Supplementary Materials
Winter Ozone Formation and VOC Incremental Reactivities in the Upper Green River
Basin of Wyoming
William P. L. Carter and John H. Seinfeld
November 10, 2011
1. Low Temperature Mechanisms for Individual VOCs
Table A-1 gives a listing of the reactions and rate constants derived for the individual
compounds for which separate low-temperature mechanisms could be derived using the SAPRC07 mechanism estimation and generation system (Carter, 2000, 2010). These consist of most of
the compounds in the UGRB ambient mixtures used in this work, except for aromatic
compounds whose mechanisms at low temperatures could not be estimated. The model species
names employed are the same as used in the SAPRC-07 mechanism documentation (Carter,
2010). That document should be for details and also for the listings for the standard SAPRC-07
mechanisms for these compounds, which are derived to be appropriate for 300 K.
Although changing the temperature affected almost all the product yield parameters for
most of the compounds whose 265 K mechanisms could be estimated, in terms of reactivity
effects the most important parameters are probably the number of NO to NO2 conversions and
the overall yield of nitrate formation in the reactions of the VOCs with OH radicals. These are
important because NO to NO2 conversions is the primary process responsible for O3 formation
and because reactions of peroxy radicals with NO forming nitrates is a significant radical and
NOx sink for many compounds. These are reflected in the yields of the "RO2C" and "RO2XC"
model species, which measure numbers of NO to NO2 conversions and NO to organic nitrate
conversions in the peroxy radical reactions. The effects of the temperature reduction on the
values of these parameters for the listed compounds are shown on Figure A-1, which gives plots
of values of those parameters derived for 265 K against values of those parameters derived for
300 K for the standard mechanism (Carter, 2010). It can be seen that the lower temperature
causes higher nitrate yields (by a factor of ~1.4) for almost all compounds, and causes lower NO
to NO2 conversions (also by a factor of ~1.4) for alkanes. The effects on NO to NO2 conversions
are much less for alkenes, aldehydes, and ketones because in most cases the main reaction routes
are less affected by competition reactions involving temperature-sensitive alkoxy radical
decompositions than is the case for the reactions of alkanes.
Table A-3 lists the reactions and rate constants for the lumped model species used in the
baseline calculations for this study. These were derived from mechanisms derived for 265 K for
the individual components of these mixtures and the compositions of the 2008 Jonah and 2008
Boulder ambient mixtures as given in Table A-2. In the case of the ALK and OLE model species
the mechanisms for the individual compounds were those derived for 265 K and given in Table
A-1. The mechanisms for the individual aromatic compounds were not modified for the lower
temperature, except for the "low reactivity aromatics" sensitivity calculations discussed below in
Section 5, but the ARO1 and ARO2 mechanisms were different because of the differences in the
A-1
compositions of the Jonah and 2008 Boulder ambient mixtures compared to the ambient mixture
used to derive the lumped species mechanisms in standard SAPRC-07 (Carter, 2010). Table A-3
also includes the "low reactivity aromatics" mechanisms for ARO1 and ARO2, which were
derived as discussed in Section 5 based on the mixture of aromatics in the Jonah 2008
simulations.
2. Photolysis Rate Calculation Input and Results
As discussed in Section 2.2 in the main text, photolysis rates used for most model
simulations for this work were calculated using the TUV model version 5.0, (TUV 2010) using
inputs considered appropriate for wintertime conditions in the UGRB. The TUV model inputs
employed are listed in Table A-4, along with a discussion of the choices in inputs used. As
discussed there, most inputs were TUV inputs, with the major difference being the value of the
parameter "alsurf", which is the surface reflectivity or albedo. These calculations use a high
value of 75% to reflect the effects of snow cover, based on the value used in the Environ (2010)
study. The default value for this parameter in the input files provided with the TUV model (TUV
2010) is 10%.
The photolysis rates used in the MIR and other reactivity scale calculations of Carter
(1994, 2000, 2010) were calculated using solar light intensities and spectra calculated by Jeffries
(1991) for 640 meters, the approximate mid-point of the mixed layer during daylight hours for
the box model scenarios used. This is referred to as the "standard" light model in the presentation
of the results in this section. That model gives very similar photolysis rates as calculated using
the TUV 5.0 model used in this work with the default albedo of 10%, being within 10% in most
cases.
Table A-5 shows mid-day SAPRC-07 photolysis rates calculated for the latitude of the
UGRB for February 22, the date of the 2008 ozone episodes modeled for this study and also for
June 20, the summer solstice (solar zenith angles of 54 and 20 degrees, respectively). The
photolysis rates are calculated both for the Jeffries (1991) model used for the Carter (1994, 2000,
2010) scenarios and for the TUV 5.0 model using the winter surface albedo of 75% for the
February scenario and using the default albedo of 10% for the June scenario. The factor
differences between various calculations are also shown, and also the averages and ranges of
these differences. The photolysis rates calculated using the two light models are very similar for
the summer scenario, but differ significantly for the wintertime scenario because of the different
surface albedos used. The differences are less when comparing the summer and winter photolysis
rates because the effect of the larger albedo in the winter is cancelled out in part by the effect of
the higher zenith angle compared to the summer.
The differences in photolysis rates calculated for the summer and depending on the
reaction and also the time of day. This is shown for two representative photolysis reactions on
Figure A-2, which shows photolysis rates calculated for the winter episode as a function of the
time of day. The summer simulation gives much higher photolysis rates at the beginning and the
end of the simulation, but gives lower values at midday in most cases, except for reactions such
as O3 photolysis to O1D that are highly sensitive to UV. This is because the season has a much
A-2
larger effect on solar zenith angles in the morning and the evening compared to the middle of the
day.
3. Scenario Input Details
The box model scenarios used to simulate the ozone episodes in the UGRB that were
modeled in this work are discussed in general terms in Section 3 of the main text. More detailed
information concerning the model inputs is given in Table A-6 and Table A-7. Table A-6 gives
the parameter values that were used and a brief discussion of their source or how they were
derived, and Table A-7 gives the values of the parameters that varied with time. The
compositions of the mixtures used to represent the ambient VOC mixtures are given in Table A2. In addition, to assess the effects of varying pollutant levels, simulations of the four scenarios
were also carried out with initial NOx or total NMHC levels varied but with all other inputs held
constant. These were used to produce the data shown in Figure 5 and Figure 9 in the main text.
Additional simulation inputs were varied for the purpose of conducting various sensitivity
calculations, as discussed below in Section 5.
4. Incremental Reactivity Tabulations
The methods used to calculate the incremental reactivities of individual VOCs for this
work are discussed in Section 3.4 of the main text, and selected results are shown on Figure 8
through Figure 11. Table A-2 gives the incremental reactivities in selected reactivity scales
calculated for all of the individual VOCs present in the ambient mixtures used in the UGRB
simulations. These include the baseline scale for the 2008 Jonah scenario and also the scale
where the HONO inputs (both initial and formed from NO2) are adjusted to yield [HONO]/[NO2]
ratios of ~3%. Reactivities in the MIR scale are shown for comparisons. These data were used to
create the reactivity comparisons plots shown in the main text.
5. Sensitivity Calculations
A number of sensitivity calculations were carried out to assess the sensitivities of peak
ozone levels in the simulations in the 2008 UGRB scenarios to modifications of various scenario
inputs. These sensitivity calculations and their results are summarized in Figure A-3, and the
major results are also summarized briefly in the main text. Most of these sensitivity calculations
were carried out using the inputs of the 2008 Jonah episode because that episode was found to be
the most sensitive to most scenario inputs, and that episode was the most similar to the 2011
episodes as discussed in the main text, at least in terms of the composition of the NMHC mixture
and the sensitivity of O3 to changes in VOC and NOx emissions. However, for comparison
purposes sensitivity calculations were also carried out using the inputs of the highly NO xsensitive 2008 Boulder episode.
The inputs for these 2008 scenarios that were varied and the results of the various
sensitivity calculations are described below. Reference is made to the simulation numbers shown
on the left side of the figure. Note that "baseline" in the discussion below refers to the default
simulations with no additional HONO input or formation from NO2.
A-3
Simulation S1 (Jonah only): Environ Scenario, CB05 mechanism. This simulation used
the same inputs for the Jonah 2008 scenario as used in the Environ (2010) study, except that a
different software system was used and the speciation of the NMHC mixture was slightly
different (Environ, 2011). The speciation of the NMHC was derived using the compositions
given in Table A-2 and the CB05 model species assignments given by Carter (2011). The
calculated maximum O3 was 110 ppb, which is reasonably close to the 120 ppb reported by
Environ (2011) using the same mechanism and similar inputs.
Simulation S2 (Jonah only): Environ Scenario, SAPRC-07 mechanism. This simulation
used the same inputs for Jonah 2008 as used in the Environ (2010) study and was the same as
Simulation 1 except that the low-temperature SAPRC-07 mechanism used for the baseline
simulations for this work was used. Thus, comparing Simulations 1 and 2 shows the effects of
changing the mechanism alone. This simulation gave 128 ppb O3, which was 16% higher than
the simulation using CB05. This is despite the fact that the CB05 mechanism was not revised to
represent low temperature conditions, while the SAPRC-07 mechanism was. The use of the
Environ (2010) inputs with the baseline mechanism resulted in ~10% higher peak O3 calculated
compared to the baseline results obtained in this work
Simulation S3: Default Urban Albedos. The photolysis rates for these simulations were
calculated with the same solar actinic fluxes as a function of zenith angle as used in the Carter
(1994, 2000, 2010) reactivity scale calculations, which are appropriate for urban albedos. All the
other model inputs, including the zenith angles as a function of time of day, were the same as the
baseline simulations. A comparison of these with the baseline simulations shows the effects of
the albedos only. This resulted lower photolysis rates at all times during the simulations, causing
in a 49% reduction in the maximum O3 for the Jonah scenario, but only a ~17% reduction for the
less sensitive 2008 Boulder scenario.
Simulation S4 (Jonah only): "Low Temperature" Aromatics Mechanism. We were unable
to derive modified mechanisms for aromatics to represent low temperature conditions, since
parameters in the mechanisms are adjusted to fit results of chamber experiments conducted
around 300 K (Carter, 2010). For this reason, the mechanisms for aromatics were not modified
for low temperature conditions for the baseline calculations. However, for this sensitivity
simulation a "low temperature" mechanisms for the lumped aromatic species ARO1 and ARO2
were derived to determine how these simulations may be affected if the lower temperature
caused significantly less reactive mechanisms for aromatics. In this model, the model species
used to represent photoreactive products such as glyoxal, methyl glyoxal, and photoreactive
unsaturated dicarbonyls such as 2-butene-1,4-dial were replaced by those used to represent nonphotoreactive products. This can be considered a reasonable lower limit reactivity assumption for
sensitivity calculation purposes; the actual aromatics mechanisms probably do not change
anywhere near this much. The "low temperature" ARO1 and ARO2 mechanisms are included in
the listing on Table A-3. This revision resulted in a 30% decrease in the peak O3 in the Jonah
2008 scenario, from 115 to 80 ppb.
Simulation S5: Standard Lumped Species Mechanisms. These simulations used the
standard SAPRC-07 mechanisms for the lumped model species (ALKx, OLEx, and AROx), as
opposed to the lumped mechanisms derived for 265 K and the compositions of the NMHC
mixtures in the UGRB as used in the baseline calculations. Thus, both the temperature for the
A-4
non-aromatics mechanisms and the compositions used to derive the mechanisms of the lumped
species were modified, but all the other inputs, including the compositions of the ambient
mixtures are the same as in the baseline calculations. These changes resulted in a ~19% increase
in maximum O3 for the Jonah simulation but only a 2% increase for the less sensitive Boulder
2008 simulation.
Simulation S6 (Jonah only): Lumped Mechanisms Based on the Standard Ambient
Mixture. In order to assess whether the differences between simulation S5 for the Jonah scenario
was due mostly to the different temperature for the lumped model species or the different
composition of the ambient mixtures, this simulation used the lumped mechanisms derived for
265 K but for the composition of the standard ambient mixture used to derive standard SAPRC07 lumped mechanisms (Carter, 2010). Thus, only the composition of the ambient mixture used
to derive the lumped mechanisms is different in this mechanism used in the baseline calculation.
All other model inputs, including the composition of the ambient mixture in terms of total
amounts of lumped and explicit model species present, were the same as in the baseline
calculation. This change resulted in only a 1% change in the maximum O3, indicating that the
composition of the mixture used to derive the lumped model species mechanisms is relatively
unimportant compared to the effect of the temperature used to derive the mechanisms in the S5
simulations. The effect of changing only the temperature used to derive the mechanisms can be
obtained by comparing simulations S6 and S5, which indicates that the temperature increase
causes a ~18% increase in calculated O3 for this scenario.
Simulation S7 (Jonah only): Urban ROG Mixture. In this simulation the composition of
the initially present NMHC's (in terms of moles of lumped model species initially present) is
based on that of the urban ambient mixture used by Carter (1994, 2000, 2010) rather than the
UGRB-specific mixtures used in the baseline calculations. The mechanisms and total ppmC of
the were the same as used in the baseline calculations, along with the other inputs. As discussed
in the main text, the reactivity of the urban mixture is much higher than that used in the 2007
Jonah simulations, and as a result this simulation, which is highly sensitive to VOC inputs, gave
almost 2.8 times more O3 than the baseline simulation.
Simulation S8: NOx Adjusted to yield MIR Conditions. In these simulations the NOx
inputs were adjusted to give the highest incremental reactivities of the ambient mixtures used in
the simulations. All the other inputs were the same as the baseline calculations. This amounted to
a reduction in initial NOx levels in the Jonah simulations and an increase in the NOx levels in the
2008 Boulder simulations. This resulted in a 43% increase in O3 in the Jonah simulation and a
31% increase in the Boulder 2008 simulation.
Simulation S9: NOx Adjusted to yield Maximum Ozone. In these simulations the NOx
inputs were adjusted to give the highest peak ozone concentrations in the simulations, with all
other inputs held the same. This also resulted in a reduction of initial NOx levels in the Jonah
simulations and an increase in the NOx levels in the 2008 Boulder simulations, as shown in
Figure 5 in the main text. This resulted in a 71% increase in O3 in the Jonah simulation and a
74% increase in the Boulder 2008 simulation.
Simulation S10: Summer Temperatures and Light Intensities. These simulations used had
inputs modified to use summer temperatures and light intensities and also used the standard
A-5
SAPRC-07 mechanism derived for 300 K. Although this mechanism uses lumped model species
mechanisms derived for the urban ambient mixture (Carter, 2010), Simulation S6 shows that the
results should not be significantly different if these were derived for the UGRB mixtures. The
temperature inputs were those of the "averaged conditions" scenario of Carter (2000, 2010), the
solar zenith angles were calculated for the summer solstice (June 20) at Jonah, and the light
model used in the Carter (1994, 2000, 2010) scenarios was employed. This resulted in a 131%
increase in maximum O3 for the Jonah scenario, but only a 33% increase for the less sensitive
Boulder scenario.
6. References
Carter, W. P. L. (1994): Development of Ozone Reactivity Scales for Volatile Organic
Compounds, J. Air & Waste Manage. Assoc., 44, 881-899.
Carter, W. P. L. (2000): Documentation of the SAPRC-99 Chemical Mechanism for VOC
Reactivity Assessment, Report to the California Air Resources Board, Contracts 92-329
and 95-308, May 8. Available at http://cert.ucr.edu/~carter/absts.htm#saprc99 and
http://www.cert.ucr.edu/~carter/ reactdat.htm.
Carter, W. P. L. (2010): Development of the SAPRC-07 Chemical Mechanism, Atmospheric
Environment, 44, 5324-5335. See also Carter, W. P. L. (2010): “Development of the
SAPRC-07 Chemical Mechanism and Updated Ozone Reactivity Scales,” Final report to
the California Air Resources Board Contract No. 03-318. January 27. Available at
www.cert.ucr.edu/ ~carter/SAPRC.
Carter, W. P. L. (2011): “Current Project Information Page: Development of an Improved
Chemical Speciation Database for Processing Emissions of Volatile Organic Compounds
for Air Quality Models,” Web page available at http://www.cert.ucr.edu/~carter/emitdb/,
updated April 28.
Environ (2010): Final technical report, 2008 Winter Box Model Study, Prepared by U.
Nopmongcol, G. Yarwood, and T. Stoeckenius, Environ International Corporation,
Novato, CA. Available at: http://deq.state.wy.us/aqd/Ozone/Appendix%20A_BoxModel
_WY_RevFinal.pdf.
Environ (2011): Input files used in the Environ simulations provided by Uarporn Nopmongcol of
Environ on January 11, 2011.
Jeffries, H. E. (1991): "UNC Solar Radiation Models," unpublished draft report for EPA
Cooperative Agreements CR813107, CR813964 and CR815779".
TUV
(2010). TUV 3.0 model version 3, November 2010. downloaded from
http://cprm.acd.ucar.edu/ Models/TUV/. Madronich, S. and S. Flocke, Theoretical
estimation of biologically effective UV radiation at the Earth's surface, in Solar
Ultraviolet Radiation - Modeling, Measurements and Effects (Zerefos, C., ed.). NATO
ASI Series Vol. I52, Springer-Verlag, Berlin, 1997.
A-6
7. List of Tables
Table A-1. Mechanisms derived for individual VOC compounds for a temperature of 265
K. Aromatic compounds are not shown because their mechanisms were not
changed. .........................................................................................................................8
Table A-2. Weight fractions and incremental reactivities for the VOCs measured in
conjunction with the UGRB episodes modeled in this study. .....................................19
Table A-3. Mechanisms derived for lumped VOC model species based on the
mechanisms of the mixtures of compounds measured at the Jonah and Boulder
site at 265 K. ................................................................................................................22
Table A-4. TUV model inputs used to calculate solar actinic fluxes the conditions of the
Jonah site on February 20, 2008. The resulting actinic fluxes were used for all
UGRB winter simulations discussed in this work. ......................................................25
Table A-5. SAPRC-07 photolysis rate constants calculated for solar noon in the UGRB
for the February 22 winter episode and for the summer solstice. ................................27
Table A-6. Box model inputs used in the simulations of the UGRB scenarios. ............................28
Table A-7. Time-dependent parameter values used in the box model inputs. See Table A4 for discussion and documentation of these values. ...................................................31
8. List of Figures
Figure A-1. Plots of low vs. standard temperature numbers of NO to NO2 conversions
and overall organic nitrate yields in the mechanisms derived for the reactions
of OH radicals with alkanes, alkenes, and alcohols and ethers. ..................................32
Figure A-2. Plots of selected photolysis rates as a function of simulated hour for both
summertime and wintertime conditions in the UGRB. ................................................32
Figure A-3. Comparison of maximum ozone levels calculated using modified
mechanisms and inputs for the conditions of the 2008 Jonah and Boulder
Scenarios. .....................................................................................................................33
A-7
Table A-1.
Mechanisms derived for individual VOC compounds for a temperature of 265 K.
Aromatic compounds are not shown because their mechanisms were not changed.
Compound
Rate parameters [a]
k(265)
A
Ea
Ethane
Propane
1.58e-13 1.34e-12 0.992
8.34e-13 1.49e-12 0.173
n-Butane
1.95e-12 1.63e-12 -0.227
Isobutane
1.83e-12 1.05e-12 -0.423
n-Pentane
3.21e-12 2.27e-12 -0.314
Iso-Pentane
3.60e-12 3.60e-12
Cyclopentane
4.29e-12 2.46e-12 -0.425
n-Hexane
4.40e-12 7.62e-12 0.223
2,2-Dimethyl Butane
1.58e-12 3.37e-11 1.608
2,3-Dimethyl Butane
5.40e-12 1.49e-12 -0.809
2-Methyl Pentane
5.20e-12 5.20e-12
-
3-Methylpentane
5.20e-12 5.20e-12
-
Cyclohexane
6.13e-12 2.93e-12 -0.521
Methylcyclopentane
5.57e-12 5.57e-12
-
-
B
Reaction
2.0 ETHANE + OH = xHO2 + RO2C + xCCHO + yROOH
2.0 PROPANE + OH = #.964 xHO2 + #.964 RO2C +
#.036 RO2XC + #.036 zRNO3 + #.22 xRCHO + #.745
xACET + yROOH + #-.111 XC
2.0 N-C4 + OH = #.884 xHO2 + #.944 RO2C + #.116
RO2XC + #.116 zRNO3 + #.045 xCCHO + #.095
xRCHO + #.767 xMEK + yROOH + #-.139 XC
2.0 2-ME-C3 + OH = #.139 xHO2 + #.806 xTBUO + #.948
RO2C + #.056 RO2XC + #.056 zRNO3 + #.004
xHCHO + #.135 xRCHO + #.004 xACET + yROOH +
#.019 XC
2.0 N-C5 + OH = #.799 xHO2 + #1.108 RO2C + #.201
RO2XC + #.201 zRNO3 + #.009 xCCHO + #.063
xRCHO + #.515 xMEK + #.22 xPROD2 + yR6OOH +
#.207 XC
- 2-ME-C4 + OH = #.895 xHO2 + #.016 xMEO2 +
#1.711 RO2C + #.089 RO2XC + #.089 zRNO3 + #.002
xHCHO + #.757 xCCHO + #.075 xRCHO + #.751
xACET + #.085 xMEK + yR6OOH + #.116 XC
2.0 CYCC5 + OH = #.711 xHO2 + #1.873 RO2C + #.289
RO2XC + #.289 zRNO3 + #.01 xCO + #.514 xRCHO
+ #.197 xMEK + yR6OOH + #.926 XC
1.0 N-C6 + OH = #.684 xHO2 + #1.214 RO2C + #.316
RO2XC + #.316 zRNO3 + #.035 xRCHO + #.649
xPROD2 + yR6OOH + #.105 XC
- 22-DM-C4 + OH = #.245 xHO2 + #.003 xMEO2 +
#.491 xTBUO + #1.607 RO2C + #.261 RO2XC + #.261
zRNO3 + #.139 xHCHO + #.648 xCCHO + #.117
xRCHO + #.128 xACET + #.003 xMEK + yR6OOH +
#.285 XC
2.0 23-DM-C4 + OH = #.814 xHO2 + #1.642 RO2C +
#.186 RO2XC + #.186 zRNO3 + #.002 xHCHO +
#.001 xCCHO + #.063 xRCHO + #1.531 xACET +
yR6OOH + #.098 XC
- 2-ME-C5 + OH = #.73 xHO2 + #1.43 RO2C + #.27
RO2XC + #.27 zRNO3 + #.548 xRCHO + #.199
xACET + #.053 xMEK + #.134 xPROD2 + yR6OOH +
#1.123 XC
- 3-ME-C5 + OH = #.782 xHO2 + #1.557 RO2C + #.218
RO2XC + #.218 zRNO3 + #.696 xCCHO + #.045
xRCHO + #.657 xMEK + #.074 xPROD2 + yR6OOH
+ #.093 XC
2.0 CYCC6 + OH = #.755 xHO2 + #.777 RO2C + #.245
RO2XC + #.245 zRNO3 + #.009 xRCHO + #.746
xPROD2 + yR6OOH + #.027 XC
- ME-CYCC5 + OH = #.361 xHO2 + #.222 xMECO3 +
A-8
Table A-1 (continued)
Compound
Rate parameters [a]
k(265)
A
Ea
n-Heptane
6.35e-12 1.76e-12 -0.807
2,3-Dimethyl Pentane
7.39e-12 7.39e-12
-
2,4-Dimethyl Pentane
4.77e-12 4.77e-12
-
2-Methyl Hexane
6.60e-12 6.60e-12
-
3-Methyl Hexane
7.02e-12 7.02e-12
-
Methylcyclohexane
9.64e-12 9.64e-12
-
n-Octane
7.46e-12 2.45e-12 -0.717
2,2,4-Trimethyl Pentane 2.80e-12 2.12e-12 -0.278
2,3,4-Trimethyl Pentane 6.60e-12 6.60e-12
-
2,3-Dimethyl Hexane
8.70e-12 8.70e-12
-
2,4-Dimethyl Hexane
8.70e-12 8.70e-12
-
2,5-Dimethyl Hexane
8.29e-12 8.29e-12
-
B
Reaction
#1.873 RO2C + #.417 RO2XC + #.417 zRNO3 + #.002
xCO + #.001 xHCHO + #.527 xRCHO + #.055
xPROD2 + yR6OOH + #1.14 XC
2.0 N-C7 + OH = #.567 xHO2 + #1.198 RO2C + #.433
RO2XC + #.433 zRNO3 + #.027 xRCHO + #.542
xPROD2 + yR6OOH + #1.069 XC
- 23-DM-C5 + OH = #.704 xHO2 + #1.511 RO2C +
#.296 RO2XC + #.296 zRNO3 + #.001 xHCHO +
#.111 xCCHO + #.042 xRCHO + #.647 xACET + #.6
xMEK + #.033 xPROD2 + yR6OOH + #.336 XC
- 24-DM-C5 + OH = #.794 xHO2 + #1.687 RO2C +
#.206 RO2XC + #.206 zRNO3 + #.051 xHCHO +
#.001 xCCHO + #.738 xRCHO + #.134 xACET +
#.011 xMEK + #.047 xPROD2 + yR6OOH + #2.769
XC
- 2-ME-C6 + OH = #.614 xHO2 + #1.262 RO2C + #.386
RO2XC + #.386 zRNO3 + #.105 xRCHO + #.069
xACET + #.512 xPROD2 + yR6OOH + #1.09 XC
- 3-ME-C6 + OH = #.621 xHO2 + #1.349 RO2C + #.379
RO2XC + #.379 zRNO3 + #.048 xCCHO + #.405
xRCHO + #.182 xMEK + #.19 xPROD2 + yR6OOH +
#1.547 XC
- ME-CYCC6 + OH = #.564 xHO2 + #1.282 RO2C +
#.436 RO2XC + #.436 zRNO3 + #.001 xHCHO +
#.254 xRCHO + #.31 xPROD2 + yR6OOH + #1.761
XC
2.0 N-C8 + OH = #.473 xHO2 + #1.106 RO2C + #.527
RO2XC + #.527 zRNO3 + #.015 xRCHO + #.458
xPROD2 + yR6OOH + #2.045 XC
2.0 224TM-C5 + OH = #.512 xHO2 + #.245 xTBUO +
#2.343 RO2C + #.243 RO2XC + #.243 zRNO3 + #.714
xHCHO + #.441 xRCHO + #.198 xACET + #.232
xMEK + #.002 xPROD2 + yR6OOH + #1.991 XC
- 234TM-C5 + OH = #.631 xHO2 + #1.609 RO2C +
#.369 RO2XC + #.369 zRNO3 + #.004 xHCHO +
#.247 xCCHO + #.039 xRCHO + #.889 xACET +
#.368 xMEK + yR6OOH + #1.032 XC
- 23-DM-C6 + OH = #.582 xHO2 + #1.402 RO2C +
#.418 RO2XC + #.418 zRNO3 + #.001 xHCHO +
#.039 xCCHO + #.097 xRCHO + #.424 xACET +
#.333 xMEK + #.19 xPROD2 + yR6OOH + #1.378 XC
- 24-DM-C6 + OH = #.502 xHO2 + #1.41 RO2C + #.498
RO2XC + #.498 zRNO3 + #.066 xHCHO + #.156
xCCHO + #.281 xRCHO + #.024 xACET + #.096
xMEK + #.183 xPROD2 + yR6OOH + #2.237 XC
- 25-DM-C6 + OH = #.492 xHO2 + #1.662 RO2C +
#.508 RO2XC + #.508 zRNO3 + #.046 xHCHO +
#.353 xRCHO + #.414 xACET + #.143 xPROD2 +
yR6OOH + #1.747 XC
A-9
Table A-1 (continued)
Compound
Rate parameters [a]
k(265)
A
Ea
2-Methyl Heptane
7.91e-12 7.91e-12
-
3-Methyl Heptane
8.32e-12 8.32e-12
-
4-Methyl Heptane
8.32e-12 8.32e-12
-
n-Nonane
9.21e-12 2.28e-12 -0.866
n-Decane
1.03e-11 2.85e-12 -0.807
n-Undecane
1.23e-11 1.23e-11
-
n-Dodecane
1.32e-11 1.32e-11
-
Propene
3.26e-11 4.85e-12 -1.002
4.55e-18 5.51e-15 3.732
5.81e-15 4.59e-13 2.297
3.54e-12 1.02e-11 0.556
1-Butene
3.83e-11 6.55e-12 -0.928
4.11e-18 3.36e-15 3.525
9.06e-15 3.14e-13 1.864
3.57e-12 1.34e-11 0.696
cis-2-Butene
6.93e-11 1.10e-11 -0.968
B
Reaction
-
2-ME-C7 + OH = #.501 xHO2 + #1.141 RO2C + #.499
RO2XC + #.499 zRNO3 + #.033 xRCHO + #.006
xACET + #.471 xPROD2 + yR6OOH + #2.063 XC
- 3-ME-C7 + OH = #.508 xHO2 + #1.175 RO2C + #.492
RO2XC + #.492 zRNO3 + #.01 xCCHO + #.083
xRCHO + #.052 xMEK + #.432 xPROD2 + yR6OOH
+ #1.979 XC
- 4-ME-C7 + OH = #.511 xHO2 + #1.195 RO2C + #.489
RO2XC + #.489 zRNO3 + #.27 xRCHO + #.064
xMEK + #.257 xPROD2 + yR6OOH + #2.458 XC
2.0 N-C9 + OH = #.409 xHO2 + #1.012 RO2C + #.591
RO2XC + #.591 zRNO3 + #.01 xRCHO + #.398
xPROD2 + yR6OOH + #3.036 XC
2.0 N-C10 + OH = #.366 xHO2 + #.949 RO2C + #.634
RO2XC + #.634 zRNO3 + #.008 xRCHO + #.358
xPROD2 + yR6OOH + #4.024 XC
- N-C11 + OH = #.339 xHO2 + #.91 RO2C + #.661
RO2XC + #.661 zRNO3 + #.006 xRCHO + #.332
xPROD2 + yR6OOH + #5.024 XC
- N-C12 + OH = #.323 xHO2 + #.887 RO2C + #.677
RO2XC + #.677 zRNO3 + #.005 xRCHO + #.317
xPROD2 + yR6OOH + #6.021 XC
- PROPENE + OH = #.984 xHO2 + #.984 RO2C + #.016
RO2XC + #.016 zRNO3 + #.957 xHCHO + #.957
xCCHO + #.027 xMEK + yROOH + #-.075 XC
- PROPENE + O3 = #.165 HO2 + #.35 OH + #.355
MEO2 + #.525 CO + #.215 CO2 + #.5 HCHO + #.5
CCHO + #.185 HCOOH + #.075 CCOOH + #.07 XC
- PROPENE + NO3 = #.927 xHO2 + #.927 RO2C +
#.073 RO2XC + #.073 zRNO3 + yROOH + XN +
#2.562 XC
- PROPENE + O3P = #.45 RCHO + #.55 MEK + #-.55
XC
- 1-BUTENE + OH = #.973 xHO2 + #.982 RO2C +
#.027 RO2XC + #.027 zRNO3 + #.913 xHCHO +
#.926 xRCHO + #.024 xMEK + #.002 xMACR + #.013
xMVK + #.008 xIPRD + yROOH + #-.049 XC
- 1-BUTENE + O3 = #.095 HO2 + #.063 xHO2 + #.128
OH + #.063 RO2C + #.303 CO + #.088 CO2 + #.5
HCHO + #.063 xCCHO + #.5 RCHO + #.185 HCOOH
+ #.425 RCOOH + #.063 yROOH + #.023 XC
- 1-BUTENE + NO3 = #.88 xHO2 + #.88 RO2C + #.12
RO2XC + #.12 zRNO3 + #.88 xRNO3 + yROOH +
#.12 XN + #-2 XC
- 1-BUTENE + O3P = #.45 RCHO + #.55 MEK + #.45
XC
- C-2-BUTE + OH = #.965 xHO2 + #.965 RO2C + #.035
RO2XC + #.035 zRNO3 + #1.93 xCCHO + yROOH +
A-10
Table A-1 (continued)
Compound
Rate parameters [a]
k(265)
A
Ea
8.29e-17 3.22e-15 1.924
3.52e-13 3.52e-13
trans-2-Butene
-
1.87e-11 1.10e-11 -0.278
8.08e-11 1.01e-11 -1.093
1.21e-16 6.64e-15 2.104
3.62e-13 1.10e-13 -0.759
1,3-Butadiene
2.15e-11 1.09e-11 -0.358
8.05e-11 1.48e-11 -0.890
2.39e-18 1.34e-14 4.537
1.00e-13 1.00e-13
-
1.94e-11 2.26e-11 0.079
1-Pentene
3.14e-11 3.14e-11
-
5.42e-18 2.13e-15 3.140
1.50e-14 1.50e-14
-
3.92e-12 1.78e-11 0.795
B
Reaction
#-.07 XC
- C-2-BUTE + O3 = #.17 HO2 + #.54 OH + #.71 MEO2
+ #.54 CO + #.31 CO2 + CCHO + #.15 CCOOH + #.14
XC
- C-2-BUTE + NO3 = #.742 xHO2 + #.137 xNO2 + #.88
RO2C + #.12 RO2XC + #.12 zRNO3 + #.275 xCCHO
+ #.742 xRNO3 + yROOH + #.12 XN + #-1.722 XC
- C-2-BUTE + O3P = MEK
- T-2-BUTE + OH = #.965 xHO2 + #.965 RO2C + #.035
RO2XC + #.035 zRNO3 + #1.93 xCCHO + yROOH +
#-.07 XC
- T-2-BUTE + O3 = #.17 HO2 + #.54 OH + #.71 MEO2
+ #.54 CO + #.31 CO2 + CCHO + #.15 CCOOH + #.14
XC
2.0 T-2-BUTE + NO3 = #.742 xHO2 + #.137 xNO2 + #.88
RO2C + #.12 RO2XC + #.12 zRNO3 + #.275 xCCHO
+ #.742 xRNO3 + yROOH + #.12 XN + #-1.722 XC
- T-2-BUTE + O3P = MEK
- 13-BUTDE + OH = #.931 xHO2 + #1.167 RO2C +
#.069 RO2XC + #.069 zRNO3 + #.695 xHCHO +
#.472 xMACR + #.459 xIPRD + yROOH + #-1.292 XC
- 13-BUTDE + O3 = #.08 HO2 + #.08 OH + #.255 CO +
#.185 CO2 + #.5 HCHO + #.185 HCOOH + #.5 MACR
+ #.375 MVK + #.125 PROD2 + #-1.375 XC
- 13-BUTDE + NO3 = #.788 xHO2 + #.118 xNO2 +
#1.024 RO2C + #.094 RO2XC + #.094 zRNO3 + #.111
xHCHO + #.44 xMVK + #.118 xIPRD + #.348 xRNO3
+ yROOH + #.534 XN + #-1.113 XC
- 13-BUTDE + O3P = #.25 HO2 + #.118 xHO2 + #.11
xMACO3 + #.228 RO2C + #.022 RO2XC + #.022
zRNO3 + #.11 xCO + #.11 xMACR + #.004 xAFG1 +
#.004 xAFG2 + #.75 PROD2 + #.25 yROOH + #-1.662
XC
- 1-PENTEN + OH = #.883 xHO2 + #1.096 RO2C +
#.117 RO2XC + #.117 zRNO3 + #.649 xHCHO +
#.029 xCCHO + #.78 xRCHO + #.028 xMACR + #.015
xMVK + #.007 xIPRD + #.053 xPROD2 + yR6OOH +
#.726 XC
- 1-PENTEN + O3 = #.095 HO2 + #.061 xHO2 + #.128
OH + #.061 RO2C + #.001 RO2XC + #.001 zRNO3 +
#.303 CO + #.088 CO2 + #.5 HCHO + #.5 RCHO +
#.061 xRCHO + #.013 MEK + #.185 HCOOH + #.425
RCOOH + #.063 yR6OOH + #.908 XC
- 1-PENTEN + NO3 = #.78 xHO2 + #1.22 RO2C + #.22
RO2XC + #.22 zRNO3 + #.78 xRNO3 + yR6OOH +
#.22 XN + #-1 XC
- 1-PENTEN + O3P = #.45 RCHO + #.55 MEK + #1.45
XC
A-11
Table A-1 (continued)
Compound
3-Methyl-1-Butene
2-Methyl-1-Butene
2-Methyl-2-Butene
cis-2-Pentene
Rate parameters [a]
k(265)
A
Ea
B
3.99e-11 5.32e-12 -1.059
-
4.52e-18 3.36e-15 3.476
-
1.39e-14 1.39e-14
-
-
3.71e-12 1.03e-11 0.537
-
6.10e-11 6.10e-11
-
-
6.79e-18 4.90e-15 3.460
-
3.32e-13 3.32e-13
-
-
1.80e-11 1.80e-11
1.05e-10 1.92e-11 -0.894
-
2.83e-16 6.51e-15 1.647
-
9.37e-12 9.37e-12
-
-
5.61e-11 2.44e-11 -0.437
6.50e-11 6.50e-11
-
-
8.38e-17 3.70e-15 1.991
-
Reaction
3M-1-BUT + OH = #.873 xHO2 + #.026 xMEO2 +
#1.038 RO2C + #.102 RO2XC + #.102 zRNO3 + #.604
xHCHO + #.117 xCCHO + #.614 xRCHO + #.112
xACET + #.008 xMACR + #.026 xMVK + #.02 xIPRD
+ #.118 xPROD2 + yR6OOH + #.402 XC
3M-1-BUT + O3 = #.095 HO2 + #.06 xHO2 + #.128
OH + #.06 RO2C + #.003 RO2XC + #.003 zRNO3 +
#.303 CO + #.088 CO2 + #.5 HCHO + #.5 RCHO +
#.06 xACET + #.013 MEK + #.185 HCOOH + #.425
RCOOH + #.063 yR6OOH + #.899 XC
3M-1-BUT + NO3 = #.805 xHO2 + #1.215 RO2C +
#.195 RO2XC + #.195 zRNO3 + #.393 xACET + #.822
xRNO3 + yR6OOH + #.178 XN + #-2.281 XC
3M-1-BUT + O3P = #.45 RCHO + #.55 MEK + #1.45
XC
2M-1-BUT + OH = #.904 xHO2 + #.905 RO2C +
#.096 RO2XC + #.096 zRNO3 + #.893 xHCHO +
#.892 xMEK + #.001 xMVK + #.011 xIPRD +
yR6OOH + #-.096 XC
2M-1-BUT + O3 = #.053 HO2 + #.72 OH + #.565
xMECO3 + #.065 xRCO3 + #.63 RO2C + #.037
RO2XC + #.037 zRNO3 + #.17 CO + #.04 CO2 +
#.667 HCHO + #.065 xHCHO + #.565 xCCHO + #.333
MEK + #.123 HCOOH + #.667 yR6OOH + #-.074 XC
2M-1-BUT + NO3 = #.894 xHO2 + #.011 xNO2 +
#1.799 RO2C + #.095 RO2XC + #.095 zRNO3 + #.011
xHCHO + #.894 xCCHO + #.011 xMEK + yR6OOH +
#.989 XN + #2.587 XC
2M-1-BUT + O3P = #.4 RCHO + #.6 MEK + #1.4 XC
2M-2-BUT + OH = #.905 xHO2 + #.905 RO2C +
#.095 RO2XC + #.095 zRNO3 + #.905 xCCHO +
#.905 xACET + yR6OOH + #-.095 XC
2M-2-BUT + O3 = #.051 HO2 + #.862 OH + #.213
MEO2 + #.7 xMECO3 + #.7 RO2C + #.162 CO +
#.093 CO2 + #.7 xHCHO + #.7 CCHO + #.3 ACET +
#.045 CCOOH + #.7 yR6OOH + #.042 XC
2M-2-BUT + NO3 = #.905 xNO2 + #.905 RO2C +
#.095 RO2XC + #.095 zRNO3 + #.905 xCCHO +
#.905 xACET + yR6OOH + #.095 XN + #-.095 XC
2M-2-BUT + O3P = MEK + XC
C-2-PENT + OH = #.904 xHO2 + #.907 RO2C + #.096
RO2XC + #.096 zRNO3 + #.897 xCCHO + #.893
xRCHO + #.01 xIPRD + yR6OOH + #-.099 XC
C-2-PENT + O3 = #.1 HO2 + #.063 xHO2 + #.318 OH
+ #.355 MEO2 + #.063 RO2C + #.318 CO + #.183
CO2 + #.5 CCHO + #.063 xCCHO + #.5 RCHO +
#.075 CCOOH + #.425 RCOOH + #.063 yR6OOH +
#.093 XC
A-12
Table A-1 (continued)
Compound
Rate parameters [a]
k(265)
A
Ea
3.70e-13 3.70e-13
trans-2-Pentene
Cyclopentene
1-Hexene
3-methylcyclopentene
-
B
-
1.79e-11 1.14e-11 -0.238
6.70e-11 6.70e-11
-
-
9.83e-17 7.10e-15 2.250
-
3.70e-13 3.70e-13
-
-
2.27e-11 1.15e-11 -0.358
6.70e-11 6.70e-11
-
-
4.79e-16 1.80e-15 0.696
-
4.20e-13 4.20e-13
-
-
2.06e-11 2.40e-11 0.079
-
3.70e-11 3.70e-11
-
-
6.02e-18 1.62e-15 2.941
-
1.80e-14 1.80e-14
-
-
4.34e-12 1.51e-11 0.656
-
6.67e-11 6.67e-11
-
-
Reaction
C-2-PENT + NO3 = #.697 xHO2 + #.106 xNO2 +
#1.004 RO2C + #.197 RO2XC + #.197 zRNO3 + #.106
xCCHO + #.106 xRCHO + #.697 xRNO3 + yR6OOH
+ #.197 XN + #-.894 XC
C-2-PENT + O3P = MEK + XC
T-2-PENT + OH = #.904 xHO2 + #.906 RO2C + #.096
RO2XC + #.096 zRNO3 + #.895 xCCHO + #.893
xRCHO + #.01 xIPRD + yR6OOH + #-.095 XC
T-2-PENT + O3 = #.1 HO2 + #.063 xHO2 + #.318 OH
+ #.355 MEO2 + #.063 RO2C + #.318 CO + #.183
CO2 + #.5 CCHO + #.063 xCCHO + #.5 RCHO +
#.075 CCOOH + #.425 RCOOH + #.063 yR6OOH +
#.093 XC
T-2-PENT + NO3 = #.697 xHO2 + #.106 xNO2 +
#1.004 RO2C + #.197 RO2XC + #.197 zRNO3 + #.106
xCCHO + #.106 xRCHO + #.697 xRNO3 + yR6OOH
+ #.197 XN + #-.894 XC
T-2-PENT + O3P = MEK + XC
CYC-PNTE + OH = #.892 xHO2 + #.006 xMACO3 +
#.941 RO2C + #.102 RO2XC + #.102 zRNO3 + #.008
xCO + #.016 xHCHO + #.875 xRCHO + #.001 xGLY
+ #.009 xMACR + #.006 xMVK + #.001 xIPRD +
yR6OOH + #1.648 XC
CYC-PNTE + O3 = #.03 HO2 + #.002 xHO2 + #.095
OH + #.116 xRCO3 + #.118 RO2C + #.007 RO2XC +
#.007 zRNO3 + #.095 CO + #.055 CO2 + #.875 RCHO
+ #.002 xRCHO + #.125 yR6OOH + #1.829 XC
CYC-PNTE + NO3 = #.183 xHO2 + #.63 xNO2 +
#.905 RO2C + #.187 RO2XC + #.187 zRNO3 + #.613
xRCHO + #.017 xMGLY + #.183 xRNO3 + yR6OOH
+ #.187 XN + #.89 XC
CYC-PNTE + O3P = #.24 MEK + #.76 PROD2 + #-.52
XC
1-HEXENE + OH = #.843 xHO2 + #1.448 RO2C +
#.157 RO2XC + #.157 zRNO3 + #.289 xHCHO +
#.463 xRCHO + #.031 xMACR + #.012 xMVK + #.006
xIPRD + #.361 xPROD2 + yR6OOH + #1.012 XC
1-HEXENE + O3 = #.095 HO2 + #.058 xHO2 + #.128
OH + #.08 RO2C + #.005 RO2XC + #.005 zRNO3 +
#.303 CO + #.088 CO2 + #.5 HCHO + #.5 RCHO +
#.058 xRCHO + #.013 MEK + #.185 HCOOH + #.425
PROD2 + #.063 yR6OOH + #.618 XC
1-HEXENE + NO3 = #.648 xHO2 + #1.39 RO2C +
#.352 RO2XC + #.352 zRNO3 + #.648 xRNO3 +
yR6OOH + #.352 XN
1-HEXENE + O3P = #.45 RCHO + #.55 MEK + #2.45
XC
3MECC5E + OH = #.835 xHO2 + #.003 xMECO3 +
A-13
Table A-1 (continued)
Compound
2-methyl-1-hexene
1-Octene
1-Nonene
Rate parameters [a]
k(265)
A
Ea
B
1.15e-16 1.15e-16
-
-
3.70e-13 3.70e-13
-
-
2.05e-11 2.05e-11
6.15e-11 6.15e-11
-
-
1.18e-17 1.18e-17
-
-
3.32e-13 3.32e-13
-
-
1.73e-11 1.73e-11
3.77e-11 3.77e-11
-
-
7.00e-18 3.36e-15 3.245
-
1.39e-14 1.39e-14
-
-
5.60e-12 5.60e-12
-
-
3.90e-11 3.90e-11
-
-
1.01e-17 1.01e-17
-
-
Reaction
#.004 xMACO3 + #.891 RO2C + #.158 RO2XC +
#.158 zRNO3 + #.005 xCO + #.016 xHCHO + #.821
xRCHO + #.001 xGLY + #.008 xMACR + #.007
xIPRD + #.002 xAFG1 + #.002 xAFG2 + yR6OOH +
#2.457 XC
3MECC5E + O3 = #.03 HO2 + #.003 xHO2 + #.095
OH + #.105 xRCO3 + #.109 RO2C + #.017 RO2XC +
#.017 zRNO3 + #.095 CO + #.055 CO2 + #.875 RCHO
+ #.003 xRCHO + #.125 yR6OOH + #2.799 XC
3MECC5E + NO3 = #.229 xHO2 + #.441 xNO2 +
#1.038 RO2C + #.33 RO2XC + #.33 zRNO3 + #.382
xRCHO + #.058 xMGLY + #.229 xRNO3 + yR6OOH
+ #.33 XN + #1.326 XC
3MECC5E + O3P = PROD2
2M1C6E + OH = #.759 xHO2 + #.896 RO2C + #.241
RO2XC + #.241 zRNO3 + #.635 xHCHO + #.016
xRCHO + #.015 xMACR + #.01 xIPRD + #.734
xPROD2 + yR6OOH + #.357 XC
2M1C6E + O3 = #.053 HO2 + #.72 OH + #.521
xMECO3 + #.047 xRCO3 + #.568 RO2C + #.099
RO2XC + #.099 zRNO3 + #.17 CO + #.04 CO2 +
#.667 HCHO + #.047 xHCHO + #.521 xRCHO + #.123
HCOOH + #.333 PROD2 + #.667 yR6OOH + #.615
XC
2M1C6E + NO3 = #.624 xHO2 + #1.414 RO2C +
#.376 RO2XC + #.376 zRNO3 + #.624 xRNO3 +
yR6OOH + #.376 XN + XC
2M1C6E + O3P = #.4 RCHO + #.6 MEK + #3.4 XC
1-OCTENE + OH = #.574 xHO2 + #1.112 RO2C +
#.426 RO2XC + #.426 zRNO3 + #.184 xHCHO +
#.287 xRCHO + #.028 xMACR + #.009 xMVK + #.007
xIPRD + #.271 xPROD2 + yR6OOH + #2.59 XC
1-OCTENE + O3 = #.095 HO2 + #.046 xHO2 + #.128
OH + #.098 RO2C + #.017 RO2XC + #.017 zRNO3 +
#.303 CO + #.088 CO2 + #.5 HCHO + #.5 RCHO +
#.046 xRCHO + #.013 MEK + #.185 HCOOH + #.425
PROD2 + #.063 yR6OOH + #2.582 XC
1-OCTENE + NO3 = #.47 xHO2 + #1.104 RO2C +
#.53 RO2XC + #.53 zRNO3 + #.47 xRNO3 + yR6OOH
+ #.53 XN + #2 XC
1-OCTENE + O3P = #.45 RCHO + #.55 PROD2 +
#3.35 XC
1-C9E + OH = #.493 xHO2 + #1.012 RO2C + #.507
RO2XC + #.507 zRNO3 + #.163 xHCHO + #.247
xRCHO + #.025 xMACR + #.008 xMVK + #.006
xIPRD + #.233 xPROD2 + yR6OOH + #3.494 XC
1-C9E + O3 = #.095 HO2 + #.039 xHO2 + #.128 OH +
#.088 RO2C + #.023 RO2XC + #.023 zRNO3 + #.303
CO + #.088 CO2 + #.5 HCHO + #.5 RCHO + #.039
A-14
Table A-1 (continued)
Compound
Rate parameters [a]
k(265)
A
Ea
1.40e-14 1.40e-14
a-Pinene
b-Pinene
d-Limonene
-
B
-
5.60e-12 5.60e-12
6.29e-11 1.21e-11 -0.866
-
6.74e-17 5.00e-16 1.053
-
7.59e-12 1.19e-12 -0.974
-
3.20e-11 3.20e-11
9.06e-11 1.55e-11 -0.928
-
8.81e-18 1.20e-15 2.583
-
2.51e-12 2.51e-12
-
-
2.70e-11 2.70e-11
-
-
1.95e-10 4.28e-11 -0.797
-
1.53e-16 2.95e-15 1.556
-
Reaction
xRCHO + #.185 HCOOH + #.438 PROD2 + #.063
yR6OOH + #3.541 XC
1-C9E + NO3 = #.404 xHO2 + #1.016 RO2C + #.596
RO2XC + #.596 zRNO3 + #.404 xRNO3 + yR6OOH +
#.596 XN + #3 XC
1-C9E + O3P = #.45 RCHO + #.55 PROD2 + #4.35 XC
A-PINENE + OH = #.793 xHO2 + #.002 xRCO3 +
#.946 RO2C + #.204 RO2XC + #.204 zRNO3 + #.001
xHCHO + #.773 xRCHO + #.011 xACET + #.001
xMGLY + #.02 xBACL + yR6OOH + #6.334 XC
A-PINENE + O3 = #.009 HO2 + #.146 xHO2 + #.728
OH + #.109 xRCO3 + #.972 RO2C + #.483 RO2XC +
#.483 zRNO3 + #.029 CO + #.008 xCO + #.017 CO2 +
#.104 xHCHO + #.077 xRCHO + #.234 xACET +
#.008 MEK + #.004 xGLY + #.127 xBACL + #.255
PROD2 + #.737 yR6OOH + #3.606 XC
A-PINENE + NO3 = #.026 xHO2 + #.52 xNO2 + #.008
xRCO3 + #.759 RO2C + #.447 RO2XC + #.447
zRNO3 + #.524 xRCHO + #.033 xACET + #.026
xRNO3 + yR6OOH + #.455 XN + #5.467 XC
A-PINENE + O3P = PROD2 + #4 XC
B-PINENE + OH = #.811 xHO2 + #.004 xRCO3 +
#.916 RO2C + #.185 RO2XC + #.185 zRNO3 + #.799
xHCHO + #.014 xRCHO + #.015 xACET + #.799
xPROD2 + yR6OOH + #3.198 XC
B-PINENE + O3 = #.123 HO2 + #.064 xHO2 + #.353
OH + #.037 xRCO3 + #.311 RO2C + #.129 RO2XC +
#.129 zRNO3 + #.393 CO + #.092 CO2 + #.23 HCHO
+ #.078 xACET + #.285 HCOOH + #.003 xMGLY +
#.061 xBACL + #.77 PROD2 + #.23 yR6OOH +
#3.008 XC
B-PINENE + NO3 = #.143 xHO2 + #.053 xRCO3 +
#1.435 RO2C + #.804 RO2XC + #.804 zRNO3 + #.001
xCO + #.001 xHCHO + #.034 xRCHO + #.183 xACET
+ #.001 xGLY + #.143 xRNO3 + yR6OOH + #.857 XN
+ #3.504 XC
B-PINENE + O3P = #.4 RCHO + #.6 PROD2 + #5.2
XC
D-LIMONE + OH = #.823 xHO2 + #.004 xRCO3 +
#.927 RO2C + #.173 RO2XC + #.173 zRNO3 + #.296
xHCHO + #.526 xRCHO + #.044 xMEK + #.01 xMVK
+ #.006 xIPRD + #.296 xPROD2 + yR6OOH + #5.054
XC
D-LIMONE + O3 = #.009 HO2 + #.016 xHO2 + #.729
OH + #.4 xMECO3 + #.036 xRCO3 + #.49 RO2C +
#.285 RO2XC + #.285 zRNO3 + #.029 CO + #.017
CO2 + #.061 xHCHO + #.407 xRCHO + #.004
xMACR + #.011 xIPRD + #.263 PROD2 + #.738
yR6OOH + #4.405 XC
A-15
Table A-1 (continued)
Compound
Rate parameters [a]
k(265)
A
Ea
1.22e-11 1.22e-11
-
Ethanol
7.20e-11 7.20e-11
3.17e-12 5.49e-13 -1.053
Acrolein
1.99e-11 1.99e-11
-
9.90e-20 1.40e-15 5.024
1.18e-15 1.18e-15
-
2.37e-12 2.37e-12
Phot Set = MACR-06
-
Isopropyl Alcohol
5.64e-12 3.63e-13 -1.574
n-Propyl Alcohol
5.99e-12 4.60e-12 -0.139
Crotonaldehyde
3.64e-11 3.64e-11
-
1.58e-18 1.58e-18
-
5.12e-15 5.12e-15
-
Butanal
7.29e-12 7.29e-12
Phot Set = MACR-06
2.83e-11 6.00e-12 -0.815
B
Reaction
-
D-LIMONE + NO3 = #.033 xHO2 + #.524 xNO2 +
#.002 xRCO3 + #.779 RO2C + #.441 RO2XC + #.441
zRNO3 + #.008 xHCHO + #.006 xCCHO + #.532
xRCHO + #.006 xMACR + #.005 xMVK + #.022
xIPRD + #.03 xRNO3 + yR6OOH + #.446 XN +
#5.398 XC
- D-LIMONE + O3P = PROD2 + #4 XC
2.0 ETOH + OH = #.95 HO2 + #.05 xHO2 + #.05 RO2C +
#.022 xHCHO + #.95 CCHO + #.039 xCCHO + #.05
yROOH
- ACROLEIN + OH = #.25 xHO2 + #.75 MACO3 + #.25
RO2C + #.161 xCO + #.079 xHCHO + #.161 xCCHO
+ #.003 xRCHO + #.079 xGLY + #.007 xMGLY +
#.25 yROOH + #-.75 XC
- ACROLEIN + O3 = #.83 HO2 + #.33 OH + #1.005 CO
+ #.31 CO2 + #.5 HCHO + #.185 HCOOH + #.5 GLY
- ACROLEIN + NO3 = #.067 xHO2 + #.928 MACO3 +
#.067 RO2C + #.005 RO2XC + #.005 zRNO3 + #.928
HNO3 + #.064 xCO + #.003 xMGLY + #.064 xRNO3
+ #.072 yROOH + #.008 XN + #-1.199 XC
- ACROLEIN + O3P = RCHO
ACROLEIN + HV = #1.066 HO2 + #.178 OH + #.234
MEO2 + #.33 MACO3 + #1.188 CO + #.102 CO2 +
#.34 HCHO + #.05 CCOOH + #-.284 XC
2.0 I-C3-OH + OH = #.973 HO2 + #.026 xHO2 + #.026
RO2C + #.026 xHCHO + #.026 xCCHO + #.973 ACET
+ #.027 yROOH + #.003 XC
- N-C3-OH + OH = #.792 HO2 + #.206 xHO2 + #.206
RO2C + #.003 RO2XC + #.003 zRNO3 + #.176
xHCHO + #.176 xCCHO + #.792 RCHO + #.021
xRCHO + #.008 xMEK + #.208 yROOH + #-.017 XC
- CROTALD + OH = #.515 xHO2 + #.455 MACO3 +
#.515 RO2C + #.03 RO2XC + #.03 zRNO3 + #.024
xCO + #.491 xCCHO + #.024 xRCHO + #.491 xGLY
+ #.545 yROOH + #-.06 XC
- CROTALD + O3 = #.835 HO2 + #.52 OH + #.355
MEO2 + #1.02 CO + #.405 CO2 + #.5 CCHO + #.075
CCOOH + #.5 GLY + #.07 XC
- CROTALD + NO3 = #.52 xHO2 + #.076 xNO2 +
#.323 MACO3 + #.596 RO2C + #.081 RO2XC + #.081
zRNO3 + #.323 HNO3 + #.286 xCO + #.076 xCCHO +
#.076 xGLY + #.011 xMGLY + #.509 xRNO3 + #.677
yROOH + #.093 XN + #-1.455 XC
- CROTALD + O3P = #.88 RCHO + #.12 MGLY + XC
CROTALD + HV = #2 HO2 + #2 CO + CCHO
- 1C4RCHO + OH = #.064 xHO2 + #.927 RCO3 + #.065
RO2C + #.009 RO2XC + #.009 zRNO3 + #.027 xCO +
#.001 xCCHO + #.063 xRCHO + #.073 yROOH +
A-16
Table A-1 (continued)
Compound
Rate parameters [a]
k(265)
A
Ea
5.86e-15 1.70e-12 2.981
Phot Set = C2CHO
t-Butyl Alcohol
9.58e-13 3.66e-13 -0.638
3-Methylbutanal
(Isovaleraldehyde)
2.70e-11 2.70e-11
-
1.90e-14 1.90e-14
-
Phot Set = C2CHO
Pentanal
(Valeraldehyde)
3.20e-11 9.90e-12 -0.616
1.50e-14 1.50e-14
-
Phot Set = C2CHO
Methyl t-Butyl Ether
2.84e-12 5.89e-13 -0.960
Hexanal
3.00e-11 3.00e-11
-
1.60e-14 1.60e-14
-
Phot Set = C2CHO
B
Reaction
#.947 XC
- 1C4RCHO + NO3 = #.011 xHO2 + #.988 RCO3 +
#.011 RO2C + #.001 RO2XC + #.001 zRNO3 + HNO3
+ #.01 xRCHO + #.012 yROOH + XC
1C4RCHO + HV = HO2 + #.98 xHO2 + #.98 RO2C +
#.02 RO2XC + #.02 zRNO3 + CO + #.98 xRCHO +
yROOH + #-.06 XC
2.0 T-C4-OH + OH = #.66 xHO2 + #.275 TBUO + #.66
RO2C + #.065 RO2XC + #.065 zRNO3 + #.66 xHCHO
+ #.66 xACET + #.725 yROOH + #-.13 XC
- 3MC4RCHO + OH = #.113 xHO2 + #.001 xMEO2 +
#.871 RCO3 + #.203 RO2C + #.015 RO2XC + #.015
zRNO3 + #.082 xCO + #.059 xHCHO + #.024 xRCHO
+ #.089 xACET + #.03 xGLY + #.001 xMGLY + #.129
yR6OOH + #1.753 XC
- 3MC4RCHO + NO3 = #.056 xHO2 + #.001 xMEO2 +
#.938 RCO3 + #.112 RO2C + #.006 RO2XC + #.006
zRNO3 + HNO3 + #.037 xCO + #.037 xHCHO + #.001
xRCHO + #.056 xACET + #.019 xGLY + #.062
yR6OOH + #1.866 XC
3MC4RCHO + HV = HO2 + #.943 xHO2 + #.971
RO2C + #.057 RO2XC + #.057 zRNO3 + CO + #.028
xHCHO + #.916 xRCHO + #.027 xACET + yR6OOH
+ #.801 XC
- 1C5RCHO + OH = #.066 xHO2 + #.88 RCO3 + #.032
xRCO3 + #.103 RO2C + #.022 RO2XC + #.022
zRNO3 + #.021 xCO + #.001 xHCHO + #.002 xCCHO
+ #.063 xRCHO + #.003 xMGLY + #.12 yR6OOH +
#1.908 XC
- 1C5RCHO + NO3 = #.014 xHO2 + #.972 RCO3 +
#.009 xRCO3 + #.024 RO2C + #.005 RO2XC + #.005
zRNO3 + HNO3 + #.001 xCCHO + #.014 xRCHO +
#.028 yR6OOH + #1.983 XC
1C5RCHO + HV = HO2 + #.924 xHO2 + #1.287
RO2C + #.076 RO2XC + #.076 zRNO3 + CO + #.924
xRCHO + yR6OOH + #.772 XC
2.0 MTBE + OH = #.764 xHO2 + #.156 xMEO2 + #1.106
RO2C + #.08 RO2XC + #.08 zRNO3 + #.206 xHCHO
+ #.02 xACET + yR6OOH + #4.098 XC
- 1C6RCHO + OH = #.078 xHO2 + #.838 RCO3 + #.036
xRCO3 + #.176 RO2C + #.048 RO2XC + #.048
zRNO3 + #.003 xCO + #.065 xRCHO + #.015 xMGLY
+ #.162 yR6OOH + #2.847 XC
- 1C6RCHO + NO3 = #.019 xHO2 + #.956 RCO3 +
#.012 xRCO3 + #.045 RO2C + #.013 RO2XC + #.013
zRNO3 + HNO3 + #.02 xRCHO + #.044 yR6OOH +
#2.958 XC
1C6RCHO + HV = HO2 + #.822 xHO2 + #1.699
RO2C + #.178 RO2XC + #.178 zRNO3 + CO + #.822
A-17
Table A-1 (continued)
Compound
Rate parameters [a]
k(265)
A
Ea
Ethyl t-Butyl Ether
9.65e-12 6.03e-13 -1.590
Methyl t-Amyl Ether
6.31e-12 6.80e-13 -1.304
diisopropyl ether
4.58e-11 4.58e-11
-
B
Reaction
xRCHO + yR6OOH + #1.466 XC
2.0 ETBE + OH = #.603 xHO2 + #.217 xMEO2 + #.029
xTBUO + #.881 RO2C + #.151 RO2XC + #.151
zRNO3 + #.032 xHCHO + #.037 xCCHO + #.011
xRCHO + #.009 xACET + #.02 xMEK + yR6OOH +
#4.515 XC
2.0 MTAE + OH = #.511 xHO2 + #.308 xMEO2 + #1.385
RO2C + #.181 RO2XC + #.181 zRNO3 + #.131
xHCHO + #.447 xCCHO + #.032 xRCHO + #.039
xACET + #.359 xMEK + #.003 xPROD2 + yR6OOH +
#1.914 XC
- IPROIPR + OH = #.019 xHO2 + #.832 xMEO2 + #.858
RO2C + #.149 RO2XC + #.149 zRNO3 + #.002
xRCHO + #.033 xACET + #.827 xMEK + #.005
xPROD2 + yR6OOH + #.831 XC
[a] Rate constants are in units of cm3 molec-1 s-1. Temperature dependence is given by k(T) = A exp(-Ea/RT)
(T/300)B, where T is the temperature in degrees k and R = 0.0019872. For photolysis reactions, the "Phot set" is
the set of absorption cross sections and wavelength-dependent quantum yields (if any) given by Carter (2010).
A-18
Table A-2.
Weight fractions and incremental reactivities for the VOCs measured in
conjunction with the UGRB episodes modeled in this study.
Mass Percent [a]
Compound
Alkanes
ethane
propane
n-butane
isobutane
n-pentane
isopentane
cyclopentane
n-hexane
2,2-dimethyl butane
2,3-dimethyl butane
2-methyl pentane
3-methyl pentane
cyclohexane
methyl cyclopentane
n-heptane
2,3-dimethyl pentane
2,4-dimethyl pentane
2-methyl hexane
3-methyl hexane
methyl cyclohexane
n-octane
3-Ethyl-3-methylpentane
2,2,4-trimethyl pentane
2,3,4-trimethyl pentane
2,3-dimethyl hexane
2,4-dimethyl hexane
2,5-dimethyl hexane
2-methyl heptane
3-methyl heptane
4-methyl heptane
n-nonane
n-decane
n-undecane
n-dodecane
Alkenes
ethene
propene
1-butene
cis-2-butene
trans-2-butene
1,3-butadiene
Incremental Reactivities [b]
Mobile
Jonah (2008) Boulder
Jonah Boulder Boulder
Standard
Trailer
HONO (2008)
(2008) (2008) (2011)
MIR Baseline
(2011)
3% NOx Baseline
22.03
19.37
7.86
7.76
3.56
5.12
0.40
1.59
0.18
0.06
1.38
0.88
1.65
0.06
0.79
0.23
1.14
0.42
0.38
2.58
0.52
0.12
0.54
0.21
0.13
0.15
0.21
0.24
0.20
0.12
0.23
0.16
0.17
0.19
1.78
0.38
6.16
16.65
2.57
0.23
0.30
1.50
0.21
0.13
1.27
0.38
1.28
0.83
1.00
0.20
0.94
0.46
0.58
2.66
0.83
0.32
0.26
0.32
0.32
0.32
0.32
0.40
0.37
0.32
0.44
0.29
0.44
0.48
31.67
15.58
4.72
4.72
2.31
2.83
0.25
1.31
0.15
0.12
0.96
0.55
1.61
1.56
0.32
1.24
0.75
0.48
1.24
0.37
0.25
0.59
0.25
1.18
3.98
-
28.50
13.17
4.53
4.71
5.28
7.51
0.49
1.19
0.19
0.15
2.11
1.26
1.98
1.52
0.40
1.56
0.94
0.61
1.56
1.15
0.32
0.75
0.31
0.64
0.66
-
0.28
0.49
1.15
1.23
1.31
1.45
2.39
1.24
1.17
0.97
1.50
1.80
1.25
2.19
1.07
1.34
1.55
1.19
1.61
1.70
0.90
1.45
1.26
1.03
1.19
1.73
1.46
1.07
1.24
1.25
0.78
0.68
0.61
0.55
0.02
0.05
0.06
0.00
0.02
0.14
0.09
-0.05
0.01
0.07
0.06
0.08
-0.05
-0.02
-0.17
-0.01
0.12
-0.09
-0.03
-0.15
-0.26
-0.14
0.17
-0.04
-0.11
-0.12
-0.11
-0.19
-0.19
-0.15
-0.35
-0.39
-0.36
-0.36
0.04
0.14
0.19
0.16
0.21
0.35
0.33
0.15
0.09
0.37
0.20
0.27
0.20
0.11
0.04
0.22
0.26
0.09
0.10
0.04
-0.09
-0.01
0.39
0.12
0.07
0.02
0.05
-0.05
-0.03
-0.04
-0.20
-0.26
-0.26
-0.27
0.01
0.05
0.04
0.09
0.01
0.08
-0.07
-0.07
-0.02
0.11
-0.09
-0.04
-0.08
-0.29
-0.23
-0.05
-0.03
-0.15
-0.20
-0.31
-0.34
-0.30
0.03
-0.10
-0.19
-0.32
-0.28
-0.26
-0.28
-0.30
-0.45
-0.51
-0.47
-0.47
0.04
0.10
0.04
0.04
0.04
0.03
25.83
0.30
0.17
0.11
0.11
0.08
0.62
0.25
0.04
0.04
0.34
1.93
0.12
-
9.00
11.66
9.73
14.24
15.16
12.61
3.64
6.34
4.84
15.32
16.89
6.09
5.34
5.54
4.00
5.27
5.71
5.84
0.86
0.23
-0.21
-1.77
-1.88
-0.22
A-19
Table A-2 (continued)
Mass Percent [a]
Compound
1-pentene
3-methyl-1-butene
2-methyl-1-butene
2-methyl-2-butene
cis-2-pentene
trans-2-pentene
cyclopentene
isoprene
1-hexene
3-methyl cyclopentene
2-methyl-1-hexene
2-Methyl-1-heptene
1-nonene
alpha-pinene
beta-pinene
d-limonene
Aromatics
benzene
toluene
ethyl benzene
m-xylene
o-xylene
p-xylene
styrene
n-propyl benzene
isopropyl benzene (cumene)
m-ethyl toluene
o-ethyl toluene
p-ethyl toluene
1,2,3-trimethyl benzene
1,2,4-trimethyl benzene
1,3,5-trimethyl benzene
indane
n-butyl benzene
m-diethyl benzene
p-diethyl benzene
1,2,4,5-tetramethyl benzene
1,2-dimethyl-4-ethyl benzene
1,3-dimethyl-4-ethyl benzene
1,4-dimethyl-2-ethyl benzene
1,2,3,5-tetramethyl benzene
naphthalene
Alkynes
acetylene
Incremental Reactivities [b]
Mobile
Jonah (2008) Boulder
Jonah Boulder Boulder
Standard
Trailer
HONO (2008)
(2008) (2008) (2011)
MIR Baseline
(2011)
3% NOx Baseline
0.05
0.05
0.05
0.05
0.05
0.05
0.04
0.05
0.06
0.06
0.11
0.12
0.14
0.15
0.15
0.15
0.13
0.13
0.13
0.13
0.13
0.13
0.10
3.80
0.18
0.16
0.22
0.32
0.36
0.16
0.39
0.39
0.06
0.13
0.07
0.57
0.28
0.05
0.20
0.18
-
0.35
0.18
1.53
0.75
0.15
0.33
0.54
0.47
-
7.21
6.99
6.40
14.08
10.38
10.56
6.77
10.61
5.49
5.10
5.10
3.25
2.60
4.51
3.52
4.55
2.70
2.88
4.86
19.21
8.65
9.01
4.80
5.68
1.63
3.11
3.31
0.35
0.25
4.25
1.82
4.70
2.32
2.53
3.47
6.72
2.77
2.87
0.94
4.77
1.57
0.69
2.07
0.38
0.18
1.43
1.55
1.51
-0.44
-0.30
0.23
-2.76
-2.06
-2.09
-2.84
-0.63
-0.16
-1.93
-0.64
-0.89
-1.03
-1.77
-0.16
-1.49
2.15
4.84
0.20
0.75
0.22
0.75
0.15
0.13
0.13
0.13
0.13
0.13
0.13
0.14
0.11
0.13
0.10
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.14
0.17
3.44
0.24
0.69
0.38
0.69
0.30
0.34
0.16
0.34
0.34
0.34
0.34
0.50
0.23
0.34
0.25
0.38
0.38
0.23
0.36
0.39
0.38
0.38
0.38
3.78
6.78
0.38
1.53
0.76
1.53
0.12
0.58
1.15
0.86
-
2.62
6.13
0.28
0.79
0.30
0.79
0.25
-
0.72
4.00
3.04
9.75
7.64
5.84
1.73
2.03
2.52
7.39
5.59
4.44
11.97
8.87
11.76
3.32
2.36
7.10
4.43
9.26
7.55
7.55
7.55
9.26
3.34
0.12
1.20
0.70
4.31
2.50
1.80
1.13
0.41
0.57
2.89
1.67
1.22
5.74
3.93
7.55
0.94
0.52
3.13
1.33
4.86
3.32
3.32
3.32
4.86
0.71
0.23
1.71
1.11
4.46
2.99
2.54
0.93
0.70
0.91
3.24
2.10
1.83
5.12
3.97
5.60
1.23
0.86
3.24
1.91
4.15
3.36
3.36
3.36
4.15
0.89
-0.04
-0.35
-0.20
-1.24
-0.92
-0.57
-0.63
-0.13
-0.18
-0.89
-0.65
-0.40
-2.06
-1.37
-1.96
-0.54
-0.17
-0.97
-0.45
-1.60
-1.23
-1.23
-1.23
-1.60
-0.87
0.08
0.46
1.05
0.67
0.95
0.31
0.47
0.00
A-20
Table A-2 (continued)
Mass Percent [a]
Compound
Oxygenates
formaldehyde
acetaldehyde
acrolein
propionaldehyde
acetone
crotonaldehyde
butanal
3-methylbutanal
pentanal (valeraldehyde)
hexanal
methanol
ethanol
isopropyl alcohol
n-propyl alcohol
tert-butyl alcohol
methyl t-butyl ether
ethyl tert-butyl ether
methyl tert-amyl ether
diisopropyl ether
Aromatic Aldehydes
benzaldehyde
Tolualdehydes
Incremental Reactivities [b]
Mobile
Jonah (2008) Boulder
Jonah Boulder Boulder
Standard
Trailer
HONO (2008)
(2008) (2008) (2011)
MIR Baseline
(2011)
3% NOx Baseline
0.13
0.01
0.01
0.01
0.01
0.14
0.03
0.07
0.07
0.10
0.06
0.02
0.01
0.01
5.09
0.08
0.11
0.07
0.11
0.19
0.03
0.04
0.02
0.02
0.29
0.09
0.17
0.51
0.25
0.26
0.03
0.02
0.23
0.13
5.80
0.29
0.34
0.29
-
-
9.46
6.54
7.45
7.08
0.36
9.39
5.97
4.97
5.08
4.35
0.67
1.53
0.61
2.50
0.41
0.73
2.01
1.69
3.52
13.85
2.42
1.75
4.17
0.15
4.59
3.40
3.06
2.66
2.29
0.15
0.17
0.13
0.41
0.07
0.14
0.19
0.28
1.76
6.24
0.80
0.80
0.63
0.09
3.32
0.41
0.65
0.28
0.31
0.27
0.23
0.31
0.46
0.16
0.34
0.52
0.62
2.16
0.18
-2.12
-2.37
-2.31
-0.02
-1.72
-2.08
-1.56
-1.85
-1.56
0.04
-0.05
0.17
-0.09
0.03
0.11
0.12
0.06
0.50
0.01
0.00
0.02
0.02
-
-
-0.67
-0.59
-0.57
-0.50
-0.75
-0.66
-1.11
-0.98
100
3.60
4.36
1.40
1.67
1.75
1.70
1.65
0.31
0.49
0.60
1.30
2.05
0.39
0.55
0.54
-0.41
0.04
-0.08
-0.15
-0.10
Ambient Mixtures used for Base ROGs
Carter (2010) Urban Mixture
Boulder (2008)
Jonah (2008)
100
Boulder (2011)
Mobile Trailer (2011)
100
100
[a] Mass fractions of measured VOCs used to determine the base ROG compositions from for
the model simulations of the UGRB scenarios. See text for a discussion of the derivations of
these compositions.
[b] Incremental reactivities are in units of grams O3 per gram VOC. "Standard MIR" is the
SAPRC-07 MIR values from Carter (2010). Jonah and Boulder baseline are the incremental
reactivities calculated for the baseline 2008 Jonah and Boulder scenarios, respectively. Jonah
HONO 3% NOx are incremental reactivities calculated for the Jonah 2008 scenario with
HONO formed from NO2 at a rate adjusted to yield HONO/NO2 ratios of approximately 3%.
A-21
Table A-3.
Model
Species
Mechanisms derived for lumped VOC model species based on the mechanisms of
the mixtures of compounds measured at the Jonah and Boulder site at 265 K.
Rate parameters [a]
k(265)
A
Ea
B
Reaction
Derived for the Jonah ambient mixture
ALK1
ALK2
ALK3
ALK4
ALK5
OLE1
OLE2
1.58e-13 1.34e-12 0.992 2.0 ALK1 + OH = xHO2 + RO2C + xCCHO + yROOH
8.34e-13 1.49e-12 0.173 2.0 ALK2 + OH = #.963 xHO2 + #.001 TBUO + #.963 RO2C + #.036
RO2XC + #.036 zRNO3 + #.002 xHCHO + #.219 xRCHO + #.745
xACET + #.999 yROOH + #-.114 XC
2.70e-12 1.67e-12 -0.251 - ALK3 + OH = #.271 HO2 + #.381 xHO2 + #.284 xTBUO + #.711
RO2C + #.064 RO2XC + #.064 zRNO3 + #.018 xHCHO + #.271
CCHO + #.03 xCCHO + #.086 xRCHO + #.005 xACET + #.271
xMEK + #.709 yROOH + #.02 yR6OOH + #.503 XC
4.43e-12 3.75e-12 -0.088 - ALK4 + OH = #.01 HO2 + #.792 xHO2 + #.007 xMEO2 + #.001
xMECO3 + #1.445 RO2C + #.19 RO2XC + #.19 zRNO3 + #.005
xHCHO + #.318 xCCHO + #.004 RCHO + #.155 xRCHO + #.005
ACET + #.31 xACET + #.21 xMEK + #.156 xPROD2 + #.001 yROOH
+ #.989 yR6OOH + #.012 XC
1.06e-11 2.58e-12 -0.744 - ALK5 + OH = #.589 xHO2 + #.015 xMEO2 + #1.127 RO2C + #.396
RO2XC + #.396 zRNO3 + #.003 xHCHO + #.011 xCCHO + #.14
xRCHO + #.04 xACET + #.048 xMEK + #.417 xPROD2 + yR6OOH +
#2.35 XC
4.03e-11 6.05e-12 -0.996 - OLE1 + OH = #.818 xHO2 + #.003 xMEO2 + #1.067 RO2C + #.179
RO2XC + #.179 zRNO3 + #.597 xHCHO + #.323 xCCHO + #.347
xRCHO + #.011 xACET + #.011 xMEK + #.014 xMACR + #.009
xMVK + #.006 xIPRD + #.125 xPROD2 + #.419 yROOH + #.581
yR6OOH + #.69 XC
5.14e-18 3.19e-15 3.379 - OLE1 + O3 = #.118 HO2 + #.036 xHO2 + #.2 OH + #.115 MEO2 +
#.053 RO2C + #.007 RO2XC + #.007 zRNO3 + #.375 CO + #.129
CO2 + #.5 HCHO + #.161 CCHO + #.006 xCCHO + #.339 RCHO +
#.024 xRCHO + #.006 xACET + #.006 MEK + #.185 HCOOH + #.024
CCOOH + #.123 RCOOH + #.166 PROD2 + #.006 yROOH + #.037
yR6OOH + #.776 XC
8.18e-15 4.28e-13 2.081 - OLE1 + NO3 = #.727 xHO2 + #1.062 RO2C + #.273 RO2XC + #.273
zRNO3 + #.038 xACET + #.43 xRNO3 + #.419 yROOH + #.581
yR6OOH + #.57 XN + #.668 XC
4.04e-12 1.38e-11 0.648 - OLE1 + O3P = #.45 RCHO + #.391 MEK + #.159 PROD2 + #1.132
XC
8.17e-11 1.29e-11 -0.969 - OLE2 + OH = #.889 xHO2 + #.001 xMACO3 + #.937 RO2C + #.11
RO2XC + #.11 zRNO3 + #.001 xCO + #.239 xHCHO + #.657 xCCHO
+ #.329 xRCHO + #.091 xACET + #.089 xMEK + #.039 xMACR +
#.001 xMVK + #.04 xIPRD + #.109 xPROD2 + #.275 yROOH + #.725
yR6OOH + #.152 XC
9.15e-17 1.05e-14 2.494 - OLE2 + O3 = #.084 HO2 + #.013 xHO2 + #.46 OH + #.235 MEO2 +
#.204 xMECO3 + #.033 xRCO3 + #.25 RO2C + #.021 RO2XC +
#.021 zRNO3 + #.266 CO + #.141 CO2 + #.203 HCHO + #.084
xHCHO + #.37 CCHO + #.069 xCCHO + #.254 RCHO + #.078
xRCHO + #.03 ACET + #.033 MEK + #.044 HCOOH + #.05 CCOOH
+ #.085 RCOOH + #.037 MACR + #.028 MVK + #.059 PROD2 +
#.271 yR6OOH + #.329 XC
A-22
Table A-3 (continued)
Model
Species
Rate parameters [a]
k(265)
A
Ea
B
1.48e-12 3.49e-13 -0.759
2.33e-11 1.53e-11 -0.220
ARO1
5.70e-12 5.70e-12
-
ARO2
2.39e-11 2.39e-11
-
Reaction
- OLE2 + NO3 = #.566 xHO2 + #.241 xNO2 + #1.107 RO2C + #.193
RO2XC + #.193 zRNO3 + #.009 xHCHO + #.257 xCCHO + #.106
xRCHO + #.091 xACET + #.001 xMEK + #.007 xMGLY + #.033
xMVK + #.009 xIPRD + #.444 xRNO3 + #.275 yROOH + #.725
yR6OOH + #.315 XN + #-.138 XC
- OLE2 + O3P = #.019 HO2 + #.009 xHO2 + #.008 xMACO3 + #.017
RO2C + #.002 RO2XC + #.002 zRNO3 + #.008 xCO + #.1 RCHO +
#.668 MEK + #.008 xMACR + #.214 PROD2 + #.019 yROOH + #.66
XC
- ARO1 + OH = #.177 HO2 + #.462 xHO2 + #.304 OH + #.462 RO2C +
#.058 RO2XC + #.058 zRNO3 + #.232 xGLY + #.147 xMGLY +
#.177 CRES + #.06 xBALD + #.185 xAFG1 + #.195 xAFG2 + #.304
AFG3 + #.023 xPROD2 + #.095 yR6OOH + #.426 yRAOOH + #-.078
XC
- ARO2 + OH = #.127 HO2 + #.537 xHO2 + #.214 OH + #.021 RCO3 +
#.537 RO2C + #.101 RO2XC + #.101 zRNO3 + #.139 xGLY + #.26
xMGLY + #.058 xBACL + #.127 CRES + #.041 xBALD + #.181
xAFG1 + #.175 xAFG2 + #.214 AFG3 + #.103 xAFG3 + #.038
xPROD2 + #.094 yR6OOH + #.543 yRAOOH + #1.638 XC
Used for the "low reactivity" aromatics model for Jonah
ARO1
5.70e-12
ARO2
2.39e-11
ARO1 + OH = #.177 HO2 + #.462 xHO2 + #.304 OH + #.462 RO2C +
#.058 RO2XC + #.058 zRNO3 + #.177 CRES + #.06 xBALD + #.684
AFG3 + #.095 yR6OOH + #.426 yRAOOH + #.023 xPROD2
ARO2 + OH = #.127 HO2 + #.537 xHO2 + #.214 OH + #.021 RCO3 +
#.537 RO2C + #.101 RO2XC + #.101 zRNO3 + #.570 xAFG3 + #.038
xPROD2 + #.094 yR6OOH + #.543 yRAOOH
Derived for the Boulder ambient mixture
ALK1
ALK2
ALK3
ALK4
ALK5
OLE1
1.58e-13 1.34e-12 0.992 2.0 ALK1 + OH = xHO2 + RO2C + xCCHO + yROOH
8.02e-13 1.43e-12 0.173 2.0 ALK2 + OH = #.69 xHO2 + #.248 TBUO + #.69 RO2C + #.062
RO2XC + #.062 zRNO3 + #.594 xHCHO + #.022 xRCHO + #.668
xACET + #.752 yROOH + #-1.028 XC
2.35e-12 1.46e-12 -0.251 - ALK3 + OH = #.007 HO2 + #.342 xHO2 + #.001 xMEO2 + #.577
xTBUO + #.954 RO2C + #.074 RO2XC + #.074 zRNO3 + #.009
xHCHO + #.007 CCHO + #.016 xCCHO + #.124 xRCHO + #.005
xACET + #.203 xMEK + #.974 yROOH + #.019 yR6OOH + #-.007
XC
5.10e-12 4.32e-12 -0.088 - ALK4 + OH = #.074 HO2 + #.654 xHO2 + #.008 xMEO2 + #.017
xMECO3 + #1.266 RO2C + #.246 RO2XC + #.246 zRNO3 + #.02
xHCHO + #.075 xCCHO + #.052 RCHO + #.207 xRCHO + #.022
ACET + #.09 xACET + #.2 xMEK + #.218 xPROD2 + #.014 yROOH
+ #.912 yR6OOH + #.091 XC
1.15e-11 2.80e-12 -0.744 - ALK5 + OH = #.547 xHO2 + #.03 xMEO2 + #.001 xTBUO + #1.145
RO2C + #.422 RO2XC + #.422 zRNO3 + #.005 xHCHO + #.014
xCCHO + #.14 xRCHO + #.043 xACET + #.064 xMEK + #.366
xPROD2 + yR6OOH + #2.4 XC
4.00e-11 6.00e-12 -0.996 - OLE1 + OH = #.833 xHO2 + #.002 xMEO2 + #1.063 RO2C + #.165
RO2XC + #.165 zRNO3 + #.625 xHCHO + #.328 xCCHO + #.365
xRCHO + #.01 xACET + #.012 xMEK + #.013 xMACR + #.009
A-23
Table A-3 (continued)
Model
Species
Rate parameters [a]
k(265)
A
Ea
B
5.09e-18 3.15e-15 3.379
-
8.15e-15 4.27e-13 2.081
-
3.99e-12 1.37e-11 0.648
-
8.18e-11 1.29e-11 -0.969
-
9.41e-17 1.08e-14 2.494
-
1.51e-12 3.57e-13 -0.759
-
2.34e-11 1.54e-11 -0.220
-
ARO1
5.85e-12 5.85e-12
-
-
ARO2
2.58e-11 2.58e-11
-
-
OLE2
Reaction
xMVK + #.006 xIPRD + #.115 xPROD2 + #.469 yROOH + #.531
yR6OOH + #.746 XC
OLE1 + O3 = #.118 HO2 + #.036 xHO2 + #.201 OH + #.117 MEO2 +
#.051 RO2C + #.006 RO2XC + #.006 zRNO3 + #.376 CO + #.13 CO2
+ #.5 HCHO + #.165 CCHO + #.009 xCCHO + #.335 RCHO + #.022
xRCHO + #.005 xACET + #.005 MEK + #.185 HCOOH + #.025
CCOOH + #.133 RCOOH + #.153 PROD2 + #.009 yROOH + #.033
yR6OOH + #.835 XC
OLE1 + NO3 = #.743 xHO2 + #1.05 RO2C + #.257 RO2XC + #.257
zRNO3 + #.034 xACET + #.438 xRNO3 + #.469 yROOH + #.531
yR6OOH + #.562 XN + #.728 XC
OLE1 + O3P = #.45 RCHO + #.407 MEK + #.143 PROD2 + #1.164
XC
OLE2 + OH = #.893 xHO2 + #.001 xMACO3 + #.938 RO2C + #.106
RO2XC + #.106 zRNO3 + #.001 xCO + #.226 xHCHO + #.677
xCCHO + #.339 xRCHO + #.094 xACET + #.092 xMEK + #.04
xMACR + #.001 xMVK + #.041 xIPRD + #.09 xPROD2 + #.284
yROOH + #.716 yR6OOH + #.203 XC
OLE2 + O3 = #.085 HO2 + #.013 xHO2 + #.452 OH + #.242 MEO2 +
#.194 xMECO3 + #.032 xRCO3 + #.24 RO2C + #.018 RO2XC +
#.018 zRNO3 + #.269 CO + #.145 CO2 + #.189 HCHO + #.085
xHCHO + #.382 CCHO + #.071 xCCHO + #.262 RCHO + #.064
xRCHO + #.031 ACET + #.034 MEK + #.042 HCOOH + #.051
CCOOH + #.088 RCOOH + #.039 MACR + #.029 MVK + #.05
PROD2 + #.258 yR6OOH + #.385 XC
OLE2 + NO3 = #.564 xHO2 + #.248 xNO2 + #1.098 RO2C + #.187
RO2XC + #.187 zRNO3 + #.01 xHCHO + #.265 xCCHO + #.109
xRCHO + #.094 xACET + #.001 xMEK + #.007 xMGLY + #.034
xMVK + #.009 xIPRD + #.438 xRNO3 + #.284 yROOH + #.716
yR6OOH + #.314 XN + #-.105 XC
OLE2 + O3P = #.019 HO2 + #.009 xHO2 + #.008 xMACO3 + #.018
RO2C + #.002 RO2XC + #.002 zRNO3 + #.008 xCO + #.09 RCHO +
#.67 MEK + #.008 xMACR + #.22 PROD2 + #.019 yROOH + #.646
XC
ARO1 + OH = #.171 HO2 + #.474 xHO2 + #.292 OH + #.474 RO2C +
#.064 RO2XC + #.064 zRNO3 + #.224 xGLY + #.142 xMGLY +
#.171 CRES + #.053 xBALD + #.173 xAFG1 + #.194 xAFG2 + #.292
AFG3 + #.055 xPROD2 + #.126 yR6OOH + #.412 yRAOOH + #-.035
XC
ARO2 + OH = #.114 HO2 + #.547 xHO2 + #.198 OH + #.032 RCO3 +
#.547 RO2C + #.109 RO2XC + #.109 zRNO3 + #.121 xGLY + #.263
xMGLY + #.077 xBACL + #.114 CRES + #.032 xBALD + #.171
xAFG1 + #.2 xAFG2 + #.198 AFG3 + #.092 xAFG3 + #.054 xPROD2
+ #.104 yR6OOH + #.552 yRAOOH + #1.68 XC
[a] Rate constants are in units of cm3 molec-1 s-1. Temperature dependence is given by k(T) = A exp(-Ea/RT)
(T/300)B, where T is the temperature in degrees k and R = 0.0019872.
A-24
Table A-4.
TUV model inputs used to calculate solar actinic fluxes the conditions of the
Jonah site on February 20, 2008. The resulting actinic fluxes were used for all
UGRB winter simulations discussed in this work.
Parameter
Value
Discussion
o3col
317
Total vertical ozone column, in Dobson Units, from surface to space.
From Table 3-1 of Environ (2010).
alsurf
0.75
Surface reflectivity (albedo: min = 0, max = 1). From Table 3-1 of
Environ (2010).
zstart
2.087
Surface elevation, km, above sea level. Number given is provided by
DEQ (2010) and also used for Environ simulation
zout
2.212
Altitude (km) above sea level for the calculated actinic fluxes. This was
set as the surface elevation + ½ the maximum inversion height.
ztemp
264.5
Temperature input. This is the average temperature used in the
scenarios. It is uncertain whether this is actually used in the flux
calculation.
tauaer
0.188
Aerosol vertical optical depth at 550 nm. The default value is 0.235 for
continental aerosol profile given in the TUV documentation. However,
in this application we use 0.188 because this is what was used in the
Environ calculations (Environ, 2011).
For the following parameters the defaults provided in the sample input
file with the TUV model that is recommended for photolysis rate
calculation (TUV, 2010) are used without modification.
nstr
4
psurf
-999
so2col
0
Total SO2 column from surface to space (Dobson Units). Default value
is zero. Profile is mostly between 0 and 1 km asl.
no2col
0
Total NO2 column from surface to space (Dobson Units). Default value
is zero. Profile is mostly between 0 and 1 km asl.
taucld
0
Total cloud optical depth. Cloud is assumed to cover entire sky
uniformly.
zstop
120
Altitude, km, of top of atmosphere.
nz
121
Number of equally spaced atmospheric levels.
Number of streams for radiative transfer. If nstr < 2, uses 2-stream
delta-Eddington. If nstr = 2 or > 2, uses n-stream discrete ordinates
Pressure (millibar) at surface. Set to negative value to use default US
Standard Atmosphere pressure profile.
zbase
4
Altitude (km above sea level) of cloud base.
ztop
5
Altitude (km above sea level) of cloud top.
ssaaer
0.99
Single scattering albedo of aerosols. Must be in range 0.0 (purely
A-25
Table A-4 (continued)
Parameter
Value
Discussion
absorbing) to 1.0 (purely scattering).
alpha
1
Exponent for wavelength (w) dependence of aerosol optical depth
(tauaer), so that tauaer1/tauaer2 = (w2/w1)^alpha.
dirsun
1
Weighting factor for direct sun component. Must be between 1.
difdn
1
Weighting factor for down-welling diffuse radiation Must be between
1.
difup
1
Weighting factor for up-welling diffuse radiation Must be between 1.
zaird
-999
Air density (molec cm-3) at the selected output altitude zout. If
negative, will use default value from US Standard Atm.
A-26
Table A-5.
SAPRC-07 photolysis rate constants calculated for solar noon in the UGRB for
the February 22 winter episode and for the summer solstice.
Photolysis Reaction
NO2 + h  NO + O
NO3 + h  NO + O2
NO3 + h  NO2 + O
O3 + h  O1D + O2
O3 + h  O3P + O2
HONO + h  HO· + NO
HNO3 + h  products
HO2NO2 + h  products
H2O2 + h  2 OH
PAN + h  products
HCHO + h  HCO· + H.
HCHO + h  H2 + CO
CH3CHO + h  CH3 + CHO
C2H5CHO + h  C2H5. + CHO·
CH3C(O)CH3 + h  Radicals
MEK absorption cross sections
CH3OOH + h  products
HCOCHO + h  HCO· + HCO·
HCOCHO + h  HCHO + H2
CH3COCHO + h  products
CH3COCOCH3 + h  2 CH3CO·
Benzaldehyde cross sections
Photoreactive aromatic ringopening product absorption cross
sections
Methacrolein + h  products
MVK + h  products
i-C3H7ONO2 + h  products
Solar Noon Photolysis Rates (min-1)
Previous model [a] TUV Model [b]
Feb 22 June 20 Feb 22 June 20
(Z=54) (Z=20) (Z=54) (Z=20)
Factor Change: Previous
vs. TUV light model
Feb 22 Feb vs. June 20
(Z=54) June (Z=20)
0.512
1.752
13.80
8.24e-4
0.0304
0.0775
2.06e-5
2.46e-4
2.88e-4
2.71e-5
1.36e-3
1.78e-3
1.47e-4
5.59e-4
1.81e-5
3.77e-4
2.09e-4
6.38e-3
1.74e-3
0.0114
0.0202
0.0314
0.241
0.704
1.907
15.35
2.68e-3
0.0367
0.1106
4.91e-5
5.02e-4
5.29e-4
5.65e-5
2.59e-3
2.97e-3
3.76e-4
1.28e-3
5.69e-5
8.81e-4
3.72e-4
8.81e-3
3.01e-3
0.0153
0.0262
0.0489
0.371
0.975
2.349
19.06
1.93e-3
0.0453
0.1584
4.87e-5
5.77e-4
6.75e-4
6.42e-5
3.21e-3
4.11e-3
3.45e-4
1.32e-3
4.24e-5
8.88e-4
4.81e-4
1.20e-2
3.84e-3
0.0204
0.0358
0.0695
0.504
0.698
1.583
12.88
2.99e-3
0.0314
0.1133
5.42e-5
5.53e-4
5.83e-4
6.24e-5
2.84e-3
3.22e-3
4.14e-4
1.41e-3
6.32e-5
9.71e-4
4.05e-4
8.70e-3
3.22e-3
0.0147
0.0250
0.0523
0.387
1.9
1.3
1.4
2.3
1.5
2.0
2.4
2.3
2.3
2.4
2.4
2.3
2.3
2.4
2.3
2.4
2.3
1.9
2.2
1.8
1.8
2.2
2.1
1.4
1.2
1.2
0.7
1.2
1.4
1.0
1.1
1.3
1.1
1.2
1.4
0.9
1.0
0.7
1.0
1.3
1.4
1.3
1.3
1.4
1.4
1.4
1.0
0.8
0.8
1.1
0.9
1.0
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.0
1.1
1.0
1.0
1.1
1.0
1.06e-4
3.99e-5
9.56e-5
1.86e-4
7.09e-5
2.15e-4
2.46e-4
9.35e-5
2.27e-4
2.04e-4
7.75e-5
2.38e-4
2.3
2.3
2.4
1.3
1.3
1.1
1.1
1.1
1.1
Average:
Range:
2.1±0.3 1.2±0.2 1.0±0.1
1.3-2.4 0.7-1.4 0.8-1.1
[a] Calculated for the zenith angles indicated using the Jeffries (1991) light model that was
employed to calculate the photolysis rates for the reactivity calculations of Carter (2010).
[b] Calculated for zenith angle of 54 degrees using TUV 5.0 with inputs given in Table A-4
except for the surface albedo parameter (alsurf) for the June 20 simulation, which used the
TUV default value of 0.1.
A-27
Table A-6.
Box model inputs used in the simulations of the UGRB scenarios.
Parameter
Jonah Boulder Boulder Trailer
Discussion
2/20/08 2/20/08 3/2/11 3/2/11
Simulation control
T0
Tend
8 AM
5 PM
Tstart
-33
7 AM
9 AM Simulation start and end time Initial time
determined by time the data indicate the
initial pollutants can be assumed to be
present. Final time is determined by times of
calculated ozone maximum.
0
Difference between solar and simulation time
in minutes. For the 2011 scenarios this is set
such that the computed zenith angles agree
with those output in the Environ (2011)
simulation. This was neglected in the 2011
simulations.
General environmental conditions
Latitude
42.44
Declination
-11.49
Temperature
264
Mixing
Height
85  250
(See Table A-7
for hourly values)
[H2O]
2611
42.72
The 2008 simulations used the latitude of
Jonah, Wyoming. The 2011 simulations used
the latitude of the Boulder site.
-7.82
Solar declination calculated for the latitude of
Jonah for February 20 for the 2008
simulations, and calculated for the latitude of
Boulder for March 2 for the 2011
simulations.
262
267 Average temperatures in K. See Table A-7 in
the Supplementary Materials for the hourly
values. Values for the 2008 scenarios are
averages of the 2m and 10m values given by
DEQ (2010) for the Jonah episode. Values
for the 2011 scenarios from data provided by
DEQ (2011) for the two locations..
Constant
Initial and final inversion height in meters, in
(therefore not scenarios where it is assumed to increase and
needed for
pollutants are diluted or entrained from aloft.
calculation) For the 2008 episodes the values used in the
Environ (2010) simulations were used. For
the 2011 episodes the inversion height data
provided by DEQ for the Boulder 3/2/11
episode indicated no signficant change in
mixing height with time, so no entrainment
of aloft polluants is assumed.
2036
2133 Average water concentration in ppm,
A-28
Table A-6 (continued)
Parameter
Jonah Boulder Boulder Trailer
Discussion
2/20/08 2/20/08 3/2/11 3/2/11
calculated from the humidity and temperature
inputs. Source of humidity inputs the same as
source of the temperature inputs described
above. See Table A-7 for hourly values
Pollutant input
Initial VOC
4.31
0.95
1.48
Initial NOx
0.136
0.018
0.114
1.35
Initial VOC levels in ppmC. Inputs for the
2008 scenarios from the total NMHC
measurements for 4-7 AM provided by DEQ
(2010). The 2011 inputs are from averages of
NMHC measurements provided by DEQ
(2011).
0.071 Initial NOx levels in ppm, based on NOx
levels provided by DEQ (2010, 2011) for
these episodes. The values used are as
follows: Jonah 2008: averages between 3 AM
and 7 AM; Boulder 2008: averages between
4 AM and 6 PM; Boulder 2011: 7 AM value
(maximum daily value); Mobile Trailer 2011:
9 AM value (maximum daily value).
A-29
Table A-6 (continued)
Parameter
% NO0
% NO20
% HONO0
O3
CO
CH4
O3 Aloft
CO Aloft
CH4 Aloft
ROG Aloft
NOx Aloft
Biogenics
VOC
Speciation
Jonah Boulder Boulder Trailer
Discussion
2/20/08 2/20/08 3/2/11 3/2/11
51%
50%
Fractions of the initial NOx that is NO, NO2,
49% - % HONO0 50% - % HONO0 and HONO. For the 2008 Jonah scenario
% HONO0 = (Nominal HONO/NO2 used in this work, the NO fraction is from the
ratio of NO to NOx for the hour 4-7 average
ratio) x % NO20
NO and NOx data provided by DEQ (2010).
Because of the variability of the Boulder NOx
data, the same ratio was used for the Boulder
scenario. The data for the 2011 episodes are
reasonably consistent with assuming equal
initial NO and NO2. Initial HONO was
assumed to be zero in the baseline
calculations, and derived as discussed in the
text for the added HONO simulations..
24
20
20 Initial O3 in ppb, and CO and methane in
0.701
1.0
1.0 PPM. Values for the 2008 scenarios are from
17.9
5.5
5.5 Environ (2011). O3 and methane values for
the 2011 scenarios from data provided by
DEQ (2011) for the Boulder scenario for O3,
and the individual scenarios for methane.
Although the observed initial O3 in the
Mobile Trailer scenario is higher, better fits
to the 2nd hour data are obtained using 20
ppb. Initial CO values for the 2011 scenarios
are estimates.
0.05
Aloft O3, CO, methane, NMOCs and NOx,
respectively, which are entrained into the
0.2
N/A
simulated parcel when the inversion height
2
increases. This is only applicable to the 2008
0.02
scenarios because the inversion height is
0.001
assumed to be constant in the 2011 scenarios.
The Environ (2010) input values are used.
The composition of the NMOC's aloft are
assumed to be the same as the initial
NMOC's, as used in the inputs provided by
Environ (2011).
0
Biogenic VOCs assumed to be negligible..
See Table A-2
The distribution of individual VOCs used to
derive the speciation of the base ROG
mixture. See text for a discussion of how
these were derived.
A-30
Table A-7.
Hour
[a]
7
8
9
10
11
12
13
14
15
16
17
Time-dependent parameter values used in the box model inputs. See Table A-4
for discussion and documentation of these values.
Jonah
2/20/08 [b]
Boulder
3/2/11
Trailer
3/2/11
Jonah
2/20/08 [b]
Boulder
3/2/11
Trailer
3/2/11
Mixing
Height (M)
Jonah
2/20/08 [b]
261
261
263
265
266
265
266
267
266
265
253
254
254
258
260
262
264
266
266
267
267
256
261
264
269
270
272
273
270
270
270
1938
1974
2345
2408
2448
2681
2917
3102
3175
3123
1049
1097
1157
1588
2019
2298
2291
2372
2503
2375
2661
1116
1382
1723
1994
2171
2347
2615
2692
2646
2646
85
95
115
125
135
150
160
200
250
250
Temperature (K)
H2O Concentration (ppm)
[a] Hours after midnight of simulation time. Values at intermediate times determined by linear
interpolation.
[b] Also used for the Boulder 2/22/08 episode.
A-31
(a) NO to NO2 Conversions
Alkanes
Alkenes
Alc., Eth.
1:1 Line
2.0
0.8
Low Temperature Mechanism
2.5
Low Temperature Mechanism
(b) Overall Nitrate Formation
1.5
1.0
0.5
0.0
Alkanes
Alkenes
Alc., Eth.
1:1 Line
0.6
0.4
0.2
0.0
0.0
1.0
2.0
3.0
0.0
Standard SAPRC-07 Mechanism
Figure A-1.
0.2
Plots of low vs. standard temperature numbers of NO to NO2 conversions and
overall organic nitrate yields in the mechanisms derived for the reactions of OH
radicals with alkanes, alkenes, and alcohols and ethers.
O3 + h  O1D + O2
0.0030
1.0
-1
0.6
Standard SAPRC-07 Mechanims
NO2 + h  O3P + NO
Photolysis rate (min )
0.4
0.0025
0.8
0.0020
0.6
0.0015
0.4
0.0010
Winter (higher albedos
and higher zenith angles)
0.2
0.0005
Summer
0.0
0.0000
8
9
10
11
12
13
14
15
16
17
8
9
10
11
12
13
14
15
16
17
Simulated time of day (hour)
Figure A-2.
Plots of selected photolysis rates as a function of simulated hour for both
summertime and wintertime conditions in the UGRB.
A-32
Jonah 2008 Scenarios
Ambient measurement on 2/20/08
88
S1) Environ scenario, CB05 mechanism
S2)
Environ scenario, SAPRC07
mechanism
-
Baseline Jonah scenario and
SAPRC-07 mechanism
S3)
With urban actinic fluxes (default
urban albedos)
S4)
With low reactivity low-temperature
aromatics mechanism
S5)
With room-temperature nonaromatic mechanisms
S6)
With lumped species based on
standard ambient mixture
S7)
With urban ROG mixture
(amount added not adjusted)
S8)
With urban ROG mixture
(amount added reactivity adjusted)
S9)
With NOx reduced to yield MIR
conditions
S10)
With NOx reduced further to yield to
yield maximum ozone
S11)
With NO2 converted to HONO to
yield HONO/NO2=3%
S12)
With Summer temperatures and
solar actinic fluxes
110
128
115
58
80
137
116
317
97
165
196
252
300
Boulder 2008 Scenarios
143
Ambient measurement on 2/21/08
-
Baseline Boulder scenario and
SAPRC-07 mechanism
S3)
With urban actinc fluxes (default
urban albedos)
S5)
With room-temperature nonaromatic VOC mechanisms
S10)
With NOx increased to yield
maximum ozone
S9)
With NOx increased further to yield
MIR conditions
S11)
With NO2 converted to HONO to
yield HONO/NO2=3%
S12)
With Summer temperatures and
solar actinic fluxes
132
110
134
229
173
131
176
0
50
100
150
200
250
300
Maximum Ozone (ppb)
Figure A-3.
Comparison of maximum ozone levels calculated using modified mechanisms and
inputs for the conditions of the 2008 Jonah and Boulder Scenarios.
A-33