Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applications
<p>Three-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy is an important method for the identification of the occurrence, chemical composition, and source of atmospheric chromophores. However, current knowledge on the identification and interpretation of fluorescent comp...
| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2023-02-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://acp.copernicus.org/articles/23/2613/2023/acp-23-2613-2023.pdf |
| _version_ | 1828005028733911040 |
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| author | T. Cao T. Cao T. Cao M. Li M. Li M. Li C. Xu C. Xu C. Xu J. Song J. Song J. Song X. Fan J. Li J. Li J. Li W. Jia W. Jia P. Peng P. Peng P. Peng P. Peng |
| author_facet | T. Cao T. Cao T. Cao M. Li M. Li M. Li C. Xu C. Xu C. Xu J. Song J. Song J. Song X. Fan J. Li J. Li J. Li W. Jia W. Jia P. Peng P. Peng P. Peng P. Peng |
| author_sort | T. Cao |
| collection | DOAJ |
| description | <p>Three-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy
is an important method for the identification of the occurrence, chemical
composition, and source of atmospheric chromophores. However, current
knowledge on the identification and interpretation of fluorescent components
is mainly based on aquatic dissolved organic matter and might not be
applicable to atmospheric samples. Therefore, this study comprehensively
investigated EEM data of different types of strong light-absorbing organic
compounds, water-soluble organic matter (WSOM) in different aerosol samples
(combustion source samples and ambient aerosols), soil dust, and purified
fulvic and humic acids supplemented by parallel factor (PARAFAC) modeling.
The results demonstrated that organic compounds with high aromaticity and
strong electron-donating groups generally present strong fluorescence
spectra at longer emission wavelengths, whereas organic compounds
substituted with electron-withdrawing groups have relatively weaker
fluorescence intensity. In particular, aromatic compounds containing nitro
groups (i.e., nitrophenols), which show strong absorption and are the major
component of atmospheric brown carbon, exhibited no significant
fluorescence. The EEM–PARAFAC method identified three fluorescent components (i.e., C1,
C2, and C3) in ambient WSOM. Although EEM–PARAFAC-derived C1 (Ex<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M1" 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="1b4178c77ca0d4bfee6c9ddd864f3a43"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-23-2613-2023-ie00001.svg" width="8pt" height="14pt" src="acp-23-2613-2023-ie00001.png"/></svg:svg></span></span>Em <span class="inline-formula">=</span> 235, <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M3" display="inline" overflow="scroll" dspmath="mathml"><mrow><mn mathvariant="normal">270</mn><mo>/</mo><mn mathvariant="normal">330</mn></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="45pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="4095a45018ee4f06801f0232da2e1364"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-23-2613-2023-ie00002.svg" width="45pt" height="14pt" src="acp-23-2613-2023-ie00002.png"/></svg:svg></span></span> nm) in ambient WSOM is generally considered to be protein-like groups, our
findings suggested that it is mainly composed of aromatic acids, phenolic
compounds, and their derivatives, with only traces of amino acids. C2 is
associated with the atmospheric chemical reaction of biomass burning and/or
biogenic organic molecules, with a relatively lower degree of oxidation, which
are more abundant in Guangzhou WSOM (56 %–69 %). C3, in contrast, is mainly
attributed to highly oxygenated organic molecules derived from soil and
atmospheric aging processes and has a relatively higher contribution in
Chuzhou WSOM (23 %). These findings provide new insights into the analysis
of chemical properties and sources of atmospheric fluorophores using the EEM
method.</p> |
| first_indexed | 2024-04-10T07:24:44Z |
| format | Article |
| id | doaj.art-11ae8089a7c54fe2bc906d269cc71728 |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-04-10T07:24:44Z |
| publishDate | 2023-02-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-11ae8089a7c54fe2bc906d269cc717282023-02-24T07:47:08ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242023-02-01232613262510.5194/acp-23-2613-2023Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applicationsT. Cao0T. Cao1T. Cao2M. Li3M. Li4M. Li5C. Xu6C. Xu7C. Xu8J. Song9J. Song10J. Song11X. Fan12J. Li13J. Li14J. Li15W. Jia16W. Jia17P. Peng18P. Peng19P. Peng20P. Peng21State Key Laboratory of Organic Geochemistry and Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, ChinaCAS Center for Excellence in Deep Earth Science, Guangzhou 510640, ChinaUniversity of Chinese Academy of Sciences, Beijing 100049, ChinaState Key Laboratory of Organic Geochemistry and Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, ChinaCAS Center for Excellence in Deep Earth Science, Guangzhou 510640, ChinaUniversity of Chinese Academy of Sciences, Beijing 100049, ChinaState Key Laboratory of Organic Geochemistry and Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, ChinaCAS Center for Excellence in Deep Earth Science, Guangzhou 510640, ChinaUniversity of Chinese Academy of Sciences, Beijing 100049, ChinaState Key Laboratory of Organic Geochemistry and Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, ChinaCAS Center for Excellence in Deep Earth Science, Guangzhou 510640, ChinaGuangdong–Hong Kong–Macao Joint Laboratory for Environmental Pollution and Control, Guangzhou 510640, ChinaCollege of Resource and Environment, Anhui Science and Technology University, Fengyang 233100, ChinaState Key Laboratory of Organic Geochemistry and Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, ChinaCAS Center for Excellence in Deep Earth Science, Guangzhou 510640, ChinaGuangdong–Hong Kong–Macao Joint Laboratory for Environmental Pollution and Control, Guangzhou 510640, ChinaState Key Laboratory of Organic Geochemistry and Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, ChinaCAS Center for Excellence in Deep Earth Science, Guangzhou 510640, ChinaState Key Laboratory of Organic Geochemistry and Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, ChinaCAS Center for Excellence in Deep Earth Science, Guangzhou 510640, ChinaUniversity of Chinese Academy of Sciences, Beijing 100049, ChinaGuangdong–Hong Kong–Macao Joint Laboratory for Environmental Pollution and Control, Guangzhou 510640, China<p>Three-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy is an important method for the identification of the occurrence, chemical composition, and source of atmospheric chromophores. However, current knowledge on the identification and interpretation of fluorescent components is mainly based on aquatic dissolved organic matter and might not be applicable to atmospheric samples. Therefore, this study comprehensively investigated EEM data of different types of strong light-absorbing organic compounds, water-soluble organic matter (WSOM) in different aerosol samples (combustion source samples and ambient aerosols), soil dust, and purified fulvic and humic acids supplemented by parallel factor (PARAFAC) modeling. The results demonstrated that organic compounds with high aromaticity and strong electron-donating groups generally present strong fluorescence spectra at longer emission wavelengths, whereas organic compounds substituted with electron-withdrawing groups have relatively weaker fluorescence intensity. In particular, aromatic compounds containing nitro groups (i.e., nitrophenols), which show strong absorption and are the major component of atmospheric brown carbon, exhibited no significant fluorescence. The EEM–PARAFAC method identified three fluorescent components (i.e., C1, C2, and C3) in ambient WSOM. Although EEM–PARAFAC-derived C1 (Ex<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M1" 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="1b4178c77ca0d4bfee6c9ddd864f3a43"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-23-2613-2023-ie00001.svg" width="8pt" height="14pt" src="acp-23-2613-2023-ie00001.png"/></svg:svg></span></span>Em <span class="inline-formula">=</span> 235, <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M3" display="inline" overflow="scroll" dspmath="mathml"><mrow><mn mathvariant="normal">270</mn><mo>/</mo><mn mathvariant="normal">330</mn></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="45pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="4095a45018ee4f06801f0232da2e1364"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-23-2613-2023-ie00002.svg" width="45pt" height="14pt" src="acp-23-2613-2023-ie00002.png"/></svg:svg></span></span> nm) in ambient WSOM is generally considered to be protein-like groups, our findings suggested that it is mainly composed of aromatic acids, phenolic compounds, and their derivatives, with only traces of amino acids. C2 is associated with the atmospheric chemical reaction of biomass burning and/or biogenic organic molecules, with a relatively lower degree of oxidation, which are more abundant in Guangzhou WSOM (56 %–69 %). C3, in contrast, is mainly attributed to highly oxygenated organic molecules derived from soil and atmospheric aging processes and has a relatively higher contribution in Chuzhou WSOM (23 %). These findings provide new insights into the analysis of chemical properties and sources of atmospheric fluorophores using the EEM method.</p>https://acp.copernicus.org/articles/23/2613/2023/acp-23-2613-2023.pdf |
| spellingShingle | T. Cao T. Cao T. Cao M. Li M. Li M. Li C. Xu C. Xu C. Xu J. Song J. Song J. Song X. Fan J. Li J. Li J. Li W. Jia W. Jia P. Peng P. Peng P. Peng P. Peng Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applications Atmospheric Chemistry and Physics |
| title | Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applications |
| title_full | Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applications |
| title_fullStr | Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applications |
| title_full_unstemmed | Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applications |
| title_short | Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applications |
| title_sort | technical note chemical composition and source identification of fluorescent components in atmospheric water soluble brown carbon by excitation emission matrix spectroscopy with parallel factor analysis potential limitations and applications |
| url | https://acp.copernicus.org/articles/23/2613/2023/acp-23-2613-2023.pdf |
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