Polychlorinated biphenyl (PCB) is one of the most widespread persistent organic pollutants. PCB theoretically consists of 209 congeners, of which around 150 have been reported at significant levels in the environment. Because environmental behavior of PCBs is congener-dependent, a comprehensive, quantitative and congener-specific (CQCS) analysis is highly demanded.1 The CQCS PCB analysis uses high-resolution gas chromatography (HRGC) with sensitive and selective detection by an electron capture detector (ECD) or a mass spectrometer (MS).There are so many PCB congeners that the analysis of an acquired chromatogram is labor-intensive and time-consuming. Therefore, a fully automated quantitative analysis is desired in an analytical laboratory where many environmental samples are routinely quantified. The important process in the analysis is the identification of each congener in accordance with its retention time. Automated identification requires precise retention times of the GC system in an analytical laboratory, since all chromatographic peaks arising from congeners should be individually quantified when they elute separately.Recently, Frame has reported a complete retention database on 27 HRGC systems using 20 stationary phases with all 209 pure congener standards commercially available. 2 The retention database includes multiple data sets measured by different GC systems with the same stationary phases. In a comparison of these data sets, different parameters of column dimensions, film thickness, temperature programs and flow rates change the retention time substantially. The retention differences are mainly due to the common behavior of congeners, which exhibit smooth curvature differences along with an increase of the retention time. Additionally, small but significant differences due to individual behavior of congeners change the elution orders as well as the resolvability of some adjacent congeners. These retention differences suggest that congener identification should not be attempted solely by matching the values in the retention database. 2 Retention indices (RI) are used to remove any influence of a specific GC condition. [3][4][5][6] However, an RI calculation can not compensate for individual congener behavior that makes the elution orders change, because it is a linear conversion. All 209 congener standards are still expensive and cannot be utilized in all analytical laboratories. We have thus developed a new calibration method that compensates for retention changes between different GC systems with the same stationary phase. In conjunction with the valuable retention database reported by Frame, 2 the proposed method can be used to predict the retention time of congeners whose standards are not available in an analytical laboratory.
ExperimentalA commercial PCB mixture (Kanechlor) was purchased from GL Sciences Inc., Japan. A PCB standard mixture was obtained from Wellington Laboratories, USA. The standard mixture contained the first and last eluted congeners in each chlorine homologue at a DB-5 c...