This paper describes the development of an electrochemical sensor glassy carbon modified with gold nanoparticles and a film of multiâwalled carbon nanotube and cobalt phthalocyanine (CoPc-fMWCNTs/AuNp/GCE) for the determination of diethylstilbestrol hormone (DES) in water samples and meat, using a square wave technique voltammetry. (SWV). The electrolyte used was Britton-Robinson buffer (BR) 0.04 mol L-1 pH 10.0. Initially it was studied the electrode configuration to be used for the development work, after the optimization of solution pH, study scan speed to evaluate the charge transfer kinetics in the redox process of the DES, the optimized parameters for SWV, the analytical curve, and finally, applying the methodology developed. The optimized parameters for SWV were f = 5 sâ1, a = 50 mV and ΔEs=1 mV. The CoPc-fMWCNTs/AuNp/GCE was ready to be used for the application since all conditions were optimized. Analytical curves were obtained in the concentration ranged from 7.9365 à 10−7 â 5.6604 à 10−6 mol Lâ1 (R = 0.9996) and there were obtained limits of detection (LOD) and quantification (LOQ) of 1.9910 x 10â7 mol Lâ1and 6.6367 x 10â7 mol Lâ1, respectively, being comparable to those reported in the literature. The repeatability and reproducibility of the proposed procedure were evaluated. The relative standard deviation (RSD) were 4.33% and 3.49%, respectively, indicating the precision of the assay. The recovery percentage was 98.56% for the water sample and 94.05% for beef sample (RSD of 0.40 and 1.55% respectively). The modified electrode has developed sensitivity, reproducibility and repeatability appropriate and consistent LOD and LOQ values with those reported in the literature. Moreover, the results obtained by the use of CoPc-fMWCNTs/AuNp/GCE proved very efficient as the detection and DES recovery, being thus a promising device in the detection and quantification of DES in water samples and food. / O presente trabalho descreve o desenvolvimento de um sensor eletroquÃmico de carbono vÃtreo modificado com nanopartÃculas de ouro, nanotubos de carbono de paredes mÃltiplas funcionalizados e ftalocianina de cobalto (CV/NpAu/NTCPMf-FcCo) para a determinaÃÃo do hormÃnio dietilestilbestrol (DES) em amostras de Ãgua e carne, utilizando a tÃcnica de voltametria de onda quadrada (VOQ). O eletrÃlito empregado foi tampÃo BrittonâRobinson (BR) 0,04 mol Lâ1 pH 10,0. Inicialmente estudou-se a configuraÃÃo do eletrodo a ser utilizado para o desenvolvimento do trabalho, depois a otimizaÃÃo do pH do meio, estudo da velocidade de varredura para avaliar a cinÃtica de transferÃncia de carga no processo redox do DES, otimizaÃÃo dos parÃmetros da VOQ, construÃÃo da curva analÃtica e por fim, a aplicaÃÃo da metodologia desenvolvida. Os parÃmetros otimizados para a VOQ foram: f = 5 sâ1, a = 50 mV e ΔEs = 1 mV. De posse de todas as condiÃÃes otimizadas para aplicaÃÃo do CV/NpAu/NTCPMf-FcCo, curvas analÃticas foram obtidas no intervalo de concentraÃÃo de 7,9365 à 10−7 â 5,6604 à 10−6 mol Lâ1 (R = 0,9996) e os limites de detecÃÃo (LD) e de quantificaÃÃo (LQ) calculados foram 1,9910 x 10â7 mol Lâ1 e 6,6367 x 10â7 mol Lâ1, respectivamente, sendo comparÃveis aos citados na literatura. A repetibilidade e a reprodutibilidade do procedimento proposto foram avaliadas. Os valores de desvio padrÃo relativo (DPR) obtidos foram 4,33% e 3,49%, respectivamente, evidenciando a precisÃo da metodologia. O percentual de recuperaÃÃo foi de 98,56% para amostra de Ãgua e 94,05% para amostra de carne bovina (DPR de 0,40 e 1,55% respectivamente). O eletrodo modificado desenvolvido apresentou sensibilidade, reprodutibilidade e repetibilidade adequados, bem como valores de LD e LQ concordantes com os relatados na literatura. Os resultados obtidos pelo emprego do CV/NpAu/NTCPMf-FcCo se mostraram muito eficientes quanto à detecÃÃo e recuperaÃÃo de DES, mostrando-se, desse modo, um dispositivo promissor na detecÃÃo e na quantificaÃÃo de DES em amostras de Ãgua e alimentos.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2017-04-25T14:08:17Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO José Vinícius O. Carneiro-Final (BC).pdf: 3473579 bytes, checksum: 53d2c12ba53b539b7c125ce7329018ff (MD5) / Made available in DSpace on 2017-04-25T14:08:17Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO José Vinícius O. Carneiro-Final (BC).pdf: 3473579 bytes, checksum: 53d2c12ba53b539b7c125ce7329018ff (MD5) Previous issue date: 2016-09-01 / Diante da necessidade de tratar os contaminantes emergentes (CEs) presentes em águas residuais, o presente trabalho surge como uma rota alternativa de processo terciário a ser implantada nas estações de tratamento de efluentes (ETEs) convencionais. A fotodegradação do diclofenaco de sódio (DCF) mediante processos oxidativos avançados (POA), ocorreu via fotocatálise heterogênea utilizando nanotubos de TiO2 (NTs de TiO2) como fotocatalisadores. Empregou-se um reator em batelada com fotocatalisadores em placa (NTs de TiO2 e NTs de TiO2-Au ) e um reator tubular carregado com um microrreator (fotocatalisador) dotado de NTs de TiO2 sensibilizado ou não com nanopartículas de ouro (NPs Au). A síntese dos NTs de TiO2 ocorreu pelo processo de anodização utilizando como substrato folhas de titânio metálico (Ti). As matrizes nanotubulares foram cristalizadas por tratamento térmico (400°C por 3h). A sensibilização com NPs de Au foi realizada in situ por redução através da radiação UV. A fotodegradação foi realizada a partir da irradiação do simulador solar NEWPORT modelo 67005 com uma lâmpada de Xenônio-Mercúrio (com potência calibrada para 1 SOL), na ausência ou presença de filtro (UV ou visível). A fase cristalina anatase dos NTs de TiO2 foi identificada pela difração de raios X (DRX). Foi estimada pelo refinamento de Rietveld uma cristalinidade de 77% para a superfície fotocatalítica, com a anatase (NTs de TiO2 cristalizados) representando 92,4% desta fase cristalina. A energia de band gap dos fotocatalisadores de 3,23 eV foi determinada pela espectroscopia de reflectância difusa. Através da microscopia eletrônica de varredura (MEVEDD) foi possível visualizar para a folha de Ti lisa, estruturas cilíndricas dos NTs de TiO2 que cresceram perpendicular ao substrato, apresentando um diâmetro médio de 78,87 nm e comprimentos na ordem de 2 µm, no caso da folha de Ti ondulada os NTs de TiO2 cresceram em direções variadas apresentando um diâmetro médio de 81,09 nm e comprimentos na ordem de 3 µm. A presença das NPs Au foi identificada pela espectroscopia de energia dispersiva (EDD). A determinação e quantificação de produto e reagente da fotocatálise heterogênea na degradação do DCF foram realizadas pela combinação de métodos analíticos (Cromatografia líquida de alta eficiência, Ressonância Magnética e Infravermelho por transformada de Fourier), obtendo uma conversão de 100% do DCF para testes no reator em batelada e de 37,0% no reator com recirculação para o melhor sistema fotocatalítico. Foi estimado através da análise de carbono orgânico total (COT) uma mineralização de 18,5% do DCF inicial para o sistema fotocatalítico mais eficiente utilizando o reator com recirculação. A ecotoxicidade do DCF e seus produtos de fotodegradação foi avaliada utilizando microcrustáceos (Artêmias Salinas) como bioindicador. / Faced with the need to address emerging contaminants (ECs) in waste water, this work is an alternative route of tertiary process to be implemented in conventional wastewater treatment plants (WTPs). Sodium diclofenac photodegradation (DCF) by advanced oxidation processes (AOP), occurred via heterogeneous photocatalysis using TiO2 nanotubes (TiO2 NTs) as photocatalysts. He employed a batch reactor with photocatalysts plate (TiO2 NTs and TiO2 - Au NTs) and a tubular reactor charged with a microreactor (photocatalyst) having TiO2 NTs sensitized or not with gold nanoparticles (NPs Au). The synthesis of TiO2 NTs occurred by anodization process using as substrate sheets of metallic titanium (Ti). The nanotubulares matrices were crystallized by heat treatment (400 ° C for 3h). The sensitization Au NPs was performed in situ by reduction by UV radiation. The photodegradation was carried from the irradiation NEWPORT solar simulator 67005 model with a xenon-mercury lamp (calibrated power for 1 SUN) in the absence or presence of filter (UV or visible). The anatase crystalline phase of TiO2 NTs was identified by X-ray diffraction (XRD). It was estimated by Rietveld refinement a crystallinity of 77% at the photocatalytic surface with anatase (TiO2 crystallized NTs) representing 92.4% of this crystalline phase. The energy band gap of 3.23 eV photocatalysts was determined by diffuse reflectance spectroscopy. By scanning electron microscopy (SEM-EDS) it was possible to view the Ti smooth sheet, cylindrical structures of TiO2 NTs that grew perpendicular to the substrate, with an average diameter of 78.87 nm and lengths in 2 µm order, in the case of the corrugated Ti sheet the TiO2 NTs grew in different directions with a mean diameter of 81.09 nm and lengths on the order of 3 µm. The presence of NPs Au was identified by energy dispersive spectroscopy (EDS). The determination and quantification of product and reactant of heterogeneous photocatalytic on the degradation of DCF were performed by a combination of analytical methods (high-performance liquid chromatography, Magnetic Resonance and Infrared Fourier transform ), whereby a conversion of 100 % DCF for testing in batch reactor and 37.0 % in the reactor for recirculating the best photocatalytic system. It was estimated by analyzing total organic carbon (TOC) a mineralization of 18.5 % of the initial DCF for more efficient photocatalyst system using the reactor with recirculation. The ecotoxicity of DCF and its photodegradation products was evaluated using microcrustaceans (Artemias Salinas) as bioindicator.

Orientadora: Profª. Drª. Lúcia Helena Gomes Coelho / Coorientador. Prof. Dr.Eduardo Lucas Subtil / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Ciência e Tecnologia Ambiental, Santo André, 2018. / Os antibióticos têm sido detectados em diversos compartimentos ambientais em concentrações traço da ordem de ng L-1 e µg L-1. Mesmo em baixos níveis, compostos farmaceuticamente ativos podem afetar a saúde humana e animal. Dentre esses micropoluentes emergentes está a amoxicilina, um antibiótico do tipo penicilina ?-lactâmico muito prescrito e consumido ao redor do mundo. Frente aos problemas relacionados com a presença dessa substância no meio ambiente, em várias situações, faz-se necessária sua remoção. O MBR (biorreator com membranas submersas) é um dos sistemas de tratamento com potencial para remover compostos emergentes do efluente. O presente trabalho teve como objetivo avaliar a eficiência de um sistema MBR piloto para remover amoxicilina de efluente sintético. Para isto, foi montada uma unidade piloto de dois estágios (tanque anóxico e aeróbio) de fluxo contínuo. A operação do sistema se deu em três fases: (1) com vazão de 1 L h-1 e TDH de 40 h; (2) adicionando 100 µg L-1 de amoxicilina no afluente e (3) alterando a vazão da condição (2) para 2 L h-1 e TDH de 20 h. A inserção de amoxicilina no afluente não impactou na eficiência de remoção de demanda química de oxigênio (DQO) e carbono orgânico dissolvido (COD), nem no processo de nitrificação, mas limitou a desnitrificação possibilitando detectar nitrito nas Fases 2 e 3. A alteração do TDH reduziu a porcentagem de remoção de COD (de 84% para 66% da Fase 2 para Fase 3), mas não influenciou na eficiência de eliminação de DQO (>94%), N-NH4+ (>98%) e N-total (>72%). A remoção de amoxicilina reduziu de 80% para 54% com a mudança da vazão. Os mecanismos de remoção de amoxicilina mediados pela atuação do lodo (adsorção e biodegradação) representam a maior fração removida do antibiótico no MBR (66%), o biofilme atua em 3% e a hidrólise contribui com apenas 2% da remoção. Análises cromatográficas confirmaram a presença de cinco produtos de degradação no afluente do sistema. Foi avaliada a sensibilidade de Vibrio fischeri, Daphnia magna, algas Chlorella vulgaris e Raphidocelis subcaptata, sementes de alface (Lactuca sativa) e mostarda (Sinapis alba) e as bactérias Escherichia coli, Bacillus subtilis e Pseudomonas fluorescens. Os ensaios de ecotoxicidade mostraram que todos os organismos são influenciados, ao mesmo tempo, pelos efeitos positivos da composição do esgoto sintético como nutrientes e pelos efeitos negativos da ação da amoxicilina. O ensaio de respirometria mostrou que concentrações de 1 a 100 µg L-1 de amoxicilina não inibiram as bactérias heterotróficas presentes na biomassa do MBR, mas concentrações de 1 a 100 mg L-1 as inibem. / Antibiotics have been detected in several environmental compartments at trace concentrations of ng L-1 and ?g L-1. Even at low levels, pharmaceutically active compounds can impact human and animal health. Among these emerging micropollutants is amoxicillin, a ?-lactamic penicillin antibiotic much prescribed and consumed around the world. Facing the problems related to the presence of this substance in the environment, in several situations, it is necessary to be removed. The MBR (a bioreactor with submerged membranes) is one of the treatment systems with the potential to remove emerging compounds from the effluent. The present work aims to evaluate the efficiency of a MBR system pilot to remove amoxicillin from synthetic wastewater. For this, a continuous flow two-stage (anoxic and aerobic tank) pilot unit was set up. The system operation occurred in three phases: (1) with a flow of 1 L h-1 and HRT = 40 h; (2) adding 100 ?g L-1 of amoxicillin to the influent and (3) altering the flow rate from condition (2) to 2 L h-1 and HRT = 20 h. The addition of amoxicillin in the inffluent did not affect COD and DOC elimination efficiency nor the nitrification process, but limited denitrification and, thus, nitrite was detected in Phase 2 and 3. The HRT change reduced the COD removal percentage (from 84% to 66 % from Phase 2 to Phase 3), but did not influence COD removal efficiency (>94%), N-NH4+ (>98%) and N-total (>72%). The amoxicillin removal decreased from 80% to 54% with flow rate change. The removal mechanisms of amoxicillin mediated by sludge (adsorption and biodegradation) represent the largest removed fraction of the antibiotic in the MBR (66%), the biofilm acts in 3% and the hydrolysis contributes only 2% of antibiotic removal. Chromatographic analyzes confirmed the presence of five degradation products in the effluent. The sensitivity of Vibrio fischeri, Daphnia magna, Chlorella vulgaris and Raphidocelis subcaptata algaes, lettuce (Lactuca sativa) and mustard (Sinapis alba) seed and the bacterias Escherichia coli, Bacillus subtilis and Pseudomonas fluorescens were evaluated. Ecotoxicity assays have shown that all organisms are influenced at the same time by the positive effects of the synthetic wastewater composition and by the negative effects of amoxicillin action. The respirometry assay showed that 1 to 100 ?g L-1 of amoxicillin concentrations did not inhibit the heterotrophic bacteria present in MBR biomass, but concentrations between 1 to 100 mg L-1 inhibit them.

Submitted by Erika Demachki (erikademachki@gmail.com) on 2015-11-12T17:47:20Z No. of bitstreams: 2 Dissertação - Lícia Aparecida da Silva - 2015.pdf: 2121079 bytes, checksum: b400adc1fa3f8a66302ba1e4bdd38eaf (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Erika Demachki (erikademachki@gmail.com) on 2015-11-12T17:50:37Z (GMT) No. of bitstreams: 2 Dissertação - Lícia Aparecida da Silva - 2015.pdf: 2121079 bytes, checksum: b400adc1fa3f8a66302ba1e4bdd38eaf (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-11-12T17:50:37Z (GMT). No. of bitstreams: 2 Dissertação - Lícia Aparecida da Silva - 2015.pdf: 2121079 bytes, checksum: b400adc1fa3f8a66302ba1e4bdd38eaf (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2015-08-13 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The present work describes the development of an analytical method for the removal of contaminant emerging Sodium Diclofenac (DCF) present in aqueous solutions. For the removal thereof, it is used as a natural adsorbent sawdust treated in acid medium. The detection and quantification of the analyte were Performed by High-Performance Liquid Chromatography (English, HPLC). The material was characterized according to the techniques of Infrared Spectroscopy and X-Ray Diffraction. The Point of Zero Charge (PZC) was obtained both for the sawdust treated in acid medium, and for the same in kind, obtaining values of 4.8 and 5.5, respectively. We chose to work with the adsorbent treated with acid in natural pH of the solution (6.43), since the adsorption was quite satisfactory (86%). It was determined the LD figures of merit (0.06 mg L-1) and LQ (0.2 mg L-1). The linearity was determined by construction of standard curves prepared in solvent and prepared curves with water samples fortified with the DCF standard. The obtained correlation coefficient was quite satisfactory (r = 0.9999) and the recovery values were between 86% and 117% to the study drug. It used Full Factorial Planning 23 for optimization of chemical variables that can have an effect on the adsorption process. The results obtained by the Pareto chart showed that the only variable that exerted influence on the adsorption was the mass of adsorbent. Therefore, it was determined by univariate optimization, as being 600 mg. To study the adsorption kinetics, it was determined the equilibration time of 180 min, and following the adsorption pseudosegunda-order model. The isotherm obtained was linearized and the result indicated that the adsorption follows the Langmuir model, ie, chemical adsorption occurs monolayer. / O presente trabalho descreve o desenvolvimento de uma metodologia analítica para a remoção do contaminante emergente Diclofenaco de Sódio (DCF) presente em soluções aquosas. Para a remoção do mesmo, utilizou-se como adsorvente natural a serragem de madeira tratada em meio ácido. A detecção e quantificação do analito foram realizadas por Cromatografia Líquida de Alta Eficiência (do inglês, HPLC). O adsorvente foi caracterizado segundo as técnicas de Espectroscopia de Infravermelho e Difração de Raios-X. O Ponto de Carga Zero (PCZ) foi obtido tanto para a serragem de madeira tratada em meio ácido, como para a mesma in natura, obtendo valores de 4,8 e 5,5, respectivamente. Optou-se por trabalhar com o adsorvente tratado com ácido em pH natural da solução (6,43), visto que a adsorção foi bastante satisfatória (86%). Determinou-se as figuras de mérito LD (0,06 mg L-1) e LQ (0,2 mg L-1). A linearidade foi determinada através da construção de curvas analíticas preparadas em solvente e curvas preparadas com amostras de água fortificadas com o padrão de DCF. O coeficiente de correlação obtido foi bastante satisfatório (r = 0,9999) e os valores de recuperação ficaram entre 86% e 117% para o fármaco em estudo. Utilizou-se Planejamento Fatorial Completo 23 para a otimização das variáveis químicas que podem exercer efeito sobre o processo de adsorção. Os resultados obtidos segundo o gráfico de Pareto demonstraram que a única variável que exerceu influência sobre a adsorção foi a massa do adsorvente. Sendo assim, a mesma foi determinada através de otimização univariada, como sendo de 600 mg. Para o estudo da cinética de adsorção, ficou definido o tempo de equilíbrio de 180 min, e a adsorção seguindo o modelo de pseudosegunda-ordem. A isoterma obtida foi linearizada e o resultado indicou que a adsorção segue o modelo de Langmuir, ou seja, ocorre adsorção química em monocamada.

In recent years, new classes of aquatic pollutants have received growing concerns from the environmentalists due to their unclear effects and increasing release into the water environment. Generally, before entering the aquatic ecosystem, many of these emerging contaminants are deemed safe active ingredients in the commercial products. This may lead to the underestimation of their potential impacts to the environment, once these substances were drained into the natural waters. So far, a wide range of emerging contaminants are still not well studied. In this thesis work, the environmental behaviors for two typical groups of emerging contaminants, which are frequently used in personal care products, are systematically probed in the aquatic ecosystem. One is the hydrophilic compounds - artificial sweeteners and the other one is the moderate hydrophobic compounds - ultraviolet (UV) filters. Acesulfame and sucralose are two of the most commonly used artificial sweeteners, which are a newly recognized class of emerging contaminants due to their widespread occurrence and extreme persistence in water environment. To date, however, their environmental behaviors, fates as well as long term ecotoxicological contributions in our water resources still remain largely unknown. In this work, a photodegradation investigation with UV/TiO2 was performed on these two artificial sweeteners, which projected their potential impacts under prolonged exposure to intensive solar irradiation. Real-time observation of the degradation profiles in both sweeteners illustrated that formation of new photo by-products under prolonged UV irradiation is highly viable. For the first time, acute toxicity for the degradates of these two sweeteners were measured and the enhancement in their ecotoxicity has been observed during the irradiation. In an attempt to neutralize this prolonged environmental threat, the feasibility of UV/TiO2 as an effective mineralization process in wastewater treatment was evaluated for both sweeteners. As a result, relatively higher removal efficiencies for acesulfame and sucralose were achieved in this study. For UV filters, a comprehensive investigation on their environmental behaviors and impacts was described in this thesis, covering the occurrence study in surface water and biota, environmental fate and their ecological risks. In the first step, an analytical method based on ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of twelve UV filters in the environmental waters, which achieved good sensitivity to sub-ng/L levels. To monitoring their occurrence in local marine environment, the regional distribution of these sunscreen compounds was monitored along the coastline of Hong Kong. At the same time, considering the intensive consumption of sunscreen products in hot weathers, seasonal variation of UV filters between summer and winter was taken into consideration in our occurrence study. Additionally, we also monitored their occurrence in the drinking water supply system of Hong Kong, including the source water in Dongjiang, raw water in local reservoirs and tap water collected from urban communities, to support a good management on the reliable water supply. Furthermore, the distribution results indicated that the incomplete removal of UV filters in the effluents could be a major source for their release into the environmental waters. Aiming to achieve the complete removal of such compounds, a powerful technique of ozonation was employed in this study and the preliminary operational conditions were further provided. Secondly, in order to gain a better understanding of their environmental fate in surface water, a simulative catalytic photodegradation study with UV/TiO2 were performed to investigate the photostability, phototoxicity and the transformation pathways of seven selected UV filters. During the photodegradation, several transformation products were primarily identified. Thirdly, since lipophilic sunscreens were easily accumulated in the biota, we also made efforts to monitor their occurrence in marine organisms of different species, including farmed fish, wild mussels, prawns and sea urchin, which were collected from local offshore areas. Last but not the least, according to the measured concentrations of UV filters in Hong Kong marine environment, we further performed the ecological risk assessment with the approach specific to the marine aquatic compartment, so as to provide the overall understanding on the environmental impacts of these UV filters.

Thesis (M.Sc. (Chemistry)) -- University of Limpopo, 2021 / The present research work deals with the study of some of the important physicochemical parameters of restaurant wastewater effluents collected from Mankweng business centre along the University of Limpopo road. Studies revealed that restaurants, food preparation facilities, engineering, paper mill, fine chemical, dyes, paint, pharmaceutical, petrochemical and textile industries are some of the major industries responsible for polluting the aquatic environments. This research attempts to review the physical, chemical, and microbial analysis of wastewater from food service establishments (FSEs) and extraction of fats, oil, and grease (FOG) and its characterization using different analytical techniques. The elemental analysis revealed that the concentration of elements such as zinc, lead and manganese were 6.44 mg/L, 0.02 mg/L and 0.53 mg/L, respectively. The concentration of these elements was above the required South African National Standards 241 (SANS241) limit, that is, ≤5mg/L, ≤0.01mg/L and ≤0.4mg/L for Zn, Pb and Mn, respectively. The elevated concentrations may be due to corrosion, acidic pH found in some samples and high organic load. High organic content in wastewater influenced the production of oxygen by microorganisms in-order to degrade the amount of waste in the wastewater and this has led to high chemical oxygen demand (COD) level ranging from 1784-7196 mg/L and biochemical oxygen demand (BOD5) from 1101.32 to 3222.32 mg/L. The study has demonstrated that the wastewater samples are contaminated with faecal coliforms because the concentration of microbes Escherichia Coli (E.coli) with a Most Probable Number (MPN) >200.5 in most samples, P. aeruginosa, Pseudomonas spp. were too numerous to count (TNC) and total coliforms at the highest concentration of 9.1x103 CFU/ml which was influenced by change in pH of the wastewater, the FOG content consists of both triglycerides and acrolein. The overall results highlight the discharge of highly polluted wastewater effluent, these FSE have resulted in pollution of nearby rivers thereby affecting the growth of vegetation and aquatic life. The results of the present investigation point out the need to implement common objectives, compatible policies, and programmes for improvement in the FSEs wastewater treatment methods. / National Research Foundation and Sasol-Inzalo Foundation

Untreated human sewage pollution in surface water is of concern because it contributes to the degradation of aquatic ecosystems and it could be a potential hazard to human health. Also, any pollution of surface water, which ultimately supplies drinking water, may affect the drinking water quality. Improper operation and maintenance of separate storm sewer systems are prominent contributors of untreated sewage to source waters, resulting from illicit connections, leakage of sewers, or cross-connections. This thesis studied anthropogenic markers to track untreated sewage in an urban watershed with separate storm sewer system, under dry weather conditions. The main feature of these chemical markers is their degradation behavior at municipal wastewater treatment plants: some markers are completely removed (labile markers), whereas others show only partial or no removal at all (conservative markers). A set of ubiquitous chemical markers with practical analytical detection limits was selected to exploit the labile vs conservative distinction, and determine if untreated human sewage was discharged from stormwater outfalls. The presence of labile markers alone was not enough to confirm the occurrence of untreated sewage in stormwater outfalls. The concentration ratios between labile and conservative markers from several chemical groups (pharmaceuticals and personal care products, over-the-counter medications, artificial sweeteners, and human metabolites) created a chemical fingerprint of untreated sewage, and it was statistically demonstrated to track untreated human sewage in local stormwater outfalls. / Civil Engineering

published_or_final_version / Biological Sciences / Doctoral / Doctor of Philosophy

Access to abstract permanently restricted to Ball State community only / Indirect effects of human population growth on stream ecosystem function : sediment respiration and nutrient uptake response to nonprescription pharmaceuticals -- Frequency and distribution of nonprescription pharmaceuticals in central Indiana streams. / Access to thesis permanently restricted to Ball State community only / Department of Biology

O interesse por técnicas analíticas que ofereçam a sensibilidade adequada, que sejam econômicas, ambientalmente corretas e capazes de processar rapidamente um grande número de amostras de diferentes complexidades é cada vez maior. Nesse aspecto, a utilização da LC no modo multidimensional é alternativa promissora, especialmente quando estratégias de extração e pré-concentração em fase sólida acopladas de forma on-line com a separação são exploradas, tanto em escala convencional quanto em escala miniaturizada. A ocorrência ambiental de contaminantes emergentes (EDCs) e seus impactos nas formas de vida aquática e terrestre têm sido motivo de preocupação. A quantificação desses analitos no ambiente exige métodos com limites de detecção (LDs) muito baixos, fazendo das estratégias column switching, com a inerente pré-concentração on-line, pertinentes para satisfazer as exigências na determinação desses compostos. Nesse cenário, o desenvolvimento e avaliação de estratégias column switching para determinação de contaminantes emergentes em amostras de interesse ambiental como aplicação modelo no estudo comparativo entre as escalas convencional e miniaturizada se faz impactante. Várias estratégias abrangendo column switching capilar e convencional foram investigadas. Colunas extratoras preenchidas com fases comerciais foram avaliadas, e tiveram seu desempenho testado no acoplamento com diversas colunas analíticas. Métodos em column switching capilar e convencional foram desenvolvidos e validados, tendo sido avaliadas as principais figuras de mérito. Os LQs atingidos em CS-UHPLC-ESI-MS/MS variaram de 0,001 ng mL-1 (BP e BzP) a 0,1 ng mL-1 (E3, E2 e EE2); para o método CS-cLC-ESI-MS/MS, os LQs foram maiores, variando entre 0,008 ng mL-1 (BP e BzP) a 0,8 ng mL-1 (E3, E2 e EE2). A linearidade dos métodos foi atestada avaliando-se os gráficos de resíduos, coeficiente de determinação e aplicando-se ponderações quando pertinente. A exatidão e a precisão foram investigadas, apresentando valores dentro dos critérios de aceitação. Por fim, os métodos foram aplicados em amostras ambientais aquosas coletadas em São Carlos - SP, mostrando que os métodos são adequados ao fim a que se destinam. / The interest in analytical techniques that offer adequate sensitivity, that are economical, environmentally friendly and capable of rapidly processing many samples of different complexities is increasing. In this regard, the use of LC in the multidimensional mode is a promising alternative, especially when solid phase extraction and preconcentration strategies coupled online with the separation are explored, both on a conventional scale and on a miniaturized scale. The environmental occurrence of emerging pollutants (EDCs) and their impacts on aquatic and terrestrial life forms have been of concern. Quantification of these analytes in the environment requires methods with very low detection limits (LDs), making column switching strategies with the inherent preconcentration online relevant to satisfy the requirements in determining these compounds. In this scenario, the development and evaluation of column switching strategies for the determination of emerging contaminants in samples of environmental interest as an application model in the comparative study between conventional and miniaturized scales is striking. Several strategies covering capillary and conventional column switching were investigated. Extraction columns filled with commercial phases were evaluated, and their performance was tested in the coupling with several analytical columns. Methods in capillary and conventional column switching modes were developed and validated, and the main figures of merit were evaluated. The LQs reached in CS-UHPLC-ESI-MS / MS ranged from 0.001 ng mL-1 (BP and BzP) to 0.1 ng mL-1 (E3, E2 and EE2); for the CS-cLC-ESI-MS / MS method, the LQs were higher, ranging from 0.008 ng mL-1 (BP and BzP) to 0.8 ng mL-1 (E3, E2 and EE2). The linearity of the methods was attested by evaluating the residual plots, coefficient of determination and applying weighted calibration when needed. Accuracy and precision were investigated, presenting values within the acceptance criteria. Finally, the methods were applied in samples collected in São Carlos - SP, showing that the methods are suitable for the purpose.