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By Ivan F. Avery

PRODUCTION of carbon black decreased 4 percent in 1961. Output in the major producing States of Texas and Louisiana decreased 1 percent and 8 percent, respectively. Production of channel black continued downward, declining 10 percent in 1961 compared with 9 percent in 1960. Furnace black production also decreased 3 percent from 1960. Total domestic sales, however, increased 2 percent, Sales to most major consumers increased, but sales to the ink industry decreased 10 percent. Producer's stocks decreased 5,083,000 pounds during the year. Exports decreased 4 percent. SCOPE OF REPORT Carbon black is a very pure grade of quasi-graphitic carbon; particle diameters range from 50 to 5,000 angstrom units. Annual reports were submitted to the Bureau of Mines by operators of all commercial plants in the United States.

Jan 1, 1962

By Ben A. Kornhauser

The mineral industry consisted primarily of natural gas production and of urea fertilizer, which was manufactured for domestic agriculture. Copper and iron deposits were being developed. Information regarding the mineral industry of Afghanistan was sparse. The Government continued to emphasize the development of mineral resources that could benefit the economy of the U.S.S.R. and repay Soviet grants. The northern half of the country, north of the Hindu Kush mountain range and adjacent to the U.S.S.R., received considerable Soviet aid to develop mineral resources.

Jan 1, 1986

By R. W. Watson

This Bureau of Mines report summarizes some recent results on the sensitivity of various experimental explosive systems using ammonium nitrate (AN) as the oxidizing agent. The sensitivity survey included drop-weight and friction testing and sensitivity to initiation by projectile impact and a No.8 blasting cap. It was found that certain types of AN prills can result in cap-sensitive mixtures when combined with No.2 diesel fuel (Fa); prilled AN mixed with nitromethane also result in cap-sensitive mixtures. Mixtures of AN prills and neat 1-and 2-nitropropane were not cap-sensitive, and the use of powdered or grained aluminum in AN-FO did not adversely affect the sensitivity except possibly to increase its sensitivity to friction.

Jan 1, 1974

By D. Harrington

In general, mining is carried on underground, that is, in confined places where it is difficult to obtain adequate lighting and frequently in rock strata requiring much care to prevent caving. Moreover, explosives must be used in mining with the numerous hazards associated with them, and some mines give off explosive or irrespirable gases; also, ma- chinery must be used, usually under conditions much more hazardous than on the surface. These and many other considerations cause mining to be probably the most hazardous occupation in which large numbers of our fellow countrymen are employed. Prevention of accidents in the mining industry is far more complicated than in surface industrial work, even of the more hazardous types, because the different elements that enter into possible accident occurrence are ascertained more readily above ground and suitable action can be taken against them; moreover, errors in connection with prevention of accidents in surface industrial work usually affect only one or, possibly, a few persons, while in zines one human error may readily cause an explosion or other untoward occurrence resulting in the death of scores or even hundreds of persons. This difficulty in the prevention of accidents in and around mines is well-known, and most countries and States have regulations to guard the safety and, to a much smaller extent, the health of workers in mining and allied industries. In general, the State laws and regu- lations regarding the welfare of mine workers are merely a skeletonized outline of some more or less fundamental minimum requirements and are far too general to do much more than suggest some procedure which may or may not be safe or healthful. Most of them are grotesquely out-of-date as applied to present-day conditions, and none of them is adequate to protect life, limb, health, or property. Unquestionably, there is great need for a closer correlation of the laws and regulations of the various States with regard to safety in the mining and allied industries, and while mining conditions vary far too much for a standardized mine safety law applicable to all of the States, on the other hand there are numerous standard and fairly fundamental safety pro- visions which apply to all mines and which should be embodied in the mining codes of all States. Undoubtedly, these standardized safety requirements would be opposed by a consider- able part of the industry, but the ultimate effect would be beneficial to the owners, work- ers, and the general public. For many years progressive mining companies in the United States have not been satisfied to operate only within the meager safety requirements of the State laws or regulations and have adopted additional and far more effective safety procedure of their own, although com- plying also with the State laws and regulations. As a result of this forward-locking policy, zany of these companies have made astonishing progress in the reduction of accidents.

Dec 1, 1935

By E. R. Maize, R. D. Currie

"Good ventilation is one of the first requisites in the safe and efficient operation of a coal mine. If a mine is gassy, the uninterrupted circulation of an adequate supply of fresh air is imperative if that mine is to operate with a relative degree of safety. That ventilation is not •only a safety consideration, but is an extremely important economic factor is shown by the fact that in many mines 50 per cent of the total power cost is for ventilation.The system used in the Graceton Coal & Coke Co. mine, Graceton, Pa., is believed to be unusual in many ways. Its application in this mine has re¬sulted in good ventilation of the working faces, no interruption to the venti¬lating current through the use of doors. a large- portion of the air circulated by the fan reaching the working places, low velocity air currents on traveling and haulage ways, low water gage and power consumption of the fan, and well-ventilated gob areas.This investigation was made possible through the courtesy of W. H. Robertson, mine superintendent. Fred Roberts, mining engineer, and Floyd Phillippi, mine foreman, assisted in the collection of information.The Graceton mine is a slope, opening the Upper Freeport or E bed, on the Pennsylvania Railroad about midway between Blairsville and Indiana at Graceton, Indiana County, Pa. The production is approximately 1,000 tons of coal per day and about 170 men are employed underground. The mine is considered gassy and was found to be liberating approximately 300,000 cubic feet of methane in 24 hours. The return airways terminate at a circular, concrete lined shaft 12 feet in diameter and about 115 feet deep at which is the exhaust fan.Mining is done by a block system with flat or level entries turned off the main slope at intervals of 1,350 feet, off which the butt headings are turned up the grade parallel to the slope. Rooms, which are about 225 feet long and 12 feet wide, are turned off the butt headings on 80-foot centers, leaving a block about 68 feet thick between rooms.Haulage on the main slope is by rope, with the hoist on the surface. This hoist is electrically driven through a 500-h.p., 2,300-volt motor. The rope used in this haulage is 1-1/8 inches in diameter. There are five electric trolley locomotives - one 10-ton and four 6-ton - which do all of the hauling in the flat and butt entries.Before it is blasted all of the solid coal and as much of the pillar coal as can be cut with safety is undercut by permissible mining machines. Shooting is done by shot firers who use permissible explosives, electric detonators, and dry-cell, nonpermissible batteries.In rooms where conditions are normal, timbering consists of two rows of posts on 4-foot centers. Posts are required to be within 6 feet of the face in machine-cut places and within 3 feet of the face in hand-mined places. Timbering on entries, where required, is of two types: a bar hitched into the ribs and supported by the coal, or 3-piece sets. The legs of the 3- piece sets used on the slope are set well back into the rib to prevent their being. knocked out by a wreck."

May 1, 1932

By C. Pritchard

John Marks said in his acceptance of the Hartman Award in 2008, "I guess that without the occasional complaint, your mine is probably over-ventilated" (Marks, 2008). Miners are seldom in this situation and spend much of the time trying to find enough air to keep an operation running. With examination, there are usually changes that can be made to increase the efficiency of ventilation systems. Mine ventilation air is a costly commodity, especially by the time it has been heated or cooled and moved to the bottom of the shaft and through the mine airways. Modifications that result in surplus mine ventilation air could bring financial and environmental benefits. Some issues mine operators have needed to address recently are increased airflow requirements to dilute diesel particulates in metal and nonmetal mines, to ventilate reserves that are deeper, hotter, and further away from fans and shafts, and to meet demands from increased production. This paper discusses successful methods to find additional usable air when there is no extra ventilation capacity. Most of the options presented in this paper are useful for metal/ nonmetal operations but some may be applicable to coal as well.

Jan 1, 2010

By W. P. Yant, G. W. Jones

During the testing of porcelain insulators with a " 60 - cycle flash - over apparatus " , gases are liberated having an odor greatly resembling that of ozone . Since the two main constituents of normal air are nitrogen and oxygen , and high voltages (approximately 90,000 volts ) are used during the tests , the conditions are favorable for the production of ozone or oxides of nitrogen , and perhaps both simultaneously . The presence of these gases is only noticeable during the testing period . They soon disappear after the test is over . No fatalities have ever resulted from these gases at the plant visited nor are there any records of any of the men who worked on the tests being confined to their homes from this cause . New employees sometimes complain of a depressed feeling and shortness of breath , which is most noticeable after leaving work and getting into fresh air , but they som become accustomed to it and no ill effects are noticed . In view of previous work*** which the Bureau of Mines has done on oxides of nitrogen in connection with mine gases and problems in gas analysis , tests were made at the plant of the Westinghouse High Voltage Insulator Company at Derry , Pa . to determine the kind and amount of gases liberated .

Jun 1, 1923

Develop a simple and practical technique to measure in situ rock mass properties for realistic design and stability evaluation of underground structures. Background The Bureau of Mines has developed basic principles and techniques to determine in situ rock mass properties including Poisson's ratio, deformation modulus, and yield and failure strengths. An instrumentation package consisting of three pressure cells is installed in a single drill hole. Cell pressure response data are acquired and used to calculate and determine the rock mass properties. How It Works A test hole of BX size (approximately 5.7 cm) or larger is drilled to the approximate depth of the measuring point. The last portion of the test hole is drilled with precision bits to EX size (approximately 3.8 cm). The instrumentation package, which consists of one 3.8-cm-diameter cylindrical pressure cell (CPC) and two 5.7-cm-diameter cement-capsulated, flat borehole pressure cells (BPC's), is then installed. A complete history of cell response to changing strata loads is acquired on a continuous basis with a chart-type hydraulic pressure recorder. From these cell pressure data, Poisson's ratios, deformation moduli, and yield and failure strengths are calculated and determined.

Jan 1, 1990

By Oliver Bowles

Since 1922 when the Bureau of Mines issued a report2 covering the slate industry in detail, changes in technology have taken place which have an important bearing on the industry. The present paper comprises a record of these changes. Though the value of slate, for roofing, structural, blackboard, sanitary, and electrical uses is generally recognized, it has many competitors. To meet this constantly increasing competition producers are promoting economies in manufacture, and improving processes, thereby lessening costs of production, and are placing on the market products of the highest possible quality, thus creating satisfaction and confidence on the part of the user. This endeavor to place the industry on a better basis, both as regards processes and products, is shown in the recent developments in technology which are presented herein. Valuable assistance in obtaining data for this paper was given by W. S. Hays, secretary of the National Slate Association, N. M. Male, president of the National Slate Association, and Robert Notvest, consulting engineer, Cleveland, O.

Jan 1, 1926

By Robert R. Stein

Occupational noise caused by the rock drills used in mining was investigated by the U.S. Bureau of Mines. Using a large reverberation chamber and an automated drill test fixture (ADTF), the sound power levels of mining drills were measured to determine if there are types of drills that are advantageous from a noise production standpoint. Test results show that while there are not large variations among types of drills, there are still some choices that could produce a positive effect on overall noise exposure. It is also shown that lower noise exposures are possible using larger drills because of higher production rates and better operator positioning.

Jan 1, 2010

By Ann G. Kim

Gas samples containing 02, N2, H2, He, CO2, CO, CH4, and trace amounts of C 2 to C6 hydrocarbons are analyzed by a gas chromatographic method that utilizes both thermal conductivity and flame ionization detectors. A porous polymer support and molecular sieve columns are used with argon as the carrier gas. A column selector valve makes it possible to perform a complete analysis either on one 1-ml sample in 40 minutes or on two samples in 20 minutes, one sample for each detector. Samples are introduced either by on-column injection or through a gas sampling valve. By varying operational parameters, the speed, sensitivity, and accuracy of analysis may be modified to suit a particular situation.

Jan 1, 1974

By Charles D. Litton

An overview of state-of-the-art technology in fire detectors is presented by the Bureau of Mines regarding their use in the mining industry. Detectors are categorized according to the characteristics of a fire to which they respond. Operating principles of the various detectors, their application, and the advantages and disadvantages of each are discussed.

Jan 1, 1979

By J. M. Stuve

A novel calorimetric solution technique, recently developed at the Bureau of Mines, was tested using synthetic samples of chalcocite (CU2S) and covellite (CuS). The solution of these refractory sulfides was accomplished by oxidation with bromine in a moderately acidic, aqueous solution. The resulting values for the standard enthalpies of formation (?Hf°, 298.15) for CU2S(c) and CuS(c) were -18.1 ±1.1 kcal/mol and -13.3 ±1.1 kcal/mol, respectively. These values are in good agreement with published formation values derived from other methods of physicochemical measurement.

Jan 1, 1982

By W. E. Miller, G. S. Scott, G. W. Jones

"INTRODUCTION One of the major activities of the Bureau of Mines is the promotion of safety in mining and the mineral industries. Research is undertaken in connection with these problems to determine the explosion and ignition hazards of combustible gases, liquids, and solids and to investigate means of reducing them.Occasionally the Bureau is asked to determine inflammability or ignition temperatures to enhance safety in nonrnineral industries. From time to time it has complied with such requests when no other agency was available to do the work and the investigation could be conducted with a minimum of time and expense. The present investigation is one of this class.Nicotine (C10H14N2), a colorless combustible liquid having a boiling point of 246°C, is usually obtained from tobacco and its products by extraction processes. When heated to its boiling point it decomposes; the purified product is obtained from tobacco extractions by distillation at reduced pressures or is distilled in a current of inert gas.It has an unpleasant odor, a burning taste, and in the undiluted state is highly toxic. Under certain conditions it can be oxidised to nicotinic acid and in the near future may therefore become of considerable economic importance. Nicotinic acid is a component of the vitamin B complex now commonly used to fortify white flour and other foods that normally are deficient in these vitamins."

May 1, 1942

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

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

Mar 1, 1992

By T. J. McDonald

The methods used and the results obtained in the application of high-expansion foam on a recent fire in an operating mine in western Pennsylvania were reviewed. This is the first instance where foam has been applied extensively to a fire under actual mining conditions although considerable research has been conducted and experimental fires have been controlled. The Bureau of Mines began investigating the foam-plug technique in 1957 in its experimental coal mine, following reports of successful trials in Eng-land, where the basic methods, using the normal ventilating current, were developed. Early in the research it was apparent that the normal ventilating current in mines in the United States would not provide adequate air pressure to drive a foam plug the distance that might be required. Subsequently, the Bureau of Mines developed a portable high-expansion foam generating unit consisting of a fan having relatively high pressure potential, net, sprays, and metering equipment. To date, foam generators have been constructed by the Bureau, by at least one operating coal company, and by one manufacturer of safety equipment. A number of units from the latter supplier have been adopted by coal-mining companies as an integral part in their firefighting installations.

Jan 1, 1961

It is suggested in chapter 1 that emergency activities (including escape) are not individualistic. They tend to be group responses. If escapes from mine fires are group activities, then preparation for such events must take group behavior into account. This chapter explores the hypothesis that the miners who escaped from the three mines under study did so as members of groups. For development of this chapter, the database was examined for evidence of the existence of escape groups and for instances when individualistic behavior was paramount. Illustrations of group and/or individualistic behavior were analyzed and representative examples are provided in the following discussion. The nature of groups was discussed in chapter 3 and the following working definition was offered: "We mean by a group a number of persons who communicate with one another often over a span of time, and who are few enough so that each person is able to communicate with all the others, not at second-hand, through other people, but face-to-face" [Homans 1950]. To determine whether or not groups existed during the fire evacuations, it is important that the concept of group be clearly defined. Therefore, the discussion started in chapter 3 will be elaborated here. The defining characteristics of group given in chapter 3 were taken from Homans [1950]. They include size, person-to-person com¬munication, feelings that members have for each other, explicit and implicit rules for behavior, and common activities. An additional characteristic that is sometimes used to define groups is cohesiveness. Kiesler and Kiesler [1970] state, "Cohesiveness would include not only the attraction that the group holds for its members but also any other force operating on the individual to stay in the group." Variables said to contribute to cohesiveness include "(1) the attractiveness of a group for its members," and "(2) the coordination of the efforts of the members" [Keisler 1970]. One source of the attraction to a group occurs when "the goals or exterior tasks confronting the group are consistent with those of the individual person, and can best be handled by group action" [Cartwright and Zander 1968, in Davis 1969]. In other words, a common goal and a coordinated effort mounted to achieve that goal contributes toward the creation of a cohesive group. As discussed in the earlier review of research (chapter 1), groups have frequently been studied in laboratory or simulation settings. These methods allowed control over variables of interest. Kiesler and Kiesler [1970] state, however, that they "find group variables conceptually imprecise and experimentally difficult to work with." Experimental control, in other words, is difficult to achieve in the study of groups. The richness of the naturalistic mine fire data may provide an opportunity for an examination of groups that cannot be found in laboratories or simulations because this environment was not

Jan 1, 2000

By Robert C. Hickman

"INTRODUCTION The Cline mine has been worked intermittently for copper and gold since 1895. Scheelite has recently been detected with the aid of a ""Mineralite"" on the old waste dumps of the mine. Four diamond-drill holes were drilled by the Bureau of Mines from August 13 to September 25, 1946. Results of this drilling showed the vein to pinch at depth and to carry no mineralization of economic importance.ACKNOWLEDGMENTSIn its program of investigation of mineral deposits, the Bureau of Mines has as its primary objective the more effective utilization of our mineral resources to the end that they make the greatest possible contribution to national security and economy. It is the policy of the Bureau to publish the facts developed by each project as soon as practicable after its conclusion. The Mining Branch, Lowell B. Moon, chief, conducts preliminary examinations, does the actual investigation work, and prepares the final report. The Metallurgical Branch, Oliver C. Ralston, chief, analyzes samples and makes beneficiation tests.The project was under the general supervision of Mitchell H. Kline, chief, Raleigh Division, Mining Branch.Acknowledgment is due Dr. Jasper L. Stuckey, State geologist, for logging the drill core and to J. B. Zadra and associates, Metallurgical Branch, College Park, Md., for analytical determinations."

Feb 1, 1948

This surveillance report summarizes data on work-related fatal and nonfatal injuries, illnesses, and hazardous exposures in the mining industry for the 10-year period 1986-1995. The term "surveillance," as used in public health, may be new to many readers of this report. With regard to occupational safety and health, the goal of surveillance is to describe the occurrence of work-related injuries, illnesses, and known hazardous exposures; to identify new hazards that may occur due to the introduction of new technology or other factors; and to assess the effects of preventive measures designed to improve worker safety and health. Surveillance provides an overall picture, which can be used to focus resources on areas most in need of prevention programs or further research. Surveillance generally requires the use of multiple sources of data, all of which have their own strengths and limitations. Surveillance in the U. S. mining industry is complicated by the fact that U.S. national data systems that provide information on mining are based on two different definitions of the mining industry. One is established by the Mine Safety and Health Administration (MSHA), the other by the Standard Industrial Classification (SIC) System [Office of Management and Budget 1987] and the 1980 U. S. Bureau of the Census (BOC) Classification System [U.S. Bureau of the Census 1982]. The mining industry as defined by MSHA is based on the regulatory jurisdiction of that agency. Reporting requirements for injuries, illnesses, and workplace exposures are stipulated under the Federal Coal Mine Health and Safety Act of 1969 and the Federal Mine Safety and Health Amendments Act of 1977. Of note is that the oil and gas extraction industry falls outside of MSHA jurisdiction. The Occupational Safety and Health Administration (OSHA) was charged with enforcement in the oil and gas industry under the Occupational Safety and Health Act of 1970. Under the SIC, the definition of mining covers the extraction of naturally occurring minerals, including liquids (petroleum), gases (natural gas) and solids (coal, metal, and nonmetallic minerals). Exploration and development of mineral properties are also included in the SIC definition of the mining industry. The SIC was developed by the Office of Management and Budget for use in classifying establishments based on the type of economic activity in which they are engaged and serves as the industry classification standard for all establishment based Federal economic statistics. This classification is important for occupational safety and health surveillance because it also serves as the industry classification system for all data on work-related injuries and illnesses collected by the U.S. Bureau of Labor Statistics (BLS). The U.S. Bureau of the Census uses an industry coding scheme similar to that used by the SIC. For the mining industry, the categorization is identical in both systems. Death certificate data made available by the National Center for Health Statistics (NCHS) are categorized under this system. Death certificate data are particularly important for surveillance of mortality from work-related illnesses. Key differences between the SIC/BOC categorization system and the MSHA system can be summarized as follows: • MSHA excludes the oil and gas industry, which is classified as part of the mining industry under SIC/BOC. • MSHA excludes work that is done off of mine property; work off of mine property is included under SIC/BOC if it is performed by an establishment falling into one of the SIC/BOC mining industry codes. • MSHA includes mine-associated mills and processing plants; these are classified under the manufacturing industry, rather than mining, according to the SIC/BOC coding structure. Since the data collected by MSHA and the data collected by BLS and NCHS using the SIC/BOC classification system are both important sources of information on the mining industry and in many cases serve different purposes, data from both systems are presented in this report. In general, data using the SIC/BOC system are comparable across U.S. industries and should be used when comparing mining to other U.S. industries. Much of the data in this report are presented in the form of frequencies or rates. A frequency provides only a count of the number of cases without providing any information about the risk of occurrence. Rates provide an estimate of the risk of injury or illness. The reader is cautioned, however, that rates based on small numbers can be unstable; thus, any inferences should be drawn with care. In this report, no rates are presented for groups in which there were fewer than three cases. The incidence of most injury and illness conditions differs by age, sex, and race. For this reason, data in many surveillance reports are adjusted for these demographic factors. It was not possible to do this for most of the rates in this report because information on demographics was not available. With the exception of the proportionate mortality ratios (PMRs), all data presented are unadjusted. A detailed account of the sources of data is in appendix A. The methods used in data selection and analysis are described in appendix B.

Jan 5, 2000

By N. S. Dalal, X. Shi

"It has been recently suggested that the exceptionally high antitumor and antibacterial activity of natural fredericamycin A (FMA) is related to its ability to spontaneously generate the superoxide anion (02-) and hydroxyl (""OH) radicals in aerobic solutions [Hilton, B. D., Misra, R., & Zweier, J. L. (1986) Biochemistry 25, 5533]. With a view to understand the mechanistic details, attempts were made to reproduce earlier electron spin resonance (ESR) evidence for the oxygenated free radical formation in well-aerated solutions of natural FMA in dimethyl sulfoxide and dilute H 20 2• Little or no evidence was obtained for the formation of the 0 2- and methoxy (""OCH3) radicals, while the detected formation of the 'OH and methyl ('CH3) radicals was attributable largely to mechanisms not involving FMA. These results thus reopen the T question regarding the mechanism of its exceptionally high tumoricidal-bacteriocidal activity. This paper reports on an electron spin resonance (ESR) investigation of the formation of oxygenated free radicals in solutions of natural fredericamycin A (abbreviated as FMA) which has recently been reported to be a highly potent anti¬tumor antibiotic (Pandey et al., 1981; Warnick-Pickle et al., 1981). The impetus for this undertaking was provided by recent reports (Hilton et al., 1986; Stinson, 1986) suggesting that the strong tumoricidal activity with high therapeutic—toxic index of FMA was related to its ability for the spontaneous generation of superoxide anion (02-) and hydroxyl (OH) radicals. For example, the suggested mechanism for the formation of 02- by FMA was (Hilton et al., 1986)FMA-OH + O2 FMA-O + H+ + 02-Here FMA—OH is simply the FMA molecule emphasizing the —OH moiety which becomes FMA-O, the free radical rep¬resenting the oxidized form of the drug. While some other highly effective anticancer drugs in current clinical application, such as bleomycin, are also thought to exert their antitumor effects via the formation of reactive drug-based or oxygenated free radicals (Carmichael et al., 1985; Gianni et al., 1983), FMA was considered unique in that only in this case the free radical formation was thought to be spontaneous, rather than through a metal- or an enzyme-activated process (Hilton et al., 1986; Stinson, 1986). Thus it was suggested (Hilton et al., 1986; Stinson, 1986) that FMA could be the forerunner of a new class of anticancer drugs. However, we noted that while the hypothesis seemed plausible, the reported ESR spectral evidence appeared to be ambiguous. Because of the high significance of the earlier conclusions (Stinson, 1986), we undertook a systematic ESR study of the radical formation in FMA solutions, and as discussed below, our conclusions disagree with those reported earlier."

Jan 1, 1989