Journal of Atmospheric Chemistry
Oligomeric products and formation mechanisms from acid-catalyzed reactions of methyl vinyl ketone on surrogate ambient aerosols
KA MAN.CHAN1, DAN DAN HUANG1, YONGJIE Li1, MAN NIN CHAN2*, JOHN H. SEINFELD2, 3 and CHAK K. CHAN1, 4, **
1Division of Environment, Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong
2 Division of Engineering and Applied Science, California Institute of Technology, Pasadena, California, USA
3 Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California, USA
4 Department of Chemical and Biomolecular Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong
*present address: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, USA
** Corresponding Author, e- mail:
Figure S1. A schematic diagram of experimental setup
Figure S2. GC-MS analysis of aldol dimers (a) TIC of MVK reacting with SA particles at 80% RH – showing AD140, (b) TIC of MVK reacting with SA particles at 80% RH with derivatization, (c) Mass spectrum of AD140 at RT 12.02 min of Figure S2a, (d) Mass spectrum of AD140 at RT 12.28 min of Figure S2a, (e) EIC of m/z 212 (AD140 derivatives) formed from reacting with SA particles at 80% RH with derivatization, (f) Mass spectrum of derivatized AD140 at RT 17.65 min of Figure S2e, (g) TIC of MVK reacting with SA particles at 40% RH – showing AD122, (h) TIC of MVK reacting with SA particles at 40% RH with derivatization – showing AD122, (i) Mass spectrum of AD122 at RT 11.98 min of Figure S2g, (j) Mass spectrum of AD122 at RT 12.24 min of Figure S2g, (k) Mass spectrum of AD122 at RT 12.03 min of Figure S2h, (l) Mass spectrum of AD122 at RT 12.29 min of Figure S2h.
Figure S3. GC-MS analysis of aldol trimers (a) TIC of MVK reacting with SA particles at 40% RH – showing AT192, (b) Mass spectrum of AT192 at RT 19.43 min of Figure S3a, (c) Mass spectrum of AT192 at RT 19.91 min of Figure S3a, (d) EIC of m/z 264 (AT192 derivatives) formed from reacting with SA particles at 40% RH, (e) Mass spectrum of derivatized AT192 at RT 21.86 min of Figure S3d, (f) Mass spectrum of derivatized AT192 at RT 22.42 min of Figure S3d.
Figure S4. GC-MS analysis of dimers (a) TIC of MVK reacting with SA particles at 80% RH – showing D158, (b) Mass spectrum of D158-1 at RT 15.7 min of Figure S4a, (c) Mass spectrum of D158-2 at RT 16.28 min of Figure S4a, (d) Mass spectrum of D158-2 at RT 16.61 min of Figure S4a, (e) TIC of MVK reacting with SA at 80% RH with derivatization – showing D158 derivatives, (f) Mass spectrum of D158-1 at RT 18.13 min of Figure S4e, (g) Mass spectrum of D158-2 at RT 19.22 min of Figure S4e, (h) Mass spectrum of D158-2 at RT 19.53 min of Figure S4e.
Figure S5. GC-MS analysis of tetramers (a) TIC of MVK reacting with SA particles at 80% RH – showing T298, (b) Mass spectrum of T298 at RT 26.35 min of Figure S5a, (c) Mass spectrum of T298 at RT 26.48 min of Figure S5a, (d) Mass spectrum of T298 at RT 26.68 min of Figure S5a, (e) TIC of MVK reacting with SA at 80% RH with derivatization – showing T298 derivatives, (f) Mass spectrum of derivatized T298 at RT 26.57 min of Figure S5e, (g) Mass spectrum of derivatized T298 at RT 26.94 min of Figure S5e, (h) Mass spectrum of derivatized T298 at RT 27.08 min of Figure S5e.
Table S1. A summary of identified products from acid-catalyzed reactions of MVK
Oligomers / Product ID / Proposed structures*Aldol dimer / AD122 /
AD140 /
Dimer / D158-1 /
D158-2 /
Aldol trimer / AT192 /
AT210 /
Tetramer / T298-1 /
T298-2 /
Hexamer / H438 /
*Only one possible isomer is shown for simplicity
Scheme S1. Proposed fragmentation pathways of aldol dimer and its TMS derivative
Scheme S2. Proposed fragmentation pathways of aldol trimer and its TMS derivative
Scheme S3. Proposed fragmentation pathways of dimer D158-1 and its TMS derivative
Scheme S4. Proposed fragmentation pathways of dimer D158-2 and its TMS derivative
Scheme S5. Proposed fragmentation pathways of tetramer and its TMS derivative