ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-6283-2010 Measurement of atmospheric nitrous acid at Bodgett Forest during BEARPEX2007 Ren X. 1 Gao H. 2 Zhou X. 2 3 Crounse J. D. 4 Wennberg P. O. 5 6 Browne E. C. 7 LaFranchi B. W. 7 11 Cohen R. C. 7 8 McKay M. 9 12 Goldstein A. H. 9 Mao J. 10 13 Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, FL, USA Department of Environmental Health Sciences, State University of New York at Albany, Albany, NY, USA Wadsworth Center, New York State Department of Health, Albany, NY, USA Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA Division of Engineering and Applied Sciences, California Institute of Technology, Pasadena, CA, USA Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA Department of Earth and Planetary Science, University of California at Berkeley, Berkeley, CA, USA Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, CA, USA Department of Meteorology, Pennsylvania State University, University Park, PA, USA now at: Center for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, Livermore, CA, USA now at: California Air Resources Board, Sacramento, CA, USA now at: School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA 12 07 2010 10 13 6283 6294 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/10/6283/2010/acp-10-6283-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/6283/2010/acp-10-6283-2010.pdf

Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH) in the lower troposphere. Understanding HONO chemistry, particularly its sources and contribution to HO<sub>x</sub> (=OH+HO<sub>2</sub>) production, is very important for understanding atmospheric oxidation processes. A highly sensitive instrument for detecting atmospheric HONO based on wet chemistry followed by liquid waveguide long path absorption photometry was deployed in the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at Blodgett Forest, California in late summer 2007. The median diurnal variation shows minimum HONO levels of about 20–30 pptv during the day and maximum levels of about 60–70 pptv at night, a diurnal pattern quite different from the results at various other forested sites. Measured HONO/NO<sub>2</sub> ratios for a 24-h period ranged from 0.05 to 0.13 with a mean ratio of 0.07. Speciation of reactive nitrogen compounds (NO<sub>y</sub>) indicates that HONO accounted for only ~3% of total NO<sub>y</sub>. However, due to the fast HONO loss through photolysis, a strong HONO source (1.59 ppbv day<sup>−1</sup>) existed in this environment in order to sustain the observed HONO levels, indicating the significant role of HONO in NO<sub>y</sub> cycling. The wet chemistry HONO measurements were compared to the HONO measurements made with a Chemical Ionization Mass Spectrometer (CIMS) over a three-day period. Good agreement was obtained between the measurements from the two different techniques. Using the expansive suite of photochemical and meteorological measurements, the contribution of HONO photolysis to HO<sub>x</sub> budget was calculated to be relatively small (6%) compared to results from other forested sites. The lower HONO mixing ratio and thus its smaller contribution to HO<sub>x</sub> production are attributed to the unique meteorological conditions and low acid precipitation at Blodgett Forest. Further studies of HONO in this kind of environment are needed to test this hypothesis and to improve our understanding of atmospheric oxidation and nitrogen budget.

 References % vor jede Referenz Acker, K., Febo, A., Trick, S., Perrino, C., Bruno, P., Wiesen, P., Möller, D., Wieprecht, W., Auel, R., Giusto, M., Geyer, A., Platt, U., and Allegrini, I.: Nitrous acid in the urban area of Rome, Atmos. Environ., 40, 3123–3133, 2006a. Acker, K., Möller, D., Wieprecht, W., Meixner, F. X., Bohn, B., Gilge, S., Plass-Dülmer, C., and Berresheim, H.: Strong production of OH from HNO<sub>2</sub> at a rural mountain site, Geophys. Res. Lett., 33, L02809, doi:10.1029/2005GL024643, 2006b. Acker, K. and Möller, D.: Atmospheric variation of nitrous acid at different sites in Europe, Environ. Chem., 4, 242–255, 2007. Alicke, B., Geyer, A., Hofzumahaus, A., Holland, F., Konrad, S., Pätz, H. W., Schäfer, J., Stutz, J., Volz-Thomas, A., and Platt, U.: OH formation by HONO photolysis during the BERLIOZ experiment, J. Geophys. Res., 108, 8247, doi:10.1029/2001JD000579, 2003. Allegrini, I., Cortiello, M., Febo, A., and Perrino, C.: Generation of standard atmospheres of nitrous acid, In Physico-Chemical Behaviour of Atmospheric Pollutants, Kluwer Academic Publishers, Dodrecht, 140–144, 1990. Ammann, M., Kalberer, M., Jost, D. T., Tobler, L., Rössler, E., Piguet, D., Gäggeler, H. W., and Baltensperger, U.: Heterogeneous production of nitrous acid on soot in polluted air masses, Nature, 395, 157–160, 1998. Appel, B. R., Winer, A. M., Tokiwa, Y., and Biermann, H. W.: Comparison of atmospheric nitrous acid measurements by annular denuder and optical absorption systems, Atmos. Environ., 24A, 611–616, 1990. Arens, F., Gutzwiller, L., Baltensperger, U., Gäggeler, H. W., and Ammann, M.: Heterogeneous reaction of NO<sub>2</sub> on diesel soot particles, Environ. Sci. Technol., 35, 2191–2199, 2001. Aubin, D. G. and Abbatt, J. P. D.: Interaction of NO<sub>2</sub> with hydrocarbon soot: Focus on HONO yield, surface modification, and mechanism, J. Phys. Chem. A, 111, 6263–6273, 2007. Beine, H. J., Amoroso, A., Dominé, F., King, M. D., Nardino, M., Ianniello, A., and France, J. L.: Surprisingly small HONO emissions from snow surfaces at Browning Pass, Antarctica, Atmos. Chem. Phys., 6, 2569–2580, doi:10.5194/acp-6-2569-2006, 2006. Bejan, I., Abd-el-Aal, Y., Barnes, I., Benter, T., Bohn, B., Wiesen, P., and Kleffmann, J.: The photolysis of ortho-nitrophenols: a new gas phase source of HONO, Phys. Chem. Chem. Phys., 8, 2028–2035, 2006. Bouvier-Brown, N. C., Goldstein, A. H., Gilman, J. B., Kuster, W. C., and de Gouw, J. A.: In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007: implications for gas- and particle-phase chemistry, Atmos. Chem. Phys., 9, 5505–5518, doi:10.5194/acp-9-5505-2009, 2009. Bröske, R., Kleffmann, J., and Wiesen, P.: Heterogeneous conversion of NO2 on secondary organic aerosol surfaces: A possible source of nitrous acid (HONO) in the atmosphere?, Atmos. Chem. Phys., 3, 469–474, doi:10.5194/acp-3-469-2003, 2003. Carr, S., Heard, D. E., and Blitz, M. A.: Comment on "Atmospheric hydroxyl radical production from electronically excited NO<sub>2</sub> and H<sub>2</sub>O", Science, 324, 5925, doi:10.1126/science.1166669, 2009. Crounse, J. D., McKinney, K. A., Kwan, A. J., and Wennberg, P. O.: Measurement of gas-phase hydroperoxides by chemical ionization mass spectrometry, Anal. Chem., 78, 6726–6732, 2006. Day, D. A., Farmer, D. K., Goldstein, A. H., Wooldridge, P. J., Minejima, C., and Cohen, R. C.: Observations of NO<sub>x</sub>, SPNs, SANs, and HNO<sub>3</sub> at a Rural Site in the California Sierra Nevada Mountains: summertime diurnal cycles, Atmos. Chem. Phys., 9, 4879–4896, doi:10.5194/acp-9-4879-2009, 2009. Elshorbany, Y. F., Kurtenbach, R., Wiesen, P., Lissi, E., Rubio, M., Villena, G., Gramsch, E., Rickard, A. R., Pilling, M. J., and Kleffmann, J.: Oxidation capacity of the city air of Santiago, Chile, Atmos. Chem. Phys., 9, 2257–2273, doi:10.5194/acp-9-2257-2009, 2009. Faloona, I. C., Tan, D., Lesher, R. L., Hazen, N. L., Frame, C. L., Simpas, J. B., Harder, H., Martinez, M., Di Carlo, P., Ren, X., and Brune, W. H.: A laser-induced fluorescence instrument for detecting tropospheric OH and HO<sub>2</sub>: Characteristics and calibration, J. Atmos. Chem., 47, 139–167, 2004. Farmer, D. K. and Cohen, R. C.: Observations of HNO<sub>3</sub>, SAN, SPN and NO<sub>2</sub> fluxes: evidence for rapid HOx chemistry within a pine forest canopy, Atmos. Chem. Phys., 8, 3899–3917, doi:10.5194/acp-8-3899-2008, 2008. 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. Febo, A., Perrino, C., and Allegrini, I.: Measurement of nitrous acid in Milan, Italy, by DOAS and diffusion denuders, Atmos. Environ., 30, 3599–3609, 1996. Fenn, M. E., Huntington, T. G., McLaughlin, S. B., Eagar, C., Gomez, A., and Cook, R. B.: Status of soil acidification of North America, J. Forest Sci., 52, Special Issue, 3–13, 2006. Finlayson-Pitts, B. J., Wingen, L. M., Sumner, A. L., Syomin, D., and Ramazan, K. A.: The heterogeneous hydrolysis of NO<sub>2</sub> in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism, Phys. Chem. Chem. Phys., 5, 223–242, 2003. George, C., Strekowski, R. S., Kleffmann, J., Stemmler, K., and Ammann, M.: Photoenhanced uptake of gaseous NO<sub>2</sub> on solid organic compounds: A photochemical source of HONO, Faraday Discuss., 130, 195–210, 2005. Goldstein, A. H., Hultman, N. E., Fracheboud, J. M., Bauer, M. R., Panek, J. A., Xu, M., Qi, Y., Guenther, A. B., and Baugh, W.: Effects of climate variability on the carbon dioxide, water, and sensible heat fluxes above a ponderosa pine plantation in the Sierra Nevada (CA), Agr. Forest Meteorol., 101, 113–129, 2000. Harrison, R. M., Peak, J. D., and Collins, G. M.: Tropospheric cycle of nitrous acid, J. Geophys. Res., 101, 14429–14439, 1996. Heland, J., Kleffmann, J., Kurtenbach, R., and Wiesen, P.: A new instrument to measure gaseous nitrous acid (HONO) in the atmosphere, Environ. Sci. Technol., 35, 3207–3212, 2001. Hirokawa, J., Kato, T., and Mafuné, F.: In situ measurements of atmospheric nitrous acid by chemical ionization mass spectrometry using chloride ion transfer reactions, Anal. Chem., 81, 8380–8386, 2009. Honrath, R. E., Lu, Y., Peterson, M. C., Dibb, J. E., Arsenault, M. A., Cullen, N. J., and Steffen, K.: Vertical fluxes of NO<sub>x</sub>, HONO, and HNO<sub>3</sub> above the snowpack at Summit, Greenland, Atmos. Environ., 36, 2629–2640, 2002. Huang, G., Zhou, X., Deng, G., Qiao, H., and Civerolo, K.: Measurements of atmospheric nitrous acid and nitric acid, Atmos. Environ., 36, 2225–2235, 2002. Kleffmann, J., Kurtenbach, R., Lörzer, J. C., Wiesen, P., Kalthoff, N., Vogel, B., and Vogel, H.: Measured and simulated vertical profiles of nitrous acid. Part I: Field measurements, Atmos. Environ., 37, 2949–2955, 2003. Kleffmann, J., Gavriloaiei, T., Hofzumahaus, A., Holland F., Koppmann, R., Rupp, L., Schlosser, E., Siese, M., and Wahner, A.: Daytime formation of nitrous acid: a major source of OH radicals in a forest. Geophys. Res. Lett., 32, L05818, doi:10.1029/2005GL022524, 2005. Kleffmann, J., Lörzer, J. C., Weisen, P., Kern, C., Trick, S., Volamer, R., Rodenas, M., and Wirtz, K.: Intercomparison of the DOAS and LOPAP techniques for the detection of nitrous acid (HONO), Atmos. Environ., 40, 3640–3652, 2006. Kleffmann, J. and Wiesen, P.: Technical Note: Quantification of interferences of wet chemical HONO LOPAP measurements under simulated polar conditions, Atmos. Chem. Phys., 8, 6813–6822, doi:10.5194/acp-8-6813-2008, 2008. LaFranchi, B. W., Wolfe, G. M., Thornton, J. A., Harrold, S. A., Browne, E. C., Min, K. E., Wooldridge, P. J., Gilman, J. B., Kuster, W. C., Goldan, P. D., de Gouw, J. A., McKay, M., Goldstein, A. H., Ren, X., Mao, J., and Cohen, R. C.: Closing the peroxy acetyl nitrate budget: observations of acyl peroxy nitrates (PAN, PPN, and MPAN) during BEARPEX 2007, Atmos. Chem. Phys., 9, 7623–7641, doi:10.5194/acp-9-7623-2009, 2009. Langridge, J. M., Gustafsson, R. J., Griffiths, P. T., Cox, R. A., Lambert, R. M., and Jones, R. L.: Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas? Atmos. Environ., 43, 5128–5131, 2009. Li, S., Mathews, J., and Sinha, A.: Atmospheric hydroxyl radical production from electronically excited NO<sub>2</sub> and H<sub>2</sub>O, Science, 319, 1657–1660, 2008. Mao, J., Ren, X., Chen, S., Brune, W. H., Chen, Z., Martinez, M., Harder, H., Lefer, B., Rappenglück, B., Flynn, J., and Leuchner, M.: Atmospheric oxidation capacity in the summer of Houston 2006: Comparison with summer measurements in other metropolitan studies, Atmos. Environ., doi:10.1016/j.atmosenv.2009.01.013, in press, 2010. Menz, F. C. and Seip, H. M.: Acid rain in Europe and the United States: an update, Environ. Sci. Policy, 7, 253–265, 2004. Murphy, J. G., Day, D. A., Cleary, P. A., Wooldridge, P. J., and Cohen, R. C.: Observations of the diurnal and seasonal trends in nitrogen oxides in the western Sierra Nevada, Atmos. Chem. Phys., 6, 5321–5338, doi:10.5194/acp-6-5321-2006, 2006. Ndour, M., D'Anna, B., George, C., Ka, O., Balkanski, Y., Kleffmann, J., Stemmler, K., and Ammann, M.: Photoenhanced uptake of NO2 on mineral dust: Laboratory experiments and model simulations, Geophys. Res. Lett., 35, L05812, doi:10.1029/2007GL032006, 2008. Neftel, A., Blatter, A., Hesterberg, R., and Staffelbach, Th.: Measurements of concentration gradients of HNO<sub>2</sub> and HNO<sub>3</sub> over a semi-natural ecosystem, Atmos. Environ., 30, 3017–3025, 1996. Park, J. -Y. and Lee, Y. -N.: Solubility and decomposition kinetics of nitrous acid in aqueous solution, J. Phys. Chem., 92, 6294–6302, 1988. Pérez, I. M., Wooldridge, P. J., and Cohen, R. C.: Laboratory evaluation of a novel thermal dissociation chemiluminescence method for in situ detection of nitrous acid, Atmos. Environ., 41, 3993–4001, 2007. Qin, M., Xie, P., Su, H., Gu, J., Peng, F., Li, S., Zeng, L., Liu, J., Liu, W., and Zhang, Y.: An observational study of the HONO–NO<sub>2</sub> coupling at an urban site in Guangzhou City, South China, Atmos. Environ., 43, 5731–5742, doi:10.1016/j.atmosenv.2009.08.017, 2009. Ren, X., Harder, H., Martinez, M., Lesher, R. L., Oliger, A., Simpas, J. B., Brune, W. H., Schwab, J. J., Demerjian, K. L., He, Y., Zhou, X., and Gao, H.: OH and HO<sub>2</sub> chemistry in the urban atmosphere of New York City, Atmos. Environ., 37, 3639–3651, 2003. Ren, X., Brune, W. H., Oliger, A., Metcalf, A. R., Simpas, J. B., Shirley, T., Schwab, J. J., Bai, C., Roychowdhury, U., Li, Y., Cai, C., Demerjian, K. L., He, Y., Zhou, X., Gao, H., and Hou, J.: OH, HO<sub>2</sub> and OH Reactivity during the PMTACS–NY Whiteface Mountain 2002 Campaign: Observations and Model Comparison, J. Geophys. Res., 111, D10S03, doi:10.1029/2005JD006126, 2006. Schartz, S. E. and White, W. H.: Solubility equilibria of the nitrogen oxides and oxyacids in dilute aqueous solution, Adv. Environ. Sci. Eng., 1–45, 1981. Staffelbach, T., Neftel, A., and Horowitz, L. W.: Photochemical oxidant formation over southern Switzerland 2. Model results, J. Geophys. Res., 102, 23363–23373, 1997. Stemmler, K., Ammann, M., Dondors, C., Kleffmann, J., and George, C.: Photosensitized reduction of nitrogen dioxide on humic acid as a source of nitrous acid, Nature, 440, 195–198, 2006. Stockwell, W. R., Kirchner, F., and Kuhn, M.: A new mechanism for regional atmospheric chemistry modeling, J. Geophys. Res., 102, 25847–25879, 1997. Stutz, J., Oha, H. -J., Whitlow, S. I., Anderson, C., Dibb, J. E., Flynn, J. H., Rappenglück, B., and Lefer, B.: Simultaneous DOAS and mist-chamber IC measurements of HONO in Houston, TX, Atmos. Environ., doi:10.1016/j.atmosenv.2009.02.003, in press, 2010. Thomas, S., Ren, X., Stutz, J., Dibb, J., Zheng, J., Wood, E., and Rappenglück, B: Intercomparison of nitrous acid measurement methods during SHARP in Houston, TX, in preparation, 2010. Thornton, J. A., Wooldridge, P. J., and Cohen, R. C.: Atmospheric NO<sub>2</sub>: In situ laser-induced fluorescence detection at parts per trillion mixing ratios, Anal. Chem., 72, 528–539, 2000. Vogel, B., Vogel, H., Kleffmann, J., and Kurtenbach, R.: Measured and simulated vertical profiles of nitrous acid, Part II–-model simulations and indications for a photolytic source, Atmos. Environ., 37, 2957–2966, 2003. Winer, A. M. and Biermann, H. W.: Long pathlength differential optical absorption spectroscopy (DOAS) measurements of gaseous HONO, NO<sub>2</sub> and HCHO in the California South Coast Air Basin, Res. Chem. Intermed., 20, 423–445, 1994. Wolfe, G. M., Thornton, J. A., Yatavelli, R. L. N., McKay, M., Goldstein, A. H., LaFranchi, B., Min, K.-E., and Cohen, R. C.: Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN) above a Ponderosa pine forest, Atmos. Chem. Phys., 9, 615–634, doi:10.5194/acp-9-615-2009, 2009. Yokelson, R. J., Crounse, J. D., DeCarlo, P. F., Karl, T., Urbanski, S., Atlas, E., Campos, T., Shinozuka, Y., Kapustin, V., Clarke, A. D., Weinheimer, A., Knapp, D. J., Montzka, D. D., Holloway, J., Weibring, P., Flocke, F., Zheng, W., Toohey, D., Wennberg, P. O., Wiedinmyer, C., Mauldin, L., Fried, A., Richter, D., Walega, J., Jimenez, J. L., Adachi, K., Buseck, P. R., Hall, S. R., and Shetter, R.: Emissions from biomass burning in the Yucatan, Atmos. Chem. Phys., 9, 5785–5812, doi:10.5194/acp-9-5785-2009, 2009. Zhou, X., Beine, H. J., Honrath, R. E., Fuentes, J. D., Simpson, W., Shepson, P. B., and Bottenheim, J. W.: Snowpack photochemical production of HONO: A major source OH in the Arctic boundary layer in springtime, Geophys. Res. Lett., 28, 4087–4090, 2001. Zhou, X., Civerolo, K., Dai, H., Huang, G., Schwab, J., and Demerjian, K.: Summertime nitrous acid chemistry in the atmospheric boundary layer at a rural site in New York State, J. Geophys. Res., 107, 4590, doi:10.1029/2001JD001539, 2002a. Zhou, X., He, Y., Huang, G., Thornberry, T. D., Carroll, M. A., and Bertman, S. B.: Photochemical production of nitrous acid on glass sample manifold surface, Geophys. Res. Lett., 29, 1681, doi:10.1029/2002GL015080, 2002b. Zhou, X., Gao, H., He, Y., Huang, G., Bertman, S., Civerolo, K., and Schwab, J.: Nitric acid photolysis on surfaces in low-NOx environments: significant atmospheric implications, Geophys. Res. Lett., 30, 2217, doi:10.1029/2003GL018620, 2003. Zhou, X., Huang, G., Civerolo, K., Roychowdhury, U., and Demerjian, K. L.: Summertime observations of HONO, HCHO, and O<sub>3</sub> at the summit of Whiteface Mountain, New York, J. Geophys. Res., 112, D08311, doi:10.1029/2006JD007256, 2007. Ziemba, L. D., Dibb, J. E., Griffin, R. J., Anderson, C. H., Whitlow, S. I., Lefer, B. L., Rappenglück, B., and Flynn, J.: Heterogeneous conversion of nitric acid to nitrous acid on the surface of primary organic aerosol in an urban atmosphere, Atmos. Environ., doi:10.1016/j.atmosenv.2008.12.024, in press, 2010.