Submitted by Natalia de Souza Gonçalves (natalia.goncalves@ufpe.br) on 2016-09-20T15:04:29Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO (Márcia) Biblioteca Central.pdf: 1682032 bytes, checksum: 35e933b22b504982d914efa83ebacef0 (MD5) / Made available in DSpace on 2016-09-20T15:04:29Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO (Márcia) Biblioteca Central.pdf: 1682032 bytes, checksum: 35e933b22b504982d914efa83ebacef0 (MD5) Previous issue date: 2016-02-15 / CAPES / O extenso desenvolvimento da produção animal tem promovido o crescimento do consumo de antibióticos para o controle e profilaxia de doenças e parasitas, sendo seu uso indiscriminado o responsável por dois problemas ambientais: a contaminação dos recursos hídricos e o aumento da resistência bacteriana, uma vez que ocorre mudanças no seu material genético. O sulfametoxazol (SMX) é uma sulfonamida, um dos grupos de antibióticos mais utilizados. Neste trabalho foram estudadas as interações físico-químicas da molécula do sulfametoxazol na forma pura, em duas camadas (0 – 20 cm e 20 – 60 cm) do solo de pastagem do município de São João, localizado na microrregião de Garanhuns, PE. Os ensaios de adsorção foram realizados em laboratório a 24 ºC, pelo método “batch”, e a concentração de sulfametoxazol foi determinada por cromatografia líquida de alta eficiência (CLAE). Nos ensaios de cinética de sorção foi utilizada solução de SMX na concentração de 10-4 mol.L-1, enquanto para as isotermas de sorção foram utilizadas soluções nas concentrações de 10-3; 5.10-4; 10-4; 5.10-5; 10-5; 5.10-6 mol.L-1. Para as camadas de solo, a cinética de adsorção do sulfametoxazol é melhor descrita com um modelo de segunda ordem e as isotermas de sorção são lineares. Os valores de KD e KOC foram 2,6 e 1,18 cm3.g-1 e 355 (log(KOC) = 2,55) e 206 (log(KOC) = 2,31) cm3.g-1, respectivamente, para as camadas 0 – 20 cm e 20 – 60 cm. Para este tipo de solo, a interação do SMX é predominantemente com a matéria orgânica e praticamente inexiste com os argilominerais. Os resultados obtidos no presente trabalho mostram que o antibiótico sulfametoxazol apresenta baixa adsorção em ambas camadas, oferecendo um maior risco de contaminação das águas subterrâneas existentes nessa região em pH ≈ 7. / The extensive development of animal production has promoted the growth of consumption of antibiotics for the control and prophylaxis of diseases and parasites, and the indiscriminate use accounts for two environmental problems: the contamination of water resources and increased bacterial resistance, since changes occur in its genetic material. The sulfamethoxazole (SMX) belongs to the sulfonamides, one of the most widely used antibiotics groups. In this work, the physical chemical interactions of sulfamethoxazole molecule pure were studies, in two soil layers (0 – 20 cm and 20 – 60 cm) in the county of São João, located in the micro region of Garanhuns, PE. The sulfamethoxazole concentration was determined by high performance liquid chromatography (HPLC). For soil layers, the sulfamethoxazole kinetic adsorption was fast and best described as a second order model an the adsorption isotherms are linear; the reactivity of sulfamethoxazole with organic matter is dominant although has practically nonexistent reactivity of sulfamethoxazole with the clay minerals. The adsorption tests were carried out in the laboratory at 24 ºC, and divided into kinectis of adsorption isotherm and adsorption in function of pH, since sulfamethoxazole is an ionizable molecule. The results obtained in the present work show that the sulfamethoxazole antibiotic it exhibits low adsorption on both layers, offering a higher risk of contamination of groundwater existing in this region in pH ≈ 7.

La disponibilité de la ressource en eau potable est en train de diminuer dans diverses régions, en lien avec la demande croissante d'eau douce, de la demande en produits alimentaires (Agriculture et élevage) et des effets des changements climatiques au niveau mondial à cause de la croissance démographique. Les pratiques agricoles inadaptées peuvent conduire à des pollutions des eaux superficielles et souterraines par des pesticides, des produits pharmaceutiques, des métaux, des nutriments, ou des sédiments et colloïdes. L'augmentation de la demande en produits animaliers est un des principaux facteurs qui conduisent à l'augmentation de l'utilisation d'antibiotiques, notamment de la famille des sulfonamides comme le sulfametoxazole (SMX). Malgré les grandes quantités de SMX utilisées tant en santé humaine qu'animale, et malgré le risque de contamination des ressources en eau associés à ce type de molécule, leur devenir dans les sols est encore mal compris et est peu documenté. C'est dans ce contexte que nous avons entrepris l'étude des interactions physico-chimiques, la dégradation, l'impact et le transfert du SMX dans deux sols aux propriétés physico-chimiques similaires mais issus de zones géographiques différentes (Recife, Brésil et Mâcon, France), et présentant différents contextes climatiques (tropical et tempéré) et différents usages (urbain et agricole). L'étude des interactions physico-chimiques a consisté à caractériser les processus de sorption et leurs cinétiques ainsi que l'effet du pH des sols, en lien avec l'ionisabilité de la molécule de SMX (2 pKa). La dégradation (biotique et abiotique) de la molécule antibiotique a été évaluée pour 3 concentrations différentes (10-3, 10-4 et 10-5M) pour évaluer l'effet des propriétés des sols sur la toxicité et la biodisponibilité du SMX. Les sols de Macon et Recife non contaminés au SMX présentent une biodiversité importante et semblable comme l'ont montré les indices de Shannon (H') et de Simpson. L'addition d'antibiotiques aux 2 sols modifie rapidement leur biodiversité microbienne et induit des changements de structures et de composition de la communauté bactérienne. Une bactérie du genre Arthrobacter est spécifiquement stimulée dans les deux sols par l'ajout de SMX, mais elle n'est pas cultivable, en revanche, nous avons pu isoler une souche de Burkholderia fortement stimulée par la présence de l'antibiotique, qui représente plus de 30% de la communauté bactérienne et qui présente des capacités de dégradation de l'antibiotique très importantes. La dégradation du SMX dans les deux sols s'avère rapide à faible concentration (10-5M) et plus lente (Mâcon) voire inexistante (Recife) à plus forte concentration (10-3M). La mobilité du SMX a été évaluée par des essais de transport en colonnes de sols remaniés conduites à 0,2; 0,45 et 0,7 mL.min-1. Les concentrations en SMX étant déterminées par HPLC-UV. L'identification des processus hydrodynamiques dans les deux sols et des processus de transfert du SMX a été réalisée avec le modèle de convection - dispersion avec retard (CDE sous CXTFIT). Les cinétiques de sorption ont été bien décrite avec un modèle de second ordre et le SMX suit une adsorption de type Langmuir. La mobilité du SMX s'est avérée plus importante dans le sol de Mâcon que dans le sol de Recife en lien avec une plus forte teneur en oxydes de fer très réactifs dans ce dernier, suggérant un risque plus élevé de contamination des eaux naturelles dans le cas du sol de Mâcon. Ce risque est toutefois contrebalancé par la faible persistance dans les deux sols du SMX qui, à faible concentration, est rapidement dégradé. Mots clés : Sol, antibiotique, Sulfametoxazol, sorption, transport, dégradation, impact, polluants émergents / The availability of fresh water in various regions, has been decreasing due to the increasing demand of water resources, the growing demand for food (agriculture and livestock) and the effects of climate change on a global level due to global population growth. Inadequate agricultural practices can lead to pollution of surface and groundwater with pesticides, pharmaceuticals, pollutants, nutrients and sediments, since the main entry of these products into the environment is resulting from their use in human and veterinary medicine. Increased demand in livestock is one of the factors that led to an increased use of antibiotics, such as sulfamethoxazole, and despite the large amount of sulfamethoxazole that is used both in human medicine and in veterinary medicine, and the risk of contamination of aquifers associated this molecule, its fate in soil is still unclear and poorly documented. Thus, the physico-chemical, biological interactions were studied, the impact associated with bacterial resistance and the transport of sulfamethoxazole (SMX) in two different soils but have similar particle size characteristics, the soils are of different geographical origins (Recife, Brazil and Macon, France), uses (urban and rural) and climatic conditions (tropical and temperate). The sorption tests were divided into kinetics of sorption isotherm and sorption in function of pH, since sulfamethoxazole is an ionizable molecule. The biodegradation tests were performed at three different concentrations of sulfamethoxazole (10-3, 10-4 and 10-5 M) to evaluate the effect of soil characteristics and concentration of the SMX on biodegradation of SMX molecule. The soils untreated, Macon and Recife, have an equivalent diversity, according to the calculation of the Shannon index (H ') and Simpson index. Assays of miscible displacement in soil columns with KBr and sulfamethoxazole were satisfactory for flow rates 0.2; 0.45 and 0.7 mLmin-1. The concentration of sulfamethoxazole was determined by high performance liquid chromatography (HPLC). Identification of the mechanisms involved in the transport process and the determination of parameters hidrodispersive soil through the elution curves of KBr and sulfamethoxazole were performed using the CDE model (convection-dispersion) through CXTFIT program. Sorption kinetics was best described with the second-order model and the sorption isotherms were linear. The CDE model adequately represents the experimental data of the elution curves of the sulfamethoxazole. The soil Recife, relative to Macon, had the lowest risk of groundwater contamination existing in this region / A disponibilidade de água doce, em diversas regiões, vem diminuindo em função docrescimento da demanda de recursos hídricos, do crescimento da demanda poralimentos (agricultura e pecuária) e dos efeitos da mudança climática em nível mundialdevido ao crescimento da população mundial. As práticas agrícolas inadequadas podemlevar à poluição das águas superficiais e subterrâneas com pesticidas, fármacos,poluentes, nutrientes e sedimentos. O aumento da demanda na pecuária é um dos fatoresque conduziu a um aumento do uso de antibióticos, como o sulfametoxazol, e apesar dagrande quantidade utilizada tanto na medicina humana como na veterinária, e do riscode contaminação dos aquíferos associados a essa molécula, seu destino no solo aindanão está claro e é pobremente documentado. Os objetivos deste trabalho foram estudaras interações físico-químicas e biológicas, o impacto associado à resistência bacteriana eo transporte do sulfametoxazol (SMX) em dois solos distintos, embora comcaracterísticas granulométricas semelhantes. Os solos são de diferentes origensgeográficas (Recife, Brasil e Macon, França), usos (urbano e agrícola) e condiçõesclimáticas (tropical e temperada). Os ensaios de sorção foram divididos em: cinética,isoterma de sorção e sorção em função do pH, uma vez que o sulfametoxazol é umamolécula ionizável. Os ensaios de biodegradação foram realizados em trêsconcentrações diferentes do sulfametoxazol (10-3, 10-4 e 10-5M) para avaliar o efeito dascaracterísticas dos solos e da concentração do SMX sobre a biodegradação da moléculado SMX. Os solos não tratados Macon e Recife têm uma diversidade equivalente,segundo o cálculo do índice de Shannon (H'), e do índice de Simpson. Os ensaios dedeslocamento miscível em colunas de solo com o KBr e o sulfametoxazol foramsatisfatórios para as vazões de 0,2; 0,45 e 0,7 mL.min-1. A identificação dosmecanismos envolvidos no processo de transporte e a determinação dos parâmetroshidrodispersivos dos solos, através das curvas de eluição do KBr e do sulfametoxazol,foram realizadas utilizando o modelo CDE (convecção-dispersão). A cinética de sorçãofoi melhor descrita com o modelo de segunda ordem e as isotermas de sorção foram nãolineares. O modelo CDE representou adequadamente os dados experimentais das curvasde eluição do sulfametoxazol. O solo Recife, em relação ao Macon, apresentou o menorrisco de contaminação do lençol freático existente nessa região.

<p>In this research, liquid-liquid dispersion of viscous fluids was studied in an SMX static mixer in the laminar regime. Backlighting technique was used for flow visualization, and the Hough transform for circle detection was used in OpenCV to automatically detect and measure drop diameters for obtaining the size distribution. Silicone oil and an aqueous solution of high fructose corn syrup were used for dispersed and continuous phases respectively, and sodium dodecyl sulfate was used as the surfactant to modify the interfacial tension. Experiments were conducted at varying viscosity ratios and flow rates-each at zero, low (~200 ppm) and high (~1000 ppm) surfactant concentrations. The effect of holdup was explored only for a few cases, but it was found to have a minimal effect on the weighted average diameter D₄₃.</p> <p>It was found that the superficial velocity and the continuous phase viscosity had a dominant effect on D₄₃. The tail at the higher end of the droplet size distribution decreased with increasing superficial velocity and continuous phase viscosities. It was also found that D₄₃ decreased with lowering of the interfacial tension. Furthermore, the effect of the dispersed phase viscosity was significant only at non zero surfactant concentrations.</p> <p>An approximate model has been proposed that relates D₄₃ to the capillary number. It is based on an energy analysis of the work done by the viscous and surface forces on a drop of an initial diameter that is largely determined by the gap distance between the cross bars in the element</p> / Master of Applied Science (MASc)