ORIGINAL PAPER A routine accredited method for the analysis of polychlorinated biphenyls, organochlorine pesticides, chlorobenzenes and screening of other halogenated organics in soil, sediment and sludge by GCxGC-μECD Alina M. Muscalu & Eric J. Reiner & Steven N. Liss & Tony Chen & Gerry Ladwig & David Morse Received: 11 April 2011 /Revised: 12 May 2011 /Accepted: 13 May 2011 /Published online: 2 June 2011 # Her Majesty the Queen in Right of Canada 2011 Abstract The analysis of persistent organic pollutants is a real challenge due to the large number of compounds with varying chemical and physical properties. Gas chromatography with electron capture detection or mass spectrometry has been the method of choice for the past 50 years. Comprehensive two- dimensional gas chromatography (GCxGC) coupled with micro-electron capture detector (μECD) is a new method that can analyze polychlorinated biphenyls (PCBs), organochlorine pesticides (OCs) and chlorobenzenes (CBz) in a single analytical run with enhanced selectivity and sensitivity over single column methods and can also be used to screen for other halogenated organics in environmental samples. An accredited routine method using commercially available LECO GCxGC- μECD and a column combination DB-1×Rtx-PCB has been developed to analyse PCBs/OCs/CBz in soils, sediments and sludges. The method provides quantification of Aroclors and Aroclor mixtures to within 15% of target values and sub- nanogrammes per gramme detection limits. Keywords GCxGC . Comprehensive two-dimensional gas chromatography . PCB . Organochlorine pesticides . Chlorobenzenes . μECD . Routine method . POPs Introduction Industrial chemicals have been used for almost 200 years in a wide variety of applications as solvents, precursors, reagents, surfactants, flame retardants and pesticides [1, 2]. Over 100,000 chemicals are currently in use with over 30,000 considered to be in wide commercial use (>907 kg/ year) [3]. Many of these compounds are persistent, toxic and bioaccumulative, and many of them are halogenated. Unfortunately, only a small number of these compounds are regulated. The Stockholm Convention on persistent organic pollutants (POPs) [4, 5] came into force on May 2004 in order to reduce and eliminate 12 compounds including nine legacy organochlorine pesticides (OC), the industrial chemicals, polychlorinated biphenyls (PCBs) [6] and the unintentionally produced polychlorinated dibenzo-p-diox- ins (PCDDs) and polychlorinated dibenzofurans (PCDFs) [7]. An additional nine pesticides, flame retardants and surfactants were added to the list in 2009, and three additional groups of compounds are currently under review. All of the Stockholm compounds are halogenated com- pounds, and most of them, especially the recently added ones, are routinely detected in environmental samples. Published in the special issue Comprehensive Multidimensional Separations with Guest Editors James Harynuk and Philip Marriott. Electronic supplementary material The online version of this article (doi:10.1007/s00216-011-5114-0) contains supplementary material, which is available to authorized users. A. M. Muscalu : E. J. Reiner (*) : T. Chen : G. Ladwig : D. Morse Laboratory Services Branch, Ontario Ministry of the Environment, Toronto, ON M9P 3V6, Canada e-mail: eric.reiner@ontario.ca A. M. Muscalu Department of Chemistry, University of Waterloo, Waterloo, ON N2L 3G1, Canada S. N. Liss School of Environmental Studies, Queens University, Kingston, ON K7L 3N6, Canada Anal Bioanal Chem (2011) 401:2403–2413 DOI 10.1007/s00216-011-5114-0