GCxGC-TOFMS and GCxGC-ECD OF PBDEs Jack Cochran 1 , Frank L. Dorman 2 , Eric Reiner 3 , Terry Kolic 3 , and Karen MacPherson 3 1 LECO Corporation, 815 Pilot Road, Suite C, Las Vegas, Nevada, 89119 2 Restek Corporation, 110 Benner Circle, Bellefonte, Pennsylvania, 16823-8812 3 Ministry of the Environment, 125 Resources Road, Toronto, Ontario M9P 3V6 Introduction The polybrominated diphenyl ethers (PBDEs) used as flame-retardants in a wide variety of household and industrial products are by now well-known environmental contaminants 1 . PBDEs are produced commercially as mixtures containing relatively few major congeners and these are the ones often monitored in analytical schemes. Decabromodiphenyl ether (BDE 209) is the most widely used PBDE flame-retardant in the world 2 and it is this congener that complicates the gas chromatography-mass spectrometry (GC-MS) analysis of PBDEs, as it is has a high molecular weight, is nonvolatile, and can thermally degrade. In some labs, the analysis of BDE 209 is accomplished separately (using a shorter GC column) from the other commonly analyzed tri- to heptabromo- BDEs 3,4 . The group of Björklund is one of the most active in documenting solutions to PBDE GC analysis problems, including investigation of injection systems 5 and columns 6 to maximize response for BDE 209 and permit its simultaneous GC analysis with the rest of the PBDE congeners. On-column injection showed the highest yield for PBDEs, but they recommended temperature programmed, pulsed splitless injection for dirty samples. Their column study suggested short, inert, thin film columns should be used for the higher molecular weight PBDEs, but the low capacity of these columns could be problematic for dirtier samples. For detection of PBDEs, the electron capture detector (ECD), ion trap and quadrupole MS (low resolution), and high resolution (HR) MS with electron ionization and electron capture negative ionization have been employed 5-10 . For quadrupoles and HRMS, selected ion recording is often used to increase sensitivity and selectivity. MS/MS experiments can accomplish this for the ion trap. Recently, we applied vacuum-outlet GC with a 0.53mm column and TOFMS to the analysis of seventeen PBDEs in biosolids, including BDE 209, although the limit of detection for 209 was relatively high 11 . A relatively new way to solve separation problems is to use comprehensive two- dimensional GC (GCxGC). GCxGC is a way to increase peak capacity by applying two independent separations to a sample in one analysis. Typically, GCxGC involves a serial column configuration (differing phases) separated by a thermal modulator. A separation is performed on the first column, and then effluent from the first column is continually 291 Table of Contents Author Index