Journal of Chromatography A, 994 (2003) 179–189 www.elsevier.com / locate / chroma Attempt to unravel the composition of toxaphene by comprehensive two-dimensional gas chromatography with selective detection a,b, b a a b * ´ P. Korytar , L.L.P. van Stee , P.E.G. Leonards , J. de Boer , U.A.Th. Brinkman a Netherlands Institute for Fisheries Research, P .O. Box 68, 1970 AB IJmuiden, The Netherlands b Department of Analytical Chemistry and Applied Spectroscopy, Free University, de Boelelaan 1083, 1081 HV Amsterdam, The Netherlands Received 22 November 2002; received in revised form 3 March 2003; accepted 7 March 2003 Abstract Comprehensive two-dimensional gas chromatography (GC3GC) coupled with micro electron-capture and time-of-flight mass spectrometric (TOF-MS) detection has been used to analyse technical toxaphene. An HP-13HT-8 column combination yielded highly structured chromatograms and revealed a complex mixture of over 1000 compounds what is significantly higher number than in any study before. The analysis of a mixture of 23 individual congeners and TOF-MS evaluation of technical toxaphene showed that the chromatogram is structured according to the number of chlorine substituents in a molecule. The nature of the compounds (bornane and camphene) does not appear to have any influence. The sum of the peak areas of all congeners in each group was calculated using laboratory-written software; based on these results, the composition of technical toxaphene as a function of the number of chlorine substituents was provisionally calculated and was found that hepta- and octachlorinated compounds represents 75% of the total toxaphene area.  2003 Elsevier Science B.V. All rights reserved. Keywords: Gas chromatography, comprehensive two-dimensional; Toxaphene; Terpenes; Organochlorine compounds 1. Introduction relatively short (ca. 0.5 m) second-dimension column with different separation characteristics. In most In the past few years, comprehensive two-dimen- instances, a non-polar first column is combined with sional GC, or GC3GC, has emerged as an extremely a more polar second column, and the time span of powerful separation technique. Much higher peak each effluent fraction from the first column that is capacities can be obtained than in conventional trapped, refocused and, next, transported to the multidimensional GC, or GC–GC, because each second-dimension column, is on the order of 3–6 s. successive small fraction eluting from the conven- The final result is usually displayed as a two-dimen- tional-size first-dimension column is subjected, in sional contour plot. real time, to a second, orthogonal separation, on a The first problem that had to be solved when GC3GC was introduced [1] was designing a robust and user-friendly interface between the two columns. *Corresponding author. Tel.: 131-25-556-4607; fax: 131-25- Without going into details, it may suffice here to say 556-4644. ´ E-mail address: Peter.Korytar@wur.nl (P. Korytar). that, with the introduction of nearly comprehensive 0021-9673 / 03 / $ – see front matter  2003 Elsevier Science B.V. All rights reserved. doi:10.1016 / S0021-9673(03)00438-2