Uma das principais preocupações em relação à crescente ocorrência de cianobactérias em sistemas aquáticos está relacionada à capacidade de algumas espécies em produzir e liberar toxinas, entre elas as microcistinas, que podem afetar a saúde humana. O processo convencional de tratamento de água é muitas vezes insuficiente para remover a toxina dissolvida na água. Entre as tecnologias que podem ser utilizadas para removê-la, estão os filtros de carvão ativado granular (CAG). Essa pesquisa se dedicou ao aprofundamento do conhecimento sobre o desempenho de colunas de CAG quando operadas para remover microcistina de águas de abastecimento. A água de estudo foi composta por água de poço artesiano contaminada por extrato de microcistina (MC), produzindo soluções com concentrações iniciais de MC-LR que variaram entre 14 µg/L e 92 µg/L. Em ensaios de adsorção em colunas de leito fixo, sob regime contínuo, foram avaliados três tipos de CAG, de origens diferentes, sendo um vegetal (CAG-Ccoco) e dois minerais (CAG-Hulha e CAG-Linhito). A partir das curvas de ruptura dos ensaios, foram avaliadas as remoções de microcistina e a capacidade de adsorção desse poluente pelos carvões ativados. Ao ajustar modelos matemáticos (Bohart-Adams, Thomas e Yoon-Nelson) às curvas de ruptura, foi possível obter informações sobre a capacidade de adsorção dos carvões. Os resultados mostraram que o CAG-Linhito possui melhor capacidade de adsorção (164 µg/g), seguido pelo CAG-Ccoco (79 µg/g) e, por último, GAG-Hulha (62 µg/g). A maior capacidade de adsorção de microcistina do CAG-Linhito foi atribuída ao maior volume de mesoporos (0,53 cm³/g) presente em sua estrutura (CAG-Ccoco = 0,05 cm³/g e CAG-Hulha = 0,06 cm³/g). A adsorção de microcistina por colunas de CAG se mostrou eficiente para remoção do poluente do meio líquido, em especial com a utilização do CAG-Linhito. / One of the main concerns about the increasing occurrence of cyanobacteria in aquatic systems is related to the ability of some species to produce and release toxins, including microcystins, which may affect human health. The conventional water treatment process is often insufficient to remove the toxin dissolved in the water. Among the technologies that can be used to remove microcystins are granular activated carbon (GAC) filters. This research focused on knowledge enhancement about the performance of GAC columns when operated to remove microcystin from supply water. The study water was composed of artesian well water contaminated by microcystin (MC) extract, producing solutions with initial concentrations of MC-LR that varied between 14 µg / L and 92 µg / L. In adsorption tests on fixed bed columns, under continuos regime, three types of GAC were evaluated, from different sources, being one vegetal (GAC-Ccoco) and two minerals (GAC-Hulha and GAC-Linhito). From the breakthrough curves, the microcystin removals and the adsorption capacity of this pollutant by activated carbons were evaluated. By adjusting mathematical models (Bohart-Adams, Thomas and Yoon-Nelson) to the breakthrough curves, it was possible to obtain information about the adsorption capacity of the GAC. The results showed that GAC-Linhito had better adsorption capacity (164 µg/g), followed by GAC-Ccoco (79 µg/g) and, finally, GAC-Hulha (62 µg/g). The highest adsorption capacity of GAC-Linhito was attributed to the higher volume of mesopores (0.53 cm³/g) present in its structure (GAC-Ccoco = 0.05 cm³/g GAC-Coal = 0.06 cm³/g). The adsorption of microcystin by GAC columns proved to be efficient for removal of the pollutant from the liquid medium, especially with the use of GAC-Linhito.

Made available in DSpace on 2017-07-20T13:41:56Z (GMT). No. of bitstreams: 1 Vitor da Silveira Freitas.pdf: 1933649 bytes, checksum: a5cfbb4c538352e89ea78bce140383ec (MD5) Previous issue date: 2015-02-03 / Endocrine disrupters (EDs) are substances that simulate, mimic or block the action of natural hormones in humans and other animals. Its presence in surface water and wastewater generates harmful effects that is proven in some fish species, but studies about effects in humans are still controversial. Among the EDs is the 17α-ethinylestradiol (EE2), a synthetic hormone used contraceptives and hormone replacement treatments. This work evaluated the removal of EE2 in water prepared in laboratory, by the conventional treatment in bench scale (CT), CT with addition of powdered activated carbon (CT + PAC) and CT with a subsequent step of heterogeneous photocatalysis using TiO2 (CT + TiO2). The study water was prepared by adding kaolin to raise the turbidity up to 100 ± 10 NTU and, EE2 to a final concentration of 40 mg L-1. The CT was constituited by coagulation using aluminum sulfate (12 mg L-1), followed by flocculation, sedimentation and filtration. The CT + PAC differed by the addition of powdered activated carbon at concentrations of 5 mg L-1 and 7.5 mg L-1 before the coagulation step. The CT + TiO2 step was made of the way after the completion of the CT, 1 L of sample was stored and treated by the heterogeneous photocatalysis. The CT showed removal of EE2 41,75% and 44,33%. The treatment that added activated carbon proved to be more effective removing EE2 (59.63% and 62.25%), and the removal percentage increased with increasing the concentration of powdered activated carbon. The CT + TiO2 also proved an effective treatment, removing 52,5 to 56,4% of EE2. / Interferentes endócrinos (IEs) são substâncias que simulam, bloqueiam ou memetizam a ação de hormônios naturais em humanos e outros animais. Sua presença em águas superficiais e residuárias gera efeitos nocivos já comprovados em espécies de peixes, porém estudos sobre efeitos causados em seres humanos ainda são controversos. Entre os IEs, está o 17α-etinilestradiol (EE2), hormônio sintético utilizado em pílulas anticoncepcionais e tratamentos de reposição hormonal. Neste trabalho foi avaliada a remoção do EE2 em água preparada para estudo utilizando tratamento convencional (TC), TC com adição de carvão ativado em pó (TC + CAP) e TC com posterior etapa de fotocatálise heterogênea utilizando TiO2 (TC + TiO2). Os ensaios foram realizados em equipamento de jarteste, com sulfato de alumínio como coagulante. A água de estudo foi preparada adicionando-se caulinita para elevar a turbidez até 100 ± 10 uT e EE2 (Sigma-Aldrich®) até concentração final de 40 mg L-1. O TC foi constituído de coagulação com dosagem de sulfato de alumínio de 12 mg L-1 seguida de floculação, sedimentação e filtração. O TC + CA diferenciou-se pela adição de carvão ativado em pó nas concentrações de 5 mg L-1 e 7,5 mg L-1 antes da etapa de coagulação. O TC + TiO2 foi realizado com 1 L de amostra após TC, a qual foi armazenada e efetuada a etapa de fotocatálise heterogênea. O TC apresentou remoção de EE2, na ordem de 41,8% e 44,3%. O TC + CAP apresentou melhor eficiência de remoção do EE2 (59,6% e 62,3%), e sua porcentagem de remoção aumentou com aumento da concentração de carvão ativado em pó. Com TC + TiO2 obteve-se eficiência de remoção de EE2 de 52,5 a 56,4% nos ensaios realizados.

O tratamento de águas residuárias industriais, submetido constantemente a cargas de choque, é pouco estudado no Brasil, sendo limitado o grau de conhecimento que se tem no mundo sobre os mecanismos de remoção de disruptores endócrinos nos sistemas de tratamento físico-químicos e biológicos. O presente trabalho traz um estudo de caso, envolvendo uma indústria com uma composição de produtos muito diversificada, com despejos líquidos de unidades isoladas de qualidades diversas e que tem como uma das principais matérias-primas, nonil fenóis, conhecidos disruptores endócrinos. Os mecanismos de remoção de carga orgânica e a avaliação da toxicidade da água residuária ao processo biológico de tratamento foram estudados em escala de laboratório, enquanto que a sua tratabilidade por coagulação, floculação, flotação com ar dissolvido seguido de sistema de lodos ativados, em escala piloto. Avaliou-se, também, a aplicabilidade do tratamento biológico com carvão ativado em pó. A grande variação qualitativa e quantitativa da água residuária bruta requer uma unidade de equalização com tempo de detenção de pelo menos 30 horas. O maior responsável por esta variação de qualidade é o processo da unidade química, cujo efluente é proveniente de lavagens de tanques e reatores. Apesar da reduzida eficiência de remoção de DQO obtida com a coagulação, floculação e flotação com ar dissolvido (20 a 30%), constatou-se que este tratamento é essencial para a redução da toxicidade ao processo biológico. A dosagem de coagulante e o pH ótimos variam conforme a característica do despejo e devem ser determinadas diariamente. No sistema biológico, observou-se uma remoção significativa da DQO do efluente bruto gerado na indústria, não apenas por biodegradação, mas também por volatilização e adsorção. Os testes de bancada evidenciaram remoções de DQO por arraste com ar de 47 a 77 % e por adsorção no lodo biológico, de 42%. Apesar dos constantes choques de carga orgânica e de poluentes tóxicos, conseguiu-se atingir o estado estacionário com variações máximas da concentração de sólidos em suspensão voláteis no tanque de aeração entre 20 e 30%. Neste período, a idade do lodo situou-se em torno de 25 a 30 dias e o tempo de detenção hidráulico foi de 3,8 dias. A eficiência média de remoção de DQO neste período foi de 86%. Os testes com a unidade piloto demonstraram que a utilização de carvão ativado em pó (CAP) produz resultados satisfatórios, comprovando a redução de poluentes tóxicos da água residuária e refletindo em uma significativa melhora na biodegradabilidade do efluente, com aumento da concentração de sólidos em suspensão voláteis no tanque de aeração (de 1380 mg/L para 3820 mg/L) e redução da amplitude de variação da DQO do efluente tratado que passou de 600 a 3200 mgO2/L para o sistema sem CAP para 300 a 600 mgO2/L para o sistema com CAP. Notou-se, também, com a adição de CAP, melhoria na sedimentação do lodo. Pode-se concluir também que o sistema de tratamento atendeu a legislação atual do Estado de São Paulo, com uma remoção média de 80% da DBO5. / Wastewater treatment systems continuously receiving shock loads and the behavior of contaminants under unsteady state conditions are not very well documented in our country, with limited degree of knowledge in the world on the removal of specific pollutants like endocrine disrupting chemicals (EDC) in physical chemical and biological wastewater treatment systems. The present work brings a case study regarding an industry which wastewaters were generated from plants with multiproducts and campaign production with variable composition, and with nonylphenols as one of their raw materials which is known as an endocrine disrupting chemical. The organic load and toxicity removal mechanisms of the wastewater to the biological treatment were studied in bench scale whilst their treatability was evaluated through coagulation, flocculation, dissolved air flotation followed by activated sludge, in pilot scale. The feasibility of the addition of powdered activated carbon to the biological system was also studied. The large qualitative and quantitative variability of the wastewater requires an equalization time of at least 30 hours. The main responsible for this variability in quality is the chemical unit process which wastewaters are originated from reactors and tanks cleanings. Although the low efficiency in COD removal obtained with coagulation, flocculation and dissolved air flotation (20 to 30%), it was found that this process is essential to the toxicity reduction for the biological process. Optimum pH and coagulant dose vary with the wastewater characteristics, and must be determined on a daily basis. On the biological system, it was observed important raw wastewater COD elimination not only through biodegradation, but also through volatilization and adsorption. Bench tests revealed COD elimination of 47 to 77% by air stripping and 42% by adsorption onto the biological sludge. Despite of constant organic and toxic shock loads, it had been possible to reach the steady state during which the maximum variation on the volatile suspended solids concentration was 20 to 30%. During this period, sludge age was around 25 to 30 days, and the hydraulic detention time was 3,8 days. Average efficiency on COD removal in this period was 86%. Tests results with PAC dosage on the pilot plant showed satisfactory, proving the reduction of toxic compounds from the wastewater and resulting in biodegradability improvement. The increase of volatile suspended solids in the aeration tank was from 1380 mg/L to 3820 mg/L, and reduction in the range of variation of remaining treated water COD from 600 to 3200 mgO2/L (system without CAP) down to 300 to 600 mgO2/L (system with CAP). The improvement on the sludge sedimentation with PAC addition was also remarkable. One can also conclude the treatment system attained the current legislation of the State of São Paulo, with 80% BOD5 removal.

Abstract Biomass is the most abundant renewable material present on Earth and has been widely used e.g. in energy production. Recently, new applications for biomass utilization have been developed, e.g. the use of biomass as a raw material for synthesizing new chemicals. This research aimed to produce activated carbon (AC) from waste wood-based materials and peat through carbonization followed by physical or chemical activation. Physical steam activation and chemical activation generate the porosity in AC after the carbonization. The desired properties of AC (porosity, pore size distribution, surface functionality) are dependent on the application in which AC is used. The first part of the research focused on setting up the carbonization and activation device. The most important variables affecting carbonization and activation and the AC properties were studied. The process parameters were optimized through the design of experiments (DOE). The results showed that in the physical activation, the most important variables affecting the characteristics of AC are the holding time, temperature, and the steam feed. Consequently, a model for tailoring the microporosity or mesoporosity of AC and maximizing the yield is proposed. The second part of the research focused on chemical activation using zinc chloride. The aim was to study the effect of activation variables on the yield and properties of AC. Finally, the use of AC as an adsorbent was studied. Especially, the applicability of birch sawdust based activated carbon on the removal of dyes, zinc metal, nitrate, phosphate, and sulfate ions was evaluated. Based on the results, a difference was shown between one and two step process for carbonization and activation, and a single-step process was suggested to maximize the quality of AC. / Tiivistelmä Biomassa on maapallon eniten saatavilla olevaa uusiutuvaa materiaalia, jota on hyödynnetty jo pitkään mm. energiantuotannossa. Viime aikoina uusia biomassan käyttökohteita on kehitetty laajalti, kuten esimerkiksi uusien kemikaalien valmistukseen. Tässä tutkimuksessa puupohjaista jätebiomassaa ja turvetta hyödynnetään fysikaalisesti ja kemiallisesti aktivoidun aktiivihiilen valmistuksessa. Fysikaalinen höyryaktivointi ja kemiallinen aktivointi lisäävät aktiivihiilen huokoisuutta hiilestyksen jälkeen. Aktiivihiilen halutut ominaisuudet (huokoskokojakauma, pinnan toiminnalliset ryhmät) määräytyvät käyttökohteen mukaan. Tutkimuksen ensimmäisessä vaiheessa keskityttiin hidas pyrolyysilaitteiston ja aktivointilaitteiston rakentamiseen sekä hiilestyksen ja aktivoinnin kannalta keskeisimpien muuttujien tutkimiseen. Prosessimuuttujien vaikutusten tarkastelussa ja optimoinnissa hyödynnettiin koesuunnitteluohjelmaa. Tulosten perusteella todettiin, että fysikaalisessa aktivoinnissa olennaisimmat muuttujat olivat lämpötila, pitoaika sekä höyrysyöttö. Tämän pohjalta esitettiin malli aktiivihiilen mikro- ja mesohuokoisuuden muokkaamiseksi ja saannon maksimoimiseksi. Tutkimuksen toisessa vaiheessa tutkittiin kemiallista aktivointia hyödyntämällä sinkkikloridia aktivointikemikaalina. Tavoitteena oli selvittää eri aktivointimuuttujien vaikutusta saantoon ja aktiivihiilen laatuun. Tutkimuksen viimeisessä vaiheessa tutkittiin valmistettujen aktiivihiilien käyttöä adsorbenttina. Erityisesti tutkittiin koivupurusta valmistetun aktiivihiilen soveltuvuutta väriaineiden, metallien ja anionien sidontaan. Tutkimuksen keskeisenä tuloksena voitiin osoittaa merkittävä ero yksi- ja kaksivaiheisen hiilestyksen ja aktivoinnin välillä, ja ehdotettiin yksivaiheista prosessia hiililaadun optimoimiseksi. / Sommario La biomassa è il materiale rinnovabile più abbondante presente sulla Terra ed è stata intensamente usata e.g. nella produzione di energia. Recentemente sono state sviluppate nuove applicazioni per la biomassa, ad esempio come materiale di base per sintetizzare nuovi prodotti chimici. Lo scopo di questa ricerca è produrre carbone attivo (CA) attraverso attivazione fisica e chimica da materiali legnosi di scarto come segatura, cippato e torba. L’attivazione fisica e l’attivazione chimica, creano la porosità nel CA dopo la carbonizzazione. Il prodotto finale può essere usato in differenti applicazioni in base a diversi fattori tra cui la distribuzione della porosità e la tipologia dei gruppi funzionali presenti sulla superficie. La prima fase della ricerca è stata dedicata alla progettazione e installazione dell’hardware necessario per l’attivazione e nell’individuazione dei parametri di processo più importanti. I parametri di processo sono stati ottimizzati attraverso il design of experiments (DOE) e sono state considerate le differenti variabili che interagiscono nella formazione del CA. I risultati hanno mostrato che i parametri di processo più importanti che influiscono sulle caratteristiche del CA sono il tempo, la temperatura di attivazione e la quantità di vapore iniettato nel reattore. È stato proposto un modello per progettare CA microporoso o mesoporoso con massa finale massimizzata. La seconda parte della ricerca è stata incentrata sull’attivazione chimica con cloruro di zinco. Lo scopo é stato studiare l’effetto delle variabili di attivazione su massa finale e proprietà del carbone attivo. Infine, è stata studiato il CA come adsorbente. In particolare è stata considerata l’applicabilità del CA da segatura di betulla per la rimozione di coloranti, zinco metallico, ioni di nitrato, fosfato e solfato. In base a questi risultati, una differenza é stata evidenziata tra il processo di carbonizzazione e attivazione a uno o due stadi, ed il processo a singolo stadio è stato proposto per massimizzare la qualità del CA.

Limiter les émissions de dioxyde de carbone (CO2) est devenu un enjeu d’envergure internationale, notamment pour les industries des secteurs énergétique, chimique et métallurgique. À cette fin, des technologies de captage de CO2 ont été développées durant ces dernières décennies. Dans cette étude, nous nous intéressons à trois types de technologies de captage de CO2 : par absorption chimique à la MEA, par séparation membranaire et par adsorption sur charbon actif. Le CO2 considéré est émis par une centrale à charbon puis directement valorisé au sein d’un procédé de fabrication sur le même site. L’objectif de cette étude est de quantifier les bénéfices environnementaux de l’installation d’une technologie de captage de CO2, en comparaison à la configuration actuelle, sans captage du CO2. Notre approche associe modélisation systémique des procédés et analyse de cycle de vie (ACV). La méthodologie adoptée consiste à modéliser le système complet (la centrale, le procédé de fabrication et les différentes unités de captage) en utilisant un logiciel de diagrammes de flux (Aspen Plus), puis à déterminer les impacts environnementaux par une ACV. Les résultats montrent que le procédé par adsorption chimique à la MEA est fortement pénalisé par l’utilisation du solvant, tant en ce qui concerne la consommation énergétique que les impacts environnementaux. Le procédé membranaire montre des impacts environnementaux importants, malgré une consommation énergétique bien plus faible, en raison de l’utilisation massive de polymères (matériaux membranaires). Enfin, le procédé par adsorption au charbon actif présente des impacts environnementaux moins élevés que les deux autres procédés dans la grande majorité des catégories d’impact. / Limiting carbon dioxide (CO2) emissions is a major global issue, particularly for the energy, chemical and metallurgical industries. To this end, CO2 capture technologies have been developed in recent decades. In this study, we focused on three types of CO2 capture technologies: chemical absorption by MEA, membrane separation and activated carbon adsorption. The CO2 considered is emitted by a coal-fired power station and then directly valorized within a manufacturing process on the same site. The objective of this study was to quantify the environmental benefits of installing a CO2 capture technology in comparison to the current configuration, without CO2 capture. Our approach combined process modeling and life cycle assessment. The methodology adopted was to model the complete system (the power plant, the manufacturing process and the various capture units) using a flowsheeting software (Aspen Plus), then to determine the environmental impacts by LCA. The results show that the MEA chemical adsorption process is strongly penalized by the use of the solvent, both regarding the energy consumption and the environmental impacts. The membrane process exhibits significant environmental impacts, despite a much lower energy consumption, due to the massive use of polymers (membrane materials). Finally, the activated carbon adsorption process has lower environmental impacts than the other two processes in the vast majority of impact categories.

Le biogaz issu de la dégradation anaérobie de matières organiques peut remplacer le gaz naturel dans plusieurs applications. Pour une meilleure valorisation énergétique du biogaz, ce travail s’intéresse à l’élimination des composés organiques volatils du silicium (siloxanes) dans biogaz par l’adsorption sur des matériaux poreux. Trois charbons actifs (CA) commerciaux ont été utilisés pour l’adsorption des siloxanes. Leurs propriétés physicochimiques sont caractérisées par plusieurs techniques. Un CA montre excellent capacité d’adsorption d’octaméthylcyclotétrasiloxane (D4) ce qui est bien supérieur que l’autre. En présence de la vapeur, les capacités d’adsorption des CA peuvent être réduites plus ou moins fort dépendant de dégrée d’humidité relative et la présence des sites hydrophiles sur la surface de CA. Ainsi, la capacité des échantillons possédant ces sites spécifiques est réduite après la thermodésorption à cause de la formation des espèces non volatiles sur la surface de CA. Tests avec d’autres siloxanes ont montré que le phénomène de polymérisation s’est produit avec de réactivité et de mécanisme différent, dépendant de la nature du CA et de siloxane. La polymérisation est toujours plus importante pour le CA qui présent plus de sites hydrophiles, conduisant également à sa plus faible régénérabilité / Biogas issued from the anaerobic digestion of organic materials is a renewable energy source that can replace natural gas in many applications. For a better energy recovery of biogas, this work focuses on the elimination of the volatile organic compounds of silicon (siloxanes) in biogas by the adsorption onto porous materials. Three commercial activated carbons (CA) were used for the adsorption of siloxanes. Their physicochemical properties are characterized by several techniques. Measurement of adsorption capacity of octamethylcyclotetrasiloxane (D4) revealed a CA that works better than the others. In presence of water vapor, the adsorption capacities of all AC can be reduced more or less depending on the degree of relative humidity and the presence of the hydrophilic sites on the surface of AC. Also, D4 adsorption capacity of samples with these specific sites is reduced after thermodesorption due to formation of nonvolatile species on the surface of AC. Tests with other siloxanes showed that the polymerization phenomenon occurred with different reactivity and mechanism, depending on the nature of the CA and siloxane. The polymerization is always more important for the CA which has more hydrophilic sites, thus leading to its lower regenerability

The efficiency of wastewater treatment systems is commonly measured by the reductions of parameters such as biological oxygen demand (BOD), chemical oxygen demand (COD) and total suspended solids (TSS) and/or reductions in levels of selected macro compounds (e.g. long-chained hydrocarbons and inorganic compounds). Less attention has generally been paid to micropollutants with high potential toxic effects, such as polycyclic aromatic compounds (PACs), including unsubstituted and alkylated polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes, polychlorinated biphenyls (PCBs), human pharmaceuticals and by-products formed during the treatment process. These organic micropollutants occur in wastewaters at trace and ultra-trace levels, therefore their detection requires advanced, costly analyses and large sample volumes. Furthermore, concentrations of micropollutants can fluctuate widely both diurnally and between days. Thus, in order to understand the fate of micropollutants in wastewaters there is a need to develop sampling techniques that allow representative samples to be readily collected. In the work underlying this thesis two types of diffusive passive samplers, semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs), were used to monitor non-polar and polar organic micropollutants in wastewaters subjected to various treatment processes. The pollutants sequestered in these samplers represent micropollutants in the dissolved phase that are available for aquatic organisms. Further, since they collect pollutants in an integrative manner, i.e. they sample continuously during the selected exposure time (usually approx. one to ca. three weeks), the results provide time-weighted average (TWA) concentrations. In addition, the effects of various environmental factors on the uptake of analyzed micropollutants in POCISs and SPMDs were investigated using laboratory calibration and in situ calibration with performance reference compounds (PRCs). The results confirm that SPMDs are good sampling tools for investigating the efficacy of wastewater treatment processes for removing non-polar PACs and PCBs, and the effects of varying the process settings. In addition, analyses of process streams in municipal sewage treatment plants demonstrated that conventional sewage treatment processes are not optimized for removing dissolved four-ringed PAHs, some of the five-ringed PAHs, and tri- to hexa-chlorinated biphenyls. The removal of bioavailable PACs was enhanced by adding sorbents with high sorption capacities to the sludge used in the activated sludge treatment step, and a biologically activated carbon system was designed that robustly removed bioavailable PACs, with removal efficiencies of 96.9-99.7 percent across the tested ranges of five varied process parameters. In situ SPMD calibration data acquired show that uptake of PACs, described by SPMD sampling rates (Rs), were four to eight times higher than published laboratory calibrated Rs values, mainly due to strong (bio)fouling and turbulence effects. In addition, the laboratory calibration study demonstrated that temperature affects the POCIS uptake of pharmaceuticals. The uptake of four pharmaceuticals was higher, by 10-56 percent, at 18 °C compared to 5 °C. For two of the pharmaceuticals our data indicate that the uptake was lower by 18-25 percent at 18 °C. Our results also indicate that uptake of the studied pharmaceuticals was in the linear phase throughout the 35 day exposure period at both temperatures. Finally, calibration studies enabled aqueous concentrations of micropollutants to be more accurately estimated from amounts collected in the passive samplers.

A stable mixed culture, deposited as ATCC 55644, previously shown to degrade petroleum hydrocarbons at relatively high concentrations was used as the source of inoculum. This culture was grown in Stanier’s minimal media, either in the presence of different concentrations of naphthalene, nitrobenzene and toluene (NNT) or naphthalene and toluene (NT) as the sole source of C and/or N. Results showed that the majority of the strains isolated from the mixed culture were able to grow in the presence of NNT or NT. A total of 20 different isolates were isolated from the mixed culture. Individual isolates were grown in Stanier’s minimal medium containing a single hydrocarbon as the source of carbon or carbon and nitrogen. Only one strain was found to grow solely in the presence of nitrobenzene as the source of C and N. Most of the other isolates were able to grow in the presence of naphthalene, toluene, acenaphthene, anthracene, fluoranthene and phenanthrene, n-dodecane, hexadecane, n-pentadecane, n-tetradecane, and n-octadecane. Planktonic and immobilized cells of the controlled mixed culture (ATCC 55644) were grown in separate Sequential Batch Reactors (SBR) using Stanier's media, to which naphthalene, nitrobenzene and toluene were added as the sole source of C and/or N. Biodegradation was determined by measuring the residual hydrocarbon in the SBR and the amount of trapped volatile organic carbon (VOC) and the evolved CO2. Gas chromatography data showed that immobilized cells were able to degrade NNT faster than the planktonic cells. This observation was confirmed by CO2 evolution. Over time the loading of hydrocarbon was significantly increased from a starting level of 400 ppm (Naphthalene), 100 ppm (Nitrobenzene), and 500 ppm (toluene), to a final level of 3000 ppm (Naphthalene), 400 ppm (Nitrobenzene), and 1600 ppm (toluene). While increasing nutrient loading, the frequency of re-feeding with hydrocarbons was changed from an initial re-feeding every 60 hrs to a final re-feeding frequency of 18 hrs. The experiments clearly showed that the attached, mixed microbial community was able to effectively and rapidly degrade high concentrations of hydrocarbons. This demonstrated the practical advantages of employing attached, mixed microbial cultures in a SBR.

Heat actuated adsorption heat pumps offer the opportunity to improve overall energy efficiency in waste heat applications by eliminating shaft work requirements accompanying vapor compression cycles. The coefficient of performance (COP) in adsorption heat pumps is generally low. The objective of this thesis is to model the adsorption system to gain critical insight into how its performance can be improved. Because adsorption heat pumps are intermittent devices, which induce cooling by adsorbing refrigerant in a sorption bed heat/mass exchanger, transient models must be used to predict performance. In this thesis, such models are developed at the adsorbent particle level, heat/mass exchanger component level and system level. Adsorption heat pump modeling is a coupled heat and mass transfer problem. Intra-particle mass transfer resistance and sorption bed heat transfer resistance are shown to be significant, but for very fine particle sizes, inter-particle resistance may also be important. The diameter of the adsorbent particle in a packed bed is optimized to balance inter- and intra-particle resistances and improve sorption rate. In the literature, the linear driving force (LDF) approximation for intra-particle mass transfer is commonly used in place of the Fickian diffusion equation to reduce computation time; however, it is shown that the error in uptake prediction associated with the LDF depends on the working pair, half-cycle time, adsorbent particle radius, and operating temperatures at hand. Different methods for enhancing sorption bed heat/mass transfer have been proposed in the literature including the use of binders, adsorbent compacting, and complex extended surface geometries. To maintain high reliability, the simple, robust annular-finned-tube geometry with packed adsorbent is specified in this work. The effects of tube diameter, fin pitch and fin height on thermal conductance, metal/adsorbent mass ratio and COP are studied. As one might expect, many closely spaced fins, or high fin density, yields high thermal conductance; however, it is found that the increased inert metal mass associated with the high fin density diminishes COP. It is also found that thin adsorbent layers with low effective conduction resistance lead to high thermal conductance. As adsorbent layer thickness decreases, the relative importance of tube-side convective resistance rises, so mini-channel sized tubes are used. After selecting the proper tube geometry, an overall thermal conductance is calculated for use in a lumped-parameter sorption bed simulation. To evaluate the accuracy of the lumped-parameter approach, a distributed parameter sorption bed simulation is developed for comparison. Using the finite difference method, the distributed parameter model is used to track temperature and refrigerant distributions in the finned tube and adsorbent layer. The distributed-parameter tube model is shown to be in agreement with the lumped-parameter model, thus independently verifying the overall UA calculation and the lumped-parameter sorption bed model. After evaluating the accuracy of the lumped-parameter model, it is used to develop a system-level heat pump simulation. This simulation is used to investigate a non-recuperative two-bed heat pump containing activated carbon fiber-ethanol and silica gel-water working pairs. The two-bed configuration is investigated because it yields a desirable compromise between the number of components (heat exchangers, pumps, valves, etc.) and steady cooling rate. For non-recuperative two-bed adsorption heat pumps, the average COP prediction in the literature is 0.39 for experiments and 0.44 for models. It is important to improve the COP in mobile waste heat applications because without high COP, the available waste heat during startup or idle may be insufficient to deliver the desired cooling duty. In this thesis, a COP of 0.53 is predicted for the non-recuperative, silica gel-water chiller. If thermal energy recovery is incorporated into the cycle, a COP as high as 0.64 is predicted for a 90, 35 and 7.0°C source, ambient and average evaporator temperature, respectively. The improvement in COP over heat pumps appearing in the literature is attributed to the adsorbent particle size optimization and careful selection of sorption bed heat exchanger geometry.

Contaminated sediments represent a common environmental problem because they can sequester large quantities of contaminants which can remain long after the source of pollution has been removed. From the sediment these hazardous compounds are released into the sediment porewater where it can partition into organisms in the sediment and bioaccumulate up the food web; leading to an ecological and human health concern. The objective of this work is to investigate an emerging option in contaminated sediment remediation; specifically an option for in-situ treatment known as active capping. Conventional capping uses clean sediment or sands to separate contaminated sediment from overlying water and biota. Active capping is the use of a sorptive amendment to such a cap to improve its effectiveness. This work focuses on granular materials as direct amendments to conventional caps including; granular activated carbon (GAC), iron/palladium amended GAC, alumina pillared clay, rice husk char, and organically modified clays. All materials were investigated in batch sorption tests of benzene, chlorobenzene, and naphthalene in DI water. Additionally porewaters from three sites were extruded and the concentrations of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were measured. At Manistique Harbor and Ottawa River PCBs were identified as the primary contaminant of concern while PAHs were the contaminant of concern at the Grand Calumet River. At these sites a solvent extraction method was used to analyze the sediment concentrations of the contaminants of concern. From the former batch tests activated carbon and a commercially available organoclay were chosen for further investigation. This includes PAHs in batch sorption tests using extruded sediment porewater to investigate matrix effects, and PCB sorption in distilled water. / text