ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-7209-2011 Yields of hydrogen peroxide from the reaction of hydroxyl radical with organic compounds in solution and ice Hullar T. 1 Anastasio C. 1 Department of Land, Air and Water Resources, University of California, Davis, One Shields Avenue, Davis, CA 95616, USA 22 07 2011 11 14 7209 7222 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.net/11/7209/2011/acp-11-7209-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/7209/2011/acp-11-7209-2011.pdf

Hydrogen peroxide (HOOH) is a significant oxidant in atmospheric condensed phases (e.g., cloud and fog drops, aqueous particles, and snow) that also photolyzes to form hydroxyl radical (<sup>•</sup>OH). <sup>•</sup>OH can react with organics in aqueous phases to form organic peroxyl radicals and ultimately reform HOOH, but the efficiency of this process in atmospheric aqueous phases, as well as snow and ice, is not well understood. We investigate HOOH formation from <sup>•</sup>OH attack on 10 environmentally relevant organic compounds: formaldehyde, formate, glycine, phenylalanine, benzoic acid, octanol, octanal, octanoic acid, octanedioic acid, and 2-butoxyethanol. Liquid and ice samples with and without nitrate (as an <sup>•</sup>OH source) were illuminated using simulated solar light, and HOOH formation rates were measured as a function of pH and temperature. For most compounds, the formation rate of HOOH without nitrate was the same as the background formation rate in blank water (i.e., illumination of the organic species does not produce HOOH directly), while formation rates with nitrate were greater than the water control (i.e., reaction of <sup>•</sup>OH with the organic species forms HOOH). Yields of HOOH, defined as the rate of HOOH production divided by the rate of <sup>•</sup>OH production, ranged from essentially zero (glycine) to 0.24 (octanal), with an average of 0.12 ± 0.05 (95 % CI). HOOH production rates and yields were higher at lower pH values. There was no temperature dependence of the HOOH yield for formaldehyde or octanedioic acid between −5 to 20 °C and ice samples had approximately the same HOOH yield as the aqueous solutions. In contrast, HOOH yields in formate solutions were higher at 5 and 10 °C compared to −5 and 20 °C. Yields of HOOH in ice for solutions containing nitrate and either phenylalanine, benzoate, octanal, or octanoic acid were indistinguishable from zero. Our HOOH yields were approximately half those found in previous studies conducted using γ-radiolysis, but this difference might be due to the much lower (and more environmentally relevant) <sup>•</sup>OH formation rates in our experiments.

 References 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. Anastasio, C. and McGregor, K. G.: Chemistry of fog waters in California's Central Valley: 1. In situ photoformation of hydroxyl radical and singlet molecular oxygen, Atmos. Environ., 35, 1079–1089, 2001. Anastasio, C., Faust, B. C., and Allen, J. M.: Aqueous-phase photochemical formation of hydrogen-peroxide in authentic cloud waters, J. Geophys. Res.-Atmos., 99, 8231–8248, 1994. 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.-Atmos., 103, 3487–3504, 1998. Barrie, L. A., Gregor, D., Hargrave, B., Lake, R., Muir, D., Shearer, R., Tracey, B., and Bidleman, T.: Arctic contaminants – sources, occurrence, and pathways, Sci. Total Environ., 122, 1–74, 1992. Beine, H., and Anastasio, C.: The photolysis of flash-frozen dilute hydrogen peroxide solutions, J. Geophys. Res., 116, D14302, doi:10.1029/2010JD015531, 2011. Bell, R. P., Rand, M. H., and Wynnejones, K. M. A.: Kinetics of the hydration of acetaldehyde, T. Faraday. Soc., 52, 1093–1102, 1956. Bielski, B. H. J., Cabelli, D. E., Arudi, R. L., and Ross, A. B.: Reactivity of HO$_2^\put(2.0,2.0)\circle*1.5$/$^\put(2.0,2.0)\circle*1.5$~O$_2^-$ radicals in aqueous-solution, J. Phys. Chem. Ref. Data, 14, 1041–1100, 1985. 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. Chameides, W. L. and Davis, D. D.: The free-radical chemistry of cloud droplets and its impact upon the composition of rain, J. Geophys. Res.-Ocean. Atmos., 87, 4863–4877, 1982. Chameides, W. L. and Davis, D. D.: Aqueous-phase source of formic acid in clouds, Nature, 304, 427–429, 1983. Christensen, H. C. and Gustafsson, R.: Radiolysis of aqueous toluene solutions, Acta. Chem. Scand., 26, 937–946, 1972. Chu, L. and Anastasio, C.: Quantum yields of hydroxyl radical and nitrogen dioxide from the photolysis of nitrate on ice, J. Phys. Chem. A, 107, 9594–9602, http://dx.doi.org/10.1021/jp0349132doi:10.1021/jp0349132, 2003. Chu, L. and Anastasio, C.: Formation of hydroxyl radical from the photolysis of frozen hydrogen peroxide, J. Phys. Chem. A, 109, 6264–6271, http://dx.doi.org/10.1021/jp051415fdoi:10.1021/jp051415f, 2005. Chu, L. and Anastasio, C.: Temperature and wavelength dependence of nitrite photolysis in frozen and aqueous solutions, Environ. Sci. Technol., 41, 3626–3632, http://dx.doi.org/10.1021/es062731qdoi:10.1021/es062731q, 2007. Collett, J. L., Herckes, P., Youngster, S., and Lee, T.: Processing of atmospheric organic matter by California radiation fogs, Atmos. Res., 87, 232–241, http://dx.doi.org/10.1016/j.atmosres.2007.11.005doi:10.1016/j.atmosres.2007.11.005, 2008. Deguillaume, L., Leriche, M., Monod, A., and Chaumerliac, N.: The role of transition metal ions on HO<sub>x</sub> radicals in clouds: a numerical evaluation of its impact on multiphase chemistry, Atmos. Chem. Phys., 4, 95–110, http://dx.doi.org/10.5194/acp-4-95-2004doi:10.5194/acp-4-95-2004, 2004. Desideri, P. G., Lepri, L., Checchini, L., and Santianni, D.: Organic compounds in surface and deep antarctic snow, Int. J. Environ. Anal. Chem., 55, 33–46, 1994. Dibb, J. E. and Arsenault, M.: Should not snowpacks be sources of monocarboxylic acids?, Atmos. Environ., 36, 2513–2522, 2002. Dubowski, Y., Colussi, A. J., and Hoffmann, M. R.: Nitrogen dioxide release in the 302 nm band photolysis of spray-frozen aqueous nitrate solutions. Atmospheric implications, J. Phys. Chem. A, 105, 4928–4932, 2001. Ervens, B., George, C., Williams, J. E., Buxton, G. V., Salmon, G. A., Bydder, M., Wilkinson, F., Dentener, F., Mirabel, P., Wolke, R., and Herrmann, H.: CAPRAM 2.4 (MODAC mechanism): An extended and condensed tropospheric aqueous phase mechanism and its application, J. Geophys. Res.-Atmos., 108, 4426, http://dx.doi.org/10.1029/2002jd002202doi:10.1029/2002jd002202, 2003. Faust, B. C.: Generation and use of simulated sunlight in photochemical studies of liquid solutions, Rev. Sci. Instrum., 64, 577–578, 1993. Faust, B. C.: Photochemistry of clouds, fogs, and aerosols, Environ. Sci. Technol., 28, A217–A222, 1994. Faust, B. C. and Allen, J. M.: Aqueous-phase photochemical formation of hydroxyl radical in authentic cloudwaters and fogwaters, Environ. Sci. Technol., 27, 1221–1224, 1993. Finlayson-Pitts, B. J. and Pitts, J. N.: Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications, Academic Press, San Diego, 969~pp., 2000. Fries, E., Sieg, K., Puttmann, W., Jaeschke, W., Winterhalter, R., Williams, J., and Moortgat, G. K.: Benzene, alkylated benzenes, chlorinated hydrocarbons and monoterpenes in snow/ice at Jungfraujoch (46.6° N, 8.0° E) during CLACE 4 and 5, Sci. Total Environ., 391, 269–277, http://dx.doi.org/10.1016/j.scitotenv.2007.10.006doi:10.1016/j.scitotenv.2007.10.006, 2008. Galbavy, E. S., Anastasio, C., Lefer, B. L., and Hall, S. R.: Light penetration in the snowpack at Summit, Greenland: Part I – Nitrite and hydrogen peroxide photolysis, Atmos. Environ., 41, 5077–5090, http://dx.doi.org/10.1016/j.atmosenv.2006.04.072doi:10.1016/j.atmosenv.2006.04.072, 2007. Galbavy, E. S., Ram, K., and Anastasio, C.: 2-Nitrobenzaldehyde as a chemical actinometer for solution and ice photochemistry, J. Photochem. Photobiol. A-Chem., 209, 186–192, http://dx.doi.org/10.1016/j.jphotochem.2009.11.013doi:10.1016/j.jphotochem.2009.11.013, 2010. Grannas, A. M., Shepson, P. B., and Filley, T. R.: Photochemistry and nature of organic matter in Arctic and Antarctic snow, Global Biogeochem. Cy., 18, GB1006, doi:Gb1006 10.1029/2003gb002133, 2004. Grannas, A. M., Hockaday, W. C., Hatcher, P. G., Thompson, L. G., and Mosley-Thompson, E.: New revelations on the nature of organic matter in ice cores, J. Geophys. Res.-Atmos., 111, D04304 http://dx.doi.org/10.1029/2005jd006251doi:10.1029/2005jd006251, 2006. Grollert, C. and Puxbaum, H.: Lipid organic aerosol and snow composition at a high alpine site in the fall and the spring season and scavenging ratios for single compounds, Water Air Soil Poll., 117, 157–173, 2000. 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 3.0, Atmos. Environ., 39, 4351–4363, http://dx.doi.org/10.1016/j.atmosenv.2005.02.016doi:10.1016/j.atmosenv.2005.02.016, 2005. Howard, P. H. and Meylan, W. M.: Handbook of Physical Properties of Organic Chemicals, Lewis Publishers, Boca Raton, Fla., 1997. Hutterli, M. A., McConnell, J. R., Bales, R. C., and Stewart, R. W.: Sensitivity of hydrogen peroxide (H<sub>2</sub>O$_2)$ and formaldehyde (HCHO) preservation in snow to changing environmental conditions: Implications for ice core records, J. Geophys. Res.-Atmos., 108, 4023, http://dx.doi.org/10.1029/2002jd002528doi:10.1029/2002jd002528, 2003. Hutterli, M. A., McConnell, J. R., Chen, G., Bales, R. C., Davis, D. D., and Lenschow, D. H.: Formaldehyde and hydrogen peroxide in air, snow and interstitial air at South Pole, Atmos. Environ., 38, 5439–5450, http://dx.doi.org/10.1016/j.atmosenv.2004.06.003doi:10.1016/j.atmosenv.2004.06.003, 2004. Jacobi, H. W., Annor, T., and Quansah, E.: Investigation of the photochemical decomposition of nitrate, hydrogen peroxide, and formaldehyde in artificial snow, J. Photochem. Photobiol. A-Chem., 179, 330–338, http://dx.doi.org/10.1016/j.jphotochem.2005.09.001doi:10.1016/j.jphotochem.2005.09.001, 2006. Kok, G. L., McLaren, S. E., and Staffelbach, T. A.: HPLC determination of atmospheric organic hydroperoxides, J. Atmos. Ocean. Tech., 12, 282–289, 1995. Laniewski, K., Boren, H., and Grimvall, A.: Identification of volatile and extractable chloroorganics in rain and snow, Environ. Sci. Technol., 32, 3935–3940, 1998. Legrand, M. and Deangelis, M.: Origin and variations of light carboxylic acids in polar precipitation, J. Geophys. Res.-Atmos., 100, 1445–1462, 1995. Legrand, M. and Mayewski, P.: Glaciochemistry of polar ice cores: A review, Rev. Geophys., 35, 219–243, 1997. Lelieveld, J. and Crutzen, P. J.: Influences of cloud photochemical processes on tropospheric ozone, Nature, 343, 227–233, 1990. Lelieveld, J. and Crutzen, P. J.: The role of clouds in tropospheric photochemistry, J. Atmos. Chem., 12, 229–267, 1991. Mazzoleni, L. R., Ehrmann, B. M., Shen, X. H., Marshall, A. G., and Collett, J. L.: Water-Soluble Atmospheric Organic Matter in Fog: Exact Masses and Chemical Formula Identification by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Environ. Sci. Technol., 44, 3690–3697, http://dx.doi.org/10.1021/es903409kdoi:10.1021/es903409k, 2010. Moller, D.: Atmospheric hydrogen peroxide: Evidence for aqueous-phase formation from a historic perspective and a one-year measurement campaign, Atmos. Environ., 43, 5923–5936, http://dx.doi.org/10.1016/j.atmosenv.2009.08.013doi:10.1016/j.atmosenv.2009.08.013, 2009. Nese, C., Schuchmann, M. N., Steenken, S., and von Sonntag, C.: Oxidation vs. fragmentation in radiosensitization. Reactions of alpha-alkoxylalkyl radicals with 4-nitrobenzonitrile and oxygen. A pulse radiolysis and product analysis study, J. Chem. Soc. Perk. T 2, 1037–1044, 1995. Pan, X.-M., Schuchmann, M. N., and von Sonntag, C.: Hydroxyl-radical-induced oxidation of cyclohexa-1,4-diene by O<sub>2</sub> in aqueous solution. A pulse radiolysis and product study, J. Chem. Soc. Perk. T 2, 1021–1028, 1993a. Pan, X.-M., Schuchmann, M. N., and von Sonntag, C.: Oxidation of benzene by the OH radical. A product and pulse radiolysis story in oxygenated aqueous solution, J. Chem. Soc. Perk. T 2, 289–197, 1993b. Perrier, S., Houdier, S., Domine, F., Cabanes, A., Legagneux, L., Sumner, A. L., and Shepson, P. B.: Formaldehyde in Arctic snow. Incorporation into ice particles and evolution in the snowpack, Atmos. Environ., 36, 2695–2705, 2002. Piesiak, A., Schuchmann, M. N., Zegota, H., and von Sonntag, C.: beta-hydroyethylperoxyl radicals: a study of the gamma-radiolysis and pulse radiolysis of ethylene in oxygenated aqueous solutions, Z. Naturforsch, 39B, 1262–1267, 1984. Qiu, R., Green, S. A., Honrath, R. E., Peterson, M. C., Lu, Y., and Dziobak, M.: Measurements of $J$(NO$_3^-)$ in snow by nitrate-based actinometry, Atmos. Environ., 36, 2563–2571, 2002. Ram, K. and Anastasio, C.: Photochemistry of phenanthrene, pyrene, and fluoranthene in ice and snow, Atmos. Environ., 43, 2252–2259, http://dx.doi.org/10.1016/j.atmosenv.2009.01.044doi:10.1016/j.atmosenv.2009.01.044, 2009. Satsumabayashi, H., Nishizawa, H., Yokouchi, Y., and Ueda, H.: Pinonaldehyde and some other organics in rain and snow in central Japan, Chemosphere, 45, 887–891, 2001. Schuchmann, H. P. and von Sonntag, C.: Methylperoxyl radicals: a study of the gamma-radiolysis of methane in oxygenated aqueous solutions, Z. Naturforsch, 39B, 217–221, 1984. Schuchmann, M. N. and von Sonntag, C.: Radiation chemistry of carbohydrates. Part 14. Hydroxyl-radical induced oxidation of d-glucose in oxygenated aqueous solution, J. Chem. Soc. Perk. T 2, 1958–1963, 1977. Schuchmann, M. N. and von Sonntag, C.: Radiation chemistry of alcohols 22. Hydroxyl radical-induced oxidation of 2-methyl-2-propanol in oxygenated aqueous solution. A product and pulse radiolysis study J. Phys. Chem., 83, 780–784, 1979. Schuchmann, M. N. and von Sonntag, C.: Hydroxyl radical induced oxidation of diethyl ether in oxygenated aqueous solution. A product and pulse radiolysis study, J. Phys. Chem., 86, 1995–2000, 1982. Schuchmann, M. N. and von Sonntag, C.: The radiolysis of uracil on oxygenated aqueous solutions. A study by product analysis and pulse radiolysis, J. Chem. Soc. Perk T 2, 1525–1531, 1983. Schuchmann, M. N., Zegota, H., and von Sonntag, C.: Acetate peroxyl radicals, OOCH<sub>2</sub>CO$_2^-$: a study on the gamma-radiolysis and pulse radiolysis or acetate in oxygenated aqeous solutions, Z. Naturforsch, 40B, 215–221, 1985. Schuchmann, M. N. and von Sonntag, C.: The rapid hydration of the acetyl radical. A pulse radiolysis study of acetaldehyde in aqueous solution, J. Am. Chem. Soc., 110, 5698–5701, 1988. Schuchmann, M. N., Schuchmann, H. P., and von Sonntag, C.: Hydroxyl radical induced oxidation of acetaldehyde dimethyl acetal in oxygenated aqueous solution. Rapid °O$_2^-$ release from the CH<sub>3</sub>C(OCH$_3)_2$O<sub>2</sub> radical, J. Am. Chem. Soc., 112, 403–407, 1990. Schuchmann, M. N., Schuchmann, H. P., and von Sonntag, C.: Oxidation of hydromalonic acid by OH radicals in the presence and in the absence of molecular oxygen. A pulse-radiolysis and product study, J. Phys. Chem., 99, 9122–9129, 1995. Sigg, A. and Neftel, A.: Evidence for a 50-percent increase in H<sub>2</sub>O<sub>2</sub> over the past 200 years from a Greenland ice core, Nature, 351, 557–559, 1991. Sigma-Aldrich: http://www.sigmaaldrich.com/etc/medialib/docs/Sigma-Aldrich/Product_Information_Sheet/p6148pis.Par.0001.File.tmp/p6148pis.pdf (last access: 30 January 2011), 2010. Stefanic, I., Bonifacic, M., Asmus, K. D., and Armstrong, D. A.: Absolute rate constants and yields of transients from hydroxyl radical and H atom attack on glycine and methyl-substituted glycine anions, J. Phys. Chem. A, 105, 8681–8690, 2001. Stemmler, K. and von Gunten, U.: OH radical-initiated oxidation of organic compounds in atmospheric water phases: part 1. Reactions of peroxyl radicals derived from 2-butoxyethanol in water, Atmos. Environ., 34, 4241–4252, 2000. 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. Technol., 43, 8105–8112, http://dx.doi.org/10.1021/es901742fdoi:10.1021/es901742f, 2009. Ulanski, P., Bothe, E., Rosiak, J., and von Sonntag, C.: Radiolysis of the poly(acrylic acid) model 2,4-dimethylglutaric acid: a pulse radiolysis and product study, J. Chem. Soc. Perk. T 2, 5–12, 1996. von Sonntag, C. and Schuchmann, H.-P.: Peroxyl Radicals in Aqueous Solutions, in: Peroxyl Radicals, edited by: Alfassi, Z. B., John Wiley and Sons, Chichester, 1997. Warneck, P. and Wurzinger, C.: Product quantum yields for the 305-nm photodecomposition of NO$_3^-$ in aqueous solution, J. Phys. Chem., 92, 6278–6283, 1988. Zegota, H., Schuchmann, M. N., and von Sonntag, C.: Cyclopentylperoxyl and cyclohexylperoxyl radicals in aqueous solution. A study by product analysis and pulse radiolysis, J. Phys. Chem., 88, 5589–5593, 1984. Zellner, R., Exner, M., and Herrmann, H.: Absolute OH quantum yields in the laser photolysis of nitrate, nitrite, and dissolved H<sub>2</sub>O<sub>2</sub> at 308 and 351 nm in the temperature range 278–353 K, J. Atmos. Chem., 10, 411–425, 1990. Zhang, Q. and Anastasio, C.: Chemistry of fog waters in California's Central Valley – Part 3: concentrations and speciation of organic and inorganic nitrogen, Atmos. Environ., 35, 5629–5643, 2001. Zhang, Q. and Anastasio, C.: Free and combined amino compounds in atmospheric fine particles (PM$_2.5)$ and fog waters from Northern California, Atmos. Environ., 37, 2247–2258, http://dx.doi.org/10.1016/s1352-2310(03)00127-4doi:10.1016/s1352-2310(03)00127-4, 2003. Zhao, J., Levitt, N. P., and Zhang, R. Y.: Heterogeneous chemistry of octanal and 2,4-hexadienal with sulfuric acid, Geophys. Res. Lett., 32, L09802, http://dx.doi.org/10.1029/2004gl022200doi:10.1029/2004gl022200, 2005. Zhou, X. L., Davis, A. J., Kieber, D. J., Keene, W. C., Maben, J. R., Maring, H., Dahl, E. E., Izaguirre, M. A., Sander, R., and Smoydzyn, L.: Photochemical production of hydroxyl radical and hydroperoxides in water extracts of nascent marine aerosols produced by bursting bubbles from Sargasso seawater, Geophys. Res. Lett., 35, L20803, http://dx.doi.org/10.1029/2008gl035418doi:10.1029/2008gl035418, 2008.