Development of an analytical method for determining hindered phenolic antioxidants in exhaust emissions from light-duty vehicles

Six hindered phenolic antioxidants (HPAs) from emissions of light-duty diesel and gasoline vehicles were determined. Vehicles were tested on a dynamometer that conducted a typical city-driving protocol and their exhaust samples were collected on filters. A high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) method was developed for the determination of HPAs in the exhaust samples. Method detection limits reached low ng/m3 in exhaust after optimization of experimental conditions. Identification and quantification were proven to be reliable for these phenols in lightly-loaded and ambient filter samples. In heavily loaded samples, matrix interferences existed, which decreased recoveries of surrogate in both filter and disk. However, matrix spike samples showed good recoveries of target HPAs. In vehicle emission samples, the highest level of HPAs was 2,6-di-tert-butylphenol at 52.7 ng/m3 (28.9 pg/mm2 on filter) in emission of a 2009 Volkswagen Jetta with a diesel engine. Most HPAs were not detected or near detection limits. Therefore, the additives of phenol antioxidants in fuels were mostly oxidized during the combustion process. Further, the 2009 diesel Jetta produced about 7 times more of HPAs than the 2008 Pontiac G5 with a gasoline engine. In addition, it is discovered that engines operated at a colder ambient temperature (−7 °C) yielded more HPA emissions than at the warmer condition (25 °C), because the combustion efficiency of engines are normally reduced at a lower temperature.