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Trace gases in the atmosphere: Sources,

their chemical fate, and why we care

• 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

Barrow, Alaska (71°N) Bluff, New Zealand (47°S)


• Our most northerly • Our most southerly
sampling location sampling location
• Photo: Looking north at • Photo: Looking south towards
the Arctic coast (June 2002) Antarctica (September 1998)
07/23/09
Monitoring changes in NMHCs
Long­term changes in NMHCs are difficult to monitor because are have 
relatively low concentrations and are short­lived 
­ show wide spatial and temporal and variability
Monitoring changes in NMHCs
Long­term changes in NMHCs are difficult to monitor because are have 
relatively low concentrations and are short­lived 
­ show wide spatial and temporal and variability

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

The PEM-Tropics campaign


was flown over the tropical
Pacific Ocean in summer
1996 and spring 1999.
The objective was to study
air quality in one of the
Earth’s most remote areas.

The NASA DC-8 in Tahiti

On the tarmac,
exchanging filled
canisters with empty
ones in preparation for
the next flight
Yokota Air Force Base, Japan

Along the runway, with


the NASA DC-8 aircraft
in the background.

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

Ethanol 1.69 4 days

Methanol 0.71 16 days

Acetone 0.43 16 days

Acetaldehyde 6.84 11 hours


Alkyl Nitrate Formation:

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

August 1999 Comparison


4500
Mixing Ratio (pptv, CH4 &

Chicago
4000
Houston
3500 New York
CO in ppbv)

3000 Oklahoma City


2500 San Diego
Salt Lake City
2000
1500
1000
500
0
CH4

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

Mixing Ratio (ppt)


38 9700+
8800 to 9700
Latitude (N)

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