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PubMed2000

Analysis of halogenated C1/C2-trace compounds in marine atmosphere.

Patterns of volatile ECD-active substances in marine air at the ultra trace level were investigated. The protocol used carbon based adsorbents, thermodesorption and thick film HRGC-ECD together with a second ECD in line with oxygen doped make-up gas. The latter ECD mode leads to an increased sensitivity for chloromethane. dichloromethane, and other important chlorinated substances with an otherwise low response at an ECD driven with oxygen-free nitrogen or argon/methane. The experimental set-up is easily to employ. Air samples were taken on two cruises of the German research vessel R/V "Polarstem" in the Atlantic Ocean to determine the background pattern of all volatile halocarbons from CF3Cl to CHI3 in marine air.

Atlantic Ocean↗
PubMed1978

Chemical structure and biodegradability of halogenated aromatic compounds. Substituent effects on dehydrogenation of 3,5-cyclohexadiene-1,2-diol-1-carboxylic acid.

The dehydrogenation of substituted 3,5-cyclohexadiene-1,2-diol-1-carboxylic acids by dihydrodihydroxybenzoic acid dehydrogenases from benzoate grown cells of Alcaligenes eutrophus and Pseudomonas sp. B 13 and 3-chlorobenzoate grown cells of the latter organism was examined. No significant differences (Km and Vrel values) were detected for the enzymes from both organisms. The same dihydrodihydroxybenzoic acid dehydrogenase is formed in Pseudomonas sp. B13 during growth on benzoate as well as on 3-chlorobenzoate. The lower turnover rates of 3- and 5-chlorodrodihydroxybenzoic acid compared to dihydrodihydroxybenzoic acid are counterbalanced by an increase in specific activity. With the exception of 4-substituted dihydrodihydroxybenzoic acids exhibiting relative high Km values, only slight sterical and electronic substituent effects are evident. Reaction rates were never reduced to a critical level.

Alcaligenes↗
PubMed2005

Organic air pollutants inside and outside residences in Shimizu, Japan: levels, sources and risks.

Concentrations of 38 organic air pollutants including aromatic hydrocarbons (AHCs), carbonyl compounds (CCs), volatile organic halogenated compounds (VOHCs), and organophosphorus compounds (OPCs) were measured in indoor and outdoor air in an industrial city, Shimizu, Shizuoka Prefecture, Japan. Levels of pollutants tended to be higher indoors than outdoors in both summer and winter except for benzene, carbon tetrachloride, trichloroethylene, tetrachloroethylene, and dichlorvos (DDVP). This trend was especially pronounced for CCs such as formaldehyde and acetaldehyde. For the organic air pollutants, the concentrations of AHCs and VOHCs substantially increased in winter, but not those of CCs and OPCs; the trends were similar for both indoors and outdoors. We investigated possible indoor sources of pollutants statistically. Multiple regression analysis of corresponding indoor and outdoor concentrations and the responses to our questionnaire showed that indoor concentrations of certain AHCs were significantly affected by their outdoor concentrations and cigarette smoking. For formaldehyde, indoor concentrations were significantly affected by house age and the presence of carpet or pets. For p-dichlorobenzene (pDCB), the concentrations in bedroom trended to be higher than those in other indoors and outdoors, suggested that mothballs for clothes present in bedrooms are the principal indoor source of pDCB. We compared indoor and outdoor pollutant concentrations to acceptable risk limits for 11 organic air pollutants. In indoors without smoking samples, the geometric mean concentrations of benzene, formaldehyde, acetaldehyde, carbon tetrachloride, pDCB, and DDVP exceeded the equivalent concentration representing the upper bound of one-in-one-hundred-thousand (1x10(-5)) excess risk over a lifetime of exposure.

Air Pollutants↗
PubMed2001

Sonochemical degradation for toxic halogenated organic compounds.

This paper describes the degradation of p-chlorophenol using three different ultrasonic devices. The dissipated power in the reaction matrix was measured based on calorimetric method. The study showed that hydrogen peroxide can improve the sonochemical reaction and gases dissolved in reaction matrix can affect the process to a small extent. The reaction mechanism and kinetics of degradation were also investigated.

Calorimetry↗
PubMed2004

Two trace analytical methods for determination of hydroxylated PCBs and other halogenated phenolic compounds in eggs from Norwegian birds of prey.

Two new trace analytical methods are presented for identification and quantification of phenolic compounds in complex biological matrixes such as bird of prey eggs. One method is based on derivatization with methyl chloroformate prior to GC/high-resolution MS (HRMS) analysis in electron impact ionization mode. Alternatively, the underivatized phenolic analytes were separated and detected by HPLC coupled to time-of-flight MS (TOF-MS) in the negative ion electrospray ionization mode. For both methods, the egg samples were homogenized and dried with acidified sodium sulfate, cold column-extracted, and cleaned up by gel permeation chromatography and subsequently a Florisil column. Recovery rates for pentachlorophenol (PCP), tetrabromobisphenol A (TBBPA), and selected hydroxylated PCBs (HO-PCBs) from spiked hen's eggs (spiking level 1 ng/g of wet weight (ww)) were in the range of 56-98% for the HPLC/MS method and 57-108% for GC/MS including derivatization. Typical detection limits of the HPLC/TOF-MS method were 5 pg/g ww (1-2 pg injected) for HO-PCBs and PCP and 20 pg/g ww (3 pg injected) for TBBPA. The GC/HRMS method achieved detection limits of approximately 1 pg/g ww in predatory bird eggs for all analytes (0.2 pg injected for derivatized TBBPA and 0.05 pg injected for derivatized HO-PCBs and PCP). Eight eggs from four different Norwegian predatory bird species were analyzed. The concentrations determined with the two different quantification methods corresponded well with each other. PCP and TBBPA were found in all samples at concentrations up to 1350 and 13 pg/g ww, respectively (GC/HRMS values). A total of 55 penta- to nonachloro-HO-PCB congeners were detected in the eight eggs, 10 of those could be structurally identified. The maximum HO-PCB congener concentration was found for 4-HO-CB 187 in a peregrine falcon egg with estimated 388 pg/g ww. Another peregrine falcon egg was highest contaminated with sum HO-PCBs (estimated 2.1 ng/g ww). This level was 1.2 per thousand of the sum PCBs value for the same egg. Furthermore, indications were found that the HO-PCB congener distribution pattern could be species specific for predatory birds.

Journal Article↗
PubMed1978

Chemical structure and biodegradability of halogenated aromatic compounds. Two catechol 1,2-dioxygenases from a 3-chlorobenzoate-grown pseudomonad.

1. Two catechol 1,2-dioxygenases, pyrocatechase I and pyrocatechase II, were found in 3-chlorobenzoate-grown cells of Pseudomonas sp. B 13. The latter enzyme showed high relative activities with 3- and 4-chlorocatechol compared with catechol. 2. In benzoate-grown cells, only pyrocatechase I was induced. It was purified 29-fold with a final specific activity of 20 mumol of catechol oxygenated/min per mg of protein and an overall yield of 22%. Because of the instability of pyrocatechase II on chromatography and dialysis, no increase of specific activity was obtained during the purification experiments. 3. Molecular weights of pyrocatechase I and pyrocatechase II were 82000 and 67000 respectively. 4. For both pyrocatechases the pH optimum was found to be at 8.0.5. Inhibitions of the two pyrocatechases by Cu2+ and Hg2+ ions and p-chloromercuribenzoate were different. The effect on pyrocatechase I after incubation for 20 h with the heavy metals was decreased by addition of 1 mM-2-mercaptoethanol to the reaction mixture. The inhibition of pyrocatechase II was even enhanced under these conditions. 6. Extradiol cleavage of 3-methylcatechol in addition to intradiol fission at a ratio of 1:14 was observed only with pyrocatechase I.

Benzoates↗
PubMed2005

Direct observation of excitons and a continuum of one-dimensional Mott insulators: a reflection-type third-harmonic-generation study of Ni-halogen chain compounds.

The third-harmonic-generation (THG) spectrum was measured for a NiBr-chain compound, which is a one-dimensional Mott insulator, in a reflection configuration. A sharp peak and a shoulder structure in the THG spectrum are attributed to three-photon resonance to an exciton and a continuum, respectively. The band-edge energy, the exciton binding energy, and the spectral weights for the exciton and the continuum were determined from comparative studies of linear absorption, THG, and electroreflectance spectra. The excitonic effect is more pronounced in the NiCl chain than in the NiBr chain.

Journal Article↗
PubMed1994

Metabolism and genotoxicity of the halogenated alkyl compound tris(2,3-dibromopropyl)phosphate.

1. The genotoxicity of the flame retardant tris(2,3-dibromopropyl)phosphate (Tris-BP) was studied in vivo. Results showed that Tris-BP was highly clastogenic, but it could only initiate a low number of preneoplastic foci in the rat liver in vivo. In Drosophila, Tris-BP could be classified as a cross-linking agent, because it was more clastogenic than mutagenic. The use of completely deuterated Tris-BP as a metabolic probe revealed that cytochrome P450 and most likely the formation of 2-bromoacrolein (2BA) from Tris-BP is important for the observed genotoxic effects. 2. In contrast to the high mutagenicity of Tris-BP and 2BA in Salmonella typhimurium, we were unable to detect an increase in mutation frequency of 2BA on the hprt locus of human TK6 cell line. In another system, using a shuttle vector modified with 2BA:DNA-adducts, also no increase in mutation frequency could be detected in human cells. This low mutagenicity of 2BA corresponds with its low mutagenicity in Drosophila and its low induction of preneoplastic foci in the rat liver. 3. Several DNA adducts of 2BA have been identified, including an unstable 3-(bromooxypropyl)thymidine adduct which has the potential to form cross-links and a cyclic 3,N4-(bromo)propeno-deoxycytidine adduct which can possibly be involved in the clastogenicity of Tris-BP. 4. Taken together, these data indicate that Tris-BP and 2BA may not effectively induce gene mutations in eukaryotic systems, but rather be potent clastogens. Risk assessment of these and related compounds should therefore be based on the knowledge of clastogens rather than mutagens.

Acrolein↗
PubMed1995

Genetic adaptation of bacteria to halogenated aliphatic compounds.

The bacterial degradation and detoxification of chlorinated xenobiotic compounds requires the production of enzymes that are capable of recognizing and converting compounds which do not occur at significant concentrations in nature. We have studied the catabolic route of 1,2-dichloroethane as an example of a pathway for the conversion of such a synthetic compound. In strains of Xanthobacter and Ancylobacter that have been isolated on 1,2-dichloroethane, the first catabolic step is catalyzed by a hydrolytic haloalkane dehalogenase. The enzyme converts 1,2-dichloroethane to 2-chloroethanol but is also active with many other environmentally important haloalkanes such as methylchloride, methylbromide, 1,2-dibromoethane, epichlorohydrin, and 1,3-dichloropropene. Further degradation of 2-chloroethanol proceeds by oxidation to the carboxylic acid and dehalogenation to glycolate. The aldehyde dehydrogenase prevents toxicity of the reactive chloroacetaldehyde that is formed as an intermediate and is necessary for establishing a functional 2-chloroethanol degradative pathway in a strain that is not capable of growth on this compound.

Adaptation, Physiological↗
PubMed2006

Effect of immersion chilling of broiler chicken carcasses in monochloramine on lipid oxidation and halogenated residual compound formation.

This study was conducted to evaluate the effect of immersion chilling of broiler chicken carcasses in tap water (TAP) or TAP containing 50 ppm of monochloramine (MON) with respect to chloroform formation, total chlorine content, 2-thiobarbituric acid (TBA) values, and fatty acid profiles. Ten broiler chicken carcasses were chilled in TAP or MON for 6 h. After exposure, the carcasses were removed and cut in half along the median plane into right and left halves. After roasting the left halves, samples of the breast, thigh, and skin (with fat) were collected, subjected to fatty acid profiling, and assayed for chloroform, total chlorine, and TBA. The uncooked right halves of each carcass were stored at 4 degrees C for 10 days and then roasted. After roasting these right halves, samples of breast, thigh, and skin (with fat) were collected from each carcass half, subjected to fatty acid profiling, and assayed for chloroform, total chlorine, and TBA. There were no statistical differences between TAP- and MON-treated fresh or stored products with regard to chloroform levels, total chlorine content, TBA values, or fatty acid profiles.

Animals↗
PubMedDate not supplied

[Risk of infectious hepatitis and risk of anesthetic gases in operating rooms: considerations on 3 cases of chronic hepatic pathology].

Three subject with professional activity in operating theatre and with a diagnosis of chronic viral "C" hepatitis are considered. All cases (Two surgeons and an anesthetist) had been continuously exposed to low level of airborne anesthetic compounds (Nitrous oxide and halogenated compounds). According to possible, but not proved, synergic effects, two cases with a clinical picture of active chronic hepatitis were classified as unqualified to specific work. The third case, affected by a persistent chronic hepatitis, was admitted to operating activities only for four hours a week, i.e. only an operating session a week. Hepatitis B and C markers must be always monitored during the medical surveillance in exposed people of operating theatre.

Air Pollutants, Occupational↗
PubMed1986

Induction of porphyria in cultured chick-embryo hepatocytes by halogenated aromatic compounds.

Chick-embryo liver cells in culture were used to study the mechanism by which hexachlorobenzene (HCB) and other chlorobenzenes cause hepatic porphyria with accumulation of uroporphyrin (URO). The actions of the chlorobenzenes were similar to those of 3,4,3',4'-tetrachlorobiphenyl (TCB), but pretreatment with 3-methylcholanthrene (MC) or hexachlorobenzene was needed for maximum accumulation of URO. HCB was as potent and almost as rapid as the biphenyl in causing URO accumulation, but tetrachlorobenzenes caused little URO accumulation. Ellipticine, an inhibitor of cytochrome P-448, stopped the accumulation of URO. A mechanism is proposed for the action of the chlorobenzenes that involves binding to cytochrome P-448 and production of active oxygen species that oxidize uroporphyrinogen.

Animals↗
PubMed2003

Occurrence and source of brominated organic compounds in surface waters.

Monitoring of organic halogen compounds, measured as adsorbable organically bound bromine (AOBr), in an eutrophic lake, which is influenced by treated waste water, revealed repeatedly high concentrations of organobromine compounds in late summer, whereas five times lower values were measured during the rest of the year. It was possible to reproduce the in situ observed AOBr increase in the laboratory. Batch experiments were performed with lake water from two different lakes and an algae culture. It could be shown that the AOBr production is not limited to strong waste water influenced lakes. Furthermore, the AOBr formation requires light and the presence of algae, and thus is most probably biotic in nature. A low content of nutrients favours the formation of organic bromine compounds. To our knowledge this is the first report about the seasonally occurrence of naturally produced organic bromine compounds in lakes/surface waters.

Adsorption↗