Analytical approach and occurrence for the determination of mass concentration of PCDD/PCDF and dl-PCB in flue gas emissions using long-term sampling devices

In this work, a reliable methodology for the simultaneous analysis of PCDD/PCDF and dioxin-like PCB (dl-PCB) in flue gas emissions collected using continuous sampling devices is proposed. The analytical scheme followed the minimum requirements described in the EU standard EN-1948:1,2,3,4 according to samples containing large amounts of dioxins and dl-PCBs or samples collected over a long period of time of about 4 weeks. Parameters, such as reproducibility, precision, limits of detection (LOD), limits of quantification (LOQ), extract aliquot size, analytical blanks, extraction efficiency, as well as the amount of internal standards required for an accurate determination, were assessed.The findings demonstrate the suitability of the proposed analytical scheme for the analysis of PCDD/PCDF and PCB in samples collected using long-term sampling devices. The analysis of five different 5% v/v sample aliquots reported %RSD values lower than 10% for all of the 29 congeners at both low and high levels. Similarly, %RSD values were 3.2 and 2.0 for the low level samples and 0.9 and 1.1%RSD for the high level extracts for PCDD/PCDF and dl-PCB, respectively expressed in total TEQ units. Re-extraction provided values less than 3%, expressed in TEQ. Based on blank analyses, LOD values of 100 pg I-TEQ for PCDD/PCDF and 10 pg WHO-TEQ for dl-PCB were achieved when 5% v/v aliquots were analyzed.Finally, the proposed analytical approach was tested with samples from a wide range of combustion processes such as hazardous and municipal waste incinerators, as well as cement kilns (with and without waste co-incineration).

► A method for the analysis of PCDD/Fs and dl-PCBs in samples from long-term sampling systems is presented.
► Long-term sampling systems have proved to be suitable for the simultaneous sampling of PCDD/Fs and dl-PCBs.
► A criteria for the aliquot size to be used in analysis is set-up depending on sampling time and thermal process.
► The proposed methodology was tested on samples from incinerators and cement kilns.