Physical and chemical processes of wintertime secondary nitrate aerosol formation

Abstract

The UCD/CIT model was modified to include a process analysis (PA) scheme for gas and particulate matter (PM) to study the formation of secondary nitrate aerosol during a stagnant wintertime air pollution episode during the California Regional PM_2.5/PM₁₀ Air Quality Study (CRPAQS) where detailed measurements of PM components are available at a few sites. Secondary nitrate is formed in the urban areas from near the ground to a few hundred meters above the surface during the day with a maximum modeled net increase rate of 4 μg·m^-3·d^-1 during the study episode. The secondary nitrate formation rate in rural areas is lower due to lower NO₂. In the afternoon hours, near-surface temperature can be high enough to evaporate the particulate nitrate. In the nighttime hours, both the gas phase N₂O₅ reactions with water vapor and the N₂O₅ heterogeneous reactions with particle-bound water are important for secondary nitrate formation. The N₂O₅ reactions are most import near the surface to a few hundred meters above surface with a maximum modeled net secondary nitrate increase rate of 1 μg·m^-3·d^-1 and are more significant in the rural areas where the O₃ concentrations are high at night. In general, vertical transport during the day moves the nitrate formed near the surface to higher elevations. During the stagnant days, process analysis indicates that the nitrate concentration in the upper air builds up and leads to a net downward flux of nitrate through vertical diffusion and a rapid increase of surface nitrate concentration.

Keywords

secondary nitrate aerosol / N₂O₅ heterogeneous reaction / process analysis

References

[1] Herner J D, Aw J, Gao O, Chang D P, Kleeman M J. Size and composition distribution of airborne particulate matter in northern California: I—particulate mass, carbon, and water-soluble ions. Journal of the Air & Waste Management Association, 2005, 55(1): 30-51

[2] Harrison R M, Deacon A R, Jones M R. Sources and processes affecting concentrations of PM₁₀ and PM_2.5 particulate matter in Birmingham (UK). Atmospheric Environment, 1997, 31(24): 4103-4117

[3] Lonati G, Giugliano M, Butelli P, Romele L, Tardivo R. Major chemical components of PM_2.5 in Milan (Italy). Atmospheric Environment, 2005, 39(10): 1925-1934

[4] Celis J E, Morales J R, Zaror C A, Inzunza J C. A study of the particulate matter PM10 composition in the atmosphere of Chillan, Chile. Chemosphere, 2004, 54(4): 541-550

[5] Seinfeld J H, Pandis S N. Atmospheric Chemistry and Physics: From Air Pollution to Climate Change. 2006, New York: Wiley-Interscience

[6] Foley K M, Roselle S J, Appel K W , Bhave P V, Pleim J E, Otte T L, Mathur R, Sarwar G, Young J O, Gilliam R C, Nolte C G, Kelly J T, Gilliland A B, Bash J O. Incremental testing of the Community Multiscale Air Quality (CMAQ) modeling system version 4.7. Geoscientific Model Development, 2010, 3(1): 205-226

[7] Riemer N, Vogel H, Vogel B, Schell B, Ackermann I, Kessler C, Hass H. Impact of the heterogeneous hydrolysis of N₂O₅ on chemistry and nitrate aerosol formation in the lower troposphere under photosmog conditions. Journal of Geophysical Research-Atmospheres, 2003, 108(D4)

[8] Bertram T H, Thornton J A. Toward a general parameterization of N₂O₅ reactivity on aqueous particles: the competing effects of particle liquid water, nitrate and chloride. Atmospheric Chemistry and Physics, 2009, 9(21): 8351-8363

[9] Chang W L, Bhave P V, Brown S S, Riemer N, Stutz J, Dabdub D. Heterogeneous Atmospheric chemistry, ambient measurements, and model calculations of N₂O₅: a review. Aerosol Science and Technology, 2011, 45(6): 655-685

[10] Stutz J, Alicke B, Ackermann R, Geyer A, White A, Williams E. Vertical profiles of NO₃, N₂O₅, O₃, and NO_x in the nocturnal boundary layer: 1. Observations during the Texas air quality study 2000. Journal of Geophysical Research—Atmospheres, 2004, 109(D12)

[11] Jang J C C, Jeffries H E, Tonnesen S. Sensitivity of ozone to model grid resolution-II. Detailed process analysis for ozone chemistry. Atmospheric Environment, 1995, 29(21): 3101-3114

[12] Herner J D, Ying Q, Aw J, Gao O, Chang D P Y, Kleeman M J. Dominant mechanisms that shape the airborne particle size and composition distribution in central California. Aerosol Science and Technology, 2006, 40(10): 827-844

[13] Zhang, Y, Wen X Y, Wang K, Vijayaraghavan K, Jacobson M Z. Probing into regional O-3 and particulate matter pollution in the United States: 2. An examination of formation mechanisms through a process analysis technique and sensitivity study. Journal of Geophysical Research-Atmospheres, 2009, 114

[14] Kleeman M J, Cass G R. A 3D Eulerian source-oriented model for an externally mixed aerosol. Environmental Science & Technology, 2001, 35(24): 4834-4848

[15] Ying Q, Kleeman M J. Source contributions to the regional distribution of secondary particulate matter in California. Atmospheric Environment, 2006, 40(4): 736-752

[16] Ying Q, Lu J, Allen P, Livingstone P, Kaduwela A, Kleeman M J. Modeling air quality during the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS) using the UCD/CIT source-oriented air quality model-Part I. Base case model results. Atmospheric Environment, 2008, 42: 8954-8966

[17] Ghosal S, Hemminger J C. Surface adsorbed water on NaCl and its effect on nitric acid reactivity with NaCl powders. Journal of Physical Chemistry B, 2004, 108(37): 14102-14108

[18] Zhang Y, Liu P, Liu X H , Pun B , Seigneur C , Jacobson M Z , Wang W X. Fine scale modeling of wintertime aerosol mass, number, and size distributions in central California. Journal of Geophysical Research-Atmospheres, 2010, 115

[19] Pun B K, Balmori R T F, Seigneur C. Modeling wintertime particulate matter formation in central California. Atmospheric Environment, 2009, 43(2): 402-409

[20] Livingstone P L, Magliano K, Gürer K, Allen P D, Zhang K M, Ying Q, Jackson B S, Kaduwela A, Kleeman M, Woodhouse L F, Turkiewicz K, Horowitz L W, Scott K, Johnson D, Taylor C,O’Brien G, DaMassa J, Croes B E, Binkowski F, Byun D. Simulating PM concentration during a winter episode in a subtropical valley: Sensitivity simulations and evaluation methods. Atmospheric Environment, 2009, 43(37): 5971-5977

[21] Ying Q, Lu J, Kaduwela A, Kleeman M. Modeling air quality during the California Regional PM₁₀/PM_2.5 Air Quality Study (CPRAQS) using the UCD/CIT Source Oriented Air Quality Model-Part II. Regional source apportionment of primary airborne particulate matter. Atmospheric Environment, 2008, 42(39): 8967-8978

[22] Chen J J, Ying Q, Kleeman M J. Source apportionment of wintertime secondary organic aerosol during the California regional PM₁₀/PM_2.5 air quality study. Atmospheric Environment, 2010, 44(10): 1331-1340

[23] Ying Q, Kleeman M. Regional contributions to airborne particulate matter in central California during a severe pollution episode. Atmospheric Environment, 2009, 43(6): 1218-1228

[24] Goodin W R, McRae G J, Seinfeld J H. Comparison of interpolation methods for sparse data-application to wind and concentration fields. Journal of Applied Meteorology, 1979, 18(6): 761-771

[25] Goodin W R, McRae G J, Seinfeld J H. Objective analysis technique for constructing 3-dimensional urban-scale wind fields . Journal of Applied Meteorology, 1980, 19(1): 98-108

[26] Held T, Ying Q, Kaduwela A, Kleeman M. Modeling particulate matter in the San Joaquin Valley with a source-oriented externally mixed three-dimensional photochemical grid model. Atmospheric Environment, 2004, 38(22): 3689-3711

[27] Judith C, John W, Douglas L, Susanne H. Particulate nitrate measurements duringCRPAQS. 2004, Desert Research Institute, Aerosol Dynamics In: Reno, NV, Berkeley CA.

[28] Ying Q, Lu J, Kleeman M J. Modeling air quality during the California Regional PM10/PM2.5 Air Quality Study (CRPAQS) using the UCD/CIT source oriented air quality model-part III. Regional source apportionment of secondary and total airborne particulate matter. Atmospheric Environment, 2009, 43: 419-430

[29] Evans M J, Jacob D J. Impact of new laboratory studies of N2O5 hydrolysis on global model budgets of tropospheric nitrogen oxides, ozone, and OH. Geophysical Research Letters, 2005, 32(9): L09813

RIGHTS & PERMISSIONS

Higher Education Press and Springer-Verlag Berlin Heidelberg