AEROSOL MASS SPECTROMETER MEASUREMENTS ON BOARD THE G1 AIRCRAFT DURING THE NEW ENGLAND AIR QUALITY S

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AEROSOL MASS SPECTROMETER MEASUREMENTS ON BOARD
THE G1 AIRCRAFT DURING THE NEW ENGLAND AIR
QUALITY STUDY 2002/2004

• John Jayne, Tim Onasch, Manjula Canagaratna,
  Scott Herndon
• Doug Worsnop
• Aerodyne Research, Inc.
• Mike Alexander, Alex Laskin, Tom Jobson, John
  Hubbe
• Pacific Northwest National Laboratory
• Peter Daum, Larry Kleinman, Stephen Springston
• Brookhaven National Lab

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NEAQS Campaigns Improve understanding of
sources, production and transport of pollutants
in NE area

• Gulfstream 1 (G1) participation
• Worcester, MA.
• July 1-Aug 11, 2002
• Worcester regional airport
• Latrobe, PA.
• July 25 Aug 14, 2004
• Arnold Palmer regional airport

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AMS Deployment on the G1 Aircraft
Double Diffuser Cone Gas/Aerosol Inlet System -
Fred Brechtel
AMS Package
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Real Time Chemical and Physical Composition of
Aerosols
Aerosol Sampling
Sampling frequency 30 sec. 3 km spatial
resolution
AMS
Nitrate Sulfate Ammonium Alkanes Organics
Aromatics Etc..
Mass distribution
Chemical composition
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NEAQS 2002 Worcester, MA
17 research flights, 3-4 hr duration
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NEAQS 2002 Sulfate Plume
July 22, 2002
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Vertical Profile over the NOAA Ship Ron
Brown Flight Track on July 22, 2002
Ron Brown
Ron Brown
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G1 Flight Track Horizontal Transects over NOAA
Ron Brown
July 22, 2002
Altitude (ft)
NOAA Ship R.H. Brown
Latitude (deg.)
Longitude (deg.)
Air masses are layered
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What Is the Origin of the Sulfate Plume?
Back trajectory shows high sulfate air mass at
1.3 km originating from Ohio Valley
Back trajectory shows high SO2 air mass at 0.5 km
originating within New England Region
NOAA Hysplit model trajectories from July 22-20
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NEAQS 2004 Latrobe, PA
Arnold Palmer Region Airport, LBE
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Flight Tracks SO2 Emissions
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PA area coal fired power plant as viewed from G1
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NEAQS 2004 Plume Study - South Western PA Aug. 9,
2004
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Sulfate Plumes from two PA area Coal Fired Power
Plants
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Forward trajectories show plumes being
transported to New England Area
Typical winds are S-SW
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Quick Summary

• 2002 measurements made in NE show sulfate plumes
  originating from Ohio Valley area
• 2004 measurements made in Ohio Valley Area show
  sources being transported to NE

Lets look at the Chemical and Microphysical
properties of the aerosol
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Typical Aerosol Mass Spectrum Latrobe, PA area
Electron impact ionization following flash
vaporization at 600C
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Plume Study PA Aerosol is Acidic in Fresh
Plumes
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SO2 Sulfate plumes NEAQS 2002
Older/more-processed
Newer/less-processed
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The organic component of the aerosol mass
spectrum NEAQS 2004, PA
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The organic component of the aerosol mass
spectrum NEAQS 2004, PA
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Typical terrain in western PA area study
Significant biogenic emissionsSOA
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Ratio of m/z 44 to total organic is a measure of
the degree of oxidation
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NEAQS 2002 New Jersey flight track
Urban / Industrialized Area
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Observations of Primary Organic Particles
Traffic Emissions

• Evidence of primary organic particles in small
  particle mode.
• Small mode typical of primary traffic exhaust
  emissions

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Summary

• Ohio Valley Area appears to be a significant
  source of sulfate for the New England area.
• High levels of sulfate observed as direct
  emission from PA area coal fired power plants.
• In rural PA area organic aerosol is highly
  oxidized.
• SOA (biogenic sources).
• In NY/NJ area a measurable fraction of the
  organic aerosol is primary emitted HC (consistent
  with vehicle traffic) which adds to the oxidized
  organic aerosol background.

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Acknowledgements
PNNL Team John Hubbe Carl Berkowitz Alex
laskin Victor Morris John Schmelzer Larry
Berg Rich Barchet
BNL Team Larry Klineman Yi-Nan Lee Xiao-Ying
Yu Steven Springston Gunnar Sennum Jain Wang
Funding DOE ACP DOE SBIR NSF STTR ONR SBIR
Pilot Bob Hannigan
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Organic component of aerosols

• Highly oxidized organic components
• No significant stratification of the oxidation
  age of the organics.

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Organic NEAQS 2004 Aug. 9, 2004
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Measurable Mass at 8000 ft
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Northeastern Corridor Emissions profile Power
plant and city sources. Flight Track on July 16
Power Plant Emissions?
Traffic Emissions?
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Aerosol Mass Spectrometer (AMS)
Particle
Aerodynamic Sizing
Particle Beam
Composition
Generation
Quadrupole Mass Spectrometer
Chopper
Thermal Vaporization Electron Impact Ionization
TOF Region
Aerodynamic Lens (2 Torr)
Pump
Pump
Pump
Particle Inlet (1 atm)
100 transmission (40-600 nm), aerodynamic
sizing, linear mass signal. Development of an
Aerosol Mass Spectrometer for Size and
Composition Analysis of Submicron Particles.
Jayne et al., Aerosol Science and Technology
331-2(49-70), 2000.
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Constant altitude profile Down wind/up wind of
coastal sources. Flight Track on July 14

• Aerosol composition is dominated by sulfates and
  organics

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Chemically-resolved size distributions

• Apparent internally mixed accumulation mode
  aerosol particles.

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Local sources of sulfur emissions

• Sulfate aerosol up wind and down wind of costal
  sources exhibit different sulfate-to-total sulfur
  ratios
• Evidence that SO2 is mixing up from local
  sources on the eastern seaboard. High levels of
  background particulate mass on this day may be
  inhibiting new particle production.

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Degree of Sulfate Neutralization

• The degree of sulfate neutralization is sulfate
  mass loading dependent, suggesting that ammonia
  is the limiting factor.

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Morning Traffic Events are Fresh Organic
Compounds (Mainly Hydrocarbons)
0.15
0.03
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Observations of Primary Organic Particles
Traffic Emissions

• Evidence of primary organic particles in small
  particle mode.
• Small mode typical of primary traffic exhaust
  emissions

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NEAQS 2002 Vertical Transects
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• The nonrefractory submicron aerosol mass loadings
  were composed primarily of organics and sulfate
  species. Mass loadings were lt45 ?g/m3.
• Air masses passing through the NE region at a
  constant altitude were influenced by emissions
  (SO2 and organics) within the coastal area.
• Air masses were found to be vertically layered.
  Back trajectories indicate that the polluted
  layers (July 22nd) were transported from the Ohio
  River Valley region (outside of the Northeastern
  region).
• The oxidative age of sulfate aerosols in air
  masses were tracked by the SO4Stotal ratio, back
  trajectories, and the size and growth of sulfate
  particles. These markers illustrate the
  influence of local sources in the lower
  atmosphere and the influx of aerosols from
  sources outside of the region at altitude.
• Air masses with relatively high SO2 and low
  sulfate were observed to contain bimodal sulfate
  size distributions small growth mode (from a
  nucleation event) and accumulation mode. In
  contrast, air masses with relatively low SO2 and
  high particulate sulfate were observed to contain
  only accumulation mode sulfate particles.
• The sulfate to total sulfur ratio increases with
  altitude, indicating that higher air masses
  contained older, more processed particles.
• The organic components of the aerosol appear
  highly oxidized and, for the most part,
  independent of the air mass stratification and/or
  age of the sulfate component.
• Observations of primary traffic emissions at
  lower altitudes down wind of city sources
  highlight organic emissions from the NE region.

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Stratification of sulfate aging
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Mass Spectrum of Oxidized versus Hydrocarbon
containing aerosol
Hydrocarbon
Oxidized carbon