Miniaturised sample preparation method for the multiresidual determination of regulated organohalogenated pollutants and related compounds in wild bird eggs

A simplified, miniaturised matrix solid-phase dispersion (MSPD)-based method allowing the simultaneous extraction and purification of contaminants belonging to selected families of regulated persistent organic pollutants (POPs), i.e. polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and penta- to octa-polybrominated diphenyl ethers (PBDEs), and related contaminants of emerging concern, such as deca-BDE and Dechlorane Plus (DP), has been proposed. Wild bird eggs were used as biotic fat-containing model matrices. Once optimised, the procedure allowed sample preparation to be accomplished within 30 min, in a single step, and with minimal sample and reagent consumption and waste generation. These features contributed to speeding up and greening the analytical process as compared to the large-scale multistep procedures for these types of analyses. The method was combined with gas chromatography-quadrupole mass spectrometry (GC-qMS) for PCB and OCP analysis and with GC-negative ion chemical ionisation-quadrupole mass spectrometry (NCI-qMS) for PBDE and DP determination. The complete analytical method provided satisfactory recoveries of the target compounds (above 83% for all analytes, except for PBDE 209, 63%), although as small an amount of sample as 0.300 g was used. The repeatability of the complete procedure was less than 16% (with the only exception for PCB 153, which looked to be affected by an interference). The limits of detection were in all cases lower than 34 pg g dry weight (as calculated for real samples), demonstrating the feasibility of the proposed procedure for accurate determination of the target compounds in biological samples. The proposed procedure was applied to the analysis of the target POPs in unhatched eggs of wild bird species. [Figure not available: see fulltext.].Authors thank Junta de Andalucía (Consejería de Medio Ambiente y Ordenación del Territorio) for the financial support (Project 22/2011). The monitoring team (ICTS, Reserva Biológica de Doñana, EBD-CSIC) is thanked for the field sampling. The authors also thank financial support provided by MINECO (projects CTQ2012-32957 and AGL2016-80475-R; AEI/FEDER, UE), Fundación Ramón Areces and MAGRAMA (projects EG042010 and 14CAES001). Roscales, J.L., acknowledges his contract under project 14CAES001.Peer Reviewe