Talanta 87 (2011) 143–151 Contents lists available at SciVerse ScienceDirect Talanta j ourna l ho me page: www.elsevier.com/locate/talanta Application of low-temperature CP-Sil 88 column for the isomeric analysis of toxic 2378-substituted PCDD/Fs in incinerator flyash and sewage sludge using a triple quadrupole GC–MS/MS Jude A. Onwudili a,∗ , Yaghoub Hajizadeh a , Safari Zainal a , John Upton b , Paul T. Williams a a Energy and Resources Research Institute, University of Leeds, LS2 9JT, UK b Agilent Technologies (Formerly Varian), Oxford OX5 1QU, UK a r t i c l e i n f o Article history: Received 19 May 2011 Received in revised form 16 September 2011 Accepted 27 September 2011 Available online 1 October 2011 Keywords: Dioxins Furans Analysis/mass spectrometry Flyash Sewage sludge a b s t r a c t The seventeen 2378-substituted polychlorinated dibenzo-p-dioxins and dibenzo-p-furans (PCDD/Fs) congeners have been separated and analyzed in sewage sludge and incinerator flyash samples using a CP-Sil 88 column (50 m × 0.25 mm I.D., 0.25 m film thickness) operating at a maximum oven tem- perature of 240 ◦ C. The column was used on a Varian 450-GC with a Varian 320-MS Triple Quadrupole. Calibration standards were used to determine the transition chemistries of the 2378-substituted PCDD/F congeners in the gas chromatography/mass spectrometry (GC–MS/MS) system. The five-point calibration curve for each of the congeners showed very good linearity with R 2 values greater than 0.999. The recov- ery of labelled compounds ranged from 50% to 120%. Analytical results from a reference flyash (BCR-490) and a reference sewage sludge (BCR-677) compared very well with the certified values, giving percent- age deviations in I-TEQ (international toxic equivalents) of 4.93% and 0.53%, respectively. Results from ‘real’ flyash samples underscored the level of progress made in the abatement of dioxin emissions from incinerators; the old incinerator flyash contained much higher PCDD/F concentrations than the modern one. In addition, the concentrations profiles of PCDD/Fs in the ‘real’ sewage sludge from two UK wastew- ater treatment plants (WWTPs) showed that one contained a total PCDD/Fs content of 314 ng I-TEQ kg -1 , while the other gave a total of 53 ng I-TEQ kg -1 . Over an 18-month period of operation, no significant loss of analytical performance was observed from the low-temperature column. © 2011 Elsevier B.V. All rights reserved. 1. Introduction Incineration of the organic fraction of municipal and industrial solid wastes and other organic-rich wastes (e.g. sewage sludge) has the advantage of efficient energy recovery from these wastes, and also leads to dramatic mass and volume reductions. Incinera- tion has therefore become the main alternative to the landfilling of these types of wastes. Incineration of organic wastes will continue to contribute to the achievements of the targets of the EU Land- fill Directive, which requires member states to drastically reduce the amount of biodegradable wastes sent to landfills [1]. However, operation of incinerators can often generate significant negative public perception with respect to the possible release or emission of incomplete combustion products to the environment. Such emis- sions include the highly toxic polychlorinated dibenzo-p-dioxins ∗ Corresponding author at: School of Process, Environmental and Materials Engi- neering, Faculty of Engineering, University of Leeds, LS2 9JT, UK. Tel.: +44 113 343 2353; fax: +44 113 246 7310. E-mail address: j.a.onwudili@leeds.ac.uk (J.A. Onwudili). (PCDD) and polychlorinated dibenzofurans (PCDF). Other sources of PCDD/Fs in the environment include releases from automo- bile exhausts, pulp and paper mill effluents, household washing machine effluents and the production/use of organochlorine com- pounds [2–4]. PCDD/Fs are a chemical group of 210 chlorinated tricyclic aro- matic hydrocarbons and environmentally stable micro-pollutants, known as one of the most hazardous compounds to human health and the environment [5–7]. There are serious concerns about the high toxicity of PCDD/Fs congeners with chlorina- tion in the 2378 positions as confirmed by studies carried out by several multi-lateral bodies such as the United States Environmental Protection Agency (USEPA), Ontario Ministry of Environment and the European Commission [8,9]. Hence in recent years, stringent regulations have been enforced to reduce the release of these and many other hazardous pollutants into the environment [10]. The required analysis of PCDD/Fs within often complex matrices poses a significant problem to the analyst. Analysis of PCDD/Fs in environmental matrices requires several steps that include extraction/isolation, clean-up and/or pre-concentration before 0039-9140/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.talanta.2011.09.053