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TROPOSPHERIC CHEMISTRY
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.
HANK: ACD’s Regional Chemistry-Transport Model– Application to field campaign analysis– Community based regional model.
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
MIRAGE : Megacity Impacts on the Regional And Global Environment– a new initiative with significant societal importance. – Potential for substantial University involvement.
Reactive Carbon Research Initiative.
– Building upon existing capabilities to address new issues.– Significant potential for University Involvement.
MOPITT:The MOPITT Experiment on Terra– Enhanced by close relations to ACD. MOZART & HANK data assimilation– A community service funded by NASA & Canadian Agencies
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 2
Atmospheric Chemistry DivisionNational Center for Atmospheric Research
TOPSE: Tropospheric Ozone Production
About the Spring Equinox
Chris Cantrell
Scientist III – Atmospheric Radical Studies24-26 October 2001, NSF Review
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 3
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 4
Specific Scientific Questions
1) 2-D morphology and evolution of ozone? 2) Rates of in-situ ozone production? 3) Distribution and evolution of radicals and
reservoirs? 4) Sources and partitioning of reactive odd-
nitrogen? 5) Composition and evolution of volatile organic
compounds? 6) Can models adequately describe and integrate
processes affecting atmospheric chemistry in TOPSE region? In Northern Hemisphere?
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 5
ACD Internal Retreat March, 1997Develop Preliminary White Paper Summer/Fall, 1997Develop Science Proposal Winter, Spring, 1998Letter of Intent to RAF April, 1998TOPSE Proposal Distribution (NSF, Universities, Agencies) June, 1998TOPSE Science Meeting Advertisement (EOS) Aug, 1998TOPSE Open Workshop October, 1998Proposal Submission to NSF Jan/Feb, 1999OFAP Request for Advanced Reservation Spring, 1999Director’s Fund Request (LIDAR installation) Spring, 1999NSF Funding Approvals Fall, 1999Aircraft Integration/Testing Dec, 1999/Jan, 2000TOPSE Mission Feb – May, 2000Mid-mission Science Meeting (NCAR) Mar, 2000First Science Team Meeting (NCAR) Nov, 2000AGU Special Session May, 2001Second Science Team Meeting (Boston) May, 2001Open Access to TOPSE Data Archive June, 2001TOPSE Manuscripts to JGR (1st round) Oct, 2001
TOPSE Development Calendar
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 6
TOPSE Investigators: Measurements
Measurement InvestigatorsRemote Ozone/Aerosols (DIAL) Browell et al., NASAAcidic Trace Gases/7-Be Talbot, Dibb, et al. UNHNMHC, Halocarbons, RONO2 Blake et al., UCINO2, Peroxynitrates Cohen, Thornton et al., UCBSpeciated Peroxides Heikes, Snow, URIOH, H2SO4 Eisele, Mauldin, NCARHO2, RO2 Cantrell, Stephens, NCARHNO3 Zondlo, NCARNOx, NOy, Ozone Ridley, Walega, NCARCH2O, H2O2 Fried, NCARJ values Shetter, Lefer et al., NCARPAN, PPN Flocke, Weinheimer, NCARCO, N2O Coffey, Hannigan, NCARUltrafine Aerosols Weber, GITMission Scientists/P.I.s Atlas, Cantrell, Ridley, NCAR
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 7
TOPSE Investigators: Modeling/Collaboration
Modeling/Collaboration InvestigatorsRegional/Forecast Model (HANK) Klonecki, Hess et al., NCARGlobal Model Analysis Tie, Emmons et al., NCAR
(MOZART) Brasseur et al., MPIProcess and Radiation Models Madronich et al., NCARGlobal Model/Process Studies Jacob, Evans, Harvard U.Stratosphere/Troposphere Exch. Allen, Pickering, U. Md.Regional/other Models Wang et al., Rutgers U.Meteorological Forecast/ Moody, Cooper, Wimmers, U.Va.
Remote SensingOzonesonde Network Merrill, URI; Fast, PNWL
GOME BrO Richter, Burrows, U. BremenMet. Forecasts (UT/LS) Newman, NASAPolar Sunrise Expt., 2000 Shepson, Purdue;
Bottenheim, Can. Met. Serv.
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 8
Joel Thornton University of California-Berkeley Graduate studentRebecca Rosen University of California-Berkeley Graduate studentDouglas Day University of California-Berkeley Graduate studentJennifer Murphy University of California-Berkeley Graduate studentDaniel Murphy New Mexico Tech Undergraduate (Senior Thesis)Julie Snow University of Rhode Island Post-DoctoralFan Lei University of Maryland Graduate StudentDouglas Orsini Georgia Tech Post-DoctoralBaoan Wang Georgia Tech Graduate StudentMat Evans Harvard University Post-DoctoralAndrzej Klonecki NCAR ASPCraig Stroud NCAR ASPBrian Wert University of Colorado Graduate StudentAnthony Wimmers University of Virginia Graduate StudentOwen Cooper University of Virginia Graduate StudentJennifer Andrews University of Virginia Undergraduate StudentMark Zondlo NCAR ASPJohn Hair Old Dominion University Post-DocAlton Jones Old Dominion University Graduate StudentAaron Katzenstein UCI Graduate studentBarbara Barletta UCI Graduate studentSimone Meinardi UCI PostdocAlex Choi UCI Graduate studentChangsub Shim Rutgers Univ Graduate studentLinsey Debell Univ. New Hampshire Graduate studentEric Scheuer Univ. New Hampshire Graduate studentUnfunded collaborators:Barkley Sive, Assistant Professor at Central Michigan UniversityOliver Wingenter, Assistant Professor at New Mexico Tech UniversityJodye Selco, Assistant Professor at The University of Redlands
TOPSE Educational Activities
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 9
90
80
70
60
50
40
30
Latit
ude
-140 -120 -100 -80 -60 -40 -20Longitude
Denver
Winnipeg
Churchill
Thule
Alert
TOPSE Flight Tracks: Feb - May, 2000
1 2 3 4 5 6 7
Deployment Number
TOPSE Flight Tracks
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 10
• 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
Some TOPSE Highlights
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 11
• In-situ photochemical processes• Measured radicals consistent with models (so far)• Model/measurement of photolysis frequencies in agreement• Some model/measurement discrepancy for CH2O, H2O2, HNO3
• Calculated increase in in-situ ozone production in spring• Stratosphere-troposphere exchange
• Remote sensing (satellite/lidar) indicate folds/streamers/STE(?)• In-situ encounters with lower stratosphere during flights• 7Be measurements suggest significant fraction of tropospheric
ozone is from stratosphere. Seasonal modulation by photochemistry, but near constant ozone flux from stratosphere
• 3-D modeling• HANK/MOZART
(Models used/evaluated extensively in campaign)• DAO/Harvard (underway)
Some TOPSE Highlights (cont’d)
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 12
Median Latitude and Altitude Profiles
(Blake – UCI)
Latitude Profiles: Altitude Profiles
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 13
TOPSE SULFATE MIXING RATIO GEOMETRIC MEAN ALTITUDE PROFILE
(Latitudes 58oN to 85oN)
Aerosol sulfate mixing ratio (pptv)
0 50 100 150 200 250
Pre
ssu
re A
ltitu
de
(m
ete
rs)
0
2000
4000
6000
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
1
2
3
4
5
6
7
1988 GTE/ABLE 3A Summertime SO42- Averages
(Scheuer, Talbot, Dibb – UNH)
Evolution of Sulfate Aerosol Vertical Distribution
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 14
6000
4000
2000
0
Pre
ssur
e A
ltitu
de (
m)
250200150100500Ozone (ppbv)
140
120
100
80
60
40
Day of Y
ear
(Ridley, Walega)
Ozone vertical profile: Evolution during winter-spring
BR_O3
52.315 53.8957.04
59.63562.86 63.065
74.61
30
40
50
60
70
80
90
100
0 1 2 3 4 5 6 7 8
Mission
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 15
Deployment 1 Deployment 3
Deployment 6Deployment 5
Deployment 4
Deployment 7
Average Ozone Distributions During TOPSE(Browell et al., NASA)
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 16
February1.7 ppb/mo
May12 ppb/mo
April14 ppb/mo
March7 ppb/mo
(Y. Wang, Rutgers Univ)
Model calculated O3 production and loss40 – 60 N; integrated surface to 9 km
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 17
7Be vs O3
Observed “stratospheric influence”
7Be – O3 relationship and stratospheric influence during TOPSE
(Dibb et al., UNH)
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 18ODE from Thule to east side of Baffin Island
Surface Ozone Depletion Over Baffin Bay
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 19
Transport of surface ozone hole to Hudson Bay
Chris Cantrell TOPSE: Tropospheric Ozone Production about the Spring Equinox 20
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 post-doctoral students
• 1st round of scientific papers to be published mid-to-late 2002.
Peter Hess HANK 37
Atmospheric Chemistry DivisionNational Center for Atmospheric Research
HANK:
ACD’s Regional Chemistry-Transport Model
developed by
Peter Hess1
with contributions from
A. Klonecki, J.F. Lamarque, M. Barth, L. Smith, S. Madronich
1Theoretical Studies and Modeling Section
Peter Hess HANK 38
HANK - Model Overview
Chemical Transport Model driven from MM5
• 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 39
HANK SCIENCE
• Mauna Loa Photochemistry Experiment1
– 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)
1Hess, 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 40
Pacific Basin Simulations (MLOPEX)
Adjoint Trajectory forpollutant plume to Hawaii
Same trajectory in height- longitude plane
Chemical transformations and rainout along the trajectory
Peter Hess HANK 41
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 42
HANK - Plans
• MIRAGE modeling• Real time and forecast modeling of forest fire pollution• Continued development of adjoint technique
– applications to data assimilation/inverse modeling – CO2 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. McHenry (NCSC), Carlie Coats (NCSC), M. Trainer (NOAA, AL), B. Skamarock (NCAR), G. Peng, (Aerospace Corporation), J. Wegiel (AFWA), S. Yvon-Lewis (NOAA, AOML)
Fred Eisele ACD contribution to TRACE-P 43
Atmospheric Chemistry DivisionNational Center for Atmospheric Research
ACD Contributions to the NASA TRACE-P*Campaign
Fred EiseleSenior 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 44
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• University of Rhode Island• Max-Planck-Institut fur Meteorologie• Nagoya University
Fred Eisele ACD contribution to TRACE-P 45
MISSION OBJECTIVES
Determine Asian outflow pathways
Determine the chemical evolution of outflow
Fred Eisele ACD contribution to TRACE-P 46
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 47
Measurement ACD Participants
• Actinic flux Shetter, Lefer, Hall, Cinquini
• OH, H2SO4, HNO3, MSA Eisele, Mauldin, Kosciuch, Zondlo
• HO2/RO2 Cantrell• Alcohols/Carbonyls Apel• CH2O 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 48
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 49
• 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 50
Measurement University collaboration- Instrument uniqueness
Actinic flux only group doing these measurements in US
OH, H2SO4,MSA only airborne CIMS technique for OH,
HNO3 MSA, and (in US) for H2SO4- Georgia Tech
HO2/RO2 only airborne HO2/RO2 CIMS in US
Alcohol/Carbonyls only airborne - GC/MS system – U of Miami
CH2O only airborne CH2O 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 51
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 52
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
Sasha Madronich MIRAGE 53
Atmospheric Chemistry DivisionNational 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 MadronichSenior ScientistTheoretical Studies and Modeling (TSM)
Sasha Madronich MIRAGE 54
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 55
Working Groups
ACD: C. Cantrell, A. Guenther, P. Hess, S. Madronich, S. Massie, J. Orlando, R. Shetter, G. Tyndall, Frank Flocke
ASP: S. Durlak, A. Gettelman
MMM: F. Chen, W. Dabberdt, W. Skamarock, T. Warner
ESIG: B. Harriss, K. Miller, K. Purvis
ATD: L. Radke
Sasha Madronich MIRAGE 56
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 57
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+NO2)
0
200
400
600
800
0 1 2 3
Time, days
Co
nce
ntr
atio
n, p
pb
O3
NO2
O3+NO2
S. Rivale (SOARS) and S. Madronich, unpubl. 1999
Sasha Madronich MIRAGE 58
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 59
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 60
Radiation in Polluted Environments
Photolysis rates in polluted conditions:
Outside Mexico City (Tres Marias) 15 April 94
6 9 12 15 18
Local time, hrs.
Mexico City 11 Feb 94
0.E+00
2.E-03
4.E-03
6.E-03
8.E-03
1.E-02
6 9 12 15 18
Local time, hrs
J NO
2, s
-1
JNO2_exp
clean
wo=0.95
wo=0.80
Castro et al. 2001
Sasha Madronich MIRAGE 61
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 62
Urban Metabolism - 1
World’s largest cities
Sasha Madronich MIRAGE 63
Urban Metabolism - 2
Emissions in developing cities are very different than in developed cities
Urban NOx Emissions
0
20
40
60
80
100
1980 2000 2020 2040 2060 2080
Year
% to
t NO
x fr
om
urb
an 30-40N
16-23N
Mayer et al. 2000
Aerosol Emissions
0
20
40
60
80
100
1980 2000 2020 2040
Year
% o
f Tot
al
Underdeveloped
Developed
240Tg/yr
513 Tg/yr
Wolf et al. 1997
Sasha Madronich MIRAGE 64
Site Selection Criteria - 1
Megacity characteristics (ranked by population in 2000)
Sasha Madronich MIRAGE 65
Site Selection Criteria - 2
Pollution signal strength relative to background
CO from MOPPIT
Sasha Madronich MIRAGE 66
Site Selection - 5
Sasha Madronich MIRAGE 67
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 68
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
Elliot Atlas Reactive Carbon Research Initiative 69
Atmospheric Chemistry DivisionNational Center for Atmospheric Research
Reactive Carbon Research Initiative
Elliot AtlasSenior Scientist
Stratospheric/Tropospheric Measurements Group
24-26 October 2001, NSF Review
Elliot Atlas Reactive Carbon Research Initiative 70
Significance
•Impact on tropospheric oxidant cycles•Urban, regional, global scales•Upper troposphere/lower stratosphere
•Biosphere-atmosphere exchanges•Carbon exchange•Nitrogen cycling
•Role in aerosol processes and climate•Aerosol organic composition/processing•Hygroscopic properties/nucleation
•Impact on stratospheric chemistry•Organic halogen •Methane/water vapor
Reactive Carbon in the Atmosphere
From P. Shepson
From A. Guenther
From J. SeinfeldFrom P. Newman/SOLVE
Elliot Atlas Reactive Carbon Research Initiative 71
MotivationTo better understand the evolution, fate and interactions of reactive carbon in the atmosphere.
Issues1. 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?
Reactive Carbon Research Initiative
Elliot Atlas Reactive Carbon Research Initiative 72
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 terpenesAnthropogenic – Toluene; Selected others
Implementation in process studies and incorporation in larger field efforts.
Elliot Atlas Reactive Carbon Research Initiative 73
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 74
Reactive Carbon Research Initiative
Atmospheric history of reactive carbonLaboratory Investigations:
Basic alkoxy/peroxy radical investigationsAromatics oxidationIsoprene/Terpene product studies
Model Investigations:Updated Master MechanismGas-aerosol partitioning
Field Investigations:Process studies: Predicted vs. measured productsSurvey 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 75
HCHO Yield
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00
z (k
m)
0
2
4
6
8
10
12
14
16
NCAR
1997 evaluation
Most Models
Formaldehyde Yield From OH + Ethene
Temperature effects on CH2O yield
(G. Tyndall, J. Orlando)
1997 evaluation
NCAR
Elliot Atlas Reactive Carbon Research Initiative 76
Isoprene and oxidation products in Houston
OH and O3
Cl
CH3
CH2 CH2
+ CH3
OCH CH2
MVK
CH2 C
CH3
CH
O
MACR
H2CO
Formaldehyde
OH or O3
Isoprene
ClCl
C
CH3
CH CH
O
CMBA isomers
CH3
CH2 CH2
+ CH2 C
CH3
C CH2Cl
O
CMBOIsoprene
9/1/2000 00:00 9/1/2000 12:00 9/2/2000 00:00 9/2/2000 12:00 9/3/2000 00:001E-3
0.01
0.1
1
10Houston 2000
pp
b
time (local)
Isoprene Methacrolein Methyl Vinyl Ketone CMBO CMBA
Daniel Riemer, UMEric Apel, NCAR
Isoprene
Methacrolein
Methyl Vinyl Ketone
CMBO/CMBA
Chloromethylbutenone(CMBO)
Chloromethylbutenalisomers (CMBA)
Elliot Atlas Reactive Carbon Research Initiative 77
Reactive Carbon Research Initiative
Carbon – nitrogen interactions
Laboratory Investigations:Product/yield studies:
Hydroxy-, multifunctional nitratesPANs
Model Investigations:Updated Master MechanismGas-aerosol partitioning
Field Investigations:Process studies: Predicted vs. measured productsSurvey studies: Investigations related to specific
source regions (Biogenic emissions),Role of PANs in UT/LS region
Elliot Atlas Reactive Carbon Research Initiative 78
Initial pathways for isoprene oxidation
(from Sprengnether et al., submitted)
Elliot Atlas Reactive Carbon Research Initiative 79
-Pinene oxidation scheme
(Kamens and Jaoui, 2001)
Elliot Atlas Reactive Carbon Research Initiative 80
Overlaid Chromatogram Plots
File: f:\bear_vg data_aug_01\aug 29 2001 #012.smsSample: L1- 1st Operator: AtlasScan Range: 1 - 4860 Time Range: 3.33 - 32.73 min. Date: 8/29/01 3:26 PMSample Notes: 3 ul int std, 8/22 -23 2319-1105
5 10 15 20 25minutes
10%
20%
30%
40%
50%
Norm Ion: 46 all aug 29 2001 #012.sms -0.046971 min offsetIon: 62 all aug 29 2001 #012.sms 0.028137 min offsetIon: 169 all aug 29 2001 #012.sms 0.109292 min offset
46 = NO2-
62 = NO3-
Isoprene + multifunctionalnitrates
C4-C6 + alkyl nitrates Terpene
nitrates?
m/e=169
GC-NICI-MS of complex organic nitrates in Blodgett Forest
(Cohen,Day –UCB;Atlas,Flocke – NCAR)
CH3
CH3
CH3OH
ONO2
Elliot Atlas Reactive Carbon Research Initiative 81
Reactive Carbon Research Initiative
Aerosol processes and organic interactions
Laboratory Investigations:Organic acid formationSecondary product/aerosol reactionsRole of organics in nucleation
Model Investigations:Updated mechanismGas-aerosol partitioningIncorporation in larger scale models
Field Investigations:Process studies: Predicted vs. measured productsSurvey studies: Investigations related to specific
source regions (Biogenic emissions/Urban plume)
Elliot Atlas Reactive Carbon Research Initiative 82
74%
3%6%
11%
6%
Anhydrosugars
Sugars/sugar alcohols
Di-/triacids
Oxo-/hydroxyacids
Aromatics
(Graham et al., JGR)
Anhydrosugars Di-/tricarboxylic acidsArabinosan Malonic acidXylosan Methylmalonic acidGalactosan Maleic acidMannosan Succinic acidLevoglucosan Methylsuccinic acid1,6-Anhydro-b-D-glucofuranose Fumaric acidN -Acetyl-2-aminoglucosan Glutaric acid
Sugars/sugar alcohols Adipic acidGlycerol Tricarballylic acidThreitol Azelaic acidErythritol Oxo-/hydroxyacidsXylose Glyoxylic acidArabitol Pyruvic acidFructose Lactic acidMannose Glycolic acidGalactose Glyceric acidGlucose Malic acidMannitol Hydroxymalonic acidSorbitol 2-Ketoglutaric acidInositol 2-Hydroxyglutaric acidSucrose Threonic acidTrehalose Tartaric acid
4-Ketopimelic acidAromatic acids
3-Hydroxybenzoic acid4-Hydroxybenzoic acidVanillinPhthalic acidVanillic acidSyringaldehyde3,4-Dihydroxybenzoic acidVanilethanediolSyringic acid
Composition of WSOC in biomass burning aerosol from Amazonia
Sample F12, 0.17 µg m-3
identified
Sample P2, 10.50 µg m-3
identified
Elliot Atlas Reactive Carbon Research Initiative 83
Organics…A role in new particle formation?
Critical nucleation cluster (tentative identification)
NH3 H2SO4 H2SO4(Hanson and Eisele)
Amines vs. ammonia? Organic acids vs. sulfuric?
RNH2 R(OH)COOH
Elliot Atlas Reactive Carbon Research Initiative 84
Reactive Carbon Research Initiative
Radicals and oxidants
Laboratory Investigations:Photochemically active organics as radical sourceRO2 speciation as tool to understand reactive carbon
degradation
Model Investigations:Role of reactive carbon in cycling OH/HO2/RO2
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 85
M easured Species Calspan Oct 19, 1998
0
50
100
150
200
250
300
10:00 11:00 12:00 13:00 14:00
Tim e of Day
Co
nce
ntr
ati
on
a-pinene, ppbv*10 RO2, pptv NO, ppbv*50 NOx, ppbv*50O3, ppbv CN/200 RH% LW C*500
Figure 2.
Observations of RO2 – cloud interactions
Cantrell et al.
Elliot Atlas Reactive Carbon Research Initiative 86
Reactive Carbon Research Initiative
Emission and deposition fluxes
Laboratory Investigations:Leaf/Branch level emission studies
Model Investigations:Flux parameterization/Controlling variablesGas-aerosol partitioningIncorporation in larger scale models
Field Investigations:Process studies: Evaluation of emission fluxes from different environments; Estimation of deposition fluxesSurvey studies: Improved estimation of speciated VOC emissions/oxidation products (esp. biogenic VOC)
Elliot Atlas Reactive Carbon Research Initiative 87
OxyVOC emissions from a Colorado alfalfa field before and after cutting
1.2
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
ace
tald
eh
yde
, ace
ton
(m
g/m
^2
*h)
12:008/12/00
12:008/13/00
12:008/14/00
12:008/15/00
Datatime
10
5
0
me
tha
no
l (mg
/m^
2*h
)
acetaldehyde methanol aceton
Cutting
growing
drying
Rinne et al. GRL 28: 3139-3142 (2001)
e
(Rinne, Guenther)
Elliot Atlas Reactive Carbon Research Initiative 88
Reactive Carbon Research Initiative
Development of tools and techniques
LaboratoryFlow tube and smog chamberIntegrated MS techniquesGas-aerosol partitioning
ModelIncorporation and update with relevant results
Field Gas phase chemistry:
PTR/MS, MS/MS, Fast GC/MS, TDLemissions and oxidation products
Aerosol organic chemistry:Aerosol Ion Trap: particle compositionLC/MS: water soluble organic carbon
Elliot Atlas Reactive Carbon Research Initiative 89
New instrument development (examples)
Aeros ol I n le t
(15 lpm )
Sam pleC ollec t ion
F ilam ent
Sheath G as
(1 lpm )
L inear
Ac tuator Ion izat ionR egion
C ollis ion
C ham ber
To Mas sSpec t rom eter
34"
Ultrafine OrganicAerosol Instrument(J. Smith)
LC/MS/MS for water soluble organics (E. Atlas)
Elliot Atlas Reactive Carbon Research Initiative 90
Reactive Carbon Research Initiative
Relationship to existing and planned research
MIRAGEFocus on reactive carbon evolution/TracersAerosol characterization/reactionsLaboratory investigations
UT/LSVOC as sources of ROx VOC as transport tracers/halogen sources
CloudsWater soluble organic characteristicsVOC partitioningSource tracer measurement
Biosphere, Chemistry and ClimateFlux estimates of VOC from different environments
John C. Gille The MOPITT Experiment on Terra 91
Atmospheric Chemistry DivisionNational Center for Atmospheric Research
John GilleSenior ScientistMOPITT and HIRDLS Groups24-26 October 2001, NSF Review
The MOPITT Experiment on Terra
John C. Gille The MOPITT Experiment on Terra 92
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 CH4
Demonstrate capability to make and use measurements of tropospheric composition from space
Applications: Improve knowledge of sources, sinks and transformationsTesting and improvement of model transport and chemistry
John C. Gille The MOPITT Experiment on Terra 93
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. McConnell, York University G.D. Peskett, Oxford University H.G. Reichle, North Carolina State University N. Roulet, McGill University
Further information at
http://www.eos.ucar.edu/mopitt/home.html
John C. Gille The MOPITT Experiment on Terra 94
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
Jean-Francois Lamarque Debbie Mao Jianguo Niu Dan Packman BarbTunison Juying Warner Valery Yudin Dan Ziskin
The NCAR/ACD MOPITT Team
95The MOPITT Experiment on TerraJohn C. Gille
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 96
MOPITT Instrument
MOPITT Instrument: 8 channel nadir viewing gas correlation radiometer
4 channels @ 4.7 m - thermal emission from atmosphere and sfc.
4 channels @ 3.3 m - 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 97
- 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 hPa with 10% precision
- CO total column with 10% precision
- CH4 total column with 1% precision
- Level 3 data products (initially a research product) - Gridded global CO distribution
- Gridded global CH4 distribution
MOPITT StandardScientific Products
John C. Gille The MOPITT Experiment on Terra 98
MOPITT Data Processing
1.00.80.60.40.2
2240222022002180216021402120
1.5
1.0
0.5
2240222022002180216021402120
CO
H2O
Other
Tran
smit
tan
ceR
adia
nce
(x1
0-3)
[W/(
m2 s
r c
m-1
)]
Wavenumber (cm-1)
MOPITT Thermal Channel Gas Transmittances
Top of Atmosphere Radiance and Channel Response
Wavenumber (cm-1)
L1
NCEP
Clim
Input Cloud Retrieval L2
Forward Model Maximum
Likelihood
method
John C. Gille The MOPITT Experiment on Terra 100
March
Dec
June
Sept
Monthly mean (2000) CO 700 mb
John C. Gille The MOPITT Experiment on Terra 101
MOPITT Level 2 CO Column
MOPITT Level 2 CO total column shows:
Aug 20-27 2000
• High CO amounts correlate with areas of industrial pollution and biomass burning
• Inter-continental transport• Good comparison with in-
situ aircraft and FTIR data
Plumes from western forest fires clearly seen
John C. Gille The MOPITT Experiment on Terra 102
MOPITT Data Assimilation in MOZART 2
John C. Gille The MOPITT Experiment on Terra 103
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 105
Initial Example of Single Cooler Data
John C. Gille The MOPITT Experiment on Terra 106
Future plans
Three Major Thrusts
• Algorithm improvements
– e.g. Retrieve CH4 column data
– Reduce retrieval bias, other artifacts– Cloud detection and clearing, using MODIS data
• Data quality assessment (“Validation”)– vs. A/C profile measurements fromTrace-P, CMDL, other– vs. ground based FTIR column measurements
• Application of data– To studies of transports, sources, chemical impacts– Inverse modeling to constrain surface emissions– Participation in campaign planning (e.g. MIRAGE)
John C. Gille The MOPITT Experiment on Terra 107
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