Normalmente, a causa da toxicidade do efluente de uma estação de tratamento de esgotos não é conhecida. Devido à complexidade dos efluentes não domésticos por ela recebidos, um programa de redução de toxicidade deve ser implementado, contemplando desde a descarga no corpo d?água até a fonte de poluição. A identificação do(s) poluente(s) que causa(m) impacto na estação e o mecanismo de toxicidade, tipicamente, não são simples de serem determinados a partir de dados de caracterização tradicional de águas residuárias. Além disso, a toxicidade pode estar ligada à presença de compostos refratários ou sub-produtos gerados na própria estação de tratamento de esgotos. Devido ao efeito sinérgico dos poluentes, a metodologia dos limites locais nem sempre pode ser aplicada. Desta forma, o presente trabalho foi desenvolvido com o objetivo de determinar as classes de poluentes presentes na água residuária de uma indústria química, que causa toxicidade e inibição na estação de tratamento de esgotos de Suzano (ETE Suzano), sistema convencional de lodos ativados, localizada na Região Metropolitana de São Paulo, e propor, a partir dos resultados obtidos, tecnologias de pré-tratamento para o referido efluente. Ensaios de fracionamento da água residuária industrial seguidos de testes de avaliação da toxicidade refratária modificados por Ferraresi (2001) foram realizados, utilizando-se um reator que simulava as condições atuais da estação e outros dois que avaliavam a condição futura, nas condições críticas de máxima vazão do efluente industrial pré-tratado e mínima da ETE-Suzano. Os resultados dos ensaios de fracionamento indicaram que compostos voláteis, adsorvíveis e material particulado eram os principais responsáveis pela inibição à nitrificação e pela toxicidade conferida ao efluente final da ETE-Suzano. Desta forma, arraste com ar, adsorção em carvão e coagulação, floculação e sedimentação ou flotação com ar dissolvido são tecnologias que podem ser utilizadas como pré-tratamento do efluente industrial estudado. / Typically, the cause of effluent aquatic toxicity is unknown. Due to this and the complex makeup and varying toxicants in individual waste streams, a toxicity reduction program must usually begin at the discharge and proceed upstream to find the source. The key toxicant(s) and the actual toxic mechanism are normally not apparent from traditional characterization data and may consist of refractory organics or by-products generated in biological treatment process. Due to the complex interaction between toxicants, threshold concentration for specific compounds cannot be universally applied. The research work was carried out to identify classes of pollutants from chemical industry effluent that causes toxicity and inhibition at Suzano Wastewater Treatment Plant (Suzano WTP), a conventional activated sludge process, located at São Paulo Metropolitan Region and to suggest based on results, pretreatment technologies to this wastewater. Methods applied in effluent treatment scenarios (e.g., air stripping, powdered carbon, coagulation, flocculation and sedimentation) and Refractory Toxicity Assessment (RTA) according Ferraresi (2001) were used. A reactor simulated the real condition of Suzano WTP and two others, future condition with maximum flow rate of treated industrial wastewater and minimum flow rate of sewage. Volatile compounds, adsorbed and particulate material present in industrial effluent caused inhibition in activated sludge process and effluent WTP toxicity. Thus, air stripping, carbon adsorption and coagulation, flocculation and sedimentation or air dissolved flotation were efficient technologies to pretreat this industrial effluent.

Neste trabalho, fibras de eucalipto pré-tratadas diferentemente com ácido e/ou enzima foram investigadas visando se verificar alterações estruturais decorrentes dos pré-tratamentos. Na caracterização foram empregadas técnicas de microscopia eletrônica, de fluorescência (campo de claro), de fluorescência confocal de varredura a laser (CLSM) e de tempo de vida de imagem de fluorescência (FLIM). Além disso, foi também empregada espectrocopia de fluorescência, absorção no ultravioleta e vísivel (UV-Vis), no infravermelho (FT-IR) e ressonância magnética nuclear (RMN). Para a caracterização das fibras via microscopia e espectroscopia de fluorescência foi necessário a produção de filmes de fibras de eucalipto. Os resultados demonstraram um aumento na intensidade da fluorescência das fibras em função dos pré-tratamentos. As imagens de microscopia permitiram conhecer a estrutura morfológica das fibras. Para aumentar a fluorescência das fibras e facilitar a visualização por microscopia de fluorescência, nós depositamos o polieletrólito poli(cloreto de tetraidrotiofeno de xililideno) (PTHT), precursor do poli(p-fenileno vinileno) (PPV). Pelas imagens CLSM observou-se a afinidade do PTHT-PPV pelas as fibras que, foi investigada pelo método arraste. A distribuição de tempos de vida associado à imagem FLIM da fibra de eucalipto indicou a presença do PTHT-PPV nas superfícies da fibra e a lignina no interior da parede da mesma. O PTHT-PPV apresentou um tempo de decaimento de fluorescência mais curto do que a lignina. As análises composicionais das fibras de eucalipto e do bagaço de cana-de-açúcar in natura evidenciaram sinais relacionados à lignina, hemicelulose e celulose. / In this dissertation, eucalyptus fibers pretreated with different acid and / or enzyme were investigated in order to study the resulting structural changes of the fibers. The characterization was made using several microscopy techniques such as, electronic microscopy, confocal laser scanning microscopy (CLSM) and fluorescence lifetime imaging microscopy (FLIM). In addition, we used fluorescence spectroscopy, absorption in the ultraviolet and visible (UV-Vis), infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR). It was necessary to produce films of eucalyptus fibers for the characterization of fibers via microscopy and fluorescence spectroscopy. The results showed changes in the fluorescence intensity of the fibers as function of the pre-treatments. The microscopy images were used to study the morphological structure of fibers. To increase the fluorescence of the fibers and facilitate its visualization via fluorescence microscopy, e deposited a polyelectrolyte precursor of PPV poly(p-phenylenevinylene), the poly-(xylylidenetetrahydro-thiophenium chloride). CLSM images revealed an affinity between the PTHT-PPV and the fibers. This affinity was investigated by a method consisting of spinning a solution containing the fibers and subsequent optical analysis. The results confirmed the affinity of PTHT-PPV with eucalyptus fibers. The lifetime distribution associated with the FLIM image of eucalyptus fiber indicated the presence of PTHT-PPV on the fiber surface and lignin in the inner wall of the fibers. Also, the PTHT-PPV showed fluorescence decay time shorter than the lignin. The analysis of the composition of eucalyptus fibers, we used sugar cane bagasse in natura to facilitate the identification of functional groups. The results showed signs related to lignin, cellulose and hemicellulose.

According to national and international policies in order to protect environment regarding renewable sources of energy, biogas is one of the best alternative to reduce waste and pollution and getting energy. Biogas is the gas that is produced by some kinds of microorganisms in anaerobic condition from organic waste treatment. Technology of biogas plants is varies and there is no standard procedure that is applicable worldwide. Methane (biogas), which is produced from wastes and it is known widely since 1973. By organic waste degradation methane is produced and waste volume will be reduced. Some surveys prove that during anaerobic digestion only 50% of organic matter is degraded. Anaerobic degradation has some steps that are hydrolysis, acidogenesis, acetogenesis and methanogenesis. Since hydrolysis is rate-limited step it can be improved by some pretreatment and some action like improving monitoring system can show that the efficiency of biogas will increase. There are three main pretreatment methods. During this study digestate sludge from different waste treatment plants were pretreated. First experience was pretreating digestate sludge from Sobacken, Falköping, Västerås by Enzyme Addition (Cellolase) and the measuring of biogas (methane) has done by Gas Chromatograph (GC). Second experience was pretreating digestate sludge by Acid (Sulfuric acid). The data of those measurements are shown that the amount of biogas was increased two times in the case of Västerås by enzyme addition, which is about 70% of theoretical expectation of this pretreatment and pretreating digestate sludge of Sobacken by acid pretreatment could increase the amount of biogas two times as well that was about 60% of theoretical estimation. By proper gas chromatograph and choosing one kind of waste and pretreating that by just one kind of pretreatment in each experience and following the results and going further the biogas efficiency will increase significantly because still 50% organic matter is inside the digester. / Uppsatsnivå: D

Hydrothermal liquefaction is a thermochemical technique for obtaining crude bio-oil from lignocellulosic biomass with moderate temperature and pressure. The crude bio-oil can then be upgraded to various biofuels and bioproducts. Hydrothermal liquefaction is amenable to use of biomass feedstocks that have high-moisture. The overall goal of this research is to demonstrate the effectiveness of white rot fungus (WRF) as a pretreatment option in the production of bio-oil from switchgrass through hydrothermal liquefaction. If WRF is an effective pretreatment, it could be a cost-effective option for commercialization, allowing hydrothermal liquefaction to be used on an industrial scale to produce high quality bio-oil capable of replacing some of the fossil fuel liquids used today. This thesis specifically focuses on the investigation of the effects of particle size and culture time on lignin degradation using Phanerochaete chrysosporium as a pretreatment method on switchgrass. In addition, the conversion efficiency of WRF treated switchgrass was compared to that of torrefied switchgrass and untreated switchgrass after the pyrolysis conversion process. The results indicate that WRF outperforms torrefaction as a pretreatment method for the conversion of sugar-based components, thus may be an attractive alternative for fermentation conversion processes, but probably not for thermochemical processes.

<p>Algae is regarded as a good potential substrate for biogas production, due to high cells productivity, low cellulose and zero lignin content. Two parts were included in this study: first, cultivations of micro-algae (<em>Chlorella sorokiniana</em> and <em>Tetraselmis suecica</em>) at two different nitrate concentrations, also the effect of addition of CO₂ on algae grow was investigated in this first part. Second, batch fermentations of the cultivated micro-algae as well as a powder <em>Chlorella</em> (obtained from Raw Food Shop) and a dry mix filamentous algae (collected in the pounds in the park at the back of the Tema-building and then dried) were performed. In this part also effects of thermo-lime pretreatment (room temperature, 80^oC, 105^oC and 120^oC) on the algae biogas potentials was investigated.</p><p> </p><p>Both strains of micro-algae cultured at low nitrate gave more CH₄ yield: 319 (±26) mL and 258 (±12) mL CH₄per added gVS was obtained during the degradation of <em>Chlorella sorokiniana </em>grown at 0.4mM-N and 2mM-N level, respectively. For<em> Tetraselmis suecica</em> 337 (±37) mL and 236 (±20) mL CH₄ per added gVS was obtained at 2.4mM-N and 12mM-N level, respectively. Powder <em>Chlorella</em> gave the highest biogas production (719 ±53 mL/added gVS) and CH₄ yields (392 ±14 mL/added gVS), followed by the dry filamentou<em>s</em> algae (661 ±20 mL biogas and 295 ±9 mL CH₄ per added gVS) and <em>Tetraselmis suecica</em> (12 mM-N; 584 ±7 mL biogas and 295 ±9 mL CH₄ per added gVS).</p><p> </p><p>A negative effect of lime treatment at room temperature on CH₄ yield of algal biomass was obtained. Lime treatment at 120^oC showed the fastest degradation rate for <em>Tetraselmis</em> <em>suecica </em>and powder <em>Chlorella</em> during the initial 5 days of incubation.  </p><p> </p><p><em>Chlorella sorokiniana</em> and <em>Tetraselmis suecica</em> cultures flushed with biogas containing 70% and also CO₂ enriched air (5% CO₂) did not increase cells growth (measured as OD₆₀₀) if compared to references grown under air. On the contrary, a clearly inhibition effect on the algal cells growth was observed in some cultures.</p>

<p>In this study, six dc Magnetron Sputtered (dcMS) CrN hard coatings were deposited on pretreated High Speed Steel (HSS) to achieve different interface architectures. The aim was to correlate the interfacial microstructure to the adhesion of the coatings. The substrates were pretreatment using the Ionized Physical Vapor Deposition (IPVD) method High Power Impulse Magnetron Sputtering (HIPIMS) using a Cr target in an inert atmosphere varying the substrate bias ($U_b$) between 0 V and 1100 V at ambient temperature as well as at a substrate temperature of 400$^\circ$C. The deposition parameters were chosen to show how kinetically induced diffusion, etching and implantation changes the interface chemistry and structure and to investigate their effect on the adhesion on the film. At elevated temperatures, the diffusion will be thermally driven. Annealing of the deposited samples were, therefore, performed at 900 K in an Ar atmosphere. The films were characterized employing XRD, HR-TEM, A-STEM and by scratch test measurements to see how the the interface microstructure can be correlated to the adhesion of the coating. The study shows that a sputter cleaned substrate surface with well preserved crystal structure of the substrate enhances the adhesion of the coating by promotion of local epitaxial growth. However, annealing was also shown to have a large effect on the adhesion enhancement by allowing for interdiffusion in the interface region and due to promotion of interface strain relaxation. Implantation of target material on the other hand had limited influence on the adhesion compared to the clean oxide free surfaces. The low adhesion improvement when gradually changing the chemical composition at the interface is assumed to stem from that the radiation induced defects and strain diminished the positive effect of this gradient.</p>

In this study, six dc Magnetron Sputtered (dcMS) CrN hard coatings were deposited on pretreated High Speed Steel (HSS) to achieve different interface architectures. The aim was to correlate the interfacial microstructure to the adhesion of the coatings. The substrates were pretreatment using the Ionized Physical Vapor Deposition (IPVD) method High Power Impulse Magnetron Sputtering (HIPIMS) using a Cr target in an inert atmosphere varying the substrate bias ($U_b$) between 0 V and 1100 V at ambient temperature as well as at a substrate temperature of 400$^\circ$C. The deposition parameters were chosen to show how kinetically induced diffusion, etching and implantation changes the interface chemistry and structure and to investigate their effect on the adhesion on the film. At elevated temperatures, the diffusion will be thermally driven. Annealing of the deposited samples were, therefore, performed at 900 K in an Ar atmosphere. The films were characterized employing XRD, HR-TEM, A-STEM and by scratch test measurements to see how the the interface microstructure can be correlated to the adhesion of the coating. The study shows that a sputter cleaned substrate surface with well preserved crystal structure of the substrate enhances the adhesion of the coating by promotion of local epitaxial growth. However, annealing was also shown to have a large effect on the adhesion enhancement by allowing for interdiffusion in the interface region and due to promotion of interface strain relaxation. Implantation of target material on the other hand had limited influence on the adhesion compared to the clean oxide free surfaces. The low adhesion improvement when gradually changing the chemical composition at the interface is assumed to stem from that the radiation induced defects and strain diminished the positive effect of this gradient.

The rapid accumulation of municipal solid waste is a significant environmental concern in our rapidly growing world. Due to its low cost, high energy recovery and limited environmental impact anaerobic digestion (AD) is a promising solution for stabilizing the organic fraction of municipal solid waste (OFMSW). Hydrolysis is often the rate-limiting step during AD of wastes with high solid content; this step can be accelerated by pretreatment of waste prior to AD. This thesis presents the results of alkaline pretreatment of OFMSW using NaOH and KOH. Four different pH levels 10, 11, 12 and 13 at two temperatures 23±1°C and 80±1°C were examined to study the effects of the pretreatment on (i) enhancing the solubility of the organic fraction of the waste, and (ii) enhancing the AD process and the biogas production. The effects on solubility were investigated by measuring changes in the soluble COD (SCOD) concentrations of pretreated wastes and the enhanced AD was investigated by measuring volatile solids (VS) destruction, total COD (TCOD) and SCOD removal in addition to biogas and methane production using biochemical methane potential (BMP) assay and semi-continuous laboratory reactor experiments. Pretreatment at pH 13 at 80±1°C demonstrated the maximum solubility for both NaOH and KOH pretreated samples; however the BMP analysis demonstrated that pretreatment at pH 12 at 23±1°C showed the greatest biogas yield relative to the removed VS for both chemicals. Thus pretreatment at pH 12 at 23±1°C using NaOH and KOH were examined using semi-continuous reactors at three different HRTs: 10, 15 and 20 days. Pretreatment demonstrated a significant improvement in the AD performance at SRTs of 10 and 15 days.

The rapid accumulation of municipal solid waste is a significant environmental concern in our rapidly growing world. Due to its low cost, high energy recovery and limited environmental impact anaerobic digestion (AD) is a promising solution for stabilizing the organic fraction of municipal solid waste (OFMSW). Hydrolysis is often the rate-limiting step during AD of wastes with high solid content; this step can be accelerated by pretreatment of waste prior to AD. This thesis presents the results of alkaline pretreatment of OFMSW using NaOH and KOH. Four different pH levels 10, 11, 12 and 13 at two temperatures 23±1°C and 80±1°C were examined to study the effects of the pretreatment on (i) enhancing the solubility of the organic fraction of the waste, and (ii) enhancing the AD process and the biogas production. The effects on solubility were investigated by measuring changes in the soluble COD (SCOD) concentrations of pretreated wastes and the enhanced AD was investigated by measuring volatile solids (VS) destruction, total COD (TCOD) and SCOD removal in addition to biogas and methane production using biochemical methane potential (BMP) assay and semi-continuous laboratory reactor experiments. Pretreatment at pH 13 at 80±1°C demonstrated the maximum solubility for both NaOH and KOH pretreated samples; however the BMP analysis demonstrated that pretreatment at pH 12 at 23±1°C showed the greatest biogas yield relative to the removed VS for both chemicals. Thus pretreatment at pH 12 at 23±1°C using NaOH and KOH were examined using semi-continuous reactors at three different HRTs: 10, 15 and 20 days. Pretreatment demonstrated a significant improvement in the AD performance at SRTs of 10 and 15 days.

Technologies for pretreatment of waste activated sludges (WAS) prior to digestion are of increasing interest to wastewater treatment utilities because of their promise for improving sludge digestibility and reducing the mass of biosolids remaining after digestion. While there has been considerable study of pretreatment processes, a common approach to describing the impact of pretreatments on sludge biodegradability has not been developed. The overall objective of this study was to develop protocols that can be employed to characterize the impact of pretreatment processes on WAS digestion. Sonication and ozonation were employed as models of physical and chemical pretreatment technologies respectively. A range of physical, chemical and biological responses were evaluated to assess the impact of pretreatment on WAS properties as well as digestibility. WAS samples that were generated over a range of solids residence times (SRTs) under controlled operating conditions were employed to facilitate an assessment of the interaction between pretreatment and WAS properties on digestibility. The VS, COD and soluble TKN responses indicated that a significant fraction of the WAS solids were solublized by sonication and ozonation, however, it appeared that the types of materials which were solublized was affected by the SRT at which the WAS was generated and the level of pretreatment. The results indicated that the impact of pretreatment on biodegradability of WAS was not described by solublization values exclusively without considering the SRT of the sludge and the level and type of pretreatment. A higher level of proteinaceous materials was preferentially solublized as the result of pretreatment. Respirometry revealed that both sonication and ozonation substantially reduced the viable heterotrophs in the sludge and modestly increased the readily biodegradable fraction of COD. The ultimate yields of CH4 and NH4 in BMP tests and VFAs in BAP tests revealed that pretreatment marginally increased the ultimate digestibility of the sludges. Only a high dose of ozonation substantially increased the digestibility of the 15 day SRT sludge. However, both sonication and ozonation substantially increased the rate of hydrolysis which is typically the rate limiting process in WAS digestion. The BMP test was not a useful test to evaluate the rate of methane generation due to inhibition of methanogens in the early days of BMP test for pretreated sludges. The comparison between VFA and ammonia responses in day 10 of BAP test and ultimate values of these responses after 60 days in BMP test revealed linear relationships between these responses. According to these relationships, a set of models were introduced in this study. The models can be employed to predict the ultimate methane and ammonia generation using soluble COD, VFA or ammonia responses in day 10 of BAP tests. The BAP test was determined to be a shorter test (10 days) than the BMP (55 to 60 days) test and could provide information on the rates of hydrolysis and acidification/ammonification processes. Characterization of biodegradable and non-biodegradable material in WAS samples was conducted using a simplified ADM1 model. The characterization also revealed that proteins are a substantial fraction of biodegradable materials. The estimated ammonia, VFA and methane values from the stoichiometric model were similar to the corresponding values from the experiments. This supported the validity of the simplified model for all sludges employed in this study.