Supplement of Atmos. Chem. Phys., 15, 2825–2841, 2015http://www.atmos-chem-phys.net/15/2825/2015/doi:10.5194/acp-15-2825-2015-supplement© Author(s) 2015. CC Attribution 3.0 License.
Supplement of
Characterization of primary and secondary wood combustion productsgenerated under different burner loads
E. A. Bruns et al.
Correspondence to:A. S. H. Prévôt ([email protected])
Table S1. Characterization of primary gas phase and particle phase emissions measured from the smog chamber.
Expt.
Wood burned
per chamber air
volume
(×103 kg/m3)
CO2
(ppm)*
CO
(ppm)*
CH4
(ppm)*
THC
(ppmC)* NOx (ppb)*
Total PM
(µg/m3)*
Organic
(µg/m3)+*
PAH
(µg/m3)*
BC
(µg/m3)*
NO3
(µg/m3)*
SO4
(µg/m3)*
NH4
(µg/m3)*
Cl
(µg/m3)*
1 0.562±0.008 540±20 21.0±0.4 2.53±0.02 6.7±0.7 153.6±0.8 454±7 395±7 15±1 41.9±0.4 10.2±0.8 3.3±0.1 2.0±0.2 1.16±0.05
2 0.635±0.004 615±8 24.30±0.09 3.90±0.02 7.4±0.4 175.0±0.8 162±3 98±3 3.3±0.5 54.9±0.9 6.2±0.5 1.8±0.1 1.0±0.1 0.38±0.05
3 0.5227±0.0001 515.6±0.2 14.46±0.04 7.65±0.02 2.5±0.1 147.6±0.1 118±5 31±1 1.5±0.3 80±5 5.0±0.3 1.1±0.1 0.79±0.09 0.13±0.04
4 1.239±0.004 1191±9 55.5±0.1 2.931±0.008 16.5±0.3 312.3±0.9 164±3 97±3 16±1 56.5±0.3 6.6±0.4 2.4±0.2 0.72±0.05 0.74±0.07
5 0.669±0.001 649±2 26.82±0.06 1.6362±0.0009 6.2±0.1 160±2 116±1 27±1 3.6±0.3 80.2±0.4 6.9 ±0.4 1.2±0.1 0.8±0.1 0.22±0.05
6 1.6908±0.0003 1600.2±0.6 96.00±0.07 11.919±0.007 26±0.2 360.5±0.9 291±4 99±3 13.7±0.7 177±3 8.4±0.4 4.1±0.3 0.95±0.06 2.0±0.1
+Organics includes PAHs. *Deviations are ±2s calculated from the error propagation of the sample standard deviation of the measurements.
3
Figure S1. Representative photographs of the loaded wood combustion chamber (lined with vermiculite) before burning for (a) average and (b) high load conditions. Logs were approximately 30 cm in legnth and 10 cm in diameter and firestarters were intersperse among the logs.
4
Figure S2. Fits of all parent PAH ions above m/z 200 from experiment 4 before aging.
Stick Individual ion fits Sum of fits Signal
202.25202.20202.15202.10202.05202.00201.95m/z
300
200
100
0
Sig
nal (
Hz/
ns)
0
13CC15H9
C16H10
226.25226.20226.15226.10226.05226.00225.95225.90m/z
150
100
50
0
Sig
nal (
Hz/
ns)
0
13CC17H9
C18H10
230.20230.15230.10230.05230.00229.95m/z
120
80
40
0
Sig
nal (
Hz/
ns)
C17H10O
252.25252.20252.15252.10252.05252.00251.95m/z
250
200
150
100
50
0
Sig
nal (
Hz/
ns)
13CC19H11
C20H12
276.2276.1276.0275.9m/z
80
60
40
20
0
13CC21H11
C22H12
302.3302.2302.1302.0301.9m/z
15
10
5 13CC23H13
C24H14
300.3300.2300.1300.0299.9m/z
12
8
4
0
13CC23H11
C24H12
5
Figure S3. Representative ratios of associated ions to parent ions from primary emissions from experiment 4.
1.0
0.8
0.6
0.4
0.2
0.0
Rat
io to
C1
8H10
-420 -360 -300 -240 -180 -120 -60 0
Time after lights on (min)1.0
0.8
0.6
0.4
0.2
0.0
Rat
io to
C22
H12
-420 -360 -300 -240 -180 -120 -60 0
Time after lights on (min)
1.0
0.8
0.6
0.4
0.2
0.0
Rat
io to
C16
H10
-420 -360 -300 -240 -180 -120 -60 0
Time after lights on (min)
[M-2H]+
[M-H]+
[M+H]+
6
Figure S4. Average ratio of emission factors measured from AMS and filter analysis for emissions before aging (a) and during aging (b) for average and high load experiments. AMS data are the sum of the indicated parent signal and all associated ions. Black line indicates perfect agreement between the two analysis methods.
40
35
30
25
20
15
10
5
0
AM
S:fi
lter
202 226 230 252 276
Molecular weight (filter) or parent peak m/z (AMS)
1.00.80.60.40.20.0
20
15
10
5
0
AM
S:fi
lter
202 226 230 252 276
Molecular weight (filter) or parent peak m/z (AMS)
1.00.80.60.40.20.0
Average load High load
a
b
7
Figure S5. Time traces of individual PAH ions 1 h prior to initiation of photochemistry until the end of the experiment for m/z>200 (a-c, experiments 4-6) and m/z<200 (d-f, experiments 4-6). Wall losses and dilution have been accounted for.
0.25
0.20
0.15
0.10
0.05
0.00
360300240180120600-60
1.0
0.8
0.6
0.4
0.2
0.0
21601800144010807203600
1.0
0.8
0.6
0.4
0.2
0.0
300240180120600-60
0.6
0.5
0.4
0.3
0.2
0.1
0.0
21601800144010807203600
0.8
0.6
0.4
0.2
0.0
300240180120600-60
0.30
0.25
0.20
0.15
0.10
0.05
0.00
360300240180120600-60
m/z 128 139 152 163 165 168 176 178 189 196 199
m/z 202 226 230 252 276 300 302
Time after lights on (min) Time after lights on (min)
Mas
s lo
adin
g of
PA
H p
eaks
> m
/z 2
00 (
µg/m
3 )
a (1) d (4)
e (5)
f (6)
b (2)
c (3)
Mas
s lo
adin
g of
PA
H p
eaks
< m
/z 2
00 (
µg/m
3 )
8
Figure S6. AMS mass spectra for average load experiments (a-c; experiments 1-3) and high load experiments (d-f; experiments 4-6). Mass spectra from experiments 1, 2, 4, 5 correspond to an OH exposure of 1.6×107 molec cm-3 h. Experiments 3 and 6 correspond to 3 h of aging. The legend in (a) applies to (a-f).
0.06
0.04
0.02
0.00
300250200150100500
0.15
77 105
13355
4428
0.06
0.04
0.02
0.00
300250200150100500
0.12
5569 85
4428
0.06
0.04
0.02
0.00
300250200150100500
0.14
554428
0.06
0.04
0.02
0.00
300250200150100500
0.12
7710
5
4428
0.06
0.04
0.02
0.00
300250200150100500
0.14
77
105
4428
0.06
0.04
0.02
0.00
300250200150100500
0.14
5569
4428
m/z m/z
Nor
mal
ized
inte
nsity
Organic (non-PAH) PAH Nitrate Sulfate Ammonium Chloride
a(1)
f(6)
c(3)
e(5)
b(2)
d(4)
9
Figure S7. Mass spectrum of CxHy fragments ≤m/z 80 from experiment 4 for (a) primary emissions and (b) after exposure to 1.6×107 molec OH cm-3 h.
8x10-2
7
6
5
4
3
2
1
0
80706050403020100
50 77
63
39
5165
27
15
8x10-2
7
6
5
4
3
2
1
0
80706050403020100
41
4351
5763
69
71 77
27
15
39
55
Sig
nal n
oram
lized
to to
tal C
xHy
m/z
a
b
10
Figure S8. Fraction of the total oxygenated ions ≥m/z80 for experiment 2 and 4 (not including [CO2]
+). For comparison, this fraction was also determined during an alpha-pinene photo-oxidation experiment.
0.5
0.4
0.3
0.2
0.1
0.0
300240180120600-60
Experiment 4 Experiment 2 Alpha-pinene photo-oxidationF
ract
ion
of o
xyge
nate
d si
gnal
> m
/z 8
0
Time after lights on (min)
11
Figure S9. Time trace of gas phase m/z 129 normalized to the reagent ion signal (m/z 21) and the primary naphthalene signal measured using PTR-MS during experiment 4. Trace has been corrected for dilution during aging.
1.0
0.8
0.6
0.4
0.2
0.0
m/z
129
nor
mal
ized
to p
rimar
y si
gnal
300240180120600Time after lights on (min)