Quantification of endocrine disruptors and pesticides in water by gas chromatography–tandem mass spectrometry. Method validation using weighted linear regression schemes

Amulti-residue methodology based on a solid phase extraction followed by gas chromatography–tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC–MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.

Estimation of pollutant partition in sandy soils with different water contents

The objectives of this work were: (1) to identify an isotherm model to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) to develop a methodology for the estimation of the contaminant distribution in the different phases of the soil; and (3) to evaluate the influence of soil water content on the contaminant distribution in soil. For sandy soils with negligible contents of clay and natural organic matter, contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene (TCE), and perchloroethylene (PCE), it was concluded that: (1) Freundlich’s model showed to be adequate to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) the distribution of the contaminants in the different phases present in the soil could be estimated with differences lower than 10% for 83% of the cases; and (3) an increase of the soil water content led to a decrease of the amount of contaminant in the solid and non-aqueous liquid phases, increasing the amount in the other phases.

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.

Development of a simple analytical method for the simultaneousdetermination of paracetamol, paracetamol-glucuronide andp-aminophenol in river water

Paracetamol is among the most worldwide consumed pharmaceuticals. Although its occurrence in the environment is well documented, data about the presence of its metabolites and transformation products is very scarce. The present work describes the development of an analytical method for the simultaneous determination of paracetamol, its principal metabolite (paracetamol-glucuronide) and its main transformation product (p-aminophenol) based on solid phase extraction (SPE) and high performance liquid chromatography coupled to diode array detection (HPLC-DAD). The method was applied to analysis of river waters, showing to be suitable to be used in routine analysis. Different SPE sorbents were compared and the use of two Oasis WAX cartridges in tandem proved to be the most adequate approach for sample clean up and pre-concentration. Under optimized conditions, limits of detection in the range 40–67 ng/L were obtained, as well as mean recoveries between 60 and 110% with relative standard deviations (RSD) below 6%. Finally, the developed SPE-HPLC/DAD method was successfully applied to the analysis of the selected compounds in samples from seven rivers located in the north of Portugal. Nevertheless all the compounds were detected, it was the first time that paracetamol-glucuronide was found in river water at concentrations up to 3.57 μg/L.

Response surface methodology applied to SPE for the determination of ibuprofen in various types of water samples

Over the last few years, there has been a growing concern about the presence of pharmaceuticals in the environment. The main objective of this study was to develop and validate an SPE method using surface response methodology for the determination of ibuprofen in different types of water samples. The influence of sample pH and sample volume on the ibuprofen recovery was studied. The effect of each studied independent variable is pronounced on the dependent variable (ibuprofen recovery). Good selectivity, extraction efficiency, and precision were achieved using 600 mL of sample volume with the pH adjusted to 2.2. LC with fluorescence detection was employed. The optimized method was applied to 20 water samples from the North and South of Portugal.

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.

Optimization of a microplate-based assay to assess esterase activity in the alga Pseudokirchneriella subcapitata

The present work describes the optimization of a short-term assay, based on the inhibition of the esterase activity of the alga Pseudokirchneriella subcapitata, in a microplate format. The optimization of the staining procedure showed that the incubation of the algal cells with 20 μmolL−1 fluorescein diacetate (FDA) for 40 min allowed discrimination between metabolic active and inactive cells. The shortterm assay was tested using Cu as toxicant. For this purpose, algal cells, in the exponential or stationary phase of growth, were exposed to the heavy metal in growing conditions. After 3 or 6 h, cells were subsequently stained with FDA, using the optimized procedure. For Cu, the 3- and 6-h EC50 values, based on the inhibition of the esterase activity of algal cells in the exponential phase of growth, were 209 and 130 μg L−1, respectively. P. subcapitata cells, in the stationary phase of growth, displayed higher effective concentration values than those observed in the exponential phase. The 3- and 6-h EC50 values for Cu, for cells in the stationary phase, were 443 and 268 μgL−1, respectively. This short-term microplate assay showed to be a rapid endpoint for testing toxicity using the alga P. subcapitata. The small volume required, the simplicity of the assay (no washing steps), and the automatic reading of the fluorescence make the assay particularly well suited for the evaluation of the toxicity of a high number of environmental samples.

Monitorização de sistema de baterias para veículos elétricos

Uma das maiores preocupações do mundo neste momento prende-se com o facto da grande dependência do petróleo e seus aglomerados. Esta dependência causa dois problemas: novos estudos fomentam o começo da escassez deste produto, atirando para cima o preço deste material precioso, e a poluição que que este causa. Um dos sectores mais dependentes e que mais polui, é o dos transportes. Nos últimos anos, o mundo teve finalmente noção deste problema e uma das apostas neste sector é o desenvolvimento da célula de combustível, uma tecnologia que utiliza água como combustível, podendo ser reutilizada. É uma tecnologia ainda em fase de introdução pelo que, para já, a médio prazo não será solução. Uma solução intermédia é a utilização de energia elétrica como ―combustível‖. Apesar de grande parte da produção de energia elétrica ser a partir da queima de derivados de petróleo, os motores elétricos são por si só muito mais eficientes comparando com os motores de combustão. Não se vai aqui debater se são uma solução com viabilidade devido à questão da transferência da dependência do petróleo do sector dos transportes para o sector da produção de energia elétrica. O objetivo deste trabalho será desenvolver um sistema de faça a gestão do ―combustível‖ dos veículos elétricos, ou seja, baterias. Essa gestão tem como objetivo aumentar a autonomia do veículo e prolongar o tempo de vida das baterias. Na primeira fase, uma introdução à atualidade dos veículos elétricos, fazendo uma análise às diferentes soluções. Serão referidas os diferentes tipos de baterias e suas características, passando depois para exemplos de sistemas de gestão de baterias. A explicação da ideia para este sistema vem com o capítulo projeto, ficando a implementação para o capítulo seguinte.

Practical software improve design and performance of a randomly packed air stripping column for removing volatile organic compounds from water

STRIPPING is a software application developed for the automatic design of a randomly packing column where the transfer of volatile organic compounds (VOCs) from water to air can be performed and to simulate it’s behaviour in a steady-state. This software completely purges any need of experimental work for the selection of diameter of the column, and allows a choice, a priori, of the most convenient hydraulic regime for this type of operation. It also allows the operator to choose the model used for the calculation of some parameters, namely between the Eckert/Robbins model and the Billet model for estimating the pressure drop of the gaseous phase, and between the Billet and Onda/Djebbar’s models for the mass transfer. Illustrations of the graphical interface offered are presented.

Assessment of heavy metals in the surroundings of coal-fired power plant

This paper aims to survey metal concentrations in soils in the vicinity of a coal-firedpower plant located in southwest of Portugal. Two annual sampling campaigns were carried out to measure a hypothetical soil contamination around the coal plant. The sampling area was divided into two subareas, both centered in the emission source, delimited by two concentric circles with radius of 6 km and 20 km. About 40 samplings points were defined in the influence area. Metals measurements were performed with a portable analytical X-ray dispersive energy fluorescence spectrometer identifying about 20 different elements in each sampling point. The most relevant elements measured included As, Cu, Fe, Hg, Pb, Ti and Zn in both sampling areas. Considering the results obtained in the first sampling campaign, arsenic is predominantly higher within the 6-20 km sampling area. The second sampling campaign showed that both sampling areas presented relatively similar metal concentrations except for Fe, Mn, Sr and Zn which concentration is higher within the 6-20 km sampling area. Also, As, Fe, Mn and Ti concentrations decreased significantly from the first to the second sampling campaign and their concentration were predominately higher in the NE-E and E-SE directions.

Optimization of HS-SPME analytical conditions using factorial design for trihalomethanes determination in swimming pool water samples

Trihalomethanes (THMs) are widely referred and studied as disinfection by-products (DBPs). The THMs that are most commonly detected are chloroform (TCM), bromodichloromethane (BDCM), chlorodibromomethane (CDBM), and bromoform (TBM). Several studies regarding the determination of THMs in swimming pool water and air samples have been published. This paper reviews the most recent work in this field, with a special focus on water and air sampling, sample preparation and analytical determination methods. An experimental study has been developed in order to optimize the headspace solid-phasemicroextraction (HS-SPME) conditions of TCM, BDCM, CDBM and TBM from water samples using a 23 factorial design. An extraction temperature of 45 °C, for 25min, and a desorption time of 5 min were found to be the best conditions. Analysis was performed by gas chromatography with an electron capture detector (GC-ECD). The method was successfully applied to a set of 27 swimming pool water samples collected in the Oporto area (Portugal). TCM was the only THM detected with levels between 4.5 and 406.5 μg L−1. Four of the samples exceeded the guideline value for total THMs in swimming pool water (100 μgL−1) indicated by the Portuguese Health Authority.

Optimization of River Water Quality Surveys by Multivariate Analysis of Physicochemical, Bacteriological and Ecotoxicological Data

This study aims to optimize the water quality monitoring of a polluted watercourse (Leça River, Portugal) through the principal component analysis (PCA) and cluster analysis (CA). These statistical methodologies were applied to physicochemical, bacteriological and ecotoxicological data (with the marine bacterium Vibrio fischeri and the green alga Chlorella vulgaris) obtained with the analysis of water samples monthly collected at seven monitoring sites and during five campaigns (February, May, June, August, and September 2006). The results of some variables were assigned to water quality classes according to national guidelines. Chemical and bacteriological quality data led to classify Leça River water quality as “bad” or “very bad”. PCA and CA identified monitoring sites with similar pollution pattern, giving to site 1 (located in the upstream stretch of the river) a distinct feature from all other sampling sites downstream. Ecotoxicity results corroborated this classification thus revealing differences in space and time. The present study includes not only physical, chemical and bacteriological but also ecotoxicological parameters, which broadens new perspectives in river water characterization. Moreover, the application of PCA and CA is very useful to optimize water quality monitoring networks, defining the minimum number of sites and their location. Thus, these tools can support appropriate management decisions.

An uncertainty and sensitivity analysis applied to the prioritisation of pharmaceuticals as surface water contaminants from wastewater treatment plant direct emissions

In this study, the concentration probability distributions of 82 pharmaceutical compounds detected in the effluents of 179 European wastewater treatment plants were computed and inserted into a multimedia fate model. The comparative ecotoxicological impact of the direct emission of these compounds from wastewater treatment plants on freshwater ecosystems, based on a potentially affected fraction (PAF) of species approach, was assessed to rank compounds based on priority. As many pharmaceuticals are acids or bases, the multimedia fate model accounts for regressions to estimate pH-dependent fate parameters. An uncertainty analysis was performed by means of Monte Carlo analysis, which included the uncertainty of fate and ecotoxicity model input variables, as well as the spatial variability of landscape characteristics on the European continental scale. Several pharmaceutical compounds were identified as being of greatest concern, including 7 analgesics/anti-inflammatories, 3 β-blockers, 3 psychiatric drugs, and 1 each of 6 other therapeutic classes. The fate and impact modelling relied extensively on estimated data, given that most of these compounds have little or no experimental fate or ecotoxicity data available, as well as a limited reported occurrence in effluents. The contribution of estimated model input variables to the variance of freshwater ecotoxicity impact, as well as the lack of experimental abiotic degradation data for most compounds, helped in establishing priorities for further testing. Generally, the effluent concentration and the ecotoxicity effect factor were the model input variables with the most significant effect on the uncertainty of output results.

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.

Avaliação do efeito da microfauna do tanque de arejamento no efluente final

O presente trabalho, efetuado na Estação de Tratamento de Águas Residuais do Freixo (ETAR do Freixo), decorreu durante um período de nove meses, (entre Dezembro de 2012 e Agosto de 2013), e teve como principais objetivos: - a observação microscópica e respetiva identificação dos organismos presentes nas lamas ativadas dos reatores biológicos da ETAR (incidindo nos protozoários, metazoários e bactérias filamentosas); - estabelecer a relação entre os organismos identificados/quantidade respetiva e a sedimentabilidade das lamas ativadas e sua influência no processo de depuração; - avaliar a variação das espécies identificadas com as alterações processuais. Para o efeito, a metodologia utilizada foi: - a colheita diária de amostras em vários pontos da ETAR; - a determinação dos parâmetros operacionais e caracterização das amostras recolhidas, tendo sido efetuadas 6039 análises físico-químicas, incluindo ao afluente à ETAR, ao afluente e ao conteúdo dos dois reatores biológicos, à corrente de recirculação de lamas e ao efluente; - a visualização diária microscópica ótica sem contraste de fase dos microrganismos presentes nos reatores biológicos; - a visualização microscópica ótica com contraste de fase da microfauna presente nos reatores biológicos, sendo efetuadas 16 identificações e quantificações dos protozoários presentes nas lamas ativadas dos dois reatores e 10 identificações e quantificações das bactérias filamentosas presentes nos dois reatores biológicos. O início do estudo ocorreu num período em que se começou a verificar um aumento excessivo de espumas nos decantadores secundários, resultando numa fraca sedimentabilidade das lamas e numa menor qualidade do efluente final. Na tentativa de reduzir a excessiva ascensão do manto de lamas que se verificou, foram efectuadas alterações operacionais, consistindo: - na alteração da razão de recirculação da decantação secundária para os reatores biológicos; - na introdução de um composto altamente concentrado em matéria orgânica na corrente de recirculação de lamas; - na alteração da extração de lamas biológicas. Verificou-se que as alterações processuais efetuadas foram muito eficazes na diminuição do manto de lamas da decantação secundária, bem como muito eficazes na qualidade do efluente final. Durante os meses de Fevereiro a Agosto fez-se o acompanhamento diário de todas as condições de operação de modo a manter e validar o procedimento de operação, o qual se considerou muito eficaz em termos de obtenção de uma água tratada de excelente qualidade. Durante o estudo efetuado, verificou-se que a população microbiológica existente nos dois reatores biológicos se manteve praticamente inalterada durante todo o período, sendo os móveis de fundo e os sésseis os grupos dominantes. Esta dominância traduziu-se na elevada qualidade do efluente final que se observou a partir do mês de Fevereiro, tendo dificultado o estudo de novas condições de operação, mas facilitando a validação do procedimento adotado. No que se refere às bactérias filamentosas, verificou-se que são diversas as espécies presentes nos reatores biológicos e que existem em grande abundância, sendo que o Tipo 0092 é claramente dominante. O excessivo crescimento deste tipo de bactérias mostrou ser o maior problema a nível microbiológico no processo de tratamento da instalação, tornando-se crítico no período de inverno em que a temperatura e os picos de pluviosidade se mostraram condições favoráveis ao seu desenvolvimento. Para além da temperatura outros fatores mostraram-se responsáveis pelo seu crescimento tais como a razão Alimento/Microrganismo (A/M), a idade das lamas, a carga mássica afluente e o teor de oxigénio dissolvido nos reatores biológicos. Pode-se concluir que apesar de não se trabalhar com os valores teóricos dos parâmetros microbiológicos e operacionais considerados ideais, a ETAR do Freixo, possui um tratamento bastante eficaz na remoção da carga orgânica, na remoção de nutrientes e na remoção de sólidos suspensos totais, apesar da não existência de uma etapa de afinação final como a filtração.