- Comparison of 2,4,6-trichlorophenol conversion to PCDD/PCDF on a MSWI- fly ash and a model fly ash
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We performed experiments on two different matrices with 2,4,6- trichlorophenol as precursor to Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD)/F. A municipal solid waste incinerators (MSWI) and a model fly ash were spiked in two different ways. The experiments demonstrated a three times higher formation potential of the trichlorophenol to PCDD on MSWI fly ash compared with the model fly ash used. For both fly ashes the PCDD yield was higher when gaseous trichlorophenol was fed continuously compared to mixing the fly ashes prior to the experiments with the total amount of the precursor. Despite dilution of the fly ashes tenfold with an inactive matrix the conversion of the chlorophenol was very high. (C) 2000 Elsevier Science Ltd.
- Hell,Altwicker,Stieglitz,Addink
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- Role of copper chloride in the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans during incineration
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Combustion experiments in a laboratory-scale fluidized-bed reactor were performed to elucidate the role of copper chloride in formation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) during model waste incineration. The amounts of PCDDs and PCDFs formed, the homologue profiles, and the isomer distributions were measured in the flue gas from incineration of model wastes containing various levels of copper. A correlation was found between the Cu content of the waste and the proportion of each congener. An increase in copper enhanced the formation of certain congeners, showing that copper acts as a catalyst for formation of PCDDs and PCDFs. An increase in the copper content of the waste decreased the CO concentration in the flue gas and reduced the formation of PCDDs and PCDFs during incineration. This indicates that copper also works as an oxidation catalyst to promote combustion, leading to lower concentrations of products of incomplete combustion. It is indispensable to consider both roles of the catalyst, i.e., enhancement and suppression, in the formation of PCDDs and PCDFs during waste incineration, which are estimated separately from the isomer distributions and the amounts of PCDDs and PCDFs formed.
- Hatanaka, Takeshi,Kitajima, Akio,Takeuchi, Masao
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- Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene
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The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C2 through C8 organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene. (C) 2000 Elsevier Science Ltd.
- Taylor, Philip H.,Wehrmeier, Andreas,Sidhu, Sukh S.,Lenoir, Dieter,Schramm,Kettrup
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p. 1297 - 1303
(2007/10/03)
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- Influence of variation in combustion conditions on the primary formation of chlorinated organic micropollutants during municipal solid waste combustion
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The aim of this study was to investigate the influence of variation in combustion conditions on the primary formation of organic micropollutants (OMPs). The flue gas samples were taken at a relatively high flue gas temperature (650°C), to enable mechanistic studies on the high temperature formation (primary formation). Eleven experiments were performed in a laboratory scale fluidized bed reactor fed with an artificial municipal solid waste (MSW). The samples were analyzed for mono- to octachlorinated dibenzo- p-dioxins and dibenzofurans (CDDs/Fs), tri- to decachlorinated biphenyls (CBs), di- to hexachlorinated benzenes (CBzs), and di- to pentachlorinated phenols (CPhs). In addition to chlorinated OMPs, nonchlorinated dibenzo-p- dioxin (DD), dibenzofuran (DF), and biphenyl (BP) were analyzed. The experiments show that variations in the CE influence the degree of chlorination of the organic micropollutants. A correlation between low CE and formation of non- and low-chlorinated DMPs was seen and a distinct relationship of higher chlorinated homologues and efficient combustion condition. Thus, the DiCDFs and DiCBzs are formed during low combustion efficiency (CE), while the PeCDF and PeCBzs formation take place at higher CE. The distribution between primary and secondary air is important for the formation of higher CDD/Fs and CBzs. The primary formation of CDDs and CDFs is through different mechanisms. The CDDs are mainly formed by condensation of CPhs, while the CDFs are formed through a non- or a low-chlorinated precursor followed by further chlorination reactions.
- Wikstroem,Tysklind,Marklund
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p. 4263 - 4269
(2007/10/03)
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- Isomer distributions of polychlorinated dibenzo-p-dioxins/dibenzofurans formed during de novo synthesis on incinerator fly ash
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Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) emitted from municipal waste incinerators appear to have a chlorination pattern that is quite constant across various samples and conditions. This suggested that these patterns may be controlled by thermodynamic properties of the individual PCDD/F congeners, such as the free Gibbs energy of formation (Δg°(f,T)). This would make prediction of the isomer composition of a particular sample (and hence its TEQ value) possible, based on values of ΔG°(f,T). A laboratory scale study was carried out with activated carbon on fly ash as the source of PCDD/F formation. Although it was found that the isomer distributions within homologues were independent of the reaction time (proof of thermodynamic control), other observations (lack of equilibrium/isomerization between isomers and lack of similarity between isomer distributions measured and predicted by ΔG°(f,T)) contradicted the possibility of thermodynamic control. Hence, this study could not confirm that de novo formation of PCDD/F could explain thermodynamically controlled isomer distributions in incinerators. Some recommendations for further work- time-based studies with precursors, isomerization studies with single congeners, and more data on ΔG°(f,T) values of PCDD/F-were made. Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) emitted from municipal waste incinerators appear to have a chlorination pattern that is quite constant across various samples and conditions. This suggested that these patterns may be controlled by thermodynamic properties of the individual PCDD/F congeners, such as the free Gibbs energy of formation (ΔG°f,T). This would make prediction of the isomer composition of a particular sample (and hence its TEQ value) possible, based on values of ΔG°f,T. A laboratory scale study was carried out with activated carbon on fly ash as the source of PCDD/F formation. Although it was found that the isomer distributions within homologues were independent of the reaction time (proof of thermodynamic control), other observations (lack of equilibrium/isomerization between isomers and lack of similarity between isomer distributions measured and predicted by ΔG°f,T) contradicted the possibility of thermodynamic control. Hence, this study could not confirm that de novo formation of PCDD/F could explain thermodynamically controlled isomer distributions in incinerators. Some recommendations for further work - time-based studies with precursors, isomerization studies with single congeners, and more data on ΔG°f,T values of PCDD/F - were made.
- Addink, Ruud,Govers, Harrie A. J.,Olie, Kees
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p. 1888 - 1893
(2007/10/03)
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- Synthesis and application of alkyl-substituted dibenzofurans as antitumorigenic agents
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Provided is a method of inhibiting estrogen activity by administering a biologically active amount of a substituted dibenzofuran or substituted dibenzodioxin.
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- Isomer-Specific Separation of 2378-Substituted Polychlorinated Dibenzo-p-dioxins by High-Resolution Gas Chromatography/Mass Spectrometry
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All polychlorinated dibenzo-p-dioxin (PCDD) isomers containing four and more chlorine substituents were prepared by micropyrolysis of chlorophenolates.The synthesis included the preparation of all 22 tetra-, 14 penta-, 10 hexa-, 2 hepta-, and octachlorinated species (tetra- to octa-CDD).The gas chromatographic and mass spectrometric properties of these isomers were studied.High resolution gas chromatography (HRGC) on a 55-m Silar 10c glass capillary column allowed the separation of many of these isomers and allowed the unambiguous assignment of the toxic and environmentally hazardous 2378-substituted isomers (2378-tetra-, 12378-penta-, 123478-, 123678-, and 123789-hexa-CDD).Analyses were carried out to determine the occurence of these isomers in environmental samples and in fly ash from municipal incinerators.
- Buser, Hans Rudolf,Rappe, Christoffer
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p. 442 - 448
(2007/10/02)
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- High-resolution gas chromatography of the 22 tetrachlorodibenzo-p-dioxin isomers
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The 22 tetrachlorodibenzo-p-dioxins (TCDDs) were synthesized in microgram quantities by a simple pyrolysis procedure from different potassium chlorophenates. The separation of these TCDD isomers was studied on high-resolution glass capillary columns with different stationary phases (Silar 10c, OV-17, OV-101) and by use of mass spectrometric detection. Conditions were found that allowed the unambiguous assignment of many of these isomers, including the very toxic 2378-TCDD. The determination of the various TCDD isomers is illustrated in the analysis of samples from known contaminated areas in Seveso, Italy, and in eastern Missouri, and the method is also applied to the analysis of fish from the Tittabawassee River in Michigan and fly ash samples from municipal incinerators in Switzerland.
- Buser,Rappe
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p. 2257 - 2262
(2007/10/02)
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