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By Yeonuk Choi, Gus Van Weert

cyanide control in effluents is becoming a critical environmental issue for the gold extraction industry. Silver impregnated carbon removes free cyanide effectively to the ppb level from solution in high throughput columns. By re-calcining the cyanide saturated carbon, the impregnated silver is restored to activity and the cyanide destroyed outside the effluent stream. Many gold mills already have an activation kiln on site, which could make retrofit relatively easy.

Jan 1, 1993

By Diane Schwegler-Berry, Vincent Castranova, Chang-geng Moe, Jane Y. C. Ma, Mark D. Moore, Joseph K. H. Ma, Carl J. Malanga, Ji-Hee Kane

"Effects of Bisbenzylisoquinoline Alkaloids on Alveolar Macrophages: Correlation between Binding Affinity. Inhibitory Potency and Antifibrotic Potential. CASTRANOVA, V., KANG, J-H., MA. J. K. H., Mo, C-H., MALANGA, L. J., MOORE M. D., SCHWEGLER-BERRY, D.. AND MA. J. Y. C. (1991). Toxicol. Appl. Pharmacol 108, 242-252. The Chinese have conducted extensive studies concerning the medicinal properties of plant products. In this investigation the ability of three bisbenzylisoquinoline alkaloids to inhibit particle-induced activation of alveolar macrophages was evaluated and this inhibitory potential was correlated with the ability of those drugs to bind to membrane components. Tetrandrine. i.e.. an herbal medicine used as an antifibrotic agent in China, was a potent inhibitor of particle-stimulated oxygen consumption, superoxide release, and hydrogen peroxide secretion by alveolar macrophages. Tetrandrine also exhibited substantial binding affinity for membrane lipids and alveolar macrophages. In contrast, tubocurine, an analogue with little antifibrotic potential, exhibited low binding affinity and had little effect on macrophage activation. Methoxyadiantifoline, an alkaloid of unknown antifibrotic potential, exhibited inhibitory and binding properties similar to those of tetrandrine. The data indicate that a strong relationship exists between the antifibrotic potential of these alkaloids and their ability to bind to alveolar macrophages and inhibit particle-induced activation of these phagocytes. These drugs should serve as useful probes to evaluate the role of alveolar macrophages in pulmonary fibrosis. © 1991 Academic Press, Inc.Chronic silicosis is a fibrotic disease resulting from occupational exposure to silica dust. It is manifested initially by an increase in the quantity of pulmonary surfactant (Dethloff et al., 1986). However, in later stages it is characterized by an increase in collagen formation and the development of concentric hyalinized nodular lesions in the lung (Ziskind et al., 1976). Although mechanisms for the progression of silicosis have not yet been completely defined, activation of alveolar macrophages by respirable silica particles is believed to play an important role in the etiology of this disease. Studies from our laboratory have shown that both in vitro and in vivo silica exposures result in a stimulation of macrophage release of reactive products capable of damaging the lung parenchyma (Castranova et al., 1990; Goodman et al., 1990). In addition, exposure of al¬veolar macrophages to silica results in the release of fibrogenic factors which enhance the proliferation of fibroblasts and the synthesis of collagen by these pneumocytes (Leibovich and Ross, 1976; Bitterman et al., 1982, 1983).The bisbenzylisoquinoline alkaloids, which represent the largest group among the iso-quinoline compounds isolated from the plant kingdom, are known to exhibit a broad rangeof pharmacological activities. Tetrandrine, for example, an alkaloid isolated from the root of Stephania tetrandra, has been tested for its antitumor, antihypertensive, and antisilicotic effects (Kupchan and Atland, 1973; Zeng et al., 1985; Yu et al., 1983). It is currently used in China as a treatment for angina, hypertension, and silica-induced pulmonary fibrosis (Li et al., 1981). Several related bisbenzylisoquinoline alkaloids such as methoxyadiantifoline and tubocurine have also been evaluated for medicinal effects. Methoxyadiantifoline has been shown to exhibit effects on the cardiovascular system similar to those reported for tetrandrine (Jia et al., 1988). However, to date, the antifibrotic activity of methoxyadiantifoline has not been evaluated. In contrast to tetrandrine, tubocurine, a structural analogue of this drug, has been reported to be relatively ineffective against fibrosis (Mo et al., 1982)."

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 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 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 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 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. 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

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 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 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 R. V. Ramani, R. Bhaskar

"An airborne dust cloud is an ensemble of particles of varied size, density, shape and states of aggregation. An understanding and quantifying of the dispersion and deposition of the dust generated in mines is essential to the development of measures for reducing worker exposure to dust. In coal mining, the major portion of the dust is generated during the cutting of coal using a shearer or a continuous miner.The major phenomenon affecting ambient concentration is the deposition of dust. Particle deposition may take place due to the effect of gravitational, inertial, electrostatic, and thermal forces, and mechanisms such as Brownian and eddy diffusion and inertial impaction, The three major mechanisms of deposition in turbulent flow in mines are diffusion (Brownian and eddy), sedimentation and inertial impaction. The mechanisms determining particle deposition are size depend,From a review of the literature, there appears to be a knowledge gap in the understanding of the deposition phenomena in mine airways. In order to obtain a better understanding of the deposition of dust for various particle sizes, and to develop a set of data for evaluating predictive mathematical models for dust-flow in mines, a series of dust flow experiments was performed under controlled conditions in mine airways. It appears that the deposition data generally follow the theoretical behavior of dust based on the combined effect of diffusional and gravitational deposition. In this paper, the findings of the study on the deposition of dust in mine airways and its dependence on size, velocity and concentration are discussed. A set of deposition equations that could be used to determine the approximate deposition at various points in a mine airway are presented.The major factor affecting ambient dust concentration in mine airways is the deposition of dust. Particle deposition may take place due to the effect of gravitational, inertial, electrostatic, and thermal forces, and mechanisms such as Brownian diffusion, eddy diffusion and inertial impaction. The major mechanisms of deposition in turbulent flow in mines are diffusion (Brownian and eddy), sedimentation and inertial impaction. Inertial impaction is significant only during changes in direction, but the change in direction of flow with resultant powerful eddies may cause increased re-entrainment of the particles, thus having a compensating effect. While the literature in aerosol sciences contain several references on deposition, most studies were done in small diameter tubes for diffusional deposition (Liu and Agarwal, 1974). The deposition data from small diameter, short tube experiments may not be applicable to studying deposition in mine airways that have large areas and extend several hundred meters. Further, the change in concentration along the length of a mine airway may significantly affect the deposition, an aspect that may not be easily determined in short tubes in laboratory experiments."

Mar 1, 1992

By Jr. Watts, B. K. Cantrell, D. H. Carlson, K. L. Rubow

"The use of diesel equipment in underground coal mines is controversial because ""whole diesel exhaust"" is regarded as ""a potential occupational carcinogen"" by the National Institute for Occupational Safety and Health (NIOSH). Threshold limit values (TLVs) are recommended for the gaseous pollutants; CO, CO2, NO, NO2, SO2, and some hydrocarbons emitted in diesel exhaust. There is, however, no TLV recommended for diesel exhaust aerosols (DEA) nor is there a standard method for sampling these aerosols.The University of Minnesota and the Bureau of Mines have collaborated to develop a personal diesel exhaust aerosol sampler (PDEAS) which utilizes size selective, inertial impaction and gravimetric analysis. During the field tests of this sampler, numerous air quality measurements were conducted in underground coal mines using diesel equipment. The objective of this report is to present these data and to assess the impact of diesel face haulage equipment on mine air quality.Air quality data were collected in four underground coal mines using continuous mining methods with diesel haulage equipment. Daily samples were collected at the section intake, haulageway, and on haulage vehicles. Both full-and partial-shift samples were collected using a variety of aerosol instruments, including the PDEAS and the micro-orifice, uniform deposit impactor (MOUDI) which sample the mine aerosol diesel exhaust fraction. Two of the mines were also monitored for the major gaseous constituents found in diesel exhaust CO, CO2, NO, NO2, and SO2. These measurements were made by either collecting bag samples for subsequent gas analysis or by Palmes dosimeters.The concentrations of CO, CO2, NO, NO2, and SO2, were well below regulated levels. The mine average DEA concentration determined by the PDEAS in the haulageway for the three mines surveyed using this instrument was 0.79 mg/m3, with a standard deviation of 0.19 mg/m3. DEA contributed 65% of the respirable aerosol, at this location. These results were the same as the mean DEA concentrations calculated from size distribution measurements obtained using the MOUDI. This was 0.78 mg/m3, with a standard deviation of 0.22 mg/m3."

Mar 1, 1992

By L. M. Chan, D. H. Carlson, J. H. Johnson

"This paper discusses the evaluation and application of a portable parked-vehicle tailpipe emissions measurement apparatus (EMA). The EMA consists of an exhaust dilution system and a portable instrument package. The EMA instantaneously dilutes and cools a sample of exhaust with compressed nitrogen or air at a known dilution ratio, thereby presenting it to instruments as it is presented to personnel in the surrounding environment. The operating principles and governing equations of the EMA are presented.A computational method is presented to determine the engine operating and performance parameters from the exhaust CO2 concentrations along with an assumed engine overall volumetric efficiency and brake specific fuel consumption. The parameters determined are fuel / air ratio, mass flow rates of fuel, air and exhaust emissions, and engine brake torque and horsepower. These calculated engine parameters are used to characterize engine load when performing EMA in-field tailpipe sampling without a dynamometer, and to detect deteriorated engines.Evaluations of the EMA by comparison of diesel tailpipe measurements with those made using laboratory-grade instruments showed that the EMA measurements are accurate and reproducible. The results also show that the EMA is capable of detecting emission concentration changes resulting from engine faults. Calculated engine operating and performance parameters correlate and compare well with laboratory-measured values.The EMA in-field engine loading and tailpipe sampling procedures for parked vehicles are presented, and results of the EMA field measurements are also presented. Low coefficients of variation for repeat EMA tailpipe measurements on diesel-powered haulage vehicles in four underground mines indicate that the EMA in-field engine loading and tailpipe sampling procedures are reproducible.An analysis of EMA tailpipe measurements for three haulage vehicles in one mine shows that the EMA can: 1) identify haulage vehicles that emit excessively high pollutant concentrations, and 2) provide data needed to evaluate and determine the efficiency and effectiveness of tailpipe emission control devices.Finally, recommendations for a proposed commercial EMA system are presented. This commercial system would overcome many of the adverse features of the prototype EMA used in these tests."

Mar 1, 1992

By Jr. Watts, J. L. Ambs, B. K. Cantrell, K. L. Rubow

"The University of Minnesota and the U.S. Bureau of Mines collaborated to develop and field test a personal diesel exhaust aerosol sampler (PDEAS). The PDEAS was field tested in five underground coal mines that use continuous miners and a variety of diesel vehicles, including diesel haulage and utility vehicles. One mine was surveyed a second time, with the haulage vehicles fitted with a low-temperature disposable diesel exhaust filter (DDEF). Aerosol samples were collected with a variety of instruments, including the PDEAS and the microorifice, uniform-deposit impactor (MOUDI). This paper presents the diesel exhaust aerosol (DEA) concentration data collected in these mines and assesses the impact of diesel face-haulage equipment, with and without exhaust filters, on underground mine air quality.The average DEA concentration at the haulageway location for five mines, determined by the PDEAS, was 0.89 mg/m3, with a standard deviation of 0.44 mg/m3 • DEA contributed 52 pct, of the respirable aerosol at the haulageway location. Use of the DDEF at one mine reduced DEA by 95 pct, with a standard deviation of 6 pct, and filter life averaged 10 h. DEA contributed a large proportion of the respirable aerosol concentrations in mines with diesel equipment, and a substantial reduction was achieved with use of a DDEF. INTRODUCTIONDiesel equipment is gaining popularity in underground coal mines. There are an estimated 1,951 units of diesel equipment in 152 underground coal mines compared with 1,100 units in 110 mines 5 years ago (J).5 This increased use is due to the recognition that diesel-powered vehicles are more versatile, which can contribute to increased productivity compared with their electrically powered counterparts. Approximately 33 pct of the diesel vehicles haul coal, 45 pct haul personnel and materials, and- 22 pct perform other duties, such as roof bolting, rock dusting, and road maintenance. Most mines using diesel equipment are located in Kentucky, Utah, Virginia, and Colorado."

Mar 1, 1992