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Frontiers of Environmental Science & Engineering

Front Envir Sci Eng Chin    2011, Vol. 5 Issue (3) : 348-361     https://doi.org/10.1007/s11783-011-0343-1
RESEARCH ARTICLE
Physical and chemical processes of wintertime secondary nitrate aerosol formation
Qi YING()
Zachry Department of Civil Engineering, Texas A&M University, College Station, TX 77845-3136, USA
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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 PM2.5/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     
Corresponding Author(s): YING Qi,Email:qying@civil.tamu.edu   
Issue Date: 05 September 2011
 Cite this article:   
Qi YING. Physical and chemical processes of wintertime secondary nitrate aerosol formation[J]. Front Envir Sci Eng Chin, 2011, 5(3): 348-361.
 URL:  
http://journal.hep.com.cn/fese/EN/10.1007/s11783-011-0343-1
http://journal.hep.com.cn/fese/EN/Y2011/V5/I3/348
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Fig.1  Predicted and observed episode-averaged hourly overall PM nitrate incremental change rates for Fresno (a,b) and Angiola (c,d). The whiskers on the figure are standard deviation calculated using all the available data points for that hour
Fig.2  Episode-averaged hourly PM nitrate incremental change due to horizontal transport (H. Transp.), vertical transport (V. Transp.), emission, deposition and secondary nitrate formation (G-to-P+ Hetero.) at (a) Fresno and (b) Angiola
daily contributionFresnoAngiola
increase / (μg·m3·h-1, %)decrease / (μg·m3·h-1, %)increase / (μg·m3·h-1, %)decrease / (μg·m3·h-1, %)
H. Transp.2.369.9-6.7629.64.8026.4-3.7822.1
V. Transp.5.2121.9-11.1048.66.2234.1-10.2960.3
emission3.1613.30.000.00.130.70.000.0
dry deposition0.000.0-4.2218.50.000.0-2.1612.7
G-to-P+ Hetero.13.1055.0-0.763.37.0638.8-0.855.0
overall23.83100.0-22.84100.018.20100.0-17.07100.0
Tab.1  Daily contribution of horizontal transport (H. Transp.), vertical transport (V. Transp.), emission, dry deposition and secondary nitrate formation (g-to-p+ Hetero.) to the surface nitrate concentration at Fresno and Angiola averaged over the entire episode
Fig.3  Episode averaged vertical distribution of O, NO, NO and PM nitrate at Fresno and Angiola for hours 1-5, 6-10, 11-13, 14-16 and 17-24. NO concentration at Fresno is ~5 times higher than that at Angiola and is plotted using different -axis scales. Elevation is in units of km
Fig.4  Episode averaged vertical distribution of the overall hourly nitrate concentration change rate (μg·m·h) and the contribution to the overall rate due to horizontal transport (H. Transp.), vertical transport (V. Transp.) and secondary nitrate formation due to gas-to-particle partitioning and heterogeneous reaction (G-to-P+ Hetero.) at Fresno and Angiola for hours 1-5, 6-10, 11-13, 14-16 and 17-24. Elevation is in units of km
Fig.5  Episode-averaged hourly vertical profiles of overall secondary nitrate formation rates (a,d), nitrate formation due to NO heterogeneous reaction (b,e) and nitrate formation due to gas-to-particle partitioning of HNO (c,f) at Angiola and Fresno. Units are μg·m·h. The scales for panels (a) and (d), and (c) and (f) are different
Fig.6  Averaged daily nitrate concentration change rate due to horizontal transport (H. Transp.), vertical transport (V. Transp.), emission (Emiss.), dry deposition (D. Dep.) and secondary nitrate formation (g-to-p+ Hetero.) processes for the rapid nitrate increase days (December 27th-30th, 2000) and the remaining episode days averaged over the central SJV region. Units are μg·m·h
Fig.7  Averaged daily vertical profiles of wind speed (a), ambient temperature (b), overall nitrate change rate (c), and nitrate change rate due to horizontal transport (d), vertical transport (e) and secondary nitrate formation (f) for the rapid nitrate increase days (December 27th-30th, 2000) and the remaining episode days averaged over the central SJV region. The units for the process rates are μg·m·d
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