1Biomedical Omics Group, Korea Basic Science Institute, Cheongju and Goldschmidt 2019 Flash Talk Analysis of Organic Mixtures from Particulate Matters by Using GCxGC/High Resolution Mass Spectrometer M.-H. Park1, K.-S. Jang1, K. Park2, and Y. H. Kim1* 1Biomedical Omics Group, Korea Basic Science Institute, Cheongju and 2School of Earth Science and Environmental Engneering, Gwangju Institute of Science and Technology, Gwangju, Republic of Korea Hello, everyone. The title of my flash talk is “Analysis of organic mixture from particulate matters by using GCxGC/high resolution mass spectrometer” Next slide.

Introduction Maps of the sampling sites Major clusters of air mass backward trajectories in Gwangju, Korea during winter season In winter, PM generated in China was sometimes moved into Korea within 1~2 days due to the west and northeast wind from China. The sampling of PM2.5 were conducted daily during one month from Dec 27, 2018 to Jan 25, 2019 simultaneously in China (Beijing) and Korea (Gwangju). However, preliminary data were obtained for PM2.5 samples collected during the three days at each site. Especially, PM2.5-bound parent polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs were mainly identified and quantified. Particulate matters less than 2.5 μm (PM2.5) in the ambient atmosphere are of current interest due to their effects on the climate change and human health. The left figure show the maps of the two sampling sites. The Peking University site in Beijing, china is here (가리키며). The Gwangju Institute of Science and Technology site in Gwangju, Korea is here(가리키며). In winter, PM generated in China was sometimes moved into Korea within 1~2 days due to the west and northeast wind from China. The sampling of PM2.5 were conducted daily during one month from Dec 27, 2018 to Jan 25, 2019 simultaneously in China (Beijing) and Korea (Gwangju). However, preliminary data were obtained for PM2.5 samples collected during the three days at each site. Especially, PM2.5-bound parent polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs were mainly identified and quantified.

PM2.5 mass conc. and PAH conc. at two urban sites HD HD PM2.5 (μg/m3) 32.85 ± 25.29 Haze event day - HD, Nonevent day - ND PM2.5 (μg/m3) 30.44 ± 20.76 - This show PM2.5 mass and PAH concentrations in two urban sites. The PAH concentration in Beijing site was much more higher than that in Gwangju site. For example, comparing PM2.5 mass and PAH concentrations on the haze event days (11th Jan in Beijing and 13th Jan in Gwangju) of two sites, the PM2.5 mass concentration in Beijing site was 1.7 times higher than that in Gwangju site. However, the PAH concentration in Beijing site was 11.6 times higher than that in Gwangju site. HD

Analytical workflow for chemical characteristics of PM2.5 High-volume sampler were used to collect PM2.5 on quartz filters with 1000 L/min of sampling flow rate every day. 1. Sampling of PM2.5 3. GCxGC/HRMS analysis 4. Identification and Quantification 2. Extraction of organic components The quartz filter sample was extracted dichloromethane (DCM). The DCM extract was filtered using a PTFE syringe and then dried under a nitrogen stream. PTFE filtration LECO Pegasus GC-HRT 4D Injection mode : Splitless Injection temperature : 250 °C Columns : 1st : RTX-5MS (30m x 0.25mm x 0.25μm) 2nd : Rxi-17sil-MS (1.3m x 0.15mm x 1.25μm) Oven temperature : 2nd oven temp. was programmed at a 10 °C offset relative to the 1st oven. Modulator : The temp. offset was 20 °C with 2nd column dimension time of 8 s and hot pulse duration of 1.5 s. MS Conditions : The ion source temp. was 250 °C with electron ionization of 70 eV. The collected mass range m/z 35-650 with acquisition rate of 120 spectra/s and mass resolution of 25,000. 40 °C 300 °C 2 min 4 °C/min 12 min 1st oven temp. This slide show analytical workflow for chemical characteristics of PM2.5. To collect PM2.5 samples, high-volume sampler were used on quartz filters with 1000 L/min of sampling flow rate every day. To extract the organic components in PM2.5 samples, the quartz filter sample was extracted dichloromethane (DCM). The DCM extract was filtered using a PTFE syringe and then dried under a nitrogen stream. Using two-dimensional gas chromatography/high resolution mass spectrometer, the organic components in PM2.5 samples were identified and quantified.

Identification of PAHs compounds in PM2.5 with GCxGC/HRMS Name Formula Observed Ion m/z Expected 7H-Benz[de]anthracen-7-one C17H10O 230.0721 230.0726 1st R.T (s) 2nd R.T (s) Mass Accuracy (ppm) Similarity Area 2712 4.216 -2.17 864 1073838 PKU11 C17H10O CHR-d12 FLUA-d10 230.0721 100.0304 200.0617 230 101 202 Name Formula Observed Ion m/z Expected Benzo[ghi]fluoranthene C18H10 226.0773 226.0777 1st R.T (s) 2nd R.T (s) Mass Accuracy (ppm) Similarity Area 2760 4.232 -1.61 856 409912 GIST13 C18H10 226.0773 This show how we identify the polycyclic aromatic hydrocarbon (PAH) components by using GCxGC /HRMS. The PAH components were identified by the comparison of their electron-impact (EI) mass spectral peak patterns with those of Wiley and NIST libraries and confirmed by high resolution data of molecular ion peaks. For example, this spot was identified as 7H-benz[de]anthracen-7-one based on the similarity and elemental composition (C17H10O). 113.0381 226 113

Identification and classification of 261 PAHs and derivatives in PM2.5 Total 261 species of PAHs and derivatives were identified including parent, alkyl PAHs, oxygenated PAHs, and heterocyclic aromatic hydrocarbons. The nitrated PAHs were not identified. The identified oxygenated PAHs can be divided into carbonyl–, hydroxyl- and carboxyl-OPAHs.

Distributions of individual PAH compounds PHE ANT PKU3 PKU11 BaA PHE - Phenanthrene, ANT - Anthracene, MPHE - Methylphenanthrene, FLUA - Fluorathene, PYR - Pyrene, CHR - Chrysene, BaA - Benzo[a]anthracene, PER – Perylone, BaP – Benzo[a]pyrene, BeP – Benzo[e]pyrene, BbF – Benzo[b]fluorathene, BkF – Benzo[k]fluorathene, BghiP – Benzo[g,h,i]perylene, IcdP – Indeno[1,2,3-cd]pyrene, DahA – Dibenzo[a,h]anthracene, PIC – Picene, COR – Coronene, DiBP - Dibenzopyrene The individual PAH concentrations in the haze event day of Beijing site were much more higher than those in the haze event and nonevent days of Gwangju site. Especially, in Beijing site, the concentrations of phenanthrene (PHE) and benzo[a]anthrancene (BaA) in the haze event day of 3rd Jan. were very high but those not in the haze event day of 11th Jan. Still now, I don’t know why. We need further to analyze the samples of PM2.5 collected in the other days.

Summary Using GCxGC/HRMS, total 261 species of parent, alkyl and oxygenated PAHs were identified in PM2.5 collected in winter haze event and nonevent days. The parent PAHs were also quantified and compared between the PM2.5 samples of Beijing and Gwangju sites. The PAH concentration (ng/m3) in the haze event day (3rd Jan) of Beijing was 24.4 times higher than that in the nonevent day (5th Jan) of Gwangju site. However, the PAH concentration in the haze event day (22th Jan) of Gwangju site was 2.4 times higher than that in the nonevent day (20th Jan) of Beijing site. The individual PAH compounds measured in the PM2.5 of Beijing site were much more higher than those in the PM2.5 of Gwangju site. I’ll briefly summarize the main issues. Thank you for your attentions.