Functional role of macrobenthos in estuarine sediment dynamics

Thesis submitted to the Universidade Nova de Lisboa,Faculdade de Ciências e Tecnologia for the degree of Doctor of Philosophy in Environmental Engineering

NiII, CuII and ZnII complexes with a sterically hindered scorpionate ligand (TpmsPh) and catalytic application in the diasteroselective nitroaldol (Henry) reaction

The Ni-II and Zn-II complexes [MCl(Tpms(Ph))] (Tpms(Ph) = SO3C(pz(Ph))(3), pz = pyrazolyl; M = Ni 2 or Zn 3) and the Cu-II complex [CuCl(Tpms(Ph))(H2O)] (4) have been prepared by treatment of the lithium salt of the sterically demanding and coordination flexible tris(3-phenyl-1-pyrazolyl)methanesulfonate (Tpms(Ph))(-) (1) with the respective metal chlorides. The (Tpms(Ph))(-) ligand shows the N-3 or N2O coordination modes in 2 and 3 or in 4, respectively. Upon reaction of 2 and 3 with Ag(CF3SO3) in acetonitrile the complexes [M(Tpms(Ph))-(MeCN)](CF3SO3) (M = Ni 5 or Zn 6, respectively) were formed. The compounds were obtained in good yields and characterized by analytic and spectral (IR, H-1 and C-13{H-1} NMR, ESI-MS) data, density functional theory (DFT) methods and {for 4 and [(Bu4N)-Bu-n](Tpms(Ph)) (7), the tatter obtained upon Li+ replacement by [(Bu4N)-Bu-n](+) in Li(Tpms(Ph))} by single crystal X-ray diffraction analysis. The Zn-II and Cu-II complexes (3 and 4, respectively) act as efficient catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehydes and nitroethane to the corresponding beta-nitroalkanols (up to 99% yield, at room temperature) with diastereoselectivity towards the formation of the anti isomer, whereas the Ni-II complex 2 only shows a modest catalytic activity.

X Radiation dose implications in screening patients with ferromagnetic IOFBs prior to MRI: a literary review

Patients scheduled for a magnetic resonance imaging (MRI) scan sometimes require screening for ferromagnetic Intra Orbital Foreign Bodies (IOFBs). To assess this, they are required to fill out a screening protocol questionnaire before their scan. If it is established that a patient is at high risk, radiographic imaging is necessary. This review examines literature to evaluate which imaging modality should be used to screen for IOFBs, considering that the eye is highly sensitive to ionising radiation and any dose should be minimised. Method: Several websites and books were searched for information, these were as follows: PubMed, Science Direct, Web of Knowledge and Google Scholar. The terms searched related to IOFB, Ionising radiation, Magnetic Resonance Imaging Safety, Image Quality, Effective Dose, Orbits and X-ray. Thirty five articles were found, several were rejected due to age or irrelevance; twenty eight were eventually accepted. Results: There are several imaging techniques that can be used. Some articles investigated the use of ultrasound for investigation of ferromagnetic IOFBs of the eye and others discussed using Computed Tomography (CT) and X-ray. Some gaps in the literature were identified, mainly that there are no articles which discuss the lowest effective dose while having adequate image quality for orbital imaging. Conclusion: X-ray is the best method to identify IOFBs. The only problem is that there is no research which highlights exposure factors that maintain sufficient image quality for viewing IOFBs and keep the effective dose to the eye As Low As Reasonably Achievable (ALARA).

MBR activated sludge filterability characterization in cross flow filtration

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do grau de Mestre em Engenharia do Ambiente, perfil Sanitária

Mechanical behavior and localized failure modes in a porous basalt from the Azores

Basaltic rocks are the main component of the oceanic upper crust, thus of potential interest for water and geothermal resources, storage of CO2 and volcanic edifice stability. In this work, we investigated experimentally the mechanical behavior and the failure modes of a porous basalt, with an initial connected porosity of 18%. Results were acquired under triaxial compression experiments at confining pressure in the range of 25-200 MPa on water saturated samples. In addition, a purely hydrostatic test was also performed to reach the pore collapse critical pressure P*. During hydrostatic loading, our results show that the permeability is highly pressure dependent, which suggests that the permeability is mainly controlled by pre-existing cracks. When the sample is deformed at pressure higher than the pore collapse pressure P*, some very small dilatancy develops due to microcracking, and an increase in permeability is observed. Under triaxial loading, two modes of deformation can be highlighted. At low confining pressure (Pc < 50 MPa), the samples are brittle and shear localization occurs. For confining pressure > 50 MPa, the stress-strain curves are characterized by strain hardening and volumetric compaction. Stress drops are also observed, suggesting that compaction may be localized. The presence of compaction bands is confirmed by our microstructure analysis. In addition, the mechanical data allows us to plot the full yield surface for this porous basalt, which follows an elliptic cap as previously observed in high porosity sandstones and limestones.

Energy efficiency of quadruped gaits

This paper studies periodic gaits of quadruped locomotion systems. The purpose is to determine the best set of gait and locomotion variables during walking, for different robot velocities, based on two formulated performance measures. A set of experiments reveals the influence of the gait and locomotion variables upon the proposed indices, namely that the gait and the locomotion parameters should be adapted to the robot forward velocity.

Post-processing Techniques in Free Boundary Flows during Liquid Composite Moulding Processes

Post-processing a finite element solution is a well-known technique, which consists in a recalculation of the originally obtained quantities such that the rate of convergence increases without the need for expensive remeshing techniques. Postprocessing is especially effective in problems where better accuracy is required for derivatives of nodal variables in regions where Dirichlet essential boundary condition is imposed strongly. Consequently such an approach can be exceptionally good in modelling of resin infiltration under quasi steady-state assumption by remeshing techniques and with explicit time integration, because only the free-front normal velocities are necessary to advance the resin front to the next position. The new contribution is the post-processing analysis and implementation of the freeboundary velocities of mesolevel infiltration analysis. Such implementation ensures better accuracy on even coarser meshes, which in consequence reduces the computational time also by the possibility of employing larger time steps.

Deep crustal structure across a young passive margin from wide-angle and reflection seismic data (The Sardinia Experiment) - I. Gulf of Lion's margin

The conjugate margins system of the Gulf of Lion and West Sardinia (GLWS) represents a unique natural laboratory for addressing fundamental questions about rifting due to its landlocked situation, its youth, its thick sedimentary layers, including prominent palaeo-marker such as the MSC event, and the amount of available data and multidisciplinary studies. The main goals of the SARDINIA experiment, were to (i) investigate the deep structure of the entire system within the two conjugate margins: the Gulf of Lion and West Sardinia, (ii) characterize the nature of the crust, and (iii) define the geometry of the basin and provide important constrains on its genesis. This paper presents the results of P-wave velocity modelling on three coincident near-vertical reflection multi-channel seismic (MCS) and wide-angle seismic profiles acquired in the Gulf of Lion, to a depth of 35 km. A companion paper [part II Afilhado et al., 2015] addresses the results of two other SARDINIA profiles located on the oriental conjugate West Sardinian margin. Forward wide-angle modelling of both data sets confirms that the margin is characterised by three distinct domains following the onshore unthinned, 33 km-thick continental crust domain: Domain I is bounded by two necking zones, where the crust thins respectively from 30 to 20 and from 20 to 7 km over a width of about 170 km; the outermost necking is imprinted by the well-known T-reflector at its crustal base; Domain II is characterised by a 7 km-thick crust with anomalous velocities ranging from 6 to 7.5 km/s; it represents the transition between the thinned continental crust (Domain I) and a very thin (only 4-5 km) "atypical" oceanic crust (Domain III). In Domain II, the hypothesis of the presence of exhumed mantle is falsified by our results: this domain may likely consist of a thin exhumed lower continental crust overlying a heterogeneous, intruded lower layer. Moreover, despite the difference in their magnetic signatures, Domains II and III present the very similar seismic velocities profiles, and we discuss the possibility of a connection between these two different domains.

Deep crustal structure across a young passive margin from wide-angle and reflection seismic data (The Sardinia Experiment) - II. Sardinia's margin

Geophysical data acquired on the conjugate margins system of the Gulf of Lion and West Sardinia (GLWS) is unique in its ability to address fundamental questions about rifting (i.e. crustal thinning, the nature of the continent-ocean transition zone, the style of rifting and subsequent evolution, and the connection between deep and surface processes). While the Gulf of Lion (GoL) was the site of several deep seismic experiments, which occurred before the SARDINIA Experiment (ESP and ECORS Experiments in 1981 and 1988 respectively), the crustal structure of the West Sardinia margin remains unknown. This paper describes the first modeling of wide-angle and near-vertical reflection multi-channel seismic (MCS) profiles crossing the West Sardinia margin, in the Mediterranean Sea. The profiles were acquired, together with the exact conjugate of the profiles crossing the GoL, during the SARDINIA experiment in December 2006 with the French R/V L'Atalante. Forward wide-angle modeling of both data sets (wide-angle and multi-channel seismic) confirms that the margin is characterized by three distinct domains following the onshore unthinned, 26 km-thick continental crust : Domain V, where the crust thins from 26 to 6 km in a width of about 75 km; Domain IV where the basement is characterized by high velocity gradients and lower crustal seismic velocities from 6.8 to 7.25 km/s, which are atypical for either crustal or upper mantle material, and Domain III composed of "atypical" oceanic crust.The structure observed on the West Sardinian margin presents a distribution of seismic velocities that is symmetrical with those observed on the Gulf of Lion's side, except for the dimension of each domain and with respect to the initiation of seafloor spreading. This result does not support the hypothesis of simple shear mechanism operating along a lithospheric detachment during the formation of the Liguro-Provencal basin.

Modified Particle Swarm Optimization Applied to Integrated Demand Response and DG Resources Scheduling

The elastic behavior of the demand consumption jointly used with other available resources such as distributed generation (DG) can play a crucial role for the success of smart grids. The intensive use of Distributed Energy Resources (DER) and the technical and contractual constraints result in large-scale non linear optimization problems that require computational intelligence methods to be solved. This paper proposes a Particle Swarm Optimization (PSO) based methodology to support the minimization of the operation costs of a virtual power player that manages the resources in a distribution network and the network itself. Resources include the DER available in the considered time period and the energy that can be bought from external energy suppliers. Network constraints are considered. The proposed approach uses Gaussian mutation of the strategic parameters and contextual self-parameterization of the maximum and minimum particle velocities. The case study considers a real 937 bus distribution network, with 20310 consumers and 548 distributed generators. The obtained solutions are compared with a deterministic approach and with PSO without mutation and Evolutionary PSO, both using self-parameterization.

Sondagem de Belverde (Cenozóico, Península de Setúbal, Portugal). Diagrafias

In the aim of the project "Recognition of the Miocene of the distal region of the Lower Tagus Basin through a borehole with continuous sampling", Temperature, Natural Gamma Ray, Neutron (almost in all the borehole), Sonic, SP and SPR (in two small sections in upper and lower parts of the Miocene Series) geophysical logs were carried on. Interpretation of those logs and comparison with chronological, lithostratigraphical, micropaleontological and clay mineraIs data; helped in the definition of depositional sequences and to obtain paleoenvironmental reconstructions that could lead to a better understanding of the evolution of the Setúbal Península and Lisboa regions Miocene gulf. Log data agree with the lithologic succession observed in the Belverde borehole, essentially silty sandstones/sandy siltstones (with variable clay content) to clays, often with marly intercalations. Sonic logs (and Neutron logs, in general) reflect the sediments porosity. The higher acoustic velocities are often related to compact/massive layers as claystones and/or limestones and rather fossiliferous marly layers. Lower values are obtained for porous, silty sandstones (fossiliferous and with scarce clay content) and bio-calcareous sandstones. As indicative, we obtained the mean values of 2500-3000m/s for the higher velocities and 1300-1600m/s for the lowest ones. ln Natural Gamma Ray log, the radiation peaks can be correlated to often fossiliferous marly micaceous layers. Radioactive micas are present. It seems that the gamma peaks and the depositional sequences previously defined for the Lower Tagus Basin (see Antunes et al., 1999, 2000; Pais et al., 2002) can be correlated, taking also into account the whole available micropaleontological, palynological and isotopic evidence.

Estimation of the Crustal Bulk Properties Beneath Mainland Portugal from P-Wave Teleseismic Receiver Functions

In this work, we present results from teleseismic P-wave receiver functions (PRFs) obtained in Portugal, Western Iberia. A dense seismic station deployment conducted between 2010 and 2012, in the scope of the WILAS project and covering the entire country, allowed the most spatially extensive probing on the bulk crustal seismic properties of Portugal up to date. The application of the H-κ stacking algorithm to the PRFs enabled us to estimate the crustal thickness (H) and the average crustal ratio of the P- and S-waves velocities V p/V s (κ) for the region. Observations of Moho conversions indicate that this interface is relatively smooth with the crustal thickness ranging between 24 and 34 km, with an average of 30 km. The highest V p/V s values are found on the Mesozoic-Cenozoic crust beneath the western and southern coastal domain of Portugal, whereas the lowest values correspond to Palaeozoic crust underlying the remaining part of the subject area. An average V p/V s is found to be 1.72, ranging 1.63-1.86 across the study area, indicating a predominantly felsic composition. Overall, we systematically observe a decrease of V p/V s with increasing crustal thickness. Taken as a whole, our results indicate a clear distinction between the geological zones of the Variscan Iberian Massif in Portugal, the overall shape of the anomalies conditioned by the shape of the Ibero-Armorican Arc, and associated Late Paleozoic suture zones, and the Meso-Cenozoic basin associated with Atlantic rifting stages. Thickened crust (30-34 km) across the studied region may be inherited from continental collision during the Paleozoic Variscan orogeny. An anomalous crustal thinning to around 28 km is observed beneath the central part of the Central Iberian Zone and the eastern part of South Portuguese Zone.

Mantle beneath the Gibraltar Arc from receiver functions

P and S receiver functions (PRF and SRF) from 19 seismograph stations in the Gibraltar Arc and the Iberian Massif reveal new details of the regional deep structure. Within the high-velocity mantle body below southern Spain the 660-km discontinuity is depressed by at least 20 km. The Ps phase from the 410-km discontinuity is missing at most stations in the Gibraltar Arc. A thin (similar to 50 km) low-S-velocity layer atop the 410-km discontinuity is found under the Atlantic margin. At most stations the S410p phase in the SRFs arrives 1.0-2.5 s earlier than predicted by IASP91 model, but, for the propagation paths through the upper mantle below southern Spain, the arrivals of S410p are delayed by up to +1.5 s. The early arrivals can be explained by elevated Vp/Vs ratio in the upper mantle or by a depressed 410-km discontinuity. The positive residuals are indicative of a low (similar to 1.7 versus similar to 1.8 in IASP91) Vp/Vs ratio. Previously, the low ratio was found in depleted lithosphere of Precambrian cratons. From simultaneous inversion of the PRFs and SRFs we recognize two types of the mantle: 'continental' and 'oceanic'. In the 'continental' upper mantle the S-wave velocity in the high-velocity lid is 4.4-4.5 km s(-1), the S-velocity contrast between the lid and the underlying mantle is often near the limit of resolution (0.1 km s(-1)), and the bottom of the lid is at a depth reaching 90 100 km. In the 'oceanic' domain, the S-wave velocities in the lid and the underlying mantle are typically 4.2-4.3 and similar to 4.0 km s(-1), respectively. The bottom of the lid is at a shallow depth (around 50 km), and at some locations the lid is replaced by a low S-wave velocity layer. The narrow S-N-oriented band of earthquakes at depths from 70 to 120 km in the Alboran Sea is in the 'continental' domain, near the boundary between the 'continental' and 'oceanic' domains, and the intermediate seismicity may be an effect of ongoing destruction of the continental lithosphere.

Ambient noise tomography of the East African Rift in Mozambique

Seismic ambient noise tomography is applied to central and southern Mozambique, located in the tip of the East African Rift (EAR). The deployment of MOZART seismic network, with a total of 30 broad-band stations continuously recording for 26 months, allowed us to carry out the first tomographic study of the crust under this region, which until now remained largely unexplored at this scale. From cross-correlations extracted from coherent noise we obtained Rayleigh wave group velocity dispersion curves for the period range 5–40 s. These dispersion relations were inverted to produce group velocity maps, and 1-D shear wave velocity profiles at selected points. High group velocities are observed at all periods on the eastern edge of the Kaapvaal and Zimbabwe cratons, in agreement with the findings of previous studies. Further east, a pronounced slow anomaly is observed in central and southern Mozambique, where the rifting between southern Africa and Antarctica created a passive margin in the Mesozoic, and further rifting is currently happening as a result of the southward propagation of the EAR. In this study, we also addressed the question concerning the nature of the crust (continental versus oceanic) in the Mozambique Coastal Plains (MCP), still in debate. Our data do not support previous suggestions that the MCP are floored by oceanic crust since a shallow Moho could not be detected, and we discuss an alternative explanation for its ocean-like magnetic signature. Our velocity maps suggest that the crystalline basement of the Zimbabwe craton may extend further east well into Mozambique underneath the sediment cover, contrary to what is usually assumed, while further south the Kaapval craton passes into slow rifted crust at the Lebombo monocline as expected. The sharp passage from fast crust to slow crust on the northern part of the study area coincides with the seismically active NNE-SSW Urema rift, while further south the Mazenga graben adopts an N-S direction parallel to the eastern limit of the Kaapvaal craton. We conclude that these two extensional structures herald the southward continuation of the EAR, and infer a structural control of the transition between the two types of crust on the ongoing deformation.

Destruction of the tar present in syngas by combustion in porous media

The cleaning of syngas is one of the most important challenges in the development of technologies based on gasification of biomass. Tar is an undesired byproduct because, once condensed, it can cause fouling and plugging and damage the downstream equipment. Thermochemical methods for tar destruction, which include catalytic cracking and thermal cracking, are intrinsically attractive because they are energetically efficient and no movable parts are required nor byproducts are produced. The main difficulty with these methods is the tendency for tar to polymerize at high temperatures. An alternative to tar removal is the complete combustion of the syngas in a porous burner directly as it leaves the particle capture system. In this context, the main aim of this study is to evaluate the destruction of the tar present in the syngas from biomass gasification by combustion in porous media. A gas mixture was used to emulate the syngas, which included toluene as a tar surrogate. Initially, CHEMKIN was used to assess the potential of the proposed solution. The calculations revealed the complete destruction of the tar surrogate for a wide range of operating conditions and indicated that the most important reactions in the toluene conversion are C6H5CH3 + OH <-> C6H5CH2 + H2O, C6H5CH3 + OH <-> C6H4CH3 + H2O, and C6H5CH3 + O <-> OC6H4CH3 + H and that the formation of toluene can occur through C6H5CH2 + H <-> C6H5CH3. Subsequently, experimental tests were performed in a porous burner fired with pure methane and syngas for two equivalence ratios and three flow velocities. In these tests, the toluene concentration in the syngas varied from 50 to 200 g/Nm(3). In line with the CHEMKIN calculations, the results revealed that toluene was almost completely destroyed for all tested conditions and that the process did not affect the performance of the porous burner regarding the emissions of CO, hydrocarbons, and NOx.