Nicolas Brun*, Anil Kumar Mandariya, Junteng Wu, Francesco Battaglia, Jian Xu, Manon Rocco, Laurent Poulain, Mathieu Cazaunau, Antonin Berge, Edouard Pangui, Brice Temime-Roussel, Bénédicte Picquet-Varrault, Jean-Louis Clément, Aline Gratien, Paola Formenti, Liang Wen, Thomas Schaefer, Andreas Tilgner, Hartmut Herrmann, Jean-François Doussin and Anne Monod*,
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The mechanisms remained unresolved due to the lack of organic speciation and the Relative Humidity (RH) did not allow the seed particles to deliquesce. This study presents chemical speciation of the gas and the particle phases during the uptake of gaseous glyoxal on deliquesced AS seed particles (RH ≥ 80 ± 3%) in the CESAM simulation chamber. The chemical speciation of the particles was performed using AMS measurements complemented by a CHARON-PTR-ToF-MS. The influence of H<sub>2</sub>O<sub>2</sub> addition, seed acidity and UV–vis photolysis was explored. Fast reactive uptake of gaseous glyoxal on AS particles was consistently observed in all experiments. The combined measurements from the two mass spectrometers enabled source apportionment analysis through positive matrix factorization of the AMS data and led to the identification and quantification of three dominant processes: (i) glyoxal hydration, (ii) fast dark aging of glyoxal, including the formation of brown carbon and (iii) photochemical aging. The CHARON-PTR-ToF-MS allowed the identification of individual products, such as oxazole and imidazole-2-carboxaldehyde, appearing within minutes during the chamber experiments. A detailed mechanism of glyoxal uptake was proposed, highlighting significant differences in kinetics and dominant reaction pathways compared to the glyoxal reactivity in the bulk aqueous phase.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 6","pages":"1350–1366 1350–1366"},"PeriodicalIF":2.9000,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Online Speciation of Glyoxal Multiphase Reactions on Deliquesced Ammonium Sulfate Particles\",\"authors\":\"Nicolas Brun*, Anil Kumar Mandariya, Junteng Wu, Francesco Battaglia, Jian Xu, Manon Rocco, Laurent Poulain, Mathieu Cazaunau, Antonin Berge, Edouard Pangui, Brice Temime-Roussel, Bénédicte Picquet-Varrault, Jean-Louis Clément, Aline Gratien, Paola Formenti, Liang Wen, Thomas Schaefer, Andreas Tilgner, Hartmut Herrmann, Jean-François Doussin and Anne Monod*, \",\"doi\":\"10.1021/acsearthspacechem.4c0036910.1021/acsearthspacechem.4c00369\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The reaction between glyoxal and ammonia in bulk Ammonium Sulfate (AS) aqueous solutions is known to be slow under acidic conditions, limiting its atmospheric relevance in wet acidic aerosol conditions. However, previous chamber experiments observed the formation of chromophores during the reactive uptake of gaseous glyoxal on ammonium sulfate particles within minutes. The mechanisms remained unresolved due to the lack of organic speciation and the Relative Humidity (RH) did not allow the seed particles to deliquesce. This study presents chemical speciation of the gas and the particle phases during the uptake of gaseous glyoxal on deliquesced AS seed particles (RH ≥ 80 ± 3%) in the CESAM simulation chamber. The chemical speciation of the particles was performed using AMS measurements complemented by a CHARON-PTR-ToF-MS. The influence of H<sub>2</sub>O<sub>2</sub> addition, seed acidity and UV–vis photolysis was explored. Fast reactive uptake of gaseous glyoxal on AS particles was consistently observed in all experiments. The combined measurements from the two mass spectrometers enabled source apportionment analysis through positive matrix factorization of the AMS data and led to the identification and quantification of three dominant processes: (i) glyoxal hydration, (ii) fast dark aging of glyoxal, including the formation of brown carbon and (iii) photochemical aging. The CHARON-PTR-ToF-MS allowed the identification of individual products, such as oxazole and imidazole-2-carboxaldehyde, appearing within minutes during the chamber experiments. A detailed mechanism of glyoxal uptake was proposed, highlighting significant differences in kinetics and dominant reaction pathways compared to the glyoxal reactivity in the bulk aqueous phase.</p>\",\"PeriodicalId\":15,\"journal\":{\"name\":\"ACS Earth and Space Chemistry\",\"volume\":\"9 6\",\"pages\":\"1350–1366 1350–1366\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-05-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Earth and Space Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsearthspacechem.4c00369\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Earth and Space Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsearthspacechem.4c00369","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Online Speciation of Glyoxal Multiphase Reactions on Deliquesced Ammonium Sulfate Particles
The reaction between glyoxal and ammonia in bulk Ammonium Sulfate (AS) aqueous solutions is known to be slow under acidic conditions, limiting its atmospheric relevance in wet acidic aerosol conditions. However, previous chamber experiments observed the formation of chromophores during the reactive uptake of gaseous glyoxal on ammonium sulfate particles within minutes. The mechanisms remained unresolved due to the lack of organic speciation and the Relative Humidity (RH) did not allow the seed particles to deliquesce. This study presents chemical speciation of the gas and the particle phases during the uptake of gaseous glyoxal on deliquesced AS seed particles (RH ≥ 80 ± 3%) in the CESAM simulation chamber. The chemical speciation of the particles was performed using AMS measurements complemented by a CHARON-PTR-ToF-MS. The influence of H2O2 addition, seed acidity and UV–vis photolysis was explored. Fast reactive uptake of gaseous glyoxal on AS particles was consistently observed in all experiments. The combined measurements from the two mass spectrometers enabled source apportionment analysis through positive matrix factorization of the AMS data and led to the identification and quantification of three dominant processes: (i) glyoxal hydration, (ii) fast dark aging of glyoxal, including the formation of brown carbon and (iii) photochemical aging. The CHARON-PTR-ToF-MS allowed the identification of individual products, such as oxazole and imidazole-2-carboxaldehyde, appearing within minutes during the chamber experiments. A detailed mechanism of glyoxal uptake was proposed, highlighting significant differences in kinetics and dominant reaction pathways compared to the glyoxal reactivity in the bulk aqueous phase.
期刊介绍:
The scope of ACS Earth and Space Chemistry includes the application of analytical, experimental and theoretical chemistry to investigate research questions relevant to the Earth and Space. The journal encompasses the highly interdisciplinary nature of research in this area, while emphasizing chemistry and chemical research tools as the unifying theme. The journal publishes broadly in the domains of high- and low-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. ACS Earth and Space Chemistry publishes Articles, Letters, Reviews, and Features to provide flexible formats to readily communicate all aspects of research in these fields.