Economic, environmental and mixed objective functions in non-linear process optimization using simulated annealing and tabu search

Screening of topologies developed by hierarchical heuristic procedures can be carried out by comparing their optimal performance. In this work we will be exploiting mono-objective process optimization using two algorithms, simulated annealing and tabu search, and four different objective functions: two of the net present value type, one of them including environmental costs and two of the global potential impact type. The hydrodealkylation of toluene to produce benzene was used as case study, considering five topologies with different complexities mainly obtained by including or not liquid recycling and heat integration. The performance of the algorithms together with the objective functions was observed, analyzed and discussed from various perspectives: average deviation of results for each algorithm, capacity for producing high purity product, screening of topologies, objective functions robustness in screening of topologies, trade-offs between economic and environmental type objective functions and variability of optimum solutions.

Voltammetric analysis of mancozeb and its degradation product ethylenethiourea

The purpose of this work was to develop a reliable alternative method for the determination of the dithiocarbamate pesticide mancozeb (MCZ) in formulations. Furthermore, a method for the analysis of MCZ's major degradation product, ethylenethiourea (ETU), was also proposed. Cyclic voltammetry was used to characterize the electrochemical behavior of MCZ and ETU, and square-wave adsorptive stripping voltammetry (SWAdSV) was employed for MCZ quantification in commercial formulations. It was found that both MCZ and ETU are irreversibly reduced (− 0.6 V and − 0.5 V vs Ag/AgCl, respectively) at the surface of a glassy carbon electrode in a mainly diffusion-controlled process, presenting maximum peak current intensities at pH 7.0 (in phosphate buffered saline electrolyte). Several parameters of the SWAdSV technique were optimized and linear relationships between concentration and peak current intensity were established between 10–90 μmol L− 1 and 10–110 μmol L− 1 for MCZ and ETU, respectively. The limits of detection were 7.0 μmol L− 1 for MCZ and 7.8 μmol L− 1 for ETU. The optimized method for MCZ was successfully applied to the quantification of this pesticide in two commercial formulations. The developed procedures provided accurate and precise results and could be interesting alternatives to the established methods for quality control of the studied products, as well as for analysis of MCZ and ETU in environmental samples.

Electrochemical sensor for simultaneous determination of herbicide MCPA and its metabolite 4-chloro-2-methylphenol. Application to photodegradation environmental monitoring

The development and application of a polyaniline/carbon nanotube (CNT) cyclodextrin matrix (PANI-β-CD/MWCNT)-based electrochemical sensor for the quantitative determination of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) and its main transformation product 4-chloro-2-methylphenol in natural waters are described. A simple cyclic voltammetry-based electrochemical methodology, in phosphate buffer solution at pH 6.0, was used to develop a method to determine both MCPA and 4-chloro-2-methylphenol, without any previous extraction or derivatization steps. A linear concentration range (10 to 50 μmol L−1) and detection limits of 1.1 and 1.9 μmol L−1, respectively, were achieved using optimized cyclic voltammetric parameters. The proposed method was successfully applied to the determination of MCPA and 4-chloro-2-methylphenol in natural water samples with satisfactory recoveries (94 to 107 %) and in good agreement with the results obtained by an established high-performance liquid chromatography technique, no significant differences being found between the methods. Interferences from ionic species and other herbicides used for broad-leaf weed control were shown to be small. The newly developed methodology was also successfully applied to MCPA photodegradation environmental studies.

Influence of environmental temperature and humidity on the acute ventilatory response to exercise in asthmatic adolescents

Asthma is a chronic inflammatory disorder of the respiratory airways affecting people of all ages, and constitutes a serious public health problem worldwide (6). Such a chronic inflammation is invariably associated with injury and repair of the bronchial epithelium known as remodelling (11). Inflammation, remodelling, and altered neural control of the airways are responsible for both recurrent exacerbations of asthma and increasingly permanent airflow obstruction (11, 29, 34). Excessive airway narrowing is caused by altered smooth muscle behaviour, in close interaction with swelling of the airway walls, parenchyma retractile forces, and enhanced intraluminal secretions (29, 38). All these functional and structural changes are associated with the characteristic symptoms of asthma – cough, chest tightness, and wheezing –and have a significant impact on patients’ daily lives, on their families and also on society (1, 24, 29). Recent epidemiological studies show an increase in the prevalence of asthma, mainly in industrial countries (12, 25, 37). The reasons for this increase may depend on host factors (e.g., genetic disposition) or on environmental factors like air pollution or contact with allergens (6, 22, 29). Physical exercise is probably the most common trigger for brief episodes of symptoms, and is assumed to induce airflow limitations in most asthmatic children and young adults (16, 24, 29, 33). Exercise-induced asthma (EIA) is defined as an intermittent narrowing of the airways, generally associated with respiratory symptoms (chest tightness, cough, wheezing and dyspnoea), occurring after 3 to 10 minutes of vigorous exercise with a maximal severity during 5 to 15 minutes after the end of the exercise (9, 14, 16, 24, 33). The definitive diagnosis of EIA is confirmed by the measurement of pre- and post-exercise expiratory flows documenting either a 15% fall in the forced expiratory volume in 1 second (FEV1), or a ≥15 to 20% fall in peak expiratory flow (PEF) (9, 24, 29). Some types of physical exercise have been associated with the occurrence of bronchial symptoms and asthma (5, 15, 17). For instance, demanding activities such as basketball or soccer could cause more severe attacks than less vigorous ones such as baseball or jogging (33). The mechanisms of exercise-induced airflow limitations seem to be related to changes in the respiratory mucosa induced by hyperventilation (9, 29). The heat loss from the airways during exercise, and possibly its post-exercise rewarming may contribute to the exercise-induced bronchoconstriction (EIB) (27). Additionally, the concomitant dehydration from the respiratory mucosa during exercise leads to an increased interstitial osmolarity, which may also contribute to bronchoconstriction (4, 36). So, the risk of EIB in asthmatically predisposed subjects seems to be higher with greater ventilation rates and the cooler and drier the inspired air is (23). The incidence of EIA in physically demanding coldweather sports like competitive figure skating and ice hockey has been found to occur in up to 30 to 35% of the participants (32). In contrast, swimming is often recommended to asthmatic individuals, because it improves the functionality of respiratory muscles and, moreover, it seems to have a concomitant beneficial effect on the prevalence of asthma exacerbations (14, 26), supporting the idea that the risk of EIB would be smaller in warm and humid environments. This topic, however, remains controversial since the chlorified water of swimming pools has been suspected as a potential trigger factor for some asthmatic patients (7, 8, 20, 21). In fact, the higher asthma incidence observed in industrialised countries has recently been linked to the exposition to chloride (7, 8, 30). Although clinical and epidemiological data suggest an influence of humidity and temperature of the inspired air on the bronchial response of asthmatic subjects during exercise, some of those studies did not accurately control the intensity of the exercise (2, 13), raising speculation of whether the experienced exercise overload was comparable for all subjects. Additionally, most of the studies did not include a control group (2, 10, 19, 39), which may lead to doubts about whether asthma per se has conditioned the observed results. Moreover, since the main targeted age group of these studies has been adults (10, 19, 39), any extrapolation to childhood/adolescence might be questionable regarding the different lung maturation. Considering the higher incidence of asthma in youngsters (30) and the fact that only the works of Amirav and coworkers (2, 3) have focused on this age group, a scarcity of scientific data can be identified. Additionally, since the main environmental trigger factors, i.e., temperature and humidity, were tested separately (10, 28, 39) it would be useful to analyse these two variables simultaneously because of their synergic effect on water and heat loss by the airways (31, 33). It also appears important to estimate the airway responsiveness to exercise within moderate environmental ranges of temperature and humidity, trying to avoid extreme temperatures and humidity conditions used by others (2, 3). So, the aim of this study was to analyse the influence of moderate changes in air temperature and humidity simultaneously on the acute ventilatory response to exercise in asthmatic children. To overcome the above referred to methodological limitations, we used a 15 minute progressive exercise trial on a cycle ergometer at 3 different workload intensities, and we collected data related to heart rate, respiratory quotient, minute ventilation and oxygen uptake in order to ensure that physiological exercise repercussions were the same in both environments. The tests were done in a “normal” climatic environment (in a gymnasium) and in a hot and humid environment (swimming pool); for the latter, direct chloride exposition was avoided.

Estudo de esmalte estufa aquoso definitivo

Mestrado em Engenharia Química

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.

Estudo da obtenção de gelatina a partir de raspa Wet-Blue da indústria de curtumes

Mestrado em Engenharia Química. Ramo Tecnologias de Protecção Ambiental.

Comparing the content of instruments assessing environmental factors using the International Classification of Functioning, Disability and Health

Purpose: To describe and compare the content of instruments that assess environmental factors using the International Classification of Functioning, Disability and Health (ICF). Methods: A systematic search of PubMed, CINAHL and PEDro databases was conducted using a pre-determined search strategy. The identified instruments were screened independently by two investigators, and meaningful concepts were linked to the most precise ICF category according to published linking rules. Results: Six instruments were included, containing 526 meaningful concepts. Instruments had between 20% and 98% of items linked to categories in Chapter 1. The highest percentage of items from one instrument linked to categories in Chapters 2–5 varied between 9% and 50%. The presence or absence of environmental factors in a specific context is assessed in 3 instruments, while the other 3 assess the intensity of the impact of environmental factors. Discussion: Instruments differ in their content, type of assessment, and have several items linked to the same ICF category. Most instruments primarily assess products and technology (Chapter 1), highlighting the need to deepen the discussion on the theory that supports the measurement of environmental factors. This discussion should be thorough and lead to the development of methodologies and new tools that capture the underlying concepts of the ICF.

Desenvolvimento de metodologias analíticas para a determinação de resíduos de pesticidas em Vinhos do Douro e Vinhos do Porto

A produção de vinho é uma actividade de elevada importância ao nível económico, ambiental e social. Como tal, a protecção da vinha e/ou da uva através da utilização de pesticidas assume um papel fundamental nesta actividade, permitindo um aumento no rendimento da produção. No entanto, a transferência destes compostos da uva para o vinho é inevitável, ocorrendo, na maioria dos casos, em quantidades reduzidas. Apesar de, geralmente, a quantidade de pesticidas que pode ser transferida para o vinho não apresentar problemas relevantes para a saúde pública, o desenvolvimento de metodologias que permitam garantir um controlo rigoroso da qualidade do vinho é de elevada importância. O controlo deste produto, assim como de qualquer produto alimentar, não deve ser de certa forma virtual, levando a uma desconfiança crescente do consumidor. Ao longo deste trabalho foram desenvolvidos dois métodos para a determinação de pesticidas em diferentes tipos de vinhos, por SPME-GC-MS/MS. O primeiro método desenvolvido visa a determinação de 8 pesticidas organofosforados e o segundo método permite a determinação de 7 pesticidas, 4 organoclorados e 3 dicarboximidas. Foram estudadas quatro matrizes diferentes: vinho branco do Douro, vinho tinto do Douro, vinho branco do Porto e vinho tinto do Porto. As metodologias adoptadas permitiram a obtenção de bons resultados, apesar das condições adoptadas não serem as mais vantajosas para alguns dos compostos estudados. Dada a complexidade das matrizes, a detecção por espectrometria de massa mostrou ser fundamental para a identificação inequívoca de cada um dos pesticidas. Verificaram-se, de um modo geral, bons resultados ao nível da linearidade, para as gamas de concentrações escolhidas, para os dois métodos. Obtiveram-se também bons resultados para os limites de detecção e quantificação, cujos valores se situam abaixo dos limites máximos de resíduos para as uvas, impostos pela regulamentação europeia, para a maioria dos compostos. No caso dos organofosforados, os limites de detecção variam entre 0,05 μg/L e 13,00 μg/L para os pesticidas clorpirifos-metilo e metidatião, respectivamente. Os limites de quantificação variam entre 0,18 μg/L e 43,32 μg/L, também para os pesticidas clorpirifos-metilo e metidatião. No que se refere ao método para os pesticidas organoclorados e dicarboximidas, foram calculados vários limites de detecção para cada composto, em cada matriz estudada, a partir das rectas de calibração diárias, resultando num conjunto de valores com variações significativas entre cada um, para o mesmo pesticida e na mesma matriz. No entanto, apenas os limites de quantificação foram validados, recorrendo-se aos estudos de repetibilidade e precisão intermédia. Obtiveram-se os seguintes limites de quantificação: captana 52,10 μg/L; clortalonil 20,95 μg/L; dicofol 4,37 μg/L; folpete 93,60 μg/L; iprodiona 274,70 μg/L; procimidona 76,04 μg/L e vinclozolina 10,03 μg/L. Os pesticidas metidatião e captana apresentam-se como os compostos mais problemáticos, uma vez que os limites de quantificação obtidos não permitem a garantia do cumprimento dos limites máximos de resíduos regulamentados. Demonstra-se também que, apesar do efeito de matriz ser significativo na determinação de todos os compostos analisados, o mesmo pode ser atenuado, procedendo-se às calibrações nas respectivas matrizes. Observaram-se variações significativas ao nível da resposta do equipamento ao longo do tempo, quer pela alteração das condições operatórias, quer pela decomposição de alguns compostos ao longo do tempo. Este efeito, evidenciado nos estudos das precisões intermédias e repetibilidades, levou à adopção de um método de validação diferente para a determinação de pesticidas organoclorados e dicarboximidas, recorrendo-se então a calibrações diárias e sequências de trabalho mais pequenas.

Novos artigos e sistemas no processamento do couro

A necessidade de diminuir os consumos de energia, não só por questões financeiras mas também por questões ambientais, faz com que sejam feitos esforços no sentido da implementação de energias renováveis bem como da melhoria e expansão das soluções técnicas já conhecidas. Uma das maiores fontes de energia renovável, senão mesmo a maior, é a energia solar que, no futuro, terá uma contribuição muito significativa, quer na satisfação dos consumos energéticos, quer na racionalização da sua utilização, isto é, na melhoria da eficiência do consumo. O presente trabalho focou-se na procura de um sistema solar térmico para o pré-aquecimento da água quente a ser utilizada numa fábrica de curtumes, a empresa Curtumes Aveneda, Lda. Em simultâneo, desenvolveram-se e optimizaram-se processos de produtos específicos que o mercado exige actualmente, visando uma economia de recursos (matérias-primas, água e energia), objectivando sempre a sua viabilidade económica. No que respeita à procura do sistema solar térmico, inicialmente foram realizados levantamentos relativos ao consumo de água, quente e fria, na respectiva empresa. Esta avaliação focou-se em todos os sectores consumidores intensivos de água, tais como a ribeira, curtume e a tinturaria, excluindo o sector de acabamento uma vez que o consumo aqui é insignificante relativamente aos sectores citados anteriormente. Com base no levantamento efectuado foi dimensionado um sistema solar térmico para o pré aquecimento da água quente que conduz a uma economia anual de 107.808,3 kWh de energia térmica, representativa de 29% do consumo anual de energia térmica de aquecimento de água. Foi efectuada análise económica deste investimento que mostrou um índice de rentabilidade superior à unidade e um tempo de retorno do investimento de 9 anos. Desenvolveu-se com sucesso um produto de couro a partir de wet-blue, designado por crispado, produto normalmente produzido a partir da pele em tripa e muito difícil de obter a partir de wet-blue. Este produto caracteriza-se pela sua forma granular irregular e firme da pele. O processo desenvolvido foi ainda optimizado no sentido da redução do consumo de água e de energia. Tendo em conta a necessidade da empresa também se tentou melhorar as características do couro wet-white, muito solicitado actualmente, com resultados positivos no que respeita à temperatura de contracção do couro e às propriedades físico-mecânicas mas sem se atingir o principal objectivo que seria tornar a cor mais clara e mais pura. Foram desta forma dados contributos importantes para a empresa que, assim, dimensionou um sistema mais económico para o aquecimento de água que vai adoptar e ficou com um processo disponível para produzir um produto até então não conseguido.

Air pollution from traffic emissions in Oporto, Portugal: health and environmental implications

Air pollution represents a serious risk not only to environment and human health, but also to historical heritage. In this study, air pollution of the Oporto Metropolitan Area and its main impacts were characterized. The results showed that levels of CO, PM10 and SO2 have been continuously decreasing in the respective metropolitan area while levels of NOx and NO2 have not changed significantly. Traffic emissions were the main source of the determined polycyclic aromatic hydrocarbons (PAHs; 16 PAHs considered by U.S. EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) in air of the respective metropolitan area. The mean concentration of 18 PAHs in air was 69.9±39.7 ng m−3 with 3–4 rings PAHs accounting for 75% of the total ΣPAHs. The health risk analysis of PAHs in air showed that the estimated values of lifetime lung cancer risks considerably exceeded the health-based guideline level. Analytical results also confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere. FTIR and EDX analyses showed that gypsum was the most important constituent of black crusts of the characterized historical monument Monastery of Serra do Pilar classified as “UNESCO World Cultural Heritage”. In black crusts, 4–6 rings compounds accounted approximately for 85% of ΣPAHs. The diagnostic ratios confirmed that traffic emissions were the major source of PAHs in black crusts; PAH composition profiles were very similar for crusts and PM10 and PM2.5.

Toxicity of chromated copper arsenate: a study in mice

Chromated copper arsenate (CCA) was widespread used as a chemical wood preservative with application in the construction of playground equipment, fences, jetties, and naval. Environmental protection agency (EPA) had limited the use of CCA-treated wood on 2002, due to probable implications on both human and environmental health. Although this fact, several industries pursue the use of this product within their manufactories. In addition, the durability of this wood for 60 years, makes these treated products an hazard to the public health. In the present work, studies were explored exposing mice to CCA, during 14, 24, 48, and 96 h for the assessment of acute toxicity of CCA. Kidney and liver were removed, prepared for histology and for metalloid, and copper content evaluation by high resolution inductively coupled plasma mass spectroscopy. The histological results evidenced apparently normal structures for control animals and group exposed to As2O5. On the contrary, the renal sections of the animals treated with CCA revealed epithelium cells desquamation, hyaline, and granular casts in renal tubules lumen. Furthermore, high levels of arsenic were detected in the kidney of animals treated with CCA over 14 and 48 h, being significantly greater than controls. Although this approach underlines the potential hazard of CCA on some vital organs, further testing may be required to establish the impacts on other functions.

Molinate quantification in environmental water by a glutathione-S-transferase based biosensor

A glutathione-S-transferase (GST)based biosensor was developed to quantify the thiocarbamate herbicide molinate in environmental water.The biosensor construction was based on GST immobilization onto a glassy carbon electrode via aminosilane–glutaraldehyde covalent attachment. The principle supporting the use of this biosensor consists of the GST inhibition process promoted by molinate. Differential pulse voltammetry was used to obtain a calibration curve for molinate concentration, ranging from 0.19 to 7.9 mgL -1 and presenting a detection limit of 0.064 mgL- 1. The developed biosensor is stable,and reusable during 15 days.The GST-based biosensor was successfully applied to quantify molinate in rice paddy field floodwater samples. The results achieved with the developed biosensor were in accordance with those obtained by high performance liquid chromatography. The proposed device is suitable for screening environmental water analysis and, since no sample preparation is required, it can be used in situ and in real-time measurements.

Cleanup of industrial effluents containing heavy metals: a new opportunity of valorising the biomass produced by brewing industry

Heavy metal pollution is a matter of concern in industrialised countries. Contrary to organic pollutants, heavy metals are not metabolically degraded. This fact has two main consequences: its bioremediation requires another strategy and heavy metals can be indefinitely recycled. Yeast cells of Saccharomyces cerevisiae are produced at high amounts as a by-product of brewing industry constituting a cheap raw material. In the present work, the possibility of valorising this type of biomass in the bioremediation of real industrial effluents containing heavy metals is reviewed. Given the autoaggregation capacity (flocculation) of brewing yeast cells, a fast and off-cost yeast separation is achieved after the treatment of metal-laden effluent, which reduces the costs associated with the process. This is a critical issue when we are looking for an effective, eco-friendly, and low-cost technology. The possibility of the bioremediation of industrial effluents linked with the selective recovery of metals, in a strategy of simultaneous minimisation of environmental hazard of industrial wastes with financial benefits from reselling or recycling the metals, is discussed.

Produção de biodiesel mediante ecovalorização de óleos alimentares: otimização de estratégias de produção e de controlo de qualidade

Os biocombustíveis são combustíveis com origem em matérias-primas naturais e renováveis, como óleos vegetais, gorduras animais, óleos e gorduras residuais entre outros, utilizados como substitutos de combustíveis minerais, como o gasóleo ou gasolina. Esta alternativa aos combustíveis de origem fóssil, tem-se vindo a revelar cada vez mais atrativa, sobretudo devido aos seus benefícios ambientais, destacando-se entre ele s o facto de serem biodegradáveis, não tóxicos e emitirem menos gases aquando da sua combustão, não contribuindo deste modo para o aumento do efeito de estufa na atmosfera. Na execução do presente trabalho, assume-se como finalidade o desenvolvimento de procedimentos laboratoriais sistemático de modo, com o intuito de elaborar um controlo de qualidade para a produção do biodiesel que permita a implementação de novas medidas processuais melhorando a produção de biodiesel. Este trabalho é resultado do estágio no Ecoparque Braval Valorização e Tratamento de Resíduos Sólidos, S.A. Com a avaliação sistemática e contínua, tanto da matéria-prima usada na produção do biodiesel, como do produto final em si, através de procedimentos laboratoriais específicos para o efeito, visa-se que em distintas fases do processo de produção do biodiesel seja compreendido o que ocorre de forma efetiva, e assim se assumam medidas preventivas e corretivas com o intuito de melhorar a qualidade do produto final. Na elaboração deste trabalho foram também reunidos esforços no sentido de controlar as especificações do óleo à entrada das instalações e iniciar o controlo de qualidade do produto final através de análises comparativas elaboradas no laboratório da Unidade de Produção de Biodiesel do Ecoparque Brava! - Valorização e Tratamento de Resíduos Sólidos, S.A. Outra abordagem do trabalho em questão, incide no estudo do efeito da variação das condições operatórias, nomeadamente a razão molar metanol/óleo , quantidade de catalizador na produção de biodiesel, nomeadamente, na quantidade de glicerina obtida como subproduto da reação e na facilidade de separação de fases. Neste sentido, o trabalho proposto pretende controlar a qualidade da matéria-prima usada, a qualidade do produto final e apresentar os aspetos-chave que deve m ser considerados para urna melhor gestão do s recursos de produção do biocombustível.