Biocomplexity and Air Quality

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Biosphere-Atmosphere Interactions Chemistry
Climate
Peter Harley Biosphere-Atmosphere
Interactions Atmospheric Chemistry Division
(Integrated Science Program)?
June 24, 2009
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Zitrone-komplett1 A Drama in One Act
A dramatic, if somewhat unrealistic, example of
how biosphere and atmosphere can interact

Movie kindly provided by Prof. Dr. Thorsten
Hoffmann Institute of Inorganic and Analytical
Chemistry Johannes Gutenberg University of Mainz
The plot First it shows a young chemist
peeling the lemon, then the ozone filled flask (I
do not know concentration exactly however,
several hundred ppm ozone, I guess) and a piece
of lemon peel thrown into the flask. After a
while, my young colleague got bored and increased
the density of the aerosol clouds by putting four
pieces of lemon peel into the flask.
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Courtesy of Nick Hewitt
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Outline

• Who am I and how did I get here?
• Long-winded Introduction
• What our group does?
• How we do it
• Why we do it
• Modeling
• Questions?

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Peter Harley This is your life Education 1971 B
.A. (History) College of Wooster (Ohio)? (Senior
Independent Study Thesis The Origins and
Development of Strategic Bombing Doctrine Before
World War II)? 1976 M.S. (Biology) University of
Michigan 1979 Ph.D. (Botany) University of
Michigan (Thesis Development of a photosynthesis
model for soybean)? Employment Systems Ecology
Research Group, San Diego State (photosynthesis
modeling Sphagnum moss, North Slope, AK)? Duke
University (Effects of elevated CO2 on cotton
photosynthesis)? 1991- present NCAR
Biosphere-Atmosphere Interactions Group (Physical
and biological regulation of BVOC emissions)?
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Early history of climate modeling
1950s Simple physical models atmosphere
unchanging primarily concerned with weather
prediction There is very little hope for the
possibility of deducing a theory for the general
circulation of the atmosphere from the complete
hydrodynamic and thermodynamic equations.
(Bolin, 1952)? 1960s Recognition of changing
atmosphere (Keeling, 1960)? Earth viewed from
space (1969)? 1970s Coupled ocean-atmosphere
models (NOAA)? Aerosols seen to be increasing
cooling effect (?)? . . . Because CH4 has no
direct effects on climate, it is considered to
be of no importance. . . (1971)? O3 hole,
recognition that chemistry is important CFCs,
CH4, O3 recognized as greenhouse gases Gaia,
A New Look at Life on Earth (Lovelock,
1979)? 1988 Earth System Sciences A Closer View,
NASA, Washington, D. C.
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Early history of climate modeling
1950s Simple physical models atmosphere
unchanging primarily concerned with weather
prediction There is very little hope for the
possibility of deducing a theory for the general
circulation of the atmosphere from the complete
hydrodynamic and thermodynamic equations.
(Bolin, 1952)? 1960s Recognition of changing
atmosphere (Keeling, 1960)? Earth viewed from
space (1969)? 1970s Coupled ocean-atmosphere
models (NOAA)? Aerosols seen to be increasing
cooling effect (?)? . . . Because CH4 has no
direct effects on climate, it is considered to
be of no importance. . . (1971)? O3 hole,
recognition that chemistry is important CFCs,
CH4, O3 recognized as greenhouse gases Gaia,
A New Look at Life on Earth (Lovelock,
1979)? 1988 Earth System Sciences A Closer View,
NASA, Washington, D. C.
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Early history of climate modeling
1950s Simple physical models atmosphere
unchanging primarily concerned with weather
prediction There is very little hope for the
possibility of deducing a theory for the general
circulation of the atmosphere from the complete
hydrodynamic and thermodynamic equations.
(Bolin, 1952)? 1960s Recognition of changing
atmosphere (Keeling, 1960)? Earth viewed from
space (1969)? 1970s Coupled ocean-atmosphere
models (NOAA)? Aerosols seen to be increasing
cooling effect (?)? . . . Because CH4 has no
direct effects on climate, it is considered to
be of no importance. . . (1971)? O3 hole,
recognition that chemistry is important CFCs,
CH4, O3 recognized as greenhouse gases Gaia,
A New Look at Life on Earth (Lovelock,
1979)? 1988 Earth System Sciences A Closer View,
NASA, Washington, D. C.
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The crew of Apollo 8 had been trained for just
about every eventuality, save one the
awe-inspiring sight of seeing our own planet
hanging over an empty lunar horizon. . .
The "Earthrise" image of the world rising in the
dark vastness of space over a sun-lit lunar
landscape became an iconic reminder of our lonely
planet's splendid isolation and delicate
fragility.
. . . established our planetary facthood and
beauty and rareness (dry moon, barren space) and
began to bend human consciousness.
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The whole Earth from space, as photographed by
the Apollo 17 crew in 1972. Arguably the most
influential image to come out of the American
space program
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Early history of climate modeling
1950s Simple physical models atmosphere
unchanging primarily concerned with weather
prediction There is very little hope for the
possibility of deducing a theory for the general
circulation of the atmosphere from the complete
hydrodynamic and thermodynamic equations.
(Bolin, 1952)? 1960s Recognition of changing
atmosphere (Keeling, 1960)? Earth viewed from
space (1969)? 1970s Coupled ocean-atmosphere
models (NOAA)? Aerosols seen to be increasing
cooling effect (?)? . . . Because CH4 has no
direct effects on climate, it is considered to
be of no importance. . . (1971)? O3 hole,
recognition that chemistry is important CFCs,
CH4, O3 recognized as greenhouse gases Gaia,
A New Look at Life on Earth (Lovelock,
1979)? 1988 Earth System Sciences A Closer View,
NASA, Washington, D. C.
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GAIA A New Look at Life on Earth
The only feasible explanation of the Earths
highly improbable atmosphere was that it was
being manipulated on a day-to-day basis from the
surface, and that the manipulator was life
itself. The significant decrease in entropyor
as a chemist would put it, the persistent state
of disequilibrium among the atmospheric gaseswas
on its own clear proof of lifes activity.
James Lovelock, 1979
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Earths Improbable Atmosphere
Oxidizing Reducing Inert
If life on Earth ceased, all the elements in the
crust, oceans and atmosphere would react together
until a state close to chemical equilibrium was
reached. The planet would become a hot,
waterless, and inhospitable place.
(290oC) James Lovelock, 1979
Mars Venus Dead Earth Earth
O2 CO2 CH4 H2 N2 Ar
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Lovelocks Gaia Contribution
Whether or not you accept the extreme versions of
the Gaia hypothesis, the publication of
GAIA, A New Look at Life on Earth (1979)
influenced the way in which scientists and the
general public view the Earth system. It is
still being debated 30 years later. Focused
attention on the role of the Biosphere in
Atmospheric processes. Promoted
interdisciplinary research (now strongly
supported by NCAR). Stimulated research to
prove/disprove GAIAN regulatory
mechanisms. Helped foster a systems approach
to Earth Science in which the Earth is viewed as
a complex system, with biogeochemical cycling of
matter and energy between Geosphere, Hydrosphere,
Biosphere and Atmosphere with important
interactions and feedbacks between them.
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Early history of climate modeling
1950s Simple physical models atmosphere
unchanging primarily concerned with weather
prediction There is very little hope for the
possibility of deducing a theory for the general
circulation of the atmosphere from the complete
hydrodynamic and thermodynamic equations.
(Bolin, 1952)? 1960s Recognition of changing
atmosphere (Keeling, 1960)? Earth viewed from
space (1969)? 1970s Coupled ocean-atmosphere
models (NOAA)? Aerosols seen to be increasing
cooling effect (?)? . . . Because CH4 has no
direct effects on climate, it is considered to
be of no importance. . . (1971)? O3 hole,
recognition that chemistry is important CFCs,
CH4, O3 recognized as greenhouse gases Gaia,
A New Look at Life on Earth (Lovelock,
1979)? 1988 Earth System Sciences A Closer View,
NASA, Washington, D. C.
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Climate interactions this 1974 summary of
feedbacks was a pioneering attempt to show the
complexity of the climate system. It basically
ignored biology.
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The Bretherton Diagram - Complex
Mitchell K. Hobish, Earth Systems Science,
Section 16, Remote Sensing Tutorial
http//rst.gsfc.nasa.gov/Sect16/Sect16_3.html
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The Bretherton Diagram- Simplified
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GCM Geneology
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How is Earth System Science different from other
types of geoscience?
ESS deals with the relationships between physical
and biological systems instead of the systems
themselves. Earth System Science uses holistic
rather than reductionist approaches. Earth
System Science is interdisciplinary, including
many academic disciplines No single discipline
can fully address the scope of ESS.
Does all this seem blindingly obvious to you?!
If so, perhaps weve made some progress.
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Geospheres
Atmosphere
Anthroposphere
Biosphere
Hydrosphere
Lithosphere and Pedosphere
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Atmosphere Biosphere
Many of the ways in which the Atmosphere impacts
the Biosphere are self-evident, primarily
manifested through the climate system (rainfall,
temperature, radiation, length of growing season,
etc.)? Another obvious impact is via pollutants
(O3, NOx, SO2, acid rain, etc.) and increasing
atmospheric CO2 (photosynthesis, plant
transpiration, ocean acidity, etc.)?
Atmosphere Biosphere
Biosphere affects the Atmosphere largely through
its role in Biogeochemical cycling (of carbon,
nitrogen, water, etc.)? Perhaps less obvious
effects on atmospheric chemistry and climate.
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Biosphere-Atmosphere Interactions
Radiation
TRACE GASES
AEROSOL
H2O
Energy
CO2
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Biosphere-Atmosphere Interactions
Alex Guenther, Group leader Tiffany Duhl Jim
Greenberg Peter Harley Thomas Karl Saewung
Kim Andrew Turnipseed Christine Wiedinmyer
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VOCs Emitted from Vegetation gt1000 compounds
identified
Amazon, 2004
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Volatile Organic Compounds (VOC) emitted from
Vegetation
R. Fall 1999
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TRACE GASES
Isoprene (C5H8)? Monoterpenes (C10H16)? Sesquiterp
enes (C15H24)? Oxygenated compounds
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Global Estimates of VOC EmissionsTotal 1290
Tg yr-1 (90 biogenic)?
Anthropogenic non-methane VOC 142 Tg yr-1
Isoprene 503 Tg yr-1
Other reactive BVOC 260 Tg yr-1
Other non-reactive BVOC 260 Tg yr-1
Monoterpenes 127 Tg yr-1
Seinfeld and Pandis, 1998 Guenther et al. 1995
Middleton 1995
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Tools for Investigating Trace Gas Fluxes
Analysis using ambient concentrations, isotopes
and oxidation products Satellite data (e.g. HCHO)?
Regional Characterization
Years
Process studies
Tower-based flux meas. systems
Days
Aircraft and blimp-based flux measurement systems
Enclosure flux meas. systems
TIME SCALE
Hours
Seconds
Leaf
Canopy
Landscape
Regional/global
SPATIAL SCALE
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Enclosure Measurements
Concentration in outflow air
Concentration in inflow air
Flux (CO-CI)/f/A
CO is concentration in outlet airstream CI is
concentration in inlet airstream f is flow rate A
is leaf area or leaf mass
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BVOC from trees

• Quercus spp. Isoprene
• Liquidambar spp. Isoprene/MT
• Eucalyptus spp. Isoprene/MT
• Pinus spp. MT

Other BVOC probably common to all
vegetation Methanol Leaf alcohols Acetone
Sesquiterpenes Acetaldehyde
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Above-Canopy Tower for Measuring Ecosystem Trace
Gas Exchange
CO2 H2O O3 NOx BVOC Isoprene
Monoterpenes Methanol Acetone
etc. Aerosols
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Above-Canopy Towers for Measuring Ecosystem
Exchange
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NCAR tethered blimp sampling system
VOC sampler
Humidity, Temper., Winds
Particles, O3, CO, CO2
VOC sampler
VOC sampler
Boundary Layer
VOC sampler
30 min integrated sample between ascent and
descent
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Aircraft Studies
Brazil, CAPOS 2004
Thomas Karl et al.
Biomass Burning / Biogenic Emission Study
Beinderante, INPE
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Why Do We Care?Implications of Biogenic and
Fire Emissions

• Air Quality
• Visibility
• Radiation
• Climate
• Water Cycling

• Human health
• Agriculture
• Ecology
• Policy
• Management

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Ozone H2CO CO CH4
oxidize
TRACE GASES
Isoprene Monoterpenes Sesquiterpenes Oxygenated
VOC
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Regional Air Quality Ozone (O3)?

• Criteria Pollutant
• Concentrations are regulated by the Clean Air Act
• National Ambient Air Quality Standards (NAAQS)?
• O3 lt 120 ppbv (1-hour average)?
• O3 lt 80 ppbv (8-hour average)?
• Why is it regulated?
• unhealthy to breath
• harmful to materials
• destroys plants (agriculture)?

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Regional Air Quality Ozone (O3)?
Ozone produced through atmospheric chemical
reactions Nitrogen Oxides (NOx)
VOC sunlight
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Simplified Catalytic Cycle of Tropospheric Ozone
Production
Players VOC volatile organic compounds NOx
nitrogen oxides RO2 peroxy radicals hv
radiation
Ozone
O2
O
Catalyst
hv
OH
NOx emissions
NO
NO2
HNO3
fossil fuel combustion biomass burning (soil,
lightning)?
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How do we control air pollution?

• O3 is created in the atmosphere
• not directly emitted
• not linear!
• Need to understand the emissions and chemistry to
  know what to control...
• Biogenic emissions can be an important component
  of the VOCs in certain areas...
• Need to measure and understand
• Biogenic VOC emissions!!

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Why Do We Care?Implications of Biogenic and
Fire Emissions

• Air Quality
• Visibility
• Radiation
• Climate
• Water Cycling

• Human health
• Agriculture
• Ecology
• Policy
• Management

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Ozone H2CO CO CH4
Organic Aerosol
Secondary Organic Aerosol
oxidize
AEROSOL
TRACE GASES
Fire Smoke Spores PollenBacteria
Isoprene Monoterpenes Sesquiterpenes Oxygenated
VOC
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Radiation
Radiation
CCN
Organic Aerosol
Secondary Organic Aerosol
AEROSOL
Fire Smoke Spores PollenBacteria HUMLIS
Precipitation
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What do we do with the measurements?

• Develop vegetation emission models
• Inputs to chemistry and climate models
• Simulate atmospheric processes
• Earth System Modeling
• Goals
• better understand current and past conditions
• try to predict future conditions

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Biogenic Emissions Modeling

• MEGAN
• Model of Emissions of Gases and Aerosols from
  Nature
• Based on Guenther et. al., Atmospheric Chemistry
  and Physics, 2006
• 134 emitted chemical species
• Isoprene
• Monoterpenes
• Oxygenated compounds
• Sesquiterpenes
• Nitrogen oxide
• Lumped to 20 categories
• 1 km2 resolution

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METEOROLOGICAL AND PHENOLOGICAL VARIABLES
CONTROLLING ISOPRENE EMISSION

• LIGHT
• Diffuse and direct radiation
• Instantaneous and accumulated
• (24 hrs and 10 days)

• TEMPERATURE (Leaf-level)
• instantaneous and accumulated
• (24 hrs, 10 days)

?T
?L
T
PAR

• LEAF AGE
• Max emission mature
• Zero emission new

LAI
SUMMER
Month
SOIL MOISTURE ? suppressed under drought
Guenther et al., 2006
Slide from C. Heald (CSU)
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Model of Emissions of Gases and Aerosols from
Nature MEGAN
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MEGANModel of Emissions of Gases and Aerosols
from Nature Global model with 1 km2 and hourly
resolution
Designed for regional and global emission
modeling web site bai.acd.ucar.edu Guenther et
al. (2006) Atmos. Chem. Physics
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TROFFEE 2006
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Landusechange - Isoprene Fluxes
Amazon River
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Regional Chemical Modeling
Jack Chen Washington State Univ.
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Some things to think about ...

• How will climate change impact BVOC emissions?
• And how will the emissions impact climate change?
  
• How are we changing biosphere-atmosphere
  exchanges?
• urbanization
• agriculture
• replanting forests
• What are the important feedbacks between the
  biosphere and the atmosphere?
• CO2
• aerosols
• H2O

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BVOC in the atmosphere
Thanks for your attention!