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.

Electrochemical immunosensor for multiplexed detection of food-borne pathogens using nanocrystal bioconjugates and MWCNT screen-printed electrode

Bacterial food poisoning is an ever-present threat that can be prevented with proper care and handling of food products. A disposable electrochemical immunosensor for the simultaneous measurements of common food pathogenic bacteria namely Escherichia coli O157:H7 (E. coli), campylobacter and salmonella were developed. The immunosensor was fabricated by immobilizing the mixture of anti-E. coli, anticampylobacter and anti-salmonella antibodies with a ratio of 1:1:1 on the surface of the multiwall carbon nanotube-polyallylamine modified screen printed electrode (MWCNT-PAH/SPE). Bacteria suspension became attached to the immobilized antibodies when the immunosensor was incubated in liquid samples. The sandwich immunoassay was performed with three antibodies conjugated with specific nanocrystal ( -E. coli-CdS, -campylobacter-PbS and -salmonella-CuS) which has releasable metal ions for electrochemical measurements. The square wave anodic stripping voltammetry (SWASV) was employed to measure released metal ions from bound antibody nanocrystal conjugates. The calibration curves for three selected bacteria were found in the range of 1 × 103 – 5 × 105 cells mL−1 with the limit of detection (LOD) 400 cells mL−1 for salmonella, 400 cells mL−1 for campylobacter and 800 cells mL−1 for E. coli. The precision and sensitivity of this method show the feasibility of multiplexed determination of bacteria in milk samples.

A multiresidue method for the analysis of carbamate and urea pesticides from soils by microwave-assisted extraction and liquid chromatography with photodiode array detection

A multiresidue approach using microwave-assisted extraction and liquid chromatography with photodiode array detection was investigated for the determination of butylate, carbaryl, carbofuran, chlorpropham, ethiofencarb, linuron,metobromuron, and monolinuron in soils. The critical parameters of the developed methodology were studied. Method validation was performed by analyzing freshly and aged spiked soil samples. The recoveries and relative standard deviations reached using the optimized conditions were between 77.0 ± 0.46% and 120 ± 2.9% except for ethiofencarb (46.4 ± 4.4% to 105 ± 1.6%) and butylate (22.1 ± 7.6% to 49.2 ± 11%). Soil samples from five locations of Portugal were analysed.

Determination of carbamate and urea pesticide residues in fresh vegetables using microwave-assisted extraction and liquid chromatography

An analytical multiresidue method for the simultaneous determination of seven pesticides in fresh vegetable samples, namely, courgette (Cucurbita pepo), cucumber (Cucumis sativus), lettuce (Lactuca sativa, Romaine and Iceberg varieties) and peppers (Capsicum sp.) is described. The procedure, based on microwave-assisted extraction (MAE) and analysis by liquid chromatography– photodiode array (LC–PDA) detection was applied to four carbamates (carbofuran, carbaryl, chlorpropham and EPTC) and three urea pesticides (monolinuron, metobromuron and linuron). Extraction solvent and the addition of anhydrous sodium sulphate to fresh vegetable homogenate before MAE were the parameters optimised for each commodity. Recovery studies were performed using spiked samples in the range 250–403 µgkg- 1 in each pesticide. The pesticide residues were extracted using 20mL acetonitrile at 60 ºC, for 10 min. Acceptable recoveries and RSDs were attained (overall average recovery of 77.2% and RSDs are lower than 11%). Detection limits ranged between 5.8 µgkg- 1 for carbaryl to 12.3 µgkg- 1 for carbofuran. The analytical protocol was applied for quality control of 41 fresh vegetable samples bought in Oporto Metropolitan Area (North Portugal). None of the samples contained any detectable amounts of the studied compounds.

Screening of carbamates and ureas in fresh and processed tomato samples using micowave-assisted extraction and liquid chromatography

An analytical method, based on microwave-assisted extraction and liquid chromatography with diode array detection, for the determination of six carbamate and three urea pesticides in fresh and processed tomato samples is described. Significant parameters affecting extraction efficiency were optimized. Under optimum microwave-assisted extraction conditions (20mL acetonitrile, for 10 minutes, at 60º C), pesticides were extracted with recoveries ranging from 57.6 to 102% (RSDs<7%). Quantification limits between 6.5 and 39.6 µg=kg were obtained. A total number of 28 different fresh tomato samples and 6 processed tomato products were analysed. Confirmation of suspicious samples was performed by LC-MS.

Evaluation of formaldehyde in foundry waste sands using liquid chromatography

The industrial manufacturing of metallic objects results in a high level of foundry waste sands that may contain toxic compounds such as formaldehyde. The formaldehyde content of foundry waste sands was evaluated by liquid chromatography. Samples were collected during various steps of the industrial processes. Results showed that the phenolic alkaline process generated waste sands with higher formaldehyde content than the furanic process; the highest value was 7.6×10-3% (w/w). In this work, formaldehyde content decreased with time in all of the samples studied, revealing that most formaldehyde was released to the occupational environment.

Determination of free formaldehyde in foundry resins as its 2,4-dinitrophenylhydrazone by liquid chromatography

Formaldehyde is a toxic component that is present in foundry resins. Its quantification is important to the characterisation of the resin (kind and degradation) as well as for the evaluation of free contaminants present in wastes generated by the foundry industry. The complexity of the matrices considered suggests the need for separative techniques. The method developed for the identification and quantification of formaldehyde in foundry resins is based on the determination of free carbonyl compounds by derivatization with 2,4-dinitrophenylhydrazine (DNPH), being adapted to the considered matrices using liquid chromatography (LC) with UV detection. Formaldehyde determinations in several foundry resins gave precise results. Mean recovery and R.S.D. were, respectively, >95 and 5%. Analyses by the hydroxylamine reference method gave comparable results. Results showed that hydroxylamine reference method is applicable just for a specific kind of resin, while the developed method has good performance for all studied resins.

Impact of vehicular traffic emissions on particulate-bound PAHs: levels and associated health risks

Considering vehicular transport as one of the most health‐relevant emission sources of urban air, and with aim to further understand its negative impact on human health, the objective of this work was to study its influence on levels of particulate‐bound PAHs and to evaluate associated health risks. The 16 PAHs considered by USEPA as priority pollutants, and dibenzo[a, l]pyrene associated with fine (PM2.5) and coarse (PM2.5–10) particles were determined. The samples were collected at one urban site, as well as at a reference place for comparison. The results showed that the air of the urban site was more seriously polluted than at the reference one, with total concentrations of 17 PAHs being 2240% and 640% higher for PM2.5 and PM2.5–10, respectively; vehicular traffic was the major emission source at the urban site. PAHs were predominantly associated with PM2.5 (83% to 94% of ΣPAHs at urban and reference site, respectively) with 5 rings PAHs being the most abundant groups of compounds at both sites. The risks associated with exposure to particulate PAHs were evaluated using the TEF approach. The estimated value of lifetime lung cancer risks exceeded the health‐based guideline levels, thus demonstrating that exposure to PM2.5‐bound PAHs at levels found at urban site might cause potential health risks. Furthermore, the results showed that evaluation of benzo[a] pyrene (regarded as a marker of the genotoxic and carcinogenic PAHs) alone would probably underestimate the carcinogenic potential of the studied PAH mixtures.

Preemption-light multiprocessor scheduling of sporadic tasks with high utilisation bound

Known algorithms capable of scheduling implicit-deadline sporadic tasks over identical processors at up to 100% utilisation invariably involve numerous preemptions and migrations. To the challenge of devising a scheduling scheme with as few preemptions and migrations as possible, for a given guaranteed utilisation bound, we respond with the algorithm NPS-F. It is configurable with a parameter, trading off guaranteed schedulable utilisation (up to 100%) vs preemptions. For any possible configuration, NPS-F introduces fewer preemptions than any other known algorithm matching its utilisation bound. A clustered variant of the algorithm, for systems made of multicore chips, eliminates (costly) off-chip task migrations, by dividing processors into disjoint clusters, formed by cores on the same chip (with the cluster size being a parameter). Clusters are independently scheduled (each, using non-clustered NPS-F). The utilisation bound is only moderately affected. We also formulate an important extension (applicable to both clustered and non-clustered NPS-F) which optimises the supply of processing time to executing tasks and makes it more granular. This reduces processing capacity requirements for schedulability without increasing preemptions.

An improved preemption delay upper bound for floating non-preemptive region

In embedded systems, the timing behaviour of the control mechanisms are sometimes of critical importance for the operational safety. These high criticality systems require strict compliance with the offline predicted task execution time. The execution of a task when subject to preemption may vary significantly in comparison to its non-preemptive execution. Hence, when preemptive scheduling is required to operate the workload, preemption delay estimation is of paramount importance. In this paper a preemption delay estimation method for floating non-preemptive scheduling policies is presented. This work builds on [1], extending the model and optimising it considerably. The preemption delay function is subject to a major tightness improvement, considering the WCET analysis context. Moreover more information is provided as well in the form of an extrinsic cache misses function, which enables the method to provide a solution in situations where the non-preemptive regions sizes are small. Finally experimental results from the implementation of the proposed solutions in Heptane are provided for real benchmarks which validate the significance of this work.

The utilization bound of non-preemptive rate-monotonic scheduling in controller area networks is 25%

Consider a distributed computer system comprising many computer nodes, each interconnected with a controller area network (CAN) bus. We prove that if priorities to message streams are assigned using rate-monotonic (RM) and if the requested capacity of the CAN bus does not exceed 25% then all deadlines are met.

Finding an upper bound on the increase in execution time due to contention on the memory bus in COTS-based multicore systems

Contention on the memory bus in COTS based multicore systems is becoming a major determining factor of the execution time of a task. Analyzing this extra execution time is non-trivial because (i) bus arbitration protocols in such systems are often undocumented and (ii) the times when the memory bus is requested to be used are not explicitly controlled by the operating system scheduler; they are instead a result of cache misses. We present a method for finding an upper bound on the extra execution time of a task due to contention on the memory bus in COTS based multicore systems. This method makes no assumptions on the bus arbitration protocol (other than assuming that it is work-conserving).

Conjecture about global fixed-priority preemptive multiprocessor scheduling of implicit-deadline sporadic tasks: the utilization bound of SM-US(sqrt(2)-1) is sqrt(2)-1

Consider global fixed-priority preemptive multiprocessor scheduling of implicit-deadline sporadic tasks. I conjecture that the utilization bound of SM-US(√2−1) is √2-1.

Calculating an upper bound on the finishing time of a group of threads executing on a GPU: a preliminary case study

Graphics processor units (GPUs) today can be used for computations that go beyond graphics and such use can attain a performance that is orders of magnitude greater than a normal processor. The software executing on a graphics processor is composed of a set of (often thousands of) threads which operate on different parts of the data and thereby jointly compute a result which is delivered to another thread executing on the main processor. Hence the response time of a thread executing on the main processor is dependent on the finishing time of the execution of threads executing on the GPU. Therefore, we present a simple method for calculating an upper bound on the finishing time of threads executing on a GPU, in particular NVIDIA Fermi. Developing such a method is nontrivial because threads executing on a GPU share hardware resources at very fine granularity.

The utilization bound of uniprocessor preemptive slack-monotonic scheduling is 50%

Consider the problem of scheduling a set of sporadically arriving implicit-deadline tasks to meet deadlines on a uniprocessor. Static-priority scheduling is considered using the slack-monotonic priority-assignment scheme. We prove that its utilization bound is 50%.