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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 F. W. Lee

List of GEOPHYSICAL ABSTRACTS

Jul 1, 1932

By H. J. Heinen

To maximize productivity through improved minerals processing technology, the U.S. Department of the Interior, Bureau of Mines, is investigating particle agglomeration techniques as a means of increasing the percolation rates of leach solutions in heap leaching of clayey gold-silver ores. Simulated heap leach experiments were conducted on 50-pound charges of ore that were contained in 5.5-inch-diameter columns, 5 feet in height. Results indicated that the percolation rate of cyanide leach solution could be enhanced markedly by mixing the ore with controlled amounts of lime, flocculants, and water, and then aging the mixture prior to the column leach step. Experimental results obtained on 20-mesh silver tailings and gold ore crushed to 3/8 inch and to 1 inch showed that it was possible to increase percolation rates as much as 100-fold without sacrificing silver-gold extraction. Larger scale tests conducted in 24-inch-diameter, 16-foot-high columns closely paralleled bench-scale results. By improving percolation leaching, these techniques have the potential of helping to solve environmental problems associated with tailings disposal as well as making an important economic impact on gold-silver recovery operations. Investigations are continuing to develop binders superior to lime for particle agglomeration pretreatment.

Jan 1, 1979

By Charles A. Seitz

This Bureau of Mines report describes a chromatographic method for analyzing impurities in helium that utilizes a helium carrier gas contain-ing 25 to 30 ppm Ne. An example of the effect of trace amounts of nitrogen, methane, and moisture on the detector's response is shown. The added neon in the carrier does away with irregularities of the analysis which were experienced when the carrier contained up to 3 ppm Ne. The addition of 25 to 30 ppm Ne causes a loss of sensitivity, but the re-maining sensitivity is adequate for routine analyses. The high-neon carrier allows positive and more linear responses for eight impurities: neon, hydrogen, argon, oxygen, nitrogen, methane, carbon dioxide, and ethane. Neon concentration levels of 0.02 to 125 ppm in helium carrier gases were studied. The high-neon carrier has been in successful rou-tine use in Bureau of Mines helium facilities since October 1981.

Jan 1, 1985

By ALICE V. Petar

Thallium is one of the rare metals that has come into commercial use within recent years . Its comparative scarcity , combined with a resemblance to the common metal lead , have retarded the development of uses for thallium . Although production is still measured in pounds rather than in tons , it is now finding application in a number of fields . Perhaps the earliest commercial use of thallium was as a constituent of optical glass of higher refractive power than similar glasses containing lead . One of the later applications to attract attention was the use of the oxysulphide in a sensitive electrical device similar to the selenium cell . The " Thalofide " cell , which was patented in 1919 , constituted for a time the most important outlet for thallium. During the next few years the limited use of thallium and its salts in other fields was insufficient to absorb an annual production of a few hundred pounds , and the price dropped from $ 16 or $18 per pound in 1922 to $ 5 per pound in 1924 . Beginning in 1925 several new uses were developed , especially as a poison for rodents and ants , and as a result the demand for thallium increased sufficiently to cause a recovery in price to the present level of from $12 to $15 per pound .

Jun 1, 1931

This publication summarizes the research (in-house and contract projects) programmed by the Bureau of Mines for fiscal year 1985 (October 1, 1984-September 30, 1985) under its Health and Safety Technology Program. The objective of these projects is to provide an ordered and sequenced advance toward the Bureau's overall goal of providing the system technology required to create a more healthful and safer working environment for the Nation?s mining and minerals processing workers.

Jan 1, 1985

By A. M. Evans

"INTRODUCTION Exploration of the Iron Mountain and Bader iron-ore deposits in Llano County and the Gamble deposit in Mason County, Texas, was begun by the Bureau of Mines in January and completed in May 1944. The deposits had been examined by A. B. Needham, district engineer of the Bureau, in November 1942. Detailed geophysical studies by the gravity method as well as with a dip needle were made by the Bureau of Economic Geology 3/ of the University of Texas and the Federal Geological Survey. 4/ACKNOWLEDGMENTSIn the 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 exploration project as soon as practicable after its completion. The Mining Branch, Lowell B. Moon, chief, conducts preliminary examinations, performs the actual exploratory work, and prepares the final report. The Metallurgical Branch, R. G. Knickerbocker, chief, analyzes samples and performs beneficiation tests."

Apr 1, 1947

By G. R. Hopkins

[A new record in fuel efficiency at petroleum refineries was established in 1939, when a the average e B.t.u. requirements per barrel of crude oil processed declined to a new low of 557,000 B.t.u. (see fig, 1).]

Jan 1, 1941

By William J. Krisko

This contract final report summarizes the design, fabrication and testing of a "line brattice air curtain" device under Bureau of Mines Contract H0357097. The purpose of this program was to develop the concept of using an air curtain for coursing ventilating air parallel with the air curtain From the last open crosscut to the face in exhausting ventilation systems to replace the line brattice cloth in room and pillar coal mining operations. The final design of the air curtain device consists of a 10-foot long closed end pipe with c: slot cut along its length. Pressurized air is delivered to the open end with a hydraulically-driven blower. A sheet of air emanates from the slot and is directed toward the mine roof. An invisible sheet of air is thus created between the top of the machine and mine roof and acts a an extension of the existing conventional line brattice.

Jan 1, 1977

By J. P. May

This U.S. Bureau of Mines report identifies and evaluates factors responsible for dump-point accidents involving mobile mining equipment. Information regarding the occurrence and severity of the accidents, the industries affected, the types of equipment involved, the primary and contributing causes, and pertinent Federal regulations is included. The aim of this report is to provide information that will aid mine operators in the recognition of hazards associated with mobile equipment operation near the dump points of stockpiles and waste dumps.

Jan 1, 1990

By W. K. Collins

Engineered scavenger compounds (ESC's) developed by the U.S. Bureau of Mines are a novel class of compounds that selectively can recover a desired element from a solid or molten alloy. Lithium titanate (L2Ti307 or Li2O?3Ti02) is used as an ESC to recover lithium (Li) from aluminum-lithium (Al-Li) alloys. X-ray diffraction measurements have shown that Li2Ti307 undergoes a phase change during scavenging from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of lithium in the matrix of the material and the effect of temperature. Although both phases are metastable, the hexagonal phase that forms during the scavenging of lithium from Al-Li alloys appears to be the more stable phase. Recovering lithium from the ESC by electrodeposition does not cause the structure to revert to the orthorhombic phase. The orthorhombic and the hexagonal structures of Li2Ti307 have similar scavenging capacities for lithium. This report proposes a new mechanism for the phase transformation.

Jan 1, 2010

By Lester G. Morrel

THE RICH and varied occurrences of metallic ores in Australia, extensive nickel deposits on New Caledonia and phosphate rock on several widely scattered small islands were important aspects of the economy of the South Pacific area. Relatively small quantities of gold and nonmetallic minerals produced in New Zealand, Fiji, and the Territory of Papua-New Guinea remained important to the domestic economies of these islands, but had little importance to overall world mineral supplies. The value of mineral commodities produced in this area in 1964 was estimated at $658 million,3 compared with $585 million in 1963. The year's greatest commodity gains were in bauxite and aluminum, beryl concentrate, manganese ore, nickel smelter products, tin, and coal. Annual increases were recorded in virtually all countries and possessions in the area except Papua-New Guinea, where the drop in output of alluvial gold accounted for a decline of about $160,000. Mineral industry activities in Australia overshadowed those in all other parts of the South Pacific in 1964. Outstanding developments were the sales contract negotiations and physical preparation for exploiting the rich iron ore discoveries in Western Australia, the initiation of domestic crude oil production, the commissioning of two new steal mills and an alumina refinery and a start on the new alumina-aluminum project based on Cape fork bauxite deposits. The principal mineral development in 1864 in New Zealand was the progress on plans of the Newzealand Steel Co. to use indigenous iron sans as the resource base for a local steel industry. In New Caledonia, additions and expansion of the nickel mining and smelting facilities continued throughout the year. Plans for extensive geophysical studies were announced by the Government Geological Departments of British Solomon Islands and Fiji.

Jan 1, 1966

By Albert E. Long

During the summer and fall of 1948 the Bureau of Mines, in cooperation with the U. S. Geological Survey, conducted 6xperiments in diamond core drilling in the Phosphoria formation in southeastern Idaho and southwestern Wyoming. Nearly all of the diamond core drilling in the Phosphoria formation has been done by mining companies interested in finding and developing phosphate-bearing beds amenable to stripping. The recovery of sludge; and enough core (usually 30 to 60 percent) to identify certain marker beds produced by current drilling practices meets both the primary requirement of mining companies in determining depth of overburden and their secondary need to determine the phosphate content of relatively thick minable units whose general composition and nature are already fairly well established.

Jan 1, 1949

By William H. Lyon

In 1950 the Program Staff of the Department of the Interior undertook an exploratory study in the projection of energy requirements of the nation. This work was reported in Bureau of Mines Information Circular 7582 by H. J. Barnett. In that preliminary study Mr. Barnett, after exploring the nature of the energy economy in some detail, evolved a method for estimating how much energy will be required in the future, based on estimates of trends in efficiency of energy utilization in specific applications, the physical output of specific energy-consuming industries, size of the population, productivity advances in the economy at large, consumer preferences, and other factors. Considerable new information was developed regarding the nature of energy demands and the possible levels of requirements for each fuel under various assumed business conditions. The study analyzed the interrelationships, including substitutions, among the fuels and emphasized the need for viewing the energy economy as an integrated albeit complex whole. This exploratory study showed a need for a single comprehensive statistical re-port that would assemble and show in a uniform manner the diverse published statistical data on energy commodities now scattered through many publications. A particularly important need was for a set of historical statistics showing the production and consumption of all energy on a B.t.u. basis. As the prospective size and nature of the future energy requirements of the nation are matters of continuing importance, this report was prepared to assist further investigations of the subject. In this report the authors undertake to assemble and present in tabular form, on a uniform basis, the production and use of each of the fuels and electric energy in the United states for three census years -1929, 1939, and 1947. The year 1947, rather than a later year, was selected because it is the most recent year for which census data are available showing the consumption of fuel by each of the manufacturing industries. It is hoped that making data for these 3 years available in one re-port will provide the needed statistical background for further studies of fuel requirements and supplies.

Jan 1, 1951

By J. H. Field

Synthesis of hydrocarbons by the Fischer-Tropsch reaction in a hot-gas- recycle system was demonstrated to be technically feasible. This project was undertaken, by the Bureau of Mines, to determine if the system was operable and to ascertain the optimum conditions for the production of gasoline. Carbon steel turnings packed with a void volume from 88 to 90 pct. were satisfactory catalysts, but steel catalysts with greater void volume, either turnings or steel wool, were not as active. Good temperature control with a pressure drop of less than 0.5 pounds per square inch (p.s,i,) per foot of catalyst bed of turnings was obtained by operating with a recycle to fresh feed ratio of 20 and by splitting the total gas flaw and injecting portions into the reactor at different entry ports.

Jan 1, 1961

By Robert Bottge

When a company develops a mineral property in a remote area of Alaska, it must consider how best to house its personnel. This Bureau of Mines report examines the economics of two options: company towns and company camps. The price required to maintain a 15% discounted-cash-flow rate of return (DCFROR) was derived for hypothetical 1,000-st/d cut-and-fill mines and 50,000-st/d open-pit mines located in three different regions of the State, One set of hypothetical mines utilizes a townsite; the other utilizes a relatively new concept, a fly-in camp or commuting operation, in which two shifts of employees operate the mine and all associated facilities for 1 week before being replaced by a second crew. The study shows that operating costs were higher for mines employing the commuting option than for mines having a company town because of the additional wages paid for overtime hours; however, the price required to obtain a 15% DCFROR for the single-product copper concentrate, f.0.b. the mill site, was significantly lower owing to the lower investment costs for the camp-type operation. The economic advantage for those mines utilizing the camp increases from south to north and from the coast toward the interior.

Jan 1, 1986

By H. R. Wells

The Blackbird district, Lemhi County, Idaho, has long been recognized as a potential source of cobalt and copper. However, the comparatively low grade and small size of the known ore bodies, the small demand for cobalt, and. the lack of adequate roads throughout the region precluded extensive exploration of the early discoveries in the area. Recent advances in alloy metallurgy, accentuated by wartime activities, greatly increased the demand for sources of domestic cobalt. Beginning In 1941, engineers of the Bureau of Mines conducted an examination and exploration program in the Blackbird district. This work was supplemented by an exploration program by engineers of the Howe Sound Mining Co., 730 Fifth Ave., New York 19, N.Y.

Jan 1, 1948

By Paul M. Tyler

"In preparing this paper the writer has perforce depended mainly upon published information, including the catalogs and pamphlets issued by importers and dealers such as the Diamond Drill Carbon Co. and J. K. Smit & Zonen. Special acknowledgment is made to various articles published by S. H. Ball. The writer of this paper, however, is alone responsible for statements herein contained and since he has often found it necessary to rationalize apparently conflicting opinions of recognized authorities on this little-known subject, he will welcome constructive criticism from the trade.Two types of diamond are extensively used for industrial purposes. One type, known as bort or bortz (boort, boart, bowr, etc.), consists of diamonds of the gem variety but unfit for cutting into gems. They may be colorless, yellow, brown, or gray. The other type, carbonado, known in the trade as ""carbon"" or ""black diamond,"" differs greatly from the white diamond, being opaque and apparently amorphous or noncrystalline. Actually, instead of forming a large single crystal as in a gem stone, carbon diamond comprises a mass of microscopic crystals that interlock to form a tough, homogeneous material with no planes of cleavage. It is found in various colors -- black, dark green, brown, and gray -- but usually it has .a dark lustrous black surface, with a resinoid or submetallic appearance, often resembling fine-grained steel. Upon exposure to the air the broken surface gradually darkens to an ash-gray color. Ballas is a special type of carbonado in which the crystals are definitely-oriented around a central nucleus. They are harder and tougher than ordinary carbonado but are much scarcer. The Cape ballas is reputed to be not quite so tough as Brazilian ballas but tougher than carbon or bort.The diamond crystals are isometric and take a variety of forms. The cleavage is octahedral and well marked. A crack is easily -started parallel to an octahedral face, and bort or gem diamonds are notoriously brittle, especially when subjected to sudden shock. Even carbonado, while it has a high resistance to slowly applied pressures, may be chipped or broken by a sharp blow.Exposed to radioactive rays, the diamond becomes phosphorescent; this property is often utilized to distinguish it from quartz, topaz, or glass. The unusually high refractive index likewise aids in its identification in the case of a more or less transparent stone. At the temperature of the electric arc, diamond is converted into graphite, another form of Carbon but one of the softest mineral substances. At a much lower temperature, as low as 1,5620 F., the diamond may be burned like ordinary carbon in an atmosphere of oxygen, and according to some authorities there is danger of burning a diamond if overheated even in air."

Mar 1, 1932

By Takashi Ohya, George V. Keller, Richard G. Geyer

One aspect of a program to improve the chances of survival following coal mine disasters is the development of a communications system which will allow surviving miners to make their circumstances known to rescue teams. At present, it appears that an electromagnetic system may be most practical. The development and design of an effective electromagnetic communications link for signalling between mine workings and the surface requires knowledge of pertinent physical properties of the rocks overlying the mine workings and the characteristics of the ambient noise against which a communications signal must be recognized. Knowledge of the overburden electrical transmission properties is useful not only for determining a practical operating transmitter frequency at a given mine, but also for ensuring the best possible electromagnetic coupling for routine or emergency communication purposes. Field studies of the electrical transmission properties of the overburden of coal mines in Colorado, Illinois, and Pennsylvania generally show that a rela- tively uniform and unimodal electrical conductivity distribution exists provided that the region has not been subject to considerable structural or metamorphic deformation such as that observed in the Gary District of West Virginia. Measurements of ambient surface electromagnetic noise levels at several mines in Colorado, Illinois, and West Virginia were taken and analyzed and are presented in the form of amplitude histogram plots both as a function of frequency and time of day. These amplitude histograms may be used in conjunction with overburden resistivity data in implementing an uplink communications beacon system which will yield a specified signal-to-noise ratio at the surface. Numerous C.W. field transmission tests were made in various coal mining environments with use made of either a buried vertical-axis transmitting loop or a short insulated grounded current line. These transmission tests were made from 20 Hz to 20,000 Hz in frequency and at several geographic surface receiving sites. The results of these field measurements show, in general, good agreement with theoretically calculated results. Since the produced surface magnetic field from a buried vertical-axis loop source or the produced surface horizontal electric field from a buried horizontal current line show better agreement with theoretical results, they could be used for beacon location system. One criterion would be in detecting the equatorial and polar null lines of the horizontal electric field component which is normal to the direction of emplacement of a buried transmitting line current source. A second criterion would be in the surface mapping of the maximum in the vertical magnetic field directly over a vertical-axis loop transmitter and the associated null in the vertical magnetic field at a horizontal offset distance which is about 1.4 times the depth of burial of the transmitter. Finally, a third criterion would lie in the surface mapping of the null in the horizontal magnetic field directly over the vertical-axis beacon and the associated maximum in the horizontal magnetic field at an offset distance from the transmitter axis of half the depth of burial of the loop transmitter. In mapping the vertical magnetic field over a buried vertical-axis loop transmitter, the size effect of the transmitter loop must be taken into account when the separation distances between the transmitter and receiving sensor are less than ten times the effective radius of the source loop; increasing the size of the transmitting source relative to the source-receiver separation distance shifts the null in the vertical magnetic field to greater offsets. In mapping either the vertical or horizontal magnetic field over a buried vertical-axis loop transmitter, care should be exercised in ascertaining that measured nulls and maxima are along radials through the axis of the buried source loop. For the main part, coupling experiments show that ambient electromagnetic noise in coal mining districts is less of a problem above 1000 Hertz. But secondary and perhaps undesirable maxima and null phenomena (as well as penetration problems) would occur in many coal mine provinces in the behavior of the surface horizontal magnetic field (over a buried vertical-axis loop transmitter) if transmission frequencies as high as 10 kHertz were used.

By J. B. Gayle

During the past several decades, there has been a steady increase in the number and size of experimental ovens used for carbonization research. Although many were originally intended principally for studies of coal expansion, current practice usually includes determinations of the properties of the experimental cokes. With respect to size and shatter characteristics, the cokes from the larger experimental ovens closely approximate those from duplicate charges carbonized in commercial ovens; however, they are consistently lighter and frequently less resistant to degradation by abrasive forces. To minimize these differences, some operators dry the experimental charges before carbonization. The resulting higher dry coal charge densities do, in fact, yield cokes with gravities closely approximating those produced commercially from the same coal or blend but without drying. The drying of the experimental charges may be criticized on the grounds that it represents a departure from commercial practice and may result in oxidation of the samples; for these reasons, the practice has not been universally adopted.

Jan 1, 1961