Long-term sampling of dioxin-like substances from a clinker kiln stack using alternative fuels

The aim of this work is to characterize atmospheric emissions of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) from a cement production plant where the existing clinker production line was completely replaced by a new state-of-the-art installation. The project started in April 2008 with the installation of a long-term sampling system in the stack of the clinker kiln that used petroleum coke as fuel; PCDD/PCDF and dl-PCB emissions were then evaluated for a two year period. To carry out the second part of the study, in 2010 the sampling system was moved to the new installation in which, apart from conventional fuel, recovered derived fuel (RDF) and WWTP sludge were used as alternative fuels. For both the old and new clinker kilns, PCDD/PCDF emission values were well below the limit established by the European Waste Incineration Directive 2000/76/CE (EWID) of 100 pg I-TEQ/Nm(3); values ranged from 0.43 to 2.02 and from 0.07 to 3.31 pg I-TEQ/Nm(3), respectively. dl-PCBs accounted for approximately 25% of the WHO-TEQ toxicity. These results prove that the installation is capable of reducing PCDD/PCDF and dl-PCB emissions when alternative fuels are integrated into the process. In the case of PCDDs/PCDFs, the major contributions to total TEQ were usually from 2,3,7,8-TCDD (owing to its relative abundance) and 2,3,4,7,8-PeCDF (due to its high I-TEF of 0.5); while for dl-PCBs, the major contribution was from PCB-126. The slight shift in the congener profile between the old and new installations was characterized and a regression model was proposed for dl-PCB emissions depending on the RDF flow rate in the clinker.