Supplement of Atmos. Meas. Tech., 8, 1–18, 2015
http://www.atmos-meas-tech.net/8/1/2015/
doi:10.5194/amt-8-1-2015-supplement
© Author(s) 2015. CC Attribution 3.0 License.
Supplement of
Application of high-resolution time-of-flight chemical ionization mass
spectrometry measurements to estimate volatility distributions of
α-pinene and naphthalene oxidation products
P. S. Chhabra et al.
Correspondence to: P. S. Chhabra ([email protected])
1 Average Relative Sensitivity
An average sensitivity factor was applied for species detected by the acetate-CIMS based upon literature data
from Veres et al. (2010); Yatavelli et al. (2012); Aljawhary et al. (2013). Sensitivities measured for various
acids normalized to the formic acid sensitivity are compiled in Supplemental Table 1. The average relative
acetate-CIMS sensitivity, 1.3 ± 0.8, is multiplied to the measured 5.5 ± 0.9 Hzppt−1 sensitivity of formic
acid. Thus, to all acid signals (except formic), we apply a total sensitivity of 7.1 ± 4.6 Hzppt−1 .
Supp. Table 1. Relative sensitivities of various organic acids and their corresponding references. Since pyruvic acid
appears twice, the average is used the in the determination of the average relative acetate-CIMS sensitivity.
Organic Acid
Relative Sensitivity to Formic Acid
Reference
succinic acid
2.20119
Aljawhary et al. (2013)
malonic acid
2.09693
Aljawhary et al. (2013)
glyoxylic acid
1.861
Aljawhary et al. (2013)
1.24072
Aljawhary et al. (2013)
oxalic acid
pyruvic acid
1.39841
Aljawhary et al. (2013)
tartaric acid
0.892451
Aljawhary et al. (2013)
citric acid
0.53865
Aljawhary et al. (2013)
pinonic acid
1.76795
Aljawhary et al. (2013)
pyruvic acid
1.45291
Veres et al. (2010)
glycolic acid
1.79056
Veres et al. (2010)
methacrylic acid
0.233644
Veres et al. (2010)
acrylic acid
0.695613
Veres et al. (2010)
propionic acid
0.0348808
Veres et al. (2010)
palmitic acid
0.54
Yatavelli et al. (2012)
azelaic acid
0.88
Yatavelli et al. (2012)
tricarballyic acid
2.6
Yatavelli et al. (2012)
2
2 Estimation of Uncertainty in Vapor Pressures and Partitioning
We derive a correlation of uncertainty as a function of vapor pressure from Figure 12 of Pankow and Asher
(2008), reproduced here as Supplemental Figure 1. The parameter σF IT represents the average of the absolute
Supp. Fig. 1. Figure 12 reproduced from Pankow and Asher (2008) illustrating decadally binned averages of σF IT as a
function of the log of experimental vapor pressure.
deviations between the logarithm of predicted and experimental pressures, decadally binned according to the
log of the experimental vapor pressure:
σF IT =
NC N
T ,i X
1X
log10 p0L,i (Tj,i )P − log10 p0L,i (Tj,i )E N i=1 j=1
(1)
To estimate σF IT as a function of vapor pressure, data from Response Figure 1 from temperatures 273.15
to 333.15K were extracted and fitted with an exponential function (σCORR ) as shown in Response Figure 2,
where:
σCORR = y0 + Ae
−(p0
L,i −x0 )
τ
(2)
The average absolute deviation from the mean is less than or equal to the standard deviation, and for a normal
p
distribution the ratio of the mean absolute deviation to the standard deviation is 2/π (Geary, 1935). Thus,
3
1.6
Coefficient values ± one standard deviation
y0
= 0.21115 ± 0.045
A
= 1.5042 ± 0.0814
τ
= 4.0382 ± 0.478
X0
= -13.1307
1.4
σFIT
1.2
1.0
0.8
0.6
0.4
-12
-10
-8
-6
-4
-2
Averaged Log pL,i0 (atm) - experimental
0
Supp. Fig. 2. Exponential correlation between σF IT and average log of vapor pressure binned to the nearest integer
to provide a more conservative estimate of the error, we divide σCORR by
−(p0
L,i −x0 )
y0 + Ae
p
σSIM =
τ
p
2/π:
2/π
(3)
where σSIM represents the uncertainty in SIMPOL vapor pressure (in log(atm)) used in our analysis. σSIM
is propagated through the analysis and from which uncertainties in c∗ and ξi are calculated using standard
error propagation rules. Because log10 (p0L,i ) and log10 (c∗i ) differ by a constant,
σlog10 c∗i = σSIM
(4)
Thus:
∗
σc∗i = 10log10 ci σlog10 c∗i (ln10)
(5)
and
σξi =
σc∗i
c∗
i
COA 1 + COA
4
2
(6)
C11H21O3
C12H21O4
0.14
0.12
C11H19O2
C11H19O3
0.0
0.2 0.4 0.6 0.8 1.0
Fraction of Mass Moved
C10H17O4
C9H15O2
Mass Defect
C11H19O6
C9H17O3
0.10
C10H15O3
C10H15O4
C6H9O
0.06
C8H9O4C9H9O4
C7H9O4
C9H9O5
C8H9O5
C5H9O4C6H9O4
C4H5O2C5H5O2
C2H3O C3H3O
C6H5O3
C3H5O3
C4H5O3
C5H5O3
C2HO
C2HO2
C6H5O4
C3H5O4 C5H5O4
C3H3O3
C5H3O3
C2H3O3C2H3O4
C4H3O3
C5H3O4
C3H3O4
C4H3O4
C4H3O5
C2HO3
50
C10H11O7
C7H9O5
C7H9O6C8H9O6
C8H7O5
C7H7O5
C6H7O6C7H7O6
C2H5O4
C4H3O2
C3H3O2
0.00
CHO2
C10H17O7
C8H11O3
C7H7O3
C6H7O3
C4H7O3
C5H7O3
C6H7O4
C7H7O4
C5H7O4
C3H5O C4H5O
C11H17O6
C11H15O6
C10H15O6
C10H13O3
C7H13O3
C8H13O3
C10H15O7
C7H13O4
C8H13O4
C10H13O4
C9H13O4
C8H13O5
C7H11O2
C10H13O5
C8H11O2
C9H13O5
C9H13O6
C10H13O6
C6H11O3
C7H11O3
C9H13O7
C10H13O7
C7H11O4
C9H11O4
C8H11O4
C7H11O5
C9H11O5
C7H9O2
C8H11O5
C8H11O6
C6H9O3
C7H9O3
C4H7O2C5H7O2C6H7O2
0.04
C11H17O5
C12H17O5
C10H15O5
C9H13O3
0.08
0.02
C12H19O5
C10H17O2
C5H5O5
C7H5O5
C6H5O5
C7H5O6
C6H3O5
α-pinene/O3
C6H3O6
C2HO4C3HO4
100
150
m/z
200
Supp. Fig. 3. Mass defect plot of α-ozonolysis CIMS spectra (Expt. 1). The text of each marker represents the chemical
formula of the identified CIMS anion. The size of each marker represents the mass fraction of that ion in the spectra. The
color of each ion is scaled to indicate how much of its signal is subtracted and given to its base ion (molecular formula
less C2 H4 O2 ). A gray color indicates less than 1% of the signal is moved.
5
-2
Mass Defect
8x10
0.00 0.05 0.10 0.15 0.20 0.25
Fraction of Mass Moved
6
C13H11O3
C5H11O5
C5H9O3
C4H7O2
4
C9H7O3
C10H7O3
C3H5O2
C7H5O3
C8H5O3
C3H5O3
2
C4H5O4
C3H5O4
C3H3O
C3H3O2 C4H3O2
C2H3O3
0
C9H7O4
C10H7O4
C9H7O5
C10H7O5
C8H5O2
C4H3O3
C10H5O4
C9H5O4
C7H5O4
C8H5O4
C7H5O5 C8H5O5C9H5O5
C10H5O5
C7H5O6
C6H3O3 C3H5O6C4H5O6
C4H3O5
CHO2
C10H5O6
C7H5O7
C4H3O4C5H3O4
C6H3O5
C2HO3
naphthalene
C6H3O6
C2HO4
50
100
150
m/z
200
Supp. Fig. 4. Mass defect plot of naphthalene photooxidation CIMS spectra (Expt. 12). The text of each marker
represents the chemical formula of the identified CIMS anion. The size of each marker represents the mass fraction of
that ion in the spectra. The color of each ion is scaled to indicate how much of its signal is subtracted and given to its
base ion (chemical formula less C2 H4 O2 ). A gray color indicates less than 1% of the signal is moved.
6
2.0
1.8
1.6
H/C
1.4
6
1324
5 8
9
7
0.5
1.0
1.2
1.0
0.8
0.6
0.0
1.5
2.0
O/C
1.
2.
3.
4.
5.
6.
7.
8.
9.
pinonic acid
hydroxy pinonic acid
norpinonic acid
pinic acid
norpinic acid
3-hydroxy-2,2-dimethylglutaric acid
3-hydroxyglutaric acid
3-methyl-1,2,3-butanetricarboxylic acid
terebic acid
Supp. Fig. 5. Van Krevelen plot of tracer acids from the α-pinene system, as shown in Figure 3, Panel A. Tracers are
numbered, corresponding to their proposed identities shown below. Tracers identified by Yu et al. (1999) are in black and
tracers identified by Claeys et al. (2013) are in red.
7
2.0
1.8
1.6
H/C
1.4
1.2
1.0
0.8
13 42
56
7 8 9 10
0.6
0.0
0.5
1.0
1.5
2.0
O/C
1. cinnamic acid
2. dihydroxy cinnamic acid
3. benzoic acid
4. hydroxy benzoic acid
5. formyl cinnamic acid
6. carboxycinnamic acid
7. phthaldehydic acid
8. phthalic acid
9. hydroxy phthalic acid
10. dihydroxy phthalic acid
Supp. Fig. 6. Van Krevelen plot of tracer acids from the naphthalene system, as shown in Figure 3, Panel B
(Kautzman et al., 2009). Tracers are numbered, corresponding to their proposed identities shown below.
8
10
10
0.6
0.8
1.4
0.6
0
-5
A
1.4
0
B
10
8
6
4
2
0
Gas
12
Carbon Number
×5
10
8
6
4
2
0
2
0
Carbon Number
×20
10
10
0.6
0.8
5
1.0 1.2
O/C
0.6
1.4
Log c*
Log c*
1.0 1.2
O/C
-5
Gas
12
0.8
5
Log c*
Log c*
5
1.0 1.2
O/C
0
0.8
5
1.0 1.2
O/C
1.4
0
-5
-5
C
12
D Particle
Particle
10
8
6
4
2
12
0
10
8
6
4
Carbon Number
Carbon Number
Supp. Fig. 7. Estimated Log c* as a function of carbon number and O/C for two different naphthalene photooxidation
experiments. Panels A and C represent extracted gas and particle spectra of Expt. 12 respectively, and Panels B and D
represent the same of Expt. 15. Marker size is proportional to the fraction of mass. The factor and arrow in red represents
the relative mass scale between gas and particle spectra. For example ×20 between panels B and D indicate that markers
of equal area represent equal fractions in their respective phases and 20 times more mass in the gas-phase spectrum.
9
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