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Digital Annex for the following thesis: Vila-Viçosa, C. (2023). Natural History, Biogeography and Evolution of the Iberian white oak syngameon (Quercus L. Sect. Quercus). Ph.D. Thesis, Faculdade de Ciências da Universidade do Porto, Portugal Abstract: The genus Quercus L. is one of the most diverse and important group of woody plants, particularly when considering that they are the trees that rule the Northern Hemisphere forests. Oaks have an intricate Biogeography that criss-crosses diverse climatic and edaphic gradients, encompassing a huge ambiguity in terms of species delimitation. Frequently, the taxonomic proposals brought by traditional Linnaean Botany are either insufficient or rather inflate the number of species and nomenclatural assignments, which are further diluted into inconsistent taxonomic ranks, varying from species to subspecies and varieties. The supremacy given to morphological characters that are inherently fragile and plastic, spread across the distribution areas of distinct lineages, may carry ambiguity on the identification and proper species delimitation. From the oaks that are distributed across the Western Palearctic region, the ones that are deciduous or brevi-deciduous present higher levels of ambiguity in terms of species number and their delimitation. This ambiguity is particularly strong in the circummediterranean region and in the transitional areas between the two major biogeographic Regions of the western Palearctic region, the Euro-Siberian and Mediterranean. This degree of uncertainty, which increases towards the Southern European Peninsulas, is amplified by the ease that the different species of oaks tend to hybridize among them. The present work provides a holistic framework that covers multiple areas, from the taxonomic and evolutive study of this genus, to biogeography and molecular characterization. Its major objective was to resolve the species delimitation of the Iberian deciduous and marcescent oaks and putative introgression among them, enhancing the available knowledge about species diversity, which can foster suitable species and forest conservation. A specific objective was to cross-reference the natural history revision and the different taxonomic treatments brought by distinct authors, with personal observations. These data were then incorporated into ecological modelling and molecular characterization, which in the end fed a newly updated taxonomic proposal. In Section A we obtained results from extensive field, herbaria, and literature review, updating the nomenclature of the Portuguese and western Mediterranean oaks. Section B was supported by Section A’s in-depth review and enabled finer species distribution models, nurturing both hindcast (since ca. 20 Kyr) and forecast (2070-2100) exercises of the range dynamics of Mediterranean oaks species. The study of past and future range shifts solved important pending biogeographic questions, especially related to past range-shifts. Such past-range shifts improved our knowledge on species responses to climate dynamics and allowed a better anticipation of future responses of range shifts driven by climate change. Section C encompassed the molecular characterization of Iberian white oak species and their hybrids, whose delimitation is often faltering when one intends to infer about species rank, or hypothesize about the participation of parent taxon in natural hybrid swarms. This work allowed us to solve the phylogenetic backbone of western Palearctic white oaks, suggesting a significant segregation of the Iberian pedunculate oaks and unveiling two subsections inside Section Quercus. These subsections are biogeographically well-segregated and present diverse levels of introgression among species. Results demonstrated the efficiency of RADSeq for rebuilding the reticulate phylogeny of the Eurasian white oaks, showcasing the significance of the Iberian Peninsula as a major hotspot for oak diversity. We implemented a circular approach to these methods, which retro-fed themselves in terms of insight generation, enabling a powerful strategy to solve the evolutionary history of this difficult groups of plants. We estimate that the reticulate historical biogeography of the western Palearctic white oaks deserves further scrutiny by adding vicariant oak populations from northern Africa, the Near East and southern European Peninsulas. Methods should again follow this similar additive and sequential process of adjoining deep Natural History examination, with extensive fieldwork in type populations and genome-wide molecular surveys, in order to solve this group of plants. With the present work, we were able to significantly improve on the depiction of the basic unit of Biodiversity (the Species), in the complex Quercus genus. We provided tools to enable further efforts for the conservation of the Mediterranean oak forests, which overwhelm one of the most important (and one of the most threatened) Biomes for plant conservation at the global scale.

Abstract High power pseudocapacitors are extremely relevant to answer specific needs in the current energy transition arena and to implement an efficient renewable energy society. However, literature shows that are still open gaps concerning improvement of their energy density at high power, conversion efficiency, cost and cycle life. Electrodes based on active transition metal compounds, and in particular metal sulphides, evidence high potential to meet these objectives. This work discusses the dependence on the synthesis route of the charge storage mechanism of manganese sulphide-based materials and relates the pseudocapacitive response of these electrodes with their polycrystalline nature. Results reveal that a manganese oxy-sulphide mixture can achieve a high specific capacitance of 231 F.g−1 at 0.5 A/g in a 0.65 V active window. These values represent a 31.5 % increase compared to pure rambergite, γ-MnS, and 436 % compared to pure hausmannite Mn3O4 prepared under the same conditions. Moreover, the results show that manganese oxy-sulphide electrodes are characterized by good charge retention (73%), and superior long term capacity retention (above 86%) after 5000 cycles, evidencing potential for high power energy storage applications.

AbstractThe protic ionic liquid (PIL) N‐butylimidazolium trifluoromethanesulfonate ([BIm][TfO]) was obtained for the first time and incorporated into a sol–gel‐derived di‐ureasil matrix with a concentration of X=5, 10, and 30 %, where X is the ratio of the mass of PIL per mass of poly(oxyethylene). Four years after their synthesis, the resulting quasi‐anhydrous electrolytes remained amorphous, homogeneous, flexible, and thermally stable below 200 °C. SEM/EDS data revealed the presence of the PIL at the surface of the xerogels with X>5 %, demonstrating that this type of morphological characterization is mandatory to avoid misleading ionic conductivity values. The highest ionic conductivity was produced in the washed sample with X=30 % (3.5×10−5 and 2.1×10−3 S cm−1 at 25 and 170 °C, respectively). The present family of electrolytes yielded higher conductivities than the N‐ethylimidazolium trifluoromethanesulfonate‐based analogues introduced earlier by our group and may thus be considered as promising candidates for applications in fuel cells.

Abstract This work assesses the impacts of aggressive driving behavior on pollutants emissions and energy consumption at a city level. Furthermore, it performs an economic analysis considering the potential avoided emissions and fuel savings and discusses potential policy measures to address this topic. The results showed that aggressive driving significantly impacts energy consumption and emissions, with energy consumption increasing by more than ∼200% and emissions by 330% for aggressive driving compared to non-aggressive driving (in MJ/km and in g/km, respectively). This increment was found to be even higher for diesel vehicles than for gasoline vehicles. On the contrary, gasoline vehicles showed higher percentages of increase for most emissions (CO, NOx and NO). Results also revealed that aggressive driving impacts are higher for local streets when examining the city level. Moreover, the economic analysis showed that significant cost reductions may be achieved by avoiding aggressive driving, reaching up to 52.5 k€ on a daily basis. In conclusion, this study is of particular relevance to policy makers and urban planners, enabling to obtain a comprehensive overview of the impacts of aggressive driving behaviors at a city level and providing new insights to perform further developments and to assess the feasibility of the implementation of policy measures.

M.J.M. acknowledges funding from FCT through the grant SFRH/BPD/115566/2016. ALTALUZ (Reference PTDC/CTM-ENE/5125/2014). The optical properties of localized surface plasmon resonances (LSPR) sustained by self-assembled silver nanoparticles are of great interest for enhancing light trapping in thin film photovoltaics. First, we report on a systematic investigation of the structural and the optical properties of silver nanostructures fabricated by a solid-state dewetting process on various substrates. Our study allows to identify fabrication conditions in which circular, uniformly spaced nanoparticles are obtainable. The optimized NPs are then integrated into plasmonic back reflector (PBR) structures. Second, we demonstrate a novel procedure, involving a combination of opto-electronic spectroscopic techniques, allowing for the quantification of useful and parasitic absorption in thin photovoltaic absorber deposited on top of the PBR. We achieve a significant broadband useful absorption enhancement of 90% for 0.9 µm thick μc-Si:H film and demonstrate that optical losses due to plasmonic scattering are insignificant below 730 nm. Finally, we present a successful implementation of a plasmonic light trapping scheme in a thin film a-Si:H solar cell. The quantum efficiency spectra of the devices show a pronounced broadband enhancement resulting in remarkably high short circuit current densities (Jsc). preprint published

ScopeThis study was designed to evaluate the influence of ethanol on the bioavailability of blackberry anthocyanins.Methods and resultsA total of 18 participants were recruited to consume 250 mL of a blackberry puree (650 mg of anthocyanins) without (BBP) or with 12% ethanol (BBP 12%). Venous blood was collected from participants at baseline and at 15, 30, 60, and 120 min after puree ingestion. Urine samples were collected at baseline and at 120 min. Plasma and urine concentration of anthocyanins and anthocyanin conjugates were quantified by HPLC‐DAD. Methyl‐cyanidin‐glucuronide (Me‐Cy‐Glucr) and 3′‐methyl‐cyanidin‐3‐glucoside (3′‐Me‐Cy3glc) were the main anthocyanin conjugates detected in all plasma and urine samples. Urinary concentration of these anthocyanin conjugates were positively correlated with their plasma concentration. Ethanol increased plasma Cmax of Me‐Cy‐Glucr and 3′‐Me‐Cy3glc. Participants were then stratified according to their body mass index (BMI) and body fat mass. After BBP consumption, plasma Cmax of Me‐Cy‐Glucr and 3′‐Me‐Cy3glc tended to be decreased in overweight/obese participants, in comparison to normal weight participants. The increase on plasma Cmax of Me‐Cy‐Glucr and 3′‐Me‐Cy3glc induced by ethanol was more pronounced in the group of overweight/obese participants.ConclusionsEthanol seems to enhance Cy3glc metabolism that appears to be compromised in overweight and obese individuals.

In this study, air concentrations of BaP in two different seasons (winter 2015 and summer 2016) and BaP levels in ground vegetation from Tarragona County were used as control simulations performed with the WRF-CHIMERE air quality modelling system, in order to reproduce the incidence of that hazardous chemical in air and soils. The CTM was validated for the present climatology, showing a good ability to represent air and soil concentrations of BaP over the target domain (petrochemical, chemical, urban and background sites), particularly in the winter. Then, the variation of the BaP concentrations in air and soils were simulated for the time series 1996-2015 and for the climate change scenario RCP8.5 (2031-2050). While an increase is projected for the levels in air, particularly in chemical and remote sites where the variation can go up to 10%, in terms of soil deposition the findings are the opposite, with an evident decrease in soil BaP concentrations, particularly for background sites. Finally, a potential health effect of BaP for the local population (lung cancer) was assessed. Although according to the projections the EU threshold for BaP atmospheric incidence (1 ng m-3) will not be reached by 2050, there will be an increase in the life-time risk of lung cancer, particularly in the most populated areas within the simulation domain.

Abstract Portugal’s performance concerning the Refuse Derived Fuel (RDF) strategy, with particular focus on perspectives for the Northern Region based on the current status of integrated municipal waste management systems in that region, was evaluated. Legal documents, official reports and the market were analyzed. The 2015 national installed capacity of waste treatment technologies, from which the high calorific value fraction (HCVF) for RDF production is obtained, is not far from what was predicted for 2013. However, only around 11% of the HCVF had such destiny and the amount of effectively produced RDF was only 30% of the material sent to RDF production (around 30 kt). In Northern Portugal, no RDF production plant was in operation in 2015; the amount of HCVF was estimated to range from 105 to 204 kt for 2015 and around 2.4 times more is expected in 2020. The strategy laydown for RDF failed so far, and thus, low diversion of waste from landfills is observed, mostly due to low landfill taxes and low HCVF quality, resulting in RDF being non-competitive with the imported higher quality product from countries with very high landfilling fees. Moreover, co-incineration and dedicated recovery solutions are scarce. In the Northern region, the HCVF may be treated in the existing municipal waste incinerator or the RDF might be recovered in new dedicated plants, receiving also non-hazardous waste fractions from other origin. Overall, to ensure a sustainable municipal waste management, the intensification of the reuse, preparation for reuse and recycling of waste components from source segregated collection must be significantly promoted.