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An Overview of the ASKOS Campaign in Cabo Verde
Eleni Marinou, Jesús Yus-Díez, Griša Močnik, 2023, published scientific conference contribution

Abstract: In the framework of the ESA-NASA Joint Aeolus Tropical Atlantic Campaign (JATAC), the ASKOS experiment was implemented during the summer and autumn of 2021 and 2022. ASKOS comprised roughly 9 weeks of measurements in the Saharan dust outflow towards the North Atlantic, with operations conducted from the Cabo Verde Islands. Through its unprecedented dataset of synergistic measurements in the region, ASKOS will allow for the calibration and validation of the aerosol/cloud product from Aeolus and the preparation of the terrain for EarthCARE cal/val activities. Moreover, ASKOS marks a turning point in our ability to study Saharan dust properties and the processes affecting its atmospheric transport, as well as the link to other components of the Earth’s system, such as the effect of dust particles on cloud formation over the Eastern Atlantic and the effect of large and giant particles on radiation. This is possible through the synergy of diverse observations acquired during the experiment, which include intense 24/7 ground-based aerosol, cloud, wind, and radiation remote sensing measurements, and UAV-based aerosol in situ measurements within the Saharan air layer, up to 5.3 km altitude, offering particle size-distributions up to 40 μm as well as sample collection for mineralogical analysis. We provide an outline of the novel measurements along with the main scientific objectives of ASKOS. The campaign data will be publicly available by September of 2023 through the EVDC portal (ESA Validation Data Center).
Keywords: experimental campaign, remote sensing, lidar, radar, radiosondes, radiation, desert dust, in-situ, aerosol, optical properties, scattering, absorption, ASKOS
Published in RUNG: 25.09.2023; Views: 310; Downloads: 4
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In Situ Techniques for Characterization of Layered Double Hydroxide-Based Oxygen Evolution Catalysts
Andraž Mavrič, Matjaž Valant, 2023, review article

Abstract: Functional layered double hydroxide (LDH) usually contains different cationic substitutes to increase the activity of the oxygen evolution reaction (OER). The intrinsic OER activity of LDH materials is connected with the chemical composition and dispersion of metal cations substitutions in the matrix phase. The potential induced phase transitions, in particular hydroxide-to-oxyhydroxide transitions, are a predisposition for the high OER activity of LDH materials and can be followed by coupling the electrochemical experiments with spectroscopic techniques. The understanding of LDH catalysts under electrochemical conditions also allows an understanding of the behavior of OER catalysts based on transition metals, metal-chalcogenides, -pnictides, -carbides, and metal–organic frameworks. The surfaces of those materials are intrinsically poor OER catalysts. However, they act as precursors to catalysts, which are oxidized into a metal (oxy)hydroxide. This review summarizes the use of in situ techniques for the characterization of LDH-based OER electrocatalysts and presents the influence of these techniques on the understanding of potential induced phase transitions, identification of active sites, and reaction mechanisms.
Keywords: oxygen evolution reaction, layered double hydroxide, in-situ characterization
Published in RUNG: 14.07.2023; Views: 595; Downloads: 5
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CO[sub]2 activation over nanoshaped CeO[sub]2 decorated with nickel for low-temperature methane dry reforming
Kristijan Lorber, Janez Zavašnik, Iztok Arčon, Matej Huš, Janvit Teržan, Blaž Likozar, Petar Djinović, original scientific article

Abstract: Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into H2 and CO (syngas). CeO2 nanorods, nanocubes, and nanospheres were decorated with 1−4 wt % Ni. The materials were structurally characterized using TEM and in situ XANES/EXAFS. The CO2 activation was analyzed by DFT and temperature-programmed techniques combined with MS-DRIFTS. Synthesized CeO2 morphologies expose {111} and {100} terminating facets, varying the strength of the CO2 interaction and redox properties, which influence the CO2 activation. Temperature-programmed CO2 DRIFTS analysis revealed that under hydrogen-lean conditions mono- and bidentate carbonates are hydrogenated to formate intermediates, which decompose to H2O and CO. In excess hydrogen, methane is the preferred reaction product. The CeO2 cubes favor the formation of a polydentate carbonate species, which is an inert spectator during DRM at 500 °C. Polydentate covers a considerable fraction of ceria’s surface, resulting in less-abundant surface sites for CO2 dissociation
Keywords: surface carbonates, in situ characterization, Ni XANES, Ni EXAFS, spectator species, CeO2 nanoshapes, CO2 activation
Published in RUNG: 13.07.2022; Views: 1090; Downloads: 0
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Structure and population of complex ionic species in FeCl[sub]2 aqueous solution by X-ray absorption spectroscopy
Uroš Luin, Iztok Arčon, Matjaž Valant, 2022, original scientific article

Abstract: Technologies for mass production require cheap and abundant materials such as ferrous chloride (FeCl2). The literature survey shows the lack of experimental studies to validate theoretical conclusions related to the population of ionic Fe-species in the aqueous FeCl2 solution. Here, we present an in situ X-ray absorption study of the structure of the ionic species in the FeCl2 aqueous solution at different concentrations (1–4 molL−1) and temperatures (25–80 ◦C). We found that at low temperature and low FeCl2 concentration, the octahedral first coordination sphere around Fe is occupied by one Cl ion at a distance of 2.33 (±0.02) Å and five water molecules at a distance of 2.095 (±0.005) Å. The structure of the ionic complex gradually changes with an increase in temperature and/or concentration. The apical water molecule is substituted by a chlorine ion to yield a neutral Fe[Cl2(H2O)4]0. The observed substitutional mechanism is facilitated by the presence of the intramolecular hydrogen bonds as well as entropic reasons. The transition from the single charged Fe[Cl(H2O)5]+ to the neutral Fe[Cl2(H2O)4]0 causes a significant drop in the solution conductivity, which well correlates with the existing conductivity models.
Keywords: structure, population, ionic species, aqueous ferrous chloride, in situ X-ray absorption spectroscopy
Published in RUNG: 24.01.2022; Views: 1399; Downloads: 41  (1 vote)
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In-situ XAS study of catalytic N[sub]2O decomposition over CuO/CeO[sub]2 catalysts
Maxim Zabilsky, Iztok Arčon, Petar Djinović, Elena Tchernychova, Albin Pintar, 2021, original scientific article

Abstract: We performed in‐situ XAS study of N 2 O decomposition over CuO/CeO 2 catalysts. The Cu K‐edge and Ce L 3 ‐edge XANES and EXAFS analyses revealed the dynamic and crucial role of Cu 2+ /Cu + and Ce 4+ /Ce 3+ ionic pairs during the catalytic reaction. We observed the initial formation of reduced Cu + and Ce 3+ species during activation in helium atmosphere at 400 °C, while concentration of these species decreased significantly during steady‐state nitrous oxide degradation reaction (2500 ppm N 2 O in He at 400 °C). In‐situ EXAFS analysis further revealed a crucial role of copper‐ceria interface in this catalytic reaction. We observed dynamic changes in average number of Cu‐Ce scatters under reaction conditions, indicating an enlarging the interface between both copper and ceria phases, where electron and oxygen transfer occurs.
Keywords: in-situ XAS, Cu EXAFS, CuO/CeO2 nanorod catalys, N2O decomposition
Published in RUNG: 29.01.2021; Views: 1935; Downloads: 0
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In-situ Fe K-edge XAS analysis of ionic species in the highly-concentrated FeCl2 aqueous solutions for Power-to-Solid energy storage technology
Uroš Luin, Iztok Arčon, Matjaž Valant, unpublished conference contribution

Keywords: In situ Fe K-edge XAS, highly-concentrated FeCl2 aqueous solutions, local structure, coordination number, Power-to-Solid, energy storage technology
Published in RUNG: 28.01.2021; Views: 2339; Downloads: 62  (1 vote)
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Improving bacterial cellulose films by ex-situ and in-situ modifications: a review
Patricia Cazón, Manuel Vazquez, 2021, review article

Abstract: The high intake of plastic materials for food packaging causes environmental problems due to the nonbiodegradable properties of these materials. High, low and very low-density polyethylene, polyethylene terephthalate, polyvinyl chloride, polystyrene and polypropylene are the main materials used. Biodegradable polymers from natural sources are potential raw materials to develop novel food packaging. Bacterial cellulose is a material with extraordinary properties that is gaining special interest for applications in the Food Industry. The excellent mechanical properties, thermal stability and barrier to water vapor, oxygen and UV radiation of bacterial cellulose compared to other polysaccharides make this material very attractive and a potential alternative to non-biodegradable synthetic materials. Nevertheless, bacterial cellulose films are limited due to their lower elasticity. Therefore, the aim of this review is to provide an overview of the ex-situ and in-situ modifications of bacterial cellulose to improve its properties for the development of films for food packaging.
Keywords: Bacterial cellulose, In-situ modifications, Ex-situ modifications, Food packaging.
Published in RUNG: 09.12.2020; Views: 2147; Downloads: 0
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X-ray absorption spectroscopy analysis: in situ, operando, in vivo
Iztok Arčon, 2020, published scientific conference contribution abstract (invited lecture)

Abstract: X-ray absorption spectroscopy (XAS) is a powerful tool for characterisation of local structure and chemical state of selected elements in different new functional materials and biological or environmental samples. The XAS spectroscopy is based on extremely bright synchrotron radiation X-rays sources, which allow precise characterisation of bulk, nanostructured or highly diluted samples. With its two methods (XANES and EXAFS) it enables monitoring changes in valence states and local structures of constituent elements during chemical reactions under controlled reaction conditions, and it offers a possibility of a combination of X-ray spectroscopy and microscopy with sub-micron lateral resolution, crucial for analysis of biological samples on sub-cellular level. In this talk some typical examples of advanced XAS analysis will be presented.
Keywords: X-ray absorption spectroscopy, EXAFS, XANES, in-situ, operando
Published in RUNG: 17.10.2020; Views: 2690; Downloads: 0
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Comparison and complementary use of in situ and remote sensing aerosol measurements in the Athens Metropolitan Area
S. Vratolis, Griša Močnik, Konstantinos Eleftheriadis, 2020, original scientific article

Abstract: In the summer of 2014 in situ and remote sensing instruments were deployed in Athens, in order to study the concentration, physical properties, and chemical composition of aerosols. In this manuscript we aim to combine the measurements of collocated in situ and remote sensing instruments by comparison and complementary use, in order to increase the accuracy of predictions concerning climate change and human health. We also develop a new method in order to select days when a direct comparison on in situ and remote sensing instruments is possible. On selected days that displayed significant turbulence up to approximately 1000 m above ground level (agl), we acquired the aerosol extinction or scattering coefficient by in situ instruments using three approaches. In the first approach the aerosol extinction coefficient was acquired by adding a Nephelometer scattering coefficient in ambient conditions and an Aethalometer absorption coefficient. The correlation between the in situ and remote sensing instruments was good (coefficient of determination equal to 0.69). In the second approach we acquired the aerosol refractive index by fitting dry Nephelometer and Aethalometer measurements with Mie algorithm calculations of the scattering and absorption coefficients for the size distribution up to a maximum diameter of 1000 nm obtained by in situ instruments. The correlation in this case was relatively good ( equal to 0.56). Our next step was to compare the extinction coefficient acquired by remote sensing instruments to the scattering coefficient calculated by Mie algorithm using the size distribution up to a maximum diameter of 1000 nm and the equivalent refractive index (), which is acquired by the comparison of the size distributions obtained by a Scanning Mobility Particle Sizer (SMPS) and an Optical Particle Counter (OPC). The agreement between the in situ and remote sensing instruments in this case was not satisfactory ( equal to 0.35). The last comparison for the selected days was between the aerosol extinction Ångström exponent acquired by in situ and remote sensing instruments. The correlation was not satisfactory ( equal to 0.4), probably due to differences in the number size distributions present in the air volumes measured by in situ and remote sensing instruments. We also present a day that a Saharan dust event occurred in Athens in order to demonstrate the information we obtain through the synergy of in situ and remote sensing instruments on how regional aerosol is added to local aerosol, especially during pollution events due to long range transport.
Keywords: Aerosol mixing in the vertical, In situ — Remote sensing comparison, Regional aerosol addition to local aerosol
Published in RUNG: 09.04.2020; Views: 2601; Downloads: 0
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When a Wh-Word Refuses to Stay in Situ
Artur Stepanov, Ali Al Moussaoui, 2020, original scientific article

Abstract: Richards (2010, 2016) suggests that a language’s choice between the wh-movement option and the wh-in-situ option is made on the basis of language-specific prosodic properties that determine whether or not a prosodic wh-domain containing both the interrogative C and the wh-phrase can be established. A wh-domain in this sense roughly corresponds to a piece of prosodic structure in which these two key elements are separated by as few prosodic boundaries as possible, ideally zero. Prosodic boundaries demarcate structural units of the sentence, known as Minor or Intermediate Phrases that may trivially or nontrivially correspond to syntactic constituents.
Keywords: prosodic domain, Minor Phrase, wh-in-situ, wh-movement, Lebanese Arabic, French, Italian
Published in RUNG: 01.04.2020; Views: 2934; Downloads: 253
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