An efficient clean-up method for the GC-MS determination of methylsulfonyl-PCBs/DDEs extracted from various marine mammal tissues.

Existing methods for analyzing methylsulfonyl-PCBs in animal tissues require multiple laborious clean-up steps prior to quantitation. In this paper, we report a new, efficient method for the isolation and determination of methylsulfonyl-PCB metabolites in the blubber, liver, kidney, lung, and milk from mammals of marine origin using: solvent extraction, GPC fractionation, and clean-up on an adsorption chromatography column prior to analysis by gas chromatography-mass spectrometry. The method is rapid and can be completed in about half the analysis time required by most other reported methods. The method exhibits excellent analyte recoveries (89-95%), and good reproducibilities with CV's ranging from 3-12% depending on analyte concentration. Detection limits are approximately 1 ng/g lipid. The method is further validated by comparing its quantitative results to that of an independent reference analytical method for several different marine mammal blubber samples. Finally, the method is applied to profile the distribution of methylsulfones among the various tissue types studied for a single bottle-nose dolphin (Tursiops truncatus) sample. In addition, the extent of their transplacental transfer from mother to unborn fetus for several pilot whale (Globicephala melaena) mother-fetus pairs is examined.

Screening for planar chlorobiphenyl congeners in tissues of marine biota by high-performance liquid chromatography with photodiode array detection.

A rapid method has been developed to screen for planar chlorobiphenyl (CB) congeners, as well as certain other CBs and DDTs, in tissue samples from marine biota. The analytes were extracted from tissue matrices with 1:1 hexane/pentane (v/v) and interfering compounds were separated from the CBs on a gravity-flow column packed with acidic, basic and neutral silica gel eluted with 1:1 hexane/methylene chloride (v/v). Subsequently, the planar CB congeners were resolved from the DDTs and other CBs by HPLC on Cosmosil PYE analytical columns cooled to 9 degrees C and were measured by an ultraviolet (UV) photodiode array (PDA) detector. Two important advantages of PDA over conventional UV detection were the ability to identify individual analytes by comparing their UV spectra to those of reference standards and the ability to establish the spectral homogeneity (purity) of the analytes by comparing spectra within a peak to the apex spectrum. The HPLC/PDA method was tested with tissue samples from fish, shellfish and marine mammals; concentrations of certain CBs and DDTs in samples determined by screening compared favorably with those in the same samples analyzed by a comprehensive method (e.g., gas chromatography/high resolution mass spectrometry). However, the HPLC/PDA method was about an order of magnitude less sensitive than determinations by comprehensive methods.