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PubMed1998

Which conditions promote a remanent (persistent) bactericidal activity of chlorine covers?

The interaction of disinfectants containing active chlorine compounds (hypochlorite, chloramine T) with skin surfaces produces a so called chlorine cover which is a true chemical transformation of the protein matrix of the outermost horny skin layer by forming covalent N-Cl bonds. Though its intensity can easily be measured, the results on its remanent (persistent) bactericidal action until now have not been described consistently. While Gottardi and Karl observed a well-defined remanent action which correlated with the cover strength in the artificially with E. coli contaminated arm, Koller, Rotter, and Gottardi were not able to prove it, neither in artificially contaminated hands nor in the case of the resident bacterial colonization. To clarify these not consistent results, the bactericidal activity of chlorine covers on transient (dry contamination of the finger tips with Micrococcus luteus) as well as on resident colonization (after wearing gloves for 3 h) has been re-investigated using contact plates for recovering the bacteria. The results are showing that the remanent bactericidal action of chlorine covers strongly depends on the skin milieu, with moist conditions caused by sweat (surgical gloves) favoring the bactericidal activity. Elution experiments prove that protein constituents (detected by UV-spectrometry) continuously are transported to the skin-surface. It is obvious that the latter equilibrate with the chlorine cover by forming bactericidal N-Cl compounds with the effect that oxidation capacity fixed at the protein matrix is mobilized enabling the remanent bactericidal action.

Chloramines↗

PubMed2006

Chlorination of aromatic compounds in micellar media: regioselectivity.

Chlorination of phenol and ortho-chlorophenol was studied in micellar media in order to observe the effect on regioselectivity. Hydrogen peroxide/hydrochloric acid-aqueous system, which is environmentally a safer route was employed for chlorination. Selectivity ratio was found to be dependent on the nature and concentration of the surfactant. Ortho/para selectivity ratio up to 12 was realized for the chlorination of phenol. 2,6-/2,4-dichlorophenol ratio up to 1.01 was realized for the chlorination of ortho-chlorophenol.

Journal Article↗

PubMed2000

Chlorination of pyridinium compounds. Possible role of hypochlorite, N-chloramines, and chlorine in the oxidation of pyridinoline cross-links of articular cartilage collagen type II during acute inflammation.

Reactive oxygen species produced by activated neutrophils and monocytes are thought to be involved in mediating the loss of collagen and other matrix proteins at sites of inflammation. To evaluate their potential to oxidize the pyridinoline (Pyd) cross-links found in collagen types I and II, we reacted hydrogen peroxide (H(2)O(2)), hypochlorous acid/hypochlorite (HOCl/OCl(-)), and singlet oxygen (O(2)((1)delta g)) with the Pyd substitutes, pyridoxamine dihydrochloride and vitamin B(6), which share the same chemical structure and spectral properties of Pyd cross-links. Neither H(2)O(2) (125-500 microm) nor O(2)((1)delta g) (10-25 microm) significantly changed the spectral properties of pyridoxamine or vitamin B(6). Reaction of HOCl/OCl(-) (12.5-50 microm) with pyridoxamine at pH 7.2 resulted in a concentration-dependent appearance of two new absorbance peaks and a decrease in fluorescence at 400 nm (excitation 325 nm). The new absorbance peaks correlated with the formation of an N-chloramine and the product of its subsequent reaction with pyridoxamine. In contrast, the extent to which HOCl reacted with vitamin B(6), which lacks a primary amine group, was variable at this pH. At lysosomal pH 5.5, Cl(2)/HOCl/OCl(-) reacted with both pyridoxamine and vitamin B(6). Four of the chlorinated products of this reaction were identified by gas chromatography-mass spectrometry and included 3-chloropyridinium, an aldehyde, and several chlorinated products with disrupted rings. To evaluate the effects of Cl(2)/HOCl/OCl(-) on Pyd cross-links in collagen, we exposed bone collagen type I and articular cartilage type II to HOCl. Treatment of either collagen type with HOCl at pH 5. 0 or 7.2 resulted in the oxidation of amine groups and, for collagen type II, the specific decrease in Pyd cross-link fluorescence, suggesting that during inflammation both oxidations may be used by neutrophils and monocytes to promote the loss of matrix integrity.

Cartilage, Articular↗

PubMed2006

A novel on-site system for the treatment of pharmaceutical laboratory wastewater by supercritical water oxidation.

For the on-site treatment of laboratory waste, we have been developing a compact-sized reaction system for the treatment of laboratory wastewater using supercritical water oxidation (SCWO) technology. Pharmaceutical laboratory wastewater is one of the most difficult wastewaters to treat because of its high concentration of halogenated organic compounds. We proposed a new cascade process in which two reactors are consecutively combined, carrying out hydrolysis in the first reactor followed by SCWO in the second reactor, for the complete removal of halogenated organic compounds. Dichloromethane was chosen as a representative model of chlorinated compounds. There have been many previous studies on the hydrolysis of dichloromethane, which results in the coproduction of formaldehyde and HCl. However, there has been less investigation on the kinetics of formaldehyde oxidation in supercritical water. In this study, we focus on the oxidation of formaldehyde in supercritical water with and without a catalyst. As a result, formaldehyde can be completely decomposed at 400 degrees C and 25 MPa within a very short contact time in a heterogeneous system with a MnO(2) catalyst.

Drug Compounding↗

PubMed1989

[The hygienic and epidemiologic importance of water disinfection in pools used for medical rehabilitation].

The water in the medical rehabilitation pools has some specific features in respect to hygiene--and--epidemiological casualty, bringing to an increase of infection risks by many diseases. It presents a way to communicate carriers from one patient to another, and thus the risk of infection. Major infections communicated by pool water are the nose, mouth, ear and larynx infections, and all the other ones are only sporadic and of minor importance in the periods of passive epidemiological situations. Apart from the microbiological contaminations and chemical agents (nitrogenous compounds), the chemical parameters of water present important factors. Chlorine compounds used for water disinfection have their advantages and disadvantages, and their disinfection action is influenced by numerous factors.

Disinfection↗

PubMed2005

Formation of toxic chemicals including dioxin-related compounds by combustion from a small home waste incinerator.

We investigated combustion in a small home waste incinerator and analyzed both flue gas and residual ash for formation of the dioxin-related compounds polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls and their precursors polychlorinated benzenes, polychlorinated phenols, polychlorinated diphenyl ethers, and polychlorinated biphenyls. Particularly, we investigated the effect of the incinerated material's composition on both the congener ratios of released compounds and the total concentration of all congeners of each compound. Eight different samples were prepared for incineration with four samples consist entirely paper, dead leaves, natural wood, or building materials. The remaining four samples contained mostly paper, but also other components such as fiber, non-chlorine-containing plastics, chlorine-containing plastics, and copper electric wire. The presence of non-chlorine-containing plastic in combustion samples did not increase overall dioxin or dioxin-precursor emissions. In contrast, chlorine-containing plastic resulted in a several-fold increase in total polychlorinated dioxins released, in both flue gas and residual ash. Copper wire resulted in a further several-fold increase in total polychlorinated dioxins and dioxin precursors released, with one exception: the addition of chlorine-containing plastic resulted in a many-fold increase in polychlorinated biphenyls, but only a modest further increase ( approximately 52%) with the further addition of copper. Homologue ratios tended toward higher-chlorine compounds as chlorine-containing plastic and Cu were added, but the results were far from uniform. Our results show that toxic dioxin release from small home waste incinerators must be considered significant, especially if even small amounts of chlorine-containing plastics or copper are burned.

Air Pollutants↗

PubMedDate not supplied

Volatiles from four Astragalus species: phenological changes and their chemotaxonomical application.

This paper shows the changes of the volatile compounds from four Astragalus species at three phenological stages: leaf development, flowering and fructification, which might be connected with the plant defense. After GC/MS analyses of Astragalus glycyphyllos L., A. hamosus L., A. cicer L. and A. spruneri Boiss., different groups of volatile compounds were found: hydrocarbons, alcohols, aldehydes and ketones, esters, terpenes, chlorinated compounds, etc. Identified volatiles were used for a cluster analysis in order to make chemotaxonomic conclusions for these evolutionary different species.

Alcohols↗

PubMed1990

Airborne Toxic Elements and Organic Substances (ATEOS) project: overview.

The approach and conclusions of the ATEOS project will be examined with an emphasis on future design considerations and strategies to address and reduce exposures. The ATEOS was a five year project that conducted field sampling in the summer and winter for the years 1981 through 1983. Eighty-five outdoor air pollutants were measured including the composition of inhalable particulate mass, and volatile organic compounds. The particulate mass components measured were the non-polar through polar organic fractions, polycyclic aromatic hydrocarbons, SO4(-2), trace elements and alkylating agents. From the numerous volatile organic compounds present in the atmosphere measurements were made of 10 chlorinated compounds, the automobile by products, e.g., benzene, o and p xylene, and 13 solvents. Other measurements included local meteorology. Besides the wealth of variables an important component of the study was the selection of the outdoor sites. The approach was to choose specific types of population--industrial-commercial locales with increasing (or decreasing) complexity. The sites were located in the New Jersey urban centers of Newark, Elizabeth and Camden, and a rural setting in Ringwood, N.J. The Newark site was the most complex industrial-commercial-residential interface followed in decreasing order by Elizabeth, Camden and Ringwood. The manuscript will emphasize the characteristics of the measured variables in relation to the differences in the neighborhoods surrounding each site. Summary information on source-receptor modeling, pollution accumulation processes, episode analyses, and exposure assessment studies will be presented. These will be all evaluated with respect to future study design questions, including monitoring frequency, epidemiological exposure assessments and indoor air pollution.

Air Pollutants↗

PubMed1991

Gas chromatographic-mass spectrometric analysis of urban-related aquatic and airborne volatile organic compounds. Study of the extracts obtained by water closed-loop stripping and air adsorption with charcoal and polyurethane foam.

The distribution of volatile organic compounds (VOC) in urban-influenced air and river waters was investigated. The aquatic VOC were extracted with the closed-loop stripping technique (CLST) and the airborne compounds were studied using two methods, charcoal and polyurethane foam adsorption. In both types of samples, C1-C5 alkylbenzenes and n-alkanes constitute the two major VOC groups, and the presence of these groups indicates a predominance of petroleum products in these two environmental compartments. Chlorinated compounds such as polychlorobenzenes, polychloronaphthalenes and hexachlorobutadiene are abundant in water samples, whereas tetrachloroethene is the predominant chlorinated airborne VOC. The compounds collected with each sampling system can be described in terms of ranges of volatility. These ranges (expressed as mmHg vapour pressure at 25 degrees C) can be defined approximately as 140 (methylcyclopentane)-0.65 (n-undecane) for charcoal, 5.1 (n-nonane)-0.000061 (n-docosane) for polyurethane foam and 29 (toluene)-0.000029 (n-eicosane) for the CLST. Parallel air sampling with charcoal and polyurethane foam is therefore needed to cover a VOC range similar to that afforded by the CLST in water.

Adsorption↗

PubMed1985

Chemical contamination of water supplies.

Man-made organic chemicals have been found in drinking water for many years. Their numbers and varieties increase as our analytical capabilities improve. The identified chemicals comprise 10 to 20% of the total organic matter present. These are volatile or low molecular weight compounds which are easily identified. Many of them are carcinogenic or mutagenic. Chlorinated compounds have been found in untreated well water at levels up to 21,300 micrograms/L and are generally present at higher levels in chlorine-treated water than in untreated water. Aggregate risk studies for cancer are summarized. The most common sites are: bladder, stomach, colon, and rectum. Such studies cannot be linked to individual cases. However, they are useful for identifying exposed populations for epidemiologic studies. Five case-control studies were reviewed, and significant associations with water quality were found for: bladder cancer in two studies, colon cancer in three and rectal cancer in four. A large study by the National Cancer Institute found that there had been a change in the source of raw water for 50% of the persons in one area between the years 1955 and 1975. Such flaws in the data may preclude finding a causal relation between cancer and contaminants in drinking water. Large case-control and cohort studies are needed because of the low frequency of the marker diseases, bladder and rectal cancer. Cohort studies may be precluded by variations in the kinds of water contaminants. Definitive questions about these issues are posed for cooperative effort and resolution by water chemists, engineers, and epidemiologists.

Carcinogens↗

PubMed1991

Organochlorine pesticides and polychlorinated biphenyls in human adipose tissue.

Halogenated organic compounds are highly lipophilic chemicals that are persistent in the environment as a result of their use and chemical stability. Some of these compounds are also present in the environment as metabolites or oxidation products of a parent compound or as by-products formed in the production of chlorinated compounds. Chronic exposure to the general population results mainly through the food chain. Because they are lipophilic, and because many are metabolized slowly, these chemicals tend to concentrate in body fat tissue. This contribution has described these halogenated organic compounds, discussed their use, regulation and prohibition throughout the world, and reviewed published studies on the levels of these chemicals found in the adipose tissue of humans and animals. For many years, residues of halogenated organic compounds have been detected in the human adipose tissue of individuals in a number of countries, including those in Europe, Asia, and Africa, as well as in the U.S. The levels detected have been used as an index of the level of general population exposure of these compounds over time. Over the past two decades, most countries have observed a steady decline of this level of exposure, reflecting a reduction in the use of these compounds, restrictions on or banning of their use, and a corresponding decrease in their environmental levels. The levels of concentrations vary from chemical to chemical as well as from isomer to isomer. Since the use of aldrin and dieldrin has now been banned or restricted in the U.S. and a number of other countries, residue levels have slowly decreased. Mean values in human adipose tissue in the U.S. and some foreign countries ranged from 0.04 to 0.40 ppm for dieldrin. Aldrin was detected only in Argentina and Poland in the 1970s and endrin was not detected anywhere at anytime. By 1978, all products containing BHC registered in the U.S. has been either discontinued or reformulated to incorporate lindane rather than BHC. The potential for exposure to BHC is virtually nonexistent in the U.S.; however, exposure to lindane is possible since products containing this chemical are still marketed, and used particularly in the manufacture of human medicine. DDT was banned for agricultural purposes in the U.S. in 1972, although it is still used elsewhere for public health vector control. Since the decline in use of DDT, however, the average levels of concentration have also declined. Heptachlor, chlordane, and trans-nonachlor (a component of both heptachlor and chlordane) are chlorinated cyclodienes.(ABSTRACT TRUNCATED AT 400 WORDS)

Adipose Tissue↗

PubMed1993

Presence and importance of organochlorine solvents and other compounds in Germany's groundwater and drinking water.

Organochlorine compounds are widely used in Germany although the inland production of chlorinated solvents has greatly decreased since 1985. Data on groundwater contamination are incomplete, but there are some regional data sets from the States (Länder). Approximately 25% of the groundwater samples contain more than 1 microgram/l of a single solvent, the most prominent ones being tri- and tetrachloroethene, 1,1,1-trichloroethane and dichloromethane, but also chloroform. The most important causes for contaminations of the groundwater are unprotected storage and leaking sewage systems. Abandoned waste sites are, besides chlorinated compounds, also a source of many other contaminants. A ranking procedure according to their exposure potential (concentration, incidence, toxicology) is proposed. The compound of greatest concern is vinyl chloride, which is formed from tri- and tetrachloroethene under reducing conditions in the subsoil. The most important contaminant in drinking water is tetrachloroethene followed by 1,1,1-trichloroethane and trichloroethane. Chlorobenzene may also be present on occasion, while only about 20% of the finished drinking waters contain more chloroform after treatment than before. Only about 10% of all analyses of drinking water derived from groundwater shows the presence of organochlorine solvents and most of these show total concentrations less than 2 micrograms/l. The degradation product, vinyl chloride, was found up to now only in different groundwaters. To stabilize and to improve the situation, which still is much more favorable for drinking than for groundwater, precautions are going to be taken which should assure that these and other problematic substances which endanger water are used only in closed systems and rigid safety measures be imposed on their disposal and transport.

Germany↗

PubMed1999

Chlorinated pesticide residues in surface sediments from the River Kaveri, south India.

Chlorinated compounds have preferential attraction for organic phases found in sediments. Usage of chlorinated pesticides in agriculture and vector control is more in developing countries. The residue levels of HCH isomers, and DDT, and its metabolites were quantified in surface sediments from the River kaveri and Coleroon in Tamil Nadu state, South India. The concentration of HCH ranged from 4.35 to 158.4 ng g-1 (dry wt.). Among the isomers of HCH, alpha-HCH is predominant followed by beta and gamma-HCH. The levels of DDT varied from 0.69 to 4.85 ng g-1 (dry wt.). Among the DDT compounds, p,p'-DDE quantified more (> 40%) in all the sites. This suggests that p,p'-DDE is a major breakdown (dehydrochlorination) product of DDT in the sediment compartment. Higher concentration of HCH residues reveals its large usage in agriculture. The flux of pesticide residues from land to river including downward flux to sediment is less.

Fresh Water↗

PubMed2004

Statistical method to evaluate the occurrence of PCB transformations in river sediments with application to Hudson River data.

Polychlorinated biphenyls (PCBs) were produced in the mid 1900s for industrial use. The term PCBs refers to 209 theoretically possible chlorinated compounds of the biphenyl molecule (congeners). The number and location of the chlorines govern both the environmental fate and toxicity of each congener. Changes in the distribution of congeners in river sediments can result from congener transformation and/or preferential congener transport. This study exploits the distribution of PCB congeners, specifically congeners that maintain a constant ratio relationship in the commercially manufactured PCB mixtures (Aroclors), to quantify the likelihood of congener distribution shifts in river sediment. By using relative abundances, the influence of total PCB bias is eliminated. Correlated congeners (tracker pairs) maintain a constant relative proportion in sequentially more-highly chlorinated Aroclors, thus there is no need to know the source contaminating Aroclors a priori. Using the Frame et al. database of Aroclor congener distributions, 276 pairs of correlated congeners, constructed from 95 individual congeners, are identified. A comparison study of Aroclors and Hudson River sediments included 218 of the 276 tracker pairs. Conclusive evidence of a shift in the congener proportions is found in 120 of the 218 cases, a much greater number than expected if no change in congener distribution had occurred.

Databases, Factual↗

PubMed2002

The application of thermal desorption GC/MS with simultaneous olfactory evaluation for the characterization and quantification of odor compounds from a dairy.

Few analytical methods exist that combine chemical and sensory analysis of odorous compounds in whole air. Volatile organic compounds were collected by sampling air downwind from a small dairy through sorbent tubes of Tenax TA and Carboxen 569. Samples were analyzed by thermal desorption into a cryotrap and subsequent gas chromatographic separation, followed by simultaneous olfactometry and mass spectrometry. Because compounds are concentrated during sampling, sensory analysis encountered compounds at a concentration 40 times that in air, making this a useful method for identifying trace compounds participating in odor. Twenty odorous and nonodorous compounds were identified and quantified, including straight-chain and aromatic hydrocarbons, chlorinated compounds, alcohols, ketones, aldehydes, and organic acids, at air concentrations of 0.55-320.20 microg/m(3). Compound peaks were characterized by odors ranging from offensive to pleasant, demonstrating the integrative nature of olfaction. This method could be useful in studying many kinds of odors in air.

Animals↗

PubMed2003

The effect of various disinfectants on detection of avian influenza virus by real time RT-PCR.

An avian influenza (AI) real time reverse transcriptase-polymerase chain reaction (RRT-PCR) test was previously shown to be a rapid and sensitive method to identify AI virus-infected birds in live-bird markets (LBMs). The test can also be used to identify avian influenza virus (AIV) from environmental samples. Consequently, the use of RRT-PCR was being considered as a component of the influenza eradication program in the LBMs to assure that each market was properly cleaned and disinfected before allowing the markets to be restocked. However, the RRT-PCR test cannot differentiate between live and inactivated virus, particularly in environmental samples where the RRT-PCR test potentially could amplify virus that had been inactivated by commonly used disinfectants, resulting in a false positive test result. To determine whether this is a valid concern, a study was conducted in three New Jersey LBMs that were previously shown to be positive for the H7N2 AIV. Environmental samples were collected from all three markets following thorough cleaning and disinfection with a phenolic disinfectant. Influenza virus RNA was detected in at least one environmental sample from two of the three markets when tested by RRT-PCR; however, all samples were negative by virus isolation using the standard egg inoculation procedure. As a result of these findings, laboratory experiments were designed to evaluate several commonly used disinfectants for their ability to inactivate influenza as well as disrupt the RNA so that it could not be detected by the RRT-PCR test. Five disinfectants were tested: phenolic disinfectants (Tek-trol and one-stroke environ), a quaternary ammonia compound (Lysol no-rinse sanitizer), a peroxygen compound (Virkon-S), and sodium hypochlorite (household bleach). All five disinfectants were effective at inactivating AIV at the recommended concentrations, but AIV RNA in samples inactivated with phenolic and quaternary ammonia compounds could still be detected by RRT-PCR. The peroxygen and chlorine compounds were effective at some concentrations for both inactivating virus and preventing amplification by RRT-PCR. Therefore, the RRT-PCR test can potentially be used to assure proper cleaning and disinfection when certain disinfectants are used.

Animals↗

PubMed1990

Interaction of chlorinated phenols with thyroxine binding sites of human transthyretin, albumin and thyroid binding globulin.

Previous results (Brouwer and van den Berg, Toxicol. Appl. Pharmacol., 85 (1986) 301) indicated preferential binding of a hydroxylated metabolite of tetrachlorobiphenyl to transthyretin (TTR) a carrier of thyroxine (T4). In the present study it was investigated whether the T4 binding site of TTR could be occupied specifically by hydroxylated chlorinated aromatic compounds using chlorinated phenol congeners as model compounds in a competition assay with [125I]T4. Chlorinated aromatics such as 2,3-dichlorobenzene and 3,4,3',4'-tetrachlorobiphenyl, and phenols such as 4-hydroxybiphenyl and phenol were inefficient competitors. All chlorinated phenols tested were competitors for the T4 binding site of TTR. The ranking in competition was pentachlorophenol (PCP) greater than trichlorophenols greater than dichlorophenols greater than monochlorophenols. Structures with chlorine in both ortho positions to the hydroxyl group were more efficient competitors. The relative affinity of binding of pentachlorophenol (PCP) to TTR was about twice that of T4. Scatchard analysis showed that PCP mainly decreased the affinity constant K11 while the binding capacity R1 was not altered, indicating a competitive type of inhibition. PCP was also able to compete with T4 sites on albumin with a relative affinity of 0.25. T4 binding to thyroid binding globulin (TBG) was much less affected by interference of PCP (relative affinity 0.001). The results indicate a specific interaction of chlorophenols with the T4 binding site of TTR.

Binding Sites↗

PubMed2002

The natural chlorine cycle--fitting the scattered pieces.

Chlorine is one of the most abundant elements on the surface of the earth. Until recently, it was widely believed that all chlorinated organic compounds were xenobiotic, that chlorine does not participate in biological processes and that it is present in the environment only as chloride. However, over the years, research has revealed that chlorine takes part in a complex biogeochemical cycle, that it is one of the major elements of soil organic matter and that the amount of naturally formed organic chlorine present in the environment can be counted in tons per km(2). Interestingly enough, some of the pieces of the chlorine puzzle have actually been known for decades, but the information has been scattered among a number of different disciplines with little or no exchange of information. The lack of communication appears to be due to the fact that the points of departure in the various fields have not corresponded; a number of paradoxes are actually revealed when the known pieces of the chlorine puzzle are fit together. It appears as if a number of generally agreed statements or tacit understandings have guided perceptions, and that these have obstructed the understanding of the chlorine-cycle as a whole. The present review enlightens four paradoxes that spring up when some persistent tacit understandings are viewed in the light of recent work as well as earlier findings in other areas. The paradoxes illuminated in this paper are that it is generally agreed that: (1) chlorinated organic compounds are xenobiotic even though more than 1,000 naturally produced chlorinated compounds have been identified; (2) only a few, rather specialised, organisms are able to convert chloride to organic chlorine even though it appears as if the ability among organisms to transform chloride to organic chlorine is more the rule than the exception; (3) all chlorinated organic compounds are persistent and toxic even though the vast majority of naturally produced organic chlorine is neither persistent nor toxic; (4) chlorine is mainly found in its ionic form in the environment even though organic chlorine is as abundant or even more abundant than chloride in soil. Furthermore, the contours of the terrestrial chlorine cycle are outlined and put in a concrete form by constructing a rough chlorine budget over a small forested catchment. Finally, possible ecological roles of the turnover of chlorine are discussed.

Chlorides↗