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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

By H. B. Humphrey, F. E. Cash

The Southern Appalachian coal field extends southward across Tennessee in a belt about 50 miles wide between the eastern and middle sections of the State. The earliest record of the production of coal in Tennessee is for 1840, and the first inspection laws were passed in 1881. In 1887, a second act of the legislature created the office of Chief Inspector, but little was done until 1891 when a new act was passed giving to the Department of Mines added duties and powers. Since that time, except for the years 1915 to 1918, com¬ prehensive annual reports have been published. Data for the tables given in this paper are taken from these annual reports, from those of the Southern Appalachian Coal Operators' Association, and from the publications of the United States Bureau of Mines, which has main¬ tained a station at Jellico, Tenn., since 1911. Complete figures for 1930 are not available yet and they are not included in the averages. The State Department of Mines, the operating companies, and the United States Bureau of Mines cooperate in accident-prevention work. It is the purpose of this report to present in uniform tables the available statistics in regard to fatal accidents in Tennessee and in the coal mines of the United States, in order that the progress in mine safety in Tennessee may be compared with that of the country as a whole, and the present period may be compared with various periods of the past, to indicate the main points of attack in the reduction of accidents.

Sep 1, 1931

By R. J. Hundhausen

The Takilma-Waldo copper district in Josephine County, Oreg., was studied by the Bureau of Mines from September 1950 to April 1.951 and from December 1953 to April 1954. Funds for the investigation were provided by the Bureau of Mines and the California-Oregon Power Co., Medford, Oreg., on a cooperative basis. The copper mines in the district are credited with a total production of ore worth $1,700,000. Since 1933 the mines have been unproductive and, except for minor exploration, largely inactive. The history of the district indicates that the copper deposits were mined principally during periods of high metal prices.

Jan 1, 1956

By G. L. Hundley

An anhydrous chlorination process has been developed by the Bureau of Mines for the production of copper, ferric oxide, and sulfur from chalcopyrite. The first part of the process is a chlorination step in which elemental sulfur and a mixture of iron-copper chlorides are produced. This paper describes the second step of the process in which the copper and iron chlorides are reacted with oxygen to selectively convert the iron chloride to ferric oxide and chlorine leaving the copper in the chloride form. The chlorides are pulverized and dropped countercurrent to a flow of oxygen in a vertical 20-cm-diam. reactor at 800° C. By leaching with brine, the copper chloride may be separated from the insoluble iron oxide and reduced to copper powder by electrowinning. It has been demonstrated that 70 to 80 pct of the iron can be converted to oxide in a single-stage operation with a chlorine content in the offgas of 80 pct. After removal of the oxygen, this chlorine could be recycled to the chlorination step. A two-stage operation will convert 98 to 99 pct of the iron in the mixture to insoluble oxides. The offgas from the second stage contains 70 pct chlorine.

Jan 1, 1974

By T. L. Iapalucci

To determine the behavior of chlorine in coal combustion, the Bureau of Mines burned 10 chlorine-containing coals, high-, medium-, and low-volatile, in a laboratory-scale pulverized-coal combustor. At carbon-combustion efficiencies of 94 to 98 percent, 1.6 to 7.1 percent of the chlorine or an average of 4 percent of the chlorine in the coal was retained in the ash; the balance, predominantly hydrogen chloride, was evolved in the combustion gas. Sulfur retention in the ash ranged from 2.3 to 10.7 percent or an average of 6.3 percent, Addition of alkali and alkaline earth carbonates to a medium-volatile coal containing 0.27 percent chlorine by preferentially reacting with the chlorine increased the Cl/S atom ratio in the ash, Lithium carbonate addition at 0.43 percent and K2C03 at 1.59 percent increased the C1/S ratio in the ash from 0.2 to 0.6.

Jan 1, 1969

By H. E. Powell

A laboratory mineral-dressing investigation was conducted by the Federal Bureau of Mines on four limonitic and four sideritic iron ores from the North Basin of the east Texas iron-ore district. The samples, composited from drill cores, were considered representative of the iron-ore reserves of the area. The objectives of this research were twofold: (1) To devise a mineral-dressing method whereby the yield from currently mined east Texas iron ores might be increased and the grade improved, and (2) to extend such treatment to include the lower grade ferruginous materials that are not amenable to beneficiation by simple washing and, therefore, are not being exploited. Of the mineral-dressing methods used in this investigation, magnetic separation of roasted are was shown to be the most effective. Results show that, by this method, a laboratory recovery of 82 percent of the iron is attainable at a grade surpassing that obtained by current plant practice and that both limonite and siderite are amenable to concentration by the process. The existence of large deposits of iron are in eastern Texas has been recognized for over 100 years. These ores were first exploited during the Civil War and were mined intermittently until about 1911. From that time until 1944 when the Defense Plant Corporation financed the erection of three blast furnaces to use these east Texas ores, production was almost at a standstill.4/

Jan 1, 1960

By N. S. Dalal, A. H. Hoffman, X. Shi, D. E. Banks, J. K. H. Ma, Y. Rojanasakul

Excessive production of reactive oxygen radicals by alveolar macrophages is proposed to play an important role in oxidative lung injury. A major product of oxygen radical formation is the highly reactive hydroxyl radical (•OH) generated via a biologic Fenton reaction. In addition to its known ability to induce lipid peroxidation, recent studies have suggested that the •OH may exert its cytotoxic effect through the alteration of [Ca2+], homeostasis. To test this potential mechanism as well as to investigate the relationship between •OH and Ca" overloading in cytotoxic injury, isolated rat alveolar macrophages were exposed to externally generated radical system, H2O2 (0.01 to 1 mM) and Fe (1 mM) and their [Ca2+] levels and cell injury were monitored using quantitative fluorescence microscopy with the aid of the specific Ca" indicator, Fura-2, and membrane integrity indicator, propidium iodide. Electron spin resonance measurements using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) confirmed the production of the .OH radical by this system. Upon the addition of the radicals, the macrophages displayed a rapid initial rise in [Ca2+] which was followed by a slower but more pronounced [Ca2+], elevation that reached a level 3 to 5 times higher than the basal level. This process preceded cell death as evident by nuclear propidium iodide fluorescence. Depletion of extracellular Ca" inhibited both the [Ca2+], response and cell injury. Preincubation of the cells with the Ca" channel blocker verapamil or .0H radical scavenger mannitol similarly inhibited the [Ca2+], rise and loss of viability. Firefly luciferase assay of cellular ATP content demonstrated that the alterations in [Ca2+], following .0H treatment preceded the depletion of ATP. Changes in membrane potential caused by Na* substitution with K* had no significant effect on either the unstimulated or stimulated [Ca"], levels. Taken together, these measurements indicate that .OH-induced injury in alveolar macrophages is associated with the alteration in [Ca2+], homeostasis. The mechanism of •OH-induced [Ca2+] loading is not due to nonspecific membrane damage or energy depletion, but mainly due to an increase in Ca2+ influx through Ca2+ selective channels. This Ca2+ over-load state as well as energy depletion caused by the oxidant may activate certain cellular degradative processes leading to cell injury and death.

Nov 1, 1995

By R. H. Nicholas

Shuttle cars have undeniably proved their worth as a means of transporting coal underground; however, several factors have arisen in connection with their possible improvement. This report .discusses the effect of shuttle cars that employ rough-tread and smooth-tread tires on mine roadbed, the amount of dust thrown into suspension by the use of such tire treads, and the service rendered by each type of tire. Involved, also, in this study are observations on the use of different amounts of calcium chloride on the haulageways.

Jan 1, 1949

By Ernesto Villaescusa, Andres Brzovic

Rock masses of the primary copper ore at the El Teniente Mine are very competent and massive. The rock mass contains almost no open discontinuities. Nevertheless, there is a high frequency network of small discontinuities coupled with widely spaced faults. A data collection campaign designed to characterize the rock structure was recently implemented. The results show that conventional analysis in terms of discontinuity frequency does not predict differences between two studied sectors. However, when an empirical definition of a weak discontinuity is applied, appreciable differences between the two sectors appear in terms of discontinuity frequency and predicted in situ block size distributions. These differences are in accordance with actual observations at the mine site. Due to the geological features of the primary copper ore, rock mass classification schemes cannot be readily applied to characterize these rock masses.

Jan 5, 2007

By T. C. Campbell

This Bureau of Mines publication presents an analysis of information related to the transportation of bituminous coal by unit trains and slurry pipelines. Even for short hauls from mines to markets, transport costs frequently account for between one-third and one-half of the delivered price of coal. Minimizing these costs has become an even more critical objective for hauls from the western mines than for hauls from farther east. Factors related to minimizing costs and transporting the western coal receive special attention. Although no general rule of preference is likely to be developed that can be applied to all shipments, both rail and pipeline service will be needed on an increasing scale. The study should provide useful background information and analysis for government and industry in approaching investment decisions in the mining and transportation industries.

Jan 1, 1975

By M. S. Seehra, R. S. Pandurangi

"The interaction of amorphous silica particles with several hydrogen bonding agents (H2O,, C2H,OH, C,H,NO) was investigated by monitoring the changes in the bulk and surface IR vibrational modes of silica using photoacoustic spectroscopy, It is argued that the intensity of the silanol band at 3747 cm-1 provides (an inverse) quantitative measure of the interaction of surface groups, along with the shift in the broad hydroxyl band, the interaction following the order C,H,NO > C2H2OH > H2O.The use of IR spectroscopy to study the adsorption on solid surfaces is well documented in the literature,"" For example, hydroxylation of a clean silica surface results in the formation of the free silanol group Si-OH, with a sharp IR band near 3747 cm-1. Further hydroxylation produces a broad band near 3500 cm-1, which is believed to result from various hydrogen-bonded silanol bands leading to a multilayered surface structure of few nm.3-6 Earlier studies had indicated a relationship between the surface silanol band and various chemical activities of silica such as cytotoxicity,7-9 catalysis,10-12 and others.13 Recent studies from our group14-in which the intensity of the silanol band and cytotoxicity of silica, heat-treated at various temperatures up to 1095°C, were investigated-have provided a strong correlation between cytotoxicity and intensity of the silanol band.Coating of silica by PVPNO (polyvinyl-2-pyridine N-oxide with the empirical formula C7H8N0), a strong hydrogen bonding agent, is known to reduce the cytotoxicity of silica, presumably by chemically blocking the silanol groups from phospholipids.15 This interaction of the hydrogen bonding agents with the silica can be studied by IR spectroscopy, and Knozinger16 and Rouxlet and Semples17 have used transmission IR spectroscopy to study the effect of various chemicals on the surface IR modes of silica. However, one of the major disadvantages of transmission IR spectroscopy is that the sample preparation (grinding and mixing with KBr and pelletizing) usually distorts the surface modes (see, e.g., Ref. 14) and there is always a doubt about the effect of the sample preparation on the measured properties, In recent years, photoacoustic (PA) spectroscopy has become the technique of choice for studying the IR spectra of samples in their natural state, since no sample preparation is necessary.18,19 Moreover, according to a recent paper,20 the relative intensity of the surface modes in PA spectroscopy of silica particles is much higher than that in transmission FT-IR spectroscopy. Consequently PA spectroscopy is ideal for studying the surface chemistry, In this work, we have used PA spectroscopy to investigate the interaction of three hydrogen bonding agents (C7H8NO, C2H5OH, and H20) with the silica surface by monitoring changes in the surface IR modes, Our results show that the surface IR modes get perturbed to a larger extent than the bulk IR modes in interaction with the hydrogen bonding agents, Moreover, whereas in the earlier studies, the shift of the broad silanol band near 3500 cm-1 was used as a measure of the interaction with hydrogen bonding agents,16,17 here we show that the relative decrease in the intensity of the sharp silanol band near 3747 cm-1 also serves as a quantitative parameter for the relative surface coverage and surface modification, Details of this work are given below,The Cab-O-Sil samples of silica used here were obtained from the Cabot Corporation of Tuscola, IL, In our earlier studies,14,20 we have shown these particles to be amorphous and about 0.05 am in size, For coverage of these particles with H20 and C2H50H, the following procedure was employed. About 5 mg of silica was mixed with 50 mL of the liquid (H2O or C2H5OH) and refluxed for one hour, The remaining liquid was allowed to evap¬orate to dryness and 1 mg of the treated sample was used to collect the PA spectra. In the case of PVPNO, the amount that binds to Cab-O-Sil is taken from the data on quar"

Mar 1, 1992

By W. P. Diamond

The Bureau of Mines has been involved in the drilling of vertical, horizontal, and directional coalbed gas drainage boreholes for mine safety since 1964. In that time, boreholes have been drilled in most of the major coal regions of the United States under a wide variety of geologic conditions. Many of the geologic conditions that occur in the coal measures are detrimental to gas drainage; others may be beneficial. Analytical techniques to determine the gas content of coal samples and evaluate regional trends of gas distribution have been developed. Drilling techniques that maximize the acquisition of coalbed gas data and geologic information have been determined. Although some of the geologic factors influencing the placement and potential success of coalbed gas drainage boreholes have been reported in papers on individual projects, a complete, systematic compilation has not previously been available. The objective of this paper is to pro- vide information on specific geologic factors that should be considered prior to, during, and after the drilling of coalbed gas drainage bore-holes. Many of the commonsense considerations that have been learned through many years of Bureau of Mines experience, but have generally not been reported formally, are included for those who may be considering coalbed gas drainage drilling for the first time, or who have not had the opportunity to encounter a substantial number of geologic situations.

Jan 1, 1982

By A. Viksne

A series of tests were conducted by the Bureau of Mines to determine the best means of reducing noise generated by the detonating cord that is utilized for trunklines in quarry blasting. Ten different types of detonating cord were tested and evaluated for their acoustic qualities. The results of the investigation showed that noise levels produced by "low-core-load-per-foot" detonating cord "not covered" were lower than those produced by "high-core-load-per-foot" detonating cord covered with 6 inches of unconsolidated material.

Jan 1, 1972

By Edward L. McHugh

The appraisal of mineral resources of the Challis National Forest, Idaho, by the U.S. Bureau of Mines, was made so that the mineral resources of the forest could be appropiately considered in land use planning. Information from this study is intended to tip the U.S. Forest Service to incorporate mineral resource data into forest plans The study was done in conjunction with the U.S. Geological Survey, which released a companion report on the geology and mineral potential of the Challis National Forest in 1989. This summary report is derived from a more detailed USBM Open-File Report (MLA 6-91) that includes descriptions of mines and prospects, commodity profiles, and development cost models. Since the 1860's mines within the Challis National Forest have produced mineral commodities worth more than $590 million at current (1989) commodity prices. Identified mineral resources have a gross value of about $2 billion at current prices, including 8 strategic or critical minerals. The U.S. Bureau of Mines study identified and described 723 active and inactive mineral properties within the forest. Mineral properties with identified resources were evaluate to determine their economic significance, and an assessment was made of the feasibility of mineral development. Of the 2,516,191 acres in the Challis National Forest, about 390,000 acres were classified as having mining development interest. Commercially important mineral production, mainly of molybdenum, gold, and silver from the Challis National Forest is likely for the foreseeable future.

Jan 1, 1991

By A. Visnapuu

The Bureau of Mines, as a part of its goal to minimize occupational hazards associated with mining and mineral processing operations, has developed and field tested a compact exhaust air muffler for mechanized, jumbo-mounted pneumatic rock drills. The muffler is constructed of 1/8-inch sheet steel and has nominal dimensions of 1-3/4 by 9 by 13 inches. A directed air passage, flexible neoprene baffles, and an expandable slit-type outlet are incorporated to reduce drill exhaust air noise and eliminate muffler icing. Field tests in actual mining operations showed a l5-dbA reduction in exhaust noise and an 8-to 12-dbA reduction in overall drilling noise with no icing problems or decrease in drill performance. Data are presented on muffler construction, laboratory, and field test results.

Jan 1, 1979

By D. D. Fischer

Recovery and separation of molybdenum and rhenium from a process solution was accomplished by a technique developed by the Federal Bureau of Mines involving a combined solvent extraction and activated carbon adsorption procedure. The processing sequence required treatment of the solution with S02 to reduce the chlorate ion and adjust the pR prior to solvent extraction of molybdenum and rhenium with a tertiary amine. Molybdenum and rhenium were stripped from the organic phase with an NH40H solution, and the strip solution was then passed through activated carbon to preferentially adsorb the rhenium. After washing entrained molybdenum from the column with a brine solution, rhenium was eluted with an MeOH-H20 mixture. The activated carbon was regenerated with water. Molybdenum was recovered as (NH4)6Mo7024 by evaporating the column effluent. Rhenium in the column eluate was reextracted with a tertiary amine, stripped from the organic phase with dilute NH40H, and recovered as NH4Re04 by evaporating the strip solution. The final (NR4)Re04 product contained < 80 ppm impurities. Sodium sulfate was crystallized from the first solvent-extraction raffinate by lowering the solution temperature to 0° C. Precious metals contained in the original process solution were adsorbed onto the activated carbon.

Jan 1, 1975

By Sidney Katell

This report covers the period January 1963 through December 1963; it is a continuation of the series that began with the publication of Information Circular 7516 in October 1949. Also, it is the fifth in a series of reports prepared under a cooperative agreement between the Bureau of Mines and the American Association of Cost Engineers. The agreement provides for the publication of an annual cost bibliography with the work load involved in the preparation shared equally. The abstracted articles, concerned with all facets of cost engineering in the field of chemical and petroleum plants and related subjects, are from the following sources: 1. American Association of Cost Engineers Bulletin. 2. Bureau of Mines Information Circulars. 3. Bureau of Mines Reports of Investigations. 4. Chemical Engineering. 5. Chemical Engineering Progress. 6. Chemical Week. 7. Coal Age. 8. Coal--Today and Tomorrow. 9. Coal Utilization. 3/ 10. Cost Engineering. 11. Hydrocarbon Processing and Petroleum Refiner. 12. Industrial and Engineering Chemistry. 13. Nucleonics. 14. Oil and Gas Journal. 15. Petroleum Management. 16. World Oil.

Jan 1, 1964

By Sidney Katell

This report covers the period January 1963 through December 1963; it is a continuation of the series that began with the publication of Information Circular 7516 in October 1949. Also, it is the fifth in a series of reports prepared under a cooperative agreement between the Bureau of Mines and the American Association of Cost Engineers. The agreement provides for the publication of an annual cost bibliography with the work load involved in the preparation shared equally. The abstracted articles, concerned with all facets of cost engineering in the field of chemical and petroleum plants and related subjects, are from the following sources:

Jan 1, 1964

By Harold J. Rose

The economic situation in Switzerland during recent years has resulted in theoretical studies , engineering development work , and many commercial installations of ingenious methods for using energy more efficiently . The purpose of the present investigation was to learn of recent Swiss developments for the more effective use of coal , which comprises 98.9 percent of the romaining known mineral - fuel reserves of the United States .

Jun 1, 1947

By F. P. Haver

Because State and Federal agencies have limited the amount of sulfur oxides that can be discharged to the atmosphere, most copper smelters plan to convert the S02 in offgases to sulfuric acid. In some cases, however, it might be preferable to use a nonsmelting method to fix the sulfur in the form of a discardable product. Research by the Federal Bureau of Mines has shown that sulfur in copper concentrate can be converted into insoluble anhydrite (CaS04) by roasting the concentrate with lime (CaO). After leaching the calcine to recover metal values, the residue may be discarded without harm to the environment. The process can use a rougher flotation product, thus reducing separation costs and saving valuable minerals (for example, molybdenite) that are now lost in making cleaner concentrate. In tests, rougher concentrate was pelletized with the theoretical amount of lime and roasted for 1 hour in a 6-1/2-inch-ID by 11-foot-long rotary kiln at 700° C. Sulfur retention was about 97 percent. Leaching the calcine with 20 percent RCI extracted approximately 99 percent of the copper, 73 percent of the iron, and 91 percent of the molybdenum. After the molybdenum was removed from the leach solution by adsorption on activated carbon, copper with a purity in excess of 99 percent was obtained by cementation on sponge iron. The strip solution then could be spray-roasted at 500° C to recover the RCI for recycle and obtain F2O3 as a byproduct.

Jan 1, 1975