Overview of DWDM/ODC Project

Abstract

This article introduces the main achievements resulting from the DWDM/ODC project. The five areas of research activity within the DWDM/ODC project cover some of the main issues of design and development of dense wavelength division multiplexing systems for transparent optical networks. These issues are: performance assessment with arbitrary optical filtering; performance of signaling formats; dispersion compensation strategies for directly and externally modulated systems in presence of nonlinear transmission-induced degradation; and the impact of noise and crosstalk in the extent of transparent optical networks. All five areas of research activity have contributed significantly to a better understanding of the limitations present in dense wavelength division multiplexing systems.     

Analysis of polybrominated diphenyl ethers in atmospheric deposition and snow samples by solid-phase disk extraction

An extraction method for the quantitative analysis of polybrominated diphenyl ethers (PBDEs) in aqueous samples has been evaluated. The analytical methodology includes the sample filtration through glass fiber filter and subsequent extraction of dissolved phase compounds by C18 solid-phase disk extraction. Dependence of extraction efficiency on factors such as pollutant concentrations, sample volume, and stability during storage has been investigated. Mean extraction efficiencies of 97% for total PBDEs (13 tri- to heptabrominated congeners at spiking levels in the range of 15-90pg) with a RSD between 9 and 20% were achieved. Higher recoveries were observed for the more volatile PBDEs (112%) in relation to more brominated congeners (88%). The developed methodology was successfully applied to the analysis of these compounds in atmospheric deposition and snow samples from remote sites in Europe with method detection and quantitation limits in the range of 2.1-10pgL(-1) for almost all congeners, which allow the determination of PBDEs in remote areas with levels in the range of low to medium pgL(-1) for SigmaPBDEs.     

Analysis of whole congener mixtures of polybromodiphenyl ethers by gas chromatography–mass spectrometry in both environmental and biological samples at femtogram levels

A sensitive and selective method for the determination of the whole congener distribution of polybromodiphenyl ethers in environmental and biological samples in one single instrumental run is described. The method is based on gas chromatography coupled to low-resolution mass spectrometry in negative ion chemical ionization mode. It allows determination of these compounds at concentration levels lower than 10⁻¹⁴ g. A programmed temperature vaporization injector has been used to ensure maximum compound transfer to the chromatographic column while maintaining low thermal degradation levels of the more brominated congeners. Selectivity was increased by modification of the MS source parameters for optimization of the abundance of the high mass fragment ions. Under optimized condition, good repeatability (1.7–9.1%) and reproducibility (4.1–20%), and low detection limits, ranging between 1.5 and 15 pg ml⁻¹, were obtained. These features afforded reliable quantification of these compounds in snow and human samples at the concentrations in which these compounds are found.     

Gas chromatographic–mass spectrometric analysis of polychlorostyrene congener mixtures in sediments,human sera and cord sera

Complex mixtures of polychlorostyrenes are produced and released into the environment by reaction of chlorine with graphite at high temperatures, e.g. in electrodes. The occurrence of these compounds in the environment or human tissues is often indicative of pollution from electrolytic processes. Combined gas chromatography coupled to electron impact and negative ion chemical ionization mass spectrometry is described here for the analysis of these compounds in sediments, human venous sera and cord sera. This method has allowed a specific congener identification and quantification of the chlorostyrene mixtures present in fluvial sediments polluted by effluents from a chlorine-alkali plant. Besides octachlorostyrene, the mixture of compounds identified involved the six possible heptachlorostyrenes, fifteen hexachlorostyrenes and seven pentachlorostyrenes, having concentrations in the range of 76–16 000 ng g⁻¹ dry weight. In human sera from the population exposed to airborne emissions from this plant these compounds ranged between 17 and 63 ng L⁻¹ and the distributions were dominated by octachlorostyrene, three heptachlorostyrenes, including β,β-2,3,4,5,6-heptachlorostyrene, and α-2,3,4,5,6-hexachlorostyrene. Both distribution patterns showed major differences in composition despite the common pollution source that was influencing both types of samples. The method also revealed qualitative differences between maternal and cord sera from the exposed population.     

Reassessment of the structural composition of the alkenone distributions in natural environments using an improved method for double bond location based on GC-MS analysis of cyclopropylimines

The usefulness of n-propyl-, iso-propyl-, and cyclopropylamines for the location of double bonds positions in C37-C40 alkenones after formation of imino derivatives has been evaluated. Cyclopropylamine is the best reagent for its high reaction yields, GC retention time difference between derivatives and precursor compounds, and absence of generation of byproducts. The use of this C3 amine involves higher sensitivity and ease of application than previously reported C5 amines. Examination of a large group of alkenones from cultures of Emiliania huxleyi, water particles, and recent and ancient sediments with cyclopropylamine derivatization shows that, in all cases, the double bonds were located at the same carbon atom distance from the carbonyl group, and spaced in intervals of five methylene groups either from the carbonyl or between them, e.g., at sites 7, 14, 21, and 28. This result represents a correction from previous assumptions in which double-bond positions were situated by reference to the methyl end. 4,4-Dimethyloxazoline derivatization of hexatriacontenoates showed that these compounds have also their unsaturations with seven carbon atom spacing and counting by reference to the carboxyl group. The concurrence of both series of isomers in compounds of different oxygen functionalities indicates that the precursor haptophycean algal species have a major biosynthetic pathway leading to the formation of these lipids. The data presented in this work unify the structures of the known alkenones in the present and the recent past under a common metabolic pathway.     

Rapid and simplified method for the quantitative analysis of polycyclic aromatic hydrocarbons, lipid biomarkers and organochlorine compounds in marine settling particles

We report on a distinctly improved method for the determination of polycyclic aromatic hydrocarbons (PAHs), lipid biomarkers and organochlorine compounds (OCs) in sediment trap studies involving large numbers of samples of limited particle amounts (20–50?mg). It is based on gas chromatography hyphenated to mass spectrometry. One protocol enables analysis of PAHs and lipids, the other that of the OCs. Both have identical extraction and clean-up procedures, the first involving alkaline hydrolysis and the latter hydrolysis with concentrated sulfuric acid. The limits of detection and quantification for PAHs are 0.1–5.7 and 0.1–9.5?ng?g^?1, respectively. For lipids, they are 0.01–0.12 and 0.01–0.21?μg?g^?1, and for OCs they are 0.1–1.0 and 0.3–1.1?ng?g^?1. The method was applied to sediment traps deployed in the northwestern Mediterranean and provided useful fingerprints to understand sources, ways of transport and fates of these species.

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

The resolution of chromatograms with overlapping peaks by means of different statistical functions

The effectiveness of diverse functions of statistical distribution (log—normal, gamma and Weibull) is examined for the elucidation of chromatograms with overlapping peaks. A Gauss function and a modified Gauss function are used for comparison with the results obtained by the other functions. The generalized least-squares method is applied for adjustment; this is done automatically by the specially designed DAFNA program written in Fortran IV. The use of those functions in the resolution of experimental chromatograms is preceded by an outline of the difficulties involved in the elucidation of overlapping profiles.     

Quantification,confirmation and screening capability of UHPLC coupled to triple quadrupole and hybrid quadrupole time‐of‐flight mass spectrometry in pesticide residue analysis

The potential of three mass spectrometry (MS) analyzers (triple quadrupole, QqQ; time of flight, TOF; and quadrupole time of flight, QTOF) has been investigated and compared for quantification, confirmation and screening purposes in pesticide residue analysis of fruit and vegetable samples. For this purpose, analytical methodology for multiresidue determination of 11 pesticides, taken as a model, has been developed and validated in nine food matrices for the three mass analyzers coupled to ultra high pressure liquid chromatography. In all cases, limits of quantification around 0.01 mg/kg were reached, fulfilling the most restrictive case of baby‐food analysis. Regarding absolute sensitivity, the lower limits of detection were obtained, as expected, for QqQ (100 fg), whereas slightly higher limits (300 fg) were obtained for both TOF and QTOF. Confirmative capacity of each analyzer was studied for each analyte based on the identification points (IPs) criterion, useful for a comprehensive comparison. QTOF mass analyzer showed the highest confirmatory capacity, although QqQ normally led to sufficient number of IPs, even at lower concentration levels. The potential of TOF MS was also investigated for screening purposes. To this aim, around 50 commercial fruits and vegetables samples were analyzed, searching for more than 400 pesticides. TOF MS proved to be an attractive analytical tool for rapid detection and reliable identification of a large number of pesticides thanks to the full spectrum acquisition at accurate mass with satisfactory sensitivity. This process is readily boosted when combined with specialized software packages, together with theoretical exact mass databases. Several pesticides (e.g. carbendazim in citrus and indoxacarb in grape) were detected in the samples. Further unequivocal confirmation of the identity was performed using reference standards and/or QTOF MS/MS experiments. Copyright © 2010 John Wiley & Sons, Ltd.