Search Documents

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 Edward Roberts

This is a progress report of an investigation by personnel of the Bureau of Mines from June to September 1951 to introduce preservative chemicals into growing timber. It also describes in detail the impregnation process, known as the collar method, developed by the United States Department of Agriculture2/ Twenty-eight trees were treated by this method, and a complete record was kept of each individual tree and of each timber cut from it. These timbers have been placed in a coal mine, and their tendency to decay is compared to that of adjacent untreated sets. Although several years will be required before final conclusions can be drawn, this report explains the appearance and encouraging results of the treated timber to date. Also included are some comparative costs of untreated timber, treated timber by the commercial pressure method, and treated timber by the collar method. INTRODUCTION In the hope of increasing the useful life of cut timber, experiments to impregnate growing trees with wood-preservative chemicals by utilizing the natural flow of sap have been carried on for centuries. None of the various methods used in these experiments has ever gained any widespread use because they have been commercially impractical.

Jan 1, 1953

By William J. Campbell

One of the principal objectives of the Bureau of Mines program for developing super refractory materials is to obtain fundamental data on the physical properties of refractory oxides. This particular investigation obtained accurate thermal expansion coefficients for alpha alumina and evaluated, critically, those coefficients with other published values. High-temperature X-ray diffractometer measurements, by the Bureau, showed that alpha alumina expands anisotropically with expansion parallel to the c axis approximately 10 percent greater than parallel to the a axis. Thermal expansion characteristics of four different alumina samples were determined up to 1,200° C.; the results are presented in both tabular and graphical form. The combined random and systematic errors in the measurements are considered less than 3 percent above 500° C, and approximately 2 percent at 1,000° C. No differences in expansion were observed between the samples or between the heating or cooling cycles.

Jan 1, 1961

By J. S. Dunning

The objective of this research by the U.S. Bureau of Mines was to determine the effects of AI additions on the sulfidation resistance of Fe-Cr-Ni alloys. A series of Fe-Cr-Ni alloys with and without -additions of 4 pet AI were tested in a wet S vapor atmosphere at 677 C. A study of the morphology and composition of corrosion scales indicated a different corrosion mechanism for AI-free alloys compared with AI-containing alloys. Aluminum-containing alloys formed a compact, tightly adherent layer at the metal-scale interface that reduced corrosion rates by a factor of 3 to 10 compared with that of AI-free alloys. The thin, adherent AI-containing scale limited inward diffusion of 0 and S to the base metal and outward diffusion of Ni from the base metal. Aluminum-containing alloys formed a three-layer scale in oxidizing-S environments, while AI-free alloys formed a less protective two-layer scale.

Jan 1, 1989

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 A. H. Beebe

This paper describing the operations of the Cresson mine of the Cresson Consolidated Gold Mining & Milling Co. at Cripple Creek, Colorado, is one of a series of papers on mining methods and costs being prepared by the United States Bureau of Mines. The Cresson has recently been the most, important mine in the Cripple Creed district. During 1932 and 1933 an average of 230 tons of new ore (excluding dump material) that averaged about $10 in gold was shipped daily; 150 to 175 men were employed. Stoping was by the shrinkage method exclusively. The ore was screened washed, and hand-sorted at the surface and shipped to the Golden Cycle mill at Colorado Springs for treatment. A considerable proportion of the production was made by lessees working under the so-called "split-check" system. The authors are indebted to the management of the Cresson Consolidated Gold Mining & Milling Co. for permission to publish this paper.

Jan 1, 1934

By D. Harrington

"The fire boss in coal mining and the shift boss in metal mining, though held responsible to a large extent for safety of underground employees and of the mine, are, it seems to me, not always vested with sufficient authority nor given compensation commensurate with their duties. The metal-mine shift boss, although his position as regards his relations between employer and employee, is frequently an unenviable one, has as a rule much more authority than the fire boss and is not expected to perform the menial tasks required of the latter by many coal-mining companies.In most coal-mining States the coal-mine foreman and the fire boss are re¬quired to possess a certificate of competency obtained by passing an examination. The foreman is legally responsible for the safety of the miners, as in most instances the superintendent is not required to pass an examination. Although the foreman is held legally responsible for the safety of the miners, the law does not, in general, compel the superintendent or other higher officials to delegate sufficient authority to the foreman to enable him to put his wishes or judgment into effect; and this condition has tended in many instances towards perpetuation of unsafe conditions.The fire boss is held legally responsible for conditions in his ""beat"", but he is generally given only such authority as the mine foreman sees fit to delegate, frequently very little, Moreover, the fire boss is generally required to cover his ""beat"" within two hours before the entrance of the underground workers. Only too often his territory is so great that in order to reach all the working faces and chalk the required date at the face, he must travel at a rapid walk or even run. When such haste is necessary to cover the required ground, it is manifestly im¬possible for the fire boss to make a careful inspection or examination of the roof, timbering, wiring, gas, etc., at each place, and doubtless in his hurry many unsafe conditions escape his notice."

Sep 1, 1920

By Arden D. Fugate

This work was conducted to determine a feasible process for converting siliceous fluoride offgases to a commercially usable product. The offgases were generated by pyrohydrolytic defluorination of low-grade fluorspar in a gas-fired rotary kiln, and fluorine was collected as a hydrofluoric-fluosilicic acid. A silicon-free fluoride solution for further processing was then produced by neutralizing the acidic scrubber solution with anhydrous ammonia, silicon being separated as orthosilicic acid. Ninety to ninety-nine percent of the fluorine originally present remained in solution as ammonium fluoride. Silicon was also separated from synthetic fluosilicic acids, having F-to-Si weight ratios ranging from 3.50 to 14.3. The solutions below a ratio of 4.06, the F-to-Si ratio of H2SiF6, containing dissolved silicon were desiliconized as completely as those containing less than the stoichiometric quantity of silicon. An electrolytic-grade cryolite was recovered from the ammonium fluoride solution by reacting with either sodium aluminate or alumina trihydrate and sodium hydroxide. A product containing 97 to 100 percent of the fluorine, represented by Na3A1F6, was recovered, and 94 to 99 percent of the theoretical yield was realized.

Jan 1, 1963

By J. B. Zink, M. J. Peterson

A semiquantitative spectrochemical method was developed and applied to the analysis of ash of U.S. coals . A low- temperature ashing procedure was used to minimize the loss of volatile elements . The analytical procedure provides for the estimation of 68 elements including major , minor , and trace constituents . Standards for the trace elements were prepared in a synthetic base mixture that approximates the average composition of U.S. coal ashes . Excitation was achieved with a d- c arc , spectra were recorded photographically , and interpretation was made by visual comparison of spectra of unknowns with spectra of graded standards series . Thirty- six trace elements were found in the analysis of 900 samples . Details of the procedure are presented , including sample and standards preparation , excitation and exposure conditions , spectral lines used , and approximate limits of detectability .

Jan 1, 1964

By T. C. Campbell

This Bureau of Mines publication presents an analysis of information related to the transportation of bituminous coal by unit trains and slurry pipelines. Even for short hauls from mines to markets, transport costs frequently account for between one-third and one-half of the delivered price of coal. Minimizing these costs has become an even more critical objective for hauls from the western mines than for hauls from farther east. Factors related to minimizing costs and transporting the western coal receive special attention. Although no general rule of preference is likely to be developed that can be applied to all shipments, both rail and pipeline service will be needed on an increasing scale. The study should provide useful background information and analysis for government and industry in approaching investment decisions in the mining and transportation industries.

Jan 1, 1975

By G. L. Oldright

[This paper is the fifth 4/ of a series of publications on smelting in the load blast furnace. The objects of this investigation are to determine the conditions obtaining within the blast furnace by direct experimentation, and to correlate the behavior of the furnace at various tines with the main factors governing the operation of the blast furnace, and metallurgical losses.]

Jan 1, 1929

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 E. C. Perkins, R. S. Lang, D. M. Taylor, H. Dolezal

The amenability of titaniferous slags and domestic mineral concentrates to chlorination was determined in a 6 - inch diameter fluidized bed chlorinator . Ilmenites from Valley County , Idaho ; Aiken , S.C ,; Trail Ridge , Fla .; and MacIntyre , N.Y .; and a titaniferous magnetite from Iron Mountain , Wyo . , were used in preparing the slags . The domestic minerals tested were an ilmenite concentrate from Valley County , Idaho , and a rutile concentrate from Magnet Cove , Ark . A high - grade Australian rutile was used as a standard for comparison . The impurity content of the slags and minerals tested , which was the most critical factor affecting their performance , was dependent on the geographical source of the material . All of the materials tested were amenable to chlorination in a fluidized bed although some required special operating conditions . Titanium extractions and chlorine utilization were over 90 percent for most of the slags and the Australian rutile . The Valley County , Idaho , ilmenite performed well in the reactor despite its 34 percent iron content .

Jan 1, 1963

By George L. Gates

The Bureau of Mines studied pressure-buildup data from a number of California gas wells to determine if the reservoir properties calculated from these data correlated with field-observed reservoir properties. Pressure-buildup curves from 24 wells showed distinct changes in slope, indicating changes in permeability of the reservoir rock. Calculated distances from the wells to indicated permeability changes were in fair agreement with distances deter-mined in the field. Pressure-buildup curves from three wells had more than one distinct change in slope, indicating multiple permeability changes. Thus field data supported the theoretical relations used to calculate reservoir properties from pressure-time relations measured in gas wells.

Jan 1, 1967

By B. C. Parks

This is the first of a series of reports on the relation between microscopic composition and chemical and physical properties of banded bituminous coals. It describes the relation between microscopic composition and behavior during thermal decomposition of a heterogeneous, high-volatile A bituminous coal from the Chilton bed in West Virginia. The standard free-swelling test was used as a simple means of studying the effect of heat on the coal. Although swelling indexes are not precise indicators of coal behavior in the coke oven and have limited value in caking investigations, they are reliable for predicting expansion of coal in a fuel bed and have practical value in the study of fuels. The swelling test also supplements other useful laboratory tests for determining the plastic and expansion properties of coal.

Jan 1, 1957

By Doug Scott

Develop tools that companies can use to comply with 29 CFR 1910.1200.

By D. P. Schlick

The German experience in dealing with the health hazard of respirable dust in underground mines is reported from first-hand observation in this Bureau of Mines paper. The report covers-- 1. The control of dust by water infusion, water spraying, and ventilation. 2. The sampling devices (tyndalloscope , konimeter , and BAT-I) and methods used to determine the dust concentrations in mines. 3. The systems of classifying hazardous and safe dust levels in mines. 4. The research facilities devoted to theoretical and applied work on mine dust and pneumoconiotic disease. Tile major research projects on dust and disease now underway in West Germany are outlined in an appendix.

Jan 1, 1970

By D. W. Bridges, R. O. Dannenberg, Laird Crocker

Preliminary solvent extraction studies , reported by the Bureau of Mines (5) , have been continued and expanded to improve on the previous estimate of process requirements . The solvent extraction portion of the process was examined at a scale large enough to enable meaningful extrapolation of the results to geometrically similar equipment of plant size . About 82 pct of the beryllium was recovered from approximately 0.5 pct beryllium oxide (Be0) Spor Mountain , Utah , ore by a process involving ( 1 ) sulfuric acid leaching , ( 2 ) counter current decantation (CCD ) washing , (3 ) iron ( III) reduction by sodium hydrosulfide ( NaHS ) , ( 4 ) beryllium solvent extraction by di - 2- ethylhexyl phosphoric acid ( EHPA) , ( 5 ) caustic stripping of beryllium- bearing EHPA, (6 ) hydrolysis of sodium beryllate - caustic strip liquor , and (7 ) calcination of beryllium hydroxide (Be ( OH ) 2 ) formed in step (6 ) . The resulting beryllia assayed 98 to 99 pct Be0 and was suitable for most nonnuclear uses . Best overall results were obtained by using pH 2 , 1.6 grams of BeO per liter of leach liquor as feed and 0.25 N EHPA in kerosine containing 2 wt vol pct (grams per 100 ml of solution ) isodecanol ( IDA ) as solvent . Analysis of the data indicated that a commercial plant would achieve 95- pct overall extraction operating at 45 ° C with 20 hp per 1,000 gal of dispersion in each of seven mixer- settlers , having 290 gal per ton of ore hourly mixer capacity and 90 gal per ton of ore hourly settler capacity . At least 79 lb H2SO4 , 13 lb sodium hydroxide (NaOH ) , 3 lb NaHS , 0.25 lb kerosine , 0.07 lb polyacrylic flocculant , 0.03 lb EHPA , and 0.007 lb IDA would be required in H2SO4 leaching and subsequent processing to recover 1 lb BeO .

Jan 1, 1964

By John J. Henn

As part of the U.S. Department of the Interior programs on rutile, authorized by the Office of Emergency Preparedness in June 1967 under provisions of the Defense Production Act, the Bureau of Mines reviewed available literature on major proposed processes for producing rutile substitutes. The processes are grouped according to the major processing step, and important operating features are described. Sixty-one references are cited.

Jan 1, 1970

By P. M. Gruzensky

Several experiments have been carried out in efforts to evaluate qualitatively a variety of electrolytes for refining bismuth. Most extensive work was done with the basic tartrate, hydrochloric acid, and hydrofluosilicic acid electrolytes. Deposits that are smooth and adherent can be obtained from these three electrolytes if low cathode current densities are employed. All three electrolytes were effective in purifying crude bismuth considerably, with additional purification indicated in each instance by a reelectrolysis step. With the basic tartrate electrolyte best results were obtained when the electrolyte was at 40° C, and contained at least 100 grams of bismuth per liter, An apparent disadvantage was depletion of bismuth from this electrolyte, causing the deposits to become spongy and nonadherent.

Jan 1, 1956