NASAs Research Program in Tropospheric Chemistry

Jay Al-Saadi Tropospheric Chemistry Program Earth Science Division Science Mission Directorate NASA Headquarters

Student Airborne Research Program, June 20, 2011

Atmospheric Composition: Emission, Transformation, Transport, Removal

CLIMATE FORCING (regional to global scales)

AIR QUALITY (local to regional and global scales)

EMISSION (urban to local scales)

Credit: CCSP Strategic Plan (illustrated by P. Rekacewicz).

Tropospheric Chemistry before 1970

Stratosphere Troposphere

Background

O3

O3

Deposition

Tropospheric Chemistry aFer 1970

Stratosphere Troposphere

Background

O3

Tropospheric chemical processes largely determine the abundance of atmospheric trace gases, including greenhouse gases.

O3

Deposition

H. Levy II (1971, 1972); Chameides and Walker (1973)

Emission
(NOx, CO, Hydrocarbons, Aerosol, SO2, NH3)

Transformation/Oxidation
(O3, OH, CH2O, HO2, RO2, Aerosol)

Removal
(HNO3, H2O2, ROOH, Aerosol)

Observed from space routinely or developmentally

NASA Tropospheric Chemistry Field Campaigns (1983-2008)

Chemical Instrument Testing and Evaluation (CITE) missions in the beginning of the TCP airborne program developed measurement techniques that are being used to this day. NASA TCP airborne studies have propelled advances in tropospheric chemistry in terms of understanding of global sources, sinks, and chemical transformation.

NASA Tropospheric Airborne Measurements

NASA airborne campaigns have generated a 25 year record of tropospheric ozone and its key precursors (NO and CO).
NMVOC data records available over the past 20 years Expanded species list in more recent field studies (OH, peroxy radicals, OVOCs)

Particle composition measurements extend over 20 years. Observations made in past 10+ years provide more complete data of particle loading, number size distribution, optical properties, and chemical compositions.

Violations of National Ambient Air Quality Standards (NAAQS) are primarily related to ozone and fine particulate matter.

Ozone concentrations in ppm, 2007 (fourth highest daily max 8-hour concentration).

Annual average PM2.5 concentrations in g/m3, 2007

* Yellow and Red symbols represent levels in violation of NAAQS

Taken from National Air Quality-Status and Trends through 2007 (http://www.epa.gov/airtrends/2008/)

Air quality concerns overlap with short-lived, non-CO2 climate forcing

(IPCC Fourth Assessment Report)

Tropospheric Ozone Significance

Environmentally Important: Ozone is a pollutant adversely impacting health and agriculture. Chemically Important: Ozone initiates the oxidation cycles responsible for removing most polluting gases from the atmosphere. These oxidation cycles also influence ozone itself. Climatically Important: Ozone influences climate directly as a greenhouse gas and is most important in the upper troposphere where temperatures are cold. Ozone exerts an indirect influence through the oxidation of other greenhouse gases.

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Aerosols Significance

Environmentally Important: Aerosols adversely impact health, reduce visibility, and acidify precipitation. Chemically Important: Aerosols are critical to atmospheric removal processes. Climatically Important: Aerosols influence Earths energy balance directly through the scattering and absorption of radiation as well as indirectly through modification of clouds (e.g., distribution and optical properties).

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Airborne Field Campaign Strategy: Maximize the value of satellite data for improving models of atmospheric composition and climate
Satellites: MLS, CALIPSO, MODIS, MISR, OMI, MOPITT, AIRS, ... Aircraft: ER-2, DC-8, P-3B, GH, B200,...

Ground-Based Networks: AERONET, MPLNET, SHADOZ, AQS, Global and Regional Models: CTMs, GCMs, ESMs
Understanding Attribution Prediction

Calibration and Validation Retrieval development Correlative information Small scale structure, processes

Model error evaluation Data assimilation Emissions inversion Diagnostic studies

NASA DC-8!

NASA P-3B!

NASA B-200!

ARCTAS Airborne Platforms and Payloads

DC-8

P-3B

B-200

HSRL, LAABS, APS

DC-8 (185 ight hours)" Spring (1-20 April)" California (18-24 July)" Summer (26 Jun-13 July)" 9 sorties" 4 sorties" 9 sorties"

P-3B (158 ight hours)" 8 sorties" 1 sortie" 12 Sorties"

B-200 (150 ight hours)" 27 sorties"

21 Sorties"

DC-8! P-3B! B200!

DOE ISDAC" NOAA ARCPAC" Eureka

Summit

SPRING"
POLARCAT- GRACE POLARCAT- France

SUMMER"
NSF pre-HIPPO"

CARB"

ARCTAS validation of OMI BrO demonstrated a stratospheric origin for some Arctic high-BrO events
These events had been previously assumed to originate from sea salt reactions in the boundary layer ARCTAS flights showed no coincidence between high-BrO events seen by OMI and elevated BrO in the boundary layer These events were found instead to correlate with ozone column and tropopause pressure, implying a lower stratospheric origin O3 column ptropopause BrO column

DC-8 track

The ARCTAS data imply the presence of 5-10 ppt inorganic bromine in the lower stratosphere originating from very short-lived (VSL) bromocarbons, with important consequences for our understanding of stratospheric ozone
Salawitch et al., GRL 2010

Investigating Emissions and Evolution of Trace Gases and Aerosols from Biomass Burning Plumes Measured during the ARCTAS-2008 Field Campaign
A. Hecobian, Z. Liu, C. Hennigan, Y. Wang, L. G. Huey, J. Jimenez, M. Cubison, S. Vay, G. Diskin, G. Sachse, A. Wisthaler, Y. Kondo, N. Moteki, A. Weinheimer, D. Knapp, P. Wennberg, J. Crounse and R. J. Weber

Part 1: Statistical Summary of all Biomass Burning Plumes Intercepted by the NASA DC-8
Identified fire sources and calculated emission ratios (dX/dCO) for: CO2, acetonitrile, hydrogen cyanide, toluene, benzene, CH4, NOx, O3, PAN and fine aerosol particulate components nitrate, sulfate, ammonium, organic aerosols, water soluble organic carbon and black carbon mass

495 Plumes From Various Sources Identified & Characterized

Example: Characteristics of dSulfate/dCO in Various Plumes

Georgia Institute of Technology

ARCTAS spring observations of black carbon (BC) aerosol combined with AIRS CO revealed complex source origins
AIRS CO on April 16, 2008
Russian re plume

DC-8 BC observations from Y. Kondo and GEOS-Chem model simulation

Altitude, km

DC-8 track (re plume)

BC, ng C m-3 STP

ARCTAS flights validated AIRS CO observations of large Russian fire and Asian pollution influences over Arctic in spring Both fires and anthropogenic sources were found to contribute to Arctic BC Anthropogenic BC is mainly from Asia above 2 km, but European and North American influences are also important below 2 km (driving deposition to snow) Model source attribution for BC is corroborated by correlations with sulfate
Fisher et al., ACP 2010; Wang et al., submitted to ACP

Characterization of trace gases measured over Alberta oil sands mining operations:
75 speciated C2-C10 volatile organic compounds (VOCs), CO2, CO, CH4, NO, NOy, O3 and SO2
Isobel Simpson, Simone Meinardi, Barbara Barletta, Nicola Blake, Glenn Diskin, Henry Fuelberg, Katrine Gorham, Greg Huey, F. Sherwood Rowland, Stephanie Vay, Andrew Weinheimer, Melissa Yang, Donald Blake

Motivation and significance: Despite the increasing importance of oil sands in the energy market, this is the first peer-reviewed study to characterize trace gas emissions from Alberta oil sands surface mines Result highlights (82 measured species): 15 compounds were not enhanced over the oil sands:
- e.g., O3, CFCs, CCl4, CH3CCl3, CHBr3, CH2Br2, CHBrCl2, MTBE, furan

9 compounds showed minimal enhancements:

- e.g., HFC-134a, HCFC-141b, H-1211, H-1301, CH3Br, CH3I, CH3Cl

58 compounds were strongly enhanced:

- e.g., SO2, NO, NOy, CO2, CO, CH4, C2-C9 alkanes, C2-C4 alkenes, C5C6 cycloalkanes, C6-C9 aromatics, isoprene, - & -pinene, HCFC-22, CHCl3, C2Cl4, CH2Cl2, methanol, acetone, MEK, MAC, MVK, DMS, OCS

Surprises: SO2 maximum (38.7 ppbv) was comparable to Mexico City n-Heptane showed the strongest enhancement over bkgd. Monoterpenes appear to have an oil sands source CH3Cl failed to be drawn down because of soil removal OCS failed to be drawn down because of vegetation removal A natural gas signal was not evident, despite strong usage
Figure 1. Time series of selected trace gases measured during ARCTAS Flight 23 (July 10, 2008). Samples over oil sands mining: shaded.

Satellites! Models! Information synthesis! 2 yrs! Improved knowledge;! publications in scientic journals! 5 yrs! 10 yrs! Improved model predictions! Aircraft!

Summary assessments for policymakers:! Intergovernmental Panel on Climate Change! Arctic Council! UNEP Hemispheric Transport of Pollution Assessment!

Better-informed decisions to protect the environment!

A NASA / NSF / NRL airborne field campaign focusing on atmospheric composition, chemistry, and climate over Southeast Asia related to:
Natural, biomass burning, and pollution impacts on

atmospheric composition, radiation, and clouds Asian monsoon circulation and marine convection impacts on upper troposphere/lower stratosphere composition

Anticipated deployment period: August - September 2012

Air Quality From Space

Significant progress has been made over the past ~15 years in satellite remote sensing of atmospheric composition relevant to air quality Survey Articles:
Martin, Invited Review Article: Satellite Remote Sensing of Surface Air Quality Atmos Env, 2008. Fishman et al., Remote Sensing of Tropospheric Pollution from Space Bulletin of the American Meteorological Society, June 2008 Hoff and Christopher, 2009 Critical Review of the Air and Waste Management Association Remote Sensing of Particulate Pollution from Space: Have We Reached the Promised Land? J. Air & Waste Manage. Assoc., June 2009 Burrows, Platt, and Borrell, eds. The Remote Sensing of Tropospheric Composition From Space, Springer-Verlag, 2011
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(AQHI)

Key pollutants: PM2.5, O3, NO2

Smog Alert, Toronto

Courtesy Randall Martin, Dalhousie University

Current NASA satellite observations relevant to Tropospheric Composition

A legacy of the Earth Observing System (EOS) vision Ozone (O3): Aura-OMI, Aura-MLS, Aura-TES Carbon Monoxide (CO): Terra-MOPITT, Aqua-AIRS, Aura-TES Nitrogen Dioxide (NO2): Aura-OMI Formaldehyde (CH2O): Aura-OMI Aerosol: Terra-MODIS and MISR, Aqua-MODIS, Aura-OMI, CALIPSO Global observations approximately once per day Launch dates: Terra 1999, Aqua 2002, Aura 2004, Calipso 2006

Terra 10:30

NO2 observations from OMI: High resolution information on anthropogenic emissions

Strengths: Atmospheric NO2 abundance is weighted toward surface, therefore column measurement can yield useful information on variability in surface emissions Atmospheric lifetime of NO2 is less than one day near the surface, therefore observed enhancements are in close proximity to sources. Limitations: Stratospheric abundance of NO2 must be subtracted to give a tropospheric residual (similar to ozone), however, tropospheric NO2 dominates the column in polluted areas. Partitioning between NO2 and NO must be assessed to estimate total NOx, although NO2 typically constitutes ~80% of near-surface NOx Emission of NOx undergoes large diurnal variability

Formaldehyde (HCHO or CH2O) observations from OMI: Oxidation of biogenic and other hydrocarbon emissions
Strengths: Atmospheric CH2O abundance is weighted toward surface with no significant stratospheric burden Oxidation of most hydrocarbons result in CH2O, therefore it is an excellent proxy for the integrated influence of hydrocarbons on ozone photochemistry Limitations: CH2O is not directly emitted, but rather is a byproduct of photochemistry. With a short lifetime (hours), it undergoes large changes throughout the day. Atmospheric lifetime of CH2O is less than one day, observed enhancements occur at variable distances from hydrocarbon sources, depending on their atmospheric lifetime.

OMI HCHO/NO2:

Air Quality Indicator*

*Based on Sillman [1995] Martin et al. [2004]

NOx + VOCs Ozone

If HCHO/NO2 is low then one must reduce anthropogenic

hv

VOCs to lower ozone.

If HCHO/NO2 is high then one must reduce NOx to lower ozone. NOTE: HCHO/NO2 gives info on the sensitivity of instantaneous ozone production, not the ozone concentration!

Application of Ozone Monitoring Instrument Observations to a SpaceBased Indicator of NOx and VOC Controls on Surface Ozone Formation

Ozone production is controlled by reducing VOC emissions in downtown LA.

Natural VOCs from trees are so high in the East that ozone production is primarily controlled by reducing NOx emissions.

Reduce VOC Emissions Transition Reduce NOx Emissions

The OMI formaldehyde (HCHO) to nitrogen dioxide (NO2) ratio for August 2005. Harmful levels of surface ozone can form through a complex series of reactions involving volatile organic compounds (VOCs) and nitrogen oxides (NOx) in the presence of sunlight. Ozone will decrease when emissions of anthropogenic VOCs are reduced when the ratio is < 1 (e.g., Los Angeles, Chicago). It will decrease when NOx emissions are reduced when the ratio is > 2. In this way, the ratio is an air quality indicator.
Duncan et al., Atmospheric Environment, 2010

GEO-CAPE will significantly improve observational capability for Air Quality in 4 key areas:
1. High temporal resolution measurements to capture changes in pollutant distributions due to changing photochemistry, emissions and meteorology 2. High spatial resolution measurements to access the city scale with continuous full-coverage of North America 3. Exploitation of multispectral observations to improve information content in vertical profile 4. Key contributor to an integrated observing system in conjunction with observations from the ground-based, suborbital and satellite platforms of US and international partners http://geo-cape.larc.nasa.gov/
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WRF-chem simulation of surface CO, July 16-20, 2006 (courtesy David Edwards, NCAR) 4km horizontal resolution, hourly 16km horizontal resolution, twice daily

A Geostationary Air Quality Constellation

http://www.ceos.org/images/ACC/AC_Geo_Position_Paper_v4.pdf

NASA GEO-CAPE NOAA GOES R/S

ESA, Eumetsat Sentinel-4 + MTG

KARI MP-GeoSat GEMS JAXA GMAP-ASIA

Geostationary orbit offers the potential for continuous (many times per day) observation within the satellite field of view, but one satellite views only part of the globe Harmonization of planned geostationary missions for air quality, along with planned lowEarth orbit continuity missions, will enable an integrated global observing system fulfilling the visions of GEO/GEOSS Help address over-arching policy relevant science questions posed by the United Nations Hemispheric Transport of Air Pollution reports (2007, 2010) For each region in the Northern Hemisphere, can we define source/receptor relationships and the influence of intercontinental transport on the exceedance of established standards or policy objectives for the pollutants of interest? How will changes in emissions in each of the other countries in the Hemisphere change pollutant concentrations or deposition levels and the exceedance of 32 established standards or policy objectives for the pollutants of interest?

EV-1 Airborne DISCOVER-AQ (PI Jim Crawford, NASA LaRC) Relevance to GEO-CAPE and AQ from space
Systematic and concurrent observation of column-integrated, surface, and verticallyresolved distributions of aerosols and trace gases relevant to air quality as they evolve throughout the day. 1-month campaigns over 3-4 US cities 2011-2014.
Continuous lidar mapping of aerosols with HSRL on board B-200 Continuous mapping of trace gas columns with ACAM on board B-200 In situ profiling over surface measurement sites with P-3B Continuous monitoring of trace gases and aerosols at surface sites to include both in situ and columnintegrated quantities Surface lidar and balloon soundings

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Summary

Air Quality and Climate Change are different manifestations of the same problem stemming from human impacts (i.e., energy consumption), albeit with different time horizons. Air Quality is fundamentally a surface concern, however it requires an understanding of the full atmosphere. Observing near-surface pollution from space is very challenging. NASA airborne and satellite observations are critical to all aspects of Air Quality and Climate research including emissions, transformation (photochemical and physical) and transport.

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Population and economic development are primary drivers for anthropogenic emissions which are increasing rapidly in Southeast Asia Strong anthropogenic sources are intermingled with strong biogenic and natural emissions across both terrestrial and marine environments

Anthropogenic VOCs Zhang et al., ACP, 2009

Marine biogenic emissions Warwick et al., JGR, 2006

Shipping emissions Wang et al., ES&T, 2008

1. How are surface (pollutant and natural) emissions in the tropics redistributed via deep convection throughout the troposphere? 2. What is the evolution of gases and aerosols in deep convective outflow and what are the implications for the UT/LS chemistry?
3.

What influences and feedbacks do aerosol particles from anthropogenic pollution and biomass burning exert on local meteorology through changes in the atmospheric heat budget (i.e., semi-direct effect) or though microphysical changes in clouds (i.e., indirect effects)?

ER-2: Upper Troposphere to Lower Stratosphere Cruise altitude 18-21 km, range 3000 nmi, endurance 8-10 h Payload: Emphasis on remote sensing of aerosols and radiation with capability to observe basic chemical tracers NSF/NCAR GV: Mid-to-Upper Troposphere Ceiling 14 km, range 4000 nmi, endurance 8-10 h Payload: Emphasis on detailed atmospheric composition and photochemistry for gases and aerosols as well as cloud microphysics DC-8: Surface to Upper Troposphere Ceiling 12 km, range 4000 nmi, endurance 8-10 h Payload: Emphasis on detailed atmospheric composition and photochemistry for gases and aerosols, detailed radiation measurements, and remote sensing of ozone and aerosols

Global NOx Sources (teragrams of nitrogen per year)

Source Fossil Fuels Biomass Burning Soil Emissions Aircraft Lightning Magnitude (uncertainty) 22 (13-31) 8 (3-15) 7 (4-12) 0.85 (0.5-1) 5 (2-20)

Global Hydrocarbon Sources (teragrams of carbon per year)

Source Possible Range Fossil Fuels 46-95 Biomass Burning 25-80 Emission from Foliage 800-1500 Soils/Oceans/Grasslands 15-30

Scientific Value of Airborne Observations

Most effective way to obtain wide-ranging yet detailed atmospheric surveys: Discovery Comprehensive investigations of specific atmospheric processes: Understanding
Wide range of measurements for atmospheric parameters and trace species in gas and particulate phase critical to our understanding of air-quality and climate change related issues High spatial (Horizontal: 0.2 12 km; Vertical: 10 300 m) and temporal (1s minutes) resolutions

Validate and provide context for longer term satellite and ground observations: Monitoring Evaluate and improve models: Prediction

Atmospheric Pollutants: Emission and Transformation O2

NO 2

O3

STRATOSPHERE TROPOSPHERE
HCHO
OH
H2O, H2O2, HNO3

O3
H2 O

Aerosol SO2 NH3 Aerosol

NO2 OH NO

CO

Trace species in Red can be routinely observed from space Trace species in Green are being observed in research efforts

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Why Geostationary? High temporal resolution

Hourly NO2 surface concentration and integrated column calculated by CMAQ air quality model: Houston, TX, June 22-23, 2005

OMI accurately detects column NO2 - once per day and with varying horizontal resolution

Low Earth Orbit measurements once per day provide limited information for AQ models Geo-CAPE would provide NO2 measurements every 30-60 minutes during sunlit hours 42