This study attempts to clarify the effects of chlorine content in waste on the formation mechanisms of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in full scale incinerators by proposing and using the principal component analysis (PCA) to compare the congener profiles of PCDD/Fs in the stack flue gases of 17 emission sources, including incinerators and vehicles. Four incinerators, among these 17 emission sources, were sampled and analyzed in this study, and the data for the other 13 emission sources were selected from previous studies. These 17 emission sources can be classified into four categories, including medical waste incinerators (MWIs, H1-H5), municipal solid waste incinerators (MSWIs, M1-M8), vehicle fuel combustion (unleaded gas-fueled vehicles, UGFV; diesel-fueled vehicles, DFV, n = 2) and polyvinylchloride (PVC) facility vent combustors (PVC1 and PVC2, n = 2). PCA was conducted for these emission sources with the fractions of 17 2,3,7,8-congeners in the stack flue gases as variables to clarify the effect of chlorine content in feeding wastes on the emission of PCDD/Fs. From the results of PCA, we extrapolated that the threshold value of the chlorine content was at 0.8-1.1%, and the formation mechanisms of PCDD/Fs are influenced first by whether the chlorine content in the feeding waste is over or below the threshold value then by other factors, which furnaces or APCDs represent. When the chlorine level in the waste is below the threshold value at 0.8-1.1%, the formation of PCDDs dominates, probably because the chlorine is used to chlorinate the non-substituted phenol to produce chlorophenols, which are important precursors for PCDDs. rather than chlorinate the dibenzofuran. While the chlorine level in the waste exceeds this threshold (0.8-1.1%), the rates of formation of PCDFs increase faster than those of PCDDs, probably because the chlorine content in the waste contributes to the deterioration of combustion conditions, and many products of incomplete combustion (PICs) like PAHs, will grow to a substantial level. When PCDD/Fs are formed from PAHs, the formation rates of PCDFs are higher than those of PCDDs.
Copyright 2002 Elsevier Science B.V.