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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.

Diesel engine exhausts from a common rail 3.0 L F1C diesel engine were analyzed at two different load conditions of the WLTC testing cycle downstream of both the diesel particulate filter (DPF) and selective catalytic reactor (SCR) to verify their effect on the characteristics of carbon particulate matter. An array of chemical, physical and spectroscopic techniques (gas chromatography coupled with mass spectrometry (GC-MS), mobility analyzer, UV-Visible absorption and fluorescence spectroscopy) was applied for characterizing polycyclic aromatic hydrocarbons (PAH), heavy aromatic compounds and soot, constituting the particulate matter (PM) sampled from the exhaust. The engine was operated in half load (HL) (188 Nm, representing the more common condition for engine in urban traffic) and full load (FL) (452 Nm, representing the best performance of the engine operation) conditions, at the same engine speed (2000 rpm). Soot formation was enhanced in HL condition, with respect to FL, but, just because of the much lower soot amount, the after-treatment systems in this last condition resulted to be less efficient in the soot abatement. Indeed, the abatement through DPF was about 40% lower in the FL condition with respect to HL condition, and any significant further concentration decrease was found after SCR, in both conditions. By contrast, PAH concentration after DPF abatement was found to be higher in the HL with respect to FL condition. A further PAH concentration decrease of about 30% was found after the SCR in the HL condition whereas in FL the reduction was only about 5-6%. Also the heavy aromatic compounds having molecular weight above the GC-MS detection limit (300 u), were mitigated by SCR. Therefore, SCR did not cause a further soot reduction, whereas it was effective in largely reducing PAH and heavy aromatics emissions, especially in the lower temperature condition featuring the half-load condition, when combustion efficiency is worse. Moreover, SCR system reduced the emission of small particles probably due to an enhanced agglomeration of particles, with beneficial effect on the harmfulness to human health.

Sustainability assessment and rating systems are intended to foster more sustainable design, construction, operation, maintenance and disassembly/deconstruction promoting and making possible a better integration of environment, societal, and cost concerns with other traditional decision criteria. The use of improved and building technologies can contribute considerably to better environmental cycle and then to the sustainability of the constructions. It is widely recognised in the of Building Sustainability Assessment that Life Cycle Assessment (LCA) is a much preferable method for evaluating the environmental pressure caused by materials, Building assemblies and the whole life-cycle of a building. Nevertheless, LCA tools are not extensively used in building design and most of building sustainability assessment and systems are not comprehensive or consistently LCA-based. Reasons for this failure above all related to the huge variety and amount of material flows and processes of building’s Lifecycle and to the complexity of the stages of a LCA. This paper will present the difficulties and possible solutions to integrate more accurate environmental methods in rating systems. In this context, the paper will also present the work that is being carried out in the development of the Portuguese Building Sustainability Assessment system (SBTool PT)

The search for affordable high performance electrode materials in photoelectrochemical hydrogen production by solar water splitting is an ongoing quest. Hematite is a photoanode material with an electronic band gap suitable for efficient absorption of visible light in a photoelectrochemical cell (PEC). Although its poor electronic structure makes hematite a controversial candidate for PEC, it remains promising because it is an earth abundant, chemically stable and low cost material – necessary prerequisites for PEC to become a competitive cost-efficient solar fuel economy. In addition to reviewing some recent PEC research on hematite and its relevant physical and chemical characteristics, we show how hematite obtained by a low cost synthesis can be refined by hydrothermal treatment and further functionalized by coating with phycocyanin, a light harvesting protein known for photosynthesis in blue-green algae.

A methodology for the sizing of domestic hot water heating and storage systems is defined, by assuming an extreme operating condition cycle composed of only two parts, a water consumption period and a system repositioning period. In both parts to respond to the extreme hot water demanding conditions, the heating is always on. The subsequent exergy analysis of this domestic hot water production system compares the irreversibility and the exergy efficiency of the water storage and the tankless situation. To carry out such analysis, some basic assumptions were made: a constant temperature heat source, a short duration operating cycle and a constant thermal energy supply. Under these circumstances it is shown that the hot water storage system leads to lower exergy losses while the tankless system is more exergy efficient, but requiring a higher instantaneous thermal power input. The use of the joule effect electricity, as the system heat source, be it a water storage one or a tankless one, maximizes the system irreversibility losses and minimizes the system exergy efficiency. The tankless system, with the joule effect electricity heat source is the worst situation.

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.

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.