Laboratory simulation for the aqueous OH-oxidation of methyl vinyl ketone and methacrolein: Significance to the in-cloud SOA production

Transcription

1 Laboratory simulation for the aqueous OHoxidation of methyl vinyl ketone and methacrolein: Significance to the incloud SOA production X. Zhang, Z. M. Chen, and Y. Zhao State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing , China Supplementary material Table S1. Mechanisms for the photooxidation of MACR and MVK in the box model. Fig. S1. Direct photolysis of hydrogen peroxide (experimental and simulated data). Fig. S. MACR/MVK decay via UVphotolysis and OHoxidation. Fig. S. Time series of standard carbonyls in mm H O solution in darkness. Fig. S4. Time series of standard organic acids in mm H O solution in darkness. Fig. S5. Modeled OH via H O photolysis. Correspondence to: Z.M. Chen (zmchen@pku.edu.cn)

2 Table S1. Mechanisms for the photooxidation of MACR and MVK in the box model. No Reaction Rate constant (M 1 s 1 ) 98 K Reference 1 O + hv OH (s 1 ) a Warneck, 1999 H O + OH HO H O Liao and Gurol, 1995 H + HO O H O + O + OH.7 Liao and Gurol, HO O H O + O Liao and Gurol, MACR + OH 0.5 CH (OH)C (CH )CHO CH C(OH)(CH )CHO b Gligorovski et al., 009 MVK + OH 0.7 CH (OH)C HC(O)CH + 0. CH CH(OH)C(O) CH b Fitted 6 7 CH (OH)C (CH )CHO + O (OH)C(OO )(CH )CHO c Marchaj et al., CH C(OH)(CH )CHO + O OOCH C(OH)(CH )CHO c Marchaj et al., 1991 CH (OH)C HC(O)CH + O (OH)C(OO)HC(O)CH c Marchaj et al.,

3 10 CH CH(OH)C(O)CH + O OOCH CH(OH)C(O) CH c Marchaj et al., CH (OH)C(OO)(CH )CHO O CH C(O)CHO + CH OH + 0. CH (OH)C(O)CHO + 0. CH CH (OH)C(O)CH CHO d Glowa et al., OOCH C(OH)(CH )CHO OHCC(OH)(CH )CHO O d Glowa et al., OOCH C(OH)(CH )CHO OHCC(OH)(CH )CHO + CH (OH)C(OH)(CH )CHO + O d Glowa et al., OOCH C(OH)(CH )CHO HCHO + CH C (OH)CHO + O d Glowa et al., CHO + O CO + OH Hart et al., CHO HCHO COOH Hart et al., CH C (OH)CHO + O C(OO)(OH)CHO e von Sonntag, CH C(OO )(OH)CHO 0.8 CH COOH CHO OHCCOOH+ 0.8 CH + 0. CH C(O)CHO+ 0. OH f Glowa et al., CH (OH)C(OO )HC(O)CH CH (OH)C(O)C(O)CH O d Glowa et al., CH (OH)C(OO )HC(O)CH (OH)C(O)C(O)CH + CH (OH)CH(OH)C(O)CH + O d Glowa et al., CH 1.4 CH (OH)C(OO)HC(O)CH O (OH)CHO+ 1.4 CH CO CH OH CH C(O)CHO d Glowa et al., 000

4 OOCH CH(OH)C(O)CH OHCCH(OH)C(O)CH O d Glowa et al., 000 OOCH CH(OH)C(O)CH OHCCH(OH)C(O)CH + CH (OH)CH(OH)C(O)CH + O d Glowa et al., OOCH CH(OH)C(O)CH HCHO + CH C(O)C H(OH) + O d Glowa et al., CH CO + O CO Glowa et al., CH CO O + CO + CH Glowa et al., CH CO + OH COOH Glowa et al., CH CO COCOCH Glowa et al., CH CO + CH O O CHO + CH COOH g Herrmann et al., CH (OH)CHO + OH (OH)COOH O O Warneck, 00 1 CH (OH)COOH + OH CH(OH)COOH O Scholes and Willson, 1967 CH(OH)COOH + O OOCH(OH)COOH Herrmann et al., 000 OOCH(OH)CO OH O (OH) COOH O 5 Herrmann et al., CH(OH) COOH + OH HOOCCOOH O O Ervens et al., 00

5 5 CH (OH)CHO + OH (OH) CHCH(OH) O Warneck, 00 6 CH(OH) COOH O HCOOH + CO O 0. Tan et al., (OH) CHCH(OH) + OH OCOOH O Buxton et al., CH C(O)CH(OH) + O C(O)CH(OH) OO von Sonntag, 1987 Herrmann et al., CH C(O)CH(OH)OO C(O)CHO O.1 10 Bothe et al., 1978 Herrmann et al., CH C(O)CH(OH)OO CH C(O)COOH O Bothe et al., 1978 Herrmann et al., CHOCOOH + OH HOOCCOOH O O Stefan and Bolton, HCHO O (OH) 0.18 (F) (B) Bell and Evans, CH (OH) + OH H O O COOH Chin and Wine, (F) 44 HCOOH HCOO (B) Harned and Owen, 1958 Graedel and Weschler, HCOOH + OH H O O + CO Chin and Wine, HCOO + OH OH O + CO Buxton et al., 1988

6 47 CH C(O)CHO O CH C(O)CH(OH) 1.5 (F) 0.5 (B) Betterton and Hoffmann, CH C(O)CH(OH) + OH C(O)C(OH) O Ervens et al., CH C(O)C(OH) + O C(O)C(OH) OO von Sonntag, CH C(O)C(OH) OO C(O)COOH O h Buxton et al., CH C(O)COOH CH C(O)COO (F) (B) Herrmann et al., CH C(O)COO COO + hv CH (s 1 ) Lim et al., CH C(O)COO O CH COO O + CO 0.11 Carlton et al., CH C(O)COOH + OH CH C(O)COOH O Ervens et al., CH C(O)COOH + O O CH C(O)COOH Herrmann et al., O CH C(O)COOH OHCC(O)COOH O Herrmann et al., CH COOH CH COO (F) (B) Herrmann et al., CH COOH + OH HOOCCOOH Stefan et al., CH COO HOOCCOO + OH Stefan et al., 1996

7 60 HOOCCOOH + OH CO O O Buxton et al., HOOCCOO + OH CO O + O Buxton et al., (F) 6 HOOCCOOH HOOCCOO Meyerstein, 1971 (B) 6 CH + O Marchaj et al., 1991 O 64 CH O + CH O OH CHO + O Herrmann et al., CH OH + O OOCH OH von Sonntag, OOCH OH OH CHO + O von Sonntag, 1987 a: Estimated according to the Warneck, 1999 parameterization; b: The branching ratios were in analogy to those of gasphase reactions. The rate constant was estimated in analogy to that of MACR; c: Estimated in analogy to the addition O to 1C 4 H 9 and C 4 H 9 radical; d: Estimated in analogy to the methyl ethyl ketone peroxy radical reaction; e: Estimated in analogy to isopropanol; f: Estimated in analogy to the combination of CH C(O )(OH)COCH radical; g: Estimated in analogy to the combination of CH O radical; h: Estimated in analogy to glyoxal;

8 References: Bell, R. P. and Evans, P. G.: Kinetics of the dehydration of methylene glycol in aqueous solution, Proc. R. Soc., 91, 97, Betterton, E. A. and Hoffmann, M. R.: Henry s law constants of some environmentally important aldehydes, Environ. Sci. Technol.,, , Bothe, E., Schuchmann, M. N., SchulteFrohlinde, D., and von Sonntag, C.: HO elimination from ahydroxalkylperoxyl radicals in aqueous solution. Photochem. Photobiol., 8, , Buxton, G. V., Greenstock, C. L., Helman, W. P., and Ross, A. B.: Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals, (OH, O ) in aqueous solution, J. Phys. Chem. Ref. Data 17, , Carlton, A. G., Lim, H. J., Altieri, K., Seitinger, S., and Turpin, B. J.: Link between isoprene and secondary organic aerosol (SOA): pyruvic acid oxidation yields low volatility organic acids in clouds, Geophys. Res. Lett.,, L068, doi: /005GL0574, 006. Chin, M. and Wine, P. H.: A temperaturedependent competitive kinetics study of the aqueous phase reactions of OH radicals with formate, formic acid, acetate, acetic acid and hydrated formaldehyde, Aquatic and Surface Photochem., Lewis Publishers, Boca Raton, Ervens, B., Gligorovski, S., and Herrmann, H.: Temperaturedependent rate constants for hydroxyl radical reactions with organic compounds in aqueous solutions, Phys. Chem. Chem. Phys., 5, , 00. Gligorovski, S. and Herrmann, H.: Kinetics of reactions of OH with organic carbonyl compounds in aqueous solution, Phys. Chem. Chem. Phys., 6, , 009. Glowa, G., Driver, P., and Wren, J. C.: Irradiation of MEKII: A detailed kinetic model for the degradation under of butanone in aerated aqueous solutions steadystate gammaradiolysis conditions, Radiation Phys. Chem., 58, 49 68, 000. Graedel, T. E. and Weschler, C. J.: Chemistry within aqueous atmospheric aerosols and raindrops, Rev. Geophys. Space Phys., 19, , Harned, H. S. and Owen, B. B.: The physical chemistry of electrolytic solutions, Reinhold, New York, Hart, E. J., Thomas, J. K., and Gordon, S.: A review of the radiation chemistry of singlecarbon compounds and some reactions of the hydrated electron in aqueous solution, Radiat. Res. Suppl. 4, 74 88, 1964.

9 Herrmann, H., Reese, A., Ervens, B., Wicktor, F., and Zellner, R.: Laboratory and modeling studies of tropospheric multiphase conversions involving some C 1 and C peroxyl radicals, Phys. Chem. Earth 4, 87 90, Herrmann, H., Ervens, B., Jacob, H. W., Wolke, R., Nowacki, P., and Zellner, R.: CAPRAM.: A chemical aqueous phase radical mechanism for tropospheric chemistry, J. Atmos. Chem., 6, 1 0, 000. Herrmann, H., Tilgner, A., Barzaghi, P., Majdik, Z., Gligorovski, S., Poulain, L., and Monod, A.: Towards a more detailed description of tropospheric aqueous phase organic chemistry: CAPRAM.0, Atmos. Environ., 9, , 005. Liao, C. H. and Gurol, M. D.: Chemical oxidation by photolytic decomposition of hydrogen peroxide, Environ. Sci. Technol., 9, , Lim, H. J., Carlton, A. G., and Turpin, B. J.: Isoprene forms secondary organic aerosol through cloud processing: model simulations, Environ. Sci. Technol., 9, , 005. Marchaj, A., Kelley, D. G., Bakac, A., and Espenson, J. H.: Kinetics of the reactions between alkyl radicals and molecular oxygen in aqueous solution, J. Phys. Chem., 95, , Meyerstein, D.: Trivalent Copper I A pulse radiolytic study of the properties of the aquocomplex, Inorg. Chem., 10, 68 41, Scholes, G. and Willson, R. L.: γradiolysis of aqueous thymine solutions: determination of relative reaction rates of OH radicals, Trans. Faraday Soc., 6, , Stefan, M. I., Hoy, A. R., and Bolton, J. R.: Kinetics and mechanism of the degradation and mineralization of acetone in dilute aqueous solution sensitized by the UV photolysis of hydrogen peroxide, Environ. Sci. Technol., 0, 8 90, Stefan, M. I. and Bolton, J. R.: Reinvestigation of the acetone degradation mechanism in dilute aqueous solution by the UV/H O process, Environ. Sci. Technol.,, , Tan, Y., Perri, M. J., Seitzinger, S. P., and Turpin, B. J.: Effects of precursor concentration and acidic sulfate in aqueous glyoxaloh radical oxidation and implications for secondary organic aerosol, Environ. Sci. Technol., 4, , 009. von Sonntag, C.: The chemical basis of radiation biology, Taylor & Francis, 1987.

10 Warneck, P.: The relative importance of various pathways for the oxidation of sulphur dioxide and nitrogen dioxide in sunlit continental fair weather clouds, Phys. Chem. Chem. Phys., 1, , Warneck, P.: Incloud chemistry opens pathway to the formation of oxalic acid in the marine atmosphere, Atmos. Environ., 7, 4 47, 00. Fig. S1. Direct photolysis of hydrogen peroxide (experimental and simulated data).

11 Fig. S. MACR/MVK decay via UVphotolysis and OHoxidation.

12 Fig. S. Time series of standard carbonyls in mm H O solution in darkness.

13 Fig. S4. Time series of standard organic acids in mm H O solution in darkness.

14 Fig. S5. Modeled OH via H O photolysis.