Comment on acp-2021-531 Article Swipe
YOU?
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· 2021
· Open Access
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· DOI: https://doi.org/10.5194/acp-2021-531-rc2
· OA: W4207016939
<strong class="journal-contentHeaderColor">Abstract.</strong> In the summer of 2018, a comprehensive field campaign, with measurements on HONO and related parameters, was conducted at the foot (150 m a.s.l.) and the summit of Mt. Tai (1534 m a.s.l.) in the central North China Plain (NCP). With the implementation of a 0-D box model, the HONO budget with six additional sources and its role in radical chemistry at the foot station were explored. We found that the model default source, NO <span class="inline-formula">+</span> OH, could only reproduce 13 % of the observed HONO, leading to a strong unknown source strength of up to 3 ppbv h<span class="inline-formula"><sup>−1</sup></span>. Among the additional sources, the NO<span class="inline-formula"><sub>2</sub></span> uptake on the ground surface dominated (<span class="inline-formula">∼</span> 70 %) nighttime HONO formation, and its photo-enhanced reaction dominated (<span class="inline-formula">∼</span> 80 %) daytime HONO formation. Their contributions were sensitive to the mixing layer height (MLH) used for the parameterizations, highlighting the importance of a reasonable MLH for exploring ground-level HONO formation in 0-D models and the necessity of gradient measurements. A <span class="inline-formula">Δ</span>HONO<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M10" display="inline" overflow="scroll" dspmath="mathml"><mrow><mo>/</mo><mi mathvariant="normal">Δ</mi></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="16pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="70487647a1f237ca782af0f088ac6be0"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-22-1035-2022-ie00001.svg" width="16pt" height="14pt" src="acp-22-1035-2022-ie00001.png"/></svg:svg></span></span>NO<span class="inline-formula"><sub><i>x</i></sub></span> ratio of 0.7 % for direct emissions from vehicle exhaust was inferred, and a new method to quantify its contribution to the observations was proposed and discussed. Aerosol-derived sources, including the NO<span class="inline-formula"><sub>2</sub></span> uptake on the aerosol surface and the particulate nitrate photolysis, did not lead to significant HONO formation, with their contributions lower than NO <span class="inline-formula">+</span> OH. <span id="page1036"/>HONO photolysis in the early morning initialized the daytime photochemistry at the foot station. It was also a substantial radical source throughout the daytime, with contributions higher than O<span class="inline-formula"><sub>3</sub></span> photolysis to OH initiation. Moreover, we found that OH dominated the atmospheric oxidizing capacity in the daytime, while modeled NO<span class="inline-formula"><sub>3</sub></span> appeared to be significant at night. Peaks of modeled NO<span class="inline-formula"><sub>3</sub></span> time series and average diurnal variation reached 22 and 9 pptv, respectively. NO<span class="inline-formula"><sub>3</sub></span>-induced reactions contribute 18 % of nitrate formation potential (<span class="inline-formula"><i>P</i></span>(HNO<span class="inline-formula"><sub>3</sub></span>)) and 11 % of the isoprene (C<span class="inline-formula"><sub>5</sub></span>H<span class="inline-formula"><sub>8</sub></span>) oxidation throughout the whole day. At night, NO<span class="inline-formula"><sub>3</sub></span> chemistry led to 51 % and 44 % of <span class="inline-formula"><i>P</i></span>(HNO<span class="inline-formula"><sub>3</sub></span>) or the C<span class="inline-formula"><sub>5</sub></span>H<span class="inline-formula"><sub>8</sub></span> oxidation, respectively, implying that NO<span class="inline-formula"><sub>3</sub></span> chemistry could significantly affect nighttime secondary organic and inorganic aerosol formation in this high-O<span class="inline-formula"><sub>3</sub></span> region. Considering the severe O<span class="inline-formula"><sub>3</sub></span> pollution in the NCP and the very limited NO<span class="inline-formula"><sub>3</sub></span> measurements, we suggest that besides direct measurements of HO<span class="inline-formula"><sub><i>x</i></sub></span> and primary HO<span class="inline-formula"><sub><i>x</i></sub></span> precursors (O<span class="inline-formula"><sub>3</sub></span>, HONO, alkenes, etc.), NO<span class="inline-formula"><sub>3</sub></span> measurements should be conducted to understand the atmospheric oxidizing capacity and air pollution formation in this and similar regions.