Title Page
ABSTRACT
Contents
CHAPTER 1. INTRODUCTION 14
CHAPTER 2. EXPERIMENTAL 18
2.1. Experiment 18
2.2. Method 19
CHAPTER 3. RESULT & DISCUSSION 21
3.1. Measurement Overview 21
3.1.1. Summer season in July to September 2021 21
3.1.2. Early winter season in 2021 (2021 GMAP) 22
3.1.3. Early summer season in 2022 (2022 SIJAQ) 23
3.2. Factors influencing H₂O₂ concentrations 25
3.2.1. Comparison with previous study 25
3.2.2. Diurnal variation 26
3.2.3. Correlation between H₂O₂ and O₃ 27
3.2.4. Comparison of chemical species with 2016 KORUS-AQ 28
3.3. Impact of synoptic meteorology 31
3.3.1. Meteorological regime 31
3.3.2. Photochemical regime 32
3.3.3. Nonlinearity between H₂O₂ and O₃ 34
CHAPTER 4. CONCLUSION 38
REFERENCES 89
Table 1. H₂O₂ formation process 78
Table 2. H₂O₂ sink process 79
Table 3. List of data set by month 80
Table 4. Method and time resolution of gas phase, particle phase species and meteorological data 81
Table 5. Instrumental Conditions of HPLC-Fluorescence for H₂O₂ analysis 82
Table 6. Chemical reagent of HPLC-Fluorescence for H₂O₂ analysis 83
Table 7. Measurement statistics of chemical and meteorological parameters during sampling period in July-Sep, 2021 84
Table 8. Measurement statistics of chemical and meteorological parameters during sampling period in May-June, 2022 85
Table 9. H₂O₂ measurements (ppbv) during summer in previous studies 86
Table 10. Measurement statistics of chemical and meteorological parameter sduring summer sampling period (2021~2022) 87
Table 11. Comparison of chemical and meteorological parameters by 3 periods during 2022 SIJAQ 88
Figure 1. Geographical location of sampling site, Korea University in Seoul(KU) 41
Figure 2. Enzyme reaction of fluorescent dimer formation 41
Figure 3. The schematics of H₂O₂ measurement system using glass coil for sampling coupled with HPLC for chemical analysis 42
Figure 4. Time series of reactive gases (O₃, Ox, H₂O₂, NO, NO₂, NOy, SO₂, CO), PM₂.₅ mass, composition and meteorological parameters (temperature,...[이미지참조] 43
Figure 5. Time series of reactive gases (O₃, Ox, H₂O₂, NO, NO₂, NOy, SO₂, CO), PM₂.₅ mass, composition and meteorological parameters (temperature,...[이미지참조] 44
Figure 6. Time series of reactive gases (O₃, Ox, H₂O₂, NO, NO₂, NOy, TVOC, SO₂, CO), PM₂.₅ mass, composition and meteorological parameters...[이미지참조] 45
Figure 7. Windrose of Korea University during sampling period 46
Figure 8. Peak height detected on chromatography (Retention time: H₂O₂ 4.96 min, Organic peroxide 7.8 min) 47
Figure 9. Time series of H₂O₂ and organic peroxide during 5/5~5/6, 2022 47
Figure 10. The histogram(frequency) of H₂O₂ 48
Figure 11. Not clear diurnal variation of H₂O₂, O₃ on cloudy day 48
Figure 12. Diurnal Variation during 2022 SIJAQ (a) H₂O₂, (b) O₃, (c) Ox, (d) TVOC, (e) SO₂, (f) CO, (g) NO₂, (h) NO, (i) NOy, (j) NOz, (k) PM₂.₅, (l) PM₁₀[이미지참조] 49
Figure 13. Correlation between H₂O₂ and O₃ during summer color scaled with hour. 50
Figure 14. Gas, aerosol species concentration in H₂O₂ and O₃ domain. (a) TVOC, (b) CO, (c) SO₂, (d) NO₂, (e) NO, (f) Ox, (g) NOz, (h) NOy, (i) NOz/NOy[이미지참조] 51
Figure 15. Gas, aerosol species concentration in H₂O₂ and O₃ domain. (a) PM₂.₅, (b) PM₁₀, (c) SO₄²¯, (d) NO₃-, (e) NH₄⁺, (f) Temperature, (g) Relative... 52
Figure 16. Correlation between TVOC and NOx color scaled with (a) H₂O₂, (b) O₃, (c) Ox, (d) PM₂.₅[이미지참조] 53
Figure 17. Correlation between TVOC and NOz color scaled with (a) H₂O₂, (b) O₃, (c) Ox, (d) PM₂.₅[이미지참조] 54
Figure 18. Comparison of diurnal variation of H₂O₂, O₃ during (a) 2022 SIJAQ and (b) 2016 KORUS-AQ (May~June) 55
Figure 19. Correlation between H₂O₂ and O₃ color scaled with (a) hour, (b) year 56
Figure 20. Comparison of diurnal variation between 2016 KORUS-AQ and 2022 SIJAQ campaign 57
Figure 21. Correlation between TVOC and NOx between 2022 SIJAQ and 2016 KORUS-AQ. (a) The lines represent the linear regression.[이미지참조] 58
Figure 22. Correlation between TVOC and NOz color scaled by Month-day (daily)[이미지참조] 59
Figure 23. Correlation between TVOC and NOz (1 hour average) color scaled (a) O₃, (b) PM₂.₅, (c) H₂O₂[이미지참조] 60
Figure 24. Correlation between TVOC and NOz (daily max) with (a) O₃, (b) PM₂.₅, (c) H₂O₂[이미지참조] 61
Figure 25. Correlation between O₃ and PM₂.₅ color-scaled by H₂O₂ during (a) 2022 SIJAQ, (b) 2016 KORUS-AQ 62
Figure 26. Windrose of Korea University during 3 periods 63
Figure 27. The synoptic charts (ground) of May-June, 2022. (a) P1 (2022.05.07), (b) P2 (2022.05.23), (c) P2 (2022.05.25), (d) P3 (2022.06.04) 64
Figure 28. Backward trajectories (48 hour, 500m) by 3 periods 65
Figure 29. (a) Correlation between TVOC and (a) NOx, (b) NOz by 3 periods during 2022 SIJAQ[이미지참조] 66
Figure 30. Box whisker plots of daily variation (a) O₃, (b) PM₂.₅, (c) H₂O₂ by 3 periods. 'R' means rainy day. 67
Figure 31. Comparison of chemical species by 3 periods. The range between upper and lower is the 95th percentiles. (a) H₂O₂, (b) O₃, (c) Ox, (d) PM₂.₅, (e)...[이미지참조] 68
Figure 32. Comparison of meteorological factors by 3 periods. The range between upper and lower is the 95th percentiles. (a) Temperature, (b) Relative...[이미지참조] 69
Figure 33. Comparison of diurnal variation by 3 periods. (a) H₂O₂, (b) O₃, (c) PM₂.₅, (d) SO₄²¯ 70
Figure 34. Box whisker plots of NO₂/Ox ratio divided into day (06:00~20:00) and night (21:00~05:00) and compared with 3 periods[이미지참조] 71
Figure 35. Box whisker plots of O₃ difference between daytime and nighttime by 3 periods 72
Figure 36. Correlation between H₂O₂ and O₃ by heatwave period (2021.07.27~2021.07.29) and 3 periods 73
Figure 37. Daily variation of inorganic ion (SO₄²¯, NO₃-, NH₄⁺), OC, PM₂.₅ and gaseous species (H₂O₂, O₃, H₂SO₄, SO₂) on (a) May 23, 2022, (b) June 3, 2022 74
Figure 38. (a) Number concentration of particle (14~400 nm) on May 21 to 25, 2022 (b) Number concentration of particle (14~400 nm) on June 1 to 4, 2022 75
Figure 39. Time series of (a) H₂O₂, O₃, (b) PM₂.₅, CO during heatwave (July 27~29, 2021) 76
Figure 40. Backward trajectories (48 hour, 500m) during heatwave in July 27~29, 2021 77
Figure 41. Time series of PM₂.₅ and inorganic ions (SO₄²¯, NO₃-, NH₄⁺) in Bulgwang-dong, Seoul in July, 2021 77