Challenges in the application of conventional PCB quantitation methods to studies of "invasive" freshwater organisms

We describe significant and unexpected errors in application of a conventional method for the quantitative determination of polychlorinated biphenyls (PCBs) in unusual biological tissue samples. A standard method based upon microwave-assisted extraction (MAE) and gas chromatography tandem mass spectrometry (GC-MS/MS) was applied to a variety of "invasive" freshwater organisms, representing a variety of genera. The 12 "co-planar" PCBs (co-PCBs) were determined at ng g(-1) levels in small samples (ca. 750-1000 mg) of eight freshwater species (n = 172). We found that the conventional method could lead to random and relatively large changes in retention times. A nearly five-fold increase in retention variability was observed for "lower" organisms compared to that observed in the analysis of predatory fish tissue. These unexpected retention time changes would result in misidentifications, and become problematic not only for non-selective detectors such as electron capture but also for MS-based approaches. That is, for electron impact (EI) ionization methods, molecular ions (M(+)) are produced by loss of Cl not only for congeners in the same homolog class but also for fragments of higher homologs (e.g. M - 35 and M - 37), thereby yielding false positive measurement of the target congener when the retention time windows overlap.