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By N. S. Dalal, Xiaoya Sun, Xianglin Shi

"The in vivo toxicity of vanadium(V) has been found to correlate with the depletion of cellular glutathione and related non-protein thiols. With a view to understanding the mechanism for this observation, we have investigated the oxidation of glutathione, cysteine N·acetylcystcinc and pcnicil· lamine by vanadium(V), using electron spin resonance (ESR) and ESR spin trapping methodology. The spin trap used was 5,5-dimethyl-l-pyrroline I-oxide (DMPO). It is found that the oxidation of these thiols by vanadium(V) generates the corresponding thiyl radicals and vanadilim- (IV) complexes. The results suggest that free radical reactions play a significant role in the depletion of cellular thiols by vanadium(V) and hence in vanadium(V) toxicity. 1. INTRODUCTIONThis communication reports on the identification of thiyl radicals formed as intermediates in the reaction of vanadium(V) with glutathione (GSH) and related nonprotein thiols. This study was undertaken because the biochemical mechanism of vanadium toxicity is still not fully understood,. despite being a topic of current research activity [1-20). As to possible clues, it is known that vanadium is most toxic when administered in its pentavaient state [21), and that vanadium(V) administration into laboratory mice reduces cellular levels of NAD(P)H and GSH [22). While the oxidation of NAD(P)H by vanadium has been studied extensively [16-20), that of glutathione and related non-protein thiols has been paid less attention. On the other hand, GSH and related thiols are important cellular antioxidants [23). Their functions include decomposing lipid peroxides and protecting cell membranes [23-25). Thus any reduction in the cellular contents of such nonprotein thiols after vanadium exposure may result in the accumulation of lipid peroxides which might ultimately lead to tissue injury. With a view of finding the mechanism for this thiol depletion process, we have investigated reactions of non-protein thiols with vanadium(V). Particular attention has been paid to the detection of thiyl radicals, since it has been postulated [l] (but not experimentally proven) that the glutathionyl radical (GS·) might be an intermediate in the reaction between vanadium(V), NADH and GSH. We have used electron spin resonance (ESR) and ESR spin trapping methodology for investigating the reactions of GSH, cysteine, N-acetylcysteine and penicillamine with vanadium(V). The results show that the corresponding thiyl radicals are indeed formed in the one-electron reduction of vanadium(V) by all of the above mentioned thiols."

Jan 1, 1990

By E. E. Donath, L. L. Hirst, L. C. Skinner

Two processes are available for the production of synthetic fuels from coal high-pressure hydrogenation and the carbon monoxide-hydrogen synthe- sis. This paper presents some ideas and new developments in coal hydrogen- ation that have been incorporated in an estimate for the production of 30,000 barrels per day of liquid fuels, mainly gasoline. A few comparisons of the processes will be helpful before discussion of the details of pro- posed improvements in the hydrogenation process. The principle of the high-pressure hydrogenation process ie the addi- tion of hydrogen at pressurea in the range of 3,000 to 10,000 p.s.i. to coal at elevated temperature and with the help of catalysts. On the other hand, the principle in the Fischer-Tropsch synthesis is the complete break-down of coal into a mixture of carbon monoxide and hydrogen, followed by the catalytic combination of these two gasse into hydrocarbons or suitable catalysts. For the synthesis, moderately elevated pressures of about 350 p.8.1. will bo used in the immediate future, although it can be carried on at atmosphoric pressure with certain catalysts. The products of these two processes using coal as raw material are almost as differont as hydrocarbons can be. The products of the high-pres- sure hydrogenation of coal reflect the original constitution of the coal. They are, therefore, rich in ring compounds, both aromatic and naphthenic, but, due to the action of highly comprcesed hydrogen and catalyst, are satu- rated and very stable. These constituents give the gasoline a high octane number and excellent rich-mixture performance, combined with good gum and storage stability. Therefore, this gasoline is suitable for aviation gaso- line or base stock. The Diesel fuel can be hydrogenated to a centane number of 45 or higher, which is entirely satisfactory for operating normal Diesel

Dec 1, 1948

By Nicholas Kyriazi

The Bureau of Mines subjected three commercial compressed-oxygen self-contained self-rescuers to a series of laboratory treatments designed to simulate various environmental conditions in underground coal mines. The environmental treatments consisted of extremes of temperature and of shock and vibration. The tests were designed to predict the ability of the self-rescuers to withstand those environmental stresses without causing a decrease in wearer protection. A critical concern was internal damage to an apparatus that would cause it to malfunction or seriously degrade its performance without any obvious external signs. The Bureau has previously tested chemical oxygen self-contained self-rescuers in a similar research program. Although the three compressed-oxygen units are not as sturdy as the chemical oxygen self-rescuers tested previously, they performed reliably after treatments on treadmill tests with human subjects and on machine tests using a breathing and metabolic simulator. Serious damage was caused by both the heat treat-ment of 71° C (venting of the 02 bottle in most cases), and in the shock treatment (breaking open of the case and dislodging of the components). When physical damage is obvious, a complete refurbishing of the damaged self-rescuer is recommended.

Jan 1, 1983

By J. F. Smith

A series of studies of emissions from large coal-fired steam generators have included measurements of the concentrations of oxides of sulfur and oxides of notrogen. The sampling equipment, method of sampling, and analytical techniques used for processing of these samples are detailed. A method based on the precipitation of benzidine sulfate was developed for determining both SO3 and total oxides of sulfur in the presence of interfering acidic components in the stack gases. In addition, difficulties encountered with sampling and analytical techniques are also described.

Jan 1, 1968

By Alexander May

The U.S. Bureau of Mines conducted studies to determine if phosphate slag stockpiles at Tennessee Valley Authority's National Fertilizer Development Center were hazardous materials. The stockpiles were not hazardous materials as determined by Environmental Protection Agency (EPA) extraction procedure (EP) toxicity test. Radium-226 concentration was 28.7 pCi/g in slag and 2.1 pCi/g in background material. Radium-226 was not leached from the slag. Fluoride concentration was 3.87 pct in slag, 0.18 pct in subsurface material under slag, and 0.08 pct in the background. Slag material permeability was 1.65 x 10-3 cm/s, and subsurface material permeability was 3.24 x 10-6 cm/s. Rain water, trapped in a depression on top of the east slag stockpile, became seepage water at the base of the stockpile. Concentrations of EPA toxic elements in seepage water were much less than concentrations from an EPA EP toxicity test on the slag. Twelve elements-Na, Mg, Ca, Sr, Ba, Cr, Mn, Co, Cu, Cd, AI, and P-had higher concentrations in seepage water than in rain water on top of the slag stockpiles, or in creek water adjacent to stockpile bases, indicating that they were leached from slag stockpiles.

Jan 1, 1990

By A. U. Miller

Definite progress has been made in accident prevention in Illinois during the past few years; the State Department of Mines and Minerals is receiving excellent cooperation from coal companies and employees, the companies are making greater effort to maintain their mines in good condi- tion, and the employees are eliminating more unsafe practices. As a result, some coal companies have made commendable safety records that prove that coal can be mined with a comparatively low accident rate. However, there is need for further improvement, as the accident rate of the State as a whole is much higher than it should be. During the 55-year period 1882-1936, in- clusive, reports of the State Department of Mines and Minerals show a total of 7,005 (an average of 127.36 per year) men killed in and around the coal mines. Of this number, 6,425 (91.7 percent) were killed underground, 346 (4.9 percent) in the shaft, and 234 (3.3 percent) on the surface. Of the fatalities underground, 3,300 (51.3 percent) were killed by falls of roof, sides, or face coal, 1,167 (18.1 percent) by haulage, 639 (9.9 percent) by handling explosives, 579 (9 percent) by explosions, 151 (2.3 percent) by electricity, and 589 (9.1 percent) by other means. Of the fatalities in the shaft, 171 men (46.5 percent) were killed by falling down the shaft, 14 (41.6 percent) by the cage, and 31 (8.9 percent) otherwise. On the surface, 113 (48.2 percent) of the fatalities were due to railroad cars, 51 (21.7 percent) to machinery, and 70 (29.9 percent) to other causes. The fact that 7,005 lives (an average of 127.36 per year) were lost during 1882-1936 is sufficient evidence that in the past too little interest has been taken in safety by either the management or workers. A realization of this deplorable loss of life should act as an incentive to the industry to make greater effort to prevent accidents in the future. After an accident occurs, the facts pertaining to it become history, and anything that may be done afterward cannot change in any way the damage that has already been done, such as loss of life, personal injury, and destruction of property. The main benefit that can be derived from an acci- dent is that suitable procedure may be adopted and some lesson may be learned to aid in preventing a similar accident in the future. All accidents, par- ticularly serious ones, therefore should be investigated and an effort made

Apr 1, 1938

By Terry L. Muldoon

The report describes the development of preliminary requirement specifications for standardized operating controls for roof bolting machines used in underground coal mining. According to recent statistics, roof bolting continues to be one of the most hazardous occupations in underground coal mining. The two principal hazards to the roof bolter operator are the machine itself and roof falls during the bolting cycle. The lack of standardization of machine controls is a major contributor to this hazardous situation. Observations of roof bolting operations and discussions with roof bolter manufacturers coupled with detailed analyses of roof bolter control design specifications were performed during this study. Detailed roof bolter operator task analyses, commonality of control analyses, and classical link analyses were also performed. The results of these analyses were then used to produce preliminary requirement specifications for standardized controls.

Jan 1, 1980

This publication contains 10 papers presented at a symposium on ATRS systems in Charleston, WV, on June 23, 1983. Included are papers by MSHA Technical Support (Roof Control), West Virginia Institute of Technology, the Bureau of Mines, and seven roof bolter manufacturers and/or designers of ATRS systems. These papers summarize the most recent developments in ATRS technology and can serve as a guide to potential designers, developers, and users of ATRS systems.

Jan 1, 1985

By D. L. Hollis

An arc plasma reactor, constructed and used for studying extractive metallurgical processing, was adapted by the U.S. Bureau of Mines to separate gases of different masses by using the high rate of plasma rotation. With argon and helium as input gases, peripheral reactor outlet ports had a measured average increase of about 10 pet in argon concentration relative to helium with the plasma on compared with plasma off for the same gas inlet concentrations in both cases. Approximately the same average increase in argon concentration occurred from the peripheral outlet port compared with a central outlet probe with the plasma on. There was no difference with the plasma off.

Jan 1, 2010

By John R. Hoskins

Uniaxial compressive strength of rock is usually determined in the laboratory from cylindrical samples that vary in diameter from 5/8 to 8 inches, using a spherically seated compression head of unspecified size. The Bureau of Mines conducted a series of tests on limestone, marble, sand-stone, granite, and plaster of paris to determine the influence of the spherical head sizes and the specimen diameters themselves on the uniaxial compressive strength. Cylindrical samples of several different diameters of each rock type, all having a length of twice their diameter, were prepared and broken using at least three different diameter spherical heads. Analysis of the data shows that spherical head size does not significantly affect the uniaxial compressive strength of cylindrical rock samples. However, the diameter of the rock specimens does significantly affect the uniaxial compressive strength. Within the range of specimen diameters tested, a coefficient of variation of 6.4 percent for plaster of paris can be attributed to the selection of specimen diameter alone. Similarly, a maximum coefficient of variation of 4.7 percent for the rock types tested can be attributed to the specimen diameter alone.

Jan 1, 1969

By Larman J. Heath

Liquid incendiaries were burned within the interstices of several different types of sandstone cores to determine the technical feasibility of increasing sandstone permeability by this method. Fuel-oxidant mixtures were tested in 186 cores; six cores exploded when ignited. In virtually all instances, the explosion completely pulverized the sandstone cores. In addition n those cores damaged by explosions, 24 cores were fractured so severely that permeability tests were impossible. Although combustion gener¬ally increased the permeability, specific mixtures at given pressures were inconsistent in their ignition and burning behavior. Tests indicated that the heat of burning incendiaries significantly increased sandstone permeability. The improved permeability ratios were usually less than 2, but one was 10.3. Permeability alteration by other in situ methods was not as effective as that by flame propagation.

Jan 1, 1971

By F. A. Skirvin

Purification techniques were investigated for removing low-level metallic impurities from tungsten hexachloride. These techniques included distillation) fused-salt scrubbing) zone refining) and adsorption. Fractional distillation of tungsten hexachloride was found to be an effective purification method. The impurity levels of molybdenum) iron) nickel) copper) magnesium) and manganese were reduced to provide a tungsten halide sample which contained a total of less than 10 ppm detectable metallic impurities. Purification by fused-salt scrubbing of tungsten hexachloride in a lithium chloride-potassium chloride eutectic produced a hexachloride product which was of approximately the same quality as that obtained by distillation. Zone refining and adsorption did not appear to be as effective as distillation or fused-salt scrubbing.

Jan 1, 1967

By E. M. Tignor

A research program to aid development of improved methods for increased production of petroleum from partly depleted reservoirs is a vital part of the Bureau of Mines effort to effect true conservation of that mineral resource. This report presents results of an investigation to identify the clay minerals within some Appalachian petroleum-reservoir sands, the effect of clay content on the fluid-flow behavior of those sands, and the use of brines in water-flooding operations. Permeability measurements using kerosine, calcium chloride brine, simulated oilfield brine, potassium chloride brine, sodium chloride brine, and distilled water were made on reservoir-rock cores. Clay fractions were separated from sand grains of disaggregated portions of each core sample, and the clay minerals were identified by the differential thermal analysis method. Relations of the permeability to various fluids were developed.

Jan 1, 1957

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 Wallace W. Roepke

The Bureau of Mines determined coal-cutting forces and primary dust generation of four styles of radial gage bits as used on end rings of continuous mining machines. Direct comparisons for reference were made with two widely used conical plumb-bob types having 60' and 90' (nominal) included tip angles. The cutting forces for all of the gage bits were similar to those of the 60°-tip plumb-bob bit. All bits except the RAD-3 gage bit generated similar amounts of primary total dust at shallow cutting, but during deeper cutting, the amounts varied and the gage bits produced as much as 2-1/2 times the dust produced by the 60° bit. This seems atypical since past experience has always shown differences in dust generation at shallow cutting. The specific energy was more like that found previously with other bits, since the values were spread at shallow cutting but became nearly similar at deeper cuts. The 90° bit and the RAD-3 gage bit are not recommended for use except in extremely difficult cutting conditions where dust and forces are of secondary importance. The choice among the remaining four bits can be made on the basis of dust, energy, forces, or cost, as circumstances dictate.

Jan 1, 1983

By Charles Vaught

The purpose of this study was to determine mine workers' state of fie-fighting preparedness and the technology being used to detect and respond to underground coal mine fires. To investigate this problem, 214 underground coal miners were interviewed by U.S. Bureau of Mines researchers. Frequency distributions of workers' responses are presented in this report, along with segments of narrative accounts, to profile miners' fire-fighting capabilities. The data indicated that much variability exists from mine to mine and that there are several important changes operators may undertake in order to make miners better prepared to deal with fire underground: select appropriate sensors, establish and test a warning and communication protocol, construct a system capable of delivering hundreds of gallons of water per minute for sustained periods, institute formal fire preparedness audits, develop case studies of events that occur at an operation to use as teaching and assessment tools, and provide structured practice that can be incorporated into fire drills.

Jan 1, 2010

By J. K. Whyatt

Assuring ground control safety in many mining and tunneling projects depends, at least in part, on an understanding of in situ stress conditions that will be encountered. Yet it is rarely practical to conduct more than a very limited number of stress measurements. Stresses along the route of a proposed excavation are typically interpolated from available measurements, often assuming a linear variation of stress with depth (or elevation). However, projects where multiple stress measurements are conducted often report more complex variations of in situ stress, usually in apparent relationship to geologic structures. These structures often include lithologies of contrasting elastic properties. A method is proposed for estimating stresses in these cases by first back-calculating regional loads from available stress measurements and then modeling the distribution of stress throughout the rock mass. The method has been successfully applied to a set of in situ stress measurements from the Coeur d’Alene Mining District of northern Idaho, USA. Results provided new insights into district stress conditions and the distribution of rockburst hazards along mine drifts and between various mines. This success should transfer readily to suitable deep tunneling projects.

By J. R. Koehler

Effective barrier pillar design is essential for safe and productive underground coal mining. This U.S. Bureau of Mines report presents an overview of available barrier pillar design methodologies that incorporate sound engineering principles while remaining practical for everyday usage. Nomographs and examples are presented to assist in the determination of proper barrier pillar sizing. Additionally, performance evaluation techniques and criteria are included to assist in determining the effectiveness of selected barrier pillar configurations.

Jan 1, 1995

Ground-water and tailings pond monitoring in the Upper Santa Cruz Basin Mines Task Force's Special Studies Area has been performed to determine the nature and extent of aquifer contamination from copper tailings pond's recharge in the basin. A monitoring program for each of three mining areas (Mines A, B, and D) was developed. Analysis of data shows that recharge from Mine A's ponds has caused increased hardness, sulfate and total dissolved solids in local ground water. However, pumpage in the area has controlled most of the water's movement. Pond recharge from Mine B has led to similar conditions, and the degraded water is moving towards a local public-supply well. Pumpage from Mine D's interceptor wells is controlling some, but not all, of the movement of recharge seepage from Mine D's ponds. Recommendations include the need for enhanced monitoring programs at each current mine site, development of a monitoring program for Mine C's area, development of water budgets for all mines, investigation of tailings pond compaction and sliming, establishment of mine closure plans for containment of recharged pond water, and the need for additional interceptor wells in several locations.

Jan 1, 1983

By C. J. Wilhelm, John M. Devine, Ludwig Schmidt

"Steel tanks often corrode rapidly in oil fields where the Gas produced with crude contains an appreciable quantity of hydrogen sulphide. In many instances working tanks have been discarded after only six months of service because of failure induced by corrosion.Aluminum has been used for some time in the fabrication of certain equipment incidental to the handling of oils containing hydrogen sulphide gas in solution, and has exhibited no carious corrosive action. These uses indicated that aluminum tanks,be equally effective in counter- acting hydrogen sulphide corrosion. Consequently, in the spring of 1920, an all-aluminum stock tank of 500 barrels capacity and a ""composite"" tank of equal capacity, having a steel bottom and bottom ring and an aluminum top and top ring, were placed in service on the State-Lassiter lease of the Gulf Production Co, in Crane County, Tex. These tanks were under observation for one year, the toot being sponsored by the Gulf Production Co., the Aluminum Co. of America, and the Parkersburg Rig and Reel Co. The results of this preliminary test sustained the belief that aluminum is highly resistance to hydrogen sulphide gas and likewise indicated the type or grade of aluminum which could be most economically used for lease tankage. However, in this preliminary test the tanks were not subjected to contact with the quantities o highly concentrated brines such as often are associated and produced with crude oil. Therefore, it was suggested by representatives of the aluminum Co. that additional tests be made to include production conditions in large quantities of brine would be handled, for pact experience had shown that aluminum often is susceptible to the corrosive action of brines."

Apr 1, 1931