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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 James S. Browning, W. H. Eddy

Laboratory batch and small - scale continuous flotation tests were conducted on a ferruginous barite - fluorspar ore from near Sweetwater , Tenn . , to determine the feasibility of producing commercial - grade fluorspar and barite concentrates . The lignin sulfonate - sodium fluoride - fatty acid method of floating fluorspar produced acid - grade concentrates . Flotation of the barite from the fluorspar tailing using petroleum sulfonate yielded concentrates suitable for use as a weighting agent in oil -well drilling muds . The continuous flotation tests , treating about 150 pounds of ore per hour , yielded fluorspar concentrates that assayed 98.3 percent CaF2 and barite concentrates that assayed 91.2 percent BaSO4 . The recovery of the two minerals was 91.2 and 85.2 percent , respectively .

Jan 1, 1964

By J. B. Gayle

Since the turn of this century, there has been increasing interest in the application of flotation processes to the beneficiation of finely divided minerals of various types, This is reflected by the large numbers of papers dealing with various aspects of this problem published annually both in this country and abroad. For the most part, such papers fall into one of three categories: 1. Those concerned with achieving, by various chemical and/or physical means, a set of conditions under which certain particles become potentially floatable while others do not. 2. Descriptive studies of plants and pilot plants effecting separations between such particles. 3. Studies of the effects of certain design and operating variables on the rates and efficiencies with which such separations can be effected.

Jan 1, 1959

By Arden D. Fugate

The Federal Bureau of Mines conducted extensive studies on solid-state defluorination (laboratory scale) and tests on molten defluorination (intermediate scale) of siliceous fluorspars. The studies were made to develop a pyrohydrolytic process for liberating fluorine from offgrade fluorspars. Test results showed that more than 90 percent of the fluorine can be evolved by solid-state defluorination at 1,300° C., and more than 97 percent can be liberated by molten-state defluorination at 1,420° C. Solid-state defluorination conditions were established by conducting tests on mixtures of ceramic-grade fluorspars and high-purity silica flour. Pelletized mixtures were defluorinated under varying conditions of time, temperature, and relative concentrations of silica, calcium fluoride, and water. The effects of adding various amounts and combinations of aluminum oxide and iron oxide on defluorination were also studied. Investigations of solid-state defluorination indicates that the following two reactions are involved: 2CaF2 + 3SiO2 = 2CaSiO3 + SiF4, and CaF2 + Sio2 + H20 = CaSiO3 + 2HF, The second reaction is dominant, although significant defluorination can be achieved by the first reaction.

Jan 1, 1961

By Raghoottma S. Pandurangi, Mohindar S. Seehra

"The interaction of amorphous 1ilica particles with several hydrogen bonding agents (H2O, C2H5OH, C7H2NO) was investigated by monitoring the changes in the bulk and surface IR vibrational modes of silica using photoacoustic spectroscopy. It is argued that the intensity of the silanol band at 3747 cm-1 provides (an inverse) quantitative measure of the interaction or surface groups, along with the shift in the broad hydroxyl band, the interaction following the order C7H2NO > C2H5OH > H2O. Index Headings: Silica; Surface vibrational modes; Photoacoustic spectroscopy; Hydrogen bonding agents.INTRODUCTIONThe use of m spectroscopy to study the adsorption on solid surfaces is well documented in the literature.1 2 For example, hydroxylation of a clean silica surface results in the formation of the free silanol group Si-OH, with a sharp IR band near 3747 cm-1• Further hydroxylation produces a broad band near 3500 cm-1, which is believed to result from various hydrogen-bonded silanol bands leading to a multilayered surface structure of few nm.3-5 Earlier studies had indicated a relationship between the surface silanol band and various chemical activities of silica such as cytotoxicity, 7- 9 catalysis, 10-12 and others.13 Recent studies from our group14-in which the intensity of the silanol band and cytotoxicity of silica, heat-treated at various temperatures up to 1095°C, were investigated have provided a strong correlation between cytotoxicity and intensity of the silanol band.Coating of silica by PVPNO (polyvinyl-2-pyridine N-oxide with the empirical formula C7H8NO), a strong hydrogen bonding agent, is known to reduce the cytotoxicity of silica, presumably by chemically blocking the silanol groups from phospholipids.15 This interaction of the hydrogen bonding agents with the silica can be studied by m spectroscopy, and Knozinger16 and Rouxlet and Semples11 have used transmission m spectroscopy to study the effect of various chemicals on the surface IR modes of silica. However, one of the major disadvantages of transmission IR spectroscopy is that the sample preparation (grinding and mixing with KBr and pelletizing) usually distorts the surface modes (see, e.g., Ref. 14) and there is always a doubt about the effect of the sample preparation on the measured properties. In recent years, photoacoustic (PA) spectroscopy has become the technique of choice for studying the IR spectra of samples in their natural state, since no sample preparation is necessary.18•19 Moreover, according to a recent paper, 20 the relative intensity of the surface modes in PA spectroscopy of silica particles is much higher than that in transmission FT-IR spectroscopy. Consequently PA spectroscopy is ideal for studying the surface chemistry. In this work, we have used PA spectroscopy to investigate the interaction of three hydrogen bonding agents (C7H8NO, C2H50H, and H20) with the silica surface by monitoring changes in the surface m modes. Our results show that the surface IR modes get perturbed to a larger extent than the bulk IR modes in interaction with the hydrogen bonding agents. Moreover, whereas in the earlier studies, the shift of the broad silanol band near 3500 cm-1 was used as a measure of the interaction with hydrogen bonding agents,16•17 here we show that the relative decrease in the intensity of the sharp silanol band near 3747 cm-1 also serves as a quantitative parameter for the relative surface coverage and surface modification. Details of this work are given below."

Jan 1, 1990

By Virgil J. Stachura

The Bureau of Mines conducted a series of delayed blasting experiments at a West Virginia contour coal mine that resulted in smoother highwalls. The 17; were smoother due to reduced overbreak and inherently safer A, to reduced likelihood of rockfall. Reduced overbreak was accomplished by an increase in the highwall hole delays, which changed the effective delay pattern geometry and the direction of burden movement. The blast delays in the highwall holes were 50 to 100 ms longer than the mine's nominal design pattern (flat V, 17- by 42-ms surface delays, 200-ms in-the-hole delay). The burden movement was effectively changed from a 45* angle to 90* with respect to the highwall. The results of the blast delay changes were evaluated using terrestrial photogrammetry to generate vertical profiles at regular intervals. This evaluation showed that delay changes produced generally smoother vertical profiles.

Jan 1, 1984

The U.S. Bureau of Mines (USBM) has developed a test procedure to compare the initiating strength of detonators by using adjustable-sensitivity liquid explosives. Various tests of detonator strength are currently used by the industry, but many of them do not quantify the ability of detonators to initiate detonation reactions in an explosive charge. The USBM used mixtures of nitromethane and ethylene diamine, the sensitivity being "fine-tuned" by 2-nitropropane. Military standard J-2, commercial No.6, and commercial No.8 detonators were evaluated using three test configurations: (1) axially immersed in the test explosive, (2) tip just touching surface of the explosive, and (3) immersed transversely in the explosive. Markedly different results were obtained for these three configurations, indicating that the directional effects are important. This explains why different detonator strength tests do not correlate well with each other. Some tests, such as the sand bomb and underwater, measure the total energy out-put, while other tests, such as the plate dent, test measure the energy in the axial direction. The USBM's test data indicate the importance of conducting the experimentation in the manner in which the detonator is actually intended to function.

Jan 1, 2010

By Martin H. Stanczyk

The direct dissolution of a typical zinc sulfide flotation concentrate by elevated temperature and pressure leaching was investigated. The concentrate assayed about 55 percent Zn, 32 percent S, 6 percent Fe, and 1 percent Pb and contained minor quantities of copper and precious metals. The influence of various factors on the dissolution of the zinc in acidic and ammoniacal pulps when using oxygen as the oxidant was determined. The tests revealed that the sphalerite was difficult to oxidize. Complete dissolution of the mineral required vigorous and intimate nixing of the gaseous, liquid, and sold phases. The addition of pyrite or sulfuric acid to water slurries of the concentrate was required to obtain a high zinc extraction when leaching under acidic conditions. The quantity of pyrite and acid used was about 0.125 and 0.25 pound, respectively, per pound of zinc sulfide contained in the leach charge. In tests with acid, about 96 percent of the zinc was extracted from the concentrate in 1 hour at 200° C. when the oxygen partial pressure was 75 pounds per square inch gage or higher. Leaching with a continuous flow of air as the oxidant gave results that were almost as good as those obtained when oxygen was used, In tests with air fed through the autoclave at 320 liters per hour, 95 percent of the zinc was dissolved in 1 hour, Acid leach solutions assaying approximately 58 grams Zn per liter and containing Fe, Ni, Cr, and Cu impurities were produced in the better tests. The leached residue consisted essentially of red iron oxide together with substantially all of the lead and precious metals.

Jan 1, 1961

Through a contract, the Bureau of Mines has funded the development of an Automated Breathing Metabolic Simulator (ABMS). The ABMS simulates man in all of the breathing and metabolic parameters for monitoring support and resuscitation equipment. For the first time, complete breathing and metabolic simulation are incorporated in the same device. Breathing rate, breathing depth, breath velocity contour, oxygen uptake, and carbon dioxide release are all variable over wide ranges, simulating conditions from sleep to hard work with respiratory exchange ratios covering the range of hypoventilation to hyperventilation. In addition, all of these parameters are remotely controlled to facilitate the use of the device in hostile test environments. The exhaled breath is also at body temperature and completely saturated. The simulation in faith¬ful to the extent of having a variable functional residual capacity and an anatomical dead space equivalent to that of humans. The ABMS will be used as a stand-in for humans in test and validation of respiratory equipment, permitting more extensive and safer evaluation in hazardous environments where human testing would have to be limited. In addition, it will greatly reduce the cost of prolonged testing in cases where simulation chambers with human subjects require three shifts of crews, including standby physicians. Perhaps most importantly, it will provide a calculated and reproducible test and validation facility. The ABMS is under complete computer control. Through a typewriter terminal the test sequence can be input into the computer which will then automatically adjust the ABMS to simulate any desired sequence of metabolic activities for time durations up to 15 hours. The computer also monitors the test procedures and provides test results printout.

Jan 1, 1973

By C. O. Hawk

Distillable oils derived from coal were desulfurized and hydrogenated at 2,500 psig in a two-step vapor-phase catalytic operation to give a product rich in saturated cyclic hydrocarbons. The first step was mainly a desulfurization at 400 C, the second a saturation at 300 C. One of the oils used as feed stock was from low-temperature carbonization of a bituminous coal, the other was from the liquid-phase hydrogenation of coal in the Bureau's pilot plant. The product from the saturation step was distilled to remove the light ends and high-boiling residue and to recover a fraction having acceptable properties with respect to heating value, density, freezing point, viscosity, and boiling range according to specifications suggested by the Air Force for ultra-high-speed aircraft fuel. Quantities of the fuel fraction available were too small for the thermal stability test approved by the Air Force. The experiments, performed on laboratory scale, comprised mostly a study of the effect of varying the oil feed rate (at constant oil-to-hydrogen ratio) on the yield of the desired fuel fraction. The yield of the fuel fraction made from low-temperature carbonization oil was a little more than 1 percent of the weight of coal carbonized; that from coal-hydrogenation oil was about 12 percent of the weight of coal hydrogenated. A few attempts to do both desulfurization and saturation in one operation with sulfur resistant catalysts, developed for vapor-phase hydrogenation or hydroforming, were unsuccessful. By leaving the low-boiling ends in both feed stocks to desulfurization, another product was obtained: a low-sulfur aromatic cut boiling below 200 C. This material would be suitable as a solvent or a chemical raw material.

Jan 1, 1965

By S. H. Ash

California leads the Nation in the number of operating metal mines and the small number of persons employed at individual mines, which reached a minimum irk 1932 with an average of seven men. The mines are scattered over the entire State, which is the second largest in area (155,562 square miles) in the United States. The mines are situated at various altitudes, with portals ranging from approximately 300 feet below sea level to almost 12,000 feet above. Many of the mines can be reached only during the summer, while at others the heat of the regions adds so the difficulties during the summer months Supplied of explosives the use (or, probably more correctly, the misuse) of which constitutes one of California's gravest mining problems; are handled and stored under condition that contribute many hazards. The problem of providing medical care is serious and complicated, especially at small mines and more particularly in the almost inaccessible mountainous regions; instances in which a knowledge of first aid would have been beneficial but was lacking, or when first aid was instrumental in saving life or limb because it was available are too numerous to be mentioned.

Jan 1, 1936

By W. E. Lamont

The Federal Bureau of Mines, in cooperation with phosphate companies in the Florida land-pebble area, made a comprehensive study of the waste clays, or "phosphate slimes," produced in the mining of phosphate rock in Florida. These slimes represent a significant ecological problem and a major deterrent to effective land recovery in the phosphate-mining areas. Physical, chemical, and mineralogical studies were made of slime samples submitted by 15 of the 16 plants in Florida in an effort to identify factors that prevent successful consolidation of the slimes and subsequent recovery of the mined lands. Results of these studies indicated that the clay mineral attapulgite, a hydrated magnesium silicate, was primarily responsible for the very poor settling characteristics of the slimes, and that the quantity of attapulgite in the slimes effectively controlled the settling rate, pulp density of terminal solids, viscosity, percent solids of filter cake, and flocculant requirements.

Jan 1, 1975

By John P. Powell

A comprehensive study of the effects of hydraulically fracturing water-flood wells in Oklahoma has been made by the Federal Bureau of Mines. This report presents results of that study and an analysis of some of the factors governing the results of fracture treatment on waterflood properties. Originally, hydraulic fracturing was used to stimulate oil production from old wells producing by primary methods, and its application to water-flooding was regarded with skepticism by most producers. However, since 1953 the number of fracture treatments of both oil and input wells in waterfloods has increased steadily. Hydraulic-fracture treatments in waterfloods have generally been successful in stimulating production from oil wells and increasing the rate of injection into input wells. Hydraulic fracturing has enabled several producers to turn probable failures into economically successful projects.

Jan 1, 1961

By W. J. McKenna

This paper, describing the milling practice at tine lead-zinc concentrator of the International Smelting Co., is one of a series of papers on milling methods being prepared by the United States Bureau of nines. The concentrator is operated as a unit of the International Smelting Co. and is located about 40 miles southwest of Salt Lake City, at Tooele, Utah. The Tooele Valley Railroad, operating between the plant and Warner, Utah, a distance of 6.5 miles, makes connection with both the Union Pacific and Denver & Rio Grande Railroads.

Jan 1, 1933

By Cheryl Hill, Michael Keane, Pamela Mike, Raghoottma Pandurangi, William Wallace, Mohindar Seebra, Val Vallyathan

"Dipalmitoyl glycerophosphorylcholine (lecithin) dispersed in physiologic saline, a model of the primary component of pulmonary surfactant, is adsorbed by respirable quartz and aluminosilicate dusts. Dust cytotoxicity as measured by erythrocyte bemolysis and pulmonary macrophage enzyme release is suppressed by this adsorption. The degree of suppression of hemolytic potential versus specific adsorption of lecithin from dispersion in saline by respirable quartz and kaolin dusts are compared with dusts' BET specific surface areas to interpret the prophylactic effect of lecithin adsorption. Dust hemolytic potential versus medium pH is presented. Fourier transform infrared spectroscopy and photo-acoustic spectroscopy of lecithin on quartz and of lecithin on kaolin are presented and reviewed with results of studies of the time course of removal of lecithin adsorbed on mineral surfaces by digestion by phospholipase enzyme. Results are discussed in terms of a model of prompt neutralization of respired mineral dusts by pulmonary surfactant, and a gradual re-toxification by digestive processes acting on the adsorbed prophylactic surfactant coating following phagocytosis. INTRODUCTIONQuartz dust of respirable size is well known to cause fibrotic lung disease, but numerous questions persist in the understanding of the initiation and progression of this disease. Our approach concentrates on physical and chemical aspects of mineral dusts early-on in their interactions with living organisms, and we have chosen simplified models to investigate that interaction.In the alveolar ·spaces of the lung, tissue is coated with a surface-active material (pulmonary surfactant), which, among other functions, mechanically stabilizes the lung from collapse by reducing the surface tension of water in the alveolar sacs.1 This surfactant is also the material that is first contacted by a mineral particle that is transported to an alveolus and is impacted there. This surfactant material has been studied extensively. The primary components are known to be proteins (about 11 % in dog lavage fluid), and phospholipids (about 88%).2 Pbosphatidyl cholines constitute roughly 80% of the phospholipid fraction; about 70% of the phosphatidyl choline fraction is dipalmitoyl lecithin (DPL).2 Respirable aluminosilicate particles are capable of adsorbing dipalmitoyl lecithin from dispersion in physiologic saline, a model for a possible initial event occurring upon deposition of a particle in a pulmonary alveolus. As may be seen from Figure 1, the DPL molecule has several fixed charges at neutral pH; a positive charge on the trimethylamine (choline) moiety, and a negative charge on the phosphate group. Also evident are the two fatty acid residues of palmitic acid, which are bonded through ester likages to the glycerol segment of the molecule. The fatty acid moieties of phosphatidyl choline make the molecule inso1uble in aqueous solutions under normal conditions, but a colloidal unit of aggregated molecules called a micelle is usually formed spontaneously above a certain minimum concentration. Small micellar vesicles are generally formed in the laboratory by using ultrasonic agitation or by solvent evaporation methods."

Jan 1, 1990

By Frank L. Hess

Vanadium, although widely spread in minute quantities through the crust of the earth, is found in few places sufficiently concentrated to be economically mined and prepared for use. Most rocks carry from a trace to a few hundredths of a per cent of vanadium oxide, and coal ash may carry about as much as the rocks, Much of the "coal" quoted in the literature as carrying vanadium has been asphaltite, and in other ccal the vanadium is of late introduction. The ash of the petroleums, though usually present in very small quantity, may carry a large percentage of vanadiun, so that production of vanadium from it has been seriously considered. Naturally the ashes of soze asphaltites similarly carry vanadium.' The great deposit at Minasragra, Peru, to which further reference will be made, is probably an altered asphaltite. Ilmenite and cther iron minerals usually carry vanadium 10 and some has been saved from the minette ores of France. 11 Many veins that carry lead copper and zinc minerals also carry a little vanadium, which, especially if the veins are in a comparatively dry region, such as the southwestern United States, northern Mexico, Northern Rhodesia, Southwest Africa, or Spain, collects in the oxidized parts of the veins as vanadinite,

Apr 1, 1932

By Milford L. Skow

Utilization of domestic ores in the winning of metallurgical alumina requires a convenj.ent method of treating siliceous bauxites and other aluminous materials. In the United states there are only small reserves of high-grade bauxite but considerably larger tonnages of low-grade material. In addition, there are large deposits of high-alumina clays. If these high-silica bauxites or high-alumina clays could be beneficiated, either by are dressing or by chemical dissolution to remove a large proportion of the silica, then the potential reserves of aluminum ores would be increased materially. Faced with a similar situation, the German industry, chiefly dependent on high-grade French bauxites prior to World War II, was compelled during the war to Use lower-grade ores. For desilicating the lower-grade bauxites before the Bayer treatment, a method was developed in which the bauxite was calcined and then given a dilute caustic leach preliminary to the pressure digestion. It was planned to regenerate the caustic by treatment of the desilication liquor with lime. As European bauxites are mineralogically different from those found in this country, preliminary work was undertaken to determine whether this process might be applied to domestic materials. The results of this work, along with a review of the German process, are presented in this report.

Jan 1, 1950

By A. P. Grossman

'This report was prepared by Shell Oil Company, Mining Ventures Department in accordance with Cooperative Agreement No. 14-09-0070-b53 dated September 10, 1976, between the United States of America, Department of the Interior, Bureau of Mines and C(b) Shale Oil I Project, Ashland Oil Inc., Shell Oil Company, Operator. After completion of this report the Shell Oil Company withdrew from participation In the C(b) Shale Oil Project and advised the Bureau of Minus that plans for publication of this report had also been withdrawn. The Bureau of Mines acting under terms of the Cooperative Agreement hereby releases this report for general information.

Jan 1, 1976

By R. M. Santmyers

Except for optical purposes and a few other special uses quartz and quartzite are to a considerable degree interchangeable. This also may be said with respect to pulverized quartz and ground silica sand, which are discussed in a separate paper of this series. All these materials, except perhaps quartz crystals of optical grade, are abundantly available in many parts of the United States. In the form of ordinary crushed stone much of it is sold at $1 a ton or less, and ordinarily

Aug 1, 1931

By E. P. Youngman

From a scientific point of view , the zircon is by far the most remarkable of the gem stones , and a satisfactory solution of the problems offered by its characters and constitution has not yet been made . 3 Three distinct forms have been recognized , differing in specific gravity , hardness , optical properties , behavior when heated , and color.4 ( See section of this paper entitled "Description and Properties . " ) Zircon as a gem stone has not been as well known as its properties warrant . It is one of the most brilliant of the precious stones (having a high refractive index) . The colorless zircon rivals the diamond in brilliance and fire play to such an extent that a judgment based entirely upon optical inspection might be erroneous . In the opinion of gem authorities , the colored stones likewise have much merit . The blue zircon ( " Starlite" ) was so named by Kunz because of its resemblance to a " star twinkling in the night . " Another gem authority describes the leaf- green stone as one possessing a restful beauty , the red stone as having a certain ( though somber) grandeur , and the golden-yellow stone as being unsurpassed in magnificence . The slowness with which the zircon , a stone frequently mentioned in ancient literature , has come into use in modern jewelery may be owing to the fact that authorities differ as to whether the colorless and the blue zircons are found as such in nature or are treated stones . Any treated stone , although the material of which it is composed may be essentially genuine , has been considered a deception . However , according to Kunz , " Starlite is now sold over the entire world ; never has anything been so well introduced. "7 Dr. Foshag, mineral curator of the United States National Museum, states that the first allotment of zircons to enter the United States was obtained in 1921 from Siam ( through France ) for scientific or museum purposes and that four or five years later the stones were adopted by the jewelers of this country . Retail jewelers are displaying the colorless type and the blue stones , especially , in finger rings , necklaces , and like ornaments . Fine crystals have been used somewhat extensively in jewelling watches and as supports for the edges of fine balances . At one time zircons were though to be appropriate in mourning jewelery .

Jul 1, 1931