ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-11-18319-2011 Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid Tan Y. 1 4 Lim Y. B. 1 Altieri K. E. 2 Seitzinger S. P. 3 Turpin B. J. 1 Department of Environmental Sciences, Rutgers University, 14 College Farm Road, New Brunswick, NJ 08901, USA Department of Geosciences, Princeton University, B80 Guyot Hall, Princeton, NJ 08544, USA International Geosphere-Biosphere Programme (IGBP), Lilla Frescativägen 4a, Stockholm, Sweden now at: Center for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, 15213, Pennsylvania, USA 28 06 2011 11 6 18319 18347 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys-discuss.net/11/18319/2011/acpd-11-18319-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/11/18319/2011/acpd-11-18319-2011.pdf

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid is an important intermediate in aqueous methylglyoxal oxidation and a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. Altieri et al. (2008) proposed that acetic acid was the precursor of oligoesters observed in methylglyoxal oxidation. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid at concentrations relevant to atmospheric waters (20 μM–10 mM) was oxidized by OH radical. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. The formation of glyoxylic, glycolic, and oxalic acids were observed. In contrast to methylglyoxal oxidation, succinic acid and oligomers were not detected. Using results from these and methylglyoxal + OH radical experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

 References Aiken,~A C., DeCarlo,~P F., Kroll,~J H., Worsnop,~D R., Huffman,~J A., Docherty,~K S., Ulbrich,~I M., Mohr,~C., Kimmel,~J R., Sueper,~D., Sun, ~Y., Zhang,~Q., Trimborn,~A., Northway,~M., Ziemann,~P J., Canagaratna,~M. ~R., Onasch,~T B., Alfarra,~M R., Prevot,~A S H., Dommen,~J., Duplissy, ~J., Metzger,~A., Baltensperger,~U., and Jimenez,~J L.: O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry, Environ. Sci. Technol., 42, 4478–4485, http://dx.doi.org/10.1021/es703009qdoi:10.1021/es703009q, 2008. Altieri,~K E., Carlton,~A G., Lim,~H.-J., Turpin,~B J., and Seitzinger, ~S P.: Evidence for oligomer formation in clouds: reactions of isoprene oxidation products, Environ. Sci. Technol., 40, 4956–4960, 2006. Altieri,~K E., Seitzinger,~S P., Carlton,~A G., Turpin,~B J., Klein,~G. ~C., and Marshall,~A G.: Oligomers formed through in-cloud methylglyoxal reactions: chemical composition, properties, and mechanisms investigated by ultra-high resolution FT-ICR mass spectrometry, Atmos. Environ., 42, 1476–1490, 2008. Altieri,~K E., Turpin,~B J., and Seitzinger,~S P.: Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry, Atmos. Chem. Phys., 9, 2533–2542, http://dx.doi.org/10.5194/acp-9-2533-2009doi:10.5194/acp-9-2533-2009, 2009. Arakaki,~T. and Faust,~B C.: Sources, sinks, and mechanisms of hydroxyl radical (OH) photoproduction and consumption in authentic acidic continental cloud waters from Whiteface Mountain, New York: the role of the Fe(r) (r $=$ II, III) photochemical cycle, J. Geophys. Res., 103, 3487–3504, 1998. Barsanti,~K C., and Pankow,~J F.: Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions – Part~3: Carboxylic and dicarboxylic acids, Atmos. Environ., 40, 6676–6686, 2006. Benson,~S.: Effects of resonance and structure on the thermochemistry of organic peroxy radicals and the kinetics of combustion reactions, J. Am. Chem. Soc., 87, 972–979, 1965. Buley,~A L., Norman,~R O C., and Pritchett,~R J.: Electron spin resonance studies of oxidation. Part VIII. Elimination reactions of some hydroxyalkyl radicals, J. Chem. Soc. B, 849–852, http://dx.doi.org/10.1039/J29660000849doi:10.1039/J29660000849, 1966. Carlton,~A G., Turpin,~B J., Lim,~H.-J., Altieri,~K E., and Seitzinger,~S.: Link between isoprene and secondary organic aerosol (SOA): pyruvic acid oxidation yields low volatility organic acids in clouds, Geophys. Res. Lett., 33, L06822, http://dx.doi.org/10.1029/2005GL025374doi:10.1029/2005GL025374, 2006. Carlton,~A G., Turpin,~B J., Altieri,~K E., Seitzinger,~S P., Mathur,~R., Roselle,~S J., and Weber,~R J.: CMAQ model performance enhanced when in-cloud secondary organic aerosol is included: comparisons of organic carbon predictions with measurements, Environ. Sci. Technol., 42, 8798–8802, 2008. El Haddad,~I., Yao~Liu, Nieto-Gligorovski,~L., Michaud,~V., Temime-Roussel,~B., Quivet,~E., Marchand,~N., Sellegri,~K., and Monod,~A.: In-cloud processes of methacrolein under simulated conditions – Part 2: Formation of secondary organic aerosol, Atmos. Chem. Phys., 9, 5107–5117, http://dx.doi.org/10.5194/acp-9-5107-2009doi:10.5194/acp-9-5107-2009, 2009. Ervens,~B. and Volkamer,~R.: Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles, Atmos. Chem. Phys., 10, 8219–8244, http://dx.doi.org/10.5194/acp-10-8219-2010doi:10.5194/acp-10-8219-2010, 2010. Ervens,~B., Carlton,~A G., Turpin,~B J., Altieri,~K E., Kreidenweis,~S. ~M., and Feingold,~G.: Secondary organic aerosol yields from cloud-processing of isoprene oxidation products, Geophys. Res. Lett., 35, L02816, doi:10.1029/2007GL031828, 2008. Fu,~T.-M., Jacob,~D J., Wittrock,~F., Burrows,~J P., Vrekoussis,~M., and Henze,~D K.: Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols, J. Geophys. Res., 113, D15303, http://dx.doi.org/10.1029/2007jd009505doi:10.1029/2007jd009505, 2008. Guzman,~M I., Colussi,~A J., and Hoffmann,~M R.: Photoinduced oligomerization of aqueous pyruvic acid, J. Phys. Chem. A, 110, 3619–3626, 2006. Hallquist,~M., Wenger,~J C., Baltensperger,~U., Rudich,~Y., Simpson,~D., Claeys,~M., Dommen,~J., Donahue,~N M., George,~C., Goldstein,~A H., Hamilton,~J F., Herrmann,~H., Hoffmann,~T., Iinuma,~Y., Jang,~M., Jenkin,~M E., Jimenez,~J L., Kiendler-Scharr,~A., Maenhaut,~W., McFiggans,~G., Mentel,~Th F., Monod,~A., Prévôt,~A S H., Seinfeld,~J H., Surratt,~J D., Szmigielski,~R., and Wildt,~J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, http://dx.doi.org/10.5194/acp-9-5155-2009doi:10.5194/acp-9-5155-2009, 2009. Kanakidou,~M., Seinfeld,~J H., Pandis,~S N., Barnes,~I., Dentener,~F J., Facchini,~M C., Van Dingenen,~R., Ervens,~B., Nenes,~A., Nielsen,~C J., Swietlicki,~E., Putaud,~J P., Balkanski,~Y., Fuzzi,~S., Horth,~J., Moortgat,~G K., Winterhalter,~R., Myhre,~C E L., Tsigaridis,~K., Vignati,~E., Stephanou,~E G., and Wilson,~J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, http://dx.doi.org/10.5194/acp-5-1053-2005doi:10.5194/acp-5-1053-2005, 2005. Khare,~P., Kumar,~N., Kumari,~K M., and Srivastava,~S S.: Atmospheric formic and acetic acids: an overview, Rev. Geophys., 37, 227–248, 1999. Krizner,~H E., De Haan,~D O., and Kua,~J.: Thermodynamics and kinetics of methylglyoxal dimer formation: a~computational study, J. Phys. Chem. A, 113, 6994–7001, 2009. Leitner,~N K V. and Dore,~M.: Mechanism of the reaction between hydroxyl radicals and glycolic, glyoxylic, acetic and oxalic acids in aqueous solution: consequence on hydrogen peroxide consumption in the \chemH_2O_2/UV and \chemO_3/H_2O_2 systems, Water Res., 31, 1383–1397, 1997. Lim,~H J., Carlton,~A G., and Turpin,~B J.: Isoprene forms secondary organic aerosol through cloud processing: model simulations, Environ. Sci. Technol., 39, 4441–4446, 2005. Lim,~Y B., Tan,~Y., Perri,~M J., Seitzinger,~S P., and Turpin,~B J.: Aqueous chemistry and its role in secondary organic aerosol (SOA) formation, Atmos. Chem. Phys., 10, 10521–10539, http://dx.doi.org/10.5194/acp-10-10521-2010doi:10.5194/acp-10-10521-2010, 2010. Limbeck,~A., Puxbaum,~H., Otter,~L., and Scholes,~M C.: Semivolatile behavior of dicarboxylic acids and other polar organic species at a~rural background site (Nylsvley, RSA), Atmos. Environ., 35, 1853–1862, 2001. Livingston,~R. and Zeldes,~H.: Paramagnetic resonance study of liquids during photolysis. III. Aqueous solutions of alcohols with hydrogen peroxide, J. Am. Chem. Soc., 88, 4333–4336, 1966. Mochida,~M., Kawamura,~K., Umemoto,~N., Kobayashi,~M., Matsunaga,~S., Lim,~H.-J., Turpin,~B J., Bates,~T S., and Simoneit,~B R T.: Spatial distributions of oxygenated organic compounds (dicarboxylic acids, fatty acids, and levoglucosan) in marine aerosols over the western pacific and off the coast of east asia: continental outflow of organic aerosols during the ACE-ASIA campaign, J. Geophys. Res., 108, 8638, http://dx.doi.org/10.1029/2002jd003249doi:10.1029/2002jd003249, 2003. Myriokefalitakis,~S., Tsigaridis,~K., Mihalopoulos,~N., Sciare,~J., Nenes,~A., Segers,~A., and Kanakidou,~M.: In-cloud oxalate formation in the global troposphere: a 3-D modeling study, Atmos. Chem. Phys. Discuss., 11, 485–530, http://dx.doi.org/10.5194/acpd-11-485-2011doi:10.5194/acpd-11-485-2011, 2011. Nemet,~I., Vikic-Topic,~D., and Varga-Defterdarovic,~L.: Spectroscopic studies of methylglyoxal in water and dimethylsulfoxide, Bioorg. Chem., 32, 560–570, 2004. Perri,~M J., Seitzinger,~S., and Turpin,~B J.: Secondary organic aerosol production from aqueous photooxidation of glycolaldehyde: laboratory experiments, Atmos. Environ., 43, 1487–1497, 2009. Perri,~M J., Lim,~Y B., Seitzinger,~S P., and Turpin,~B J.: Organosulfates from glycolaldehyde in aqueous aerosols and clouds: laboratory studies, Atmos. Environ., 44, 2658–2664, 2010. Russell,~G.: Deuterium-isotope effects in the autoxidation of aralkyl hydrocarbons: mechanism of the interaction of peroxy radicals, J. Am. Chem. Soc., 79, 3871–3876, 1957. Schuchmann,~M N., Zegota,~H., and Vonsonntag,~C.: Acetate peroxyl radicals, \chemO_2CH_2CO_2(-) – a~study on the $\gamma $-radiolysis and pulse-radiolysis of acetate in oxygenated aqueous-solutions, Z. Naturforsch Pt B, 40, 215–221, 1985. Seinfeld,~J H. and Pandis,~S N.: Atmospheric Chemistry and Physics – From Air Pollution to Climate Change, 2nd edition, John Wiley and Sons, Inc., New York, 2006. Stefan,~M I. and Bolton,~J R.: Reinvestigation of the acetone degradation mechanism in dilute aqueous solution by the UV/\chemH_2O_2 process, Environ. Sci. Technol., 33, 870–873, 1999. Sun,~Y L., Zhang,~Q., Anastasio,~C., and Sun,~J.: Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry, Atmos. Chem. Phys., 10, 4809–4822, http://dx.doi.org/10.5194/acp-10-4809-2010doi:10.5194/acp-10-4809-2010, 2010. Tan,~Y., Perri,~M J., Seitzinger,~S P., and Turpin,~B J.: Effects of precursor concentration and acidic sulfate in aqueous glyoxal – OH radical oxidation and implications for secondary organic aerosol, Environ. Sci. Techn., 43, 8105–8112, 2009. Tan,~Y., Carlton,~A G., Seitzinger,~S P., and Turpin,~B J.: SOA from methylglyoxal in clouds and wet aerosols: measurement and prediction of key products, Atmos. Environ., 44, 5218–5226, 2010. Wang,~W.-F., Schuchmann,~M N., Schuchmann,~H.-P., and Sonntag,~C V.: The importance of mesomerism in the termination of $\alpha $-carboxymethyl radicals from aqueous malonic and acetic acids, Chem.-Eur. J., 7, 791–795, 2001. Warneck,~P.: Multi-phase chemistry of C<sub>2</sub> and C<sub>3</sub> organic compounds in the marine atmosphere, J. Atmos. Chem., 51, 119–159, 2005. Yao~Liu, El Haddad,~I., Scarfogliero,~M., Nieto-Gligorovski,~L., Temime-Roussel,~B., Quivet,~E., Marchand,~N., Picquet-Varrault,~B., and Monod,~A.: In-cloud processes of methacrolein under simulated conditions – Part~1: Aqueous phase photooxidation, Atmos. Chem. Phys., 9, 5093–5105, http://dx.doi.org/10.5194/acp-9-5093-2009doi:10.5194/acp-9-5093-2009, 2009.