[Chlorine and potassium ions in infections diseases and their action with DOCA].
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This is a meta-analysis of occupational exposures to chlorinated hydrocarbon (CHC) solvents and pancreatic cancer, based primarily on studies that addressed exposure directly (agent studies) and secondarily on studies that reported data without verification of individual CHC exposures (job title studies), all of which were listed in databases for the period January 1969 to May 1998. Standardized extraction of data and double-checking of consistency of data extraction by five extractors were done. Simple random models estimated meta-relative risks. Suggestive weak excesses were found for trichloroethylene (meta-relative risk (MRR) = 1.24, 95% confidence interval (CI): 0.79, 1.97), polychlorinated biphenyls (MRR = 1.37, 95% CI: 0.56, 3.31), methylene chloride (MRR = 1.42, 95% CI: 0.80, 2.53), and vinyl chloride (MRR = 1.17, 95% CI: 0.71, 1.91) but not for carbon tetrachloride. One study addressed tetrachloroethylene (MRR = 3.08, 95% CI: 0.63, 8.99); another investigated chlorohydrin production (MRR = 4.92, 95% CI: 1.58, 11.4). Exposure-response meta-analyses for trichloroethylene and methylene chloride failed to reveal trends. Job title studies on metal degreasing and dry cleaning revealed significant MRRs (2.0 and 1.4, respectively). Publication bias was unlikely. Confounding may have remained insufficiently controlled. Unless the results are seriously biased by exposure or endpoint misclassification or by confounding, strong causal associations between CHC compounds and pancreatic cancer can be judged unlikely. Interactions between environmental and occupational agents, lifestyle factors, and genetic susceptibility remain a possibility, but the data for this meta-analysis did not address interactions.
Xenobiotic biodegradation under anaerobic conditions such as in groundwater, sediment, landfill, sludge digesters and bioreactors has gained increasing attention over the last two decades. This review gives a broad overview of our current understanding of and recent advances in anaerobic biodegradation of five selected groups of xenobiotic compounds (petroleum hydrocarbons and fuel additives, nitroaromatic compounds and explosives, chlorinated aliphatic and aromatic compounds, pesticides, and surfactants). Significant advances have been made toward the isolation of bacterial cultures, elucidation of biochemical mechanisms, and laboratory and field scale applications for xenobiotic removal. For certain highly chlorinated hydrocarbons (e.g., tetrachlorethylene), anaerobic processes cannot be easily substituted with current aerobic processes. For petroleum hydrocarbons, although aerobic processes are generally used, anaerobic biodegradation is significant under certain circumstances (e.g., O(2)-depleted aquifers, oil spilled in marshes). For persistent compounds including polychlorinated biphenyls, dioxins, and DDT, anaerobic processes are slow for remedial application, but can be a significant long-term avenue for natural attenuation. In some cases, a sequential anaerobic-aerobic strategy is needed for total destruction of xenobiotic compounds. Several points for future research are also presented in this review.
The presence of chlorinated organic compounds in breast milk of lactating women living in Osaka Prefecture, Japan, has been followed since 1972. Following the highest concentration found at the start of the measurements, contamination by polychlorinated biphenyls (PCBs) and organochlorine pesticides, such as beta-HCH and DDT declined to about 3-13% of the peak levels by the mid-1970s and continued to decrease to low-level equilibrium states. This decline varies greatly with the chemical compound. In comparison with 1970s, when the contamination of breast milk was highest, the beta-HCH level fell to about 3%, DDT to about 7%, and PCBs to about 13%, representative of different half-lives in the environment and the particular persistence of PCB. In the case of chlordane, a termite insecticide, more than 10 years have passed since its use was prohibited in Japan, but it continues to be found in human breast milk, although at a low level.
The inhibitory effect of the anti-arthritic drug D-penicillamine on the formation of hypochlorite (HOCl) by myeloperoxidase from H2O2 and Cl- was investigated. When D-penicillamine was added to myeloperoxidase under turnover conditions, Compound III was formed, the superoxide derivative of the enzyme. Compound III was not formed when D-penicillamine was added in the presence of EDTA or in the absence of oxygen. However, when H2O2 was added to myeloperoxidase, D-penicillamine and EDTA, Compound III was formed. Therefore it is concluded that formation of Compound III is initiated by metal-catalysed oxidation of the thiol group of this anti-arthritic drug, resulting in formation of superoxide anions. Once Compound III is formed, a chain reaction is started via which the thiol groups of other D-penicillamine molecules are oxidized to disulphides. Concomitantly, Compound I of myeloperoxidase would be reduced to Compound II and superoxide anions would be generated from oxygen. This conclusion is supported by experiments which showed that formation of Compound III of myeloperoxidase by D-penicillamine depended on the chloride concentration. Thus, an enzyme intermediate which is active in chlorination (i.e. Compound I) participated in the generation of superoxide anions from the anti-arthritic drug. From the results described in this paper it is proposed that D-penicillamine may exert its therapeutic effect in the treatment of rheumatoid arthritis by scavenging HOCl and by converting myeloperoxidase to Compound III, which is inactive in the formation of HOCl.
Genomic DNA from nine individual bacteria, isolated from a diclofop-methyl-degrading biofilm consortium, was extracted for genetic characterization. The degradation of diclofop-methyl produces metabolites that are known intermediates or substrates for bacteria that degrade a variety of chlorinated aromatic compounds. Accordingly, oligonucleotide primers were designed from specific catabolic genes for chlorinated organic degradation pathways, and tested by PCR to determine if these genes are involved in diclofop-methyl degradation. DNA homology between the PCR products and the known catabolic genes investigated by Southern hybridization analysis and by sequencing, suggested that novel catabolic genes are functioning in the isolates. Specific fluorescent oligonucleotides were designed for two of the isolates, following 16S rDNA sequencing and identification of each of the isolates. These probes were successfully used for fluorescent in situ hybridization (FISH) studies of the two isolates in the biofilm consortium.
Clostridium tetanomorphum and Propionibacterium shermanii were examined for intermediates in the synthetic pathway uroporphyrinogen III leads to cobyrinic acid. The isolation of two novel methylated hydroporphyrins, whose methyl groups are derived from S-adenosyl-L-methionine, is described. Spectroscopic (field desorption-mass, visible absorption) und electrophoretic studies as well as incorporation of labelled substrates indicate that they are analogues of a dihyrouroporphyrin and a tetrahydrouroporphyrin with adjacent reduced rings. Field desorption spectra of the [C2H3]- and [CH3]-tetrahydrouroporphyrin analogues show that the compound contains two methyl groups; it is concluded that the chlorine-like compound has one methyl group. Dehydrogenation experiments indicate that the methyl groups are located at one beta-carbon of the reduced rings. Incorporation experiments suggest that the tetrahydrouroporphyrin-like compound is an intermediate in cobyrinic acid biosynthesis. Studies on the utilization of a heptacarboxyporphyrinogen from C. tetanomorphum for cobyrinic acid formation are also described.
The electrochemical oxidation of several phenolic aqueous wastes has been studied using a bench-scale plant with a single-compartment electrochemical flow cell. Boron-doped diamond materials were used as the anode. Complete mineralization of the waste was obtained in the treatment of phenols not substituted with chlorine or nitrogen. Chlorinated phenolic compounds were transformed into carbon dioxide; volatile organochlorinated compounds and nitro-substituted phenols deal with the formation of polymeric materials. These polymeric materials behave as final products or treatment intermediates depending on the nature of the initial pollutant. The removal of nitro- or the chloro-group from the phenolic molecule seems to be one of the first stages in the treatment. Non-nitrogenated or chlorinated carboxylic acids have been found to be the main intermediates in the electrochemical oxidation of all the phenolic compounds tested. The efficiencies of the process depend strongly on the concentration of organic pollutants and on their nature, and not on the current density, at least in the operation range studied.
Many pesticides are degraded to become chlorinated aromatic compounds in soils. Equilibrium distribution of chlorobenzene and chlorophenol compounds in soil-water systems of Yangmingshan loam, Pingcheng silty clay loam and Annei silty loam was studied with the integral distribution equilibrium equation involving the partial solubility parameters of the chemicals. If the adsorption of chemicals on soils is partitioning in soil organic matter surrounding the soil mineral particles, the absorption constant (Kd) of a chemical in soil-water system could be stated as the distribution coefficient (or partition constant, Koc) of the chemical in the two adjunct immiscible phases--water and soil organic matter. The distribution coefficient (Koc) of chemicals calculated from the integral distribution equilibrium equation agrees well with the experimental adsorption coefficient (Kd, or experimental Koc) of chemicals determined in this study, for all the three different types of soils in water according to multiple-regression analysis. Reference data of Karger or Tijssen are employed to estimate the Koc for both polar and non-polar chemicals. The integral distribution equilibrium equation can exactly describe the distribution behavior of nonionic compound of chlorobenzenes and chlorophenols in soil-water systems.
The toxicity of chlorinated organic compounds which may be generated as a by-product of drinking water chlorination has been an issue of increasing concern. Relatively few data are available concerning their reproductive toxicity. The present study was designed to evaluate the reproductive effects of one of these compounds, 2,4,6-trichlorophenol (TCP), in male and female rats. Adult males were treated with either 0, 100, 500, or 1000 mg/kg of TCP (po) for 10 weeks, at which time semen evaluations were conducted on ejaculates recovered from the genital tract of receptive females. Fertility was assessed in the 0- and 1000-mg/kg groups. Females were treated with identical doses for 2 weeks prior to pregnancy then throughout gestation. Dams were allowed to litter and pup development was monitored until Day 42 postpartum. TCP had no effect on any sperm parameter or male fertility. Treatment of females with 1000 mg/kg of TCP produced gross maternal toxicity as reflected in increased lethality and decreased weight gains in the dams. However, no treatment-related differences were seen in litter sizes or pup survival. Male and female birth weights were significantly depressed in the 500- and 1000-mg/kg groups; these differences disappeared by Day 4 postpartum, suggesting that they were a reflection of maternal toxicity. To this extent, the reproductive processes of male and female rats do not appear to be a primary target for the effects of TCP.
Water samples of the River Elbe near Hamburg were analyzed for 145 organic chemical compounds. In part I results of the investigations concerning the following groups of compounds are presented (57 individual compounds): volatile chlorinated hydrocarbons, chloroalkylethers (haloethers), chlorobenzenes, nitrobenzenes, chloronitrobenzenes, and chloroanilines. Highest concentrations were found for the chlorinated bispropylethers and 1,7-dichloro-3,5-dioxaheptane (haloethers). Other important compounds were nitrobenzene, nitrotoluenes, and chloronitrobenzenes. The results were assessed on the basis of German surface water quality criteria.
The hydrodechlorination of dichloromethane (DCM), tetrachloroethylene (TTCE), chlorobenzene (CBZ) and 1,2-dichlorobenzene (DCBZ), all of them alone and in mixtures, over a commercial Pd/Al(2)O(3) catalyst in a continuous packed-bed reactor was studied in the present work. Results indicate that the reaction kinetics for the single compounds are pseudo-first order kinetics. The reactivity of the compounds studied is very different. So, whereas aromatic compounds and tetrachloroethylene can be fully converted at the operation conditions reported in this work, dichloromethane conversions are lower than 30% in all the cases. The hydrodechlorination of mixtures of organochlorinated compounds shows important inhibition effects, these effects increase as the number of chlorine atoms in the molecule increase. Reaction kinetics for the hydrogenation of mixtures can be represented by a Langmuir-Hinshelwood model.
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The reaction pathways of aqueous chlorination of anisole, ethylbenzene and o-methoxybenzoic acid being structural fragments of humic matter were studied using gas chromatography-mass spectrometry. Chlorine and sodium hypochlorite were used as commonly employed disinfecting agents. Comparison of the chlorinating agents was performed in terms of the assortment and relative amounts of reaction products. Detailed schemes of the selected substrates transformation were proposed. Quantum chemical calculations were applied to propose structures of the reacting particles and a numerical parameter to estimate an extent of conversion of aromatic substrates during chlorination.