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The purpose of this research was to design and develop a facile synthesis of a series of multi-headed, two-tailed anionic surfactants (3CAm1(n)2) as anti-HIV microbicides, and to compare the biological activities of these compounds to the activities of their straight-acyl chain derivatives. The synthesis requires coupling reaction of dialkylacetic acid (R2CHCOOH) (R2= n-C6H13, n-C7H15, n-C8H17, n-C9H19, n-C10H21) and Behera's amine (H2NC(CH2CH2COOtBu)3). Commercially available diethyl malonate and straight chain alkyl bromide were selected to produce dialkylacetic acid. Sodium methoxide (MeONa) was used as a base to deprotonate the acidic protons of diethyl malonate. The monoalkylmalonate (RCH(COOEt)2) was separated by vacuum distillation and then used as the starting material of the dialkylation step. This modification improved the yields of this reaction by about 10 percent from the routine procedure of introducing both alkyl groups in the same reaction. The Behera's amine was prepared from the nitrotriester (O2NC(CH2CH2COOtBu)3) by Zn° reduction. The Behera's amine was then converted into an HCl salt by using a diluted HCl solution in 1:1 EtOH/H2O. By doing so, lactam impurity can be separated by solid-liquid extraction in hexane with sonication. The Behera's amine HCl salt was then separated and converted back into Behera's amine by Et3N in dry CH2Cl2. Dialkylacetic acid was converted into its sodium salt by using aqueous NaOH solution; the sodium salt was then added to SOCl2 to yield the acyl chloride (R2CHCOCl). The coupling reaction of Behera's amine and acyl chloride was done in dry CH2Cl2 with 2.2 eq Et3N under sonication to give crude (R2CHCONHC(CH2CH2COOtBu)3), which was identified by ¹H NMR. The crude product from coupling reaction was treated with formic acid. The resulting product was the purified and isolated as a white solid by gravity column chromatography in 100:100:0.5 Hexane/EtOAc/AcOH. Five homologues (R2CHCONHC(CH2CH2COOH)3 R2= n-C6H13, n-C7H15, n-C8H17, n-C9H19, n-C10H21) were produced by this method; all were fully characterized by ¹H and ¹³C NMR, IR, and HRMS. Future improvements can be achieved by replacing the carboxylate groups with the other anionic groups, such as sulfate and phosphate, or add making tri-tailed surfactants, and by, exploring other possible way to improve the biological activities. / Master of Science

Anionic surfactants are wildly used in many industrial and household applications. Because anionic surfactants are used so widely, significant attention has focused on the removal of these contaminants from wastewater. Among various treatment techniques, biofiltration, such as trickling filter technologies, has been employed in many wastewater treatment plants (WWPTs) to remove anionic surfactants. However, current knowledge of the efficacy of trickling filter to remove anionic surfactants from wastewaters is limited. The present study characterized the performance of a high rate (i.e. roughing) trickling filter to remove anionic surfactants both at lab-scale and pilot-scale. Lab-scale tests investigated the biodegradation of anionic surfactants under controllable conditions were compared with those from previous studies by others. Pilot-scale tests investigated the efficacy of a trickling filter at removing anionic surfactants from a wastewater over an extended period of time. The data from the pilot-scale tests were used to model the performance of trickling filter at removing anionic surfactants from the wastewater, using first order and modified Velz models. The lab-scale tests indicated that high molecular weight anionic surfactants degrade faster than the low molecular weight surfactants. The biodegradation rates observed in the present study were similar to those from pervious studies by others. The pilot-scale tests indicated that roughing trickling filter could remove 11% to 29% of anionic surfactants and 4% to 22% of COD from the wastewater. Higher molecular weight anionic surfactants were more degradable. The experimental data could be accurately modeled using the modified Velz model (R² value more than 0.9). The degradation rates of modified Velz model for total anionic surfactants, high molecular weight anionic surfactants and COD were 0.053±0.0057, 0.088±0.0048 and 0.119±0.0111 (mIs)0.5 respectively. The pilot-scale test results indicated that a high rate (i.e., roughing) trickling filter was not capable of effectively removing anionic surfactants in the primary effluent at Lions Gate WWTP because a relatively large trickling filter area would be required to achieve the required surfactant removal efficiency.

Anionic surfactants are wildly used in many industrial and household applications. Because anionic surfactants are used so widely, significant attention has focused on the removal of these contaminants from wastewater. Among various treatment techniques, biofiltration, such as trickling filter technologies, has been employed in many wastewater treatment plants (WWPTs) to remove anionic surfactants. However, current knowledge of the efficacy of trickling filter to remove anionic surfactants from wastewaters is limited. The present study characterized the performance of a high rate (i.e. roughing) trickling filter to remove anionic surfactants both at lab-scale and pilot-scale. Lab-scale tests investigated the biodegradation of anionic surfactants under controllable conditions were compared with those from previous studies by others. Pilot-scale tests investigated the efficacy of a trickling filter at removing anionic surfactants from a wastewater over an extended period of time. The data from the pilot-scale tests were used to model the performance of trickling filter at removing anionic surfactants from the wastewater, using first order and modified Velz models. The lab-scale tests indicated that high molecular weight anionic surfactants degrade faster than the low molecular weight surfactants. The biodegradation rates observed in the present study were similar to those from pervious studies by others. The pilot-scale tests indicated that roughing trickling filter could remove 11% to 29% of anionic surfactants and 4% to 22% of COD from the wastewater. Higher molecular weight anionic surfactants were more degradable. The experimental data could be accurately modeled using the modified Velz model (R² value more than 0.9). The degradation rates of modified Velz model for total anionic surfactants, high molecular weight anionic surfactants and COD were 0.053±0.0057, 0.088±0.0048 and 0.119±0.0111 (mIs)0.5 respectively. The pilot-scale test results indicated that a high rate (i.e., roughing) trickling filter was not capable of effectively removing anionic surfactants in the primary effluent at Lions Gate WWTP because a relatively large trickling filter area would be required to achieve the required surfactant removal efficiency.

This thesis is concerned with aspects of the surface and colloid chemistry of various microemulsion systems stabilised by pure nonionic surfactants and alcohol as well as mixtures of nonionic and anionic surfactants. Phase equilibria and interfacial characteristics of the systems are studied with a view to their potential usefulness for enhanced oil recovery, in which salinity and temperature are important parameters. The equilibrium microemulsion phases are scanned at different temperatures and salinities and thus interfacial boundaries can be determined and optimum salinity scans can be performed accurately using a modified spectrophotometer. Several analytical techniques (e.g., high performance liquid chromatography, gas chromatography, ion-exchange chromatography, mass spectrometry, viscometry, electrical conductivity, photon correlation spectroscopy, UV-spectrophotometry, thermogravimetric analysis, transmission electron microscopy, surface and interfacial tension techniques) have been used to characterise and understand the microchemistry of the microemulsion systems. Ultra-low interfacial tensions (>0.1 µN/m) can be achieved in the microemulsion systems. Surfactant transfer between phases, and phase inversion of micro emulsions are shown to occur around the condition which produces minimum interfacial tension. Adsorption of the surfactants from aqueous and nonaqueous solutions has been investigated and the results show that the extent of adsorption can be reduced significantly in the presence of alcohols (co-solvent). The extent of adsorption increases with increasing temperature and salinity; however, it decreases with an increase in the hydrophilic head group of the surfactant. Adsorption of nonionic surfactants on quartz from the nonaqueous solution (decane) is much greater than from aqueous solution. In microemulsion applications, droplet combustion of w/o microemulsions is also studied for different surfaces (i.e. silica, oxidised Fecralloy and catalyst coated Fecralloy) in the temperature range of 313-573K. Formaldehyde and acetaldehyde are formed as intermediate combustion products. Thus the microemulsion combustion can lead to new oxygenate products. The w/o microemulsion route is used to synthesize colloidal silica of controlled particle size and morphology. The particle size can be varied by changing the molar ratio of water to TEOS using a water pH of 10.5.

Anionic surfactants are wildly used in many industrial and household applications. Because anionic surfactants are used so widely, significant attention has focused on the removal of these contaminants from wastewater. Among various treatment techniques, biofiltration, such as trickling filter technologies, has been employed in many wastewater treatment plants (WWPTs) to remove anionic surfactants. However, current knowledge of the efficacy of trickling filter to remove anionic surfactants from wastewaters is limited. The present study characterized the performance of a high rate (i.e. roughing) trickling filter to remove anionic surfactants both at lab-scale and pilot-scale. Lab-scale tests investigated the biodegradation of anionic surfactants under controllable conditions were compared with those from previous studies by others. Pilot-scale tests investigated the efficacy of a trickling filter at removing anionic surfactants from a wastewater over an extended period of time. The data from the pilot-scale tests were used to model the performance of trickling filter at removing anionic surfactants from the wastewater, using first order and modified Velz models. The lab-scale tests indicated that high molecular weight anionic surfactants degrade faster than the low molecular weight surfactants. The biodegradation rates observed in the present study were similar to those from pervious studies by others. The pilot-scale tests indicated that roughing trickling filter could remove 11% to 29% of anionic surfactants and 4% to 22% of COD from the wastewater. Higher molecular weight anionic surfactants were more degradable. The experimental data could be accurately modeled using the modified Velz model (R² value more than 0.9). The degradation rates of modified Velz model for total anionic surfactants, high molecular weight anionic surfactants and COD were 0.053±0.0057, 0.088±0.0048 and 0.119±0.0111 (mIs)0.5 respectively. The pilot-scale test results indicated that a high rate (i.e., roughing) trickling filter was not capable of effectively removing anionic surfactants in the primary effluent at Lions Gate WWTP because a relatively large trickling filter area would be required to achieve the required surfactant removal efficiency. / Applied Science, Faculty of / Civil Engineering, Department of / Graduate

Submitted by Haroudo Xavier Filho (haroudo.xavierfo@ufpe.br) on 2016-07-01T14:17:21Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação Versão em PDF.pdf: 1393964 bytes, checksum: 9f6914af2635718fc925ce4690531587 (MD5) / Made available in DSpace on 2016-07-01T14:17:21Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação Versão em PDF.pdf: 1393964 bytes, checksum: 9f6914af2635718fc925ce4690531587 (MD5) Previous issue date: 2015-01-30 / CAPES / O LAS é um tensoativo usado na fabricação de produtos de limpeza, sendo sua degradação no tratamento aeróbio altamente eficaz. Todavia, em ambientes anaeróbios, sua biodegradação depende de vários fatores, como a composição e concentração de alguns compostos dos esgotos. Por isso, as eficiências de degradação do LAS neste ambiente são distintas, variando de 0 a 78%. No Brasil, devido a uma carência na área do saneamento, alternativas mais baratas para o tratamento de esgoto estão sendo amplamente utilizadas. Os reatores anaeróbios do tipo UASB são um exemplo destas alternativas, devido a sua alta eficiência de remoção de matéria orgânica. Entretanto, atualmente em uma estação de tratamento de esgoto, o objetivo não é apenas a matéria orgânica de fácil degradação, mas também compostos recalcitrantes e nutrientes. Este trabalho teve como objetivo aplicar em um reator contínuo, alimentado com esgoto real, um modelo de otimização, realizado em laboratório com regime em batelada, para verificar reprodutibilidade da influência de alguns parâmetros na dinâmica de sorção/dessorção do LAS em reatores utilizados em estações de tratamento de esgoto convencionais. Foram realizados dois experimentos. O experimentoI foi o monitoramento de um reator UASB em escala de laboratório. Este reator era alimentado com esgoto de uma estação de tratamento real, ETE Mangueira. Alterações no afluente foram realizadas para proporcionar a adsorção do LAS na biomassa. O pH foi ajustado para 6. Seguindo um planejamento fatorial 2K, o reator foi operado em 4 fases alterando a concentração de óleo, entre 0 e 5 g/L e a oxigenação ou não do LAS. O experimento II foi um teste de laboratório de adsorção e de dessorção, utilizando a mesma biomassa do reator do primeiro experimento. Foram submetidas diferentes concentrações de LAS (10, 20 e 100 mg/L), e diferentes tempos de mistura. Durante o período de operação, observou-se a ocorrência de adsorção e dessorção do LAS no lodo, bem como biodegradação, quando a adsorção foi baixa; as eficiências de degradação do LAS total nas diversas fases experimentais variaram de 0 a 33%. Os homólogos C12 e C13 foram os que sofreram maior degradação durante todo período de operação, com eficiências de 42 e 57% de sua massa inicial, respectivamente, na fase com alteração apenas do pH; o C13 foi o homólogo de maior taxa de adsorção, 97% de sua massa inicial. Isto ocorreu quando a concentração de óleo foi de 5 g/L e não foi realizado aeração do LAS. No teste de adsorção, os resultados obtidos mostraram que a adsorção na biomassa seca depende da disponibilidade de LAS no líquido. No teste de dessorção o comportamento de liberação de LAS no meio aquoso foi lento. Os testes mostraram capacidade reversível da adsorção do LAS, comprovando que a dinâmica de adsorção e dessorção do LAS no reator depende da composição do meio líquido e da forma de operação do reator, e que sua indisponibilidade no meio solúvel impede a degradação. Logo, o processo de adsorção inibe a degradação do LAS em ambientes anaeróbios e os resultados obtidos no teste de otimização em laboratório foram também observados em reatores operados com esgoto real. / LAS is a surfactant used in the manufacture of cleaning products, and its degradation in the highly efficient aerobic treatment. However, in anaerobic environments, biodegradation depends on several factors, including the composition and concentration of certain compounds of sewage. Therefore, the LAS this environmental degradation efficiencies are different, ranging from 0 to 78%. In Brazil, due to a lack in the sanitation area, cheaper alternatives for the treatment of sewage are being widely used. The anaerobic reactor of the UASB type are an example of these alternatives, due to its high removal efficiency of organic matter. However, currently a sewage treatment plant, the aim is not only the organic matter degradation easily, but also nutrients and recalcitrant compounds. This study aimed to apply in a continuous reactor, fed with real wastewater, an optimization model, conducted in laboratory batch system to check reproducibility of the influence of some parameters on dynamic sorption / desorption of LAS reactors used in stations Conventional sewage treatment. Two experiments were conducted. The first was a monitoring of a UASB reactor at laboratory scale. This reactor was fed with sewage a real treatment plant, ETE hose. Changes in the influent were performed to provide the adsorption of LAS biomass. The pH was adjusted to 6. By following a factorial design 2K, the reactor was operated at four stages by changing the concentration of oil, between 0 and 5 g / L and oxygenation or not the LAS. The second experiment was a laboratory test adsorption and desorption using the same biomass from the first reactor experiment. They underwent different concentrations of LAS, 10, 20 and 100 mg / L, and different mixing times. During the operation period, it was observed the occurrence of adsorption and desorption of LAS in the sludge as well as biodegradation when adsorption was low; The degradation efficiency of the total LAS in the different experimental phases ranging from 0 to 33%. The C12 and C13 homologues have suffered the greatest degradation during the entire operating period, efficiency 42 and 57% of their initial mass, respectively, in phase with the pH change only; the C13 was the counterpart of higher adsorption rate, 97% of its initial mass. This occurred when the oil concentration was 5 g / L and aeration was not performed LAS. In the adsorption test, the results showed that adsorption of dry biomass depends on the availability of LAS in the liquid. In desorption test the LAS release behavior in aqueous media was slow. The tests showed reversible adsorption capacity of the LAS, proving that the dynamics of adsorption and desorption of LAS in the reactor depends on the composition of the liquid medium and form of reactor operation, and that their unavailability in the middle soluble prevents degradation. Therefore, the adsorption process inhibits the degradation of LAS in anaerobic environments and the results obtained in laboratory test optimization are also observed in reactors operated with real sewage.

Surfactants are surface-active agents decreasing surface tension to simplify removing dirt. Surfactants can be divided into four basic classes: anionic, cationic, non-ionic and amfolytic. In Czech Republic there are mostly used anionic surfactants nowadays which get into waste water through detergents. The thesis deals with the spectrophotometric determination of anionic surfactants and the study of interferences to this method.

Made available in DSpace on 2016-06-02T19:31:40Z (GMT). No. of bitstreams: 1 1959.pdf: 1033941 bytes, checksum: 78e3218226ae4e1376a101c0d5d8d71f (MD5) Previous issue date: 2008-04-25 / Financiadora de Estudos e Projetos / The main anionic surfactants world widely used are the sodium dodecyl benzene sulfonate (LAS) and sodium dodecyl sulfate (DSS), which are mainly used in the manufacturing of domestic and personal hygiene products. As a consequence of the great and increasing consumption of LAS and DSS there is an increasing wareness regarding the adverse effects of these compounds to the organisms and environment. The present study aimed to evaluate the acute and chronic toxicity of the compounds LAS and DSS to the cladocerans Daphnia similis, Ceriodaphnia dubia and Ceriodaphnia silvestrii. It was also evaluated the toxicity of the water and sediments of four reservoirs and one stream of São Paulo State Analyses of LAS concentrations in the water of these reservoirs were also performed by Liquid chromatography. Acute toxicity tests indicated a value of CE(I)50;48h for LAS of 14.17 mg L-1 to D. similis, 11.84 mg L-1 to C. dubia and 13.51 mg L-1 to C. silvestrii. Significant changes in the viability of the cladoceran offsprings were observed for C. dubia and C. silvestrii exposed to the LAS, with values of CENO equal to 1.0 mg L-1 to C. dubia and 2.5 mg L-1 to C. silvestrii. It was concluded that the maximum permissible concentration of 0.5 mg L-1 surfactants as established by the resolution CONAMA nº. 357/2005 (Brazilian Ministry of Environment) in order to protect aquatic communities is adequate, considering the sensitivity of the native species C. silvestrii. The results of the acute toxicity tests with DSS indicated a CE(I)50;48h value of 12.82; 4.37 and 5.42 mg L-1, for D. similis, C. dubia and C. silvestrii, respectively. A CENO value of 2.0 mg L-1 was obtained in the chronic toxicity tests for C. silvestrii. The surfactant LAS was detected in all the water samples collected in the Lobo (Broa), Lagoa Dourada and Fazzari reservoirs, but at concentrations lower than 5 mg L-1 (the method limit of detection). The toxicity tests with environmental samples revealed that there is no toxicity in the water of the Lobo and Lagoa Dourada sampled, however the water of Monjolinho Reservoir was toxic to D. similis and Fazzari stream was toxic to D. similis and C. dubia. Only the sediment of Monjolinho Reservoir was not toxic to cladocerans. / Os principais surfactantes aniônicos disponíveis no mercado mundial são o dodecil benzeno sulfonato de sódio (LAS) e o dodecil sulfato de sódio (DSS), utilizados principalmente em produtos de limpeza doméstica e de higiene pessoal. Devido ao grande consumo mundial de LAS e de DSS há uma crescente preocupação sobre os efeitos adversos destes compostos no ambiente e aos organismos. Este trabalho teve por objetivo avaliar a toxicidade aguda e crônica do LAS e do DSS aos organismos-teste Daphnia similis, Ceriodaphnia dubia e Ceriodaphnia silvestrii. Foi também avaliada a toxicidade da água e dos sedimentos em quatro reservatórios e um riacho do estado de São Paulo por meio de testes de toxicidade aguda e da análise quantitativa do surfactante LAS. Os testes de toxicidade aguda indicaram uma CE(I)50;48h do LAS de 14,17 mg L-1 para D. similis, 11,84 mg L-1 para C. dubia e 13,51 mg L-1 para C. silvestrii. Nos testes crônicos realizados foi observada significativa alteração viabilidade da progênie de C. dubia e C. silvestrii exposta ao LAS, com valores de CENO igual a 1,0 mg L-1 para C. dubia e 2,5 mg L-1 para C. silvestrii. Pode-se concluir que o valor máximo permissível de surfactantes de 0,5 mg L-1, estabelecido pela Resolução CONAMA nº. 357/2005 em águas destinadas à proteção das comunidades aquáticas, é adequado para a espécie nativa C. silvestrii. Nos testes de toxicidade aguda de DSS foram obtidos valores de CE(I)50;48h de 12,82; 4,37 e 5,42 mg L-1, para D. similis, C. dubia e C. silvestrii, respectivamente. No ensaio de toxicidade crônica obteve-se valor de CENO igual a 2,0 mg L-1 para C. silvestrii. O surfactante LAS foi detectado nas amostras de água dos Reservatórios do Lobo (Broa), Lagoa Dourada e Represa do Monjolinho em concentração inferior a 5 mg L-1. Os testes revelaram que não há toxicidade aguda aos cladóceros da água da Lagoa Dourada e do Reservatório do Lobo, havendo, contudo, toxicidade da água da Represa do Monjolinho para D. similis e da água do Córrego do Fazzari para os cladóceros D. similis e C. dubia. Somente a amostra de sedimento da Represa do Monjolinho não causou toxicidade aos cladóceros.