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By B. L. Razzaboni, P. Bolsaitis

"The formation of reactive oxygen species resulting from the interaction of silica dust particles with red blood cell membranes was investigated; particularly, the effect of surface hydroxyl (silanol) group concentration on the rate of formation of such reactive oxygen species was investigated. The rate of formation was measured indirectly through the effect of catalase, a hemoprotein peroxidase, on silica-induced hemolysis. It was found that the addition of exogenous catalase to erythrocytes markedly reduces the hemolysis caused by silica particles. Furthermore, the amount of catalase required for deactivation of silica per unit area of particle surface is lower for fumed silica particles and calcined crystalline particles than for uncalcined, crystalline silica, suggesting a correlation between the concentration of OH groups at the silica particle surface and its potential for generation of H2O 2• The addition of albumin, a copper chelator, also decreases hemolysis. These results suggest that the hemolysis caused by silica particles is at least partly related to the formation of H2O2 at the particle surface and its subsequent reaction with Cu+ ions. The relationship between the concentration of surface silanol groups on the silica surface and the amount of catalase required to decrease hemolysis may also provide a method for testing potential fibrogenicity of respirable dusts. IntroductionReactive hydroxyl groups on silica surfaces are known to be cytotoxic and are believed to play a major role in silicosis (1-9). It has been proposed that this cytotoxicity results from hydrogen bonding to cell membranes and a resulting increase in membrane fluidity and permeability (4). Surface hydroxyl groups on silica surfaces have also been shown to interact with carbonyl oxygens in cell membranes (1,5). An extensive study by Nolan et al. (6) of the relationship between the negative surface charge resulting from ionized silanol groups and the hemolytic activity of crystalline a-quartz (Min-U-Sil) has shown a positive correlation between hemolytic activity and the surface concentration of silanol groups. These authors demonstrated that the hydrogen bonding of polyvinyl-N-oxide (PVPNO) with silanol groups, as well as the bonding of metal cations to the ionized sm- groups, results in significant decreases in hemolytic activity. Furthermore, it has been found that the complete removal of surface hydroxyl groups from the surface of respirable silica particles nearly eliminates the hemolytic potential of silica (7), suggesting that hydroxyl groups might be involved in other cytotoxic processes associated with silica-induced lung injury. Reactive oxygen species have been .implicated in cellular damage caused by respirable silica particles. Evidence for the presence .of oxygen radical species (02, OH°, H2O2) generated by silica, especially on freshly formed surfaces, has been produced by various investigators. Kalbanev et al. (8) detected H2O 2 in aqueous suspensions of quartz. Electron spin resonance and spin trapping by Shi et al. (9) confirmed the presence of OH"" radicals in aqueous suspensions of quartz, and Gulumian and van Wyk (10) suggested that both glass and quartz produce hydroxyl radicals in the presence of H2O 2 • Gabor et al. (11) detected the presence of malondialdehydereactive lipid peroxides (i.e., lipid-0°) in cultures of macrophages and respirable silica particles using the thiobarbituric acid (TBA) reaction test. Will (12), however, reported that iron enhances the TBA value of peroxidized lipids, and Scheulen and Kappus (19) found that catalase augmented malondialdehyde formation, thereby increasing the TBA values."

Jan 1, 1990

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 Thomas C. Mowatt

Preliminary Bureau of Mines studies of mafic igneous rocks collected from the Rabbit Creek area, northwestern Alaska, indicated concentrations of platinum (412 to 1,406 ppb) and palladium (343 to 892 ppb) in five of eight samples analyzed. The samples represent boulders and cobbles of mafic/ultramafic rocks from this locality. They are not from outcrop. Petrologically, (on the hand specimen scale) the samples are crudely to well-layered and are troctolitic ± gabbroie in character, with primary igneous mafic minerals strongly altered. Small patches of interstitial sulfide minerals, including chalcopyrite, bornite, pyrrhotite, pyrite, and covellite are associated with these altered zones and elsewhere through the specimens. Copper values ranged from 0.1 to 0.3 pct in samples analyzed semiquantitatively; nickel, cobalt, and chromium contents are low. Chemical, mine alogic, and petrographic relationships suggest that the rocks of similar character outcropping in northwestern Alaska could also be considered as prospective for- concentrations or platinum, palladium, and copper.

Jan 1, 2011

By R. J. Marek

The number of persons fatally injured in the California petroleum industry in 1931 was 30, a decrease of 20 fatalities or 40 per cent from the number killed in 1930. As a result of the decrease in the number of fatalities for 1931, the fatality curve of the California petroleum industry reached its lowest point in nine years. Although reductions in personnel--which permitted the retention of a select and experienced class of workmen, decreased active field-development work, and curtailed production--undoubtedly have had a marked effect on reducing the number of fatalities in 1931, the decrease also has resulted from continued accident-prevention efforts. Statistics show that a direct relationship exists between development activity and the number of men accidentally killed in the drilling and producing division of the California petroleum industry. For example, when the average number of drilling wells in 1930 was 29 per cent less than in 1929, the number of men accidentally killed at drilling wells dropped 48 per cent; and when the average number of drilling wells in 1931 decreased 52 per cent from 1930, the number of fatalities at drilling wells decreased 58 per cent. The relationship between field-development work and fatality frequency is significant because each year at least 50 per cent of all the fatalities in the California petroleum industry occur in the drilling and producing division. This relationship should serve to guide the accident-prevention efforts of the industry, especially in the drilling and producing division, toward checking an increase in fatal accidents when development activity again takes an upward trend.

Jan 1, 1932

By R. V. Lundquist, H. Leitch

Two hydrated calcium aluminates , formed by side reactions in the leaching step and desilication step of the lime- soda sinter process , were investigated to better define their influence on alumina recovery . The two calcium aluminates , Caз [ Al ( OH) 6 ]₂ and зCa0.Al½ 03 · ( 8-12 ) H₂ ) , were prepared and identified by chemical and X- ray analysis . The relative proportions of each of these compounds formed in typical leach solutions at several temperatures were determined . The influence of free lime as a promoter of calcium aluminate formation was also investigated . The formation and precipitation from leach liquors of calcium aluminates contributes to the low alumina recoveries in the process . The presence of carbonate ion in the leach solution suppresses calcium aluminate formation and precipitation and results in higher alumina recovery . Hydrated calcium aluminates are formed in the aging of lime - soda sinters in the normal atmosphere .

Jan 1, 1963

By Irving Hartmann

The Bureau of Minas has been charged by the Congress with the responsibility for administrating the provisions of the Federal Coal-Mine Safety Act. One of the important duties of bureau inspectors under this act is to determine whether proper measures are taken to prevent mine explosions, which in moat miner includes Judea adequate rock dusting The investigation made after the explosion in Orient No. 2 mine, December 21, 1951, showed that much information is lacking on the adequacy of current rock-dusting and duet-sampling practices in the United States. To obtain such information, an intensive sampling survey was conducted by the Bureau in an Indiana coal mine. This paper summarizes the more Important findings from this survey, describes special samplings at several Pennsylvania coal miners, and discusses related studies in the Bureau's Experimental coal mine.

Jan 1, 1954

By R. D. Leitch, W. P. Yant, A. C. Fieldner, R. R. Sayers, S. J. Pearce

"The detection of leakage is a recognized problem in the safe and economic distribution and use of natural gas. Natural gas is practically odorless and therefore lacks he property of indicating significant leakage by the sense of smell, the means most widely used by gas employees and consumers for detecting leaks of the more odorous types of fuel eases. In view of the recognized value of the odor of gas for indicating leakage at the time of occurrence the Bureau of Mines has studied' the possibility of adding small amounts highly odorous substances to types of fuel gas (such as blue water gas and natural gas) that lack warning properties. These studies revealed that the mercaptans were promising substances to accomplish this purpose, not only for odorizing fuel gases but for other purposes° where it was desired to give warning through the sense of smell.Since completing the studies mentioned, the Bureau of Mines jointly with the American Gas Association has conducted further investigations dealing with the use of warning agents for fuel gases. The results of this work will be published later.The Bureau of Mines had been desirous of observing the practical use of ethyl mercaptan for detecting leakage of natural gas, particularly to determine whether the odor would permeate the ground and give indication of lea's in underground pipes. Opportunity for making these observations was recently given by E. A. Munyan, manager, gas department, Union Gas t Electric Co., who requested the bureau's cooperation in making leakage surveys of the company's distributing systems at Franklin and Middletown, Ohio."

Jun 1, 1930

By J. O. Winget

Phosphonic acid and iminodiacetic acid chelating resins were investigated to assess their potential as selective ion exchangers for separating lanthanide elements and yttrium . The affinity of phosphonic acid resin for lanthanides increases with increasing atomic number , and that of iminodiacetic acid resin for lanthanides increases with atomic number to a maximum for element 62 and then declines with atomic number throughout the remainder of the series . Elution sequences of the elements with mineral acid eluants corresponded favorably with equilibrium data , whereas the elution sequence obtained with chelating eluants was proportional to the relative values of the stability constants of the chelating agents with the lanthanides . Separation of lanthanide mixtures into groups of light and heavy elements with iminodiacetic acid resin appears feasible .

Jan 1, 1964

By E. R. Cole

This Bureau of Mines investigation was prompted by the need forr a stable anode for electrowinning metals, particularly zinc and copper, from acid solutions. The polarization behavior of Pb-Ag (1 pct Ag) anodes in H2SO4 and fluoride solutions was determined as the first step in the development of such an anode. A Luggin capillary, dc power supply, high-impedance voltmeter, and other equipment standard to an electrochemical laboratory were used in this study. It was determined that during polarization, a relatively hard, stable coating of Pb02 was formed on the surface of the lead-silver anode and the rate of formation of this coating was considerably enhanced by the presence of fluoride ions in solution. Subsequent investigations at the Bureau of Mines Rolla Research Center resulted in the development of a Pb02-coated titanium (Pb02-Ti) anode. Results of this effort were presented in Bureau of Mines Report of Investigations 8111. Additional data resulting from extensive testing of the Pb02-Ti anodes, as well as process improvements and innovations, are included in this report. The anodes were considered generally unsatisfactory for zinc electrowinning because of lower conductivity, higher oxygen overvoltages, and shorter in-cell life as compared with the Pb-Ag anodes now being used in industry. However, the PbO2-Ti anodes were used successfully to oxidize waste chromium solutions and to electrowin copper.

Jan 1, 1981

By Harold P. Rue

The problem of removing hydrogen sulphide from natural gas has become within the last few years one of major importance to the natural gas and petroleum industry. Several gas fields in the United States produce natural gas containing hydrogen sulphide, and a number of oil fields produce gas which contains hydrogen sulphide. 3 The percentage of hydrogen sulphide in natural gas produced in these fields varies from a fraction of 1 per cent to as high as 20.5 per cent by volume. Hydrogen sulphide is probably the most toxic gas associated with natural gas, and from the standpoint of health and safety it is important that the hydrogen sulphide be removed if the gas is to be used for domestic purposes. Hydrogen sulphide, besides being toxic and therefore a hazard to animal life, is under certain conditions an active corrosive agent and very destructive to equipment. The annual loss caused by the corrosive action of hydrogen sulphide on equipment amounts to hundreds of thousands, perhaps millions, of dollars. The largest percentage of natural gas produced in the United States comes from wells which also produce oil. This associated gas invariably carries with it light fractions of petroleum, which when separated from the gas, condense to the liquid form at ordinary temperatures and pressure. Commercial application is made of this natural condition, and "wet gas" is processed to obtain so-called natural gasoline by employing the principles of absorption, adsorption, or compression and subsequent expansion accompanied by cooling. In the manufacture of natural gasoline from wet gas which contains hydrogen sulphj.de, if this contaminating gas is not first removed, some of the hydrogen sulphide may oxidize to form free sulphur and water. The free sulphur will dissolve in the gasoline produced by any of the aforementioned methods and cause the product to be positive to the corrosion test and there-fore unsuitable for commercial use in that condition. The objectionable sulphur compounds can be removed by washing the gasoline with a solution of caustic soda or other chemicals, but this treatment is expensive. It is advantageous therefore to remove the hydrogen sulphide from the gas before it is processed in a natural-gasoline plant.

Jan 1, 1932

By T. E. Green, E. F. Spano, W. J. Campbell

A combined ion - exchange X- ray spectrographic method was developed and evaluated for determining trace amounts of cobalt and nickel in high - purity tungsten and tungsten trioxide . The sensitivity for both cobalt and nickel is in the range from 0.2 to 0.5 μg ( 0.04 to 0.1 ppm , based on 5 gram samples ) . Accuracy at the 5 to 20 μg level is ±10 percent of the amount present . Approximately 16 hours elapsed time is required for analysis

Jan 1, 1963

By Raymond B. Ladoo

Garnets are usually found well crystallized in the cubic system , the principal forms being rhombic dodecahedrons , tetragonal trisoctahedrons or combinations of the two , and hexoctahedrons . They also occur as rounded disseminated glassy grains and in compact massive , laminated or gramlar aggregates . They vary greatly in color , but the most common garnets , almandite and andradite , are most often found of a dark red or reddish brown color .

Apr 1, 1922

By H. A. Watson

Laboratory tests on three commercial methane detectors, two combustion- type detectors and one interferometer-type detector, were made by the Bureau of Mines to determine their response to certain single and multiple flammable gases mixed with normal and abnormal air atmospheres. Although both types of detectors responded accurately to methane-normal air mixtures, they did not show correct concentrations for other single flammable gases in air. Uniquely, the response of the interferometer-type detector to hydrogen was in a negative direction. The effects of individual gases in multiple flammable gas mixtures were approximately additive. In oxygen-deficient atmospheres the methane response of the interferometer-type detector erred on the high side, but only in very low oxygen concentrations were the combustion-type detectors affected-- showing low, erratic methane readings.

Jan 1, 1966

By Ruth F. Brinkley

This circular summarizes the research and technologic activities and publications of the Federal Bureau of Mines Division of Explosives Technology4/ during fiscal year 1959 (July I) 1958-June 30, 1959). Part I briefly describes the programs that were active during the report period and presents a summary of some of the information not published elsewhere. In many instances the results are only preliminary and are subject to revision on the basis of continuing investigations. Detailed reports of all programs not security classified will be made later. Part II lists and describes briefly the publications of the Division during fiscal year 1959. If the published material has some bearing on activities still current during the report period, this is indicated by references in Part I.

Jan 1, 1961

By Graham W. Marks

The general positions of the absorption maxima of aqueous solutions of the violet and green isomers of chromic sulfate the visible spectral region have long been known, but, to the knowledge of the writer, no comprehensive studies have ever been made. To gain further knowledge concerning these inorganic complexes and to investigate the possibilities of developing an analytical method for determining the concentrations of the violet and green isomers in a mixture, a more complete investigation was made in the spectral range from 325 to 850 millimicrons.

Jan 1, 1951

By Clarence Hall, CHARLES F. MUNROE

Of the common causes of the larger mine accidents, such as falls of roof and coal, gas and dust explosions, mine fires, and the misuse of explosives, all of which are often closely related, each must be studied and fought in a manner peculiar to itself. The last mentioned, the misuse of black powder and other explosives, is sometimes considered the least important of these causes of mine accidents; but its impor- tance is much greater than the statistics indicate, for the reason that the misuse of explosives is the true cause of many of the fatal mine fires, gas or dust explosions, and falls of roof that are credited to other causes. Both the quantity of explosives used and the number of purposes to which they are applied are increasing. They are now made at about 150 plants, in different parts of the United States, and the product of a single year is estimated at nearly 500,000,000 pounds. Nothing in all this material is a safe or "safety" explosive when in the hands of a careless or ignorant person; and this is true whether considered in connection with the shipment or the use of these explosives. In addition to the large losses of life and property resulting from an improper use of explosives in mining, the recent statistics of the railway bureau for the safe transportation of explo- sives have shown more than 400 persons killed or injured and over $3,000,000 worth of property destroyed by explosives in transit by rail. The fact that three years of cooperative effort under the wise supervision of this bureau has reduced these losses to almost nothing encourages the hope that similar cooperative effort may likewise greatly lessen losses of life and property from the use of explosives in mining. The additions to the large death roll of our mines make a recurring appeal to the public for fair treatment of the coal-mining industry, and to the miner and the manager that they join in every possible effort for greater safety. It may never be possible under conditions such as exist to-day to prevent mine accidents entirely. Little can be accomplished in that direction by either the operators or the miners working alone, but experience in all countries shows that

Jan 1, 1911

By C. W. Schultz

The vapor pressure of manganese in equilibrium with a series of liquid iron-manganese alloys was determined by the carrier gas method over a broad range of alloy composition. From these data the activities of manganese in the iron-manganese system were calculated. The system appears to be ideal.

Jan 1, 1966

By D. H. Carlson, J. H. Johnson

"The U.S. Bureau of Mines and Michigan Technological University (MTU) are collaborating to develop an apparatus for measuring diesel tailpipe emissions in underground mines. A tailpipe emissions measurement apparatus (EMA) is described that dilutes diesel exhaust and measures the concentrations of diesel particulate matter (DPM), CO, CO2, NO, and NO2 at known dilution ratios.The EMA was evaluated by side-by-side comparison of its measurements with those by laboratory grade instruments. Concentrations of CO and C02 measured by the EMA were usually within ± 14 pct of concentrations measured by laboratory-grade instruments for CO and ±20 pct for C02• EMA measured DPM concentrations were, on average, 29 pct lower than those measured by laboratory-grade instruments, with the differences being fairly consistent. The CO and C02 differences are related to the method of calculating the EMA's dilution ratio, and the difference in DPM concentrations is attributed to thermophoretic and/or condensation losses related to the EMA's unheated sample probe. Preliminary analysis of data obtained with a heated sampling probe and modifications in the sampling procedures have indicated reduced variability in DPM and in the calculated dilution ratios."

Mar 1, 1992

By Charles B. Kenahan

Vanadium is subject to only light corrosion in phosphoric acid at temperatures up to 60° C. and has a moderate corrosion rate in this acid at 100° C. It is relatively corrosion resistant in sulfuric and hydrochloric acids up to 60° C, but corrodes rapidly at 100° C. It corrodes rapidly in dilute nitric acid at 35° C. Vanadium is almost inert in 10-percent solutions of formic, acetic, lactic, tartaric, and citric acids; in 9-percent oxalic acid it corrodes slowly up to 60° C. and rapidly at 100° C. Vanadium is resistant to corrosion in substitute ocean water, tapwater, and in 3-percent sodium chloride and 10-percent sodium hydroxide solutions. It is readily attacked, however, by 20-percent ferric chloride, 20-percent cupric chloride and 5-percent mercuric chloride solutions. Vanadium is protected by contact with magnesium, aluminum, and steel SAE 4130 in substitute ocean water, by magnesium and aluminum in 3-percent sodium chloride solution, and by magnesium in tapwater. Vanadium protects copper in substitute ocean water. When vanadium and stainless steel are coupled in sulfuric acid solutions, both metals are usually unaffected by contact, whereas the corrosion rate of titanium in sulfuric acid is greatly reduced by contact with vanadium.

Jan 1, 1962

By L. W. Scott

This report presents an overview of explosionproof (X-P) enclosure research being conducted by the Bureau of Mines, This report emphasizes the increasing importance of research related to the safety con- siderations of X-P enclosures used in underground coal mines. Selected topics are included that summarize results of research in the areas of electrical clearances, reliability of enclosures with windows, safety factors in X-P enclosures, potting materials, performance tests for X-P enclosures, protection against high-voltage explosions, and innovative X-P devices.

Jan 1, 1985