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By N. S. Dalal, X. Shi

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

Jan 1, 1990

By S. R. Zimmerley

[In the course of a flotation investi~ntion, a siliceous gold ore was ground ir, R 'ball mill to ~inils 300-mesh. It mas found that the small mount of zlus 300-~esh mnterial had a go12 assw approximately twice that of the oricinal ors, md thst this oversize ~roduct also contained much abra?.ed iron. >!oreover, the gold assay of the abraded iron, which was separated ma~etic-dl:;, wno ei::ht tiaes tkat of the ore. These facts sug,~estsd th~t sone r3laticnshin existed between the abnormally high .gold content and the preseace of abrade4 iron. It was ciecided, therefore, to investl~ate furtkor ths acsoclation of the ;old nith the iron abraded from the balls durir-g grincing. As a nrelininary ex?rr>hent, a samy?le of siliceous gold ore 786 grolznd for 1-1/2 hours i;l 3 ball mill and the nuln was divided into two products electri~mag-etically. The racult s follow: ]

Jan 1, 1937

By BUREAU OF MINES

In July, 1918, the attention of the Secretary of the Interior WItS called to the rapidly increasing cost of producing gold and the declining output of that metal in the United States. Realizing the importance of the gold-mining industry, the Secretary appointed a. committee, consisting of Hennen .Iennings, chairman, J. H. Mackenzie, and Charles Janin, of the Bureau of Mines, and H. D. Me- Caskey and F. L. Ransome, of the United States Geological Survey, to,make a thorough study of the gold-mining situation in the United States. The study was to cover the increased cost of recovery and the decreased output of gold, and to consider the different measures that had been proposed to relieve the industry and stimulate production. This report embodies the results of the investigation and study made by the committee. The report presents statistical data compiled from various sources, showing the production of gold in the United States and other countries, with comparative figures for coal, iron, and other mineral products, and describes the sources and distribution of gold output in the United States. It discusses the relation of gold' production to finance and credit, the causes for the decline in gold output, and measures for the relief of the industry. The Interior Department publishes this report in the belief that the widest publicity possible should be given the findings of the committee in order that attention may be directed to the serious conditions revealed therein, and in the hope that wide discussion of the subject may result in some action being taken that will aid in upholding the gold standard ,and the gold industry.

Oct 30, 1919

By Vernon F. Swanson

Several laboratory flotation tests were conducted by the Bureau of Mines on a sample of unweathered diorite from the B. F. Camden property, Amherst County, Va. Results showed that an ilmenite concentrate analyzing 45.5 percent Ti02 (titania), 0.07 percent P205 (phosphorus pentoxide), and 2.21 percent Si02 (silicon dioxide) could be produced from a feed containing 7.72 percent Ti02 and 3.94 percent P205. Ti02 recovery in the concentrate was 47.6 percent in a batch test. The weathered saprolite material overlying the diorite required scrubbing and desliming to remove argillaceous material and preliminary flotation of apatite followed by flotation of ilmenite. The resulting concentrate analyzed 47.3 percent Ti02, 0.19 percent P205, and 0.99 percent Si02 from a starting feed of 8.99 percent Ti02 and 3.37 percent P205; TiO2 recovery was 54.5 percent.

Jan 1, 1963

By Bertrand L. Johnson

Barite, the natural sulfate of barium (BaSO4), is the most important barium mineral. Normally it is white (opaque to translucent), but impurities sometimes render it yellow, gray, blue, brown, red, or black. Brown or red stains are commonly caused by iron oxide. Barite is unusually heavy (specific gravity, about 4.5); in fact, it is one of the heaviest of the nonmetallic minerals. It is brittle and fractures unevenly. The hardness of barite ranges from 2.5 to 3 but is usually about 3. It can be scratched by a copper coin. Pure barite contains 65.7 percent BaO and A.3 percent S03. Much of the crude barite ore mined, however, contains impurities; thus it has a lower content of barite and consequently less barium oxide. Commercial analyses show its total BaSO4 content. Barium also occurs in nature as the mineral witherite (BaCO3), which, however, is not common in the United States, and commercial deposits have been found only in California. Witherite is a yellowish-white, light-gray, or Kite mineral with a specific gravity of about 3, a hardness of 3 to 4, and an uneven to subconchoidal fracture.

Jan 1, 1941

By Kenneth L. Cashdollar

While underground coal technology has progressed over time, regulations on coal dust have not kept up ? the most recent rules are more than 80 years old. The National Institute for Occupational Safety and Health and the Mine Safety and Health Administration conducted a joint survey recently on coal particle ranges as measured in US coal mine samples. In underground coal mines, dust explosions are prevented by the addition of enough rock dust (usually limestone) to make the total dust mixture inert. The rock dust acts as a heat sink for the dispersed dust mixture by reducing the temperature below the value needed to propagate an explosion. Federal regulations require 65% in combustible content in intake airways and 80% incombustible content in return airways, where the coal dust is assumed to be finer in size. The regulations also require an additional 1% incombustible for each 0.1% methane in the ventilating air in intakes and 0.4% additional incombustible for each 0.1% methane in returns.

Jan 1, 2008

Limestone formations in the United States can be subject to relatively high horizontal stresses due to the existence of tectonic loading of the limestone strata. Underground limestone mines use the room-and-pillar method, in which 12- to 18-m-wide rooms are typically excavated. The stability of these excavations can be compromised by the horizontal stress, resulting in a rockfall hazard. Rockfalls are the cause of 15% of all reportable injuries in underground limestone mines. Horizontal stress related damage can occur in the form of guttering along one or more sides of an excavation, roof beam buckling or oval shaped roof falls, with the long axis perpendicular to the major horizontal stress. Numerical analyses show that the pillar layout and orientation of the mine workings have an effect on the horizontal stress distribution within the roof. The effects of high horizontal stresses can be mitigated by orientating the heading development direction parallel to the maximum horizontal stress, reducing the number of cross-cuts and offsetting the cross-cuts to limit the potential lateral extent of horizontal stress related roof falls. The modeling approach described in this paper can be used as a tool to evaluate potential roof failure and optimize the stability of room and pillar layouts.

Jan 1, 2008

By Sean Gallagher, Rhys Llewellyn, Jay Mattos

This paper contains the results of an examination of accident, injury, employment, and production information reported to the U.S. Department of Labor's Mine Safety and Health Administration (MSHA) and provides information on some of the measures longwall mine operators are using to prevent accidents In all industries, technological advances play a key role in determining those who will survive as competitive participants in an increasingly global marketplace. While mining is among the most basic of industries, technological change is neither unfamiliar nor unwelcome to miners. Historically, technological advances in mining, particularly coal mining, have tracked closely with fluctuations in demand. In the early 1900's, coal accounted for more than three quarters of all the fuel consumed in the U.S. To meet this tremendous demand, underground cuffing machines were introduced, resulting in faster, more efficient coal extraction. Transporting coal to the surface, however, remained labor intensive. In the 1920's, nearly all underground coal was still being hand loaded. Demand for coal then declined as the price of oil, natural gas, and electricity became competitive. In the late 1930's and throughout the duration of World War II, coal demand and production was high. By 1940, more than half the coal mined was being mechanically conveyed to the surface. In 1948, the continuous mining method was introduced in the U.S., further accelerating the extraction process. By the 1950's and 1960's, however, coal production again declined as railroads converted to diesel fuel and gas and oil provided a larger share of the home heating market. Underground coal mines required even more mechanization to remain competitive as an energy source. The first longwall system was introduced in 1960. By 1995, longwalls were producing more than 189 million tons of clean coal annually, surpassing continuous mining production for the second straight year. The mining of coal and other materials has not come without a huge loss of life and considerable human suffering. More than 103,000 workers died from injuries in U.S. mines in the last 85 years. Between two and three thousand miners died each year from the turn of the century until 1931, many from underground fires and explosions. The U.S. has witnessed a tremendous drop in fatalities in underground coal mines. Credit for that is due to safety inspections and enforcement activities, better safety awareness and practices among management and labor, improved ventilation, the use of safer equipment, and increased mechanization which removed many miners from the hazards at the face and also reduced the size of the mining work force. There is little doubt that longwall mining has greatly increased underground coal mine productivity. The degree to which longwall mining has contributed to a safer work environment for underground miners is more difficult to ascertain.

By G. R. Palmer

Preliminary studies by the Bureau of Mines were conducted to determine the feasibility of a multiple-compartment, ion-exchange (MCIX) column simulator for examining the effect of multiple-orifice plates in the column. A rectangular, five-orifice, three-compartment, MCIX simulator with a cross-sectional plate area of 0.66 ft2 was used for the investigation. Orifices with open areas of 1, 3, and 5 percent were used with various operating conditions. The study was separated into three separate sections: (1) solution flow effect, (2) fluidization effect, and (3) resin transfer effect. The solution flow and fluidization studies showed that for solution flow rates of about 3 gpm/ft2, a I-percent open area plate functioned best, while at solution flow rates of 9 and 15 gpm/ft2, the best open areas were 3 and 5 percent, respectively.

Jan 1, 1981

By X. Shi, K. S. Kaspnak

"The generation of free radicals from reactions of nickel (Il)-thiol complexes with molecular oxygen and model lipid hydroperoxides was investigated by electron spin resonance (ESR) utilizing 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap. Incubation of nickel (II) [Ni(II)) with cysteine in an aerobic environment generated hydroxyl (·OH) radical, which then reacted with cysteine to generate a carbon-centered alkyl ( · R) radical. Radical generation was inhibited under a nitrogen atmosphere. Model lipid hydroperoxides, cumene hydroperoxide, and I-butyl hydroperoxide enhanced the yield of these radicals and also generated an alkoxyl (·OR) radical. Radical yield decreased by approximately half under a nitrogen atmosphere. Although histidine did not cause radical formation in the reaction between Ni(II) and cumene hydroperoxide under aerobic conditions, the addition of histidine to a mixture containing Ni(ll), cysteine, and cumene hydroperoxide under the same experimental conditions increased the yield of · R radical but lowered the yield of ·OR and ·OH radical adducts. It thus appears that histidine caused the ·OH attack to be more site-specific. Similar results were obtained utilizing 1-butyl hydroperoxide. Penicillamine or N-acetylcysteine yielded similar results except that under aerobic conditions, reaction between Ni(ll) and N-acetylcysteine without hydroperoxide did not generate a significant concentration of free radicals. Under the same experimental conditions, cystine did not generate any detectable free radicals, suggesting an important role of the -SH group in Ni(II)-mediated free radical generation. The results indicate that free radical generation from the reaction of Ni(Il)-thiol complexes and molecular oxygen, and/or lipid hydroperoxides, may play an important role in the mechanism(s) of Ni(II) toxicity and carcinogenesis. INTRODUCTIONWhile nickel is a well-recognized carcinogen [l, 2]. the underlying biochemical mechanisms remain unclear (3, 4). Recent studies suggest that these mechanisms may involve oxidative DNA damage through free radicals, especially the hydroxyl (•OH) radical [5-13]. The mechanisms of nickel carcinogenicity and toxicity may also involve lipid peroxidation [14-21]. Unlike ferrous ion [Fe(II)], the Ni(II) cation itself does not directly react with 02, H2O2, or lipid hydroperoxides to generate free radicals [12, 21]. However, it has been reported that Ni(II) complexes with certain synthetic oligopeptides, e.g., tetraglycine or glycylglycylhistidine, make Ni(II) reactive with 02. This reaction results in transitory formation of Ni(III) and degradation of the organic ligand via free radical reactions [22]. Such Ni(II)-peptide complexes are also capable of reacting with H2O2 to produce oxygen free radicals [11, 12]. Although the cellular environ¬ment may not contain these particular peptide ligands that are known to render Ni(II) redox active in vitro, it does contain a variety of oligopeptides that are capable of forming Ni(II) complexes at physiological pH, and thus may facilitate Ni(II) redox activity in vivo. These oligopeptides include glutathione (y-L glutamylycysteinylglycine), carnosine (homocarnosine (y aminobutyryl-L-histidine), and anserine ( B-alany1-3-methyl-L-histidine)."

Nov 1, 1995

By J. P. Bennett

Based on previous Bureau of Mines research indicating that improved high-temperature properties could be achieved for periclase refractories through chemical additions, the Bureau investigated the properties of full-size bricks produced from chemically modified periclase refractory grains and the suitability of making such chemical additions to Mg(OH)2 slurries prior to production of the periclase grains. In full-size brick testing, strength values, both hot and cold, for the optimized bricks were superior to those for a commercial 98-wt-pct-MgO refractory. The best results were obtained for a natural magnesite with an adjusted CaO:Si02 (C:S) ratio of 3.0 and a 1.0-wt-pct addition of Zr02 and for a seawater periclase with an adjusted C:S ratio of 2.5 and a 0.5-wt-pct addition of Mn02. For samples produced from chemically modified Mg(OH)2 slurries, additions of both Mn02 and Zr02 and an increase in C:S ratios produced significant increases in hot flexural strength, similar to those resulting from chemical additions made to periclase grains. The most effective modifications were additions of Mn02 to brine-derived periclases having a C:S ratio adjusted to 3.0. These results on chemically modified magnesia refractories indicate that such material could potentially substitute for magnesiachrome refractories containing imported chromite.

Jan 1, 1984

By Henry Kreisinger, F. K. Ovrrz, C. E. Augustine

The Bureau of Mines is conducting investigations to determine how fuels belonging to or for the use of the United States Govern- ment can be utilized with greater efficiency. As a result of these investigations a number of reports have been published, each report treating of one phase of fuel utilization. A list of these publications is given at the end of this bulletin. The efficient utilization of coal depends on the correct design of furnaces and on their proper operation. To attain both of these conditions a knowledge of the fundamental principles of combus- tion is necessary. Therefore, the study of the combustion of coal in industrial furnaces has been made a part of the bureau's fuel in- vestigations. The desirability of investigating the fundamental principles of combustion was suggested by the study of a large number of steam- ing tests made by the fuel-testing division on coals from all of the more important fields in the United States. The results of these tests have been published in Bulletin 325 of the United States Geological Survey and in Bulletin 23 of the Bureau of Mines. As a result of that study a plan to investigate the combustion of coal in a special apparatus in which all conditions could be controlled was presented to the National Advisory Board for Fuels and Struc- tural Materials at its meeting of April 10 and 11, 1906. The plan received the approval of the board, and since the establishment of the experiment station of the Bureau of Mines at Pittsburgh the investigation of the combustion of coal has been carried on intermit- tently. The history of these investigations is given in Technical Paper 63.

Jan 1, 1917

By Harold J. Miller

Loading and haulage of run-of-mine ore is frequently the highest cost in underground mining operations. These costs can be significantly reduced by use of belt conveyors, a common practice in coal and similar soft miner ii mines. This is particularly true if oversize ore and rock can he eliminated prior to conveying; thus producing a demand for crushers near the production areas. Portable feeder-breakers are extensively used in conveyorized mines, but no suitable, equivalent equipment, is available to provide these benefits to hard rock mines of low to medium headroom. A hard rock crusher capable of easy movement and readily disassembled would allow use to belt conveyors and could improve the general safety and productivity of any underground ore hauling system. This report summarizes proposals and findings made in conjunction with the newly designed M-44 Low Head Portable Crusher which is believed well capable of meeting the requirements of a "portable, underground, hard rock" machine as previously defined in earlier reports. Data gathered by use of the 1/4 Scale Model of the M-44 has substantiated and verified the concept sufficiently to justify construction of a full-size machine for further testing under actual mine conditions.

Jan 1, 1978

By E. L. Garton

[Analyses of may crude oils produced in Louisiana are included in reports that t have boon published by the Bureau of Mines. The first report, giving, analyse of 6 Louisiana crude oils, was 3 published in 1921 and this was followed a year later by Report of Investigations 2416,4/ giving 7 additional analyses. The eleven most important of these analyses were incorporated in Bulletin 291.5/ issued in 1928 In 1934 analyses of 26 crude oils produced in southern Louisiana were published.6/ The percent report presents analyses of 72 additional samples of crude oil from 45 fields in 23 parishes In Louisiana.]

Jan 1, 1939

By Thomas M. Barczak

Roof support systems are necessary to provide stable mine openings and much research has been conducted to design a variety of roof support systems that will function in various manners to ensure that stable ground conditions are achieved. Despite these advancements in technology, mistakes continue to be made in the evaluation and/or installation that significantly degrade the support capability or lead to erroneous determinations of support expectations. The purpose of this paper is to discuss misconceptions about how roof supports perform and factors that impact their performance. The goal is to present practical information that will assist mine operators and engineers in selecting, installing, and evaluating roof support systems properly, and help them to avoid mistakes that can lead to erroneous expectations and potentially catastrophic results that may lead to roof falls. The paper is limited to a discussion of secondary roof support systems and powered roof supports such as longwall shields.

By R. F. Kehrman

Voice Frequency (VF) electromagnetic trapped miner location devices were tested for reliability and effectiveness in 93 coal mines. Tests included uplink pulsed CW, downlink pulsed OW and downlink voice evaluations. Frequencies were 630, 1050, 1950 and 3030 Hertz. Overburden depths varied from 70 feet to 1550 feet. Successful communications were established at 91 of the 93 mines. Data indicate the transmitters and receivers will operate in practically all coal mine environments. Reliability and accuracy as location devices appear to depend on noise, depth and presence of metallic objects which distort the magnetic field. In addition, theoretical models appear to define best case situations in terms of noise and conductivity. Minor hardware problems were encountered, mostly involving battery contacts, switches and antenna cables on the receivers. No hardware problems occurred with the transmitters.

Jan 1, 1978

By Seth C. Schaefer

The Bureau of Mines investigated thermodynamic properties of Mn304 (manganomanganic oxide) and Mn203 (manganese sesquioxide). The standard Gibbs energies of formation (?Gf°) of Mn304 and Mn203 from their lower oxides were determined with high-temperature galvanic cells using stabilized Zr02 (zirconia) as the electrolyte. Potential measurements were obtained for the cell Pt, MnO, Mn304//Zr0 2//02(g, 0.0112 atm), Pt, with the overall cell reaction 6Mn0(c) + 02(g, 0.0112 atm) = 2Mn304(c), where- 02 refers to indicated partial pressure of oxygen at the reference electrode. Similar measurements were obtained for the cell Pt, Mn304, Mn203//ZrO2//02(g, 0.0115 atm), Pt, with the overall cell reaction 4Mn304(c) + 02(g, 0.0115 atm) = 6Mn203(c). Equilibrium oxygen pressures for the Mn0-Mn304-02 and Mn304-Mn203-02 systems were measured and may be expressed for the respective systems as [23,400 109 P02 T + 11.91 (764.9 - 1,208.6 K) and log p02 = - 11,957 + 9.66 T (968.6 - 1,208.2 K),] where pressure (p02) is in atmospheres and temperature (T) is in kelvins. Standard thermodynamic properties of Mn304 and Mn203 were derived from these measurements and auxiliary thermodynamic data from the literature.

Jan 1, 1982

By R. W. Van Dolah

A premature detonation of an explosive charge occurred on January 30, 1961, at a face being prepared for blasting in the underground Jefferson Island Salt Mine, Diamond Crystal Salt Co., Jefferson Island, Iberia Parish, La. The accidental blast injured the powderman fatally; his helper was injured also, but recovered. The accident represents the first fatality reported to the Bureau of Mines in connection with the use of ammonium nitrate-fuel oil (AN-FO) blasting agents in underground mining in the United States. Representatives of the Bureau of Mines Explosives Research Laboratory, Pittsburgh, Pa., and field representatives of the Bureau's Health and Safety Activity conducted the investigation, upon request of the manufacturer of the ammonium nitrate being used and with concurrence by the mine management.

Jan 1, 1962

By Robert M. Doerr

The oxidation kinetics of Ni-Y alloys in the range 0.04 to 8 weight-percent Y, and of high-purity Ni, were compared by the use of a sensitive volumetric apparatus. The reactions followed approximately the parabolic rate law; for oxidations in 02 at 0.5 atm and 1,200° C, the parabolic rate constant was about 0.37 + (0.064) (Y-2.11) mg cm-2 min-1/2, where Y represents the weight-percent Y in the alloy. Internal oxidation of Y occurred in the alloy specimens and the resultant Y203 particles, which were in patterns related to the eutectic structure of the alloys, served as markers showing that the subsequent oxidation of the surrounding Ni was by inward diffusion of O. The scale consisted in each case of NiO, but the inner parts of the scale on the alloy specimens included the patterned Y203 particles. The thicknesses of the inner parts of the scale depended directly on the Y concentration, and the thicknesses of the Y2O3-free outer parts of the scale were inversely related to the Y content of the alloys. There is thus a relationship between the thickness of the outer part of the scale and the protectivity of the scale. Outward diffusion of Ni and inward movement of 0, from the inner boundary of the Y2O3-free part of the scale, is proposed as a mechanism for these results.

Jan 1, 1966

THE Synthetic Liquid Fuels Act (30 U.S.C., 321-325, and amendments) became law April 5, 1944, and a period of intensive research and development in this field was begun by the Federal Bureau of Mines. As part of this program, bulletins were published on pressure hydrogenation,3 the Fischer-Tropsch synthesis,4 and nil stifle.5 The. Bureau also has published a short bibliography on coal gasification,6 mostly of a theoretical nature. Because anal gasification is prerequisite to either the Fischer-Tropsch or coal-hydrogenation processes, publishing this sizable collection of technical information in this form Will Ire valuable. The material will he presented in three parts. as follows I. United Stares Patents. II. United Kingdom, Australian, Canadian, and South African Patents. III. Other Foreign Patents. Part I appeared in early 1960. Part II follows.

Jan 1, 1962