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 (andre.prevot@psi.ch)

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)