Table 23: Source profile fractions (F) and standard deviations (Std) of VOC from photochemical assessment monitoring stations (PAMS) for diesel exhaust (HDDE), gasoline exhaust (LDGE), liquid gasoline (LGAS), evaporated gasoline (EGAS), refinery fugitives (REFG), industrial coating (INCO), primers and enamel (PMEN), and printing (PRNT).
PAMS
|
HDDE
|
LDGE
|
LGAS
|
EGAS
|
REFG
|
INCO
|
PMEN
|
PRNT
|
compound
|
F
|
Std
|
F
|
Std
|
F
|
Std
|
F
|
Std
|
F
|
Std
|
F
|
Std
|
F
|
Std
|
F
|
Std
|
Ethene
|
0.107
|
0.018
|
0.067
|
0.008
|
0.000
|
0.001
|
0.000
|
0.001
|
0.254
|
0.200
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Acetylene
|
0.019
|
0.007
|
0.074
|
0.011
|
0.000
|
0.002
|
0.000
|
0.001
|
0.004
|
0.002
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Ethane
|
0.005
|
0.005
|
0.015
|
0.004
|
0.000
|
0.001
|
0.000
|
0.001
|
0.003
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Propene
|
0.049
|
0.010
|
0.016
|
0.005
|
0.000
|
0.001
|
0.000
|
0.001
|
0.098
|
0.116
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
n-Propane
|
0.010
|
0.006
|
0.003
|
0.006
|
0.001
|
0.001
|
0.009
|
0.003
|
0.092
|
0.125
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Isobutane
|
0.009
|
0.004
|
0.004
|
0.003
|
0.008
|
0.006
|
0.030
|
0.010
|
0.321
|
0.279
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
1-Butene
|
0.036
|
0.008
|
0.033
|
0.003
|
0.001
|
0.001
|
0.007
|
0.002
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
n-Butane
|
0.029
|
0.017
|
0.015
|
0.003
|
0.044
|
0.032
|
0.087
|
0.027
|
0.003
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
t-2-Butene
|
0.000
|
0.002
|
0.005
|
0.001
|
0.002
|
0.001
|
0.008
|
0.002
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
c-2-Butene
|
0.004
|
0.002
|
0.003
|
0.001
|
0.002
|
0.001
|
0.007
|
0.002
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Isopentane
|
0.093
|
0.058
|
0.091
|
0.014
|
0.105
|
0.021
|
0.239
|
0.060
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
1-Pentene
|
0.010
|
0.003
|
0.003
|
0.001
|
0.003
|
0.002
|
0.007
|
0.002
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
n-Pentane
|
0.028
|
0.023
|
0.034
|
0.002
|
0.035
|
0.012
|
0.060
|
0.013
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Isoprene
|
0.005
|
0.002
|
0.003
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
t-2-Pentene
|
0.008
|
0.006
|
0.005
|
0.001
|
0.008
|
0.003
|
0.014
|
0.003
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
c-2-Pentene
|
0.003
|
0.003
|
0.003
|
0.001
|
0.004
|
0.002
|
0.007
|
0.001
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
2,2-Dimethylbutane
|
0.037
|
0.010
|
0.001
|
0.001
|
0.003
|
0.004
|
0.005
|
0.001
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Cyclopentane
|
0.003
|
0.004
|
0.005
|
0.001
|
0.003
|
0.003
|
0.006
|
0.001
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
2,3-Dimethylbutane
|
0.010
|
0.006
|
0.011
|
0.003
|
0.018
|
0.006
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
2-Methylpentane
|
0.030
|
0.023
|
0.036
|
0.005
|
0.048
|
0.014
|
0.046
|
0.007
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
3-Methylpentane
|
0.019
|
0.014
|
0.021
|
0.001
|
0.029
|
0.008
|
0.026
|
0.004
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.003
|
0.001
|
2-Methyl-1-pentene
|
0.013
|
0.004
|
0.001
|
0.002
|
0.002
|
0.001
|
0.002
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
n-Hexane
|
0.019
|
0.011
|
0.022
|
0.014
|
0.024
|
0.008
|
0.018
|
0.004
|
0.054
|
0.067
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Methylcyclopentane
|
0.011
|
0.010
|
0.031
|
0.024
|
0.034
|
0.013
|
0.029
|
0.007
|
0.000
|
0.001
|
0.001
|
0.001
|
0.000
|
0.005
|
0.000
|
0.006
|
2,4-Dimethylpentane
|
0.004
|
0.003
|
0.015
|
0.007
|
0.020
|
0.011
|
0.013
|
0.006
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Benzene
|
0.042
|
0.015
|
0.042
|
0.002
|
0.013
|
0.004
|
0.012
|
0.003
|
0.088
|
0.129
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
Cyclohexane
|
0.004
|
0.004
|
0.008
|
0.001
|
0.005
|
0.006
|
0.007
|
0.003
|
0.002
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
2-Methylhexane
|
0.000
|
0.001
|
0.021
|
0.009
|
0.023
|
0.005
|
0.016
|
0.005
|
0.000
|
0.001
|
0.000
|
0.007
|
0.001
|
0.001
|
0.000
|
0.006
|
2,3-Dimethylpentane
|
0.006
|
0.003
|
0.022
|
0.005
|
0.035
|
0.027
|
0.022
|
0.015
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
3-Methylhexane
|
0.012
|
0.006
|
0.016
|
0.001
|
0.025
|
0.004
|
0.017
|
0.005
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
2,2,4-Trimethylpentane
|
0.020
|
0.011
|
0.033
|
0.011
|
0.050
|
0.035
|
0.033
|
0.019
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
n-Heptane
|
0.009
|
0.005
|
0.007
|
0.003
|
0.016
|
0.003
|
0.011
|
0.003
|
0.000
|
0.001
|
0.000
|
0.007
|
0.006
|
0.002
|
0.000
|
0.006
|
Methylcyclohexane
|
0.005
|
0.004
|
0.012
|
0.003
|
0.010
|
0.005
|
0.009
|
0.004
|
0.000
|
0.001
|
0.006
|
0.002
|
0.014
|
0.003
|
0.000
|
0.006
|
2,3,4-Trimethylpentane
|
0.006
|
0.005
|
0.012
|
0.002
|
0.023
|
0.016
|
0.014
|
0.011
|
0.000
|
0.001
|
0.003
|
0.001
|
0.000
|
0.005
|
0.000
|
0.006
|
Toluene
|
0.068
|
0.038
|
0.089
|
0.005
|
0.106
|
0.029
|
0.077
|
0.027
|
0.004
|
0.002
|
0.000
|
0.007
|
0.086
|
0.021
|
0.004
|
0.001
|
2-Methylheptane
|
0.008
|
0.010
|
0.007
|
0.001
|
0.010
|
0.002
|
0.006
|
0.002
|
0.000
|
0.001
|
0.038
|
0.010
|
0.010
|
0.002
|
0.000
|
0.006
|
3-Methlyheptane
|
0.006
|
0.004
|
0.009
|
0.001
|
0.010
|
0.002
|
0.007
|
0.002
|
0.000
|
0.001
|
0.032
|
0.008
|
0.007
|
0.002
|
0.000
|
0.006
|
n-Octane
|
0.007
|
0.002
|
0.005
|
0.001
|
0.008
|
0.002
|
0.005
|
0.002
|
0.000
|
0.001
|
0.087
|
0.022
|
0.028
|
0.007
|
0.002
|
0.001
|
Ethylbenzene
|
0.012
|
0.009
|
0.014
|
0.002
|
0.022
|
0.005
|
0.013
|
0.004
|
0.001
|
0.001
|
0.026
|
0.006
|
0.045
|
0.011
|
0.043
|
0.011
|
Mp-Xylene
|
0.053
|
0.035
|
0.065
|
0.006
|
0.092
|
0.018
|
0.057
|
0.018
|
0.000
|
0.001
|
0.093
|
0.023
|
0.169
|
0.042
|
0.155
|
0.039
|
Styrene
|
0.014
|
0.003
|
0.002
|
0.001
|
0.000
|
0.002
|
0.001
|
0.001
|
0.008
|
0.004
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
o-Xylene
|
0.021
|
0.014
|
0.023
|
0.003
|
0.035
|
0.007
|
0.020
|
0.007
|
0.000
|
0.001
|
0.043
|
0.011
|
0.092
|
0.023
|
0.062
|
0.015
|
n-Nonane
|
0.006
|
0.001
|
0.001
|
0.001
|
0.003
|
0.001
|
0.002
|
0.001
|
0.000
|
0.001
|
0.000
|
0.007
|
0.028
|
0.007
|
0.083
|
0.021
|
Isopropylbenzene
|
0.004
|
0.004
|
0.002
|
0.001
|
0.002
|
0.001
|
0.000
|
0.001
|
0.068
|
0.118
|
0.005
|
0.001
|
0.009
|
0.002
|
0.007
|
0.002
|
n-Propylbenzene
|
0.005
|
0.004
|
0.003
|
0.001
|
0.007
|
0.001
|
0.003
|
0.001
|
0.000
|
0.001
|
0.010
|
0.002
|
0.013
|
0.003
|
0.024
|
0.006
|
m-Ethyltoluene
|
0.020
|
0.011
|
0.017
|
0.002
|
0.024
|
0.004
|
0.011
|
0.004
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
p-Ethyltoluene
|
0.008
|
0.005
|
0.007
|
0.001
|
0.011
|
0.002
|
0.005
|
0.002
|
0.000
|
0.001
|
0.042
|
0.010
|
0.043
|
0.011
|
0.063
|
0.016
|
1,3,5-Trimethylbenzene
|
0.011
|
0.006
|
0.010
|
0.001
|
0.013
|
0.002
|
0.006
|
0.002
|
0.000
|
0.001
|
0.044
|
0.011
|
0.036
|
0.009
|
0.078
|
0.020
|
o-Ethyltoluene
|
0.015
|
0.006
|
0.005
|
0.001
|
0.009
|
0.002
|
0.004
|
0.001
|
0.000
|
0.001
|
0.000
|
0.007
|
0.000
|
0.005
|
0.000
|
0.006
|
1,2,4-Trimethylbenzene
|
0.033
|
0.020
|
0.037
|
0.017
|
0.043
|
0.009
|
0.019
|
0.008
|
0.000
|
0.001
|
0.118
|
0.030
|
0.160
|
0.040
|
0.142
|
0.036
|
n-Decane
|
0.017
|
0.001
|
0.001
|
0.001
|
0.002
|
0.001
|
0.001
|
0.001
|
0.000
|
0.001
|
0.299
|
0.075
|
0.169
|
0.042
|
0.207
|
0.052
|
1,2,3-Trimethylbenzene
|
0.011
|
0.005
|
0.007
|
0.001
|
0.009
|
0.002
|
0.004
|
0.002
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
m-Diethylbenzene
|
0.000
|
0.001
|
0.003
|
0.001
|
0.002
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.007
|
0.006
|
0.002
|
0.008
|
0.002
|
p-Diethylbenzene
|
0.000
|
0.001
|
0.006
|
0.005
|
0.000
|
0.002
|
0.001
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
n-Undecane
|
0.031
|
0.002
|
0.000
|
0.001
|
0.001
|
0.001
|
0.000
|
0.001
|
0.000
|
0.001
|
0.153
|
0.038
|
0.079
|
0.020
|
0.118
|
0.030
|
Input data files were created by using ambient measurement at the OLC monitoring site. For PAMS source apportionment 28 compounds, which have a life time larger than toluene (8 hours) except isoprene, were used as fitting species for the CMB model. Even though isoprene has a very short life time, it was included as fitting species since it is a good tracer for biogenic emissions. Results of the model application are summarized in Table 24.
Table 24: CMB-derived contributions to VOC measured at OLC from diesel exhaust (HDDE), gasoline exhaust (LDGE), liquid gasoline (LGAS), evaporated gasoline (EGAS), refinery fugitives (REFG), industrial coating (INCO), primers and enamel (PMEN), printing (PRNT), biogenic (BIOG) and flaming prescribed burn emissions (FLAM).
Time
|
R
|
CHI
|
Percent
|
Meas
|
Calc
|
HDDE
|
LDGE
|
LGAS
|
EGAS
|
REFG
|
INCO
|
PMEN
|
PRNT
|
BIOG
|
FLAM
|
|
square
|
square
|
Conc.
|
Conc.(ppbC)
|
(%)
|
(%)
|
(%)
|
(%)
|
(%)
|
(%)
|
(%)
|
(%)
|
(%)
|
(%)
|
2/3/03 11:00
|
0.69
|
4.45
|
101.5
|
25.40
|
25.78
|
0.0
|
11.4
|
0.0
|
34.3
|
12.9
|
0.0
|
30.7
|
0.0
|
0.0
|
10.8
|
2/5/03 17:30
|
0.69
|
1.71
|
134.5
|
30.40
|
40.89
|
0.0
|
20.9
|
0.0
|
30.1
|
5.6
|
0.0
|
42.6
|
0.0
|
0.0
|
0.8
|
2/5/03 22:00
|
0.78
|
1.62
|
112.7
|
89.50
|
100.87
|
0.0
|
14.9
|
0.0
|
40.9
|
11.6
|
0.0
|
28.0
|
0.0
|
0.1
|
4.6
|
2/6/03 7:45
|
0.91
|
0.99
|
116.2
|
82.70
|
96.10
|
0.0
|
24.2
|
0.0
|
43.8
|
6.3
|
0.0
|
24.0
|
0.0
|
1.4
|
0.3
|
3/10/03 14:05
|
0.60
|
3.03
|
129.3
|
26.40
|
34.14
|
0.0
|
20.6
|
0.0
|
25.5
|
7.3
|
0.0
|
44.2
|
0.0
|
0.0
|
2.4
|
3/10/03 23:00
|
0.57
|
2.54
|
122.8
|
230.90
|
283.55
|
0.0
|
0.0
|
0.0
|
39.5
|
31.7
|
0.0
|
13.9
|
0.0
|
0.1
|
14.9
|
3/11/03 7:40
|
0.77
|
2.25
|
119.1
|
276.00
|
328.72
|
0.0
|
10.0
|
0.0
|
41.3
|
15.0
|
0.0
|
27.2
|
0.0
|
0.1
|
6.4
|
3/25/03 11:00
|
0.71
|
1.82
|
106.7
|
46.30
|
49.40
|
0.0
|
26.9
|
0.0
|
39.2
|
11.3
|
0.0
|
21.5
|
0.0
|
0.0
|
1.1
|
3/25/03 14:00
|
0.63
|
2.93
|
94.5
|
15.10
|
14.27
|
0.0
|
35.9
|
0.0
|
13.8
|
10.5
|
0.0
|
37.5
|
0.0
|
0.4
|
2.0
|
3/27/03 12:15
|
0.70
|
2.51
|
92.6
|
13.20
|
12.22
|
0.0
|
37.5
|
0.0
|
16.3
|
10.7
|
0.0
|
33.2
|
0.0
|
1.0
|
1.2
|
3/27/03 14:00
|
0.66
|
1.97
|
98.2
|
14.70
|
14.44
|
0.0
|
26.7
|
0.0
|
10.0
|
6.4
|
0.0
|
56.4
|
0.0
|
0.5
|
0.0
|
3/27/03 17:00
|
0.76
|
1.53
|
100.6
|
16.20
|
16.30
|
0.0
|
38.3
|
0.0
|
23.5
|
7.6
|
0.0
|
29.9
|
0.0
|
0.7
|
0.0
|
3/27/03 22:00
|
0.80
|
1.86
|
57.6
|
25.80
|
14.86
|
0.0
|
25.9
|
0.0
|
23.8
|
11.1
|
0.0
|
31.9
|
0.0
|
0.2
|
7.0
|
3/28/03 8:50
|
0.79
|
1.68
|
104.6
|
15.20
|
15.90
|
0.0
|
30.4
|
0.0
|
16.2
|
9.5
|
0.0
|
42.2
|
0.0
|
1.6
|
0.0
|
3/28/03 14:45
|
0.89
|
0.87
|
118.4
|
64.80
|
76.72
|
0.0
|
37.9
|
0.0
|
27.6
|
1.8
|
0.0
|
32.5
|
0.0
|
0.1
|
0.0
|
4/13/03 17:45
|
0.77
|
1.93
|
100.8
|
18.60
|
18.75
|
0.0
|
55.1
|
0.0
|
6.5
|
8.6
|
0.0
|
28.2
|
0.0
|
1.5
|
0.0
|
4/15/03 11:15
|
0.97
|
1.37
|
97.4
|
14.70
|
14.32
|
0.0
|
32.1
|
0.0
|
10.2
|
8.1
|
0.0
|
42.4
|
0.0
|
7.2
|
0.0
|
4/15/03 14:45
|
1.00
|
2.49
|
96.8
|
22.30
|
21.59
|
0.0
|
23.2
|
0.0
|
13.1
|
7.9
|
0.0
|
26.1
|
0.0
|
28.3
|
1.4
|
4/15/03 17:05
|
0.99
|
1.88
|
90.6
|
15.90
|
14.41
|
0.0
|
37.8
|
0.0
|
11.9
|
8.5
|
0.0
|
28.2
|
0.0
|
13.6
|
0.0
|
4/15/03 21:30
|
0.98
|
0.92
|
105.1
|
28.30
|
29.74
|
0.0
|
39.6
|
0.0
|
21.2
|
6.1
|
0.0
|
28.4
|
0.0
|
4.7
|
0.0
|
4/16/03 8:25
|
0.86
|
1.97
|
106.6
|
39.80
|
42.43
|
0.0
|
19.0
|
0.0
|
29.5
|
15.6
|
0.0
|
25.9
|
0.0
|
2.6
|
7.4
|
4/29/03 9:15
|
0.98
|
1.39
|
105.9
|
39.10
|
41.41
|
0.0
|
24.3
|
0.0
|
29.5
|
10.8
|
0.0
|
26.6
|
0.0
|
6.5
|
2.1
|
4/29/03 13:15
|
0.99
|
1.66
|
95.6
|
18.60
|
17.78
|
0.0
|
44.3
|
0.0
|
13.7
|
8.7
|
0.0
|
19.2
|
0.0
|
14.0
|
0.0
|
4/29/03 16:15
|
1.00
|
0.87
|
102.1
|
49.20
|
50.23
|
0.0
|
13.3
|
0.0
|
59.3
|
4.1
|
0.0
|
11.7
|
0.0
|
11.7
|
0.0
|
4/29/03 21:15
|
0.99
|
0.85
|
107.6
|
58.80
|
63.27
|
0.0
|
20.1
|
0.0
|
32.2
|
7.7
|
0.0
|
31.7
|
0.0
|
8.2
|
0.0
|
4/30/03 7:50
|
0.91
|
0.68
|
115.5
|
171.90
|
198.54
|
0.0
|
23.4
|
0.0
|
38.8
|
6.4
|
0.0
|
30.2
|
0.0
|
1.2
|
0.0
|
The model performed well, as verified by the CMB fitting parameters R-square (R2), Chi-square (2), and the calculated percent concentration (%), pointing to good agreement between the modeled and measured total carbon mixing ratios (ppbC) at OLC. Figure 29 compares the measured total VOC concentrations with the calculated values from the fitted model output for all measurements made at OLC. R-square value is variance in ambient species concentration explained by the calculated species concentrations. Chi-square represents the uncertainties of the calculated species concentrations. A large value (>4.0) means that one or more of the calculated species differs from the measured concentrations by several uncertainty intervals. To get reasonable results from the CMB model, R-square should be larger than 0.80, and Chi-square should be less than 4.0. In this study, R-square values are from 0.57 to 1.0 (0.82 ±0.14), and Chi-square values are from 0.68 to 3.03 (1.84 ±0.83; incl first sample with 4.45). Therefore, the performance parameter of CMB is in a good range, which makes the estimated results acceptable for further analysis. Figure 29 shows that there is a good agreement between the measured and calculated VOC concentrations. The linear regression in Figure 30 indicates that the CMB overestimated VOC concentrations by about 18 % compared to the measured concentrations. The CMB also provides fairly good estimation for individual chemical species compared to its measured concentration (see Figure 31).
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