Field investigation to determine the environmental source of PCBs in a pig farm.

During a national monitoring plan, a pork fat sample was declared non-compliant for the sum of dioxins and PCB-DL (EU regulation). The National Reference Laboratory together with competent authorities conducted extended investigations to determine rapidly the contamination source at the farm level. A range of samples (n = 129), representative of potential contamination sources, was selected for further characterization (fat, feed, materials, dust, soil) and was analyzed for PCDD/Fs and DL-PCBs by GC-HRMS. A hot spot was localized in the farm, which corresponded to a pre-feed storage tank, the paints of which presented huge DL-PCB concentrations (>1 × 106 pg g-1), responsible for the contamination. The present case report describes a new source of PCB contamination, previously undescribed.

Dietary exposure to polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls of the French population: Results of the second French Total Diet Study.

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) bioaccumulate through the food chain and are therefore of public health concern. Exposure to these compounds was assessed in the second French Total Diet Study (TDS). Food samples (n=583) were collected to be representative of the whole diet of the population, prepared as consumed, and analyzed. Contamination data were combined with national individual food consumption data. Mean exposure (95th percentile) to PCDD/F+DL-PCBs was assessed to be 0.57 (1.29) pg TEQ(WHO-98) (kg bw)(-1) d(-1) in the adult population and 0.89 (2.02) pg TEQ(WHO-98) (kg bw)(-1) d(-1) in the child and teenager population. Less than 4% of the population exceeded the health-based guidance value for PCDD/F+DL-PCBs. Mean exposure (95th percentile) to the six indicator PCBs (PCB 28, 52, 101, 138, 153, 180) was estimated at 2.71 (7.90) ng (kg bw)(-1) d(-1) in the adult population and 3.77 (11.7) ng (kg bw)(-1) d(-1) in the child and teenager population. Only 2.6% of the adults [CI(95%): 1.9; 3.3] and 6.5% of the children and teenagers [5.2; 7.8] exceeded the health-based guidance value for total PCBs. These results show that the contamination levels in food and therefore the exposure of the general French population to PCDD/Fs and PCBs have declined (by a factor of 3.2 for PCDD/F+DL-PCBs and about three for total PCBs) since the last evaluation, which was conducted using another methodology in 2005 and 2007, and show the efficiency of the European risk management measures which came into force after these evaluations.

Predicting PCDD/F and dioxin-like PCB contamination levels in bovine edible tissues from in vivo sampling.

European Union regulation has defined maximum levels for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/F) and dioxin-like polychlorinated biphenyls (PCB) in food from animal origin. In case of particular event where livestock is potentially exposed to a specific source of contamination, the possibility of accurate estimation of the PCDD/F and dioxin-like PCB levels in edible tissues of the animals from in vivo and weakly invasive biological matrices (fast animal recovery, no major side effects) may be of clear valuable interest. This study investigated the correlations between contamination levels determined in subcutaneous adipose tissue and blood samples obtained from living animals and those measured after slaughtering in muscle and liver. The obtained results demonstrated very good correlations between these in vivo and ex vivo samples in terms of PCDD/F and PCB contamination levels. Finally, it seems to be demonstrated that a weakly invasive biopsy of subcutaneous adipose tissue performed on living animal (potentially completed by a blood sample) can be used in order to predict contamination levels in muscle and liver destined to human consumption.

Prediction of the PCDD/F and dl-PCB 2005-WHO-TEQ content based on the contribution of six congeners: toward a new screening approach for fish samples?

Current European Union regulation regarding polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in food and feed is based on Toxic Equivalent Quotient (TEQ) concept. For confirmatory purpose, the isotope-dilution method associated to a measurement by gas chromatography coupled with high resolution mass spectrometry is usually the method of choice for precisely measuring the 29 target congeners in three separated fractions. Time and cost related to these analyses are very significant. Various kinds of screening concepts can be considered. In the present study, we elaborated and validated a prediction model for the 2005 World Health Organization TEQ in fish, based on the measurement of 4 PCDD/F and 2 non-ortho dl-PCB congeners, potentially analyzable in a single extracted fraction by gas chromatography coupled with mass spectrometry. Large independent datasets have been used for model elaboration (n=108) and validation (n=363, n=357 and n=6).

Innovative method for determination of 19 polycyclic aromatic hydrocarbons in food and oil samples using gas chromatography coupled to tandem mass spectrometry based on an isotope dilution approach.

An efficient and selective analytical method for the determination and the quantification of 19 polycyclic aromatic hydrocarbons (PAHs) in food and oil has been developed. This method includes the monitoring of 15 PAHs stated as a priority by the EU in their 2005/108 recommendation. The samples were extracted according to a selective extraction step using pressurized liquid extraction followed by a purification with polystyrene-divinylbenzene SPE. Identification and quantification were performed using GC-MS/MS, with an isotope dilution approach using (13)C-labelled PAHs. The novel combination of selective extraction followed by purification provides highly purified analytes combined to a fast and automated method. The advantages of GC-MS/MS as compared to other detection methods are tremendous in terms of sensitivity, selectivity and interpretation facilities. Limits of detection varied between 0.008 and 0.15 microg kg(-1), limits of quantification between 0.025 and 0.915 microg kg(-1) for PAHs in food. The calibration curves showed a good linearity for all PAHs (R(2)>0.99) and precision and recovery were fit for purpose. Trueness of the method was carried out using the US National Institute of Standards and Technology SRM 2977 reference material.

Analytical strategies for the direct mass spectrometric analysis of steroid and corticosteroid phase II metabolites.

The use of steroid hormones as growth promoters remains illegal in Europe. A classical approach used to control their utilization consists to measure the parent drug in target biological matrices. However, this strategy may fail when the parent drug is submitted to extensive metabolism reactions. For urine and tissue samples, chemical or enzymatic hydrolysis is usually applied in order to deconjugate glucuronide and sulfate phase II metabolites. But this treatment lead to the loss of information such as nature and relative proportions of the different conjugated forms, which can be useful, for example, to discriminate an endogenous production from an exogenous administration for natural hormones, or for other clinical or biochemical specific applications. For these purposes, direct measurement of conjugated metabolites using liquid chromatography-tandem mass spectrometry may represent a solution of choice. In this context, the mass spectrometric behavior of 14 steroid and corticosteroid phase II metabolites after electrospray ionization was investigated. Their fragmentation pathways in tandem mass spectrometry revealed some specificities within the different group of conjugates. A specific acquisition program (MRM mode) was developed for the unambiguous identification of the studied reference compounds. A more generic method (Parent Scan mode) was also developed for fishing approaches consisting to monitor several fragment ions typical of each conjugate class. A reverse phase HPLC procedure was also proposed for efficient retention and separation of the studied compounds. Finally, a protocol based on quaternary amine SPE was developed, permitting the separation of free, glucuronide, and sulfate fractions. Preliminary results on biological samples demonstrated the suitability of this analytical strategy for direct measurement of dexamethasone glucuronide and sulfate residues in bovine urine.