Recovery of acid and base from brackish water by bipolar membrane electrodialysis

Nesta dissertação pretendeu-se estudar a viabilidade do uso de eletrodiálise com membranas bipolares (BM) na recuperação de ácido clorídrico e de hidróxido de sódio a partir de um efluente industrial que contém 1.4 mol/L de cloreto de sódio. Estas membranas mostraram ser uma ferramenta eficiente para a produção de ácidos e bases a partir do respetivo sal. Foi feita uma seleção de diferentes membranas bipolares (Neosepta, Fumatech e PCA) e aniónicas (PC-SA e PC-ACID 60) na tentativa de encontrar a combinação mais adequada para o tratamento do efluente. Dependendo do critério, o melhor arranjo de membranas é o uso de PC-ACID 60 (membrana aniónica), PC-SK (membrana catiónica) e membranas bipolares do tipo Neosepta para maior pureza dos produtos; membranas bipolares Fumatech para maior eficiência de dessalinização e membranas bipolares PCA para um maior grau de dessalinização. Tecnologicamente foi possível obter uma dessalinização de 99.8% em quatro horas de funcionamento em modo batch com recirculação de todas as correntes. Independentemente da combinação usada é recomendável que o processo seja parado quando a densidade de corrente deixa de ser máxima, 781 A/m2. Assim é possível evitar o aumento de impurezas nos produtos, contra difusão, descida instantânea do pH e uma dessalinização pouco eficiente. A nível piloto o principal fornecedor de membranas e unidade de tratamento “stack” é a marca alemã PCA. Sendo assim realizaram-se ensaios de repetibilidade, contra difusão, avaliação económica e upscaling utilizando as membranas bipolares PCA. A nível económico estudou-se o uso de dois tipos de unidades de tratamento; EDQ 380 e EDQ 1600, para diferentes níveis de dessalinização (50, 75 e 80%). Tendo em conta a otimização económica, é recomendável uma dessalinização máxima de 80%, uma vez que a eficiência de processo a este ponto é de 40%. A aplicação do método com a unidade EDQ 1600 para uma dessalinização de 50% é a mais vantajosa economicamente, com custos de 16 €/m3 de efluente tratado ou 0,78 €/kg Cl- removido. O número de unidades necessárias é 4 posicionados em série.

QuEChERS: a new sample preparation approach for the determination of ibuprofen and its metabolites in soils

Ibuprofen is one of the most used active pharmaceutical ingredients worldwide. A new method for the analysis of ibuprofen and its metabolites, hydroxyibuprofen and carboxyibuprofen, in soils is presented. The extraction of these compounds from the soil matrices was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The method involves a single extraction of the investigated compounds with purified water (acidified at pH 2.5 with hydrochloric acid), and a slow and continuous addition of the QuEChERS content, followed by the addition of acidified acetonitrile (1% acetic acid), prior to the determination by liquid chromatography coupled with fluorescence detection (LC–FLD). Validation studies were carried out using soil samples with a range of organic carbon contents. Recoveries of the fortified samples ranged from 79.5% to 101%. Relative standard deviations for all matrix–compound combinations did not exceed 3%. The method quantification limits were ≤22.4 μg kg−1 in all cases. The developed method was applied to the analysis of sixteen real samples.

Estudo da implementação de um sistema de vigilância e alarme num recurso hídrico

Neste trabalho estudou-se a implementação de um sistema de vigilância e alerta da qualidade da água de um recurso hídrico, para um possível caso de poluição. Em 25 de Agosto de 2008 foram derramadas 4 toneladas de ácido clorídrico acidentalmente para as águas do rio Febros. Este rio situa-se no concelho de Vila Nova de Gaia e é um pequeno afluente do rio Douro, tendo cerca de 14 km de extensão e tem a particularidade de atravessar o Parque Biológico de Gaia. A falta de uma rápida intervenção e da existência de um plano de ação levou a que parte da fauna e flora fosse destruída. Por este motivo realizou-se este estudo que se baseou na criação de um sistema de vigilância e alerta a ser implementado neste rio. A informação da hidrogeometria do rio e da capacidade de transporte e dispersão de poluentes é indispensável para o bom funcionamento deste sistema. O coeficiente de dispersão longitudinal é um parâmetro muito importante no estudo da qualidade da água. Recorreu-se à utilização da Rodamina WT como marcador, determinando assim a evolução da sua concentração ao longo do tempo e espaço. No cálculo do coeficiente de dispersão foi utilizado o modelo Transient Storage, que demonstrou ser um bom modelo de ajuste aproximando-se dos valores medidos em campo. Para três estações diferentes com distâncias de 290, 390 e 1100 metros do ponto de injeção, obtiveram-se valores de coeficiente de dispersão de 0,18, 0,15 e 0,39 m2/s respetivamente. Os valores do ajuste expressos sob a forma de coeficiente de correlação foram 0,988, 0,998 e 0,986, para a mesma ordem de estações. A constante de rearejamento do rio foi também determinada recorrendo ao método dos marcadores inertes, utilizando o propano como marcador gasoso. A constante determinada próximo de Casal Drijo, entre 2 estações de amostragem a 140 e 290 m do local de injeção, foi de 13,4 dia-1. Com os resultados do coeficiente de dispersão e da constante de rearejamento para além da velocidade e caudal da corrente do rio conseguir-se-á construir o modelo de simulação e previsão de um possível poluente. O sistema de vigilância a implementar sugere-se assim que seja construído por duas partes, uma de análise de evolução da nuvem de poluição e plano de ação outra de monitorização contínua e emissão de alerta. Após uma análise do investimento à implementação deste sistema chegou-se à conclusão que o valor de investimento é de 15.182,00 €.

Enzymatic determination of choline in milk using a FIA system with potentiometric detection

The development of a FIA system for the determination of total choline content in several types of milk is described. The samples were submitted to hydrochloric acid digestion before injection into the system and passed through an enzymatic reactor containing choline oxidase immobilised on glass beads. This enzymatic reaction releases hydrogen peroxide which then reacts with a solution of iodide. The decrease in the concentration of iodide ion is quantified using an iodide ion selective tubular electrode based on a homogeneous crystalline membrane. Validation of the results obtained with this system was performed by comparison with results from a method described in the literature and applied to the determination of total choline in milks. The relative deviation was always < 5%. The repeatability of the method developed was assessed by calculation of the relative standard deviation (RSD) for 12 consecutive injections of one sample. The RSD obtained was < 0.6%.

Modelação do transporte e dispersão de um marcador corado no Rio Febros

O rio Febros é um pequeno curso de água, situado no concelho de Vila Nova de Gaia, com cerca de 15 km de extensão, cuja bacia hidrográfica ocupa uma área de aproximadamente 35,4 km2. Nasce em Seixezelo e desagua na margem esquerda do Rio Douro no Cais do Esteiro, em Avintes. Em Maio de 2008, um acidente de viação teve como consequência o derrame de cerca de quatro toneladas de ácido clorídrico que rapidamente convergiu às águas do rio. Apenas um dia depois, o pH desceu para três e muitos foram os peixes que morreram. A solução adoptada para evitar o desaire foi introduzir milhares de litros de água de modo a diluir o ácido presente, ao longo de todo o curso de água. Tal facto não evitou a destruição de parte de um ecossistema, que ainda nos dias de hoje se encontra em recuperação. De forma a avaliar-se o impacto destas possíveis perturbações sejam estas de origem antropogénica ou natural é necessário possuir conhecimentos dos processos químicos tais como a advecção, a mistura devida à dispersão e a transferência de massa ar/água. Estes processos irão determinar o movimento e destino das substâncias que poderão ser descarregadas no rio. Para tal, recorrer-se-á ao estudo hidrogeométrico do curso de água assim como ao estudo do comportamento de um marcador, simulando uma possível descarga. A rodamina WT será o marcador a ser utilizado devido à panóplia de características ambientalmente favoráveis. Os estudos de campo com este corante, realizados em sequência de descarga previamente estudada, fornecem uma das melhores fontes de informação para verificação e validação de modelos hidráulicos utilizados em estudos de qualidade de águas e protecção ambiental. Escolheram-se dois pontos de descarga no Febros, um em Casal Drijo e outro no Parque Biológico de Gaia, possuindo cada um deles, a jusante, duas estações de monitorização. Pelo modelo ADE os valores obtidos para o coeficiente de dispersão longitudinal para as estações Pontão d’ Alheira, Pinheiral, Menesas e Giestas foram, respectivamente, 0,3622; 0,5468; 1,6832 e 1,7504 m2/s. Para a mesma sequência de estações, os valores da velocidade de escoamento obtidos neste trabalho experimental foram de 0,0633; 0,0684; 0,1548 e 0,1645 m/s. Quanto ao modelo TS, os valores obtidos para o coeficiente de dispersão longitudinal para as estações Pontão d’ Alheira, Pinheiral, Menesas e Giestas foram, respectivamente, 0,2339; 0,1618; 0,5057e 1,1320 m2/s. Para a mesma sequência de estações, os valores da velocidade de escoamento obtidos neste trabalho experimental foram de 0,0652; 0,0775; 0,1891 e 0,1676 m/s. Os resultados foram ajustados por um método directo, o método dos momentos, e por dois métodos indirectos, os modelos ADE e TS. O melhor ajuste corresponde ao modelo TS onde os valores do coeficiente de dispersão longitudinal e da velocidade de escoamento são aqueles que melhor se aproximam da realidade. Quanto ao método dos momentos, o valor estimado para a velocidade é de 0,162 m/s e para o coeficiente de dispersão longitudinal de 9,769 m2/s. Não obstante, a compreensão da hidrodinâmica do rio e das suas características, bem como a adequação de modelos matemáticos no tratamento de resultados formam uma estratégia de protecção ambiental inerente a futuros impactos que possam suceder.

Valorização da Drêche Cervejeira: Fermentação de Pentoses

O presente trabalho tem como objetivo a otimização da etapa de fermentação dos açúcares obtidos a partir da drêche cervejeira para produção do bioetanol através da utilização das leveduras Pichia stipitis NCYC 1541 e Kluyveromyces marxianus NCYC 2791 como agentes fermentativos. O meio de cultura usado para manter as culturas destas leveduras foi Yeast Extract Peptone Dextrose (YEPD). O principal propósito deste trabalho foi o de encontrar alternativas aos combustíveis fósseis, pautando-se por soluções inofensivas para o meio ambiente e sustentáveis. Assim, o trabalho está dividido em quatro etapas: 1) caraterização química e biológica da drêche; 2) pré-tratamento ácido e hidrólise enzimática para primeiramente quebrar as moléculas de lenhina que envolvem os polímeros de celulose e hemicelulose e em seguida romper as ligações poliméricas destas macromoléculas por ação enzimática e transforma-las em açúcares simples, respetivamente, obtendo-se então a glucose, a maltose, a xilose e a arabinose; e, por último, 3) otimização da etapa de fermentação da glucose, maltose e das pentoses que constitui a condição essencial para se chegar à síntese do bioetanol de um modo eficiente e sustentável e 4) a recuperação do bioetanol produzido por destilação fracionada. A quantificação dos açúcares libertados no processo foi feita recorrendo a análises por cromatografia líquida de alta eficiência (HPLC). Neste estudo foram identificados e quantificados cinco açúcares: Arabinose, Glucose, Maltose, Ribose e Xilose. Na etapa de pré-tratamento e hidrólise enzimática foram usados os ácidos clorídrico (HCl) e nítrico (HNO3) com a concentração de 1% (m/m), e as enzimas Glucanex 100g e Ultraflo L. Foram testadas seis condições de pré-tratamento e hidrólise enzimática, alterando os parâmetros tempo de contacto e razão enzimas/massa de drêche, respetivamente, e mantendo a temperatura (50 ºC), velocidade de agitação (75 rpm) e concentração dos ácidos (1% (m/m)). No processamento de 25 g de drêche seca com 0,5 g de Glucanex, 0,5 mL de Ultraflo e um tempo de reação de 60 minutos para as enzimas foi obtida uma eficiência de 15%, em hidrolisado com 6% da celulose. Realizou-se a fermentação do hidrolisado resultante do pré-tratamento ácido e hidrólise enzimática de drêche cervejeira e de meios sintéticos preparados com os açúcares puros, usando as duas estirpes selecionadas para este estudo: Pichia stipitis NCYC 1541 e Kluyveromyces marxianus NYCY 2791. As eficiências de fermentação dos açúcares nos meios sintéticos foram superiores a 80% para ambas as leveduras. No entanto, as eficiências de fermentação do hidrolisado da drêche foram de 45,10% pela Pichia stipitis e de 36,58 para Kluyveromyces marxianus, para um tempo de fermentação de 72 horas e à temperatura de 30 °C. O rendimento teórico em álcool no hidrolisado da drêche é de 0,27 g/g, três vezes maior do que o real (0,0856 g/g), para Pichia stipitis e de 0,19 g/g seis vezes maior do que o real (0,0308 g/g), para a Kluyveromyces marxianus.

Lipid content and fatty acid profile of Senegalese sole (Solea senegalensis Kaup, 1858) juveniles as affected by feed containing different amounts of plant protein sources

A growth trial with Senegalese Sole (Solea senegalensis Kaup, 1858) juveniles fed with diets containing increasing replacement levels of fishmeal by mixtures of plant protein sources was conducted over 12 weeks. Total fat contents of muscle, liver, viscera, skin, fins and head tissues were determined, as well as fatty acid profiles of muscle and liver (GC-FID analysis). Liver was the preferential local for fat deposition (5.5–10.8% of fat) followed by fins (3.4–6.7% fat). Increasing levels of plant protein in the diets seems to be related to increased levels of total lipids in the liver. Sole muscle is lean (2.4–4.0% fat), with total lipids being similar among treatments. Liver fatty acid profile varied significantly among treatments. Plant protein diets induced increased levels of C16:1 and C18:2 n -6 and a decrease in ARA and EPA levels. Muscle fatty acid profile also evidenced increasing levels of C18:2 n 6, while ARA and DHA remained similar among treatments. Substitution of fishmeal by plant protein is hence possible without major differences on the lipid content and fatty acid profile of the main edible portion of the fish – the muscle.

Application of wetland systems in the treatment of acid rock mine drainage

The presented work was conducted within the Dissertation / Internship, branch of Environmental Protection Technology, associated to the Master thesis in Chemical Engineering by the Instituto Superior de Engenharia do Porto and it was developed in the Aquatest a.s, headquartered in Prague, in Czech Republic. The ore mining exploitation in the Czech Republic began in the thirteenth century, and has been extended until the twentieth century, being now evident the consequences of the intensive extraction which includes contamination of soil and sub-soil by high concentrations of heavy metals. The mountain region of Zlaté Hory was chosen for the implementation of the remediation project, which consisted in the construction of three cells (tanks), the first to raise the pH, the second for the sedimentation of the formed precipitates and a third to increase the process efficiency in order to reduce high concentrations of metals, with special emphasis on iron, manganese and sulfates. This project was initiated in 2005, being pioneer in this country and is still ongoing due to the complex chemical and biological phenomenon’s inherent to the system. At the site where the project was implemented, there is a natural lagoon, thereby enabling a comparative study of the two systems (natural and artificial) regarding the efficiency of both in the reduction/ removal of the referred pollutants. The study aimed to assist and cooperate in the ongoing investigation at the company Aquatest, in terms of field work conducted in Zlaté Hory and in terms of research methodologies used in it. Thereby, it was carried out a survey and analysis of available data from 2005 to 2008, being complemented by the treatment of new data from 2009 to 2010. Moreover, a theoretical study of the chemical and biological processes that occurs in both systems was performed. Regarding the field work, an active participation in the collection and in situ sample analyzing of water and soil from the natural pond has been attained, with the supervision of Engineer, Irena Šupiková. Laboratory analysis of water and soil were carried out by laboratory technicians. It was found that the natural lagoon is more efficient in reducing iron and manganese, being obtained removal percentages of 100%. The artificial lagoon had a removal percentage of 90% and 33% for iron and manganese respectively. Despite the minor efficiency of the constructed wetland, it must be pointed out that this system was designed for the treatment and consequent reduction of iron. In this context, it can conclude that the main goal has been achieved. In the case of sulphates, the removal optimization is yet a goal to be achieved not only in the Czech Republic but also in other places where this type of contamination persists. In fact, in the natural lagoon and in the constructed wetland, removal efficiencies of 45% and 7% were obtained respectively. It has been speculated that the water at the entrance of both systems has different sources. The analysis of the collected data shows at the entrance of the natural pond, a concentration of 4.6 mg/L of total iron, 14.6 mg/L of manganese and 951 mg/L of sulphates. In the artificial pond, the concentrations are 27.7 mg/L, 8.1 mg/L and 382 mg/L respectively for iron, manganese and sulphates. During 2010 the investigation has been expanded. The study of soil samples has started in order to observe and evaluate the contribution of bacteria in the removal of heavy metals being in its early phase. Summarizing, this technology has revealed to be an interesting solution, since in addition to substantially reduce the mentioned contaminants, mostly iron, it combines the low cost of implementation with an reduced maintenance, and it can also be installed in recreation parks, providing habitats for plants and birds.

Determination of tartaric acid in wines by FIA with tubular tartrate-selective electrodes

A flow injection analysis (FIA) system comprising a tartrate- (TAT) selective electrode has been developed for determination of tartaric acid in wines. Several electrodes constructed for this purpose had a PVC membrane with a complex of quaternary ammonium and TAT as anion exchanger, a phenol derivative as additive, and a more or less polar mediator solvent. Characterization of the electrodes showed behavior was best for membranes with o-nitrophenyl octyl ether as solvent. On injection of 500 μL into a phosphate buffer carrier (pH = 3.1; ionic strength 10–2 mol/L) flowing at 3 mL/min, the slope was 58.06 ± 0.6 with a lower limit of linear range of 5.0 × 10–4 mol/L TAT and R2 = 0.9989. The interference of several species, e.g. chloride, bromide, iodide, nitrate, gallic acid, tannin, sucrose, glucose, fructose, acetate, and citrate, was evaluated in terms of potentiometric selectivity coefficients. The Hofmeister series was followed for inorganic species and the most interfering organic ion was citrate. When red and white wines were analyzed and the results compared with those from an independent method they were found to be accurate, with relative standard deviations below 5.0%.

Rapid determination of tartaric acid in wines

A flow-spectrophotometric method is proposed for the routine determination of tartaric acid in wines. The reaction between tartaric acid and vanadate in acetic media is carried out in flowing conditions and the subsequent colored complex is monitored at 475 nm. The stability of the complex and the corresponding formation constant are presented. The effect of wavelength and pH was evaluated by batch experiments. The selected conditions were transposed to a flowinjection analytical system. Optimization of several flow parameters such as reactor lengths, flow-rate and injection volume was carried out. Using optimized conditions, a linear behavior was observed up to 1000 µg mL-1 tartaric acid, with a molar extinction coefficient of 450 L mg-1 cm-1 and ± 1 % repeatability. Sample throughput was 25 samples per hour. The flow-spectrophotometric method was satisfactorily applied to the quantification of tartaric acid (TA) in wines from different sources. Its accuracy was confirmed by statistical comparison to the conventional Rebelein procedure and to a certified analytical method carried out in a routine laboratory.

FIA potentiometric system based on periodate polymeric membrane sensors for the assessment of ascorbic acid in commercial drinks

Ascorbic acid is found in many food samples. Its clinical and technological importance demands an easyto- use, rapid, robust and inexpensive method of analysis. For this purpose, this work proposes a new flow procedure based on the oxidation of ascorbic acid by periodate. A new potentiometric periodate sensor was constructed to monitor this reaction. The selective membranes were of PVC with porphyrin-based sensing systems and a lipophilic cation as additive. The sensor displayed a near-Nernstian response for periodate over 1.0x10-2–6.0x10-6 M, with an anionic slope of 73.9 ± 0.9 mV decade-1. It was pH independent in acidic media and presented good selectivity features towards several inorganic anions. The flow set-up operated in double-channel, carrying a 5.0x10-4 M IO- 4 solution and a suitable buffer; these were mixed in a 50-cm reaction coil. The overall flow rate was 7 ml min-1 and the injection volume 70 µl. Under these conditions, a linear behaviour against concentration was observed for 17.7–194.0 µg ml-1, presenting slopes of 0.169 mV (mg/l)-1, a reproducibility of ±1.1 mV (n = 5), and a sampling rate of ~96 samples h-1. The proposed method was applied to the analysis of beverages and pharmaceuticals.

Hydroxycinnamic acid antioxidants: an electrochemical overview

Hydroxycinnamic acids (such as ferulic, caffeic, sinapic, and p-coumaric acids) are a group of compounds highly abundant in food that may account for about one-third of the phenolic compounds in our diet. Hydroxycinnamic acids have gained an increasing interest in health because they are known to be potent antioxidants. These compounds have been described as chain-breaking antioxidants acting through radical scavenging activity, that is related to their hydrogen or electron donating capacity and to the ability to delocalize/stabilize the resulting phenoxyl radical within their structure.The free radical scavenger ability of antioxidants can be predicted from standard one-electron potentials. Thus, voltammetric methods have often been applied to characterize a diversity of natural and synthetic antioxidants essentially to get an insight into their mechanism and also as an important tool for the rational design of new and potent antioxidants.The structure-property-activity relationships (SPARs) correlations already established for this type of compounds suggest that redox potentials could be considered a good measure of antioxidant activity and an accurate guideline on the drug discovery and development process. Due to its magnitude in the antioxidant field, the electrochemistry of hydroxycinnamic acid-based antioxidants is reviewed highlighting the structure-property-activity relationships (SPARs) obtained so far.

Photostabilization of phenoxyacetic acid herbicides MCPA and mecoprop by hydroxypropyl-β-cyclodextrin

New strategies to reduce the environmental and economic costs of pesticides use are currently under study. Microencapsulation has been used as a versatile tool for the production of controlled release agricultural formulations. In this study, the photochemical degradation of the herbicides MCPA and mecoprop has been investigated in different aqueous media such as ultrapure and river water under simulated solar irradiation. To explore the possibility of introducing cyclodextrins in the herbicide formulations, the photodegradation study of the inclusion complexes of MCPA and mecoprop with (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) was also performed. The half-lives of MCPA and mecoprop inclusion complexes were increased approximately by a factor of three related to the free molecules. Additionally, it has been shown that the photodegradation of MCPA and mecoprop is influenced by their structural features. The additional methyl group existing in mecoprop molecular structure has a positive influence on the stabilization of the radical intermediate formed in the first stage of photodegradation of both herbicides. The results found indicated that MCPA and mecoprop form inclusion complexes with HP-β-CD showing higher photostability compared to free herbicides indicating that HP-β-CD may serve as ingredient in these herbicide formulations.

Mechanical characterization of polyhydroxyalkanoate and poly (lactic acid) blends

In this work, the mechanical behavior of polyhyroxyalkanoate (PHA)/poly(lactic acid) (PLA) blends is investigated in a wide range of compositions. The mechanical properties can be optimized by varying the PHA contents of the blend. The flexural and tensile properties were estimated by different models: the rule of mixtures, Kerner–Uemura–Takayanagi (KUT) model, Nicolai–Narkis model and Béla–Pukánsky model. This study was aimed at investigating the adhesion between the two material phases. The results anticipate a good adhesion between both phases. Nevertheless, for low levels of incorporation of PHA (up to 30%), where PLA is expectantly the matrix, the experimental data seem to deviate from the perfect adhesion models, suggesting a decrease in the adhesion between both polymeric phases when PHA is the disperse phase. For the tensile modulus, a linear relationship is found, following the rules of mixtures (or a KUT model with perfect adhesion between phases) denoting a good adhesion between the phases over the composition range. The incorporation of PHA in the blend leads to a decrease in the flexural modulus but, at the same time, increases the tensile modulus. The impact energy of the blends varies more than 157% over the entire composition. For blends with PHA weight fraction lower than 50%, the impact strength of the blend is higher than the pure base polymers. The highest synergetic effect is found when the PLA is the matrix and the PHA is the disperse phase for the blend PHA/PLA of 30/70. The second maximum is found for the inverse composition of 70/30. PLA has a heat-deflection temperature (HDT) substantially lower than PHA. For the blends, the HDT increases with the increment in the percentage of the incorporation of PHA. With up to 50% PHA (PLA as matrix), the HDT is practically constant and equal to PLA value. Above this point (PHA matrix), the HDT of the polymer blends increases linearly with the percentage of addition of PHA.