Simultaneous analysis of polychlorinated biphenyls and polychlorinated naphthalenes by isotope dilution comprehensive two-dimensional gas chromatography high-resolution time-of-flight mass spectrometry

摘要

Polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) are listed as persistent organic pollutants (POPs) under the Stockholm Convention. Because they have similar physical and chemical properties, they are coeluted and are usually analyzed separately by different gas chromatography high-resolution mass spectrometry (GC-HRMS) methods. In this study, a novel method was developed for simultaneous analysis of six indicator PCBs, 12 dioxin-like PCBs, and 16 PCNs using isotope dilution comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry (GC x GC-HRTOF-MS). The method parameters, including the type of GC column, oven temperature program, and modulation period, were systematically optimized. Complete separation of all target analytes and the matrix was achieved with a DB-XLB column in the first dimension and a BPX-70 column in the second dimension. The isotope dilution method was used for quantification of the PCBs and PCNs by GC x GC-HRTOF-MS. The method showed good linearity from 5 to 500 pg mu L-1 for all the target compounds. The instrumental limit of detection ranged from 0.03 to 0.3 pg mu L-1 for the 18 PCB congeners and from 0.09 to 0.6 pg mu L-1 for the 16 PCN congeners. Repeatability for triplicate injections was always lower than 20%. The method was successfully applied to the determination of 18 PCBs present at 0.9-2054 pg g(-1) and 16 PCNs present at 0.2-15.7 pg g(-1) in three species of fish. The GC x GC-HRTOF-MS results agreed with those obtained by GC-HRMS. The GC x GC-HRTOF-MS method proved to be a sensitive and accurate technique for simultaneous analysis of the selected PCBs and PCNs. With the excellent chromatographic separation offered by GC x GC and accurate mass measurements offered by HRTOF-MS, this method allowed identification of non-target contaminants in the fish samples, including organochlorine pesticides and polycyclic aromatic hydrocarbons. (C) 2016 Published by Elsevier B.V.