Hydroxylamines and hemolytic anemia.
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The activity of the DNA-repair protein O6-alkylguanine-DNA-alkyltransferase was found to be strongly inhibited by a number of metal ions. Cd2+ was the most active followed by Cu2+, Hg2+, Zn2+ and Ag2. This inhibition is likely to result from the interaction of the metals with the cysteine-acceptor residue on the protein since the inhibition was reduced by increasing the concentration of dithiothreitol in the assay buffer. These results raise the possibility that exposure to Cd2+ could increase the mutagenicity and carcinogenicity of alkylating agents by retarding the rate of repair of alkylated DNA. However, other metals or metallic compounds which are known to be carcinogenic (such as compounds containing arsenic, lead, nickel or chromium) did not interfere with DNA repair by this protein.
OBJECTIVES: The purpose of this study was to find the optimal combination of surface pretreatment and luting cement for two-unit CoCr cantilever resin-bonded bridges. METHODS: Tensile peel, load and torque strength tests were performed using flat ground bovine teeth as substrate, four different commercially available luting cements, and CoCr beams as simulated cantilever resin-bonded bridges. The CoCr beams were pretreated with sandblasting or Rocatec. Tensile peel, load and torque strengths were determined 72h after cementation. The effects of sandblasting and Rocatec pretreatments on the morphology of the CoCr surface was investigated with SEM and EDAX analysis. RESULTS: The average strengths of the three tests showed that Rely X ARC, Resiment and Panavia were the same and significantly lower than UniFix. Rocatec showed a significantly higher average bond strength than sandblasting considering all tests. The peel test, which showed the lowest failure values, is clinically the most relevant test. This test showed that only UniFix as luting cement with sandblasting as pretreatment generates a significantly higher bond strength compared with the other cements and pretreatments. SIGNIFICANCE: Based on the results of this study the use of Unifix with sandblasting as metal surface pretreatment, is preferred for cementation of two-unit CoCr cantilever resin-bonded bridges.
New macrocyclic ligands were prepared and chromium(III) stability in the marcrocyclic cavities are reported. Two of them have four-coordinate [N2O2]:[N4], third one has five-coordinate [N2O2S] and the last one has six-coordinate [N4O2] donor macrocyclic cavities. These macrocyclic ligands have been synthesized with their chromium(III) complexes which have mononuclear nature and their structural features have been discussed on the basis of: elemental analysis, magnetic moment, electronic, IR, 1H NMR, and EPR spectral studies. All the chromium(III) complexes show magnetic moments in the range of 3.74-3.80 B.M. corresponding to high-spin configuration. However, the interaction of oxygen to the chromium ion in complexes is much weaker than that of other donor atoms. The spin-orbit coupling parameter, z, gives no significance because the splitting of doublet transition lines are too large to be explained by spin-orbit coupling. The beta values (0.75-0.79) indicate the covalent character, which is due to the presence of sigma bond between the metal/ligand. lambda values indicate that the complexes under study have substantial covalent character and their g-values have also been calculated by using spin-orbital coupling constant (lambda).
Recognizing that waste-derived chlorine can enhance heavy metal emissions by forming volatile metallic chlorides during municipal solid waste (MSW) combustion, and that in Taiwan, FeCl3-containing sewage sludge may either be landfilled or coincinerated with other MSW, this study thus investigated the effects of FeCl3 on the speciation and partitioning of heavy metals in a multimetal incineration system by using a tubular furnace and FeCl3-spiked simulated wastes. The molar ratio of chlorine content to heavy metal content (referred to as the Cl/ M ratio), ranging from 3 to 200, was used as a parameter to evaluate the effects of chlorine on the movement of heavy metals between the incinerator discharges. Results indicate that speciation and partitioning were related to the affinity between the chlorine and the heavy metals and between chlorine and hydrogen in the combustion system. The effectiveness of increasing the Cl/M ratio to the formation potential of metallic chlorides and on the shift of heavy metals from the bottom ash to the fly ash and/or the flue gases was found to have in increasing order as follows: Zn>Cu>Cr, a phenomenon basically reflecting the volatility of the heavy metals and their chlorides formed during combustion.
Ferrihydrite, which is known to form in the presence of oxygen and to be stabilized by the adsorption of Si, PO4 and SO4, is ubiquitous in the fine-grained fractions of permeable reactive barrier (PRB) samples from the U.S. Coast Guard Support Center (Elizabeth City, NC) and the Denver Federal Center (Lakewood, CO) studied by high-resolution transmission electron microscopy and selected area electron diffraction. The concurrent energy-dispersive X-ray data indicate a strong association between ferrihydrite and metals such as Si, Ca, and Cr. Magnetite, green rust 1, aragonite, calcite, mackinawite, greigite and lepidocrocite were also present, indicative of a geochemical environment that is temporally and spatially heterogeneous. Whereas magnetite, which is known to form due to anaerobic Fe0 corrosion, passivates the Fe0 surface, ferrihydrite precipitation occurs away from the immediate Fe0 surface, forming small (<0.1 microm) discrete clusters. Consequently, Fe0-PRBs may remain effective for a longer period of time in slightly oxidized groundwater systems where ferrihydrite formation occurs compared to oxygen-depleted systems where magnetite passivation occurs. The ubiquitous presence of ferrihydrite suggests that the use of Fe0-PRBs may be extended to applications that require contaminant adsorption rather than, or in addition to, redox-promoted contaminant degradation.
Green rusts, ferrous-ferric iron oxides, occur in many anaerobic soils and sediments and are highly reactive, making them important phases impacting the fate and transport of environmental contaminants. Despite their potential importance in environmental settings, reactions involving green rusts remain rather poorly described. Chromate is a widespread contaminant having deleterious impacts on plant and animal health; its fate may in part be controlled by green rust. Here we examine chromate reduction by a series of green rust phases and resolve the reaction kinetics at pH 7. The overall kinetics of the reactions are well described by the expression d[Cr(VI)]/dt = -k[Cr(VI)][GR], and this model was successfully used to predict rates of reaction at varying chromium concentrations. The rates of reduction are controlled by the concentration of ferrous iron, surface area, and chemical structure of the green rust including layer spacing. On a mass basis, green rust (GR) chloride is the most rapid reductant of Cr(VI) followed by GRCO3 and GRSO4, with pseudo-first-order rate coefficients (k(obs)) (with respect to Cr(VI) concentration) ranging from 1.22 x 10(-3) to 3.7 x 10(-2) s(-1). Chromium(III)-substituted magnetite and lepidocrocite were identified as the major oxidation products. The nature of the oxidation products appears to be independent of the anionic class of green rust, but their respective concentrations display a dependence on the initial GR. The mole fraction of Fe(III) in the Cr(x),Fe(1-x)(OH)3 x nH2O reaction product ranged from 17% to 68%, leading to a highly stabilized (low solubility) phase.
Significant inhibitory effects of the filtrate medium of anaerobically digested sewage sludge on iron oxidation by Acidithiobacillus ferrooxidans ANYL-1 were observed in our preliminary experiments, indicating the presence of inhibitory substances in anaerobically digested sewage sludge. The objectives of the present study were to identify the possible inhibitory substances and to evaluate their impacts on metal solubilization during bioleaching of sewage sludge. The results showed that the concentrations of total reducing sugars, all tested metal ions, and anions were too low to suppress iron oxidation, and only organic acids, especially acetic and propionic acids, were found at concentrations higher than their inhibitory levels. The presence of 10.8 mM acetic acid and 9.88 mM propionic acid in sewage sludge (sludge N) led to long lag periods of 6 and 7 days for solubilization of Cu and Cr, respectively, as compared to a lag period of only 1 day in the control and another sludge (sludge S) with a low level of organic acids. Meanwhile the leaching time for maximum solubilization of Zn also extended to 6 days in the presence of organic acids as compared to 3 days in the control. Acetic and propionic acids posed an unfavorable bioleaching condition for anaerobically digested sewage sludge; therefore, further studies are required to explore the means to remove the inhibitory effects to improve the heavy metal bioleaching efficiency.
We investigated a method for delivering ferrous iron into the subsurface to enhance chemical reduction of Cr(VI) in chromite ore processing solid waste (COPSW) derived from the production of ferrochrome alloy. The COPSW is characterized by high pH (8.5-11.5) and high Cr(VI) concentrations in the solid phase (up to 550 mg kg(-1)) and dissolved phase (3-57 mg L(-1)). The dominant solid-phase minerals are forsterite (Mg2SiO4), brucite (Mg-(OH)2), and hydrocalumite [Ca4(Al, Fe)2(OH)12X x 6H2O), X = (OH)2(2-), SO4(2-), CrO4(2-)]. The method utilizes FeSO4 in combination with Na2S2O4 to inhibit oxidation and precipitation of the ferrous iron, thereby preventing well and formation clogging. Laboratory batch tests using a 0.05 M FeSO4 + 0.05 M Na2S2O4 solution indicated effective treatment of both dissolved and solid-phase Cr(VI). Contrary to treatments with FeSO4 and FeCl2 alone, the combination resulted in both complete removal of Cr(VI) from solution and sustained Fe(ll) concentrations in solution after a 24 h period. A field test involving injection of 5700 L of a 0.07 M FeSO4 + 0.07 M Na2S2O4 solution into a COPSW saturated zone (pH 11.5) indicated no well and formation clogging during injection. Examination of a core collected 0.46 m from the injection well following injection indicated effective treatment of the solid phase Cr(VI) based on analysis of water, phosphate solution, and high temperature alkaline extracts. The combined reductant solution also imparted a residual treatment capacity to the COPSW allowing for subsequent treatment of dissolved phase Cr(VI); however, dissemination of the iron in the highly alkaline environment appeared to be impeded by the inability to sufficiently lower the pH with distance from the injection well to avoid precipitation of Fe(OH)2 and likely also FeCO3. Injection of a 0.2 M FeSO4 + 0.2 M Na2S2O4 solution into another COPSW saturated zone (pH 9) indicated much more effective dissemination of the injected iron.
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The novel quaternary nitride-hydride Ca(6)[Cr(2)N(6)]H was synthesized at 1000 degrees C in sealed niobium or stainless steel tubes. It crystallizes in the space group R3 (No. 148, Z = 3) with lattice constants (A) a = 9.0042(2) and c = 9.1898(3) and contains the complex anion [Cr(2)N(6)](11)(-) with a short chromium-chromium bond length of 2.26 A. To our knowledge, this is the first example of a non-nitrogen-bridged chromium-chromium dimer in an extended structure compound. Magnetic susceptibility measurements reveal the compound to be paramagnetic at room temperature and with a broad antiferromagnetic ordering centered around 55 K.
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UNLABELLED: GOAL AND SCOPE AND BACKGROUND: The application of a promising method, termed sorptive flotation, for the removal of chromium(VI) and zinc ions was the aim of the present paper. A special case of sorptive flotation is adsorbing colloid flotation. Suitable sorbent preparation techniques have been developed in the laboratory. METHODS: Sorptive flotation, consisting of the sorption and flotation processes combined in series, has proved to give fast and satisfactory treatment of the industrial streams and effluents bearing dilute aqueous solutions of zinc and chromium(VI). RESULTS AND DISCUSSION: Goethite has proved to be effective for the removal of chromium(VI) and zinc ions. Also, adsorbing colloid flotation with ferric hydroxide (as the co-precipitant) could be an alternative method to the above-mentioned separation of metal ions. In both cases, chromium(VI) (pH=4) and zinc (pH=7) removal was about 100%. CONCLUSION: The reasons for selecting the iron-based bonding materials, like goethite and/or in-situ produced ferric hydroxide, are that they are cheap, easily synthesized, suitable both for cation and anion sorption, and, furthermore, that they present low risks for adding a further pollutant to the system. Promising results were obtained. RECOMMENDATION AND OUTLOOK: The application of goethite and in-situ produced ferric hydroxide has demonstrated their effectiveness in the removal of heavy metal ions, such as chromium anions and zinc cations. A proposed continuation of current work is the utilization of similar iron oxides, for instance synthesized akaganeite. The comparison between the results reported in this paper with the results reported in the literature, also deserves attention.
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During the aerobic conversion of xanthine to uric acid by xanthine oxidase, superoxide anion and hydrogen peroxide are produced along with the hydroxyl radical. Our studies demonstrate that washed human platelets incubated with xanthine and xanthine oxidase aggregated and released [14C]serotonin. Aggregation and release were dependent on the duration of exposure to xanthine oxidase as well as the concentration of enzyme. Both reactions were inhibited by the superoxide scavenger enzyme superoxide dismutase but not by catalase, or the free radical scavenger mannitol, suggesting that they were induced by superoxide anion. Superoxide-dependent release was inhibited by prior incubation of platelets with 1 mM EDTA, 1 micronM prostaglandin E1, or 1 mM dibutyryl cyclic AMP, but was unaffected by 1 mM acetylsalicylic acid or 1 micronM indomethacin. After prolonged incubation with xanthine and xanthine oxidase there was also efflux of up to 15% of intraplatelet 51Cr, a cytosol marker. This leakage was prevented by the addition of catalase to the media but not by superoxide dismutase. Incubation with xanthine and xanthine oxidase did not produce malonyldialdehyde, the three-carbon fatty acid fragment produced during prostaglandin endoperoxide synthesis and lipid peroxidation. Prior exposure of platelets to low fluxes of superoxide anion lowered the threshold for release by subsequent addition of thrombin, suggesting a synergistic effect. We conclude that superoxide-dependent aggregation and release may be a physiologically important method to modulate hemostatic reactions particularly in areas of inflammation or vessel injury which could have high local concentrations of superoxide anion.
Water-sorption studies discriminate between passive (those containing Sn, Nb, and Ti) and reactive (those containing Zn and an alloy of CoCrMo) metal-resin composites. The reactive ones form hydrated oxides or hydroxides or both, in accord with a parabolic rate law. The nature of the chemical reaction is elucidated in two instances by analysis of the resultant gases.