Novel Puff Model Calculations of Ozone

Production Rates and Possible NO, VOC

Emissions in the LA Basin
Jacob Piland
Utah State University
Departments of Biochemistry and Computer Science

Dr. Barry Lefer, NASA HQ

Dr. Tim Bertram, UW Madison
Dr. Don Blake, UC Irvine
Steven Schill, UC San Diego

Introduction
[O3]

[O3]

VOCs
&
NOx

Models
Box Model

Puff Model

3: Introduction to Atmospheric Chemistry, Jacob, 1991

Measurement Locations
Using Long
Beach as a
production
point

[O3]

[O3]

[O3] 40ppb

Follow Sea
breezes to
Ontario
[O3] =42ppb

[O3] =81.2ppb

Estimating Route
NOAA HYSPLIT estimates
wind trajectories.
The chosen endpoint was
used as HYSPLIT shows an
almost direct route
between Long Beach and
Ontario

Reactions
A + B C + D

PC or D = k[A][B]
O3

NO
RO2
PHOx
O3

RO

OH

NO

HO2

O3
HNO3

PO3 = k1[RO2][NO] + k3[HO2][NO]

Simplifies to
PO3 = 2k[RO2][NO]
12: Introduction to Atmospheric Chemistry, Jacob, 1991

H2O2

C2H5 + HCO

Deciding Sources and Sinks

Literature

Initial Concentration:
CARB Ground Station

Initial Concentration:
Airborne Platform

Photolysis:
TUV Model

Estimated by
Sensitivity Testing

Time

Determining Time

[1]

Photochemical
Clock based off of
the ratios of Toluene
to Benzene

Hydroxyl radical
concentration taken
from a northern
hemisphere average [2]

Warneke et al., Determination of urban volatile organic compound emission ratios and comparison with an emissions database, Journal of Geophysical research, 2007 [1]
Crutzen
Fishman,
Averageof
concentrations
OH in compound
the troposphere,
andratios
the budgets
of CH4, CO,
H2an
and
CH3CCl3,.
Geophysical
Research
Letters ,1977
[2] 2007
Warnekeand
et al.,
Determination
urban volatileoforganic
emission
and comparison
with
emissions
database,
Journal
of Geophysical
research,

Second Photochemical Clock

Second Clock based off
of the ratio of m,pXylenes to Ethylbenzene
Time is found by using
the X between ratios

Initial: 2.8

The first clock is likely

an underestimate, but
both times were similar

Initial: 1.3

Nelson and Quigley, The m,p-xylenes:ethylbenzene ratio. A technique for estimating hydrocarbon age in ambient atmospheres, Atmospheric Environment, 1967

Model Checkpoint

Need to fill in more variables

Simplifying RH Concentrations
Acetaldehyde
Trimethylbenzene
Propene
Xylene
Isoprene

Duan, Jingchun et al, Concentration, sources and ozone formation potential of volatile organic compounds (VOCs) during ozone episode in Beijing, Atmospheric Research 88, 2008

Finding [RO2]
Identified 5 VOCs
responsible for ~26 percent
of Ozone formation

x4

Converted VOCs to
propene-equivalence
Converted propene (RH)
to RO2

= k2

= k2

PO3 = 2k[RO2][NO] or 2k[k2[RH]t][NO]

Model Checkpoint

The Result is 1.63 x 10-4 ppb of O3

Far short of the 40 ppb goal.

Production Rate of Ozone (ppb/s)

Production Rate of Ozone (ppb/s)

Production Rate of Ozone (ppb/s)

Production Rate of Ozone (ppb/s)

Production Rate of Ozone (ppb/s)

Effect of Emissions on PO3

VOC and NOx Sensitivity

Band of Supported Ozone Production Values

Possibilities for Future Research

Improve the puff model to a account for
dispersion
Include more VOC reactants

Account for chemical loss of NO, HO2, Ozone

Include more data points along the trajectory
of the puff model

Conclusions
A reasonable Ozone production was found for
this section of the LA Basin
It is likely that there are both increased NO
and VOC emissions in the LA Basin
This puff model provides plausible NO and
VOC emission estimates

Acknowledgements:
Steve Schill Dr. Barry Lefer Dr. Tim Bertram Dr. Don Blake
California Air Resource Board Emily Schaller Sean Freeman
Jimmy Flynn Nick Heath Rick Shetter All SARP Mentors
DC8 Flight crew S3 All My New Friends Palmdale

References
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Duan, Jingchun et al. Concentration, sources and ozone formation potential of volatile organic compounds
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