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By M. F. Koehler

[THE LITERATURE contains relatively few thermodynamic values for interoxidic compounds, and these often are unreliable. This is especially true of data for ferrites and aluminates for which heat of formation determinations may involve extreme experimental difficulties. This report contains the results of new experimental work for obtaining the heats of formation of five ferrites (Ca2Fe2O5, CaFe2O4, MgFe2O4,, NaFeO2, and LiFeO2) and one aluminate (CaAl4O7), and a review and revision of previous similar work of this laboratory on five aluminates (Ca3A12O6,, 12/7 CaO-Al2O3, CaAl2O4, NaA1O2, and LiAlO2), The results for the 11 compounds are combined with entropy and high-temperature heat content data to derive tables of heats and free energies of formation (both from the oxides and from the elements) for the temperature range 298° 1,800° K, The relative stabilities of the compounds are discussed. The presented data all have application to ceramic reactions, and those for the calcium and sodium aluminates are applicable in considering soda-lime sintering processes for extracting alumina from silicate minerals such as day and labradorite.]

Jan 1, 1961

By Richard A. Dick

Eight blasts were fired in a 2-1/2-ft bench in the Stewartville member of the Galena Limestone formation in an aggregate quarry near Stewartville, Minn. The shots were dimensionally proportional to production-size bench blasts and were about 5 to 10 percent of full scale. The effects of site, timing of initiation, and burden-to-spacing ratio were studied in a 2 x 2 x 2 factorial experiment, using three boreholes, caw;, containing a 1/2-in charge diameter of high-density ammonia dynamite, in each blast. Detonation velocity measurements indicated that the dynamite detonated satisfactorily in the 1/2-in charge diameter. The effects of the three experimental variables were analyzed by weight for the percentage of oversized material produced and for size distributions determined by screening the entire muckpiles. The bench faces were painted before each shot in an effort to determine the origin of the oversized material. The square pattern (burden and spacing = 15 in) produced finer overall fragmentation and less oversized material than the rectangular pattern (burden = 15 in; spacing = 22-1/2 in). Sites 1 and 2 were about ft apart. Although site 2 produced slightly better overall fragmentation than site 1, the amounts of oversized material produced showed no significant difference. The timing of initiation (instantaneous or delayed) did not significantly influence the overall fragmentation or the amount of oversized material produced.

Jan 1, 1973

By J. E. Murphy

A method is being developed by the Federal Bureau of Mines for recovering lead metal from galena without the generation of SO2. Lead chloride is obtained by leaching lead concentrate at a temperature of approximately 100° C with FeCl3 solution: PbS + 2FeCl. " PbC1 2 + 2FeC1 2 + S. Electrolysis of the PbCI 2 product in a fused-salt bath results in deposition of molten lead metal at the cathode and evolution of chlorine at the anode. The chlorine can then be absorbed in the spent leach solution to regenerate FeCl3 for recycling. Optimum electrolyte composition was a PbC12-LiCl eutectic containing 7.6 wt-pct LiCl. The PbCl2-NaCl eutectic also proved satisfactory. Electrolysis in the PbCl2-LiCl bath at 450° C yielded 99 pct current efficiency at a current density of 5 amp/in2 with an energy requirement of only 0.24 kW-hr/lb metal produced. This compares with 98 pct current effi¬ciency and 0.26 kW-hr/lb metal produced for the PbCI2-NaCI bath. A typical lead deposit contained less than 100 ppm total detectable metallic impurities. At the low temperature employed for electrolysis, there was essentially no vaporization of Pb or FbC12.

Jan 1, 1974

By D. G. Kuehn

Studies were conducted by the Bureau of Mines to determine the positive ions and neutral species produced in glow discharges of gas streams containing 1.0 percent NO in helium, 29 percent dry air in helium, and 1.06 percent NO in N2, Mass spectrographic measurements were conducted for gas pressures from 2.3 to 10.0 torr and dc currents from 10 to 20 mAo Ion species observed included NO+, N2 +, O2 +, N+, and 0+ with lesser amounts of He+, He2+, and N02+. Variations in various ionic and neutral species with discharge duration were interpreted to be consistent with an electrically induced dissociation of NO to produce N2 and O2. No nitrogen oxides were observed to form in glow discharges of the helium-air mixture.

Jan 1, 1975

By R. V. Lundquist

The compound 2Na2O?3CaO?5Al2O3 occurs as a minor phase in lime-soda sinters prepared for extracting aluminum from siliceous aluminum-bearing materials. About 99 percent extraction of sodium and aluminum from synthesized 2Na2O.3CaO.5Al2O3 was obtained in solutions of NaOH-Na2CO3 at leaching temperatures of 50° C and above. Extractions in water were low because insufficient NaOH was generated by hydrolysis. Extractions in NaOH solutions were limited to about 80 percent owing to the precipitation of hydrated calcium aluminates. Rapid extractions of 100 percent were obtainable in NaaC03 solutions, but the subsequent rapid precipitation of alumina trihydrate caused losses in alumina recovery.

Jan 1, 1965

By N. S. Dalal, A. H. Hoffman, X. Shi, D. E. Banks, J. K. H. Ma, Y. Rojanasakul

Excessive production of reactive oxygen radicals by alveolar macrophages is proposed to play an important role in oxidative lung injury. A major product of oxygen radical formation is the highly reactive hydroxyl radical (•OH) generated via a biologic Fenton reaction. In addition to its known ability to induce lipid peroxidation, recent studies have suggested that the •OH may exert its cytotoxic effect through the alteration of [Ca2+], homeostasis. To test this potential mechanism as well as to investigate the relationship between •OH and Ca" overloading in cytotoxic injury, isolated rat alveolar macrophages were exposed to externally generated radical system, H2O2 (0.01 to 1 mM) and Fe (1 mM) and their [Ca2+] levels and cell injury were monitored using quantitative fluorescence microscopy with the aid of the specific Ca" indicator, Fura-2, and membrane integrity indicator, propidium iodide. Electron spin resonance measurements using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) confirmed the production of the .OH radical by this system. Upon the addition of the radicals, the macrophages displayed a rapid initial rise in [Ca2+] which was followed by a slower but more pronounced [Ca2+], elevation that reached a level 3 to 5 times higher than the basal level. This process preceded cell death as evident by nuclear propidium iodide fluorescence. Depletion of extracellular Ca" inhibited both the [Ca2+], response and cell injury. Preincubation of the cells with the Ca" channel blocker verapamil or .0H radical scavenger mannitol similarly inhibited the [Ca2+], rise and loss of viability. Firefly luciferase assay of cellular ATP content demonstrated that the alterations in [Ca2+], following .0H treatment preceded the depletion of ATP. Changes in membrane potential caused by Na* substitution with K* had no significant effect on either the unstimulated or stimulated [Ca"], levels. Taken together, these measurements indicate that .OH-induced injury in alveolar macrophages is associated with the alteration in [Ca2+], homeostasis. The mechanism of •OH-induced [Ca2+] loading is not due to nonspecific membrane damage or energy depletion, but mainly due to an increase in Ca2+ influx through Ca2+ selective channels. This Ca2+ over-load state as well as energy depletion caused by the oxidant may activate certain cellular degradative processes leading to cell injury and death.

Nov 1, 1995

By Robert T. MacMillan

A process has been developed in the laboratory and expanded to semi-pilot-plant scale for recovering titania, iron, and byproducts from two types of titaniferous iron ores. A reducing roast with coke and soda ash followed by grinding and magnetic separation produced powdered iron and slag from which titania and byproducts were recovered by H2SO4 decomposition. Based on the steps tested on a. semi-pilot-plant scale supplemented by the results of the laboratory investigations, enough data are available to make a balanced flow sheet. Combined data from the laboratory and semi-pilot plant indicated that 85 to 9O percent of the titania content of the ore was recoverable and that approximately 90 percent of the iron could be recovered as a metallic-iron powder. Tahawus magnetite from the Maclntyre mine at Tahawus, N. Y., was successfully treated as follows: (1) The ore was roasted at 1,050° to 1,080° C. with carbon and soda ash, thereby reducing the iron to metal sponge and retaining the titania in the slag. (2) The metallic iron was separated, after wet grinding, by magnetic or gravity means. (3) The slag fraction was air-roasted at 850° C. and leached with NaOH to recover Na3VO4. (4) The leached solids received a dilute-H2SO4 leach to remove interfering impurities, chiefly Na2O and SiO2. (5) Titania was dissolved from the leached solids of step (4) by a H2SO4-bake followed by a water leach. (6) Titania was precipitated by seeding and boiling the resulting solution. The spent liquor was used for the dilute-H2SO4 leach in step (4). The following scheme was found to be technically feasible for recovering other byproducts of the process. (1) The gelled filtrate from the dilute-acid leach step was washed and dehydrated to produce a commercially acceptable silica gel. (2) The wash liquor containing sulfates of Na2O, Al2O3, Fe2O3, and TiO2 was combined with the highly alkaline filtrate from the wet-grind and metallic iron-separation steps, precipitating iron and titanium hydroxides, which were separated for special treatment. (3) Anhydrous Na2SO4 and Al2O3?3H2O were recoverable from the alkaline filtrate from step (2) by evaporation and carbonation, respectively, and the barren liquor was recycled to the magnetic-separation step.

Jan 1, 1952

By H. R. Shell

The systems MgO-MgFa-SiO2, at 2 and 4 weight-percent Li2O and at 3.8 and 7.7 weight-percent Na2O were investigated by solid state reaction at 1,200° C. The results are summarized in four ternary diagrams. Besides the expected humites and simpler silicates or fluorides, proto-amphibole and water-swelling fluormicas or fluormontmorillonoids were found in the systems containing lithium and monoclinic fluoramphiboles, water-swelling fluormicas or fluormont-morillonoids, and nonwater-swelling fluormicas were found in the systems containing sodium. These latter compounds were not in the base system MgO-MgF2-SiO2.

Jan 1, 1962

By Parry. V. F., W. S. Landers

"INTRODUCTION Approximately 1,250,000 tons of 2-1/2-inch and 1-1/2-inch slack, representing over half of the output from 40 to 50 mines, is produced in the Denver region each year. Part of this slack is made by crushing lump, and some of it is rescreened to make pea and modified pea sizes measuring 1-1/2 inches by 2-1/2 inches and 3/4-inch by 1-1/2 inches, round-hole. Modified pea is popular as domestic stoker fuel. Approximately 900,000 tons of slack 0 by 2-1/2 inches, 0 by 1-1/ 2 inches, and 0 by 3/4-inch in size are consumed by industrial plants, the principal consumers being a large power plant and the beet-sugar industry. The power plant uses annually 250,000 to 275,000 tons of pulverized fuel and can pulverize slack of any size, while the sugar factories consume about the same quantity of coal in stokers. The sugar factories store about 110,000 tons of 2-1/2-inch slack under water from January to October, and burn the remainder of their consumption directly during the campaign season from October to December. For this purpose, sugar-factory power plants can use any size of slack, which is recrushed to pass a 3/4- or 1/2-inch screen before burning on chain-grate stokers. About one-third of the 2-1/ 2- inch slack produced in the field is used in smaller industrial plants that employ stokers.Certain factors affect the utilization of 2-1/2-inch slack in the Denver region. The increasing production of hydroelectric power has reduced the consumption of coal at power plants slightly. If more hydropower is generated, the trend of consumption of slack might be downward, unless industrial activity offsets this greater output. Rapid increase in number of domestic stokers during recent years has necessitated preparation of greater quantities of stoker coal, with the result that more lump is crushed, and preparation facilities are changed. At present about 19 percent of the coal produced is crushed to meet the constant demand for industrial fuel as well as the increasing but variable demand for the small domestic stoker sizes. The quantity crushed has increased 12 percent during the last 6 years. These factors are shifting constantly. The trend toward the use of clean and smaller sizes for domestic stokers gives a slack having a larger proportion of fines. In future, even greater quantities of small stoker coal probably will be prepared, and the resulting greater quantities of small slack will have to be used for industrial purposes."

Aug 1, 1942

By J. L. Stauffer, S. L. Lacey, L. J. Gaydos, L. M. Demers, D. C. Kuhn

"Tumor necrosis factor alpha (TNFa) and thromboxane A2 (TXA2) are major products of the activated alveolar macrophage and serve as key mediators of lung injury. In order to determine if the synthesis ofTXA2 and the release ofTNFa are associated, the production of these inflammatory agents by the human alveolar macrophage (AM), as a result of activation by lipopolysaccharide (LPS), was assessed in the absence and presence of the thromboxane synthase inhibitors UK 38,485 (Dazmegrel) and OKY 046. UK 38,485 and OKY 046 inhibited both LPS-stimulated TXA2 production and TNFa release in a dose-dependent manner. Prostaglandin E2 (PGE2) production was not increased by UK 38,485 or OKY 046. Neither LPS nor UK 38,485 had any effect on LT84 production by AM. Neither UK 38,485 or OKY 046 had any effect on LPS-stimulated interleukin-I beta release. However, the TXA2 mimetic, U46619, did not stimulate TNFa release by AM either in the absence or presence of UK 38,485. These findings suggest that 1) UK 38,485 and OKY 046 are inhibitors of both TXA2 production and TNFa release by activated human AM, 2) UK 38,485 probably does not exert its inhibitory action on TNFa release through effects on eicosanoid production and 3) the possibility that TNFa- and TXA2-induced lung injury may be subject to amelioration by imidazole-based compounds should be further evaluated.IntroductionTumor necrosis factor alpha (TNFa), produced by monocytes and macrophages, is a potent peptide mediator of lung injury (1,2). The exaggerated release of TNFa has been implicated in the etiology of acute lung reactions such as septic shock of bacterial or viral origin (3,4). The role of TNFa is expressed primarily through its ability to activate a variety of cell types within the lung environment including polymorphonuclear leukocytes (PMNs, ref. 5), type II epithelial cells (6) and fibroblasts (7). The role of lipid mediators in lung disease has also been extensively characterized (1). In particular, the relationship between pulmonary inflammation and fibrosis and the production of oxygenated derivatives of arachidonic acid (here termed ""eicosanoids"") appears to be a key factor in a variety of disease processes in the lung (8). The alveolar macrophage (AM) synthesizes primarily prostaglandin E2 (PGE2). thromboxane A2 (TXA2) and leukotriene 84 (LT84, ref. 9). These eicosanoids have been shown to produce a variety of effects in the lung including bronchial smooth muscle dilatation (PGE2, ref. 10), vascular smooth muscle contraction and platelet aggregation (TXA2, ref. 11) and oedema and immune cell extravasation (LT84, ref. 12)."

Nov 1, 1995

By E. V. Cilento, K. A. DiGregorlo, R. C. Lantz

A kinetic model was developed to describe the production of superoxide (02) by single pulmonary alveolar macrophages (PAM). Model predictions were compared to experimental results obtained from single rat PAM. The O2 - was quantified by measuring the reduction of nitroblue tetrazolium (NBT) to a diformazan precipitate (NBTH2) from video-recorded images of individual cells. The kinetic model considered three reactions: (1) the production of extracellular 0 - from the reduction of oxygen by NADPH oxidase using intracellular NADPH as the substrate, (2) the subsequent dismutation of o2- to from O2 , and (3) the reaction of o2- and NBT. NBT specificity for o2- was analyzed by comparing results in the presence and absence of superoxide dismutase (SOD) which catalyzes the dismutation of o2- to H2o2. Measured PAM heterogeneity was accounted for by varying the concentration of intracellular NADPH, its rate of depletion, and the concentration of intracellular NADPH oxidase in the kinetic model. Model predictions compared favorably with experimental results except when SOD was present. This discrepancy may be due to diffusional limitations since NBT is a relatively small molecule (818 MW) compared to SOD (34000 MW). In addition, the cell surface is both ruffled and negatively charged, which may introduce steric hindrances and/or electrostatic effects since SOD is also negatively charged.

Jan 1, 1988

By K. Biswas, S. Iverson, S. J. Jung

Computer modeling of rock flow in ore passes is being investigated and compared using MSC Soft-ware’s Working Model 2D1 (WM2D) and Itasca Corp.’s Particle Flow Code in Two Dimensions (PFC2D). This work is being carried out by the Spokane Research Laboratory of the National Institute for Occupational Safety and Health to determine the usefulness of computer modeling to improve ore pass design. The types of tests included pendulum tests to validate WM2D simulations and simulated single-rock drop tests in both WM2D and PFC2D to understand their contact models. Simulated rock impacts at the ore pass chute and the use of inclined ore passes and doglegs were investigated in both programs. A PFC2D simulation showed that dynamic loads at the chute gate were reduced significantly when a dogleg transition was used, and simulations in which the ore pass was inclined showed significant reductions in chute impact loads compared to simulations of a vertical ore pass. A released hang-up was simulated using PFC2D.

By C. A. Frenzel

Extensive spectroscopic data are needed in making reliable vibrational assignments for use in calculating thermodynamic functions of polyatomic molecules. The fundamental vibrations of organic molecules may be observed at any wavelength from 2.5 to 200 microns (micron = µ = 10-4 centimeters), but most often in the region from 3µ to 50µ. Raman spectra generally cover the range in which fundamental vibrations occur, but equally important infrared spectra usually are not measured at wavelengths longer than 25µ. This limitation results because most infrared spectra are determined for analytical purposes, which seldom require information outside the region 2µ to 25µ. Measurements of infrared spectra in the range 15µ to 35µ recently were begun by the Bureau of Mines to obtain data needed in making vibrational assignments. This report presents the spectra of the following thirteen compounds: Tetrahydrofuran, 1-methylpyrrole, piperidine, 2-methylpyridine, 3-miuthylpyridine, 2-propanethiol, cyclopentanethiol, 2-methyl-2-butanethiol, 3,3-dimethyl-2-thiabutane, cyclohexanethiol, cyclopentyl-l-thiaethane, 2,4-dimethyl-3-thiapentane, and hexamethyldisiloxane.

Jan 1, 1960

By David Schlain

This Bureau of Mines report describes a method for electrodepositing titanium diboride from a molten salt bath. Initially, the electrolyte is a mixture of LiBO2, NaB02, Na2 Ti03 , Li2Ti03, and Ti02? The cell is operated at 900° C in a dry, inert atmosphere with consumable anodes of titanium or hot-pressed titanium diboride (TiB2) powder. Agitation of the electrolyte is essential. Current densities may be 6 to 9 amperes per square decimeter (amp/dm2) with titanium anodes and 9 to 30 amp/dm2 with titanium diboride anodes. A current density of 6 amp/dm2 is equivalent to a plating rate of about 35 micrometers per hour. The adherence of the TiB2 deposit varies with the substrate material. It is most adherent on molybdenum and on 4130 steel that has been preplated with copper and nickel, less adherent on nickel, and still less adherent on Inconel and on 4130 steel without the preplate. Cathode and anode reactions are suggested.

Jan 1, 1976

By Robert K. Koch

The Bureau of Mines investigated separating HF from HF-SiF4-H2O mixtures by passing the mixed gases through a sodium fluoride slurry in an airlift scrubber and forming a mixed precipitate of NaHF2 and Na2SiF6. The oven-dried precipitate was thermally dissociated in two stages. The first stage was carried out at 400° C and dissociated NaHF2 to NaF and HF. Condensation and analysis of the evolved HF proved it to be 97 to 99 weight-percent HF containing 0.79 to 0.99 weight-percent H2O and 10 to 93 ppm silicon. The second stage was carried out at 700° C and dissociated Na2SiF6 to NaF (for recycle) and SiF4. The quantity of HF recovered from gaseous HF-H2O-air mixtures decreased with increasing relative H2O concentrations. Air was beneficial when scrubbing extremely dilute wet HF gases. At HF partial pressures of 0.24 and 0.013 mm Hg in the scrubber entrance gases, HF partial pressures of 6.2 x 10-4 and 9 x 10-6 mm Hg were obtained, respectively, in the scrubber exit gases. Scrubber efficiencies were 99.7 and 99.3 percent.

Jan 1, 1966

By M. E. Tyrrell

Despits its high melting point (2,135° C.), resistance to attack by molten metals, and its hardness (8), spinel (MgO?Al203) synthesized by the fusion of alumina (Al 2 0.) and magnesia (MgO) is not used on a large scale as a commercial furnace lining, mainly because of the prohibitive cost. This investigation by the Federal Bureau of Mines was prompted by the possibility of producing synthetic spinel from inexpensive raw materials by methods outlined in U.S. Patent 2,029,773, "Process for Obtaining Products Containing Spinets," dated February 4, 1936. In this patent Ture B. Haglund described a process for recovering crystalline spinels from melts in the system Mg0?Al203-2CaO-SiO2, a system well suited to the use of starting materials such as dolomite CaMg(C03)2, olivine [2(Mg?Fe)0.Si02], and bauxite (Al203?2H20) which are abundant in the southeastern United States. Compositions, ranging from a low content in the eutectic mixture of 35 percent spinal and 65 percent dicalcium silicate (2 CaO?SiO2) to a high of 75 percent spinel and 25 percent dicalcium silicate, were fused in electric furnaces of the arc-resistance and internal-resistance types. So long as members of the system were in proper chemical balance, "dusting" slags could be produced over the entire range of spinel concentration.

Jan 1, 1961

By S. R. Crane

One Bureau of Mines goal is to minimize the undesirable environmental impacts associated with industrial plants emitting waste gases containing S02. To help meet this goal, a regenerable flue gas desulfurization process was developed. This process, known as the citrate process, uses a buffered weak acid solution to absorb S02 from the waste gas. The absorbed S02 is reacted with H2S to precipitate elemental sulfur and regenerate the solution for recycle. The H2S feedstock for the process, if not otherwise available, may be produced by reacting two-thirds of the recovered elemental sulfur with natural gas and steam. Laboratory investigations and pilot plant operations were conducted by the Bureau to determine if H2S from the natural gas, sulfur, and steam reaction was suitable for the citrate process. The laboratory investigations, in which an H2S generator was integrated with other citrate process operations, provided a basis for design and operation of the pilot plant. The objective of the pilot plant was primarily to provide H2S for the citrate pro-cess pilot plant at the Bunker Hill Co. lead smelter in Kellogg, Idaho. The design capacity of the pilot plant was 0.4 to 1.25 tons of H2S per day. The operation demonstrated that (1) a 77-to 79-dry-volume-percent H2S product could be produced from pilot-plant product sulfur, natural gas, and steam; (2) the product R2S regenerated the SO2-loaded citrate solution; and (3) under certain conditions over 95 percent of the natural gas could be converted to H2S.

Jan 1, 1981

By Lindsay D. Norman

Four chloride and seven fixed-nitrogen processes for recovering manganese from domestic resources are described. The chloride processes are divided into two classes (leaching and chloridization) depending upon the major operation responsible for converting the manganese minerals to the chloride from which manganese oxide products are obtained. The fixed nitrogen processes, all of which yield high-grade manganese oxide products, are essentially either leaching or roasting processes. The 11 processes include HC1 leach, HC1 chloridization, HC1 chloride volatilization, CaC12 chloride volatilization, NO2 leach, HNO3-NO2 leach, NH3-CO2-H2O system leach, (NH4)2SO4 leach, (NH4)2SO4 roast, and ammonium salt roast.

Jan 1, 1963

By L. H. Adami

Heats of formation were obtained for four anhydrous crystalline sodium borates by hydrochloric acid solution calorimetry. The heats of formation at 298.15° K from the elements are NAB02, -233.2 ±0.6 kcal/mole; Na2B07, -786.4 ±1.0 kcal/mole; NaB305, -549.9 ±0.8 kcal/mole; and Na2B6013, -1,412.5 ±2.0 kcal/mole, The heats of formation from the constituent oxides are NaB02, -31.5 ±0.8 kcal/mole; Na2B407, -78.8 ±1.3 kcal/mole; NaB305, -44.1 ±0.8 kcal/mole; and Na2B8013, -96.7 ±1.5 kcal/mole.

Jan 1, 1968

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