Development of an integrative approach for the characterization of ecological risk on marine transition ecosystems: the Sado Estuary as a case study

Estuaries and other transitional waters are complex ecosystems critically important as nursery and shelter areas for organisms. Also, humans depend on estuaries for multiple socio-economical activities such as urbanism, tourism, heavy industry, (taking advantage of shipping), fisheries and aquaculture, the development of which led to strong historical pressures, with emphasis on pollution. The degradation of estuarine environmental quality implies ecologic, economic and social prejudice, hence the importance of evaluating environmental quality through the identification of stressors and impacts. The Sado Estuary (SW Portugal) holds the characteristics of industrialized estuaries, which results in multiple adverse impacts. Still, it has recently been considered moderately contaminated. In fact, many studies were conducted in the past few years, albeit scattered due to the absence of true biomonitoring programmes. As such, there is a need to integrate the information, in order to obtain a holistic perspective of the area able to assist management and decision-making. As such, a geographical information system (GIS) was created based on sediment contamination and biomarker data collected from a decade-long time-series of publications. Four impacted and a reference areas were identified, characterized by distinct sediment contamination patterns related to different hot spots and diffuse sources of toxicants. The potential risk of sediment-bound toxicants was determined by contrasting the levels of pollutants with available sediment quality guidelines, followed by their integration through the Sediment Quality guideline Quotient (SQG-Q). The SQG-Q estimates per toxicant or class was then subjected to georreferencing and statistical analyses between the five distinct areas and seasons. Biomarker responses were integrated through the Biomarkers Consistency Indice and georreferenced as well through GIS. Overall, in spite of the multiple biological traits surveyed, the biomarker data (from several organisms) are accordant with sediment contamination. The most impacted areas were the shipyard area and adjacent industrial belt, followed by urban and agricultural grounds. It is evident that the estuary, although globally moderately impacted, is very heterogeneous and affected by a cocktail of contaminants, especially metals and polycyclic aromatic hydrocarbon. Although elements (like copper, zinc and even arsenic) may originate from the geology of the hydrographic basin of the Sado River, the majority of the remaining contaminants results from human activities. The present work revealed that the estuary should be divided into distinct biogeographic units, in order to implement effective measures to safeguard environmental quality.

Engineering of metal oxide nanoparticles for application in electrochemical devices

The growing demand for materials and devices with new functionalities led to the increased inter-est in the field of nanomaterials and nanotechnologies. Nanoparticles, not only present a reduced size as well as high reactivity, which allows the development of electronic and electrochemical devices with exclusive properties, when compared with thin films. This dissertation aims to explore the development of several nanostructured metal oxides by sol-vothermal synthesis and its application in different electrochemical devices. Within this broad theme, this study has a specific number of objectives: a) research of the influence of the synthesis parameters to the structure and morphology of the nanoparticles; b) improvement of the perfor-mance of the electrochromic devices with the application of the nanoparticles as electrode; c) application of the nanoparticles as probes to sensing devices; and d) production of solution-pro-cessed transistors with a nanostructured metal oxide semiconductor. Regarding the results, several conclusions can be exposed. Solvothermal synthesis shows to be a very versatile method to control the growth and morphology of the nanoparticles. The electrochromic device performance is influenced by the different structures and morphologies of WO3 nanoparticles, mainly due to the surface area and conductivity of the materials. The dep-osition of the electrochromic layer by inkjet printing allows the patterning of the electrodes without wasting material and without any additional steps. Nanostructured WO3 probes were produced by electrodeposition and drop casting and applied as pH sensor and biosensor, respectively. The good performance and sensitivity of the devices is explained by the high number of electrochemical reactions occurring at the surface of the na-noparticles. GIZO nanoparticles were deposited by spin coating and used in electrolyte-gated transistors, which promotes a good interface between the semiconductor and the dielectric. The produced transistors work at low potential and with improved ON-OFF current ratio, up to 6 orders of mag-nitude. To summarize, the low temperatures used in the production of the devices are compatible with flexible substrates and additionally, the low cost of the techniques involved can be adapted for disposable devices.

Magnetotransport properties of metal/LaAlO3/SrTiO3 heterostructures

The quasi two-dimensional electron gas (q2DEG) hosted in the interface of an epitaxially grown lanthanum aluminate (LaAlO3) thin film with a TiO2-termi-nated strontium titanate (SrTiO3) substrate (001) has been massively studied in the last few years. The confinement of mobile electrons to within a few nanome-ters from the interface, superconductive behavior at low temperatures and elec-tron mobility exceeding 1000 cm2/(V.s) make this system an interesting candi-date to explore the physics of spin injection and transport. However, due to the critical thickness for conduction of 4 unit cells (uc) of LaAlO3, a high tunneling resistance hampers electrical access to the q2DEG, preventing proper injection of spin polarized current. Recently, our group found that depositing a thin overlayer of Co on LaAlO3 reduces the critical thickness, enabling conduction with only 1 uc of LaAlO3. Two scenarios arise to explain this phenomenon: a pinning of the Fermi level in the metal, inducing charge transfer in the SrTiO3; the creation of oxygen vacancies at the interface between LaAlO3 and the metal, leading to an n-type doping of the SrTiO3. In this dissertation, we will report on magnetotransport of metal/LaAlO3/SrTiO3 (metal: Ti, Ta, Co, Py, Au, Pt, Pd) heterostructures with 2 uc of LaAlO3 studied at low temperatures (2 K) and high magnetic fields (9 T). We have analyzed the transport properties of the gas, namely, the carrier concen-tration, mobility and magnetotransport regime and we will discuss the results in the light of the two scenarios mentioned above.

Development of an experimental setup for metal cutting research

Analytical, numerical and experimental models have been developed over time to try to characterize and understand the metal cutting process by chip removal. A true knowledge of the cutting process by chip removal is required by the increasing production, by the quality requirements of the product and by the reduced production time, in the industries in which it is employed. In this thesis an experimental setup is developed to evaluate the forces and the temperature distribution in the tool according to the orthogonal cutting model conditions, in order to evaluate its performance and its possible adoption in future works. The experimental setup is developed in a CNC lathe and uses an orthogonal cutting configuration, in which thin discs fixed onto a mandrel are cut by the cutting insert. In this experimental setup, the forces are measured by a piezoelectric dynamometer while temperatures are measured by thermocouples placed juxtaposed to the side face of the cutting insert. Three different solutions are implemented and evaluated for the thermocouples attachment in the cutting insert: thermocouples embedded in thermal paste, thermocouples embedded in copper plate and thermocouples brazed in the cutting insert. From the tests performed in the experimental setup it is concluded that the adopted forces measurement technique shows a good performance. Regarding to the adopted temperatures measurement techniques, only the thermocouples brazed in the cutting insert solution shows a good performance for temperature measurement. The remaining solutions show contact problems between the thermocouple and the side face of the cutting insert, especially when the vibration phenomenon intensifies during the cut. It is concluded that the experimental setup does not present a sufficiently robust and reliable performance, and that it can only be used in future work after making improvements in the assembly of the thermocouples.

The influence of low-frequency noise pollution on the quality of life and place in sustainable cities: a case study from northern Portugal

Discussing urban planning requires rethinking sustainability in cities and building healthy environments. Historically, some aspects of advancing the urban way of life have not been considered important in city planning. This is particularly the case where technological advances have led to conflicting land use, as with the installation of power poles and building electrical substations near residential areas. This research aims to discuss and rethink sustainability in cities, focusing on the environmental impact of low-frequency noise and electromagnetic radiation on human health. It presents data from a case study in an urban space in northern Portugal, and focuses on four guiding questions: Can power poles and power lines cause noise? Do power poles and power lines cause discomfort? Do power poles and power lines cause discomfort due to noise? Can power poles and power lines affect human health? To answer these questions, we undertook research between 2014 and 2015 that was comprised of two approaches. The first approach consisted of evaluating the noise of nine points divided into two groups â near the sourceâ (e.g., up to 50 m from power poles) and â away from the sourceâ (e.g., more than 250 m away from the source). In the second approach, noise levels were measured for 72 h in houses located up to 20 m from the source. The groups consist of residents living within the distance range specified for each group. The measurement values were compared with the proposed criteria for assessing low-frequency noise using the DEFRA Guidance (University of Salford). In the first approach, the noise caused discomfort, regardless of the group. In the second approach, the noise had fluctuating characteristics, which led us to conclude that the noise caused discomfort.