Characterization of Organosulfates in Secondary Organic Aerosol Derived from the Photooxidation of Long-Chain Alkanes

1 Department of Environmental Sciences and Engineering, Gillings School of Global Public Health, The University of North Carolina at Chapel Hill, Chapel Hill, NC, USA 2 CAPES Foundation, Brazil Ministry of Education, Brasilia, DF 70.040-020, Brazil 3 Departamento de Química, Instituto de Ciências Exatas, Universidade Federal Rural do Rio de Janeiro, Seropédica, Brazil 4 Department of Chemistry, University of Iowa, Iowa City, IA 52242, United States


Figure S3 .
Figure S3.MS 2 spectrum and fragmentation scheme of ion at m/z 267.0552 identified in SOA formed from decalin oxidation.

Figure S4 .
Figure S4.MS 2 spectrum and fragmentation scheme of the parent ion at m/z 281.0702 identified in SOA formed from decalin oxidation.

Figure S5 .
Figure S5.MS 2 spectrum and fragmentation scheme of the parent ion at m/z 285.0654 identified in SOA formed from decalin oxidation.

Figure S6 .
Figure S6.MS 2 spectrum and fragmentation scheme of the parent ion at m/z 297.0669 identified in SOA formed from decalin oxidation.

Figure S7 .
Figure S7.MS 2 spectrum and fragmentation scheme of the parent ion at m/z 311.0427 identified in SOA formed from decalin oxidation.

Figure S8 .
Figure S8.Proposed formation pathways of OS-265, OS-281 and OS-295 from the oxidation of decalin in the presence of ammonium sulfate aerosol.ISO = isomerization reaction either through H shift (1,5-or 1,7-) or through hyderoperoxide isomerization with an R radical.

Figure S9 .
Figure S9.MS 2 spectrum and fragmentation scheme of the parent ion at m/z 249.0807 identified in SOA formed from cyclodecane oxidation.

Figure S10 .
Figure S10.MS 2 spectrum and fragmentation scheme of the parent ion at m/z 251.0953 identified in SOA formed from cyclodecane oxidation.

Figure S11 .
Figure S11.MS 2 spectrum and fragmentation scheme of the parent ion at m/z 265.0747 identified in SOA formed from cyclodecane oxidation.

Figure S12 .
Figure S12.MS 2 spectrum and fragmentation scheme of the parent ion at m/z 267.0914 identified in SOA formed from cyclodecane oxidation.

Figure S13 .Figure S14 .Figure S15 .
Figure S13.MS 2 spectrum and fragmentation scheme of the parent ion at m/z 281.0698 identified in SOA formed from cyclodecane oxidation.

Figure S16 .
Figure S16.Extracted ion chromatograms (EICs) for alkane-derived OSs identified in aerosol collected from both smog chamber experiments (in red) and field studies (in green).

Table S1 .
Proposed structures, retention times, formulas and accurate masses of organosulfates (OSs) identified in dodecane, decalin and

Table S2 .
Concentrations (ng m -3 ) of OSs quantified (using methanol) in dodecane chamber experiments in presence of ammonium sulfate aerosol.Ratios of OS quantified using acetonitrile/toluene (ACN-Tol) divided by OS quantified using methanol as solvent mixture are a Quantified using 3-pinanol-2-hydrogen sulfate (C 9 H 13 O 6 S − ) as a surrogate standard, b OSs belonging to Group−2, c quantified using octyl sulfate as a surrogate standard, d OSs belonging to Group−1.Different isomers for one ion have been summed; Ac. and No Ac.correspond to acidified and noacidified sulfate seed aerosol, respectively.

Table S3 .
Concentrations (ng m -3 ) of OSs quantified (using methanol) in decalin chamber experiments in presence of ammonium sulfate aerosol.Ratios of OS quantified using acetonitrile/toluene (ACN-Tol) divided by OS quantified using methanol as solvent mixture are a Quantified using 3-pinanol-2-hydrogen sulfate (C 9 H 13 O 6 S − ) as a surrogate standard, b OSs belonging to Group−2, c OSs belonging to Group−1.Different isomers for one ion have been summed; Ac. and No Ac.correspond to acidified and no-acidified sulfate seed aerosol, respectively.

Table S4 .
Concentrations (ng m -3 ) of OSs quantified (using methanol) in cyclodecane chamber experiments in presence of ammonium sulfate aerosol.Ratios of OS quantified using acetonitrile/toluene (ACN-Tol) divided by OS quantified using methanol as solvent mixture are a Quantified using 3-pinanol-2-hydrogen sulfate (C 9 H 13 O 6 S − ) as a surrogate standard, b OSs belonging to Group−1.Different isomers for one ion have been summed;N.d.: not detected; Ac. and No Ac.correspond to acidified and no-acidified sulfate seed aerosol, respectively.