Choosing a SARP group

You will work with and live with your mentor

Your faculty member will visit you in Irvine
during the summer several times and will be
available over skype/email

2015 Pearson Education, Inc.

Group members

Your name here!

Whole Air Sampling (WAS) Group

Mentor: Jason Schroeder
Faculty Advisor: Don Blake

Sample Collection
Over 300 canisters
filled on the DC-8

Ground Samples
Santa Barbara Channel
Salton Sea

WAS data analysis

Blake lab carries out
analysis on NMHC
system
SARP students
analyze canisters for:
CH4
CO & CO2
H2

Gases Analyzed
Compound

Formula

Compound

Formula

Compound

Formula

Methane (ppm)
Carbon Monoxide (ppb)

CH4
CO

m-Xyelene
p-Xylene

C8H10
C8H10

Methyl Bromide
Methyl Chloride

CH3Br
CH3Cl

Carbon Dioxide (ppm)

CO2

o-Xylene

C8H10

Methyl Iodide

CH3I

n-Propylbenzene

C9H12

Methylene Bromide

CH2Br2

C2H6

2-Ethyltoluene

C9H12

Methylene Chloride

CH2Cl2

Propane

C3H8

3-Ethyltoluene

C9H12

Chloroform

CHCl3

i-Butane

C4H10

4-Ethyltoluene

C9H12

Trichloroethene

C2HCl3

n-Butane

C4H10

1,2,3-Trimethylbenzene

C9H12

Tetrachloroethene

C2Cl4

i-Pentane

C5H12

1,2,4-Trimethylbenzene

C9H12

1,2-Dichloroethane

C2H4Cl2

n-Pentane

C5H12

1,3,5-Trimethylbenzene

C9H12

Bromodichloromethane

CHBrCl2

n-Hexane

C6H14

BIOGENICS (ppt)

Dibromochloromethane

CHBr2Cl

n-Heptane

C7H16

Isoprene

C5H8

Bromoform

CHBr3

n-Octane

C8H16

-pinene

C10H16

ALKYL NITRATES (ppt)

2,3-Dimethylbutane

C6H14

-pinene

C10H16

Methyl Nitrate

CH3NO3

Ethyl Nitrate

C2H5NO3

ALKANES (ppt)
Ethane

ALKENES (ppt)

HALOCARBONS (ppt)

Ethene

C2H4

CFC-11

CFCl3

i-Propyl Nitrate

C3H7NO3

Propene

C3H6

CFC-12

CF2Cl2

n-Propyl Nitrate

C3H7NO3

1-Butene

C4H8

CFC-113

CCl2FCClF2

2-Butyl Nitrate

C4H9NO3

cis-2-Butene

C4H8

CFC-114

CClF2CClF2

3-Pentyl Nitrate

C5H11NO3

trans-2-Butene

C4H8

Methyl Chloroform

CH3CCl3

2-Pentyl Nitrate

C5H11NO3

1,3-Butadiene

C4H8

Carbon Tetrachloride

CCl4

OXYGENATES (ppt)

Ethyne

C2H2

Halon-1211

CBrClF2

Ethanol

C2H5OH

Halon-1301

CBrF3

Acetone

C3H6O

HFC-134a
HCFC-22
HCFC-141b

CH2FCF3
CHF2Cl
CH3CCl2F

MAC
MVK
MTBE

C4H6O
C4H6O
C5H12O

HCFC-142b

CH2CClF2

AROMATICS (ppt)
Benzene
Toluene
Ethylbenzene

C6H6
C7H8
C8H10

Gas Chromatography System

Thermocouple
Gauge

Capacitance
Manometer
500.0

Pump

Excess
Volume

He (lush

Pump

MFC

Splitter
Box

He Carrier

FID

ECD

FID

Chromeleon

ECD

DB-5-MS

DB-5+Restek
1701

PLOT+DB-1

DB-1

Liquid
Nitrogen

Restek 1701

Sample Standard

MS
Chemstation

Modifying
Tedious!
5 detectors
2 FIDs
2 ECDs
MS

Modifying

Army of Airbenders

Master Airbender

Honorary Member Rafe Day

Rafe Day

Jean Guo
Chemical and
Trajectory Analysis of
an Air Mass Plume from
Asia

Kara Voss
Identifying Trace Gas emissions from a
Coastal Phytoplankton Bloom

Jonathan Hemingway
Using ground-based air samples as a proxy for
airborne samples over the Los Angeles Basin

Krystal Vasquez
The Los Angeles Basin as a source of long lived
greenhouse gases

Maria Viitaniemi
Trace Gas Contributions to Ozone Formation
Potential in Southern California

Joseph Nettesheim
Investigating Oxygenate Emissions and their
Impact on Ozone Formation in the San Joaquin
Valley and L.A. Basin

Eric Lebel
Dimethyl Sulfide
Emissions from
Dairies and
Agriculture as a
Potential Contributor
to Sulfate Aerosols in
the California
Central Valley

Caleb Sykora-Bodie
Contributions of Dairy Operations to Methane in
the Lower Central Valley of California

Count on it!

1st

Flight Test
Flight

Lines over the Salton Sea

Spiral over the Edwards Air Force Base

Comparison of Cans Taken

During EAFB Spiral
Thousands

Edwards Air Force Base Spiral

40
35

Altitude (ft)

30
25

C2Cl4
C2Cl4

20

2-PeONO2
2-PeONO2
3-PeONO2
3-PeONO2

15

2-BuONO

2-BuONO2 2

10
5
0
0.000

1.000

2.000

3.000

4.000

5.000

Concentration (pptv)

6.000

7.000

8.000

Where did the plume

come from?
Another area of CA?

12hr Trajectory with Coal

Plants and Fires

96hr and 120hr Trajectories

with Coal Plants and Fires

Chemical Tracers of
Coal Burning

Coal Combustion

Chloroform (CHCl3)

Altitude (ft)

Thousands

Edwards Air Force Base Spiral

40
35
30
25
20

CHCl3
20.67

15

Higher by a
factor of 3

10
5
0
0.00

5.00

10.00

15.00

20.00

25.00

Concentration (pptv)

30.00

35.00

40.00

Coal Combustion

Carbonyl Sulfide (OCS)

Altitude (ft)

Thousands

Edwards Air Force Base Spiral

40
35
30
25
20
15

Increase by
200pptv

10
5
0
450

500

550

600

650

700

Concentration (pptv)

750

800

564
OCS

Chemical Tracers Urban

Urban Areas

1,2-Dichloroethene (1,2-DCE)
Thousands

Edwards Air Force Base Spiral

40
35

Altitude (ft)

30
25

1,2-DCE
8.20

20
15

Increase of
around
30pptv

10
5
0
0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

Concentration (pptv)

40.00

45.00

50.00

Urban Areas

Tetrachloroethylene (C2Cl4)
Thousands

Edwards Air Force Base Spiral

40
35

Altitude (ft)

30
25

(C2Cl4)
2.846

20
15

Increase of
~3pptv

10
5
0
0.000

1.000

2.000

3.000

4.000

Concentration (pptv)

5.000

6.000

7.000

Forward trajectory
from coal plants
outside of air plume
trajectory

96hr backwards trajectory

120hr backwards trajectory

Field trip

Possible projects/trips
First known hydrogen vertical profile!
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
Bakersfield ground sampling for diary/oil/ng
Students determine possible fracking sites that we
will then sample at them.
Santa Barbara oil spill beach sampling

Santa Barbara last SARP

Santa Barbara last week

Ride the wild surf?

What we might see next Wednesday

Whole Air Sampling group members will learn the

importance of and par?cipate in:

Prepara?on of canisters for whole air sampling

Discussions of previous airborne and ground based studies
Flight planning-where to ll canisters
Chemical analysis of samples
Chromatogram modica?on
Data prepara?on
Methods of data interpreta?on

Group mee?ng

Tube bending on aircraJ

Happy WAS team aJer integra?on

Atmospheric sciences

UC Irvine Rowland-Blake WAS group

Air quality monitoring and
VOC measurements in
global ecosystems:
Remote background locaJons
- Pacic Basin

Areas with special condiJons

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

Pristine

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

Polluted

VolaJle organic compound sources

Biogenic:

Fossil fuel combusJon:

Isoprene
-Pinene
-Pinene

Ethyne
Benzene
Ethene

Biomass burning:

Fossil fuel evaporaJon:

Ethyne
Benzene
n-Butane

Industrial:
C2Cl4
HCFC-22
HFC-134a

Methane
i-Pentane

Hydrocarbon oxidaJon:
2-Butyl nitrate
Acetaldehyde

Oceans:
Methyl nitrate
Methyl iodide

VolaJle Organic Compounds in the atmosphere

O2 RO
2

VOCs

NO
RO

OH
HO2

NO2

O2

Oxygenated VOCs
VOCs

VOCs
NOx
SO2

O + O2 O3

VOCs VOCs
NOx NO
x

Secondary organic aerosol (SOA)

VOC reacJons 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
A1er: www.chem.wisc.edu/users/keutch/ and
www.york.ac.uk/inst/sci/APS/backgrd_les/gure4.gif

Human health eects of exposure to ozone (O3)

Seriousness of eect

Typical ozone levels:

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

Ambient air quality limits

in Saudi Arabia2:
1-hour: 120 ppbv
8-hour: 80 ppbv

Number of people aected

hEp://www.epa.gov/apG/ozonehealth/populaGon.html
hEp://www.epa.gov/glo/health.html

Ozone aect on people and animals

Ozone impact on plant yield

Major Equipment
Chassis Dynamometer
- constant dilu?on sampling
VMAS
- raw sample
Canister
- raw sample
Proton Transfer Reac?on Mass Spectrometer
(PTR-MS)
- diluted sample

LPG Vehicles Tes?ng Sequence

1st Test: Baseline

2nd Test: New cataly?c converter, O2 sensor,
EGR valve w/o Air/Fuel ra?o tuning

3rd Test: New cataly?c converter, O2 sensor,
EGR valve aJer Air/Fuel ra?o tuning

Taxi (FF1883) Emissions

Before and After Repair
Emission (g/km)

Baseline
New Converter, O2 sensor, EGR #1

New Converter, O2 sensor, EGR #2

New Converter, O2 sensor, EGR + Tuning

Emission Limit

4
3
2
1

Emission Limit

NOx + HC

CO

Expect very lifle change in i-pentane

because not much from taxis
Average mixing ratio, ppmv

Preconverter

Postconverter

180
160
140

120
100
80
60

40
20
0
i-Pentane

Propene

Ethene

Propane

n-Butane

Expect very lifle change in i-pentane because

not much from taxis
Average mixing ratio, ppmv

Preconverter

Postconverter

900
800

700
600
500
400

300
200
100

0
i-Pentane

Propene

Ethene

Propane

n-Butane

NOX

Propane + butanes/pentanes for September 2013-

March 2014
Data from EPD roadside program
45
40
y = -0.0297x + 1248.8
R = 0.0512

35
30
25
20
15
10
5
0
41520

41540

41560

41580

41600

41620

41640

41660

41680

41700

41720

41740

Propane & butanes/pentanes for May 2013-February

2014
Real?me Data from Mongkok
MK
200
180
160
140
120

y = -0.0351x + 1480.2
R = 0.02837

100
80
60
40
20
0
41380

41430

41480

41530

41580

41630

41680

NOx for May 2013-February 2014 Real?me Data

from Mongkok
MK
600

500
y = -0.1645x + 7003.3
R = 0.03432

400

300

200

100

0
41380

41430

41480

41530

41580

41630

41680

Poten?al ozone forma?on in Hong Kong based on 60 grid

samples from September 2013 and 60 in February, 2014

MIR

2013
1000
900
800
700
600
500
400
300
200
100
0

2014

- 9.4%

Total MIR

MK Sta?on
O3 (ppb)
25.00

Concentra?on (ppb)

20.00

15.00
2012
2013

10.00

2014
5.00

0.00
Jan

-5.00

Feb

Mar

Apr

VOC/NOx for May 2013-February 2014 Real?me

Data from Mongkok
MK
30

y = -0.0037x + 154.53
R = 0.00013

25

20

15

10

0
41350

41400

41450

41500

41550

41600

41650

41700

41750

Ozone forma?on dependence on NOx and

VOC concentra?ons

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

Benzene (pptv) vs CO (ppbv)

Toluene vs CO (solvents)

Propane vs CO (LPG)

HCFC-134a vs ?me (urban)

C2Cl4 vs ?me (solvents)

1,3-butadiene vs ?me (biomass

burning)

Propyne vs ?me (biomass B)

Furan vs ?me (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