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.

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.

Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

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.

Tensile behaviour of a structural adhesive at high temperatures by the extended finite element method

Component joining is typically performed by welding, fastening, or adhesive-bonding. For bonded aerospace applications, adhesives must withstand high-temperatures (200°C or above, depending on the application), which implies their mechanical characterization under identical conditions. The extended finite element method (XFEM) is an enhancement of the finite element method (FEM) that can be used for the strength prediction of bonded structures. This work proposes and validates damage laws for a thin layer of an epoxy adhesive at room temperature (RT), 100, 150, and 200°C using the XFEM. The fracture toughness (G Ic ) and maximum load ( ); in pure tensile loading were defined by testing double-cantilever beam (DCB) and bulk tensile specimens, respectively, which permitted building the damage laws for each temperature. The bulk test results revealed that decreased gradually with the temperature. On the other hand, the value of G Ic of the adhesive, extracted from the DCB data, was shown to be relatively insensitive to temperature up to the glass transition temperature (T g ), while above T g (at 200°C) a great reduction took place. The output of the DCB numerical simulations for the various temperatures showed a good agreement with the experimental results, which validated the obtained data for strength prediction of bonded joints in tension. By the obtained results, the XFEM proved to be an alternative for the accurate strength prediction of bonded structures.

Concurrent tabling

In the past few years Tabling has emerged as a powerful logic programming model. The integration of concurrent features into the implementation of Tabling systems is demanded by need to use recently developed tabling applications within distributed systems, where a process has to respond concurrently to several requests. The support for sharing of tables among the concurrent threads of a Tabling process is a desirable feature, to allow one of Tabling’s virtues, the re-use of computations by other threads and to allow efficient usage of available memory. However, the incremental completion of tables which are evaluated concurrently is not a trivial problem. In this dissertation we describe the integration of concurrency mechanisms, by the way of multi-threading, in a state of the art Tabling and Prolog system, XSB. We begin by reviewing the main concepts for a formal description of tabled computations, called SLG resolution and for the implementation of Tabling under the SLG-WAM, the abstract machine supported by XSB. We describe the different scheduling strategies provided by XSB and introduce some new properties of local scheduling, a scheduling strategy for SLG resolution. We proceed to describe our implementation work by describing the process of integrating multi-threading in a Prolog system supporting Tabling, without addressing the problem of shared tables. We describe the trade-offs and implementation decisions involved. We then describe an optimistic algorithm for the concurrent sharing of completed tables, Shared Completed Tables, which allows the sharing of tables without incurring in deadlocks, under local scheduling. This method relies on the execution properties of local scheduling and includes full support for negation. We provide a theoretical framework and discuss the implementation’s correctness and complexity. After that, we describe amethod for the sharing of tables among threads that allows parallelism in the computation of inter-dependent subgoals, which we name Concurrent Completion. We informally argue for the correctness of Concurrent Completion. We give detailed performance measurements of the multi-threaded XSB systems over a variety of machines and operating systems, for both the Shared Completed Tables and the Concurrent Completion implementations. We focus our measurements inthe overhead over the sequential engine and the scalability of the system. We finish with a comparison of XSB with other multi-threaded Prolog systems and we compare our approach to concurrent tabling with parallel and distributed methods for the evaluation of tabling. Finally, we identify future research directions.

Real-time scheduling of parallel tasks in the Linux Kernel

This paper proposes a global multiprocessor scheduling algorithm for the Linux kernel that combines the global EDF scheduler with a priority-aware work-stealing load balancing scheme, enabling parallel real-time tasks to be executed on more than one processor at a given time instant. We state that some priority inversion may actually be acceptable, provided it helps reduce contention, communication, synchronisation and coordination between parallel threads, while still guaranteeing the expected system’s predictability. Experimental results demonstrate the low scheduling overhead of the proposed approach comparatively to an existing real-time deadline-oriented scheduling class for the Linux kernel.

Supporting real-time parallel task models with work-stealing

Dynamic parallel scheduling using work-stealing has gained popularity in academia and industry for its good performance, ease of implementation and theoretical bounds on space and time. Cores treat their own double-ended queues (deques) as a stack, pushing and popping threads from the bottom, but treat the deque of another randomly selected busy core as a queue, stealing threads only from the top, whenever they are idle. However, this standard approach cannot be directly applied to real-time systems, where the importance of parallelising tasks is increasing due to the limitations of multiprocessor scheduling theory regarding parallelism. Using one deque per core is obviously a source of priority inversion since high priority tasks may eventually be enqueued after lower priority tasks, possibly leading to deadline misses as in this case the lower priority tasks are the candidates when a stealing operation occurs. Our proposal is to replace the single non-priority deque of work-stealing with ordered per-processor priority deques of ready threads. The scheduling algorithm starts with a single deque per-core, but unlike traditional work-stealing, the total number of deques in the system may now exceed the number of processors. Instead of stealing randomly, cores steal from the highest priority deque.

Parallel real-time support for distributed adaptive embedded applications

Real-time embedded applications require to process large amounts of data within small time windows. Parallelize and distribute workloads adaptively is suitable solution for computational demanding applications. The purpose of the Parallel Real-Time Framework for distributed adaptive embedded systems is to guarantee local and distributed processing of real-time applications. This work identifies some promising research directions for parallel/distributed real-time embedded applications.

A framework for the development of parallel and distributed real-time embedded systems

Embedded real-time applications increasingly present high computation requirements, which need to be completed within specific deadlines, but that present highly variable patterns, depending on the set of data available in a determined instant. The current trend to provide parallel processing in the embedded domain allows providing higher processing power; however, it does not address the variability in the processing pattern. Dimensioning each device for its worst-case scenario implies lower average utilization, and increased available, but unusable, processing in the overall system. A solution for this problem is to extend the parallel execution of the applications, allowing networked nodes to distribute the workload, on peak situations, to neighbour nodes. In this context, this report proposes a framework to develop parallel and distributed real-time embedded applications, transparently using OpenMP and Message Passing Interface (MPI), within a programming model based on OpenMP. The technical report also devises an integrated timing model, which enables the structured reasoning on the timing behaviour of these hybrid architectures.

Dynamic global scheduling of parallel real-time tasks

High-level parallel languages offer a simple way for application programmers to specify parallelism in a form that easily scales with problem size, leaving the scheduling of the tasks onto processors to be performed at runtime. Therefore, if the underlying system cannot efficiently execute those applications on the available cores, the benefits will be lost. In this paper, we consider how to schedule highly heterogenous parallel applications that require real-time performance guarantees on multicore processors. The paper proposes a novel scheduling approach that combines the global Earliest Deadline First (EDF) scheduler with a priority-aware work-stealing load balancing scheme, which enables parallel realtime tasks to be executed on more than one processor at a given time instant. Experimental results demonstrate the better scalability and lower scheduling overhead of the proposed approach comparatively to an existing real-time deadline-oriented scheduling class for the Linux kernel.

Server-based scheduling of parallel real-time tasks

Multicore platforms have transformed parallelism into a main concern. Parallel programming models are being put forward to provide a better approach for application programmers to expose the opportunities for parallelism by pointing out potentially parallel regions within tasks, leaving the actual and dynamic scheduling of these regions onto processors to be performed at runtime, exploiting the maximum amount of parallelism. It is in this context that this paper proposes a scheduling approach that combines the constant-bandwidth server abstraction with a priority-aware work-stealing load balancing scheme which, while ensuring isolation among tasks, enables parallel tasks to be executed on more than one processor at a given time instant.

Software transactional memory as a building block for parallel embedded realtime systems

The recent trends of chip architectures with higher number of heterogeneous cores, and non-uniform memory/non-coherent caches, brings renewed attention to the use of Software Transactional Memory (STM) as a fundamental building block for developing parallel applications. Nevertheless, although STM promises to ease concurrent and parallel software development, it relies on the possibility of aborting conflicting transactions to maintain data consistency, which impacts on the responsiveness and timing guarantees required by embedded real-time systems. In these systems, contention delays must be (efficiently) limited so that the response times of tasks executing transactions are upper-bounded and task sets can be feasibly scheduled. In this paper we assess the use of STM in the development of embedded real-time software, defending that the amount of contention can be reduced if read-only transactions access recent consistent data snapshots, progressing in a wait-free manner. We show how the required number of versions of a shared object can be calculated for a set of tasks. We also outline an algorithm to manage conflicts between update transactions that prevents starvation.

Analysis of temperature time-series: embedding dynamics into the MDS method

Global warming and the associated climate changes are being the subject of intensive research due to their major impact on social, economic and health aspects of the human life. Surface temperature time-series characterise Earth as a slow dynamics spatiotemporal system, evidencing long memory behaviour, typical of fractional order systems. Such phenomena are difficult to model and analyse, demanding for alternative approaches. This paper studies the complex correlations between global temperature time-series using the Multidimensional scaling (MDS) approach. MDS provides a graphical representation of the pattern of climatic similarities between regions around the globe. The similarities are quantified through two mathematical indices that correlate the monthly average temperatures observed in meteorological stations, over a given period of time. Furthermore, time dynamics is analysed by performing the MDS analysis over slices sampling the time series. MDS generates maps describing the stations’ locus in the perspective that, if they are perceived to be similar to each other, then they are placed on the map forming clusters. We show that MDS provides an intuitive and useful visual representation of the complex relationships that are present among temperature time-series, which are not perceived on traditional geographic maps. Moreover, MDS avoids sensitivity to the irregular distribution density of the meteorological stations.

A parallel programming model for ada

Over the last three decades, computer architects have been able to achieve an increase in performance for single processors by, e.g., increasing clock speed, introducing cache memories and using instruction level parallelism. However, because of power consumption and heat dissipation constraints, this trend is going to cease. In recent times, hardware engineers have instead moved to new chip architectures with multiple processor cores on a single chip. With multi-core processors, applications can complete more total work than with one core alone. To take advantage of multi-core processors, parallel programming models are proposed as promising solutions for more effectively using multi-core processors. This paper discusses some of the existent models and frameworks for parallel programming, leading to outline a draft parallel programming model for Ada.