782
V. Pekꢀarek et al. / Chemosphere 43 92001) 777±782
Crocker, H.P., Walser, R., 1970. Aromatic nuclear chlorination
by copper+II) chloride. J. Chem. Soc. C, 1982±1986.
Hell, K., Stieglitz, L., Zwick, G., Will, R., 1997. Mechanistic
aspects of the de-novo-synthesis of PCDD/PCDF on model
¯y ash. Organohalogen Compd. 31, 492±496.
are present +carbonyl, ketones, esters, oxygen and sulfur
linkages between graphitic carbon layers, oxygen het-
eroatoms within the graphitic carbon sheet). These
®ndings could explain why PCB, PCDD/F were formed
in our experiments even under conditions where only
99.999% N2 was used. Thus, the synthetized compounds
correspond probably only to oxygen which was present
in ¯y ash and activated carbon before experiment and
which could have been utilized for oxidation of Cu+I) to
Cu+II) and thus for formation of experimentally de-
tected amounts of PCB and PCDD/F formed.
Huang, H., Biesemans, M., Buekens, A., 1999. Characterization
of the nature of de-novo-synthesis by 13C NMR. Organo-
halogen Compd. 41, 105±109.
Lenoir, D., Wehrmeier, A., Schramm, K.-W., Kaune, A.,
Zimmermann, R., Taylor, P.H., Sidhu, S.S., 1998. Thermal
formation of polychlorinated dibenzo-p-dioxins and -fu-
rans: Investigation on relevant pathways. Environ. Eng. Sci.
15, 37±47.
Ling, Y.-C., Hon, C.C., 1998. A Taiwanese study of 2,3,7,8-
substitued PCDD/Fs and coplanar PCBs in ¯y ashes from
incinerator. J. Hazard. Mater. 58, 83±91.
5. Conclusions
Olie K, K, Addink, R., Schoonenboom, M., 1998. Metals as
catalysts during the formation and decomposition of
chlorinated dioxins and furans in incineration process.
J. Air Waste Manag. Assoc. 48, 101±105.
·
In all studied systems concentrations of PCDD/F
were distinctly decreasing going from oxygen rich at-
mosphere to pure nitrogen.
Sakai, S., Hiraoka, M., Takeda, N., Shiozaki, K., 1996.
Behavior of coplanar PCBs and PCNs in oxidative condi-
tions of municipal waste incineration. Chemosphere 32, 79±
88.
·
·
In all systems concentrations of PCDF were higher as
compared with PCDD.
In the atmosphere with reduced oxygen concentra-
tion the tetrachloro and pentachloro-biphenyls are
the predominant isomers with high content of PCB
77, PCB 81 and PCB 126.
ꢀ
ꢁ
ꢁ
Stach, J., Pekarek, V., Enderst, R., Het¯ejs, J., 1999. Dechlo-
rination of hexachlorobenzene on MWI ¯y ash. Chemo-
sphere 39, 2391±2399.
·
The isomer composition seems to be the product of
competition of the de novo synthetic and dechlorina-
tion reactions.
Stieglitz, L., 1998. Selected topics on the de novo synthesis of
PCDD/PCDF on ¯y ash. Environ. Eng. Sci. 15, 5±18.
Stieglitz, L., Zwick, G., Beck, J., Roth, W., Vogg, H., 1989. On
the de-novo synthesis of PCDD/PCDF on ¯y ash of
municipal waste incinerators. Chemosphere 18, 1219±1226.
Stieglitz, L., Eichberger, M., Bautz, H., Roth, W., Romer, J.,
Acknowledgements
Schild, D., 1994. Investigation of chloride transfer and
oxidation as processes in the de-novo-synthesis of PCDD/F
on ¯y ash. Organohalogen Compd. 20, 391±396.
The authors acknowledge the support of the Grant
Agency of the Czech Republic No. 104/97/S002 and
Academy of Sciences No. A4072901/1999.
Stieglitz, L., Bautz, H., Zwick, G., Will, R., 1996. On the dual
role of metal catalysts in the de-novo-synthesis of orga-
nochlorine compounds on ¯y ash from municipal waste
incinerators. Organohalogen Compd. 27, 5±9.
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