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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 Jack W. Carlson

Considering the magnitude of today's public concern with critical mineral and fuel materials, regarding both their midterm and long term availability, the Nation is fortunate to have in place and operating the coordinated data systems of the Geological Survey and the Bureau of Mines. Under the supervision and policy direction of the Assistant Secretary--Energy and Minerals, these Department of the Interior agencies have long been responsible for important mineral activities in the Federal Government. Aside from their highly respected mineral industry publications such as the monthly Mineral Industry Surveys, annual Commodity Data Summaries and topical Professional Papers and Reports of Investigation, the Bureau of Mines and Geological Survey data bases and expertise have been readily available for use in emergency situations. Policymakers and decisionmakers in government have placed major reliance upon this ready mineral data and analytical capability in World War II, the Korean War, the recent price control era, and the Arab oil embargo.

Jan 1, 1975

By M. L. Glenn

The Bureau of Mines is conducting research on Fe-based alloys using Si and Al additions to reduce the Cr required for heat-resisting appli-cations. Part of this research is being done to evaluate alloys containing (8-10)Cr-(10-14)Ni-(0-8.5)Si-(0-4) Al to determine which of these alloys have austenitic structures, as well as fabrication properties and oxidation resistance sufficient to substitute for type 304 stainless steel. Based on initial results, an Fe-lOCr-11Ni-5Si alloy and an Fe-8Cr-13Ni-5Si alloy were selected for evaluation of oxidati.on, stress rupture, and tensile properties. Both alloys have oxidation resistance at 7000 and 8000 C that is better than that of type 304 stainless steel. The stress rupture strengths are less than that of type 304 stainless steel but significantly better than that of commercial heat-resisting steels with similar Cr contents. Yield strengths of the alloys were equivalent to that of type 304. Both alloys had high tensile strengths comparable to those of stainless steels that transform to martensite during straining (e.g., type 301). These alloys have weld-hot-cracking resistance comparable to that of type 304 stainless steel. This initial study shows that Si has potential as a substitute for Cr in stainless steels for heat-resisting applications.

Jan 1, 1984

Air pollution control regulation$ already implemented or being considered for implementation require substantial investment of capital to remove the sulfur oxides from copper, lead, and zinc smelter gases. There will be an attendant increase in production costs and possibly an associated increase in the price of these metals to the consumer. The total investment and any resultant metal price increase will depend upon the control regulations that ultimately will be adopted by the individual States. Controversy has arisen between the metals industry and governmental control agencies regarding the status of stack gas desulfurization technology and the ability of industry to control sulfur oxide emissions to the degree proposed by some of the more stringent regulations currently under consideration. This paper evaluates the problems involved in achieving various degrees of control over smelter sulfur oxide emissions and the technology available to accomplish the task of assuring clean air. The estimated cost of compliance is reviewed for the copper, zinc, and lead industries, but principal at tent ion is given to the copper situation.

Jan 1, 1971

By J. Pasini

The Bureau of Mines has investigated novel methods of stimulating petroleum production from reservoirs in the Appalachian Region. An important consideration in applying stimulative production methods is the control and removal of solid precipitates from the boreholes of production wells. Where paraffin-base crude oils are produced, as in the Appalachian Region, the accumulation of paraffin may be particularly troublesome. Paraffin deposition is a major production problem that has confronted the petroleum industry for many years. Although considerable effort has been expended by industry and government, a suitable solution has not been found because of the individuality and complex nature of the deposits. Remedial methods used to prevent or remove paraffin fall generally into four classes: (1) Chemical, (2) physical, (3) operative, and (4) combination. Each class has many subclasses that apply to particular problems in different oil- producing areas. Recently, chemical inhibitors and the sonic pump have assisted operators in preventing and removing paraffin deposits. Because these methods are relatively new, their degree of application has not been completely evaluated.

Jan 1, 1963

By D. Harrington

More or less unconsciously and from sheer force of habit human beings do many things they probably would not do if the possible consequences of their acts were fully recognized and appreciated. Such carelessness ordinarily could be condoned if human life were not at stake, but it is difficult to understand why intelligent men engaged in the hazardous occupation of mining indulge with the utmost indifference in some habit or continue some custom in violation of State leas and company regulations and under circumstances that may jeopardize not only their own lives but those of scores, even of hundreds, of their fellow workers as well. The old adage that stolen sweets are the best may or nay not have some foundation, but when applied to the practice of smoking surreptitiously in a coal mine, more especially a gassy mine, it is without even remote justification. Although a relatively harmless habit in the proper environment, smoking has been the cause or suspected cause of many gas explosions and black-powder ignitions and has resulted in numerous instances of bodily injury, loss of life, and destruction of property. Likewise, many fires in both coal and metal nines, causing loss of life, have been started by smoking.

Jan 1, 1941

By C. M. Dice

This paper is one of a series being published by the Bureau of Mines on milling methods and costs. It describes briefly the procedure followed in concentrating hübnerite or? at the Ima tungsten mine, Lemhi County, Idaho. In October 1911 the Ima mill was utilizing combined gravity-concentration, flotation, and magnetic-separation units for the recovery of a tungsten concentrate and a pyritic silver concentrate approximately 120 tons of ore averaging 0.5 percent W03 is treated daily. The concentrates produced average 66 to 67 percent WO3.

Jan 1, 1943

1. A total of 14,413 mining operations reported employment to the Mine Safety and Health Administration (MSHA). Nearly half (48.9%) were sand and gravel operations, followed by stone (28.5%), coal (14.7%), nonmetal (5.7%), and metal mines (2.1%). 2. Mine operators reported 240,000 full-time equivalent workers1 (down 3.9% from 1999). Independent contractors reported 42,000 full-time equivalent workers working on mine property (up 8.6% from 1999). Coal operators accounted for 26.8% of reported employee hours, followed by stone operators (25.9%) and sand and gravel operators (12.1%). 3. Eighty-four (84) work-related mine fatalities occurred in 2000 compared to 90 the year before. •The mine fatality rate was 29.8 per 100,000 full-time equivalent workers compared to a fatality rate of4.6 per 100,000 employees for all private industry. •Thirty-one percent (31%) of the fatalities occurred in underground work areas, which account for only17% of total employment. •Although the largest number of fatalities (28) occurred among miners who work for coal operators, coal contractor employees had the highest fatality rate (61.1 per 100,000 full-time equivalent workers). 4.There were 10,839 nonfatal lost-time injuries reported to MSHA, occurring at a rate of 3.8 injuries per 100full-time equivalent workers, and resulting in a total of 417,918 lost workdays.2 •Among all employees,3 the highest injury rate occurred among coal operator employees (5.6 nonfatal injuries per 100 full-time equivalent workers). •The highest percentage (34.7%) of nonfatal lost-time injuries were due to handling materials (e.g., over-exertion in lifting, pulling, or pushing objects), which also accounted for the greatest percentage of lost workdays (29.3%). •Among the most frequently occurring injuries, the most severe (as measured by the median number of days lost) were associated with accidents involving falls of ground, the use of powered haulage, and slips or falls. •The most frequently reported part of the body injured was the back (22.9% of all injuries). Back injuries accounted for the highest percentage of lost workdays (21.6%). 5.Seven hundred sixty-seven (767) cases of occupational illness were reported to MSHA. •The most frequently reported illness was repetitive trauma, resulting in joint, tendon, or muscle inflammation or irritation (37.3%). •There were 155 (20.2%) illnesses reported as hearing loss. The majority (68.4%) of hearing loss cases occurred among surface workers. •Coal workers' pneumoconiosis accounted for 14.5% of reported illnesses.

May 15, 2002

By James Ridenour

The Gearhart Mountain Wilderness and RARE II area 6225 encompass 22,823 acres (9,236 ha) of the Fremont National Forest in southern Oregon (fig. 1). The area was studied under the provisions of the Wilderness Act of 1964 (Public Law 88-577). The U.S. Bureau of Mines determined the mineral potential of known mines, prospects, or mineralized areas, while in a separate effort the U.S. Geological Survey made geological, geochemical, and geophysical studies. MINERALIZED AREAS The study area contains no mining districts or known claims. Nearby occurrences of uranium, base metals, perlite, mercury, and diatomite apparently do not extend into the study area. Reconnaissance pan samples reveal only trace amounts of gold. No anomalous economic minerals were found in heavy mineral fractions of samples from stream beds draining the area.

Jan 1, 1982

By Louis A. Panek

An improved centrifugal-testing apparatus has been designed and built in the Bureau of Mines laboratory at College Park, Md., which is unique in that it incorporates the use of resistance gages to measure directly the strains in a rotating model without testing it to failure. Owing to this feature, a more rapid testing method can be used; furthermore, model materials need not be restricted to those of the prototype. The behavior of any structure in which strains of significant magnitude are produced by its own weight may be studied in a small model subjected to simulated gravity loading. The model is rotated in a centrifuge to induce in it centrifugal forces, which, like the gravitational forces in the full-size structure, act on the volume elements and are proportional to the masses thereof. Centrifugal testing is, therefore, applicable to the design of mine openings and to the study of similar ground-control problems. It constitutes an experimental method for determining the state of strain in a structure for which analytical methods are excessively laborious or even impossible. In previous applications of centrifugal testing by other investigators, the models usually were tested to failure, and the analysis was made from-the type of break produced. The models were made of the same materials as the proto-type, and the test results were applied only to the particular prototype represented by the model. Beam deflections were measured from photographs of the rotating model, but no means was employed either to determine the actual distribution of stress in the model or to determine quantitatively the degree of restraint imposed on the ends of the loaded model beam, that is, to determine whether the loaded model behaved as a beam with rigidly fixed ends or as some other type of beam. With the apparatus described, it is possible to determine the state of strain, and thus the boundary conditions, in a rotating test model weighing up to 90 lb., which can be subjected to centrifugal forces up to about 2,600 times the force of gravity. The load-strain relationship, applicable directly to the prototype, can be determined from a Single model test. The test results can be presented as quantitative relations between the loads, strains, and dimensions and mechanical proper-ties of the structural members and can be applied to any prototype, whatever its component materials, that satisfies the similarity requirements.

Jan 1, 1952

By Edward L. Tullis

Numerous widely distributed pegmatites of the southern Black Hills of South Dakota contain small amounts of beryl, and two minor deposits are known in the northern Black Hills. Few mines have produced more than 50 tons, and the current, rate of production for the area is about 100 tons annually. Total production, since the first records, is 2,358 tons. Most of the deposits contain less than 1 percent beryl, although the beryl zones in several deposits contain 2 percent beryl or more. Estimated reserves of beryl total 11,824 tons, and an additional 234 tons has been measured; there are other unestimated reserves. The pegmatites are in a belt about the margin of the Harney Peak batholith in the southern Black Hills, although they fail into three districts. The most important, from the point of view of production and reserves, is the Keystone district. Many deposits also are found in the vicinity of Custer and Pringle. Small amounts of beryl occur in the dikes near Hill City. A little beryl has been produced from the Tinton district in the northern Black Hills, and an undeveloped dike has been discovered on Whitewood Peak near Deadwood. The beryl-bearing pegmatites are principally coarse-grained intergrowths or massive segregations of feldspar, quartz, and mica. Some of them contain notable amounts of lithium minerals, as well as some tantalite, columbite, and cassiterite.

Jan 1, 1952

By Henry P. Chandler

COMBINED sales of abrasive materials in the United States during 1956 increased at about the same rate as the value of the Gross National Product in terms of 1954 dollars,3 which was nearly 3 percent. However, some segments of the industry did not follow the general pattern. Sales of abrasive grinding wheels increased 9 percent in value. Sales of surface-coated abrasives declined 5 percent in quantity hut increased 1 percent in value, Production of crude silicon carbide in the United States and Canada advanced both in tonnage and value, but that of abrasive-grade [ ]

Jan 1, 1958

By Donald W. Mitchell

Certification tests for urethane-foam systems and techniques for apply-ing foam safely in mines are described. Fire hazard from foam exists if flame propagates beyond the ignition source or penetrates the foam. Foam that passes the certification tests can be applied on stoppings, continuous sections of ribs of relatively wide passageways (with no foam on the roof), short sections of roof such as overcasts, roof cavities, and intersections (with no foam on the ribs), and between buntons on one wall of a shaft. Foam on the ribs and adjoining roof presents a fire hazard. Stoppings covered with foam passing the certification tests are resistant to penetration of heat, flame, and smoke than similar stopping without foam. Flame propagation can be arrested by water sprays. Spontaneous ignition of foam can be prevented.

Jan 1, 1966

By Joseph J. Wallace

1. The Pittsburgh is the most important bed in Washington County from the standpoint of present production and recoverable reserves. 2. Known measured and indicated reserves in all beds, based on a minimum thickness of 14 inches and 1,800 short tons per acre-foot of coal in place, are estimated at 4,181 million short tons as of January 1, 1954. Of this total, 4,132 million short tons is in beds 28 inches and more thick. Areas in some beds were omitted from the estimate because available data relative to the bed characteristics are too meager for making an estimate that conforms with the definitions of measured and indicated coal adopted for this study. Should future drilling or development prove reserves in these areas, such reserves should be added to the total estimated reserves.

Jan 1, 1955

By R. W. Smith

The Bureau of Mines has been engaged in a systematic evaluation of the thermodynamic properties of combustion gases. These studies were designed to provide basic thermodynamic information of high accuracy, facilitating the theoretical study of flame and combustion phenomena.4 This report is the fifth of a series5/ presenting results of the study for particular fuel-oxidant systems. These calculations have as their objective the constant pressure flame temperature of acetylene-air for a range of pressures.

Jan 1, 1954

By P. A. Bloom

Bureau of Mines research was conducted to develop effective separation methods that might be used in exploiting substantial tonnages of complex barite-fluorspar ores in Arizona. The exploitable reserves now may be increased as recent batch and continuous flotation tests demonstrated that a complex barite?-fluorspar ore from the Red Chief deposit, Yuma County, Ariz., could be selectively treated to concurrently produce (1) fluorspar and (2) a barite byproduct of marketable grade. The sample contained 24.8 percent CaF2 and 24.3 percent BaS04. Processing comprised production of a fluorspar product containing 97 percent CaF2 with an 82 percent recovery, using a sodium fluoride-lignin sulfonate-fatty acid reagent combination. Concurrent retreatment of the fluorspar tailing, using sodium cetyl sulfate as a collector, yielded a barite product of 94 percent BaS04 grade with a 71-percent recovery. The products met specifications for acid-grade fluorspar and drilling mud-type barite.

Jan 1, 1963

By R. D. Leitch

"REASONS FOR AND PURPOSE OF WORKIn 1924 the United States Public Health Service was requested to undertake a special study of stream pollution. At that time the proposal that the United States Bureau of Mines take up the study was made by the Public Health Service because in point of training and experience the personnel of the latter was considered not to be as well, suited to this type of investigation as was that of the Bureau of Mines. H. Foster Bain, then Director of this bureau, promised to undertake the work, and, accordingly, field investigations were begun in the spring of 1925. The problems of mine-drainage wastes and of gas-house and coke-oven waste were investigated in the laboratory, and a method of treatment by sodium hydrate and benzol was found to be promising. The idea was obtained by A. C. Fieldner, chief engineer of the Bureau of Mines experiment stations, while in Germany in 1924, where he was shown a practical application of the process, but no information was obtained as to definite chemical or mechanical processes. Because of the then pending American patent application by the German firm, we made no attempt to develop our findings further. Shortly after, a similar method of treatment was developed in the United States, and since that time we have devoted our attention entirely to mine drainage. This paper is a presentation of some general facts and information gathered during the past five years on coal-mine drainage.SCOPE OF WORKAt the time our work was begun there was such a diversity of opinion on the whole subject and apparently so little was accurately known, that it was decided to undertake a basic study from which (1) certain definite information might be evident, and (2) what might be considered side issues of the original investigation would be suggested for subsequent study.A stream in a district thought to be representative of those in low to average sulphur bituminous coal fields and another in a high sulpbur district were selected for study, A fair (weber of factors entered into the tentative selection of these streams, the chief ones being their accessibility and freedom from other industrial or domestic pollution, besides, of course, the presence of mine drainage in these streams."

Apr 1, 1931

By J. T. McCartney

"INTRODUCTION The surface areas of the finest fractions of a pulverized material are disproportionately larger than their weights. For instance, Pesrott and Kinney 3/ showed that, in a sample of minus 200-mesh coal, particles that are about 2 microns in diameter represent 15 percent of the entire surface area but only 1.5 percent of the total weight. Because the sur- face area is the dominating factor in the behavior of finely divided materials in many practical processes, the role of the finest particles is of great importance. The oxidation and combustion of pulverized coal, both in the dry form and in suspension in oils, and the hydrogenation to fluid hydrocarbons of mixtures of pulverized coal and heavy oil are reactions in which the surface area of the coal particles has considerable influence. This investigation of the size distribution of fine coal particles was conducted with the hope that such processes would thereby be better understood. The results should also be of value in the study of the crushing and fracture of coal."

Sep 1, 1945

By R. L. Hopkins

Fifteen alkyl cycloalkyl sulfides and three dicycloalkyl sulfides were synthesized to provide reference compounds in the search for these classes of sulfur compounds in crude oils. In synthesizing sulfides by alkaline alkylation the order in which the reactants were added was shown to determine the yield and purity of the product.

Jan 1, 1966

By Eugene Fry

The Huber-Rydalch manganese property is in the Erickson mining district of Tooele County, Utah. The district covers the southern part of Simpson Mountains, a block rising abruptly above the surrounding desert floor (fig. 1). The Ruber-Rydalch deposits and other deposits in the Simpson Mountains manganese area were examined by Bureau of Mines engineers during 1940 and 1942 under the strategic minerals program. J. T. Pardee visited the district briefly in 1918. A. E. Granger and A. F. Shride, of the Federal Geological Survey, mapped the geology of the area in 1942 and 1943. The manganese deposits occur as veinlike masses in brecciated fault zones that traverse Cambrian and pre-Cambrian quartzite, quartzite conglomerate, and phyllite. The deposits now exposed near the surface represent the oxidized portions of primary mineralization originally containing rhodochrosite and rhodonite associated with quartz and calcite and small quantities of pyrite, galena, sphalerite, and chalcopyrite. The oxide ore is composed of manganite, pyrolusite, psilomelans, and wad in a gangue of quartz, calcite, and brecciated quartzite.

Jan 1, 1949