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By R. P. Vinson

Assessment of workplace exposures is an important tool for helping to minimize dust-related occupational illness and diseases. Real-time particulate monitoring can effectively locate areas where dust controls are needed and determine how well they are working. An affordable, person-wearable, real-time dust monitor is needed. The SKC Inc. Dust Detective (SKCDD) fulfills those requirements (Disclaimer: Mention of any company or product does not imply endorsement by NIOSH). The SKCDD consists of a disposable sampling tube (DST) connected to a small hand-held sampling pump. The SKCDD was developed through a Cooperative Research and Development Agreement (CRADA) between the National Institute of Occupational Safety and Health (NIOSH) and SKC Inc. The relationship of dust concentrations measured by personal gravimetric samplers to those measured by the SKCDD was determined in a laboratory aerosol chamber. A comparison of the means and the relative standard deviation of triplicate measurements of each type of sampling device demonstrated the SKCDD to be a viable alternative means for measuring dust. While it provides accurate measurements for specific coal types, it requires correction factors (those correction factors still need to be calculated) for other coal types.

By Stephen C. Tadolini, Thomas M. Barczak, Peter (Yunqing) Zhang

A cooperative study was conducted with Emerald Coal Resources, L.P., an affiliate of Foundation Coal Corporation, and the National Institute for Occupational Safety and Health (NIOSH) to evaluate the effectiveness of (partially) pre-driven longwall recovery rooms supported with pumpable roof supports. This paper evaluates the load transfer mechanics associated with the advancement of the longwall face into the pre-driven recovery room and the widening of the room to recover the longwall shields. The results show that the yielding of the panel fender produced uncontrollable convergence that caused yielding of the shields and stiff pumpable roof supports when the face was approximately 10 ft from the recovery room. The shields continued to yield until the face advanced into the recovery room. Convergence in the pre-driven recovery room typically reached 6-8 in once the pumpable supports yielded and shed load through a declining residual load capacity prior to being cut out by the longwall shearer. Roof deformations occurred beyond the 32-ft horizon with total deformation ranging from 2 to 4 in, indicating that standing support was necessary to help control the span as the longwall face advanced into the pre-driven recovery room. Stability improved as the pumpable supports were cut out, thereby reducing the span between the shields and the outby pillars. In the end, the shields were successfully recovered under stable ground conditions. However, a disconcerting discovery was the load shedding of the outby pillars as the recovery room was mined into. It is postulated that this may be due to the progression of the rear “abutment” moving toward the recovery room as the panel fender and standing support in the recovery room yield and shed load. This behavior was not expected with a relatively narrow room that is fully supported with standing support. If this mechanism is indeed occurring, the width of the room and performance of the standing support becomes even more critical. Premature failure of the support can lead to excessive convergence on the shield line that cannot be controlled even with modern shields, resulting in roof instabilities that can lead to catastrophic results.

By K. L. Cashdollar

A project to evaluate the South African bagged stone dust explosion barrier was successfully completed at the National Institute for Occupational Safety and Health (MOSH), Pittsburgh Research Laboratory's (PRL), Lake Lynn Experimental Mine (LLEM) during the period November 1999 through May 2000. The tests were conducted in a three- entry section of the LLEM. Two types of explosions were used to evaluate the distributed and concentrated bagged barrier performance in a multi-entry mine section. The fuel zone of the first explosion type was only in the center B-drift. In the second explosion type, coal and stone dust mixtures were place in all three drifts. A total of six explosions, including two baseline and four barrier evaluation explosions, were conducted. Of the four barrier explosions, the distributed and concentrated barriers were each evaluated against the two explosion types. For these explosion tests, the distributed barrier extended from about 74 to 170 m and the concentrated barrier from about 74 to 104 m in B-drift. The distributed barrier successfully stopped flame propagation in both types of explosion tests. The flame extended further for the explosion tests where the dust was loaded in all three entries compared with dust loaded only in the center entry% but in both cases the flame was stopped within the barrier zone. The concentrated barrier was also successful in stopping flame propagation m both explosion tests. From the full-scale experimental mine test results, it can be concluded that both bagged barrier designs were effective in stopping coal dust explosions in the multiple entries of the LLEM.

By Howard C. Turnage, Dana T. Updyke

An evaluation was made of one of several improved underground communication systems sponsored by the U.S. Bureau of Mines. The system evaluated was installed in a typical metal/non-metal room and pillar mine and utilized UHF repeaters connected to a unique distributed antenna and passive reflector system which provided mine-wide communications. A microprocessor controlled data collection system was assembled and installed for the evaluation. Data consisting principally of times and durations of messages and identities of the originating transceivers was collected between February and August of 1982 (6 mos.). Analysis of the data shows that the principal benefits are reduction in time required for unscheduled maintenance and repair, enhancement of safety, and better coordination of production activities. A cost benefit analysis shows a net benefit over cost, although it is also concluded that the capacity of the system is greater than can be justified by current activity in the mine.

Jan 2, 1983

By Michael S. Contratto, Dave Marshall, Tom Brodersen

The European Union (EU) completed a new directive 2002/44/EC1 called the Physical Agents Directive (PAD) that establishes action and limit values for hand-arm and whole body vibrations. The directive specifies that: “…workers shall not be exposed above the exposure ‘limit value’.” 1 and “…once the exposure action values … are exceeded, the employer shall establish and implement a programme of technical and/or organisational measures intended to reduce to a minimum exposure to mechanical vibration and the attendant risks…” 1 The PAD limit value is effective for new machines starting July 6, 2007 and for used machines by at least July 6, 2010. These requirements apply to the users of machines, but machine manufacturers will be challenged to provide machines and information to help the users comply with the directive. Caterpillar manufactures machines with the goal of enabling our customers to comply with all regulations dealing with health and safety. Caterpillar designs all of our machines to provide a safe, comfortable and productive work environment. This study was to determine if seat suspensions could provide a reduction in the vibration environment experienced by operators of Caterpillar mid sized (<50,000KG) Track Type Tractors Methods Seat manufacturers were asked to provide seat suspensions that provide improved isolation over and above current seat suspension. Each supplier was provided with ride profiles and was asked to demonstrate the vibration reduction on a shaker table. Two suppliers provided suspensions that were compared with the current seat suspension in a field study. Three full factorial experiments were conducted. The first experiment was to evaluate overall suspension performance for four operations. The second experiment was to determine the benefit of the adjustable vertical damper at three different levels and the third experiment was to determine the effect of the fore/aft and side/side isolators. Six operators were used for the study. Acceleration was measured at the seat base and at the operator seat pad. Both the transfer function and the ISO 2631 RMS ride values were used to determine the seat suspension’s effectiveness of isolating the operator from vibration. A structured questionnaire was used to determine the operators’ subjective assessment of the seat suspensions. Results There was significant operator-to-operator variability in the vertical direction (>35%), however there was little variability in the fore/aft and side/side direction based on seat base

Jan 6, 2006

By Dennis R. Dolinar, Gabriel S. Esterhuizen

In this National Institute for Occupational Safety and Health (NIOSH) investigation, numerical modeling is used to evaluate the degree the pillar strength is increased with a rectangular pillar over a square pillar. Three-dimensional models are developed with pillar sizes and geometries typical of underground limestone mines in the United States. Physical properties for the models are based on geotechnical surveys of nearly 30 underground limestone mines. To examine the effects of pillar length on pillar strength with the modeling, a parametric study was conducted where the pillar width was held constant while the length and height were varied resulting in width-to-height ratios ranging from 0.5 to 1.5 and width to length ratios ranging from 1 to 6. There are two aspects to pillar strength and failure. At relatively low stresses, pillars can fail as a result of geologic structure. At greater depths and sufficient extraction ratios, the pillars can also fail as a result of the vertical stresses exceeding the pillar strength. The effects of increasing pillar length regarding both strength aspects are presented in this study. Equations were developed for the increase in pillar strength with both height and length based on the model results. The results from these equations were compared to those from previously developed empirical equations for rectangular pillars. For the more slender limestone pillars with a width-to-height ratio below one, there is little increase in pillar strength for length-to-width ratios above 2 and almost no increase with length for a width-to-height ratio of 0.5. Only with the more squat pillars is there a significant improvement in strength with length. The gain in pillar strength with length for the pillars is explained by the change in the ratio of the area of the pillar affected by the ends to the area of the pillar. For the squattest pillar, the change in strength is also affected by an increase in pillar confinement along the central length of the pillar as the pillar transitions from a square to a long rectangular pillar. With geologic structure, added pillar length can significantly improve the pillar strength, depending on the strike of that structure with respect to the long pillar axis.

By Thomas M. Barczak, Dennis R. Dolinar, Gabriel S. Esterhuizen

Longwall mines typically use some form of standing support for secondary roof support in longwall tailgate entries. Although there have been several new support products developed for this application, there remains no universal design criteria to optimize the application of these support technologies. The requirement for optimization and proper support selection is to understand the degree of control that the support has on the ground behavior. The ground reaction curve and numerical modeling was used to evaluate the impact of standing support on ground behavior. LaModel was used to evaluate the impact of standing support on main roof and floor behavior and pillar yielding. The conclusion drawn from this study was that standing supports do not have sufficient capacity to control main roof or floor loading or prevent the resulting convergence of the tailgate entry. However, it is imperative that this “uncontrollable convergence” be considered in the support design to prevent premature failure of the support. A FLAC model was used to evaluate the near-seam roof and floor behavior in conjunction with the global vertical and horizontal stresses. The model suggests that standing roof supports can have some impact on the ground behavior as the elastic response of the rock is exceeded and rock structure deteriorates from the stress concentrations that develop around the tailgate opening. During this phase, the capacity and stiffness of the standing support can be critical to the stability of the opening, as eventually the rock mass will be transformed into a partially detached structure whose weight must be supported by the standing support. This work is part of a ground control program of research at the National Institute for Occupational Safety and Health (NIOSH) aimed at improving mine safety by reducing roof fall injuries and fatalities.

This study presents a reservoir modeling approach to investigate the relative effects of different coalbed parameters on the migration of methane into development entries. A base coalbed reservoir model of a three-entry development section, where grids were dynamically controlled to simulate the advance of mining at a constant section advance rate, was created and calibrated for a Pittsburgh Coalbed mine in the Southwestern Pennsylvania section of the Northern Appalachian Basin. The values of coalbed parameters were varied to evaluate their effects on predicted methane emissions for various development distances. The results of these parametric simulations were then used to derive linear expressions relating these parameters to methane emissions into the workings. These models were analyzed to assess their significance and adequacy for predictive purposes. This work shows that coupling reservoir simulations with linear modeling yield a technique that can be applicable to different coalbeds. The reservoir parameters used by the linear models (coalbed thickness, pressure, sorption time constant, Langmuir parameters, permeability) can be determined by running relatively simple laboratory tests, such as adsorption equilibrium and permeability determination, on coal samples obtained either from the mining operation or from the exploratory boreholes drilled ahead of mining.

Jan 1, 2008

By D. Hinton, M. McCawley, R. C. Lantz, F. Pisano, C. Stanley

"INTRODUCTION Aerosols (5 um have not been shown to be consistently generated and characterized in inhalation chambers. Particle deposition in the lungs however may occur with particles as large as 25 um(1). Therefore, in order to closely simulate the atmosphere of an underground coal mine where the distribution is bimodal, with modes at S and 15 um (2), particles much greater than <1 um must be characterized for uniform mixing and size distribution within these chambers. The Hazelton Animal Exposure Chamber has been chosen because it has been best characterized for smaller particles (<1 um) (3), and is the major type used by most inhalation toxicology institutes such as Lovelace Inhalation Toxicology Institute and Battelle Northwest Laboratory.BACKGROUNDPreviously published studies on the inhalation of solid aerosols have attempted to characterize the distrition of particles of <2 um in diameter. There are no published reports of extensive work characterizing either the size distribution of particles <1 um or the concentration throughout the exposure chamber (Table 1).Table 1 shows the variability and sizes of several aerosols <1 um in diameter used in five previous chamber studies.Discussion of Previous StudiesThe study done by Bauermash, Bryan, Dickinson, and Burke (4)stated two major concerns in the development of the 6.5 ft. diameter chamber. The first was that a quantity of animals could be exposed to the same concentration regardless of the location of the animal, and second was that the chamber could be easily cleaned and decontaminated. The solution to the first concern required a circular chamber with the contamination air entering the chamber somewhere along the central axis. The animals could then be changed during exposure time so that each animal was exposed throughout the total volume."

Jun 1, 1988

By James D. Noll, Eileen Birch

In a previous study, the e?cacy of commercial and prototype impactors for sampling diesel particulate matter (DPM) in coal mines was investigated. Laboratory and ?eld samples were collected on quartz-?ber ?lters and analyzed for organic and elemental carbon. Coal dust contributed a minimal amount of elemental carbon when commercial cascade impactors and prototype impactors, designed by the University of Minnesota (UMN) and the US Bureau of Mines (BOM), were used to collect submicrometer dust fractions. Other impactors were not as e?ective at excluding coal dust. The impactors evaluated in that study were either not commercially available or were multi-stage, expensive, and di?cult to use for personal measurements. A commercial version of the BOM impactor, called the DPM Cassette, was recently introduced by SKCs. Tests were conducted to evaluate the performance of the DPM Cassette for measuring diesel-source elemental carbon in the presence of coal dust. Bituminous coals from three mines in two di?erent coal provinces were examined. The dust particle diameters were small and the coal dust contained a high percentage of carbon, there by giving a worst-case condition for non-anthracite coal mines. Results for the DPM Cassette were essentially identical to those obtained by the BOM impactors in a previous study. At a respirable coal dust concentration of 5.46mg m3, which is 3.8 times the regulatory limit, the DPM Cassette collected only 34µg m3 of coal-source elemental carbon.

Pillars with width-to-height ratios of less than 1.0 are frequently created in underground hard rock mines. The strength of slender pillars can be estimated using empirically developed equations. However, the equations can provide variable results when the width-to-height ratios approach 0.5. This paper investigates some of the issues affecting pillar strength at low width-to-height ratios in hard brittle rock. The investigation includes an evaluation of empirical pillar strength data presented in the literature and observations of pillar performance in underground limestone mines in the eastern United States, supplemented by numerical modeling in which failure processes and sensitivity of slender pillars to variations in rock mass properties are evaluated. The results showed that the strength of slender pillars is more variable than that of wider pillars. The numerical model results demonstrated the increasing role of brittle rock failure in slender pillar strength. The absence of confinement in slender pillars can result in a fully brittle failure process, while wider pillars, fail in a combined brittle and shearing mode. The onset of spalling in slender pillars occurs at or near the ultimate strength, while this is not the case for wider pillars. Slender pillars are shown to be more sensitive to the presence of discontinuities than wider pillars, which can partly explain the increased variability of slender pillar strength. Two examples are presented that illustrate failure initiation by brittle spalling and the sensitivity of slender pillars to the presence of discontinuities.

By Thomas M. Barczak

The transverse loading requirement for stoppings as specified in the current Code of Federal Regulations is 39 psf. This measure is based on physical testing of a freestanding wall in accordance with ASTM E 72 specifications, where the dominant parameter is the tensile strength of the sealant. A new protocol based on arching has been developed to determine the true transverse load capacity of stoppings. Arching is achieved by the restraint of the stopping against the mine roof and floor, whereby compressive forces are developed within the wall. A laboratory procedure using the NIOSH Mine Roof Simulator (MRS) to simulate rigid-arching of stoppings was developed and verified through full-scale in-mine tests. Using this protocol, a systematic study of the design parameters that affect arching capability in block stoppings was conducted. The study included a theoretical assessment of arching and development of design formulations that can accurately define the transverse load capacity of various stopping constructions under various loading conditions. This approach should lead to a safer mine environment by matching the transverse load capabilities of the stopping design to the requirements in the mine to ensure proper ventilation control is maintained.

Jan 1, 2005

By Jeffrey M. Listak

The National Institute for Occupational Safety and Health (NIOSH) conducted field tests to evaluate the effectiveness of a wet head continuous mining machine for reducing dust exposure for continuous miner operators. Wet head technology delivers water via sprays to the continuous miner&apos;s cutter head as opposed to traditional standard sprays located on the boom and body of the mining machine. The sprays, positioned directly behind each bit on the cutter head, deliver water at the point of attack, serving to cool the bits during mining to reduce the potential for frictional ignitions. The sprays also flood the coal with water to potentially suppress dust generation. Dust surveys were conducted at several mines to evaluate the wet head&apos;s effectiveness to control respirable dust exposure at the continuous miner operator location and in the immediate return. Results show that the wet head miner improved air quality at both locations to varying degrees in some cases and not in others when compared to a continuous miner with a standard spray system.

Jan 1, 2010

By R. V. Ramani, B. K. Belle

The increased effectiveness of a two-phase spray system (TPSS) over a single-phase spray system (SPSS) for dust suppression is reported in several laboratory studies. The dust collection efficiencies of SPSS and TPSS were studied in a model experimental longwall gallery facility at Pittsburgh Research Laboratory at NIOSH (USA). The experimental design consisted of two factors: pressure, and airflow. Each factor had three levels. SPSS experiments were conducted at only one pressure (1035 kPa) which is nearly 1.5 times higher than the highest air and water pressure for TPSS experiments. The results of the study are presented in this paper. While it appears that TPSS performed better than SPSS, the data is not sufficiently conclusive on this aspect. The differing spray characteristics of the chosen TPSS and SPSS nozzles did not allow a direct comparison of the two systems. In the TPSS arrangement, considerably greater turbulence in airflow is created around the shearer; it is likely that at least in the immediate vicinity of the tailgate drum, there is a roll back of the dust/mist cloud into the walkway. Therefore, positioning of the personnel upwind of the tailgate drum is necessary to avoid high dust exposures. The rate of decrease in concentration with TPSS is higher than that with SPSS. This may be due to the greater atomization of the water. The test set-up did not allow the study of conditions when coal is cut from tail to head where the potential for personal exposure is high. Changes in the experimental design are necessary to overcome some of the reasons expected for the inconclusive results.

By M. A. Reyes

This experiment investigated the effects of different machine mounted area lighting technologies on visual performance. The primary objective was to conduct a comparative evaluation of the lighting technologies based on the visual performance of thirty-six human subjects in a simulated underground mine environment. Incandescent (Incand), fluorescent (Fluor), and light-emitting diode (LED) technologies were used to create four lighting combinations. Visual performance was quantified for the detection of movement in the peripheral field of view and the identification of ground hazards. Measurements were made of the speed [response time measured in milliseconds (ms)], the accuracy (the number of targets and objects missed), and the subjective discomfort rating of the glare experienced for each lighting combination. A secondary objective explored the effects of aging on visual performance. The results indicate that lighting combinations which consisted of LED area lights significantly improved visual performance for the detection of hazards found in the peripheral field of view, as well as those found on the ground. They furthermore, indicate that age plays a significant role in visual performance.

Jan 1, 2009

Determine the advantages and operational limitations of water-let-assisted cutting used with mining equipment. Approach The Bureau of Mines con-ducted a research study to evaluate water-Jet-assisted cutting both in the laboratory and in underground mines. Earlier research on water-jet-assist was limited to laboratory studies where bit speeds and penetration depths were very low and large cutting force reductions were reported. For the past years, research by the Bureau of Mines and others has been concerned with the application of water-jet-assisted cutting under more realistic mining conditions. Study Results Water-jet-assisted cutting employs a mechanical cut-ting bit combined with a moderate to high-pressure water jet directed just in front of the bit tip to assist in the cutting process. Recent Bureau findings show that the addition of the water jet to the cutting bit can improve cutting in harder materials, significantly reduce respirable dust and bit wear, and increase product size. Some of these findings are presented as follows.

Jan 1, 1987

By J. R. Bartels

Operation of underground coal mine mobile equipment is usually done in a restricted workspace with reduced visibility. This work environment puts machine operators in awkward postures for tasks that require awareness of their surroundings and fast reactions to avoid hazardous situations. Using experienced equipment operators as a source, researchers conducted an investigation that developed a method to gather data on the needs and practices of machine operators while controlling the machine and the reasons for needing particular operational cues. The method used was an interview technique including a survey questionnaire and visual aids. The data gathered defined operator cues and work positions for the cutting and tramming phases of remote controlled continuous mining machines used in underground coal mines. Analysis techniques to determine which cues an operator sees from a variety of positions utilizing a computer simulation is shown to be potentially useful to the mining industry for design of work practices and workplace layout and could impact equipment design and selection for improved worker safety. Conclusions indicate that the survey was a good research tool to collect data and helped investigators understand important visual cues. Using this information, researchers were able to analyze the visual cues an operator can see from a given work position and posture.

Jan 1, 2009

By N. S. Dalal, X. Shi

"Electron spin resonance (ESR) spectroscopy has been employed to· examine the role of tetraperoxochromate( V) ions (Cro:-) and other Cr(V) species in the generation of hydroxyl (OH) radicals in the reaction of Cr(VI) with H2O 2 in biological media. In contrast to earlier suggestions, the present ESR studies using crystalline K3CrO8 as a source of Cro:- show that decomposition of Cro:- in water or in H2O 2 does not generate significant amounts of OH radicals. Addition of NADH to a solution containing Cro:- yields a Cr(V)-NADH complex, which readily reacts with H2O 2 to generate OH radicals. Similar results obtained from several other biological reductants, including vitamin B2 , indicate that a vacant coordination site on a Cr(V) complex facilitates its reaction with H2O 2 to generate ""OH radicals. We thus suggest that in biological media, reaction [3] instead of [1] or [2] is the major pathway for the OH radical generation: While the carcinogenic potential of Cr(Vl)-based compounds has been well established via epidemiologic and animal studies (1), the underlying biochemical mechanism is still not well understood (2). In a recent development, however, Kawanishi et al. (3) have reported that hydroxyl (OH)2 radicals might be the key species in the mechanism of Cr(VI) toxicity. As to the mechanism of the ""OH radical formation they suggest that Cr(VI) reacts with cellular hydrogen peroxide (H2O 2) to form the tetraperoxochromate(V) (Crog-) ions, which decompose to produce hydroxyl radicals. It was also suggested (3) that the ""OH radicals thus produced cause genotoxicity via DNA base modification and deoxyribose phosphate backbone alterations. More recently Aiyar et al. (4) reported the detection of OH radicals in the reaction of Cr(VI) with H2O 2 in biological media, including the reaction of ""OH radicals with deoxyguanosine to generate 8-hydroxydeoxyguanosine adducts, confirming that ""OH radicals could indeed play a significant role in the mechanism of Cr(VI) toxicity. However, the mechanism for the ""OH generation was not clarified, although the role of Crog- ions as possible precursors was mentioned, somewhat along the lines suggested by Kawanishi et al. (3). The possibility of the participation of Crog- in the ""OH generation has also been indicated by Sugiyama et al. (5), since they mention that vitamin B2 enhances the formation of""OH radicals in the reaction of Cr(VI) with H2O 2 because of the generation of Crog- in the reaction."

Jan 1, 1990

By N. S. Dalal, Xianglin Shi

"INTRODUCTIONEpidemiologic studies of workers in chromate-ore related industries, 1-3 and stainless steel welding and related occupations4 have shown that they have about 20-40 times higher risk of throat or respiratory track cancer than controls. Although the actual carcinogenic substances were not identified in these statistical studies, Cr(VI) compounds (for example, calcium chromate, zinc chromate, and lead chromate) were implicated as the causative agents, whereas Cr(III) compounds were not suspected as carcinogens. s These suggestions were supporte4 by laboratory studies wherein many Cr(VI) compounds produced sarcomas at the implant or injection sites.1,5 Squamous cell carcinomas and adenocarcinomas closely resembling human lung cancer were induced by intrabronchial implants of calcium chromate in rats, 6·7 whereas Cr(DI) oxide and Cr(lll) sulfate did not induce any tumor formation.6,7While the mechanism of the chromate-induced carcinogenicity is not fully understood, it is generally thought8 that it involves some damage to DNA. Specifically, it has been reported that: a) the chromate ion, henceforth referred to as chromate, can pass through the cell membrane and enter the cell while CR(DI) does not, 9 b) chromate does not interact with either native or denatured DNA 10 while Cr(III) does, 11 and c) the final Cr-DNA complex isolated from cellular reactions of chromate is Cr(III)-DNA, with Cr(III) binding to the phosphate groups.12,13 Thus the important question is: since Cr(DI) cannot pass through the membranes, how does Cr(III)-DNA complex form? For this to happen, Cr(VI) must be reduced to its lower oxidation states, 14 ultimately to Cr(III), by some reductants in the cellular environment. Unless this reduction occurs, the DNA would not be damaged and therefore no chromate carcinogenicity would ensue. Thus the reduction of chromate to its lower oxidation states seems to be a key step in the chromate carcinogenicity .1s One of the major reductants in cellular environments is thought to be glutathione (GSH), both outside and inside the cells.16-lB Some evidence for the role of GSH in the chromate toxicity was provided by recent studies showing that exposure of hamster cells to non-toxic levels of added selemite increases the levels of GSH as well as the Cr(VI)-induced DNA strand breaks,19 and that such DNA strand breaks in hepatocytes also change in direct proportion to the GSH content. 20,21 These observations were interpreted as implying that the reduction of chromate by GSH to some reactive intennediate is an important step in the chromate carcinogenicity. 20.21 In · the present undenaking22 we have used electron spin resonance (ESR) and spin-trap methodology to investigate the reduction of chromate by GSH and find evidence for the involvement of the glutathionyl radical (GS ·) as well as Cr(V)-intermediates."

Jan 1, 1990

By B. L. Razzaboni, P. Bolsaitis

"The formation of reactive oxygen species resulting from the interaction of silica dust particles with red blood cell membranes was investigated; particularly, the effect of surface hydroxyl (silanol) group concentration on the rate of formation of such reactive oxygen species was investigated. The rate of formation was measured indirectly through the effect of catalase, a hemoprotein peroxidase, on silica-induced hemolysis. It was found that the addition of exogenous catalase to erythrocytes markedly reduces the hemolysis caused by silica particles. Furthermore, the amount of catalase required for deactivation of silica per unit area of particle surface is lower for fumed silica particles and calcined crystalline particles than for uncalcined, crystalline silica, suggesting a correlation between the concentration of OH groups at the silica particle surface and its potential for generation of H2O 2• The addition of albumin, a copper chelator, also decreases hemolysis. These results suggest that the hemolysis caused by silica particles is at least partly related to the formation of H2O2 at the particle surface and its subsequent reaction with Cu+ ions. The relationship between the concentration of surface silanol groups on the silica surface and the amount of catalase required to decrease hemolysis may also provide a method for testing potential fibrogenicity of respirable dusts. IntroductionReactive hydroxyl groups on silica surfaces are known to be cytotoxic and are believed to play a major role in silicosis (1-9). It has been proposed that this cytotoxicity results from hydrogen bonding to cell membranes and a resulting increase in membrane fluidity and permeability (4). Surface hydroxyl groups on silica surfaces have also been shown to interact with carbonyl oxygens in cell membranes (1,5). An extensive study by Nolan et al. (6) of the relationship between the negative surface charge resulting from ionized silanol groups and the hemolytic activity of crystalline a-quartz (Min-U-Sil) has shown a positive correlation between hemolytic activity and the surface concentration of silanol groups. These authors demonstrated that the hydrogen bonding of polyvinyl-N-oxide (PVPNO) with silanol groups, as well as the bonding of metal cations to the ionized sm- groups, results in significant decreases in hemolytic activity. Furthermore, it has been found that the complete removal of surface hydroxyl groups from the surface of respirable silica particles nearly eliminates the hemolytic potential of silica (7), suggesting that hydroxyl groups might be involved in other cytotoxic processes associated with silica-induced lung injury. Reactive oxygen species have been .implicated in cellular damage caused by respirable silica particles. Evidence for the presence .of oxygen radical species (02, OH°, H2O2) generated by silica, especially on freshly formed surfaces, has been produced by various investigators. Kalbanev et al. (8) detected H2O 2 in aqueous suspensions of quartz. Electron spin resonance and spin trapping by Shi et al. (9) confirmed the presence of OH"" radicals in aqueous suspensions of quartz, and Gulumian and van Wyk (10) suggested that both glass and quartz produce hydroxyl radicals in the presence of H2O 2 • Gabor et al. (11) detected the presence of malondialdehydereactive lipid peroxides (i.e., lipid-0°) in cultures of macrophages and respirable silica particles using the thiobarbituric acid (TBA) reaction test. Will (12), however, reported that iron enhances the TBA value of peroxidized lipids, and Scheulen and Kappus (19) found that catalase augmented malondialdehyde formation, thereby increasing the TBA values."

Jan 1, 1990