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.

Multiresidue pesticides analysis in soils using modified QuEChERS with disposable pipette extraction and dispersive solid-phase extraction

QuEChERS original method was modified into a new version for pesticides determination in soils. The QuEChERS method is based on liquid–liquid portioning with ACN and was followed by cleanup step using dispersive SPE and disposable pipette tips. Gas chromatographic separation with MS detection was carried out for pesticides quantification. The method was validated using recovery experiments for 36 multiclass pesticides. Mean recoveries of pesticides at each of the four spiking levels between 10–300 µg/kg of soil ranged from 70–120% for 26 pesticides with RSD values less than 15%. The method achieved low limit of detection less than 7.6 µ g/kg. Matrix effects were observed for 13 pesticides. Matrix effects were compensated by using matrix-matched calibration. The method was applied successfully using d-SPE or DPX in the analysis of the pesticides in soils from organic farming and integrated pest management.

Two-type heterogeneous multiprocessor scheduling: Is there a phase transition? (Extended Abstract)

Consider the problem of non-migratively scheduling a set of implicit-deadline sporadic tasks to meet all deadlines on a two-type heterogeneous multiprocessor platform. We ask the following question: Does there exist a phase transition behavior for the two-type heterogeneous multiprocessor scheduling problem? We also provide some initial observations via simulations performed on randomly generated task sets.

Dynamic analysis of earthquake phenomena by means of pseudo phase plane

This paper analyses earthquake data in the perspective of dynamical systems and its Pseudo Phase Plane representation. The seismic data is collected from the Bulletin of the International Seismological Centre. The geological events are characterised by their magnitude and geographical location and described by means of time series of sequences of Dirac impulses. Fifty groups of data series are considered, according to the Flinn-Engdahl seismic regions of Earth. For each region, Pearson’s correlation coefficient is used to find the optimal time delay for reconstructing the Pseudo Phase Plane. The Pseudo Phase Plane plots are then analysed and characterised.

Analysis of the respiratory dynamics during normal breathing by means of pseudo phase plots and pressure-volume loops

This paper reports on the analysis of tidal breathing patterns measured during noninvasive forced oscillation lung function tests in six individual groups. The three adult groups were healthy, with prediagnosed chronic obstructive pulmonary disease, and with prediagnosed kyphoscoliosis, respectively. The three children groups were healthy, with prediagnosed asthma, and with prediagnosed cystic fibrosis, respectively. The analysis is applied to the pressure–volume curves and the pseudophaseplane loop by means of the box-counting method, which gives a measure of the area within each loop. The objective was to verify if there exists a link between the area of the loops, power-law patterns, and alterations in the respiratory structure with disease. We obtained statistically significant variations between the data sets corresponding to the six groups of patients, showing also the existence of power-law patterns. Our findings support the idea that the respiratory system changes with disease in terms of airway geometry and tissue parameters, leading, in turn, to variations in the fractal dimension of the respiratory tree and its dynamics.

Analysis of the nano-surface of a modified glassy carbon electrode by pseudo phase plane method

This paper presents the Pseudo phase plane (PPP) method for detecting the existence of a nanofilm on the nitroazobenzene-modified glassy carbon electrode (NAB-GC) system. This modified electrode systems and nitroazobenze-nanofilm were prepared by the electrochemical reduction of diazonium salt of NAB at the glassy carbon electrodes (GCE) in nonaqueous media. The IR spectra of the bare glassy carbon electrodes (GCE), the NAB-GC electrode system and the organic NAB film were recorded. The IR data of the bare GC, NAB-GC and NAB film were categorized into five series consisting of FILM1, GC-NAB1, GC1; FILM2, GC-NAB2, GC2; FILM3, GC-NAB3, GC3 and FILM4, GC-NAB4, GC4 respectively. The PPP approach was applied to each group of the data of unmodified and modified electrode systems with nanofilm. The results provided by PPP method show the existence of the NAB film on the modified GC electrode.

Modeling of the lung impedance using a fractional order ladder network with constant phase elements

The self similar branching arrangement of the airways makes the respiratory system an ideal candidate for the application of fractional calculus theory. The fractal geometry is typically characterized by a recurrent structure. This study investigates the identification of a model for the respiratory tree by means of its electrical equivalent based on intrinsic morphology. Measurements were obtained from seven volunteers, in terms of their respiratory impedance by means of its complex representation for frequencies below 5 Hz. A parametric modeling is then applied to the complex valued data points. Since at low-frequency range the inertance is negligible, each airway branch is modeled by using gamma cell resistance and capacitance, the latter having a fractional-order constant phase element (CPE), which is identified from measurements. In addition, the complex impedance is also approximated by means of a model consisting of a lumped series resistance and a lumped fractional-order capacitance. The results reveal that both models characterize the data well, whereas the averaged CPE values are supraunitary and subunitary for the ladder network and the lumped model, respectively.

Determinação do teor de compostos aromáticos policíclicos de óleos minerais isolantes para transformadores

Mestrado em Engenharia Química - Ramo Optimização Energética na Indústria Química

Enantiomeric fraction evaluation of pharmaceuticals in environmentalmatrices by liquid chromatography-tandem mass spectrometry

The interest for environmental fate assessment of chiral pharmaceuticals is increasing and enantioselective analytical methods are mandatory. This study presents an enantioselective analytical method for the quantification of seven pairs of enantiomers of pharmaceuticals and a pair of a metabolite. The selected chiral pharmaceuticals belong to three different therapeutic classes, namely selective serotonin reuptake inhibitors (venlafaxine, fluoxetine and its metabolite norfluoxetine), beta-blockers (alprenolol, bisoprolol, metoprolol, propranolol) and a beta2-adrenergic agonist (salbutamol). The analytical method was based on solid phase extraction followed by liquid chromatography tandem mass spectrometry with a triple quadrupole analyser. Briefly, Oasis® MCX cartridges were used to preconcentrate 250 mL of water samples and the reconstituted extracts were analysed with a Chirobiotic™ V under reversed mode. The effluent of a laboratory-scale aerobic granular sludge sequencing batch reactor (AGS-SBR) was used to validate the method. Linearity (r2 > 0.99), selectivity and sensitivity were achieved in the range of 20–400 ng L−1 for all enantiomers, except for norfluoxetine enantiomers which range covered 30–400 ng L−1. The method detection limits were between 0.65 and 11.5 ng L−1 and the method quantification limits were between 1.98 and 19.7 ng L−1. The identity of all enantiomers was confirmed using two MS/MS transitions and its ion ratios, according to European Commission Decision 2002/657/EC. This method was successfully applied to evaluate effluents of wastewater treatment plants (WWTP) in Portugal. Venlafaxine and fluoxetine were quantified as non-racemic mixtures (enantiomeric fraction ≠ 0.5). The enantioselective validated method was able to monitor chiral pharmaceuticals in WWTP effluents and has potential to assess the enantioselective biodegradation in bioreactors. Further application in environmental matrices as surface and estuarine waters can be exploited.

Siderophore Production by Bacillus megaterium: Effect of Growth Phase and Cultural Conditions

Siderophore production by Bacillus megaterium was detected, in an iron-deficient culture medium, during the exponential growth phase, prior to the sporulation, in the presence of glucose; these results suggested that the onset of siderophore production did not require glucose depletion and was not related with the sporulation. The siderophore production by B. megaterium was affected by the carbon source used. The growth on glycerol promoted the very high siderophore production (1,182 μmol g−1 dry weight biomass); the opposite effect was observed in the presence of mannose (251 μmol g−1 dry weight biomass). The growth in the presence of fructose, galactose, glucose, lactose, maltose or sucrose, originated similar concentrations of siderophore (546–842 μmol g−1 dry weight biomass). Aeration had a positive effect on the production of siderophore. Incubation of B. megaterium under static conditions delayed and reduced the growth and the production of siderophore, compared with the incubation in stirred conditions.

Analysis of Forest Fires by means of Pseudo Phase Plane and Multidimensional Scaling Methods

Forest fires dynamics is often characterized by the absence of a characteristic length-scale, long range correlations in space and time, and long memory, which are features also associated with fractional order systems. In this paper a public domain forest fires catalogue, containing information of events for Portugal, covering the period from 1980 up to 2012, is tackled. The events are modelled as time series of Dirac impulses with amplitude proportional to the burnt area. The time series are viewed as the system output and are interpreted as a manifestation of the system dynamics. In the first phase we use the pseudo phase plane (PPP) technique to describe forest fires dynamics. In the second phase we use multidimensional scaling (MDS) visualization tools. The PPP allows the representation of forest fires dynamics in two-dimensional space, by taking time series representative of the phenomena. The MDS approach generates maps where objects that are perceived to be similar to each other are placed on the map forming clusters. The results are analysed in order to extract relationships among the data and to better understand forest fires behaviour.

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

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

Desenvolvimento de Métodos de Extração de Resíduos de Antimicrobianos e Quantificação em Amostras Alimentares

O leite é um alimento complexo, pela sua composição rico em água, proteínas, lípidos, vitaminas e minerais. Devido ao seu alto valor nutricional é fundamental para a amamentação de crianças e animais em crescimento, pois fornece componentes fundamentais para o desenvolvimento e manutenção da saúde. Os antimicrobianos são amplamente utilizados como uma medida terapêutica no tratamento de infeções bacterianas, profilaxia e como promotores de crescimento (aditivos). A presença de resíduos de antimicrobianos no leite pode representar riscos para a saúde humana, como reações alérgicas em indivíduos hipersensíveis e resistências. Os objetivos deste estudo são o desenvolvimento de novos métodos de limpeza e de pré-concentração para amostras de leite, por meio de extração em fase sólida (SPE), com a finalidade de realizar uma melhor identificação e quantificação de antimicrobiana por Cromatografia Líquida de Alta Performance (HPLC). Todos os métodos desenvolvidos são de fácil execução, com taxas de recuperação dos agentes antimicrobianos viáveis, com uma percentagem de recuperação a partir de 85%. O método cromatográfico utilizado para a deteção e quantificação (HPLC-DAD) têm os limites de deteção (LD) entre 2.43ng / mL e 1.62ng / mL e os limites de quantificação (LQ) entre 7,36 ng / mL e 4.92 ng / mL, o que significa este método vai de encontro às diretrizes estipuladas pela União Europeia para os agentes antimicrobianos estudados. A combinação dos métodos propostos de limpeza e pré-concentração por SPE e multirresíduo por HPLC-DAD permite, por conseguinte, a deteção e quantificação de resíduos de antibióticos no leite, tornando esta uma alternativa importante e útil no processo de controlo de qualidade para a indústria de alimentos e outras área.

Desenvolvimento de métodos de extração de resíduos de antimicrobianos e quantificação em amostras alimentares

O leite é um alimento complexo, pela sua composição rico em água, proteínas, lípidos, vitaminas e minerais. Devido ao seu alto valor nutricional é fundamental para a amamentação de crianças e animais em crescimento, pois fornece componentes fundamentais para o desenvolvimento e manutenção da saúde. Os antimicrobianos são amplamente utilizados como uma medida terapêutica no tratamento de infeções bacterianas, profilaxia e como promotores de crescimento (aditivos). A presença de resíduos de antimicrobianos no leite pode representar riscos para a saúde humana, como reações alérgicas em indivíduos hipersensíveis e resistências. Os objetivos deste estudo são o desenvolvimento de novos métodos de limpeza e de pré- concentração para amostras de leite, por meio de extração em fase sólida (SPE), com a finalidade de realizar uma melhor identificação e quantificação de antimicrobiana por Cromatografia Líquida de Alta Performance (HPLC). Todos os métodos desenvolvidos são de fácil execução, com taxas de recuperação dos agentes antimicrobianos viáveis, com uma percentagem de recuperação a partir de 85%. O método cromatográfico utilizado para a deteção e quantificação (HPLC-DAD) têm os limites de deteção (LD) entre 2.43ng / mL e 1.62ng / mL e os limites de quantificação (LQ) entre 7,36 ng / mL e 4.92 ng / mL, o que significa este método vai de encontro às diretrizes estipuladas pela União Europeia para os agentes antimicrobianos estudados. A combinação dos métodos propostos de limpeza e pré-concentração por SPE e multirresíduo por HPLC-DAD permite, por conseguinte, a deteção e quantificação de resíduos de antibióticos no leite, tornando esta uma alternativa importante e útil no processo de controlo de qualidade para a indústria de alimentos e outras área.

European Union emissions trading scheme impact on the Spanish electricity price during phase II and phase III implementation

The European Union Emissions Trading Scheme (EU ETS) is a cornerstone of the European Union's policy to combat climate change and its key tool for reducing industrial greenhouse gas emissions cost-effectively. The purpose of the present work is to evaluate the influence of CO2 opportunity cost on the Spanish wholesale electricity price. Our sample includes all Phase II of the EU ETS and the first year of Phase III implementation, from January 2008 to December 2013. A vector error correction model (VECM) is applied to estimate not only long-run equilibrium relations, but also short-run interactions between the electricity price and the fuel (natural gas and coal) and carbon prices. The four commodities prices are modeled as joint endogenous variables with air temperature and renewable energy as exogenous variables. We found a long-run relationship (cointegration) between electricity price, carbon price, and fuel prices. By estimating the dynamic pass-through of carbon price into electricity price for different periods of our sample, it is possible to observe the weakening of the link between carbon and electricity prices as a result from the collapse on CO2 prices, therefore compromising the efficacy of the system to reach proposed environmental goals. This conclusion is in line with the need to shape new policies within the framework of the EU ETS that prevent excessive low prices for carbon over extended periods of time.