Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1991. / Vita. Abstract. Includes bibliographical references (leaves 52-55). Also available via the Internet.

A study was conducted to investigate the effect ofspray drying on concentration of sulfamethazine (SMZ) in fluid milk dried to powder «10% moisture). Antibiotic-free skim and whole (homogenized) milk were spiked at 5, 10, 50 and 100 ppb sulfamethazine levels, pasteurized and stored at 4°C till further processed. All samples were spray dried at an inlet temperature of 180 ± 2°C and outlet temperature of 100 ± 2°C and stored at -20°C until analyzed. Sulfamethazine concentration was determined quantitatively by HPLC, a microbial receptor assay (Charm-II®) and an ELISA assay (LacTek®) and qualitatively by an ELISA method (Cite®) in milk samples before and after spray drying. Dry milk samples were reconstituted (10% w/w) for all analyses. statistical determination of significant differences (p = 0.05) between fluid and dry milk samples and whole and skim milk sample~was completed by paired t-tests. Sulfamethazine concentrations increased 81.4% and 84.1% in skim and whole milk respectively at 100 ppb spiked level but were lower than expected increase of 88-91% based on their total solids for whole and skim milk as obtained by modified FDA HPLC method. At lower levels of 5 and 10 ppb, the HPLC method was not sensitive enough to provide usable data. Increase in sulfamethazine concentration from fluid to dry milk was also determined by· Charm-II® and LacTek® techniques. Poor recoveries and variability in data were evident due to binding of sulfamethazine to undetermined milk components as a result of processing and storage also due to break-down of sulfamethazine (mp = 176°C) at 1S00C during spray drying. Sulfamethazine 163 ppb by LacTek® and 94.6 ppb by Charm-II® (at a spiked level of 10 ppb fluid milk) was successfully removed from dried milk after 120 min using supercritical CO₂ (pressure = 5500 psi, 50 0 C / Master of Science

De nos jours, l'émergence de produits pharmaceutiques dans l'environnement aquatique et terrestre a été une préoccupation majeure. Ils ont été détectés dans les stations d'épuration, les sédiments et les sols ainsi qu'à la surface et dans l'eau potable. Jusqu'à présent, il y a peu d'informations dans la littérature sur le devenir de ces composés lorsqu'ils sont exposés à la lumière solaire dans les différents compartiments environnementaux. Dans le cadre de ce travail, notre objectif est l’étude de comportement des antibiotiques de la famille des Sulfonamides : Sulfaméthoxazole (STZ), Sulfathiazole (STL), Sulfamethazine (STN) et Hydrochlorothiazide (HCD) dans des solutions aqueuses lorsqu'ils sont exposés à la lumière solaire. Nous nous sommes principalement intéressés à l’étude cinétique en évaluant le rendement quantique de dégradation ainsi que l'effet de divers paramètres tels que la concentration en oxygène, le pH et la présence d'ions inorganiques. Nous nous sommes également intéressés à l'élucidation des principaux sous-produits intermédiaires. De nombreuses informations sont disponibles sur la stabilité et le devenir des composés d'origine et beaucoup moins sur leurs produits de transformation. Ces derniers peuvent présenter un niveau de toxicité plus élevé que le substrat précurseur et doivent ainsi être identifiés et analysés. L'élucidation de la structure a été obtenue en utilisant les techniques HPLC / ESI / MS et HPLC / ESI / MS2 en modes négatif et positif et par l'étude complète des différentes voies de fragmentation. Les principaux processus photochimiques impliqués sont : i) la scission du pont par photohydrolyse, ii) l'hydroxylation sélective de la partie aromatique iii) le processus de désulfonation et iiii) dans le cas de HCD une réaction de déchloration. Un mécanisme photochimique a été proposé sur la base des études cinétiques et analytiques. / Nowaday the emergence of pharmaceuticals in the aquatic and terrestrial environment have been a major concern. They have been detected in sewage-treatment plants, sediments, and soils as well as at surface and drinking water. So far, there is limited information in the literature on the fate of these compounds once they are exposed to solar light in the various environmental compartments. In the present work we have been interested in studying the behavior of antibiotics from Sulfonamide family: Sulfamethoxazole (STZ), Sulfathiazole (STL), Sulfamethazine (STN) and Hydrochlorothiazide (HCD) in aqueous solutions upon exposure to simulated solar light. We mainly concentrate our effort on the kinetic studies by evaluating the degradation quantum yield as well as the effect of various parameters such as oxygen concentration, pH and the presence of inorganic ions. The main effect was observed by molecular oxygen parameter. We also make an important effort in the elucidation of the main intermediate and stable by-products. A lot of information is available on the stability and fate of parent compounds and not so many on their transformation products. These may present a toxicity level higher than the precursor substrate and should be identified and analysed. The chemical structure elucidation was obtained by using the HPLC/ESI/MS and HPLC/ESI/MS2 techniques in negative as well as positive modes and through the complete study of the various fragmentation pathways. The main involved photochemical processes were identified as i) the scission of the bridge through a photohydrolysis process, ii) selective hydroxylation of the aromatic moiety iii) Desulfonation process and iiii) in the case of HCD to dechloration reaction. A mechanism was then proposed in the light of the kinetics and analytical studies.

Thesis (M.Sc. (Pharmacy))--Mahidol University, 1983.

Pharmaceutical compounds represent a rapidly emerging class of environmental contaminants. Such compounds were recently classified by the U.S. Geological Survey, including several antibiotics. An LC-MS/MS screening method for the top five antibiotics in drinking water was developed and validated using a Shimadzu LC-MS-IT-TOF. The separation was performed using a Waters Acquity UPLC BEH C18 column with a gradient elution. Sulfamethazine was exposed to conditions intended to mimic drinking water chlorination, and samples were collected and quenched with excess sodium sulfite. Kinetics of sulfamethazine degradation was followed as well as the formation of the major chlorinated byproduct (m/z 313). For the screening method, all five antibiotic peaks were baseline resolved within 5 minutes. Additionally, precision and accuracy of the screening method were less than 15%. Degradation of sulfamethazine upon exposure to drinking water chlorination occurred by first order kinetics with a half-life of 5.3 × 10(4) min (approximately 37 days) with measurements starting 5 minutes after chlorination. Likewise, the formation of the major chlorinated product occurred by first order kinetics with a rate constant of 2.0 × 10(-2). The proposed identification of the chlorinated product was 4-amino-(5-chloro-4,6-dimethyl-2-pyrimidinyl)-benzenesulfonamide (C12H13N4O2SCl) using MS (n) spectra and databases searches of SciFinder and ChemSpider.

No description available.

Master of Science / Department of Civil Engineering / Alok Bhandari / In the upper Midwest, subsurface tile drainage water is a major contributor of nitrate (NO[subscript]3–N) coming from fertilizers and animal manure. Movement of NO[subscript]3-N through tile drainage into streams is a major concern as it can cause eutrophication and hypoxia conditions, as in the Gulf of Mexico. Denitrifying bioreactors is one of the pollution control strategies to treat contaminated tile drainage water. These bioreactors require four conditions which are: 1) organic carbon source, 2) anaerobic conditions, 3) denitrifying bacteria and 4) influent NO[subscript]3-N. This research focuses on investigating fate of veterinary antibiotics in woodchips commonly used in in-situ reactors. Tylosin (TYL) and sulfamethazine (SMZ) are two veterinary antibiotics which are most commonly used in the United States and can be found in tile water after manure is land applied. Partition coefficients of TYL and SMZ on wood were determined by sorption experiments using fresh woodchips and woodchips from an in situ reactor. It was concluded that the woodchips were an effective means to sorb the veterinary antibiotics leached into the tile water after application of animal manure. Linear partition coefficients were calculated and phase distribution relationships were established for both the chemicals. The fresh woodchips gave inconclusive data but predictions could be made by the information determined in the experiments using woodchips from a ten year old woodchip bioreactor. Desorption was also studied and the likelihood of desorption was predicted using the Apparent Hysteresis Index. Overall, it was found that the old woodchips allowed for quick sorption of both antibiotics. It was also found that SMZ had reversible sorption on old woodchips. Thus, it was concluded that the woodchip bioreactor would not be effective for removal of veterinary antibiotics from tile drainage. More research is required for the fate of TYL and to confirm the conclusion.

A contaminação ambiental por antibióticos e antimicrobianos quimioterápicos despertou o interesse da comunidade científica devido à possibilidade do desenvolvimento de resistência bacteriana e de efeitos ecotóxicos sobre organismos não-alvo. As águas residuárias contaminadas representam a principal fonte de dispersão desses fármacos para o meio ambiente. Enquanto as tecnologias anaeróbias têm sido crescentemente aplicadas para o tratamento de águas residuárias de origem agroindustrial, frequentemente contaminadas com antimicrobianos, pouco se sabe sobre as transformações que esses micropoluentes podem sofrer durante o tratamento. O objetivo do presente trabalho foi a investigação da degradação do antimicrobiano veterinário sulfametazina (SMZ) durante o tratamento anaeróbio de água residuária de suinocultura. Para tanto, foram conduzidas três fases experimentais. Na primeira fase, ensaios em batelada foram realizados com o intuito de avaliar a contribuição da biodegradação anaeróbia e de outros fenômenos na remoção de SMZ da fase líquida. A segunda fase envolveu a operação de três reatores anaeróbios contínuos em escala de bancada alimentados com água residuária sintética contaminada com SMZ, um reator anaeróbio horizontal de leito fixo (RAHLF), um reator anaeróbio de mistura e biomassa imobilizada (RAMBI) e um reator anaeróbio de fluxo ascendente e manta de lodo (UASB). Avaliou-se o efeito da variação da DQO total afluente e do TDH na eficiência de remoção de SMZ. Na terceira fase, o RAHLF foi alimentado com água residuária de suinocultura real présedimentada e acrescida de SMZ. Os resultados obtidos durante a primeira fase permitiram o desenvolvimento de um modelo matemático de dois compartimentos que apontou a fase aquosa como o compartimento biodisponível para a degradação de SMZ. Não foram observadas diferenças expressivas de desempenho dos reatores anaeróbios na remoção de SMZ para as condições experimentais ensaiadas na segunda fase. As condições operacionais que permitiram máxima remoção de SMZ foram TDH de 24 h e DQO total afluente de 3000 mg O2.L-1, que resultaram em eficiências médias de remoção de SMZ de 74%, 71% e 70% para os reatores RAHLF, RAMBI e UASB, respectivamente. Observou-se que a biodegradação anaeróbia de SMZ é favorecida pelo aumento da velocidade de degradação de matéria orgânica, como esperado para uma transformação cometabólica. Embora a degradação de SMZ tenha sido interrompida durante a alimentação do RAHLF com água residuária de suinocultura, os resultados obtidos mostraram que a biodegradação de SMZ pode acontecer em reatores anaeróbios e pode ser favorecida por meio do controle de parâmetros de operação adequados, demonstrando o potencial de aplicação dessa tecnologia no abatimento de emissões desse fármaco. / Environmental contamination by antibiotics and antimicrobial chemotherapeutics has drawn the attention of the scientific community because of the possibility of bacterial resistance development and toxic effects on non-target organisms. Contaminated wastewaters are the main sources of antimicrobial dispersion to the environment. While anaerobic technologies have been increasingly applied to the treatment of agricultural wastewaters, which are often contaminated with antimicrobials, little is known about the changes that these micropollutants can undergo during treatment. The objective of this study was to investigate the degradation of the veterinary antimicrobial sulfamethazine (SMZ) during the anaerobic treatment of swine wastewater. Three experimental phases were performed. In the first phase, batch tests were performed in order to evaluate the contribution of anaerobic biodegradation and other phenomena to the overall removal of SMZ from the liquid phase. The second phase involved the operation of three continuous, bench-scale anaerobic reactors fed with SMZ-contaminated synthetic wastewater: a horizontal-flow anaerobic immobilized biomass (HAIB) reactor, an anaerobic stirred reactor with immobilized biomass (ASRIB) and an upflow anaerobic sludge blanket (UASB) reactor. The effect of varying the total influent COD and the HRT on SMZ removal efficiency was evaluated. In the third phase, the HAIB was fed with real presedimented swine wastewater contaminated with SMZ. The results obtained during the first phase allowed the development of a two-compartment mathematical model which established the aqueous phase as the bioavailable compartment for SMZ degradation. No significant differences in SMZ removal performance between the three reactors were observed in the second phase. The maximum removal of SMZ was observed for a HRT of 24 h and total influent COD of 3000 mg O2.L-1, which resulted in average SMZ removal efficiencies of 74%, 71% and 70% for the HAIB, ASRIB and UASB reactors, respectively. It was observed that the anaerobic biodegradation SMZ is favored by increasing the organic matter degradation rate, as expected for cometabolic transformations. Although SMZ degradation ceased when the HAIB was fed with swine wastewater, the experimental results showed that the biodegradation of SMZ occurs in anaerobic reactors and can be enhanced by controlling appropriate operating parameters, demonstrating the potential of this technology for the abatement of SMZ emission.

A contaminação ambiental por antibióticos e antimicrobianos quimioterápicos despertou o interesse da comunidade científica devido à possibilidade do desenvolvimento de resistência bacteriana e de efeitos ecotóxicos sobre organismos não-alvo. As águas residuárias contaminadas representam a principal fonte de dispersão desses fármacos para o meio ambiente. Enquanto as tecnologias anaeróbias têm sido crescentemente aplicadas para o tratamento de águas residuárias de origem agroindustrial, frequentemente contaminadas com antimicrobianos, pouco se sabe sobre as transformações que esses micropoluentes podem sofrer durante o tratamento. O objetivo do presente trabalho foi a investigação da degradação do antimicrobiano veterinário sulfametazina (SMZ) durante o tratamento anaeróbio de água residuária de suinocultura. Para tanto, foram conduzidas três fases experimentais. Na primeira fase, ensaios em batelada foram realizados com o intuito de avaliar a contribuição da biodegradação anaeróbia e de outros fenômenos na remoção de SMZ da fase líquida. A segunda fase envolveu a operação de três reatores anaeróbios contínuos em escala de bancada alimentados com água residuária sintética contaminada com SMZ, um reator anaeróbio horizontal de leito fixo (RAHLF), um reator anaeróbio de mistura e biomassa imobilizada (RAMBI) e um reator anaeróbio de fluxo ascendente e manta de lodo (UASB). Avaliou-se o efeito da variação da DQO total afluente e do TDH na eficiência de remoção de SMZ. Na terceira fase, o RAHLF foi alimentado com água residuária de suinocultura real présedimentada e acrescida de SMZ. Os resultados obtidos durante a primeira fase permitiram o desenvolvimento de um modelo matemático de dois compartimentos que apontou a fase aquosa como o compartimento biodisponível para a degradação de SMZ. Não foram observadas diferenças expressivas de desempenho dos reatores anaeróbios na remoção de SMZ para as condições experimentais ensaiadas na segunda fase. As condições operacionais que permitiram máxima remoção de SMZ foram TDH de 24 h e DQO total afluente de 3000 mg O2.L-1, que resultaram em eficiências médias de remoção de SMZ de 74%, 71% e 70% para os reatores RAHLF, RAMBI e UASB, respectivamente. Observou-se que a biodegradação anaeróbia de SMZ é favorecida pelo aumento da velocidade de degradação de matéria orgânica, como esperado para uma transformação cometabólica. Embora a degradação de SMZ tenha sido interrompida durante a alimentação do RAHLF com água residuária de suinocultura, os resultados obtidos mostraram que a biodegradação de SMZ pode acontecer em reatores anaeróbios e pode ser favorecida por meio do controle de parâmetros de operação adequados, demonstrando o potencial de aplicação dessa tecnologia no abatimento de emissões desse fármaco. / Environmental contamination by antibiotics and antimicrobial chemotherapeutics has drawn the attention of the scientific community because of the possibility of bacterial resistance development and toxic effects on non-target organisms. Contaminated wastewaters are the main sources of antimicrobial dispersion to the environment. While anaerobic technologies have been increasingly applied to the treatment of agricultural wastewaters, which are often contaminated with antimicrobials, little is known about the changes that these micropollutants can undergo during treatment. The objective of this study was to investigate the degradation of the veterinary antimicrobial sulfamethazine (SMZ) during the anaerobic treatment of swine wastewater. Three experimental phases were performed. In the first phase, batch tests were performed in order to evaluate the contribution of anaerobic biodegradation and other phenomena to the overall removal of SMZ from the liquid phase. The second phase involved the operation of three continuous, bench-scale anaerobic reactors fed with SMZ-contaminated synthetic wastewater: a horizontal-flow anaerobic immobilized biomass (HAIB) reactor, an anaerobic stirred reactor with immobilized biomass (ASRIB) and an upflow anaerobic sludge blanket (UASB) reactor. The effect of varying the total influent COD and the HRT on SMZ removal efficiency was evaluated. In the third phase, the HAIB was fed with real presedimented swine wastewater contaminated with SMZ. The results obtained during the first phase allowed the development of a two-compartment mathematical model which established the aqueous phase as the bioavailable compartment for SMZ degradation. No significant differences in SMZ removal performance between the three reactors were observed in the second phase. The maximum removal of SMZ was observed for a HRT of 24 h and total influent COD of 3000 mg O2.L-1, which resulted in average SMZ removal efficiencies of 74%, 71% and 70% for the HAIB, ASRIB and UASB reactors, respectively. It was observed that the anaerobic biodegradation SMZ is favored by increasing the organic matter degradation rate, as expected for cometabolic transformations. Although SMZ degradation ceased when the HAIB was fed with swine wastewater, the experimental results showed that the biodegradation of SMZ occurs in anaerobic reactors and can be enhanced by controlling appropriate operating parameters, demonstrating the potential of this technology for the abatement of SMZ emission.