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.

Analysis of pesticide residues in strawberries and soils by GC-MS/MS, LC-MS/MS and two-dimensional GC-timeof- flight MS comparing organic and integrated pest management farming

This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 μg kg−1 for fluazifop-pbutyl to 50 μg kg−1 for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits.

DITRANS - a multi-agent system for integrated diagnosis of power transformers

This paper describes the development and the implementation of a multi-agent system for integrated diagnosis of power transformers. The system is divided in layers which contain a number of agents performing different functions. The social ability and cooperation between the agents lead to the final diagnosis and to other relevant conclusions through integrating various monitoring technologies, diagnostic methods and data sources, such as the dissolved gas analysis.

An integrated system to support electricity tariff contract definition

This paper presents an integrated system that helps both retail companies and electricity consumers on the definition of the best retail contracts and tariffs. This integrated system is composed by a Decision Support System (DSS) based on a Consumer Characterization Framework (CCF). The CCF is based on data mining techniques, applied to obtain useful knowledge about electricity consumers from large amounts of consumption data. This knowledge is acquired following an innovative and systematic approach able to identify different consumers’ classes, represented by a load profile, and its characterization using decision trees. The framework generates inputs to use in the knowledge base and in the database of the DSS. The rule sets derived from the decision trees are integrated in the knowledge base of the DSS. The load profiles together with the information about contracts and electricity prices form the database of the DSS. This DSS is able to perform the classification of different consumers, present its load profile and test different electricity tariffs and contracts. The final outputs of the DSS are a comparative economic analysis between different contracts and advice about the most economic contract to each consumer class. The presentation of the DSS is completed with an application example using a real data base of consumers from the Portuguese distribution company.

Optimization of QuEChERS method for the analysis of organochlorine pesticides in soils with diverse organic matter

A QuEChERS method has been developed for the determination of 14 organochlorine pesticides in 14 soils from different Portuguese regions with wide range composition. The extracts were analysed by GC-ECD (where GC-ECD is gas chromatography-electron-capture detector) and confirmed by GC-MS/MS (where MS/MS is tandem mass spectrometry). The organic matter content is a key factor in the process efficiency. An optimization was carried out according to soils organic carbon level, divided in two groups: HS (organic carbon>2.3%) and LS (organic carbon<2.3%). Themethod was validated through linearity, recovery, precision and accuracy studies. The quantification was carried out using a matrixmatched calibration to minimize the existence of the matrix effect. Acceptable recoveries were obtained (70–120%) with a relative standard deviation of ≤16% for the three levels of contamination. The ranges of the limits of detection and of the limits of quantification in soils HS were from 3.42 to 23.77 μg kg−1 and from 11.41 to 79.23 μg kg−1, respectively. For LS soils, the limits of detection ranged from 6.11 to 14.78 μg kg−1 and the limits of quantification from 20.37 to 49.27 μg kg−1. In the 14 collected soil samples only one showed a residue of dieldrin (45.36 μg kg−1) above the limit of quantification. This methodology combines the advantages of QuEChERS, GC-ECD detection and GC-MS/MS confirmation producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.

Organochlorine pesticide residues in strawberries from integrated pest management and organic farming

A rapid, specific, and sensitive method based on theQuick Easy Cheap Effective Rugged and Safe (QuEChERS) method and a cleanup using dispersive solid-phase extraction with MgSO4, PSA, and C18 sorbents has been developed for the routine analysis of 14 pesticides in strawberries. The analyses were performed by three different analytical methodologies: gas chromatography (GC) with electron capture detection (ECD), mass spectrometry (MS), and tandem mass spectrometry (MS/MS). The recoveries for all the pesticides studied were from 46 to 128%, with relative standard deviation of <15% in the concentration range of 0.005-0.250 mg/kg. The limit of detection (LOD) for all compoundsmetmaximumresidue limits (MRL) accepted in Portugal for organochlorine pesticides (OCP). A survey study of strawberries produced in Portugal in the years 2009-2010 obtained from organic farming (OF) and integrated pest management (IPM) was developed. Lindane and β-endosulfan were detected above the MRL in OF and IPM. Other OCP (aldrin, o,p0-DDT and their metabolites, and methoxychlor) were found below the MRL. The OCP residues detected decreased from 2009 to 2010. The QuEChERS method was successfully applied to the analysis of strawberry samples.

Strategic bidding in electricity markets: an agent-based simulator with game theory for scenario analysis

Electricity markets are complex environments, involving a large number of different entities, with specific characteristics and objectives, making their decisions and interacting in a dynamic scene. Game-theory has been widely used to support decisions in competitive environments; therefore its application in electricity markets can prove to be a high potential tool. This paper proposes a new scenario analysis algorithm, which includes the application of game-theory, to evaluate and preview different scenarios and provide players with the ability to strategically react in order to exhibit the behavior that better fits their objectives. This model includes forecasts of competitor players’ actions, to build models of their behavior, in order to define the most probable expected scenarios. Once the scenarios are defined, game theory is applied to support the choice of the action to be performed. Our use of game theory is intended for supporting one specific agent and not for achieving the equilibrium in the market. MASCEM (Multi-Agent System for Competitive Electricity Markets) is a multi-agent electricity market simulator that models market players and simulates their operation in the market. The scenario analysis algorithm has been tested within MASCEM and our experimental findings with a case study based on real data from the Iberian Electricity Market are presented and discussed.

Integrating inaccessibility in response time analysis of CAN networks

Controller Area Network (CAN) is a fieldbus network suitable for small-scale Distributed Computer Controlled Systems, being appropriate for transferring short real-time messages. Nevertheless, it must be understood that the continuity of service is not fully guaranteed, since it may be disturbed by temporary periods of network inaccessibility [1]. In this paper, such temporary periods of network inaccessibility are integrated in the response time analysis of CAN networks. The achieved results emphasise that, in the presence of temporary periods of network inaccessibility, a CAN network is not able to provide different integrity levels to the supported applications, since errors in low priority messages interfere with the response time of higher priority message streams.

Shannon entropy analysis of the genome code

This paper studies the chromosome information of twenty five species, namely, mammals, fishes, birds, insects, nematodes, fungus, and one plant. A quantifying scheme inspired in the state space representation of dynamical systems is formulated. Based on this algorithm, the information of each chromosome is converted into a bidimensional distribution. The plots are then analyzed and characterized by means of Shannon entropy. The large volume of information is integrated by averaging the lengths and entropy quantities of each species. The results can be easily visualized revealing quantitative global genomic information.

Exact admission-control for integrated aperiodic and periodic tasks

Admission controllers are used to prevent overload in systems with dynamically arriving tasks. Typically, these admission controllers are based on suÆcient (but not necessary) capacity bounds in order to maintain a low computational complexity. In this paper we present how exact admission-control for aperiodic tasks can be eÆciently obtained. Our rst result is an admission controller for purely aperiodic task sets where the test has the same runtime complexity as utilization-based tests. Our second result is an extension of the previous controller for a baseload of periodic tasks. The runtime complexity of this test is lower than for any known exact admission-controller. In addition to presenting our main algorithm and evaluating its performance, we also discuss some general issues concerning admission controllers and their implementation.

CardioML: integrating personal cardiac information for ubiquous diagnosis and analysis

The latest medical diagnosis devices enable the performance of e-diagnosis making the access to these services easier, faster and available in remote areas. However this imposes new communications and data interchange challenges. In this paper a new XML based format for storing cardiac signals and related information is presented. The proposed structure encompasses data acquisition devices, patient information, data description, pathological diagnosis and waveform annotation. When compared with similar purpose formats several advantages arise. Besides the full integrated data model it may also be noted the available geographical references for e-diagnosis, the multi stream data description, the ability to handle several simultaneous devices, the possibility of independent waveform annotation and a HL7 compliant structure for common contents. These features represent an enhanced integration with existent systems and an improved flexibility for cardiac data representation.

Integrated biomarker responses of an estuarine invertebrate to high abiotic stress and decreased metal contamination

An integrated chemical-biological effects monitoring was performed in 2010 and 2012 in two NW Iberian estuaries under different anthropogenic pressure. One is low impacted and the other is contaminated by metals. The aim was to verify the usefulness of a multibiomarker approach, using Carcinus maenas as bioindicator species, to reflect diminishing environmental contamination and improved health status under abiotic variation. Sampling sites were assessed for metal levels in sediments and C. maenas, water abiotic factors and biomarkers (neurotoxicity, energy metabolism, biotransformation, anti-oxidant defences, oxidative damage). High inter-annual and seasonal abiotic variation was observed. Metal levels in sediments and crab tissues were markedly higher in 2010 than in 2012 in the contaminated estuary. Biomarkers indicated differences between the study sites and seasons and an improvement of effects measured in C. maenas from the polluted estuary in 2012. Integrated Biomarker Response (IBR) index depicted sites with higher stress levels whereas Principal Component Analysis (PCA) showed associations between biomarker responses and environmental variables. The multibiomarker approach and integrated assessments proved to be useful to the early diagnosis of remediation measures in impacted sites.

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.

Integrated Management of Cloud Computing Resources

Lunacloud is a cloud service provider with offices in Portugal, Spain, France and UK that focus on delivering reliable, elastic and low cost cloud Infrastructure as a Service (IaaS) solutions. The company currently relies on a proprietary IaaS platform - the Parallels Automation for Cloud Infrastructure (PACI) - and wishes to expand and integrate other IaaS solutions seamlessly, namely open source solutions. This is the challenge addressed in this thesis. This proposal, which was fostered by Eurocloud Portugal Association, contributes to the promotion of interoperability and standardisation in Cloud Computing. The goal is to investigate, propose and develop an interoperable open source solution with standard interfaces for the integrated management of IaaS Cloud Computing resources based on new as well as existing abstraction libraries or frameworks. The solution should provide bothWeb and application programming interfaces. The research conducted consisted of two surveys covering existing open source IaaS platforms and PACI (features and API) and open source IaaS abstraction solutions. The first study was focussed on the characteristics of most popular open source IaaS platforms, namely OpenNebula, OpenStack, CloudStack and Eucalyptus, as well as PACI and included a thorough inventory of the provided Application Programming Interfaces (API), i.e., offered operations, followed by a comparison of these platforms in order to establish their similarities and dissimilarities. The second study on existing open source interoperability solutions included the analysis of existing abstraction libraries and frameworks and their comparison. The approach proposed and adopted, which was supported on the conclusions of the carried surveys, reuses an existing open source abstraction solution – the Apache Deltacloud framework. Deltacloud relies on the development of software driver modules to interface with different IaaS platforms, officially provides and supports drivers to sixteen IaaS platform, including OpenNebula and OpenStack, and allows the development of new provider drivers. The latter functionality was used to develop a new Deltacloud driver for PACI. Furthermore, Deltacloud provides a Web dashboard and REpresentational State Transfer (REST) API interfaces. To evaluate the adopted solution, a test bed integrating OpenNebula, Open- Stack and PACI nodes was assembled and deployed. The tests conducted involved time elapsed and data payload measurements via the Deltacloud framework as well as via the pre-existing IaaS platform API. The Deltacloud framework behaved as expected, i.e., introduced additional delays, but no substantial overheads. Both the Web and the REST interfaces were tested and showed identical measurements. The developed interoperable solution for the seamless integration and provision of IaaS resources from PACI, OpenNebula and OpenStack IaaS platforms fulfils the specified requirements, i.e., provides Lunacloud with the ability to expand the range of adopted IaaS platforms and offers a Web dashboard and REST API for the integrated management. The contributions of this work include the surveys and comparisons made, the selection of the abstraction framework and, last, but not the least, the PACI driver developed.