A pretreatment method combined matrix solid-phase dispersion with dispersive liquid–liquid micro-extraction for polybrominated diphenyl ethers in vegetables through quantitation of gas chromatography-tandem mass spectrometry (GC-MS)

Abstract

Herein, a novel pretreatment method for extraction of polybrominated diphenyl ethers (PBDEs) using matrix solid phase dispersion (MSPD) and depth purification using dispersive liquid–liquid micro-extraction (DLLME) from vegetables was designed. The vegetables included three leafy vegetables (Brassica chinensis, Brassica rapa var. glabra Regel and Brassica rapa L.), two root vegetables (Daucus carota and Ipomoea batatas (L.) Lam.), and Solanum melongena L. First, the freeze-dried powders of vegetables and sorbents were evenly ground to a mixture, which was then loaded into a solid phase column containing two molecular sieve spacers, one positioned at the top and the other at the bottom. The PBDEs were eluted with a small amount of solvent, concentrated, redissolved in acetonitrile, and then mixed with extractant. Next, 5 mL water was added to form an emulsion and centrifuged. Finally, the sedimentary phase was collected and injected into a gas chromatography-tandem mass spectrometry (GC-MS) system. The main factors such as the type of adsorbent, ratio of sample mass and adsorbents, volume of elution solvent used in the MSPD process, as well as the types and volume of dispersant and the, extractant used in DLLME were all evaluated using the single factor method. Under optimal conditions, the proposed method showed good linearity (R² > 0.999) within the range of 1 to 1000 g kg⁻¹ for all PBDEs and satisfactory recoveries of spiked samples (82.9–113.8%, except for BDE-183 (58.5–82.5%)) and matrix effects (−3.3–18.2%). The limits of detection and the limits of quantification were in the range of 1.9–75.1 g kg⁻¹ and 5.7–25.3 g kg⁻¹, respectively. Moreover, the total pretreatment and detection time was within 30 min. This method proved to be a promising alternative to other high-cost and time-consuming and multi-stage procedures for determination of PBDEs in vegetables.