A Performance Measurement System to Manage CEN Operations, Evolution and Innovation

Part 16: Performance Measurement Systems

SOVLENT REACTIVITY AND INTERFACE EVOLUTION AT MODEL ELECTRODES FOR ENERGY APPLICATIONS

The Li-ion rechargeable battery (LIB) is widely used as an energy storage device, but has significant limitations in battery cycle life and safety. During initial charging, decomposition of the ethylene carbonate (EC)-based electrolytes of the LIB leads to the formation of a passivating layer on the anode known as the solid electrolyte interphase (SEI). The formation of an SEI has great impact on the cycle life and safety of LIB, yet mechanistic aspects of SEI formation are not fully understood. In this dissertation, two surface science model systems have been created under ultra-high vacuum (UHV) to probe the very initial stage of SEI formation at the model carbon anode surfaces of LIB. The first model system, Model System I, is an lithium-carbonate electrolyte/graphite C(0001) system. I have developed a temperature programmed desorption/temperature programmed reaction spectroscopy (TPD/TPRS) instrument as part of my dissertation to study Model System I in quantitative detail. The binding strengths and film growth mechanisms of key electrolyte molecules on model carbon anode surfaces with varying extents of lithiation were measured by TPD. TPRS was further used to track the gases evolved from different reduction products in the early-stage SEI formation. The branching ratio of multiple reaction pathways was quantified for the first time and determined to be 70.% organolithium products vs. 30% inorganic lithium product. The obtained branching ratio provides important information on the distribution of lithium salts that form at the very onset of SEI formation. One of the key reduction products formed from EC in early-stage SEI formation is lithium ethylene dicarbonate (LEDC). Despite intensive studies, the LEDC structure in either the bulk or thin-film (SEI) form is unknown. To enable structural study, pure LEDC was synthesized and subject to synchrotron X-ray diffraction measurements (bulk material) and STM measurements (deposited films). To enable studies of LEDC thin films, Model System II, a lithium ethylene dicarbonate (LEDC)-dimethylformamide (DMF)/Ag(111) system was created by a solution microaerosol deposition technique. Produced films were then imaged by ultra-high vacuum scanning tunneling microscopy (UHV-STM). As a control, the dimethylformamide (DMF)-Ag(111) system was first prepared and its complex 2D phase behavior was mapped out as a function of coverage. The evolution of three distinct monolayer phases of DMF was observed with increasing surface pressure — a 2D gas phase, an ordered DMF phase, and an ordered Ag(DMF)2 complex phase. The addition of LEDC to this mixture, seeded the nucleation of the ordered DMF islands at lower surface pressures (DMF coverages), and was interpreted through nucleation theory. A structural model of the nucleation seed was proposed, and the implication of ionic SEI products, such as LEDC, in early-stage SEI formation was discussed.

Experimentation of Rational Trust Evolution and Sustainability in Dynamic VOs

Part 10: Sustainability and Trust

The temporal evolution of the energy flux across scales in homogeneous turbulence

A temporal study of energy transfer across length scales is performed in 3D numerical simulations of homogeneous shear flow and isotropic turbulence. The average time taken by perturbations in the energy flux to travel between scales is measured and shown to be additive. Our data suggests that the propagation of disturbances in the energy flux is independent of the forcing and that it defines a ‘velocity’ that determines the energy flux itself. These results support that the cascade is, on average, a scale-local process where energy is continuously transmitted from one scale to the next in order of decreasing size.

ANALYSIS OF MACROINVERTEBRATE COMMUNITIES IN SEASONAL WETLANDS THROUGH TIME, ACROSS SPACE, AND USING SPECIES TRAITS

Restoration of natural wetlands may be informed by macroinvertebrate community composition. Macroinvertebrate communities of wetlands are influenced by environmental characteristics such as vegetation, soil, hydrology, land use, and isolation. This dissertation explores multiple approaches to the assessment of wetland macroinvertebrate community composition, and demonstrates how these approaches can provide complementary insights into the community ecology of aquatic macroinvertebrates. Specifically, this work focuses on macroinvertebrates of Delmarva Bays, isolated seasonal wetlands found on Maryland’s eastern shore. A comparison of macroinvertebrate community change over a nine years in a restored wetland complex indicated that the macroinvertebrate community of a rehabilitated wetlands more rapidly approximated the community of a reference site than did a newly created wetland. The recovery of a natural macroinvertebrate community in the rehabilitated wetland indicated that wetland rehabilitation should be prioritized over wetland creation and long-term monitoring may be needed to evaluate restoration success. This study also indicated that characteristics of wetland vegetation reflected community composition. The connection between wetland vegetation and macroinvertebrate community composition led to a regional assessment of predaceous diving beetle (Coleoptera: Dytiscidae) community composition in 20 seasonal wetlands, half with and half without sphagnum moss (Sphagnum spp.). Species-level identifications indicated that wetlands with sphagnum support unique and diverse assemblages of beetles. These patterns suggest that sphagnum wetlands provide habitat that supports biodiversity on the Delmarva Peninsula. To compare traits of co-occurring beetles, mandible morphology and temporal and spatial variation were measured between three species of predaceous diving beetles. Based on mandible architecture, all species may consume similarly sized prey, but prey characteristics likely differ in terms of piercing force required for successful capture and consumption. Therefore, different assemblages of aquatic beetles may have different effects on macroinvertebrate community structure. Integrating community-level and species-level data strengthens the association between individual organisms and their ecological role. Effective restoration of imperiled wetlands benefits from this integration, as it informs the management practices that both preserve biodiversity and promote ecosystem services.

Initial approach to irst-time seizures in pediatrics

Objective: Prove that conducting complementary studies at laboratories and imaging studies are unnecessary in irst-time unprovoked seizures, since there is no change in the evolution and prognosis of the disease, as well as the study of our population, the incidence rate and the proportion of our patients that have been studied and given maintenance treatment, so it can be determined whether or not our population should follow the suggestions of the American Academy of Pediatrics and the Spanish Pediatric Association. Methods: An observational study, including patients diagnosed with irst-time unprovoked seizures. They were followed up on by the emergency department and information was collected from their clinical history and compared with the results of the different studies between patients that suffered just one seizure and the ones that had recurrent seizures. Results: Thirty one patients were included, 14 males and 17 females. The average age was 5.5 years old. The 100% of patients were studied, and the groups were compared. The signiicant study was the electroencephalogram (EEG) with a p=0.02 (signiicance p<0.05), incidence of 41%. Conclusions: The study and diagnosis of irst-time unprovoked seizures is based on clinical manifestations. The EEG is important in the study and classiication of unprovoked seizures. Our population has an incidence and recurrence rate similar to that in the bibliography, and for that reason, this study suggests that the diagnostic and therapeutic guidelines of the American Academy of Pediatrics and the Spanish Pediatric Association should be followed.

In two waters: contemporary evolution of lagoonal and marine white seabream (Diplodus sargus) populations

Brackish water ecosystems are often exposed to wide variations in environmental variables, including temperature and salinity, which may cause strong selective pressures on organisms modifying the genetic patterns of species. The aim of this work was to test whether there is a ‘divergence-with-gene flow’ in coastal lagoon populations of white seabream (Diplodus sargus) (Ria Formosa, S Portugal and Mar Menor, SE Spain) respect to four marine populations, by using partial sequences of cyt b mitochondrial gene and information from nine microsatellite loci. Genetic diversity was highest in both coastal lagoons (Mar Menor and Ria Formosa) considering mitochondrial and nuclear markers. Although some of FST population pairwise comparisons were not significant, analyses of molecular variance (AMOVAs) detected differences between groups (coastal lagoon and marine) close to significance. Also, only two haplotypes (Cytb-17 and Cytb-18) were detected in both coastal lagoon sampling sites and these localities (Mar Menor and Ria Formosa) showed the highest number of singletons, some of them with a high number of mutations, as has been already described for other Mar Menor populations (Pomatochistus marmoratus and Holothuria polii). Also, several tests detected significant positive and balancing selection considering mtDNA and microsatellite data. These data support the hypothesis of selection as one of the drivers of the genetic differences found between coastal lagoon and marine populations. The life strategy adopted by Diplodus sargus in coastal lagoons allows it to decrease its mortality rate and improve the heritability of its genes. Also, the increase time spent in coastal lagoons with different temperatures and salinities favours the fitness selection and the maintenance of exclusive haplotypes and genotypes in coastal lagoon inhabitants favouring the ‘divergence-with-gene-flow’.

El Estribo Volcanic Complex: Evolution from a shield volcano to a cinder cone, Pátzcuaro Lake, Michoacán, México

El Estribo Volcanic Complex (EVC) is located in the northern part of the Michoacán–Guanajuato Volcanic Field within the Trans-Mexican Volcanic Belt (TMVB). El Estribo is located at the southern edge of the E-W Pátzcuaro fault that belongs to the Pátzcuaro-Jarácuaro graben, a western extension of the E-W Morelia–Acambay fault system. Stratigraphy, geochronology, chemistry, and mineral assemblages suggest that the volcanic complex was constructed in two periods separated by a ~ 100 ka volcanic hiatus: a) emission of lava flows that constructed a shield volcano between 126 ka, and b) mixed phreatomagmatic to Strombolian activity that formed a cinder cone ~ 28 ka. The magmas that fed these monogenetic volcanoes were able to use the same feeding system. The cinder cone itself was constructed by Strombolian fallouts and remobilized scoria beds, followed by an erosion period, and by a mixed phreatomagmatic to magmatic phase (Strombolian fallouts ending with lava flows). Soft-sedimentary deformation of beds and impact sags, cross-bedding, as well as pitting and hydrothermal cracks found in particles support the phreatomagmatic phase. The erupted magmas through time ejected basaltic andesitic lava flows (56.21–58.88% SiO2) that built the shield volcano and then basaltic andesitic scoria (57.65–59.05% SiO2) that constructed the cinder cone. Although they used the same feeding system, the geochemical data and the mineral chemistry of the magmas indicate that the shield volcano and the cinder cone were fed by different magma batches erupted thousands of years apart. Therefore, the location of El Estribo Volcanic Complex along an E-W fault that has generated two sector collapses of the shield volcano to the north may be directly linked to this complex redistribution of the magmatic paths to the surface. Our findings show that magmatic feeding systems within monogenetic volcanic fields could be long lived, questioning the classic view of the monogenetic nature of their volcanoes and yielding information about the potential volcanic risk of these settings, usually considered risk-free.

Evolution of classifiers for pitch estimation of piano music using cartesian genetic programming

Pitch Estimation, also known as Fundamental Frequency (F0) estimation, has been a popular research topic for many years, and is still investigated nowadays. The goal of Pitch Estimation is to find the pitch or fundamental frequency of a digital recording of a speech or musical notes. It plays an important role, because it is the key to identify which notes are being played and at what time. Pitch Estimation of real instruments is a very hard task to address. Each instrument has its own physical characteristics, which reflects in different spectral characteristics. Furthermore, the recording conditions can vary from studio to studio and background noises must be considered. This dissertation presents a novel approach to the problem of Pitch Estimation, using Cartesian Genetic Programming (CGP).We take advantage of evolutionary algorithms, in particular CGP, to explore and evolve complex mathematical functions that act as classifiers. These classifiers are used to identify piano notes pitches in an audio signal. To help us with the codification of the problem, we built a highly flexible CGP Toolbox, generic enough to encode different kind of programs. The encoded evolutionary algorithm is the one known as 1 + , and we can choose the value for . The toolbox is very simple to use. Settings such as the mutation probability, number of runs and generations are configurable. The cartesian representation of CGP can take multiple forms and it is able to encode function parameters. It is prepared to handle with different type of fitness functions: minimization of f(x) and maximization of f(x) and has a useful system of callbacks. We trained 61 classifiers corresponding to 61 piano notes. A training set of audio signals was used for each of the classifiers: half were signals with the same pitch as the classifier (true positive signals) and the other half were signals with different pitches (true negative signals). F-measure was used for the fitness function. Signals with the same pitch of the classifier that were correctly identified by the classifier, count as a true positives. Signals with the same pitch of the classifier that were not correctly identified by the classifier, count as a false negatives. Signals with different pitch of the classifier that were not identified by the classifier, count as a true negatives. Signals with different pitch of the classifier that were identified by the classifier, count as a false positives. Our first approach was to evolve classifiers for identifying artifical signals, created by mathematical functions: sine, sawtooth and square waves. Our function set is basically composed by filtering operations on vectors and by arithmetic operations with constants and vectors. All the classifiers correctly identified true positive signals and did not identify true negative signals. We then moved to real audio recordings. For testing the classifiers, we picked different audio signals from the ones used during the training phase. For a first approach, the obtained results were very promising, but could be improved. We have made slight changes to our approach and the number of false positives reduced 33%, compared to the first approach. We then applied the evolved classifiers to polyphonic audio signals, and the results indicate that our approach is a good starting point for addressing the problem of Pitch Estimation.

Vortex evolution in the wake of accelerating low-aspect-ratio plates and three-dimensional bodies of revolution

To find examples of effecient locomotion and manoeuvrability, one need only turn to the elegant solutions natural flyers and swimmers have converged upon. This dissertation is specifically motivated by processes of evolutionary convergence, which have led to the propulsors and body shapes in nature that exhibit strong geometric collapse over diverse scales. These body features are abstracted in the studies presented herein using low-aspect-ratio at plates and a three-dimensional body of revolution (a sphere). The highly-separated vortical wakes that develop during accelerations are systematically characterized as a function of planform shape, aspect ratio, Reynolds number, and initial boundary conditions. To this end, force measurements and time-resolved (planar) particle image velocimetry have been used throughout to quantify the instantaneous forces and vortex evolution in the wake of the bluff bodies. During rectilinear motions, the wake development for the flat plates is primarily dependent on plate aspect ratio, with edge discontinuities and curvature playing only a secondary role. Furthermore, the axisymmetric case, i.e. the circular plate, shows strong sensitivity to Reynolds number, while this sensitivity quickly diminishes with increasing aspect ratio. For rotational motions, global insensitivity to plate aspect ratio has been observed. For the sphere, it has been shown that accelerations play an important role in the mitigation of flow separation. These results - expounded upon in this dissertation - have begun to shed light on the specific vortex dynamics that may be coopted by flying and swimming species of all shapes and sizes towards efficient locomotion.

Monitoring and modelling the morphodynamic evolution of a breached barrier beach system

Predicting the evolution of a coastal cell requires the identification of the key drivers of morphology. Soft coastlines are naturally dynamic but severe storm events and even human intervention can accelerate any changes that are occurring. However, when erosive events such as barrier breaching occur with no obvious contributory factors, a deeper understanding of the underlying coastal processes is required. Ideally conclusions on morphological drivers should be drawn from field data collection and remote sensing over a long period of time. Unfortunately, when the Rossbeigh barrier beach in Dingle Bay, County Kerry, began to erode rapidly in the early 2000’s, eventually leading to it breaching in 2008, no such baseline data existed. This thesis presents a study of the morphodynamic evolution of the Inner Dingle Bay coastal system. The study combines existing coastal zone analysis approaches with experimental field data collection techniques and a novel approach to long term morphodynamic modelling to predict the evolution of the barrier beach inlet system. A conceptual model describing the long term evolution of Inner Dingle Bay in 5 stages post breaching was developed. The dominant coastal processes driving the evolution of the coastal system were identified and quantified. A new methodology of long term process based numerical modelling approach to coastal evolution was developed. This method was used to predict over 20 years of coastal evolution in Inner Dingle Bay. On a broader context this thesis utilised several experimental coastal zone data collection and analysis methods such as ocean radar and grain size trend analysis. These were applied during the study and their suitability to a dynamic coastal system was assessed.

Measure-valued mass evolution problems with flux boundary conditions and solution-dependent velocities

In this paper we prove well-posedness for a measure-valued continuity equation with solution-dependent velocity and flux boundary conditions, posed on a bounded one-dimensional domain. We generalize the results of an earlier paper [J. Differential Equations, 259 (2015), pp. 10681097] to settings where the dynamics are driven by interactions. In a forward-Euler-like approach, we construct a time-discretized version of the original problem and employ those results as a building block within each subinterval. A limit solution is obtained as the mesh size of the time discretization goes to zero. Moreover, the limit is independent of the specific way of partitioning the time interval [0, T]. This paper is partially based on results presented in Chapter 5 of [Evolution Equations for Systems Governed by Social Interactions, Ph.D. thesis, Eindhoven University of Technology, 2015], while a number of issues that were still open there are now resolved.

Convergent evolution of PICIs-mediated phage interference

Staphylococcal pathogenicity islands (SaPIs), the prototype members of the family of phage inducible chromosomal islands (PICIs), are extremely mobile phage satellites, which are transferred between bacterial hosts after their induction by a helper phage. The intimate relationship between SaPIs and their helper phages is one of the most studied examples of virus satellite interactions in prokaryotic cells. SaPIs encode and disseminate virulence and fitness factors, representing a driving force for bacterial adaptation and pathogenesis. Many SaPIs encode a conserved morphogenetic operon, including a core set of genes whose function allows them to parasitize and exploit the phage life cycle. One of the central mechanisms of this molecular piracy is the specific packaging of the SaPI genomes into reduced sized capsid structures derived from phage proteins. Pac phages were classically thought to be the only phages involved in the mobilisation of phage-mediated virulence genes, including the transfer of SaPIs within related and non-related bacteria. This study presents the involvement of S. aureus cos phages in the intra- and intergeneric transfer of cos SaPIs for the first time. A novel example of molecular parasitism is shown, by which this newly characterised group of cos SaPIs uses two distinct and complementary mechanisms to take over the helper phage packaging machinery for their own reproduction. SaPIbov5, the prototype of the cos SaPIs, does not encode the characteristic morphogenetic operon found in pac SaPIs. However, cos SaPIs features both pac and cos phage cleavage sequences in their genome, ensuring SaPI packaging in small- and full-sized phage particles, depending on the helper phage. Moreover, cos-site packaging in S. aureus was shown to require the activity of a phage HNH nuclease. The HNH protein functions together with the large terminase subunit, triggering cleavage and melting of the cos-site sequence. In addition, a novel piracy strategy, severely interfering with the helper phage reproduction, was identified in cos SaPIs and characterised. This mechanism of piracy depends on the cos SaPI-encoded ccm gene, which encodes a capsid protein involved in the formation of small phage particles, modifying the assembling process via a scaffolding mechanism. This strategy resembles the ones described for pac SaPIs and represents a remarkable example of convergent evolution. A further convergent mechanism of capsid size-reduction was identified and characterised for the Enterococcus faecalis EfCIV583 pathogenicity island, another member of the PICI family. In this case, the self-encoded CpmE conducts this molecular piracy through a putative scaffolding function. Similar to cos SaPIs, EfCIV583 carries the helper phage cleavage sequence in its genome enabling its mobilisation by the phage terminase complex. The results presented in this thesis show how two examples of non-related members of the PICI family follow the same evolutionary convergent strategy to interfere with their helper phage. These findings could indicate that the described strategies might be widespread among PICIs and implicate a significant impact of PICIs mediated-virulence gene transfer in bacterial evolution and the emergence of pathogenic bacteria.

Probing the innermost regions of AGN via time-resolved spectral analysis

The dynamics and geometry of the material inflowing and outflowing close to the supermassive black hole in active galactic nuclei are still uncertain. X-rays are the most suitable way to study the AGN innermost regions because of the Fe Kα emission line, a proxy of accretion, and Fe absorption lines produced by outflows. Winds are typically classified as Warm Absorbers (slow and mildly ionized) and Ultra Fast Outflows (fast and highly ionized). Transient Obscurers -optically thick winds that produce strong spectral hardening in X-rays, lasting from days to months- have been observed recently. Emission and absorption features vary on time-scales from hours to years, probing phenomena at different distances from the SMBH. In this work, we use time-resolved spectral analysis to investigate the accretion and ejection flows, to characterize them individually and search for correlations. We analyzed XMM-Newtomn data of a set of the brightest Seyfert 1 galaxies that went through an obscuration event: NGC 3783, NGC 3227, NGC 5548, and NGC 985. Our aim is to search for emission/absorption lines in short-duration spectra (∼ 10ks), to explore regions as close as the SMBH as the statistics allows for, and possibly catch transient phenomena. First we run a blind search to detect emission/absorption features, then we analyze their evolution with Residual Maps: we visualize simultaneously positive and negative residuals from the continuum in the time-energy plane, looking for patterns and relative time-scales. In NGC 3783 we were able to ascribe variations of the Fe Kα emission line to absorptions at the same energy due to clumps in the obscurer, whose presence is detected at >3σ, and to determine the size of the clumps. In NGC 3227 we detected a wind at ∼ 0.2c at ∼ 2σ, briefly appearing during an obscuration event.

On the role of AGN feedback in shaping galaxies across cosmic time

Understanding how Active Galactic Nuclei (AGN) shape galaxy evolution is a key challenge of modern astronomy. In the framework where black hole (BH) and galaxy growth are linked, AGN feedback must be tackled both at its “causes” (e.g. AGN-driven winds) and its “effects” (alteration of the gas reservoir in AGN hosts). The most informative cosmic time is z~1-3, at the peak of AGN activity and galaxy buildup, the so-called cosmic noon. The aim of this thesis is to provide new insights regarding some key questions that still remain open in this research field: i) What are the properties of AGN-driven sub-pc scale winds at z>1? ii) Are AGN-driven winds effective in influencing the life of galaxies? iii) Do AGN impact directly on star formation (SF) and gas content of their hosts? I first address AGN feedback as “caught in the act” by studying ultra-fast outflows (UFOs), X-ray AGN-driven winds, in gravitationally lensed quasars. I build the first statistically robust sample of high-z AGN, not preselected based on AGN-driven winds. I derive a first estimate of the high-z UFO detection fraction and measure the UFO duty cycle of a single high-z quasar for the first time. I also address the “effects” of AGN feedback on the life of host galaxies. If AGN influence galaxy growth, then they will reasonably impact the molecular gas reservoir first, and SF as a consequence. Through a comparative study of the molecular gas content in cosmic-noon AGN hosts and matched non-active galaxies (i.e., galaxies not hosting an AGN), we find that the host galaxies of more regular AGN (not selected to be the most luminous) are generally similar to non-active galaxies. However, we report on the possibility of a luminosity effect regulating the efficiency by which AGN might impact on galaxy growth.