TROPOSPHERIC CHEMISTRY v TOPSE Tropospheric Ozone Production About

TROPOSPHERIC CHEMISTRY v TOPSE: Tropospheric Ozone Production About the Spring Equinox – Example of a division lead community initiative supported by NSF. – The benefit of a critical mass of observational and modeling capabilities. – Training opportunity for several young university scientists. – Provides useful data for future plans UT/LS. v HANK: ACD’s Regional Chemistry-Transport Model – Application to field campaign analysis – Community based regional model. v ACD Contributions to the NASA TRACE-P Campaign – Leveraging of NSF core funds to develop instruments and gain access to unique capabilities. – Direct involvement of several universities with ACD Investigators v MIRAGE : Megacity Impacts on the Regional And Global Environment – a new initiative with significant societal importance. – Potential for substantial University involvement. v Reactive Carbon Research Initiative. – Building upon existing capabilities to address new issues. – Significant potential for University Involvement. v MOPITT: The MOPITT Experiment on Terra – Enhanced by close relations to ACD. MOZART & HANK data assimilation – A community service funded by NASA & Canadian Agencies 1

Atmospheric Chemistry Division National Center for Atmospheric Research TOPSE: Tropospheric Ozone Production About the Spring Equinox Chris Cantrell Scientist III – Atmospheric Radical Studies 24 -26 October 2001, NSF Review Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 2

Primary Objective of TOPSE To investigate the chemical and dynamic evolution of tropospheric chemical composition over mid- to high-latitude continental North America during the winter/spring transition, with particular emphasis on the springtime ozone maximum in the troposphere. Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 3

Specific Scientific Questions Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 4

TOPSE Development Calendar ACD Internal Retreat Develop Preliminary White Paper Develop Science Proposal Letter of Intent to RAF TOPSE Proposal Distribution (NSF, Universities, Agencies) TOPSE Science Meeting Advertisement (EOS) TOPSE Open Workshop Proposal Submission to NSF OFAP Request for Advanced Reservation Director’s Fund Request (LIDAR installation) NSF Funding Approvals Aircraft Integration/Testing TOPSE Mission Mid-mission Science Meeting (NCAR) First Science Team Meeting (NCAR) AGU Special Session Second Science Team Meeting (Boston) Open Access to TOPSE Data Archive TOPSE Manuscripts to JGR (1 st round) Chris Cantrell March, 1997 Summer/Fall, 1997 Winter, Spring, 1998 April, 1998 June, 1998 Aug, 1998 October, 1998 Jan/Feb, 1999 Spring, 1999 Fall, 1999 Dec, 1999/Jan, 2000 Feb – May, 2000 Mar, 2000 Nov, 2000 May, 2001 June, 2001 Oct, 2001 TOPSE: Tropospheric Ozone Production about the Spring Equinox 5

TOPSE Investigators: Measurements Measurement Remote Ozone/Aerosols (DIAL) Acidic Trace Gases/7 -Be NMHC, Halocarbons, RONO 2, Peroxynitrates Speciated Peroxides OH, H 2 SO 4 HO 2, RO 2 HNO 3 NOx, NOy, Ozone CH 2 O, H 2 O 2 J values PAN, PPN CO, N 2 O Ultrafine Aerosols Mission Scientists/P. I. s Chris Cantrell Investigators Browell et al. , NASA Talbot, Dibb, et al. UNH Blake et al. , UCI Cohen, Thornton et al. , UCB Heikes, Snow, URI Eisele, Mauldin, NCAR Cantrell, Stephens, NCAR Zondlo, NCAR Ridley, Walega, NCAR Fried, NCAR Shetter, Lefer et al. , NCAR Flocke, Weinheimer, NCAR Coffey, Hannigan, NCAR Weber, GIT Atlas, Cantrell, Ridley, NCAR TOPSE: Tropospheric Ozone Production about the Spring Equinox 6

TOPSE Investigators: Modeling/Collaboration Regional/Forecast Model (HANK) Global Model Analysis (MOZART) Process and Radiation Models Global Model/Process Studies Stratosphere/Troposphere Exch. Regional/other Models Meteorological Forecast/ Remote Sensing Ozonesonde Network Investigators Klonecki, Hess et al. , NCAR Tie, Emmons et al. , NCAR Brasseur et al. , MPI Madronich et al. , NCAR Jacob, Evans, Harvard U. Allen, Pickering, U. Md. Wang et al. , Rutgers U. Moody, Cooper, Wimmers, U. Va. GOME Br. O Met. Forecasts (UT/LS) Polar Sunrise Expt. , 2000 Richter, Burrows, U. Bremen Newman, NASA Shepson, Purdue; Bottenheim, Can. Met. Serv. Chris Cantrell Merrill, URI; Fast, PNWL TOPSE: Tropospheric Ozone Production about the Spring Equinox 7

TOPSE Educational Activities Joel Thornton University of California-Berkeley Graduate student Rebecca Rosen University of California-Berkeley Graduate student Douglas Day University of California-Berkeley Graduate student Jennifer Murphy University of California-Berkeley Graduate student Daniel Murphy New Mexico Tech Undergraduate (Senior Thesis) Julie Snow University of Rhode Island Post-Doctoral Fan Lei University of Maryland Graduate Student Douglas Orsini Georgia Tech Post-Doctoral Baoan Wang Georgia Tech Graduate Student Mat Evans Harvard University Post-Doctoral Andrzej Klonecki NCAR ASP Craig Stroud NCAR ASP Brian Wert University of Colorado Graduate Student Anthony Wimmers University of Virginia Graduate Student Owen Cooper University of Virginia Graduate Student Jennifer Andrews University of Virginia Undergraduate Student Mark Zondlo NCAR ASP John Hair Old Dominion University Post-Doc Alton Jones Old Dominion University Graduate Student Aaron Katzenstein UCI Graduate student Barbara Barletta UCI Graduate student Simone Meinardi UCI Postdoc Alex Choi UCI Graduate student Changsub Shim Rutgers Univ Graduate student Linsey Debell Univ. New Hampshire Graduate student Eric Scheuer Univ. New Hampshire Graduate student Unfunded collaborators: Barkley Sive, Assistant Professor at Central Michigan University Oliver Wingenter, Assistant Professor at New Mexico Tech University Jodye Selco, Assistant Professor at The University of Redlands Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 8

TOPSE Flight Tracks Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 9

Some TOPSE Highlights • Seasonal variation in trace gases/aerosols • Evolution strong function of altitude and latitude • Decline in NMHC; Spring maximum in sulfate • PAN most significant odd-nitrogen component of NOy • Ozone evolution in the mid-troposphere • Increase about 20 ppb from Feb-May • Covariation in PANs, aerosols; no PV trend • Photochemical/surface sources implicated • Surface ozone depletion • Observations in early spring-May; broad geographical dist’n • Br-catalyzed ozone loss (as in earlier studies, but variable) • Long-range transport of depleted air suggested • Transport processes • Most sampled air masses representative of background mid-troposphere • Distant pollution sources were encountered in layers Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 10

Some TOPSE Highlights (cont’d) • In-situ photochemical processes • • • Stratosphere-troposphere exchange • • Measured radicals consistent with models (so far) Model/measurement of photolysis frequencies in agreement Some model/measurement discrepancy for CH 2 O, H 2 O 2, HNO 3 Calculated increase in in-situ ozone production in spring Remote sensing (satellite/lidar) indicate folds/streamers/STE(? ) In-situ encounters with lower stratosphere during flights 7 Be measurements suggest significant fraction of tropospheric ozone is from stratosphere. Seasonal modulation by photochemistry, but near constant ozone flux from stratosphere 3 -D modeling • • Chris Cantrell HANK/MOZART (Models used/evaluated extensively in campaign) DAO/Harvard (underway) TOPSE: Tropospheric Ozone Production about the Spring Equinox 11

Median Latitude and Altitude Profiles Latitude Profiles: Altitude Profiles (Blake – UCI) Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 12

Evolution of Sulfate Aerosol Vertical Distribution (Scheuer, Talbot, Dibb – UNH) Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 13

Ozone vertical profile: Evolution during winter-spring (Ridley, Walega) Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 14

Average Ozone Distributions During TOPSE (Browell et al. , NASA) Deployment 1 Deployment 3 Deployment 4 Deployment 5 Deployment 6 Deployment 7 Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 15

Model calculated O 3 production and loss 40 – 60 N; integrated surface to 9 km February 1. 7 ppb/mo April 14 ppb/mo March 7 ppb/mo May 12 ppb/mo (Y. Wang, Rutgers Univ) Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 16

7 Be – O 3 relationship and stratospheric influence during TOPSE 7 Be vs O 3 Observed “stratospheric influence” (Dibb et al. , UNH) Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 17

Surface Ozone Depletion Over Baffin Bay ODE from Thule to east side of Baffin Island Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 18

Transport of surface ozone hole to Hudson Bay Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 19

Summary • An ACD-led field campaign, with observational and numerical modeling components, was organized and carried out • Critical collaborations, in measurements & numerical modeling, with colleagues throughout the scientific community • Important contributions by graduate and postdoctoral students • 1 st round of scientific papers to be published mid-to-late 2002. Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 20

Atmospheric Chemistry Division National Center for Atmospheric Research HANK: ACD’s Regional Chemistry-Transport Model developed by Peter Hess 1 with contributions from A. Klonecki, J. F. Lamarque, M. Barth, L. Smith, S. Madronich 1 Theoretical Peter Hess Studies and Modeling Section HANK 37

HANK - Model Overview Chemical Transport Model driven from MM 5 • Resolution: variable (10 x 10 km – 250 x 250 km) • Chemistry: flexible gas and aqueous chemistry mechanism (TOPSE: 54 species, 145 reactions, 25 photolysis reactions) • Transport: Deep and shallow convection, boundary layer transport, advection • Physical Removal: Episodic dry and wet deposition • Adjoint model for sensitivity studies • Data assimilation package Peter Hess HANK 38

HANK SCIENCE • • Mauna Loa Photochemistry Experiment 1 – Nature of chemical transformations and transport across the Pacific – Subtropical free troposphere is a photochemically active region Tropospheric Ozone Production about Spring Equinox – Model run in real time and forecast mode – Transport’s role in the spring equinox photochemical transition Dust transport across Atlantic (UCSB) Emissions of U. S. Forest Fires (using MOPITT satellite data) 1 Hess, P. G. , S. Flocke, J. -F. Lamarque, M. C. Barth, and S. Madronich, Episodic modeling of the chemical structure of the troposphere as revealed during the spring MLOPEX intensive, J. Geophys. Res. , 105, 26809 -26839, 2000. Vukicevic, T. and P. G. Hess, Analysis of tropospheric transport in the Pacific Basin using the adjoint technique, J. Geophys. Res. , 105, 7213 -7230, 2000. Hess, P. G. , Model and measurement analysis of springtime transport and chemistry of the Pacific basin. J. Geophys. Res. , 106, 12689 -12717, 2001. Barth, M. C. , P. G. Hess, and S. Madronich, Effect of marine boundary layer clouds on tropospheric chemistry as analyzed in a regional chemistry transport model, J. Geophys. Res. , submitted, 2001. Peter Hess HANK 39

Pacific Basin Simulations (MLOPEX) § Adjoint Trajectory for pollutant plume to Hawaii § Same trajectory in heightlongitude plane §Chemical transformations and rainout along the trajectory Peter Hess HANK 40

TOPSE Simulations CO TRANSPORT OVER POLE § HANK was run in real-time and forecast mode during TOPSE § Seasonal cycle of constituents diagnosed § Important changes in both chemistry and transport during Spring transition Peter Hess HANK 41

HANK - Plans • MIRAGE modeling • Real time and forecast modeling of forest fire pollution • Continued development of adjoint technique – applications to data assimilation/inverse modeling – CO 2 emissions • Prototype model for WRF-Chem – Coupled meteorological and chemical model – WRF-Chem development group: P. Hess (Lead, NCAR), C. Benkovitz (Brookhaven National Lab), D. W. Byun (University of Houston), G. Carmichael (University of Iowa), K. Schere (EPA), P. -Y. Whung (NOAA ), G. Grell (NOAA, FSL), J. Mc. Henry (NCSC), Carlie Coats (NCSC), M. Trainer (NOAA, AL), B. Skamarock (NCAR), G. Peng, (Aerospace Corporation), J. Wegiel (AFWA), S. Yvon-Lewis (NOAA, AOML) Peter Hess HANK 42

Atmospheric Chemistry Division National Center for Atmospheric Research ACD Contributions to the NASA TRACE-P* Campaign Fred Eisele Senior Research Associate Photochemical Oxidation & Products 24 -26 October 2001, NSF Review *(TRAnsport and Chemical Evolution over the Pacific) Fred Eisele ACD contribution to TRACE-P 43

TRACE-P University Collaborations • • • • University of California-Irvine Drexel University Florida State University Georgia Institute of Technology Harvard University (mission scientist Daniel Jacob) University of Hawaii University of Iowa Massachusetts Institute of Technology University of Miami University of New Hampshire Pennsylvania State University of Rhode Island Max-Planck-Institut fur Meteorologie Nagoya University Fred Eisele ACD contribution to TRACE-P 44

MISSION OBJECTIVES Determine Asian outflow pathways Determine the chemical evolution of outflow Fred Eisele ACD contribution to TRACE-P 45

COMMON OBJECTIVES ACD Themes that overlap with TRACE-P objectives MIRAGE Reactive Carbon Biosphere, Chemistry, and Climate Clouds UT/LS Other synergistic activities ACE Asia Fred Eisele ACD contribution to TRACE-P 46

Measurement ACD Participants • Actinic flux • • Shetter, Lefer, Hall, Cinquini OH, H 2 SO 4, HNO 3, MSA Eisele, Mauldin, Kosciuch, Zondlo HO 2/RO 2 Cantrell Alcohols/Carbonyls Apel CH 2 O Fried, Walega, Wert PAN, PPN, MPAN Flocke/Weinheimer Organic Nitrates, halocarbons Atlas, Stroud, K. Johnson, Weaver MOPITT CO Gille et al. Fred Eisele ACD contribution to TRACE-P 47

TRACE-P Data Preliminary Data from TRACE-P This Data is provided for review information only and should not be cited until TRACE-P data is officially released to the public. Fred Eisele ACD contribution to TRACE-P 48

• TRACE-P Data Slides are not being included in hard copy or on the web at NASA’s request because this data has not yet been released to the public. Fred Eisele ACD contribution to TRACE-P 49

Measurement University collaboration. Instrument uniqueness Actinic flux only group doing these measurements in US OH, H 2 SO 4, MSA only airborne CIMS technique for OH, HNO 3 HO 2/RO 2 MSA, and (in US) for H 2 SO 4 - Georgia Tech only airborne HO 2/RO 2 CIMS in US Alcohol/Carbonyls only airborne - GC/MS system – U of Miami CH 2 O only airborne CH 2 O TDL technique in US U of Tulsa and U of Colorado PAN etc. no other university airborne GC/ECD for PANs Organic Nitrate unique combination of measurements-UC Irvine MOPITT unique satellite measurements – U of Toronto Fred Eisele ACD contribution to TRACE-P 50

SUMMARY • ACD contributed significantly to the success of TRACE-P • ACD’s unique measurements complemented those of the university research community and broadened mission capabilities • ACD is continuing to develop unique capabilities to fill measure voids Fred Eisele ACD contribution to TRACE-P 51

Future TRACE-P Contributions • Final data submission in December 2001 • Manuscript preparation and submission –Spring/Summer 2002 • TRACE-P data available to the public June 1, 2002 Fred Eisele ACD contribution to TRACE-P 52

Atmospheric Chemistry Division National Center for Atmospheric Research Megacity Impacts on the Regional And Global Environment An integrated multi-disciplinary program to study the export and transformations of pollutants from large metropolitan areas to regional and global scales. Sasha Madronich Senior Scientist Theoretical Studies and Modeling (TSM) Sasha Madronich MIRAGE 53

History • 1998 Oct. : Open workshop at NCAR • 1999: Proposal for pilot Mexico City study PI’s: Darrel Baumgardner, Guy Brasseur Reviewed by NSF, not supported at that time _________________________________ • 2000 Aug. : NCAR decides to revive activity • 2000 Sept. - Nov. : NCAR planning meetings – Develop multidisciplinary plan with 5 focal areas • 2001 Jan. - present: Integrate in ACD Strategic plan • 2001 Spring - present: Define ACD role Sasha Madronich MIRAGE 54

Working Groups ACD: ASP: MMM: ESIG: ATD: Sasha Madronich C. Cantrell, A. Guenther, P. Hess, S. Madronich, S. Massie, J. Orlando, R. Shetter, G. Tyndall, Frank Flocke S. Durlak, A. Gettelman F. Chen, W. Dabberdt, W. Skamarock, T. Warner B. Harriss, K. Miller, K. Purvis L. Radke MIRAGE 55

New Scientific Foci Gas Phase Chemistry: Export of gaseous pollutants and oxidation intermediates, and their role in regional/global ozone and aerosol budgets. Aerosol Chemistry and Physics: Evolution of aerosol composition and physical properties, their interactions with gas phase species, and their role in climate directly via scattering/absorption and indirectly via cloud formation. Radiation: High pollution levels can alter incident solar radiation, modifying both photochemistry and heating rates. Local and Regional Meteorology: Large urban areas can modify local meteorology, which in turn controls ventilation and the export of gases and aerosols. Urban Metabolism: The mix of pollutants in developing cities is very different from that in large industrialized cities. Future growth of emissions will also differ depending on many socio-economic factors. Sasha Madronich MIRAGE 56

Gas Phase Photochemistry - 1 Example of non-linearity of chemistry: Downwind re -inflation of Ox production d[Ox]/dt > 0 when R(OH+CO)>R(OH+NO 2) S. Rivale (SOARS) and S. Madronich, unpubl. 1999 Sasha Madronich MIRAGE 57

Gas Phase Photochemistry - 2 Example of chemical complexity: Persistence of oxygenated organic intermediates Madronich and Calvert 1990, uptdated by C. Stroud 2001 Sasha Madronich MIRAGE 58

Aerosol Physics and Photochemistry Example of aerosol-gas phase coupling: Growth of organic aerosol by dissolution of gas phase species Aumont et al. , 2000 Sasha Madronich MIRAGE 59

Radiation in Polluted Environments Photolysis rates in polluted conditions: Castro et al. 2001 Sasha Madronich MIRAGE 60

Local and Regional Meteorology • Changed Geophysical Properties of Urban Surfaces – – – Anthropogenic sensible heat flux (up to 200 W m-2) Anthropogenic latent heat flux (not well known) Aerodynamic roughness (zo values up to several meters) Aerodynamic displacement height (tens of meters) Surface runoff Heat transfer characteristics of the “ground” (thermal conductivity and volumetric heat capacity); surface and soil wetness – Surface albedo • Potential Interactions with Air Pollution – Radiative (e. g. vertical distributions soot) – Chemical (e. g. amount and type of cloud condensation nuclei) Sasha Madronich MIRAGE 61

Urban Metabolism - 1 World’s largest cities Sasha Madronich MIRAGE 62

Urban Metabolism - 2 Emissions in developing cities are very different than in developed cities Sasha Madronich MIRAGE 63

Site Selection Criteria - 1 Megacity characteristics (ranked by population in 2000) Sasha Madronich MIRAGE 64

Site Selection Criteria - 2 Ø Pollution signal strength relative to background Sasha Madronich CO from MOPPIT MIRAGE 65

Site Selection - 5 Sasha Madronich MIRAGE 66

ACD’s Capability-based Foci • Distributions – Local emissions and concentrations – Surrounding emissions and concentrations – UV radiation • Processes – Gas phase photo-chemistry, esp. evolution of oxygenated and nitrogenated organics – Aerosol growth and interactions with gas-phase Sasha Madronich MIRAGE 67

The Next Steps • Tentative site selection • Identify key collaborators (esp. at site) • Develop proposal, distribute for critique by community with call for input, collaborations • Hold community workshop • Develop implementation plan Sasha Madronich MIRAGE 68

Atmospheric Chemistry Division National Center for Atmospheric Research Reactive Carbon Research Initiative Elliot Atlas Senior Scientist Stratospheric/Tropospheric Measurements Group 24 -26 October 2001, NSF Review Elliot Atlas Reactive Carbon Research Initiative 69

Reactive Carbon in the Atmosphere Significance • Impact on tropospheric oxidant cycles • Urban, regional, global scales • Upper troposphere/lower stratosphere • Biosphere-atmosphere exchanges • Carbon exchange • Nitrogen cycling From P. Shepson • Role in aerosol processes and climate • Aerosol organic composition/processing • Hygroscopic properties/nucleation • Impact on stratospheric chemistry • Organic halogen • Methane/water vapor Elliot Atlas From P. Newman/SOLVE Reactive Carbon Research Initiative From A. Guenther From J. Seinfeld 70

Reactive Carbon Research Initiative Motivation To better understand the evolution, fate and interactions of reactive carbon in the atmosphere. Issues 1. What are products of biogenic and anthropogenic carbon oxidation? What is the distribution of these products in the atmosphere? 2. What are links between carbon oxidation and the nitrogen cycle? 3. How does reactive carbon oxidation and product formation affect atmospheric oxidant production and loss? 4. How do reactive carbon oxidation products influence aerosol production, composition, and growth? 5. What are the significant sources (and sinks) of reactive carbon? What is variation of surface exchanges and controlling variables? Elliot Atlas Reactive Carbon Research Initiative 71

Reactive Carbon Research Initiative Approach Coordination of ACD and community research to address specific questions using a combination of existing and developing measurement technology, model simulations, laboratory studies and field investigations. Focus on quantitative understanding of selected trace gases representative of different major sources. Biogenic – Isoprene and selected terpenes Anthropogenic – Toluene; Selected others Implementation in process studies and incorporation in larger field efforts. Elliot Atlas Reactive Carbon Research Initiative 72

Reactive Carbon Research Initiative Research Foci: – Atmospheric history of reactive carbon – Carbon – nitrogen interactions – Aerosol processes and organic interactions – Radicals and oxidants – Emission and deposition fluxes – Development of tools and techniques Elliot Atlas Reactive Carbon Research Initiative 73

Reactive Carbon Research Initiative Atmospheric history of reactive carbon Laboratory Investigations: Basic alkoxy/peroxy radical investigations Aromatics oxidation Isoprene/Terpene product studies Model Investigations: Updated Master Mechanism Gas-aerosol partitioning Field Investigations: Process studies: Predicted vs. measured products Survey studies: Investigations related to specific source regions (MIRAGE, etc. ) Source profiles from developing regions. Effects of land-use change. Elliot Atlas Reactive Carbon Research Initiative 74

Temperature effects on CH 2 O yield NCAR 1997 evaluation (G. Tyndall, J. Orlando) Elliot Atlas Reactive Carbon Research Initiative 75

Isoprene and oxidation products in Houston Isoprene Methyl Vinyl Ketone Methacrolein CMBO/CMBA OH and O 3 Cl Chloromethylbutenone (CMBO) Elliot Atlas Chloromethylbutenal isomers (CMBA) Reactive Carbon Research Initiative Daniel Riemer, UM Eric Apel, NCAR 76

Reactive Carbon Research Initiative Carbon – nitrogen interactions Laboratory Investigations: Product/yield studies: Hydroxy-, multifunctional nitrates PANs Model Investigations: Updated Master Mechanism Gas-aerosol partitioning Field Investigations: Process studies: Predicted vs. measured products Survey studies: Investigations related to specific source regions (Biogenic emissions), Role of PANs in UT/LS region Elliot Atlas Reactive Carbon Research Initiative 77

Initial pathways for isoprene oxidation (from Sprengnether et al. , submitted) Elliot Atlas Reactive Carbon Research Initiative 78

a-Pinene oxidation scheme (Kamens and Jaoui, 2001) Elliot Atlas Reactive Carbon Research Initiative 79

GC-NICI-MS of complex organic nitrates in Blodgett Forest C 4 -C 6 + alkyl nitrates Isoprene + multifunctional nitrates Terpene nitrates? 46 = NO 262 = NO 3 - m/e=169 (Cohen, Day –UCB; Atlas, Flocke – NCAR) Elliot Atlas Reactive Carbon Research Initiative 80

Reactive Carbon Research Initiative Aerosol processes and organic interactions Laboratory Investigations: Organic acid formation Secondary product/aerosol reactions Role of organics in nucleation Model Investigations: Updated mechanism Gas-aerosol partitioning Incorporation in larger scale models Field Investigations: Process studies: Predicted vs. measured products Survey studies: Investigations related to specific source regions (Biogenic emissions/Urban plume) Elliot Atlas Reactive Carbon Research Initiative 81

Composition of WSOC in biomass burning aerosol from Amazonia (Graham et al. , JGR) Elliot Atlas Reactive Carbon Research Initiative 82

Organics…A role in new particle formation? Critical nucleation cluster (tentative identification) NH 3 Amines vs. ammonia? RNH 2 Elliot Atlas H 2 SO 4 (Hanson and Eisele) H 2 SO 4 Organic acids vs. sulfuric? R(OH)COOH Reactive Carbon Research Initiative 83

Reactive Carbon Research Initiative Radicals and oxidants Laboratory Investigations: Photochemically active organics as radical source RO 2 speciation as tool to understand reactive carbon degradation Model Investigations: Role of reactive carbon in cycling OH/HO 2/RO 2 Model update and prediction of oxidant production Field Investigations: Process studies: Predicted vs. measured radical sources/sinks and oxidant production. Elliot Atlas Reactive Carbon Research Initiative 84

Observations of RO 2 – cloud interactions Cantrell et al. Elliot Atlas Reactive Carbon Research Initiative 85

Reactive Carbon Research Initiative Emission and deposition fluxes Laboratory Investigations: Leaf/Branch level emission studies Model Investigations: Flux parameterization/Controlling variables Gas-aerosol partitioning Incorporation in larger scale models Field Investigations: Process studies: Evaluation of emission fluxes from different environments; Estimation of deposition fluxes Survey studies: Improved estimation of speciated VOC emissions/oxidation products (esp. biogenic VOC) Elliot Atlas Reactive Carbon Research Initiative 86

Oxy. VOC emissions from a Colorado alfalfa field before and after cutting drying e Cutting growing Rinne et al. GRL 28: 3139 -3142 (2001) (Rinne, Guenther) Elliot Atlas Reactive Carbon Research Initiative 87

Reactive Carbon Research Initiative Development of tools and techniques Laboratory Flow tube and smog chamber Integrated MS techniques Gas-aerosol partitioning Model Incorporation and update with relevant results Field Gas phase chemistry: PTR/MS, MS/MS, Fast GC/MS, TDL emissions and oxidation products Aerosol organic chemistry: Aerosol Ion Trap: particle composition LC/MS: water soluble organic carbon Elliot Atlas Reactive Carbon Research Initiative 88

New instrument development (examples) Ultrafine Organic Aerosol Instrument (J. Smith) LC/MS/MS for water soluble organics (E. Atlas) Elliot Atlas Reactive Carbon Research Initiative 89

Reactive Carbon Research Initiative Relationship to existing and planned research MIRAGE Focus on reactive carbon evolution/Tracers Aerosol characterization/reactions Laboratory investigations UT/LS VOC as sources of ROx VOC as transport tracers/halogen sources Clouds Water soluble organic characteristics VOC partitioning Source tracer measurement Biosphere, Chemistry and Climate Flux estimates of VOC from different environments Elliot Atlas Reactive Carbon Research Initiative 90

Atmospheric Chemistry Division National Center for Atmospheric Research The MOPITT Experiment on Terra John Gille Senior Scientist MOPITT and HIRDLS Groups 24 -26 October 2001, NSF Review John C. Gille The MOPITT Experiment on Terra 91

MOPITT OVERVIEW Measurements Of Pollution In The Troposphere • Joint University of Toronto/NCAR satellite instrument project • Developed from Prof. James Drummond’s sabbatical at NCAR • in 1987 University of Toronto and NCAR supporting project with their expertise Measurement Goals: Obtain long term global measurements of: Profiles and columns of Tropospheric CO Total columns of CH 4 Demonstrate capability to make and use measurements of tropospheric composition from space Applications: Improve knowledge of sources, sinks and transformations Testing and improvement of model transport and chemistry John C. Gille The MOPITT Experiment on Terra 92

MOPITT Investigators Principal Investigator - James Drummond, UT (CSA Funding) Instrument development, calibration, orbital operation Lead U. S. Investigator - John Gille, NCAR (NASA Funding) Develop, test, apply and update data processing algorithms Co-Investigators G. P. Brasseur, Max Planck Institute G. R. Davis, University of Saskatoon J. C. Mc. Connell, York University G. D. Peskett, Oxford University H. G. Reichle, North Carolina State University N. Roulet, Mc. Gill University Further information at http: //www. eos. ucar. edu/mopitt/home. html John C. Gille The MOPITT Experiment on Terra 93

The NCAR/ACD MOPITT Team John Gille US Principal Investigator David Edwards NCAR Project Leader Jarmei Chen Merritt Deeter Louisa Emmons Gene Francis David Grant Alan Hills Shu-peng Ho Boris Khattatov John C. Gille Jean-Francois Lamarque Debbie Mao Jianguo Niu Dan Packman Barb. Tunison Juying Warner Valery Yudin Dan Ziskin The MOPITT Experiment on Terra 94

History of MOPITT • • 1987 - Prof. James Drummond takes sabbatical at NCAR with John Gille Possibilities for measurement of tropospheric CO discussed 1988 - MOPITT proposed to NASA 1989 - Provisional acceptance, beginning of retrieval studies at NCAR 1990 - Acceptance for development – Development and testing of retrieval algorithms and operational code at NCAR 1999 - Launch in December 2000 - (March) Reach final orbit, begin data collection (September) Filter position determined, initial good data retrievals 2001 - (May) Cooler failure, instrument in Safe Mode (June) Begin testing Retrieval Beta version (July) Instrument restarted with single cooler (August) PMC modulation increased John C. Gille The MOPITT Experiment on Terra 95

MOPITT Instrument: 8 channel nadir viewing gas correlation radiometer 4 channels @ 4. 7 mm - thermal emission from atmosphere and sfc. 4 channels @ 3. 3 mm - reflected solar radiation Gas correlation radiometer reduces effects of interfering species, at the expense of radiative transfer complexity Sensitivity to small radiance changes The MOPITT instrument and the measurement technique are new: Lessons are being learned in both instrument operation and data processing John C. Gille The MOPITT Experiment on Terra 96

MOPITT Standard Scientific Products - Level 1 data products - Calibrated and geo-located radiances - Level 2 data products - Tropospheric CO profiles with a 22 km horizontal resolution Mixing ratios at surface, 850, 700, 500, 350, 250, 150 h. Pa with 10% precision - CO total column with 10% precision - CH 4 total column with 1% precision - Level 3 data products (initially a research product) - Gridded global CO distribution - Gridded global CH 4 distribution John C. Gille The MOPITT Experiment on Terra 97

MOPITT Data Processing L 1 NCEP Clim John C. Gille Input Cloud Retrieval Forward Model The MOPITT Experiment on Terra L 2 Maximum Likelihood method 98

Monthly mean (2000) CO 700 mb March June Sept Dec John C. Gille The MOPITT Experiment on Terra 100

MOPITT Level 2 CO Column Plumes from western forest fires clearly seen MOPITT Level 2 CO total column shows: • High CO amounts correlate with areas of industrial pollution and biomass burning • Inter-continental transport • Good comparison with insitu aircraft and FTIR data Aug 20 -27 2000 John C. Gille The MOPITT Experiment on Terra 101

MOPITT Data Assimilation in MOZART 2 John C. Gille The MOPITT Experiment on Terra 102

Accomplishments Since Launch • Diagnosis and correction of instrument artifacts, development of preliminary algorithm • Public release of preliminary CO total column and profile retrievals in September 2001 • Validation begun with comparisons against Trace -P, CMDL and other profiles and FTIR total column • Real-time data provided for TRACE-P flight planning in February-March 2001 • Assimilation of MOPITT data with the MOZART-2 CTM John C. Gille The MOPITT Experiment on Terra 103

Initial Example of Single Cooler Data John C. Gille The MOPITT Experiment on Terra 105

Future plans 1. Three Major Thrusts 1. Algorithm improvements 1. e. g. Retrieve CH 4 column data 2. Reduce retrieval bias, other artifacts 3. Cloud detection and clearing, using MODIS data 2. Data quality assessment (“Validation”) 1. vs. A/C profile measurements from. Trace-P, CMDL, other 2. vs. ground based FTIR column measurements 3. Application of data 1. To studies of transports, sources, chemical impacts 2. Inverse modeling to constrain surface emissions 3. Participation in campaign planning (e. g. MIRAGE) John C. Gille The MOPITT Experiment on Terra 106

Future Outlook Studies of tropospheric chemistry from space is in its infancy, but offers great promise Data assimilation will be extremely important in scientific studies ACD has expertise in remote sounding and data assimilation, and plans to remain involved in this kind of activity Possible future activities • Involvement in SCIAMACHY validation and data use • Interactions with Tropospheric Emission Spectrometer on Aura • “MOPITT - 2” under discussion • Evaluation of other instrumental approaches • Collaboration with other experimental groups John C. Gille The MOPITT Experiment on Terra 107