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However, the transformation pathways of BrC chromophores, especially in the presence of photochemically active species, such as nitrate, are not well understood. In this study, the nitrate-mediated aqueous-phase photooxidation of three typical BrC chromophores from biomass burning was investigated, including 4-nitrocatechol, 3-nitrosalicylic acid, and 3,4-dinitrophenol. Variations in nitrate concentrations, pH, and temperatures were systematically examined to assess their impacts on the apparent photolysis rates of these BrC chromophores. The results show that increasing nitrate concentrations significantly enhances apparent photolysis rates to 3\u20133.5 times compared to nitrate-free conditions. Also, a temperature rise from 0 to 30 \u00b0C increases apparent photolysis rates by a factor of 1.3\u20132.5 for these chromophores. However, the effect of pH varies among these chromophores, depending on the substituents and their positions on the benzene ring. High-resolution mass spectrometric analysis suggests that the photooxidation of these chromophores initiates with the addition of nitro and\/or hydroxyl groups to the benzene ring, followed by a ring-opening reaction and the formation of smaller, highly oxygenated molecules including formic acid, glyoxylic acid, malonic acid, and nitropropanoic acid. This study highlights the key role of nitrate in the aqueous-phase photooxidation of BrC, altering the aging pathways and shortening the atmospheric lifetimes of BrC. These results are of particular importance for a better understanding of BrC aging and its radiative forcing, given the increase of the nitrate mass fraction in aerosols of China in recent years.<\/jats:p>","DOI":"10.1021\/acs.est.4c06123","type":"journal-article","created":{"date-parts":[[2024,12,27]],"date-time":"2024-12-27T12:08:05Z","timestamp":1735301285000},"page":"640-649","source":"Crossref","is-referenced-by-count":12,"title":["Nitrate-Photolysis\nShortens the Lifetimes of Brown\nCarbon Tracers from Biomass Burning"],"prefix":"10.1021","volume":"59","author":[{"given":"Yi","family":"Liu","sequence":"first","affiliation":[{"name":"Institute of Earth Environment, Chinese Academy of Sciences , , ,","place":["Xi\u2019an, China, 710061"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4907-9616","authenticated-orcid":true,"given":"Ru-Jin","family":"Huang","sequence":"additional","affiliation":[{"name":"Institute of Earth Environment, Chinese Academy of Sciences , , ,","place":["Xi\u2019an, China, 710061"]},{"name":"Xi\u2019an Jiaotong University , , ,","place":["Xi\u2019an, China, 710049"]},{"name":"University of Chinese Academy of Sciences , ,","place":["Beijing, China, 100049"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3175-6778","authenticated-orcid":true,"given":"Chunshui","family":"Lin","sequence":"additional","affiliation":[{"name":"Institute of Earth Environment, Chinese Academy of Sciences , , ,","place":["Xi\u2019an, China, 710061"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wei","family":"Yuan","sequence":"additional","affiliation":[{"name":"Institute of Earth Environment, Chinese Academy of Sciences , , ,","place":["Xi\u2019an, China, 710061"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7631-9136","authenticated-orcid":true,"given":"Yong Jie","family":"Li","sequence":"additional","affiliation":[{"name":"University of Macau , , , ,","place":["Taipa, Macau SAR, China, 999078"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9588-7019","authenticated-orcid":true,"given":"Haobin","family":"Zhong","sequence":"additional","affiliation":[{"name":"Jiaxing Nanhu University , , ,","place":["Jiaxing, China, 314001"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lu","family":"Yang","sequence":"additional","affiliation":[{"name":"Institute of Earth Environment, Chinese Academy of Sciences , , ,","place":["Xi\u2019an, China, 710061"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ting","family":"Wang","sequence":"additional","affiliation":[{"name":"Institute of Earth Environment, Chinese Academy of Sciences , , ,","place":["Xi\u2019an, China, 710061"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wei","family":"Huang","sequence":"additional","affiliation":[{"name":"Institute of Earth Environment, Chinese Academy of Sciences , , ,","place":["Xi\u2019an, China, 710061"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9590-1906","authenticated-orcid":true,"given":"Wei","family":"Xu","sequence":"additional","affiliation":[{"name":"Institute of Urban Environment, Chinese Academy of Sciences , , ,","place":["Xiamen, China, 361021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2878-7469","authenticated-orcid":true,"given":"Dan Dan","family":"Huang","sequence":"additional","affiliation":[{"name":"Shanghai Academy of Environment Sciences , , ,","place":["Shanghai, China, 200233"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9518-3628","authenticated-orcid":true,"given":"Cheng","family":"Huang","sequence":"additional","affiliation":[{"name":"Shanghai Environmental Monitoring Center , , ,","place":["Shanghai, China, 200030"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2024,12,27]]},"reference":[{"issue":"10","key":"2026081212015501400_cit1","doi-asserted-by":"publisher","first-page":"4335","DOI":"10.1021\/cr5006167","article-title":"Chemistry of atmospheric brown carbon","volume":"115","author":"Laskin","year":"2015","journal-title":"Chem. 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Pollut."},{"issue":"21","key":"2026081212015501400_cit14","doi-asserted-by":"publisher","first-page":"11815","DOI":"10.1021\/acs.est.6b03024","article-title":"Molecular Characterization of Brown\nCarbon in Biomass Burning Aerosol Particles","volume":"50","author":"Lin","year":"2016","journal-title":"Environ. Sci. Technol."},{"key":"2026081212015501400_cit15","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2021.147418","article-title":"Links between the optical\nproperties and chemical compositions of brown carbon chromophores\nin different environments: Contributions and formation of functionalized\naromatic compounds","volume":"786","author":"Li","year":"2021","journal-title":"Sci. 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Total Environ."},{"issue":"11","key":"2026081212015501400_cit22","doi-asserted-by":"publisher","first-page":"7649","DOI":"10.5194\/acp-19-7649-2019","article-title":"The formation of nitro-aromatic compounds under high NOx and anthropogenic VOC conditions in urban Beijing, China","volume":"19","author":"Wang","year":"2019","journal-title":"Atmos. Chem. 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Res.: Atmos."},{"issue":"11","key":"2026081212015501400_cit29","doi-asserted-by":"publisher","first-page":"6933","DOI":"10.1021\/acs.est.1c04596","article-title":"Secondary Formation and Impacts of Gaseous Nitro-Phenolic Compounds\nin the Continental Outflow Observed at a Background Site in South\nChina","volume":"56","author":"Chen","year":"2022","journal-title":"Environ. Sci. Technol."},{"key":"2026081212015501400_cit30","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2023.161810","article-title":"Photolysis\nfrequency of nitrophenols derived from ambient measurements","volume":"869","author":"Peng","year":"2023","journal-title":"Sci. Total Environ."},{"issue":"4","key":"2026081212015501400_cit31","doi-asserted-by":"publisher","first-page":"1115","DOI":"10.1021\/acsearthspacechem.2c00021","article-title":"Decay Kinetics\nand Absorption Changes of Methoxyphenols and nitrophenols during Nitrate-Mediated\nAqueous Photochemical Oxidation at 254 and 313 nm","volume":"6","author":"Wang","year":"2022","journal-title":"ACS Earth Space Chem."},{"issue":"7","key":"2026081212015501400_cit32","doi-asserted-by":"publisher","first-page":"4030","DOI":"10.1021\/es500001q","article-title":"Arsenite oxidation\ninitiated by the UV photolysis of nitrite and nitrate","volume":"48","author":"Kim","year":"2014","journal-title":"Environ. Sci. 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Eng."},{"issue":"2","key":"2026081212015501400_cit35","doi-asserted-by":"publisher","first-page":"423","DOI":"10.3390\/molecules25020423","article-title":"Photochemistry of the\nCloud Aqueous Phase: A Review","volume":"25","author":"Bianco","year":"2020","journal-title":"Molecules"},{"issue":"45","key":"2026081212015501400_cit36","doi-asserted-by":"publisher","first-page":"9594","DOI":"10.1021\/jp0349132","article-title":"Quantum yields\nof hydroxyl radical and nitrogen dioxide\nfrom the photolysis of nitrate on ice","volume":"107","author":"Chu","year":"2003","journal-title":"J. Phys.\nChem. A"},{"key":"2026081212015501400_cit37","doi-asserted-by":"publisher","DOI":"10.1016\/j.atmosenv.2021.118401","article-title":"Formation\nand evolution of brown carbon during aqueous-phase nitrate-mediated\nphotooxidation of guaiacol and 5-nitroguaiacol","volume":"254","author":"Yang","year":"2021","journal-title":"Atmos. Environ."},{"issue":"14","key":"2026081212015501400_cit38","doi-asserted-by":"publisher","first-page":"9571","DOI":"10.5194\/acp-22-9571-2022","article-title":"A comprehensive study\nabout the in-cloud processing of nitrate through coupled measurements\nof individual cloud residuals and cloud water","volume":"22","author":"Zhang","year":"2022","journal-title":"Atmos. Chem. Phys."},{"issue":"15","key":"2026081212015501400_cit39","doi-asserted-by":"publisher","first-page":"10319","DOI":"10.5194\/acp-19-10319-2019","article-title":"Distinctions in source\nregions and formation mechanisms of secondary aerosol in Beijing from\nsummer to winter","volume":"19","author":"Duan","year":"2019","journal-title":"Atmos. Chem. Phys."},{"key":"2026081212015501400_cit40","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2022.154664","article-title":"Decade-long\ntrends in chemical component properties of PM2.5 in Beijing,\nChina (2011\u20132020)","volume":"832","author":"Wang","year":"2022","journal-title":"Kitanovski"},{"key":"2026081212015501400_cit41","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2023.165303","article-title":"Reduced atmospheric\nsulfate enhances fine particulate nitrate formation in eastern China","volume":"898","author":"Wen","year":"2023","journal-title":"Sci. Total Environ."},{"issue":"8","key":"2026081212015501400_cit42","doi-asserted-by":"publisher","first-page":"4387","DOI":"10.1021\/acs.est.6b06370","article-title":"Quantum Yield\nof Nitrite from the\nPhotolysis of Aqueous Nitrate above 300 nm","volume":"51","author":"Benedict","year":"2017","journal-title":"Environ. Sci. Technol."},{"issue":"16","key":"2026081212015501400_cit43","doi-asserted-by":"publisher","first-page":"9215","DOI":"10.1021\/acs.est.8b03441","article-title":"Formation and Evolution\nof aqSOA from Aqueous-Phase Reactions of Phenolic Carbonyls: Comparison\nbetween Ammonium Sulfate and Ammonium Nitrate Solutions","volume":"52","author":"Huang","year":"2018","journal-title":"Environ. Sci. Technol."},{"issue":"15","key":"2026081212015501400_cit44","doi-asserted-by":"publisher","first-page":"8757","DOI":"10.1021\/acs.est.9b01623","article-title":"Heterogeneous\nOxidation of SO2 in Sulfate Production during Nitrate Photolysis\nat 300 nm: Effect of pH, Relative Humidity, Irradiation Intensity,\nand the Presence of Organic Compounds","volume":"53","author":"Gen","year":"2019","journal-title":"Environ.\nSci. Technol."},{"issue":"2","key":"2026081212015501400_cit45","doi-asserted-by":"publisher","first-page":"86","DOI":"10.1021\/acs.estlett.8b00681","article-title":"Heterogeneous\nSO2 Oxidation in Sulfate Formation by Photolysis of Particulate\nNitrate","volume":"6","author":"Gen","year":"2019","journal-title":"Environ. Sci. Technol. Lett."},{"issue":"51","key":"2026081212015501400_cit46","doi-asserted-by":"publisher","first-page":"21570","DOI":"10.1021\/acs.est.3c04983","article-title":"Nitroaromatic\nCompounds from Secondary Nitrate Formation and Biomass Burning Are\nMajor Proinflammatory Components in Organic Aerosols in Guangzhou:\nA Bioassay Combining High-Resolution Mass Spectrometry Analysis","volume":"57","author":"Zhang","year":"2023","journal-title":"Environ. Sci. Technol."},{"issue":"1","key":"2026081212015501400_cit47","doi-asserted-by":"publisher","first-page":"273","DOI":"10.5194\/acp-22-273-2022","article-title":"Aqueous secondary\norganic aerosol formation from the direct photosensitized oxidation\nof vanillin in the absence and presence of ammonium nitrate","volume":"22","author":"Mabato","year":"2022","journal-title":"Atmos. Chem. 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