PCDD/F TEQ indicators and their mechanistic implications.
Stack gas samples from two incinerator facilities with different operating conditions were investigated to understand how indicators of toxic equivalency (TEQ) from among the 210 polychlorinated dibenzo-p-dioxin/furan (PCDD/F) isomers varied. This effort was motivated by the need to find more easily monitored indicator compound(s) of TEQ and to reconcile the varying indicator compounds reported in the literature. The measured isomer patterns were compared with those expected from known formation mechanisms to identify the dominant mechanism(s) and explain why certain compounds are relevant TEQ indicators. Despite differences in the facility types and operating conditions, a common pattern was found for the highly chlorinated (4Cl and higher) PCDDs/Fs. A combination of chlorination/dechlorination reactions as the dominant formation mechanism for PCDF was consistent with the observed isomer patterns, whereas condensation reactions of phenolic precursors appeared to be responsible for PCDD formation. PCDF isomers, ratherthan the PCDD isomers, were more closely related to the TEQ measure, likely because the chlorination mechanism favors 2,3,7,8-Cl-substitution more than the phenol condensation mechanism. Unlike highly chlorinated PCDD/F isomer patterns, less chlorinated PCDD/F patterns (especially, mono- and di-CDF) were sensitive to operating conditions and facility type. Competing formation mechanisms were inferred from the variation of observed isomer distribution patterns; this sensitivity resulted in relatively low correlations of these isomers with PCDD/F TEQ values. This suggests that any use of the low-chlorinated compounds as TEQ indicators for online monitoring processes are likely best suited for plant-specific, rather than universal, applications. In addition to many of the highly chlorinated (penta-CDF, hexa-, and heptaCDD/F) isomers being identified as strong TEQ indicators, 1 of 12 (8%), 5 of 17 (29%), and 5 of 28 (18%) of the separable tri-CDD, tri-CDF, and tetra-CDF isomers, respectively, were identified as strong (R2 > 0.7) TEQ indicators in both incinerators.
Office of Research & Development, National Risk Management Research Laboratory, U.S. Environmental Protection Agency (E305-01), Research Triangle Park, North Carolina 27711, USA.
Jeong-Eun
JE
Oh
Abderrahmane
A
Touati
Brian K
BK
Gullett
James A
JA
Mulholland
D000393:Air Pollutants / Q000737:chemistry / Q000592:standards* / Q000633:toxicity; D001572:Benzofurans / Q000737:chemistry / Q000592:standards / Q000633:toxicity; D000072338:Dibenzofurans, Polychlorinated; D004784:Environmental Monitoring / Q000592:standards* / Q000706:statistics & numerical data; D005544:Forecasting; D017745:Incineration / Q000592:standards* / Q000706:statistics & numerical data; D007536:Isomerism; D009657:North Carolina; D000072317:Polychlorinated Dibenzodioxins / Q000031:analogs & derivatives* / Q000737:chemistry / Q000592:standards* / Q000633:toxicity; D014116:Toxicology / Q000592:standards; D014768:Virginia
D000393:Air Pollutants; D001572:Benzofurans; D000072338:Dibenzofurans, Polychlorinated; D000072317:Polychlorinated Dibenzodioxins