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Beser M.I.,Public Health Laboratory of Valencia FISABIO | Beltran J.,Jaume I University | Yusa V.,Public Health Laboratory of Valencia FISABIO | Yusa V.,University of Valencia
Journal of Chromatography A

A sensitive and selective procedure for the determination of 12 polybrominated diphenyl ethers (BDE-28, BDE-49, BDE-47, BDE-66, BDE-100, BDE-119, BDE-99, BDE-155, BDE-154, BDE-153, BDE-139 and BDE-183) in airbone particulate matter (PM2.5) at trace level has been developed. The proposed method includes extraction PM2.5-bound PBDEs by microwave-assisted extraction (MAE) followed by gel permeation chromatography (GPC) clean-up and determination by GC-MS/MS using a programmed temperature vaporizer (PTV) in large volume injection (LVI) mode to introduce the sample to the chromatographic system. A design of experiment (DoE) approach was used for the optimization of large volume injection and microwave-assisted extraction parameters to improve these techniques efficiency. Other conditions of the method were studied: GC-MS/MS parameters, extraction solvent and matrix effect. The limit of quantification ranged from 0.063pgm-3 to 0.210pgm-3 when air volumes of 723m3 were collected. Recoveries ranged from 80% to 106%. The method was successfully applied to eight real samples collected from a residential area of the monitoring network of the Region of Valencia Government (Spain) during April-August 2012. BDE-47 and BDE-99 were quantified in six and five samples respectively. The concentrations were ranged from 0.063 to 0.112pgm-3 for BDE-47, and from 0.107 to 0.212pgm-3 for BDE-99. © 2013 Elsevier B.V. Source

Borras E.,Atmospheric Pesticide Research Group of Valencia | Tortajada-Genaro L.A.,Polytechnic University of Valencia | Rodenas M.,Atmospheric Pesticide Research Group of Valencia | Vera T.,Atmospheric Pesticide Research Group of Valencia | And 5 more authors.

The phosphorothioate structure is highly present in several organophosphorus pesticides. However, there is insufficient information about its degradation process after the release to the atmosphere and the secondary pollutants formed. Herein, the atmospheric reaction of chlorpyrifos-methyl (o,o-dimethyl o-(3,5,6-trichloropyridin-2-yl) phosphorothioate), is described for semi-urban or rural locations. The photo-oxidation under low NO. x conditions (5-55. ppbV) was reproduced in a large outdoor simulation chamber, observing a rapid degradation (lifetime. <. 3.5. h). The formation of gaseous products and particulate matter (aerosol yield 2-8%) was monitored. The chemical composition of minor products (gaseous and particulate) was studied, identifying 15 multi-oxygenated derivatives. The most abundant products were ring-retaining molecules such as o,o-dimethyl o-(3,5,6-trichloropyridin-2-yl) phosphorothioate, dimethyl 3,5,6-trichloropyridin-2-yl phosphate, o-methyl o-(3,5,6-trichloropyridin-2-yl) hydrogen phosphorothioate, 3,5,6-trichloropyridin-2-yl dihydrogen phosphate, 3,5,6-trichloropyridin-2-ol, and 3,5,6-trichloropyridine-2,4-diol. An atmospheric degradation mechanism has been proposed based on an oxidation started with OH-nucleophilic attack to P. S bond. The results have been extrapolated to other organothiophosphorus molecules, such as malathion, parathion, diazinon and methidathion, among many others, to estimate their photo-oxidative degradation and the expected products. © 2014 Elsevier Ltd. Source

Coscolla C.,Public Health Laboratory of Valencia FISABIO | Coscolla C.,Atmospheric Pesticide Research Group of Valencia | Munoz A.,Atmospheric Pesticide Research Group of Valencia | Borras E.,Atmospheric Pesticide Research Group of Valencia | And 5 more authors.
Atmospheric Environment

This work presents first data on the particle size distribution of 16 pesticides currently used in Mediterranean agriculture in the atmosphere. Particulate matter air samples were collected using a cascade impactor distributed into four size fractions in a rural site of Valencia Region, during July to September in 2012 and from May to July in 2013. A total of 16 pesticides were detected, including six fungicides, seven insecticides and three herbicides. The total concentrations in the particulate phase (TSP: Total Suspended Particulate) ranged from 3.5 to 383.1pgm-3. Most of the pesticides (such as carbendazim, tebuconazole, chlorpyrifos-ethyl and chlorpyrifos-methyl) were accumulated in the ultrafine-fine (<1μm) and coarse (2.5-10μm) particle size fractions. Others like omethoate, dimethoate and malathion were presented only in the ultrafine-fine size fraction (<1μm). Finally, diuron, diphenylamine and terbuthylazine-desethyl-2-OH also show a bimodal distribution but mainly in the coarse size fractions. © 2014 Elsevier Ltd. Source

Vera T.,Fundacion CEAM | Vera T.,Atmospheric Pesticide Research Group of Valencia | Borras E.,Fundacion CEAM | Borras E.,Atmospheric Pesticide Research Group of Valencia | And 15 more authors.

The gas-phase degradation of lindane (γ-isomer of hexachlorocyclohexane) towards OH radical was investigated under atmospheric conditions at the large outdoor European simulation chamber (EUPHORE) in Valencia, Spain. The rate coefficient for the reaction of hydroxyl radicals with lindane was measured using a conventional relative rate technique leading to a value of kOH(lindane)=(6.4±1.6)×10-13cm3molecule-1s-1 at 300±5K and atmospheric pressure. The results suggest that the tropospheric lifetime of lindane with respect to OH radicals is approximately 20days. The product distribution studies on the OH-initiated oxidation of lindane provided evidence that the major initial carbon-containing oxidation product is pentachlorocyclohexanone. 1,3-Dichloroacetone was employed as a model compound for pentachlorocyclohexanone, and an investigation of its photolysis and reaction with OH radicals under atmospheric conditions was carried out. The data indicate that the atmospheric degradation of pentachlorocyclohexanone would be relatively rapid, and would not form persistent organic compounds. Theoretical study was also employed to calculate possible degradation pathways. Mechanism for reaction of lindane with OH radicals is proposed, and C-Cl bond cleavage is discussed. OH abstraction is considered to be a reasonable way for Cl to escape during degradation. The atmospheric implications of the use of lindane as an insecticide are discussed. © 2015 Elsevier Ltd. Source

Coscolla C.,Public Health Laboratory of Valencia FISABIO | Leon N.,Public Health Laboratory of Valencia FISABIO | Pastor A.,University of Valencia | Yusa V.,Public Health Laboratory of Valencia FISABIO | Yusa V.,University of Valencia
Journal of Chromatography A

A comprehensive strategy for the analysis of current airborne pesticides has been developed using liquid chromatography coupled to high resolution mass spectrometry. The methodology includes both quantitative target analysis and post-run target screening analysis. The quantitative method was validated after a previous statistical optimisation of the main factors governing the ion source ionization and a study of the single-stage Orbitrap fragmentation through the HCD cell. The quantitative method presented recoveries ranging from 73 to 116%, with precision (RSD) lower than 20%, for the 35 substances in the scope of the target method. The full-scan accurate mass data were acquired with a resolving power of 50000 FWHM (scan speed, 2Hz), and alternating two acquisition events, ESI+ without fragmentation and ESI+ with fragmentation. The method-LOQ was 6.5pgm-3 for most of the target pesticides. For post-target screening a customized theoretical database, that included pesticides, metabolites and other substances such as emerging flame retardants was built up. For identification, accurate exact mass with less than 5ppm, and some diagnostic ions including isotopes and/or fragments were used.The strategy was applied to ten samples collected in a rural area of Valencia (Spain). Four pesticides, namely carbendazim, metalaxyl, myclobutanil and terbuthylazine, were detected in concentrations from 16pgm-3 to 174pgm-3. Some pesticides and metabolites (endothal, fenfuram, terbuthylazine-2-OH), in addition to two flame retardants were tentatively identified in the post-run target screening analysis. © 2014 Elsevier B.V. Source

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