1. 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.

2. 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.

3. PM2.5 mass conc. and PAH conc. at two urban sitesHD 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

4. 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 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.

5. Identification of PAHs compounds in PM2.5 with GCxGC/HRMS
Name
Formula
Observed
Ion m/z
Expected
7H-Benz[de]anthracen-7-one
C17H10O
1st R.T (s)
2nd R.T (s)
Mass Accuracy
(ppm)
Similarity
Area
2712
4.216
-2.17
864
PKU11
C17H10O
CHR-d12
FLUA-d10
230
101
202
Name
Formula
Observed
Ion m/z
Expected
Benzo[ghi]fluoranthene
C18H10
1st R.T (s)
2nd R.T (s)
Mass Accuracy
(ppm)
Similarity
Area
2760
4.232
-1.61
856
409912
GIST13
C18H10
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).
226
113

6. 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.

7. 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.

8. 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.