Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins part III†: Thermodegradation of organometallics and polymers

Thermodegradation of organometallics viz. RMX (where M = Mg, Ti, Pd, Sn, Si, Al; and X =halogen atom) provides corresponding haloorganics i.e. RX. 1,2‐Shifts of H and Cl on the carbene species like CH₂F. CF and CFCL₂, CF produced from R. CF. Si F₃ (R = CH₂F, CFCl₂) are preferred to that of fluorine. The thermolysis of R.CF₂. Si Cl₃ (R = CH₂F) produces chloroolefins via halogen exchange. Major products of thermal degradation of poly (vinyl chloride) (PVC) are HCl and benzene but the mechanism of PVC thermodegradation is still a matter of dispute. The thermal cracking of lignins yields substituted phenols.     

ESF Workshop

Dioxin and PCB monitoring programs for food and feeding stuff in most countries of the world, including many European Countries are currently inadequate. Better control of food production lines and food processing procedures is needed to minimize entry of dioxin to the food chain and will help to avoid dioxin contamination accidents. This would also improve the ability to trace back a possible contamination to its source. European guidelines for monitoring programs should be established to ensure comparable and meaningful results. These guidelines should define the minimum requirements for the design of monitoring programs, analytical methods, and quality assurance. Though data from Northern Europe shows that the general population exposure to dioxin and PCB has decreased during the last ten years these compounds continue to be a risk of accidental contamination of the food chain. The most prominent recent example is the Belgian dioxin contamination of feeding stuff in 1999. The Belgian dioxin contamination was not detected due to dioxin monitoring programs but by their direct biological effects seen in animals. Four other cases of dioxin contamination have been detected in Europe since 1997 due to local monitoring programs. One of them (citrus pulp pellets 1998) was in a much larger scale than the Belgian dioxin contamination. The general population's exposure to dioxins and PCBs is still in the same range (1-4 pg WHO-TEQ/kg body weight and day) as the recently revised WHO tolerable daily intake (TDI). There is concern that short-term high level exposure to dioxins, furans, and PCB may cause biological effects on the human fetal development and further research is required. Further actions to control sources building on considerable advances already made in many countries may need to be supplemented by measures to prevent direct contamination of feeding stuff or food to reduce general population exposure further.     

Some pharmacokinetic aspects of PCDDs and PCDFs in mammals after administration of a fly ash extract from a municipal incinerator

Fly ash extracts were fed to male hamster (single dose), male rat (single dose and multiple dose), pregnant and lactating female rat (multiple dose). The retention of four isomers, 2,3,7,8-TCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PnCDD and 2,3,4,7,8-PnCDF, was studied in the liver of the adults, foetuses and liver of the sucklings.

Liver retention was structure dependent and different for both species. Transportation of the isomers via the mother milk was 50–100 times more effective than via the placenta.

After a single intravenous dose of fly ash extract to male rats the elimination of these four isomers was studied in the liver, during a period of 10 days. Elimination rates for 2,3,7,8-TCDD, 1,2,3,7,8-PnCDD and 2,3,4,7,8-PnCDF were in the same range. Pharmacokinetic calculations were done on both tetra congeners, to obtain information about the validity of the published K_e values in the multiple dose experiments with male rats.

For 2,3,7,8-TCDF the K_e value was applicable, but for 2,3,7,8-TCDD the validity of the K_e could not be determined.     

Bestimmung und Bewertung der Emissionen von PCDD/PCDF,PAK und kurzkettigen Aldehyden in den Brandgasen von Kerzen

Exhaust fumes of paraffin, beeswax and stearin candles without any further paint or decorative element were analysed for the toxicological important substance classes of PCDD/PCDF, PAH and short chain aldehydes. The candle waxes and wicks were investigated for chlorinated dioxins, furans and some known precursors. Toxicological risk assessment shows that emissions of the investigated candles are much lower than all administrative limitation values — even under “worst case conditions”. Thus, they do not produce a toxicological risk for human health.