Many pharmaceuticals are found in municipal wastewater effluents due to their persistence in the human body as well as in conventional wastewater treatment processes. This discharge to the environment can lead to adverse effects in aquatic species, such as feminization of male fish. During the past decade, these findings have spawned investigations and research into suitable treatment technologies that could severely limit the discharge. Adsorption onto activated carbon has been identified as one of the two main technologies for implementation of (future) full-scale treatment. Recent research has put a closer focus on adsorption with powdered activated carbon (PAC) than on granular activated carbon (GAC). Studies where both methods are compared in parallel operation are thus still scarce and such evaluation in pilot-scale was therefore a primary objective of this thesis. Furthermore, recirculation of PAC can be used to optimize the treatment regarding the carbon consumption. Such a setup was evaluated as a separate treatment stage to comply with Swedish wastewater convention. Additionally, variation of a set of process parameters was evaluated. During successive operation at three different wastewater treatment plants an overall pharmaceutical removal of 95% could consistently be achieved with both methods. Furthermore, treatment with GAC was sensitive to a degraded effluent quality, which severely reduced the hydraulic capacity. Both treatment methods showed efficient removal of previously highlighted substances, such as carbamazepine and diclofenac, however in general a lower adsorption capacity was observed for GAC. By varying the input of process parameters, such as the continuously added dose or the contact time, during PAC treatment, a responsive change of the pharmaceutical removal could be achieved. The work in this thesis contributes some valuable field experience towards wider application of these treatment technologies in full-scale. / <p>QC 20161124</p> / MistraPharma

Organohalogen compounds are formed in swimming pool waters when natural organic matter, such as hair, urine or sweat etc., react with the used disinfectant (usually chlorine). Many of the organohalogen compounds are persistent and hazardous for human health and aquatic ecosystems. Backwash water from swimming pool facilities is often released to the sewer and contain these compounds. The connected wastewater treatment plant receives this water, where some of these compounds escapes the treatment process, into the recipient. It is therefore important to minimize the levels of organohalogen compounds in the influent water to the wastewater treatment plant. In this study, potential treatment techniques for organohalogen compounds at the swimming pool facility have been investigated. The main focus have been on an experimental column test with four filter materials applied (granular activated carbon, natural zeolites, PoloniteR and Zugol). Real backwash water was used. Furthermore, other techniques have been theoretically investigated as well. The activated carbon directly showed the most efficient removal efficiency (above 95 %), but all filter materials had a removal to a certain degree and became more efficient by time. The results further suggest that the more lipophilic organohalogen compounds are bound to particulate matter and highly affected by physical filtration. Another important conclusion is that the specific activated carbon used in the study is not suitable for the purpose, because it released very high levels of phosphorus in the beginning of the column test as well as showing some practical problems. However, other types of activated carbon exists. Next step recommended is to determine the lifetime of the filters. / När människor badar i bassänger hamnar vanligtvis naturligt organiskt material i dem, såsom urin, svett, hår och hudflagor. Desinfektionsmedlet som tillsätts (oftast klor) har som syfte att avlägsna mikroorganismer, men när naturligt organiskt material hamnar i vattnet kommer också oavsiktliga reaktioner ske och halogenerade organiska föreningar bildas. Dessa föreningar kan kvantifieras via AOX måttet (adsorberbar organisk halogen), vilket är den samlade förekomsten av alla bundna organiska halogener i ett prov. AOX består således av flera hundra olika föreningar, varav vissa är mer lipofila och benämns EOX (extraherbar organisk halogen). Många av de föreningar inkluderade i AOX är bioackumulativa, persistenta och giftiga för akvatiska organismer, även i låga koncentrationer. Förutom att vara miljöfarliga för akvatiska ekosystem, kan de också vara skadliga för människans hälsa. Filtret som renar badvattnet i simhallar behöver backspolas regelbundet och backspolvattnet, som innehåller AOX, skickas vanligen till spillvattennätet. Vid avloppsreningsverket är det visat i ett tidigare examensarbete samt i andra rapporter att en del av de inkommande AOX ämnena även följer med det utgående, renade, vattnet ut i recipienten. Det är därmed av vikt att minimera ämnena redan vid källan, det vill säga på badanläggningen. I denna masteruppsats har behandlingstekniker för halogenerade organiska föreningar undersökts. Huvudfokus har varit på experimentella kolonntester för fyra filtermaterial (granulerat aktivt kol, naturliga zeoliter, PoloniteR och Zugol), men även andra tekniker har studerats teoretiskt. I testerna användes äkta backspolvatten från en simhall. Alla material reducerade AOX till viss del och visade på effektivare reducering efter hand. Det var dock tydligt att det aktiva kolet var mest effektivt och hade hög reducering redan i första mätningen, AOX-reduceringen låg på över 95 % (jämfört med det obehandlade backspolvattnet). Vad som dock var problematiskt med det aktiva kolet var att det släppte höga halter fosfor i början av kolonntestet, vilket också bekräftades med ett skaktest. Dessutom uppvisade materialet praktiska problem. Ur ett realistiskt perspektiv med dessa problem i åtanke, blir det inte hållbart i längden att använda detta specifika kol. Det finns dock många olika typer av aktivt kol, vilka förmodligen är mer lämpliga och som inte uppvisar dessa problem, och kan användas för detta ändamål. Vidare antyder det erhållna resultatet att de mer lipofila föreningarna av AOX (EOX) är bundet till partikulärt organiskt material och därmed påverkas väsentligt av mekanisk filtrering. Det är dock viktigt med en aktiv bindning. Projektet har påverkats av covid-19 pandemin med lägre antal folk på badhusen samt mindre tillgång till laboratoriet vid KTH. En föreslagen förbättring av metoden är att ha en kontinuerlig omblandning i förvaringskärlet med det obehandlade vattnet innan det tillförs kolonnerna. Vidare nämns det att modifierade zeoliter verkar lovande samt att nästa viktiga steg för projektet är att bestämma livstiden för filtermaterialen.

Indirect potable reuse has been practiced with the potential to enhance sustainability of water resources if planned accordingly. Depending on the pretreatment implemented for potable reuse, emerging contaminants; such as pharmaceuticals, personal care products, industrial solvents, bacterial/viral pathogens, and disinfection byproducts, might be present in source water and difficult to remove via various water treatment technologies. Low molecular weight organic compounds are especially challenging to remove and may require treatment optimization. The overarching purpose of this study was to demonstrate the feasibility of a carbon-based advanced treatment train; including ozonation, biological activated carbon (BAC) filtration and granular activated carbon (GAC) adsorption to achieve water quality suitable for potable reuse and assess the impact of a range of operating conditions for emerging contaminant removal at pilot-scale. The results from this study showed that carbon-based treatment train is equally effective as more commonly used, and more costly, membrane-based treatment trains in terms of pathogen and disinfection byproduct removal. A multiple-barrier approach was implemented, with each treatment stage capable of removing total organic carbon (TOC). GAC was responsible for removal of most of the TOC and emerging contaminants and this removal depended on the number of bed volumes of water processed by GAC. Empty bed contact time was another factor that dictated the extent of TOC removal in the BAC and GAC units as the carbon media was exhausted. Among the emerging contaminants detected, sucralose, iohexol and acesulfame-k were present in the highest concentrations in the influent and were detected consistently in the GAC effluent, thus making them good indicators of treatment performance. Apart from organics removal, BAC played an important role in removal of nutrients, such as ammonia via nitrification. N-Nitrosodimethlyamine (NDMA) was formed in the treatment process by ozone, but was shown to be effectively removed by BAC. EBCT, temperature, ozone dose and presence of pre-oxidants, such as monochloramine, played an important role in determining the amount of NDMA removed. These factors can be further optimized to improve NDMA removal. Sodium bisulfite was used for dechlorinating monochloramine residual post ozone. Nitrification in the BAC was shown to be inhibited by excess of sodium bisulfite dose. Thus monochloramine residual needs to be dechlorinated with sodium bisulfite to help with NDMA degradation but at the same time the sodium bisulfite dose needs to be monitored to allow complete nitrification in the BAC. 1,4-dioxane, another contaminant of emerging concern, was monitored in the treatment process. Biodegradation of 1,4-dioxane was enhanced via addition of tetrahydrofuran as a growth substrate. Biodegradation of 1,4-dioxane can help reduce energy and capital costs associated with advanced oxidation processes that are currently used for 1,4-dioxane removal. Further, relying on biodegradation for the removal of 1,4-dioxane can help avoid the formation of disinfection byproducts associated with advanced oxidation processes such as ozone with peroxide or ultraviolet disinfection with peroxide. The results from this project can be useful for designing potable reuse treatment trains and provide a baseline for removal of organic carbon and emerging contaminants. The conventionally used reverse osmosis and ultrafiltration approach is useful for organics removal in areas where the rationale behind potable reuse is water scarcity. Operational difficulties encountered during this study can prove to be important as this treatment process is scaled up to treat a total of 120 MGD of water for managed aquifer recharge. Overall the lessons learnt from this study can give a better understanding of a carbon-based treatment and further the advancement of reuse projects that have drivers other than water scarcity. / Doctor of Philosophy / The increased growth in urban areas has been accompanied by an increase in potable water demand, leading to depletion of surface and groundwater. Further, the discharge of nutrients such as nitrogen and phosphorus into some of these water bodies can lead to algal blooms. Water reuse involves treating used water and discharging into either a surface or groundwater body. Water reuse has been sought after as a solution to prevent these nutrients being discharged into surface water and to provide a sustainable solution for depletion of water sources. Direct or indirect potable reuse can include a combination of advanced treatment methods such as membrane filtration using ultrafiltration and reverse osmosis, biological filtration, granular or powdered activated carbon adsorption and disinfection methods such as ozonation and ultraviolet disinfection. This study focused on Hampton Roads Sanitation District's managed aquifer recharge project 'sustainable water initiative for tomorrow' (SWIFT), two different advanced water treatment strategies, namely carbon-based and membrane-based were implemented on a pilot-scale (20,000 L/day). The driver for indirect potable reuse in this study was not related to water shortage but aimed at reducing the nutrients discharged into the Chesapeake Bay. Other reasons for implementing reuse included recharging the depleting groundwater levels, land subsidence, and preventing flooding and seawater intrusion near the coastal areas. Membrane-based treatments, such as reverse osmosis, have been well established and studied for potable reuse. The less frequently used carbon-based treatment, that includes used of activated carbon for adsorption and biodegradation of organics (not involving any membrane barrier), was shown to be cost-effective and provided equal protection as that of the membrane-based system in terms of removal of pathogens. Further, since there is no membrane involved in the carbon-based treatment the energy requirements are less than that of the membrane-based treatment and concentrated brine solution is not produced, which makes it favorable for potable reuse where water scarcity is not an issue. This carbon-based treatment which included ozonation and activated carbon filtration and adsorption was further monitored and optimized for removal of organic contaminants and disinfection byproducts. Emerging contaminants such as pharmaceuticals, industrial solvents and personal care products can be harmful to human health and water ecology even at low concentrations. These contaminants are often present in wastewater effluent and can enter drinking water sources if untreated. These emerging contaminants were shown to be effectively removed by ozonation and granular activated carbon adsorption. The formation of disinfection byproducts such as N-nitrosodimethylamine in the treatment process and its removal in the biological activated carbon filtration was also monitored. The impact of temperature, presence of pre-oxidants and design factors such as ozone dose and empty bed contact time affected the removal of all these contaminants. This study provided an understanding of implementing carbon-based treatment for managed aquifer recharge for optimizing removal of bulk organic carbon and emerging contaminants. The results from this study can be utilized for designing advanced water treatment systems and can prove to be a guideline for monitoring and removing emerging contaminants.

M. Tech., (Chemical Engineering, Department of Chemical Engineering, Faculty of Engineering and Technology Vaal University of Technology| / The methods used to remove potassium sulphate (K2S04) and other impurities contained within Karbochem finishing plant effluent were investigated. Reverse osmosis was explored for this application. The study was conducted in two steps. The first step focuses mainly on the effluent treatment using BW30 flatsheet as well as BW30-2540 spiral-wound reverse osmosis membranes for the rejection of potassium and sulphate ions. The membranes were supplied by Filmtec. The second step reveals the possible use of potassium sulphate obtained from the brine stream in the fertiliser and fertigation industry by a literature search. Reverse osmosis study was conducted on a laboratory scale unit using flat sheet membranes and also on a pilot plant scale using spiral wound membrane modules. The tests were conducted at a feed pressure of 20 bar(g) with the membrane rejections being 98% and 99.1% on flat sheet membrane, and 96.9% and 99.4% on spiral wound membrane for potassium and sulphates respectively. The results show that both membranes have completely desalinated. Significant reduction in the concentrations of all problematic quality parameters, especially of potassium and the sulphate ions was noted. Granular activated carbon (GAC) bed treatment was recommended for pretreatment of the effluent prior to exposure of the membrane to avoid organic fouling of the membrane. GAC treatment was tested to illustrate its effectiveness to adsorb the COD's. / NRF

This diploma thesis deals with the study of adsorption of low-molecular components of organic substances produced by phytoplankton - AOM (Algal Organic Matter) on AC (Activated Carbon) during drinking water treatment. For the experimental purpose in this thesis, there were used selected amino acids as low molecular substances of AOM that are difficult to remove by conventional water treatment process by coagulation. As adsorbent, there was used a detailed characterized of granulated activated carbon (GAC) - Filtrasorb TL 830 (FTL830) which is intended directly for the purpose of water treatment. There were realizing the equilibrium batch adsorption experiments with three different model amino acids - arginine (Arg), phenylalanine (Phe) and aspartic acid (Asp). There was investigated the efficiency of removing amino acid depending on the solution temperature and pH. Results of the adsorption experiments have shown that the temperature affects the adsorption efficiency. Adsorption is essentially described as an exothermic process but the adsorption of Arg and Phe from an aqueous solution to GAC occurs more efficiently at higher temperatures. It means that the adsorption is the endothermic process. In the case of Arg adsorption, the temperature was found to influence adsorption efficiency less than...

A presença de resíduos de fármacos em águas superficiais e de abastecimento público tem preocupado a comunidade científica devido principalmente à sua persistência na água e aos efeitos adversos causados à comunidade aquática e aos possíveis riscos à saúde humana. Dentre os fármacos comumente identificados em águas de abastecimento público, encontram-se os anti-inflamatórios, como o diclofenaco (DCF), um dos fármacos mais consumidos no Brasil e no mundo. Nesse contexto, o presente trabalho, teve como objetivo principal estudar a eficiência das etapas de tratamento de água em ciclo completo (coagulação, floculação, sedimentação, filtração em areia e desinfecção com cloro) com e sem pré-oxidação com cloro e com dióxido de cloro e adsorção em carvão ativado granular (CAG) na remoção de DCF. Também foram determinados os trialometanos (THM) e identificados os principais subprodutos do DCF formados na oxidação com cloro e dióxido de cloro. Para a determinação do DCF nas amostras de água antes e após as etapas de tratamento de água foram desenvolvidos e validados métodos analíticos de extração em fase sólida (SPE) e cromatográfico por cromatografia líquida de alta eficiência (HPLC) com detecção no ultravioleta (UV). A validação do método foi feita de acordo com a resolução n&ordm; 899 de 2003 da Agência Nacional de Vigilância Sanitária (ANVISA), considerando os requisitos para métodos bioanalíticos. Os procedimentos analíticos empregados foram efetivos e confiáveis para a identificação e quantificação do DCF nas amostras de água antes e após os processos de tratamento de água. Os ensaios de tratamento de água foram feitos em equipamento de reatores estáticos (jarteste) e filtros de escala laboratorial empregando-se água de poço artesiano não clorada preparada com substâncias húmicas aquáticas (SHA) para conferir cor verdadeira de 20 uH, caulinita para conferir turbidez de 70 uT e fortificada com 1 mg L-1 de DCF. Os resultados indicaram que as etapas de coagulação com sulfato de alumínio, floculação, sedimentação e filtração em areia não removeram o DCF. Nas etapas de préoxidação com cloro e dióxido de cloro e de pós-cloração houve remoção parcial do DCF, porém verificou-se a formação de subprodutos provenientes da oxidação do DCF. Dentre os THM, foi quantificado apenas o clorofórmio na etapa de pré-oxidação com cloro. Em geral, os resultados indicaram que o dióxido de cloro foi mais eficiente na redução do DCF e formou menos subprodutos. Entretanto, o tratamento em ciclo completo seguido da adsorção em CAG foi eficiente na remoção de DCF, com remoção maior que 99,7%. Os subprodutos formados na oxidação com cloro e dióxido identificados por cromatografia líquida acoplada a espectrometria de massas em série (LC-MS/MS) consistiram na descaboxilação/hidroxilação e substituição aromática de átomos de hidrogênio por cloro. Os subprodutos identificados na oxidação com cloro apresentaram as seguintes fórmulas moleculares: C14H11</subCl2NO3, C13H10Cl3N e C14H10Cl3NO2. Com o dióxido de cloro foi identificado o subproduto de fórmula molecular igual a C14H11Cl2NO3. / The presence of pharmaceutical residues in surface waters and in drinking water supply has concerned the scientific community, mainly in which regards their persistence in water, adverse effects on the aquatic community and possible risks to human health. Antiinflammatory drugs, as diclofenac (DCF), are among those drugs commonly identified in drinking water supply. In this context, the main objective of this study was to assess the efficiency of the different stages of the conventional drinking water treatment (coagulation, flocculation, sedimentation, sand filtration and chlorine disinfection) with and without preoxidation with chlorine and chlorine dioxide and adsorption on granular activated carbon (GAC) in the removal of DCF. The trihalomethanes (THMs) were also determined and the main by-products of DCF formed by oxidation with chlorine dioxide and chlorine were identified. For the DCF determination in water samples before and after water treatment stages analytical methods of solid phase extraction (SPE) and chromatographic method by high performance liquid chromatography (HPLC) with detection in the ultraviolet (UV) were developed and validated. The method validation was based on Resolution n&ordm; 899 of the 2003 of the Brazilian National Health Surveillance Agency (ANVISA), considering the requirements for bioanalytical methods. The analytical procedures used were effective and reliable for the identification and quantification of DCF in the water samples before and after the water treatment stages. The water treatment tests were carried out in jar test equipment and filters on laboratory scale employing non chlorinated water of artesian well prepared with aquatic humic substances (AHS) to yield 20 uH true color, kaolin turbidity of 70 NTU and DCF concentration of 1 mg L-1. The results indicated that the stages of coagulation with aluminum sulphate, flocculation, sedimentation and filtration sand did not remove DCF. In the stages of pre-oxidation with chlorine and chlorine dioxide and chlorine disinfection the DCF was partially removed, however by-products were formed from the DCF oxidation. Among the THMs, only chloroform was quantified in the pre-oxidation with chlorine. In general, the results showed that chlorine dioxide was more effective to reduce the DCF and fewer by-products were formed. Nevertheless, the complete cycle treatment followed by GAC adsorption was effective to remove DCF (&gt; 99.7%. removal). The by-products of the oxidation of DCF with chlorine and chlorine dioxide identified by liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) consisted in the descaboxylation/hydroxylation and aromatic substitution of hydrogen atoms by chlorine. The compounds identified in the oxidation with chlorine showed the following molecular formulas: C14H11</subCl2NO3, C13H10Cl3N e C14H10Cl3NO2. The by-product identified using chlorine dioxide was C14H11Cl2NO3.

O objetivo deste trabalho foi avaliar o desempenho da combinação dos processos de interozonização e sistemas pós-filtros adsorvedores na remoção de compostos orgânicos precursores e na formação de subprodutos da desinfecção, em particular os trialometanos (THM). Os ensaios foram desenvolvidos com a água filtrada proveniente da estação de tratamento de água do Alto da Boa Vista, localizada no município de São Paulo, tipo convencional, com água bruta oriunda de reservatório com elevado estado de eutrofização. O aparato experimental é constituído de um sistema de ozonização com quatro colunas em série e tempo de detenção hidráulica total de 16 minutos; e, por um sistema de quatro pós-filtros adsorvedores com diferentes tipos de carvão ativado granular, filtros F1 e F3 dotados de carvão mineral (CAG1, betuminoso) e filtros F2 e F4 compostos por carvão vegetal (CAG2, casca de coco) sendo todos operados em paralelo com valores de Tempo de Contato de Leito Vazio (TCLV) entre 15 e 20 minutos. Duas colunas receberam como afluente água filtrada pré-ozonizada (F1 e F2) e as demais colunas apenas água filtrada (F3 e F4). Os resultados indicaram que a ozonização não alterou de forma significativa os parâmetros utilizados para avaliação dos precursores, COT e UV-254 nm, e nem o THM. Inicialmente, os resultados de remoção de COT permaneceram elevados, próximos de 80% caracterizando a saturação dos leitos em torno de 240 dias para os filtros F1 e F3 (CAG1) e apenas 30 dias, com eficiências baixas para os filtros F2 e F4 (CAG2). Para THM a saturação foi próxima de 65 dias para ambos os carvões e as eficiências iniciais foram de 90% e 75%, para os filtros com CAG1 e CAG2, respectivamente. Com todos os leitos saturados, os resultados ainda indicaram boa remoção de compostos causadores de gosto e odor. Neste trabalho, os sistemas de pós-filtros adsorvedores de CAG foram efetivos para o controle das substâncias precursoras e a redução da formação de THMs, com melhores resultados para o carvão mineral CAG1 (betuminoso) independentemente do sistema de interozonização. / The main purpose of this work was to evaluate the performance of a combination of processes - inter-ozonization and post-filter GAC adsorbers systems, on the control of organic precursors and disinfection byproducts, especially trihalomethanes (THM). The experience was conducted with filtered water produced at Alto da Boa Vista conventional WTP, located at São Paulo city, where raw water comes from a high eutrofic lake. The experimental setup consists of an ozonation system with four column shaped contactors arranged in series with 16 minutes total hydraulic detention time; and, a system of four pilot scale adsorbers with different types of granular activated carbon (GAC) media, F1 and F3 filters with mineral GAC media (GAC1, bituminous) and F2 and F4 filters with vegetal GAC media (GAC2, coconut shell), all operated in parallel with empty bed contact time (EBCT) between 15 and 20 minutes. Two columns were fed with filtered and pre-ozonated water (F1 and F2) and the other two were fed with filtered water only (F3 and F4). It was observed that ozonation did not affect significantly results of precursors parameters, TOC and UV-254, and neither THM. Initially, TOC removal remained high, near 80% delineating the bed saturation around 240 days to F1 and F3 filters (GAC1) and only 30 days with low efficiency for filters F2 and F4 (GAC2). The THM bed saturation time was nearly 65 days for both media and initial efficiencies were 90% and 75% to GAC1 and GAC2, respectively. With all beds saturated, still there was a good taste and odor producing substances removal. In this work, the systems of GAC adsorbents post-filters were effective for the control of precursors and to reduce the formation of THM\'s, with better results for the CAG1 (bituminous) regardless of the use of inter-ozonization.

Os fármacos são essenciais para a preservação da saúde do homem e de animais e também na prevenção de doenças. Entretanto, seu alto consumo associado ao descarte incorreto e aos tratamentos ineficientes de águas e efluentes podem trazer grandes prejuízos ao meio ambiente como, por exemplo, a resistência bacteriana. O objetivo deste trabalho foi estudar a remoção de ampicilina (AMP), atenolol (ATN) e paracetamol (PAR), fármacos de três classes distintas, em soluções aquosas através da técnica de adsorção em carvão ativado granular (CAG). Foram realizados experimentos de adsorção em batelada avaliando o efeito dos parâmetros pH, tempo de contato e concentração de sólido adsorvente. O comportamento cinético da adsorção dos fármacos em carvão ativado granular foi avaliado por meio dos modelos de pseudo-primeira ordem, pseudosegunda ordem e difusão intrapartícula. Ainda, isotermas de equilíbrio para estes sistemas foram construídas em diferentes temperaturas (15, 25 e 35 °C) e analisadas através dos modelos de Langmuir, Freundlich e Sips. O processo de adsorção também foi avaliado através de ensaios termodinâmicos. A adsorção em coluna de leito fixo foi avaliada utilizando planejamentos experimentais para os fármacos e os efeitos da massa do leito de adsorvente (0,5 – 1,5 g) e da vazão de alimentação (10 – 15 mL min-1) foram estudados Ainda, a fim de se avaliar o comportamento dos fármacos quando em mistura, foram realizados ensaios de adsorção em batelada e em coluna de leito fixo da mistura de ampicilina e paracetamol. Os melhores resultados encontrados nos ensaios de adsorção batelada foram: pH 6 e concentração de sólido adsorvente de 10 g L-1 para os três fármacos. O tempo de adsorção mais adequado foi de 90 minutos para o ATN e 120 min para AMP e PAR. Nessas condições foi possível obter remoções de 90 %, 94 % e 96 % para a ampicilina, atenolol e paracetamol, respectivamente. O modelo cinético que melhor descreveu o processo de adsorção foi o de pseudo-primeira ordem, para os fármacos ampicilina e paracetamol, e pseudo-segunda ordem para o atenolol. As isotermas obtidas para os fármacos indicaram que o processo de adsorção é de natureza endotérmica, ou seja, a adsorção é favorecida com o aumento da temperatura. Para a AMP, o melhor ajuste das isotermas foi obtido pelo modelo de Langmuir nas temperaturas de 15 ºC e 25 ºC e pelo modelo de Sips na temperatura de 35 ºC. Para o ATN, o melhor ajuste foi obtido pelo modelo de Freundlich e, para o PAR, o modelo de Sips, nas três temperaturas estudadas. Os ensaios termodinâmicos indicaram que o processo de adsorção dos fármacos é favorável e espontâneo e comprovou a natureza endotérmica do processo Em relação aos resultados obtidos na adsorção em coluna de leito fixo foi observado que os tempos de ruptura e de saturação aumentam com o aumento da massa de sólido presente no leito e diminuem com o aumento da vazão. A massa de adsorvente apresentou efeito negativo sobre a fração de leito utilizado e foi significativa no processo de adsorção dos três fármacos. Já a vazão de alimentação só foi significativa na adsorção em leito fixo da AMP e apresentou efeito positivo na fração de leito utilizado. Os maiores volumes de efluente tratado foram obtidos com a maior massa de sólido utilizada (1,5 g) e com a menor vazão de alimentação testada (10 mL min-1). Na adsorção multicomponente em batelada, verificou-se que há concorrência entre os fármacos pelos sítios ativos do CAG disponíveis para adsorção. Os resultados obtidos nos ensaios das isotermas de adsorção mostraram que o comportamento dos fármacos em mistura é o mesmo que quando comparados individualmente. Os modelos que melhor se ajustaram aos dados experimentais foram os mesmos obtidos nos ensaios monocomponente, Langmuir para a AMP e Sips para o PAR. Da mesma forma que para os experimentos em coluna monocomponente, os ensaios multicomponentes demostraram que os tempos de ruptura e de saturação são maiores para o PAR. Entretanto, esses valores são menores do que na adsorção individual indicando que houve concorrência entre os fármacos pelos sítios do adsorvente. Os resultados encontrados indicam que a adsorção é uma alternativa viável para a remoção de fármacos, contribuindo, assim, para o avanço das pesquisas relacionadas ao tratamento de efluentes contaminados por estes poluentes. / Drugs are essential for preservation of human and animal health as well as for disease prevention. However, its high consumption associated with incorrect disposal and inefficient treatment of water and effluents can cause great damage to the environment such as bacterial resistance, for example. The objective of this work was to study the removal of ampicillin (AMP), atenolol (ATN) and paracetamol (PAR), drugs of three different classes, in aqueous solutions by adsorption technique in granular activated carbon (GAC). Adsorption experiments were carried out in batch evaluating the effect of parameters pH, contact time and concentration of solid adsorbent. The kinetic behavior of the adsorption of drugs in granular activated carbon was evaluated through the pseudofirst order, pseudo-second order and intraparticle diffusion models. Furthermore, equilibrium isotherms for these systems were made at different temperatures (15, 25 and 35 ° C) and analyzed using the Langmuir, Freundlich and Sips models. The adsorption process was also evaluated through thermodynamic tests. The fixed bed column adsorption was evaluated by experimental planning for drugs and the effects of mass of the adsorbent bed (0.5 to 1.5 g) and feed rate (10 - 15 ml min-1) were studied Also, in order to evaluate the behavior of the drugs when in mixture, adsorption tests were carried out in batch and in fixed bed column for the mixture of ampicillin and paracetamol. The best results found in the batch adsorption tests were: pH 6 and concentration of adsorbent solid of 10 g L-1 for the three drugs. The most suitable adsorption time was 90 minutes for ATN and 120 min for AMP and PAR. Under these conditions it was possible to obtain removals of 90%, 94% and 96% for ampicillin, atenolol and paracetamol respectively. The kinetic model that best described the adsorption process was the pseudo-first order for the ampicillin and paracetamol drugs and pseudo-second order for atenolol. The isotherms obtained for the drugs indicated that the adsorption process is of endothermic nature, that is, the adsorption is favored with the increase in temperature. For the AMP, the best isotherm adjustment was obtained by the Langmuir model at temperatures of 15 °C and 25 °C and by the Sips model at temperature of 35 °C. For the ATN, the best fit was obtained by the Freundlich model and, for PAR, the Sips model at the three temperatures studied. The thermodynamic tests indicated that the adsorption process of the drugs was favorable and spontaneous and confirmed the endothermic nature of the process Regarding the results obtained in adsorption in fixed bed column, it was observed that rupture and saturation times increase with the increase of the mass of solid present in the bed and decrease with the increase of flow. The adsorbent mass had a negative effect on the used bed fraction and was significant in the adsorption process of the three drugs. The feed flow was only significant in the adsorption in fixed bed of the AMP and had positive effect in the used bed fraction. The highest volumes of treated effluent were obtained with the largest mass of solid used (1,5 g) and with the lowest feed rate tested (10 mL min-1). In multicomponent adsorption in batch, it was found that there is competition between the drugs by the active sites of GAC available for adsorption. The results obtained in the adsorption isotherms tests showed that the behavior of the drugs in mixture is the same as when compared individually. The models that best fit the experimental data were the same ones obtained in the monocomponent tests, Langmuir for AMP and Sips for PAR. Similarly as for the monocomponent column experiments, the multicomponent tests showed that the break and saturation times are larger for the PAR. However, these values are lower than in individual adsorption indicating that there was competition between the drugs for the sites of the adsorbent. The results indicate that adsorption is a viable alternative for the removal of drugs, thus contributing to the advancement of research related to the treatment of effluents contaminated by these pollutants.

O objetivo deste trabalho foi avaliar o desempenho da combinação dos processos de interozonização e sistemas pós-filtros adsorvedores na remoção de compostos orgânicos precursores e na formação de subprodutos da desinfecção, em particular os trialometanos (THM). Os ensaios foram desenvolvidos com a água filtrada proveniente da estação de tratamento de água do Alto da Boa Vista, localizada no município de São Paulo, tipo convencional, com água bruta oriunda de reservatório com elevado estado de eutrofização. O aparato experimental é constituído de um sistema de ozonização com quatro colunas em série e tempo de detenção hidráulica total de 16 minutos; e, por um sistema de quatro pós-filtros adsorvedores com diferentes tipos de carvão ativado granular, filtros F1 e F3 dotados de carvão mineral (CAG1, betuminoso) e filtros F2 e F4 compostos por carvão vegetal (CAG2, casca de coco) sendo todos operados em paralelo com valores de Tempo de Contato de Leito Vazio (TCLV) entre 15 e 20 minutos. Duas colunas receberam como afluente água filtrada pré-ozonizada (F1 e F2) e as demais colunas apenas água filtrada (F3 e F4). Os resultados indicaram que a ozonização não alterou de forma significativa os parâmetros utilizados para avaliação dos precursores, COT e UV-254 nm, e nem o THM. Inicialmente, os resultados de remoção de COT permaneceram elevados, próximos de 80% caracterizando a saturação dos leitos em torno de 240 dias para os filtros F1 e F3 (CAG1) e apenas 30 dias, com eficiências baixas para os filtros F2 e F4 (CAG2). Para THM a saturação foi próxima de 65 dias para ambos os carvões e as eficiências iniciais foram de 90% e 75%, para os filtros com CAG1 e CAG2, respectivamente. Com todos os leitos saturados, os resultados ainda indicaram boa remoção de compostos causadores de gosto e odor. Neste trabalho, os sistemas de pós-filtros adsorvedores de CAG foram efetivos para o controle das substâncias precursoras e a redução da formação de THMs, com melhores resultados para o carvão mineral CAG1 (betuminoso) independentemente do sistema de interozonização. / The main purpose of this work was to evaluate the performance of a combination of processes - inter-ozonization and post-filter GAC adsorbers systems, on the control of organic precursors and disinfection byproducts, especially trihalomethanes (THM). The experience was conducted with filtered water produced at Alto da Boa Vista conventional WTP, located at São Paulo city, where raw water comes from a high eutrofic lake. The experimental setup consists of an ozonation system with four column shaped contactors arranged in series with 16 minutes total hydraulic detention time; and, a system of four pilot scale adsorbers with different types of granular activated carbon (GAC) media, F1 and F3 filters with mineral GAC media (GAC1, bituminous) and F2 and F4 filters with vegetal GAC media (GAC2, coconut shell), all operated in parallel with empty bed contact time (EBCT) between 15 and 20 minutes. Two columns were fed with filtered and pre-ozonated water (F1 and F2) and the other two were fed with filtered water only (F3 and F4). It was observed that ozonation did not affect significantly results of precursors parameters, TOC and UV-254, and neither THM. Initially, TOC removal remained high, near 80% delineating the bed saturation around 240 days to F1 and F3 filters (GAC1) and only 30 days with low efficiency for filters F2 and F4 (GAC2). The THM bed saturation time was nearly 65 days for both media and initial efficiencies were 90% and 75% to GAC1 and GAC2, respectively. With all beds saturated, still there was a good taste and odor producing substances removal. In this work, the systems of GAC adsorbents post-filters were effective for the control of precursors and to reduce the formation of THM\'s, with better results for the CAG1 (bituminous) regardless of the use of inter-ozonization.

A presença de resíduos de fármacos em águas superficiais e de abastecimento público tem preocupado a comunidade científica devido principalmente à sua persistência na água e aos efeitos adversos causados à comunidade aquática e aos possíveis riscos à saúde humana. Dentre os fármacos comumente identificados em águas de abastecimento público, encontram-se os anti-inflamatórios, como o diclofenaco (DCF), um dos fármacos mais consumidos no Brasil e no mundo. Nesse contexto, o presente trabalho, teve como objetivo principal estudar a eficiência das etapas de tratamento de água em ciclo completo (coagulação, floculação, sedimentação, filtração em areia e desinfecção com cloro) com e sem pré-oxidação com cloro e com dióxido de cloro e adsorção em carvão ativado granular (CAG) na remoção de DCF. Também foram determinados os trialometanos (THM) e identificados os principais subprodutos do DCF formados na oxidação com cloro e dióxido de cloro. Para a determinação do DCF nas amostras de água antes e após as etapas de tratamento de água foram desenvolvidos e validados métodos analíticos de extração em fase sólida (SPE) e cromatográfico por cromatografia líquida de alta eficiência (HPLC) com detecção no ultravioleta (UV). A validação do método foi feita de acordo com a resolução n&ordm; 899 de 2003 da Agência Nacional de Vigilância Sanitária (ANVISA), considerando os requisitos para métodos bioanalíticos. Os procedimentos analíticos empregados foram efetivos e confiáveis para a identificação e quantificação do DCF nas amostras de água antes e após os processos de tratamento de água. Os ensaios de tratamento de água foram feitos em equipamento de reatores estáticos (jarteste) e filtros de escala laboratorial empregando-se água de poço artesiano não clorada preparada com substâncias húmicas aquáticas (SHA) para conferir cor verdadeira de 20 uH, caulinita para conferir turbidez de 70 uT e fortificada com 1 mg L-1 de DCF. Os resultados indicaram que as etapas de coagulação com sulfato de alumínio, floculação, sedimentação e filtração em areia não removeram o DCF. Nas etapas de préoxidação com cloro e dióxido de cloro e de pós-cloração houve remoção parcial do DCF, porém verificou-se a formação de subprodutos provenientes da oxidação do DCF. Dentre os THM, foi quantificado apenas o clorofórmio na etapa de pré-oxidação com cloro. Em geral, os resultados indicaram que o dióxido de cloro foi mais eficiente na redução do DCF e formou menos subprodutos. Entretanto, o tratamento em ciclo completo seguido da adsorção em CAG foi eficiente na remoção de DCF, com remoção maior que 99,7%. Os subprodutos formados na oxidação com cloro e dióxido identificados por cromatografia líquida acoplada a espectrometria de massas em série (LC-MS/MS) consistiram na descaboxilação/hidroxilação e substituição aromática de átomos de hidrogênio por cloro. Os subprodutos identificados na oxidação com cloro apresentaram as seguintes fórmulas moleculares: C14H11</subCl2NO3, C13H10Cl3N e C14H10Cl3NO2. Com o dióxido de cloro foi identificado o subproduto de fórmula molecular igual a C14H11Cl2NO3. / The presence of pharmaceutical residues in surface waters and in drinking water supply has concerned the scientific community, mainly in which regards their persistence in water, adverse effects on the aquatic community and possible risks to human health. Antiinflammatory drugs, as diclofenac (DCF), are among those drugs commonly identified in drinking water supply. In this context, the main objective of this study was to assess the efficiency of the different stages of the conventional drinking water treatment (coagulation, flocculation, sedimentation, sand filtration and chlorine disinfection) with and without preoxidation with chlorine and chlorine dioxide and adsorption on granular activated carbon (GAC) in the removal of DCF. The trihalomethanes (THMs) were also determined and the main by-products of DCF formed by oxidation with chlorine dioxide and chlorine were identified. For the DCF determination in water samples before and after water treatment stages analytical methods of solid phase extraction (SPE) and chromatographic method by high performance liquid chromatography (HPLC) with detection in the ultraviolet (UV) were developed and validated. The method validation was based on Resolution n&ordm; 899 of the 2003 of the Brazilian National Health Surveillance Agency (ANVISA), considering the requirements for bioanalytical methods. The analytical procedures used were effective and reliable for the identification and quantification of DCF in the water samples before and after the water treatment stages. The water treatment tests were carried out in jar test equipment and filters on laboratory scale employing non chlorinated water of artesian well prepared with aquatic humic substances (AHS) to yield 20 uH true color, kaolin turbidity of 70 NTU and DCF concentration of 1 mg L-1. The results indicated that the stages of coagulation with aluminum sulphate, flocculation, sedimentation and filtration sand did not remove DCF. In the stages of pre-oxidation with chlorine and chlorine dioxide and chlorine disinfection the DCF was partially removed, however by-products were formed from the DCF oxidation. Among the THMs, only chloroform was quantified in the pre-oxidation with chlorine. In general, the results showed that chlorine dioxide was more effective to reduce the DCF and fewer by-products were formed. Nevertheless, the complete cycle treatment followed by GAC adsorption was effective to remove DCF (&gt; 99.7%. removal). The by-products of the oxidation of DCF with chlorine and chlorine dioxide identified by liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) consisted in the descaboxylation/hydroxylation and aromatic substitution of hydrogen atoms by chlorine. The compounds identified in the oxidation with chlorine showed the following molecular formulas: C14H11</subCl2NO3, C13H10Cl3N e C14H10Cl3NO2. The by-product identified using chlorine dioxide was C14H11Cl2NO3.