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Using Positive Matrix Factorization to

Investigate Sources of VOCs in


Bakersfield
Scola, Shelby1; Schroeder, Jason2; Beyersdorf,
Andreas3; Blake, Donald2
1Providence

College
2University of California Irvine
3NASA Langley Research Center

Bakerseld Air Quality & Health Implica8ons


Bakerseld has the na8ons
worst air pollu8on!
Bakerseld: 363,630 people
LA: 10,020,000 people

Ozone &
Par8culate Ma?er

h?p://www.esrl.noaa.gov/csd/projects/calnex/photos; American Lung Associa8on

Some Progress in Reducing Ozone Levels

American Lung Associa8on

3 high ozone days allowed

Max Hourly O3 in Bakerseld in June 2015

1-hour
CA standard

California EPA Air Resources Board

How is Ozone Forming?


hv
NOx + VOCs
O3

Sources of NOx:
vehicles
fuel combus8on
industry
Sources of VOCs:
Urban areas
Oil and natural gas sites
Agricultural areas
Forests

Where are the VOCs in


Bakerseld coming from?
Finlayson-Pi?s, B. J. and Pi?s, J. Chemistry of the Upper and Lower Atmosphere

Sample Gathering: Snakes on a Plane


Tube Bending
Integra8on

Photo credit: Jane Peterson

VOCs in 5 Air Samples from Bakerseld


VOC
methane
ethane
ethene
ethyne
propane
propene
i-butane
n-butane
butene
i-pentane
n-pentane

Mixing ra4o
(ppt)
1.99 106
1137
66
97
627
17
40
80
1.2
106
78

Mixing ra4o
(ppt)
n-hexane
14.2
n-heptane
7.6
isoprene
29
benzene
26
toluene
30
xylene
13
acetaldehyde 1684.25
butanal
79.6
acetone
2042.2
butanone
190
methanol
3819.2
ethanol
704.6
VOC

La8tude

i-pentane to n-pentane Ra8o

Urban inuence

Oil and natural


gas inuence

Longitude
Gilman, J.B. et al. Environ. Sci. Technol. 2013

Posi8ve Matrix Factoriza8on (PMF)

Looks for correla8ons


between dierent compounds
Creates factors (sources)

Contribu8on
of gases to
factors

EPA Posi8ve Matrix Factoriza8on (PMF) Model

Contribu8on
of factors to
cans

Our data set

Conc. of Species

CO

Propane
Ethane
Ethyne

i-pentane/n-pentane = 0.91
% of Species

Three Main Sources

Urban:
CO

CO2
Ethane
Ethene
Ethyne
Propane
Ethyltoluene

Oil & Natural Gas:


Ethane

Propane
Butane
Pentane
Hexane

Biogenics/Agriculture:
Methane
DMS
Isoprene
Alpha-pinene
Beta-pinene

Which one of these sources is


contribu8ng most to VOCs in Bakerseld?

Percent Contribu8on of Source

Where is Each VOC Coming From?


1
0.9
0.8
0.7
0.6

biogenics/agriculture

0.5

oil & natural gas

0.4

urban

0.3
0.2
0.1
0

Non-Methane Hydrocarbon (NMHC)

Overall Source Contribu8ons in Bakerseld


Sample 1
21%

48%

31%
Sample 2
28%

46%

Sample 3
27%

24%
30%

13%
59%

28%

Sample 4

All NMHCs collected


over Bakerseld

34%

Sample 5
33%
34%

21%
45%

33%
urban

oil & natural gas


45%

biogenics/agriculture

Sources of NMHCs in Bakerseld Samples


Sample 3

Sample 4

Sample 5

urban
oil & natural gas
biogenics/agriculture

28%

27%

45%

46%

24%

33%

30%

33%

34%

Sample 2
28%

13%
59%

Oil and natural gas


inuence
Urban inuence

Sample 1
48%

21%
31%

Oil and natural gas


inuence
Urban inuence

i-pentane/n-pentane propane/ethyne

Conclusions & Future Direc8ons


Most NMHCs in Bakerseld do not come from the city
45% oil and natural gas inuence
34% biogenic/agricultural inuence
21% urban inuence

PMF can be used to assess eec8veness of compound
ra8os in determining source inuences
i-pentane/n-pentane vs. propane/ethyne ra8os

Future:
run PMF with more factors
include more VOCs
calculate OH reac8vity due to each source

Acknowledgments
Dr. Jason Schroeder
Sean Freeman
Dr. Donald R. Blake
Rowland-Blake Lab
Dr. Emily Schaller
Rick She?er
DC-8 Flight Crew
UND & NSERC

THANK YOU!

References
American Lung Associa8on. State of the Air: Health Eects of Ozone and Par8cle Pollu8on.
h?p://www.stateosheair.org/2014/health-risks/?referrer=h?p://www.stateosheair.org/2014/
msas/bakerseld-ca-metropolitan-sta8s8cal-area.html (accessed Aug 1, 2015).

California Environmental Protec8on Agency. Air Resources Board: Quality Assurance Air
Monitoring Site Informa8on. h?p://www.arb.ca.gov/qaweb/site.php?s_arb_code=15257
(accessed Aug 3, 2015).

Finlayson-Pi?s, B. J. and Pi?s, J. N. Chemistry of the Upper and Lower Atmosphere: Theory,
Experiments, and Applica?ons; Academic Press: San Diego, 2000.

Gilman, J. B.; Lerner, B. M.; Kuster, W. C.; Gouw, J. A. Source signature of vola8le organic
compounds from oil and natural gas opera8ons in northeastern Colorado. Environ. Sci. Technol.
2013, 47, 1297-1305, DOI: 10.1021/es304119a

Russo, R. S.; Zhou, Y.; White, M. L.; Mao, H.; Talbot, R.; Sive, B. C. Mul8-year (20042008) record
of nonmethane hydrocarbons and halocarbons in New England: seasonal varia8ons and
regional sources. Atmos. Chem. Phys. 2010, 10, 49094929, DOI: 10.5194/acp-10-4909-2010

United States Environmental Protec8on Agency. Human Exposure and Atmospheric Sciences:
EPA Posi8ve Matrix Factoriza8on Model. h?p://www.epa.gov/heasd/research/pmf.html
(accessed Aug 3, 2015).

Ques8ons?

Conclusions & Future Direc8ons


Most NMHCs in Bakerseld do not come from the city
45% oil and natural gas inuence
34% biogenic/agricultural inuence
21% urban inuence

PMF can be used to assess eec8veness of compound
ra8os in determining source inuences
i-pentane/n-pentane vs. propane/ethyne ra8os

Future:
break up samples into more factors
include more VOCs
calculate OH reac8vity due to each source

Non-methane VOCs are more reac8ve


Rate constants for reac8ons of VOCs with OH
VOC

k (10-12 cm3/molecule s)

methane

0.00618

ethane

0.254

propane

1.12

n-butane

2.44

n-pentane

4.0

n-hexane

5.45

n-heptane

7.0

Methane is 42 8mes less reac8ve than ethane and 187 8mes less reac8ve than propane

Finlayson-Pi?s, B. J. and Pi?s, J. Chemistry of the Upper and Lower Atmosphere