Modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbons
<p>The daytime oxidation of biogenic hydrocarbons is attributed to both OH radicals and O<span class="inline-formula"><sub>3</sub></span>, while nighttime chemistry is dominated by the reaction with O<span class="inline-formula"><sub>3<...
| Main Authors: | , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Copernicus Publications
2023-01-01
|
| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://acp.copernicus.org/articles/23/1209/2023/acp-23-1209-2023.pdf |
| _version_ | 1797944910346715136 |
|---|---|
| author | S. Han M. Jang |
| author_facet | S. Han M. Jang |
| author_sort | S. Han |
| collection | DOAJ |
| description | <p>The daytime oxidation of biogenic hydrocarbons is attributed to both OH radicals and O<span class="inline-formula"><sub>3</sub></span>, while nighttime chemistry is dominated by the reaction with O<span class="inline-formula"><sub>3</sub></span> and NO<span class="inline-formula"><sub>3</sub></span> radicals. Here, daytime and nighttime patterns of
secondary organic aerosol (SOA) originating from biogenic hydrocarbons were
predicted under varying environmental conditions (temperature, humidity,
sunlight intensity, NO<span class="inline-formula"><sub><i>x</i></sub></span> levels, and seed conditions) by using the
UNIfied Partitioning Aerosol phase Reaction (UNIPAR) model, which comprises
multiphase gas–particle partitioning and in-particle chemistry. The products
originating from the atmospheric oxidation of three different hydrocarbons
(isoprene, <span class="inline-formula"><i>α</i></span>-pinene, and <span class="inline-formula"><i>β</i></span>-caryophyllene) were predicted by
using extended semi-explicit mechanisms for four major oxidants (OH,
O<span class="inline-formula"><sub>3</sub></span>, NO<span class="inline-formula"><sub>3</sub></span>, and O(<span class="inline-formula"><sup>3</sup></span>P)) during day and night. The resulting
oxygenated products were then classified into volatility–reactivity-based
lumping species. The stoichiometric coefficients associated with lumping
species were dynamically constructed under varying NO<span class="inline-formula"><sub><i>x</i></sub></span> levels, and they were applied to the UNIPAR SOA model. The predictability of
the model was demonstrated by simulating chamber-generated SOA data under
varying environments. For daytime SOA formation, both isoprene and <span class="inline-formula"><i>α</i></span>-pinene were dominated by the OH-radical-initiated oxidation showing a gradual increase in SOA yields with decreasing NO<span class="inline-formula"><sub><i>x</i></sub></span> levels. The nighttime isoprene SOA formation was processed mainly by the NO<span class="inline-formula"><sub>3</sub></span>-driven oxidation, yielding higher SOA mass than daytime at higher NO<span class="inline-formula"><sub><i>x</i></sub></span> level (isoprene <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M15" display="inline" overflow="scroll" dspmath="mathml"><mo>/</mo></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="8pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="7572a9d7afeaa92ba0e8bb6f686362bd"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-23-1209-2023-ie00001.svg" width="8pt" height="14pt" src="acp-23-1209-2023-ie00001.png"/></svg:svg></span></span> NO<span class="inline-formula"><sub><i>x</i></sub></span> <span class="inline-formula"><</span> 5 ppb C ppb<span class="inline-formula"><sup>−1</sup></span>). At a given amount of ozone, the oxidation to produce the nighttime <span class="inline-formula"><i>α</i></span>-pinene SOA gradually transited from the NO<span class="inline-formula"><sub>3</sub></span>-initiated reaction to ozonolysis as NO<span class="inline-formula"><sub><i>x</i></sub></span> levels decreased. Nighttime <span class="inline-formula"><i>α</i></span>-pinene SOA yields were also significantly higher than daytime SOA yields, although the nighttime <span class="inline-formula"><i>α</i></span>-pinene SOA yields gradually decreased with decreasing NO<span class="inline-formula"><sub><i>x</i></sub></span> levels. <span class="inline-formula"><i>β</i></span>-Caryophyllene, which rapidly produced SOA with high yields, showed a relatively small variation in SOA yields from changes in environmental conditions (i.e., NO<span class="inline-formula"><sub><i>x</i></sub></span> levels, seed conditions, and sunlight intensity), and its SOA formation was mainly attributed to ozonolysis day and night. The daytime SOA formation was generally more sensitive to the aqueous reactions than the nighttime SOA because the daytime chemistry produced more highly oxidized multifunctional products. The simulation of <span class="inline-formula"><i>α</i></span>-pinene SOA in the presence of gasoline fuel, which can compete with <span class="inline-formula"><i>α</i></span>-pinene for the reaction with OH radicals in typical urban air, suggested more growth of <span class="inline-formula"><i>α</i></span>-pinene SOA by the enhanced ozonolysis path. We concluded that the oxidation of the biogenic hydrocarbon with O<span class="inline-formula"><sub>3</sub></span> or NO<span class="inline-formula"><sub>3</sub></span> radicals is a source of the production of a sizable amount of nocturnal SOA, despite the low emission at night.</p> |
| first_indexed | 2024-04-10T20:47:05Z |
| format | Article |
| id | doaj.art-90b25494b58f45ed90e2c7d27c5272eb |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-04-10T20:47:05Z |
| publishDate | 2023-01-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-90b25494b58f45ed90e2c7d27c5272eb2023-01-24T07:28:20ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242023-01-01231209122610.5194/acp-23-1209-2023Modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbonsS. HanM. Jang<p>The daytime oxidation of biogenic hydrocarbons is attributed to both OH radicals and O<span class="inline-formula"><sub>3</sub></span>, while nighttime chemistry is dominated by the reaction with O<span class="inline-formula"><sub>3</sub></span> and NO<span class="inline-formula"><sub>3</sub></span> radicals. Here, daytime and nighttime patterns of secondary organic aerosol (SOA) originating from biogenic hydrocarbons were predicted under varying environmental conditions (temperature, humidity, sunlight intensity, NO<span class="inline-formula"><sub><i>x</i></sub></span> levels, and seed conditions) by using the UNIfied Partitioning Aerosol phase Reaction (UNIPAR) model, which comprises multiphase gas–particle partitioning and in-particle chemistry. The products originating from the atmospheric oxidation of three different hydrocarbons (isoprene, <span class="inline-formula"><i>α</i></span>-pinene, and <span class="inline-formula"><i>β</i></span>-caryophyllene) were predicted by using extended semi-explicit mechanisms for four major oxidants (OH, O<span class="inline-formula"><sub>3</sub></span>, NO<span class="inline-formula"><sub>3</sub></span>, and O(<span class="inline-formula"><sup>3</sup></span>P)) during day and night. The resulting oxygenated products were then classified into volatility–reactivity-based lumping species. The stoichiometric coefficients associated with lumping species were dynamically constructed under varying NO<span class="inline-formula"><sub><i>x</i></sub></span> levels, and they were applied to the UNIPAR SOA model. The predictability of the model was demonstrated by simulating chamber-generated SOA data under varying environments. For daytime SOA formation, both isoprene and <span class="inline-formula"><i>α</i></span>-pinene were dominated by the OH-radical-initiated oxidation showing a gradual increase in SOA yields with decreasing NO<span class="inline-formula"><sub><i>x</i></sub></span> levels. The nighttime isoprene SOA formation was processed mainly by the NO<span class="inline-formula"><sub>3</sub></span>-driven oxidation, yielding higher SOA mass than daytime at higher NO<span class="inline-formula"><sub><i>x</i></sub></span> level (isoprene <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M15" display="inline" overflow="scroll" dspmath="mathml"><mo>/</mo></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="8pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="7572a9d7afeaa92ba0e8bb6f686362bd"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-23-1209-2023-ie00001.svg" width="8pt" height="14pt" src="acp-23-1209-2023-ie00001.png"/></svg:svg></span></span> NO<span class="inline-formula"><sub><i>x</i></sub></span> <span class="inline-formula"><</span> 5 ppb C ppb<span class="inline-formula"><sup>−1</sup></span>). At a given amount of ozone, the oxidation to produce the nighttime <span class="inline-formula"><i>α</i></span>-pinene SOA gradually transited from the NO<span class="inline-formula"><sub>3</sub></span>-initiated reaction to ozonolysis as NO<span class="inline-formula"><sub><i>x</i></sub></span> levels decreased. Nighttime <span class="inline-formula"><i>α</i></span>-pinene SOA yields were also significantly higher than daytime SOA yields, although the nighttime <span class="inline-formula"><i>α</i></span>-pinene SOA yields gradually decreased with decreasing NO<span class="inline-formula"><sub><i>x</i></sub></span> levels. <span class="inline-formula"><i>β</i></span>-Caryophyllene, which rapidly produced SOA with high yields, showed a relatively small variation in SOA yields from changes in environmental conditions (i.e., NO<span class="inline-formula"><sub><i>x</i></sub></span> levels, seed conditions, and sunlight intensity), and its SOA formation was mainly attributed to ozonolysis day and night. The daytime SOA formation was generally more sensitive to the aqueous reactions than the nighttime SOA because the daytime chemistry produced more highly oxidized multifunctional products. The simulation of <span class="inline-formula"><i>α</i></span>-pinene SOA in the presence of gasoline fuel, which can compete with <span class="inline-formula"><i>α</i></span>-pinene for the reaction with OH radicals in typical urban air, suggested more growth of <span class="inline-formula"><i>α</i></span>-pinene SOA by the enhanced ozonolysis path. We concluded that the oxidation of the biogenic hydrocarbon with O<span class="inline-formula"><sub>3</sub></span> or NO<span class="inline-formula"><sub>3</sub></span> radicals is a source of the production of a sizable amount of nocturnal SOA, despite the low emission at night.</p>https://acp.copernicus.org/articles/23/1209/2023/acp-23-1209-2023.pdf |
| spellingShingle | S. Han M. Jang Modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbons Atmospheric Chemistry and Physics |
| title | Modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbons |
| title_full | Modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbons |
| title_fullStr | Modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbons |
| title_full_unstemmed | Modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbons |
| title_short | Modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbons |
| title_sort | modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbons |
| url | https://acp.copernicus.org/articles/23/1209/2023/acp-23-1209-2023.pdf |
| work_keys_str_mv | AT shan modelingdaytimeandnighttimesecondaryorganicaerosolformationviamultiphasereactionsofbiogenichydrocarbons AT mjang modelingdaytimeandnighttimesecondaryorganicaerosolformationviamultiphasereactionsofbiogenichydrocarbons |