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1.
Catalytic hydro(deoxy)genation of furfural and modelling of its reaction kinetics : dissertation
Rok Šivec, 2024, doctoral dissertation

Abstract: In recent decades, there has been a growing interest in producing biofuels and biochemicals from renewable sources. Furfural stands as one of the ligno(hemi)cellulosic biomass derived platform chemical, which can be transformed into numerous value-added products. The goal of this PhD was to systematically study hydrotreatment reactions of furfural under varying operating conditions and to gain insights into the reaction mechanism and kinetics. An extensive experimental and computational study of hydrogenation, hydrodeoxygenation, oligomerisation and etherification of furfural in a three-phase batch reactor was performed. The goals were divided into three consecutive objectives. In the first part, hydrotreatment of furfural over Pd/C catalyst under various reaction conditions, including the solvent selection (solventless conditions, tetrahydrofuran, isopropanol), atmosphere (nitrogen, hydrogen), temperature (100–200 °C), pressure (25–75 bar) and stirring speed, was studied. A reaction pathway network and a micro-kinetic model were developed, incorporating thermodynamics (hydrogen solubility), mass transfer, adsorption, desorption, and surface reactions. These phenomena and their contribution to the surface coverages, TOF’s and global reaction rates were studied. The hydrogen presence on the catalyst surface was found to influence the main reaction pathway, leading to ring, aldehyde group or full hydrogenation. In the second part, various monometallic catalysts (Pd/C, Pt/C, Re/C, Ru/C, Rh/C, Ni/C, Cu/C) were tested at 100 -200 °C with 60 bar of hydrogen and tetrahydrofuran as solvent. A generalized reaction pathway network was developed. H2 temperature-programmed reduction (H2-TPR) and CO temperature-programmed desorption (CO-TPD) were conducted, and a regression analysis of the results was subsequently performed by numerical modelling and optimisation. The obtained adsorption and desorption kinetic parameters for active metallic sites were further used in a generalized micro-kinetic model, applicable to all tested catalysts. Pd/C exhibited high activity and non-selective hydrogenation of furfural, while other catalysts showed selective aldehyde group hydrogenation followed by deoxygenation, consistent with density functional theory (DFT) calculations. Ru/C uniquely produced 2 methyltetrahydrofuran and ring-opening products at 200 °C. In silico optimization of reaction conditions for promising catalysts ((Pd/C, Pt/C, Re/C, Ni/C) aimed to maximize the yield of the target product. In the third part, the influence of support on catalytic activity was studied. Hydrotreatment of furfural over Pd/Al2O3, Pd/SiO2, Ru/Al2O3, Ru/SiO2, Ni/Al2O3, and Ni/SiO2 was performed between 150 - 200 °C, using 60 bar of hydrogen and tetrahydrofuran as solvent. The strength and rate of adsorption and desorption to/from acidic, metallic and interface site structures were determined, using H2-TPR, CO-TPD and NH3-TPD and subsequent regression analysis of the results by numerical modelling and optimisation. The resulting parameters were sequentially used in the generalized micro-kinetic model to quantify the contribution of the active metal (Ni, Pd, or Ru), support (Al2O3 or SiO2), interphase sites and their relationship on catalyst activity and selectivity. Evaluation of morphological and structural characteristics, adsorption/desorption and intrinsic reaction kinetics has indicated that the coverage of acidic sites (on alumina or silica) facilitated yielding ring hydrogenation and inhibited deoxygenation, decarbonylation and cyclic compound opening. The rates for aromatics or aldehyde functional groups were, nonetheless, affected in a different order. The used and developed methods and findings of this PhD offer useful guidelines for transforming furfural into high-value chemicals through catalytic hydrotreatment, with significant implications for future research and industrial applications.
Keywords: lignocellulosic biomass, furfural, catalytic hydrogenation, micro-kinetic mass transfer model, reaction kinetics, first-principle methods, furfuryl alcohol, tetrahydrofurfuryl alcoholv, dissertations
Published in RUNG: 08.11.2024; Views: 262; Downloads: 4
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2.
Emission of volatile organic compounds from residential biomass burning and their rapid chemical transformations
Maximillien Desservettaz, Michael Pikridas, Iasonas Stavroulas, Aikaterini Bougiatioti, Eleni Liakakou, Nikolaos Hatzianastassiou, Jean Sciare, Nikolaos Mihalopoulos, Efstratios Bourtsoukidis, 2023, original scientific article

Abstract: Biomass combustion releases a complex array of Volatile Organic Compounds (VOCs) that pose significant challenges to air quality and human health. Although biomass burning has been extensively studied at ecosystem levels, understanding the atmospheric transformation and impact on air quality of emissions in urban environments remains challenging due to complex sources and burning materials. In this study, we investigate the VOC emission rates and atmospheric chemical processing of predominantly wood burning emissions in a small urban centre in Greece. Ioannina is situated in a valley within the Dinaric Alps and experiences intense atmospheric pollution accumulation during winter due to its topography and high wood burning activity. During pollution event days, the ambient mixing ratios of key VOC species were found to be similar to those reported for major urban centres worldwide. Positive matrix factorisation (PMF) analysis revealed that biomass burning was the dominant emission source (>50 %), representing two thirds of OH reactivity, which indicates a highly reactive atmospheric mixture. Calculated OH reactivity ranges from 5 s−1 to an unprecedented 278 s−1, and averages at 93 ± 66 s−1 at 9 PM, indicating the presence of exceptionally reactive VOCs. The highly pronounced photochemical formation of organic acids coincided with the formation of ozone, highlighting the significance of secondary formation of pollutants in poorly ventilated urban areas. Our findings underscore the pressing need to transition from wood burning to environmentally friendly sources of energy in poorly ventilated urban areas, in order to improve air quality and safeguard public health.
Keywords: biomass burning, urban air quality, VOCs, emission factors, source apportionment
Published in RUNG: 13.05.2024; Views: 940; Downloads: 5
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3.
Measuring the spatial variability of black carbon in Athens during wintertime
Georgios Grivas, Iasonas Stavroulas, Eleni Liakakou, Dimitris G. Kaskaoutis, Aikaterini Bougiatioti, D. Paraskevopoulou, Evangelos Gerasopoulos, Nikolaos Mihalopoulos, 2019, original scientific article

Abstract: A first assessment of the spatial variability of ambient black carbon (BC) concentrations in the Greater Area of Athens (GAA) was carried out during an intensive wintertime campaign, when ambient levels are exacerbated by increased biomass burning for residential heating. Short-term daytime BC measurements were conducted at 50 sites (traffic and urban/suburban/regional background) and on-road along 12 routes. Daytime measurements were adjusted based on BC concentrations continuously monitored at a reference site. Indicative nighttime BC ambient concentrations were also measured at several residences across the area. Daytime BC concentrations recorded an average of 2.3 μg m-3 with considerable between-site variability. Concentrations at traffic sites were significantly higher (43% on average), compared with the rest of the sites. Varying levels were observed between background site subtypes, with concentrations at urban background sites (located near the center of Athens and the port of Piraeus) being 34% and 114% higher, on average, than at suburban and regional background sites, respectively. The traffic intensity at the nearest road and the population and built density in the surrounding area of sites were recognized as important factors controlling BC levels. On-road concentration measurements (5.4 μg m-3 on average) enabled the identification of hot-spots in the road network, with peak levels encountered along motorways (13.5 μg m-3 on average). Nighttime measurements demonstrated that wintertime BC pollution, enhanced by residential biomass burning for heating, affects the entire Athens basin. The reference site in central Athens was found to be representative of the temporal variability for daytime and nighttime BC concentrations at background locations.
Keywords: mobile measurements, microaethalometer, Athens, mapping, traffic, biomass burning
Published in RUNG: 10.05.2024; Views: 826; Downloads: 8
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4.
Long-term variability, source apportionment and spectral properties of black carbon at an urban background site in Athens, Greece
Eleni Liakakou, Iasonas Stavroulas, Dimitris G. Kaskaoutis, Georgios Grivas, D. Paraskevopoulou, Umesh Chandra Dumka, M. Tsagkaraki, Aikaterini Bougiatioti, K. Oikonomou, J. Sciare, 2020, original scientific article

Abstract: This study aims to delineate the characteristics of Black Carbon (BC) in the atmosphere over Athens, Greece, using 4-year (May 2015–April 2019) Aethalometer (AE-33) measurements. The average BC concentration is 1.9 ± 2.5 μg m−3 (ranging from 0.1 to 32.7 μg m−3; hourly values), with a well-defined seasonality from 1.3 ± 1.1 μg m−3 in summer to 3.0 ± 4.0 μg m−3 in winter. Pronounced morning and evening/night peaks are found in the BC concentrations in winter, while during the rest of the seasons, this diurnal cycle appears to flatten out, with the exception of the morning traffic peak. On an annual basis, the biomass-burning fraction (BB%) of BC accounts for 22 ± 12%, while the fossil-fuel combustion (BCff) component (traffic emissions and domestic heating) dominates during summer (83%) and in the morning hours. BCwb exhibits higher contribution in winter (32%), especially during the night hours (39%). BC levels are effectively reduced by precipitation, while they significantly build-up for wind speeds <3 m s−1 and mixing-layer height (MLH) < 500 m. Normalizing the BC diurnal course by the MLH variations on a seasonal basis reveals that the residential wood-burning emissions are mostly responsible for the large BC increase during winter nights, whereas the low BC levels during daytime in the warm season are mainly attributed to dilution into a deeper MLH. BCwb is highly correlated with other BB tracers during winter nights (e.g. levoglucosan, non-sea-salt-K+, m/z 60 fragment), as well as with the fine fraction (PM2.5) OC and EC. The Delta-C, which represents the spectral dependence of BC as the absorption difference between 370 and 880 nm, is analyzed for the first time in Athens. It exhibits a pronounced seasonality with maximum values in winter night-time, and it appears as a valid qualitative marker for wood combustion.
Keywords: black carbon, wood burning, source apportionment, mixing layer, biomass burning tracers, Athens
Published in RUNG: 10.05.2024; Views: 907; Downloads: 2
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5.
Carbonaceous aerosols in contrasting atmospheric environments in Greek cities : evaluation of the EC-tracer methods for secondary organic carbon estimation
Dimitris G. Kaskaoutis, Georgios Grivas, Christina Theodosi, M. Tsagkaraki, D. Paraskevopoulou, Iasonas Stavroulas, Eleni Liakakou, Antonis Gkikas, Nikolaos Hatzianastassiou, Cheng Wu, 2020, original scientific article

Abstract: This study examines the carbonaceous-aerosol characteristics at three contrasting urban environments in Greece (Ioannina, Athens, and Heraklion), on the basis of 12 h sampling during winter (January to February 2013), aiming to explore the inter-site differences in atmospheric composition and carbonaceous-aerosol characteristics and sources. The winter-average organic carbon (OC) and elemental carbon (EC) concentrations in Ioannina were found to be 28.50 and 4.33 µg m−3, respectively, much higher than those in Heraklion (3.86 µg m−3 for OC and 2.29 µg m−3 for EC) and Athens (7.63 µg m−3 for OC and 2.44 µg m−3 for EC). The winter OC/EC ratio in Ioannina (6.53) was found to be almost three times that in Heraklion (2.03), indicating a larger impact of wood combustion, especially during the night, whereas in Heraklion, emissions from biomass burning were found to be less intense. Estimations of primary and secondary organic carbon (POC and SOC) using the EC-tracer method, and specifically its minimum R-squared (MRS) variant, revealed large differences between the sites, with a prevalence of POC (67–80%) in Ioannina and Athens and with a larger SOC fraction (53%) in Heraklion. SOC estimates were also obtained using the 5% and 25% percentiles of the OC/EC data to determine the (OC/EC)pri, leading to results contrasting to the MRS approach in Ioannina (70–74% for SOC). Although the MRS method provides generally more robust results, it may significantly underestimate SOC levels in environments highly burdened by biomass burning, as the fast-oxidized semi-volatile OC associated with combustion sources is classified in POC. Further analysis in Athens revealed that the difference in SOC estimates between the 5% percentile and MRS methods coincided with the semi-volatile oxygenated organic aerosol as quantified by aerosol mass spectrometry. Finally, the OC/Kbb+ ratio was used as tracer for decomposition of the POC into fossil-fuel and biomass-burning components, indicating the prevalence of biomass-burning POC, especially in Ioannina (77%).
Keywords: carbonaceous aerosols, inorganic species, POC-SOC estimation, biomass burning, MRS method, Greece
Published in RUNG: 10.05.2024; Views: 786; Downloads: 7
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6.
Apportionment of black and brown carbon spectral absorption sources in the urban environment of Athens, Greece, during winter
Dimitris G. Kaskaoutis, Georgios Grivas, Iasonas Stavroulas, Aikaterini Bougiatioti, Eleni Liakakou, Umesh Chandra Dumka, Evangelos Gerasopoulos, Nikolaos Mihalopoulos, 2021, original scientific article

Abstract: This study examines the spectral properties and source characteristics of absorbing aerosols (BC: Black Carbon; BrC: Brown Carbon, based on aethalometer measurements) in the urban background of Athens during December 2016–February 2017. Using common assumptions regarding the spectral dependence of absorption due to BC (AAEBC = 1) and biomass burning (AAEbb = 2), and calculating an optimal AAEff value for the dataset (1.18), the total spectral absorption was decomposed into five components, corresponding to absorption of BC and BrC from fossil-fuel (ff) combustion and biomass burning (bb), and to secondary BrC estimated using the BC-tracer minimum R-squared (MRS) method. Substantial differences in the contribution of various components to the total absorption were found between day and night, due to differences in emissions and meteorological dynamics, while BrC and biomass burning aerosols presented higher contributions at shorter wavelengths. At 370 nm, the absorption due to BCff contributed 36.3% on average, exhibiting a higher fraction (58.1%) during daytime, while the mean BCbb absorption was estimated at 18.4%. The mean absorption contributions due to BrCff, BrCbb and BrCsec were 6.7%, 32.3% and 4.9%, respectively. The AbsBCff,370 component maximized during the morning traffic hours and was strongly correlated with NOx (R2 = 0.76) and CO (R2 = 0.77), while a similar behavior was seen for the AbsBrCff,370 component. AbsBCbb and AbsBrCbb levels escalated during nighttime and were highly associated with nss-K+ and with the organic aerosol (OA) components related to fresh and fast-oxidized biomass burning (BBOA and SV-OOA) as obtained from ACSM measurements. Multiple linear regression was used to attribute BrC absorption to five OA components and to determine their absorption contributions and efficiencies, revealing maximum contributions of BBOA (33%) and SV-OOA (21%). Sensitivity analysis was performed in view of the methodological uncertainties and supported the reliability of the results, which can have important implications for radiative transfer models.
Keywords: spectral absorption, black carbon, brown carbon, fossil fuel, biomass burning, source apportionment
Published in RUNG: 10.05.2024; Views: 943; Downloads: 0
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7.
Impacts of severe residential wood burning on atmospheric processing, water-soluble organic aerosol and light absorption, in an inland city of Southeastern Europe
Dimitris G. Kaskaoutis, Georgios Grivas, K. Oikonomou, P. Tavernaraki, Kyriaki Papoutsidaki, M. Tsagkaraki, Iasonas Stavroulas, Pavlos Zarmpas, D. Paraskevopoulou, Aikaterini Bougiatioti, 2022, original scientific article

Abstract: This study examines the concentrations and characteristics of carbonaceous aerosols (including saccharides) and inorganic species measured by PM2.5 filter sampling and a multi-wavelength Aethalometer during two campaigns in a mountainous, medium-sized, Greek city (Ioannina). The first campaign was conducted in summer and used as a baseline of low concentrations, while the second took place in winter under intensive residential wood burning (RWB) emissions. Very high winter-mean OC concentrations (26.0 μg m−3) were observed, associated with an OC/EC ratio of 9.9, and mean BCwb and PM2.5 levels of 4.5 μg m−3 and 57.5 μg m−3, respectively. Simultaneously, record-high levoglucosan (Lev) concentrations (mean: 6.0 μg m−3; max: 15.9 μg m−3) were measured, revealing a severely biomass burning (BB)-laden environment. The water-soluble OC component (WSOC) accounted for 56 ± 9% of OC in winter, exhibiting high correlations (R2 = 0.93–0.97) with BB tracers (nss-K+, BCwb, Lev), nitrate and light absorption, potentially indicating the formation of water-soluble brown carbon (BrC) from fast oxidation processes. The examination of diagnostic ratios involving BB tracers indicated the prevalence of hardwood burning, while the mean Lev/OC ratio (22%) was remarkably higher than literature values. Applying a mono-tracer method based on levoglucosan, we estimated very high BB contributions to OC (∼92%), EC (∼64%) and WSOC (∼87%) during winter. On the contrary, low levels were registered during summer for all carbonaceous components, with winter/summer ratios of 4–5 for PM2.5 and BC, 10 for OC, 30 for BCwb and ∼1100 for levoglucosan. The absence of local BB sources in summer, combined with the photochemical processing and aging of regional organic aerosols, resulted in higher WSOC/OC fractions (64 ± 13%). The results indicate highly soluble fine carbonaceous aerosol fraction year-round, which when considered alongside the extreme concentration levels in winter can have important implications for short- and long-term health effects.
Keywords: carbonaceous aerosols, biomass burning, levoglucosan, WSOC, heterogeneous chemistry, Greece
Published in RUNG: 10.05.2024; Views: 912; Downloads: 4
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8.
9.
Intra- and inter-city variability of ▫$PM_2.5$▫ concentrations in Greece as determined with a low-cost sensor network
Konstantinos Dimitriou, Iasonas Stavroulas, Georgios Grivas, Charalampos Chatzidiakos, Georgios Kosmopoulos, Andreas Kazantzidis, Konstantinos Kourtidis, Athanasios Karagioras, Nikolaos Hatzianastassiou, Spyros N. Pandis, 2023, original scientific article

Abstract: Measurements of PM2.5 concentrations in five major Greek cities over a two-year period using calibrated low-cost sensor-based particulate matter (PM) monitors (Purple Air PA-II) were combined with local meteorological parameters, synoptic patterns and air mass residence time models to investigate the factors controlling PM2.5 spatiotemporal variability over continental Greece. Fourteen sensors nodes in Athens, Patras, Ioannina, Xanthi, and Thermi (in the Metropolitan Area of Thessaloniki) were selected out of more than 100 of a countrywide network for detailed analysis. The cities have populations ranging from 65k to 3M inhabitants and cover different latitudes along the South-North axis. High correlations between the daily average PM2.5 levels were observed among all sites, indicating strong intra- and inter-city covariance of concentrations, both in cold and warm periods. Higher PM2.5 concentrations in all cities during the cold period were primarily associated with low temperatures and stagnant anticyclonic conditions, favoring the entrapment of residential heating emissions from biomass burning. Anticyclonic conditions were also connected to an increased frequency of PM2.5 episodes, exceeding the updated daily guideline value (15 μg m−3) of the World Health Organization (WHO). During the warm period, nearly uniform PM2.5 levels were encountered across continental Greece, independently of their population size. This uniformity strongly suggests the importance of long-range transport and regional secondary aerosol formation for PM2.5 during this period. Peak concentrations were associated mainly with regional northern air flows over Greece and the Balkan Peninsula. The use of the measurements from dense air quality sensor networks, provided that a robust calibration protocol and continuous data quality assurance practices are followed, appears to be an efficient tool to gain insights on the levels and variability of PM2.5 concentrations, underpinning the characterization of spatial and seasonal particularities and supporting real-time public information and warning.
Keywords: particulate matter, PM2.5, biomass burning, low-cost sensors, purple air PA-II, concentration weighted trajectory, potential source contribution function
Published in RUNG: 10.05.2024; Views: 896; Downloads: 4
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10.
Vertical profiling of fresh biomass burning aerosol optical properties over the Greek urban city of Ioannina, during the PANACEA winter campaign
Christina-Anna Papanikolaou, Alexandros Papayannis, M. Mylonaki, Romanos Foskinis, Panagiotis Kokkalis, Eleni Liakakou, Iasonas Stavroulas, O. Soupiona, Nikolaos Hatzianastassiou, Maria Gavrouzou, 2022, original scientific article

Abstract: Vertical profiling of aerosol particles was performed during the PANhellenic infrastructure for Atmospheric Composition and climatE chAnge (PANACEA) winter campaign (10 January 2020–7 February 2020) over the city of Ioannina, Greece (39.65° N, 20.85° E, 500 m a.s.l.). The middle-sized city of Ioannina suffers from wintertime air pollution episodes due to biomass burning (BB) domestic heating activities. The lidar technique was applied during the PANACEA winter campaign on Ioannina city, to fill the gap of knowledge of the spatio-temporal evolution of the vertical mixing of the particles occurring during these winter-time air pollution episodes. During this campaign the mobile single-wavelength (532 nm) depolarization Aerosol lIdAr System (AIAS) was used to measure the spatio-temporal evolution of the aerosols’ vertical profiles within the Planetary Boundary Layer (PBL) and the lower free troposphere (LFT; up to 4 km height a.s.l.). AIAS performed almost continuous lidar measurements from morning to late evening hours (typically from 07:00 to 19:00 UTC), under cloud-free conditions, to provide the vertical profiles of the aerosol backscatter coefficient (baer) and the particle linear depolarization ratio (PLDR), both at 532 nm. In this study we emphasized on the vertical profiling of very fresh (~hours) biomass burning (BB) particles originating from local domestic heating activities in the area. In total, 33 out of 34 aerosol layers in the lower free troposphere were characterized as fresh biomass burning ones of local origin, showing a mean particle linear depolarization value of 0.04 ± 0.02 with a range of 0.01 to 0.09 (532 nm) in a height region 1.21–2.23 km a.s.l. To corroborate our findings, we used in situ data, particulate matter (PM) concentrations (PM2.5) from a particulate sensor located close to our station, and the total black carbon (BC) concentrations along with the respective contribution of the fossil fuel (BCff) and biomass/wood burning (BCwb) from the Aethalometer. The PM2.5 mass concentrations ranged from 5.6 to 175.7 μg/m3, while the wood burning emissions from residential heating were increasing during the evening hours, with decreasing temperatures. The BCwb concentrations ranged from 0.5 to 17.5 μg/m3, with an extremely high mean contribution of BCwb equal to 85.4%, which in some cases during night-time reached up to 100% during the studied period.
Keywords: lidar, depolarization ratio, fresh biomass burning aerosols, domestic heating, black carbon, PM2.5
Published in RUNG: 10.05.2024; Views: 821; Downloads: 5
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