1. Page  1 Seasonal Characteristics of Nitrogen Transport over Northeast Asia Cheol-Hee Kim chkim2@pusan.ac.kr Department of Atmospheric Sciences, Pusan National University, Korea 2013.01.15 중국 베이징 스모그 2013.01.15 서울 2013.01.17 서울 2013.01.18 포항

2. Page  2 2

3. Page  3 2 Historic prospective of transboundary air Pollutants

4. Page  4 In 1961, a Scandinavian network to monitor surface water chemistry was established. Svante Odin, a Swedish meteorologist, pointed out significant decreases in the pH of rain have occurred in Scandinavia and the northeastern United States during the last two decades. He also suggested that air pollutants including acidic substances could be transported over long-range from the European continent and the British isles. [Water Air Soil Pollut., 6, 137-166 (1976)] Historic prospective of transboundary air Pollutants Pollution The term of “Transboundary air pollution” was first recognized by acid rain problem revealed in 1960s. 3

5. Page  5 Historic prospective of transboundary air Pollutants Pollution Convention on Long-Range Trans-boundary Air Pollution (CLRTAP) was adopted in 1979 among European countries, USA and Canada. During 1970s and 1980s, researches on long-range transportation of acidic Substances drastically developed in Europe and North America. 3

6. Page  6 Historic prospective of transboundary air Pollutants Pollution Because regulations of SOx and NOx emission was tightened, the topic of Transboundary air pollution was shifted from acidification phenomena to ozone issue. Although NOx and VOC emissions were regulated, ozone concentrations did not meet air quality standards in many cities because of intercontinental transportation of ozone. In 2004, Task Force on Hemispheric Transport of Air Pollution (TF-HTAP) was established under CLRTAP 3

7. Page  7 Long-Range Transport Project (LTP ) in Korea and Acid Deposition Monitoring Network in East Asia (EANET) in Japan was established. Contribution of sulfur deposition from China were examined and reported. Environmental impacts of acid deposition is considered as issues of long-term risk. Historic prospective of transboundary air pollution After 1990s, effects of acidification phenomena was paid attention among East Asian countries. 4

8. Page  8 Historic prospective of transboundary air pollution Recently, increasing in ozone concentration has been paid attention to North East Asia Although NOx and VOC concentrations have been decreased, ozone concentrations are increasing not only urban regions also in whole of Korea. Many research groups consider substantial increase in ozone concentration from Asian continent and trans- boundary transport of ozone to Korea Background ozone concentration in East Asia may increase due to hemispheric transport of air pollutants from the European continent. 4

9. Page  9 Increasing air pollutant emissions in East Asia 5

10. Page  10 Annual trend of emissions for NOx, SO 2, NMVOC in Asia NMVOC NOx SO 2 Unit: Mt yr -1 Values in parentheses indicate increase rate against 1980 Data from REAS ACP, 7, 4419-4444 (2007) 6

11. Page  11 Future prospects of NOx, SO 2, NMVOC emissions in China REAS ： Regional Emission inventory in Asia REAS_PSC ： Policy Succeed Case scenario REAS_REF ： Reference Case scenario REAS_PFC ： Policy Failure Case scenario GOME/SCIAMACHY ： NO 2 column concentration measured by GOME/SCIAMACHY SEPA ： Prediction calculated by the State Environmental Protection Administration, China (now Ministry of Environmental Protection) 7

12. Page  12 Source-Receptor Relationship for Sulfur (S) (From LTP Results)

13. Page  13 R ij : contribution of i-th emission source to j-th receptor region H ij : deposition amount over j- th receptor when emission is only from the i-th source RD : reduction percentage S-R domain and equation

14. Page  14 14 CMAQ Model Experiment

15. Page  15 15 Model Experimental Design  Domain and grid –60 km horizontal grids –20°N~55°N, 100°E~150°E –29 levels of stretched vertical grids –Model top at 19 km height  Input fields –Emission rates for SO 2, NOx, CO, VOCs, NH 3 : datasets prepared by this group except for North Korea and Taiwan. –North Korea and Taiwan for emission rates : from Street et al. (2003) (for the year 2000) –Meteorological fields : produced by RAMS with 4DDA (Domain for meteorological fields is larger than the CADM domain) –Initial and boundary concentration : zero, except for O 3 (40 ppb)

16. Page  16 16 Emission rates (unit : m gm -2 s -1 )

17. Page  17 17 Observed and simulated meteorology

18. Page  18 18 GPCP Data Simulation Monthly rainfall amount for April

19. Page  19 19 GPCP Data Simulation Monthly rainfall amount for June

20. Page  20 20 GPCP Data Simulation Monthly rainfall amount for September

21. Page  21 21 GPCP Data Simulation Monthly rainfall amount for December

22. Page  22 22 Concentrations, depositions and S-R relationship for sulfur deposition

23. Page  23 23 Seasonal and annual average surface SO 2 concentration (ppb)

24. Page  24 24 Seasonal dry deposition of sulfur (mg/m 2 )

25. Page  25 25 Seasonal wet deposition of sulfur (mg/m 2 )

26. Page  26 Total Deposition SO 2 concentration SO 4 concentration 한중일 2002 년 연평균 황 모사 패턴 중국 모델 결과 (2002 년 ) 일본 모델 결과 (2002 년 ) 한국 모델 결과 (2002 년 )

27. Page  27 27 S-R relationship for deposition of sulfur in 2002

28. Page  28 How about NOx S-R ? More complicated calculation is required!!

29. Page  29 Contents  Introduction  Recent Data of Satellite and Statistics  Results (Seasonality) - Modeling results of NO x and total-Nitrate seasonal variations - Total-Nitrate Source-Receptor relationship - Satellite measurements of seasonal variation of NO 2 - Meteorological features of long range transport of N species  Conclusion

30. Page  30 INTRODUCTION  Nitrogen oxides (NOx) play a key role in the photochemically induced catalytic production of tropospheric ozone.  NO x react to form smog, causing health effects and climate forcing.  The environmental effects of nitrogen deposition include regional scale eutrophication of natural ecosystems and acidification.  Long-range transport processes over Northeast Asia despite their short life time Formation of nitric acid and acid deposition 2NO 2 + H 2 O → HNO 2 + HNO 3 3HNO 2 → HNO 3 + 2 NO + H 2 O 4NO + 3 O 2 + 2 H 2 O → 4 HNO 3

31. Page  31 Annual trend of emissions for NOx, SO 2, NMVOC in Asia NMVOC NOx SO 2 Unit: Mt yr -1 Values in parentheses indicate increase rate against 1980 Data from REAS (ACP, 2007) 6

32. Page  32 Japan Hong Kong Eastern China (Richter et al., 2005, Nature)

33. Page  33 Planetary Boundary Layer Laboratory China increased (~ 60%) (Richter et al., 2005; Van der A et al., 2006), Korea increased (< 20%), and Japan decreased (-40 ~ -20%). China increased, Korea decreased, Japan decreased. Unit: 10 15 molecules cm -2 Satellite Observation Satellite observations (NO 2 ) Emission inventory (NO 2 )

34. Page  34 Seasonality of NOx + N-containing Species ? NO, NO 2, HNO 3, NO 3 -, PAN…. (NOx) (total nitrate) NOx + total nitrate +… = (NOy) NOx : NO + NO 2 NOy : NOx + NOz Total Nitrate: nitric acid (HNO 3 ), inorganic nitrate (including NO 3 - ), PAN as organic nitrate

35. Page  35 Model Study Horizontal Distributions and Seasonality of NOx and N-containing species (i.e., total nitrate)

36. Page  36 Model Study - Air Quality Model ; MM5, Model3/CMAQ - Source-Receptor relationship ( Applying EMEP method-3)

37. Page  37  Air Quality model –CMAQ 4.6 –Advection, horizontal and vertical diffusion –Gas-phase Chemical Mechanisms SAPRC99 chemical mechanism –Aerosol Module The 3 rd generation modal CMAQ aerosol model –Dry/Wet deposition and cloud process Air Quality Model Model results : –Concentration and dry/wet deposition Components : NOx, nitric acid (HNO 3 ), inorganic nitrate (including NO 3 - ), and PAN as organic nitrate Spatial distribution of dry and wet deposition, and monthly deposition amount –Source-receptor relationship Components : the total nitrate (sum of N from nitric acid, inorganic nitrate, and PAN) EMEP method-3

38. Page  38 Models-3/CMAQ system (Courtesy of Daewon Byun, USEPA/ORD)

39. Page  39 Emissions for 2006 SO 2 NOx VOCs CO PM 10 NH 3 Gridded emissions for 2006 (ton/yr/grid) -SO 2, CO, NOx, PM 10, and VOCs INTEX-B emission inventory (Zhang et. al., 2009) -NH 3 emissions : TRACE-P emissions inventory (Streets, et al., 2003) with projection factors derived from REAS inventory (Ohara et al., 2007).

40. Page  40 (1) Satellite measurements of NO 2 seasonality (2) Modeled NO x and total nitrate; Seasonality (3) Deposition & Total nitrate Source-Receptor relationship (4) Meteorological features of long range transport of Nitrogen species Results

41. Page  41 Satellite Measurement OMI : NO2 VCDs in 2006 Jan FebMar Apr May JunJul Aug Sep OctNov Dec

42. Page  42 Model Output : surface NO x NO x is high in winter, low in summer. High over near-source regions.

43. Page  43 Satellite Observations (NO2 Columns for 2005-2011) Lee et al. (JGR,2013, Submitted)

44. Page  44 Model Output : total-Nitrate (HNO3+NO3- +PAN) (NIER, 2010) Total nitrate is high in summer due to reactive photo-chemistry. High in downwind regions as well, as it is secondary production (NIER, 2010)

45. Page  45 Summer v.s. winter gas-aerosol partitioning of nitrate (NIER, 2010) Aerosol nitrate is prevailing over HNO 3 gas over land (with NH 4 + ) and over ocean (with NH 4 +, Na + ). HNO 3 is higher in summer (temp. is higher) Gas(HNO3) Aerosol(NO3-) SummerWinter 2 15 0.2 10

46. Page  46 Dry deposition of HNO 3 (NIER, 2010) Dry deposition of HNO 3 is higher in summer, due to high cons. and higher Vd of HNO 3 (~10cm/s) than that aerosols (0.1~1cm/s).

47. Page  47 Dry deposition of aerosol NO 3 - (NIER, 2010) As a result, dry deposition of HNO 3 is as high as that in aerosols, though aerosol nitrate conc. is much higher.

48. Page  48 Source-Receptor relationship for the total nitrate (Applying EMEP method-3)

49. Page  49 Methods of S-R relationship Source/receptor region

50. Page  50 S-R for total nitrate in 2006 (NIER, 2013) SPRING WINTERAUTUMN SUMMER >60% <40% 38% <60%

51. Page  51 Long-Range Transport of NOx and its impact on NOx Seasonality - Satellite Measurement - Surface Measurement

52. Page  52 Unit: 10 15 molecules cm -2

53. Page  53 Satellite Measurement & Meteorological Model

54. Page  54 Liang et al. (2004)

55. Page  55 Cooper et al.(2004) Future Study : Life cycle of Warm Conveyer Belt

56. Page  56 Summary  Satellite data and Model output - Seasonality of NO2 - Horizontal Distribution and Time variation  Modeling results : Hand Seasonal Variation for -NO x -total Nitrate : Total Nitrate SR relationship : Satellite seasonal variation of NO 2 : Meteorological features of long range transport of NO 2

57. Page  57 경청해 주셔서 감사합니다.