Possible

WAS projects/trips
Sampling upwind/downwind of hydrogen filling
stations
Sampling around selected airports to see if H-1301
is still in use
Dairy study for DMS/DMDS/ethanol
Porter ranch ground sampling for oil/ng
Students determine possible fracking sites that we
will then sample.

UC Irvine Rowland-Blake WAS group

Air quality monitoring and
VOC measurements in
global ecosystems:
Remote background locations
- Pacific Basin

Areas with special conditions

- Marine environments
- Agricultural waste
- Oil sands
- Biomass burning, etc.

Pristine

Worlds megacities
- Mexico City
- Hong Kong
- Karachi
- Mecca, etc.

Polluted

Volatile organic compound sources

Biogenic:

Fossil fuel combustion:

Isoprene
-Pinene
-Pinene

Ethyne
Benzene
Ethene

Biomass burning:

Fossil fuel evaporation:

Ethyne
Benzene
n-Butane

Industrial:
C2Cl4
HCFC-22
HFC-134a

Methane
i-Pentane

Hydrocarbon oxidation:
2-Butyl nitrate
Acetaldehyde

Oceans:
Methyl nitrate
Methyl iodide

Rowland-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

10.0

0
0
1.0
2.0
3.0
4.0
5.0
6.0

Time (min)
7.0
8.0
9.0

2-Butyl Nitrate
10.0
CHBr3

3-Pentyl Nitrate / 2-Pentyl Nitrate

C2Cl4

n-Propyl Nitrate

i-Propyl Nitrate

30.0

CHBrCl2

Ethyl Nitrate

CHCl3

Methyl Nitrate

20.0

C2CHCl3

CH 2Cl2

CFC-113

CFC-11

50.0

CH 3I

H-1211

Response (mV)

Sample ECD Chromatogram

mV

40.0

min

11.0
12.3

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
CH3 CCl3
H-1211
H-2402
HCFC-141b
HCFC-142b
HCFC-22
HFC-134a
1,2-DCE

C2 Cl4
C2 HCl3
CHCl3
CHBr3
CH2 Cl2
CH2 Br2
CHBrCl2
CHBr2 Cl
CH3 Cl
CH3 Br
CH3 I
C2 H5 I
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

WAS group questions/projects

1. Does fracking have a specific VOC profile
2. If fracking has a specific VOC profile is it
evident in the LA Basin
3. Are there locations in the LA Basin that exhibit
i-pentane/n-pentane ratios that differ from
gasoline evaporation

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 2016 greenhouse gas levels in the LA

Basin compare with those observed during
previous SARP missions
8. Using aircraft data can we determine if methyl
bromide is still being used for structural
fumigation for termites in the LA Basin?

9. Compare Korean missed approaches to those

in the LA Basin: what gases differ?
10. Can we estimate methane emissions from
dairies in the central valley and can we
differentiate methane emissions from cattle
from manure methane 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
Chromatogram modification
Data preparation
Methods of data interpretation

Group meeting

Team Pink

Volatile Organic Compounds in the atmosphere

O2 RO
2

VOCs

NO
RO

OH
HO2

NO2

VOCs

O3

O2

Oxygenated VOCs
VOCs
NOx
SO2

O + O2

VOCs
NOx

VOCs
NOx

Secondary organic aerosol (SOA)

VOC reactions lead to:
Tropospheric ozone (O3)
Secondary organic aerosol (SOA)

These products impact:

Air quality, global climate, health

Some VOCs are toxic:

e.g. Benzene is carcinogenic
After: www.chem.wisc.edu/users/keutch/ and
www.york.ac.uk/inst/sci/APS/backgrd_files/figure4.gif

Human health effects of exposure to ozone (O3)

Seriousness of effect

Typical ozone levels:

Pre-industrial: 1015 ppbv
Clean air: 3040 ppbv
Polluted air: 80150 ppbv

Ozone affects
people and animals
Number of people affected
http://www.epa.gov/apti/ozonehealth/population.html
http://www.epa.gov/glo/health.html

Ozone impact on plant yield

DC-8 in Korea

Inlets on the port side of DC-8

Top Gun (Iceman Crawford)

Nicola and Don in safety gear

Snakes dont load themselves

KORUSAQ using the NASA DC-8

Left Palmdale on April 29 and flew ~20 missions
around South Korea.
Returns to Palmdale TODAY!
Using flight 13 prelim WAS data to illustrate the
types of flights for DC-8
https://espo.nasa.gov/home/korusaq/node/39128

WAS can collect 168 samples per flight

and we quantify ~100 gases
Lots of data just from WAS.
Merged data available for prelim data so lots
and lots of data.
How to do a quick look at large data sets.
A quick lesson in atmospheric chemistry

Altitude (feet) vs Julian date

Latitude vs Julian date

Why did we not fly further north?

What do we do if NASA brings that DC-8

north of 38 degrees latitude???

Longitude vs Julian date

Carbon monoxide (ppb) vs Julian date

Ethyne (ppt) vs Julian date

Ethyne (ppt) vs carbon monoxide (ppb)

Ethane (ppt) vs Julian date

Chloroform (ppt) vs Julian date

Toluene (ppt) vs Julian date

Lifetimes
CFC-12 (ppt) vs altitude (feet)

CFC-11 (ppt) vs altitude (altitude)

Methylchloroform (ppt) vs altitude

Ethane (ppt) vs altitude (feet)

Ethene (ppt) vs altitude (feet)

TCE (ppt) vs altitude (feet)

n-pentane (ppt) vs altitude (feet)

2-PenONO2 (ppt) vs altitude (feet)

2-PenONO2 vs n-pentane

KORUS-AQ UC-Irvine WAS Field Data

RF 01 May 01 2016
25

WAS Ethane pptv

C2H6_CAMS_pptv
Pressure_Altitude ft

20

6000
15

x10

4000

Ethane ppt

8000

10

2000

85

90

95

100

UTC Time sec

105

110 x10

KORUS-AQ UC-Irvine WAS Field Data

RF 03 May 04 2016
6000

25 x10

Ethane__E_
P_Alt_WAS
X_C2H6_CAMS_pptv

20

4000
15

P Alt Ft

Ethane ppt

5000

3000
10

2000
5

1000
0

84

86

88

90

92

94

UTC Time sec

96 98 x103

KORUS-AQ UC-Irvine WAS Field Data

RF 03 May 04 2016
6000

25 x10
P_Alt_WAS
X_CH2O_CAMS_pptv
X_C2H6_CAMS_pptv
Ethane__E_

20

4000
15

P Alt Ft

Ethane ppt

5000

3000
10

2000
5

1000
0

84

86

88

90

92

94

UTC Time sec

96 98 x103

KORUS-AQ UC-Irvine WAS Field Data

RF 03 May 04 2016

6000

5000

5000

P_Alt_WAS
X_C2H6_CAMS_pptv
Ethane__E_

4000

20

1000 ppt offset

15

P Alt Ft

4000

25 x10

WAS Ethane ppt

6000

CAMS Ethane ppt

7000

3000
10

3000

2000

2000

1000

1000

84

86

88

90

92

94

UTC Time sec

96 98 x103

KORUS-AQ UC-Irvine WAS Field Data

RF 04 May 06 2016
6000

5000

5000

25 x10
Pressure_Altitude
Ethane__E_
X_C2H6_CAMS_pptv

4000

20

1000 ppt offset

3000

15

3000

2000

10

2000

1000

1000

P Alt Ft

4000

85

90

95

100

UTC Time sec

105

110 x10

Flight 1 UCI ethane (ppt) vs Fried

ethane (ppt)

SARP 2009-2015 benzene (ppt) vs altitude (feet)

KORUSAQ flights 1-13 toluene (ppt) vs

altitude (feet)

SARP 2009-2015 toluene (ppt) vs altitude (feet)

KORUSAQ flights 1-13 toluene (ppt) vs

altitude (feet)

KORUSAQ flights 1-13 CH3CCl3 (ppt) vs

altitude (feet)

SARP 2009-2015 CH3CCl3 (ppt) vs

altitude (feet)

SARP 2009-2015 CH3CCl3 (ppt) vs Julian day

Conclusions
Atmospheric sciences is a great/fun field in which to work
Work on important and fundamental problems
Make lots of great friends (Jim and Barry as grad students)
Four WAS SARPERs are in PhD program at Caltech
Emily is rarely wrong but Monday she made a slight slip.
She said I have the best job in the world. She is right but
she is not the only one who can say that!

NASA ARCTAS
June-July, 2008
12 flights on the NASA DC-8
1651 whole air samples collected
Flights in and around Los Angeles
photochemistry and GHG emissions (flight 13)
Flights in Canada for biomass burning

Benzene (pptv) vs CO (ppbv)

Toluene vs CO (solvents)

Propane vs CO (LPG)

HCFC-134a vs time (urban)

C2Cl4 vs time (solvents)

1,3-butadiene vs time (biomass

burning)

Propyne vs time (biomass B)

Furan vs time (biomass B)

Biomass burning plume sampled near Tahiti

September 5, 1996

Modified 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

Modified from Blake et al., 1999