Multiresidue method for the determination of organophosphorus pesticides in still wine and fortified wine using solid-phase microextraction and gas chromatography – Tandem mass spectrometry

A SPME-GC-MS/MS method for the determination of eight organophosphorus pesticides (azinphos-methyl, chlorpyriphos, chlorpyriphos-methyl, diazinon, fenitrothion, fenthion, malathion, and methidathion) in still and fortified wine was developed. The extraction procedure is simple, solvent free, and without any sample pretreatment. Limits of detection (LOD) and quantitation (LOQ) values in the range 0.1–14.3 lg/L and 0.2–43.3 lg/L, respectively, were obtained. The LOQ values are below the maximum residue levels (MRLs) established by European Regulation for grapes, with the exception of methidathion. Coefficients of correlation (R2) higher than 0.99 were obtained for the majority of the pesticides, in all different wines analyzed.

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.

Analysis of PCBs in soils and sediments by microwave-assisted extraction, headspace-SPME and high resolution gas chromatography with ion-trap tandem mass spectrometry

A procedure for the determination of seven indicator PCBs in soils and sediments using microwave-assisted extraction (MAE) and headspace solid-phase microextraction (HS-SPME) prior to GC-MS/MS is described. Optimization of the HS-SPME was carried out for the most important parameters such as extraction time, sample volume and temperature. The adopted methodology has reduced consumption of organic solvents and analysis runtime. Under the optimized conditions, the method detection limit ranged from 0.6 to 1 ng/g when 5 g of sample was extracted, the precision on real samples ranged from 4 to 21% and the recovery from 69 to 104%. The proposed method, which included the analysis of a certified reference material in its validation procedure, can be extended to several other PCBs and used in the monitoring of soil or sediments for the presence of PCBs.

New sensing materials of molecularly-imprinted polymers for the selective recognition of Chlortetracycline

As a result of the stressful conditions in aquaculture facilities there is a high risk of bacterial infections among cultured fish. Chlortetracycline (CTC) is one of the antimicrobials used to solve this problem. It is a broad spectrum antibacterial active against a wide range of Gram-positive and Gram-negative bacteria. Numerous analytical methods for screening, identifying, and quantifying CTC in animal products have been developed over the years. An alternative and advantageous method should rely on expeditious and efficient procedures providing highly specific and sensitive measurements in food samples. Ion-selective electrodes (ISEs) could meet these criteria. The only ISE reported in literature for this purpose used traditional electro-active materials. A selectivity enhancement could however be achieved after improving the analyte recognition by molecularly imprinted polymers (MIPs). Several MIP particles were synthesized and used as electro-active materials. ISEs based in methacrylic acid monomers showed the best analytical performance according to slope (62.5 and 68.6 mV/decade) and detection limit (4.1×10−5 and 5.5×10−5 mol L−1). The electrodes displayed good selectivity. The ISEs are not affected by pH changes ranging from 2.5 to 13. The sensors were successfully applied to the analysis of serum, urine and fish samples.

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.

Luminol-doped nanostructured composite materials for chemiluminescent sensing of hydrogen peroxide

Silica based nanostructured composite materials doped with luminol and cobalt(II) ion were synthesized and characterized, resulting in a highly chemiluminescent material in the presence of hydrogen peroxide. A detection system with the CL light guided from the reaction tube to the photomultiplier tube using a one millimeter glass optical fiber was developed and assessed. A linear response was observed using a semi-logarithm calibration between 50–2000 µM hydrogen peroxide with 1 µM as the limit of detection.

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM10 and PM2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO2, PM10, NO2, CO, and O3; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ngm−3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10−6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98×10−7 in PM10 and 1.06×10−6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO2, NO2, PM10, CO, and solar radiation had positive correlation with PAHs concentrations, while O3, temperature, relative humidity, and wind speed were negatively correlated.

Proof of Concept of the Electrochemical Sensing of 3-Iodothyronamine (T1AM) and Thyronamine (T0AM)

Recent studies have shown that, besides the well-recognized T3 and T4 hormones, there are other relevant thyroid hormones circulating in the human body. In particular, this is the case for 3-iodothyronamine (T1AM) and thyronamine (T0AM). One of the reasons for the lack of studies showing their precise importance is the absence of analytical methodologies available. Herein, for the first time, T1AM and T0AM are electrochemically characterized. T0AM was sensed by means of a glassy carbon electrode; furthermore, T1AM was sensed both with a graphitic surface (oxidatively) as well as with mercury (reductively). For both compounds, after oxidation, it was possible to observe the reversible redox reaction concerning the benzoquinone/hydroquinone couple, thus increasing the specificity of the electroanalysis. Therefore, this work provides the basis for an ‘at-point-of-use’ electrochemical strip test for T1AM and T0AM.

Proposta metodológica para avaliação preliminar de jazigos de shale gas

O potencial de um reservatório de shale gas e influenciado por um grande número de fatores, tais como a sua mineralogia e textura, o seu tipo e maturação de querogénio, a saturação de fluidos, os mecanismos de armazenamento de gás, a profundidade do reservatório e a temperatura e pressão de poros. Nesse sentido, o principal objetivo desta tese foi estabelecer uma metodologia de avaliação preliminar de potenciais jazigos de shale gas (estudo de afloramentos com base numa litoestratigrafia de alta resolução), que foi posteriormente aplicada na Formação de Vale das Fontes (Bacia Lusitânica, Portugal). Esta tese tem a particularidade de contribuir, não só para o aprofundamento da informação a nível geoquímico do local, mas também na abordagem inovadora que permitiu a caracterização petrofísica da Formação de Vale das Fontes. Para a aplicação da metodologia estabelecida, foi necessária a realização dos seguintes ensaios laboratoriais: Rock-Eval 6, picnometria de gás hélio, ensaio de resistência a compressão simples, Darcypress e a difracção de raios-X, aplicando o método de Rietveld. Os resultados obtidos na análise petrofísica mostram uma formação rochosa de baixa porosidade que segundo a classificação ISRM, e classificada como ”Resistente”, para alem de revelar comportamento dúctil e elevado índice de fragilidade. A permeabilidade média obtida situa a Formação no intervalo correspondente as permeabilidades atribuídas aos jazigos de tigh gas, indicando a necessidade de fracturação hidráulica, no caso de uma eventual exploração de hidrocarbonetos, enquanto a difracção de raios-X destaca a calcite, o quartzo e os filossilicatos como os minerais mais presentes na Formação. Do ponto de vista geoquímico, os resultados obtidos mostram que apesar do considerável teor médio de carbono orgânico total, a natureza da matéria orgânica analisada e maioritariamente imatura, composta, principalmente, por querogénio do tipo IV, o que indica a incapacidade de a formação gerar hidrocarbonetos em quantidades economicamente exploráveis.

Environmental/Regatta Buoy: Sensing System

Um dos principais objetivos da ciência é perceber a natureza, i.e., descobrir e explicar o funcionamento do mundo que nos rodeia. Para tal, os cientistas precisam de coligir dados e monitorar o meio ambiente. Em particular, considerando que cerca de 70% da Terra é coberta por água, a coleta de parâmetros de caracterização da água de grandes superfícies é uma prioridade. A monitorização das condições da água é feita principalmente através de bóias. No entanto, as bóias disponíveis no mercado não satisfazem as necessidades existentes. Esta é uma das principais razões que levaram o Laboratório de Sistemas Autónomos (LSA) do Instituto Superior de Engenharia do Porto a lançarem um projeto para o desenvolvimento de uma bóia reconfigurável e com dois modos de funcionamento: monitorização ambiental e baliza ativa de regata. O segundo modo é destinado a regatas de veleiros autónomos. O projeto começou há um ano com um projeto do European Project Project [1] (EPS), realizado por quatro estudantes internacionais, destinado à construção da estrutura da bóia e à selecção dos componentes mais adequados para o sistema de medição e controlo. A arquitetura que foi definida para este sistema é do tipo mestre-escravo e é composta por uma unidade de controlo mestre para a telemetria e configuração e uma unidade de controlo escrava para a medição e armazenamento de dados. O desenvolvimento do projeto continuou com dois estudantes belgas que trabalharam na comunicação e no armazenamento de dados. Este projeto, que prossegue com o desenvolvimento da medição e do armazenamento de dados do lado da unidade de controlo escrava, tem os seguintes objetivos: (i ) implementar o protocolo de comunicação na unidade de controlo escrava; (ii ) coligir e armazenar os dados dos sensores no cartão SD em tempo real; (iii ) fornecer dados em tempo útil; e (iv) recuperar dados do cartão SD em tempo diferido. As contribuições anteriores foram estudadas e foi feito um levantamento dos projetos congéneres existentes. O desenvolvimento do projeto atual começou com o protocolo de comunicação. Este protocolo, que foi projetado pelos alunos anteriores, foi um bom ponto de partida. No entanto, o protocolo foi atualizado e melhorado com novas funcionalidades. Esta última componente foi um trabalho conjunto com Laurens Allart, que esteve a trabalhar no subsistema de telemetria e de configuração durante este semestre. O protocolo foi implementado do lado da unidade de controlo escrava através de uma estrutura de múltiplas actividades paralelas (multithreaded). Esta estrutura recebe as mensagens da unidade mestre, executa as ações solicitadas e envia de volta o resultado. A bóia é um dispositivo reconfigurável multimodo que pode ser expandido com novos modos de operação no futuro. Infelizmente, sofre de algumas limitações: suporta uma carga máxima de 40 kg e tem uma área de implantação limitada pela distância máxima à estacão base.

Emerging (Bio)Sensing Technology for Assessing and Monitoring Freshwater Contamination – Methods and Applications

Ecological Water Quality - Water Treatment and Reuse

Microcystin-LR detection in water by the Fabry–Pérot interferometer using an optical fibre coated with a sol–gel imprinted sensing membrane

Cyanobacteria deteriorate the water quality and are responsible for emerging outbreaks and epidemics causing harmful diseases in Humans and animals because of their toxins. Microcystin-LR (MCT) is one of the most relevant cyanotoxin, being the most widely studied hepatotoxin. For safety purposes, the World Health Organization recommends a maximum value of 1 μg L−1 of MCT in drinking water. Therefore, there is a great demand for remote and real-time sensing techniques to detect and quantify MCT. In this work a Fabry–Pérot sensing probe based on an optical fibre tip coated with a MCT selective thin film is presented. The membranes were developed by imprinting MCT in a sol–gel matrix that was applied over the tip of the fibre by dip coating. The imprinting effect was obtained by curing the sol–gel membrane, prepared with (3-aminopropyl) trimethoxysilane (APTMS), diphenyl-dimethoxysilane (DPDMS), tetraethoxysilane (TEOS), in the presence of MCT. The imprinting effect was tested by preparing a similar membrane without template. In general, the fibre Fabry–Pérot with a Molecular Imprinted Polymer (MIP) sensor showed low thermal effect, thus avoiding the need of temperature control in field applications. It presented a linear response to MCT concentration within 0.3–1.4 μg L−1 with a sensitivity of −12.4 ± 0.7 nm L μg−1. The corresponding Non-Imprinted Polymer (NIP) displayed linear behaviour for the same MCT concentration range, but with much less sensitivity, of −5.9 ± 0.2 nm L μg−1. The method shows excellent selectivity for MCT against other species co-existing with the analyte in environmental waters. It was successfully applied to the determination of MCT in contaminated samples. The main advantages of the proposed optical sensor include high sensitivity and specificity, low-cost, robustness, easy preparation and preservation.

Distributed Sensing of Fluid Dynamic Phenomena with the XDense Sensor Grid Network

IEEE International Conference on Cyber Physical Systems, Networks and Applications (CPSNA'15), Hong Kong, China.

New sensing materials of molecularly-imprinted polymers for the selective recognition of Chlortetracycline

As a result of the stressful conditions in aquaculture facilities there is a high risk of bacterial infections among cultured fish. Chlortetracycline (CTC) is one of the antimicrobials used to solve this problem. It is a broad spectrum antibacterial active against a wide range of Gram-positive and Gram-negative bacteria. Numerous analytical methods for screening, identifying, and quantifying CTC in animal products have been developed over the years. An alternative and advantageous method should rely on expeditious and efficient procedures providing highly specific and sensitive measurements in food samples. Ion-selective electrodes (ISEs) could meet these criteria. The only ISE reported in literature for this purpose used traditional electro-active materials. A selectivity enhancement could however be achieved after improving the analyte recognition by molecularly imprinted polymers (MIPs). Several MIP particles were synthesized and used as electro-active materials. ISEs based in methacrylic acid monomers showed the best analytical performance according to slope (62.5 and 68.6 mV/decade) and detection limit (4.1 × 10−5 and 5.5 × 10−5 mol L−1). The electrodes displayed good selectivity. The ISEs are not affected by pH changes ranging from 2.5 to 13. The sensors were successfully applied to the analysis of serum, urine and fish samples.

Towards the Development of XDense, A Sensor Network for Dense Sensing

Poster in 12th European Conference on Wireless Sensor Networks (EWSN 2015). 9 to 11, Feb, 2015, pp 24-25. Porto, Portugal.