Des réactions photochimiques aux interfaces atmosphériques

The works presented in this thesis concern firstly the characterization of two new photosensitizers by spectroscopic methods. This way the kinetics of the oxidation reaction between the triplet state of the photosensitizers, imidazole-2-carboxaldehyde and 6-carboxypterin, and three halides have been determined by laser flash photolysis. Also, the reactivity of the singlet state of 6-carboxypterin with halides and four organic acids has been studied by static fluorimetry. These photosensitizers are relevant for the photochemistry at the surface of the ocean, but also at the surface of atmospheric particles. The reactions evidenced by these studies lead to the formation of very reactive radical species influencing the composition of the condensed and gas phase of the marine environment. This study then focalized on the analysis of the products formed at the organic coated air-water interface through photo-induced processes. Two different organics were used as surfactants, octanol and nonanoic acid. In the presence of a photosensitizer and UVA light, the changes in the gas phase were monitored online by SRI-ToF-MS and in the condensed bulk phase by UPLC-(ESI)-HRMS offline analysis. These analysis showed that photochemical reactions at the interface lead to the formation of functionalized and unsaturated compounds initiated by a hydrogen abstraction on the organic surfactant. These products, observed in the condensed and gas phase have the potential to contribute to the formation of aerosols. Surprisingly, some of these products were also observed in the two phases without the presence of a photosensitizer, bringing into evidence a photochemistry of nonanoic acid at the air-water interface. Potential formation mechanisms of the products and environmental consequences are discussedLes travaux présentés dans cette thèse portent premièrement sur la caractérisation de nouveaux photosensibilisateurs par des méthodes spectroscopiques. Ainsi les cinétiques de la réaction d'oxydation entre deux photosensibilisateurs à l'état triplet, imidazole-2-carboxaldehyde et 6-carboxypterine, et trois halogénures ont été déterminées par photolyse laser. La réactivité de l'état singulet de la 6- carboxypterine avec les halogénures et quatre acides organiques a été étudiée par fluorimétrie. Ces photosensibilisateurs sont relevants pour la photochimie à la surface de l'océan, mais également à la surface des particules atmosphériques. Les réactions mises en évidence mènent à la formation d'espèces radicalaires très réactives, influençant ainsi la composition de la phase condensée et gazeuse de l'environnement marin. La suite de cette étude s'est focalisée sur l'analyse des produits formés à partir de processus photo-induites à interface air-eau en présence d'une microcouche de surface d'un organique, utilisant deux organiques différents, l'octanol et l'acide nonanoique. En présence d'un photosensibilisateur et de lumière UVA, les changements en phase gaz ont été suivi par SRI-ToF-MS en ligne et en phase condensée par UPLC-(ESI)-HRMS. Ainsi on a démontré que la photochimie à la surface mène à la formation de produits fonctionnalisés et insaturés initiée par une abstraction d'hydrogène sur l'organique surfactant. Ces produits, observés en phase condensée et gazeuse, ont le potentiel de contribuer à la formation d'aérosols. Etonnamment, des produits ont également été observés dans les deux phases sans l'ajout d'un photosensibilisateur et montrant une activité photochimique de l'acide nonanoique seul à l'interface air-eau. Les mécanismes potentiels et les conséquences environnementales sont discuté

Understanding Iodine Chemistry Over the Northern and Equatorial Indian Ocean

Observations of halogen oxides, ozone, meteorological parameters, and physical and biogeochemical water column measurements were made in the Indian Ocean and its marine boundary layer as a part of the Second International Indian Ocean Expedition (IIOE-2). The expedition took place on board the oceanographic research vessel Sagar Nidhi during 4–22 December 2015 from Goa, India, to Port Louis, Mauritius. Observations of mixed layer depth, averaged temperature, salinity, and nitrate concentrations were used to calculate predicted iodide concentrations in the seawater. The inorganic iodine ocean-atmosphere flux (hypoiodous acid [HOI] and molecular iodine [I2]) was computed using the predicted iodide concentrations, measured atmospheric ozone, and wind speed. Iodine oxide (IO) mixing ratios peaked at 0.47 ± 0.29 pptv (parts per trillion by volume) in the remote open ocean environment. The estimated iodide concentrations and HOI and I2 fluxes peaked at 200/500 nM, 410/680 nmol·m−2·day−1, and 20/80 nmol·m−2·day−1, respectively, depending on the parameterization used. The calculated fluxes for HOI and I2 were higher closer to the Indian subcontinent; however, atmospheric IO was only observed above the detection limit in the remote open ocean environment. We use NO2 observations to show that titration of IO by NO2 is the main reason for this result. These observations show that inorganic iodine fluxes and atmospheric IO show similar trends in the Indian Ocean marine boundary layer, but the impact of inorganic iodine emissions on iodine chemistry is buffered in elevated NOx environments, even though the estimated oceanic iodine fluxes are higher

Surface Inorganic Iodine Speciation in the Indian and Southern Oceans From 12°N to 70°S

Marine iodine speciation has emerged as a potential tracer of primary productivity, sedimentary inputs, and ocean oxygenation. The reaction of iodide with ozone at the sea surface has also been identified as the largest deposition sink for tropospheric ozone and the dominant source of iodine to the atmosphere. Accurate incorporation of these processes into atmospheric models requires improved understanding of iodide concentrations at the air-sea interface. Observations of sea surface iodide are relatively sparse and are particularly lacking in the Indian Ocean basin. Here we examine 127 new sea surface (≤10 m depth) iodide and iodate observations made during three cruises in the Indian Ocean and the Indian sector of the Southern Ocean. The observations span latitudes from ∼12°N to ∼70°S, and include three distinct hydrographic regimes: the South Indian subtropical gyre, the Southern Ocean and the northern Indian Ocean including the southern Bay of Bengal. Concentrations and spatial distribution of sea surface iodide follow the same general trends as in other ocean basins, with iodide concentrations tending to decrease with increasing latitude (and decreasing sea surface temperature). However, the gradient of this relationship was steeper in subtropical waters of the Indian Ocean than in the Atlantic or Pacific, suggesting that it might not be accurately represented by widely used parameterizations based on sea surface temperature. This difference in gradients between basins may arise from differences in phytoplankton community composition and/or iodide production rates. Iodide concentrations in the tropical northern Indian Ocean were higher and more variable than elsewhere. Two extremely high iodide concentrations (1241 and 949 nM) were encountered in the Bay of Bengal and are thought to be associated with sedimentary inputs under low oxygen conditions. Excluding these outliers, sea surface iodide concentrations ranged from 20 to 250 nM, with a median of 61 nM. Controls on sea surface iodide concentrations in the Indian Ocean were investigated using a state-of-the-art iodine cycling model. Multiple interacting factors were found to drive the iodide distribution. Dilution via vertical mixing and mixed layer depth shoaling are key controls, and both also modulate the impact of biogeochemical iodide formation and loss processes

Iodide, iodate & dissolved organic iodine in the temperate coastal ocean

The surface ocean is the main source of iodine to the atmosphere, where it plays a crucial role including in the catalytic removal of tropospheric ozone. The availability of surface oceanic iodine is governed by its biogeochemical cycling, the controls of which are poorly constrained. Here we show a near two-year time series of the primary iodine species, iodide, iodate and dissolved organic iodine (DOI) in inner shelf marine surface waters of the Western English Channel (UK). The median ± standard deviation concentrations between November 2019 and September 2021 (n=76) were: iodide 88 ± 17 nM (range 61-149 nM), iodate 293 ± 28 nM (198-382 nM), DOI 16 ± 16 nM (<0.12-75 nM) and total dissolved iodine (dIT) 399 ± 30 nM (314-477 nM). Though lower than inorganic iodine ion concentrations, DOI was a persistent and non-negligible component of dIT, which is consistent with previous studies in coastal waters. Over the time series, dIT was not conserved and the missing pool of iodine accounted for ~6% of the observed concentration suggesting complex mechanisms governing dIT removal and renewal. The contribution of excess iodine (I*) sourced from the coastal margin towards dIT was generally low (3 ± 29 nM) but exceptional events influenced dIT concentrations by up to ±100 nM. The seasonal variability in iodine speciation was asynchronous with the observed phytoplankton primary productivity. Nevertheless, iodate reduction began as light levels and then biomass increased in spring and iodide attained its peak concentration in mid to late autumn during post-bloom conditions. Dissolved organic iodine was present, but variable, throughout the year. During winter, iodate concentrations increased due to the advection of North Atlantic surface waters. The timing of changes in iodine speciation and the magnitude of I* subsumed by seawater processes supports the paradigm that transformations between iodine species are biologically mediated, though not directly linked

Influence of the Sea Surface Microlayer on Oceanic Iodine Emissions

The influence of organic compounds on iodine (I2) emissions from the O3 + I- reaction at the sea surface was investigated in laboratory and modeling studies using artificial solutions, natural subsurface seawater (SSW), and, for the first time, samples of the surface microlayer (SML). Gas-phase I2 was measured directly above the surface of liquid samples using broadband cavity enhanced absorption spectroscopy. I2 emissions were consistently lower for artificial seawater (AS) than buffered potassium iodide (KI) solutions. Natural seawater samples showed the strongest reduction of I2 emissions compared to artificial solutions with equivalent [I-], and the reduction was more pronounced over SML than SSW. Emissions of volatile organic iodine (VOI) were highest from SML samples but remained a negligible fraction (<1%) of the total iodine flux. Therefore, reduced iodine emissions from natural seawater cannot be explained by chemical losses of I2 or hypoiodous acid (HOI), leading to VOI. An interfacial model explains this reduction by increased solubility of the I2 product in the organic-rich interfacial layer of seawater. Our results highlight the importance of using environmentally representative concentrations in studies of the O3 + I- reaction and demonstrate the influence the SML exerts on emissions of iodine and potentially other volatile species

Impacts of ocean biogeochemistry on atmospheric chemistry

26 pags., 2 figs. -- This review is a contribution to the international Surface Ocean Lower Atmosphere Study (SOLAS)Ocean biogeochemistry involves the production and consumption of an array of organic compounds and halogenated trace gases that influence the composition and reactivity of the atmosphere, air quality, and the climate system. Some of these molecules affect tropospheric ozone and secondary aerosol formation and impact the atmospheric oxidation capacity on both regional and global scales. Other emissions undergo transport to the stratosphere, where they contribute to the halogen burden and influence ozone. The oceans also comprise a major sink for highly soluble or reactive atmospheric gases. These issues are an active area of research by the SOLAS (Surface Ocean Lower Atmosphere) community. This article provides a status report on progress over the past decade, unresolved issues, and future research directions to understand the influence of ocean biogeochemistry on gas-phase atmospheric chemistry. Common challenges across the subject area involve establishing the role that biology plays in controlling the emissions of gases to the atmosphere and the inclusion of such complex processes, for example involving the sea surface microlayer, in large-scale global models.This publication resulted in part from support from the U.S. National Science Foundation (Grant OCE-1840868) to the Scientific Committee on Oceanic Research (SCOR)Peer reviewe

Estimation of reactive inorganic iodine fluxes in the Indian and Southern Ocean marine boundary layer

Iodine chemistry has noteworthy impacts on the oxidising capacity of the marine boundary layer (MBL) through the depletion of ozone (O3) and changes to HOx (OH=HO2) and NOx (NO=NO2) ratios. Hitherto, studies have shown that the reaction of atmospheric O3 with surface seawater iodide (I-) contributes to the flux of iodine species into the MBL mainly as hypoiodous acid (HOI) and molecular iodine (I2). Here, we present the first concomitant observations of iodine oxide (IO), O3 in the gas phase, and sea surface iodide concentrations. The results from three field campaigns in the Indian Ocean and the Southern Ocean during 2015 2017 are used to compute reactive iodine fluxes in the MBL. Observations of atmospheric IO by multi-axis differential optical absorption spectroscopy (MAX-DOAS) show active iodine chemistry in this environment, with IO values up to 1 pptv (parts per trillion by volume) below latitudes of 40° S. In order to compute the sea-to-air iodine flux supporting this chemistry, we compare previously established global sea surface iodide parameterisations with new regionspecific parameterisations based on the new iodide observations. This study shows that regional changes in salinity and sea surface temperature play a role in surface seawater iodide estimation. Sea air fluxes of HOI and I2, calculated from the atmospheric ozone and seawater iodide concentrations (observed and predicted), failed to adequately explain the detected IO in this region. This discrepancy highlights the need to measure direct fluxes of inorganic and organic iodine species in the marine environment. Amongst other potential drivers of reactive iodine chemistry investigated, chlorophyll a showed a significant correlation with atmospheric IO (R D 0:7 above the 99 % significance level) to the north of the polar front. This correlation might be indicative of a biogenic control on iodine sources in this region

Observations of iodine oxide in the Indian Ocean marine boundary layer : A transect from the tropics to the high latitudes

Observations of iodine oxide (IO) were made in the Indian Ocean and the Southern Ocean marine boundary layer (MBL) during the 8th Indian Southern Ocean Expedition. IO was observed almost ubiquitously in the open ocean with larger mixing ratios south of the Polar Front (PF). Contrary to previous reports, IO was not positively correlated to sea surface temperature (SST)/salinity, or negatively to chlorophyll a. Over the whole expedition, SST showed a weak negative correlation with respect to IO while chl a was positively correlated. North of the PF, chl a showed a strong positive correlation with IO. The computed HOI and I2 fluxes do not show any significant correlation with atmospheric IO. Simulations with the global CAM-Chem model show a reasonably good agreement with observations north of the PF but the model fails to reproduce the elevated IO south of the PF indicating that the current emission parametrizations are not sufficient to explain iodine chemistry in the Southern Indian Ocean

Observations of iodine oxide in the Indian Ocean marine boundary layer : A transect from the tropics to the high latitudes

Observations of iodine oxide (IO) were made in the Indian Ocean and the Southern Ocean marine boundary layer (MBL) during the 8th Indian Southern Ocean Expedition. IO was observed almost ubiquitously in the open ocean with larger mixing ratios south of the Polar Front (PF). Contrary to previous reports, IO was not positively correlated to sea surface temperature (SST)/salinity, or negatively to chlorophyll a. Over the whole expedition, SST showed a weak negative correlation with respect to IO while chl a was positively correlated. North of the PF, chl a showed a strong positive correlation with IO. The computed HOI and I2 fluxes do not show any significant correlation with atmospheric IO. Simulations with the global CAM-Chem model show a reasonably good agreement with observations north of the PF but the model fails to reproduce the elevated IO south of the PF indicating that the current emission parametrizations are not sufficient to explain iodine chemistry in the Southern Indian Ocean