Quantification of PAHs and oxy-PAHs on airborne particulate matter in Chiang Mai, Thailand, using gas chromatography high resolution mass spectrometry

Abstract

An analytical method using gas chromatography high resolution mass spectrometry was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 oxygenated PAHs (of which 4 diketones, 3 ketones, 4 aldehydes and one anhydride) on atmospheric particulate matter with an aerodynamic diameter less than 10μm (PM10). The magnetic sector mass spectrometer was run in multiple ion detection mode (MID) with a mass resolution above 10 000 (10% valley definition) and allows for a selective accurate mass detection of the characteristic ions of the target analytes. Instrumental detection limits between 0.04pg and 1.34pg were obtained for the PAHs, whereas for the oxy-PAHs they ranged between 0.08pg and 2.13pg. Pressurized liquid extraction using dichloromethane was evaluated and excellent recoveries ranging between 87% and 98% for the PAHs and between 74% and 110% for 10 oxy-PAHs were obtained, when the optimum extraction temperature of 150°C was applied. The developed method was finally used to determine PAHs and oxy-PAHs concentration levels from particulate matter samples collected in the wet season at 4 different locations in Chiang Mai, Thailand (n=72). This study brings forward the first concentration levels of oxy-PAHs in Thailand. The median of the sum of the PAHs and oxy-PAHs concentrations was 3.4ng/m3 and 1.1ng/m3 respectively, which shows the importance of the group of the oxy-PAHs as PM10 constituents. High molecular weight PAHs contributed the most to the ∑PAHs. For example, benzo[ghi]perylene was responsible for 30–44% of the ∑PAHs. The highest contribution to ∑oxy-PAHs came from 1,8-napthalic anhydride (26–78%), followed by anthracene-9,10-dione (4–27%) and 7H-benzo[de]anthracene-7-one (6–26%). Indications of the degradation of PAHs and/or formation of oxy-PAHs were observed.