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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 J. P. Powell

This report provides information on the techniques and results obtained on representative waterflooding projects in Cowley County, Kans. Records show that waterflooding was begun as early as 1935, but not until 1948 was the method expanded. The greater depths to the oil-producing formations in this area compared to those in eastern Kansas undoubtedly delayed the widespread use of secondary-recovery methods. This report presents a discussion of four waterflooding projects in Cowley County, Kans. The locations of these projects are shown in figure 1. The projects have been in operation from 1 to 7 years and have produced more than 1 million barrels of additional oil by injecting 11.5 million barrels of water. The projects are designed to take advantage of elevation and height of the separator tank to collect by gravity flow the produced brine at the respective treating or storage tanks. The closed-type water system is used on three of the projects and an open-type water conditioning system on the fourth. On one of the projects, which was drilled along a narrow shoestring formation, alternate well, were converted to input wells. However, most of the input wells for flooding converted producing wells.

Jan 1, 1958

By D. W. Butner

This Information Circular , one of a series published by the Bureau of Mines , reports on the methods and costs of mining and concentrating zinclead ore at the Highland Surprise mine in the Pine Creek area of the Coeur d'Alene region of Idaho . The mine is owned and operated by the Highland Surprise Consolidated Mining Co. , which supervises operations of the Nevada Stewart group of claims , which is adjacent on the northwest . These properties are at the extreme eastern end of a zone of fracturing that strikes northwest across the Pine Creek area . In fractures along this zone are the principal Pine Creek mines ; these are the Highland Surprise , Nevada Stewart , Sidney , Denver , V and Idaho , Liberal King , and Northern Light . Country rock at the Highland Surprise is argillite of the Prichard formation (Belt series ) . Fracturing has permitted the movement of mineral- izing agents that have replaced adjacent walls and crushed country rock with sulfides . Ore minerals are sphalerite and galena with accessory pyrite , chalcopyrite , pyrrhotite , and siderite . Three principal ore shoots were found on the Highland Surprise property . The Highland ore shoot was mined from outcrop to the 400 level . The Surprise ore body has been developed to a depth of 1,400 feet on the dip of the vein . The outcrop of the Surprise ore shoot was 150 feet long and 2 to 4 feet thick ; on the 1,150 ( lowest ) level , the ore shoot is 320 feet long and 10 to 17 feet thick , with good zinc content . Surprise ore shoot No. 2 occurs 250 feet west of No. 1 and has been mined from the 500 to the 1,000 level . From 353,000 tons of ore mined between 1910 and 1948 , the property has a recorded production of 256,000 ounces of silver , 7,500 tons of lead , 24,000 tons of zinc , and 412 tons of copper . Both shrinkage and cut and fill stoping methods are used at the Highland Surprise , but shrinkage is unsuitable for mining below the 700 level , because faulting has weakened the walls . Development of the Surprise ore , as well as exploration laterally and along the strike , is prosecuted steadily . A prospect heading is being pushed westward toward Nevada Stewart ground from the 700 level . The mill has a rated capacity of 275 tons per day and operates near capacity . Selective flotation makes zinc concentrate that is shipped to the Anaconda smelter and lead concentrate that is trucked to the Bunker Hill smelter at Kellogg .

Mar 1, 1950

By Jon K. Ahlness

The Bureau of Mines conducted laboratory and field experiments to determine tne amount of permeability reduction in uranium sandstone after its exposure to different drilling fluids. Seven polymer and two bentonite fluids were laboratory-tested in their clean condition, and six polymer fluids were tested with simulated drill cuttings added. Sandstone cores cut from samples collected at an open pit uranium mine were the test medium. The clean fluid that resulted in the least permeability reduction was an hydroxyethyl cellulose polymer fluid. The greatest permeability reduction of the clean polymers came from a shale-inhibiting synthetic polymer. Six polymer fluids were tested with simu-lated drill cuttings added to represent field use. The least permeability reduction was obtained from a multipolymer blend fluid. A field experiment was performed to compare how two polymer fluids affect formation permeability when used for drilling in situ uranium leaching wells. For this test, the polymer fluid with the best laboratory results (multipolymer blend) was compared with a commonly used polymer fluid (guar gum) that gave poorer laboratory results. When fluid injection rates for the four wells drilled with the guar gum were compared with those for the four drilled with the multipolymer blend, no statistically significant difference was found.

Jan 1, 1984

These inspection standard have been prepared for use in the Federal inspection of strip mines producing, bituminous coal, anthracite, and lignite. This circular is a revision of the Safety Code for Strip Mining, which was prepared by the Bureau of Mines and employed as a guide for Federal inspectors. Numerous changes have been made in the original code to keep the in step with improvements in the industry. With continuing changes in mining methods and facilities some of these standards may become inapplicable and further revision may be advisable. Therefore, questions regarding these standards, and suggestions regarding new standards should be brought to the attention of the Bureau of Mines. Few States haves laws pertaining to strip mines, but where such laws do exist it is possible that some of the standards may conflict with them. In cases of conflict, the intent is not to advocate noncompliance with State laws, but to suggest reconsideration of such laws or safety orders.

Jan 1, 1946

By Ludwig Schmidt

This report, the second of a series, presents the results of laboratory corrosion studies which were made in connection with a one-year test on aluminum lease tanks conducted by the United States Bureau of Mines. Part 1 of the report contains the results of the field tests. The studies were made on an oil lease in a so-called "sour district," near Borger, Tex., where free hydrogen sulphide accompanied the production of oil, gas, and salt water. Steel tanks previously used on the lease had suffered severe corrosion, because steel is inherently susceptible to attack by hydrogen sulphide. Because of the high resistivity of aluminum to the action of hydrogen sulphide, it was believed that this metal had promising possibilities as a material for the construction of lease tanks in "sour districts." The results of the one-year field test proved that aluminum lease tanks will withstand corrosion by hydrosulphide, but it as found that aluminum was susceptible to attack by salt water, which was invariably present in certain portions of the tanks, and that hydrogen sulphide accelerated this salt-water corrosion in an indirect manner, as will be explained hereinafter. In order to study corrosion conditions encountered in the tanks during the test period, a laboratory was maintained at the site of the aluminum lease tanks.

Jan 1, 1931

By Florence L. Feicht, H. H. Schrenk, Carlton E. Brown

This report describes the dropping - mercury electrode , its use in analysis , and the procedure of the Health Division of the Bureau of Mines in determining lead , cadmium , and zinc . The dropping - mercury electrode or polarograph is an electrolytic device , one electrode of which consists of mercury issuing in small drops from a capillary tube . Such electrodes have been in existence for more than 50 years, but they were not used for analytical purposes until about 1922.6/ Developments since have been rapid , especially in Czechoslovakia , Germany , Italy, and Japan and more recently in the United States . A recent bibliography / contains references to, 825 articles issued from 1903 through 1940. In 1939 Kolthoff and Lingane presented the first comprehensive critical review, in English , of the device and its use in analysis . They have recently issued a book on the same subject. Similar information also is included in a recent book10/ by Kolthoff and Laitinen . Much of the information in this and the two following sections on this device and its use in analysis was obtained from these three publications . The use of the dropping - mercury electrode in analysis is based upon the fact that the kind and amount of electro - reducible and electro - oxidizable constituents in solution can be determined from the current -voltage relationships revealed by this electrode or electrolytic device .

May 1, 1942

By H. M. Smith

Data from the Bureau of Mines routine method for the analysis of crude petroleum are used to characterize crude oils. Some data are used directly while other data are used to calculate the aromatic) naphthene) and paraffin contents of the distillation fractions and the correlation index of the paraffin-naphthene portion of the fractions. The calculated properties show significant differences in composition between crude oils. The methods of calculation and interpretation of data are explained and illustrated.

Jan 1, 1966

By R. V. Higgins

This paper describes a method and a computer program for calculating shape factors and areas of channels that turn more than 90° and conduct fluids into the backs of wells. The program represents an improvement over a previous Bureau of Mines investigation by using a 4-point Lagrange interpolation equation instead of a 3-point and by summing areas of trapezoids with either x altitudes or y altitudes. Some of the techniques reported in this paper can also be used to compute the areas between contours and the lengths of lines that turn more than 90°.

Jan 1, 1968

By W. R. Crane

Recent papers on support of roof and top rock in mines representing present practice in so far as it hits been described by engineers in all of the principal mining countries, cover a relatively aide range of topics. The papers abstracted herein include such subjects as the testing of materials of support, failure and movement of rock above workings, effect of excessive pressures on rock masses, axed the application in mines of timber, metal, concrete, packing, and filling support. It is not within the scope of this paper to present a logical and orderly discussion of the elements of support and their application to conditions influenced by the material worked or the method of mining. Only the essential facts of a paper appear in the abstracts, the idea being to give a fairly clear picture of the behavior of various types of support under brows conditions and to put into concise form important information concerning present practice, modifications of practice, and the trend toward new practice. With such valuable facts from others experience made readily available, it Is hoped that the engineer with particular and often trying problems may obtain suggestions that will be immediately helpful.

Jan 1, 1932

By Charles L. Kusik

As part of an effort to establish the extent of the domestic chromium supply that could be exploited in case of adverse changes in international chromium production and trading patterns, a two-part study was conducted for the Bureau of Mines, to assess the domestic availability of critical metals in scrap containing significant amounts of chromium. This report describes the part of the study that deals with wrought stainless steels and heat-resisting alloys. Data were collected on types of scrap, sources, quantities, and ultimate disposition, leading to the conclusion that In 1917 about 62,000 tons of contained chromium was unrecycled. Unrecovered obsolete stainless steel scrap accounts for most of these uncollected chromium values. Error margins in the amount of uncollected scrap are estimated to be 10 to 20 percent.

Jan 1, 1980

By G. E. McElroy

This report discusses the construction and use of an all-pressure psy- chrometric chart in which the requirements of simplicity of appearance and absolute accuracy have been waived, to a certain extent, to provide for the rapid determination of psychrometric data and for the rapid solution of air- conditioning problems of major interest to the mining industry. Many mines in which air-conditioning problems are important are situated at elevations far above sea level and embrace great differences in elevation - in excess of 8,000 feet in certain mines → throughout their airflow circuits. Under these conditions, the effects of variations in the pressure of the at- mosphere upon the physical properties of the mixture of air and water vapor of which it is composed are considerable and should be taken into account in the solution of problems. The simple types of psychrometric charts in common use, such as the Carrier, Bulkeley, Hill, and Goff (American Society of Heat- ing and Ventilating Engineers Guide), are not generally suitable, in that they are drawn for a single barometric pressure 29,92 inches mercury.

Dec 1, 1947

By Roy J. Greenfield

The overall purpose of this research was to improve the understanding of how the post disaster seismic location system works, what determines the signal size, what is the character of the seismic noise, how well the system can detect blows from a trapped miner, and how well the source of the blows can be located. Based on an improved understanding of the system, improvements were suggested in the seismic subarray configuration, and in the system deployment procedures. An important part of this research was to become familiar with the seismic system operation and to work with the Westinghouse Electric Corporation and MSHA personnel to modify and improve the system. To accomplish this we participated in the planning, execution, and data analysis for a number of seismic field tests. Several in-mine field tests were conducted. From these tests the capabilities of an in-mine seismic system were analyzed and specifications were made for designing an operational in-mine system. Several portions of the work done on this grant were covered in previous reports. In particular the capabilities or the presently operational surface based seismic location system has been thoroughly documented by Durkin and Greenfield (1981). Portions of the location procedures and effects of mine openings on seismic signals have also previously been published. These portions or the work will only be summarized in this final report.

Jan 1, 1982

By L. A. VANFLEET, Allen D. Look

The ever -present danger of mine fires and the possibility of hazardous atmospheric conditions in underground mines make a well-equipped mine rescue station a valuable asset to any mining district . Rescue equipment without proper maintenance provides only false security , because neglect may make the apparatus unfit for use in an emergency . Promptness in fighting mine fires is important ; frequently the first 30 minutes of action are worth many hours later . Likewise , the equipment will be of little value if enough men trained in its use are not readily available . This circular points out how such protection has been provided in an Arizona mining district by establishing a well- organized , adequately equipped , central mine rescue station. ·

Aug 1, 1950

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 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 Peter Grandone

Bureau of Mines engineers engaged in studying stimulative methods of recovering oil have been making a series of tests on the effectiveness' of methods that may be applied in water flooding oil-bearing sandstones. The report gives the test procedures and results of a study of the rates and pressures used for injecting water into several sandstone formations in the Mid-Continent fields for the purpose of learning more about the mechanics and efficiency of the flooding process and to provide useful information for operators of water floods in this area.

Jan 1, 1949

By D. G. Foot

The Bureau of Mines investigated two methods for recovering potash from carnallite ore in continuous 100-lb/h flotation units. In the insoluble-slimes flotation procedure, insoluble slimes were removed by flotation prior to potash flotation. In the direct flotation method, insoluble slimes were depressed and the potash floated directly without prior removal of the insoluble slimes. Seventy-three percent of the potash in the ore was recovered in a leached final KCl product contain-ing 59.1 pet K20 using the insoluble-slimes flotation method. The direct flotation method recovered 74.5 pct of the potash in a final product containing 60.2 pet K20. The rate of return on the investment was calculated at 13 pct for the insoluble-slimes flotation method and 15 pct for the direct flotation method, based on a Bureau economic evaluation.

Jan 1, 1984

By R. O. Pynnonen

This circular is a study by the Bureau of Mines of 346 accidents in underground iron-ore mines of the Lake Superior district from June 1949 to August 1954. These accidents caused 354 lost-time injuries, including 28 fatalities and 2 permanent-total disabilities. The accident reports were analyzed by the Bureau to show the causes of injuries and the time charges and unsafe practices or conditions that caused the accidents. Also shown are the times of occurrence, ages of the injured by job classification, and experience of the injured in mines and on the job being performed when hurt. Detailed information is presented on approximately 14 percent of the total number of Lake Superior district underground mine accidents that resulted in lost-time injuries during the period covered. These facts are presented to aid accident-prevention measures in underground mines and as a record for measuring future safety accomplishments.

Jan 1, 1956

By N. S. Dalal, Xianglin Shi

"The mechanism of vanadium(V) V ) toxicity is still not fully understood in spite of extensive current effort (1-3). The presence of a vanadium(V) V ) -dependent NAD ( P )H oxidase in cell membranes suggests that at least one of the pathways involves oxidation of NAD(P)H (1-3). Considerable effort has therefore been devoted to finding the mechanism of NAD ( P ) H-oxidation by va¬nadium( V ) (1-19). Recently Liochev and Fridovich (4, 16) provided a critical review of vanadium( V) -stimulated NAD (P )H oxidation by plasma membranes. They out¬lined a mechanism in which vanadium(V) V )-stimulated oxidation of NAD ( P )H by biomembranes involves an O2 - initiated free radical chain reaction (4 ). While the above may be the major pathway for the vanadium-me¬diated NAD (P )H oxidation in membrane-related sys¬tems, some recent results suggest that in the presence of NADPH the flavoenzyme glutathione reductase can function as a vanadium(V) V ) reductase (18). Because of the significance of this result in relationship to the mech¬anism of vanadium( V) metabolism and the novelty of the metal-reductase behavior of a flavoenzyme, we have car¬ried out additional studies on one-electron reduction of vanadium( V) by two other, related flavoenzymes: lipoyl dehydrogenase and ferredoxin-NADPH oxidoreductase. These two enzymes were selected because they are known to catalyze a one-electron reduction of Cr ( VI ) (19-21 ), which is isoelectronic with vanadium( V ).The present study also reports on the generation of hydroxyl ( • OH) radicals in the vanadium( V) -flavoen-zyme redox system without exogenous H2O2. The • OH study was undertaken because • OH radicals are known to be generated in reactions of vanadium( IV) with H2O2 (17,18,22-27). For example, Piette and co-workers (17, 22) have studied effects of vanadium(IV) IV ) on lipid per-oxidation and NADPH oxidation and suggested that va-nadium( IV) -induced • OH radical formation may play an important role in vanadium( V) toxicity. Carmichael (25, 26) investigated the reaction between a RNA /VO 2' complex and H2O2 with a view to probe the possible re-lationship between vanadium( IV) -mediated • OH radical generation and DNA damage. He has suggested that in this reaction the • OH radical adds to the C (5) carbon of uracil, causing nucleotide damage, similar to what occurs in the nucleotide /Fe2+ / H2O2 reaction (28) and in y-irradiated aqueous solutions of nucleic acids (29 ). To our knowledge, however, there is as yet no report on ·OH radical generation in any reaction involving the reduction of vanadium ( V) by a well-characterized enzyme, without exogenous H20 2 • The present study provides evidence that ·OH radicals can form in a flavoenzyme-mediated reduction of vanadium( V) to vanadium( IV) and that this process involves also the reduction of molecular oxygen ( 0 2 ) to H20 2 • The H20 2 thus generated reacts with vanadium( IV) to produce ·OH radical, in analogy with the Fenton reaction ( Fe2 + + H20 2 - Fe3 + + OH- + ·OH)."

Mar 1, 1992