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By N. S. Dalal, Xianglin Shi

"Electron spin resonance (ESR) measurements provide direct evidence for the involvement of Cr(V) in the reduction of Cr(VI)· by NAD(P)H. Addition of hydrogen peroxide (H2 O 2) to NAD(P)H-Cr(VI) reaction mixtures suppresses the Cr(V) signal and generates hydroxyl (·OH) radicals (as detected via spin trapping), suggesting that Cr(V) reacts with H2O 2 to generate the ·OH radicals. Reaction between H2O 2 and a Cr(V)·glutathione complex, and between H2O 2 and several Cr(V)-carboxylato complexes also produces ·OH radicals. These results suggest that Cr(V) complexes catalyze the generation of ·OH radicals from H2O 2, and that ·OH radicals might play a significant role in the mechanism of Cr(VI) cytotoxicity. KEY WORDS: ESR. spin trapping, Cr(VI) reduction, Cr(V), hydrogen peroxide, free radicals.INTRODUCTIONThis communication reports an ESR spin trapping detection of hydroxyl ( OH) radicals.in reactions between some Cr(V) complexes containing biologically important ligands and hydrogen peroxide (H2O 2 ). This work was undertaken because while the reduction of Cr(VI) to lower oxidation states has been suggested as a key step in the mechanism of Cr(VI) toxicity, the reaction· mechanism is not yet clear. 1 Mutagencity has been well documented for Cr(VI) via various bacterial assays, while Cr(III) has been shown not to be mutagenic.2 • 3 Since it has been reported that compounds containing Cr(VI) do not react with isolated DNA,4 the reduction of Cr(VI) by other cellular constituents has been thought to be important in the mechanism of Cr(VI) induced DNA alteration.1·4 • 5 For cellular systems earlier studies include those on the reduction of C~(VI) by microsomes,6-8 rat liver DT-diaphorase,9 and aldehyde oxidase. 10 Regarding the reduction mechanism, Jennette used ESR spectroscopy to show that a long-lived Cr(V) complex is formed as an intermediate in the microsomal reduction of Cr(VI) in the presence of NADPH.8 She postulated that Cr(V) is the ""ultimate"" carcinogenic form of chromium compounds. This conclusion has led to many further investigations of the formation of Cr(V) in the reduction of Cr(VI) under biologically relevant conditions.11 - 19 More recently, however, it has been suggested that oxygen-derived radicals generated during the Cr(VI) reduction are the species responsible for the DNA alteration.20.2• To the best of our knowledge, however, no information is available on the generation of such radicals in the reduction of Cr(VI) under biologically relevant conditions, except some preliminary results on the glutathionyl (GS·) radical formation in the reduction of Cr(VI) by glutathione (GSH). 11 - 19 We, therefore, undertook a systematic investigation of the reaction of Cr(VI) with NAD(P)H, GSH, ix-hydroxycarboxylic acids, and H2O 2 • NADPH was chosen as a model reductant because of its ubiquitous existence inside the cells, its critical role in the enzymatic Cr(VI) reduction,1·6-9 its representation of important cellular Cr(VI) reductants, and its ability to reduce other metal ions.22 GSH was chosen as another model Cr(VI) reductant because GSH also exists inside cells, it represents another important category of cellular Cr(VI) reductants, the thiols, and it also plays an important role in the Cr(VI) toxicity .1• 1 ""- 19.i3.i4 For further clarification, we also studied the reaction of Cr(VI) with several '1'.-hydroxycarboxylic acids in the presence of H2O 2 since these acids are definitively known to reduce Cr(VJ) to form stable, isolable Cr(V).25 .2 6 The results obtained indicate that Cr(V) complexes, produced in the reduction of Cr(VJ) by cellular reductants, react with H2 O 2 to generate ·OH radicals, which might be the initiators of primary events in Cr(VI) carcinogenicity."

Jan 1, 1990

The XVIth International Conference on Coal Mine Safety Research was divided into eight half-day technical sessions. In accord with the established practice of these conferences, at each session, presentation of the papers was followed by a discussion period. Questions and comments submitted in writing to the session chairman were answered or discussed by the authors of the relevant papers or by their representatives. These discussions were tape-recorded in the original language of the speaker and subsequently translated into English when necessary. Questions to which no answer was available at the time and a few comments that exceeded the scope of the session have been omitted.

Jan 1, 1975

By J. S. Kennedy, M. M. Fine

"INTRODUCTION Barite is one of the major industrial minerals whose production has increased considerably in the last 10 years. In 1935 domestic production of barite was 218,075 tons and. had increased by 1944 to 515,136 tons. 3/ Most of the primary uses for barite and barite products were developed before 1935, so the increase in barite production reflects the growth of industry in general rather than any recent developments in barite technology.The principal uses for ground and crushed barrite are as a weighting agent in heavy drilling fluids, as a filler in rubber and other materials, as a pigment and extender in paints, and as a flux in glass melt. In addition, a considerable' quantity of barite serves as the raw material for the manufacture of lithopone and barium chemicals.Specifications for barrite vary widely and depend primarily on the use to which the material is put. The primary requisites for barite used in heavy drilling muds -are that it have a minimum specific gravity of 4.2 and be very,low in soluble salts. A minimun barium sulfate content of 92 percent may be specified; but this is less important than the gravity. 4/ In addition before consumption the material must be ground to '92 percent minus 325-mesh. 5/ Lithopone and chemical manufacturers require a minimum of 94 Percent barium sulfate, a maximum of 1.0 percent iron oxide, and not more than a trace of fluorine. 6/ Barite used as fillers in light-colored products should be of fairly high grade, but the filler used in dark products may be considerably lower grade.Glass barite should contain a minimum of 96 percent barium sulfate, not more than 3 percent moisture, a maxium of 0.2 to 0.4 percent iron oxide, and not more than a trace of titanium oxide. Particle size is a matter of some importance in glass barite, also. 7/"

May 1, 1948

By Robert Lee Stahl

Comprehensive field tests were made by the Bureau of Mines at the Schwartzwalder mine near Golden, Colo., to determine whether surface geophysical techniques could be used to detect and delineate faults in uranium deposits. The tests included seismic refraction, magnetometer, electrical resistivity, airborne infrared thermal scanning, and airborne photography. Of the several geophysical techniques tested in the field, horizontal resistivity profiling with electrode spacings in the range of 10 to 15 feet was most diagnostic of faults. The method is quick, inexpensive, and accurate and can be easily used by mining company personnel to detect and delineate faults.

Jan 1, 1974

By Irving Hartmann

The Experimental Coal Mine of the Bureau of Mines has served principally as a valuable and unique testing laboratory for studies of the explosibility of coal dust and mine gas; studies of the numerous complex and interrelated chemical and physical factors that govern the ignition of coal dust and the propagation of mine explosions; and studies designed to develop measures for preventing explosions or reducing their destructive effects. These researches, coupled with educational efforts by the Bureau of Mines and enlightened safety consciousness in the mining industry, had fruitful results. This is evidenced by the remarkable reduction in the frequency of major coal-mine explosions and the number of fatalities from explosions since the Bureau of Mines was established. Despite this progress, further important unresolved problems arise; these are due in part to changes in mining conditions and methods, which have brought about increased production of fine coal dust in highly mechanized operations. To solve the new problems, research must be continued without interruption. The results of many very recent and current studies in the Experimental Coal Mine are summarized briefly, and pertinent studies by European mine-safety-research organizations are listed.

Jan 1, 1957

By K. L. Rubow

"IntroductionAir sampling for airborne contaminants requires a system for moving air, a collection method, and a procedure to determine the quantity of contaminant collected. Because occupational exposure limits and air quality standards frequently are expressed in terms of concentrations, a method of determining the volume of air sampled is also needed. The four principal components in a sampling train are shown in Figure 12-1. The inlet admits the air sample into the train; the collector(s) separates the gas, vapor, or particles from the air; the flowmeter measures the rate or total quantity of air sampled; and the pump (air mover) provides the suction required to draw an air sample through the train. Inlet sampling considerations are discussed in Chapter 21. Various types of collectors are described in subsequent chapters. Flowmeters are discussed in Chapter 7.This chapter will describe the air mover portion of the sampling train and air sampling systems that contain three or four components in a convenient package. The chapter consists of two parts. The first part contains a brief description of the different types of air movers and air sampling systems. The second part consists of tables and figures showing detailed information on a wide variety of commercially available air movers and sampling systems. ient size is filled with a liquid in which the suspected contaminant is insoluble. When the liquid is allowed to escape from the vessel, it is replaced by air from the atmosphere to be sampled. Such an air sample is an integrated sample rather than an instantaneous sample because the mass of fluid requires a finite time to empty. In fact, by employing a large vessel with controlled drainage, this method can be used to move air at low flow rates through a sample collector for extended intervals. Additional discussion of this method can be found in Chapter 17."

Dec 1, 1996

By John C. Machisak

The Nation's mining and quarrying industries have again met the annual challenge to their ingenuity--that of reducing disabling work injuries among their employees. The effectiveness of management in facing this problem and in meeting this responsibility is evident from the results of the 1961 National Safety Competition. Three hundred ninety-three or 45.3 percent of the mines and quarries participating in the competition established a new record number of participants operating throughout the competition year without a disabling work injury. Another record established in the 1961 contest was the number of participants (868) enrolled in the competition. This annual safety competition was begun in 1925 and is conducted by the Bureau of Mines, U.S. Department of the Interior. It provides for six bronze Sentinels of safety trophies which are awarded each year to the winning participant in each group. Since its inception, the competition has exerted a strong influence in the field of safety promotion. The statistical record of its accomplishments over the years gives strong support to the theory that well-organized and well- administered safety programs are effective tools to be used to reduce the number of disabling work injuries. It stimulates and holds the interest of employees and management in accident prevention. Because of this, mines and quarries participating in the contest have a more favorable safety record than those operations not enrolled.

Jan 1, 1963

By W. E. Robinson

Samples of raw oil shale and kerogen concentrates were oxidized by alkaline potassium permanganate, air, nitric acid, oxygen, and ozone to obtain information about the chemical structure of organic kerogen in oil shale. In one test, oil shale and oil-shale products were oxidized exhaustively with alkaline potassium permanganate, and the distribution of the organic carbon in the final oxidation products was determined. Comparing results of this oxidation with those obtained from other carbonaceous materials and known compounds gave information about the structure of kerogen. Alkaline potassium permanganate oxidation also was used partly to degrade kerogen into soluble products for characterization purposes. Structures present in these degradation products were indicative of type structures originally present in the kerogen. Nitric acid, oxygen, and ozone were used also for partly degrading kerogen to soluble oxidation products. Carbon-balance oxidation tests using alkaline potassium permanganate showed that Colorado oil-shale kerogen differs from many other carbonaceous materials such as coal and kerogens from other areas. Composition of the degradation products indicated that Colorado oil-shale kerogen is predominantly cycloparaffinic and saturated heterocyclic structures with some long-chain paraffinic and aromatic structures present. The ring systems may be connected through short carbon chains or bridges containing oxygen, nitrogen, and sulfur.

Jan 1, 1963

By Forest H. Majors

"INTRODUCTION The Brutch sulfur deposits were explored by the Bureau of Mines during the spring and summer of 1944. Old workings were rehabilitated and sampled, test pits and shafts were sunk, and trenches were cut through the surface alluvium.ACKNOWLEDGMENTSIn its program of exploration 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 exploratory project as soon as practicable after its conclusion. The Mining Branch, Lowell B. Moon, chief, conducts prelimi¬nary examinations, performs the actual exploratory work, and prepares the final report. The Metallurgical Branch, R. G. Knickerbocker, chief, analyzes samples and performs beneficiation tests. Both these branches are under the supervision of Dr. R. S. Dean, assistant director.Special acknowledgment is due S. R. Zimmerley, regional engineer, and Paul T. Allman, principal engineer, Bureau of Mines, Salt Lake City, for their supervisory aid, and to the metallurgical staff, Salt Lake City, for beneficiation of samples."

Oct 1, 1946

By E. S. Leaver

The gold that is not recovered by a particular process is refractory to that process. A study to determine how the refractory gold is associated in the ore constituents usually indicates the needed improvement in the process or additional methods for bettering recovery. In preliminary work, segregation of the various minerals, gangue or impurities, and data showing the reactions of each in the recovery method readily confines the refractory gold to a certain part on which extensive research can be directed. In this dissecting plan, the microscope is an important aid in locating the refractory gold but should be supplemented by chemical tests. Each ore is an individual problem until the association of the gold has been determined. Knowing the problem through the interfering minerals or elements, the solution often is only the application of part of a former known practice as an auxiliary or additional feature. In the treatment plan for most gold ores, it has been the custom to try each of the usual recovery methods or combinations thereof, accepting the best results on a basis of the lowest cost. A better plan includes knowledge of the association of the gold and the various minerals from which it is to be recovered. This presents reasonable foresight into the problems that should be expected and permits some provision for avoiding probable difficulties. The preliminary work should include: Determination of the percentage of free gold with classification showing size of gold particles to be expected; determination of the percentage of gold associated with each mineral and whether it be freed from the mineral by crushing; and an analysis of representative samples of the ore to include other valuable minerals and the form in which they occur.

Jan 1, 1934

By E. C. Fitch

This report discusses fire-resistant hydraulic fluid safety from three different directions. First, results of a survey prepared for the Fire Resistant Hydraulics Journal by the staff of the Fluid Power Research Center are analyzed. Second, operational limitations of fire-resistant hydraulic fluids are examined. Finally, laws and standards of various foreign countries are investigated. Three conclusions are derived from a close study of fire-resistant hydraulic fluid safety from these three directions. First, a significant number of experts in the fluid power industry are no in agreement about aspects of fire-resistant hydraulic fluid fire-resistance and toxicity. This indicates a need for more in depth research. Second, the use of fire-resistant hydraulic fluids involves a compromise between the decreased fire hazards and increased toxicity and machine incompatibility problems. Finlly, major foreign governmental agencies have thorough laws and standards concerning fire-resistant hydraulic fluids. These laws and standards may provide a solid framework for further international research into fire-resistant hydraulic fluid safety.

Jan 1, 1979

By W. H. Oppelt

The Federal Bureau of Mines investigated combustion of lignite in domes-tic heating equipment to obtain information on equipment performance and to evaluate testing procedures. Three types of domestic heating equipment were tested, ranging from a hand-tilled, magazine-type space heater to a ram-type overfeed stoker. Lignite was readily burned in each of the three units under various test conditions. Burnoff rates determined by adding weighed charges to the magazine were found to be in error because of shrinkage of the lignite when only a portion of the magazine capacity was consumed during a test. More reliable burnoff rates could be determined by carbon-nitrogen balances. A hand-fired magazine-type space heater (Booker heater) was operated without the furnace attachment at efficiencies to 75 pct. One test series was run with minimum supervision under conditions encountered in actual household operation. No mechanical trouble was encountered.

Jan 1, 1960

By William E. Eckard

Production of oil from a narrow shoestring sand presents problems unique in the oil industry. Especially important, from both an engineering end an economic standpoint, are the limitations imposed upon well patterns and spacings by the shape of the field. This report concerns a study of the Paola shoestring, Miami and Franklin Counties, Kane., where well density of 0.85 acre per well was not uncommon to insure profitable primary recovery in a reasonable time. However, such a great number of wells increased the operator's investment and reduced his profit considerably. It was the purpose of this study to investigate various well patterns and spacings applicable to water-flooding a shoestring reservoir and the effect of these factors upon recovery of oil and the most profitable operation of the pool. The designer of well patterns for a shoestring sand should evaluate carefully the edges of the shoestring, even though they may be considered too thin to drill. These comparatively thin edges contain large quantities of recoverable oil; moreover they are resaturated with oil as the pool is water-flooded.

Jan 1, 1951

By Kenneth G. Broadhead

The objective of this rare-earth oxalate study by the Bureau of Mines was to determine systematically by radiochemical techniques what effects, if any, could be attributed to the several variables--temperature, digestion time, acid concentration, rare-earth concentration, oxalic acid concentration, stirring, and the presence of other rare-earth ions. A Latin Square experimental design was used to evaluate statistically some of the variables. Precipitation losses ranged from near zero to about 7 percent, and mineral acid and rare-earth concentration were the predominant factors affecting completeness of precipitation. Quantitative oxalate precipitation of the rare-earth elements was achieved by controlling the experimental conditions as follows: (1) Maintaining rare-earth concentrations above 0.01M; (2) stirring the mixture several minutes after precipitation; (3) using an adequate (two to five-fold) excess of oxalic acid; (4) precipitating at room or iced temperature and digesting for at least 1 hour; (5) avoiding an excess of mineral acid and, if possible, maintaining the pH above 2.0; and (6) avoiding excess complexing agents such as EDTA (ethylenediaminetetraacetic acid). In the past 20 years research aimed at developing more efficient separation and purification techniques applicable to the rare-earth elements and yttrium has been extensive. Common to most of these procedures has been the use of oxalic acid to precipitate this group of elements selectively. However, this particular use of oxalic acid has a much earlier origin; its application in precipitating yttrium was first reported by Mosander (8)4 in 1843. Despite long and popular employment of this technique, only limited and somewhat conflicting data are available regarding the many factors affecting the degree of rare-earth oxalate precipitations.

Jan 1, 1961

By G. S. Scott. R. L. Grant

Ammonium nitrate (NH4NO3), a white crystalline chemical compound composed of 35 percent nitrogen, 60 percent oxygen, and 5 percent hydrogen, has again attracted attention, due largely to the recent catastrophe on April 16 and 17, 1947, at Texas City, Tex. The fire and subsequent explosion on the steamship Ocean Liberty, outside the harbor of Brest, France, on July 28, 1947, has fur- ther increased the interest in the properties of ammonium nitrate. As a result of the Texas City disaster, several laboratories have undertaken research to determine more certainly what causes ammonium nitrate to detonate and under what circumstances. This is not the first time that ammonium nitrate has been involved in a disaster, and its properties reviewed from the standpoint of safety. The disaster at Oppau, Germany, in 1921, which involved an equimolec- ular mixture of ammonium nitrate and ammonium sulfate, prompted an intensive study in Europe and in America. In the United States the properties of am- monium nitrate are now of especial concern because very large quantites are being manufactured and shipped in interstate commerce and abroad. Many an- monium nitrate factories, which were built during the war, will manufacture increasing amounts of this compound for use as a fertilizer. It is the purpose of this report to present a brief summary and biblio- graphy of the published experimental facts about the properties and behavior of ammonium nitrate. The reader is referred to original publications for greater details of the investigative work, and for theoretical discussions. This report also includes a survey of ammonium nitrate fertilizer of the type involved in the Texas City explosions. In the past, authorities have not always agreed on the degree of hazard involved in the manufacture and handling of ammonium nitrate, as the following quotations from the literature indicate: Munroe (82) quoted the following from Turner's Chemistry (a book pub- lished in 1835): "When this salt is exposed to fire, it liquefies, emits aqueous vapor, dries and detonates." Berthelot (14) in his book, Explosives and Their Power, 1983, wrote: "Ammonium nitrate from the point of view of its volatility, and cn account of many considerations, may be regarded as a typical explosive substance."

Jun 1, 1948

By Raghoottma S. Pandurangi, Mohindar S. Seehra, Pedro Bolsait, Bronwyn L. Razzaboni

"Surface IR (infrared) modes of crystalline and fumed (amorphous) silica particles, calcined at temperatures up to 1095°C, have been studied by Fourier transform infrared spectroscopy. The ability of these same particles to lyse cells has been measured by a hemolysis protocol. The untreated crystalline and amorphous materials differ by a factor of 40 in specific surface area, and the intensity per unit mass of the sharp surface silanol band near 3745 cm-1 in the amorphous material is an order of magnitude larger than in the crystalline material. A similar difference is observed in the lysing potential of the two materials. The intensity of the silanol band increases after calcination for both materials, reaching peak values near 500°C, followed by a dramatic drop at higher calcination temperatures, and reaching negligible values for materials calcined near 1100°C. The lysing potential data follow essentially the same pattern for both crystalline and fumed silica. These results are consistent with the hypothesis that the surface silanol groups are involved in cell lysis. Further experiments are suggested to evaluate the relationship between the surface structure of ailica particles and their potential cytotoxicity. IntroductionThe characterization of the surface structure of various allotropic forms of silica is of interest because the cytotoxicity of silica particles of respirable size has been commonly related to the chemical interaction of functional groups on the surface of such particles with the lipoproteins contained in cell membranes (1-3). It has been found that the cytotoxic potential of silica particles varies greatly with their crystalline structure (4,5), particle size (6-8), surface composition (9), and molecular surface configuration (1,10). Studies of the infrared (IR) modes of various forms of silica have been reported by a number of researchers (3 ,11-19). Several books and reviews (20-24) have dealt with the identification of functional groups on silica surfaces and the effect of heat treatment on the surface structure. The nature of the surface is said to be critical in determining the biological activity of silica dusts (3).Fourier transform infrared (FTIR) spectroscopy is a highly sensitive ·technique for identifying IR surface modes of tine particulates, and it was deemed of interest to examine the surface structure and its relation to lysing potential of two widely different types of respirable silica dust. The lysing potential of respirable dust particles has been considered a first-level test for potential cytotoxicity."

Jan 1, 1990

By D. G. Foot

The Bureau of Mines investigated energy-efficient methods for recovering potash values from process and waste brines. Laboratory pan evaporation of four chloride brines produced crude salts containing predominantly sylvite, halite, and carnallite. Six sulfate-chloride brines produced crude salts containing primarily schoenite, kainite, leonite, sylvite, carnallite, and halite. Potash grades ranged from 7.2 to 22.2 pct K20, and recoveries from 84 to 99 pct. Sylvite flotation from chloride evaporites, with amine collector, recovered 90 to 97 pct of the potash in a concentrate containing 54.3 to 60.3 pct K20. Fatty acid flotation of the high-sulfate evaporite recovered 78 pct of the sulfate minerals in a 27.8-pct-K20 concentrate. Flotation of the chloride minerals with amine collector recovered 80 pct of the potash in a 59.7-pct-K20 concentrate. Solar evaporation of 10,000 gal of brine recovered 99 pct of the potash in a crude evaporite containing 24.5 pct schoenite and 20 pct sylvite. Continuous flotation in a 100-lb/h process research unit recovered over 95 pct of the potash in schoenite and sylvite concentrates containing 28.0 and 62.3 pct K20, respectively. An economic evaluation suggested a rate of return of 3 pct for a new facility and 9 pct if. the process is adapted to fit an existing plant.

Jan 1, 1984

By Edward E. Johnson

The Bureau of 'Mines publishes in its ?Minerals Yearbook? a series of indexes on the domestic minerals industry. Among these are the index of physical volume of mineral production, indexes of stocks, and indexes of average unit mine value and implicit unit value, This report describes the material coverage of these indexes and the methods used in their construction. Detailed descriptions are given for several other mineral-oriented indexes regularly published by other government agencies. These descriptions give the index user a better understanding of what each index purports to measure and aids him in selecting the most appropriate index for his purpose.

Jan 1, 1965

By Charles S. Allbright

This report describes hydrogenation of petroleum distillate fuels in bench scale equipment and the effects of hydrogenation on the storage stability and the composition of the fuels. Two distillate fuels were hydrogenated in laboratory equipment using a commercially available cobalt molybdate catalyst. Reactor temperatures were varied from 600° to 850° F and pressures from 100 to 600 psig. Product fuels were analyzed by ASTM, Bureau of Mines, mass, and infrared methods. Hydrogenation of a catalytically cracked fuel from Oklahoma crude oil significantly improved the storage stability, reducing insoluble gum formed during 9 months of storage at 110° F from 19.0 to 1.3 mg per 100 ml fuel, average. Conversion of the olefins to other hydrocarbon types varied with the temperature of hydrogenation--at 700° to 850° F the conversion was mainly to aromatics, at 650° F about 50:50 to saturates and aromatics, at 600° F principally to saturates. Processing a fuel composed of a mixture of virgin distillate and catalytically cracked stock, both from Illinois crude, at 700° F and 200 psig effected marked improvement in stability; the buildup of insoluble gum in storage was lowered from 18.3 to less than 1 mg per 100 ml fuel.

Jan 1, 1967

By Edward E. Johnson

The Bureau of Mines publishes in its ?Minerals Yearbook? a series of indexes on the domestic minerals industry. Among these are the index of physical volume of mineral production, indexes of stocks, and indexes of average unit mine value and implicit unit value, This report describes the material coverage of these indexes and the methods used in their construction. Detailed descriptions are given for several other mineral-oriented indexes regularly published by other government agencies. These descriptions give the index user a better understanding of what each index purports to measure and aids him in selecting the most appropriate index for his purpose.

Jan 1, 1965