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Ultrasonic Effervescence: Investigations of the Nucleation and Dynamics of Acoustic Cavitation for Histotripsy-Based TherapiesEdsall, Connor William 23 January 2023 (has links)
Histotripsy is a noninvasive mechanical ablation method that uses focused ultrasound to disintegrate target tissues into acellular homogenate through the generation of acoustic cavitation and is currently being developed for numerous clinical applications. Histotripsy uses high-pressure (>10 MPa), short-duration (<15 cycles) pulses to cause the rapid expansion and collapse of nuclei at the focus resulting in large applied stress and strain in the adjacent tissue. At a sufficiently high pressure above the target medium's intrinsic cavitation threshold and an adequate number of applied pulses, cavitation "bubble clouds" create precise lesions with high fidelity to the region of the focus. Despite advances in histotripsy, additional research is still needed to better understand the acoustic cavitation nucleation process and its effects on therapies using focused ultrasound. This understanding is critical to better predict and control pulse dose for more rapid and efficient ablation procedures, to reduce off-target cavitation events for safer focused ultrasound therapies, and to localize ablation for high-precision procedures near critical structures or treatments without active imaging guidance.
In this dissertation, I investigate the nucleation and dynamics of ultrasonically generated acoustic cavitation for novel applications of focused ultrasound. My Ph.D. thesis focuses on (1) investigating the effect of histotripsy pulsing parameters on bubble cloud cavitation nucleation, bubble dynamics, and ablation efficiency, (2) investigating the effect of nuclei characteristics on the threshold for cavitation nucleation and resulting bubble dynamics for therapeutic applications, and (3) developing methods alter select characteristics and dynamics of acoustic cavitation by adjusting pulsing parameters to optimize ablation efficiency in conventional and nanoparticle-mediated histotripsy. The culmination of this thesis will advance our understanding of the nucleation and behavior of acoustic cavitation from pulsed focused ultrasound and develop innovative systems to improve the efficacy, efficiency, and safety of clinical focused ultrasound therapies. / Doctor of Philosophy / Histotripsy is a noninvasive focused ultrasound method that precisely destroys target tissues such as tumors through the acoustic generation of cavitation and is currently being developed for numerous clinical applications. Histotripsy uses high-pressure, short-duration pulsed soundwaves to cause the bubbles to rapidly expand and collapse within a precise region called the focus. This rapid cavitation results in large mechanical strain in the targeted tissue. With increasingly higher pressure, numerous bubbles form in the shape of cavitation "bubble clouds" that create lesions, closely matching their shape, in the target tissue after a sufficient number of pulses have been applied. Despite advances in histotripsy, additional research is still needed to better understand the initiation of the acoustic cavitation process in histotripsy and its effects on focused ultrasound therapies. This understanding is critical to better predict and control ablation procedures, improve procedure efficiency, reduce off-target cavitation events for safer focused ultrasound therapies, and further increase ablation precision for procedures near critical structures or treatments without active image guidance.
In this dissertation, I investigate the initiation, growth, and collapse of ultrasonically generated acoustic cavitation for novel applications of focused ultrasound. My Ph.D. thesis focuses on (1) investigating the effect of histotripsy pulsing parameters on bubble cloud cavitation initiation, bubble growth and collapse, and treatment efficiency, (2) investigating the effect of particle characteristics on the threshold for cavitation initiation and resulting bubble behavior for therapeutic applications, and (3) adjusting pulsing parameters to optimize ablation efficiency in conventional and particle mediated histotripsy. The culmination of this thesis will advance our understanding of the initiation and behavior of acoustic cavitation from pulsed focused ultrasound and develop innovative systems to improve the efficacy, efficiency, and safety of clinically focused ultrasound therapies.
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Hydroxyl Radical Production via Acoustic Cavitation in Ultrasonic Humidifier SystemsAltizer, Chase Duncan 12 June 2018 (has links)
Ultrasonic humidifiers use sound vibrations at frequencies higher than can be heard by humans (> 20,000 Hz) to generate aerosolized water also have potential for inducing sonochemical reactions for chemicals present in water. This research focuses on examining oxidants formed within ultrasonic humidifiers, as well as the oxidants effects of contaminants in water used in the systems. Hydroxyl radicals were found using DMPO as a spin trap. Caffeine and 17β-estradiol, as pharmaceutical contaminants of drinking water, were both emitted from the humidifier when present in the water reservoir and would enter breathing air. Emitted 17β-estradiol was found at 60% of the initial concentration filled in the ultrasonic humidifier after 480 minutes. Caffeine exhibited less degradation than 17β-estradiol. Degradation of both pharmaceuticals was attributed to ultrasonic processes, most likely oxidation with hydroxyl radicals produced. Bromide as a contaminant of the fill water was found to remain constant over time. / MS / Ultrasonic humidifiers carry health benefits from humidified air, but also have potential for chemical reactions within the systems that can impact human health. This research focuses on examining oxidants formed in ultrasonic humidifiers, as well as the degradation of contaminants in water used in the ultrasonic humidifiers. Hydroxyl radicals were found to be generated within the humidifier system. Caffeine and 17β-estradiol, a common estrogen, are possible contaminants in drinking water, which may be used to fill a humidifier. Both were introduced and emitted from the ultrasonic humidifier. Emitted 17β-estradiol was found at 60% of the initial concentration filled in the ultrasonic humidifier at the start of 8 hours. Degradation of both pharmaceuticals was attributed to ultrasonic processes, most likely oxidation with hydroxyl radicals produced.
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The Role of Acoustic Cavitation in Ultrasound-triggered Drug Release from Echogenic LiposomesKopechek, Jonathan A. January 2011 (has links)
No description available.
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Characterisation of Single and Multibubble Cavitation Through Analysis of Molecular, Atomic and Ionic Line Emissions / Caractérisation des cavitations mono- et multi-bulle via l'analyse des lignes d'émission moléculaires, atomiques et ioniquesSchneider, Julia 12 April 2012 (has links)
La cavitation acoustique (formation, croissance et effondrement de bulles de gaz dans un liquide soumis aux ultrasons) est à l'origine de réactions chimiques (sonochimie) via la génération de conditions extrêmes lors de l'effondrement des bulles. Des températures de 103-104K et des pressions de l'ordre de 1000 atm sont atteintes au cœur des bulles [1]. Dans ces conditions, les liaisons chimiques des molécules volatiles présentes dans les bulles peuvent être rompues, formant, dans le cas de solutions aqueuses, des radicaux OH et H. Par ailleurs, l'effondrement violent des bulles de cavitation peut être accompagné par l'émission de lumière, sonoluminescence (SL), qui est le sujet d'étude de ce travail. Cette émission lumineuse est formée d'un continuum, de l'UV au proche IR, similaire à l'émission d'un corps noir, sur lequel peuvent se superposer des lignes d'émission atomiques ou moléculaires.On distingue deux types de SL: la SL mono-bulle (SBSL) et la SL multibulle (MBSL). En général, les spectres de MBSL se différencient de ceux de SBSL par la présence de lignes d'émission (d'atomes alcalins, de radicaux hydroxy… [2]), si bien que les mécanismes d'émission ainsi que la nature des conditions à l'intérieur des bulles lors de leur effondrement ont longtemps été considérés comme différents pour les systèmes mono- et multi-bulles. Un pont a été érigé entre les deux systèmes par le travail de Liang et al. [3] qui mit en évidence les conditions expérimentales permettant l'apparition de lignes dans le spectre de SBSL. Dans ce contexte, l'objectif de ce travail était de comparer les émissions de SBSL (27 kHz) et MBSL à haute et basse fréquences (20, 203, 607 kHz) pour différentes solutions aqueuses. Un sonoréacteur monobulle a été développé, dans lequel la température, la nature et la pression de gaz dissous ainsi que la pression acoustique sont contrôlés. Les électrolytes étudiés étaient : NaCl et les chlorures de lanthanides luminescents Ce3+, Tb3+, Eu3+ et Gd3+. Ces derniers peuvent être excités soit par absorption de photons dans l'UV soit par collisions avec des particules énergétiques [4].Dans la première partie de ce travail, les conditions à l'intérieur d'une monobulle lors de son effondrement ont été estimées via un fit du continuum par l'équation de Planck du corps noir. Les températures du corps noir obtenues sont de l'ordre de 104K, en accord avec des études précédentes. Elles sont indépendantes de la présence de NaCl et de la pression acoustique alors que l'intensité de SL y est très sensible. Les résultats obtenus remettent en question l'utilisation du modèle du corps noir en SL. Des lignes d'émission atomique et moléculaire se superposent parfois au continuum de SL : en MBSL, et en SBSL dans certaines conditions particulières (pression d'argon suffisante, faible pression acoustique) [3, 5]. Ce travail met en évidence la similarité entre la forme de l'émission de OH en SBSL et en MBSL à 20kHz, ce qui indique des conditions intrabulles très proches dans les conditions expérimentales étudiées [6]. En SBSL sous 70mbar d'Ar, l'intensité des lignes diminue lorsque la pression acoustique augmente, jusqu'à leur disparition dans le continuum. Cette évolution peut apparaître comme un lien entre SBSL et MBSL.Par ailleurs, cette étude confirme que la concentration en sodium à l'interface bulle-liquide, qui peut être enrichie par l'utilisation d'un contre-ion tensioactif, est le paramètre clé de l'observation de l'émission du sodium en SBSL, suggérant que l'excitation du sodium a lieu soit à l'interface de la bulle, soit en son cœur, après injection de gouttelettes. La seconde partie de cette étude concerne l'effet de la fréquence ultrasonore et de la puissance acoustique sur l'intensité de luminescence des ions lanthanides en MBSL. La luminescence des ions Tb3+, Ce3+ et Eu3+ est ainsi observée. La comparaison des rendements de SL et de photoluminescence indique qu'à l'exception de Ce3+, l'excitation par photons est min / The importance of acoustic cavitation, i.e., the formation, growth and collapse of gaseous cavities in liquid exposed to ultrasound, in sonochemistry is based on the generation of extreme conditions upon bubble collapse. Temperatures and pressures inside the collapsing bubble are approximated to reach 104 K and 1000 atm, respectively [suslick-1999]. Under such conditions chemical bonds of the solvent vapour or volatile solutes present in the bubble core are easily cleaved, which in the case of aqueous systems, leads to the formation of chemically reactive OH and H radicals. These primary radicals either recombine leading to chemiluminescence, or diffuse into solution, where they are liable to react with other species. Of particular importance in this work is the light emission that accompanies cavitation, termed sonoluminescence (SL). This emission is a broad continuum ranging from 200nm to 900 nm, resembling the emission of a blackbody, which can be superimposed with atomic or molecular emission lines comparable to bremsstrahlung. It is necessary to distinguish two forms of SL, single-bubble (SBSL) and multibubble (MBSL). In general, MBSL spectra differ from SBSL spectra in that they contain emission lines, e.g., from alkali atoms or hydroxyl radicals [matula-1995]. Consequently, it was, until recently considered that the mechanisms of light emission, and the nature of the bubble interior upon collapse were fundamentally different for the single and multibubble systems. Considering that MBSL is a cloud of single bubbles a bridging theory is desired.With this background the objective of the present work was to conduct a comparative spectroscopic analysis of SBSL, driven at 27 kHz, and MBSL generated from low and high ultrasonic frequencies (20, 203 and 607 kHz) of aqueous electrolyte solutions. Therefore a single bubble sonoreactor was developed, where the temperature, gas content and type, as well as the acoustic pressure could be controlled. The electrolytes of choice were: sodium chloride and chlorides of the luminescent lanthanide ions, Ce3+, Tb3+, Eu3+ and Gd3+, which can be excited by UV light absorption and collisions with energetic particles [kulmala-1995]. In the first part of this work the conditions upon bubble collapse were approximated by fitting the broad-band continuum of SBSL spectra of water with 70 mbar of argon and a 0.5 M NaCl solution with 70 mbar of argon using Planck's law of blackbody radiation. The obtained blackbody temperatures are in the range of 104 K, which is in good agreement with previous studies, but with the discrepancy of being independent of the presence of NaCl and the acoustic pressure, whereas the SL intensity increased by a factor of more than 10 upon increased acoustic pressure. The different trends followed by SL intensity and blackbody temperatures question the blackbody model. Another observation questioning the blackbody model is the appearance of atomic and molecular emission lines in MBSL and as recently observed also in SBSL [liang-2007, young-2001]. The present work proofed that the key factors for line emission in SBSL are small amounts of argon and low acoustic pressure. Moreover, the work revealed that the shape of the OH• radical emission is very similar to that in MBSL spectra, indicating the strong similarity of intrabubble conditions in MBSL and SBSL under certain experimental conditions [schneider-2011]. An increase of the acoustic pressure caused the continuum to overlap the lines until they become indistinguishable giving the usually in SBSL observed featureless continuum. This advance is a big step toward bridging the gap between SBSL and MBSL. Furthermore this study reveals that the concentration of the sodium ion at the interface of a single bubble can be enriched with a surface active counterion and the concentration is crucial for the observation of the sodium line in SBSL, suggesting that excitation of sodium either takes place at the interface of the
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Passive Imaging and Measurements of Acoustic Cavitation during Ultrasound AblationSalgaonkar, Vasant Anil January 2009 (has links)
No description available.
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Cristallisation de ZnSO4,7H2O sous ultrasons : Étude expérimentale et étude microscopique / Sono-crystallization of ZnSO4.7H20Harzali, Hassen 24 June 2011 (has links)
La cristallisation assistée par ultrasons permet de diminuer le temps d'induction et la largeur de la zone métastable, de modifier la distribution de tailles, de modifier le faciès des cristaux et d'augmenter le nombre des cristaux formés. L'origine microscopique de cet effet reste à ce jour non élucidée. Les ultrasons de puissance engendrent dans un liquide la naissance et l'oscillation très violente de milliards de petites bulles de gaz, phénomène appelé cavitation. Le cycle d'une de ces bulles sur une période acoustique consiste en une phase explosive suivie d'une implosion violente. A la fin de l'implosion, la pression peut atteindre 1 GPa. Plusieurs hypothèses sur les mécanismes mis en jeu sont proposées dans la littérature : refroidissement de la solution et augmentation de la pression au voisinage de l'interface, évaporation du solvant dans la bulle, et ségrégation des molécules ou des ions du soluté au voisinage de la bulle lors de la phase implosive. Afin d'examiner l'influence de la pression, des expériences de cristallisation du sulfate de zinc heptahydraté ont été menées (mesure de temps d'induction). Ce sel présente une solubilité indépendante de la pression entre 0 et 10 000 bars. Nos expériences ont montré que le temps d'induction est fortement diminué en présence d'ultrasons. Ce résultat nous permet d'affirmer que la pression au voisinage de la bulle n'entre pas en jeu dans le mécanisme de la nucléation primaire du ZnSO4,7H2O en présence d'ultrasons. Après l'étude de l'effet de la sursaturation, nous avons essayé d'exploré l'effet de la puissance ultrasonore, du gaz dissous et de la hauteur du liquide dans la cuve sur le temps d'induction. Il a été constaté que les ultrasons permettent de diminuer le temps d'induction. Il a été observé que la courbe du temps d'induction en fonction de la hauteur de la solution présente un minimum. Un autre volet de cette thèse réservé à la modélisation et la simulation. Dans un premier temps, la concentration en clusters ou agrégats moléculaires au voisinage de la bulle été calculée dans le cas du ZnSO4,7H2O grâce à la théorie de la ségrégation en fonction de la pression acoustique. La simulation montre qu'il y a une sur-concentration des clusters (jusqu'à 25 fois supérieure à la concentration stationnaire) augmentant ainsi la probabilité de contact des clusters, durant un temps très court, pouvant ainsi modifier le processus global de nucléation. Dans un deuxième temps, la modélisation/simulation de l'acoustique par COMSOL est réalisée en vue de déterminer les résonances de notre système (liquide + parois de la cuve). Les résonances observées sont cohérentes avec les mesures de temps d'induction. / Power ultrasound is known to enhance crystals nucleation, and nucleation times can be reduced by oneup to three orders of magnitude for several organic or inorganic crystals. The precise physics involved in this phenomenon still remains unclear, and various mechanisms involving the action of inertial cavitation bubbles have been proposed. In this paper, two of these mechanisms, pressure and ségrégation effects, are examined. The first one concerns the variations of supersaturation induced by the high pressures appearing in the neighbourhood of a collapsing bubble, and the second one results from the modification of clusters distribution in the vicinity of bubble. Crystallisation experiments were performed on zinc sulphate heptahydrate ZnSO4. 7H2O, which has been chosen for its pressure-independent solubility, so that pressure variations have no effect on supersaturation. As observed in past studies on other species, induction times were found lower under insonification than under silent conditions at low supersaturations, which casts some doubts on a pure pressure effect. The interfacial energy between the solid and the solution was estimated from induction times obtained in silent conditions, and, using classical nucléation theory, the steady-state distribution of the clusters was calculated. Segregation theory was then applied to calculate the over-concentrations of n-sized clusters at the end of the collapse of a 4 lmbubble driven at 20 kHz by different acoustic pressures. The over-concentration of clusters close to the critical size near a collapsing bubble was found to reach more than one order of magnitude, which may favour the direct attachment process between such clusters, and enhance the global nucleation kinetics. The effects of acoustic cavitation on crystallization of ZnSO4. 7H2O was observed in a sono-reactor build-up from a large emitting area transducer located at the bottom of the vessel. The experimental results have shown that the dissipated acoustic power passes through a maximum at about 15±1 cm, and that the induction-time passes through a minimum for the same liquid-level. The dissipated-power and the induction-time are found to be well correlated as the liquid height was varied. The acoustics of the sono-reactor was studied with linear acoustics, accounting for the wall vibrations by using the COMSOL software. Theoretical dissipated acoustic powers were compared to the experimental ones.
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Caractérisation et régulation des régimes de cavitation ultrasonore pour la sonoporation cellulaire / Characterization and control of the regimes of ultrasonic cavitation for cells sonoporationCornu, Corentin 03 July 2018 (has links)
Dans l’objectif de limiter les effets destructeurs de l’implosion de bulles de cavitation ultrasonore, un régime d’oscillations stables de bulles doit potentiellement être visé pour des applications thérapeutiques sensibles comme l’ouverture de la barrière hémato-encéphalique. Cependant, garantir une activité d’oscillations stables est difficile de par le caractère stochastique de la cavitation ultrasonore, et de la coexistence de bulles oscillantes (cavitation stable) et implosantes (cavitation inertielle) au sein d’un nuage de bulles. Il est donc nécessaire de contrôler spatialement et temporellement le phénomène de cavitation en discriminant les régimes de cavitation stable ou inertielle, au cours de la durée d’un tir ultrasonore, et ce en régime pulsé. Dans une première étude, la dynamique d’un nuage de bulles monodisperses et uniformément réparties dans l’espace met en évidence l’effet de l’interaction entre bulles sur le seuil de cavitation stable : il s’abaisse en pression et la fréquence de résonance des bulles se décale en fonction de la densité de bulle. Il est ainsi montré qu’il existe une densité de bulle optimale pour l’émission de la composante sous-harmonique. Ensuite, une stratégie de contrôle est développée, basée sur une boucle de rétroaction régulant la signature acoustique d’un régime donné de cavitation. L’utilisation de la stratégie d’asservissement permet de discriminer les régimes de cavitation stable et inertielle au cours du temps, mais aussi de garantir une activité de cavitation plus stable temporellement, plus reproductible, et ce pour des énergies acoustiques moyennes délivrées inférieures. Enfin, le processus de contrôle est utilisé expérimentalement pour des applications in-vitro de sonoporation cellulaire. Tout d’abord, une étude de sonoporation en cavitation inertielle régulée met en évidence l’amélioration de la reproductibilité des taux de sonoporation obtenus, et la possibilité de s’affranchir de l’utilisation d’agents de contraste comme agents de nucléation. Ensuite, une étude en cavitation stable régulée met en évidence la possibilité de sonoporer des cellules en limitant les activités de cavitation inertielle, et donc potentiellement en limitant la lyse cellulaire / In the aim of limiting the destructive behavior of collapsing cavitation bubbles, an exclusively stable cavitation state is targeted for sensitive therapeutics applications like blood-brain barrier opening. Ensuring a stable cavitation regime is complex because of (i) the coexistence of stably oscillating bubbles and collapsing bubbles in the same bubble cloud, and (ii) the stochastic behavior of the phenomenon during time. Therefore, it is necessary to control spatially and temporally the cavitation activity, by discriminating the stable from the inertial regime. Firstly, the theoretical study of the dynamics of a monodisperse and homogeneous cloud shows a modification of the stable cavitation threshold as a function of the bubble density: the subharmonics emission threshold is lowered and the resonance frequency is shifted. The study leads also to the expression of a particular microbubbles density leading to optimized subharmonics emission. Secondly, a real-time control strategy based on a feedback loop process on subharmonics emission is designed. The use of this strategy allows discriminating the two cavitation states during time, and ensures a better reproducibility, time-stability and an acoustic energy gain. The control device is used for cells sonoporation in-vitro. In a first study, the sonoporation by inertial cavitation control is performed in a stationary ultrasonic field configuration. This leads to high sonoporation efficiency coupled to the possibility of counterbalancing the use of supplementary nuclei (encapsulated microbubbles). In a second one, the stable cavitation control applied in a focused ultrasound configuration field pinpoints the possibility of sonoporating cells without inertial cavitation, and then to limit cell lysis
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Effects of ultrasonic cleaning on membrane-adherent biofilms derived from a laboratory-scale bioreactorRosi, Anton Nilo Warren 08 October 2018 (has links)
No description available.
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Processos de tratamento não convencionais para degradação do antibiótico sulfadiazina em meio aquoso. / Non-conventional treatment processes for the degradation of the antibiotic sulfadiazine in aqueous medium.Acosta, Arlen Mabel Lastre 25 April 2016 (has links)
A presença de antibióticos no meio ambiente aquático tem causado crescente preocupação mundial. Além dos relatos de resistência de bactérias a antibióticos, essa classe de fármacos também pode causar efeitos tóxicos e atuar como perturbadores endócrinos em diversos organismos vivos e, possivelmente, em humanos. Dentre os antibióticos comumente usados destacam-se as sulfonamidas, detectadas em águas subterrâneas e superficiais. Os processos avançados de oxidação (POA) têm sido apontados como tecnologias eficientes para tratamento de poluentes recalcitrantes em diferentes matrizes aquosas. Dentre os POA, o processo foto-Fenton é uma alternativa para a degradação de compostos não biodegradáveis, incluindo fármacos. Uma vez que a principal limitação do processo é o intervalo de pH (2,5- 4,0), a reação pode ser vantajosamente conduzida empregando-se substâncias bio-orgânicas solúveis (BOS) como agentes complexantes de Fe3+ em condições ligeiramente ácidas (pH 5). Por sua vez, o emprego da energia ultrassônica tem sido menos estudado. Nesse contexto, o objetivo deste trabalho é estudar a degradação do antibiótico sulfadiazina (SDZ) por meio do processo foto-Fenton na presença de substâncias bio-orgânicas solúveis (UVvis/ Fe3+/H2O2/BOS) e do processo de cavitação por meio de ultrassom (US). Os resultados obtidos mostram que a sulfadiazina é eficientemente degradada por ultrassom de alta frequência. As maiores porcentagens e taxas de remoção são obtidas usando menor frequência de operação (580 kHz), maior potência dissipada e em pH ligeiramente ácido (melhor condição: pH 5,5). Além disso, a reação de Fenton, combinada com o tratamento US, melhorou notavelmente a degradação da SDZ, particularmente quando quantidades extras de H2O2 foram adicionadas ao sistema. Por sua vez, o uso de BOS como aditivos no processo foto-Fenton apresenta influência marcante na fotodegradação da SDZ em condições ligeiramente ácidas (pH 5). Os BOS podem estabilizar espécies de ferro em solução aquosa em pH próximos ao neutro, o que constitui uma propriedade de grande interesse. Sob as condições estudadas, o BOS CVT230 foi mais eficiente do que FORSUD, provavelmente devido às diferenças nos grupos funcionais presentes na composição destas substâncias. Finalmente, foram calculados os indicadores de consumo de energia elétrica por ordem de grandeza (EEO) para o processo de ultrassom (1572 kW h m-3 ordem-1) e área do coletor por ordem de grandeza (ACO) para o processo foto-Fenton (8,07 m2 m-3 ordem-1). / The potential impacts of antibiotic residues in the environment have become an emerging concern during recent years due to their relation with the development of resistant bacteria, and in some cases to their ability to cause toxic and endocrine disrupting effects in humans and other living organisms. Highlighted among the commonly used antibiotics are the sulfonamides, detected in groundwater and surface water. Advanced oxidation processes (AOP) might constitute an important alternative to deal with pharmaceuticals degradation. Among them, the photo-Fenton process has been widely used. One of its major drawbacks is the highly acidic pH needed (2,5-4,0) to avoid the formation of photochemically inactive iron oxides and hydroxides. The ability of soluble bio-organic substances (SBO) to complex metal cations such as iron is useful for the development of photo-Fenton at mild acidic conditions (pH 5). In turn, the use of ultrasonic energy has been less studied. In this context, the aim of this work is to study the degradation of the antibiotic sulfadiazine (SDZ) by the photo-Fenton process in the presence of soluble bio-organic substances (UV-vis/Fe3+/H2O2/SBO) and by ultrasonic cavitation (US). The results confirm that SDZ is effectively degraded by highfrequency ultrasound. Higher SDZ percent removals and removal rates were observed for the lowest operating frequency (580 kHz), higher dissipated power, and in slightly acidic solution (pH 5.5). On the other hand, SDZ degradation is highly improved in the case of the US/ Fe(II)/H2O2 system. The use of the SBO as Fenton additives in turn has a remarkable influence in SDZ photodegradation at slightly acid conditions (pH 5). This could be ascertained to the complexation of iron by the SBO, hence maintained in the reaction medium as a photoactive species. Under the studied conditions, the BOS CVT230 was more efficient than FORSUD, probably due to differences in the functional groups present in the composition of these substances. Finally, the figures-of merit electrical energy per order (EEO) and collector area per order (ACO) were calculated for the ultrasound (1572 kW h m-3 ordem-1) and photo-Fenton (8,07 m2 m-3 ordem-1) processes respectively.
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Processos de tratamento não convencionais para degradação do antibiótico sulfadiazina em meio aquoso. / Non-conventional treatment processes for the degradation of the antibiotic sulfadiazine in aqueous medium.Arlen Mabel Lastre Acosta 25 April 2016 (has links)
A presença de antibióticos no meio ambiente aquático tem causado crescente preocupação mundial. Além dos relatos de resistência de bactérias a antibióticos, essa classe de fármacos também pode causar efeitos tóxicos e atuar como perturbadores endócrinos em diversos organismos vivos e, possivelmente, em humanos. Dentre os antibióticos comumente usados destacam-se as sulfonamidas, detectadas em águas subterrâneas e superficiais. Os processos avançados de oxidação (POA) têm sido apontados como tecnologias eficientes para tratamento de poluentes recalcitrantes em diferentes matrizes aquosas. Dentre os POA, o processo foto-Fenton é uma alternativa para a degradação de compostos não biodegradáveis, incluindo fármacos. Uma vez que a principal limitação do processo é o intervalo de pH (2,5- 4,0), a reação pode ser vantajosamente conduzida empregando-se substâncias bio-orgânicas solúveis (BOS) como agentes complexantes de Fe3+ em condições ligeiramente ácidas (pH 5). Por sua vez, o emprego da energia ultrassônica tem sido menos estudado. Nesse contexto, o objetivo deste trabalho é estudar a degradação do antibiótico sulfadiazina (SDZ) por meio do processo foto-Fenton na presença de substâncias bio-orgânicas solúveis (UVvis/ Fe3+/H2O2/BOS) e do processo de cavitação por meio de ultrassom (US). Os resultados obtidos mostram que a sulfadiazina é eficientemente degradada por ultrassom de alta frequência. As maiores porcentagens e taxas de remoção são obtidas usando menor frequência de operação (580 kHz), maior potência dissipada e em pH ligeiramente ácido (melhor condição: pH 5,5). Além disso, a reação de Fenton, combinada com o tratamento US, melhorou notavelmente a degradação da SDZ, particularmente quando quantidades extras de H2O2 foram adicionadas ao sistema. Por sua vez, o uso de BOS como aditivos no processo foto-Fenton apresenta influência marcante na fotodegradação da SDZ em condições ligeiramente ácidas (pH 5). Os BOS podem estabilizar espécies de ferro em solução aquosa em pH próximos ao neutro, o que constitui uma propriedade de grande interesse. Sob as condições estudadas, o BOS CVT230 foi mais eficiente do que FORSUD, provavelmente devido às diferenças nos grupos funcionais presentes na composição destas substâncias. Finalmente, foram calculados os indicadores de consumo de energia elétrica por ordem de grandeza (EEO) para o processo de ultrassom (1572 kW h m-3 ordem-1) e área do coletor por ordem de grandeza (ACO) para o processo foto-Fenton (8,07 m2 m-3 ordem-1). / The potential impacts of antibiotic residues in the environment have become an emerging concern during recent years due to their relation with the development of resistant bacteria, and in some cases to their ability to cause toxic and endocrine disrupting effects in humans and other living organisms. Highlighted among the commonly used antibiotics are the sulfonamides, detected in groundwater and surface water. Advanced oxidation processes (AOP) might constitute an important alternative to deal with pharmaceuticals degradation. Among them, the photo-Fenton process has been widely used. One of its major drawbacks is the highly acidic pH needed (2,5-4,0) to avoid the formation of photochemically inactive iron oxides and hydroxides. The ability of soluble bio-organic substances (SBO) to complex metal cations such as iron is useful for the development of photo-Fenton at mild acidic conditions (pH 5). In turn, the use of ultrasonic energy has been less studied. In this context, the aim of this work is to study the degradation of the antibiotic sulfadiazine (SDZ) by the photo-Fenton process in the presence of soluble bio-organic substances (UV-vis/Fe3+/H2O2/SBO) and by ultrasonic cavitation (US). The results confirm that SDZ is effectively degraded by highfrequency ultrasound. Higher SDZ percent removals and removal rates were observed for the lowest operating frequency (580 kHz), higher dissipated power, and in slightly acidic solution (pH 5.5). On the other hand, SDZ degradation is highly improved in the case of the US/ Fe(II)/H2O2 system. The use of the SBO as Fenton additives in turn has a remarkable influence in SDZ photodegradation at slightly acid conditions (pH 5). This could be ascertained to the complexation of iron by the SBO, hence maintained in the reaction medium as a photoactive species. Under the studied conditions, the BOS CVT230 was more efficient than FORSUD, probably due to differences in the functional groups present in the composition of these substances. Finally, the figures-of merit electrical energy per order (EEO) and collector area per order (ACO) were calculated for the ultrasound (1572 kW h m-3 ordem-1) and photo-Fenton (8,07 m2 m-3 ordem-1) processes respectively.
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