Modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in Beijing, China

Modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in Beijing, China

<p>Comprehensive chlorine heterogeneous chemistry is incorporated into the Community Multiscale Air Quality (CMAQ) model to evaluate the impact of chlorine-related heterogeneous reaction on diurnal and nocturnal nitrate formation and quantify the nitrate formation from gas-to-particle partitio...

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Main Authors: X. Qiu, Q. Ying, S. Wang, L. Duan, J. Zhao, J. Xing, D. Ding, Y. Sun, B. Liu, A. Shi, X. Yan, Q. Xu, J. Hao
Format: Article
Language:English
Published: Copernicus Publications 2019-05-01
Series:Atmospheric Chemistry and Physics
Online Access:https://www.atmos-chem-phys.net/19/6737/2019/acp-19-6737-2019.pdf
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record_format Article
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language English
format Article
sources DOAJ
author X. Qiu
X. Qiu
Q. Ying
S. Wang
S. Wang
L. Duan
L. Duan
J. Zhao
J. Xing
J. Xing
D. Ding
D. Ding
Y. Sun
B. Liu
A. Shi
X. Yan
Q. Xu
Q. Xu
J. Hao
J. Hao
spellingShingle X. Qiu
X. Qiu
Q. Ying
S. Wang
S. Wang
L. Duan
L. Duan
J. Zhao
J. Xing
J. Xing
D. Ding
D. Ding
Y. Sun
B. Liu
A. Shi
X. Yan
Q. Xu
Q. Xu
J. Hao
J. Hao
Modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in Beijing, China
Atmospheric Chemistry and Physics
author_facet X. Qiu
X. Qiu
Q. Ying
S. Wang
S. Wang
L. Duan
L. Duan
J. Zhao
J. Xing
J. Xing
D. Ding
D. Ding
Y. Sun
B. Liu
A. Shi
X. Yan
Q. Xu
Q. Xu
J. Hao
J. Hao
author_sort X. Qiu
title Modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in Beijing, China
title_short Modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in Beijing, China
title_full Modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in Beijing, China
title_fullStr Modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in Beijing, China
title_full_unstemmed Modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in Beijing, China
title_sort modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in beijing, china
publisher Copernicus Publications
series Atmospheric Chemistry and Physics
issn 1680-7316
1680-7324
publishDate 2019-05-01
description <p>Comprehensive chlorine heterogeneous chemistry is incorporated into the Community Multiscale Air Quality (CMAQ) model to evaluate the impact of chlorine-related heterogeneous reaction on diurnal and nocturnal nitrate formation and quantify the nitrate formation from gas-to-particle partitioning of <span class="inline-formula">HNO<sub>3</sub></span> and from different heterogeneous pathways. The results show that these heterogeneous reactions increase the atmospheric <span class="inline-formula">Cl<sub>2</sub></span> and <span class="inline-formula">ClNO<sub>2</sub></span> level (<span class="inline-formula">∼ 100</span>&thinsp;%), which further affects the nitrate formation. Sensitivity analyses of uptake coefficients show that the empirical uptake coefficient for the <span class="inline-formula">O<sub>3</sub></span> heterogeneous reaction with chlorinated particles may lead to the large uncertainties in the predicted <span class="inline-formula">Cl<sub>2</sub></span> and nitrate concentrations. The <span class="inline-formula">N<sub>2</sub>O<sub>5</sub></span> uptake coefficient with particulate <span class="inline-formula">Cl<sup>−</sup></span> concentration dependence performs better in capturing the concentration of <span class="inline-formula">ClNO<sub>2</sub></span> and nocturnal nitrate concentration. The reaction of OH and <span class="inline-formula">NO<sub>2</sub></span> in the daytime increases the nitrate by <span class="inline-formula">∼15</span>&thinsp;% when the heterogeneous chlorine chemistry is incorporated, resulting in more nitrate formation from <span class="inline-formula">HNO<sub>3</sub></span> gas-to-particle partitioning. By contrast, the contribution of the heterogeneous reaction of <span class="inline-formula">N<sub>2</sub>O<sub>5</sub></span> to nitrate concentrations decreases by about 27&thinsp;% in the nighttime, when its reactions with chlorinated particles are considered. However, the generated gas-phase <span class="inline-formula">ClNO<sub>2</sub></span> from the heterogeneous reaction of <span class="inline-formula">N<sub>2</sub>O<sub>5</sub></span> and chlorine-containing particles further reacts with the particle surface to increase the nitrate by 6&thinsp;%. In general, this study highlights the potential of significant underestimation of daytime concentrations and overestimation of nighttime nitrate concentrations for chemical transport models without proper chlorine chemistry in the gas and particle phases.</p>
url https://www.atmos-chem-phys.net/19/6737/2019/acp-19-6737-2019.pdf
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spelling doaj-0f06703676d84eba93099d7a468ad9eb2020-11-25T01:33:43ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242019-05-01196737674710.5194/acp-19-6737-2019Modeling the impact of heterogeneous reactions of chlorine on summertime nitrate formation in Beijing, ChinaX. Qiu0X. Qiu1Q. Ying2S. Wang3S. Wang4L. Duan5L. Duan6J. Zhao7J. Xing8J. Xing9D. Ding10D. Ding11Y. Sun12B. Liu13A. Shi14X. Yan15Q. Xu16Q. Xu17J. Hao18J. Hao19State Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, ChinaState Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, School of Environment, Tsinghua University, Beijing 100084, ChinaZachry Department of Civil Engineering, Texas A&M University, College Station, Texas 77843-3138, USAState Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, ChinaState Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, School of Environment, Tsinghua University, Beijing 100084, ChinaState Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, ChinaState Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, School of Environment, Tsinghua University, Beijing 100084, ChinaState Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, ChinaState Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, ChinaState Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, School of Environment, Tsinghua University, Beijing 100084, ChinaState Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, ChinaState Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, School of Environment, Tsinghua University, Beijing 100084, ChinaState Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, ChinaBeijing Environmental Monitoring Center, Beijing 100048, ChinaBeijing Municipal Research Institute of Environmental Protection, Beijing 100037, ChinaBeijing Municipal Research Institute of Environmental Protection, Beijing 100037, ChinaState Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, ChinaState Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, School of Environment, Tsinghua University, Beijing 100084, ChinaState Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, ChinaState Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, School of Environment, Tsinghua University, Beijing 100084, China<p>Comprehensive chlorine heterogeneous chemistry is incorporated into the Community Multiscale Air Quality (CMAQ) model to evaluate the impact of chlorine-related heterogeneous reaction on diurnal and nocturnal nitrate formation and quantify the nitrate formation from gas-to-particle partitioning of <span class="inline-formula">HNO<sub>3</sub></span> and from different heterogeneous pathways. The results show that these heterogeneous reactions increase the atmospheric <span class="inline-formula">Cl<sub>2</sub></span> and <span class="inline-formula">ClNO<sub>2</sub></span> level (<span class="inline-formula">∼ 100</span>&thinsp;%), which further affects the nitrate formation. Sensitivity analyses of uptake coefficients show that the empirical uptake coefficient for the <span class="inline-formula">O<sub>3</sub></span> heterogeneous reaction with chlorinated particles may lead to the large uncertainties in the predicted <span class="inline-formula">Cl<sub>2</sub></span> and nitrate concentrations. The <span class="inline-formula">N<sub>2</sub>O<sub>5</sub></span> uptake coefficient with particulate <span class="inline-formula">Cl<sup>−</sup></span> concentration dependence performs better in capturing the concentration of <span class="inline-formula">ClNO<sub>2</sub></span> and nocturnal nitrate concentration. The reaction of OH and <span class="inline-formula">NO<sub>2</sub></span> in the daytime increases the nitrate by <span class="inline-formula">∼15</span>&thinsp;% when the heterogeneous chlorine chemistry is incorporated, resulting in more nitrate formation from <span class="inline-formula">HNO<sub>3</sub></span> gas-to-particle partitioning. By contrast, the contribution of the heterogeneous reaction of <span class="inline-formula">N<sub>2</sub>O<sub>5</sub></span> to nitrate concentrations decreases by about 27&thinsp;% in the nighttime, when its reactions with chlorinated particles are considered. However, the generated gas-phase <span class="inline-formula">ClNO<sub>2</sub></span> from the heterogeneous reaction of <span class="inline-formula">N<sub>2</sub>O<sub>5</sub></span> and chlorine-containing particles further reacts with the particle surface to increase the nitrate by 6&thinsp;%. In general, this study highlights the potential of significant underestimation of daytime concentrations and overestimation of nighttime nitrate concentrations for chemical transport models without proper chlorine chemistry in the gas and particle phases.</p>https://www.atmos-chem-phys.net/19/6737/2019/acp-19-6737-2019.pdf

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