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By N. S. Dalal, X. Shi, P. M. Gannett

"Chromates are known to induce tumors (1, 2), mutations (3), and DNA damage (4-6). However, the underlying biochemical mechanism(s) is (are) not fully understood (6). Recent studies have indicated that hydroxyl (·OH) radical may play an important role (7-11). The mechanistic studies of Cr(Vl)-related ·OH radical generation in biochemical systems have shown the reaction of a Cr(V) species with hydrogen peroxide (H20 2 } through a Fenton-like mechanism to be one of the important steps (9-11): Cr(V) + H20 2 - Cr(VI) + ·OH + OH-. (1)In biological systems the Cr(V) species are generated via the reduction of Cr(VI) by a variety of components, such as microsomes (12), mitochondria (13), mitochondrial electron transfer complexes (14), and at least three flavoenzymes (glutathione reductase (GSSG-R),3 lipoyl dehydrogenase, and ferredoxin-NADP+ oxidoreductase) (9, 15, 16). In the case of flavoenzymes, Cr(V) formation is accompanied by the reduction of molecular oxygen ( 0 2 ) to H20 2 • The Cr(V) species then reduces H20 2 to generate •OH radicals and Cr(VI) (16).To understarid the mechanism by which Cr(V}-generated ·OH radicals cause cytotoxicity, Aiyar et al. (8) investigated the reaction of Cr(VI) and H20 2 to generate ·OH radical and its reaction with 2'-deoxyguanine (dG) to form 8-hydroxy-2'-deoxyguanine (8-0HdG}:"

Mar 1, 1992

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

While Cr(VI) is a known carcinogen, the underlying biochemical mechanism is still not fully understood (1). In a pioneering study Jennette (2) utilized electron spin resonance (ESR) spectroscopy to demonstrate that a long-lived Cr(V) species is generated during the reduction of Cr(VI) by microsomes in the presence of NADPH. Later Wetterhahn and co-workers (3, 4) showed that incubation of chromate with isolated rat liver mitochondria causes the reduction of Cr(VI), as well as the formation of a Cr(V) species. Analogous Cr(V) species have also been detected in the reduction of Cr(VI) by other cellular systems such as Hanserulla polymorphared (5) and blood cells (6, 7). All these as well as other studies (8-12) have suggested that this Cr(V) species plays a significant role in the mechanism of Cr(VI) toxicity. Thus far, however, the chemical structure of this dominant Cr(V) species formed in cellular systems has not been identified, and this observation provided an impetus for the present investigation. Another reason for undertaking this study was that some recent reports (10-16) suggest that hydroxyl ('OH) radicals may also play an important role in the mechanism of Cr(VI) toxicity. In particular, it has been shown that OH radicals are formed in reactions between Cr(V) species and H2O2 (13-16), and that the radical yield depends on the chemical structure of the Cr(V) species (15). For example, while Cr(V)-diol complexes efficiently generate OH radicals, another Cr(V) species, the tetraperoxochromate (CrO3/8) ion, does not (15). Thus in the present study, we focused our attention on the following: (a) structural identification of the Cr(V) species generated in the reduction of Cr(VI) by subcellular as well as cellular systems, using microsomes, mitochondria, and Escherichia coli; (b) possible detection of OH radical in the same systems since there is no earlier report of chromium-mediated generation of 'OH radicals in a cellular system; (c) possible involvement of molecular oxygen in chromium-related OH radical generation since a recent report (17) indicated that Cr(VI) mutagenesis is strongly oxygen dependent; and (d) elucidation of the mechanism of OH radical formation in these systems.

Mar 1, 1992

By M. S. Seehra, R. S. Pandurangi

"The interaction of amorphous silica particles with several hydrogen bonding agents (H2O,, C2H,OH, C,H,NO) 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 of surface groups, along with the shift in the broad hydroxyl band, the interaction following the order C,H,NO > C2H2OH > H2O.The use of IR spectroscopy to study the adsorption on solid surfaces is well documented in the literature,"" 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.3-6 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 C7H8N0), 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 IR spectroscopy, and Knozinger16 and Rouxlet and Semples17 have used transmission IR 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, C2H5OH, and H20) with the silica surface by monitoring changes in the surface IR 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,The Cab-O-Sil samples of silica used here were obtained from the Cabot Corporation of Tuscola, IL, In our earlier studies,14,20 we have shown these particles to be amorphous and about 0.05 am in size, For coverage of these particles with H20 and C2H50H, the following procedure was employed. About 5 mg of silica was mixed with 50 mL of the liquid (H2O or C2H5OH) and refluxed for one hour, The remaining liquid was allowed to evap¬orate to dryness and 1 mg of the treated sample was used to collect the PA spectra. In the case of PVPNO, the amount that binds to Cab-O-Sil is taken from the data on quar"

Mar 1, 1992

By R. L. Grayson, W. E. Wallace, T. Simonyi, J. C. Harrison

"Application of an SEM-based methodology suggests a reason for past contradictory results on the relationship between quartz and coal workers' pneumoconiosis (CWP). Results indicate that coal seams with the same bulk analysis of quartz may have different amounts of surface-availablequartz. Our research shows that the amounts of pure and surface-available quartz in a respirable dust vary directly with the rank of a coal seam, except in the case where rock materials are mined. The estimated amount of surface-available quartz therefore provides a measure of the quartz-related fibrogenic potential of a respirable dust.INTRODUCTIONFrom our previous work (Grayson, 1991), we have shown that the amount of pure quartz in a respirable coal mine dust sample appears to vary directly with the rank of the seam (using fixed carbon as the basis for comparison), except when a substantial rock parting, roof or floor are mined. Our other work (Wallace et al., 1989) showed that high-silica particles in a clay mine may generally be coated with clay, rendering the quartz core non-available for surface reaction in the lung. The combination of these findings led us to hypothesize that the coating phenomenon may indeed be present in coal mines as well, and that a rank relationship may be present regarding this phenomenon. Thus higher rank coal seams may have more surface-available quartz as well as more pure quartz particles in their respirable dusts. The scientific protocol for testing this hypothesis and the results obtained to date are discussed in this paper. Thus far, there is no reason to doubt that the relationship holds."

Mar 1, 1992

By Jianmin Qin, Raja V. Ramani, Wilson Miola

"The number of underground work entities operating under reduced dust standards in U.S. coal mines has been increasing since the start of the decade of the 80s and is currently approaching 10,000. The concern for controlling the quartz levels in airborne respirable dust in coal mine has manifested itself in several improvements in equipment selection and operation, face ventilation practices, and dust control procedures. At the same time, fundamental studies have been initiated on determining the source-sink relationships of the airborne quartz dust. The P-7 method is the prescribed method for the determination of quartz in the respirable airborne dust samples from coal mines. Questions have been raised on the reliability of the P-7 infrared spectrometry method for quartz analysis in powders. No specific method has been defined for quartz determination in bulk samples from the mine.In a recent study on the relationship between quartz in the airborne dust and that in the materials being mined, both infrared (IR) and x-ray diffraction (XRD) methods were used on a suite of samples from several coal mines. These samples encompassed airborne respirable dust samples, airborne total dust samples, the oversize fraction from the respirable samplers, ROM samples, channel samples, and chip samples from the face, roof, and floor materials. In this paper, the sample preparation and analysis procedures for the samples are discussed. The data, analysis results, and comparisons of the P-7 and XRD results are presented. The quartz percent determined for the same sample by the two methods are different. In 85% of the samples analyzed, the quartz percents determined by the XRD method are higher than those obtained by the P-7 method. However, there is a strong linear relationship between the results from the two methods. Further, the XRD method indicates an average of 20 percent more quartz than that from the P-7 method. The reasons for the differences in the results and the need for additional studies are explored.Since the enactment of the Federal Coal Mine Health and Safety Act of 1969 and the Federal Occupational Safety and Health Act of 1970, the prevalence of free silica as an occupational hazard in dusty work environments has been a matter of increasing concern. In underground coal mining, sometimes, roof, floor, clay veins and other non-coaly material must also be mined along with the coal. Mining these materials may increase the amount of quartz in the airborne dust (Pimentel and Adam, 1985; Taylor et al., 1984; Colinet et al., 1985). The problem of high quartz levels in the respirable airborne dust is widespread in continuous miner sections. In addition to the need for controlling the silica amount in mine atmosphere, a need for a sensitive, easily performed method for the determination of free silica in airborne dust samples was also recognized."

Mar 1, 1992

By R. Hogg, E. Kaya

"The presence of agglomerated particles in airborne dust in coal mines has been confirmed by SEM examination of static samples collected on substrates. In addition, the effect of agglomerated particles on the performance of cascade impactors and cyclone-type personal samplers has been studied. Simple procedures have been developed for evaluating the extent of agglomeration in air-borne dust by comparing the observed size-selectivity of the sampling devices with that expected under idealized conditions. Applications of these techniques in the laboratory and in underground mines are discussed.INTRODUCTIONAirborne dust is invariably present in mine atmospheres. Particle size is a primary factor in determining the behavior of the dust, its effects on miners' health and the effectiveness of dust control measures. Obviously, agglomeration of the dust particles can have important effects on: ""natural"" dust removal processes such as settling• the use of water sprays etc., for dust control• pulmonary deposition characteristicsIn addition, the presence of agglomerates could influence the effective toxicity of the dust. For example, ultrafine particles are often thought to be relatively unimportant in the development of respiratory ailments because of their low deposition efficiency. However, the latter could be substantially increased if such particles were present in larger agglomerates. It is by no means obvious that there should be significant agglomeration of the airborne dust in a mine atmosphere. In fact, calculations based on the classical coagulation theories indicate that, at the kinds of dust concentrations that exist even in what would be regarded as “very dusty"" atmospheres, the coagulation half-time* .should be of the order of weeks or even months. On this basis, agglomeration would be expected to be essentially negligible. On the other hand, laboratory experiments (Polat et al., 1991) have revealed very extensive agglomeration in the airborne dust released during the crushing of individual coal and mineral particles. It is postulated that such agglomeration occurs immediately at the point of dust generation. In other words, many of the fine fragments produced on fracture are never completely separated from their neighbors."

Mar 1, 1992

By C. P. Fang, V. A. Marple, K. L. Rubow

"Studies of the flow fields and particle impaction characteristics are more complicated in multi-nozzle impactors than in single-nozzle impactors, since the jets of air must penetrate cross-flowing air to impinge on the impaction plate. Results of heat and mass transfer analysis are employed to describe the cross-flow pattern in multi-nozzle impactors. A cross-flow parameter has been derived to predict the deflection of the air jet by the cross-flow. This parameter is expressed as a function of the geometric parameters for the multi-nozzle impactor. DnN 4D,, where N is the number of nozzles, Dn the nozzle diameter and D, the nozzle cluster diameter. Empirical particle collection data show that multi-nozzle impactors operate satisfactorily, if the cross-flow parameter is less than a critical value of 1.2. Impactors operating with a cross-flow parameter larger than this critical value are shown to possess poor particle collection characteristics.Inertial impactors of many designs have been used for sampling aerosol particles. Impactors can be single stage, consisting of a nozzle and an impaction plate, or a cascade impactor with several stages in series. The simplest design for a stage is a single nozzle with a flat impaction plate. However, many designs use stages with multiple nozzles of identical size, which allows for compact impactors to be designed at rather substantial flow rates and moderate pressure drops.Nearly all of the theoretical work, and much of the experimental work, has been performed on single-nozzle impactors. The results of single-nozzle impactor analysis are often applied to multiple-nozzle impactors, which are assumed to be a group of individual nozzles, each operating as though they were single nozzles. However, an important fact is often ignored: the interaction of flow from adjacent nozzles can change not only the fluid mechanics in the impaction region, but also the locations of the jet stagnation points, and the impaction characteristics of each nozzle.The effect of multiple nozzles on the particle collection characteristics of impactors has been studied by a few investigators. May (1964), Fletch et al. (1967), Friedrichs (1968), and Vaughan (1986) reported that the quantity of particles in deposits of nozzles in the first two stages of the Andersen multi-nozzle cascade impactor were not equal. The inner deposits appeared to contain fewer particles than the outer ones. However, Vaughan (1986) in addition showed that many of the deposits in the outer three rows were missing on the first stage, even though the outer deposits that were present were larger than the inner deposits.May (1964) conducted experiments and explained the phenomenon of smaller deposits near the center than near the edge. He noted that in Andersen cascade impactors the air issuing from the nozzles moves radially outward along the narrow channel between the nozzle plate and the impaction plate. This flow at 28.31min -1 created a pressure difference of about 1 mm water between the inner and outer sections of the channel. The effect was most pronounced in the first two stages, where the pressure drop across the nozzles was also about 1 mm water. Here, the flow velocities in the nozzles, and hence the deposits, were smallest at the center and increased toward the periphery of the impaction plate. since the pressure drop across the nozzles was the smallest at the center and a maximum at the periphery. This effect was negligible in the lower stages because of a larger pressure drop across the nozzles. According to May (1964), this effect could be eliminated by increasing the nozzle-to-impaction-plate distance to three nozzle diameters and improving the nozzle arrangement to allow air flow to escape to the periphery more easily."

Mar 1, 1992

By E. V. Cilento, R. C. Laotz, K. A. DiGregorio

"PULMONARY ALVEOLAR macrophages (PAM) protect the lungs by providing a first line of defense against inhaled foreign debris and bacteria. In this role PAM phagocytize foreign matter, secrete enzymes that augment microbial killing and digestion, and produce reactive oxygen me-tabolites (2, 3, 18, 19, 22, 26). However, in addition to this antibacterial function, PAM participate in a diversity of functions, such as tissue repair, lipoprotein metabolism, and immunoregulatory activities (11, 22).Studies have suggested the existence of a heterogeneous population of PAM with respect to immunologic function, enzyme release, phagocytosis, morphological characteristics, expression of membrane receptors, ad-herence, and superoxide (O2•) release (4-7, 10, 16, 21, 23, 28). This heterogeneity has been observed by analyz¬ing subfractions of PAM separated by cell density frac-tionation. For example, using guinea pig PAM, Dauber et al. (7) showed heterogeneity in cell density and size, morphological characteristics, and cytochemical properties, whereas Holian and co-workers (16) reported variations in migration, chemotaxis, O2• release, and pinocytosis among subfractions collected. Similarly, O'Neill et al. (21) observed functional heterogeneity in rat PAM with regard to phagocytosis, O2 • release, and lysosomal enzyme activity.Several investigations have reported a correlation between PAM activity and cell volume. Most studies have shown that O2 release from PAM increased with decreasing cell size (15, 21, 25), although Bielefeldt Ohmann and Babiuk (4) reported a decreasing trend. However, Gallin (13) has suggested that significant variability may even exist within density-defined or cell-volume subfractions that could lead to misinterpretation of results concerning PAM heterogeneity.A better understanding of the heterogeneity in O2 production may be obtained by using single cell meas-urements to evaluate whether functionally distinct sub-populations actually do exist. As such, the present study was designed to examine heterogeneity in O2 • release from single PAM using a recently developed electrooptical technique (8). The initial oxygen metabolite, O2•, produced by NADPH oxidase at the surface of the plasma membrane, was measured by quantifying the reduction of nitro blue tetrazolium (NBT I to a diformazan precipitate. Measurements were made from video recordings of individual cells stimulated by their adherence to the bottom of a culture dish. The cell volume and degree of spreading also were determined directly from the same video recordings, and the data were correlated with the initial rate and maximum amount of diformazan produced by the same cell."

Mar 1, 1992

By R. Burrell, N .. L. Lapp

"Except for asthma and pulmonary infections, the types of lung disease that have been of immunologic interest the longest are the various mineral pneumoconioses. Because of their chronicity, type of pathology produced, and well-known immunotoxic properties associated with the dusts inciting them, the pneumoconioses have long drawn attention to the possibility that the immune system has not only been modulated but that its effectors have possibly contributed to their pathogenesis. All of the mineral dusts reviewed here have definite immunomodulating properties and act on various cellular and molecular components of the immune system. Further, each has an immunotoxic potential to induce either hypersensitivity (as in the case of beryllium) or other types of immune injury. This article reviews the immunologic aspects of the four major occupational minerals that have an immunologic impact on the lung: asbestos (particularly chrysotile), silica or quartz, beryllium, and coal mine dust.These agents have many things in common, yet each is distinctive. Although the possibility still exists that these mineral particles can adsorb intrinsic tissue antigens or extrinsic organic antigens to their surfaces and initiate immune responses to the adsorbed antigens, only one, beryllium, can act as an antigen itself. Silica is a profound macrophage toxin and thereby exerts many effects on those factors controlled by macrophages. Asbestos has undergone the most immunologic studies resulting in a much dearer picture of how it may contribute to immunopathology. Coal mine dust is the agent about which least is known immunologically, partly because there is no such thing as purified coal mine dust or a standard by which coal mine dust can be defined. Indeed, there are studies that use only the dust from the ground coal itself, whereas other studies use the total dust collected from air samples of a working mine in the belief that other types of dusts (e.g., silica from roof bolt drilling, from sand ground on the rails by cars, and from surface drilling) contribute to the disease (Figs. 1 to 5). This properly is coal mine dust and is poorly characterized. Yet, workers exposed to these dusts share similar reactive characteristics and they may be considered collectively as well as individually."

Mar 1, 1992

"Correlatina Lung Crackle Usina Holographic lnterf erometryAli Afshari, MS, West Virginia University, 1989The Effect or Surfactants on Suppression of Non-Wettable ParticlesAli Alaboyun, MS, Mineral Engineering, The Pennsylvania State University, 1989Geochemical Characterization of Kerogem, ShaJes, and Coal .Refme ~ted with Allegheny Fonnationof Cases of Northern West VirginiaDick Andre, MS, West Virginia University, 1987Particle Concentrations in a Hazelton Inhalation ChamberShahram Bavani, MS, West Virginia University, 1985Use and Potential of Luer Holographic Interferometry and Subsidence Model Study of an Underground.Room and Pillar MineRichard Begley, MS, West Virginia University, 1984Development of a Mechanistic Model for Prediction of Subsidence in a Longwall MineRichard Begley, PhD, West Virginia University, 1990.Redesign of Micro-Orifice Unifonn Deposit ImpactorSteve Behm, MS, University of Minnesota, 1991A Fracture Mechanics Study of Crack Propagation Mechanism in Coal: The Mechanics of Fine FragmentFonnationZ. T. Bieniawski and R. Karl Zipf, Jr., Mining Engineering Department, The Pennsylvania State University,University Park, PA. Final Report, October 1, 1988A Mathematical Model for the Prediction of Ambient Dust Concentrations in Mine AtmospheresR. Bhaskar, MS, Mining Engineering and Operations Research, The Pennsylvania State University, 1984Spatial and Temporal Behavior of Dust in Mines-Theoretical and Experimental StudiesR. Bhaskar, PhD, Mining Engineering, The Pennsylvania State University, 1987Experimental Studies of Dispersion and Deposition of Fane Particles in a Wind Tunnel and Mine AirwayKlaus Bode, MS, Mining Engineering, The Pennsylvania State University, 1991Perf'onnance of the High Yield Technology PM - 100 - Particle 11ux MonitorRobert Caldow, MS, University of Minnesota, 1987Development of Improved Methods for Monitoring and Control of Diesel Particulate in an Underground CoalMineD. H. Carlson, B. C. Cornilsen, P. L. Loyselk, X. Shan and J. H. Johnson, Michigan Technological University,Houghton, Ml. Final Report, June 15, 1991"

Mar 1, 1992

By Danqing Xu, A. W. Khair

"This paper presents a laboratory simulation of regrinding and resulting dust generation. An Automated Rotary Coal Cutting Simulator (ARCCS) was modified to conduct regrinding experiment. In order to estimate the effects of coal properties and operating parameters on regrinding and dust generation, an orthogonal fractional factorial experimental design was implemented in regrinding experiment. Marple personal cascade impactors, Series 290, were used to measure dust concentration during experiment. Three types of coal seams, namely, Waynesburg, Pittsburgh, and Lower Kittanning, were used to represent different coal properties. Experimental results and complete parametric analysis were presented.In a rotary cutting system, all the broken coal and part of the remaining coal from previous cutting cycles must be transported through part or entire circumference of the cutting drum. This transportation of already recovered coal through the cutting zone of rotary head makes it a rotary grinder. Some of the coal particles will be subjected to secondary fragmentation or regrinding in the process. The potential effect on dust generation by regrinding is significant because the cutting head utilizes kinetic energy to comminute recov¬ered coal material. The moving bits and bit blocks on the cutting head impact coal particles and transfer some of their kinetic energy to the particles. After obtaining kinetic energy, coal particles are free to impact one another and they also impact the coal seam or cutting head. During impact, high impact force and high internal stress concentration are created in the particles. Kinetic energy is transformed into strain energy. When stored strain energy exceeds allowable strain energy, the particles will break. A great amount of respirable dust will be generated due to impact failure. In reality, regrinding occurs at the same time as primary cutting. The particles to be ground are the result of primary cutting. Both primary cutting and regrinding produce dust. Therefore, it is impossible to separate regrinding from primary cutting. In order to study respirable dust generation by regrinding and analyze the influencing parameters, a laboratory approach was adopted. In this approach, it is possible to study the regrinding separating from primary cutting."

Mar 1, 1992

By N. S. Dalal, Xianglin Shi

"The mechanism of vanadium(V) V ) toxicity is still not fully understood in spite of extensive current effort (1-3). The presence of a vanadium(V) V ) -dependent NAD ( P )H oxidase in cell membranes suggests that at least one of the pathways involves oxidation of NAD(P)H (1-3). Considerable effort has therefore been devoted to finding the mechanism of NAD ( P ) H-oxidation by va¬nadium( V ) (1-19). Recently Liochev and Fridovich (4, 16) provided a critical review of vanadium( V) -stimulated NAD (P )H oxidation by plasma membranes. They out¬lined a mechanism in which vanadium(V) V )-stimulated oxidation of NAD ( P )H by biomembranes involves an O2 - initiated free radical chain reaction (4 ). While the above may be the major pathway for the vanadium-me¬diated NAD (P )H oxidation in membrane-related sys¬tems, some recent results suggest that in the presence of NADPH the flavoenzyme glutathione reductase can function as a vanadium(V) V ) reductase (18). Because of the significance of this result in relationship to the mech¬anism of vanadium( V) metabolism and the novelty of the metal-reductase behavior of a flavoenzyme, we have car¬ried out additional studies on one-electron reduction of vanadium( V) by two other, related flavoenzymes: lipoyl dehydrogenase and ferredoxin-NADPH oxidoreductase. These two enzymes were selected because they are known to catalyze a one-electron reduction of Cr ( VI ) (19-21 ), which is isoelectronic with vanadium( V ).The present study also reports on the generation of hydroxyl ( • OH) radicals in the vanadium( V) -flavoen-zyme redox system without exogenous H2O2. The • OH study was undertaken because • OH radicals are known to be generated in reactions of vanadium( IV) with H2O2 (17,18,22-27). For example, Piette and co-workers (17, 22) have studied effects of vanadium(IV) IV ) on lipid per-oxidation and NADPH oxidation and suggested that va-nadium( IV) -induced • OH radical formation may play an important role in vanadium( V) toxicity. Carmichael (25, 26) investigated the reaction between a RNA /VO 2' complex and H2O2 with a view to probe the possible re-lationship between vanadium( IV) -mediated • OH radical generation and DNA damage. He has suggested that in this reaction the • OH radical adds to the C (5) carbon of uracil, causing nucleotide damage, similar to what occurs in the nucleotide /Fe2+ / H2O2 reaction (28) and in y-irradiated aqueous solutions of nucleic acids (29 ). To our knowledge, however, there is as yet no report on ·OH radical generation in any reaction involving the reduction of vanadium ( V) by a well-characterized enzyme, without exogenous H20 2 • The present study provides evidence that ·OH radicals can form in a flavoenzyme-mediated reduction of vanadium( V) to vanadium( IV) and that this process involves also the reduction of molecular oxygen ( 0 2 ) to H20 2 • The H20 2 thus generated reacts with vanadium( IV) to produce ·OH radical, in analogy with the Fenton reaction ( Fe2 + + H20 2 - Fe3 + + OH- + ·OH)."

Mar 1, 1992

By V. A. Marple, K. L. Rubow, S. M. Behm

"An eight-stage cascade impactor, with cut-sizes ranging from 0.056 to 18 um at a flow rate of 30 L/min, has been developed, calibrated, and tested in field programs. This impactor, called a microorifice uniform deposit impactor, has several features not normally found in cascade impactors. Ultrafine particles as small as 0.056 um are collected while keeping the pressure drop moderate by utilizing multiple nozzles (up to 2000) as small as 52 um in diameter. At each stage the collected particles are deposited uniformly over the entire impaction plate by rotating the impaction plate relative to the nozzles and by the correct radial placement of the nozzles. The particle cutoff characteristics (collection efficiency curves) of each stage and inter-stage losses were determined by means of monodisperse aerosols. The cutoff characteristics were found to be sharp and similar for all stages.Inertial impactors are widely used for the size-selective collection of aerosol particles. One reason for their wide usage is that the principle of operation is simple: a jet of particle-laden air is directed at a flat impaction plate. Large particles are collected on the plate while smaller particles follow the airflow out of the impaction region and are not collected. The division between the size of particles collected and those that are not is quite sharp. Secondly, the particles in an impactor are classified by their aerodynamic diameter (an important size parameter in many fields of study, including those related to respirable particle health effects). Thirdly, it is easy to collect particles in discrete size ranges by passing the aerosol through a number of stages (one stage consisting of a nozzle and impaction plae) in series, with each subsequent stage collecting particles smaller than the one before it. This is known as a cascade impactor. Finally, impactors can classify particles over a wide range of particle sizes: as low as 0.005 um (Fernandez de la Mora et al., 1990) and as large as approximately 50 um (Vanderpool et al., 1987).This paper describes a general purpose cascade impactor that has been developed in our laboratory and used in a variety of studies including visibility studies (McMurry et al., 1986; McMurry and Zhang, 1989), underground mine studies (Marple et al., 1986; Rubow and Marple, 1988; Rubow et al., 1988), and general atmospheric pollution studies (Macias et al., 1981; Dzubay et al., 1984). The impactor, called a microorifice uniform deposit impactor (MOUDI model 100, MSP Corp., Minneapolis, Minn.), is the integration of two earlier impactor de¬velopments: the microorifice impactor (M01) (Kuhlmey et al., 1981) and the uniform deposit impactor (UDI) (Marple et al., 1981).The MOUDI has several features normally not found in other cascade impactors. These include collection of particles as small as 0.056 um in aerodynamic diameter with a moderate pressure drop, uniform particle collection on the impaction plates, inter-changeable impaction plates to allow for the plates to be easily and quickly changed in the field, and covers for these substrates to provide a means for safe storage and/or transport of the collected particles to the laboratory for analysis."

Mar 1, 1992

By R. V. Ramani, J. Qin, R. A. Jankowski

"Longwall mining is generally recognized as safer, more productive and economic when compared to room and pillar underground coal mining. There has been, however, increasing concern for the control of airborne coal dust concentrations in long wall faces. The airborne dust cloud at a longwall face is a complex aerosol system containing particles of varied size, density, shape and state of aggregation. For the development of more effective dust control practices in longwall faces, it is necessary to understand more clearly the characteristics of the longwall dust cloud.In this paper, results of a research study on dust concentration distributions along longwall faces are presented. The objective of this study is to characterize the longwall dust cloud behaviour and provide necessary fundamental data for a better understanding of the longwall dust problem. MSA personal samplers and gravimetric total dust samplers were employed to collect respirable and total airborne dust samples. The size distribution of these samples was determined by MicroTrac SPA. The instantaneous respirable airborne dust concentrations were recorded using RAM-I. The dust concentrations are related to face operations, particularly the shearer location and activities. The size distribution of airborne dust, instantaneous respirable airborne dust concentration, and air quantity distributions along longw all faces reveal a complex dust flow phenomenon. Additional fundamental studies are needed for characterizing the temporal and spatial behaviour of the dust cloud at longwall faces.IntroductionModern mechanized longwall mining was introduced in the United States in the 1960's and has become more common in the last twenty years. United States longwalls are multiple-entry retreating faces. According to a recent survey, 91 of the 102 longwall faces employ double-drum shearers (1). Several recently installed longwall faces have consistently produced over 4 000 to 5 000 tons per shift over extended periods of operation. The trend in under-ground coal mining in the U.S. certainly is toward the introduction of longwalls. This trend is true not only for new mines but also for renovation of existing mines. While longwall mining has many advantages over other mining methods, including improved safety, such as higher pro-duction. greater productivity and enhanced reserve recov-ery, it is associated with severe problems of dust control. The increase in longwall production has been accompanied by an increase in respirable dust problems which limit realizing the full potential of the longwall mining system. Despite the efforts to develop improved equipment and operational procedures to control the dust levels at longwall faces, it is still difficult to bring several double-drum shearer operations into compliance with the Federal stand¬ards of 2,0 mg/m 3 respirable dust without loss of produc¬tion. In fiscal year 1987, fifty-eight of the longwall sections were found to be in non-compliance once, and an additional 31 were cited two or more times'''. If the full potential of the longwall mining method is to be realized, new measures must be implemented to control the dust concentration to mandated levels. There is a need for detailed and extensive sampling of longwall faces to understand the dust source-sink relationships and the transient ambient concentrations. These must be related to the mining activities on the face. This paper is to characterize the longwall dust cloud behavior through a series of experiments in operating faces and provide necessary fundamental data for further studies to develop improved dust control practices."

Mar 1, 1992

By Raja V. Ramani, Wilson Miola

"The potential health effects of quartz-bearing airborne dust in mine and mill atmospheres point to the need for the quantification of quartz content in the source material for determining the source-sink relationships and for choosing applicable control measures. While a standard method exists from a regulatory point of view for the sampling of coal mine atmospheres for determining (i) respirable dust concentrations and (ii) the amount of quartz in the samples, there is no generally accepted standard method for quartz analysis in bulk samples of coal and host rocks. Generally, the bulk sample is reduced to a powder for producing quartz analysis samples. Extensive controls arc necessary to ensure representativeness of the analysis samples when these are very minute fractions of the bulk samples. Since the amount of analysis sample is not limited, alternative methods for quartz analysis may also be tried. It is, however, necessary to adopt a procedure which will satisfy several statistical requirements to guarantee representativeness of the quartz analysis samples.In this paper, the important factors in the preparation of quartz analysis samples from the host rocks and bulk samples are discussed. The method developed to prepare the analysis samples is outlined. The results of application of the procedures are presented. The procedure developed for quartz analysis sample preparation is based on sound statistical foundations. The procedure has been validated for reproducibility and homogeneity.The current methods used for quartz analysis in powders are the P-7 infrared spectrometry and quantitative X-Ray Diffraction (XRD). Both have similar restrictions concerning the sample characteristics and operational problems, which arc intrinsic to radiation beams, device geometry, mechanics and controls of the radiation behavior. Although improvements can be made in the spectrometers and diffractometers, some of the most important steps are the procedures for analysis sample preparation from bulk samples and for calibration of the instruments. The sample preparation process is often referred to as one of grinding and sizing the bulk sample to generate the powder for the scanning devices. The particle sizes are referred to and their influence emphasized but the representativeness of the sample is assumed. Assuring sample representativeness during the sample preparation procedures is critical.For the sampling of airborne respirable dust in coal mines, the collection devices, the collection procedures and the analysis procedures are defined. This is not true for bulk samples where weights must be reduced thousands of times to generate the analysis samples for the scanning devices. The specifications to be developed may include bulk sample amount, sample reduction procedures, sample particle size distribution and sample amounts. However, the common problem of insufficient sample amount which is often encountered with mine airborne dust samples need not exist for bulk samples. Further, the same bulk sample can yield analysis samples for several experiments. The latter, of course, requires sample homogeneity.Three concepts are important in the selection of any procedure for sample preparation and analysis. These arc accuracy, reproducibility and representativeness. The adopted procedure has to guarantee a homogeneous sample representative of the population, a defined level of accuracy and reproducibility. Important statistical concepts are embedded in these requirements, particularly with respect to estimation and dispersion errors. Accuracy and reproducibility are totally different though not independent concepts. Estimation is related to accuracy and the true value. Dispersion is related to reproducibility and is measured by the classical statistical standard deviation of the distribution of a series of measurements or analysis performed over the same lot or analysis sample. The dispersion variance (or dispersion error) does not tell a"

Mar 1, 1992

By H. Polat, Q. Hu, S. Chander

"The collection efficiency of dust particles was determined in a laboratory dust chamber equipped with a water spray. Measurements were made in the presence of selected nonionic, cationic and anionic surfactants. For the nonionic and the anionic reagents, efficiency was maximum in a narrow range of concentration. The surfactant concentration corresponding to high collection efficiency was usually much below the commonly used concentration of l "", however. In comparison, much higher collection efficiency was observed for a cationic surfactant at extremely low concentrations. For delineating the mechanism of capture of dust particles, surface tension and contact angle results were used to obtain a correlation between the work of adhesion and the efficiency of collection. Such a correlation was reasonable for the nonionic surfactants but not for charged surfactants. In the latter case, electrostatic interactions between charged droplets and particles were more important, especially for the cationic reagent. INTRODUCTIONSeveral methods are used to control dust in mines. These include: ventilation, foam, scrubbers and sprays. This article is concerned with improving the effectiveness of water sprays, which are widely used to remove dust particles during continuous mining, by adding small quantities of surfactants. Water sprays produce small droplets which act as collectors of dust particles suspended in air. Sprays directed at the actual source of dust have the additional property of wetting the coal before the ·particles become airborne (Hamilton, 1974). Wetting agents, also called surfactants, arc known to play an important role in many applications where dust is a problem. However, conflicting reports exist in the literature with regard to the effectiveness of surfactants in water sprays (for a review, see Chander et al., 1988). In spite of the conflicting reports, the use of surfactants for dust control has increased over the years. In a recent study by the Bureau of Mines, a 27'6 reduction in respirable dust levels was observed in a mine test when surfactants were added to sprays (Foley, 1991)."

Mar 1, 1992

By E. D. Regad, W. E. Wallace, P. S. Mike, C. A. Hill, V. Vallyathan, M. J. Keane

"Respirable-sized quartz, a well-established fibrogenic mineral dust, is compared with kaolin in erythrocyte hemolysis assays aher treatment with saline dispersion of dipalmitoyl phosphatidylcholine, a primary phospholipid component of pulmonary surfactant. Both dusts are rendered inactive after treatment, but the membranolytic activity is partly to fully restored aher treatment with phospholipase Ai. an enzyme normally associated with cellular plasma membranes and lysosomes. Phospholipid-coated dusts were incubated for periods of 2-72 h at a series of applied enzyme concentrations, and the adsorbed lipid species and hemolytic activity were quantitated at each time for both dusts. Surfactant was lost more readily from quartz than from kaolin, with consequent more rapid restoration of mineral surface hemolytic activity for quartz. Interactions of surfactant and mineral surface functional groups responsible for the mineral-specific rate differences, and implications for determining the mineral surface bioavailability of silica and silicate dusts, are discussed. INTRODUCTIONMineral particles depositing in the lung acinus will contact an aqueous coating containing surfactant molecules spread on the air-liquid interface and dispersed within this hypophase; the primary components of that surfactant are diacyl lecithin phospholipids (King and Clements, 1972; King, 1982). Adsorption of this surfactant can suppress the cytotoxicity of mineral dusts (Marks, 1957). Suppression of hemolytic activity, a measure of membranolytic potential and an indicator of bioavailability of the mineral surface, of respirable-sized quartz and kaolin clay dusts with the adsorption of dipalmitoyl glycerophosphorylcholine or dipalmitoyl lecithin (DPL) has been measured (Wallace et al., 1985). Such contact and adsorption of pulmonary surfactant in vivo may provide a first defense system of the lung against respired dusts."

Mar 1, 1992

By L. M. Demers, D. C. Kuhn

It has been suggested that radicals on the surface of dust particles are key chemical factors in the pathophysiology that results from the occupational inhalation of coal and silica dust. In addition, oxygenated derivatives of arachidonic acid (eicosanoidsJ have been implicated as important biochemical mediator5 of mineral dust-induced lung disease through their role in bronchial and vascular smooth muscle reactivity, inflammation, and fibrosis. Therefore, we assessed eicosanoid production by the rat alveolar macrophage (AM) exposed in vitro to mineral dusts with varying surface chemical characteristics in order to determine if radicals associated with the mineral dust could influence the production of proinflammatory mediators in the lung environment. Primary cultures of rat AM were exposed to freshly fractured or "stale" bituminous coal dust, as well as untreated silica or silica calcined to 500 and 1100°C. Prostaglandin E1 (PGE;V, thromboxane Ai (T}(Ay, and leukotriene 84 (LTB; levels in incubation medium were determined by specific radioimmunoassay. When AM were exposed to freshly fractured coal dust, PGE2 production was markedly increased. In contrast, exposure of AM to "stale" dust significantly reduced PGE1 production. Exposure of AM to freshly fractured coal dust resulted in a significant increase in production by AM, while exposure to stale coal dust did not influence AM TXA1 production. Neither "fresh" nor "stale" coal dust had any effect on LTB4 production. In vitro exposure of AM to untreated silica resulted in a significant increase in TXA1 PGE.,, TXA; and LTB4 production compared with control. However, exposure of AM to silica calcined to 11oo•c resulted in eicosanoid levels that were not significantly different from control. These effects were still apparent 8 wk after calcination of the silica particles. Silica was a more potent activator of AM eicosanoid production than was coal, and amorphous fumed silica was a more potent activator of AM eicosanoid production than was crystalline silica. These findings suggest that radicals associated with respirable coal and silica particles may play a key role in the ability of mineral dust to activate AM eicosanoid production and therefore may be important in the pathophysiological consequences of occupational mineral dust inhalation.

Mar 1, 1992

By P. Wearden, K. Bryner, K. Vrana, V. Castranova, R. Dey, R. Reist, J. Blackford

"Summary: Fibroblast proliferation and enhancement of collagen synthesis are key steps in the development and progression of pulmonary fibrosis. The current investigation presents a fibroblast proliferation assay to detect the release of competence factors from pneumocytes. The specific objective of this study was to define cell culture conditions for fibroblasts that would allow selective detection of competence factors in test media. The results indicate the following: (a) fibroblasts should be cultured for 2 days in plasma-free medium rather than 2% plasma to assure complete quiescence; (b) 1% plasma was optimum for producing progression activity for the bioassay of a competence factor, while 0.5% plasma did not produce sufficient progression activity (yielding false negatives) and 2% plasma often contained significant competence activity (yielding false positives); and (c) fresh plasma should be used since the progression activity of plasma was adversely affected by freezing and thawing. Under these conditions, this bioassay can be employed with either rat or human lung fibroblasts to detect competence factors such as platelet-derived growth factor (PDGF), at levels as low as 25 ng/ml.Fibrotic lung disease, as a consequence of occupational exposure to silica dust. is characterized by the development of concentric hyalinized nodular lesions in the lung and the progressive loss of pulmonary diffusion capacity. Proliferation of pulmonary fibroblasts and enhanced synthesis of collagen by these pneumocytes have been shown to be key steps in the development of chronic silicosis ( 1 ). The regulation of lung fibroblast proliferation by cytokines released from alveolar macrophages may be an important pathogenetic mechanism in the development of the fibrotic process (2). Some cytokines stimulate fibroblast proliferation by activating specific phases of the cell cycle (3,4). In particular, platelet-derived growth factor (PDGF) promotes fibroblast proliferation by inducing the movement of quiescent (G0 ) cells into the G1 phase of the cell cycle (5). Insulin-like growth factor (IGF) and transforming growth factor-P (TGF-P). on the other hand, regulate the rate of transition of fibroblasts from G 1 into the S phase (5,6). These two classes of cytokines have been termed competence and progression factors, respectively. One approach used to examine the release of cytokines from macrophages is the fibroblast proliferation assay in which quiescent fibroblasts are exposed to culture supematants from macrophages exposed to various stimuli. In most of these assays, the supernatant contains fetal calf serum (FCS), which provides the competence factor(s) necessary to facilitate the proliferation of fibroblasts (7-9). Recently, a fibroblast proliferation assay using platelet-poor .plasma [lacking competence factor(s)] as a substitute for FCS bas been described (I 0, 11 ). In this assay, the release of a competence-inducing PDGF-like growth factor from rat and human macrophages can be distinguished from other cytokines that act as progression factors."

Mar 1, 1992

By N. S. Dalal, X. Shi

While it is known that vanadate and related compounds of pentavalent vanadium ( V (V)) exert potent toxic effects on a wide variety of biological systems, the underlying biochemical mechanism is still not fully understood ( 1- 3). One of the pathways is thought to involve the oxidation of NAD ( P) H. Thus, considerable effort has been devoted to finding the mechanism of NAD ( P) H oxidation by Vcvi (1-15). Erdmann et al. (5) first noted that vanadate stimulated the oxidation of NADH by plasma membranes and attributed this effect to a membrane containing NAD(P)H-dependent V(V) reductase. Later studies by Liochev and Fridovich indicated that endogenous superoxide ( 02 ) plays a central role in this reaction ( 4, 12, 13) . They proposed that NAD ( P) H dehydrogenases or oxidases produce 02, which causes VCV ) to stimulate NAD ( P) H oxidation via the following free radical chain mechanism ( 4, 12, 13) :

Mar 1, 1992