Académique Documents
Professionnel Documents
Culture Documents
• Remote
• Biomass burning
• Rural air quality
• Urban smog
CH4 CHBrCl2 1-Pentene Styrene
CO CH2BrCl Isoprene Isopropylbenzene
CO2 CHBr3 trans-2-Pentene Propylbenzene
OCS Ethyl Chloride cis-2-Pentene 1,2,4-Trimethylbenzene
DMS 1,2-DCE 2,2-Dimethylbutane n-Decane
CS2 MeONO2 2,3-Dimethylbutane alpha-Pinene
F-12 EtONO2 2-Methylpentane beta-Pinene
F-11 i-PrONO2 3-Methylpentane Acetaldehyde
F-113 n-PrONO2 n-Hexane Acetone
F-114 2-BuONO2 Methylcyclopentane Butanal
H-1211 3-PenONO2 Cyclohexane Butanone
H-2402 2-PenONO2 n-Heptane Ethanol
HFC 134a Ethane 2,2,4-Trimethylpentane Methanol
HCFC 22 Ethene 2,3,4-Trimethylpentane
HCFC 142b Ethyne n-Octane
HCFC 141b Propane Benzene
CHCl3 Propene Toluene
MeCCl3 i-Butane Ethylbenzene
CCl4 n-Butane m-Xylene
CH2Cl2 1-Butene p-Xylene
C2HCl3 i-Butene o-Xylene
C2Cl4 trans-2-Butene 3-Ethlytoluene
CH3Cl cis-2-Butene 4-Ethyltoluene
CH3Br i-Pentane 1,3,5-Trimethylbenzene
CH3I n-Pentane 2-Ethyltoluene
CH2Br2 1,3-Butadiene n-Nonane
Global Methane Sampling
CH4 monitoring
• 1978 to present
Sampling
frequency
• 4 trips a year
(Mar, Jun, Sep, Dec)
• 3-week period
Number of
samples
• 60-80 per trip
Locations (40-45)
• Alaska
• Pacific Northwest
• Baja California
07/23/09 • Central Pacific
• South Pacific
Sampling Method
Site selection
• Along coast
• On-shore wind
Sampling
duration
• 1 minute
Pressure of
sample
• Canister is filled
Kodiak Island, Alaska (57.8°N), June 2002 from near-
vacuum to
ambient pressure
07/23/09
Sample Collection: 71°N to 47°S
Wide Latitudinal Variation
March 1999
2500
Mixing Ratio (pptv)
2000
Ethane
• Most sources
1500 in NH
1000
500
0
60 30 0 -30 -60
N Latitude S
Data from University of California, Irvine
Strong Seasonal Cycle
Summit, Greenland, June 1997 June 1998
3000
2500 Ethane
Ethane (pptv)
2000
1500
1000
500
0
June Sep Dec Mar June
• Follows seasonal cycle of OH
Data from University of California, Irvine
Swanson et al., in press
Global Annual Methane Average
1800
10% increase in 21
1750 years
• 1620 ppbv in 1983
1700 • 1776 ppbv in 2003
1650 Average growth rate
(1983-2003)
1600
• 7.6 ± 0.2 ppbv yr-1
1550 Seasonal average
Annual average Changing growth
1500 pattern
1975 1980 1985 1990 1995 2000 2005 • Smooth in 1980s
Year • Variable in 1990s
• Slowing down in early
2000s
Biomass Burning
Lightning fire was “domesticated” by our
ancestors at least 200,000 years ago.
Biomass burning includes the burning of the
world's vegetation forests, savannas, and
agricultural lands. Also burning wood and
agricultural resides for fuel
Importance of Biomass Burning
Biomass burning is now recognized as making significant contributions
to the global budgets of many radiatively and chemically active gases,
contributing as much as:
•40% of carbon dioxide
• 38% of tropospheric O3
• 24% of NMHCs
May have increased by as much as 50% since
1850 largely as a result of increasing rates of
deforestation (Houghton 1991).
Enhanced frequency of fires may be an
important positive feedback on a warming Earth.
DC-8 before integration
Pacific Exploratory Mission - Tropics A and B
On the tarmac,
exchanging filled
canisters with empty
ones in preparation for
the next flight
Yokota Air Force Base, Japan
During a typical
8-hour science flight,
we collected about
150 pressurized
air samples.
Biomass burning plume sampled near Tahiti
September 5, 1996
Modified from Browell et al., 1999 and Blake et al., 1999
10Day Backwards Trajectories arriving near Tahiti
September 5, 1996
Pollution plume came all the way from biomass burning in Africa
Modified from Blake et al., 1999
The atmosphere is a giant photoreactor
Emissions of : carbonyls
Volatile Organic Compounds (VOCs)
+ hν peroxides
Light hydrocarbons, alcohols,
carbonyls, acids, halogenated HC… Ozone
+ O2
organic nitrates
and NO + NO2 = NOx
organic aerosols
Formation of Tropospheric Ozone
NO NO2
O3
Formation of Tropospheric Ozone
NO NO2
O3
O2
Formation of Tropospheric Ozone
NO NO2 Needs:
O3 O3 + NO → NO2
O2
Formation of Tropospheric Ozone
NO NO2 Needs:
O3 O3 + NO → NO2
O2
With Hydrocarbons
O3 + hυ O(1D) + O2
O(1D) + H20 2 HO
HO• + RH + O2 → RO2• + H2O
HO• radicals are the principal sink for CH4, HCFCs,
and many other greenhouse gases.
Formation of Tropospheric Ozone
No Hydrocarbons
NO NO2 Needs:
O3 O3 + NO → NO2
O2
With Hydrocarbons
RO2•
NO
Formation of Tropospheric Ozone
No Hydrocarbons
NO NO2 Needs:
O3 O3 + NO → NO2
O2
With Hydrocarbons
RO2• RO•
NO NO2
Formation of Tropospheric Ozone
No Hydrocarbons
NO NO2 Needs:
O3 O3 + NO → NO2
O2
With Hydrocarbons
RO2• RO•
NO NO2
O2 O3
Formation of Tropospheric Ozone
No Hydrocarbons
NO NO2 Needs:
O3 O3 + NO → NO2
O2
With Hydrocarbons
RO2• RO• Uses HC radicals for
rapid conversion of
NO → NO2
NO NO2
O2 O3
Lifetimes
Oxygenate MIR (g O3/g C) Lifetime
Minor Pathway
Major Pathway
RONO2
Alkyl Nitrate RO .
NO2 + hν NO + O(3P)
NO +
NO
O2
HO2 ROOH
.
OH H2O M
R.
RH O2 ROO O3
Hydrocarbon Alkylperoxy M + NO2
radical
R’OO.
ROONO2
ROOR’
Daily evolution of photochemical air pollution
Rushhour emissions of NO and HCs
followed by:
• Rapid conversion of NO → NO2
and formation of aldehydes
• Then buildup of O3, peaking at
noon
Q: What about the other Greenhouse Gases & Aerosols?
August 1999 City Study
Chicago
4000
Houston
3500 New York
CO in ppbv)
CO
Isoprene
Propene
i-Butane
Hexane
Propane
i-Pentane
Benzene
Ethane
Ethene
n-Butane
Ethyne
n-Pentane
Toluene
Hydrocarbon
Mixing Ratio (pptv, CH4 &
CO in ppbv)
0
2000
4000
6000
8000
10000
CH4
CO
Ethane
Ethene
Ethyne
Propane
Propene
i-Butane
n-Butane
Hydrocarbon
i-Pentane
Oklahoma City by Season (1999-2000)
n-Pentane
Isoprene
Hexane
May
August
Oklahoma City by Season (1999-2000)
Benzene
February
November
Toluene
September 2001 Study
Sample Locations
42
40
38
36
34
32
30
-106 -104 -102 -100 -98 -96 -94 -92 -90
September 2001 Ethane
42
40
7900 to 8800
7000 to 7900
36
6100 to 7000
5200 to 6100
4300 to 5200
34 3400 to 4300
2500 to 3400
1600 to 2500
32 700 to 1600
30
-106 -104 -102 -100 -98 -96 -94 -92 -90
Longitude (W)
Source
% Downwind % from
Storage Tank Literature **
Methane 69.2* 62.9
Ethane 10.9 14.6
Ethene 0.0
Ethyne 0.0
Propene 0.0
Propane 10.0 10.3
CH3Cl 0.0
i-Butane 1.2 1.2
n-Butane 5.1 8.2
i-Pentane 1.1 0.5
n-Pentane 1.8 0.6
Benzene 0.0
Toluene 0.1
Hexane 0.5 0.7
Heptane 0.2
* Subtracted 1.81 ppmv Methane Background Concentration
** Berger and Anderson, Modern Petroleum (1992)
Regional Study #2: April 28 to May 3, 2002
April 2002 Study
Ethane n-Butane
April 2002 Study
Propane Ethyne
April 2002 Study
Methane
Emissions Estimates
Compound Emissions
methane 4.2 – 6.4 Tg/yr
ethane 0.30 – 0.46 Tg/yr
propane 0.20 – 0.29 Tg/yr
nbutane 75 – 110 Gg/yr
ibutane 31 – 46 Gg/yr
npentane 18 – 26 Gg/yr
ipentane 17 – 25 Gg/yr
Photo Album
by Don Blake