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By R. L. Grayson

"Compliance standards for respirable dust, which are reduced because of high quart: concentrations, have become an industry-wide problem. Research on the physical and chemical character of quart-classified particles in respirable coal mine dusts indicates that they may exist in intermixed layers or may be coated by clay or coal material. The relative amount of intermixing varies with the coal seam being mined. If most of the quart: particles of a mine dust are ""pure,"" then the dust may have a high fibrogenic risk potential because of truly free silica and the compliance standard should be lowered. lf, however, quart: is locked inside another material matrix, or coated, a reduced compliance standard may not be appropriate.Although much research has been done on coal workers' pneumoconiosis (CWP) over the past decades, the etiologic agents of the disease still have not been pinpointed. The predominant methods of characterizing respirable coal mine dusts were bulk analysis techniques for determination of elemental and mineralogical concentrations, the results of which were used in statistical analyses to determine relationships between dust composition and the occurrence of CWP. These methods are incapable of finding the etiologic agents in the dust primarily because of complicated and confounding physiochemical factors, which may be discovered if the focus of characterization was done on a dust particle level.The SEM/EDXA-based research discussed here shows a significant difference in the number of ""pure"" quartz particles in respirable dusts collected from different mines. Some of the results have been reported previously (Grayson, Andre, and Simonyi, 1988). Concurrent research by other investigators (Wallace et al., 1989) demonstrates an SEM/EDXA-based methodology to pinpoint the location of the ""contaminating"" substance(s ) in a quartz-classified particle. The research of the European Economic Community has also begun analyses on the respirable-dust-particle level (Robock and Bauer, 1988).Since the compensatory and intangible costs of CWP are substantial in the United States, it is important that the etiologic agents be determined and then either controlled or neutralized in a cost-effective way. This line of research is especially important consid-ering the forecasted. near-term growth of coal production and the evolution of high productivity longwall panels (an immediate problem in compliance) and continuous mining sections ( a probable future problem).This need has been accentuated now that nearly all respirable dust samples submitted to MSHA are analyzed for free silica (Tomb, Parobeck, and Gem, 1986). Today a real problem exists in the coal industry, both underground and surface, because of high quartz levels in respirable dusts causing substantially reduced compliance standards (Murphy, 1989).The combined results of the respirable dust particle investigators indicate that conventional bulk sample analyses may not faithfully represent the amount of biologically available or active quartz in all mines with a high level (greater than 5% ) of quartz in the dust For example, some mine dusts might contain predominantly occluded (or coated) quartz particles where bulk analysis would result in anomalously high ""free silica"" measurements. The same result would occur when quartz particles are intermixed substantially with other minerals that can alter the surface of the composite particle away from a quartz-behaving character."

Mar 1, 1992

By Vincent Castranova, Jane Y. C. Ma, Joseph K. H. Ma, Chang-geng Mo, Carl J. Malanga

"A group of bisbenzylisoouinoline alkaloids has been shown to exhibit various degrees of effectiveness in preventing silica-induced fibrosis in animal models [1, 2]. The objective the present study was to characterize the binding of several of these alkaloids to phosphatidylcholine vesicles and rat alveolar macrophages using fluorometric and equilibrium dialysis methods, respectively. The lipid binding affinity of these alkaloids was found to depend upon several structural factors including hydrophobic substitutions, chiral configurations, and double oxygen bridge-restricted conformation of the benzylisoquinoline moieties. Tetrandrine, which is a highly effective agent in preventing fibrosis, showed strong binding to both lipid vesicles and alveolar macrophages. In contrast, certain analogues of tetrandrine such as curine and tubocurine, which have little or no effect on silicosis, exhibited only weak binding to lipid vesicles and almost no binding to cells. The moderate binding affinity of fangchinoline to vesicles and cells corresponded to a moderate effectiveness of the compound as an antifibrogenic agent. Methoxyadiantifoline, an alkaloid of unknown antifibrogenic potential, also exhibited high binding affinities for lipid and cells. In conclusion, the results of these studies indicate that alveolar macrophages exhibit large binding capacities for certain members of this class of bisbenzylisoquinoline alkaloids. A positive correlation was observed between binding affinity to alveolar macrophages and the reported antifibrotic potency of these compounds. These data also suggest that the ability of these drugs to interact with alveolar macrophages may be a key step in inhibition of the progression of silica-induced pulmonary disease.INTRODUCTIONInhalation of crystalline silica is associated with the development of silicosis. This fibrotic disease is characterized by the appearance of concentric hyalinized nodular lesions in the lungs with the progressive development of pulmonary dysfunction [3, 4]. Many theories concerning the etiology of silicosis involve silica-induced activation of alveolar macrophages. Evidence indicates that in vitro silica exposures result in the generation of chemiluminescence, and the release of superoxide and hydrogen peroxide from alveolar macrophages [5]. Activation of alveolar macrophages has also been demonstrated after intratracheal instillation or inhalation of silica [5, 6]. Such excess release of reactive products from pulmonary phagocytes has been associated with damage to the lung parenchyma [7, 8]. In addition, silica exposure results in the release of mediators from alveolar macrophages, which enhance proliferation of fibroblasts and collagen synthesis by these pneumocytes [9-12]."

Mar 1, 1992

By B. K. Cantrell, K. L. Rubow

"Quantifying exposure to diesel exhaust aerosol in an underground coal mine depends on the ability to measure this component of respirable mine aerosol separately from coal dust. Such measurement is complicated by the carbonaceous nature of both the diesel and coal dust particulate that make up the respirable aerosol. Hence, special sampling and analytical techniques must be used to distinguish between these two aerosol components.As part of a continuing study of diesel exhaust aerosol characteristics, the U.S. Bureau of Mines has applied size selective sampling together with gravimetric analysis to separate and measure respirable diesel exhaust and coal dust aerosol concentrations in diesel-equipped underground coal mines. This technique is based on the premise that the diesel portion of the aerosol is predominantly submicrometer and the mineral dust portion is mostly greater than 1 µm in size. In the study, chemical mass balance (CMB) modeling, based on the distribution of chemical elements in aerosol and aerosol source material samples, is used to referee the analysis of diesel exhaust and mineral dust aerosol concentrations from the size selective sampling results.Based on the results of the study, the Bureau, in cooperation with the University of Minnesota and the U.S. Mine Safety and Health Administration (MSHA), have developed a prototype personal diesel exhaust aerosol sampler for underground coal mines. The sampler has three stages: a preclassifier stage to select for respirable aerosol, an inertial impaction stage with an aerodynamic diameter(d) size cut at 0.8 µm to separate diesel aerosol from mineral dust and collect the mineral dust, and a final filtration stage to collect the diesel fraction of the sample. The sampler has been evaluated in both laboratory and field experiments conducted by the Bureau, MSHA, and the Generic Minerals Technology Center for Respirable Dust (GMTC-RD)."

Mar 1, 1992

By J. M. Mutmansky, L. Xu

"IntroductionSince the establishment of the star,just concentration of 2 mg/m3, a strong effort has made by mining engineers and researchers to provide better dust control equipment and procedures for underground coal mines.Particular areas of success have been implementation of better coal-cutting strategy to control dust generation, better design of water sprays for dust suppression and air movement, use of scrubbers, and improved design of face ventilation systems. A drastic improvement occurred over time such that the average dust concentrations for continuous miner operators dropped from 6.5 mg/m3 in 1968 to 1.3 mg/m3 in 1980 and for auger, cutter, longwall, and roof bolter occupations from 2.7 mg/m3 in 1973 to 1.6 mg/m3 in 1980 (Niewiadomski, 1983).While dust concentrations in mining sections have been dropping considerably, one problem area has been mining sections where quartz is a considerable portion of the airborne dust. The federal regulations require that quartz content must be held below 0.1 mg/m3 in the air regardless of the concentration of the total dust. This legislation limits the allowable dust concentration to a ""reduced standard"" of 10/ (% quartz) when the quartz content of respirable dust in the mine atmosphere is more than 5%. Today, approximately one-third of underground coal mining operations have designated areas with more stringent dust standards in place, and many mines experience considerable difficulty in meeting these standards (Jankowski, and Babbitt, 1989).It is well known that metal miners subjected to respirable dusts high in quartz have a higher incidence of silicosis than those exposed to dust low in quartz. However, the role of quartz in the development of coal workers' pneumoconiosis is still a highly controversial question, in spite of the large number of research projects devoted to this subject over the last 20 years. Because coal seams contain less quartz than metal ores and quartz often comes from sources outside the coal seam (e.g., roof and floor), it is difficult to relate studies that deal with the quartz content in coal seams and the incidence of coal workers' pneumoconiosis. Hamilton, Ogden, and Vincent (1983) have provided a plausible explanation for the incidence of the disease by hypothesizing that the quartz content does not affect the probability of developing pneumoconiosis until some threshold value (generally thought to be about 10%) is exceeded.The objective of the research studies summarized here was to obtain a better understanding of quartz occurrences in airborne coal mine dust by studying the variations of the quartz levels in different dust sizes and the relationship between the quartz content in airborne coal mine dust and the quartz content in the mined material. The implications of the results to control of dust in high-quartz sections will also be discussed."

Mar 1, 1992

By Raja V. Ramani, Sachin Shankar

"Re-entrainment refers to dislodgement of particles deposited by both atmospheric and nonatmospheric processes and their subsequent insertion into a flowing field. Formation of sand dunes, snow drifts, soil erosion and fugitive dust emissions are a few examples of the natural occurrence of re-entrainment. Re-entrainment studies have been done for the estimation of potential hazards from nuclear fallouts. The phenomenon of re-entrainment has been utilized for the cleaning of wafers and filters. Re-entrainment is associated with both surface and underground mining activities. However, studies on dust re-entrainment in mine atmospheres are limited. Understanding the re-entrainment phenomenon is important because dust particles lying seemingly harmless on the ground and adhering to numerous surfaces can get re-entrained and become a health and safety hazard.There are significant differences in the kind of re-entrainment encountered in underground mines and those in other fields of interest. These major differences are air velocity, direction of air flow, particle size, amount of particles, and time of exposure. While numerous studies have been done in other fields to identify the role of interacting variables and their contribution to the mechanisms of re-entrainment, no similar reported work is available for dust in mine atmospheres.In this paper, recent research efforts on re-entrainment are reviewed. The most suitable form of representing re-entrainment in underground coal mine atmosphere is presented. Various approaches to studying re-entrainment phenomenon in mines are also outlined.In the mineral industries, formation of dust particles of widely varying sizes is a natural outcome of the fragmentation required in mining the solid resources. Fine particles in mine atmospheres, particularly in the respirable size range, are a threat to the health and safety of the miners when present in high concentrations. In 1980 the National Academy of Sciences (NAS) Committee on the Measurement and Control of Respirable Dust in Mines recommended that the spatial and temporal characteristics (of fragments produced in coal mining) need to be understood so that the exposure of workers to the dust can be controlled. Recently several studies have been performed to understand the fundamental behavior of the airborne respirable dust in mine airways (Bhaskar, 1987; Qin, 1988; Polat, 1989; Bode, 1990)."

Mar 1, 1992

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

"It has been known for some time that sizes of aqueous particles may be affected by flow-induced relative humidity (RH) changes. The RH of air flowing through an impactor decreases as a result of pressure drop through the impactor and increases because of aerodynamic cooling within the high-speed jets, as illustrated in Figure 1. Because the sizes of aqueous particles depend on RH, the impaction stage on which such particles are collected may be different from the stage where they ought to be col¬lected, based on the particle size at the sampler inlet.Fuchs (1980) reviewed literature on water vapor condensation in impactors. The reviewed impactors operated at jet velocities of 100-250 m/s. Particle size increases ow¬ing to water vapor condensation were found in all cases. In one case (Khorguani et al., 1970), it was found that very small droplets (Dp <_ 0.02 um) containing sodium chloride and silver iodide were collected in an impactor with a cut point of 0.32 µm and a jet velocity of 100 m/s. Fuchs believed that such particles could not be captured in an impactor without having been enlarged by condensation. Winkler (1974) sampled at¬mospheric dust with a rectangular nozzle impactor that had a nozzle cross section of 0.3 x 15 mm, a cut size of 0.4 um, and an average jet velocity of 100 m/s. No adhesive was used on the impaction plate. The collection efficiency increased as air humidity was increased from 20% to 100%. The effect was especially noticeable in the increased collection efficiency for hygroscopic particles, and was attributed to condensation.Extensive theoretical and experimental research work on the distortion of the particle size distributions in impactors was done by Biswas and coworkers (1985, 1987). The impactors employed in the study were a low-pressure impactor with high jet velocity stages (Hering et al., 1978, 1979) and a conventional six-stage impactor, Sierra's model 226, operated in the incompressible regime. Ammonium sulfate aerosols were chosen for the study. In the low-pressure impactor, an orifice operating at a Mach number of 1 causes a sudden pressure drop, significantly reducing the RH in the next two stages (stages 5 and 6). This results in a 0.15-um diameter ammonium sulfate droplet shrinking to about 0.07 um at stage 5 when the inlet RH is 95%. In stage 7, the tempera¬ture drop is considerable because the jet speed is sonic. For an inlet RH of 95%, a 0.03 um droplet grows to about 0.06 um. However, the same size droplet at an inlet RH of 25% grows to only 0.04 um. For the Sierra model 226 cascade impactor that is operated with a Mach number of 0.27 at the last stage (stage VI), it was found that for an inlet RH of about 67%, particle growth would occur in stage VI. At 80% RH, both stages V and VI were affected. Biswas et al. (1987) stated that Mach number alone does not determine the size biasing; the type of aerosol, the inlet conditions, the temperature and pressure ratio, and the impactor geometry (throat length, jet-to-plate distance, etc.) must be considered for each stage in evaluating the distortion of the particle size distribution."

Mar 1, 1992

"The following articles were produced through funding under Generic Mineral Technology Center for Respirable Dust research. Full articles appear in the proceedings, 3rd Symposium in the Mineral Industries, published in 1991 by the Society for Mining, Metallurgy and Exploration, Inc.Personal Diesel Exhaust Aerosol SamplerV.A. Marple, K.L. Rubow, and Y. TaoParticle Technology, Mechanical Engineering Department, University of Minnesota, Minneapolis, Minnesota(Section ill. Diesel I: Diesel Particulate Measurement, pp. 73-81)Abstract. Techniques are being developed for measuring the mass concentration of respirable diesel exhaust particles found in underground coal mines. Studies have been conducted over the past five years to investigate size selective 18Dlpling techniques to measure the respirable mass concentrations of diesel exhaust and mine dust aerosol particles in underground coal mines. Results from these studies have been used to develop design and performance criteria for a personal diesel exhaust aerosol sampler.Three personal diesel exhaust aerosol samplers have subsequently been designed and evaluated in both laboratory and field settings. These samplers use size selective classifiers for the determination of respirable mass concentrations of mineral dust and diesel exhaust particles. Their designs are based on the premise that diesel exhaust particles are predominantly less than 0.8 µm while mineral dust is greater than 0.8 µm.One design, selected for field evaluation, consists of a 10 mm nylon respirable dust cyclone followed by a 0.8 µm cutpoint impactor and afterfilter. The cyclone removes the nonrespirable particles while the inertial impactor state, collects the mineral dust on an impaction plate and allows the diesel particles to penetrate to an afterfilter. The two sample fractions of the respirable particles ( <0.8 µ.m and >0.8 µm) are gravimetrically analyzed to determine the concentrations of the diesel and mineral dust portions in the respirable coal mine aerosol."

Mar 1, 1992

By N. S. Dalal, J. F. Mega, X. Shi, V. Vallyathan

Several studies have suggested that pulmonary toxicity to asbestos and silica may be mediated through oxidant-induced cell injury. We have reported recently that surface radicals associated with freshly fractured silica may be an imponant factor in cell injury and induction of pulmonary disease. Although the generation of oxygenated radicals in dust-cell interactions has been demonstrated, there are no data correlating the toxicity of a dust with the level of oxygen radical generation by the dust during its interaction with phagocytic cells. In the present study, we have investigated the in vitro generation of oxygen free radicals from human neutrophils and rat alveolar macrophages stimulated with freshly fractured silica, aged silica, amosite, crocidolite, chrysotilc, and a nontoxic dust, barite. Electron spin resonance (ESR) with the aid of a spin trap phenyl-N-ten-butyl nitronc (PBN) was used to measure the oxygen radicals generated during phagocytosis of the dusts. The relative toxicity index and ESR peak heights, on an equal surface area basis and normalized to barite as one, showed a direct relationship. The normalized toxicity indices and peak heights were: silica, 3.5 versus 2; chrysotile, 4 versus 2; crocidolite, 11 versus 8; and amosite, 26 versus 13. Addition of hydroxyl radical scavengers such as catalase, dimethyl sulfoxide, 1,3 dimethyl-2-thiourea (DMTU), sodium benzoate, and mannitol prevented the radical generation. Carmustine, a glutathione reductase- glutathione peroxidase inhibitor, caused a 5-fold increase in the radical generation. These results indicate that a nontoxic dust such as barite generates toxic oxygen radicals at a minimal level that can be quenched by the normal cellular defense system. For toxic dusts such as silica, amositc, chrysotile, and crocidolite, the potential for oxygen radical generation is enhanced by their surface propenies, physical dimensions, and the surface-based radical-generating redox sites. The enhanced radical generation may impair the cellular defense system, resulting in cell injury. Use of scavengers, chelators, and potentiating agents suggests the membrane-based oxidase system as the probable primary source of the radical-generating system. The data presented herein suggest the generation of oxygen free radicals as an important primary event in silica- as well as asbestos-induced cell injury.

Mar 1, 1992

By M. W. Barger, J. K. H. Ma, J. Y. C. Ma, V. Castronova

The objective of this study was to investigate the effects of various bisbenzylisoquinoline (BBIQ) alkaloids on respiratory burst activity of alveolar macrophages and to characterize the interaction of these drugs with alveolar phagocytes. BBIQ alkaloids were chosen for study because they exhibit a wide range of antifibrotic potencies in a rat model, with tetrandrine being very effective and tubocurarine being ineffective. These drugs inhibited zymosan-stimulated oxygen consumption with a potency sequence of tetrandrine (IT) = fangchinoline (FA) > berbamine (BE) ., cepharanthine (CE) "" cycleanine (CY} ~ tubocurarine (TU). This inhibition of respiratory burst activity could not be attributed to a drug-induced decline in the ATP content of these pneumocytes. Drug binding to alveolar macrophages was directly dependent on temperature and drug concentration. The sequence for binding capacity was FA > TT = BE = CY > CE ~ TU. Therefore, there was no simple relationship between binding capacity and inhibitory potency. Binding capacity was not related to lipophilicity of these alkaloids. In addition, tetrandrine failed to bind to metabolically dead cells or sonicated macrophage preparations. These data suggest that the interaction of BBIQ alkaloids with phagocytes is not simply nonspecific binding to membrane lipids. Alteration of the cytoskeletal system with vinblastine, taxol, or cytochalasin B decreased tetrandrine binding by approximately 33% when adtkd separately and by 93% when added jointly. Pre-exposure of alveolar macrophages to stimulants increased the ability of BBIQ alkaloids to inhibit both oxygen consumption and superoxide release. These data suggest that the mechanism by which BBIQ alkaloids inhibit activation of phagocytes involves microtubules and bules and microfilaments. Pre-exposure of macrophages to stimulants would change the conformation of cytoskeletal components and may make these structures more susceptible to drug interaction.

Mar 1, 1992

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 V. A. Marple, K. L. Rubow, Y. Tao

"A personal diesel exhaust aerosol sampler has been designed and evaluated in both laboratory and field settings. The sampler uses size selective sampling for the determination of the respirable mass concentrations of mineral dust and diesel exhaust particulate matter found in underground coal mines. This design is based on the premise that diesel exhaust particulate matter is predominantly less than 0.8 um while mineral dust is greater than 0.8 gm. Operating at a flow rate of 2 L/min, the sampler consists of a 10 mm Dorr-Oliver respirable dust cyclone followed by an 0.8 gm cutpoint impactor and an afterfilter. Field evaluations consisted of sampling at 6 different locations in these underground coal mines. Measured aerosol concentration less than and greater than 0.8 um have been compared with a well characterized cascade impactor.Techniques must be developed for measuring the mass concentration of diesel exhaust particulate matter found in underground coal mines due to the health concerns associated with worker exposure to diesel exhaust particulate matter. Diesel exhaust particles are in the respirable size range and have been regarded as a potential occupational carcinogen by NIOSH (1988). Furthermore, a 1988 MSHA advisory committee directed MSHA to develop a sampling protocol for assessing worker exposure to diesel exhaust particles.The University of Minnesota and the Bureau of Mines, over the past 4 years have measured the size distribution of diesel exhaust particles and mineral dust, both in the laboratory and underground mines (Cantrell, 1987; Cantrell et al., 1987; Cantrell and Rubow. 1988; Marple et al, 1986; Rubow et al., 1988: and Watts et al., 1989). To date, measurements have been made in nine coal mines. Seven mines utilized diesel-powered equipment at the mine face while two used electric-powered equipment. The results of these field tests indicate that mineral dust and diesel exhaust particles can be differentiated on the basis of particle size. The measured particle size distributions have been found to be bimodal with a saddle point at 0.8 um. This has led to the hypothesis that one method for measuring worker exposure to diesel exhaust particles would be to collect size fractionated particle samples separated at 0.8 um with the diesel particles being less than 0.8 um and the mineral dust particles greater than 0.8 um.Aerosol size distribution measurements, using a micro-orifice uniform deposit impactor (MOUDI), have been conducted in the mine intake air portal, intake entry to the working section, haulageway, and section return entry. The MOUDI is a ten stage cascade impactor with particle cutpoints ranging from 0.1 to 15 um aerodynamic diameter (Marple and Rubow. 1984b; Marple et al., 1989). The sampling flow rate is 30 L/min."

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 B. K. Cantrell, K. L. Rubow

"The US Bureau of Mines and the University of Minnesota have developed design and performance criteria for a personal diesel exhaust aerosol sampler for underground coal mines. These are based on the premise that size can be used to separate diesel exhaust aerosol, which is mostly submicron in size, from coal dust aerosol, which is mostly greater than a micron in size. The sampler has three stages: a respirable aerosol preclassifier, a 0.8-um aerodynamic diameter inertial impactor to collect mineral dust and a final filter to collect the diesel aerosol. Using a sample flow rate of 2 L/min and gravimetric analysis to within 0.1 mg, the measure sub-0.8 um diesel aerosol has an a-priori limit of detection of 0.3 mg/m3.A miner working in an underground coal mine with diesel equipment is exposed to a wide array of pollutants from the diesel exhaust. These include CO, CO2. NO, NO2, SO2, diesel exhaust aerosol, and a variety of hydrocarbon compounds. A quantitative definition of the health risk resulting from these exposures remains elusive. During the past several years, though, progress has been made in defining the problem.Results from epidemiological studies by Garshick et al. (1988 ), animal inhalation studies by Mauderly eta). (1986), Iwai et al. (1986), and Brightwell et al. (1986) and in vitro studies by Lewtas et al. (1986) have provided sufficient data for the National Institute of Occupational Safety and Health (NOSH) to recommend that ""whole diesel exhaust be regarded as a 'potential occupational carcinogen,' as defined in the Cancer Policy of the Occupational Safety and Health Administration"" (NIOSH, 1988). NIOSH further stated that ""though the excess risk of cancer in diesel-exhaust-exposed workers has not been quantitatively estimated, it is logical to assume that reduction in exposure to diesel exhaust in the workplace would reduce the excess risk.""The Mine Safety and Health Administration (MSHA) has also been directed by an advisory committee to establish a diesel exhaust aerosol standard and to establish regulations to minimize exposure to diesel pollutants in underground coal mines (MSHA,1988). Both reports point out the need for development of measurement techniques for respirable diesel aerosol.In the past four years, the US Bureau of Mines (Cantrell,1987 and Cantrell, et al. 1987), in cooperation with Marple, et al. (1986), at the University of Minnesota's Particle TechnologyLaboratory (PTL), have studied the use of size-selective sampling techniques to measure the mass concentration of diesel aerosol in underground coal mines. Results from these studies have been used to develop design and performance criteria for a personal diesel exhaust aerosol sampler for use in underground coal mines.These criteria are based on the premise that size-selectivesampling techniques,can be used to separate diesel exhaust aerosol, which is predominantly submicron in size, from coal dust aerosol, which is mostly greater than a micron in size. In addition to the performance criteria, this paper discusses the laboratory and field test data used to develop the criteria."

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 D. H. Carlson, J. H. Johnson

"The U.S. Bureau of Mines and Michigan Technological University (MTU) are collaborating to develop an apparatus for measuring diesel tailpipe emissions in underground mines. A tailpipe emissions measurement apparatus (EMA) is described that dilutes diesel exhaust and measures the concentrations of diesel particulate matter (DPM), CO, CO2, NO, and NO2 at known dilution ratios.The EMA was evaluated by side-by-side comparison of its measurements with those by laboratory grade instruments. Concentrations of CO and C02 measured by the EMA were usually within ± 14 pct of concentrations measured by laboratory-grade instruments for CO and ±20 pct for C02• EMA measured DPM concentrations were, on average, 29 pct lower than those measured by laboratory-grade instruments, with the differences being fairly consistent. The CO and C02 differences are related to the method of calculating the EMA's dilution ratio, and the difference in DPM concentrations is attributed to thermophoretic and/or condensation losses related to the EMA's unheated sample probe. Preliminary analysis of data obtained with a heated sampling probe and modifications in the sampling procedures have indicated reduced variability in DPM and in the calculated dilution ratios."

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