PCDD,

Dioxin and Furan Emissions. The emissions of polychlorinated dibenzo-/)-dioxins (PCDD) and polychlorinated dibenzo-furans (PCDF) from incinerators (4) are of interest to the pubHc, scientists, and engineers. The U.S. EPA classifies 2,3,7,8-tetrachlorodibenzo-/)-dioxin (2,3,7,8-TCDD) as the most potent carcinogenic compound it has evaluated. It is also Hsted as the agency s most potent reproductive toxin (4). 

The proposed mechanism by which chlorinated dioxins and furans form has shifted from one of incomplete destmction of the waste to one of low temperature, downstream formation on fly ash particles (33). Two mechanisms are proposed, a de novo synthesis, in which PCDD and PCDF are formed from organic carbon sources and Cl in the presence of metal catalysts, and a more direct synthesis from chlorinated organic precursors, again involving heterogeneous catalysis. Bench-scale tests suggest that the optimum temperature for PCDD and PCDF formation in the presence of fly ash is roughly 300°C. 

Both CI2 and HCl have been shown to chlorinate hydrocarbons on fly ash particles. Pilot-scale data involving the injection of fly ash from municipal waste combustion (33) show that intermediate oxygen concentrations (4—7%) produce the highest levels of PCDD and PCDF. These data also show significant reductions in PCDD and PCDF emissions with the upstream injection of Ca(OH)2 at about 800°C. 

Chlorobenzenes are stable compounds and decompose slowly only under excess heating at high temperatures to release some HCl gas and traces of phosgene. It is possible, under certain limited conditions of incomplete combustion or pyrolysis, to form polychlorinated dibenzo-/)-dioxins (PCDDs) and dibenzofurans (PCDFs) from chlorobenzenes (Cm OROCARBONS and cm OROHYDROCARBONS, toxic aromatics). 

The methods, which allow in one procedure of analysis to overcome, for example, most pesticides which are used in agricultural practice in the present time, get development and introduction in practice. The contribution of the Ukrainian scientists in field of chromatographic analysis of Persistent Organic Pollutants (POPs, chlorinated hydrocarbons, PCB s) and supertoxicants, such as PCDDs, is estimated. 

Method 1613 of US Environmental Protection Agency (US EPA) was used for the PCDD detection in the objects of environment (water, soil etc.). PCDD detection was done with the help of Polaris Q gas chromatograph/ mass spectrometer on mass-spectrum of electronic impact in the MS-MS mode. Division of isomer PCDD was carried out on a capillary column from the sintered quartz DB-5 MS (60 m x 0,25 mm, thickness of tape 0,25 p.m). The same device was used for detection of fungicides formulations active ingredients in soil. 

The results of analysis of samples from Desnyansky and Dniper water-supply stations water are given in the report concerning the contents of PCDD and soil samples concerning the contents of triazoles. 

In addition to their endocrine disrupting properties, it must be appreciated that many of the chemicals in question possess more general toxic properties, which may be potentiated by metabolism by the organism. Several PAHs, PCBs and PCDDs are carcinogenic, while certain phthalate esters can enhance the excretion of zinc, potentially leading to zinc deficiency. Zinc, an essential element, plays a vital role in spermatogenesis and mature T-cell production. Deficiency may result in abnormalities of the male reproductive system, depletion of spermatogenesis and suppression of the immune system. 

The specific molecular mechanisms by which PCDDs and PCDFs are initially formed and become part of the PIC remain largely unknown and are theoretical. The theoretical basis for conjecture is derived primarily from direct observations in municipal solid waste incinerators. The emissions of... 

Creosote PIC are comprised of PCDD/PCDF, flyash and soot, NO, SOj, COj, HCl, and various PAHs ... 

It is assumed that 0.5% of the PIC are comprised of gaseous forms of PCDD/PCDF. 

Available Fuel, Lbs Lbs Fuel Tor Energy Lbs Flyash Total Lbs Gaseous + PM Lbs NO., SO, CO, Other Lbs PCDD/ PCDF... 

Time, Hrs Distance from Source, m PCDD/PCDF Concentration, uglm ... 

G. Schomburg, H. Husmann and E. Hiibinger, Multidimensional separation of isomeric species of cWor inated hydrocarbons such as PCB, PCDD and PCDF , 7. High Resolut. Chromatogr. Chromatogr. Commun. 8 395-400 (1985). 

In general, capillary gas chromatography provides enough resolution for most determinations in environmental analysis. Multidimensional gas chromatography has been applied to environmental analysis mainly to solve separation problems for complex groups of compounds. Important applications of GC-GC can therefore be found in the analysis of organic micropollutants, where compounds such as polychlorinated dibenzodioxins (PCDDs) (10), polychlorinated dibenzofurans (PCDFs) (10) and polychlorinated biphenyls (PCBs) (11-15), on account of their similar properties, present serious separation problems. MDGC has also been used to analyse other pollutants in environmental samples (10, 16, 17). 

Zebiihr et al. (29) developed an automated system for determining PAHs, PCBs and PCDD/Fs by using an aminopropyl silica column coupled to a porous graphitic carbon column. This method gives five fractions, i.e. aliphatic and monoaromatic hydrocarbons, polycyclic aromatic hydrocarbons, PCBs with two or more ortho-chlorines, mono-ort/io PCBs, and non-ortho PCBs and PCDD/Fs. This method employed five switching valves and was successfully used with extracts of sediments, biological samples and electrostatic filter precipitates. 

Y. Zebuelir, C. Naef, D. Broman, K. Eexen, A. Colmsjo and C. Oestman, Sampling techniques and cleanup procedures for some complex environmental samples with respect to PCDDs and PCDPs and other organic contaminants , Chemosphere 19 39-44(1989). 

These results show the fate of aromatic bromine compounds during municipal waste incineration bromine is exchanged by chlorine on the surface of fly ash at the electrostatic precipitator at 250-3(X)°C. But the toxic potential at brominated dibenzodioxins and furans is not reduced by these transformations. The increase of PCDD/F concentration in MWI by adding bromine compounds has been pointed out by Lahl and coworkers (ref. 26). 

Some characteristic physical properties of PBDD/F have been determined and can be found elsewhere 8-14. An important property for environmental behaviour is the vapour pressure. Vapour pressures of some PBDD has been measured by a special new technique 30. pig. 12 shows extrapolated vapour pressures of PCDD and PCDF and of corresponding PBDD and PBDF. 

Fig. 12. Extrapolated Vapor Pressures of PCDD and PCDF and of corresponding PBDD and PBDF.

The use of aromatic brominated compounds as flame retardants has been a potential source of environmental contamination. Incomplete incineration of these compounds and wastes (plastics, textiles, oils etc...) containing brominated flame retardants caused formation of brominated/chlorinated dibenzodioxines (PBDDs/ PCDDs) and dibenzofurans (PCDFs/PBDFs) (refs. 1 - 4). 

Energy recovery from packaging waste is discussed, with particular reference to the co-combustion of mixed plastics with other conventional fuels such as wood, coal and peat. Experimental work is described in which a project was established to evaluate the possibility of energy recovery from a circulating fluidised bed boiler using packaging from different sources as fuel. The role of sulphur in the formation of PCDD/F in the combustion process was also studied. 

PCDDs have been released into the environment in a number of different ways. Sometimes this has been due to the use of a pesticide that is contaminated with them. 2,4,5-T and related phenoxyalkanoic herbicides have been contaminated with them as a consequence of the interaction of chlorophenols used in the manufacturing... 

TCDD has been more widely studied than other PCDDs, and will be taken as an example for the whole group of compounds. It is a stable solid with a melting point of 306°C. Its water solubility is very low, which has been estimated to be 0.01-0.2 pg/L its log is 6.6. More highly chlorinated PCDDs are even less soluble in water. 

PCDFs are similar in many respects to PCDDs but have been less well studied, and will be mentioned only briefly here. Their chemical structure is shown in Figure 7.1. Like PCDDs, they can be formed by the interaction of chlorophenols, and are found in commercial preparations of chlorinated phenols and in products derived from phenols (e.g., 2,4,5-T and related phenoxyalkanoic herbicides). They are also present in commercial polychlorinated biphenyl (PCB) mixtures, and can be formed... 

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