Identification of pesticide transformation products in food by liquid chromatography/time-of-flight mass spectrometry via "fragmentation-degradation" relationships

The identification of transformation products of pesticides in foodstuffs is a crucial task difficult to tackle, due to the lack of standards and scarce information available. In this work, we describe a methodology for the identification and structural elucidation of pesticide transformation products in food. The proposed strategy is based on the use of liquid chromatography electrospray time-of-flight mass spectrometry (LC/TOFMS): accurate mass measurements of (molecule and fragment) ions of interest are used in order to establish relationships between fragmentation of the parent pesticides in the instrument (in-source CID fragmentation) and possible degradation products of these pesticides in food. Examples of this strategy showing the potential of LC/TOFMS to determine unknown pesticides in food are described in two different real samples, suggesting that pesticides often are transformed into degradation products in the same fashion that they are fragmented in the instrument. Using the proposed approach and without using standards a priori, based solely on accurate mass measurements of ions and "fragmentation-degradation" relationships, we have identified two parent pesticides (amitraz and malathion) along with six degradation products, m/z 253 (N,N'-bisdimethylphenylformamidine), 163 (N-2,4-dimethylphenyl-N-methyl formamidine), 150 (2,4-dimethylformamidine), and 122 (2,4-dimethylaniline) from amitraz, and m/z 317 and 303, due to ether hydrolysis of methyl and ethyl groups from malathion. Structures for these species were proposed, and the potential of the proposed approach was critically discussed.     

Modified Gutenberg–Richter Coefficient for Damage Evaluation in Reinforced Concrete Structures Subjected to Seismic Simulations on a Shaking Table

This paper presents analysis and discussion of the \(b\) - and ib-values calculated from the acoustic emission (AE) signals recorded during dynamic shake-table tests conducted on a reinforced concrete (RC) frame subjected to several uniaxial seismic simulations of increasing intensity until collapse. The intensity of shaking was controlled by the peak acceleration applied to the shake-table in each seismic simulation, and it ranged from 0.08 to 0.47 times the acceleration of gravity. The numerous spurious signals not related to concrete damage that inevitably contaminate AE measurements obtained from complex dynamic shake-table tests were properly filtered with an RMS filter and the use of guard sensors. Comparing the \(b\) - and ib-values calculated through the tests with the actual level of macro-cracking and damage observed during testing, it was concluded that the limit value of 0.05 proposed in previous research to determine the onset of macro-cracks should be revised in the case of earthquake-type dynamic loading. Finally, the \(b\) - and ib-values were compared with the damage endured by the RC frame evaluated both visually and quantitatively in terms of the inter-story drift index.     

Simulation of a hydrogen production and purification system for a PEM fuel-cell using bioethanol as raw material

A process to produce “fuel-cell grade” hydrogen from ethanol steam reforming is analyzed from a thermodynamic point of view. The hydrogen purification process consists of WGS and COPROX reactors. Equations to evaluate the efficiency of the system, including the fuel cell, are presented. A heat exchange network is proposed in order to improve the exploitation of the available power. The effect of key variables such as the reformer temperature and the ethanol/water molar feed ratio on the fuel-cell efficiency is discussed. Results show that it is feasible to carry out the energy integration of the hydrogen catalytic production and purification—PEM fuel-cell system, using ethanol as raw material. The technology of “fuel-cell grade” hydrogen production using ethanol as raw material is a very attractive alternative to those technologies based in fossil fuels.     

Corrosion mechanisms in ADI parts

The objective of this research is to study the influence of microstructure and grinding on the corrosion resistance of ADI in salt water. Immersion and electrochemical tests were performed on samples austempered at two different temperatures and ground. The results indicate that the dissolution rate increases as the nodule count does, and it is also affected by the microstructure and by the surface changes introduced during grinding. A porous layer is formed on ADI-corroded surface due to the selective dissolution of ferrite, and a preferential dissolution of the matrix around graphite is noticeable. Ground surfaces are less corrosion resistant than polished ones.     

Quantitation and accurate mass analysis of pesticides in vegetables by LC/TOF-MS

A quantitative method consisting of solvent extraction followed by liquid chromatography/time-of-flight mass spectrometry (LC/TOF-MS) analysis was developed for the identification and quantitation of three chloronicotinyl pesticides (imidacloprid, acetamiprid, thiacloprid) commonly used on salad vegetables. Accurate mass measurements within 3 ppm error were obtained for all the pesticides studied in various vegetable matrixes (cucumber, tomato, lettuce, pepper), which allowed an unequivocal identification of the target pesticides. Calibration curves covering 2 orders of magnitude were linear over the concentration range studied, thus showing the quantitative ability of TOF-MS as a monitoring tool for pesticides in vegetables. Matrix effects were also evaluated using matrix-matched standards showing no significant interferences between matrixes and clean extracts. Intraday reproducibility was 2-3% relative standard deviation (RSD) and interday values were 5% RSD. The precision (standard deviation) of the mass measurements was evaluated and it was less than 0.23 mDa between days. Detection limits of the chloronicotinyl insecticides in salad vegetables ranged from 0.002 to 0.01 mg/kg. These concentrations are equal to or better than the EU directives for controlled pesticides in vegetables showing that LC/TOF-MS analysis is a powerful tool for identification of pesticides in vegetables. Robustness and applicability of the method was validated for the analysis of market vegetable samples. Concentrations found in these samples were in the range of 0.02-0.17 mg/kg of vegetable.     

Enhancing IEEE 802.11p/WAVE to provide infotainment applications in VANETs

IEEE 802.11p/WAVE (Wireless Access for Vehicular Environment) is the emerging standard to enable wireless access in the vehicular environment. Most of the research contributions in this area has focused on safety-related applications, while comfort and information/entertainment applications (such as on board Internet access, point-of-interest notification, e-map download) have been considered only recently. Notwithstanding, the user interest in this kind of applications is expected to become a big market driver in a near future. In this paper, an extension to IEEE 802.11p is proposed that is compliant with the multi-channel operation of the WAVE architecture and targets at the support of non-safety applications, while preserving the delivery of safety services. The proposed W-HCF (WAVE-based Hybrid Coordination Function) protocol leverages controlled access capabilities on top of the basic contention-based access of the IEEE 802.11p; it exploits vehicles’ position information and coordination among WAVE providers in order to improve performances of delay-constrained and loss-sensitive non-safety applications.     

Thermodynamic Analysis of Glycerol Steam Reforming

A thermodynamic analysis of steam reforming of glycerol using the stoichiometric method has been performed. Since the aim of this work is to study product distribution and coke formation in equilibrium, two different models have been proposed: (a) CO as primary product and (b) CO₂ as primary product. Moreover, substantial information regarding the behavior of the different reactions could be acquired. Product distribution at equilibrium has been investigated in a broad range of conditions: temperature (600–1200 K), water‐to‐glycerol feed molar ratio (0:1–10:1), and pressure (1–9 atm). Glycerol conversion results completely over the whole range of the mentioned conditions. Consequently, product distribution at equilibrium is determined by water gas shift (WGS) and methanation or methane steam reforming reactions. Finally, high temperatures and a high water‐to‐glycerol feed molar ratio favor hydrogen production and decrease both methane and coke.     

Degradation of sulfamethoxazole in water by solar photo-Fenton. Chemical and toxicological evaluation

In this work, the photocatalytic degradation of the antibiotic sulfamethoxazole (SMX) by solar photo-Fenton at pilot plant scale was evaluated in distilled water (DW) and in seawater (SW). Degradation and mineralization of SMX were strongly hindered in SW compared to DW. The influence of H₂O₂ and iron concentration on the efficiency of the photocatalytic process was evaluated. An increase in iron concentration from 2.6 to 10.4 mg L⁻¹ showed only a slight improvement in SMX degradation and mineralization. However, an increase in H₂O₂ concentration up to 120 mg L⁻¹ during photo-Fenton in DW decreased SMX solution toxicity from 85% to 20%, according to results of Daphnia magna bioassays. The same behaviour was not observed after photo-Fenton treatment in SW. Despite 45% mineralization in SW, toxicity increased from 16% to 86% as shown by Vibrio fischeri bioassays, which suggests that the intermediates generated in SW are different from those in DW. A SMX degradation pathway during the photo-Fenton treatment in DW is proposed.