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By N. S. Dalal, Xianglin Shi

"Electron spin resonance (ESR) measurements provide direct evidence for the involvement of Cr(V) in the reduction of Cr(VI)· by NAD(P)H. Addition of hydrogen peroxide (H2 O 2) to NAD(P)H-Cr(VI) reaction mixtures suppresses the Cr(V) signal and generates hydroxyl (·OH) radicals (as detected via spin trapping), suggesting that Cr(V) reacts with H2O 2 to generate the ·OH radicals. Reaction between H2O 2 and a Cr(V)·glutathione complex, and between H2O 2 and several Cr(V)-carboxylato complexes also produces ·OH radicals. These results suggest that Cr(V) complexes catalyze the generation of ·OH radicals from H2O 2, and that ·OH radicals might play a significant role in the mechanism of Cr(VI) cytotoxicity. KEY WORDS: ESR. spin trapping, Cr(VI) reduction, Cr(V), hydrogen peroxide, free radicals.INTRODUCTIONThis communication reports an ESR spin trapping detection of hydroxyl ( OH) radicals.in reactions between some Cr(V) complexes containing biologically important ligands and hydrogen peroxide (H2O 2 ). This work was undertaken because while the reduction of Cr(VI) to lower oxidation states has been suggested as a key step in the mechanism of Cr(VI) toxicity, the reaction· mechanism is not yet clear. 1 Mutagencity has been well documented for Cr(VI) via various bacterial assays, while Cr(III) has been shown not to be mutagenic.2 • 3 Since it has been reported that compounds containing Cr(VI) do not react with isolated DNA,4 the reduction of Cr(VI) by other cellular constituents has been thought to be important in the mechanism of Cr(VI) induced DNA alteration.1·4 • 5 For cellular systems earlier studies include those on the reduction of C~(VI) by microsomes,6-8 rat liver DT-diaphorase,9 and aldehyde oxidase. 10 Regarding the reduction mechanism, Jennette used ESR spectroscopy to show that a long-lived Cr(V) complex is formed as an intermediate in the microsomal reduction of Cr(VI) in the presence of NADPH.8 She postulated that Cr(V) is the ""ultimate"" carcinogenic form of chromium compounds. This conclusion has led to many further investigations of the formation of Cr(V) in the reduction of Cr(VI) under biologically relevant conditions.11 - 19 More recently, however, it has been suggested that oxygen-derived radicals generated during the Cr(VI) reduction are the species responsible for the DNA alteration.20.2• To the best of our knowledge, however, no information is available on the generation of such radicals in the reduction of Cr(VI) under biologically relevant conditions, except some preliminary results on the glutathionyl (GS·) radical formation in the reduction of Cr(VI) by glutathione (GSH). 11 - 19 We, therefore, undertook a systematic investigation of the reaction of Cr(VI) with NAD(P)H, GSH, ix-hydroxycarboxylic acids, and H2O 2 • NADPH was chosen as a model reductant because of its ubiquitous existence inside the cells, its critical role in the enzymatic Cr(VI) reduction,1·6-9 its representation of important cellular Cr(VI) reductants, and its ability to reduce other metal ions.22 GSH was chosen as another model Cr(VI) reductant because GSH also exists inside cells, it represents another important category of cellular Cr(VI) reductants, the thiols, and it also plays an important role in the Cr(VI) toxicity .1• 1 ""- 19.i3.i4 For further clarification, we also studied the reaction of Cr(VI) with several '1'.-hydroxycarboxylic acids in the presence of H2O 2 since these acids are definitively known to reduce Cr(VJ) to form stable, isolable Cr(V).25 .2 6 The results obtained indicate that Cr(V) complexes, produced in the reduction of Cr(VJ) by cellular reductants, react with H2 O 2 to generate ·OH radicals, which might be the initiators of primary events in Cr(VI) carcinogenicity."

Jan 1, 1990

By Carroll W. DeKock

Thermodynamic data for selected metal sulfates were critically evaluated and compiled as part of the Bureau of Mines program to provide a scientific base for use in developing new technology and predicting the feasibility of new processes. Values for Cp°, S°, H° - H°298, -(G° - H°298)/T, ?Hf°, ?Gf°, and log Kf as a function of temperature are given in tabular form. Thermodynamic data were compiled for VOSO4, Cr2(SO4)3, MnSO4, FeSO4, Fe2(SO4)3, CoSO4, NiSO4, Cu2SO4, CuSO4, CuO-CuSO4, ZnSO4, and ZnO-2ZnSO4, together with their stable hydrates.

Jan 1, 1982

By A. C. Richardson

[During the past two and a half sears the U. S. Bureau of Mines and the University of Alabama, with the cooperation of the different coal operators, have been making an extensive studs of coal preparation in the State of Alabama. Considerable time has been devoted to the studs of the washing characteristics of the Mars Lee bed and the various methods used In preparing from it a low-ash coal suitable for the manufacture of metallurgical coke. One of the phases of this problem is the utilization of middlings products from the washing plants. This paper gives the results of treating jig middlings on a coal-washing table at the Bureau of Mines laboratory at Tuscaloosa, Ala. The sample used was secured from the Sayreton washery of the Republic Steel Corporation, Sayreton, Ala. WASHERY PRACTICE The Mary Lee bed is very bony, and operators find it difficult to produce from this bed a washed coal much under 10 per cent ash. Experience has shown that in the preparation of a coking coal from the Mary Lee bed it is best to use a process which permits the recovery of a middlings product. Middlings are desirable because separation according to specific gravity is never perfect, and a middlings product makes possible a low ash in the primary warned coal without excessive losses of combustible in the refuse. The general washery practice on the Mary Lee bed is to crush the run-of-mine coal through some maximum screen size and wash it upon some one type of jig without re-treatment of any of the products made. The maximum size treated varies from 3 inch to J inch. The middlings product from multiple-cell jigs is usually termed "boiler fuel" and when possible is utilized as such. At present the production of boiler fuel is often in excess of power requirements, and the surplus, due to its high ash content, becomes waste.]

Jan 1, 1931

By R. W. Van Dolah

The Bureau of Mines t.ced its investigations into sympathetic detonation of ammonium nitrate (AN) and ammonium nitrate-fuel oil (AN-FO) to define the scaling law for safe separation from detonating AN-FO. Both missile- and non-missile-producing AN-FO donors, weighing up to 5,400 pounds, were employed with acceptors of the same size. The usual cube-root scaling law was not confirmed; exponents for the relationship S = f(Wx) for AN were 0.51 with non¬missile-producing donors and 0.61 for missile-producing donors. For AN-FO an exponent of 0.80 was indicated in the missile-producing case. AN-F0 in polyethylene bags appeared somewhat more easily initiated than bulk AN-FO. The efficacy of barricades in protecting AN charges was investigated. detonation distances were reduced from one-third to one-seventh when filled barricades were employed. The investigation was extended to dynamite with both types of donors. With 1,600-pound missile-producing donors and an equivalent weight of dynamite, initiation would be expected in 50 percent of the trials at 167 feet. The corresponding value in the non-missile case was 67 feet. The data developed in this program of sympathetic detonation will allow the development of a rational set of safe separation distances for AN, AN-FO, and explosives.

Jan 1, 1966

By Oliver Q. Leone

The effect of oxygen content in the anode metal on titanium electrorefining characteristics was studied. Increasing quantities of oxygen in the anode resulted in increased anode scale formation, decreased anode and cathode current efficiencies, lower titanium recovery efficiencies, and higher oxygen content of the cathode products. The titanium electrorefining process performed best when the anodes did not contain more than 0.5 percent oxygen, although anode dissolution was recorded for alloys containing up to 25 percent oxygen. Back emf affords a useful index of an alloy to electrorefining.

Jan 1, 1965

By Charles J. Stehlik

This report deals with the changing behavior of mine roof bolt and roof rock as a result of repetitious production blasting . Observations were made in the upper shale production headings at the White Pine Copper Co. room and pillar mine , White Pine , Mich . Roof bolt compression pads and a stratascope were used in the investigations , which were carried out in three separate test sites in which nearly identical procedure produced comparative , repetitive , and anomalous observations . Results indicate roof bolt tension change and roof quality deterioration anomalies were coincident with blasting . The hypothesized cause of the anomalies is a seismic shock generated by the blasts .

Jan 1, 1964

By R. M. Santmyers

Of the sand and miscellaneous silica produced in the United States , ordinary sand and gravel are , of course , the most important, at least as regards volume of output . The building- construction industry absorbs approximately 75 per cent of the total value of all quartz and silica , as shown in Table 2 of Quartz and Silica, Part I, under "General summary . " Because of their unusual physical properties tripoli and diatomite find extremely wide uses in industry, and as the commercial deposits of these ninerals , especially tripoli , are scattered, large quantities enter into interstate commerce . Whereas ordinary sand and gravel are bulky commodities , these specialties have a fairly high unit value and hence can be transported relatively long distances .

Aug 1, 1931

By A. C. Richardson

During the past two and a half years the U. S. Bureau of Mines and the University of Alabama, with the cooperation of the different coal operators, have been making an extensive study of coal preparation in the State of Alabama. Considerable time has been devoted to the study of the washing characteristics of the Mary Lee bed and the various methods used in preparing from it a low-ash coal suitable for the manufacture of metallurgical coke. One of the phases of this problem is the utilization of middlings products from the washing plants. This paper gives the results of treating jig middlings on a coal-washing table at the Bureau of Mines laboratory at Tuscaloosa, Ala. The sample used was secured from the Sayreton washery Of the Republic Steel Corporation, Sayreton, Ala.

Jan 1, 1931

This Bureau of Hines report on underground mine communications addresses methods and equipment to meet the communication requirements of working sections and places of coal and metal-nonmetal mines. A review of the status of trapped miner detection is also presented.

Jan 1, 1977

This report, the fourth in an annual series, outlines recent trends and developments in the minerals industry. Discussed are new methods, equipment, techniques, and systems used to more effectively extract and process mineral products. Environmental considerations, health and safety standards, price controls, inflation, material shortages, and more dependence on foreign imports were problems faced by the minerals industry. Although productivity increased for most mineral commodities, the annual rate of increase has slowed in recent years, indicating a maturing technological situation. Growing concern for energy resulted in increased interest and research in alternative fuel sources. The primary concerns of metallurgists were pollution control and improved efficiency and performance of metallurgical processes, especially for reduction of energy consumption.

Jan 1, 1974

By J. R. Thoenen

During 1928 questionnaires covering the calendar year 1927 were sent to over 1700 quarries: producing stone for purposes other thaw cutting to dimension. These inclined producers of stone for limn burning; cement manufacture, rip rag, and crushed stone. The various rinds of stone represented were limestone, trap rock, sandstone, granite, and marble. Replies received from limestone producers prior to November, 1928, were compiled into tables and published in February, 1925, as a preliminary report (Bureau of Mines Report of Investigation 2911).

Jan 1, 1930

By G. R. Peterson

To determine the availability of aluminum from world bauxite resources, the Bureau of Mines investigated 139 bauxite deposits worldwide and evaluated the potential production of aluminum based on the demonstrated resources of bauxite ore from 91 mines and deposits in 22 market economy countries. The demonstrated resources of the bauxite mines and deposits included in this study represent an in situ resource of 20.2 billion metric tons of bauxite. Total identified bauxite resources in market economy countries amount to roughly 31.9 billion tons. Of the demonstrated resource, some 18.8 billion tons of bauxite considered minable provide a production potential of 3.6 billion tons of primary aluminum. Given the wide geographic distribution of bauxite deposits, stable supplies of bauxite for aluminum production seem assured well into the next century. However, a tight market situation could develop during the 1990's unless the real price of aluminum increases enough to stimulate massive new investments in production capacity, particularly in refining and smelting. This study indicates that a real price of at least $0.85 per pound (in January 1980 dollars) would be necessary to stimulate the required investments and provide a sufficient rate of return on invested capital.

Jan 1, 1983

By Albert E. Long

During the summer and fall of 1948 the Bureau of Mines, in cooperation with the U. S. Geological Survey, conducted 6xperiments in diamond core drilling in the Phosphoria formation in southeastern Idaho and southwestern Wyoming. Nearly all of the diamond core drilling in the Phosphoria formation has been done by mining companies interested in finding and developing phosphate-bearing beds amenable to stripping. The recovery of sludge; and enough core (usually 30 to 60 percent) to identify certain marker beds produced by current drilling practices meets both the primary requirement of mining companies in determining depth of overburden and their secondary need to determine the phosphate content of relatively thick minable units whose general composition and nature are already fairly well established.

Jan 1, 1949

By G. G. Campbell

The Bureau of Mines in cooperation with Quaker State Refining Corp. conducted two underground-combustion oil-recovery experiments in the Venango Second sandstone in the Reno pool, Foster-Rena-Oil City field, Sugar Creek Township) Venango County, Pa.) to determine the applicability of the process for reservoirs producing Pennsylvania-grade paraffin-base crude oil. Tests were terminated when analyses of produced gas showed that a self-sustaining combustion front did not exist. It was thought that insufficient fuel had been deposited in the formation. Laboratory retort tests made after the second field test was concluded showed that crude oil from the Reno area would deposit enough fuel to support combustion if air flux, temperature, and time were maintained within defined limits.

Jan 1, 1967

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 A. S. Swanson

The Babb fault vein in Crittenden and Livingston Counties, Ky. (fig. 1), is one of an extensive series of such veins in the Western Kentucky and Southern Illinois fluorspar district. First operated in 1904, the production to May 1, 1944, was estimated at 143,000 tons of fluorite ore. There are five mines (fig. 2) on the Babb fault zone - Guill ,Kentucky Babb, Delhi-Babb, Eagle-Babb and Howard-Barnes. The Bureau of Mines developed four of these properties by core drilling from July 9, 1943, to May 1, 1944. During that period a total of 8,177.8 feet of diamond drilling was completed in 28 holes.

Jan 1, 1950

By Dhanesh Chandra

[The U.S. Ucparunent of tlIe III LeriOr, Bureau of 1?Ilnes, lnta dcvcltil- (I a m.?tl,nd to extract nickel, i:ob.tll and IlIIicr Valuc:l,1, mrl?tl., lrom I.ow grad:, dumusI it Inlet itc.: :isin;; a rarb-i mnnnxid:: reducl.iun and ,innnonln/mumonlum sull,h.Ito Icitcll Col lowed by solved. evil let foil and clot tr:,winnfu,;. 'I 'o rain bcLtur undcI'sLandin;; uI the producLs reduced rind leached with the s;:Item, the liureau of t?Ilite; was enf,ngod In a 1 uinL sl.utly IIt1I the Uuttvcr ltc~:c:n-ch LnstiI-IL-. 'I'hr'ut;;h C(Im:drlod ahplit I¬L ion:; of a rotnbIW)L11nl ill eleu Lyon :utJ uplical inicrnscopy, cle trun beau micru,inal?;st?s and X-r.iv tcchnitlaes, Lhc factors jilt] ucncing low nickul e::lracl.on yLrids Iron, ccrlnin l;tteritos wul the hcuefhe al yCferL front addil.I:un u1. r:u)plowt' ruug,ounus and halides have bucn rrvealod. IL leas ht'en shown their nt nliJcrate Lion terlperuLuri's (5S0°C - 6501C) Lhe 111LACl extraction ylolds were low hccausc of the futmetlt-m of rufrill t,urv sillc:Ite compicxcs during ciii lit Hi [hut COOL.tlu sig nlficnnt anutunls of nickel .Lrui LhaL arc resistant Lu discolullull it, a su6r.C?quent ammnnlIca1 Jcaeh. 'This formation ill rulracLorv rnngtieves is altrlbuU?d Lo the prc.srnCV of aluauinum combined with c.ilicun jn addlt.lon In tnnl;neni~im in I.lic Lalerites, Iligb exII.Ictlon yields were oblalneJ when none or only a few I ,fraCLot' e, were InrmeJ. Hit s;intc rcfrarlnry cowl, Icxc5 also lend Lo surround Ow IaaIIiable meI.allle iron-IIIcI:el :iILoy CIUSisling ill the mau'ix, tIll: rrhv nreveu)Ling cuntacr ,Itlt LI5U Jeacl: solution; this, huwrvcr, ran ho ovu:rcoml by At ti itlon .111.11 retieCtiun. 'I'hc eIIcc l of prr.reJIctlun .,Ill itivi's vucli i's lye iii', ',udlum "Ill orIde, hv,Irogrn CIIInrILIC, etc., and Lht? 1111,Lre:InrLlI'll he'e:tleg un Lbe cxLt,icLitin are also iilsr.ussod 111 Lhe rcl,olt.]

Jan 1, 1979

By D. Randolph Berry

The U.S. Bureau of Mines awarded a contract to Foster-Miller Associates, Inc. (FMA) to provide recommendations on the safest, most practical methods for complying with new regulations requiring that all underground coal miners have a self-contained, self-rescuer (SCSR) -a device capable of supplying, in an emergency, 1 hr of self-contained oxygen (no breathing of mine air). This report develops information and recommendations which could be used during the early stages of nationwide compliance, especially in the areas of inspection, testing, and underground storage of SCSRs. Volume I contains an Executive Summary, Introduction, Definitions, Recommended Guidelines for District Managers and Mine Operators, and a Storage Plan Checklist and Sample Form.

Jan 1, 1981

By R. R. Wells

This report summarizes the results of preliminary mineral-dressing studies by the Bureau of Mines on five samples of copper-bearing ore from various Alaska de-posits. The work on each sample was not extensive enough to warrant individual publication. The results, however, indicate the possibilities and limitations of concentration of the respective ores. The information therefore may be helpful in future development of these ore bodies. Four of the five samples tested were submitted to the laboratory by engineers of the Bureau of Mines as part of the examinations and survey investigations of strategic-mineral deposits in Alaska. This program is conducted to assist development of mineral resources in the Territory and particularly to aid economic exploitation of marginal or complex ores. The fifth sample was submitted by engineers of the Defense Minerals Exploration Administration.

Jan 1, 1956

By James M. Stuckey

In a search for improved methods of upgrading tar obtained by low-temperature carbonization of coal, monoethanolamine (MEA) was found to be effective in extracting tar acids from coal tar distillates derived from a subbitunwous and a lignite coal. Patch extractions showed that both yield and purity of the extracted acids improved with increasing volume ratios of monoethanolamine to tar acid, varied from 1:4 to 8:1. Yield improved, but purity decreased as the concentration of monoethanolamine was changed from 30 to 70 volume-percent, and as the concentration of tar acid in distillate was increased ad from 14 to 45 percent. In a continuous countercurrent extraction employing a double solvent (monoethanolamine and hexane) approximately 80 percent of the tar acids was extracted from 170° to 350° C. tar distillate when using 1.6:1 volume ratios of amine:tar acids. Tar acids isolated from his extract, although of improved purity, contained appreciable quantities of neutral oils and some tar bases. Aqueous monoethanolamine was not effective for extracting the last 10 to 15 percent of tar acids in 170° to 350° C. distillate oil from lignite coal. The highest yield of isolated tar acids and the best recovery of monoethanolamine were obtained by diluting the extract with water and saturating with C02. Some losses of solvent were encountered when aqueous monoethanolamine solutions were heated through decomposition of the amine with the liberation of ammonia.

Jan 1, 1960