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PubMed1992

Toxic effects of bleached and unbleached paper mill effluents in primary cultures of rainbow trout hepatocytes.

Toxic effects of unbleached (sulfate or sulfite) and bleached (sulfate) paper mill effluents were studied in a primary culture of rainbow trout liver cells. The effluents and control water from a clean area were extracted with diethyl ether and added to the cultures dissolved in dimethyl sulfoxide. Plasma membrane integrity was studied by measuring lactate dehydrogenase (LDH) leakage. The cellular content of glutathione (GSH) was used as an indicator of oxidative stress and the formation of reactive intermediates. Dose-response studies indicated that unbleached effluents contained more potent toxic substances than bleached effluents. Both unbleached and bleached effluents contained organic diethyl ether-extractable substances which increased cytochrome P450-dependent 7-ethoxyresorufin-O-deethylase (EROD) activities. The inducing effects were seen at concentrations substantially lower than those decreasing GSH content and increasing LDH leakage. Possible EROD inducing substances in bleached effluents are chlorinated organic compounds. Inducing compounds in unbleached effluents are yet to be identified. Furthermore, at higher concentrations the effluents contained substances that inhibited the cytochrome P450 system. The results show that the trout primary hepatocyte cultures afford a convenient in vitro method for screening cytochrome P450 inducing components extracted from industrial effluents to investigate mechanisms by which wastewaters cause injury in cells.

Abietanes↗

PubMed1986

Mutagenic properties of spent bleaching liquors from sulphite pulps and a comparison with kraft pulp bleaching liquors.

Parameters influencing the mutagenic properties of spent bleaching liquors from sulphite pulps have been studied. In addition a comparison has been made between the properties of spent liquors from sulphite and kraft pulp bleaching. In the sulphite process the cooking base had no influence on the mutagenicity of the chlorination stage. In contrast, removing the extractives before chlorination especially for dissolving pulp resulted in an increase in mutagenic activity. The mutagenicity decreased significantly after substituting 40% of the chlorine with chlorine dioxide. Sequential addition of chlorine and chlorine dioxide resulted in higher activity than simultaneous or premixed chlorination as observed for liquors from kraft pulp. Increasing the pH of the extracts or addition of sulphur dioxide decreased the mutagenicity. Expressed as 10(7) revertants per kappa number and ton pulp the mutagenicity varied between 10 and 40 for sulphite pulp while the corresponding figures for kraft pulp were 100-225.

Chlorine↗

PubMed1985

Mechanism of chloroform formation by chlorine and its inhibition by chlorine dioxide.

Chlorination of drinking waters leads to the formation of trihalomethanes arising from the reaction of chlorine and organic substances. Therefore, chlorine dioxide (ClO2) which does not produce trihalomethanes is being considered as an alternative disinfectant. It has been reported that rat blood chloroform levels were significantly decreased after treatment with ClO2. Studies were conducted to investigate the mechanisms of chloroform formation by chlorine (HOCl) and its inhibition by ClO2 (5 mg/liter) in the presence of HOCl (5, 10, 20 mg/liter) using sodium citrate (1 mM) as an organic substance. When citrate was reacted with HOCl, beta-ketoglutaric acid, monochloroacetone, dichloroacetone, and trichloroacetone were produced as reaction intermediates and chloroform as a final product. There was a linear relationship between the concentrations of HOCl and the formation of chloroform. When ClO2 was substituted for HOCl, neither chloroform was formed nor citrate concentration was changed. Further, chloroform formation was inhibited by ClO2 in the presence of HOCl and citrate and the degree of inhibition depends on the ratio of ClO2/HOCl. Gas chromatograph/mass spectrometer analysis indicates that this inhibition is related to the reaction of ClO2 with beta-ketoglutaric acid to form malonic acid. Chlorine dioxide also oxidizes other intermediates such as monochloroacetone and dichloroacetone to acetic acid. These studies indicate that ClO2 inhibits chloroform formation from citrate and HOCl by the oxidation of the intermediates which were involved in the reaction of chloroform formation.

Acetone↗

PubMed1985

Effects of ClO2 on the absorption and distribution of dietary iodide in the rat.

Aqueous chlorine dioxide (ClO2), an alternative disinfectant for drinking water, was found to decrease gastrointestinal (GI) bioavailability of dietary iodide. It has been previously reported that subchronic exposure to ClO2 decreases thyroxine (T4) levels in nonhuman primates. In this study in vitro experiments with animal feed, isolated rat stomachs, as well as in vivo studies with intact rats, showed that ClO2 in drinking water (at in situ concentrations as low as 2 ppm) oxidizes iodide to its reactive elemental (radical) state, binding it to organic substances present in the GI tract. A single instance of acute exposure to ClO2, however, did not decrease blood iodide levels, or thyroid glandular uptake of iodine.

Animals↗

PubMed1986

The effects of Love Canal soil extracts on maternal health and fetal development in rats.

The effects of a solvent extract of the surface soil of the Love Canal chemical dump site, Niagara Falls, New York, and of a natural extract, or leachate, which is drained from the canal for treatment, on the maternal health and fetal development were determined in rats. The solvent extract, which was contaminated with 2,3,7,8-tetrachlorodibenzo-p-dioxin (2, 3,7,8-TCDD) at 170 ppb and numerous other chlorinated organic compounds with the primary identified components being the isomers of benzenehexachloride (BHC), was dissolved in corn oil and administered by gavage to pregnant rats at 0,25,75, or 150 mg crude extract/kg/day on Days 6-15 of gestation. A 67% mortality was observed at the highest dose. The rats were sacrificed on Day 20. Dose-related increases in relative liver weight accompanied by hepatocyte hypertrophy were observed at all dose levels. Fetal birthweight was decreased at 75 and 150 mg extract/kg/day. No major treatment-related soft tissue or skeletal malformations, except for delayed ossification, were observed. Based on literature values for BHC, all of the observed toxicity could be accounted for by the BHC contaminants of the extract. The crude organic phase of the leachate was administered to pregnant rats at 0,10,100, or 250 mg/kg/day as described above. Maternal weight gain decreased at 100 and 250 mg/kg/day, accompanied by 5 and 14% maternal mortality, and 1 and 3 dead fetuses, respectively. Early resorptions and the percentage of dead implants increased whereas fetal birthweights were decreased at 250 mg/kg/day. No major treatment-related soft tissue or skeletal malformations, except for delayed ossification, were observed. The primary components of the complex leachate by mass were tetrachloroethanes; however, 2,3,7,8-TCDD, which was present at 3 ppm, probably accounted for all the observed toxicity.

Abnormalities, Drug-Induced↗

PubMed1990

Chlorine dioxide and hemodialysis.

In the United States chlorination of potable water supplies has been the standard method of disinfection for about 75 years. In recent times concern has been raised about the propensity of chlorination to introduce potentially carcinogenic trihalomethanes (THM) such as chloroform into finished water. The levels of THM introduced depend on many factors including the quality of the raw water. Numerous community water treatment facilities are experiencing difficulty in meeting current U.S. Environmental Protection Agency standards, and it is likely that the permissible levels may be lowered in the future. An alternative to chlorination which does not generate THM during disinfection is chlorine dioxide, but there are concerns about the acute and chronic toxicity of ClO2 and its disinfection by-products, chlorite and chlorate. Deleterious effects of moderately high levels of these oxychlorines have been demonstrated experimentally on red blood cells, thyroid function, and development in laboratory animals. Adverse effects in controlled prospective studies in humans and in actual use situations in community water supplies have as yet failed to reveal clear evidence of adverse health effects. Among groups who may be at special risk from this suggested alternative are patients who must undergo chronic extracorporeal hemodialysis. The special needs, precautions, and experience to date in regard to finished water are reviewed. Again, very limited human experience has failed to reveal adverse health effects. Further study, caution, and extreme vigilance are indicated, but dialysis patients in carefully controlled facilities may be at no greater risk than the general population.

Animals↗

PubMed1991

Genotoxicity studies of the reaction of chlorine or chlorine dioxide with L-tryptophan.

Non-volatile reaction products generated from the reactions of 70 mM aqueous chlorine or chlorine dioxide with 10 mM L-tryptophan were shown to be direct-acting mutagens to Salmonella typhimurium TA100 and TA98. Several of the fluorescent bands obtained after thin-layer chromatographic fractionation of the XAD-2/8 resin concentrates of the reaction mixtures were shown to be more mutagenic than the reaction mixtures using the Ames Salmonella/microsome assay. In addition, these fractions were shown to be capable of increasing significantly the frequency of sister chromatid exchange in Chinese hamster ovary cells in the absence of rat liver S9 mix. GC/MS analysis of the products in a highly mutagenic fraction of the aqueous chlorine reaction products identified 1,1,3-trichloropropanone, 1,1,3,3-tetrachloropropanone and dichloroquinoline.

Animals↗

PubMed1988

Effects of cold disinfectants on the mechanical properties and the surface topography of nickel-titanium arch wires.

The effects of disinfectants on the mechanical properties and surface topographies were determined for 0.017 x 0.025-inch Nitinol and Titanal wires. Three disinfectants approved by the American Dental Association were tested at maximum antimicrobial concentrations: 2% acidic glutaraldehyde, chlorine dioxide, and iodophor. Bending and tensile tests were evaluated to determine whether the stiffness, strength, or range of the wires changed after disinfectant treatment. Laser spectroscopy was used to detect surface changes from corrosion or tarnish after treatment. No detrimental changes were detected in the mechanical properties or surface topography of either wire product after disinfectant treatment. Nitinol was found to be stronger and stiffer than Titanal. On average, Titanal exhibited five times more specular reflectivity than Nitinol.

Chlorine↗

PubMed1996

Oxidation of spin-traps by chlorine dioxide (ClO2) radical in aqueous solutions: first ESR evidence of formation of new nitroxide radicals.

The reactivities of the chlorine dioxide (ClO2), which is a stable free radical towards some water-soluble spin-traps were investigated in aqueous solutions by an electron spin resonance (ESR) spectroscopy. The ClO2 radical was generated from the redox reaction of Ti3+ with potassium chlorate (KClO3) in aqueous solutions. When one of the spin-traps, 5,5-dimethyl-1-pyrroline N-oxide (DMPO), was included in the Ti3+-KClO3 reaction system, ESR spectrum due to the ClO2 radical completely disappeared and a new ESR spectrum [aN(1) = 0.72 mT, aH(2) = 0.41 mT], which is different from that of DMPO-ClO2 adduct, was observed. The ESR parameters of this new ESR signal was identical to those of 5,5-dimethylpyrrolidone-(2)-oxyl-(1) (DMPOX), suggesting the radical species giving the new ESR spectrum is assignable to DMPOX. The similar ESR spectrum consisting of a triplet [aN(1) = 0.69 mT] was observed when the derivative of DMPO, 3,3,5,5-tetramethyl-1-pyrroline N-oxide (M4PO) was included in the Ti3+-KClO3 reaction system. This radical species is attributed to the oxidation product of M4PO, 3,3,5,5-tetramethylpyrrolidone-(2)-oxyl-(1) (M4POX). When another nitrone spin-trap, alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN) was used as a spin-trap, the ESR signal intensity due to the ClO2 radical decreased and a new ESR signal consisting of a triplet [aN(1) = 0.76 mT] was observed. The similar ESR spectrum was observed when N-t-butyl-alpha- nitrone (PBN) was used as a spin-trap. This ESR parameter [a(N)(1) = 0.85 mT] was identical to the oxidation product of PBN, PBNX. Thus, the new ESR signal observed from POBN may be assigned to the oxidation product of POBN, POBNX. These results suggest that the ClO2, radical does not form the stable spin adducts with nitrone spin-traps, but oxidizes these spin-traps to give the corresponding nitroxyl radicals. On the other hand, nitroso spin-traps, 5,5-dibromo-4-nitrosobenzenesulfonate (DBNBS), and 2-methyl-2-nitrosopropane (MNP) did not trap the ClO2 radical. This result indicates that an unpaired electron of the ClO2 radical is localized on oxygen atom, because nitroso spin-traps cannot form the stable spin adduct with oxygen-centered radical.

Chlorates↗

PubMed2005

Activity of selected oxidizing microbicides against the spores of Clostridium difficile: relevance to environmental control.

BACKGROUND: Clostridium difficile is an increasingly common nosocomial pathogen, and its spores are resistant to common environmental surface disinfectants. Many high-level disinfectants (eg, aldehydes) are unsuitable for environmental decontamination because they need several hours of contact to be sporicidal. This study tested the potential of selected oxidative microbicides to inactivate C. difficile spores on hard surfaces in relatively short contact times at room temperature. METHODS: The spores of a clinical isolate of C. difficile were tested using disks (1 cm diameter) of brushed stainless steel in a quantitative carrier test. The spores of C. sporogenes and Bacillus subtilis, common surrogates for evaluating sporicides, were included for comparison. The clostridia were grown separately in Columbia broth (CB), and B. subtilis was grown in a 1:10 dilution of CB. Each disk received 10 microL test spores with an added soil load, and the inoculum was dried. One disk each was placed in a glass vial and overlaid with 50 microL test formulation; controls received an equivalent volume of normal saline with 0.1% Tween 80. At the end of the contact time the microbicide was neutralized, the inoculum recovered from the disks by vortexing, the eluates were membrane filtered, and the filters placed on plates of recovery medium. The colony-forming units (CFU) on the plates were recorded after 5 days of incubation. The performance criterion was > or = 6 log(10) (> or = 99.9999%) reduction in the viability titer of the spores. The microbicides tested were domestic bleach with free-chlorine (FC) levels of 1000, 3000, and 5000 mg/L; an accelerated hydrogen peroxide (AHP)-based product with 70,000 mg/L H2O2 (Virox STF); chlorine dioxide (600 mg/L FC); and acidified domestic bleach (5000 mg/L FC). RESULTS: Acidified bleach and the highest concentration of regular bleach tested could inactivate all the spores in < or = 10 minutes; Virox STF could do the same in < or = 13 minutes. Regular bleach with 3000 mg/L FC required up to 20 minutes to reduce the viability of the all the spores tested to undetectable levels; chlorine dioxide and the lowest concentration of regular bleach tested needed approximately 30 minutes for the same level of activity. CONCLUSIONS: Acidified bleach, Virox STF, and regular bleach (3000-5000 mg/L FC) could inactivate C. difficile spores on hard environmental surfaces in approximately 10 to 15 minutes under ambient conditions. All of these products are strong oxidizers and should be handled with care for protection of staff, but acidified and regular bleach with high levels of FC also release chlorine gas, which can be hazardous if inhaled by staff or patients.

Chlorine Compounds↗

PubMed2005

The inactivation of bovine cathepsin B by novel N-chloro-acetyl-dipeptides: application of the Houghten 'tea bag' methodology to inhibitor synthesis.

In this study, a series of N-chloro-acetylated dipeptides were synthesised by the application of Houghten's methodology of multiple analog peptide syntheses (MAPS). The peptides, all of which contain a C-terminal free acid, were tested as inactivators of bovine cathepsin B, in an attempt at exploiting the known and, amongst the cysteine proteinases, unique carboxy dipeptidyl peptidase activity of the protease. We have succeeded in obtaining a number of effective inactivators, the most potent of which-chloroacetyl-Leu-Leu-OH, inactivates the enzyme with an apparent second-order rate constant of 3.8 x 10(4)M(-1)min(-1). In contrast, the esterified analog, chloroacetyl-Leu-Leu-OMe, inactivates the enzyme some three orders of magnitude less efficiently, lending credence to our thesis that a free carboxylic acid moiety is an important determinant for inhibitor effectiveness. This preliminary study has highlighted a number of interesting features about the specificity requirements of the bovine proteinase and we believe that our approach has great potential for the rapid delineation of the subsite specificities of cathepsin B-like proteases from various species.

Acetylation↗

PubMed2005

Catalytic dechlorination kinetics of p-dichlorobenzene over Pd/Fe catalysts.

p-Dichlorobenzene (p-DCB) was dechlorinated using Pd/Fe bimetallic catalytic reductants synthesized by chemical deposition. Batch experiments demonstrated that the Pd/Fe bimetallic particles could effectively dechlorinate p-DCB, p-DCB and its intermediate chlorobenzene were removed completely at a Pd loading of 0.02% (weight ratio of Pd to Fe) and Pd/Fe power to solution ratio about 4g 75 ml-1 in 90 min. Dechlorination was affected by various factors such as the reaction temperature, pH, Pd loading percentage over Fe and the introduction of Pd/Fe catalysts et al. Chlorobenzene represents partially stable dechlorinated intermediates in the generation of benzene and part of p-DCB was dechlorinated to benzene indirectly on the surface of Pd/Fe. The dechlorination of p-DCB took place on the surface of the Pd/Fe bimetallic particles in a pseudo-first-order reaction, the activation energy of the dechlorination reaction was determined to be 80.0 kJ mol-1 at the temperature range of 287-313 K.

Catalysis↗

PubMed2005

Carbon/electron source dependence of polychlorinated biphenyl dechlorination pathways for anaerobic granules.

The effect of acclimating anaerobic granules from commercial bioreactors with different carbon/electron sources on their ability to reductively dechlorinate a tri-(2,3,4-CB) and heptachlorobiphenyl (2,2',3,3',4,5,6-CB) was studied. The anaerobic granules were first grown in upflow anaerobic sludge blanket (UASB) reactors fed with two different mixtures of carbon/electron sources, i.e., propionate/butyrate/methanol and formate/methanol. Differences in dechlorination patterns for 2,2',3,3',4,5,6-CB were observed in batch experiments inoculated with granules from these two sets of UASB reactors. Variation of the carbon/electron source, during the dechlorination process, had no effect on the dechlorination pathway, but the extents and rates of dechlorination were highest for ethanol and formate and lowest for pyruvate fed batches. Pre-acclimation of different anaerobic sludges to polychlorinated biphenyls (PCBs) shortened the lag period, but did not influence the PCB dechlorination pathway. This is the first time that similar acclimation conditions for several anaerobic microbial communities prior to inoculation were reported to yield similar substrate specificities for the reductive dechlorination of specific PCB congeners. This research demonstrates a successful strategy for the development of biocatalysts to serve as the inoculum of partially decontaminated sites in order to provide microorganisms with specificities complementary to those of naturally occurring dechlorinators.

Bacteria, Anaerobic↗

PubMed2005

Dechlorination of PCBs by electrochemical reduction with aromatic radical anion as mediator.

Mediated electrochemical reduction was applied to the dechlorination of polychlorinated biphenyls (PCBs) in tetra-n-butylammonium perchlorate/dimethylformamide solution. Rapid and complete dechlorination was possible with biphenyl or naphthalene as the mediator, whereas the reaction was much slower with anthracene or 9,10-diphenylanthracene. The reaction rate was so high with naphthalene or biphenyl radical anion that differences in reactivity could not be observed between congeners. Side reactions, other than biphenyl formation, could occur depending upon the mediators and the substrates, but contributed less than 10% of the total products in the case of naphthalene-mediated dechlorination. Almost all chloride ion formed in the dechlorination remained in the cathode solution. The order of the reaction was determined to be 0.5 for the substrate and 1 for the mediator (naphthalene) in the dechlorination of 2-chlorobiphenyl; identical to results for the mediated dechlorination of 1-chloronaphthalene. The reaction rate in practical PCB dechlorination could be estimated with the use of the initial concentration of the mediator and chlorine content of the solution provided that the problem of the deactivation of the electrode surface could be solved.

Carbon↗

PubMed2005

Pathways and kinetics of carbon tetrachloride and chloroform reductions by nano-scale Fe and Fe/Ni particles: comparison with commercial micro-scale Fe and Zn.

Groundwater and wastewater contaminated with chlorinated organic compounds (COCs) can be treated with zero-valent metals. The practicality of this treatment method depends on the reduction rates of the target compounds and their byproducts. In this study, nano-scale Fe and Fe/Ni particles were synthesized so that they could be used to rapidly degrade carbon tetrachloride (CT) and chloroform (CF). Their BET surface areas were around two orders higher than those of commercial micro-scale Fe and Zn particles. Batch reduction experiments carried out with a metal loading of 2.5 gl(-1) showed that complete reduction of CT by the nano-scale Fe/Ni and Fe particles could be achieved within 20 min and 60 min, respectively. With the commercial micro-scale Fe and Zn particles applied at 125 gl(-1), complete CT reduction could only be achieved after 4h and 1.5h, respectively. Reductions of CT and CF with the nano-scale particles followed pseudo-first-order kinetics, and the specific reaction rate constants with the nano-scale Fe/Ni particles were 2-8 times higher than those of the nano-scale Fe particles. CT was degraded through hydrogenolysis to CF, and subsequently via both complete reduction pathway to methane and hydrogenolysis pathway to dichloromethane (DCM). Significantly more methane was generated with the use of the nano-scale Fe/Ni particles than with the nano-scale Fe particles. While the commercial Zn particles were more reactive than the commercial Fe particles, they failed to transform CT directly into methane, causing accumulation of DCM in the aqueous phase.

Carbon Tetrachloride↗

PubMed2005

Brominated-chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenyl ethers at low temperatures.

Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2',4,4'-tetrabromo diphenyl ether (BDE 47) and 2,2',4,4',5,5'-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 degrees C and 500 degrees C. The formed reaction products were analysed by high resolution gas chromatography-low resolution mass spectrometry (HRGC-LRMS). Among others brominated-chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated-chlorinated benzenes.

Bromobenzenes↗

PubMed2005

Synergic effect of calcium oxide and iron (III) oxide on the dechlorination of hexachlorobenzene.

Dechlorination of hexachlorobenzene (HCB) was achieved by a mixture of commercial CaO and alpha-Fe2O3 (CaO/alpha-Fe2O3) in closed systems at temperatures of 300 degrees C and 350 degrees C, which exhibited a synergic effect compared to CaO or alpha-Fe2O3 alone, and the dechlorination efficiency was dramatically enhanced. When CaO and alpha-Fe2O3 coexisted, HCB was dechlorinated by about 98% after 0.5 h reaction at 300 degrees C. All TeCB-, TrCB-, and DCB-isomers were detected, showing the presence of more than one dechlorination pathway. The pathway to form 1,2,4-TrCB must be a major pathway because the greatest amount of 1,2,4-TrCB was detected. There existed discrepancy of the material balance between the starting and dechlorinated materials. It implies that besides dechlorination other decomposition processes may be present. The mechanism of synergic effect of calcium and iron oxides was investigated.

Calcium Compounds↗

PubMed2005

Influences of pH and current on electrolytic dechlorination of trichloroethylene at a granular-graphite packed electrode.

Electrolytic dechlorination using a granular-graphite packed cathode is an alternative method for the remediation of chlorinated organic compounds. Its effectiveness under various conditions needs experimental investigation. Dechlorination of trichloroethylene (TCE) was conducted under various conditions in an electrolytic reactor with a platinum-gauze anode and a granular-graphite packed cathode. The higher the applied current, the more TCE was eliminated and more hydrogen and oxygen gasses were generated. Current efficiency decreased with a decrease in TCE concentration during each dechlorination experiment. But, the current efficiency concentration coefficient (CECC), which was defined as current efficiency divided by concentration, was a better indicator of current efficiency. The CECC was not significantly affected by current, but it varied with pH value. The pH effects were results of the involvement of electrolytes in the proton reduction and the electron transfer at the cathode. A lower pH value favored TCE dechlorination in potassium chloride, which is an electrolyte that was not involved in cathode reactions with protons and electrons. In ammonium acetate and potassium nitrate, which involve proton reduction and/or electron transfer, the pH value affected TCE dechlorination through proton limitation and electron competition.

Electrodes↗