Online analysis of secondary organic aerosols from OH ...

18
© CSIRO 2017 Environ. Chem. 2017, 14, 7590 doi:10.1071/EN16128_AC Supplementary material Online analysis of secondary organic aerosols from OH-initiated photooxidation and ozonolysis of α-pinene, β-pinene, Δ 3 -carene, and d-limonene by thermal desorption– photoionisation aerosol mass spectrometry Wenzheng Fang, A,B,C Lei Gong A and Liusi Sheng A,C A National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China. B Present address: Section for Earth and Environmental Sciences, Department of Environmental Science and Analytical Chemistry, Bolin Centre for Climate Research, Stockholm University, Svante Arrhenius Väg 8, Stockholm 10691, Sweden. C Corresponding authors. Email: [email protected]; [email protected]

Transcript of Online analysis of secondary organic aerosols from OH ...

Page 1: Online analysis of secondary organic aerosols from OH ...

© CSIRO 2017 Environ. Chem. 2017, 14, 75–90 doi:10.1071/EN16128_AC

Supplementary material

Online analysis of secondary organic aerosols from OH-initiated photooxidation and ozonolysis of α-pinene, β-pinene, Δ3-carene, and d-limonene by thermal desorption–photoionisation aerosol mass spectrometry

Wenzheng Fang,A,B,C Lei GongA and Liusi ShengA,C

ANational Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei

230029, China.

BPresent address: Section for Earth and Environmental Sciences, Department of Environmental

Science and Analytical Chemistry, Bolin Centre for Climate Research, Stockholm University, Svante

Arrhenius Väg 8, Stockholm 10691, Sweden.

CCorresponding authors. Email: [email protected]; [email protected]

Page 2: Online analysis of secondary organic aerosols from OH ...

This file includes:

Experimental details, Chemicals, monoterpene oxidation pathways, and additional information as noted in text.

This material is available from the journal on line.

Experimental details

TD-VUV-TOF-PIAMS. The aerosol sampling rate through the 200 µm diameter flow-limiting orifice was

~4.3 cm3 atm s-1, which was calculated taking into account the pumping speed of the turbo pump and the pressure

in the chamber. The aerodynamic lens consists of five apertures that focus particles into a narrow beam. After

particles exited the final 3.00 mm nozzle of the aerodynamic lens, they are accelerated into a vacuum by the gas

expansion. The particles then passed through three stages of differential pumping system. Once entered the

ionization region in the detection chamber, the aerosols impacted on a heater tip which inserted between the

TOF optics. The particle spot deposited on the heater tip was about 1 mm diameter. The nascent vapor expanded

back into the source region was ionized by the tunable VUV SR. The particle spot deposited on the heater tip is

about 1 mm diameter in this study. The source chamber was evacuated by a Laboud turbo molecular pump

(model TMP-2203LMC; 360 L s-1), and the differential chamber was pumped by a Laboud vacuum compound

molecular pump (model TG383M; 1600 L s-1). The detection chamber was pumped by a Laboud turbo molecular

pump (TMP-1103LMPC; 1000 L s-1). The chambers are collimated to each other. An aperture with a diameter

of 3 mm was used to connect the source chamber and the differential chamber, while a 4 mm diameter aperture

was used to connect the differential chamber and the detection chamber. The pressure in the detection chamber

was ~7 × 10-5 Pa during sampling aerosols.

SR from an undulator-based U14-A beamline of 800 MeV electron storage ring at the NSRL, is dispersed with

a 6 m length monochromator, which cover the photon energy from 7.5 to 22.5 eV for 370 grooves mm−1. The

energy resolving power (E/E) of VUV SR is above 2000 when the widths of the entrance and exit slits are

adjusted to 80 m. The photon flux is about 1013 photons S−1 and the photon beam spot size is ~500 μm in the

region where the photon and particle beam intersect. The absolute wavelength of monochromator was precisely

calibrated with the known IEs of inert gases. The reflectron mass spectrometer is characterized with a field free

flight distance of 1.4 m, an ion mirror, and a multichannel plate detector. The ion signal was amplified by a

preamplifier (VT120C, ORTEC, USA) and recorded with a time-of-flight multiscaler (FAST Comtec P7888,

Page 3: Online analysis of secondary organic aerosols from OH ...

Germany).

The ions can be detected with a reflectron TOF mass spectrometer at different energies. A small positive

bias voltage was applied to drive the ions produced by VUV photoionization into the second stage of ion optics,

where a 165 V positive electric pulse repelled the ions periodically into an acceleration region.

The heater tip is a 6 mm diameter copper rod coupled to a cartridge heater (Watlow) driven by a power

controller (Watlow CV). The heater was mounted on a linear translator, which can change the distance between

the hot surface and the VUV light. This distance is a balance between maximizing the vapor density reaching

the ionization beam and minimizing the electrical field interference caused by the tip between the plates.

The synchrotron light was passed through an argon rare-gas filter to remove higher order harmonics produced

by the undulator, and the pressure of the gas filter chamber was ~5 Torr in this study.

SMPS. The aerosol physical characteristics (size, number and volume distribution) was provided by Scanning

Mobility Particles Sizer (SMPS) spectrometer (TSI, Inc., model 3936), consisting a Differential Mobility

Analyzer (DMA) and an Ultrafine Condensation Particle Counter (UCPC). The observed BSOA mass

concentration was determined assuming an aerosol density (ρ) of 1.2 g/cm3, as measured by previously for SOA

from α-pinene ozonolysis (e.g. Zelenyuk et al., 2008 and Camredon, et al., 2010).1,2 The SMPS was operated to

scan from 0 to 1000 nm (actual particle scanned size about 10-700 nm).

Chemicals. All chemicals were used as purchased without further purification (with the exception of methyl

nitrite): α-Pinene (99%, Sigma-Aldrich), β-Pinene (99%, Sigma-Aldrich), 3-Carene (98%, Sigma-Aldrich), d-

Limonene (99%, Sigma-Aldrich), sodium nitrate (> 99%, Third Reagent Manufactory, Tianjin, China), methanol

(> 99%, Third Reagent Manufactory, Tianjin, China).

Photolysis of methyl nitrite (CH3ONO) at wavelengths λ >300 nm:

CH3ONO + hν → CH3O• + NO (1)

CH3O• + O2 → HCHO + HO2 (2)

HO2 + NO → OH + NO2 (3)

Page 4: Online analysis of secondary organic aerosols from OH ...

Figure S1. Schematic diagram of Smog Chamber system. SE = sample extraction for GC/MS analysis. SMPS:

A differential mobility analyzer (DMA, TSI, 3081) coupled with a condensation nuclei counter (TSI, CNC-

3760) was used to monitor size distribution of particles inside the chamber.

Page 5: Online analysis of secondary organic aerosols from OH ...

Figure S2. The temporal profile of BSOA mass during the four monoterpene photooxidation experiments,

shaded area are the aerosol mass spectra collection time period, black squares (B) for d-limonene+OH, red circle

dots for 3-carene+OH, blue triangles for α-pinene+OH, and purple star for β-pinene+OH.

Page 6: Online analysis of secondary organic aerosols from OH ...

Figure S3. The temporal profile of BSOA mass and O3 concentration during the four monoterpene ozonolysis

experiments, shaded area are the aerosol mass spectra collection time period, purple line (B) for O3 concentration

during d-limonene+O3, red line (C) for O3 concentration during 3-carene+O3, olive line (D) for O3 concentration

during α-pinene+O3, blue line (E) for O3 concentration during β-pinene+ O3 experiments, purple dashed (F) for

BSOA mass during d-limonene+O3, red dashed (G) for BSOA mass during 3-carene+O3, olive line (H) for

BSOA mass during α-pinene+O3, blue line (I) for BSOA mass during β-pinene+ O3 experiments.

Page 7: Online analysis of secondary organic aerosols from OH ...

Figure S4. TD-VUV-TOF-PIAMS mass spectrum of BSOA formed during the α-pinene+O3+methenol, taken

at 10.5 eV with 453 K desorption temperature. (Sufficient methanol was injected to the reaction chamber)

Page 8: Online analysis of secondary organic aerosols from OH ...

Figure S5. Partial tentatively proposed reaction pathways for secondary organic aerosol products formed from

OH-initiated photooxidation of β-pinene. ((#) denotes the molecular weight of the compound, ‘Re’ means

rearrangement)

Page 9: Online analysis of secondary organic aerosols from OH ...

Figure S6. Partial tentatively proposed reaction pathways for secondary organic aerosol products formed from

O3 oxidation of β-pinene. ((#) denotes the molecular weight of the compound, ‘Re’ means rearrangement)

Page 10: Online analysis of secondary organic aerosols from OH ...

Figure S7. Partial tentatively proposed reaction pathways for secondary organic aerosol products formed from

OH-initiated photooxidation of 3-carene. ((#) denotes the molecular weight of the compound, ‘Re’ means

rearrangement)

Page 11: Online analysis of secondary organic aerosols from OH ...

Figure S8. Partial tentatively proposed reaction pathways for secondary organic aerosol products formed from

O3 oxidation of 3-carene. ((#) denotes the molecular weight of the compound, ‘Re’ means rearrangement)

Page 12: Online analysis of secondary organic aerosols from OH ...

Figure S9. Partial tentatively proposed reaction pathways for secondary organic aerosol formed from O3

oxidation of d-limonene. ((#) denotes the molecular weight of the compound, ‘Re’ means rearrangement)

Page 13: Online analysis of secondary organic aerosols from OH ...

Table S1. Comparison of initial concentrations of precursors and related parameters for the OH-initiated

photooxidation and dark ozonolysis of α-pinene, β-pinene, 3-carene, and d-limonene in smog chamber

experiments from the literatures.

[monoterpene]0

(ppb)

[O3]0 OH scavenger Seed aerosol RH(%),

T(K)

SOA mass

(µg/m3, max)

Ref.

limonene/O3 10000 1000-

10000

- - 0-1,

298

3

α-pinene/OH 137-347 - (NH4)2SO4 500-600 4

3-carene/O3 15000-20000 10000-

15000

cyclohexane - Dry,

295

5

α-pinene/O3 180,

159

210,

120

-

CO

- 293-297K 230,

90

6

α-pinene/OH 50

50

- - (NH4)2SO4

7

α-pinene/O3 252 1300-

1400

- - 1%,

292-297

367-441 8

limonene/OH 2.88-5.33 - 29-30, 274-1592 9

limonene/O3 90-650 20-810 - background

seed

269-302 130-3390 10

α-pinene/OH 940-980 - 18-40,

295-315

995-1254 11

α-pinene/OH

β-pinene/OH

limonene/OH

3-carene/OH

1400-1600,

1300-1600,

900-1300,

800-1200

2-5,

297

12

α-pinene/ O3 350-820 250-

600

- - 55-100,

279-296

504-2190 13

α-pinene/O3,

3-carene/O3

44,

72

200,

300

2-butanol 310K 14

α-pinene/ O3 600-880 470-

650

- - 55-100,

268-297

1860-2720 15

α-pinene/O3,

β -pinene/O3,

3-carene/O3

50-110 35-370 2-butanol (NH4)2SO4 310K 11-65 16

α-pinene-OH 3750-4940 - 30, 298 17

β-pinene/OH 2000 - 31, 298 17

limonene/OH 2880 - 30, 298 17

α-pinene/O3 100-880 57-470 background

seed

25-32, 268-

309

17

α-pinene/OH 1000 background

seed

18-40, 295-

315

18

α-pinene/OH 280 - 50 250 19

α-pinene/OH 109 (NH4)2SO4 43, 293 199 20

β-pinene/OH 170 (NH4)2SO4 50, 293 293 20

3-carene/OH 109 (NH4)2SO4 52, 294 236 20

limonene/OH 120 (NH4)2SO4 45, 294 399 20

α-pinene/O3

(flow tube reactor)

90 - 21

α-pinene/OH 963 - 72-86,

303

22

Page 14: Online analysis of secondary organic aerosols from OH ...

Table S2. The other unspecified ions detected in the TD-VUV-TOF-PIAMS mass spectra from OH-initiated

photooxidation and ozonolysis of α-pinene and the corresponding ion relative intensity (%).

m/z (Relative Ion intensity (%)*): 222 (19.2a), 166 (7.5b), 142 (22.7b), 128 (19.2a, 23.5b), 126 (29.2a, 53.4b),

125 (64.1a, 89.1b), 124 (43.8a, 59.3b), 123 (30.6a, 42.7b), 122 (19.6a, 20.2b), 121 (21.7a, 43.9b), 114 (16.0a,

21.3b), 113 (20.2a, 16.2b), 112 (24.0a, 15.9b), 111 (45.8a, 56.1b), 110 (37.5a, 36.5b), 109 (51.3a, 43.9b), 108

(41.5a, 37.9b), 107 (37.9a, 42.8b), 101 (14.9b), 100 (24.6a, 44.1b), 99 (48.1a, 57.7b), 98 (100a,b), 97 (98.4a, 85b),

96 (32.3a, 28.9b), 95 (39.9a, 45.6b), 94 (15.5a, 19.1b), 93 (12.2a, 28.8b), 87 (18.8a, 40.9b), 86 (20.4a, 22.3b), 85

(18.8a, 24.8b), 84 (22.7a, 31.4b), 83 (40.0a, 51.4b), 82 (53.1a, 77.1b), 81 (37.5a, 37.1b), 80 (16.2a, 19.5b), 79

(9.6a), 74 (29.1a, 29.3b), 72 (18.5a, 28.9b), 71 (51.9a, 89.8b), 70 (28.7a, 25.7b), 69 (31.7a, 38.0b), 68 (15.2a,

18.6b), 60 (11.1a, 70.2b), 59 (67.3a), 58 (25.0a, 34.3b)

aOH-initiated photooxidation of α-pinene; bozonolysis of α-pinene; base peak m/z 98 all.

*Relative ion intensity (%) was from TD-VUV-TOF-PIAMS mass spectra of OH-initiated photooxidation of α-

pinene and ozonolysis of α-pinene at 10.00 eV and 10.50 eV respectively.

Table S3. The other unspecified ions detected in the TD-VUV-TOF-PIAMS mass spectra from OH-initiated

photooxidation and ozonolysis of β-pinene and the corresponding relative ion intensity (%).

m/z (Relative Ion intensity (%)*): 234 (7.1a), 230 (5.3a), 224 (5.6a), 214 (4.9a), 206 (7.6b), 202 (8.4a), 176

(8.3b), 158 (23.4a), 144 (21.0a), 142 (70.3a, 11.5b), 134 (18.2a, 6.9b), 132 (4.3b), 130 (14.4a), 128 (52.0a, 12.2b),

126 (71.8a, 8.6b), 125 (52.3a, 13.5b), 124 (62.9a, 9.3b), 123 (31.4a, 19.6b), 122 (30.3a, 6.9b), 121 (15.3a, 30.4b),

120 (12.0a, 6.8b), 118 (23.3a), 116 (17.7a, 4.5b), 115 (23.6a, 5.3b), 114 (23.5a, 7.9b), 113 (32.0a, 5.7b), 112 (48.5a,

7.9b), 111 (59.1a, 8.2b), 110 (100a, 19.9b), 109 (56.3a, 31.2b), 108 (56.9a, 7.9b), 107 (12.1a, 8.7b), 106 (13.7a,

5.2b), 102 (17.9a, 7.0b), 101 (28.9a, 9.0b), 100 (36.3a, 9.7b), 99 (30.9a, 7.2b), 98 (92.3a, 8.9b), 97 (36.8a, 32.1b),

96 (91.4a, 19.1b), 95 (26.9a, 32.2b), 94 (41.4a, 8.7b), 93 (14.1a, 9.0b), 92 (26.3a, 6.3b), 88 (13.3a, 9.0b), 87 (11.9a,

8.0b), 86 (31.7a, 5.9b), 85 (45.9a, 9.2b), 84 (98.3a, 10.0b), 83 (44.6a, 40.8b), 82 (42.6a, 20.1b), 81 (15.1a, 14.7b),

80 (28.9a), 76 (13.9a), 75 (30.9a), 74 (9.8a, 8.1b), 72 (32.3a, 100b), 71 (24.2a, 7.8b), 70 (42.3a, 8.0b), 69 (15.4a,

8.8b), 68 (28.9a, 7.8b), 60 (71.4a, 5.8b), 59 (57.4a, 46.6b), 58 (11.7a, 8.7b), 56 (51.4a, 5.3b)

aOH-initiated photooxidation of β-pinene; base peak m/z 110.

bozonolysis of β-pinene; base peak m/z 72.

*Relative ion intensity (%) from TD-VUV-TOF-PIAMS mass spectra of OH-initiated photooxidation of β-pinene

and ozonolysis of β-pinene at 10.00 eV and 10.50 eV respectively.

Page 15: Online analysis of secondary organic aerosols from OH ...

Table S4. The other unspecified ions detected in the TD-VUV-TOF-PIAMS mass spectra from OH-initiated

photooxidation and ozonolysis of 3-carene and the corresponding relative ion intensity (%).

m/z (Relative Ion intensity (%)*): 212 (4.1a), 196 (3.3a), 194 (3.3a), 182 (6.3b), 167 (27.6 b), 166 (25.3b), 158

(3.9a, 6.9b), 150 (10.1b), 142 (7.7a, 12.5b), 139 (45.8a, 34.5b), 138 (13.8b), 134 (13.1a, 7.9b), 132 (6.4a), 128

(8.4a, 14.8b), 127 (37.4a, 30.2b), 126 (20.2a, 27.2b), 125 (100a, b), 124 (53.1a, 35.4b), 123 (31.1a, 30.2b), 122

(15.1a, 10.5b), 121 (12.5a, 27.1b), 116 (6.7b), 114 (6.4a, 17.0b), 113 (13.3a, 23.4b), 112 (14.1a, 21.4b), 111 (62.6a,

61.6b), 110 (29.2a, 43.7b), 109 (43.7a, 46.0b), 108 (22.0a, 44.8b), 107 (36.6a, 52.6b), 106 (6.9a, 8.0b), 104 (8.5a),

102 (4.4a, 8.0b), 101 (6.3a), 100 (9.8a, 22.9b), 99 (18.2a, 46.9b), 98 (11.9a, 17.6b), 97 (25.9a, 43.6b), 96 (16.0a,

37.8b), 95 (20.6a, 16.4b), 94 (11.6a, 15.7b), 93 (15.8a, 36.8b), 92 (9.5a), 88 (4.6a), 87 (15.0b), 86 (7.6a, 16.7b),

85 (15.3a, 35.8b), 84 (10.2a, 30.1b), 83 (16.7a, 27.8b), 82 (24.0a, 32.0b), 81 (14.9a, 10.1b), 80 (6.4a), 74 (6.4a,

17.9b), 73 (7.4), 72 (8.9a, 61.9b), 71 (22.4a, 45.6b), 70 (10.2a, 55.7b), 69 (17.9a, 27.3b), 68 (6.8a), 59 (23.0a,

50.1b), 58 (11.3a, 38.1b), 56 (4.7a)

aOH-initiated photooxidation of 3-carene; bozonolysis of 3-carene; base peak m/z 125 all.

*Relative ion intensity (%) from TD-VUV-TOF-PIAMS mass spectra of OH-initiated photooxidation of 3-

carene and ozonolysis of 3-carene at 10.00 eV and 10.50 eV respectively.

Table S5. The other unspecified ions detected in the TD-VUV-TOF-PIAMS mass spectra from OH-initiated

photooxidation and ozonolysis of d-limonene and the corresponding relative ion (%).

m/z (Relative ion intensity (%)*): 244 (5.1a), 240 (5.2a), 228 (5.9a), 226 (6.7a), 212 (17.4a), 210 (6.4a), 158(3.9a,

13.5b), 155 (34.4a), 142 (42.3b), 139 (45.8a), 134 (9.1a), 132 (9.8a, 12.4b), 130 (7.0a), 128 (52.3a, 92.1b), 127

(41.5a, 51.5b), 126 (41.7a, 68.8b), 125 (31.5ª, 72.1b), 124 (24.3ª, 64.0b), 123 (26.2ª, 46.7b), 122 (19.8ª, 43.6b),

121 (17.1ª, 35.7b), 116 (7.2ª, 15.2b), 114 (13.6ª, 39.1b), 112 (28.3ª, 46.8b), 110 (61.9ª, 76.1b), 108 (44.3ª, 61.1b),

107 (80.3b), 106 (12.6ª), 100 (13.6ª, 33.6b), 98 (45.7ª, 59.8b), 96 (22.6ª, 55.4b), 95 (57.0ª, 80.9b), 94 (18.0ª,

30.5b), 93 (23.8ª, 26.8b), 92 (18.5ª, 24.5b), 88 (12.2b), 87 (10.6ª, 21.1b), 86 (13.9ª, 27.9b), 85 (20.7ª, 38.6b), 84

(55.0ª, 63.1b), 83 (20.5ª, 44.2b), 82 (33.3ª, 53.3b), 81 (25.2ª, 47.9b), 80 (8.2a), 74 (9.5ª, 18.1b), 73 (20.0b), 72

(12.7ª, 39.2b), 71 (20.5ª, 61.9b), 70 (12.5ª, 24.2b), 69 (12.8ª, 35.4b), 68 (8.7ª, 19.4b), 59 (12.1a), 58 (14.6ª, 40.2b)

aOH-initiated photooxidation of d-limonene; bozonolysis of d-limonene; base peak m/z 153.

*Relative ion intensity (%) from TD-VUV-TOF-PIAMS mass spectra of OH-initiated photooxidation of d-

limonene and ozonolysis d-limonene at 10.00 eV and 10.50 eV respectively.

Page 16: Online analysis of secondary organic aerosols from OH ...

References

[1] Zelenyuk, A., et al., A new real-time method for determining particles’ sphericity and density:

application to secondery organic aerosol formed by ozonolysis of α-Pinene, Environ. Sci. Technol. 2008,

42, 8033. doi: 10.1021/es8013562

[2] M. Camredon, J. F. Hamilton, M. S. Alam, K. P. Wyche, T. Carr, I. R. White, P. S. Monks, A. R. Richard,

W. J. Bloss, Distribution of gaseous and particulate organic composition during dark α-Pinene ozonolysis.

Atmos. Chem. Phys. 2010, 10, 2893. doi:10.5194/acp-10-2893-2010

[3] M. L. Walser, Y. Desyaterik, J. Laskin, A. Laskin, A. S. Nizkorodov, High-resolution mass spectrometric

analysis of secondary organic aerosol produced by ozonation of limonene. Phys. Chem. Chem. Phys. 2008,

10, 1009. doi:10.1039/B712620D

[4] P. S. Chhabra, A. T. Lambe, M. R. Canagaratna, H. Stark, J. T. Jayne, T. B. Onasch, P. Davidovits, J. R.

Kimmel, D. R. Worsnop, Chemistry of α-Pinene and naphthalene oxidation products generated in a

Potential Aerosol Mass (PAM) chamber as measured by acetate chemical ionization mass spectrometry.

Atmos. Meas. Tech. Discuss. 2014, 7, 6385. doi:10.5194/amtd-7-6385-2014

[5] Y. Ma, R. A. Porter, D. Chappell, A. T. Russell, G. Marston, Mechanisms for the formation of organic

acids in the gas-phase ozonolysis of 3-carene. Phys. Chem. Chem. Phys. 2009, 11, 4184.

doi:10.1039/B818750A

[6] M. Camredon, J. F. Hamilton, M. S. Alam, K. P. Wyche, T. Carr, I. R. White, P. S. Monks, A. R. Richard,

W. J. Bloss, Distribution of gaseous and particulate organic composition during dark α-Pinene ozonolysis.

Atmos. Chem. Phys. 2010, 10, 2893. doi:10.5194/acp-10-2893-2010

[7] N. C. Eddingsaas, C. L. Loza, L. D. Yee, J. H. Seinfeld, P. O. Wennberg, α-Pinene photooxidation under

controlled chemical conditions-Part 1: gas-phase composition in low- and high-NOx environments. Atmos.

Chem. Phys. 2012, 12, 6489. doi:10.5194/acp-12-6489-2012

[8] F. Yasmeen, R. Vermeylen, N., Maurin, E. Perraudin, J-F. Doussin, M. Claeys, Characterisation of

tracers for aging of α-Pinene secondary organic aerosol using liquid chromatographry/negative ion

electrospray ionization mass spectrometry. Environmental chemistry 2012, 9, 236. doi:10.1071/EN11148

Page 17: Online analysis of secondary organic aerosols from OH ...

[9] M. Jaoui, E. Corse, T. Kleindienst, J. Offenberg, M. Lewandowski, E. O. Endey, Analysis of secondary

organic aerosol compounds from the photooxidation of d-Limonene in the presence of NOx and their

detection in ambient PM2.5. Environ. Sci. Technol. 2006. 40, 3819. doi:10.1021/es052566z

[10] S. Leungsakul, M. Jaoui, R. M. Kamens, Kinetic mechanism for predicting secondary aerosol

formation from the reaction of d-limonene with ozone. Environ. Sci. Technol. 2005, 39, 9583.

doi:10.1021/es0492687

[11] M. Jaoui, R. M. Kamens, Mass balance of gaseous and particulate products analysis form α-

Pinene/NOx/air in the presence of natural sunlight. J. Geophys. Res. 2001, 106, D12541.

doi:10.1029/2001JD900005

[12] B. R. Larsen, D. Di Bella, M. Glasius, R. Winterhalter, N. R. Jensen, J. Hjorth, Gas-phase OH oxidation

of monoterpenes: gaseous and particulate products. J. Atmos. Chem. 2001, 38, 231.

doi:10.1023/A:1006487530903

[13] R. M. Kamens, M. Jang. C. J. Chien, K. Leach, Aerosol formation from the reaction of α-Pinene and

ozone using a gas-particle kinetics-aerosol partitioning model. Environ. Sci. Technol. 1999, 33, 1430.

doi:10.1021/es980725r

[14] J. Yu, R. C. Flagan, J. H. Seinfeld, Identification of products containing -COOH, -OH, and -C=O in

atmospheric oxidation of hydrocarbons. Environ. Sci. Technol. 1998, 32, 2357. doi:10.1021/es980129x

[15] M. Jang, R. M. Kamens, Newly characterized products and composition of secondary aerosols from

the reaction of α-pinene with ozone. Atmos. Environ. 1999, 33, 459. doi:10.1016/S1352-2310(98)00222-2

[16] J. Yu, D. R. Cocker ш, R. J. Griffin, R. C. Flagan, J. H. Seinfeld, Gas-phase ozone oxidation of

monoterpenes: gaseous and particulate products. Journal of Atmospheric Chemistry 1999, 34, 207.

doi:10.1023/A:1006254930583

[17] M. Jaoui, T. E. Kleindienst, M. Lewandowski, J. H. Offenberg, E. O. Edney, Identification and

quantification of aerosol polar oxygenated compounds bearing carboxylic or hydroxy groups. 2. Organic

tracer compounds from monoterpenes. Environ. Sci. Technol. 2005, 39, 5661. doi:10.1021/es048111b

[18] R. M. Kamens, M. Jaoui, Modeling aerosol formation from α-Pinene + NOx in the presence of natural

Page 18: Online analysis of secondary organic aerosols from OH ...

sunlight using gas-phase kinetics and gas-particle partitioning theory. Environ. Sci. Technol. 2001, 35, 1394.

doi:10.1021/es001626s

[19] H. Hellén, A. Metzger, A. Gascho, J. Duplissy, T. Tritscher, A. S. H. Prevot, U. Baltensperger, Using

proton transfer reaction mass spectrometry for online analysis of secondary organic aerosols. Environ. Sci.

Technol. 2008, 42, 7347. doi:10.1021/es801279m

[20] A. Lee, A. H. Goldstein, J. H. Kroll, N. L. Ng, V. Varutbangkul, R. C. Flagan, J. H. Seinfeld, Gas-

phase products and secondary aerosol yields from the photooxidation of 16 different terpenes. J. Geophys.

Res. 2006, 111, D17305. doi:10.1029/2006JD007050

[21] P. M. Winkler, J. Ortega, T. Karl, L. Cappellin, H. R. Friedli, K. Barsanti, P. H. McMurry, J. N. Smith,

Identification of the biogenic compounds responsible for size-dependent nanoparticle growth. Geophysical

Research Letters 2012, 39, L20815. doi:10.1029/2012GL053253

[22] Y. Yu, M. J. Ezell, A. Zeleyuk, D. Imre, L. Alexander, J. Ortega, B. D’Anna, C. Harmon, S. N. Johnson,

B. J. Finlayson-Pitts, Photooxidation of alpha-pinene at high relative humidity in the presence of increasing

concentrations of NOx. Atmos. Environ. 2008, 42, 5044. doi:10.1016/j.atmosenv.2008.02.026

doi:10.5194/gmd-5-1471-2012