Valorização energética do biogás de um aterro de resíduos sólidos urbanos

Actualmente, a sociedade depara-se com um enorme desafio: a gestão dos resíduos sólidos urbanos. A sua produção tem vindo a aumentar devido à intensificação das actividades humanas nas últimas décadas. A criação de um sistema de gestão dos resíduos é fundamental para definir prioridades nas acções e metas para que haja uma prevenção na produção de resíduos. Os resíduos sólidos urbanos quando dispostos de forma inadequada podem provocar graves impactos ambientais, tendo sido neste trabalho demonstrado que através de uma gestão eficiente destes é possível aproveitar o potencial energético do biogás e consequentemente diminuir o consumo de combustíveis fósseis reduzindo o impacto ambiental. Os aterros sanitários devem funcionar como a ultima etapa do sistema de tratamento dos resíduos sólidos urbanos e são uma alternativa a ter em conta se forem tomadas todas as medidas necessárias. Estima-se que os aterros sejam responsáveis pela produção de 6-20% do metano existente e que contribuam com 3-4% da produção anual de gases efeito de estufa provenientes de actividades antropogénicas1. É, portanto, fundamental proceder a uma impermeabilização do solo e à criação de condições para recolha do biogás produzido durante a decomposição dos resíduos. Foi estimada a produção de biogás, de acordo com o modelo “LandGEM”, no entanto comparando esta produção com a produção medida pelo explorador, constatou-se uma diferença significativa que pode ser justificada pelo: modo de funcionamento do aterro (longos períodos de paragem); desvio dos resíduos rapidamente biodegradáveis para valorização; a existência de uma percentagem superior ao normal de oxigénio no biogás; a utilização de escórias e cinzas, e a correspondente redução da humidade devido ao compactamento exercido sobre os resíduos durante a sua deposição. Visto tratar-se de um estudo de viabilidade económica da valorização do biogás, foram propostos três cenários para a valorização do biogás. O 1º cenário contempla a instalação de um sistema gerador de energia para comercialização junto da Rede Eléctrica Nacional. O 2º Cenário contempla a instalação de um sistema alternativo de alimentação à caldeira da central de valorização energética de forma a substituir o combustível utilizado actualmente. E o 3º Cenário vem de encontro com os resultados observados actualmente onde se verifica uma reduzida produção/recolha de biogás no aterro. Assim é proposto um sistema gerador de energia que garanta o auto-consumo da exploração do aterro (26 MWh/ano). Qualquer um dos cenários apresenta uma VAL negativa o que leva a concluir que não são viáveis. No entanto, através da análise de sensibilidade, verificamos que estes são claramente afectados por factores como o benefício e o investimento anual, concluindo-se que com alterações nos factores de cálculo, como por exemplo, um aumento no consumo de combustível auxiliar da caldeira (2º cenário), ou com um aumento da factura eléctrica (3º cenário), ou com o aumento do tempo de retorno do investimento inicial(1º cenário), os projectos podem-se tornar viáveis. Por fim importa referir que independentemente da valorização é fundamental continuar a eliminar a máxima quantidade de metano produzida para tentar diminuir o impacto que este tem sobre o ambiente.

Avaliação da eco-eficiência de uma empresa de serviços: caso prático

Mestrado em Engenharia Química

Determination of 24 pesticide residues in fortified wines by solid-phase microextraction and gas chromatography tandem mass spectrometry

The present work describes a solid-phase microextraction (SPME) gas chromatography_tandem mass spectrometry (MS/MS) method to quantify 24 pesticides in fortified white wine and fortified red wine. In this study “fortified wine” refers to a wine in which fermentation is arrested before completion by alcohol distillate addition, allowing sugar and alcoholic contents to be higher (around 80-100 g/L total sugars and 19-22% alcohol strength (v/v)). The analytical method showed good linearity, presenting correlation coefficients (R2) ≥ 0.989 for all compounds. Limits of detection (LOD) and quantitation (LOQ) in the ranges of 0.05-72.35 and 0.16-219.23 μg/L, respectively, were obtained. LOQs are below the maximum residue levels (MRL) set by European Regulation for grapes. The proposed method was applied to 17 commercial fortified wines. The analyzed pesticides were not detected in the wines tested.

Organochlorine pesticide residues in strawberries from integrated pest management and organic farming

A rapid, specific, and sensitive method based on theQuick Easy Cheap Effective Rugged and Safe (QuEChERS) method and a cleanup using dispersive solid-phase extraction with MgSO4, PSA, and C18 sorbents has been developed for the routine analysis of 14 pesticides in strawberries. The analyses were performed by three different analytical methodologies: gas chromatography (GC) with electron capture detection (ECD), mass spectrometry (MS), and tandem mass spectrometry (MS/MS). The recoveries for all the pesticides studied were from 46 to 128%, with relative standard deviation of <15% in the concentration range of 0.005-0.250 mg/kg. The limit of detection (LOD) for all compoundsmetmaximumresidue limits (MRL) accepted in Portugal for organochlorine pesticides (OCP). A survey study of strawberries produced in Portugal in the years 2009-2010 obtained from organic farming (OF) and integrated pest management (IPM) was developed. Lindane and β-endosulfan were detected above the MRL in OF and IPM. Other OCP (aldrin, o,p0-DDT and their metabolites, and methoxychlor) were found below the MRL. The OCP residues detected decreased from 2009 to 2010. The QuEChERS method was successfully applied to the analysis of strawberry samples.

Maximização da valorização energética em aterros sanitários recorrendo a equipamentos baseados no Ciclo Orgânico de Rankine (ORC)

Atualmente, os aterros sanitários representam uma solução para a gestão e tratamento dos resíduos sólidos urbanos. Da deposição, ocorrem duas formas de emissões ao longo do tempo, a produção de biogás e de lixiviados, que resultam sobretudo da decomposição da matéria orgânica. Um dos principais constituintes do biogás é o metano, o qual tem elevado poder calorífico. O presente trabalho aborda, a maximização da valorização energética em aterros sanitários, recorrendo a equipamentos baseados no Ciclo Orgânico de Rankine (ORC) para a produção de eletricidade. É apresentado como caso de estudo a central de valorização energética da Suldouro, em Sermonde, que produz eletricidade a partir do biogás resultante da decomposição da matéria orgânica depositada em aterro. O biogás é utilizado como combustível para os motogeradores utilizados para o seu aproveitamento energético, sendo que apenas cerca de 40% do potencial energético contido no biogás é transformado em eletricidade, registando-se perdas sobretudo nas emissões dos gases de exaustão e na água de arrefecimento dos motores. Para avaliação do potencial da recuperação energética dos gases de escape é avaliado o desempenho termodinâmico do ciclo ORC. Para tal foi desenvolvida uma ferramenta em MATLAB utilizando como modelo a configuração do ORC com recuperador de calor. O cálculo das propriedades termodinâmicas dos fluidos foi obtido através da criação de uma sub-rotina que chama o programa CoolProp. Este programa restitui propriedades como a entalpia, entropia, pressões e temperaturas em cada ponto do ciclo, permitindo assim ao utilizador otimizar o tempo na obtenção de resultados. A avaliação económica é fundamental na tomada de decisões por parte do investidor e dos financiadores do projeto. É então apresentada a análise económica e efetuada uma análise de sensibilidade, onde foram efetuadas variações nos vetores mais importantes de forma a poder avaliar-se o impacto em termos da sua rentabilidade. A ferramenta desenvolvida permite obter de forma prática, os três indicadores económicos extremamente influentes no que se refere à tomada de decisão. A utilização dos sistemas ORC e os seus benefícios não se esgotam na maximização dos aproveitamentos da valorização energética em aterros sanitários. Também a recuperação de calor para a produção de energia elétrica pode ter um impacto importante em muitos setores intensivos de energia, contribuindo significativamente para a redução do consumo e aumentando a eficiência de todo o processo de produção.

Comparison of Disposable Pipette Extraction and Dispersive Solid-Phase Extraction in the QuEChERS Method for Analysis of Pesticides in Strawberries

In this study, we sought to assess the applicability of GC–MS/MS for the identification and quantification of 36 pesticides in strawberry from integrated pest management (IPM) and organic farming (OF). Citrate versions of QuEChERS (quick, easy, cheap, effective, rugged and safe) using dispersive solid-phase extraction (d-SPE) and disposable pipette extraction (DPX) for cleanup were compared for pesticide extraction. For cleanup, a combination of MgSO4, primary secondary amine and C18 was used for both the versions. Significant differences were observed in recovery results between the two sample preparation versions (DPX and d-SPE). Overall, 86% of the pesticides achieved recoveries (three spiking levels 10, 50 and 200 µg/kg) in the range of 70–120%, with <13% RSD. The matrix effects were also evaluated in both the versions and in strawberries from different crop types. Although not evidencing significant differences between the two methodologies were observed, however, the DPX cleanup proved to be a faster technique and easy to execute. The results indicate that QuEChERS with d-SPE and DPX and GC–MS/MS analysis achieved reliable quantification and identification of 36 pesticide residues in strawberries from OF and IPM.

Sectors and routes in solid waste collection

Collecting and transporting solid waste is a constant problem for municipalities and populations in general. Waste management should take into account the preservation of the environment and the reduction of costs. The goal with this paper is to address a real-life solid waste problem. The case reveals some general and specific characteristics which are not rare, but are not widely addressed in the literature. Furthermore, new methods and models to deal with sectorization and routing are introduced, which can be extended to other applications. Sectorization and routing are tackled following a two-phase approach. In the first phase, a new method is described for sectorization based on electromagnetism and Coulomb’s Law. The second phase addresses the routing problems in each sector. The paper addresses not only territorial division, but also the frequency with which waste is collected, which is a critical issue in these types of applications. Special characteristics related to the number and type of deposition points were also a motivation for this work. A new model for a Mixed Capacitated Arc Routing Problem with Limited Multi-Landfills is proposed and tested in real instances. The computational results achieved confirm the effectiveness of the entire approach.

Electric vehicles in urban areas: test cases using a scenario simulator

Electric vehicles introduction will affect cities environment and urban mobility policies. Network system operators will have to consider the electric vehicles in planning and operation activities due to electric vehicles’ dependency on the electricity grid. The present paper presents test cases using an Electric Vehicle Scenario Simulator (EVeSSi) being developed by the authors. The test cases include two scenarios considering a 33 bus network with up to 2000 electric vehicles in the urban area. The scenarios consider a penetration of 10% of electric vehicles (200 of 2000), 30% (600) and 100% (2000). The first scenario will evaluate network impacts and the second scenario will evaluate CO2 emissions and fuel consumption.

A study on dynamic state information (DSI) around users for safe urban life

To select each node by devices and by contexts in urban computing, users have to put their plan information and their requests into a computing environment (ex. PDA, Smart Devices, Laptops, etc.) in advance and they will try to keep the optimized states between users and the computing environment. However, because of bad contexts, users may get the wrong decision, so, one of the users’ demands may be requesting the good server which has higher security. To take this issue, we define the structure of Dynamic State Information (DSI) which takes a process about security including the relevant factors in sending/receiving contexts, which select the best during user movement with server quality and security states from DSI. Finally, whenever some information changes, users and devices get the notices including security factors, then an automatic reaction can be possible; therefore all users can safely use all devices in urban computing.

Contexts-management strategy in considering the security in urban computing based on urban design

Urban Computing (UrC) provides users with the situation-proper information by considering context of users, devices, and social and physical environment in urban life. With social network services, UrC makes it possible for people with common interests to organize a virtual-society through exchange of context information among them. In these cases, people and personal devices are vulnerable to fake and misleading context information which is transferred from unauthorized and unauthenticated servers by attackers. So called smart devices which run automatically on some context events are more vulnerable if they are not prepared for attacks. In this paper, we illustrate some UrC service scenarios, and show important context information, possible threats, protection method, and secure context management for people.

Minimização de odores em contentores de resíduos sólidos

Mestrado em Engenharia Química

Analysis of six fungicides and one acaricide in still and fortified wines using solid-phase microextraction-gas chromatography/tandem mass spectrometry

A multiresidue gas chromatographic method for the determination of six fungicides (captan, chlorthalonil, folpet, iprodione, procymidone and vinclozolin) and one acaricide (dicofol) in still and fortified wines was developed. Solid-phase microextraction (SPME) was chosen for the extraction of the compounds from the studied matrices and tandem mass spectrometry (MS/MS) detection was used. The extraction consists in a solvent free and automated procedure and the detection is highly sensitive and selective. Good linearity was obtained with correlation coefficients of regression (R2) > 0.99 for all the compounds. Satisfactory results of repeatability and intermediate precision were obtained for most of the analytes (RSD < 20%). Recoveries from spiked wine ranged from 80.1% to 112.0%. Limits of quantification (LOQs) were considerably below the proposedmaximumresidue limits (MRLs) for these compounds in grapes and below the suggested limits for wine (MRLs/10), with the exception of captan.

Espresso coffee residues: a valuable source of unextracted compounds

Espresso spent coffee grounds were chemically characterized to predict their potential, as a source of bioactive compounds, by comparison with the ones from the soluble coffee industry. Sampling included a total of 50 samples from 14 trademarks, collected in several coffee shops and prepared with distinct coffee machines. A high compositional variability was verified, particularly with regard to such water-soluble components as caffeine, total chlorogenic acids (CGA), and minerals, supported by strong positive correlations with total soluble solids retained. This is a direct consequence of the reduced extraction efficiency during espresso coffee preparation, leaving a significant pool of bioactivity retained in the extracted grounds. Besides the lipid (12.5%) and nitrogen (2.3%) contents, similar to those of industrial coffee residues, the CGA content (478.9 mg/100 g), for its antioxidant capacity, and its caffeine content (452.6 mg/100 g), due to its extensive use in the food and pharmaceutical industries, justify the selective assembly of this residue for subsequent use.

Pesticide residues in Portuguese strawberries grown in 2009–2010 using integrated pest management and organic farming

Pesticides are among the most widely used chemicals in the world. Because of the widespread use of agricultural chemicals in food production, people are exposed to low levels of pesticide residues through their diets. Scientists do not yet have a total understanding of the health effects of these pesticide residues. This work aims to determine differences in terms of pesticide residue content in Portuguese strawberries grown using different agriculture practices. The Quick, Easy, Cheap, Effective, Rugged, and Safe sample preparation method was conducted and shown to have good performance for multiclass pesticides extraction in strawberries. The screening of 25 pesticides residue was performed by gas chromatography–tandem mass spectrometry. In quantitative validation, acceptable performances were achieved with recoveries of 70–120 and <12 % residual standard deviation for 25 pesticides. Good linearity was obtained for all the target compounds, with highly satisfactory repeatability. The limits of detection were in the range of 0.1–28 μg/kg. The method was applied to analyze strawberry samples from organic and integrated pest management (IPM) practices harvested in 2009–2010. The results showed the presence of fludioxonil, bifenthrin, mepanipyrim, tolylfluanid, cyprodinil, tetraconazole, and malathion when using IPM below the maximum residue levels.

Interlaboratory validation of an environmental monitoring method for trace analysis of endocrine disrupting compounds

Environmental pollution continues to be an emerging study field, as there are thousands of anthropogenic compounds mixed in the environment whose possible mechanisms of toxicity and physiological outcomes are of great concern. Developing methods to access and prioritize the screening of these compounds at trace levels in order to support regulatory efforts is, therefore, very important. A methodology based on solid phase extraction followed by derivatization and gas chromatography-mass spectrometry analysis was developed for the assessment of four endocrine disrupting compounds (EDCs) in water matrices: bisphenol A, estrone, 17b-estradiol and 17a-ethinylestradiol. The study was performed, simultaneously, by two different laboratories in order to evaluate the robustness of the method and to increase the quality control over its application in routine analysis. Validation was done according to the International Conference on Harmonisation recommendations and other international guidelines with specifications for the GC-MS methodology. Matrix-induced chromatographic response enhancement was avoided by using matrix-standard calibration solutions and heteroscedasticity has been overtaken by a weighted least squares linear regression model application. Consistent evaluation of key analytical parameters such as extraction efficiency, sensitivity, specificity, linearity, limits of detection and quantification, precision, accuracy and robustness was done in accordance with standards established for acceptance. Finally, the application of the optimized method in the assessment of the selected analytes in environmental samples suggested that it is an expedite methodology for routine analysis of EDC residues in water matrices.