Levels, patterns and risk assessment of PCDD/Fs and dl-PCBs through dietary exposure in the Valencian Region (Spain).

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin like polychlorinated biphenyls (dl-PCBs) levels were measured in representative vegetable oils and animal origin foodstuffs collected in a Total Diet Study carried out in the Valencian Region (Spain). A total amount of 3,300 food samples were collected and grouped into 5 main food groups: vegetable oils, meat and meat products, eggs, milk and dairy products and fish and sea products. The samples were analysed using gas chromatography coupled to high-resolution mass spectrometry (GC-HRMS). The food group which presented the highest concentration in wet weight (ww) for the sum of PCDD/Fs and dl-PCBs was fish and sea products (0.5 pg TEQ g-1 ww), whereas meat and meat products (0.6 pg TEQ g-1 lipid) showed the highest levels expressed in lipid terms. Occurrence data of PCDD/F and dl-PCBs were combined with consumption data to estimate the dietary exposure of adults (>15 years) and children (6-15 years). Finally, the estimated weekly intake (EWI) was calculated using a deterministic approach and considering the food consumption of the population, with fish and sea products being the main food group contributor. Likewise, considering the worst-case scenario (Upper Bound, UB), average EWI were 1.8 and 3.4 pg TEQ kg-1 body weight (bw) week-1 for adults and children, respectively. For children, the average EWI was almost twice above the tolerable weekly intake (TWI) of 2 pg TEQ kg-1 bw week-1 set by EFSA in 2018. In terms of risk characterisation, the overall obtained results showed that 19 % of adults and 43 % of children may exceed the TWI when using UB.

Determination of 21 per- and poly-fluoroalkyl substances in paper- and cardboard-based food contact materials by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry.

In this work, a new analytical method was developed and validated for the determination of the total content of 21 per- and poly-fluoroalkyl substances (PFASs) in paper- and cardboard-based food contact materials (FCMs). This method is based on green ultrasound-assisted lixiviation followed by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS). The method was validated in various paper- and cardboard-based FCMs, showing good linearity (R2 ≥ 0.99), limits of quantification (1.7-10 µg kg-1), accuracy (74-115%), and precision (RSD < 20%). The eco-friendly characteristics of the proposed analytical method were assessed according to the analytical eco-scale, demonstrating that it can be considered an excellent green analytical method (EcoScale score > 75). Finally, 16 field samples of paper- and cardboard-based FCMs, including pizza boxes, popcorn boxes, paper bags and cardboard boxes for potato fries, ice cream tubs, pastry trays, and cardboard-based packaging for cooked Spanish omelets, fresh grapes, frozen fish, and salads were analyzed, showing that they comply with the current European regulations regarding the studied PFASs. The developed method is currently accredited according to UNE-EN ISO/IEC 17025 by the Spanish National Accreditation Body (ENAC) to be implemented for official control analysis of FCMs in the Public Health Laboratory of Valencia, Generalitat Valenciana (Valencia, Spain).

Determination of 21 perfluoroalkyl substances and organophosphorus compounds in breast milk by liquid chromatography coupled to orbitrap high-resolution mass spectrometry.

The human exposure to perfluoroalkyl (PFASs) and organophosphorus (OPs) compounds is a cause of concern and its determination in biological matrices, including human milk, is an emergent approach for evaluate their exposure. A comprehensive strategy for the quantitative determination of 21 PFASs and OPs compounds in breast milk was developed. The proposed method includes an extraction and clean-up procedure based on the QuEChERs methodology followed by an ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) determination. The full-scan mass data were acquired with a resolution of 50000 FWHM and a mass accuracy better than 5 ppm. Method validation was performed in terms of recovery, repeatability, linearity and limit of quantification. The obtained recoveries varied between 70 and 120% with a precision (RSD) lower than 25%. The limit of quantification (LOQ) ranged between 1.9 and 19.0 ng g-1 lipid weight for OPs, and between 0.066 ng mL-1 and 0.666 ng mL-1 for PFASs. A breast milk reference material was used in order to check the validated method. The developed analytical strategy was applied to 20 breast milk samples collected from mothers living in the Valencian Region (Spain). All of the OPs analyzed except tris(2-chloroethyl) phosphate (TCEP) were detected in at least one sample. In all samples, perfluoro-n-pentanoic acid (PFPeA), perfluoro-n-octanoic acid (PFOA) and sodium perfluoro-1-octanesulfonate (PFOS) were the most frequently detected analytes. Concentration of total OPs (∑OPs) and total PFASs (∑PFASs) ranged from 1.9 to 37.7 ng g-1 lipid weight and from 0.066 to 0.356 ng mL-1, respectively.

Probabilistic risk assessment of the exposure to polybrominated diphenyl ethers via fish and seafood consumption in the Region of Valencia (Spain).

The study was carried out to estimate the dietary intake of polybrominated diphenyl ethers (PBDEs) in the Region of Valencia (Spain) in order to evaluate the resultant risk. The PBDE levels in fish and seafood (a total of 206 samples) were determined. Dietary intake was estimated using results of PBDE analyses in fish and seafood marketed in the Region of Valencia over the period 2007-2012 and data of the first Valencian Food Consumption Survey, conducted in 2010. Two scenarios were assumed for left-censored results: the lower-bound (LB) scenario, in which unquantified results (below the limit of quantification (LOQ)) were set to zero and the upper-bound (UB) scenario, in which unquantified results were set to the LOQ and two approaches (deterministic and probabilistic) were compared. The mean PBDE concentration in fish and seafood from Valencian markets was between 0.97 and 3.87 ngg(-1) w.w. and was similar to that reported recently by European Food Safety Authority (EFSA). Among the analysed congeners, BDE-47 showed the highest levels and salmon, mackerel and swordfish were the most contaminated species. The average estimated daily intake of the sum of PBDEs (upper bound scenario; probabilistic approach) for adults and children were 0.137 ngkg(-1) body weight (b.w.) day and 0.180 ngkgb.w.(-1)d(-1), respectively. In relation to risk analysis, calculated margins of exposure (MOEs) for the BDE-47, -99 and -153 congeners for children and do not indicate a health concern with respect to current dietary exposure in the Valencian Region and only 0.05% of the adult population and a 0.1% of children could be in risk derived by BDE-99 intake through fish.

Design of experiment approach for the optimization of polybrominated diphenyl ethers determination in fine airborne particulate matter by microwave-assisted extraction and gas chromatography coupled to tandem mass spectrometry.

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 723m(3) 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.

Determination of per- and polyfluorinated substances in airborne particulate matter by microwave-assisted extraction and liquid chromatography-tandem mass spectrometry.

A sensitive and confirmatory analytical method has been developed for the determination of 12 ionic per- and polyfluorinated alkyl substances (PFAS) in fine airborne particulate matter (PM2.5) at trace levels. The proposed method includes extraction of PM2.5-bound PFAS by microwave-assisted extraction (MAE) followed by centrifugation and injection into the liquid chromatograph coupled to a triple quadrupole tandem mass spectrometry system (LC-MS/MS). The main parameters affecting the performance of MAE were optimised using statistical design of experiments (DoE). Recoveries ranged from 83 to 120% and the method quantification limit (MQL) was 1.4 pg m(-3), when air volumes of 720 m(3) were sampled. This method was successfully applied to 41 samples collected from five stations of the monitoring network of the Valencian Regional Government (Spain) during April-July 2010. Eight out of 12 PFCs investigated were quantified in at least one sample (PFBA, PFPeA, PFHxS, 6:2 FTS, PFOA, PFNA, PFOS and PFDA). The measured concentrations ranged from 1.4 to 34.3 pg m(-3).