Ground-based measurements of atmospheric trace gases using differential optical absorption spectroscopy and comparisons with satellite observations

Κύριο αντικείμενο αυτής της διατριβής είναι ο υπολογισμός της κατακόρυφης στήλης ατμοσφαιρικών αερίων με εστίαση στο διοξείδιο του αζώτου (ΝΟ2) χρησιμοποιώντας την τεχνική της φασματοσκοπίας διαφορικής οπτικής απορρόφησης (DOAS) και συγκρίσεις με δορυφορικά δεδομένα. Η διατριβή αποτελείται από δύο κύρια μέρη. Το πρώτο μέρος περιλαμβάνει την τεχνική περιγραφή και τον χαρακτηρισμό των τριών συστημάτων Multi-Axis DOAS που αναπτύχθηκαν στο Εργαστήριο Φυσικής της Ατμόσφαιρας (ΕΦΑ) στη Θεσσαλονίκη, καθώς και μια αξιολόγηση της λειτουργίας και της ποιότητας των μετρήσεων του συστήματος στο πλαίσιο της εκστρατείας CINDI-2 που πραγματοποιήθηκε στο Cabauw της Ολλανδίας τον Σεπτέμβριο του 2016. Στο δεύτερο μέρος, παρουσιάζονται μετρήσεις της τροποσφαιρικής και στρατοσφαιρικής στήλης NO2, καθώς και συγκρίσεις τους δορυφορικές παρατηρήσεις. Πιο συγκεκριμένα, εξετάζεται η επίδραση της χωρικής μεταβλητότητας του ΝΟ2 κοντά στην επιφάνεια στις συγκρίσεις επίγειων και δορυφορικών μετρήσεων. Στο πλαίσιο αυτό, τα τρία όργανα MAX-DOAS του ΕΦΑ εγκαταστάθηκαν σε διαφορετικές τοποθεσίες στην ευρύτερη περιοχή της Θεσσαλονίκης που χαρακτηρίζονται από διαφορετικά επίπεδα ρύπανσης και υπολογίστηκαν συντελεστές διόρθωσης με τη βοήθεια ενός μοντέλου ποιότητας αέρα, οι οποίοι εφαρμόστηκαν σε δορυφορικά δεδομένα προκειμένου να προσαρμοστούν στη χωρική ανάλυση των επίγειων μετρήσεων. Επιπλέον, παρουσιάζονται τα αποτελέσματα των μετρήσεων της τροποσφαιρικής στήλης του ΝΟ2 στη ρυπασμένη περιοχή της Guangzhou της Κίνας και συγκρίνονται με αντίστοιχες δορυφορικές μετρήσεις. Διερευνήθηκε επίσης η επίδραση των κριτηρίων αντιστοίχισης των επίγειων και των δορυφορικών τροσφαιρικών στηλών του NO2. Τέλος, υπολογίστηκαν οι συγκεντρώσεις του στρατοσφαιρικού NO2 για πρώτη φορά στη Θεσσαλονίκη από την ανάλυση DOAS των φασματικών μετρήσεων ακτινοβολίας που πραγματοποιήθηκαν στο ζενίθ κατά το λυκόφως για μια περίοδο 7 ετών (Απρίλιος 2011 - Απρίλιος 2018).

Towards Remote Sensing of Atmospheric Trace Gases in the UV spectral range using Dual-Comb spectroscopy

<p>The development of increasingly sensitive and robust instruments and new methodologies are essential to improve our understanding of the Earth’s climate and air pollution. In this context, Dual-Comb spectroscopy (DCS) appears as an emerging spectroscopy methodology to detect in situ, without air-sampling, atmospheric trace-gases.</p><p>DCS is a Fourier-transform type experiment that takes advantage of mode-locked femtosecond (fs) pulses. This methodology appears highly relevant for atmosphere remote-sensing studies because of its very fast acquisition rate (>kHz) that reduces the impact of atmospheric turbulences on the retrieved spectra. DCS has been successfully applied in near-infrared (NIR) spectral ranges for atmospheric greenhouse gas monitoring (water vapor, carbon dioxide, and methane) [1-2].</p><p>Its implementation in the UV range would offer a new spectroscopic intrumentation to target the most reactive species of the atmosphere (OH, HONO, BrO...) as they have their greatest absorption cross-sections in the UV range. UV-DCS would therefore be an answer to the lack of variability of today operationnal and in situ monitoring instrument for those reactive molecules.</p><p>We will present a potential light source for remote sensing UV-DCS and discuss the degree of immunity of UV-DCS to atmospheric turbulences. We will show to which extent the characteristics of the currently available UV sources are compatible with the unambiguous identification of UV absorbing gases by UV-DCS. We will finally present the performances of UV-DCS in terms of concentration detection limit for several UV absorbing molecules (OH, BrO, NO<sub>2</sub>, OClO, HONO, CH<sub>2</sub>O, SO<sub>2</sub>). This sensitivity study has been recently published [3] and the main results will be presented.</p><p> </p><p>[1] Rieker, G.B.; Giorgetta, F.R.; Swann, W.C.; Kofler, J.; Zolot, A.M.; Sinclair, L.C.; Baumann, E.; Cromer, C.;Petron, G.; Sweeney, C.; et al. « Frequency-comb-based remote sensing of greenhouse gases over kilometer air Paths ». Optica 1, p. 290–298 (2014)</p><p>[2] Oudin, J.; Mohamed, A.K.; Hébert, P.J. "IPDA LIDAR measurements on atmospheric CO2 and H2O using dual comb spectroscopy," Proc. SPIE 11180, International Conference on Space Optics — ICSO 2018, p. 111802N (12 July 2019)</p><p>[3] Galtier, S.; Pivard, C.; Rairoux, P. Towards DCS in the UV Spectral Range for Remote Sensing of Atmospheric Trace Gases. Remote Sens., 12, p.3444 (2020)</p>

Transition from unclassified Ktedonobacterales to Actinobacteria during amorphous silica precipitation in a quartzite cave environment

The orthoquartzite Imawarì Yeuta cave hosts exceptional silica speleothems and represents a unique model system to study the geomicrobiology associated to silica amorphization processes under aphotic and stable physical–chemical conditions. In this study, three consecutive evolution steps in the formation of a peculiar blackish coralloid silica speleothem were studied using a combination of morphological, mineralogical/elemental and microbiological analyses. Microbial communities were characterized using Illumina sequencing of 16S rRNA gene and clone library analysis of carbon monoxide dehydrogenase (coxL) and hydrogenase (hypD) genes involved in atmospheric trace gases utilization. The first stage of the silica amorphization process was dominated by members of a still undescribed microbial lineage belonging to the Ktedonobacterales order, probably involved in the pioneering colonization of quartzitic environments. Actinobacteria of the Pseudonocardiaceae and Acidothermaceae families dominated the intermediate amorphous silica speleothem and the final coralloid silica speleothem, respectively. The atmospheric trace gases oxidizers mostly corresponded to the main bacterial taxa present in each speleothem stage. These results provide novel understanding of the microbial community structure accompanying amorphization processes and of coxL and hypD gene expression possibly driving atmospheric trace gases metabolism in dark oligotrophic caves.

Atmospheric Lifetimes of Halogenated Hydrocarbons: Laboratory Measurements and Improved Estimations from an Analysis of Modeling Results.

<p>Reactions with hydroxyl radicals and photolysis are the main processes dictating a compound’s residence time in the atmosphere for a majority of trace gases.  In case of very short-lived halocarbons their reaction with OH dictates both the atmospheric lifetime and active halogen release.  Therefore, the accuracy of OH kinetic data is of primary importance for the comprehensive modeling of a compound’s impact on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP), each of which are dependent on the atmospheric lifetime of the compound.</p><p> </p><p>Atmospheric modeling provides total lifetimes for a number of compounds as well as their partial lifetimes due to specific photochemical removal process (reactions with OH in the troposphere, reactions with OH in the stratosphere, reactions with O(<sup>1</sup>D), and UV photolysis), and partial lifetimes associated with the atmospheric removal regions (troposphere and stratosphere).  We have analyzed these results in an effort to find a correlation useful for estimating the lifetimes of other atmospheric trace gases based only on laboratory data of their photochemical properties.  Based on this analysis, we suggest an improved semi-empirical approach for deriving a “best” value of the total atmospheric lifetime due to photochemical removal processes based on laboratory derived photochemical properties of a compound, which is consistent with both empirically derived tropospheric lifetime of Methyl Chloroform and results of rigorous atmospheric modeling.  These aspects will be illustrated in this presentation for a variety of atmospheric trace gases.</p><p> </p><p>The ability to conduct high accuracy laboratory determinations of OH reaction rate constants over the temperature range of atmospheric interest, thereby decreasing the uncertainty of input kinetic data to 2-3% will be demonstrated as well.</p>