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.

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%.

Soil remediation time to achieve clean-up goals I: influence of soil water content

The current models are not simple enough to allow a quick estimation of the remediation time. This work reports the development of an easy and relatively rapid procedure for the forecasting of the remediation time using vapour extraction. Sandy soils contaminated with cyclohexane and prepared with different water contents were studied. The remediation times estimated through the mathematical fitting of experimental results were compared with those of real soils. The main objectives were: (i) to predict, through a simple mathematical fitting, the remediation time of soils with water contents different from those used in the experiments; (ii) to analyse the influence of soil water content on the: (ii1) remediation time; (ii2) remediation efficiency; and (ii3) distribution of contaminants in the different phases present into the soil matrix after the remediation process. For sandy soils with negligible contents of clay and natural organic matter, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) if the soil water content belonged to the range considered in the experiments with the prepared soils, then the remediation time of real soils of similar characteristics could be successfully predicted, with relative differences not higher than 10%, through a simple mathematical fitting of experimental results; (ii) increasing soil water content from 0% to 6% had the following consequences: (ii1) increased remediation time (1.8–4.9 h, respectively); (ii2) decreased remediation efficiency (99–97%, respectively); and (ii3) decreased the amount of contaminant adsorbed onto the soil and in the non-aqueous liquid phase, thus increasing the amount of contaminant in the aqueous and gaseous phases.

Construction and evaluation of cysteine selective electrodes for FIA analysis of pharmaceuticals

A flow injection analysis (FIA) system comprising a cysteine selective electrode as detection system was developed for determination of this amino acid in pharmaceuticals. Several electrodes were constructed for this purpose, having PVC membranes with different ionic exchangers and mediator solvents. Better working characteristics were attained with membranes comprising o-nitrophenyl octyl ether as mediator solvent and a tetraphenylborate based ionic-sensor. Injection of 500 µL standard solutions into an ionic strength adjuster carrier (3x10-3 M) of barium chloride flowing at 2.4mL min-1, showed linearity ranges from 5.0x10-5 to 5.0x10-3 M, with slopes of 76.4±0.6mV decade-1 and R2>0.9935. Slope decreased significantly under the requirement of a pH adjustment, selected at 4.5. Interference of several compounds (sodium, potassium, magnesium, barium, glucose, fructose, and sucrose) was estimated by potentiometric selectivity coefficients and considered negligible. Analysis of real samples were performed and considered accurate, with a relative error to an independent method of +2.7%.

Soil remediation time to achieve clean-up goals II: influence of natural organic matter and water contents

This work reports a relatively rapid procedure for the forecasting of the remediation time (RT) of sandy soils contaminated with cyclohexane using vapour extraction. The RT estimated through the mathematical fitting of experimental results was compared with that of real soils. The main objectives were: (i) to predict the RT of soils with natural organic matter (NOM) and water contents different from those used in experiments; and (ii) to analyse the time and efficiency of remediation, and the distribution of contaminants into the soil matrix after the remediation process, according to the soil contents of: (ii1) NOM; and (ii2) water. For sandy soils with negligible clay contents, artificially contaminated with cyclohexane before vapour extraction, it was concluded that: (i) if the NOM and water contents belonged to the range of the prepared soils, the RT of real soils could be predicted with relative differences not higher than 12%; (ii1) the increase of NOM content from 0% to 7.5% increased the RT (1.8–13 h) and decreased the remediation efficiency (RE) (99–90%) and (ii2) the increase of soil water content from 0% to 6% increased the RT (1.8–4.9 h) and decreased the RE (99–97%). NOM increases the monolayer capacity leading to a higher sorption into the solid phase. Increasing of soil water content reduces the mass transfer coefficient between phases. Concluding, NOM and water contents influence negatively the remediation process, turning it less efficient and more time consuming, and consequently more expensive.

Selective recognition in potentiometric transduction of amoxicillin by molecularly imprinted materials

The indiscriminate use of antibiotics in foodproducing animals has received increasing attention as a contributory factor in the international emergence of antibiotic- resistant bacteria (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004). Numerous analytical methods for quantifying antibacterial residues in edible animal products have been developed over years (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004; Botsoglou and Fletouris in Handbook of food analysis, residues and other food component analysis, Marcel Dekker, Ghent, 2004). Being Amoxicillin (AMOX) one of those critical veterinary drugs, efforts have been made to develop simple and expeditious methods for its control in food samples. In literature, only one AMOX-selective electrode has been reported so far. In that work, phosphotungstate:amoxycillinium ion exchanger was used as electroactive material (Shoukry et al. in Electroanalysis 6:914–917, 1994). Designing new materials based on molecularly imprinted polymers (MIPs) which are complementary to the size and charge of AMOX could lead to very selective interactions, thus enhancing the selectivity of the sensing unit. AMOXselective electrodes used imprinted polymers as electroactive materials having AMOX as target molecule to design a biomimetic imprinted cavity. Poly(vinyl chloride), sensors of methacrylic acid displayed Nernstian slopes (60.7 mV/decade) and low detection limits (2.9×10-5 mol/L). The potentiometric responses were not affected by pH within 4–5 and showed good selectivity. The electrodes were applied successfully to the analysis of real samples.

Economic, environmental and mixed objective functions in non-linear process optimization using simulated annealing and tabu search

Screening of topologies developed by hierarchical heuristic procedures can be carried out by comparing their optimal performance. In this work we will be exploiting mono-objective process optimization using two algorithms, simulated annealing and tabu search, and four different objective functions: two of the net present value type, one of them including environmental costs and two of the global potential impact type. The hydrodealkylation of toluene to produce benzene was used as case study, considering five topologies with different complexities mainly obtained by including or not liquid recycling and heat integration. The performance of the algorithms together with the objective functions was observed, analyzed and discussed from various perspectives: average deviation of results for each algorithm, capacity for producing high purity product, screening of topologies, objective functions robustness in screening of topologies, trade-offs between economic and environmental type objective functions and variability of optimum solutions.

Cleanup of industrial effluents containing heavy metals: a new opportunity of valorising the biomass produced by brewing industry

Heavy metal pollution is a matter of concern in industrialised countries. Contrary to organic pollutants, heavy metals are not metabolically degraded. This fact has two main consequences: its bioremediation requires another strategy and heavy metals can be indefinitely recycled. Yeast cells of Saccharomyces cerevisiae are produced at high amounts as a by-product of brewing industry constituting a cheap raw material. In the present work, the possibility of valorising this type of biomass in the bioremediation of real industrial effluents containing heavy metals is reviewed. Given the autoaggregation capacity (flocculation) of brewing yeast cells, a fast and off-cost yeast separation is achieved after the treatment of metal-laden effluent, which reduces the costs associated with the process. This is a critical issue when we are looking for an effective, eco-friendly, and low-cost technology. The possibility of the bioremediation of industrial effluents linked with the selective recovery of metals, in a strategy of simultaneous minimisation of environmental hazard of industrial wastes with financial benefits from reselling or recycling the metals, is discussed.

CIDER - envisaging a COTS communication infrastructure for evolutionary dependable real-time systems

It is foreseen that future dependable real-time systems will also have to meet flexibility, adaptability and reconfigurability requirements. Considering the distributed nature of these computing systems, a communication infrastructure that permits to fulfil all those requirements is thus of major importance. Although Ethernet has been used primarily as an information network, there is a strong belief that some very recent technological advances will enable its use in dependable applications with real-time requirements. Indeed, several recently standardised mechanisms associated with Switched-Ethernet seem to be promising to enable communication infrastructures to support hard real-time, reliability and flexible distributed applications. This paper describes the motivation and the work being developed within the CIDER (Communication Infrastructure for Dependable Evolvable Real-Time Systems) project, which envisages the use of COTS Ethernet as an enabling technology for future dependable real-time systems. It is foreseen that the CIDER approach will constitute a relevant stream of research since it will bring together cutting edge research in the field of real-time and dependable distributed systems and the industrial eagerness to expand Ethernet responsabilities to support dependable real-time applications.

Setting target rotation time in PROFIBUS based real-time distributed applications

In this paper, we analyse the ability of Profibus fieldbus to cope with the real-time requirements of a Distributed Computer Control System (DCCS), where messages associated to discrete events must be made available within a maximum bound time. Our methodology is based on the knowledge of real-time traffic characteristics, setting the network parameters in order to cope with timing requirements. Since non-real-time traffic characteristics are usually unknown at the design stage, we consider an operational profile where, constraining non-real-time traffic at the application level, we assure that realtime requirements are met.

Non pre-emptive scheduling of messages on SMTV token-passing networks

Fieldbus communication networks aim to interconnect sensors, actuators and controllers within distributed computer-controlled systems. Therefore, they constitute the foundation upon which real-time applications are to be implemented. A specific class of fieldbus communication networks is based on a simplified version of token-passing protocols, where each station may transfer, at most, a single message per token visit (SMTV). In this paper, we establish an analogy between non-preemptive task scheduling in single processors and the scheduling of messages on SMTV token-passing networks. Moreover, we clearly show that concepts such as blocking and interference in non-preemptive task scheduling have their counterparts in the scheduling of messages on SMTV token-passing networks. Based on this task/message scheduling analogy, we provide pre-run-time schedulability conditions for supporting real-time messages with SMTV token-passing networks. We provide both utilisation-based and response time tests to perform the pre-run-time schedulability analysis of real-time messages on SMTV token-passing networks, considering RM/DM (rate monotonic/deadline monotonic) and EDF (earliest deadline first) priority assignment schemes

Real-time fieldbus communications using Profibus networks

This paper provides a comprehensive study on how to use Profibus fieldbus networks to support real-time industrial communications, that is, on how to ensure the transmission of real-time messages within a maximum bound time. Profibus is base on a simplified timed token (TT) protocol, which is a well-proved solution for real-time communication systems. However, Profibus differs with respect to the TT protocol, thus preventing the application of the usual TT protocol real-time analysis. In fact, real-time solutions for networks based on the TT protocol rely on the possibility of allocating specific bandwidth for the real-time traffic. This means that a minimum amount of time is always available, at each token visit, to transmit real-time messages, transversely, with the Profibus protocol, in the worst case, only one real-time message is processed per token visit. The authors propose two approaches to guarantee the real-time behavior of the Profibus protocol: (1) an unconstrained low-priority traffic profile; and (2) a constrained low-priority traffic profile. The proposed analysis shows that the first profile is a suitable approach for more responsive systems (tighter deadlines), while the second allows for increased nonreal-time traffic throughput

Pre-run-time schedulability analysis of P-NET fieldbus networks

P-NET is a fieldbus industrial communication standard, which uses a Virtual Token Passing MAC mechanism. In this paper we establish pre-run-time schedulability conditions for supporting real-time traffic with P-NET. Essentially we provide formulae to evaluate the minimum message deadline, ensuring the transmission of real-time messages within a maximum time bound

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 tighter analysis of the worst-case endto- end communication delay in massive multicores

"Many-core” systems based on the Network-on- Chip (NoC) architecture have brought into the fore-front various opportunities and challenges for the deployment of real-time systems. Such real-time systems need timing guarantees to be fulfilled. Therefore, calculating upper-bounds on the end-to-end communication delay between system components is of primary interest. In this work, we identify the limitations of an existing approach proposed by [1] and propose different techniques to overcome these limitations.