Biogenic chemistry in a region of declining emissions: Insights from the NASA SEAC 4 RS Campaign

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Avice Wilkins
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Jacob, Katherine Travis, Patrick Kim, Eloise

Robert Yantosca, Melissa Payer Sulprizio

Princeton University and Ronald Cohen, Alan

1 Biogenic chemistry in a region of declining emissions: Insights from the NASA SEAC 4 RS Campaign Jenny A. Fisher University of Wollongong with Daniel Jacob, Katherine Travis, Patrick Kim, Eloise Marais, Karen Yu, Christopher Miller, Lei Zhu, Robert Yantosca, Melissa Payer Sulprizio Harvard University Jingqiu Mao, Fabien Paulot Princeton University and Ronald Cohen, Alan Fried, Alan Goldstein, Thomas Hanisco, Jose Jimenez, Paul Wennberg, Armin Wisthaler SEAC4RS/SOAS PIs

2 Southeast US has an ozone pollution problem Ozone Max EPA, ppb Many sites exceed 75 ppb standard

Southeast US has an ozone pollution problem 28-21 Ozone Max EPA, 214 4-65 ppb 66-7 71-75 76-9 91-112 Many sites exceed 75

3 Southeast US has an ozone pollution problem Ozone Max EPA, ppb Many sites exceed 75 ppb standard Ground-level ozone MODELS OBSERVATIONS Models show large biases in ground-level ozone Fiore et al., 29 Month

4 Southeast US also has a PM2.5 pollution problem August-September 213 PM2.5 Many sites exceed 12 μg m -3 standard Majority of PM2.5 is organic aerosol Kim, Jacob, Fisher et al., 215

5 Southeast US: a global isoprene emission hotspot in summer Estimated Isoprene Emissions, July 29 Satellite HCHO (OMI), July 26 Stavrakou et al., 212 Harvard-Smithsonian Center for Astrophysics

6 Isoprene photo-oxidation cascade impacts ozone, nitrogen and aerosol budgets Isoprene + OH

7 Isoprene photo-oxidation cascade impacts ozone, nitrogen and aerosol budgets Isoprene + OH + HO2 + NO Isoprene Peroxides Isoprene Nitrates

8 Isoprene photo-oxidation cascade impacts ozone, nitrogen and aerosol budgets Isoprene + OH + HO2 + NO Isoprene Peroxides Isoprene Nitrates Increased OA

9 Isoprene photo-oxidation cascade impacts ozone, nitrogen and aerosol budgets Isoprene + OH + HO2 + NO Isoprene Peroxides Isoprene Nitrates Increased OA NOX sink Decreased O3 N deposition

10 Isoprene photo-oxidation cascade impacts ozone, nitrogen and aerosol budgets Isoprene + OH + HO2 + NO Isoprene Peroxides Isoprene Nitrates Increased OA NOX sink Decreased O3 N deposition NOX reservoir Increased O3 downwind

11 Isoprene oxidation pathway depends on NOX Isoprene + OH + HO2 + NO Isoprene Peroxides Isoprene Nitrates NOX-dependent: low NOX vs. high NOX Increased OA NOX sink Decreased O3 N deposition NOX reservoir Increased O3 downwind

12 and NOX emissions are rapidly declining Satellite NO2 (OMI): difference molec cm Southeast US -2 NOX emissions metric tons Russell et al., Hidy et al., 214

and NOX emissions are rapidly declining Satellite NO2 (OMI): 211-25 difference molec cm Southeast US -2 NOX emissions 5 1 15 metric tons 2 1 6 1 1 6-5 Russell

13 and NOX emissions are rapidly declining Satellite NO2 (OMI): difference molec cm Southeast US -2 NOX emissions metric tons Russell et al., Hidy et al., 214 There is a critical need to understand biogenic chemistry, and the atmospheric response to declining NOX emissions.

14 NASA SEAC 4 RS aircraft campaign provides unprecedented constraints on biogenic chemistry Aug-Sept 213 isoprene emissions & DC-8 flight tracks Kim, Jacob, Fisher et al., 215

DC-8 interior HO 2 MVK, MACR, HCHO + isoprene peroxides NO X MVK, MACR, HCHO + isoprene

15 NASA SEAC 4 RS aircraft campaign provides unprecedented constraints on biogenic chemistry DC-8 exterior Species measured during SEAC 4 RS: ISOPRENE + OH ISOPO 2 HPALDs DC-8 interior HO 2 MVK, MACR, HCHO + isoprene peroxides NO X MVK, MACR, HCHO + isoprene nitrates (1st generaon ) organic aerosols isoprene nitrates (2nd generaon) Houston Daily News

16 GEOS-Chem simulation: a framework for testing emissions & chemistry Simulated O3 in surface air.25 x.3125 over North America MEGANv2.1 isoprene, monoterpene emission Recent updates to isoprene chemistry New monoterpene nitrate chemistry

17 GEOS-Chem simulation: a framework for testing emissions & chemistry Simulated O3 in surface air.25 x.3125 over North America MEGANv2.1 isoprene, monoterpene emission Recent updates to isoprene chemistry New monoterpene nitrate chemistry

18 SEAC 4 RS data imply NOX emissions are 2x too high in US national inventory Aug 213 Southeast US NOX emissions [Mg] industry 11 mobile 27 electricity 53 soils fires 46 6 Travis, Jacob, Fisher et al., in prep. (data: T. Ryerson)

19 SEAC 4 RS data imply NOX emissions are 2x too high in US national inventory Aug 213 Southeast US NOX emissions [Mg] industry 11 mobile 27 Reduce emissions by 5% electricity 53 soils fires 46 6 Travis, Jacob, Fisher et al., in prep. (data: T. Ryerson)

20 SEAC 4 RS data imply 4 NOX emissions are 2x too o DC8 NOx: -1.5km N high in US national inventory 35 o N Aug 213 Southeast US NOX emissions [Mg] industry 11 3 o N Model - Observed NOX Modeled - Observed NOx mobile o N 35 o N soils fires o N Reduce emissions by 5% DC8 NOx: -1.5km 9 o W 85 o W 8 o W ppb electricity 53 Without scaling by 5% ppb 25 o N 9 o W 85 o W 8 o W ppb Travis, Jacob, Fisher et al., in prep. (data: Without T. Ryerson) scaling by 5% ppb

21 DC8 NOx: -1.5km SEAC4RS data imply NO are 2x too X emissions 4 N high in US national inventory o Aug 213 Southeast US 35oN NOX emissions [Mg] Model - Observed NOX Modeled - Observed NOx 3oN 25ooN N 4 Reduce emissions by 5% DC8 NOx: -1.5km 9oW 85oW oW 2. ppb SEAC4RS: Southeast.25x.3125 Observed & modeled median profiles 35oN 1 8 DC8 GEOS-Chem 3oN ppb O3, ppbv Without scaling by 5% HCHO, ppbv 25oN oW 85oW NO X ppbv NOx,.4.5 8oW 2. ppb PAN HNO3+NO3- Travis, Jacob, Fisher et al., in prep. (data: T. Ryerson, J. scaling Dibb) by 5% Without ppb

22 Reducing NOX emissions by 5%: no bias in Southeast US ozone Southeast US Surface Stations Probability per ppbv.1.5 Observation GEOS-Chem MDA8 ozone [ppbv] Nsites = 18 Travis, Jacob, Fisher et al., in prep. (data: A. Thompson)

23 Reducing NOX emissions by 5%: no bias in Southeast US ozone Probability per ppbv Southeast US Surface Stations.1.5. Observation GEOS-Chem MDA8 ozone [ppbv] Nsites = 18 Altitude, km Southeast US Ozonesondes Huntsville Idabel Stlouis Ellington Houston SONDE MODEL SmithPoint O 3, ppb O 3, ppb O 3, ppb Travis, Jacob, Fisher et al., in prep. (data: A. Thompson)

24 Isoprene and monoterpene are dominant aerosol sources during SEAC 4 RS SEAC 4 RS aerosols Model aerosols Kim, Jacob, Fisher et al., 215

25 Isoprene and monoterpene are dominant aerosol sources during SEAC 4 RS SEAC 4 RS aerosols Model aerosols Organic Carbon in surface air Kim, Jacob, Fisher et al., 215

26 Isoprene and monoterpene are dominant aerosol sources during SEAC 4 RS SEAC 4 RS aerosols Model aerosols Organic Carbon in surface air Kim, Jacob, Fisher et al., 215

27 Isoprene, monoterpenes, and oxidation products also well simulated during SEAC 4 RS Isoprene Monoterpenes HCHO MVK+MACR Observed + ISOPOOH median Modelled median Altitude, km Concentration, pptv 1 2 Fisher et al., in prep. (data: A. Wisthaler, T. Hanisco)

28 SEAC 4 RS data provides test of high- vs. low-nox isoprene oxidation partitioning Isoprene + OH Altitud Median Vertical Profiles, Observed & Modelled ISOPOOH ISOPN HPALD HO2 ISOPOOH isomerize +NO HPALD ISOPN r =.7 r =.8 r =.5 Model- obs. correlaons in surface air Travis, Jacob, Fisher et al., in prep. (data: P. Wennberg)

29 SEAC 4 RS data provides test of high- vs. low-nox isoprene oxidation partitioning Simulated isoprene oxidation pathways Isom. 6% HO2 17% Isom. 14% NO 45% HO2 38% NO 76% NO x emission Travis, Jacob, Fisher et al., in prep.

30 SEAC 4 RS data provides test of high- vs. low-nox isoprene oxidation partitioning Simulated isoprene oxidation pathways + NO + HO2 1% isomerization 7 3 Travis, Jacob, Fisher et al., in prep.

31 SEAC 4 RS data provides test of high- vs. low-nox isoprene oxidation partitioning Simulated isoprene oxidation pathways + NO Reaction with NO is dominant isoprene fate across Southeast what are the impacts? + HO2 1% isomerization 7 3 Travis, Jacob, Fisher et al., in prep.

32 Dominant fate of organic nitrates (RONO2): formation of more highly functionalized RONO2 Simulated organic nitrate fates Isoprene ISOPN, 9.3 nitrate Gg N (ISOPN) month % Oxidation Dry deposition Aerosol uptake Wet deposition Photolysis Isoprene + OH, NO ISOPN 2nd generation isoprene nitrates Fisher et al., in prep.

33 A diversity of species contribute to RONO2 observed during SEAC 4 RS Isoprene + OH, NO ISOPN 2nd generation isoprene nitrates 4 Observed RONO2 3 Altitude, km ANs, pptv Fisher et al., in prep. (data: R. Cohen, P. Wennberg)

34 A diversity of species contribute to RONO2 observed during SEAC 4 RS Isoprene + OH, NO ISOPN 2nd generation isoprene nitrates 4 Observed RONO2 4 Modelled RONO2 3 3 Altitude, km 2 Altitude, km ANs, pptv ANs, pptv Fisher et al., in prep. (data: R. Cohen, P. Wennberg)

35 A diversity of species contribute to RONO2 observed during SEAC 4 RS Isoprene + OH, NO Monoterpenes + OH, NO ISOPN 2nd generation isoprene nitrates MONIT 2nd generation monoterpene nitrates 4 Observed RONO2 4 Modelled RONO2 3 3 Altitude, km 2 Altitude, km ANs, pptv ANs, pptv Fisher et al., in prep. (data: R. Cohen, P. Wennberg)

36 A diversity of species contribute to RONO2 observed during SEAC 4 RS Isoprene + OH, NO Monoterpenes + OH, NO ISOPN 2nd generation isoprene nitrates MONIT 2nd generation monoterpene nitrates 4 Observed RONO2 4 Modelled RONO2 3 3 Altitude, km 2 Altitude, km ANs, pptv ANs, pptv Fisher et al., in prep. (data: R. Cohen, P. Wennberg) ParAculate RONO 2

37 RONO2 losses are dominated by deposition: implications for nitrogen inputs to ecosystems Simulated RONO2 loss pathways Wet deposition Aerosol uptake 7% 13% Chemical Loss Photolysis 22% Dry deposition 54% Fisher et al., in prep.

RONO2 losses are dominated by deposition: implications for nitrogen inputs to ecosystems Simulated RONO2 loss pathways Simulated % N deposition from RONO2 Wet deposition Aerosol

38 RONO2 losses are dominated by deposition: implications for nitrogen inputs to ecosystems Simulated RONO2 loss pathways Simulated % N deposition from RONO2 Wet deposition Aerosol uptake 7% 13% Chemical Loss Photolysis 22% Dry deposition 54% % Organic nitrates responsible for 7-8% of total N deposition over the Southeast: ~2 Gg N Fisher et al., in prep.

39 Most RONO2 losses are terminal NOX sinks Simulated RONO2 loss pathways Wet deposition Aerosol uptake 7% 13% Chemical Loss Photolysis 22% Dry deposition 54% Fisher et al., in prep.

40 Most RONO2 losses are terminal NOX sinks Simulated RONO2 loss pathways Wet deposition Aerosol uptake 7% 13% Chemical Loss Photolysis 22% NOX recycling Dry deposition 54% NOX sinks Fisher et al., in prep.

41 Most RONO2 losses are terminal NOX sinks Simulated RONO2 loss pathways Wet deposition Aerosol uptake 7% 13% Chemical Loss Photolysis 22% Organic nitrates contribute 1-15% of Southeast US NOX sink NOX recycling Dry deposition 54% NOX sinks Fisher et al., in prep.

42 Role of RONO2 as sink for NOX depends on balance between NOX and BVOC emissions Low-NOX, high BVOC: ~7% NOX sink from ANs Simulated % NOX lost via organic nitrates High-NOX, low BVOC: ~2% NOX sink from ANs % Fisher et al., in prep.

Role of RONO2 as sink for NOX depends on balance between NOX and BVOC emissions Low-NOX, high BVOC: ~7% NOX sink from ANs Simulated % NOX lost via organic nitrates

43 Role of RONO2 as sink for NOX depends on balance between NOX and BVOC emissions Low-NOX, high BVOC: ~7% NOX sink from ANs Simulated % NOX lost via organic nitrates High-NOX, low BVOC: ~2% NOX sink from ANs % As NOX emissions decrease, organic nitrates will become an increasingly important sink. Fisher et al., in prep.

44 Southeast Australia: another predicted isoprene emission hotspot MEGAN inventory January 25 isoprene emissions LPJ-GUESS inventory Zeng et al., 215

45 Southeast Australia: another predicted isoprene emission hotspot MEGAN inventory January 25 isoprene emissions LPJ-GUESS inventory Zeng et al., 215 OMI NO2 tropospheric column, Jan 215 and a region of low NO2! 1 15 mol cm -2 KNMI / TEMIS

46 Correlation between isoprene nitrates & HCHO implies isoprene is dominant HCHO source ISOPN+MVKN+MACRN, pptv Isoprene Nitrates, pptv SEAC 4 RS isoprene nitrates vs HCHO Observed: slope=.28, r=.78 GEOS-Chem: slope=.25, r= HCHO, pptv Fisher et al., in prep. (data: T. Hanisco, P. Wennberg)

47 Models currently underestimate HCHO in Southeast Australia Wollongong HCHO columns Observed NIWA-UKCA TM5 GEOS-Chem CAM-chem Zeng, Williams, Fisher et al., 215

48 Satellite HCHO observations will help us test models of Australian isoprene emission OMI HCHO columns, DJF mol cm -2 J. Greenslade

49 Satellite HCHO observations will help us test models of Australian isoprene emission OMI HCHO columns, DJF mol cm -2 HCHO Column (1 15 mol cm OMI HCHO columns, mean yearly J F M A M J J A S O N D Month J. Greenslade

50 Satellite HCHO observations will help us test models of Australian isoprene emission OMI HCHO columns, DJF (an aircraft campaign would help, too!) mol cm -2 HCHO Column (1 15 mol cm OMI HCHO columns, mean yearly J F M A M J J A S O N D Month J. Greenslade

Satellite HCHO observations will help us test models of Australian isoprene emission OMI HCHO columns, 24-213 DJF (an aircraft campaign would

51 Satellite HCHO observations will help us test models of Australian isoprene emission OMI HCHO columns, DJF (an aircraft campaign would help, too!) mol cm -2 HCHO Column (1 15 mol cm OMI HCHO columns, mean yearly J F M A M J J A S O N D Month J. Greenslade

52 Take-home messages Thanks to NASA Tropospheric Chemistry Program & University of Wollongong Vice Chancellor s Fellowship for funding this work.

53 Take-home messages 1. Regionally interesting locations (Southeast US, Southeast Australia?) can help us answer globally relevant questions 2. Biogenic chemistry is critical for broader issues of air quality and composition (ozone, PM) especially as traditional pollution sources decline Thanks to NASA Tropospheric Chemistry Program & University of Wollongong Vice Chancellor s Fellowship for funding this work.

Uncertainties in isoprene-no x -O 3 chemistry: Implications for surface ozone over the eastern United States PAR TEMP

Uncertainties in isoprene-no x -O 3 chemistry: Implications for surface ozone over the eastern United States ISOPRENE + NO x O 3 PAR TEMP Leaf Area Arlene M. Fiore Telluride Atmospheric Chemistry Workshop