Evaluation of the capabilities of atmospheric pressure chemical ionization source coupled to tandem mass spectrometry for the determination of dioxin-like polychlorobiphenyls in complex-matrix food samples

The use of the novel atmospheric pressure chemical ionization (APCI) source for gas chromatography (GC) coupled to triple quadrupole using tandem mass spectrometry (MS/MS) and its potential for the simultaneous determination of the 12 dioxin-like polychlorobiphenyls (DL-PCBs) in complex food and feed matrices has been evaluated. In first place, ionization and fragmentation behavior of DL-PCBs on the APCI source under charge transfer conditions has been studied followed by their fragmentation in the collision cell. Linearity, repeatability and sensitivity have been studied obtaining instrumental limits of detection and quantification of 0.0025 and 0.005 pg µL-1 (2.5 and 5 fg on column) respectively for every DL-PCB. Finally, application to real samples has been carried out and DL-PCB congeners (PCB 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) have been detected in the different samples in the range of 0.40 to 10000 pg g-1. GC-(APCI)MS/MS has been proved as a suitable alternative to the traditionally accepted confirmation method based on the use of high resolution mass spectrometry and other triple quadrupole tandem mass spectrometry techniques operating with electron ionization. The development of MS/MS methodologies for the analysis of dioxins and DL-PCBs is nowadays particularly important, since this technique was included as a confirmatory method in the present European Union regulations that establish the requirements for the determination of these compounds in food and feed matrices.The authors acknowledge the financial support of Generalitat Valenciana, (research group of excellence PROMETEO/2009/054 and PROMETEO II 2014/023 and Collaborative Research on Environment and Food-Safety (ISIC/2012/016)

Emissions of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) from a cement kiln using a continuous monitoring system

Resumen de la comunicación presentada en PIC2015 – the 14th International Congress on Combustion By-Products and Their Health Effects, Umeå, Sweden, 14-17 June 2015.The aim of the present study was to assess the emission of di2erent persistent organic pollutants from a cement plant over a period of one year, under normal operating conditions. In this way, a Dioxin Monitoring System (a long-term sampling device manufactured by Monitoring Systems) was installed in the clinker kiln stack of the cement plant, located in the vicinity of the University of Alicante. The factory has a production capacity of 150 t/h of clinker and uses petroleum coke as primary fuel, but also alternative fuels such as SRF (solid recovered fuel), ASR (automotive shredder residue), sewage sludge, waste tires, and meat and bone meal wastes, with an enerKy substitution level of about 40 %. The study consisted of a total of 13 samples, namely: • Ten samples collected in 3Q4 week periods, for the determination of brominated dioxins and furans (PBDD/Fs). • Three samples collected during one-week periods, for the determination of polycyclic aromatic hydrocarbons (PAHs).Support for this work was provided by the following projects: • Ministry of Science and Innovation (Spain): CTQ2011Q23618. • Ministry of Economy and Competitiveness (Spain): CTQ2013Q41006QR. • Valencian Community Government (Spain): PROMETEOII/2014/007

Potential of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry for screening and quantification of hexabromocyclododecane

A fast method for the screening and quantification of hexabromocyclododecane (sum of all isomers) by gas chromatography using a triple quadrupole mass spectrometer with atmospheric pressure chemical ionization (GC-APCI-QqQ) is proposed. This novel procedure makes use of the soft atmospheric pressure chemical ionization source, which results in less fragmentation of the analyte than by conventional electron impact (EI) and chemical ionization (CI) sources, favoring the formation of the [M – Br]+ ion and, thus, enhancing sensitivity and selectivity. Detection was based on the consecutive loses of HBr from the [M – Br]+ ion to form the specific [M – H5Br6]+ and [M – H4Br5]+ ions, which were selected as quantitation (Q) and qualification (q) transitions, respectively. Parameters affecting ionization and MS/MS detection were studied. Method performance was also evaluated; calibration curves were found linear from 1 pg/μL to 100 pg/μL for the total HBCD concentration; instrumental detection limit was estimated to be 0.10 pg/μL; repeatability and reproducibility, expressed as relative standard deviation, were better than 7 % in both cases. The application to different real samples [polyurethane foam disks (PUFs), food, and marine samples] pointed out a rapid way to identify and allow quantification of this compound together with a number of polybrominated diphenyl ethers (BDE congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two other novel brominated flame retardants [i.e., decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)] because of their presence in the same fraction when performing the usual sample treatment.The authors acknowledge the financial support of Generalitat Valenciana, (research group of excellence PROMETEO/ 2009/054 and PROMETEO II 2014/023 and Collaborative Research on Environment and Food-Safety (ISIC/2012/016)). The authors also acknowledge the financial support given by the Spanish Ministry of Economy and Competitiveness and European funding from FEDER program (project AGL2012-37201) and (UNEP). The authors are grateful to Dr. José Luis Acuña and Mrs. Sonia Romero for providing the marine samples

Oceanic Sink and Biogeochemical Controls on the Accumulation of Polychlorinated Dibenzo-p-dioxins, Dibenzofurans, and Biphenyls in Plankton.

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in plankton samples from the Atlantic, Pacific and Indian Oceans collected during the Malaspina circumnavigation cruise. The concentrations of PCDD/Fs and dl-PCBs in plankton averaged 14 and 240 pg gdw-1, respectively, but concentrations were highly variable. The global distribution of PCDD/Fs and dl-PCBs was not driven by proximity to primary sources in continents, but significantly correlated with plankton biomass. These trends are consistent with the interactions between atmospheric deposition, biomass dilution, and settling fluxes of organic matter in the water column, as key processes driving the POPs plankton phase concentrations in the global oceans. The application of a model of the air-water-plankton diffusive exchange of PCDD/Fs and PCBs reproduce in part the influence of biomass on plankton phase concentrations, and suggest future modelling prioritiesThe estimated oceanic sink (Atlantic, Pacific and Indian Oceans) due to settling fluxes of organic matter bound PCDD/Fs and dl-PCBs is of 400 Kg y-1 and 10500 kg y-1, respectively. This oceanic sink is 3 and 8 times lower, for PCDD/Fs and dl-PCBs respectively, than the atmospheric inputs due to gross diffusive absorption and dry deposition. These important atmospheric inputs, among other observations, confirm that atmospheric deposition supports and drives the accumulation of dl-PCBs and PCDD/Fs in plankton from the oligotrophic oceans.MALASPINA (CSD2008 00077)Versión del editor5,228

Decontamination trends in the aquacultured fish gilthead seabream (Sparus aurata) after feeding long-term a PCDD/F spiked feed

8 pages, 2 figures, 5 tablesAquacultured fish gilthead seabream (Sparusaurata), previously exposed to low levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) trough the diet for a 13 months period, were fed on a clean feed for another 22 months. Gilthead seabream is a protandrous hermaphrodite species and this “decontamination” period coincided with the stages of sex differentiation, maturity and reproduction of the fish. PCDD/F levels in the fish tissues (i.e. muscle, liver, perivisceral fat and gonads), expressed in pg WHO-TEQ g−1 fresh weight, showed a general decreasing trend during the “decontamination” period. However, this general trend varied among tissues and was also dependent on sex and lipid contents. Toxicological effects affecting fish behaviour and hepatic marker responses were also evaluated. The results pointed out that exposure to PCDD/Fs did not have an impact on fish development and reproduction, since the proportion of sexes found after the sex reversal process was within the normal range described for this species. In addition, long-term exposure to low PCDD/F levels did not significantly affect the response of most of the biochemical markers considered. On the contrary, some of them (e.g. EROD activity) showed variations in their responses during the sex differentiation process and onwards. Finally, the hepatic AhR mRNA levels increased during dioxin exposure but they returned to values typical for non-exposed fish after the “decontamination” periodThis project was supported by the Spanish National Plan for Research PN2003 ref. AGL2003 02283-ALI and ‘‘Proyectos Intramurales de 30 de Marzo de 2004. Consejo Superior de Investigaciones Científicas (CSIC), Ministerio de Educación (200680I106)”. Additional funding from Ministerio Ciencia e Innovación (CGL2008-01898) is also acknowledged. M. Ábalos acknowledges an I3PDR contract from CSIC in the framework of the I3P projectPeer reviewe

PCDD/F and DL-PCB levels in meat from broilers and rabbits fed with fish-oil enriched feeds

The aim of this study was to assess the effect on the final levels of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in meat when fats, in particular fish oils, are included as ingredients in feeds. Two types of animals (broilers and rabbits) were fed with three different experimental feeds containing varying amounts of two selected fish oils. PCDD/Fs and DL-PCBs were determined in the fish oils, the feeds and in the animals’ meat. For broilers, PCDD/F and DL-PCB profiles in meat samples were similar to those found in the corresponding feeds, even though bioaccumulation of the highest chlorinated PCDD/F congeners seemed to decrease. Depending on the treatment, PCDD/F and the sum of PCDD/F and DL-PCB levels were 1.11–4.60 and 6.03–16.71 pg WHO-TEQ/g fat, respectively. For most of the cases, these values exceeded the maximum established by the Commission Regulation (EC) No. 1881/2006. In contrast, the levels of these contaminants in the corresponding feeds ranged from 0.11 to 0.54 pg WHO-TEQ/g, in the case of PCDD/Fs, and from 0.59 to 1.75 pg WHO-TEQ/g, when DL-PCBs were also included. These levels were, in general, below the maximum allowed by the Commission Directive 2006/13/EC. The results of the experiments with rabbits were not as conclusive as those for broilers although bioaccumulation appeared to be slower.This work was supported by the European Union (6th EC Framework Programme) in the framework of the Feeding fats safety project (Contract no.: Food-CT-2004-07020). The authors are grateful to project partners from the Universitat Autònoma de Barcelona (UAB), Universitat Politècnica de Valencia (UPV) and Universitat de Barcelona (UB) for preparing the feeds and raising the animals as well as for their helpful comments during the preparation of this article. M. Ábalos acknowledges an I3PDR contract from CSIC in the framework of the I3P project.Peer reviewe

Potential of Atmospheric Pressure Chemical Ionization Source for the Quantification of a Wide Range of Halogenated Persistent Pollutants in Complex Samples

Trabajo presentado a la XV Reunión científica de la Sociedad Española de Cromatografía y Técnicas Afines - SECyTA 2015. Castellón de la Plana, 27-30 de octubre de 2015.Gas chromatographs coupled to mass spectrometers (GC-MS) have been extensively applied for the determination of volatile and semi-volatile, non-polar, compounds in fields like food safety, environmental or toxicological studies. Most methods reported in the literature use electron ionization (EI) [1], which may result in extensive fragmentation of analytes compromising both, selectivity and sensitivity. This makes also difficult the application of tandem MS due to lack of specific/abundant precursor ions [2]. The analysis of persistent organic pollutants, including brominated flame retardants (BFRs), polychlorinated dibenzodioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls (dl-PCBs), relies on the use of methods based on GC-MS operating in EI or negative chemical ionization (NCI) modes using quadrupole, triple quadrupole, ion trap or magnetic sector analyzers [3]. These halogenated contaminants are examples of compounds for which a softer, reproducible and robust ionization technique might be favorable since they show high fragmentation in EI and low specificity in NCI [4]. In this work the potential of atmospheric pressure chemical ionization (APCI) combined with GC and triple quadrupole mass analyzer has been investigated, using BFRs, PCDD/PCDF and dl-PCBs as model compounds for their determination in different complex samples, including marine samples, milk, feed and animal fat and interlaboratory studies samples. Ionization and fragmentation behavior of 14 PBDEs and 3 novel BFRs as well as 10 PCDD/PCDF and 7 dl-PCB congeners by APCI has been studied. The formation of highly abundant (quasi) molecular ions has been the main goal because of the expected improvement in specificity obtained when using it as precursor ion in tandem MS. The convenience of using modifiers for the ionization step has been studied and discussed for each family of compounds with the aim of obtaining the maximum sensitivity in combination of acceptable reproducibility and optimum specificity/selectivity. The improved detectability (LODs between 1 and 20 fg) achieved when using APCI compared to EI has been demonstrated. The application to different complex samples has shown the feasibility of the methods at trace levels for unambiguous identification and determination of the compounds investigated. These results highlight the potential of APCI as the reference for quantification of halogenated pollutants in the next years. [1] J. Cristale, J. Chromatogr. A. 1241 (2012) 1–12. [2] D. Wang, Mass Spectrom. Rev. 29 (2010) 737–75. [3] B. Gómara, Anal. Chim. Acta. 597 (2007) 121–8. [4] H.M. Stapleton, Anal. Bioanal. Chem. 386 (2006) 807–817.Peer reviewe

Opportunities for ATM The multimedia network of the future

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