Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 10 3 2010 10.5194/acpd-10-6829-2010 http://www.atmos-chem-phys-discuss.net/10/6829/2010/ http://www.atmos-chem-phys-discuss.net/10/6829/2010/acpd-10-6829-2010.html http://www.atmos-chem-phys-discuss.net/10/6829/2010/acpd-10-6829-2010.pdf 6829 6869 2010-03-11 Isotope modeling of nitric acid formation in the atmosphere using ISO-RACM: testing the importance of NO oxidation, heterogeneous reactions, and trace gas chemistry G. Michalski gmichals@purdue.edu F. Xu Department of Chemistry, Earth and Atmospheric Sciences, Purdue University 550 Stadium Mall Dr. West Lafayette, West Lafayette, IN, USA Here we present ISO-RACM, an isotope mass balance model that utilizes the Regional Atmospheric Chemistry Mechanism to predict Δ¹⁷O values in atmospheric nitrate. A large number of simulations were carried out that varied atmospheric parameters that are important in altering the magnitude and range of Δ¹⁷O values generated in photochemically produce nitrate. These parameters included temperature, relative humidity, actinic flux, aerosol surface area and chemical speciation, and three different N₂O₅ uptake parameterizations. Trace gas mixing ratios were also varied including CH₄, CO, NO_x, O₃, volatile organic compounds and biogenic organic compounds. The model predicts that there are seasonal, latitudinal and diurnal variations in Δ¹⁷O values due to changes in actinic flux with lower values corresponding to higher actinic fluxes. There was also a minor positive correlation between higher Δ¹⁷O values and increased temperature. There were distinct differences in Δ¹⁷O depending on which N₂O₅ parameterization was used, mostly the result of changing relative humidity being a factor in two of the parameterization schemes. Changing CO and CH₄ mixing ratios had negligible impact on Δ¹⁷O values but significant variation in magnitude and range were predicted with NO_x, O₃, and organic loading. High NO_x and O₃ generated high Δ¹⁷O with a narrow (10 ‰) range, while high organics led to low Δ¹⁷O values and a wider range of possible values. Implications for using Δ¹⁷O to evaluate NO_x-NO_y chemistry and aerosol formation processes are discussed, as is needed future research. Alexander, B., Hastings, M. G., Allman, D. J., Dachs, J., Thornton, J. A., and Kunasek, S. A.: Quantifying atmospheric nitrate formation pathways based on a global model of the oxygen isotopic composition ($\Delta^17$O) of atmospheric nitrate, Atmos. Chem. Phys., 9, 5043–5056, 2009. Alexander, B., Park, R. J., Jacob, D. J., Li, Q. B., Yantosca, R. M., Savarino, J., Lee, C. C. W., and Thiemens, M. H.: Sulfate formation in sea-salt aerosols: Constraints from oxygen isotopes, J. Geophys. Res., 110(D10), D10307, doi:10.1029/2004JD005659, 2005. Atkinson, R.: Atmospheric chemistry of VOCs and NO_x, 2063–2101, 2000. Bauer, S. E., Koch, D., Unger, N., Metzger, S. M., Shindell, D. T., and Streets, D. G.: Nitrate aerosols today and in 2030: a global simulation including aerosols and tropospheric ozone, Atmos. Chem. Phys., 7, 5043–5059, 2007. Bedison, J. E. and Mcneil, B. E.: Is the growth of temperate forest trees enhanced along an ambient nitrogen deposition gradient?, Ecology, 90(7), 1736–1742, 2009. Bhattacharya, S. K. and Thiemens, M. H.: New evidence for symmetry dependent isotope effects: atomic oxygen + carbon monoxide reaction, Z. Naturforsch. A., 44(5), 435–444, 1989. Bhattacharya, S. K., Savarino, J., and Thiemens, M. H.: A new class of oxygen isotopic fractionation in photodissociation of carbon dioxide: potential implications for atmospheres of Mars and Earth, Geophys. Res. Lett., 27(10), 1459–1462, 2000. Bhattacharya, S. K., Pandey, A. and Savarino, J.: Determination of intramolecular isotope distribution of ozone by oxidation reaction with silver metal, J. Geophys. Res., 113, D03303, doi:10.1029/2006JD008309, 2008. Brown, S. S., Ryerson, T. B., Wollny, A. G., Brock, C. A., Peltier, R., Sullivan, A. P., Weber, R. J., Dube, W. P., Trainer, M., Meagher, J. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Variability in nocturnal nitrogen oxide processing and its role in regional air quality, Science, 311(5757), 67–70, 2006. Brown, S. S., Stark, H., Ryerson, T. B., Williams, E. J., Nicks, D. K., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Nitrogen oxides in the nocturnal boundary layer: Simultaneous in situ measurements of NO₃, N₂O$_5$, NO₂, NO, and O₃, J. Geophys. Res., 108(D9), 4299, doi:10.1029/2002JD002917, 2003. Chang, J. S., Brost, R. A., Isaksen, I. S. A., Madronich, S., Middleton, P., Stockwell, W. R., and Walcek, C. J.: A 3-Dimensional Eulerian Acid Deposition Model – Physical Concepts and Formulation, J. Geophys. Res., 92(D12), 14681–14700, 1987. Davis, J. M., Bhave, P. V., and Foley, K. M.: Parameterization of N2O5 reaction probabilities on the surface of particles containing ammonium, sulfate, and nitrate, Atm. Chem. Phys., 8(17), 5295–5311, 2008 Delmas, R. J.: Ice-core records of global climate and environment changes, P. Indian AS-Earth, 107(4), 307–319, 1998. Dentener, F., Drevet, J., Lamarque, J. F., Bey, I., Eickhout, B., Fiore, A. M., Hauglustaine, D., Horowitz, L. W., Krol, M., Kulshrestha, U. C., Lawrence, M., Galy-Lacaux, C., Rast, S., Shindell, D., Stevenson, D., Van Noije, T., Atherton, C., Bell, N., Bergman, D., Butler, T., Cofala, J., Collins, B., Doherty, R., Ellingsen, K., Galloway, J., Gauss, M., Montanaro, V., Muller, J. F., Pitari, G., Rodriguez, J., Sanderson, M., Solmon, F., Strahan, S., Schultz, M., Sudo, K., Szopa, S., and Wild, O.: Nitrogen and sulfur deposition on regional and global scales: A multimodel evaluation, Global Biogeochem. Cy., 20(4), GB4003 doi:10.1029/2005GB002672, 2006. Dubey, M. K., Mohrschladt, R., Donahue, N. M., and Anderson, J. G.: Isotope-specific kinetics of hydroxyl radical (OH) with water (H₂O): Testing models of reactivity and atmospheric fractionation, J. Phys. Chem A, 101(8), 1494–1500, 1997. Fenn, M. E., Haeuber, R., Tonnesen, G. S., Baron, J. S., Grossman-Clarke, S., Hope, D., Jaffe, D. A., Copeland, S., Geiser, L., Rueth, H. M., and Sickman, J. O.: Nitrogen emissions, deposition, and monitoring in the western United States, 391–403, 2003. Finlayson-Pitts, B. J. and Pitts Jr., J. N.: Chemistry of the Upper and Lower Atmosphere, Academic Press, San Diego, 2000. Friedl, R. R., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Keller-Rudek, H., Wine, P. H., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., Huie, R. E., and Orkin, V. L.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 15, Jet Propulsion Laboratory, JPL Publication 06-2, 2006. Freyer, H. D.: Seasonal-Variation of N-15–N-14 Ratios in Atmospheric Nitrate Species, Tellus~B, 43(1), 30–44, 1991. Galloway, J. N.: Acid deposition: perspectives in time and space, Water Air Soil Poll., 85(1), 15–24, 1995. Galloway, J. N., Dentener, F. J., Capone, D. G., Boyer, E. W., Howarth, R. W., Seitzinger, S. P., Asner, G. P., Cleveland, C. C., Green, P. A., Holland, E. A., Karl, D. M., Michaels, A. F., Porter, J. H., Townsend, A. R., and Vorosmarty, C. J.: Nitrogen cycles: past, present, and future, Biogeochemistry, 70(2), 153–226, 2004. Gladysheva, O. G., Dmitriev, P. B., Barkov, N. I., Ekaikin, A. A., and Nikonorov, V. V.: Nitrate content of snow at Vostok station, Antarctica, Geomagn. Aeronomy, 43(5), 665–669, 2003. Gross, A. and Stockwell, W. R.: Comparison of the EMEP, RADM2 and RACM mechanisms, J. Atmos. Chem., 44(2), 151–170, 2003. Gross, A., Sorensen, J. H., and Stockwell, W. R.: A multi-trajectory chemical-transport vectorized gear model: 3-D simulations and model validation, J. Atmos. Chem., 50(3), 211–242, 2005. Hallquist, M., Stewart, D. J., Baker, J., and Cox, R. A.: Hydrolysis of N₂O$_5$ on submicron sulfuric acid aerosols, J. Phys. Chem A, 10(17), 3984–3990, 2000. Hansen, J., Sato, M., Ruedy, R., Nazarenko, L., Lacis, A., Schmidt, G. A., Russell, G., Aleinov, I., Bauer, M., Bauer, S., Bell, N., Cairns, B., Canuto, V., Chandler, M., Cheng, Y., Del Genio, A., Faluvegi, G., Fleming, E., Friend, A., Hall, T., Jackman, C., Kelley, M., Kiang, N., Koch, D., Lean, J., Lerner, J., Lo, K., Menon, S., Miller, R., Minnis, P., Novakov, T., Oinas, V., Perlwitz, J., Perlwitz, J., Rind, D., Romanou, A., Shindell, D., Stone, P., Sun, S., Tausnev, N., Thresher, D., Wielicki, B., Wong, T., Yao, M., and Zhang, S.: Efficacy of climate forcings, J. Geophys. Res., 110(D18), D18104, doi:10.1029/2005JD005776, 2005. Hastings, M. G., D. M. Sigman and E. J. Steig, Seasonal variations in N and O isotopes of nitrate in snow at Summit, Greenland: Implications for the study of nitrate in snow and ice cores, J. Geophys. Res., 109, D20306, doi:10.1029/2004JD004991, 2004. Haywood, J. and Boucher, O.: Estimates of the direct and indirect radiative forcing due to tropospheric aerosols: A review, Rev. Geophys., 38(4), 513–543, 2000. Horowitz, L. W., Fiore, A. M., Milly, G. P., Cohen, R. C., Perring, A., Wooldridge, P. J., Hess, P. G., Emmons, L. K., and Lamarque, J. F.: Observational constraints on the chemistry of isoprene nitrates over the eastern United States, J. Geophys. Res., 112(D12), D12S08, doi:10.1029/2006JD007747, 2007. Johnston, J. C. and Thiemens, M. H.: The isotopic composition of tropospheric ozone in three environments, J. Geophys. Res., 102(D21), 25395–-25404, 1997. Kirchner, F. and Stockwell, W. R.: Effect of peroxy radical reactions on the predicted concentrations of ozone, nitrogenous compounds, and radicals , J. Geophys. Res., 101, 21007, 1996. Krankowsky, D., Bartecki, F., Klees, G. G., Mauersberger, K., Schellenbach, K., and Stehr, J.: Measurement of heavy isotope enrichment in tropospheric ozone, Geophys. Res. Lett., 22(13), 1713–1716, 1995. Kuhn, M., Builtjes, P. J. H., Poppe, D., Simpson, D., Stockwell, W. R., Andersson-Skold, Y., Baart, A., Das, M., Fiedler, F., Hov, O., Kirchner, F., Makar, P. A., Milford, J. B., Roemer, M. G. M., Ruhnke, R., Strand, A., Vogel, B., and Vogel, H.: Intercomparison of the gas-phase chemistry in several chemistry and transport models, Atmos. Environ., 32(4), 693–709, 1998. Li, S., Wang, T. J., Zhuang, B. L., and Han, Y.: Indirect radiative forcing and climatic effect of the anthropogenic nitrate aerosol on regional climate of China, Adv. Atmos. Sci., 26(3), 543–552, 2009. Lohmann, U. and Lesins, G.: Stronger constraints on the anthropogenic indirect aerosol effect, Science, 298(5595), 1012–1015, 2002. Luz, B., Barkan, E., Bender, M. L., Thiemens, M. H., and Boering, K. A.: Triple-isotope composition of atmospheric oxygen as a tracer of biosphere productivity, Nature, 400(6744), 547–550, 1999. Lyons, J. R.: Transfer of mass-independent fractionation in ozone to other oxygen-containing radicals in the atmosphere, Geophys. Res. Lett., 28(17), 3231–3234, 2001. Magill, A. H., Aber, J. D., Currie, W. S., Nadelhoffer, K. J., Martin, M. E., McDowell, W. H., Melillo, J. M., and Steudler, P.: Ecosystem response to 15 years of chronic nitrogen additions at the Harvard Forest LTER, Massachusetts, USA, Forest Ecol. Manag., 196(1), 7–28, 2004. Mentel, T. F., Sohn, M., and Wahner, A.: Nitrate effect in the heterogeneous hydrolysis of dinitrogen pentoxide on aqueous aerosols, Phys. Chem. Chem. Phys., 1(24), 5451–5457, 1999. Michalski, G., Scott, Z., Kabiling, M., and Thiemens, M.: First Measurements and Modeling of $\Delta^17$O in Atmospheric Nitrate, Geophys. Res. Lett., 30(16), 1870, doi:10.1029GL017015, 2003. Michalski, G. and Bhattacharya, S. K.: The role of symmetry in the mass independent isotope effect in ozone, Proc. Nat. Acad. Sci., 106, 5493–5496, 2009. Michalski, G., Böhlke, J. K., and Thiemens, M. H.: Long Term Atmospheric Deposition as the Source of Nitrate and Other Salts in the Atacama Desert, Chile: New Evidence from Mass-Independent Oxygen Isotopic Compositions, Geochim. Cosmochim. Ac., 68, 4023–4038, 2004. Miller, M. F.: Isotopic fractionation and the quantification of $^17$O anomalies in the oxygen three-isotope system: an appraisal and geochemical significance, Geochim. Cosmochim. Ac., 66(11), 1881–1889, 2002. Morin, S., Savarino, J., Frey, M. M., Domine, F., Jacobi, H. W., Kaleschke, L., and Martins, J. M. F.: Comprehensive isotopic composition of atmospheric nitrate in the Atlantic Ocean boundary layer from 65~degrees~S to 79~degrees~N, J. Geophys. Res., 114, D05303, doi:10.1029/2008JD010696, 2009. Morin, S., Savarino, J., Bekki, S., Gong, S., and Bottenheim, J. W.: Signature of Arctic surface ozone depletion events in the isotope anomaly ($\Delta^17$O) of atmospheric nitrate, Atmos. Chem. Phys., 7, 1451–1469, 2007. Morton, J., Barnes, J., Schueler, B., and Mauersberger, K.: Laboratory Studies of Heavy Ozone, J. Geophys. Res., 95(D1), 901–907, 1990. Mozurkewich, M. and Calvert, J. G.: Reaction Probability of N₂O$_5$ on Aqueous Aerosols, J. Geophys. Res., 93(D12), 15889–15896, 1988. Myhre, G.: Consistency Between Satellite-Derived and Modeled Estimates of the Direct Aerosol Effect, Science, 325(5937), 187–190, 2009. Paerl, H. W., Boynton, W. R., Dennis, R. L., Driscoll, C. T., Greening, H. S., Kremer, J. N., Rabalais, N., and Seitzinger, S. P.: Atmospheric deposition of nitrogen in coastal waters: Biogeochemical and ecological implications, in: Nitrogen loading in coastal water bodies: an atmospheric perspective, edited by: Valigura, R. A., Alexander, R. B., Castro, M. S., Meyers, T., Paerl, H. W., Stacey, P. E., and Turner, R. E., American Geophysical Union, Washington, 11–52, 2001. Patris, N., Cliff, S. S., Quinn, P. K., Kasem, M., and Thiemens, M. H.: Isotopic analysis of aerosol sulfate and nitrate during ITCT-2k2: Determination of different formation pathways as a function of particle size, J. Geophys. Res., 112(D23), D23301, doi:10.1029/2005JD006214, 2007. Peiro-Garcia, J. and Nebot-Gil, I.: Ab initio study of the mechanism of the atmospheric reaction: NO₂+O$_3->$ NO₃+O₂, J. Comput. Chem., 24(13), 1657–1663, 2003. Peiro-Garcia, J. and Nebot-Gil, I.: Ab initio study of the mechanism and thermochemistry of the atmospheric reaction NO+O$_3->$NO₂+O₂, J. Phys. Chem A, 106(43), 10302–10310, 2002. Perring, A. E., Wisthaler, A., Graus, M., Wooldridge, P. J., Lockwood, A. L., Mielke, L. H., Shepson, P. B., Hansel, A., and Cohen, R. C.: A product study of the isoprene + NO₃ reaction, Atmos. Chem. Phys., 9, 4945–4956, 2009. Platt, U. F., Winer, A. M., Biermann, H. W., Atkinson, R., and Pitts, J. N.: Measurement of Nitrate Radical Concentrations in Continental Air, Environ. Sci. Technol., 18(5), 365–369, 1984. Redpath, A. E., Menzinger, M., and Carrington, T.: Molecular-Beam Chemiluminescence: Kinetic and internal energy dependence of NO+O₃–$>$NO₂*–$>$NO₂+hn reaction, Chem. Phys., 27(3), 409–431, 1978. Riemer, N., Vogel, H., Vogel, B., Schell, B., Ackermann, I., Kessler, C., and Hass, H.: Impact of the heterogeneous hydrolysis of N₂O$_5$ on chemistry and nitrate aerosol formation in the lower troposphere under photosmog conditions, J. Geophys. Res., 108(D4), 4144, doi:10.1029/2002JD002436, 2003. Rockmann, T., Brenninkmeijer, C. A. M., Sauerssig, G., Bergamaschi, P., Crowley, J. N., Fischer, H., and Crutzen, P. J.: Mass-independent oxygen isotope fractionation in atmospheric CO as a result of the reaction CO+OH, Science, 281(5376), 544–546, 1998. Rodhe, H., Dentener, F., and Schulz, M.: The global distribution of acidifying wet deposition, Environ. Sci. Technol., 36(20), 4382–4388, 2002. Samet, J. M., Dominici, F., Curriero, F. C., Coursac, I., and Zeger, S. L.: Fine particulate air pollution and mortality in 20~US~cities, 1987–1994, pp 1742–1749, 2000. Savarino, J. and Thiemens, M. H.: Mass-independent oxygen isotope ($^16$O, $^17$O, $^18$O) fractionation found in H_x, O_x reactions, J. Phys. Chem A, 103(46), 9221–9229, 1999. Savarino, J. and Thiemens, M. H.: Analytical procedure to determine both $\delta^18$O and $\delta^17$O of H₂O₂ in natural water and first measurements, Atmos. Environ., 33(22), 3683–3690, 1999. Savarino, J., Bhattacharya, S. K., Morin, S., Baroni, M., and Doussin, J. F.: The NO+O₃ reaction: A triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly, J. Chem. Phys., 128(19), 194303, doi:10.1063/1.2917581, 2008. Schwartz, J. and Neas, L. M.: Fine particles are more strongly associated than coarse particles with acute respiratory health effects in schoolchildren, Epidemiology, 11(1), 6–10, 2000. Scheuner, E. T. and Makeschin, F.: Impact of atmospheric nitrogen deposition on carbon dynamics in two scots pine forest soils of northern germany, Plant Soil, 275(1–2), 43–54, 2005. Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics: from air pollution to climate change, New York, Wiley, 1998. Sinha, A., Lovejoy, E. R., and Howard, C. J.: Kinetic-Study of the Reaction of HO₂ with Ozone, J. Chem. Phys., 87(4), 2122–2128, 1987. Stark, H., Brown, S. S., Goldan, P. D., Aldener, M., Kuster, W. C., Jakoubek, R., Fehsenfeld, F. C., Meagher, J., Bates, T. S., and Ravishankara, A. R.: Influence of nitrate radical on the oxidation of dimethyl sulfide in a polluted marine environment, J. Geophys. Res., 112(D10), D10S10, doi:10.1029/2006JD007669, 2007. Stockwell, W. R., Kirchner, F., Kuhn, M., and Seefeld, S.: A new mechanism for regional atmospheric chemistry modeling, J. Geophys. Res., 102(D22), 25847–25879, 1997. Thiemens, M. H. and Heidenreich~III, J. E.: The mass-independent fractionation of oxygen: a novel isotope effect and its possible cosmochemical implications, Science, 219(4588), 1073–1075, 1983. Thiemens, M. H. and Jackson, T.: Pressure dependency for heavy isotope enhancement in ozone formation, Geophys. Res. Lett., 17(6), 717–719, 1990. Thiemens, M. H. and Jackson, T.: Production of isotopically heavy ozone by ultraviolet light photolysis of oxygen, Geophys. Res. Lett., $14$(6), 624–627, 1987. Tuazon, E. C., Atkinson, R., Plum, C. N., Winer, A. M., and Pitts, J. N.: The Reaction of Gas-Phase N₂O$_5$ with Water-Vapor, Geophys. Res. Lett., 10(10), 953–956, 1983. Urey, H. C.: Thermodynamic properties of isotopic substances, J. Chem. Soc., 562–581, 1947. Viswanathan, R. and Raff, L. M.: Theoretical investigations of the reaction dynamics of polyatomic gas-phase systems: the ozone + nitric oxide reaction, J. Phys. Chem., 87(17), 3251–3266, 1983. Wahner, A., Mentel, T. F., and Sohn, M.: Gas-phase reaction of N₂O$_5$ with water vapor: Importance of heterogeneous hydrolysis of N₂O$_5$ and surface desorption of HNO₃ in a large teflon chamber, Geophys. Res. Lett., 25(12), 2169–2172, 1998. Wahner, A., Mentel, T. F., Sohn, M., and Stier, J.: Heterogeneous reaction of N₂O$_5$ on sodium nitrate aerosol, J. Geophys. Res., 103(D23), 31103–31112, 1998. Yvon, S. A., Plane, J. M. C., Nien, C.-F., Cooper, D. J. and Saltzman, E. S.: Interaction between nitrogen and sulfur cycles in the polluted marine boundary layer, J. Geophys. Res., 101(D1), 1379–1386, 1996.