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Increase the productivity of domestic mining operations by improving the performance of rock drilling systems. Approach Investigate the use of chemical solutions at zero surface charge concentrations as drilling fluid additives to enhance penetration rates and extend bit life. Background Bureau researchers have investigated the use of chemical additives to enhance drilling performance and have found that the most efficient drilling occurred when the drilling fluid was able to maintain a zero surface charge (ZSC) on the rock surface. Laboratory drilling studies using 5/8-inch diameter diamond-impregnated coring bits on rock types such as quartzite, granite, taconite, and marble. Cationic compounds were used as the surface charge neutralizing additives during these tests. The drilling studies demonstrated enhanced drilling performance, however, only at the singular additive concentration that produced the ZSC condition. Bureau researchers made a breakthrough when they found that polyethylene oxide, although a nonionic polymer, was able to maintain the ZSC condition over a wide range of concentrations. Success using polyethylene oxide as the drilling fluid additive during subsequent laboratory tests prompted testing under field conditions.

Jan 1, 1991

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 Stephen C. Tadolini, Dennis R. Dolinar

The risk of injury caused by minor roof falls continues to increase in underground mining. Most ground control injuries result from small rock falls that occur in a supported area, but do not involve the failure of the support system. In the roof, these are the "skin failures" that occur between previously installed primary or secondary bolting systems. To minimize skin failures and the associated accidents, several devices were designed and tested in the laboratory to maximize stiffness, minimize material thickness and weight, and ease material storage and handling on roof bolting machines. The goal of this project was to design and evaluate devices that can be installed with traditional primary or secondary roof supports, and that are easy to handle/install under temporary or previously supported roof.

By W. S. Landers

This bulletin is a detailed study of low-temperature, entrained-bed carbonization of a Texas lignite. The lignite studied was from the Sandow strip mine and is representative of the Rockdale formation of the Wilcox formational group. Carbonization was conducted in a continuous entrained-bed reactor at several temperatures in the 8801 to 1,52°C F range, and at air-coal ratios it the 0 to 10.30 scf/lb range (moisture- and ash-free basis). Carbonization rates ranged from 97.1 to 410.0 lb/hr (as-received basis), At the higher air-to-coal ratios employed, all or most of the carbonization heat was provided by internal combustion with air in the reactor. At the lower air-to-coal ratios, parts of the heat for carbonization was supplied externally. It was demonstrated that the entrained-bed carbonization of lignite is a complex reaction and that several variables, of which carbonization temperature, air-to-lignite ratio, and the average size of lignite are important, act together to influence both the carbonization yields and the properties of the resultant products, Process variables established by pant tests were used to design the industrial scale carbonizer operated at Rockdale, Texas, by the Texas Power & Light Company as agents for the Aluminum Company of America. Properties of the carbonization product obtained from the industrial scale reactor were essentially the same as those obtained from the pilot plant reactor operated under the same conditions.

Jan 1, 1968

By Jack Wasserman, Don Wasserman, Logan Mullinix, Shekhar Khanal, Kelly Neal

This paper presents current finding on truck driver average exposure to acceleration for several different manufacturer’s cab-over trucks on a variety of roads in different countries. The predominant time, for this aspect of the study has been spent in the area around London, England and Warsaw, Poland. The ECE directive 2002/44/EC has provided specific guidelines for vehicle operators 8 hour average acceleration exposure. The primary considerations have been on truck design including the air-ride driver’s seat. The truck manufacturers have produced truck cabs that have some separate suspension from the truck frame. The truck seat manufacturers have been producing air-ride suspension seats for the cab. Both of these designs have had the objective of meeting the ECE directive and providing the vehicle drivers with some degrees of comfort. This paper will provide some information on the ability of the vehicles to operate on a variety of roads and meet the objectives. Method The primary method for evaluation of the driver’s exposure has been the use of a seat pad attached to the driver’s seat. Although this sensor system provides the critical information for the driver, an understanding of the reasons for the values requires additional measurements. The initial study in England used both driver and passenger seat pads, as shown in Figure 1, as well as triaxial accelerometers mounted on the base of the seat. The latest studies used significantly more transducers to better understand the relative rotations and translations on the truck frame, the cab, and the driver. [ ]

Jan 6, 2006

"INTRODUCTIONMany of the facilities and much of the equipment available to the Generic Mineral Technology Center for Respirable Dust are highly specialized and therefore, unique to the universities associated with the Center as illustrated in FIGURES 30 through 39.For example, a sample bank of 1300 U.S. coal specimens housed in the Coal Research Section, Deike Building of The Pennsylvania State University has been characterized for physical, elemental, mineralogical and maceral compositions. The results of this research have been used to initiate a study of the relationship between pneumoconioses and coal properties. Selected samples from this bank have been used in animal (primate) studies at the Milton S. Hershey (Penn State) and West Virginia University Medical Centers. These laboratory facilities for research in the medical and biological disciplines is state-of-the-art and includes a primate colony where dust research is currently underway. The Materials Research Laboratory and the Rock Mechanics Laboratory at PSU, and the Mechanical Systems Design and Control Laboratory, the Rock Mechanics Laboratory and the Mine Electronic System Laboratory at WVU are equipped for fundamental research on dust generation and characterization. While the majority of respirable dust research projects fall into these two categories, dust generation and characterization and interaction of dust and lung, there are other laboratory facilities available to the Center which are unparalleled in the type of equipment and expert personnel that they contribute to the program. The Mine Particle Laboratory located at the University of Minnesota and the Diesel Engine Laboratory at Michigan Technological University are examples. They house equipment and instrumentation that is unique to these facilities. much of it having been developed specifically for dust research by the research scientists there. The dust collection equipment and the fine particles measurement, characterization and analysis apparatus are essential to research in the areas of dust collection, particle characterization and diesel particulates. In addition to university laboratories, the research facilities of the National Institute for Occupational Safety and Health (NIOSH) are available to the Center through its relationship With West Virginia University."

Aug 31, 1989

By Donald P. Tuchman, Robert P. Vinson, Steven J. Page, Linda J. McWilliams, Gerald J. Joy, Steven E. Mischler, Jon C. Volkwein

The United States National Institute for Occupational Safety and Health, through an informal partnership with industry, labor, and the United States Mine Safety and Health Administration, has developed and tested a new instrument known as the Personal Dust Monitor (PDM). The new dust monitor is an integral part of the cap lamp that coal miners normally carry to work and provides continuous information about the concentration of respirable coal mine dust within the breathing zone of that individual. Previous laboratory testing demonstrated that there is a 95% con?dence that greater than 95% of individual PDM measurements fall within ±25% of reference measurements. The work presented in this paper focuses on the relationship between the PDM and respirable dust concentrations currently measured by a coal mine dust personal sampler unit utilizing a 10 mm Dorr Oliver nylon cyclone. The United Kingdom Mining Research Establishment instrument, used as the basis for coal mine respirable dust standards, had been designed speci?cally to match the United Kingdom British Medical Research Council (BMRC) criterion. The personal sampler is used with a 1.38 multiplier to convert readings to the BMRC criterion. A strati?ed random sampling design incorporating a proportionate allocation strategy was used to select a sample of mechanized mining units representative of all US underground coal mines. A sample of 180 mechanized mining units was chosen, representing approximately 20% of the mechanized mining units in production at the time the sample was selected. A total of 129 valid PDM/personal sampler dust sample sets were obtained. A weighted linear regression analysis of this data base shows that, in comparison with the personal sampler, the PDM requires a mass equivalency conversion multiplier of 1.05 [95% C.I. (1.03, 1.08)] when the small intercept term is removed from the analysis. Removal of the intercept term results in a personal sampler equivalent concentration increase of 2.9% at a PDM measurement of 2.0 mg m-3.

By Chris Jobes, Alan Mayton, N. Kumar Kittusamy, Dean Ambrose

NIOSH researchers conducted a study to compare seat designs on underground coal mine haulage vehicles. The objective of the study was to support prior findings that NIOSH-designed seats, which incorporated ergonomic design features (e.g., viscoelastic foam padding and low-back support), are improved designs. Based on measured levels of vehicle jarring/jolting and perceived discomfort, researchers evaluated four different designs - two in-use and two NIOSH-developed, ergonomic designs. Researchers collected data using a short questionnaire, a linear, visual analog scale, and accelerometers with a data recorder. Results showed that vehicle operators favored the NIOSH seats with added adjustability, low-back support, and improved seat padding over the existing seats. In addition, the measurements indicated all NIOSH seats performed better than the existing seat, under the no-load (worse of two) conditions, in reducing peak acceleration, crest factor, and RMS acceleration. The authors summarize the data collected and operator preferences for seat designs and different foam padding arrangements.

By J. Torma-Krajewski, M. Lehman

In 2005, NIOSH and Badger Mining Corporation entered a partnership to implement ergonomic interventions, including a systematic process, to address exposures to risk factors that may result in musculoskeletal disorders or other types of injuries/illnesses. As a result of this partnership, an ergonomics process was integrated with the existing safety and health program to promote an on-going application of ergonomic principles, and over 40 task-specific interventions were implemented during the first year of the process. This paper presents details of the process integration, and several examples of task-specific interventions that reduced exposures to risk factors.

By A. Mayton, A. Brien, W. Porter, O&apos

In 2004, management at Unimin's Gleason, TN operation began implementing ergonomic interventions specifically targeted to reduce risk of musculoskeletal injuries (MSIs). Together with corporate and site management, Unimin identified work site hazards and began to modify work practices/equipment. Some interventions were relatively simple and were implemented immediately. Others, like improvements to a mobile shredder, were more complex but were eventually resolved through a participatory approach with employees, management, manufacturers and NIOSH. This paper discusses ergonomic interventions that were successfully implemented using a bottom-up approach to reducing the risk of injury.

By J. Torma-Krajewski, C. Hipes

Although many mining companies apply ergonomic principles, it is usually done either informally and/or reactively. An example of an informal approach is replacing worn equipment (such as seats) with models that have ergonomic features. Another example is modifying a task to eliminate safety hazards. Such approaches reduce risk-factor exposures that can lead to musculoskeletal disorders (MSDs). A reactive approach is followed when modifying a task/ equipment after an MSD occurs. However, neither of these approaches involves a systematic method of proactively applying ergonomic principles to actually prevent injuries or illnesses. This paper discusses how Vulcan Materials Company applied ergonomic principles and implemented interventions to reduce risk-factor exposures.

By N. Kumar Kittusamy

ALTHOUGH MANYSTUDIES HAVE SHOWN an association between operating heavy construction equipment and symptoms of musculoskeletal disorders (MSDs), little research has been performed that systematically characterizes the exposure of operating engineers to ergonomic hazards. This study evaluated: 1) vibration at the seat/operator interface;2) transmissibility of vibration in the Z-axis; 3) psychophysical ratings of vibration level and vibration discomfort; and 4) postural requirements of the job. Results indicate that the digging operation had higher levels of total weighted acceleration than high- or low-idling conditions. Transmissibility data showed that the seat amplified vibration, particularly in the lower frequencies. Seats demonstrated that they may not be sufficient in protecting operators from long-term effects of vibration exposure. High positive correlation was found among subjective ratings (vibration discomfort and vibration level), but moderate positive correlation was found between subjective ratings and quantitative vibration levels. Postural evaluations revealed that the operators were required to assume awkward postures of the neck, shoulder and trunk while performing their jobs. Work-related injuries and illnesses pose a continuing threat to the health and well-being of American workers. The construction industry has been historically recognized as having higher rates of fatality, injury and illness than other industries (McVittie285+; BLS). In 1994, an estimated 218,800 lost-work-day injuries were reported in the construction industry (BLS). Construction also had the second-highest incidence rate for sprains and strains. Although the industry has made progress since then, injuries and illnesses, including MSDs, continue to because for concern.

By Ron Merkel, A. Mayton

Operators of underground mobile equipment, particularly shuttle cars, are often exposed to significant levels of whole-body vibration (WBV) and shock. The human factors group at the NIOSH-Pittsburg Research Center has investigated the use of viscoelastic foam to reduce shock for the equipment operator and improve seats on mine shuttle cars.

By F. C. Turin, K. M. Cornelius

1. INTRODUCTION Underground mining in the USA has undergone significant change in the past 20 years. Two key elements have been increased mechanization and a more educated work force in spite of these changes, many jobs continue to be labor-intensive and repetitive in nature. They entail tasks that, performed over time, can take a toll on the soft tissues and joints. The problem may be compounded by an aging mining workforce. In 1996 the mean age of the coal mining work force was 45 years and the median total years of experience was 20 (NMA 1998). As a person ages, the body resilience to chronic wear and. tear is reduced, which may cause a worker to pay an increasingly higher health price for performing the same task. Mining companies, like many others, are becoming more aware of cumulative effects to the worker as reports of these types of injuries rise. . Conducting a job analysis is an important step when considering a job redesign or modification to reduce worker cumulative trauma exposure. A basic approach to job analysis is to examine the types of aches and pains reported, the tasks performed, and work site conditions. The US Bureau of Mines (USBM) conducted an evaluation of roof-bolting tasks performed at an underground coal mine concerned about early warning signs of cumulative trauma. This evaluation will comprise the primary focus of this chapter. The approach used for the roof-bolting race study may be applicable to other work environments. 2. FUNDAMENTALS OF CUMULATIVE TRAUMA EXPOSURE Musculoskeletal injury is a term used to describe a wide range of soft tissue disorders that affect the nerves, tendons and muscles. Common examples include lower back pain, tendinitis and carpal tunnel syndrome. The majority of these injuries are not the result of sudden mishaps, but usually develop gradually from repeated wear and tear. Symptoms may not appear immediately, but can take weeks, months or even years. Symptoms may result from many types of activities, performed at work or at home, and it is often difficult to attribute there to a single event. In fact, it is more common to identify factors that may have contributed to the development of the condition. The terms repetitive strain injuries or cumulative trauma disorders (CTD) have been commonly used to refer to disorders that have occurred due to work-related activities. Three main risk factors contribute to CTD: force, repetition and awkward postures. Any one or combination of these may contribute to the development of CTD. Therefore, the design of equipment in conjunction with the required tasks should be evaluated when attempting to reduce these risk factors. Examining the layout of the work area to help identify tasks which may contribute to cumulative trauma is necessary. The following list (Putz-Anderson 1988), describes ergonomics concerns that, overall, should be minimized at the work area: • Crowding or cramping the worker: a work area layout may unnecessarily constrain movements of the worker. • Twisting or turning: placement of tools and materials may require the worker to twist the spine to fulfill the requirements of the job. • Repeated reaching motions: the layout of the work area may require the worker to lean to reach and grasp the necessary tools and controls. • Misalignment of body parts: the arrangement of the work area may require the worker to frequently have one shoulder higher than the other or have the neck or spine bent to one side. While many of these concerns are a function of equipment design and environmental conditions, making workers aware of these issues may help them to adapt their work habits to reduce risk of injury. Additionally, this information is useful when conducting an ergonomic evaluation of a work area and associated tasks. 3. UNDERGROUND MINING ENVIRONMENT The underground mining environment is a unique challenge. It is more difficult to develop controls for an underground mine site as compared with a factory setting where equipment and facilities can be more easily designed to reduce worker force, posture and repetitive exposures. In an underground mine, workers are required to perform labor-intensive tasks that often cannot be avoided due to environment constraints. The dynamic nature of the environment does not allow easy implementation of mechanical assists to reduce force exposure. Many of the tasks performed by workers are repetitive. Restrictive work areas due to low ceiling height, low lighting levels and large pieces of equipment cause workers to perform these tasks in postures that are not desirable. Designers of underground mining equipment can control how a machine will function, but not the environment in which it will be used, Hazards in an underground mine cannot be completely removed by redesigning the system. There are many hazards and information sources that must be continually monitored by workers including their position in relation to large pieces of mobile equipment and unpredictable geological anomalies. Thus, immediate dangers may take priority over awareness of ergonomic considerations while performing a job. 4. CASE STUDY OF UNDERGROUND ROOF BOLTING 4.1. Roof Bolting and Cumulative Trauma Exposure In an underground coalmine, after an area is mined it is necessary to support the roof to keep it from collapsing. Since 1950, the primary method for supporting the mine roof has been installation of roof bolts. Long bolts installed into the roof compress the layers of strata achieving a uniformly distributed support anchorage. Roof bolts, typically 6-8 feet long, are installed by workers using large roof-bolting machines. There are different types of machines

By D. Caruso

The health and financial costs of cumulative injuries are plaguing the mining industry. Industry leaders are concentrating on reducing the risk of injury to their workers through design and redesign of work environments. While ergonomics is not a currently regulated field, many mines are realizing that the only way to tackle their most costly injuries, cumulative injuries, is to make the proactive choice to understand those injuries, their root causes and to make workplace changes to prevent them from occurring. Reduction of these injuries not only improves the health and morale of the workers but increases productivity and profit for the companies. Knowledge and reporting of ergonomic risk factors by employees and ergonomics committees is key to these changes and to the reduction of cumulative injuries. NIOSH is developing strong relationships with industry associations and equipment manufacturers to leverage their communication abilities to transfer knowledge to their customers and make a difference in the health and safety of U.S. miners. The benefits of a formalized approach to reducing these injuries along with examples will be presented.

By Rudolf E. Greuer, Linneas W. Laage, Xinton Chang

The usual run time errors occur when illegal mathematical operations are attempted by MFIRE For exam¬ple, if the user enters a negative value for the input variable HEAT to model a heat sink or cooling station, a run tame error will occur because an exponential function is employed to better model the changing temperature dis¬tribution in the airways. DATA FILE ERRORS Two types of data file errors can occur. 1 An error may occur because the input data file itself is invalid This may be caused by: The data file cannot be found due to incorrect spelling, drive, or path specification Check the spelling and path at the prompt for location of the data file. The data file contains non-ASCII symbols Check op¬eration of the text processor to insure that only ASCII characters are produced Delete all non-ASCII and/or all out of place characters. 2 Data are accepted by the program, but are incorrect for the data types or ranges or the combination causes a data inconsistency This may be due to. An invalid character is located where a numerical value is required The input data value is outside the reasonable range The input data is insufficient to build the model for simulation. The input data exceeds the capacity of the program. PROGRAM ERROR DETECTION When the program is running, tracing messages are given on the screen indicating the group and lines of data that have been read and the section of the program that is executing Program termination indicates that problems are caused by the subsequent (not read) data file section. For each detected error, descriptive message starting with * ERROR * is issued and the program terminates. When a possibly wrong value and/or its calculated intermediate result is detected, a descriptive message starting with * WARNING * is issued and the program continues. If a modification of input value or calculated intermediate result is automatically made by the program, descrip¬tive message starting with * ATTENTION * is issued and the program continues. LOCATING ERRORS If a message indicates that the error condition occurred due to the data input file, locate and correct the data item. If no error message is issued, but the simulation results are not as expected, carefully check the list of input data shown in the output file WARNING messages and ATTENTION messages may reveal an error in the input data even though the program continues to operate Insure that the default values or modifications adopted by the program run are acceptable. Anomalistic data, though not incorrect or impossible, may lead to an unusual simulation For example, making a fan unusually powerful may prevent a normal strength fire from affecting the airflow distribution in the system Much care must be employed before considering an ex¬treme case. If a message indicates that the accuracy criterion in the temperature section of the program was not satisfied, a table detailing the current parameters of airways which have large fluctuation in the average air temperature from iteration to iteration is produced If the pattern of the parameters is clearly cyclical, while the variation of natural ventilation pressure is stable or cyclical from iteration to iteration, then, most likely there is no single equilibrium stage for the event If the variation of natural ventilation pressure decreases steadily though slowly, increasing the value of data item variables MADJ or ITN (on control line number 1) may allow convergence.

Jan 1, 1990

By Michael J. Brnich

On November 20, 1968, a massive explosion rocked the underground workings of Mountaineer Coal Co.?s Farmington No. 9 Mine in West Virginia. Of the 99 miners who were working in the mine at the time of the explosion, only 21 survived and escaped the mine. This group included eight who were rescued from the Mahan?s Run air shaft. Nearly 40 years after the event, researchers from the NIOSH Pittsburgh Research Laboratory conducted oral history interviews with two of the eight survivors rescued from the shaft. The Farmington No. 9 Mine disaster ultimately led to passage of the Federal Coal Mine Health and Safety Act of 1969 (amended in 1977).

May 1, 2009

By N. S. Dalal, X. Shi

"SUMMARYElectron spin resonance (ESR) measurements provide direct evidence for the involvement of the glutathionyl radical, as well as an isolable Cr(V)-glutathione intermediate in the Cr(VI) glutathione redox reactions. These results indicate a new mechanism for the reduction of Cr(VI) by glutathione in relationship to cellular environment and suggest that synergistic reactions of Cr(V) and GS· might be responsible for the (unexpected) increase in the Cr(VI)-induced DNA-strand breaks at high glutathione levels.INTRODUCTIONWhile the reduction of Cr(VI) by glutathione (GSH) is thought to be a critical' step in the pathogenesis of the Cr(VI)-exposure related carcinogenesis1- 4, the exact reduction mechanism is not yet understood. The following reaction steps have been suggested :(A) Initial step:Cr04 2- + GSH - GSCrOa - (1)(B) At high GSH levels:GSCroa- + GSH - Cr( IV) + GSSG (2)(C) At low GSH levels: GSC rO a - - Cr ( V ) + GS ·(3)Thus far, however, in these reactions, the GS· radical has eluded spectroscopic detection, while the evidence for the Cr(V) formation has been reported positives as well as negative2·. Her~ we present spin-trap ESR evidence for the formation of the GS· radical, and a definitive ESR detection of an isolable cr(V)-GSH intermediate in Cr(VI)-GSH reactions.MATERIALS. AND METHODSESR spectra were obtained at X-band (-9.7 GHz) using a Bruker ER200D ESR spectrometer. The magnetic field was calibrated with a self-tracking NMR Gaussmeter (Bruker, Model ER035M) and the microwave frequency was measured with a Hewlett-Packard (Model 5340A) frequency counter. The spin probes, a-(4-pyridyl-1-oxide) -N -tert-butylnitrone (4-POBN) and 5,5-dimethyl~1-pyrroline-1-ox1de (DMPO) were purchased from Aldrich, K2Cr201 from Fisher and used without further purification. All experiments were done at room temperature."

Jan 1, 1989

By N. S. Dalal, X. Shi, V. Vallyathan

"Electron spin resonance (ESRJ spectrum of the hydroxyl (· OH) radical spin adduct with .the spin trap 5,5-dimethyl-1-pyrrolintt-N-oxide has been obtained in suspensions of freshly ground quartz particles. The concentration of the spin adduct (and hence of the • OH radicals) increases with the amount of grinding. The dust's potential for the generation of the· OH radicals is maximum when fresh (i.e., immediately after grinding) and decreases to 50% in about a day on storage in air. Studies involving metal chelates .indicate that the • OH radical formation involves mainly the silica surface and H20 rather than the Fenton reaction. The results suggest that hydroxyl radical reaction(s) could be important in the lipid peroxidation and fibrogenicity by quartz dust, particularly .in acute silicosis. INTRODUCTIONIn this paper we report on our electron spin resonance (ESR) detection of the formation of hydroxyl (·OH) radicals in aqueous suspensions of freshly crushed quartz particles. This work was undertaken with a view to find possible clues to the role of free radicals in the pathogenesis of quartz-induced fibrogenicity, commonly known as silicosis. We noted that while silicosis is one of the major health hazards in coal and mineral industries, the mechanism by which the quartz particles exert their toxic action on cells and the process(es) by which these actions progress to fibrogenesis are still poorly ·understood (Reiser and Last, 1979; Singh and .Rahman, 1987). It is generally thought, nevertheless, that the action of quartz particles on the biological membranes is the starting point of the silicotic process (Parazzi et - al., 1968). A possible clue to the mechanism of the membrane damage by quartz particles, in terms of the role of oxygenated free radicals, is suggested by the following observations. A suspension of quartz particles in contact with alveolar macrophages has been reported (Gabor et al., 1975; Koike et al., 1982) to initiate an enhancement of lipid peroxidation, defined broadly as the oxidative deterioration of polyunsaturated components of lipids. Hydroxyl (· OH) radicals are known to be capable of peroxidation by abstracting hydrogen atoms from cell-membrane lipids (Halliwell and Gutteridge, 1985) and of initiating lipid peroxidation in lysosomal membranes. (Fong et al., 1973). Arong other lines, it is known that exposure of cell membranes, fatty acids, and unsaturated food oils to ionizing radiation, which generates· OH radicals, causes rapid peroxidation (Halliwell and Gutteridge, 1985). Thus • OH radicals (and also other oxygenated species such as Oi, 10 2, and H20 2) might be expected to play a role in the toxicity of quartz. Earlier studies of the aqueous chemistry of quartz suspensions have reported detection of H2O 2 (Kalbanev et al., 1980), implicating the formation of ·OH radicals as transient species. However, we are not aware of any report of the detection of • OH radicals in quartz reactions, and thus the present study was undertaken. Since it-is known that, because of their high reactivity (hence short lifetime) in aqueous media, the • OH radicals cannot be detected via ESR directly (Finkelstein et al., 1980; Buettner, 1982) we have used .ESR combined with the spin-trap methodology (Finkelstein et al., 1980) for studying the· OH formation. The results show that· OH radicals are indeed formed in aqueous suspensions of freshly ground quartz; thus pointing to ·a possible new clue to the cytotoxicity of freshly formed quartz particles and thereby to silica fibrogenicity."

Jan 1, 1988

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

"Electron spin resonance (ESR) measurements show that grinding of quartz particles in air produces silicon-based (Si- and SiO-) radicals which decay with aging in air. ESR spin trapping measurements provide evidence for the generation of hydroxyl and possibly superoxide radicals from a suspension of fresh quartz particles. The hydroxyl radical generation potential of the fresh quartz particles decreases on storing in ambient air and on the addition of catalase, superoxide dismutase, desferoxamine, or DMSO. Silica-induced lipid peroxidation also decreases on storing the fresh particles in ambient air. These findings suggest that oxygenated radicals play a role in the biochemical mechanism of pneumoconiosis in general and acute silicosis in particular.INTRODUCTIONThis communication summarizes our electron spin resonance (ESR) investigation of the formation of oxygenated radicals by freshly crushed quartz particles in a cell-free aqueous medium, and its potential role in the biochemical mechanism of acute silicosis. This study was undertaken because the mechanisms by which the quartz particles exert their toxic action on cells and the process(es) by which these actions progress to fibrogenesis are still not well understood. 1-3 It is generally believed, however, that the action of quartz particles on the cell membrane is the starting point of the silicotic process. 1,4 Since the first step must involve surface reactions, characterization of the chemical structure of the surface of quartz particles has been the subject of several recent studies!-' For example, we reported that mechanical crushing of quartz under normal atmosphere generates silicon-based (Si• and SiO•) radicals which decay with time, and that these radicals are associated with a higher cytotoxicity of fresh quartz dust as compared to that of an aged dust from the same stock. 6,8 Independently Fubini and coworkers' have also reported on the formation of Si• and SiO• -type of radicals from quartz particles crushed under atmospheric conditions. Gulumian and van Wyk9 have reported that quartz particles react with hydrogen peroxide (H202) to generate hydroxyl (•OH) radicals. These authors9 suggested that this process might contribute to quartz's pathogenicity but the mechanism of the -OH radical formation was not clarified. Earlier, Gabor and Anca10 had suggested that the cytotoxicity of quartz particles might be associated with the generation of some factor or factors possessing the properties of a free radical and hence capable of promoting the peroxidative chain cleavage of polyunsaturated fatty acid moieties of the phospholipids in the cell membrane. More recently, Weitzman and Graceffa 11 reported that asbestos is able to catalyze the generation of -OH radicals from H2O2. Their later work12 indicated that lipid peroxidation might be one of the mechanisms of tissue injury by asbestos."

Jan 1, 1989