Validation Including Uncertainty Estimation of a GC–MS/MS Method for Determination of Selected Halogenated Priority Substances in Fish Using Rapid and Efficient Lipid Removing Sample Preparation

Abstract

A rapid method is proposed for the determination of selected H2SO4 stable organic compounds—eight organochlorines (OCs; hexachloro-1,3-butadiene, pentachlorobenzene, hexachlorobenzene, hexachlorocyclohexane—HCH—isomers, heptachlor) and six polybrominated diphenyl ethers (PBDEs; BDE-28, 47, 99, 100, 153, 154)—in fish samples. In the method, a modified QuEChERS (quick, easy, cheap, effective, rugged and safe) sample preparation using pH-tuned dispersive liquid–liquid microextraction (DLLME) and H2SO4 digestion fish extract clean-up is followed by gas chromatography–triple quadrupole tandem mass spectrometry (GC–QqQ-MS/MS) analysis. The method was validated in terms of linearity, limits of the method, recovery, accuracy, analysis of standard reference material (NIST SRM 1946), and estimation of combined uncertainty of the measurement (top-down approach). For validation, chub composite samples were used, and subsequently, the method was successfully applied to analysis of real samples of eight fish species. Finally, the method passed the analytical Eco-Scale evaluation as “an acceptable green analysis method”, and showed its advantages (simplicity, rapidity, low cost, high extract clean-up efficiency, good sensitivity) when compared to other reported QuEChERS based methods.

Validation and Evaluation of Selected Organic Pollutants in Shrimp and Seawater Samples from the NW Portuguese Coast

“…ME values were between −9% and −212% for OCPs, 1% and 29% for OPPs, 3% and −174% for BFRs, −16% and −107% for PCBs and 38% and 61% for SMs ( Table S5 ). For all the compounds analyzed, 49.0% of the analytes suffered ion suppression, 21.6% ion enhancement and 29.4% were in the range of −20–20%, not considered the ME [ 32 , 33 ].…”

“…The recoveries for shrimp samples were calculated using spiked samples at three levels, 16, 24 and 32 ng/g w / w for OCPs, 16, 28 and 40 ng/g w / w for OPPs and 8, 14 and 20 ng/g w / w for BFRs, PCBs and SMs, with each level in triplicate. The ME was calculated, as previously described [ 32 ], using standard solutions prepared in n-hexane compared to spiked blank samples. A positive result corresponds to an enhancement of the analytical response, whereas a negative value corresponds to a suppression effect.…”

“…A positive result corresponds to an enhancement of the analytical response, whereas a negative value corresponds to a suppression effect. Values within the 20% signal variation are not considered as a ME [ 32 , 33 ]. The uncertainty was determined following the “top-down” approach, using validation data and the uncertainty of the purity of analytical standards.…”

Headspace Gas Chromatography-Mass Spectrometry for Volatile Components Analysis in Ipomoea Cairica (L.) Sweet Leaves: Natural Deep Eutectic Solvents as Green Extraction and Dilution Matrix

“…Static headspace gas chromatography mass spectrometry (SHS-GC-MS) is a powerful and efficient way to profile the composition of complex volatile components due to its effectiveness in simultaneous chromatographic separation and structural identification [21,22]. Compared to direct injection, SHS sampling is clean and convenient as a gas extraction technique for GC-MS analysis.…”

Rapid Methods for Assessing Food Safety and Quality

“…One of these pre-treatment assays for sample preparation is based on the QuEChERS method, with the advantages summarized in its acronym (quick, easy, cheap, effective, rugged, and safe). The study of Nagyová and Tölgyessy [5] reported the validation of a rapid and non-laborious method for the determination of selected H 2 SO 4 stable halogenated priority pollutants (eight organochlorines and six polybrominated diphenyl ethers) in nine different fish species. A modified QuEChERS sample preparation followed by gas chromatography-triple quadrupole tandem mass spectrometry analysis was described.…”