Real-Time Detection of Gas-Phase Organohalogens from Aqueous Photochemistry Using Orbitrap Mass Spectrometry

SSCI-VIDE+CARE+MRT:CEM:SPR:CGOInternational audienceMarine short-lived halogenated compounds, emitted from algae, phytoplankton, and other marine biota, significantly affect both the troposphere and the stratosphere. Here, we show that such compounds might also be photochemically produced through photosensitized reactions in surface water. Gas-phase products were detected and identified by high-resolution mass spectrometry, more particularly by means of an atmospheric pressure chemical ionization source coupled to an Orbitrap mass spectrometer. Under simulated solar irradiation, halogenated organic compounds were produced and detected in the gas phase when a proxy of dissolved organic matter, i.e., 4-benzoylbenzoic acid, was excited into its triplet state. We present a mechanism explaining the formation of a variety of such halogenated compounds. These photochemical reactions take place at the air/sea interface and are, therefore, a potential source of short-lived halogenated compounds in the atmosphere, participating in the tropospheric halogen cycle

Seawater analysis by ambient mass-spectrometry-based seaomics

An analytical method coupled to multivariate statistical analysis was developed based on transmissionmode direct analysis in real-time quadrupole time-of-flight mass spectrometry (TM-DART-QTOF-MS) to interrogate lipophilic compounds in seawater samples without the need for desalinization. An untargeted metabolomics approach is addressed here as seaomics and was successfully implemented to discriminate the sea surface microlayer (SML) from the underlying water (ULW) samples (n D 22, 10 paired samples) collected during a field campaign at the Cabo Verde islands during September-October 2017. A panel of 11 ionic species detected in all samples allowed sample class discrimination by means of supervised multivariate statistical models. Tentative identification of the species enriched in the SML samples suggests that fatty alcohols, halogenated compounds, and oxygenated boron-containing organic compounds are available at the surface for air-water transfer processes. A subset of SML samples (n D 5) were subjected to on-site experiments during the campaign by using a lab-tofield approach to test their secondary organic aerosol (SOA) formation potency. The results from these experiments and the analytical seaomics strategy provide a proof of a concept that can be used for an approach to identifying organic molecules involved in aerosol formation processes at the air- water interface.Fil: Zabalegui, Nicolás. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; ArgentinaFil: Manzi, Malena. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; ArgentinaFil: Depoorter, Antoine. Universite Lyon 2; FranciaFil: Hayeck, Nathalie. Universite Lyon 2; FranciaFil: Roveretto, Marie. Leibniz Institute for Tropospheric Research ; AlemaniaFil: Li, Chunlin. Leibniz Institute for Tropospheric Research ; AlemaniaFil: Van Pinxteren, Manuela. Leibniz Institute for Tropospheric Research ; AlemaniaFil: Herrmann, Hartmut. Leibniz Institute for Tropospheric Research ; AlemaniaFil: George, Christian. Universite Lyon 2; FranciaFil: Monge, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; Argentin

Marine organic matter in the remote environment of the Cape Verde islands-an introduction and overview to the MarParCloud campaign

The project MarParCloud (Marine biological production, organic aerosol Particles and marine Clouds: a process chain) aims to improve our understanding of the genesis, modification and impact of marine organic matter (OM) from its biological production, to its export to marine aerosol particles and, finally, to its ability to act as ice-nucleating particles (INPs) and cloud condensation nuclei (CCN). A field campaign at the Cape Verde Atmospheric Observatory (CVAO) in the tropics in September-October 2017 formed the core of this project that was jointly performed with the project MARSU (MARine atmospheric Science Unravelled). A suite of chemical, physical, biological and meteorological techniques was applied, and comprehensive measurements of bulk water, the sea surface microlayer (SML), cloud water and ambient aerosol particles collected at a ground-based and a mountain station took place. Key variables comprised the chemical characterization of the atmospherically relevant OM components in the ocean and the atmosphere as well as measurements of INPs and CCN. Moreover, bacterial cell counts, mercury species and trace gases were analyzed. To interpret the results, the measurements were accompanied by various auxiliary parameters such as air mass back-trajectory analysis, vertical atmospheric profile analysis, cloud observations and pigment measurements in seawater. Additional modeling studies supported the experimental analysis. During the campaign, the CVAO exhibited marine air masses with low and partly moderate dust influences. The marine boundary layer was well mixed as indicated by an almost uniform particle number size distribution within the boundary layer. Lipid biomarkers were present in the aerosol particles in typical concentrations of marine background conditions. Accumulation-and coarse-mode particles served as CCN and were efficiently transferred to the cloud water. The ascent of ocean-derived compounds, such as sea salt and sugar-like compounds, to the cloud level, as derived from chemical analysis and atmospheric transfer modeling results, denotes an influence of marine emissions on cloud formation. Organic nitrogen compounds (free amino acids) were enriched by several orders of magnitude in submicron aerosol particles and in cloud water compared to seawater. However, INP measurements also indicated a significant contribution of other non-marine sources to the local INP concentration, as (biologically active) INPs were mainly present in supermicron aerosol particles that are not suggested to undergo strong enrichment during ocean-atmosphere transfer. In addition, the number of CCN at the supersaturation of 0.30 % was about 2.5 times higher during dust periods compared to marine periods. Lipids, sugar-like compounds, UV-absorbing (UV: ultraviolet) humic-like substances and low-molecularweight neutral components were important organic compounds in the seawater, and highly surface-active lipids were enriched within the SML. The selective enrichment of specific organic compounds in the SML needs to be studied in further detail and implemented in an OM source function for emission modeling to better understand transfer patterns, the mechanisms of marine OM transformation in the atmosphere and the role of additional sources. In summary, when looking at particulate mass, we see oceanic compounds transferred to the atmospheric aerosol and to the cloud level, while from a perspective of particle number concentrations, sea spray aerosol (i.e., primary marine aerosol) contributions to both CCN and INPs are rather limited. © Author(s) 2020

Marine organic matter in the remote environment of the Cape Verde islands – an introduction and overview to the MarParCloud campaign

The project MarParCloud (Marine biological production, organic aerosol Particles and marine Clouds: a process chain) aims to improve our understanding of the genesis, modification and impact of marine organic matter (OM) from its biological production, to its export to marine aerosol particles and, finally, to its ability to act as ice-nucleating particles (INPs) and cloud condensation nuclei (CCN). A field campaign at the Cape Verde Atmospheric Observatory (CVAO) in the tropics in September–October 2017 formed the core of this project that was jointly performed with the project MARSU (MARine atmospheric Science Unravelled). A suite of chemical, physical, biological and meteorological techniques was applied, and comprehensive measurements of bulk water, the sea surface microlayer (SML), cloud water and ambient aerosol particles collected at a ground-based and a mountain station took place. Key variables comprised the chemical characterization of the atmospherically relevant OM components in the ocean and the atmosphere as well as measurements of INPs and CCN. Moreover, bacterial cell counts, mercury species and trace gases were analyzed. To interpret the results, the measurements were accompanied by various auxiliary parameters such as air mass back-trajectory analysis, vertical atmospheric profile analysis, cloud observations and pigment measurements in seawater. Additional modeling studies supported the experimental analysis. During the campaign, the CVAO exhibited marine air masses with low and partly moderate dust influences. The marine boundary layer was well mixed as indicated by an almost uniform particle number size distribution within the boundary layer. Lipid biomarkers were present in the aerosol particles in typical concentrations of marine background conditions. Accumulation- and coarse-mode particles served as CCN and were efficiently transferred to the cloud water. The ascent of ocean-derived compounds, such as sea salt and sugar-like compounds, to the cloud level, as derived from chemical analysis and atmospheric transfer modeling results, denotes an influence of marine emissions on cloud formation. Organic nitrogen compounds (free amino acids) were enriched by several orders of magnitude in submicron aerosol particles and in cloud water compared to seawater. However, INP measurements also indicated a significant contribution of other non-marine sources to the local INP concentration, as (biologically active) INPs were mainly present in supermicron aerosol particles that are not suggested to undergo strong enrichment during ocean–atmosphere transfer. In addition, the number of CCN at the supersaturation of 0.30 % was about 2.5 times higher during dust periods compared to marine periods. Lipids, sugar-like compounds, UV-absorbing (UV: ultraviolet) humic-like substances and low-molecular-weight neutral components were important organic compounds in the seawater, and highly surface-active lipids were enriched within the SML. The selective enrichment of specific organic compounds in the SML needs to be studied in further detail and implemented in an OM source function for emission modeling to better understand transfer patterns, the mechanisms of marine OM transformation in the atmosphere and the role of additional sources. In summary, when looking at particulate mass, we see oceanic compounds transferred to the atmospheric aerosol and to the cloud level, while from a perspective of particle number concentrations, sea spray aerosol (i.e., primary marine aerosol) contributions to both CCN and INPs are rather limited

Formation et vieillissement des aérosols : impact de la photochimie hétérogène

Interfaces are ubiquitous in the environment, and in addition many key atmospheric processes, such as gas deposition, aerosol and cloud formation are, at one stage or the other, strongly affected by physical and chemical processes occurring at interfaces. Unfortunately, these heterogeneous reactions are not fully understood to date and limit our ability to simulate and quantify the impact of aerosols due to large uncertainties in their formation and their evolution in the troposphere. This thesis aims to improve our knowledge about photochemical reactions at the air/liquid interfaces, which could be crucial for the assessment of their atmospheric impacts. Firstly, the reactivity of stearic acid at the air/water interface under irradiation was studied in different matrices thanks to a very sensitive tool, the Langmuir trough. We observed that monolayers of stearic acid undergo degradation under irradiation, even in the absence of photosensitizers. Experiments with monolayers in different surface states indicate that surface pressure influences this reactivity. APCI-Orbitrap coupling was used to detect and identify halogenated compounds produced from an irradiated solution containing a photosensitizer, 4-benzoylbenzoic acid. The effects of octanol as a surfactant and citric acid as a proton donor on these photosensitized reactions were also examined. In addition, the formation of secondary aerosols and their aging in the marine environment (at Cape-Verde) were studied in different conditions. The experiments clearly demonstrate the existence of photosensitized processes at the air/sea interface as a source of marine secondary aerosols. Finally, work on the photochemistry of organic matter from phytoplanktons gave information on their reactivity in the liquid phase. Overall, the results obtained during this thesis show that the photochemistry studied here can have a significant impact on the superficial microlayer of the oceans and, by extension, on marine aerosolsLes interfaces sont omniprésentes dans l'environnement et, de plus, de nombreux processus atmosphériques clés, comme les dépôts de gaz, la formation d'aérosol et de nuages, sont, à un stade ou à un autre, fortement touchés par les processus physiques et chimiques qui se produisent aux interfaces. Malheureusement, ces réactions hétérogènes ne sont pas entièrement comprises à ce jour et limitent notre capacité à simuler et quantifier l’impact des aérosols du fait de grandes incertitudes quant à leur formation et leur évolution dans la troposphère. Ce travail de thèse se propose donc d’améliorer nos connaissances sur les réactions photochimiques aux interfaces air/liquide afin d’obtenir une compréhension fondamentale des processus sous-jacents, ce qui pourrait être crucial pour l'évaluation de leurs impacts atmosphériques. Premièrement la réactivité de l’acide stéarique à l’interface air/eau sous irradiation a été étudiée dans différentes matrices grâce un outil très sensible, la balance de Langmuir. Nous avons observé la dégradation des monocouches d’acide stéarique sous irradiation et ce, même en l’absence de photosensibilisateur. Les expériences réalisées avec des monocouches dans différents états de surface indiquent que la pression de surface exerce une influence sur cette réactivité. Le couplage APCI-Orbitrap a été utilisé pour détecter et identifier des composés halogénés produits à partir d’une solution irradiée contenant un photosensibilisateur à savoir l’acide 4-benzoylbenzoïque. Les effets de l’octanol comme surfactant et de l’acide citrique comme donneur de protons sur ces réactions photosensibilisées ont également été examinés. De plus, la formation d’aérosols secondaires et leur vieillissement en milieu marin (au Cap-Vert) ont été étudiés sous différents aspects. Les expériences démontrent clairement l’existence de processus photosensibilisés à l’interface air/mer en tant que source d’aérosols secondaires marins. Pour finir, des travaux sur la photochimie de la matière organique issue de phytoplanctons ont permis de récolter des informations sur leur réactivité dans la phase liquide. Globalement, les résultats obtenus durant cette thèse montrent que la photochimie étudiée ici peut avoir une incidence importante sur la microcouche superficielle des océans et, par extension, sur les aérosols marin

Formation et vieillissement des aérosols : impact de la photochimie hétérogène

Interfaces are ubiquitous in the environment, and in addition many key atmospheric processes, such as gas deposition, aerosol and cloud formation are, at one stage or the other, strongly affected by physical and chemical processes occurring at interfaces. Unfortunately, these heterogeneous reactions are not fully understood to date and limit our ability to simulate and quantify the impact of aerosols due to large uncertainties in their formation and their evolution in the troposphere. This thesis aims to improve our knowledge about photochemical reactions at the air/liquid interfaces, which could be crucial for the assessment of their atmospheric impacts. Firstly, the reactivity of stearic acid at the air/water interface under irradiation was studied in different matrices thanks to a very sensitive tool, the Langmuir trough. We observed that monolayers of stearic acid undergo degradation under irradiation, even in the absence of photosensitizers. Experiments with monolayers in different surface states indicate that surface pressure influences this reactivity. APCI-Orbitrap coupling was used to detect and identify halogenated compounds produced from an irradiated solution containing a photosensitizer, 4-benzoylbenzoic acid. The effects of octanol as a surfactant and citric acid as a proton donor on these photosensitized reactions were also examined. In addition, the formation of secondary aerosols and their aging in the marine environment (at Cape-Verde) were studied in different conditions. The experiments clearly demonstrate the existence of photosensitized processes at the air/sea interface as a source of marine secondary aerosols. Finally, work on the photochemistry of organic matter from phytoplanktons gave information on their reactivity in the liquid phase. Overall, the results obtained during this thesis show that the photochemistry studied here can have a significant impact on the superficial microlayer of the oceans and, by extension, on marine aerosolsLes interfaces sont omniprésentes dans l'environnement et, de plus, de nombreux processus atmosphériques clés, comme les dépôts de gaz, la formation d'aérosol et de nuages, sont, à un stade ou à un autre, fortement touchés par les processus physiques et chimiques qui se produisent aux interfaces. Malheureusement, ces réactions hétérogènes ne sont pas entièrement comprises à ce jour et limitent notre capacité à simuler et quantifier l’impact des aérosols du fait de grandes incertitudes quant à leur formation et leur évolution dans la troposphère. Ce travail de thèse se propose donc d’améliorer nos connaissances sur les réactions photochimiques aux interfaces air/liquide afin d’obtenir une compréhension fondamentale des processus sous-jacents, ce qui pourrait être crucial pour l'évaluation de leurs impacts atmosphériques. Premièrement la réactivité de l’acide stéarique à l’interface air/eau sous irradiation a été étudiée dans différentes matrices grâce un outil très sensible, la balance de Langmuir. Nous avons observé la dégradation des monocouches d’acide stéarique sous irradiation et ce, même en l’absence de photosensibilisateur. Les expériences réalisées avec des monocouches dans différents états de surface indiquent que la pression de surface exerce une influence sur cette réactivité. Le couplage APCI-Orbitrap a été utilisé pour détecter et identifier des composés halogénés produits à partir d’une solution irradiée contenant un photosensibilisateur à savoir l’acide 4-benzoylbenzoïque. Les effets de l’octanol comme surfactant et de l’acide citrique comme donneur de protons sur ces réactions photosensibilisées ont également été examinés. De plus, la formation d’aérosols secondaires et leur vieillissement en milieu marin (au Cap-Vert) ont été étudiés sous différents aspects. Les expériences démontrent clairement l’existence de processus photosensibilisés à l’interface air/mer en tant que source d’aérosols secondaires marins. Pour finir, des travaux sur la photochimie de la matière organique issue de phytoplanctons ont permis de récolter des informations sur leur réactivité dans la phase liquide. Globalement, les résultats obtenus durant cette thèse montrent que la photochimie étudiée ici peut avoir une incidence importante sur la microcouche superficielle des océans et, par extension, sur les aérosols marin

Formation and ageing of aerosols : impact of heterogeneous photochemistry

Les interfaces sont omniprésentes dans l'environnement et, de plus, de nombreux processus atmosphériques clés, comme les dépôts de gaz, la formation d'aérosol et de nuages, sont, à un stade ou à un autre, fortement touchés par les processus physiques et chimiques qui se produisent aux interfaces. Malheureusement, ces réactions hétérogènes ne sont pas entièrement comprises à ce jour et limitent notre capacité à simuler et quantifier l’impact des aérosols du fait de grandes incertitudes quant à leur formation et leur évolution dans la troposphère. Ce travail de thèse se propose donc d’améliorer nos connaissances sur les réactions photochimiques aux interfaces air/liquide afin d’obtenir une compréhension fondamentale des processus sous-jacents, ce qui pourrait être crucial pour l'évaluation de leurs impacts atmosphériques. Premièrement la réactivité de l’acide stéarique à l’interface air/eau sous irradiation a été étudiée dans différentes matrices grâce un outil très sensible, la balance de Langmuir. Nous avons observé la dégradation des monocouches d’acide stéarique sous irradiation et ce, même en l’absence de photosensibilisateur. Les expériences réalisées avec des monocouches dans différents états de surface indiquent que la pression de surface exerce une influence sur cette réactivité. Le couplage APCI-Orbitrap a été utilisé pour détecter et identifier des composés halogénés produits à partir d’une solution irradiée contenant un photosensibilisateur à savoir l’acide 4-benzoylbenzoïque. Les effets de l’octanol comme surfactant et de l’acide citrique comme donneur de protons sur ces réactions photosensibilisées ont également été examinés. De plus, la formation d’aérosols secondaires et leur vieillissement en milieu marin (au Cap-Vert) ont été étudiés sous différents aspects. Les expériences démontrent clairement l’existence de processus photosensibilisés à l’interface air/mer en tant que source d’aérosols secondaires marins. Pour finir, des travaux sur la photochimie de la matière organique issue de phytoplanctons ont permis de récolter des informations sur leur réactivité dans la phase liquide. Globalement, les résultats obtenus durant cette thèse montrent que la photochimie étudiée ici peut avoir une incidence importante sur la microcouche superficielle des océans et, par extension, sur les aérosols marinsInterfaces are ubiquitous in the environment, and in addition many key atmospheric processes, such as gas deposition, aerosol and cloud formation are, at one stage or the other, strongly affected by physical and chemical processes occurring at interfaces. Unfortunately, these heterogeneous reactions are not fully understood to date and limit our ability to simulate and quantify the impact of aerosols due to large uncertainties in their formation and their evolution in the troposphere. This thesis aims to improve our knowledge about photochemical reactions at the air/liquid interfaces, which could be crucial for the assessment of their atmospheric impacts. Firstly, the reactivity of stearic acid at the air/water interface under irradiation was studied in different matrices thanks to a very sensitive tool, the Langmuir trough. We observed that monolayers of stearic acid undergo degradation under irradiation, even in the absence of photosensitizers. Experiments with monolayers in different surface states indicate that surface pressure influences this reactivity. APCI-Orbitrap coupling was used to detect and identify halogenated compounds produced from an irradiated solution containing a photosensitizer, 4-benzoylbenzoic acid. The effects of octanol as a surfactant and citric acid as a proton donor on these photosensitized reactions were also examined. In addition, the formation of secondary aerosols and their aging in the marine environment (at Cape-Verde) were studied in different conditions. The experiments clearly demonstrate the existence of photosensitized processes at the air/sea interface as a source of marine secondary aerosols. Finally, work on the photochemistry of organic matter from phytoplanktons gave information on their reactivity in the liquid phase. Overall, the results obtained during this thesis show that the photochemistry studied here can have a significant impact on the superficial microlayer of the oceans and, by extension, on marine aerosol

Development of Sampling and Analysis Methods to Identify and Quantify Gas Emissions in the Sewerage Network Développement de Méthodes

Les auteurs remercient également le personnel du Grand Lyon (Claire Gibello, Fabien Kapp, Gaétan Jeanperrin, Thierry Vespier) pour leurs agréables collaborations.International audienceIncreasing population and urbanization have direct consequences on the sewer functioning. In order to identify and quantify gases and VOCs likely to be present in the sewers, methodological studies of sampling in sewer using airbags, canisters and adsorbent tubes were assessed, and methods of analysis by GC-MS were developed. The results obtained lead to propose improvements to sampling protocols in the sewers. The gas quantification is complicated by low gas concentrations, environment heterogeneity and a high hygrometry.Démographie et urbanisation croissantes ont des conséquences directes sur le fonctionnement des réseaux d’assainissement. Afin d’identifier, voire quantifier les gaz et les composés organiques volatils susceptibles d’être présents en réseau, des études méthodologiques de prélèvements en réseau, au moyen de sacs gonflables, canisters, tubes adsorbants, ont été explorées, et des méthodes d’analyses par chromatographie en phase gazeuse couplée à la spectrométrie de masse ont été mises au point. Les résultats obtenus permettent de proposer des améliorations des protocoles des prélèvements en réseau d’assainissement. La quantification des gaz est compliquée de par les faibles concentrations des espèces, l’hétérogénéité du milieu et une forte présence d’humidité