Atmospheric Chemistry Division National Center for Atmospheric Research

Atmospheric Chemistry Division National Center for Atmospheric Research NCAR/ACD Biosphere-Atmosphere Trace Gas Exchange Alex Guenther Scientist III Biosphere-Atmosphere Interactions Group 24 -26 October 2001, NSF Review Alex Guenther Biosphere-Atmosphere Trace Gas Exchange

Biosphere-atmosphere trace gas exchange, earth system coupling and human forcing Air pollutants Trace gas Emission Chemical Radiative Environment balance Physical O 3, NOx, CH 4 Environment RONO 2 , OH, N 2 O, CO 2 Trace gas Temper. , Human deposition Activities light Biosphere Landcover change Alex Guenther Biosphere-Atmosphere Trace Gas Exchange 2

Days Hours • Regional/global modeling • Model evaluation • Process studies Enclosure flux meas. systems Leaf Satellite derived estimates of global distributions Tower-based flux meas. systems Aircraft and blimpbased flux measureme nt systems Seconds TIME SCALE Years Trace Gas Flux Studies Canopy Landscape Analysis using ambient concentrations, isotopes and oxidation products Regional/global SPATIAL SCALE Alex Guenther Biosphere-Atmosphere Trace Gas Exchange 3

Research Activities and Products Instrument Development Tools for Universities and Others Flux Measurement Systems Flux Measurements Database and Algorithm Development and Evaluation Alex Guenther Measurement Database Emission Inventories (IGAC-GEIA) Emission Models (BEIS/GLOBEIS) Coupled Models (CCSM, WRF) Biosphere-Atmosphere Trace Gas Exchange 4

Flux System Development and Technology Transfer Enclosure Systems • • Automated multi-enclosure system with online GC and fast response VOC analysis Inexpensive leaf cuvette measurement systems Eddy Flux Systems • • Relaxed eddy accumulation Disjunct eddy accumulation and eddy covariance Tethered Balloon Sampling Systems • VOC samplers, integrated ozone, CO 2, T, RH University Users & Technology Transfer Recipients: Georgia Tech. , U. Colorado, Wash. State U. , South Dakota Tech. , U. C. Irvine, U. C. Berkeley, Philadelphia University, U. Wisconsin, U. Wyoming, ETH-Zurich, Edinburgh U. , Lancaster U. , U. Witwatersrand, U. Sao Paulo, U. Aviero Alex Guenther Biosphere-Atmosphere Trace Gas Exchange

1996 -2001 NCAR/ACD Tropical BVOC Studies SAFARI La Selva (Costa Rica) EXPRESSO (S. Africa) (C. Africa) LBA (Amazon) Alex Guenther Xishuangbanna (China) Biosphere-Atmosphere Trace Gas Exchange 6

Tropical BVOC Investigators NCAR/ACD staff: Bill Baugh, Guy Brasseur, Jim Greenberg, Alex Guenther, Peter Harley, Lee Klinger, Sasha Madronich NCAR/ACD students and post-docs: Brad Baker, Sue Durlak, Bai Jianhui, Pierre Prevost, Janne Rinne, Dominique Serca, Perola Vasconcellos, Lee Vierling University Collaborators: Paulo Artaxo, Clobite Bouka-Biona, Deborah Clark, Nick Hewitt, Toni James, Jules Loemba, Hank Loescher, Yadvinder Mahli, Williams Martins, Luanne Otter, Sue Owen, Emiliano Pegoraro, Elmar Veenendaal, Oscar Vega Other Collaborators: Chris Geron, Juergen Kesselmeier, Luciana Vanni Gatti, Qing Jun Alex Guenther Biosphere-Atmosphere Trace Gas Exchange 7

Why Investigate Tropical Biogenic VOC? 1. Large fraction of global biogenic VOC emissions 2. Strong vertical transport 3. Rapid land use change Alex Guenther Isoprene from other regions (21%) Isoprene from tropics (79%) Biosphere-Atmosphere Trace Gas Exchange 8

NCAR/ACD Enclosure Measurements Tropical rainforests Costa Rica: 50% (weighted average) W. Amazon: 40% What fraction of woody plants emit isoprene? E. Amazon : 25% Congo: 20% (weighted average) South China: 15% (weighted average) Tropical savannas African savannas (3 types): 5 -15% (weighted) African savannas (4 types): 25 -50% (weighted) Australian savannas (2 types): 55 -70% (weighted average) Alex Guenther Biosphere-Atmosphere Trace Gas Exchange 9

Isoprene Emission Response Do tropical and temperate plants respond similarly? Temperature growth envir. Alex Guenther Light growth environment Biosphere-Atmosphere Trace Gas Exchange 10

NCAR/ACD Eddy Flux Measurements Mean Midday Net Flux Tropical Isoprene Flux Summary Costa Rica: 1. 5 -3 mg C m-2 h-1 E. Amazon: 1 -3 mg C m-2 h-1 Congo: 1 -2. 5 mg C m-2 h-1 Botswana: <0. 5 mg C m-2 h-1 S. Africa: <0. 5 mg C m-2 h-1 Diurnal Variations Tapajos, Brazil Maun, Botswana Alex Guenther Biosphere-Atmosphere Trace Gas Exchange 11

NCAR/ACD Concentration Measurements Average midday mixed-layer isoprene from aircraft and blimp sampling W. Amazon: 15 -34 ppb. C (forest) 8 ppb. C (pasture/forest) E. Amazon: 2 ppb. C (pasture/forest) Congo: 5 ppb. C (forest) Central Africa: 2 ppb. C (degraded forest) Oxy-VOC over tropical landscapes Hexanal, hexenol, hexenal: 0. 1 - 1. 5 ppb. C Acetone, methanol, toluene, formaldehyde, acetaldehyde: 1 – 10 ppb. C Alex Guenther Characterizing the combined influence of regional emissions, transport and chemistry Biosphere-Atmosphere Trace Gas Exchange 12

Modeling BVOC Emission Distributions at 1 km 2 spatial resolution Foliage density % broadleaf tree foliage % shrub foliage Floristic regions Alex Guenther Biosphere-Atmosphere Trace Gas Exchange 13

Characterizing Tropical Floristic Regions (regions with genetically related vegetation) 1. NCAR/ACD/BAI studies (14) 3. Studies from similar regions (17) 2. Other tropical studies (4) 4. Default values (8) Alex Guenther Biosphere-Atmosphere Trace Gas Exchange 14

NCAR/ACD Tropical BVOC Publications EXPRESSO special section of J. Geophysical Research 104 (1999) NCAR/ACD authorship on tropical BVOC papers • 7 published (5 EXPRESSO, 2 LBA) • 6 submitted (2 EXPRESSO, 1 LBA, 1 China, 1 Costa Rica, 1 SAFARI/KALAHARI) • 10 in preparation (5 LBA, 4 SAFARI, 1 China) The authorship of these publications includes more than 35 university and other collaborators Alex Guenther Biosphere-Atmosphere Trace Gas Exchange 15

Future Directions for Biosphere-Atmosphere Trace Gas Exchange Investigations ACD MIRAGE Initiative ACD Reactive Carbon Init. ACD Bio. Chem. Climate Init. NCAR Biogeosci. Initiative NCAR Wildfire Initiative Alex Guenther Landcover change: plantations, crop, urban Secondary org. aerosols Reactive C and N interact. Terpenoid, oxy. VOC, org. N, O 3, NH 3, NOy exchange Aircraft flux measurements Trace gases (C, N, O 3) and the carbon cycle Climate variability, stress (flood, fire, frost) Biosphere-Atmosphere Trace Gas Exchange Community Climate System Model (CCSM) Weather Research and Forecast Model (WRF) 16

Atmospheric Chemistry Division National Center for Atmospheric Research ACD Participation in NCAR Initiatives 1) Biogeosciences Initiative 2) Wildfire Initiative Elisabeth A. Holland Scientist 3, Global Modeling Group, affiliated with Biosphere, Atmosphere Interactions Group, ACD, and Land Section in CGD 23 -24 October 2001, NSF Review Beth Holland NCAR Initiatives

Human forcing and chemistry coupling Air pollutants Chemical Radiative Environment balance Physical O 3, NOx, CH 4 Environment RONO 2 , OH, CO 2 , N 2 O, NOy Trace gas temp, Biogenic VOC deposition light Emission Human Activities Biosphere Landcover change Beth Holland NCAR Initiatives 18

Chemistry CO 2, CH 4, N 2 O O 3, VOCs, NOx, aerosols Biogeochemistry Aerodynamics Carbon Assimilation Decomposition Mineralization Water Biogeophysics Energy Minutes-To-Hours Heat Moisture Momentum Microclimate Canopy Physiology Days-To-Weeks Years-To-Centuries Beth Holland Climate Temperature, Precipitation, Radiation, Humidity, Wind Evaporation Transpiration Snow Melt Infiltration Runoff Hydrologic Cycle Phenology Intercepted Water Snow Soil Water Hydrology Bud Break Leaf Senescence Species Composition Ecosystem Structure Nutrient Availability Water Gross Primary Production Plant Respiration Microbial Respiration Nutrient Availability Watersheds Ecosystems Surface Water Subsurface Water Geomorphology Species Composition Ecosystem Structure Vegetation Dynamics NCAR Initiatives Disturbance Fires Hurricanes Ice Storms Windthrows 19

Fit with NSF Geosciences Plan NSF Geosciences Beyond 2000: Understanding and Predicting Earth’s Environment and Habitability, section on Planetary Metabolism: “Understanding how the fluxes of mass and energy among various components of the solid and fluid Earth link to biological activity on and beneath its surface represents a fundamental goal of current research. This understanding of planetary metabolism bears directly on key scientific questions concerning the co-evolution of different components of the Earth system including life, as well as on the most pressing environmental questions of our time. Present understanding of these issues is very incomplete; the attack on the problem will require extensive interdisciplinary collaboration and will rely upon the achievements of all. This attack will employ a hierarchy of models; it will include interdisciplinary problem analysis and the synthesis, interpretation, and application of global-scale data sets, including those obtained by continuous monitoring from space and from new land ocean-based observing systems. “ This plan fits with two of the ” five primary challenges facing researchers in the study of planetary metabolism: 1. determining how the biogeochemical cycles of carbon, nitrogen, oxygen, phosphorus, and sulfur are coupled; 5. developing sufficiently sophisticated models to explain historic events and predict future changes in planetary metabolism. ” http: //www. geo. nsf. gov/adgeo/geo 2000 Beth Holland NCAR Initiatives

WHY NOW? • Decade of land model development led by Gordon Bonan has produced the state of the art model for surface energy, water and carbon dioxide exchange and a framework which facilitated the implementation of surface chemical exchanges. • Component models of reactive C and N exchanges have been developed by Alex Guenther and me and are ready for implementation in the land model. This effort was conducted in parallel with Gordon’s effort. • The growing number of measurements of surface fluxes and concentrations of reactive carbon and nitrogen are now available for model evaluation. • Fast track development of this model coupling will give us a tool to articulate and refine key global science questions for the next 5 -10 years. Beth Holland NCAR Initiatives

Wet and Dry Deposition Fluxes for the U. S. dry deposition flux of particulate NH 4+ wet deposition flux of NH 4+ dry deposition flux of gaseous HNO 3 wet deposition flux of NO 3 - dry deposition flux of particulate NO 3 - Beth Holland NCAR Initiatives 22

Wet and Dry Deposition Fluxes for Europe wet deposition of NH 4+ wet deposition flux of NO 317. 1 8. 1 1. 9 8. 6 4. 1 0. 9 0. 0 dry deposition of gaseous HNO 3 dry deposition of gaseous NO 2 Beth Holland dry deposition of particulate NH 4+ dry deposition of particulate NO 3 - 11. 2 11. 1 3. 1 5. 6 5. 5 1. 6 0. 0 NCAR Initiatives 23

Model Comparisons Beth Holland NCAR Initiatives 24

Societal Relevance • The coupling of biosphere feedbacks to the chemical and climate system was identified as a key gap in our understanding of current and future changes in atmospheric composition in the IPCC 2001 report. • The coupling directly and indirectly impacts concentrations of key greenhouse gases specified in the Kyoto protocol: CO 2 , CH 4, N 2 O, and O 3, • This will provide us with the tools for evaluating future climate, atmospheric composition, and air quality needed for integrated assessments. Beth Holland NCAR Initiatives

Partners ACD: Alex Guenther, Bill Baugh, Doug Kinnison, J. F. Lamarque, Danny Mc. Kenna, Robbie Staufer, Xuexi Ti, Stacy Walters, Christine Wiedinmyer CGD: Gordon Bonan, Sam Levis, Phil Rasch, Peter Thornton University Collaborations: Inez Fung, UC-Berkeley Bill Parton, Colorado State University Beth Holland NCAR Initiatives 26

Science Questions • How do the bio-atmospheric cycles of carbon and nitrogen interact to influence the oxidizing capacity of the atmosphere and climate? – now? – over the course of recent decades? – pre-industrially – and in the future? • How is this coupling influenced by key processes? – urbanization? – wildfires? – land cover change? – human activity? Beth Holland NCAR Initiatives

Biogeosciences Initiative: Measurements • • Goals of Measurement Component: – Sensor development – Deployment on airborne, surface network, balloon platforms Instrument Development Goals: – Continue improvements to airborne CO and CO 2 trace gas measurements, initially funded by the NCAR Directors’ Opportunity Fund, and internal ACD and ATD funds. – Conversion of an existing O 2/N 2 shipboard instrument for airborne operations. – Development of an improved chemical/meteorological tethersonde, applying the same technology to improved chemical sensors for ATD’s surface flux system. These advances may lead eventually to new capabilities for dropsondes and surface towers. Collaborative effort involving ACD, ATD, MMM, and RAP Beth Holland NCAR Initiatives

ACD Wildfire Research Questions • Are there relationships between the processes controlling oxygenated VOC emissions from ambient temperatures and wildfire heat stressed vegetation ? • Do VOC emissions have a significant role in wildfire combustion physics ? • Are the landcover databases developed for biogenic emission modeling useful for wildfire modeling? Beth Holland NCAR Initiatives 29

Atmospheric Chemistry Division National Center for Atmospheric Research MOZART and future global tropospheric modeling in ACD Danny Mc. Kenna Division Director 24 -26 October 2001, NSF Review Danny Mc. Kenna MOZART and global tropospheric modeling

MOZART: Model for OZone And Related chemical Tracers MOZART was developed by ACD as a contribution to NSF’s Global Tropospheric Chemistry Program (GTCP). MOZART was to develop a community tool capable of: • Understanding the influence of photochemical and transport processes on the global distribution of chemical compounds in the atmosphere. • Quantifying the global and regional budgets of these compounds • Assisting in the interpretation of field measurements and in the assimilation of space observations • Predicting the evolution of the atmospheric composition in response to natural and human-induced perturbations Danny Mc. Kenna MOZART and global tropospheric modeling

MOZART Development and User Community ACD Other Institutions – Danny Mc. Kenna – Guy Brasseur (MPI, Hamburg) – Louisa Emmons – Denise Mauzerall (Princeton) – Doug Kinnison – Mike Newchurch (University of Alabama) – J. F. Lamarque – Don Wuebbles (Univ. of Illinois) – Xuexi Tie – Derek Cunnold (Georgia Tech) – Stacy Walters – Larry Horowitz (NOAA GFDL) – Claire Granier (NOAA, SACNRS) – Didier Hauglustaine (SACNRS, Paris) – J. -F. Muller (Belgian Inst. Space Aeronomy) – Martin Schultz (MPI Hamburg) CGD – Phil Rasch Web Page… http: //acd. ucar. edu/models/MOZART/ Danny Mc. Kenna MOZART and global tropospheric modeling

MOZART is a Community Model - Three Versions • MOZART-1: is a Global Tropospheric Chemical-Transport Model • Brasseur et al. , 103, No. D 21, J. Geophys. Res. , 28265 -28289, 1998. • MOZART-2: is a revised version of MOZART-1 • Improvements in the surface emissions, chemical mechanism, and advection. • Description paper (Horowitz et al. , JGR, in preparation, 2001). • Release by January 1, 2002. • MOZART-3: extension of MOZART-2. Stratospheric and Mesospheric chemical and physical processes. • EOS/Aura pre-launch algorithm development. • EOS/Aura HIRDLS data assimilation. • The MOZART-3 framework “test bed” for WACCM chemistry development • Estimated release Spring/Summer 2002. Danny Mc. Kenna MOZART and global tropospheric modeling

MOZART Structure Data Assimilation Analyzed Met. Fields e. g. , MOPITT CO, CH 4 HIRDLS Species e. g. , DAO, ECMWF, NCEP MOZART MATCH Transport + Physics Versions 1, 2, 3 Preprocessor Incorporates: Climate Model Met. Fields e. g. , MACCM 3 Danny Mc. Kenna 1) Machine Architecture 2) Chem. Mech. /Solution Approach 3) Emissions 4) Wet/Dry Deposition 5) Advection, Diff. , Convection 6) Input/output MOZART and global tropospheric modeling

MOZART-2 Description • Resolution (typical) – 278, 528 Grid Cells: • Surface to approximately 40 km altitude – 1 -2 km resolution • Horizontal Resolution: 2. 8° X 2. 8 ° • Dynamical Processes: • Met. Fields: Driven by MACCM 3 or Analyzed Fields (e. g. , NCEP)- winds and temperatures • Advection: Flux-form semi-Lagrangian advection scheme of Lin and Rood [1996] • Convection: Rediagnosed from MATCH using Hack [1994] for mid-level convections and Zhang and Mac. Farlane [1995] scheme for deep convection • Boundary layer exchange: Parameterization of Holstag and Boville [1993] • Wet and Dry Deposition: • Wet deposition: - Represented as a first-order loss process within the chemistry operator, using large scale and convective precipitation rates diagnosted by MATCH. - Highly soluble species are removed by in-cloud scavenging and below cloud washout (Brasseur et al. , 1998) - Mildly soluble species removed by in-cloud scavenging (Giorgi and Chamedes, 1985) • Dry surface deposition: uses the approach of Wesely [1989] Danny Mc. Kenna MOZART and global tropospheric modeling

MOZART-2 Description Continued • Chemical Constituents and Mechanism: • Approximate 65 Chemical Species: • Contained in Ox, NOx, HOx; plus CH 4, C 2 H 6, C 3 H 8, C 2 H 4, C 3 H 6, C 4 H 10, isoprene, terpenes • 133 gas-phase, 2 heterogeneous, and 33 photolytic reactions • Source Gas Emissions: • Surface Emission: CO, NOx, CH 4, CH 3 OH, C 2 H 6, C 3 H 8, C 2 H 4, C 3 H 6, C 4 H 10, C 5 H 8, C 10 H 16, CH 3 COCH 3 • NOx Lightning Emission: 5 Tg N yr-1 [Pickering et al, 1998] • Aircraft Emissions: CO, CH 4, NOx (0. 44 Tg N yr-1) [NASA, 1995] • Stratospheric Constituents Constrained for: • NOx, HNO 3, N 2 O 5, CH 4, CO, and N 2 O (middle atmosphere model STARS, Brasseur et al. , 1997), • O 3 below 100 h. Pa (Logan, 1999) to thermal tropopause; above 100 h. Pa (HALOE data, et al. , 1999), • 10 -day relaxation time constant is used for all species. • Computational Costs (using the current Blackforest configuration) • 1 model year 1. 0 wall clock day (5 models years per wall clock day soon!) Danny Mc. Kenna MOZART and global tropospheric modeling Rande

Examples of Problems Addressed with MOZART • Comparison of simulations of key tropospheric constituents with observations: - Ozonesonde data, ground-based CO, Aircraft NOx etc… • Analysis of field observations and other measurement programs: -TOPSE O 3, • Analysis and assimilation of space observations: - MOPITT (CO) and GOME (NO 2) • Impact of aerosols on concentration of gas-phase compounds - IPCC Intercomparison - Sensitivity study with TOPSE NOx data Danny Mc. Kenna • Long-range transport of emissions from Asia and other industrial regions. - Tagged CO source regions. - Mauzerall et al. , , J. Geophys. Res. , 105, 17, 89517, 910, 2000. • Role of lightning and biomass burning on ozone. - Hauglustaine et al. , Geophys. Res. Lett. , 26, 3305 -3308, 1999. - Hauglustaine et al. , J. Atmos. Chem. , 38, 277294, 2001. - Tie et al. , J. Geophys. Res. , 106 (D 3), 3167, 2001. • Impact of tropospheric O 3 on agricultural yields in China - Mauzerall et al. , 2002. MOZART and global tropospheric modeling

MOZART-2 Accomplishments Comparison of O 3 with Ozonesondes (Logan, 1999) Altitude, h. Pa Horowitz et al. , JGR, in prep. , 2001. Ozone (PPBV) Danny Mc. Kenna MOZART and global tropospheric modeling

MOZART-2 Accomplishments Comparison to surface CO CMDL Data CO (PPBV) Horowitz et al. , JGR, in prep. , 2001. Month Danny Mc. Kenna MOZART and global tropospheric modeling

MOZART-2 Accomplishments Comparison to Aircraft NOx Observations Altitude, km Horowitz et al. , JGR, in prep. , 2001. NOx (pptv) Danny Mc. Kenna MOZART and global tropospheric modeling

MOZART-2 Accomplishments TOPSE Campaign, Ozone Change Emmons et al. , JGR, in prep. , 2001. Danny Mc. Kenna MOZART and global tropospheric modeling

MOZART-1 Accomplishments Black Carbon Intercomparison, IPCC 2001 • Sulfate aerosols Sulfur surface emissions Gas-phase sulfuric acid Aqueous phase chemistry Wet and dry depositions Transport • Blackcarbon aerosols Surface emission Hydrophobic and hydrophilic conversion Wet and dry depositions Transport Model (ng C m-3) Several types of aerosols are currently calculated in MOZART, including • Ammonium Nitrate Chemical transformation Transport IPCC Climate Change 2001, Chapter 5, Figure 5. 10. Danny Mc. Kenna Observations (ng C m-3) MOZART and global tropospheric modeling

MOZART-2 Accomplishments CO tagging Danny Mc. Kenna MOZART and global tropospheric modeling

Earth System Transport Model • Continued support for MOZART • Progressive migration to a new Earth System Transport Model (ESTM), - MOZART Chemistry / Solver - MATCH transport & physics - CSM Land/ocean models coupled to emission modules • CCM-Chemistry as above, but… - CSM dynamics & transport Common Framework for Offline CTM and on-line GCM Danny Mc. Kenna MOZART and global tropospheric modeling

On-Line Chemistry Mode CCSM Land Use Model Emission Model MOZART Chemistry Atmospheric Model (CCM 3) Ocean Model Danny Mc. Kenna Deposition Model MOZART and global tropospheric modeling

Chemistry Transport Mode with Interactive Land CCSM-Framework Land Use Model Emission Model MOZART Chemistry MATCH Transport Deposition Model Analyzed Met. Fields, Ocean Data e. g. , DAO, ECMWF, NCEP Danny Mc. Kenna MOZART and global tropospheric modeling

Potential Chemistry / Climate Studies • O 3 Budget of the Troposphere - Trends in relative contributions from stratosphere and human induced change. - Temporal changes in the stratosphere flux of O 3 - What influences ozone more: climate change or emission change? • Influence of oxidants on aerosol formation - Changes in the availability of SO 2, O 3, H 2 O 2, HNO 3, & NH 3 - Feedback to cloud scale and large scale dynamics • Influence of Climate on Greenhouse and other gas emissions. - Land use and climate change influence CH 4 and N 2 O production. - Feedback onto primary production and emission. • Influence of O 3 loss on composition, climate, and transport - Can O 3 loss stabilize the Arctic Vortex? - Can trends in CH 4 and N 2 O be simulated? - Can O 3 loss influence tropospheric temperature trends? Danny Mc. Kenna MOZART and global tropospheric modeling