ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-9-20881-2009 Hydroxyl radical reactivity at the air-ice interface Kahan T. F. 1 Zhao R. 1 Donaldson D. J. 1 2 Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto, M5S 3H6 Ontario, Canada Department of Physical and Environmental Sciences, University of Toronto at Scarborough, Toronto, M1C 1A4 Ontario, Canada 05 10 2009 9 5 20881 20911 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/9/20881/2009/acpd-9-20881-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/9/20881/2009/acpd-9-20881-2009.pdf

Hydroxyl radicals are important oxidants in the atmosphere and in natural waters. They are also expected to be important in snow and ice, but their reactivity has not been widely studied in frozen aqueous solution. We have developed a spectroscopic probe to monitor the formation and reactions of hydroxyl radicals in situ. Hydroxyl radicals are produced in aqueous solution via the photolysis of nitrite, nitrate, and hydrogen peroxide, and react rapidly with benzene to form phenol. Similar phenol formation rates were observed in aqueous solution and bulk ice. However, no reaction was observed at the air-ice interface, or when bulk ice samples were crushed prior to photolysis to increase their surface area. We also monitored the heterogeneous reaction between benzene present at air-water and air-ice interfaces with gas-phase OH produced from HONO photolysis. Rapid phenol formation was observed on water surfaces, but no reaction was observed at the surface of ice. Under the same conditions, we observed rapid loss of the polycyclic aromatic hydrocarbon (PAH) anthracene at the air-water interface, but no loss was observed at the air-ice interface. Our results suggest that the reactivity of hydroxyl radicals toward aromatic organics is similar in bulk ice samples and in aqueous solution, but is significantly suppressed in the quasi-liquid layer (QLL) that exists at the air-ice interface.

 References Anastasio, C. and Chu, L.: Photochemistry of Nitrous Acid (HONO) and Nitrous Acidium Ion (H2ONO+) in Aqueous Solution and Ice, Environ. Sci. Technol., 43, 1108–1114, 2009. Anastasio, C., Galbavy, E. S., Hutterli, M. A., Burkhart, J. F., and Friel, D. K.: Photoformation of hydroxyl radical on snow grains at Summit, Greenland, Atmos. Environ., 41, 5110–5121, 2007. Ardura, D., Kahan, T. F., and Donaldson, D. J.: Self-association of naphthalene at the air-ice interface, J. Phys. Chem., 113, 7353–7359, 2009. Aubin, D. G. and Abbatt, J. P. D.: Interaction of NO2 with hydrocarbon soot: Focus on HONO yield, surface modification, and mechanism, J. Phys. Chem., 111, 6263–6273, 2007. Carrera, G., Fernandez, P., Vilanova, R. M., and Grimalt, J. O.: Persistent organic pollutants in snow from European high mountain areas, Atmos. Environ., 35, 245–254, 2001. Chu, L. and Anastasio, C.: Quantum yields of hydroxyl radical and nitrogen dioxide from the photolysis of nitrate on ice, J. Phys. Chem., 107, 9594–9602, 2003. Chu, L. and Anastasio, C.: Formation of hydroxyl radical from the photolysis of frozen hydrogen peroxide, J. Phys. Chem., 109, 6264–6271, 2005. Chu, L. and Anastasio, C.: Temperature and wavelength dependence of nitrite photolysis in frozen and aqueous solutions, Environ. Sci. Technol., 41, 3626–3632, 2007. Cincinelli, A., Stortini, A. M., Checchini, L., Martellini, T., Del Bubba, M., and Lepri, L.: Enrichment of organic pollutants in the sea surface microlayer (SML) at Terra Nova Bay, Antarctica: influence of SML on superfacial snow composition, J. Environ. Monit., 7, 1305–1312, 2005. Clifford, D., T. Bartels-Rausch and D. J. Donaldson: Suppression of aqueous surface hydrolysis by monolayers of short chain organic amphiphiles, Phys. Chem. Chem. Phys., 2007. Compoint, M., Toubin, C., Picaud, S., Hoang, P. N. M., and Girardet, C.: Geometry and dynamics of formic and acetic acids adsorbed on ice, Chem. Phys. Lett., 365, 1–7, 2002. Cotter, E. S. N., Jones, A. E., Wolff, E. W., and Bauguitte, S. J.-B.: What controls photochemical NO and NO<sub>2</sub> production from Antarctic snow? Laboratory investigation assessing the wavelength and temperature dependence, J. Geophys. Res., 108, 8-1–8-10, 2003. Daly, G. L. and Wania, F.: Organic contaminants in mountains, Environ. Sci. Technol., 39, 385–398, 2005. Domine, F., Albert, M., Huthwelker, T., Jacobi, H. W., Kokhanovsky, A. A., Lehning, M., Picard, G., and Simpson, W. R.: Snow physics as relevant to snow photochemistry, Atmos. Chem. Phys., 8, 171–208, 2008. Domine, F. and Shepson, P. B.: Air-snow interactions and atmospheric chemistry, Science, 297, 1506–1510, 2002. Dubowski, Y., Colussi, A. J., Boxe, C., and Hoffmann, M. R.: Monotonic increase of nitrite yields in the photolysis of nitrate in ice and water between 238 and 294 K, J. Phys. Chem., 106, 6967–6971, 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., 105, 4928–4932, 2001. Dubowski, Y. and Hoffmann, M. R.: Photochemical transformations in ice: Implications for the fate of chemical species, Geophys. Res. Lett., 27, 3321–3324, 2000. Febo, A., Perrino, C., Gherardi, M., and Sparapani, R.: Evaluation of a High-Purity and High-Stability Continuous Generation System for Nitrous-Acid, Environ. Sci. Technol., 29, 2390–2395, 1995. Fernandez, P., Carrera, G., Grimalt, J. O., Ventura, M., Camarero, L., Catalan, J., Nickus, U., Thies, H., and Psenner, R.: Factors governing the atmospheric deposition of polycyclic aromatic hydrocarbons to remote areas, Environ. Sci. Technol., 37, 3261–3267, 2003. Franz, T. P. and Eisenreich, S. J.: Accumulation of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in the snowpack of Minnesota and Lake Superior, J. Great Lakes Res., 26, 220–234, 2000. 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, 2007. Grannas, A. M., Bausch, A. R., and Mahanna, K. M.: Enhanced aqueous photochemical reaction rates after freezing, J. Phys. Chem., 111, 11043–11049, 2007. Grannas, A. M., Jones, A. E., Dibb, J., Ammann, M., Anastasio, C., Beine, H. J., Bergin, M., Bottenheim, J., Boxe, C. S., Carver, G., Chen, G., Crawford, J. H., Domine, F., Frey, M. M., Guzman, M. I., Heard, D. E., Helmig, D., Hoffmann, M. R., Honrath, R. E., Huey, L. G., Hutterli, M., Jacobi, H. W., Klan, P., Lefer, B., McConnell, J., Plane, J., Sander, R., Savarino, J., Shepson, P. B., Simpson, W. R., Sodeau, J. R., von Glasow, R., Weller, R., Wolff, E. W., and Zhu, T.: An overview of snow photochemistry: evidence, mechanisms and impacts, Atmos. Chem. Phys., 7, 4329–4373, 2007. Herbert, B. M. J., Villa, S., and Halsall, C.: Chemical interactions with snow: Understanding the behavior and fate of semi-volatile organic compounds in snow. Ecotoxicology and Environmental Safety, 63, 3–16, 2006. Jacobi, H. W., Annor, T., and Quansah, E.: Investigation of the photochemical decomposition of nitrate, hydrogen peroxide, and formaldehyde in artificial snow, J. Photochemi. Photobiol., 179, 330–338, 2006. Jaffrezo, J. L., Clain, M. P., and Masclet, P.: Polycyclic Aromatic-Hydrocarbons in the Polar Ice of Greenland – Geochemical Use of These Atmospheric Tracers. Atmos. Environ., 28, 1139–1145, 1994. Kahan, T. F. and D. J. Donaldson: Photolysis of polycyclic aromatic hydrocarbons on water and ice surfaces, J. Phys. Chem., 111, 1277–1285, 2007. Kahan, T. F. and Donaldson, D. J.: Heterogeneous ozonation kinetics of phenanthrene at the air-ice interface, Environ. Res. Lett., 3, 045006, doi:10.1088/1748-9326/3/4/045006, 2008. Kahan, T. F., Reid, J. P., and Donaldson, D. J.: Spectroscopic probes of the quasi-liquid layer on ice, J. Phys. Chem., 111, 11006–11012, 2007. Kahan, T. F., Zhao, R., Jumaa, K. B., and Donaldson, D. J.: Anthracene Photolysis in Aqueous Solution and Ice: Photon Flux Dependence and Comparison of Kinetics in Bulk Ice and at the Air-Ice Interface, Environ. Sci. Technol., submitted, 2009. Klan, P. and Holoubek, I.: Ice (photo)chemistry, Ice as a medium for long-term (photo)chemical transformations – environmental implications. Chemosphere, 46, 1201–1210, 2002. Klan, P., Klanova, J., Holoubek, I., and Cupr, P.: Photochemical activity of organic compounds in ice induced by sunlight irradiation: The Svalbard project, Geophys. Res. Lett., 30, 46-1–46-4, 2003. Klanova, J., Klan, P., Heger, D., and Holoubek, I.: Comparison of the effects of UV, H<sub>2</sub>O<sub>2</sub>/UV and $\gamma\alpha\mu\mu\alpha$-irradiation processes on frozen and liquid water solutions of monochlorophenols, Photochem. Photobiol. Sci., 2, 1023–1031, 2003. Klanova, J., Klan, P., Nosek, J., and Holoubek, I.: Environmental ice photochemistry: Monochlorophenols, Environ. Sci. Technol., 37, 1568–1574, 2003. Masclet, P., Hoyau, V., Jaffrezo, J. L., and Cachier, H.: Polycyclic aromatic hydrocarbon deposition on the ice sheet of Greenland. Part I: Superficial snow, Atmos. Environ., 34, 3195–3207, 2000. Matykiewiczova, N., Kurkova, R., Klanova, J., and Klan, P.: Photochemically induced nitration and hydroxylation of organic aromatic compounds in the presence of nitrate or nitrite in ice, J. Photochem. Photobiol., 187, 24–32, 2007. Melnikov, S., Carroll, J., Gorshkov, A., Vlasov, S., and Dahle, S.: Snow and ice concentrations of selected persistent pollutants in the Ob-Yenisey River watershed, Sci. Total Environ., 306, 27–37, 2003. Mmereki, B. T. and Donaldson, D. J.: Direct observation of the kinetics of an atmospherically important reaction at the air-aqueous interface, J. Phys. Chem., 107, 11038–11042, 2003. Pan, X., Bass, A. D., Jay-Gerin, J.-P., and Sanche, L.: A mechanism for the production of hydrogen peroxide and the hydroperoxyl radical on icy satellites by low-energy electrons, Icarus, 172, 521–525, 2004. Qiu, R., Green, S. A., Honrath, R. E., Peterson, M. C., Lu, Y., and Dziobak, M.: Measurements of J(NO<sub>3</sub>)(-) 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, 2009. Schrimpff, E., Thomas, W., and Herrmann, R.: Regional Patterns of Contaminants (Pah, Pesticides and Trace-Metals) in Snow of Northeast Bavaria and Their Relationship to Human Influence and Orographic Effects, Water Air Soil Poll., 11, 481–497, 1979. Slater, J. F., Currie, L. A., Dibb, J. E., and Benner, B. A.: Distinguishing the relative contribution of fossil fuel and biomass combustion aerosols deposited at Summit, Greenland through isotopic and molecular characterization of insoluble carbon, Atmos. Environ., 36, 4463–4477, 2002. Stella, L., Seraglia, R., Sturaro, A., Rella, R., and Traldi, P.: On the photochemical oxidation of benzene and its relevance at environmental level, Rapid Comm, Mass Spectrom,, 22, 257–260, 2008. Tubaro, M., Marotta, E., Seraglia, R., and Traldi, P.: Atmospheric pressure photoionization mechanisms. 2. The case of benzene and toluene, Rapid Comm. Mass Spectrom., 17, 2423–2429, 2003. Vione, D., Falletti, G., Maurino, V., Minero, C., Pelizzetti, E., Malandrino, M., Ajassa, R., Olariu, R. I., and Arsene, C.: Sources and sinks of hydroxyl radicals upon irradiation of natural water samples, Environ. Sci. Technol., 40, 3775–3781, 2006. Wang, X. P., Xu, B. Q., Kang, S. C., Cong, Z. Y., and Yao, T. D.: The historical residue trends of DDT, hexachlorocyclohexanes and polycyclic aromatic hydrocarbons in an ice core from Mt. Everest, central Himalayas, China, Atmos. Environ., 42, 6699–6709, 2008. Wang, X. P., Yao, T. D., Wang, P. L., Yang, W., and Tian, L. D.: The recent deposition of persistent organic pollutants and mercury to the Dasuopu glacier, Mt. Xixiabangma, central Himalayas, Sci. Total Environ., 394, 134–143, 2008. Zheng, W., Jewitt, D., and Kaiser, R. I.: Formation of hydrogen, oxygen, and hydrogen peroxide in electron-irradiated crystalline water ice, Astrophys. J., 639, 534–548, 2006.