Abstract. The photochemical box model CiTTyCAT is used to analyse the absence of oxygen mass-independent anomalies (O-MIF) in volcanic sulfates produced in the troposphere. An aqueous sulfur oxidation module is implemented in the model and coupled to an oxygen isotopic scheme describing the transfer of O-MIF during the oxidation of SO2 by OH in the gas-phase, and by H2O2, O3 and O2 catalysed by TMI in the liquid phase. Multiple model simulations are performed in order to explore the relative importance of the various oxidation pathways for a range of plausible conditions in volcanic plumes. Note that the chemical conditions prevailing in dense volcanic plumes are radically different from those prevailing in the surrounding background air. The first salient finding is that, according to model calculations, OH is expected to carry a very significant O-MIF in sulfur-rich volcanic plumes and, hence, that the volcanic sulfate produced in the gas phase would have a very significant positive isotopic enrichment. The second finding is that, although H2O2 is a major oxidant of SO2 throughout the troposphere, it is very rapidly consumed in sulfur-rich volcanic plumes. As a result, H2O2 is found to be a minor oxidant for volcanic SO2. According to the simulations, oxidation of SO2 by O3 is negligible because volcanic aqueous phases are too acidic. The model predictions of minor or negligible sulfur oxidation by H2O2 and O3, two oxidants carrying large O-MIF, are consistent with the absence of O-MIF seen in most isotopic measurements of volcanic tropospheric sulfate. The third finding is that oxidation by O2∕TMI in volcanic plumes could be very substantial and, in some cases, dominant, notably because the rates of SO2 oxidation by OH, H2O2 and O3 are vastly reduced in a volcanic plume compared to the background air. Only cases where sulfur oxidation by O2∕TMI is very dominant can explain the isotopic composition of volcanic tropospheric sulfate.
Ce manuel est un grand classique. Articule en 37 modules de cours, il offre un panorama complet des Sciences de la Terre et de l'Univers, du Big Bang a l'origine de l'Homme en passant par toutes les disciplines des Sciences de la Terre (tectonique des plaques, geologie structurale, geophysique, mineralogie, petrographie, geochimie, geomorphologie, sedimentologie...). Dans cette 15e edition, en couleur et actualisee, l'organisation des chapitres a ete revue et les chapitres sur la petrologie, la volcanologie, les chaines de montagne ont ete tres profondement remanies. Un nouveau site compagnon, www.elements-geologie.com, accompagne cette 15e edition.
On Earth, most of the nitrogen (N) accessible for life is trapped in dinitrogen (N2), which is the most stable atmospheric molecule. In order to be metabolised by living organisms, N2 has to be converted into assimilable forms, also called fixed N. Nowadays, nearly all the N-fixation is achieved through biological and anthropogenic processes. However, in early environments of the Earth, before the emergence of life, N-fixation must have occurred via natural abiotic processes. Electrical discharges, including from thunderstorms and also lightning associated with volcanic eruptions is one of the most invoked processes. The occurence of volcanic lightning during explosive eruptions is frequent, and convincing laboratory experimentations support the role of this phenomenon, however no evidence of substantial N-fixation has been found in volcanic records. Here we report on the discovery of large amounts of nitrates in volcanic deposits from Neogene caldera-forming eruptions, which are well correlated with the concentrations of species directly emitted by volcanoes such as sulphur and chlorine. The multi-isotopic composition (δ18O, Δ17O) of the nitrates reveals that they originate from the atmospheric oxidation of nitrogen oxides formed by volcanic lightning that occur during the eruption. According to these volcanic nitrate records, our first estimates suggest that about 60 Tg of N can be fixed during a large explosive event. Our findings hint at a unique role potentially played by subaerial explosive eruptions in supplying essential ingredients for the emergence of life on Earth.
