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Trace gases in the atmosphere: Sources, their chemical fate, and why we care

Remote locations Biomass burning Rural air quality Urban smog

Whole Air Sampler (WAS)


Possible projects
1. Are waste water treatment facilities contributing significant amounts of VOCs to the urban atmosphere to affect ozone levels 2. What gases are being emitted from water treatment plants 3. Does the airborne distribution of water treatment emitted gases support their ground locations

4. What is the LAX VOC emission fingerprint 5. How important are marine VOC emissions on the Los Angeles basin air quality 6. Are there certain areas of the LA Basin that emit proportionally more greenhouse gases

7. How do greenhouse gas levels in 2012 compare with those observed in NASAs ARCTAS project flown in 2008 8. Are there ANY significant sources of CFCs and methyl chloroform in the LA Basin 9. Using aircraft data can we determine if methyl bromide is still being used for structural fumigation for termites in the LA Basin?

10. Has chlorinated solvent use in the LA Basin changed since ARCTAS 11. Do we see chlorinated solvents in water treatment facilities or local rivers 12. Have OVOC emissions from dairies changed during the past four years. 13. Can we estimate methane emissions from dairies in the central valley and can we isolate methane emissions from cattle from manure emissions.

Whole Air Sampling group members will learn the importance of and participate in:

Preparation of canisters for whole air sampling Discussions of previous airborne and ground based studies Flight planning-where to fill canisters Chemical analysis of samples Data preparation Methods of data interpretation

(Rafe) Day of infamy

Field work

Team Pink

Blake Lab Analytical Capabilities


Trace gas analysis (canisters)
Gas Chromatography (GC) Flame Ionization Detection (FID) Electron Capture Detection (ECD) Mass Spectrometric Detection (MSD)

Sensitive, speciated VOC detection


Identification and quantification of >100 VOCs (and thousands of cans)
NMHCs Halos Alkyl-NO3 DMS OCS LOD Accuracy Precision 3 ppt 5% 2% 10 ppq 5% 1% 10 ppq 10% 1% 1 ppt 5% 1% 10 ppt 5% 2%

UC-Irvine laboratory

Trace Gas Analysis System

Response (mV)
10.0 20.0 30.0 40.0 50.0 0 0 mV 1.0 2.0 3.0 H-1211 4.0 CFC-11 5.0 CH3I 6.0 CH2Cl2 Methyl Nitrate 7.0 CHCl3 Ethyl Nitrate 8.0 9.0 10.0 3-Pentyl Nitrate / 2-Pentyl Nitrate 11.0 min 12.3 CHBr3 C2CHCl3 CHBrCl2 n-Propyl Nitrate C2Cl4 2-Butyl Nitrate i-Propyl Nitrate

Sample ECD Chromatogram

Time (min)

CFC-113

Flame ionization detector chromatogram: response vs time (Gulf sample)

Some compounds and their atmospheric effects


Hydrocarbons
CH4: greenhouse gas Tropospheric O3 precursors
methane ethane ethene ethyne propane propene propyne i-butane n-butane c-2-butene t-2-butene 1-butene i-pentane n-pentane n-hexane benzene toluene isoprene styrene m-xylene o-xylene p-xylene 1,3,5-TMB 1,2,4-TMB 1,3-butadiene c-2-pentene t-2-pentene n-octane n-nonane etc.

Halocarbons
CFCs: strong greenhouse gases Many: stratospheric O3 depletors
CFC-11 CFC-12 CFC-113 CFC-114 CCl4 CH3CCl3 H-1211 H-2402 HCFC-141b HCFC-142b HCFC-22 HFC-134a 1,2-DCE C2Cl4 C2HCl3 CHCl3 CHBr3 CH2Cl2 CH2Br2 CHBrCl2 CHBr2Cl CH3Cl CH3Br CH3I C2H5I etc.

Carbon monoxide
Urban air pollutant Decreases global OH

Sulfur compounds
Cloud condensation nuclei Affect global albedo
DMS DMDS OCS CS2

Organic nitrates
Transport NOx (= NO + NO2) NOx = trop. O3 precursor
MeONO2 EtONO2 1-PrONO2 2-PrONO2 2-BuONO2 2-PeONO2 3-PeONO2

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 Central Pacific South Pacific
6/19/12

Sample Collection: 71N to 47S

Barrow, Alaska (71N) Our most northerly sampling location Photo: Looking north at the Arctic coast (June 2002)
6/19/12

Bluff, New Zealand (47S) Our most southerly sampling location Photo: Looking south towards Antarctica (September 1998)

Global Annual Methane Average


10% increase in 21 years 1620 ppbv in 1983 1776 ppbv in 2003 Average growth rate (1983-2003) 7.6 0.2 ppbv yr-1 Changing growth pattern Smooth in 1980s Variable in 1990s Slowing down in early 2000s

What can we say about lifetime, source locations


and removal?

Wide Latitudinal Variation


March 1999
Ethane

Data from University of California, Irvine


Strong Seasonal Cycle


Summit, Greenland, June 1997 - June 1998
Ethane

Follows seasonal cycle of OH



Data from University of California, Irvine
Swanson et al., 2003

We work with NASA, NOAA, NSF, and groups around the world studying processes important to global climate change, startospheric ozone depletion, and urban pollution

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 Earths 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"

Modied from Browell et al., 1999 and Blake et al., 1999


Atmospheric hydrocarbon removal: lifetimes


HO + RH + O2 RO2 + H2O

Ethane + OH ~20 days in tropics CO + OH ~20 days in tropics Ethyne + OH ~6 days in tropics Ethene + OH ~1 day in tropics Propene + OH ~6 hours in tropics

Biomass burning plume sampled near Tahiti


September 5, 1996"

Modied from Browell et al., 1999 and Blake et al., 1999


10-Day Backwards Trajectories arriving near Tahiti


September 5, 1996
- Pollution plume came all the way from biomass burning in Africa

Modied from Blake et al., 1999


City Study: LUCK?

Oklahoma City by Season (1999-2000)

September 2001 Study

September 2001 Ethane

Regional Study #2: April 28 to May 3, 2002

April 2002 Study

April 2002 Study

April 2002 Study

Source

** Berger and Anderson, Modern Petroleum (1992)

Emissions Estimates
Compound
methane
ethane
propane
n-butane
i-butane
n-pentane
i-pentane
Emissions
4.2 6.4 Tg/yr
0.30 0.46 Tg/yr
0.20 0.29 Tg/yr
75 110 Gg/yr
31 46 Gg/yr
18 26 Gg/yr
17 25 Gg/yr

2 years ago

Photo Album
by Don Blake

The atmosphere is a giant photoreactor


Emissions of :

Volatile Organic Compounds (VOCs)


Light hydrocarbons, alcohols,


carbonyls, acids, halogenated HC

and NO + NO2 = NOx

- carbonyls

+ h
+ O2

- peroxides
- Ozone
- organic nitrates
- organic aerosols

Formation of Tropospheric Ozone


O3

NO

NO2

Formation of Tropospheric Ozone


O3

NO

NO2

O2

Formation of Tropospheric Ozone


O3

NO

NO2

Needs:
O3 + NO NO2

O2

Formation of Tropospheric Ozone


O3

NO

NO2

Needs:
O3 + NO NO2

O2

With Hydrocarbons

O3 + h O(1D) + O2
O(1D) + H2O 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

O3

NO

NO2

Needs:
O3 + NO NO2

O2

With Hydrocarbons

RO2
NO

Formation of Tropospheric Ozone



No Hydrocarbons

O3

NO

NO2

Needs:
O3 + NO NO2

O2

With Hydrocarbons

RO2
NO

RO
NO2

Formation of Tropospheric Ozone



No Hydrocarbons

O3

NO

NO2

Needs:
O3 + NO NO2

O2

With Hydrocarbons

RO2
NO

RO
NO2
O2
O3

Formation of Tropospheric Ozone



No Hydrocarbons

O3

NO

NO2

Needs:
O3 + NO NO2

O2

With Hydrocarbons

RO2
NO

RO
Uses HC radicals for
NO2

rapid conversion of
NO NO2

O2

O3

Alkyl Nitrate Formation:


Minor Pathway
Alkyl Nitrate

RONO2

Major Pathway
RO

NO
OH Hydrocarbon H2O

NO2 + h
NO

NO + O(3P) O2

RH

R.

O2

Alkylperoxy radical

ROO

HO2

ROOH

M O3

M + NO2 ROONO2

ROO. ROOR

Daily evolution of photochemical air pollution


Rush-hour emissions of NO and HCs followed by:


Rapid conversion of NO NO2 and formation of aldehydes
Then build-up of O3, peaking at noon

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