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.

Development of an FIA system with amperometric detection for determination of bentazone in estuarine waters

On the basis of its electrochemical behaviour a new flow-injection analysis (FIA) method with amperometric detection has been developed for quantification of the herbicide bentazone (BTZ) in estuarine waters. Standard solutions and samples (200 µL) were injected into a water carrier stream and both pH and ionic strength were automatically adjusted inside the manifold. Optimization of critical FIA conditions indicated that the best analytical results were obtained at an oxidation potential of 1.10 V, pH 4.5, and an overall flow-rate of 2.4 mL min–1. Analysis of real samples was performed by means of calibration curves over the concentration range 2.5x10–6 to 5.0x10–5 mol L–1, and results were compared with those obtained by use of an independent method (HPLC). The accuracy of the amperometric determinations was ascertained; errors relative to the comparison method were below 4% and sampling rates were approximately 100 samples h–1. The repeatability of the proposed method was calculated by assessing the relative standard deviation (%) of ten consecutive determinations of one sample; the value obtained was 2.1%.

Two protocols without periodicity for the global and preemptive scheduling problem of multi-mode real-time systems upon multiprocessor Platforms

We consider the problem of scheduling a multi-mode real-time system upon identical multiprocessor platforms. Since it is a multi-mode system, the system can change from one mode to another such that the current task set is replaced with a new task set. Ensuring that deadlines are met requires not only that a schedulability test is performed on tasks in each mode but also that (i) a protocol for transitioning from one mode to another is specified and (ii) a schedulability test for each transition is performed. We propose two protocols which ensure that all the expected requirements are met during every transition between every pair of operating modes of the system. Moreover, we prove the correctness of our proposed algorithms by extending the theory about the makespan determination problem.

Disposable immunosensor using a simple method for oriented antibody immobilization for label-free real-time detection of an oxidative stress biomarker implicated in cancer diseases

This work proposes a novel approach for a suitable orientation of antibodies (Ab) on an immunosensing platform, applied here to the determination of 8-hydroxy-2′-deoxyguanosine (8OHdG), a biomarker of oxidative stress that has been associated to chronic diseases, such as cancer. The anti-8OHdG was bound to an amine modified gold support through its Fc region after activation of its carboxylic functions. Non-oriented approaches of Ab binding to the platform were tested in parallel, in order to show that the presented methodology favored Ab/Ag affinity and immunodetection of the antigen. The immunosensor design was evaluated by quartz-crystal microbalance with dissipation, atomic force microscopy, electrochemical impedance spectroscopy (EIS) and square-wave voltammetry. EIS was also a suitable technique to follow the analytical behavior of the device against 8OHdG. The affinity binding between 8OHdG and the antibody immobilized in the gold modified platform increased the charge transfer resistance across the electrochemical set-up. The observed behavior was linear from 0.02 to 7.0 ng/mL of 8OHdG concentrations. The interference from glucose, urea and creatinine was found negligible. An attempt of application to synthetic samples was also successfully conducted. Overall, the presented approach enabled the production of suitably oriented Abs over a gold platform by means of a much simpler process than other oriented-Ab binding approaches described in the literature, as far as we know, and was successful in terms of analytical features and sample application.

Disposable immunosensor with simple antibody orientation for label-free real-time detection of a cancer biomarker

This work proposes a novel approach for a suitable orientation of antibodies (Ab) on an immunosensing platform, applied here to the determination of 8-hydroxy-2’-deoxyguanosine (8OHdG), a biomarker of oxidative stress that has been associated to chronic diseases, such as cancer. The Anti-8OHdG was bound to an amine modified gold support through its Fc region after activation of its carboxylic functions. Non-oriented approaches of Ab binding to the platform were tested in parallel, in order to show that the presented proposal favored Ab/Ag affinity. The immunosensor design was evaluated by Quartz-Crystal microbalance with Dissipation, Atomic Force Microscopy, Electrochemical Impedance Spectroscopy (EIS) and Square-Wave Voltammetry. EIS was also a suitable technique to follow the analytical behavior of the device against 8OHdG. The affinity binding between 8OHdG and the antibody immobilized in the gold modified platform increased the charged transfer resistance across the electrochemical sep-up. The observed behavior was linear from 0.02 to 7.0 ng/mL of 8OHdG concentrations. The interference from Glucose, Urea and Creatinine was found negligible. An attempt of application to synthetic samples was also successfully conducted. Overall, the presented approach enabled the production of suitably oriented Abs over a gold platform by means of a much simpler process than other oriented-Ab binding approaches described in the literature, as far as we know, and was successful in terms of analytical features and sample application.

Sulfadiazine-selective determination in aquaculture environment: Selective potentiometric transduction by neutral or charged ionophores

Solid-contact sensors for the selective screening of sulfadiazine (SDZ) in aquaculture waters are reported. Sensor surfaces were made from PVC membranes doped with tetraphenylporphyrin-manganese(III) chloride, α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin ionophores that were dispersed in plasticizer. Some membranes also presented a positive or a negatively charged additive. Phorphyrin-based sensors relied on a charged carrier mechanism. They exhibited a near-Nernstian response with slopes of 52 mV decade−1 and detection limits of 3.91 × 10−5 mol L−1. The addition of cationic lipophilic compounds to the membrane originated Nernstian behaviours, with slopes ranging 59.7–62.0 mV decade−1 and wider linear ranges. Cyclodextrin-based sensors acted as neutral carriers. In general, sensors with positively charged additives showed an improved potentiometric performance when compared to those without additive. Some SDZ selective membranes displayed higher slopes and extended linear concentration ranges with an increasing amount of additive (always <100% ionophore). The sensors were independent from the pH of test solutions within 2–7. The sensors displayed fast response, always <15 s. In general, a good discriminating ability was found in real sample environment. The sensors were successfully applied to the fast screening of SDZ in real waters samples from aquaculture fish farms. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in locus measurements of sulfadiazine or parent-drugs.

Determination of electricity consumers’ load profiles via weighted evidence accumulation clustering using subsampling

With the electricity market liberalization, the distribution and retail companies are looking for better market strategies based on adequate information upon the consumption patterns of its electricity consumers. A fair insight on the consumers’ behavior will permit the definition of specific contract aspects based on the different consumption patterns. In order to form the different consumers’ classes, and find a set of representative consumption patterns we use electricity consumption data from a utility client’s database and two approaches: Two-step clustering algorithm and the WEACS approach based on evidence accumulation (EAC) for combining partitions in a clustering ensemble. While EAC uses a voting mechanism to produce a co-association matrix based on the pairwise associations obtained from N partitions and where each partition has equal weight in the combination process, the WEACS approach uses subsampling and weights differently the partitions. As a complementary step to the WEACS approach, we combine the partitions obtained in the WEACS approach with the ALL clustering ensemble construction method and we use the Ward Link algorithm to obtain the final data partition. The characterization of the obtained consumers’ clusters was performed using the C5.0 classification algorithm. Experiment results showed that the WEACS approach leads to better results than many other clustering approaches.

A real time pricing approach to deal with excessive wind power situations

The introduction of wind power generation in several countries around the world, including in European countries, where energy policy directives have encouraged the use of renewables, led to several changes in market and power systems operation. The intensive integration of these sources has led to situations in which the demand is lower than the available renewable resources. In these situations a part of the available generation is wasted if not used for storage or to supply additional demand. This paper proposes a real time demand response methodology based on changing the electricity price for the consumers expecting an increase in the demand in the periods in which that demand is lower than the available renewable generation. The consumers response to the changes in electricity price is characterized by their price elasticity of demand considered distinct for each consumer type. The proposed methodology is applied to the Portuguese power system, in the context of the Iberian electricity market (MIBEL). The renewable-based producers are considered as special producers, with special tariffs, and so it is important to use the energy available as it will be paid anyway. In this context, consumers are entities actively participating in the operation of the market.

Real-time energy resources scheduling considering intensive wind penetration

The use of distributed energy resources, based on natural intermittent power sources, like wind generation, in power systems imposes the development of new adequate operation management and control methodologies. A short-term Energy Resource Management (ERM) methodology performed in two phases is proposed in this paper. The first one addresses the day-ahead ERM scheduling and the second one deals with the five-minute ahead ERM scheduling. The ERM scheduling is a complex optimization problem due to the high quantity of variables and constraints. In this paper the main goal is to minimize the operation costs from the point of view of a virtual power player that manages the network and the existing resources. The optimization problem is solved by a deterministic mixedinteger non-linear programming approach. A case study considering a distribution network with 33 bus, 66 distributed generation, 32 loads with demand response contracts and 7 storage units and 1000 electric vehicles has been implemented in a simulator developed in the field of the presented work, in order to validate the proposed short-term ERM methodology considering the dynamic power system behavior.

Energy resource scheduling in a real distribution network managed by several virtual power players

Smart Grids (SGs) appeared as the new paradigm for power system management and operation, being designed to integrate large amounts of distributed energy resources. This new paradigm requires a more efficient Energy Resource Management (ERM) and, simultaneously, makes this a more complex problem, due to the intensive use of distributed energy resources (DER), such as distributed generation, active consumers with demand response contracts, and storage units. This paper presents a methodology to address the energy resource scheduling, considering an intensive use of distributed generation and demand response contracts. A case study of a 30 kV real distribution network, including a substation with 6 feeders and 937 buses, is used to demonstrate the effectiveness of the proposed methodology. This network is managed by six virtual power players (VPP) with capability to manage the DER and the distribution network.

Adaptive tool for automatic data collection of real electricity markets

The study of electricity markets operation has been gaining an increasing importance in last years, as result of the new challenges that the electricity markets restructuring produced. This restructuring increased the competitiveness of the market, but with it its complexity. The growing complexity and unpredictability of the market’s evolution consequently increases the decision making difficulty. Therefore, the intervenient entities are forced to rethink their behaviour and market strategies. Currently, lots of information concerning electricity markets is available. These data, concerning innumerous regards of electricity markets operation, is accessible free of charge, and it is essential for understanding and suitably modelling electricity markets. This paper proposes a tool which is able to handle, store and dynamically update data. The development of the proposed tool is expected to be of great importance to improve the comprehension of electricity markets and the interactions among the involved entities.

Real-time energy resources scheduling considering short-term and very short-term wind forecast

This paper proposes an energy resources management methodology based on three distinct time horizons: day-ahead scheduling, hour-ahead scheduling, and real-time scheduling. In each scheduling process it is necessary the update of generation and consumption operation and of the storage and electric vehicles storage status. Besides the new operation condition, it is important more accurate forecast values of wind generation and of consumption using results of in short-term and very short-term methods. A case study considering a distribution network with intensive use of distributed generation and electric vehicles is presented.

Virtual power players dealing with excessive wind power situations using real time pricing

The increasing importance given by environmental policies to the dissemination and use of wind power has led to its fast and large integration in power systems. In most cases, this integration has been done in an intensive way, causing several impacts and challenges in current and future power systems operation and planning. One of these challenges is dealing with the system conditions in which the available wind power is higher than the system demand. This is one of the possible applications of demand response, which is a very promising resource in the context of competitive environments that integrates even more amounts of distributed energy resources, as well as new players. The methodology proposed aims the maximization of the social welfare in a smart grid operated by a virtual power player that manages the available energy resources. When facing excessive wind power generation availability, real time pricing is applied in order to induce the increase of consumption so that wind curtailment is minimized. The proposed method is especially useful when actual and day-ahead wind forecast differ significantly. The proposed method has been computationally implemented in GAMS optimization tool and its application is illustrated in this paper using a real 937-bus distribution network with 20310 consumers and 548 distributed generators, some of them with must take contracts.

Modelling real solar cell using PSCAD/MATLAB

This paper presents the development of a solar photovoltaic (PV) model based on PSCAD/EMTDC - Power System Computer Aided Design – including a mathematical model study. An additional algorithm has been implemented in MATLAB software in order to calculate several parameters required by the PSCAD developed model. All the simulation study has been performed in PSCAD/MATLAB software simulation tool. A real data base concerning irradiance, cell temperature and PV power generation was used in order to support the evaluation of the implemented PV model.

LMP triggered real time demand response events

Recent changes in power systems mainly due to the substantial increase of distributed generation and to the operation in competitive environments has created new challenges to operation and planning. In this context, Virtual Power Players (VPP) can aggregate a diversity of players, namely generators and consumers, and a diversity of energy resources, including electricity generation based on several technologies, storage and demand response. Demand response market implementation has been done in recent years. Several implementation models have been considered. An important characteristic of a demand response program is the trigger criterion. A program for which the event trigger depends on the Locational Marginal Price (LMP) used by the New England Independent System operator (ISO-NE) inspired the present paper. This paper proposes a methodology to support VPP demand response programs management. The proposed method has been computationally implemented and its application is illustrated using a 32 bus network with intensive use of distributed generation. Results concerning the evaluation of the impact of using demand response events are also presented.