was taken from a stock of crystalline silica, Min-U-Sil; obtained from Pennsylvania Sand Glass Corporation, fractionated in air with a particle classifier. The small size fraction retained for use was 80% less than S micrometer particle diameter, with an area equivalent median diameter of 1.24 micrometers as estimated by automated image analysis. The silica was at least 98.S mass percent silica as determined by X-ray energy spectrometric analysis; and the crystalline form was alpha-quartz as determined by X-ray diffraction. It's specific surface area was 3.97 square meters per gram as determined by nitrogen adsorption isotherm methods. I"

Jan 1, 1990

By D. A. Baker

This report describes the elemental characterization of chromite and related materials at the Bureau of Mines, Albany Research Center. Analytical methods for determining the major constituents, representing extensive experience, refinement, and development, are described and fully annotated. This presentation should allow other laboratories to use these methods and obtain comparable results with a minimum of time needed for familiarization with individual methods.

Jan 1, 1990

By J. C. Edwards

To have the capability to predict the development of localized spontaneous heating within a porous coalbed that is subjected to forced air ventilation or in an otherwise quiescent environment in which buoyancy develops, the Bureau of Mines developed three time-dependent mathematical models, which were used to calculate the temperature increase associated with chemisorption of oxygen by the coal. In each model, spontaneous heating is driven by an Arrhenius first-order reaction between the oxygen and coal. Two models are two-dimensional, and one is one-dimensional. In the first two-dimensional model, a constant-velocity forced convection airflow is specified; and in the other, buoyant flow is allowed to develop in the absence of forced convection. The third model evaluates the airflow from Darcy's law and a specification of the pressure at the surface of a one-dimensional porous coalbed. Numerical computations demonstrated how each model could be used to predict the onset of spontaneous heating when the porous coalbed was subjected to constraints of an imposed internal heat source or a high temperature airflow. The effects of particle size and coalbed compaction upon spontaneous heating were examined with the third model.

Jan 1, 1990

Develop methods of enhancing and measuring the high-temperature softening and melting properties of iron oxide pellets reduced under simulated blast furnace smelting conditions. Approach Add dolomite and Limestone flux and a low-cost organic binder, such as starch, carboxyl methylcellose (CMC), or waste papermill sludge, to the iron oxide concentrate to produce hematite (ferric oxide) pellets with superior high-temperature metallurgical properties. Simultaneous increases in softening temperature, gas permeability, and enhanced metallization rates are sought to improve blast furnace productivity and energy efficiency. Background In the past, bentonite, an inorganic binder, was the only additive (binder) used in the production of pellets made from iron ore concentrate. Research has shown that the reducibility of conventional (acid) pellets can be increased by the addition of flux or an organic binder. The increase in pellet reducibility results in less wustite in the center of the pellet at high temperatures, such as those obtained in the cohesive zone of the blast furnace.

Jan 1, 1990

By Agnes Y. Lee

As part of the U.S. Bureau of Mines program to improve base metal leach systems, pressure leaching of galena (PbS) concentrates in fluosilicic acid (H2SiF6) solution was investigated. Lead extraction was 93 pct when PbS was pressure leached in H2SiF6 at 95° C with 2OO-psig O2 pressure for 40 min, using ferric nitrate [Fe(N03)3] as a catalyst. The effects of several catalysts, O2 pressure, time, and acid concentration on leaching were determined. The purified leach solution was electrowon to recover high-purity Pb metal. The H2SiF6 used in leaching and electrowinning can be recycled continuously. A flow diagram was proposed based on this investigation. Elemental sulfur (SO) was recovered from the leach residue by solvent extraction. A method was also developed for treating the flnal residue to segregate the important byproduct elements such as Ag, Cu, and Zn and enable their recovery by standard commercial processes.

Jan 1, 1990

By John C. Edwards

To have the capability to predict the development of localized spontaneous heating within a porous coalbed that is subjected to forced air ventilation or in an otherwise quiescent environment in which buoyancy develops, the Bureau of Mines developed three time-dependent mathematical models, which were used to calculate the temperature increase associated with chemisorption of oxygen by the coal. In each model, spontaneous heating is driven by an Arrhenius first-order reaction between the oxygen and coal. Two models are two-dimensional, and one is one-dimensional. In the first two-dimensional model, a constant-velocity forced convection airflow is specified; and in the other, buoyant flow is allowed to develop in the absence of forced convection. The third model evaluates the airflow from Darcy's law and a specification of the pressure at the surface of a one-dimensional porous coalbed. Numerical computations demonstrated how each model could be used to predict the onset of spontaneous heating when the porous coalbed was subjected to constraints of an imposed internal heat source or a high- temperature airflow. The effects of particle size and coalbed compaction upon spontaneous heating were examined with the third model.

Jan 1, 1990

By Eric R. Bauer

This U.S. Bureau of Mines study was conducted to gain a basis for recommending methods to predict and prevent the occurrence of cutter roof failure, a common ground control problem in mines of the Northern Appalachian Coal Basin. This was accomplished by determining the geologic and engineering factors responsible for cutter development at six mines affected by cutter roof failure. Three distinct factors were found to be initiators of cutter roof failure: (1) high horizontal roof stress, (2) surface topographic variations, and (3) geologic anomalies. Effective control of cutter roof was obtained through improved bolting techniques, entry and mine reorientation, and entry and pillar size modifications, but only when selected based on the actual cause of failure.

Jan 1, 1990

By Eugene V. Cilento, R. Clark Lantz, K. A. DiGregorio

"This laboratory bas developed a sensitive electro-optical method to quantify the initial rate (R) and total amount (MAX) of superoxide (02) produced by single pulmonary alveolar macrophages (PAM). The method uses a microscope-based TV system to visualize PAM in culture, and to video record the images during the time the cells produce 02. MAX and R are calculated from measurement of temporal changes in optical density in the images due to precipitated diformazan formed by the reaction of O2-, produced by each PAM, with nitroblue tetrazolium present in the culture medium. To date, values of Rand MAX, measured due to adherence of PAM to the dish, have been compared to values obtained when quartz, coal mine dust (CMD), and kaolin . were added to the medium (in vitro). Rand MAX have also been calculated for PAM lavaged from animals exposed to quartz and CMD in the WVU Inhalation Facility. Presently, experiments are being done using which will permit PAM to be restirnulated by different dusts to help establish a dose response relation~ p and a means to study the role of lung surfactant on modifying the acute toxicity of inbaled dusts. Ultimately, this methodology should provide useful insight into establishing the role of 02 in PAM dysfunction due to inhalation of dusts, and in lung diseases such as pneumoconioses. INTRODOCTIONPAM are free cells found in the lungs which protect the lungs by removing foreign debris and bacteria. This is accomplished, in part, by the process of phagocytosis, whereby foreign matter is internalized into vesicles known as primary phagosomes. Phagocytosis also involves the chemical breakdown of inhaled dusts and the killing of microbes. Detoxification is aided by the respiratory burst, which is a metabolic response of the cell to foreign substances, that results in the production of highly reactive oxidizing agents from the partial reduction of extracellular oxygen to superoxide (02) at the surface of the plasma membrane. Superoxide undergoes either spontaneous or enzyme catalyzed dismutation reactions to form hydrogen peroxide (H202) and subsequently hydroxyl radical (OH•) and singlet oxygen (02 t ). However, while these oxygen metabolites aid in the killing of microbes they also may destroy endogenous tissue. For example, 02 has been linked to the aging process and to many diseases including emphysema, diabetes, and cancer.'' Therefore, a better understanding of the production of 02 is extremely important since an abnonnally low production could result in damage by inhaled dusts and bacteria while an abnormally high production could result in direct damage to the lung tissue by the phagocytes. Inhalation of respirable sized mineral dusts, such as quartz (silica), coal mine dusts (CMD), and asbestos, results in various pulmonary disorders. PAM are thought to play an important role since evidence suggests that the first step in fibrogenesis is an interaction of dust particles with PAM. Generally, in vivo exposure of animals to mineral dusts results in increased respiratory burst activity, migratory patterns, phagocytic behavior, and secretory potential of PAM, and for this reason these have been implicated to be pivotal events in the pathogenesis of pulmonary diseases.1 In addition to stimulation of resident PAM, an influx of monocytes into the lung and/or production of new macrophages generally occurs in response to fibrogenic dust inhalation. Further, PAM may attract and stimulate fibroblasts, which normally synthesize proteins and collagen during rep~ of tissue, by secreting chemoattractants and enzymes. Thus, PAM may be involved in pulmonary disorders through failure or partial loss of their defensive capability, or indirectly, through release of other mediators."

Jan 1, 1990

By Jaffrey Y. Foley

Placer gold and platinum-group metals (PGM) In the Slate Creek area, northern Chistochina Mining District, are derived from silicified and carbonate-altered, Cretaceous-Tertiary (?) dikes and related mafic and ultramafic rocks. Gold In the placer deposits is also derived from Tertiary conglomerate and altered Jurassic-Cretaceous argilllte. The argilllte and Igneous bedrock sources show a unique Ag-Au-Cu-Hg-PGM association that Is attributed to a combination of magmatic, hydrothermal, and supergene processes. The bedrock and placer deposits contain a variety of gold silver-lead-copper and PGM alloys. The observed geochemical, mineralogic, and alteration features are consistent with current geological models for turbidite-hosted gold deposits. No economic gold or PGM lodes were Identified, but several areas warranting more detailed investigation were Identified. Conventional geochemical sampling and analysis of small sample splits weighing between 10 and 30 grams were shown to be unreliable as a consistent means of identifying gold- and PGM-bearing bedrock. Pan concentration of pulverized rock samples was shown to be a more effective, but still Imperfect means of Identifying gold and PGM source rocks. Geochemical data and mineralogic examination indicate that gold and PGM in potential lode sources are very finely and erratically disseminated, are chemically combined with other elements, and may not be entirely free-milling or amenable to simple gravity concentration.

Jan 1, 1990

By C. W. Whitten

Iron ore deposits in south-central Missouri have emerged as a possible resource for the rare-earth elements. The Pea Ridge Iron Mine is one such deposit. Rare-earth minerals at the Pea Ridge Iron Mine are contained in breccia pipes consisting primarily of silicon oxides and feldspars. These pipes extend up through the magnetite ore body and appear to be alterations and replacement of earlier hematite. The mineralogy of these pipes is very complex and varied, which could complicate the concentration and extraction of the rare-earth minerals. This U.S. Bureau of Mines !eport represents a study by characterization of the mineral phases to assess the amenability and development of concentration and extraction techniques. Previous characterization of rare-earth minerals has been mainly by transmitted light microscopy. This method along with reflected light microscopy, scanning electron microscopy, and X-ray diffraction was used to identify and characterize the rare-earth and associated minerals. The minerals identified were the major ore minerals, magnetite and hematite; the rare-earth phosphates, monazite and xenotime; the rare-earth silicate, allanite; the minor associated minerals, cassiterite, pyrite, and apatite; and the gangue minerals, feldspar, quartz, and actinolite.

Jan 1, 1990

By N. S. Dalal, X. Shi

"Electron spin resonance (ESR) measurements on solutions and isolated powders provide direct evidence for the involvement of Cr(V) species in the reduction of Cr(VI) by NAD(P)H. ESR analysis of an isolated Cr(V)NAD( P)H solid yields 6 11 = 1.9831 and 6.i. = 1.9772, indicating that the unpaired electron occupies the d22 orbital of the Cr(V) ion, with square-pyramidal geometry. Addition of hydrogen peroxide (H2 0 2 ) to the N AD(P)HCr( VI) reaction mixtures suppresses the Cr(V) species and generates hydroxyl (""OH) radicals. The ""OH radicals were detected via ESR spin trapping, employing 5,5-dimethyl-1-pyrroline-N-oxide and a-(4-pyridyl-1- oxide)-N-tert-butylnitrone as spin traps. The dependence of Cr(V) and ""OH radical formation on the H20 2 and Cr(VI) concentrations indicates that the Cr(V) species react with H20 2 to generate the ""OH radicals. Similar results were obtained by using various diols (arabinose, cellobiose, FAD, fructose, glyceraldehyde, ribose, and tartaric acid), a-hydroxycarboxylic acids, and glutathione. Investigations with superoxide dismutase showed no significant participation of 02 in the generation of OH radicals. These results thus indicate that the Cr(V) complexes, produced in the reduction of Cr(VI) by cellular reductants, react with H20 2 to generate ""OH radicals, which might be the initiators of the primary events in the Cr(VI) cytotoxicity.In this paper we report an electron spin resonance (ESR)3 spectroscopic detection of Cr(V) species in the reduction of potassium dichromate, henceforth called Cr(VI), by NAD(P)H and other diols. Also reported here is the detection of the hydroxyl (""OH) radical in the reaction between hydrogen peroxide (H2O 2) and a variety of Cr(V) complexes. This work was undertaken because while the reduction of Cr(VI) to lower oxidation states has been suggested as a key step m the mechanism of Cr(VI) toxicity, mutagenicity, and DNA alteration, the details are not yet clear (1-5).Earlier studies on the mechanism of Cr(VI) reduction in cellular systems include those on the reduction of chromate by microsomes (6-8), rat liver DT-diaphorase (9), and aldehyde oxidase (10). All these studies imply that Cr(VI) can be reduced to Cr(Ill) by cellular constituents. Regarding the mechanism of Cr(Vl) carcinogenicity, Jennette postulated that Cr(V) is the ultimate carcinogenic form of chromium compounds (8). This conclusion has led to many further investigations of the formation of Cr(V) in the reduction of Cr(VI) under biologically relevant conditions (11-33). More recently, however, Kawanishi and co-workers (34) have investigated the mechanism of DNA cleavage induced by Cr(VI) in the presence of H20 2 and have argued that it is not Cr(V) itself that is carcinogenic, but it is the reactive oxygenated species (02, 10 2 , ""OH) (produced by the decomposition of the Crv(02) ¾ - ion) that cause the DNA alteration."

Jan 1, 1990

By Raghoottma S. Pandurangi, Mohindar S. Seehra

"The interaction of amorphous 1ilica particles with several hydrogen bonding agents (H2O, C2H5OH, C7H2NO) was investigated by monitoring the changes in the bulk and surface IR vibrational modes of silica using photoacoustic spectroscopy. It is argued that the intensity of the silanol band at 3747 cm-1 provides (an inverse) quantitative measure of the interaction or surface groups, along with the shift in the broad hydroxyl band, the interaction following the order C7H2NO > C2H5OH > H2O. Index Headings: Silica; Surface vibrational modes; Photoacoustic spectroscopy; Hydrogen bonding agents.INTRODUCTIONThe use of m spectroscopy to study the adsorption on solid surfaces is well documented in the literature.1 2 For example, hydroxylation of a clean silica surface results in the formation of the free silanol group Si-OH, with a sharp IR band near 3747 cm-1• Further hydroxylation produces a broad band near 3500 cm-1, which is believed to result from various hydrogen-bonded silanol bands leading to a multilayered surface structure of few nm.3-5 Earlier studies had indicated a relationship between the surface silanol band and various chemical activities of silica such as cytotoxicity, 7- 9 catalysis, 10-12 and others.13 Recent studies from our group14-in which the intensity of the silanol band and cytotoxicity of silica, heat-treated at various temperatures up to 1095°C, were investigated have provided a strong correlation between cytotoxicity and intensity of the silanol band.Coating of silica by PVPNO (polyvinyl-2-pyridine N-oxide with the empirical formula C7H8NO), a strong hydrogen bonding agent, is known to reduce the cytotoxicity of silica, presumably by chemically blocking the silanol groups from phospholipids.15 This interaction of the hydrogen bonding agents with the silica can be studied by m spectroscopy, and Knozinger16 and Rouxlet and Semples11 have used transmission m spectroscopy to study the effect of various chemicals on the surface IR modes of silica. However, one of the major disadvantages of transmission IR spectroscopy is that the sample preparation (grinding and mixing with KBr and pelletizing) usually distorts the surface modes (see, e.g., Ref. 14) and there is always a doubt about the effect of the sample preparation on the measured properties. In recent years, photoacoustic (PA) spectroscopy has become the technique of choice for studying the IR spectra of samples in their natural state, since no sample preparation is necessary.18•19 Moreover, according to a recent paper, 20 the relative intensity of the surface modes in PA spectroscopy of silica particles is much higher than that in transmission FT-IR spectroscopy. Consequently PA spectroscopy is ideal for studying the surface chemistry. In this work, we have used PA spectroscopy to investigate the interaction of three hydrogen bonding agents (C7H8NO, C2H50H, and H20) with the silica surface by monitoring changes in the surface m modes. Our results show that the surface IR modes get perturbed to a larger extent than the bulk IR modes in interaction with the hydrogen bonding agents. Moreover, whereas in the earlier studies, the shift of the broad silanol band near 3500 cm-1 was used as a measure of the interaction with hydrogen bonding agents,16•17 here we show that the relative decrease in the intensity of the sharp silanol band near 3747 cm-1 also serves as a quantitative parameter for the relative surface coverage and surface modification. Details of this work are given below."

Jan 1, 1990

"The mission of the Respirable Dust Center is to enhance the health, safety and productivity of the miners 'through advancing the fundamental .understanding of all aspects of respirable dust associated with mining and milling and the interaction of dus.t and lungs for reducing the incidence and severity of respirable dust disease. All Dust Center activities are focussed to be responsive to this mission which is shared by several federal agencies closely associated with the Generic Mineral Technology Center for Respirable Dust such as USBM, M,SHA, and NIOSH, and the mining industry. While significant progress has been achieved in making mine atmospheres cleaner and healthier, respirable dust disease remains the nations worst industrial hazard. GOALSThe goals of the Respirable Dust Center have been formulated to recognize the diverse scientific, engineering and medical aspects of respirable dust as well as the need to enhance the interaction, education and technology transfer in the respirable dust area.The Center goals are to:1. Enhance the understanding of the scientific, engineering and biological characteristics of fine and respirable mineral particles, fibers, organic aerosols, and complex particles found in the mining and milling atmospheres.2. Advance the understanding of the physical behavior of airborne respirable dust particles in flowing streams under different. stimuli during mining and milling.3. Advance fundamental understanding of the causative mechanisms for the occupationally related lung impairments and the airway diseases of mine and mill workers.4. Establish the relationship between natural and cultural factors (mine geology, mineralogy, mining and milling methods, equipment and control measures) in the generation, exposures, and pathogenic properties of fine particles.5. Contribute to the development of control mechanisms for reducing ambient respirable dust concentrations, worker exposure, the incidence and severity of dust related lung disorders and disease prevention in mining and milling atmospheres.6. Enhance functional integration among the various research personnel in the Center, as well as, with other groups, such as MSHA, NIOSH and USBM involved in respirable dust research and control.7. Develop technically trained personnel for employment in the mineral industry for respirable dust research and control.8. Enhance the availability of respirable dust-related information utilizing several technology transfer avenues."

Jan 1, 1990

By Bernard J. Steblay

The U.S. Bureau of Mines has attempted to use ultrasonic signal travel-time measurements to measure loaded roof bolt strains. The strain measurements are then related to roof bolt loads through equations or empirical calibrations. Such techniques offer the potential of accurate, rapid bolt load measurement that does not disturb the anchotage. This report presents 6e research findings for a specific type of ultrasonic measurement instrument using a pulsed-phase-Iock-Ioop technique. This technique measures signal travel time indirectly by measuring frequency changes. A complete development of the applicable theory and detailed derivations of key equations is presented along with empirical laboratory and field results. The differences between anticipated and measured behaviors are analyzed and discussed. The report identifies problems encountered in applying pulsed-phase-Iock-Ioop technology to roof bolt load measurement and provides potential solutions to many of them. A key assumption of pulsed-phase-lock-loop theory is that driving and reflected signal frequencies will always be equal. Findings showed that not only were actual frequencies not equal but they were not stable or simply related. Reflection wave shape also was not stable. The ramification of these findings and ways to minimize their adverse effects are presented.

Jan 1, 1990

By B. Olson, V. A. Marple, D. J. Radet

"Gravitational forces have been found to be an important factor in defining the particle collection efficiency curve of inertial impactors for large particles. In general it was found that if the parameter G = gW /V 0 2 (g is the gravitational acceleration. w is the nozzle diameter and V 0 is the average fluid velocity at the nozzle throat) in greater than 10-3 the efficiency curve would shift to lower panicle sizes. No effect could be seen for lower values of G.IN'IRODUCTIONInertial impactors have long been used as classifiers for airborne particles. By proper design of the nozzles and flow rate it is possible to classify particles with a fairly sharp cut in the particle size range from approximately .02 µm to 50 µm. Because of inertial impactors wide usage they have been extensively studied calibrated and evaluated. Most of these studies have been experimental calibrations of single stages using monodisperse aerosol particles. However, due to impactor simplicity. i.e. a jet of particle laden air impinging upon a flat plate with large inertia particles crossing the streamlines and impacting upon the plate the impactor also lends itself to theoretical evaluation.The most comprehensive method for analyzing impactors theoretically is to use finite difference solutions to the Navier-Stokcs equations and solve for the velocity components and pressure at node points of a grid placed over the area of interest. Using iteration and relaxation techniques the value of the velocity vectors can be determined at these node points with good accuracy. Once the velocities arc known, theoretical particles of known size can be placed into the now field and their trajectories determined by analyzing their equation of motion using numerical methods.Rader and Marple (1985) have performed theoretical analysis on impactors and have included such factors as Ultra-Stoksian .drag and the physical diameter of the particle in their analysis. However, even with these· factors included, there appears to be discrepancy · between the experimental and theoretical results when the particle size is larger than approximately 4 or 5 µm. One possible reason for this discrepancy could be the effect of gravity on the particle as it passes through the impactor. Therefore, a program was initiated to study the effects of gravitational forces on the collection· efficiency of particles in impactors. The results of that study arc presented here."

Jan 1, 1990

By Gloria L. Walker

The Bureau of Mines Information and Analysis Directorate collects worldwide data on virtually every commercially important non fuel mineral commodity. These data form the base for tracking and assessing the health of the minerals sector of the U.S. economy. This data collection activity was instituted by the 47th Congress in an appropriations act of August 7, 1882 (22 Stat. 329), to place the collection of mineral statistics on an annual basis. The most recent authority for the Bureau of Mines Information and Analysis activity is the National Materials and Minerals Policy, Research and Development Act of 1980 (Public Law 96-479, 96th Congress), which strengthens protection for proprietary data provided to the U.S. Department of the Interior by persons or firms engaged in any phase of mineral or mineral-material production or consumption.

Jan 1, 1990

By Nabil A. Bibawy

An improved method for preparing gravimetric standard gas mixtures of helium-4 in nitrogen has been developed by the U.S. Bureau of Mines. A single-pan 12-kg analytical balance that has a sensitivity of 3 mg is used to prepare the mixture. The balance will accommodate a cylinder having a volume of approximately 4 L that weighs approximately 5 kg. The method has been improved to a precision of ±O.04 pct by performing four successive dilutions, by improved handling of gases in the manifold, and by using an improved analytical method to select high-purity gases.

Jan 1, 1990

By N. S. Dalal, X. Shi

"Electron spin resonance (ESR) measurements provide evidence for the formation of Cr(V) intermediates in the enzymatic reduction of Cr(VI) by glutathione reductase (GSSG-R) in the presence of NADPH, indicating an initial single-electron transfer step in the reduction mechanism. Depending on the pH, at least two different Cr(V) species are generated which are relatively long-lived. In addition, we have detected the hydroxyl (·OH) radical formation during the GSSG-R catalyzed reduction of Cr(VI) by spin trapping, employing 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and a-(4-pyridyl-1-oxide)-N-tert-butylnitrone (4-POBN) as spin traps. Superoxide dismutase (SOD) causes only a minor effect on the ·OH radical and Cr(V) formation, indicating that the ~ - is not significantly involved in the reaction mechanism. Catalase enhances the Cr(V) formation and substantially inhibits the ·OH radical formation, indicating the involvement of hydrogen peroxide (H20 2) in the reaction mechanism. Addition of H20i suppresses Cr(V) and enhances the ·OH radical fonnation. Measurements involving N-ethylmaleimide show that the Cr(V) species, produced enzymatically by the reduction of Cr(VI) by GSSG-R, react with H2O2 to generate ·OH radicals, which might participate in the initiation of Cr(VI) carcinogenicity.INTRODUCTIONC(VI) compounds have been found to exert serious toxic and carcinogenic effects on humans and animals [1-4) and to cause mutations in bacteria and transformation of mammalian cells [5-8). In contrast, most Cr(lll) compounds are relatively nontoxic, noncarcinogenic, and nonmutagenic [9, 10]. Cr(VI) and Cr(lll) oxidation states are different in their metabolic pathways: Cr(VI) ions are rapidly transported across cellular membranes [2, 11-13), while Cr(lll) moieties do not easily penetrate cells and are not oxidized by cellular constituents [3]. Since it is known that the reduction of Cr(Vl) is required for its reaction with DNA [2], the molecular mechanisms for the intracellular Cr(VI) reduction have been the focus of studies during the past decade but the details are still not understood."

Jan 1, 1990

By L. M. Demers, D. C. Kuhn, N. El-Ayouby, C. F. Stanley

"Oxygenated metabolites of arachidonic acid (MJ are produced by the alveolar macrophage (AM) and have been shown to mediate inflammatory reactions. We therefore assessed the production of eicosanoids by AM harvested from the lungs of rats ex· posed to a bituminous coal dust for 2 wk in an inhalation chamber in order to determine if AA metabolism was altered in a manner that may promote an inflammatory response in the lung. Exposure to coal dust resulted in a 66% increase in the number of AM harvested, an increase in thromboxane A2 (TxA;i) and leukotriene 84 (LTB,j) production to 222% and 181% of control values, respectively, and a decrease in prostaglandin E2 (PGE:i) production to '62% of control values. In AM harvested from rats allowed to breath clean air for 2 wk following coal dust exposure, PGE2 production returned to control levels but TxA2 and LTB4 production remained elevated. The TxA2 synthesis inhibitor UK 38,485 reduced TxA2 production in dust-exposed AM both immediately and 2 wk following exposure. Thus, exposure of rats to coal dust significantly alters the metabolism of AA in AM, with potentially important aspects of AA metabolism remaining altered even after a 2-wk recovery period. Based on the established role of eicosanoids in inflammatory and fibrotic processes, these results suggest that the alteration of AM eicosanoid production as a result of the inhalation of coal mine dust may be an important factor in the pathophysiology of coal workers' pneumoconiosis.The authors are grateful to Joan Greenwood and Barbara Scheetz for their excellent technical assistance and to Brenda Pavone for the preparation of the manuscript. This research was supported by the U.S. Department of The Interior's Mineral Institute Program administered through the Generic Mineral Technology Center for Respirable Dust under grant 1135142.Request for reprints should be sent to Douglas C. Kuhn, Ph.D., Department of Pathology, The M.S. Hershey Medical Center, Hershey, PA 17033.INTRODUCTIONPulmonary alveolar macrophages (AM) are activated by foreign particles and microorganisms that enter the small airways (Kass et al., 1966; Herscowitz, 1985). This defensive reaction involves phagocytosis, lysosomal enzyme release, and the generation of reactive oxygen species by the AM (Snella, 1986; Rich et al., 1987). A number of agents, including phorbol esters, zymosan, adenosine diphosphate, organic hydroperoxides, and calcium ionophore, have been shown to activate the AM in vitro (Badger, 1986; Marshall and Lands, 1986; Snella, 1986). The AM response to these activators appears to be mediated in part by the oxygenated metabolites of arachidonic acid (AA) (Bertram et al., 1988; Demers et al., 1987; Mcleish et al., 1987).The AM may metabolize AA through cyclooxygenase- and lipoxygenase- catalyzed pathways to produce a variety of eicosanoids including prostaglandin (PG) E2, thromboxane (Tx) A2, leukotriene (LT) B4, LTC4, LTD4, and several hydroxyeicosatetraenoic acid derivatives (HETEs) (Willis, 1970; Camp et al., 1983; Poubelle et al., 1986). The production of these eicosanoids may enhance the. defensive ability of the challenged lung since they stimulate chemotactic cell recruitment to the site of invasion, enhance extravasation of circulating immune cells, and promote local vasodilatation. However, continued stimulation of the AM population, with the consequent production of proinflammatory eicosanoids, may ultimately enhance the disease process by contributing to chronic bronchoconstriction, fibrosis, and the persistent release of toxic oxygen species."

Jan 1, 1990

By R. V. Ramani, R. Bhaskar

One of the primary means of .control of health hazards from respirable contaminants in mine atmospheres is through design and operation of mines to meet mine health and safety regulations and recommended practices. A U.S. National Academy of Sciences study concluded that for significant progress in coal mine dust control, research should be directed more toward obtaining fundamental understanding of the origin, transport and characteristics of respirable coal mine dust. Theoretical and experimental studies on transport of dust in mine airways, particularly coordinated efforts to validate theory with practice, are scarce. Some empirical models, developed on the basis of experimental data, are available but these models cannot be applied to new .conditions. The purpose of this paper· is to present the results of theoretical and experimental studies on the transport and deposition of dust in mine airways. This study is a part of an on-going research project in the Generic Mineral Technology Center on Respirable Dust. In the paper, the assumptions of the modeling phase of the project and the development of a convection-diffusion equation for dust transport in mine airways will be outlined. The important aspect of the modeling effort.is the capture of the deposition phenomenon. The experiments performed under controlled conditions in a typical mine airway as well as under normal mine operating conditions will be discussed. The comparison of the model predictions ·with experimental results will be made to identify critical areas of agreements and deviations. The implications of the findings and areas for further research and development will be identified.

Jan 1, 1990