Design of experiment approach for the optimization of polybrominated diphenyl ethers determination in fine airborne particulate matter by microwave-assisted extraction and gas chromatography coupled to tandem mass spectrometry

A sensitive and selective procedure for the determination of 12 polybrominated diphenyl ethers (BDE-28, BDE-49, BDE-47, BDE-66, BDE-100, BDE-119, BDE-99, BDE-155, BDE-154, BDE-153, BDE-139 and BDE-183) in airbone particulate matter (PM2.5) at trace level has been developed. The proposed method includes extraction PM2.5-bound PBDEs by microwave-assisted extraction (MAE) followed by gel permeation chromatography (GPC) clean-up and determination by GC-MS/MS using a programmed temperature vaporizer (PTV) in large volume injection (LVI) mode to introduce the sample to the chromatographic system. A design of experiment (DoE) approach was used for the optimization of large volume injection and microwave-assisted extraction parameters to improve these techniques efficiency. Other conditions of the method were studied: GC-MS/MS parameters, extraction solvent and matrix effect. The limit of quantification ranged from 0.063 pg m−3 to 0.210 pg m−3 when air volumes of 723 m3 were collected. Recoveries ranged from 80% to 106%. The method was successfully applied to eight real samples collected from a residential area of the monitoring network of the Region of Valencia Government (Spain) during April–August 2012. BDE-47 and BDE-99 were quantified in six and five samples respectively. The concentrations were ranged from 0.063 to 0.112 pg m−3 for BDE-47, and from 0.107 to 0.212 pg m−3 for BDE-99.