61 |
Efficacité de zones tampons humides à réduire les teneurs en pesticides des eaux de drainage / Effectiveness of constructed wetlands to reduce the pesticide concentrations in drain waterVallée, Romain 24 April 2015 (has links)
En Lorraine, le drainage fréquent des sols argileux favorise les transferts des intrants agricoles (pesticides et engrais) vers les eaux de surface. Dans ce cas, les bandes enherbées réglementaires (BCAE de la PAC) installées en bordure de cours d’eau sont court-circuitées et ne jouent plus leur rôle épurateur vis-à-vis des eaux de surface. Ainsi, des zones tampons humides artificielles (ZTHA) sont préconisées pour prendre le relais des bandes enherbées. Généralement, ces ZTHA sont installées à l’échelle du bassin versant ou du groupe de parcelles et sont donc de taille conséquente, les rendant concurrentielles de la surface agricole utile (SAU). L’objectif de ce projet de recherche est donc d’évaluer l’efficacité de deux ZTHA de taille réduite, installées dans la bande enherbée entre la parcelle drainée et le ruisseau. Pour cela, une approche multi-échelles intégrant des expériences de laboratoire en batch, des suivis dynamiques en bacs pilotes et un monitoring à la parcelle a été mise en place. Afin d’évaluer l’efficacité des ZTHA au cours des saisons de drainage 2012/13 et 2013/14, le suivi des teneurs en nitrate et de 79 pesticides a été réalisé dans les eaux en entrée et en sortie des ZTHA, ainsi que dans diverses matrices environnementales (sols, sédiment, paille, végétaux). Pour les deux dispositifs, la réduction du flux de nitrate s’est montrée stable, comprise entre 5,4 et 10,9 %, alors que la réduction du flux de pesticides s’est montrée très variable, comprise entre -618,5 et 100 %. Cette variabilité a été expliquée par quatre comportements distincts des molécules. Les fortes valeurs négatives d’efficacité ont été expliquées par une contamination des dispositifs à la suite d’épisodes de ruissellement connexes pour des molécules solubles telles que le 2,4-MCPA ou l’isoproturon. Pour ces deux molécules, l’étude de sorption a montré leur faible affinité avec les matrices environnementales, facilitant leur transport par les eaux de ruissellement et de drainage. D’autres molécules, telles que le boscalide ou l’OH-atrazine, ont présenté des abattements proches de 0. Pour le boscalide, ce comportement a été montré au laboratoire, en accord avec ses fortes capacités d’adsorption et de désorption observées lors des études de sorption et en bacs pilotes. Enfin, certaines molécules ont montré des abattements, allant de 9,9 à 100 %, en lien avec leur faible persistance (2,4-MCPA, clopyralid, mésosulfuron-méthyl,…) ou leur forte affinité pour les matrices environnementales (diflufenicanil, propiconazole, propyzamide,…). Ces ZTHA de taille réduite, installées dans les bandes enherbées, sont donc efficaces pour limiter la contamination des eaux de surface par les eaux de drainage agricole. Ainsi, la multiplication de ces dispositifs à l’échelle de la parcelle dans le paysage agricole permettrait de réduire la contamination des eaux de surface par les pesticides et les nitrates tout en préservant la SAU. Toutefois, l’efficacité de ces ZTHA restant limitée vis-à-vis de certains pesticides présentant un Koc faible et une DT50 élevée, leur installation ne doit pas remettre en cause la réduction en amont des apports phytosanitaires sur les parcelles / In Lorraine, the drainage of clay soils contributes to transfer of agricultural inputs (pesticides and fertilizers) towards surface waters. In this case, the regulatory grass strips (CAP regulation) installed along rivers are bypassed and no longer effective in purifying surface water. Thus, constructed wetlands (CWs) are recommended to take over grass cover bands. Generally, these CWs are installed at watershed scale or at that of several plots and they are therefore quite huge, making them competitive in the cultivated land. The objective of this project is to assess the effectiveness of two small CW, installed in the grass cover band between the drained plot and the river. For this, a multi-scale approach was set up integrating laboratory experiments in batch, pilot study taking into account the water dynamics and monitoring at field scale. The effectiveness of CW was assessed during the 2012/13 and 2013/14 drainage seasons. The nitrate and 79 pesticides concentrations were monitored at inlet and outlet of CWs and in various substrates (soils, sediment, straw and plants). For both devices, the removal efficiencies measured for nitrate were stable and ranged from 5.4 to 10.9 % of inlet amounts while the reduction of pesticide flows was very variable, ranging from -618.5 to 100 %. This variability was explained by four distinct behaviors. The high negative efficiency values were attributed to neighboured runoff events after heavy rains, for soluble molecules such as 2,4-MCPA or isoproturon. For both molecules, the sorption study showed low affinity for environmental substrates, facilitating their transport by runoff and drainage water. Other molecules such as boscalid or OH-atrazine showed effectiveness close to 0 %. For boscalid, this behavior has been observed in laboratory sorption and pilots studies, in agreement with its strong adsorption and desorption capacities. Finally, some molecules have shown reductions ranging from 9.9 to 100 %, in agreement with their low persistence (2,4-MCPA, clopyralid, mesosulfuron-methyl, ...) or their high affinity for environmental substrates (diflufenican, propiconazole or propyzamide). These small CWs, located in the grass cover bands, are effective in minimizing the contamination of surface waters by agricultural drainage water. Thus, multiplying the number of these devices at the plot scale in the agricultural landscape would reduce the contamination of surface waters by pesticides and nitrates while preserving the cultivated land. However, the effectiveness of these CWs are limited for pesticides with a low Koc and a long DT50; thus their installation in plot must not call into question the reduction in the use of pesticides
|
62 |
Dynamics of Rydberg atom lattices in the presence of noise and dissipationAbdussalam, Wildan 22 August 2017 (has links) (PDF)
The work presented in this dissertation concerns dynamics of Rydberg atom lattices in the presence of noise and dissipation. Rydberg atoms possess a number of exaggerated properties, such as a strong van der Waals interaction. The interplay of that interaction, coherent driving and decoherence leads to intriguing non-equilibrium phenomena.
Here, we study the non-equilibrium physics of driven atom lattices in the presence of decoherence caused by either laser phase noise or strong decay. In the first case, we compare between global and local noise and explore their effect on the number of excitations and the full counting statistics. We find that both types of noise give rise to a characteristic distribution of the Rydberg excitation number. The main method employed is the Langevin equation but for the sake of efficiency in certain regimes, we use a Markovian master equation and Monte Carlo rate equations, respectively.
In the second case, we consider dissipative systems with more general power-law interactions. We determine the phase diagram in the steady state and analyse its generation dynamics using Monte Carlo rate equations. In contrast to nearest-neighbour models, there is no transition to long-range-ordered phases for realistic interactions and resonant driving. Yet, for finite laser detunings, we show that Rydberg atom lattices can undergo a dissipative phase transition to a long-range-ordered antiferromagnetic phase. We identify the advantages of Monte Carlo rate equations over mean field predictions.
Having studied the dynamics of Rydberg atom lattices, we study an application of the strong interactions in such systems for quantum information processing. We investigate the coherent exchange of a single photon between a superconducting microwave cavity and a lattice of strongly interacting Rydberg atoms in the presence of local electric field fluctuations plaguing the cavity surface. We show that despite the increased sensitivity of Rydberg states to electric fields, as compared to ground state atoms, the Rydberg dipole-dipole interaction can be used to protect the system against the dephasing induced by the local noise. Using $1/f$ and laser phase noise models, we show that compared to the case with non-interacting atoms, our system exhibits longer coherence lifetimes and larger retrieval efficiency of the photon after storing into the atoms.
|
63 |
Deformations and instabilities of soap films / Déformation de films de savon et instabilitésShabalina, Evgenia 09 October 2019 (has links)
Les mousses liquides soumises à du cisaillement présentent une très grande viscosité, mais l'origine locale de la dissipation se produisant pendant cette déformation est encore mal comprise. Dans le but d'apporter quelques éléments de réponses à cette importante question ouverte, notre travail décrit le comportement observé sur quelques films connectés lorsqu'une déformation leur est appliquée. Nous avons créé un montage permettant de fabriquer un pattern élémentaire de mousse, et de modifier la taille de chaque film en contrôlant la géométrie du cadre qui le supporte. Ce montage original, auquel s'ajoute une combinaison d'appareils optiques, nous permet de révéler les processus se produisant dans le film, notamment la compétition entre son allongement ou compression, et l'extraction d'un nouveau film depuis les ménisques raccordant les films. Nous montrons de plus que cette compétition dynamique dans un film donné est affectée par la déformation de ses premiers et seconds films voisins. La géométrie particulière du montage nous a également permis de découvrir et de décrire pour la première fois une instabilité gravitationnelle se produisant lorsqu'un film épais se situe au-dessus d'un film plus mince. Nous avons mesuré la longueur d'onde de l'instabilité et l'avons comparée à des prédictions théoriques en régime linéaire. Ces différents écoulements affectent la distribution d'épaisseur dans le film, et peuvent ainsi jouer un rôle important sur la viscosité ou sur la stabilité des mousses 3D. Finalement, le montage utilisé pourra s'avérer utile à l'avenir comme rhéomètre de films liquides. / Liquid foams under shearing exhibit a large effective viscosity, and the understanding of the local origin of the dissipation occurring during deformation is unknown. In the aim to contribute to this important open problem, we tried to describe the behavior of a few connected films under deformation. We created a setup allowing to make an elementary foam sample and to modify each film size by controlling the shape of the deformable frame supporting the films. This original setup together with a combination of optical devices allowed us to reveal processes happening in the film, and especially the competition between film stretch or compression, and extraction of a new film from the menisci connecting the films. Importantly, we show that this dynamical competition in a given film is affected by the deformation of its first and even second neighbors. The unique geometry of the setup gave us the opportunity to discover and describe for the first time a gravitational instability which takes place when a thicker film is on top of a thinner one. We measured the wavelength and compared it to theoretical predictions in the linear regime. These different flows affect the thickness distribution, and may thus play an important role in the viscosity or in the stability of 3D foams. As a perspective, the designed setup could prove to be useful as a liquid film rheometer.
|
64 |
Experimental approach to the problem of the Navier-Stokes singularities / Approche expérimentale du problème des singularités de Navier-StokesDebue, Paul 25 September 2019 (has links)
L’objectif de cette thèse est de chercher, dans un écoulement turbulent réel, d'éventuelles traces des singularités que pourraient développer les solutions des équations d'Euler ou de Navier-Stokes incompressibles 3D. En effet, la question de leur régularité mathématique est toujours ouverte. Dans cette thèse, on postule l'existence de singularités dans les équations d'Euler ou de Navier-Stokes, et on cherche des traces de ces singularités dans des champs de vitesse 3D mesurés dans un écoulement turbulent tourbillonnaire modèle, l'écoulement de von Kármán. La répartition de ces possibles empreintes de singularités, la structure de l'écoulement en leur voisinage ainsi que leur évolution temporelle sont étudiées. Nous nous appuyons sur le travail des mathématiciens Duchon et Robert pour chercher des traces de singularités et cherchons des valeurs extrêmes du terme de Duchon-Robert calculé à toute petite échelle, c’est-à-dire dans la zone dissipative : c’est ce que l’on appelle « traces de singularités ». Nous calculons le terme de Duchon-Robert à partir de champs de vitesse obtenus expérimentalement au centre d’un écoulement de von Kármán turbulent. Les champs de vitesse sont mesurés par vélocimétrie par image de particules tomographique (TPIV), résolue en temps ou non. Dans un premier temps, nous analysons les statistiques du terme de Duchon-Robert échelle par échelle et les comparons à celles de la dissipation visqueuse et à celles du terme de transfert inter-échelles apparaissant dans les équations LES. Dans un deuxième temps, nous analysons la topologie du champ de vitesse autour des événements extrêmes du terme de Duchon-Robert d'abord à partir des invariants du gradient de la vitesse puis par observation directe des champs de vitesse. Dans un troisième temps, nous présentons les résultats préliminaires d’une étude eulérienne de l’évolution temporelle des événements extrêmes du terme de Duchon-Robert. / This thesis is devoted to the experimental search for prints of the singularities that might occur in the solutions of the 3D incompressible Euler or Navier-Stokes equations. Indeed, the existence of solutions to these partial differential equations has been proven but it is still unknown whether these solutions are regular, i.e. whether they blow up in finite time or not. In this thesis, we postulate the existence of such singularities and look for prints of them in 3D velocity fields acquired experimentally in a turbulent swirling flow. The distribution, 3D structure and time evolution of these prints are detailed. Our detection of prints of possible singularities is based on the work of the mathematicists Duchon and Robert. We look for extreme values of the Duchon-Robert term at small scales, i.e. in the dissipative range. That is what we call prints of singularities. We compute the Duchon-Robert term on velocity fields which are acquired experimentally at the center of a von Kármán turbulent swirling flow. The velocity field is measured by tomographic particle image velocimetry (TPIV), either time-resolved or not. In a first part we perform a scale-by-scale analysis of the statistics of the Duchon-Robert term and compare them to the statistics of the viscous dissipation and of the inter-scale energy transfer terms involved in the LES equations. In a second part, we analyze the topology of the velocity field around the extreme events of the Duchon-Robert term. We first use a method based on the invariants of the velocity gradient tensor (VGT) and then observe directly the velocity fields. A third part presents preliminary results of an Eulerian study of the time-evolution of the extreme events of the Duchon-Robert term.
|
65 |
États limites de piliers de ponts en béton armés d’armature en spires hélicoïdalesCalixte, Christopher January 2015 (has links)
Les tremblements de terre survenus à San Fernando en 1971, à Loma Prieta en 1989, à Northridge en 1994 et au Chili en 2010 ont permis de découvrir les déficiences des ouvrages construits selon les anciennes normes de conception parasismique. Deux des causes majeures de ces déficiences ont été le manque de confinement des sections critiques et les problèmes liés au recouvrement à la base. De ces leçons, les nouvelles normes de construction au Québec adoptent la philosophie du dimensionnement à la performance, interdissent le recouvrement à la base et recommandent un détail de ferraillage plus rigoureux.
Étudier le comportement sismique des piliers de ponts au Québec en suivant la philosophie du dimensionnement est l'objectif principal d'un ensemble de projets, dont celui-ci, qui est en cours au Centre de recherche en génie parasismique (CRGP) de l'Université de Sherbrooke. Pour leur réalisation, le pont Chemin des dalles, situé dans la région de Trois-Rivières, a été retenu comme pont type. Étudier le comportement sismique des piliers de ponts en béton armé d'armatures en
spires hélicoïdales est l'objectif spécifique de ce projet de maîtrise. De ce fait, un spécimen à échelle réelle a été conçu, construit, instrumenté et testé au laboratoire de structures de l'Université de Sherbrooke. Le renforcement du pilier en béton par des spires hélicoïdales a permis de ceinturer les barres d'armatures longitudinales, d'avoir un comportement plus ductile et une grande capacité à dissiper de l'énergie.
En utilisant la méthode par poussée progressive, les états limites et d'endommagement, et les indicateurs liés à la ductilité, à la dissipation d'énergie, à l'endommagement et à l'amortissement du pilier construit ont été déterminés. Certaines réponses du pilier ont été prédites à l'aide de logiciels d'éléments finis. Ces prédictions ont été assez proches de celles mesurées lors de l'essai réalisé au laboratoire. La cartographie de l'endommagement a été aussi prédite. Pour situer l'endommagement du pilier, des formulations sur l'évaluation de la longueur de la rotule plastique ont été utilisées.
Le pilier à l'étude a eu un comportement assez ductile, une bonne capacité à dissiper de l'énergie et une stabilité de capacité. La quantification des états d'endommagement du pilier testé, en se basant sur la description des états limites, a été comparable à celles proposées pour d'autres piliers.
|
66 |
Thermal analysis and design improvement of light module fixtureLindén, Ronja, Samuelsson, Henrik January 2016 (has links)
Introduction One of the products made by SAAB Avionics Systems in Jönköping was in need of a better cooling solution. The product, a Head-Up Display, holds a LED that was overheating when run at desired input power. The purpose of this thesis was to identify the design weaknesses in the current solution regarding heat dissipation and produce new design proposals that fulfill the requirements. The parts analyzed consist of a LED light source, adjustment plates and a heat sink. The adjustment plates and heat sink where covered in a surface treatment. Theoretical framework A simulation of a finite element model was set up of the current solution in order to identify the influence of the different parts and their thermal properties. The simulation was set up as a steady state thermal model. The FEM and steady state equations used during this are mentioned and shortly explained. The state of modern research was found in order to find new innovative ways of solving the heat problem. Method In order to understand the current solution, experimentswere carried out. Interviews were used in order to get the correct information easily. A literature study was preformed to understand the different theories. Reverse engineering was applied to get a detailed understanding of the functionality both mechanically and thermally. Brainstorming was used to generate new solutions, which was followed by a feasibility evaluation and Pugh’s method to sort out the best concepts. Implementation and Result Based on the simulations it can be concluded that some of the developed solutions pass the requirements and can be implemented right away. Some need some more work in order to fully pass the demands. Conclusions The thermal flow was greatly affected by the properties of the aluminum in the adjustment plates and heat sink, though there was not much room for thickness reduction. However, the oxide layer and the surface roughness also had a great impact on the high junction temperature. The requirements where therefore met when adjustment plates and interfaces were removed, to lower the amount of oxide and air between the LED and the heat sink. But the oxide layers needed to be thinner and the surface roughness needed to be reduced in order to meet requirements. If the oxide layers need to stay at current thickness or the surface roughness cannot be changed, the heat sink needs to be redesigned. The recommended concepts were smaller than the current solution. If this space is utilized with a bigger heat sink, the goals can be met with greater ease. There is also room for improvement when it comes to heat sink heat spreader pattern. Discussion The discussion covers what knowledge which was needed to write this thesis and how different problems that occurred along its path were solved. Sustainability in different ways was also discussed.
|
67 |
Simulation of a plasmonic nanowire waveguideMalcolm, Nathan Patrick 03 September 2009 (has links)
In this work a Finite Difference Time Domain (FDTD) simulation is employed to explore local field enhancement, plasmonic coupling, and charge distribution patterns. This 3D simulation calculates the magnetic and electric field components in a large matrix of Yee cells using Maxwell’s equations. An absorbing boundary condition is included to eliminate reflection back into the simulation chamber, and a sample system of cells is checked for convergence. In the specific simulations considered here, a laser pulse of single wavelength is incident on a silicon substrate, travels through an embedded ZnO nanowire (NW) waveguide only (due to an Ag filter), then incites plasmonic coupling at the gap between an Au nanoparticle tip and an Au substrate, an Au nanoparticle (NP), or a trio of Au nanoparticles incident on an angled Si substrate. The angle between the axis of the NW and the normal of the substrate is varied from 0-60°. The NP perpendicular deflection with respect to the NW axis is also varied from -115 - 75 nm. The enhancement patterns reveal superior signal to noise ratio compared to Near Field Scanning Optical Microscopy (NSOM), three times smaller than the NP diameter 100 nm, as well as resolution and spot size of less than 50 nm. This method of Apertureless NSOM (ANSOM) using a NW waveguide grown on a transparent microcantilever therefore shows promise for imaging of single molecules incident on a substrate and NP-labeled cell membrane. / text
|
68 |
Dynamique des jonctions SNS diffusivesSpahr, Kevin January 2014 (has links)
Le but de ce projet de maîtrise est d’explorer la dynamique des jonctions Supraconducteur/métal Normal/Supraconducteur (SNS) diffusives dans un régime de fréquence de l’ordre du temps électron-phonon, soit l’échelle de temps sur laquelle un électron diffuse sur les phonons. Les jonctions utilisées possèdent des bornes en niobium tandis que le métal normal est de l’aluminium. Les mesures sont réalisées à des températures supérieures à 1.4 K, soit au-dessus de la température critique de l’aluminium (1.20 K) et largement en dessous de celle du niobium (9.26 K).
On étudie ces jonctions en mesurant leurs caractéristiques courant-tension lorsqu’elles
sont excitées avec un signal radio-fréquence (rf). Pour une demi-période d’excitation
sinusoïdale (demi-cycle), on observe deux possibilités : soit la jonction reste dans l’état
supraconducteur, soit elle transite vers l’état normal. En variant la fréquence et l’amplitude de l’excitation, on relève la statistique de ces transitions. On met ainsi en évidence des changements dans le comportement dynamique de la jonction lorsqu’on varie les paramètres de l’excitation.
Si l’on fixe la fréquence d’excitation à une valeur suffisamment basse et qu’on augmente progressivement l’amplitude de cette excitation, on observe une variation graduelle du pourcentage de cycles (ou demi-cycles) d’excitation sinusoïdale où la jonction transite de l’état supraconducteur à l’état normal. Pour les très basses fréquences, cette variation se fait sur un intervalle d’amplitude d’excitation qui coïncide avec la largeur de la distribution du courant critique de la jonction. En augmentant la fréquence d’excitation, cette variation est de plus en plus abrupte et devient un saut discontinu au-delà d’une fréquence critique [florin]*. Ce saut discontinu à haute fréquence s’accompagne d’une hystérèse.
Pour un régime de fréquence intermédiaire, les cycles présentant une transition vers l’état normal se regroupent dans le temps et forment des blocs de transitions vers l’état normal. On a montré que la durée moyenne de ces regroupements croît exponentiellement avec la fréquence. Par exemple, pour une température de 1.4 K, la durée moyenne de ces regroupements peut varier de sept ordres de grandeur sur la plage de radio-fréquence étudiée. Enfin, ces comportements dynamiques sont fortement dépendants de la température.
En caractérisant ces changements de comportement en fonction des divers paramètres d’excitation et de la température, on met en évidence que le bruit thermique associé au bain de phonons fait partie intégrante du mécanisme causant les regroupements dans le régime de fréquence intermédiaire. À suffisamment basse fréquence (ou à toutes les fréquences dans l’approximation que la dynamique n’affecte pas le « bain »), la caractérisation de ce régime transitoire constitue en soi une « mesure » de l’occurrence d’événements rares, ici les fluctuations thermiques menant la jonction à transiter vers l’état normal.
|
69 |
Fate of pharmaceuticals in aquatic environments in Northern SwedenKalyva, Maria January 2017 (has links)
The occurrence of pharmaceuticals in aquatic environments originating from human consumption has received increased scientific attention during the last decades due to concerns regarding their combined environmental effects. This concerns stress the need of studies quantifying dissipation rates of pharmaceutical in aquatic ecosystems. The aims of this study were: i) to assess the degradation rates of trimethoprim (TPR), diphenhydramine (DPH), diclofenac (DCL), oxazepam (OXZ) and hydroxyzine (HDZ) in laboratory incubations, and ii) to compare laboratory assessment of dissipation rates with previously measured in situ half-lives of these drugs in a pond ecosystem. I hypothesized that the dissipation of these five drugs dissolved, in laboratory incubations, is affected by common environmental parameters such as temperature, UV-light, organic solutes and presences of sediments. In line with my hypothesis, all substances were affected by my treatments. Here, main parameters affecting the dissipation of the drugs were UV light and to a lesser temperature (i.e. through microbial degradation). All drugs were found to be affected by sediment sorption, especially HDZ where 95 % of the applied pharmaceutical was adsorbed. Laboratory estimate with highest environmental relevance (low TOC and 3 °C water temperature or low TOC, sediments and UV light) seemed to predict field estimates fairly well for all of the drugs beside OXZ and DCL. Given the strong adsorption for sediments seen in the laboratory incubations, it seems likely that the mismatch between laboratory inferred half-lives and the in situ half-lives for OXZ was likely caused by sediment exchange processes releasing drugs initially adsorbed to the sediments into water column over time.
|
70 |
Dinâmica de tebuthiuron e hexazinona em solos sob aplicação de biocarvão / Tebuthiuron and hexazinone fate in soils with biochar amendmentPierri, Letícia de 23 February 2018 (has links)
A aplicação de biocarvão ao solo tem sido divulgada como prática com vantagens agrícolas e ambientais. Devido à sua elevada reatividade, o biocarvão pode interagir com contaminantes orgânicos e inorgânicos do solo, diminuindo o potencial poluidor de elementos tóxicos e pesticidas. Contudo, a eficácia de herbicidas pré-emergentes pode ser anulada devido à presença de biocarvão no solo, o que impõe a necessidade de doses maiores e resulta no aumento do risco de contaminação ambiental. Adicionalmente, pode haver maior persistência de pesticidas no solo devido à retenção e menor disponibilidade das moléculas em solos com biocarvão. As reações que ocorrem entre o biocarvão e os pesticidas dependem das próprias características do solo e da molécula, além do tempo de interação com o solo (aging) e das propriedades intrínsecas ao biocarvão (biomassa de origem, T°C de pirólise e granulometria). O tebuthiuron e a hexazinona são herbicidas com elevado potencial de lixiviação e podem ter seu destino alterado em função da presença de biocarvão no solo. Estas moléculas possuem elevado tempo de meia-vida (t1/2) e biodegradam lentamente no ambiente edáfico. Assim, processos oxidativos avançados (POA) podem acelerar a decomposição dos herbicidas, sendo ainda uma maneira de integrar o biocarvão em processos químicos para a dissipação de poluentes. Objetivou-se avaliar os efeitos da aplicação de biocarvão na dinâmica dos herbicidas tebuthiuron e hexazinona em solos, tendo-se como objetivos específicos: i) verificar o comportamento sortivo desses herbicidas frente à aplicação de biocarvões produzidos a partir de diferentes matérias-primas e T°C de pirólise, incluindo a influência de fatores como o aging dos herbicidas no solo, tamanho das partículas do biocarvão e disponibilidade de carbono orgânico dissolvido (COD) no solo promovida pela adição do biocarvão; ii) avaliar se a interação entre os herbicidas e o biocarvão afeta a eficiência de controle de braquiária (Brachiaria decumbens); iii) analisar a influência do biocarvão na dissipação e lixiviação de tebuthiuron e hexazinona; e iv) identificar o potencial de uso do biocarvão em POA, como suporte para catalisadores metálicos heterogêneos e como fonte de ferro para reações de Fenton, bem como avaliar o desempenho destes materiais na catálise oxidativa de hidrocarbonetos e dos herbicidas. Experimentos de sorção, (verificando a influência de biocarvões de diferentes matérias-primas e T°C de pirólise, aging e granulometria, além da avaliação em solos de texturas contrastantes), bem como de dissipação e lixiviação foram conduzidos, utilizando-se herbicidas radiomarcados. Em paralelo, a liberação de COD pelos biocarvões e pelos solos foi quantificada, enquanto que um experimento de eficiência de controle sobre braquiária em casa de vegetação foi conduzido. Os biocarvões foram, ainda, avaliados quanto ao potencial de uso como suporte para catalisadores metálicos e para reações de Fenton, avaliando-se sua performance para a oxidação dos herbicidas e de hidrocarbonetos. Apesar de não alterar a classe de lixiviação de tebuthiuron e hexazinona em curto prazo, quando considerado o efeito do aging, a presença de biocarvão de palha de cana-de-açúcar 550°C (PC550) no solo, independentemente da granulometria, pode auxiliar no manejo de herbicidas com elevada mobilidade, especialmente em solos de textura arenosa e com baixo teor de carbono. Neste caso, o herbicida tebuthiuron teve sua classificação alterada de \"molécula lixiviável\" (Kd,app < 5,0 L kg-1) para \"molécula não-lixiviável\" (Kd,app > 5,0 L kg-1). No entanto, o biocarvão de dejeto de galinha 350°C (DG350) aumenta o COD do solo, resultando na diminuição da sorção dos herbicidas. A adição dos biocarvões PC550 e DG350 ao solo não modificam a eficiência de controle de braquiária por moléculas altamente solúveis. Doses a partir das doses recomendadas em campo promovem controle eficiente, independentemente da presença ou não de biocarvão no solo. Tebuthiuron e hexazinona são moléculas recalcitrantes no ambiente, sendo muito baixas suas taxas de mineralização e de dissipação, tanto na presença como na ausência dos biocarvões PC550 e DG350. A presença de biocarvão no solo pouco influenciou a dissipação dessas moléculas. Os biocarvões PC550 e DG350 diminuem o potencial de lixiviação da hexazinona no solo de textura areia franca, mas não afetam o movimento vertical do tebuthiuron nas mesmas condições. Apesar do menor potencial para degradação de tebuthiuron e hexazinona em relação à epoxidação de hidrocarbonetos, a inserção do biocarvão para a síntese de catalisadores mostrou-se eficiente e permitiu o emprego deste material em processos de catálise industrial e ambiental, podendo auxiliar para o manejo da remediação de poluentes e contribuindo para expandir o uso do biocarvão. / Biochar amendments to soil has been claimed as a practice with agricultural and environmental advantages. Due to its high reactivity, biochar can interact with organic and inorganic soil contaminants, reducing the pollution potential of toxic elements and pesticides. However, pre-emergent herbicides efficacy can be negatively affected by biochar additions to the soil, which may impose higher doses and increase the environmental contamination risk. In addition, there may be increasing in the pesticide\'s persistence due to retention and lower availability of the molecules induced by biochar amendment to the soil. The interactions between biochar and the pesticides depend on the characteristics of the soil and the herbicide itself, besides the aging and the biochar\'s properties (biomass, pyrolysis T°C and granulometry). Tebuthiuron and hexazinone are herbicides with leaching potential and may have their fate modified due to the presence of biochar in the soil. These molecules have a high half-life time (t1/2) and biodegrade slowly in the environment. Thus, advanced oxidative processes (AOP) can accelerate the decomposition of herbicides and can be a way of incorporate biochar in chemical processes towards pollutants dissipation. We aimed to evaluate the effects of biochar amendments on tebuthiuron and hexazinone dynamics in soils, and the specific objectives were: i) to verify the sorption behavior of these herbicides in response to biochar\'s amendment from different feedstock and pyrolysis T°C, including the influence of factors such as herbicide aging on the soil, biochar particle size and availability of dissolved organic carbon (DOC) in the soil promoted by biochar addition; ii) to evaluate if the interaction between the herbicides and the biochars affects braquiária (Brachiaria decumbens) control efficiency; iii) to analyze the biochars influence on the dissipation and leaching of tebuthiuron and hexazinone; and iv) to identify the potential use of biochar in AOP as heterogeneous metal catalysts support and as a source of iron for Fenton reactions, as well as to evaluate the performance of these materials in oxidative catalysis of hydrocarbons and herbicides. Sorption experiments, (checking the influence of biochars from different feedstocks and pyrolysis T°C, aging and granulometry, as well as accessing the differences among soil textures), and dissipation and leaching experiments were conducted using radiolabeled herbicides. In parallel, the release of DOC by the biochars and soils was quantified, whereas an experiment in a greenhouse for braquiária control was conducted. The biochars were also evaluated for use as metal catalysts supports and for Fenton reactions, evaluating their performance for herbicides and hydrocarbons oxidation. Although it does not change tebuthiuron and hexazinone leaching class in short term, when considering the aging, the sugarcane straw biochar pyrolyzed at 550°C (PC550), regardless of granulometry, may be useful in the management of high mobility herbicides, especially in sandy soils with low carbon content. In this case, tebuthiuron had its classification modified from \"leachable\" (Kd,app < 5.0 L kg-1) for \"non-leachable\" molecule (Kd,app > 5.0 L kg-1). However, the biochar from poultry manure pyrolyzed at 350°C (DG350) increases the DOC content in the soil, resulting in decreased sorption of the herbicides. The additions of PC550 and DG350 to the soil does not modify the control efficiency of braquiária by highly soluble molecules. Doses higher than the recommended ones promote efficient control, regardless of the presence or absence of biochar in the soil. Tebuthiuron and hexazinone are highly recalcitrant molecules in the environment, having low rates of mineralization and dissipation both in the presence or absence of the biochars PC550 and DG350. The biochar application to the soil barely influenced the herbicides dissipation. The biochars PC550 and DG350 decrease the leaching potential of hexazinone in the sandy soil, but do not affect tebuthiuron leaching in the same conditions. Despite the lower potential for tebuthiuron and hexazinone degradation in relation to the epoxidation of hydrocarbons potential, biochar insertion in the synthesis of catalysts has been proved to be efficient, allowing the use of these wastes in industrial and environmental catalysis processes for pollutants remediation purposes and helping to expand the biochar range of uses.
|
Page generated in 0.0496 seconds