Comparison of HPLC and solid phase clean-up methods for identification of PCBs in cod-liver oil by HRGC/MS-SIM technique

Abstract

A group of non-planar PCBs (IUPAC nos. 28, 52, 101, 118, 138, 153, and 180) was identified in a cod-liver oil product by using high resolution gas chromatography-mass spectrometry (HRGC/MS) in electron impact (EI) and negative chemical ionization (NCI) modes. The cod-liver oil samples were prepared either in a cyano column by high performance liquid chromatography (HPLC) or by a solid phase extraction (SPE) clean-up procedure that included e.g. purified charcoal treatment. The two methods of sample preparation were evaluated on the basis of the detectabilities of the congeners. The GC/MS-SIM method allowed quantitative monitoring of congeners nos. 52, 101, 118, 138, 153, and 180 at low concentration levels. Detection limits were 1.2 pg and 130 fg (m/z 292.00) in EI and NCI modes, respectively. The determination levels in EI and NCI were 1.8 pg and 290 fg in HPLC followed by HRGC/MS and 170 pg and 27 pg in SPE followed by HRGC/MS. The linear range was from 5.0 pg/μl to 1.0 ng/μl and from 1.0 pg/μl to 1.0 ng/μl in EI and NCI modes, respectively. In addition, the co-planar PCBs, PCDDs, and PCDFs were also screened and two of the chlorinated furanes were identified by HRGC/MS-NCI after separation from non-planar PCBs by SPE. In this case the only congeners that could be quantified were 2,3,4,7,8-PCDF and 1,2,3,4,6,7,8-HCDF, the detection limit for them being 740 fg (m/z 351.90) with NCI. SPE allows the separation of the planar and non-planar compounds, but LC separation is more effective for separation of the compounds of interest from the matrix. LC clean-up is easier and faster to perform than SPE clean-up.