Removal of BrO3 − from drinking water samples using newly developed agricultural waste-based activated carbon and its determination by ultra-performance liquid chromatography-mass spectrometry

Activated carbon was prepared from date pits via chemical activation with H3PO4. The effects of activating agent concentration and activation temperature on the yield and surface area were studied. The optimal activated carbon was prepared at 450 °C using 55 % H3PO4. The prepared activated carbon was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric-differential thermal analysis, and Brunauer, Emmett, and Teller (BET) surface area. The prepared date pit-based activated carbon (DAC) was used for the removal of bromate (BrO3 −). The concentration of BrO3 − was determined by ultra-performance liquid chromatography-mass tandem spectrometry (UPLC-MS/MS). The experimental equilibrium data for BrO3 − adsorption onto DAC was well fitted to the Langmuir isotherm model and showed maximum monolayer adsorption capacity of 25.64 mg g−1. The adsorption kinetics of BrO3 − adsorption was very well represented by the pseudo-first-order equation. The analytical application of DAC for the analysis of real water samples was studied with very promising results.

Avaliação preliminar da contaminação por BTEX, em água subterrânea de poços tubulares, no município de Natal-RN

Among the different types of pollutants typically attributed to human activities, the petroleum products are one of the most important because of its toxic potential. This toxicity is attributed to the presence of substances such as benzene and its derivatives are very toxic to the central nervous system of man, with chronic toxicity, even in small concentrations. The area chosen for study was the city of Natal, capital of Rio Grande do Norte, where samples were collected in six different areas in the city, comprising 10 wells located in the urban area, being carried out in three distinct periods March/2009, December / June/2010 and 2009, and were evaluated for contamination by volatile hydrocarbons (BTEX - benzene, toluene, ethylbenzene and xylenes), so this work aimed to assess the quality of groundwater wells that supply funding for public supply and trade in the urban area of the city of Natal, in Rio Grande do Norte, contributing to the environmental assessment of the municipality. The analysis of BTEX in water was performed according to EPA Method 8021b. Was used the technique of headspace (TriPlus TP100) coupled to high resolution gas chromatography with selective photoionization detector (PID) and flame ionization (FID) - model Trace GC Ultra, Thermo Electron Corporation brand. The procedure adopted allowed the detection of concentrations of the order of μg.L-1. Data analysis with respect to BTEX in groundwater in the area monitored so far, shows that water quality is still preserved, because it exceeds the limits imposed by the potability Resolution CONAMA Nº. 396, April 2008

Geochemical analysis at ODP Site 207-1259 from the Demerara Rise in the western equatorial Atlantic

Organic carbon-rich shales deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 were drilled during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic variations in marine and detrital sediment contribution, depositional processes, and bottom water redox conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V, Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites was generally dominated by marine material (carbonate, organic matter, opal) although relationships of detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular, and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older Cenomanian-Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms controlling continental supply and ocean redox state were time-invariant and kept the western equatorial Atlantic margin widely anoxic over millions of years.

MULTIMODAL PERFORMANCE AND RELIABILITY ANALYSIS OF THE PIERRE AUGER OBSERVATORY NORTH SITE

The Pierre Auger Cosmic Ray Observatory North site employs a large array of surface detector stations (tanks) to detect the secondary particle showers generated by ultra-high energy cosmic rays. Due to the rare nature of ultra-high energy cosmic rays, it is important to have a high reliability on tank communications, ensuring no valuable data is lost. The Auger North site employs a peer-to-peer paradigm, the Wireless Architecture for Hard Real-Time Embedded Networks (WAHREN), designed specifically for highly reliable message delivery over fixed networks, under hard real-time deadlines. The WAHREN design included two retransmission protocols, Micro- and Macro- retransmission. To fully understand how each retransmission protocol increased the reliability of communications, this analysis evaluated the system without using either retransmission protocol (Case-0), both Micro- and Macro-retransmission individually (Micro and Macro), and Micro- and Macro-retransmission combined. This thesis used a multimodal modeling methodology to prove that a performance and reliability analysis of WAHREN was possible, and provided the results of the analysis. A multimodal approach was necessary because these processes were driven by different mathematical models. The results from this analysis can be used as a framework for making design decisions for the Auger North communication system.

Analysis of the main phenomena affecting solid rocket motors internal ballistics

In solid rocket motors, the absence of combustion controllability and the large amount of financial resources involved in full-scale firing tests, increase the importance of numerical simulations in order to asses stringent mission thrust requirements and evaluate the influence of thrust chamber phenomena affecting the grain combustion. Among those phenomena, grain local defects (propellant casting inclusions and debondings), combustion heat accumulation involving pressure peaks (Friedman Curl effect), and case-insulating thermal protection material ablation affect thrust prediction in terms of not negligible deviations with respect to the nominal expected trace. Most of the recent models have proposed a simplified treatment to the problem using empirical corrective functions, with the disadvantages of not fully understanding the physical dynamics and thus of not obtaining predictive results for different configurations of solid rocket motors in a boundary conditions-varied scenario. This work is aimed to introduce different mathematical approaches to model, analyze, and predict the abovementioned phenomena, presenting a detailed physical interpretation based on existing SRMs configurations. Internal ballistics predictions are obtained with an in-house simulation software, where the adoption of a dynamic three-dimensional triangular mesh together with advanced computer graphics methods, allows the previous target to be reached. Numerical procedures are explained in detail. Simulation results are carried out and discussed based on experimental data.

Altered transcriptional and epigenetic regulation affects brain cells proliferation and differentiation in the ultra-rare genetic demyelinating disease AGC1 deficiency: a study on in vitro models

AGC1 deficiency is a rare demyelinating disease caused by mutations in the SLC25A12 gene, which encodes for the mitochondrial glutamate-aspartate carrier 1 (AGC1/Alarar), highly expressed in the central nervous system. In neurons, impairment in AGC1 activity leads to reduction in N-acetyl-aspartate, the main lipid precursor for myelin synthesis (Profilo et al., 2017); in oligodendrocytes progenitors cells, AGC1 down regulation has been related to early arrest proliferation and premature differentiation (Petralla et al., 2019). Additionally, in vivo AGC1 deficiency models i.e., heterozygous mice for AGC1 knock-out and neurospheres from their subventricular zone, respectively, showed a global decrease in cells proliferation and a switch in neural stem cells (NSCs) commitment, with specific reduction in OPCs number and increase in neural and astrocytic pools (Petralla et al., 2019). Therefore, the present study aims to investigate the transcriptional and epigenetic regulation underlying the alterations observed in OPCs and NSCs biological mechanisms, in either AGC1 deficiency models of Oli-neu cells (murine immortalized oligodendrocytes precursors cells), partially silenced by a shRNA for SLC25A12 gene, and SVZ-derived neurospheres from AGC1+/- mice. Western blot and immunofluorescence analysis revealed significant variations in the expression of transcription factors involved in brain cells’ proliferation and differentiation, in association with altered histone post-translational modifications, as well as histone acetylases (HATs) and deacetylases (HDACs) activity/expression, suggesting an improper transcriptional and epigenetic regulation affecting both AGC1 deficiency in vitro models. Furthermore, given the large role of acetylation in controlling in specific time-windows OPC maturation (Hernandez and Casaccia; 2015), pharmacological HATs/HDACs inhibitions were performed, confirming the involvement of chromatin remodelling enzymes in the altered proliferation and early differentiation observed in the AGC1 deficiency models of siAGC1 Oli-neu cells and AGC1+/- mice-derived neurospheres.

Analysis and Evaluation of Tiny Machine Learning applications

The aim of TinyML is to bring the capability of Machine Learning to ultra-low-power devices, typically under a milliwatt, and with this it breaks the traditional power barrier that prevents the widely distributed machine intelligence. TinyML allows greater reactivity and privacy by conducting inference on the computer and near-sensor while avoiding the energy cost associated with wireless communication, which is far higher at this scale than that of computing. In addition, TinyML’s efficiency makes a class of smart, battery-powered, always-on applications that can revolutionize the collection and processing of data in real time. This emerging field, which is the end of a lot of innovation, is ready to speed up its growth in the coming years. In this thesis, we deploy three model on a microcontroller. For the model, datasets are retrieved from an online repository and are preprocessed as per our requirement. The model is then trained on the split of preprocessed data at its best to get the most accuracy out of it. Later the trained model is converted to C language to make it possible to deploy on the microcontroller. Finally, we take step towards incorporating the model into the microcontroller by implementing and evaluating an interface for the user to utilize the microcontroller’s sensors. In our thesis, we will have 4 chapters. The first will give us an introduction of TinyML. The second chapter will help setup the TinyML Environment. The third chapter will be about a major use of TinyML in Wake Word Detection. The final chapter will deal with Gesture Recognition in TinyML.

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.

Drug of abuse analysis: new methods in herbal and biological matrices for medicinal chemistry and forensic investigation

In this Ph.D. project, original and innovative approaches for the quali-quantitative analysis of abuse substances, as well as therapeutic agents with abuse potential and related compounds were designed, developed and validated for application to different fields such as forensics, clinical and pharmaceutical. All the parameters involved in the developed analytical workflows were properly and accurately optimised, from sample collection to sample pretreatment up to the instrumental analysis. Advanced dried blood microsampling technologies have been developed, able of bringing several advantages to the method as a whole, such as significant reduction of solvent use, feasible storage and transportation conditions and enhancement of analyte stability. At the same time, the use of capillary blood allows to increase subject compliance and overall method applicability by exploiting such innovative technologies. Both biological and non-biological samples involved in this project were subjected to optimised pretreatment techniques developed ad-hoc for each target analyte, making also use of advanced microextraction techniques. Finally, original and advanced instrumental analytical methods have been developed based on high and ultra-high performance liquid chromatography (HPLC,UHPLC) coupled to different detection means (mainly mass spectrometry, but also electrochemical, and spectrophotometric detection for screening purpose), and on attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) for solid-state analysis. Each method has been designed to obtain highly selective, sensitive yet sustainable systems and has been validated according to international guidelines. All the methods developed herein proved to be suitable for the analysis of the compounds under investigation and may be useful tools in medicinal chemistry, pharmaceutical analysis, within clinical studies and forensic investigations.

Retrieval of atmospheric trace gases from DOAS/MAX-DOAS ground-based spectra

The study of the atmospheric chemical composition is crucial to understand the climate changes that we are experiencing in the last decades and to monitor the air quality over industrialized areas. The Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) ground-based instruments are particularly suitable to derive the concentration of some trace gases that absorb the Visible (VIS) and Ultra-Violet (UV) solar radiation. The zenith-sky spectra acquired by the Gas Analyzer Spectrometer Correlating Optical Differences / New Generation 4 (GASCOD/NG4) instrument are exploited to retrieve the NO2 and O3 total Vertical Column Densities (VCDs) over Lecce. The results show that the NO2 total VCDs are significantly affected by the tropospheric content, consequence of the anthropogenic activity. Indeed, they present systematically lower values during Sunday, when less traffic is generally present around the measurement site, and during windy days, especially when the wind direction measured at 2 m height is not from the city of Lecce. Another MAX-DOAS instrument (SkySpec-2D) is exploited to create the first Italian MAX-DOAS site compliant to the Fiducial Reference Measurements for DOAS (FRM4DOAS) standards, in San Pietro Capofiume (SPC), located in the middle of the Po Valley. After the assessment of the SkySpec-2D’s performances through two measurement campaigns taken place in Bologna and in Rome, SkySpec-2D is installed in SPC on the 1st October 2021. Its MAX-DOAS spectra are used to retrieve the NO2 and O3 total VCDs, and aerosol extinction and NO2 tropospheric vertical profiles over the Po Valley exploiting the Bremen Optimal estimation REtrieval for Aerosol and trace gaseS (BOREAS) algorithm. Promising results are found, with high correlations against both in-situ and satellite data. In the future, these data will play an important role for air quality studies over the Po Valley and for satellite validation purposes.

High temporal resolution insights into early life histories: integrating histomorphometric, trace element and isotopic analyses of dental hard tissues in archaeological populations from Italy

Teeth, with their high mineralisation, incremental growth, and lack of remodelling, serve as biological archives that document an individual's development. This project aims to utilise the potential of teeth in bioarchaeological studies to achieve three primary objectives: 1) to investigate the application of histological and histochemical methods in reconstructing developmental bio-chronologies and early life histories; 2) to refine the temporal precision of isotopic analysis of dentine collagen by developing a novel protocol that integrates micro-sampling techniques with high-resolution histomorphometrics; and 3) to synthesise data from enamel and dentine for a comprehensive understanding of early life development and dietary transitions. This study adopts an integrated multidisciplinary bioarchaeological approach, conducting histomorphometric analysis on enamel and dentine across deciduous and permanent dentitions. It applies high-temporal resolution trace element analysis to enamel using LA-ICPMS and δ13C and δ15N isotope analyses through sequential micro-sampling to dentine of permanent teeth. Samples were selected from diverse archaeological contexts across the Italian peninsula, covering the Upper Palaeolithic, Copper Age, and Early Medieval periods, providing insight into diachronic variations in infant development and life history. Findings highlight the efficacy of histological and histochemical techniques in accurately determining growth rates, physiological stress, dietary shifts (particularly timing of weaning), and age at death in infant remains. The consistency and comparison between enamel and dentine underscores the enhanced insight obtained from integrating information from both tissues. Importantly, the newly proposed protocol significantly improves the temporal accuracy of dentine collagen analysis, facilitating precise chronological placement of the results over broad developmental associations. This study reaffirms the significance of teeth as valuable bioarchaeological instruments. By introducing and testing multidisciplinary methods, it provides deeper insights into early life history and cultural practices across diverse chronological contexts, highlighting the importance of advanced methodologies in extracting detailed, accurate, and nuanced information from past populations.

Design of a wearable platform for PPG analysis with multicore low-power processor

Photoplethysmography (PPG) sensors allow for noninvasive and comfortable heart-rate (HR) monitoring, suitable for compact wearable devices. However, PPG signals collected from such devices often suffer from corruption caused by motion artifacts. This is typically addressed by combining the PPG signal with acceleration measurements from an inertial sensor. Recently, different energy-efficient deep learning approaches for heart rate estimation have been proposed. To test these new solutions, in this work, we developed a highly wearable platform (42mm x 48 mm x 1.2mm) for PPG signal acquisition and processing, based on GAP9, a parallel ultra low power system-on-chip featuring nine cores RISC-V compute cluster with neural network accelerator and 1 core RISC-V controller. The hardware platform also integrates a commercial complete Optical Biosensing Module and an ARM-Cortex M4 microcontroller unit (MCU) with Bluetooth low-energy connectivity. To demonstrate the capabilities of the system, a deep learning-based approach for PPG-based HR estimation has been deployed. Thanks to the reduced power consumption of the digital computational platform, the total power budget is just 2.67 mW providing up to 5 days of operation (105 mAh battery).

Many-body approach to the BCS-BEC crossover for an imbalanced ultra-cold Fermi gas

The aim of this thesis is the study of the normal phase of a mass imbalanced and polarized ultra-cold Fermi gas in the context of the BCS-BEC crossover, using a diagrammatic approach known as t-matrix approximation. More specifically, the calculations are implemented using the fully self-consistent t-matrix (or Luttinger- Ward) approach, which is already experimentally and numerically validated for the balanced case. An imbalance (polarization) between the two spin populations works against pairing and superfluidity. For sufficiently large polarization (and not too strong attraction) the system remains in the normal phase even at zero temperature. This phase is expected to be well described by the Landau’s Fermi liquid theory. By reducing the spin polarization, a critical imbalance is reached where a quantum phase transition towards a superfluid phase occurs and the Fermi liquid description breaks down. Depending on the strength of the interaction, the exotic superfluid phase at the quantum critical point (QCP) can be either a FFLO phase (Fulde-Ferrell-Larkin-Ovchinnikov) or a Sarma phase. In this regard, the presence of mass imbalance can strongly influence the nature of the QCP, by favouring one of these two exotic types of pairing over the other, depending on whether the majority of the two species is heavier or lighter than the minority. The analysis of the system is made by focusing on the temperature-coupling-polarization phase diagram for different mass ratios of the two components and on the study of different thermodynamic quantities at finite temperature. The evolution towards a non-Fermi liquid behavior at the QCP is investigated by calculating the fermionic quasi-particle residues, the effective masses and the self-energies at zero temperature.

Bimbo: a gender analysis

This thesis aims to propose a gender analysis of the bimbo, that is the stereotype of a sexually attractive yet stupid woman. The presence of this cultural phenomenon in a number of aspects of mainstream pop culture gives rise to interesting research that deals with linguistics, the notion of prejudice, truth, and morality. Starting from notable bimbo figures like Marilyn Monroe, going through Anna Nicole Smith, and ending with the rising Gen Z Bimbo TikTok, this work reads the bimbo as a gender performance of femininity thanks to the lens provided by philosophers Judith Butler and Jean Baudrillard. The bimbo’s link to cosmetic surgery makes it possible to trace a brief outline of the feminist theory in relation to the understanding of the body as a political site. Ultimately, the subtle borders between the reenactment of the male gaze and a conscious reappropriation will be discussed. Because of the contingent nature of the bimbo, the purpose of this work is not necessarily to rewrite her as a feminist, but to present and embrace the at times contradicting multitudes of this pop culture trope.

Analysis Of The Dna Fourier Transform-infrared Microspectroscopic Signature Using An All-reflecting Objective.

The Fourier transform-infrared (FT-IR) signature of dry samples of DNA and DNA-polypeptide complexes, as studied by IR microspectroscopy using a diamond attenuated total reflection (ATR) objective, has revealed important discriminatory characteristics relative to the PO2(-) vibrational stretchings. However, DNA IR marks that provide information on the sample's richness in hydrogen bonds have not been resolved in the spectral profiles obtained with this objective. Here we investigated the performance of an all reflecting objective (ARO) for analysis of the FT-IR signal of hydrogen bonds in DNA samples differing in base richness types (salmon testis vs calf thymus). The results obtained using the ARO indicate prominent band peaks at the spectral region representative of the vibration of nitrogenous base hydrogen bonds and of NH and NH2 groups. The band areas at this spectral region differ in agreement with the DNA base richness type when using the ARO. A peak assigned to adenine was more evident in the AT-rich salmon DNA using either the ARO or the ATR objective. It is concluded that, for the discrimination of DNA IR hydrogen bond vibrations associated with varying base type proportions, the use of an ARO is recommended.