Simultaneous determination of 16 brominated flame retardants in food and feed of animal origin by fast gas chromatography coupled to tandem mass spectrometry using atmospheric pressure chemical ionisation.

A gas chromatography tandem mass spectrometry method using atmospheric pressure chemical ionisation was developed for the monitoring of 16 brominated flame retardants (7 usually monitored polybromodiphenylethers (PBDEs) and BDE #209 and 8 additional emerging and novel BFRs) in food and feed of animal origin. The developed analytical method has decreased the run time by three compared to conventional strategies, using a 2.5m column length (5% phenyl stationary phase, 0.1mm i.d., 0.1µmf.t.), a pulsed split injection (1:5) with carrier gas helium flow rate at 0.48mLmin(-1) in one run of 20 min. For most BFRs, analytical data were compared with the current analytical strategy relying on GC/EI/HRMS (double sector, R=10000 at 10% valley). Performances in terms of sensitivity were found to meet the Commission recommendation (118/2014/EC) for nBFRs. GC/APCI/MS/MS represents a promising alternative for multi-BFRs analysis in complex matrices, in that it allows the monitoring of a wider list of contaminants in a single injection and a shorter run time.

Country-specific chemical signatures of persistent organic pollutants (POPs) in breast milk of French, Danish and Finnish women.

The present study compares concentrations and chemical profiles of an extended range of persistent organic pollutants (dioxins, polychlorobiphenyls, brominated flame retardants and organochlorine pesticides) in breast milk samples from French (n = 96), Danish (n = 438) and Finnish (n = 22) women. Median exposure levels observed in French women (WHO-TEQ2005 PCDD/F = 6.1 pg/g l.w., WHO-TEQ2005 dl-PCB = 4.3 pg/g l.w., sum of 6 ndl-PCB = 85.2 ng/g l.w., sum of 7 i-PBDE = 1.5 ng/g l.w.) appeared overall lower than in Danish and Finnish women for all examined POPs, except for α-HBCD (2-fold higher level at 0.6 ng/g l.w.). Furthermore, the observed exposure levels of dioxins and PCBs were higher in Danish women (WHO-TEQ2005 PCDD/F = 13.2 pg/g l.w., WHO-TEQ2005 dl-PCB = 6.6 pg/g l.w., sum of 6 ndl-PCB = 162.8 ng/g l.w.) compared to Finnish women (WHO-TEQ2005 PCDD/F = 9.0 pg/g l.w., WHO-TEQ2005 dl-PCB = 4.6 pg/g l.w., sum of 6 ndl-PCB = 104.0 ng/g l.w.), whereas the concentrations of PBDEs were similar for Danish and Finnish women (sum of 7 i-PBDE = 4.9 and 5.2 ng/g l.w. respectively). The organochlorine (OC) pesticide contamination profile, determined in a subset of French samples, was dominated by p,p'-DDE (56.6%), followed by ß-HCH (14.2%), HCB (9.7%) and dieldrin (5.2%), while other compounds were only minor contributors (<5%). The three countries appeared to be discriminated by the observed contamination patterns of the PCDD/F versus PCB, and the 1,2,3,6,7,8-HxCDD versus 1,2,3,4,7,8-HxCDD ratios, in addition to the relative contributions of specific congeners to the contamination profile (PCBs #118 and #156, PBDEs #28, #47, #99 and #153). In conclusion, unique chemical signatures were observed for each country on the basis of some POP congeners. Future biomonitoring studies will need to consider the high variability of individual exposure profiles in relation to multiple exposure sources but also physiological and metabolic differences.

Broad spectrum analysis of 109 priority compounds listed in the 76/464/CEE Council Directive using solid-phase extraction and GC/EI/MS

A single multiresidue method was developed to determine 109 priority organic compounds included in the 76/464/EEC Council Directive on Pollution of the European Union. Such Directive includes 132 priority pollutants with a broad spectrum of polarities to be analyzed in drinking and surface waters, with the aim to protect water quality. From this list, the compounds analyzed included benzidines, chloroanilines, chloronitrobenzenes, chloronitrotoluenes, chlorophenols, chloronitrotoluidines, PAHs, PCBs, pesticides, phenylurea, and triazine herbicides. The method was developed in four steps. First, automated off-line solid-phase extraction using polymeric sorbent Oasis 60 mg cartridges was optimized to trap 109 compounds. Second, gas chromatography coupled to mass spectrometry with electron impact ionization (GC/EI/MS) was used in selected ion monitoring (SIM) mode for tentative identification of target analytes. Third, GC/EI/MS under full scan conditions was used for spectrum identification and analyte confirmation. Last, quantification was performed from SIM chromatogram using surrogates and internal standard. This method offered excellent sensitivity and selectivity, and the preconcentration of 200 mL permitted the achievement of limits of detection at the low nanogram/liter level and recoveries between 70 and 120%. Such methodology was applied to determine 109 organic compounds in French surface waters, and several pollutants were detected at levels from ppt to ppb. This multiresidue method developed was highly reproducible and robust and permitted a high sample throughput.