Implementation of comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry for the simultaneous determination of halogenated contaminants and polycyclic aromatic hydrocarbons in fish

Abstract

In the presented study, comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS) was shown to be a powerful tool for the simultaneous determination of various groups of contaminants including 18 polychlorinated biphenyls (PCBs), seven polybrominated diphenyl ethers (PBDEs), and 16 polycyclic aromatic hydrocarbons (PAHs). Since different groups of analytes (traditionally analyzed separately) were included into one instrumental method, significant time savings were achieved. Following the development of an integrated sample preparation procedure for an effective and rapid isolation of several groups of contaminants from fish tissue, the GC × GC-TOFMS instrumental method was optimized to obtain the best chromatographic resolution and low quantification limits (LOQs) of all target analytes in a complex mixture. Using large-volume programmable temperature vaporization, the following LOQs were achieved-PCBs, 0.01-0.25 μg/kg; PBDEs, 0.025-5 μg/kg; PAHs 0.025-0.5 μg/kg. Furthermore, several capillary column combinations (BPX5, BPX50, and Rxi-17Sil-ms in the first dimension and BPX5, BPX50, Rt-LC35, and HT8 in the second dimension) were tested during the experiments, and the optimal separation of all target analytes even of critical groups of PAHs (group (a): benz[a]anthracene, cyclopenta[cd]pyrene and chrysene; group (b): benzo[b]fluoranthene, benzo[j]fluoranthene and benzo[k]fluoranthene; group (c): dibenz[ah]anthracene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene) was observed on BPX5 × BPX50 column setup. Moreover, since the determination of target analytes was performed using TOFMS detector, further identification of other non-target compounds in real life samples was also feasible.

Recent development in analysis of persistent organic pollutants under the Stockholm Convention

“…So far, routine procedures {e.g., sulfuric-acid treatment [15,21] and gel-permeation chromatography [10]}, and multi-column separation using acidified and/ or alkalinized silica, alumina, and Florisil, silver-nitrateimpregnated silica absorbents [8,[12][13][14][15][16][20][21][22][23]60] are being widely adopted and becoming absolutely necessary. Some authors [9,11,25,26,28,33,42,47] combined extraction and clean-up in one run and substantially reduced the solvent used and time required for sample preparation.…”

The Occurrence of 16 EPA PAHs in Food – A Review

“…Benzo[ b ]fluoranthene, benzo[ j ]fluoranthene, and benzo[ k ]fluoranthene data were reported as their sum, because of substantial co-elution. Although the use of comprehensive GC × GC may allow separation PAHs from matrix interferences in vegetable oil or fish samples, it did not succeed in improving the separation of critical pairs of PAHs ( 107 , 108 ). Insufficient resolution was reported also for cyclopenta[ cd ]pyrene, which interfered with benz[ a ]anthracene, and for indeno[1,2,3 -cd ]pyrene and dibenz[ a,h ]anthracene ( Figure 2 ).…”

Polycyclic Aromatic Hydrocarbons (PAHs) and Organochlorinated Pesticides (OCPs) in Yellowtail (Seriola lalandi) from three Spatially Distinct Locations along the Coast of South Africa: Levels, Sources and Fish Size Effec

“…Simultaneous analysis of OCs from purified fish extract was carried out according to a modified method described by Kalachova et al [24] with a GC Thermo Scientific TRACE TM 1310 (USA) automated injection, coupled to TSQ 8000 Mass Spectrometer detector (MSD) (USA). The GC column length was 15 m, with an internal diameter (ID) of 0.25 mm and thickness of 0.25 µm (P/N 13620-127).…”