Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 6 2009 10.5194/acpd-9-27099-2009 http://www.atmos-chem-phys-discuss.net/9/27099/2009/ http://www.atmos-chem-phys-discuss.net/9/27099/2009/acpd-9-27099-2009.html http://www.atmos-chem-phys-discuss.net/9/27099/2009/acpd-9-27099-2009.pdf 27099 27165 2009-12-16 Nitrogen oxide chemistry in an urban plume: investigation of the chemistry of peroxy and multifunctional organic nitrates with a Lagrangian model I. M. Pérez B. W. LaFranchi R. C. Cohen rccohen@berkeley.edu Dept. of Chemistry, University of California Berkeley, Berkeley, CA, USA Dept. of Earth and Planetary Sciences, University of California Berkeley, Berkeley, CA, USA now at: Air Division, US EPA, Region 9, San Francisco, CA, USA Air quality in the outflow from urban centers affects millions of people, as well as, natural and managed ecosystems downwind. In locations where there are large sources of biogenic VOCs downwind of urban centers, the outflow is characterized by a high VOC reactivity due to biogenic emissions and low NO_x. However most field and chamber studies have focused on limiting cases of high NO_x or of near zero NO_x. Recent measurements of a wide suite of VOCs, O₃ and meteorological parameters at several locations within the Sacramento urban plume have provided a detailed benchmark for testing our understanding of chemistry in a plume transitioning from high NO_x to low NO_x and high VOC reactivity. As an additional simplification, the strong mountain valley circulation in the region makes this urban plume a physical realization of a nearly idealized Lagrangian plume. Here, we describe a model of this plume. We use a Lagrangian model representing chemistry based on the Master Chemical Mechanism (MCM) v3.1 along with mixing and deposition. We discuss the effects of entrainment of background air, the branching ratio for the production of isoprene nitrates and the effects of soil NO_x emissions on the composition of the evolving plume. The model predicts that after 2–3 h of chemical processing only 45% of the peroxynitrates (ΣPNs) are PAN and that most (69%) RONO₂ are secondary alkyl nitrate products of the reaction of OH with RONO₂. We find the model is more consistent with the observations if: a) the yield of ΣPNs from large and multi-functional aldehydes is close to zero; and b) the reaction between OH and RONO₂ produces multifunctional nitrates as opposed to either HNO₃ or NO₂ as is typical in most currently adopted reaction mechanisms. Model results also show that adding NO_x emissions throughout the transect increases the available NO_x in the downwind regions, but modeled ozone concentrations were little affected by the increased NO_x. Atkinson,~R. and Arey,~J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, S197–S219, 2003. Baker,~B., Guenther,~A., Greenberg,~J., Goldstein,~A., and Fall,~R.: Canopy fluxes of 2-methyl-3-buten-2-ol over a ponderosa pine forest by relaxed eddy accumulation: field data and model comparison, J Geophys. Res., 104, 26107–26114, 1999. Bloss,~C., Wagner,~V., Bonzanini,~A., Jenkin,~M E., Wirtz,~K., Martin-Reviejo,~M., and Pilling,~M J.: Evaluation of detailed aromatic mechanisms (MCMv3 and MCMv3.1) against environmental chamber data, Atmos. Chem. Phys., 5, 623–639, 2005a. Bloss,~C., Wagner,~V., Jenkin,~M E., Volkamer,~R., Bloss,~W J., Lee,~J D., Heard,~D E., Wirtz,~K., Martin-Reviejo,~M., Rea,~G., Wenger,~J C., and Pilling,~M J.: Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons, Atmos. Chem. Phys., 5, 641–664, 2005b. Bytnerowicz,~A. and Fenn,~M E.: Nitrogen deposition in California forests: a review, Environ. Pollut., 92, 127–146, 1996. CARB: California Air Resources Board Air Quality Database, http://www.arb.ca.gov/aqd/aqdcd/aqdcd.htm, 2009. Carrasco,~N., Doussin,~J F., Picquet-Varrault,~B., and Carlier,~P.: Tropospheric degradation of 2-hydroxy-2-methylpropanal, a photo-oxidation product of 2-methyl-3-buten-2-ol: kinetic and mechanistic study of its photolysis and its reaction with~\chemOH radicals, Atmos. Environ., 40, 2011–2019, 2006. Carroll,~J J. and Dixon,~A J.: Regional scale transport over complex terrain, a case study: tracing the Sacramento plume in the Sierra Nevada of California, Atmos. Environ., 36, 3745–3758, 2002. Chen,~X., Hulbert,~D., and Shepson,~P.: Measurement of the organic nitrate yield from~\chemOH reaction with isoprene, J Geophys. Res., 103, 25563–25568, 1998. Chuong,~B. and Stevens,~P S.: Measurements of the kinetics of the~\chemOH-initiated oxidation of isoprene, J Geophys. Res., 107, 4162, doi:10.1029/2001JD000865, 2002. Cleary,~P A., Murphy,~J G., Wooldridge,~P J., Day,~D A., Millet,~D B., McKay,~M., Goldstein,~A H., and Cohen,~R C.: Observations of total alkyl nitrates within the Sacramento Urban Plume, Atmos. Chem. Phys. Discuss., 5, 4801–4843, 2005. Cleary,~P A., Wooldridge,~P J., Millet,~D B., McKay,~M., Goldstein,~A H., and Cohen,~R C.: Observations of total peroxy nitrates and aldehydes: measurement interpretation and inference of OH radical concentrations, Atmos. Chem. Phys., 7, 1947–1960, 2007. Day,~D A., Wooldridge,~P J., Dillon,~M B., Thornton,~J A., and Cohen,~R C.: A thermal dissociation laser-induced fluorescence instrument for in situ detection of~\chemNO_2, peroxy nitrates, alkyl nitrates, and~\chemHNO_3, J Geophys. Res., 107, 4046, doi:10.1029/2001JD000779, 2002. Day,~D A., Dillon,~M B., Wooldridge,~P J., Thornton,~J A., Rosen,~R S., Wood,~E C., and Cohen,~R C.: On alkyl nitrates,~\chemO_3, and the \qutmissing~NO_y, J Geophys. Res., 108, 4501, doi:10.1029/2003JD003685, 2003. Day,~D A., Wooldridge,~P J., and Cohen,~R C.: Observations of the effects of temperature on atmospheric~\chemHNO_3, $§igma$ANs, $§igma$PNs, and~\chemNOx: evidence for a temperature-dependent~HO_x source, Atmos. Chem. Phys., 8, 1867–1879, 2008. Day,~D A., Farmer,~D K., Goldstein,~A H., Wooldridge,~P J., Minejima,~C., and Cohen,~R C.: Observations of~NO_x, $§igma$PNs, $§igma$ANs, and~\chemHNO_3 at a Rural Site in the California Sierra Nevada Mountains: summertime diurnal cycles, Atmos. Chem. Phys., 9, 4879–4896, 2009. Dillon,~M., Lamanna,~M., Schade,~G., Goldstein,~A., and Cohen,~R.: Chemical evolution of the Sacramento urban plume: transport and oxidation, J Geophys. Res., 107, 4046, doi:10.1029/2001JD000969, 2002. Dreyfus,~G B., Schade,~G W., and Goldstein,~A H.: Observational constraints on the contribution of isoprene oxidation to ozone production on the western slope of the Sierra Nevada, California, J Geophys. Res., 107, doi:10.1029/2001JD001490, 2002. Farmer,~D K. and Cohen,~R C.: Observations of~\chemHNO_3, $§igma $AN, $§igma $PN and~\chemNO_2 fluxes: evidence for rapid~HO_x chemistry within a pine forest canopy, Atmos. Chem. Phys., 8, 3899–3917, 2008. Haagen-Smit,~A J.: Chemistry and physiology of Los Angeles smog, Ind. Eng. Chem., 44, 1342–1346, 1952. Harley,~R A., Hooper,~D S., Kean,~A J., Kirchstetter,~T W., Hesson,~J M., Balberan,~N T., Stevenson,~E D., and Kendall,~G R.: Effects of reformulated gasoline and motor vehicle fleet turnover on emissions and ambient concentrations of benzene, Environ. Sci. Technol., 40, 5084–5088, 2006. Herman,~D J., Halverson,~L J., and Firestone,~M K.: Nitrogen dynamics in an annual grassland: oak canopy, climate, and microbial population effects, Ecol. Appl., 13, 593–604, 2003. 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, D12S08, doi:10.1029/2006JD007747, 2007. Ito,~A., Sillman,~S., and Penner,~J E.: Global chemical transport model study of ozone response to changes in chemical kinetics and biogenic volatile organic compounds emissions due to increasing temperatures: sensitivities to isoprene nitrate chemistry and grid resolution, J Geophys. Res., 114, D09301, doi:10.1029/2008JD011254, 2009. Kramp,~F. and Volz-Thomas,~A.: On the budget of~\chemOH radicals and ozone in an urban plume from the decay of C-5-C-8 hydrocarbons and~NO_x, J Atmos. Chem., 28, 263–282, 1997. Kurpius,~M., McKay,~M., and Goldstein,~A.: Annual ozone deposition to a Sierra Nevada ponderosa pine plantation, Atmos. Environ., 36, 4503–4515, 2002a. Kurpius,~M R., McKay,~M., and Goldstein,~A H.: Annual ozone deposition to a Sierra Nevada ponderosa pine plantation, Atmos. Environ., 36, 4503–4515, 2002b. 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, 2009. Lamanna,~M. and Goldstein,~A.: In situ measurements of C-2-C-10 volatile organic compounds above a Sierra Nevada ponderosa pine plantation, J Geophys. Res., 104, 21247–21262, 1999. Madronich,~S.: Photodissociation in the Atmosphere .1. Actinic Flux and the Effects of Ground Reflections and Clouds, J Geophys. Res., 92, 9740–9752, 1987. Madronich,~S. and Flocke,~S.: The role of solar radiation in atmospheric chemistry, in: Handbook of Environmental Chemistry, edited by: Boule,~P., Springer-Verlag, Heidelberg, 1998. Magneron,~I., Mellouki,~A., Le Bras,~G., Moortgat,~G K., Horowitz,~A., and Wirtz,~K.: Photolysis and~\chemOH-initiated oxidation of glycolaldehyde under atmospheric conditions, J Phys. Chem A, 109, 4552–4561, 2005. Millet,~D B., Donahue,~N M., Pandis,~S N., Polidori,~A., Stanier,~C O., Turpin,~B J., and Goldstein,~A H.: Atmospheric volatile organic compound measurements during the Pittsburgh air quality study: results, interpretation, and quantification of primary and secondary contributions, J Geophys. Res., 110, D07S07, doi:10.1029/2004JD004601, 2005. 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, 2006a. Murphy,~J G., Day,~D A., Cleary,~P A., Wooldridge,~P J., Millet,~D B., Goldstein,~A H., and Cohen,~R C.: The weekend effect within and downwind of Sacramento: Part 2. Observational evidence for chemical and dynamical contributions, Atmos. Chem. Phys. Discuss., 6, 11971–12019, 2006b. Murphy,~J G., Day,~D A., Cleary,~P A., Wooldridge,~P J., Millet,~D B., Goldstein,~A H., and Cohen,~R C.: The weekend effect within and downwind of Sacramento – Part~1: Observations of ozone, nitrogen oxides, and VOC reactivity, Atmos. Chem. Phys., 7, 5327–5339, 2007. Patchen,~A K., Pennino,~M J., Kiep,~A C., and Elrod,~M J.: Direct kinetics study of the product-forming channels of the reaction of isoprene-derived hydroxyperoxy radicals with~\rm NO, Int J. Chem. Kinetics., 39, 353–361, 2007. Paulot,~F., Crounse,~J D., Kjaergaard,~H G., Kroll,~J H., Seinfeld,~J H., and Wennberg,~P O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates, Atmos. Chem. Phys., 9, 1479–1501, 2009. Perring,~A E., Bertram,~T H., Wooldridge,~P J., Fried,~A., Heikes,~B G., Dibb,~J., Crounse,~J D., Wennberg,~P O., Blake,~N J., Blake,~D R., Brune,~W H., Singh,~H B., and Cohen,~R C.: Airborne observations of total~\chemRONO_2: new constraints on the yield and lifetime of isoprene nitrates, Atmos. Chem. Phys., 9, 1451–1463, 2009. Roberts,~J M., Stroud,~C A., Jobson,~B T., Trainer,~M., Hereid,~D., Williams,~E., Fehsenfeld,~F., Brune,~W., Martinez,~M., and Harder,~H.: Application of a sequential reaction model to PANs and aldehyde measurements in two urban areas, Geophys. Res. Lett., 28, 4583–4586, 2001. Roberts,~J M., Marchewka,~M., Bertman,~S B., Goldan,~P., Kuster,~W., de Gouw,~J., Warneke,~C., Williams,~E., Lerner,~B., Murphy,~P., Apel,~E., and Fehsenfeld,~F C.: Analysis of the isoprene chemistry observed during the New England air quality study (NEAQS) 2002 intensive experiment, J Geophys. Res., 111, doi:10.1029/2006JD007570, 2006. Roberts,~J M., Marchewka,~M., Bertman,~S B., Sommariva,~R., Warneke,~C., de Gouw,~J., Kuster,~W., Goldan,~P., Williams,~E., Lerner,~B M., Murphy,~P. and Fehsenfeld,~F C.: Measurements of PANs during the New England air quality study 2002, J Geophys. Res., 112, doi:10.1029/2007JD008667, 2007. Rosen,~R., Wood,~E., Wooldridge,~P., Thornton,~J., Day,~D., Kuster,~W., Williams,~E., Jobson,~B., and Cohen,~R.: Observations of total alkyl nitrates during Texas Air quality study 2000: implications for O-3 and alkyl nitrate photochemistry, J Geophys. Res., 109, D07303, doi:10.1029/2003JD004227, 2004. Schade,~G W. and Goldstein,~A H.: Fluxes of oxygenated volatile organic compounds from a ponderosa pine plantation, J Geophys. Res., 106, 3111–3123, 2001. Schade,~G W., Dreyfus,~G B., and Goldstein,~A H.: Atmospheric methyl tertiary butyl ether (MTBE) at a rural mountain site in California, J Environ. Qual., 31, 1088–1094, 2002. Snow,~J A., Heikes,~B G., Shen,~H., O'Sullivan,~D W., Fried,~A., and Walega,~J.: Hydrogen peroxide, methyl hydroperoxide, and formaldehyde over North America and the North Atlantic, J Geophys. Res., 112, D12S07, doi:10.1029/2006JD007746, 2007. Spaulding,~R S., Schade,~G W., Goldstein,~A H., and Charles,~M J.: Characterization of secondary atmospheric photooxidation products: evidence for biogenic and anthropogenic sources, J Geophys. Res., 108, doi:10.1029/2002JD002478, 2003. Sprengnether,~M., Demerjian,~K L., Donahue,~N M., and Anderson,~J G.: Product analysis of the~\chemOH oxidation of isoprene and 1,3-butadiene in the presence of~\rm NO, J Geophys. Res., 107, 4268, doi:10.1029/2001JD000716, 2002. Steiner,~A L., Tonse,~S., Cohen,~R C., Goldstein,~A H., and Harley,~R A.: Influence of future climate and emissions on regional air quality in California, J Geophys. Res., 111, D18303, doi:10.1029/2005JD006935, 2006. Stickler,~A., Fischer,~H., Bozem,~H., Gurk,~C., Schiller,~C., Martinez-Harder,~M., Kubistin,~D., Harder,~H., Williams,~J., Eerdekens,~G., Yassaa,~N., Ganzeveld,~L., Sander,~R., and Lelieveld,~J.: Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign, Atmos. Chem. Phys., 7, 3933–3956, 2007. Tarnay,~L., Gertler,~A W., Blank,~R R., and Taylor,~G E.: Preliminary measurements of summer nitric acid and ammonia concentrations in the Lake Tahoe Basin air-shed: implications for dry deposition of atmospheric nitrogen, Environ. Pollut., 113, 145–153, 2001. TC4 Data Archive, http://espoarchive.nasa.gov/archive/arcs/tc4/, 2009. Tuazon,~E C. and Atkinson,~R.: A product study of the gas-phase reaction of isoprene with the~\chemOH radical in the presence of~NO_x, Int J. Chem. Kinet., 22, 1221–1236, 1990. van Ooy,~D J. and Carroll,~J J.: The spatial variation of ozone climatology on the western slope of the Sierra-Nevada, Atmos. Environ., 29, 1319–1330, 1995. 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, 2009. Wooldridge,~P J., Perring,~A E., Bertram,~T H., Flocke,~F M., Roberts,~J M., Singh,~H B., Huey,~L G., J A Thornton, J G Murphy, Fry,~J L., Rollins,~A W., LaFranchi,~B W., and Cohen,~R C.: Total peroxy nitrates ($§igma$PNs) in the atmosphere: the thermal dissociation-laser induced fluorescence (TD-LIF) technique and comparisons to speciated PAN measurements, Atmos. Meas. Tech. Discuss., 2, 3055–3097, 2009. Zaveri,~R A., Berkowitz,~C M., Kleinman,~L I., Springston,~S R., Doskey,~P V., Lonneman,~W A., and Spicer,~C W.: Ozone production efficiency and~NO_x depletion in an urban plume: interpretation of field observations and implications for evaluating~\chemO_3-NO_x-VOC sensitivity, J Geophys. Res., 108, 4436, doi:10.1029/2002JD003144, 2003.