Georges Scholl

Levels of dechloranes and polybrominated diphenyl ethers (PBDEs) in human serum from France.

Human exposure to dechloranes has been evaluated in Western Europe (France) with the analysis of Dechlorane Plus (DP), Dechloranes (Dec) 602, 603 and 604, Chlordene Plus (CP) and Mirex in 48 serum samples collected between 2003 and 2005. While no production source has been identified in Europe until now, detection frequencies for all investigated dechloranes were high, except for Dec 604 which was below detection limit for all samples. The mean DP concentration was 1.40±1.40ng/g lipid weight (lw), lower than levels reported in serum from Chinese population, but higher than levels reported in Canadian human milk. To the best of our knowledge, this is the first time that ∑5dechlorane levels are reported for human serum. A specific pattern of contamination was found (Dec 603>DP>Mirex>Dec 602>CP) compared to other biota samples that have been analyzed from Europe, with Dec 603 as the most abundant dechlorane (mean level: 2.61±2.63ng/g lw). Dec 603 and CP levels were correlated with age and with levels of some bioaccumulative organochlorine pesticides (OCPs). These results indicate that bioaccumulation properties should be further investigated and taken in consideration when assessing human exposure to dechloranes. For comparison purposes, polybrominated diphenyl ether (PBDE) levels were also measured for BDE-47, -99, -100, -153 and -154 in the serum samples. As expected, BDE-47 and BDE-153 were the major congeners with mean levels of 2.06±1.80ng/g lw and 1.39±0.97ng/g lw, respectively. The mean ∑5PBDE levels (4.32±2.99ng/g lw) were in the range typical of Western Europe levels, but lower than the mean ∑5dechlorane levels (6.24±4.16ng/g lw). These results indicate that the attention to dechloranes should be continued if research indicates toxicological concerns.

Importance of Fat Oxidation in Starch-Based Emulsions in the Generation of the Process Contaminant Furan

The formation of the possibly carcinogenic process contaminant furan was studied in starch-based emulsions during heat treatments as applied for sterilization. Fresh and oxidized soybean, sunflower, high-oleic sunflower, olive, linseed, and rapeseed oils were compared. Results indicated that both the oil type, in particular, the fatty acid composition, and the oxidation degree of the oil determined the susceptibility of the oils to generate furan upon heating. Thus, oils containing the nutritionally relevant omega-3 unsaturated alpha-linolenic acid proved to be able to generate significant amounts of furan if the oils were oxidized. No clear relationship between p-anisidine values of various oils and the amount of generated furan could be observed. However, in the case of soybean oil, significantly more furan was produced upon an increase in oxidation degree. Surprisingly, furan formation in food-relevant systems containing fresh lipids proved to be a minor route (up to 1.5 ppb furan) compared to a previously studied vitamin C containing model system (up to 13 ppb furan).

Furan formation from lipids in starch-based model systems, as influenced by interactions with antioxidants and proteins.

The formation of furan upon sterilization of a lipid-containing starch gel was investigated in the presence of various antioxidants, namely, α-tocopherol, β-carotene, and ascorbic acid, with and without proteins. Results indicated that α-tocopherol did not significantly influence furan formation from oxidized lipids. β-Carotene, suggested previously to be a furan precursor itself, did influence the generation of furan in a concentration-dependent manner, although to a limited extent. Surprisingly, the presence of lipids seemed to limit the furan generation from β-carotene. Interestingly, the addition of ascorbic acid to the emulsions containing soybean or sunflower oils considerably enhanced the formation of furan from these oils. This was also the case when fresh oils were applied, shown previously to be nearly unable to generate furan. This observation can be explained by an intensified ascorbic acid degradation stimulated by the presence of lipids.

POPs in free-ranging pilot whales, sperm whales and fin whales from the Mediterranean Sea: Influence of biological and ecological factors.

The pilot whale Globicephala melas, the sperm whale Physeter macrocephalus, and the fin whale Balaenoptera physalus are large cetaceans permanently inhabiting the Mediterranean Sea. These species are subjected to numerous anthropogenic threats such as exposure to high levels of contaminants. Therefore, selected persistent organic pollutants POPs (29 PCBs, 15 organochlorine compounds, 9 PBDEs and 17 PCDD/Fs) were analysed in blubber biopsies of 49 long-finned pilot whales, 61 sperm whales and 70 fin whales sampled in the North Western Mediterranean Sea (NWMS) from 2006 to 2013. Contamination profile and species feeding ecology were then combined through the use of stable isotopes. δ(13)C, δ(15)N values and POPs levels were assessed through IR-MS and GC-MS respectively. To assess the toxic potency of the dioxin-like compounds, the TEQ approach was applied. δ(15)N values were 12.2±1.3‰ for sperm whales, 10.5±0.7‰ for pilot whales and 7.7±0.8‰ in fin whales, positioning sperm whales at higher trophic levels. δ(13)C of the two odontocetes was similar and amounted to -17.3±0.4‰ for sperm whales and -17.8±0.3‰ for pilot whales; whilst fin whales were more depleted (-18.7±0.4‰). This indicates a partial overlap in toothed-whales feeding habitats, while confirms the differences in feeding behaviour of the mysticete. Pilot whales presented higher concentrations than sperm whales for ΣPCBs (38,666±25,731 ng g(-1)lw and 22,849±15,566 ng g(-1) lw respectively), ΣPBDEs (712±412 ng g(-1) lw and 347±173 ng g(-1) lw respectively) and ΣDDTs (46,081±37,506 ng g(-1) lw and 37,647±38,518 ng g(-1) lw respectively). Fin whales presented the lowest values, in accordance with its trophic position (ΣPCBs: 5721±5180 ng g(-1) lw, ΣPBDEs: 177±208 ng g(-1) lw and ΣDDTs: 6643±5549 ng g(-1) lw). Each species was characterized by large inter-individual variations that are more related to sex than trophic level, with males presenting higher contaminant burden than females. The discriminant analysis (DA) confirmed how DDTs and highly chlorinated PCBs were influential in differentiating the three species. Pollutant concentrations of our species were significantly higher than both their Southern Hemisphere and North Atlantic counterparts, possibly due to the particular Mediterranean geomorphology, which influences pollutants distribution and recycle. Dioxin-like PCBs accounted for over 80% of the total TEQ. This study demonstrated (1) an important exposure to pollutants of Mediterranean cetaceans, often surpassing the estimated threshold toxicity value of 17,000 ng g(-1) lw for blubber in marine mammals; and (2) how the final pollutant burden in these animals is strongly influenced not only by the trophic position but also by numerous other factors such as sex, age, body size and geographical distribution.

Levels of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls in human milk from different regions of France

We report on the pilot study carried out before the start of the Elfe project (French longitudinal study from childhood). A total of 44 samples of mature human milk were collected at home 8 weeks after delivery. A total of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), 12 dioxin-like (DL) polychlorinated biphenyls (PCBs), and 6 non dioxin-like (NDL)-PCBs were measured. For total TEQ (PCDD/Fs and DL-PCBs), the geometric mean concentration was 17.81 pg TEQ(WHO05)/g lipids. Relative PCDD, PCDF, and DL-PCB contributions to the arithmetic mean TEQ(WHO05) were 38%, 18%, and 44%, respectively. The use of TEF(WHO05) instead of TEF(WHO98) resulted in a 27% reduction of the total TEQ value. Although PCDD levels did not significantly change (less than 0.5% increase), PCDF and DL-PCB levels both decreased by 35% and 38%, respectively. Levels have been compared to data obtained during a previous non-reported national study conducted in 1998 (TEF(WHO98)) in French lactaria (n=244). The mean of PCDD/Fs has decreased about 39.4% (18.8 pg TEQ(WHO98)/g lipids in 1998 vs 11.4 pg TEQ(WHO98)/g lipids in pilot study), respectively 41.5% for PCDDs (10.6 pg TEQ(WHO98)/g lipids in 1998 vs 6.2 pg TEQ(WHO98)/g lipids in pilot study) and 36.7% for PCDFs (7.9 pg TEQ(WHO98)/g lipids in 1998 vs 5.0 pg TEQ(WHO98)/g lipids in pilot study). For the sum of the 6 NDL-PCBs, the 2007 geometric mean concentration in milk was 176.3 ng/g lipids. The arithmetic mean lipid concentration in 2007 breast milk was 26.4 g/l (range from 6.0 to 46.7 g/l). A PCDD/F and DL-PCB daily intake was estimated to be 62.3 pg TEQ(WHO05)/kg body weight per day (85.0 pg TEQ(WHO98)/kg body weight per day) for a baby of 5 kg of body weight fed daily with 700 ml of maternal milk containing 25 g/l of lipids.

Dioxin levels in fertilizers from Belgium: determination and evaluation of the potential impact on soil contamination.

Dioxins are harmful persistent organic pollutants (POPs) to which humans are exposed mostly via the consumption of animal products. They can enter the food chain at any stage, including crop fertilization. Fertilizers belong to several categories: synthetic chemicals providing the essential elements (mostly N, P and K) that are required by the crops but also organic fertilizers or amendments, liming materials, etc. Ninety-seven samples of fertilizers were taken in Belgium during the year 2011 and analyzed after a soft extraction procedure for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) using GC-IDHRMS. Only small qualitative differences could be observed between the main fertilizer categories since the PCDD:PCDF:DL-PCB average ratio obtained with the results expressed in TEQ was often close to 30:30:40 (typically for sewage sludge) or 40:30:30 (typically for compost). The median dioxin levels determined were generally lower than recorded previously and were the highest for sewage sludge and compost (5.6 and 5.5 ng TEQ/kg dry weight (dw), respectively). The levels in other fertilizers were lower including manure for which the median value was only 0.2 ng TEQ/kg dw. Several fertilization scenarios relying on the use of those fertilizers were assessed taking into consideration the application conditions prevailing in Belgium. From this assessment it could be concluded that the contribution of fertilizers to the overall soil contamination will be low by comparison of other sources of contamination such as atmospheric depositions. At the field scale, intensive use of compost and sewage sludge will increase dramatically the dioxin inputs compared with other fertilization practices but this kind of emission to the soil will still be relatively low compared to the dioxin atmospheric depositions.

Estimation of furan contamination across the Belgian food chain

This paper provides an estimate of the furan content of Belgian foods. The objective of the study was to achieve the best food chain coverage with a restricted number of samples (n = 496). The geographic distribution, different market chains and labels, and consumption frequencies were taken into account in the construction of the sampling plan. Weighting factors such as contamination levels, consumption frequency and the diversity of food items were applied to set up the model. The very low detection capabilities (CCβ) of the analytical methods used (sub-ppb) allowed reporting of 78.2% of the overall dataset above CCβ and, in particular, 96.7% for the baby food category. The highest furan levels were found in powdered roasted bean coffee (1912 µg kg−1) with a mean of 756 µg kg−1 for this category. Prepared meat, pasta and rice, breakfast cereals, soups, and baby food also showed high mean furan contents ranging from 16 to 43 µg kg−1. Comparisons with contamination surveys carried out in other countries pointed out differences for the same food group and therefore contamination levels are related to the geographical origin of food items.

Risk assessment of Belgian adults for furan contamination through the food chain

Risk assessment is an interdisciplinary process used to quantify the risk linked to a hazard. In the present paper it is applied to quantify the risk linked to furan ingestion through the food chain for the Belgian adult population. Two approaches, deterministic and probabilistic, were carried out in parallel. The deterministic method relied on a case study, whereas the probabilistic approach involved statistical distributions of contamination and consumption data to calculate a statistical distribution of the daily intake. First, the deterministic method revealed a low estimated daily intake (EDI) for the average population (380 ng*(kgbw*day)–1) and a huge contribution of coffee consumption to the EDI (55%). Increasing or decreasing the daily coffee consumption by one cup can affect the EDI by about 22%. Afterwards, the probabilistic approach showed that the average population has a low EDI (494 ng*(kgbw*day)−1), and that high contamination levels were only registered in a small proportion of the population. Finally, a comparison of the RfDchronic oral showed that less than 10% of the Belgian population had an EDI above the reference dose proposed by the USEPA; the majority of the population had an EDI 20% below the reference dose. The margin of exposure (MoE) approach indicated that the level of risk related to furan intake through ingestion is low, with a MoE > 10,000 for more than 10% of the population and no result < 100.

The performance of atmospheric pressure gas chromatography–tandem mass spectrometry compared to gas chromatography–high resolution mass spectrometry for the analysis of polychlorinated dioxins and polychlorinated biphenyls in food and feed samples

Recently, gas chromatography tandem mass spectrometry (GC-MS/MS) has been added in European Union (EU) legislation as an alternative to magnetic sector high resolution mass spectrometry (HRMS) for the analysis of dioxins and dioxin like polychlorinated biphenyls (dl-PCB) in food and feed. In this study the performance of APGC-MS/MS compared to GC-HRMS is investigated and compared with EU legislation. The study includes the legislative parameters, relative intermediate precision standard deviation (SRw,rel), trueness, sensitivity, linear range and ion ratio tolerance. In addition, over 200 real samples of large variety and spanning several orders of magnitude in concentration were analyzed by both techniques and the selectivity was evaluated by comparing chromatograms. The SRw,rel and trueness were evaluated using (in-house) reference samples and fulfill to EU legislation, though the SRw,rel was better with GC-HRMS. The sensitivity was considerably better than of GC-HRMS while the linear range was similar. Ion ratios were mostly within the tolerable range of ±15%. A (temporary unresolved) systematic deviation in ion ratio was observed for several congeners, yet this did not lead to exceeding of the maximum ion ratio limits. The APGC-MS/MS results for the non-dioxin-like-PCBs (ndl-PCBs) were negatively biased, particularly for PCB138 and 153 in contaminated samples. The selectivity of APGC-MS/MS was lower for several matrices. Particularly for contaminated samples, interfering peaks were observed in the APGC chromatograms of the native compounds (dioxins) and labeled internal standards (PCBs). These can lead to biased results and ultimately to false positive samples. It was concluded that the determination of dioxins and PCBs using APGC-MS/MS meets the requirements set by the European Commission. However, due to generally better selectivity and SRw,rel, GC-HRMS is the preferred method for monitoring purposes.

Dietary early-life exposure to contaminated eels does not impair spatial cognitive performances in adult offspring mice as assessed in the Y-maze and the Morris water maze

Many environmental contaminants are introduced via the diet and may act as neurotoxins and endocrine disrupters, especially influencing growing organisms in early life. The purpose of this study was to examine whether dietary exposure of dams to fish naturally contaminated with xenobiotics, especially with polychlorinated biphenyls (PCBs) and heavy metals (e.g., mercury and lead), resulted in cognitive function deficits in adult offspring mice. Daily, four groups of dams (n = 10/group) ingested standard diet plus paste with/without eels, during gestation and lactation, from gestational day (GD) six until post natal day (PND) 21 (weaning). Dams orally ingested a standardized amount of eel (0.8 mg kg(-1) d(-1)) containing the six non-dioxin-like (NDL) PCBs (Σ6 NDL-PCBs: 28, 52, 101, 138, 153, and 180) at 0, 85, 216, and 400 ng kg(-1) d(-1). Results showed that early-life exposure to contaminated eels did not (compared to non-exposed controls) impair immediate working memory in the Y-maze in the offspring assessed at PND 38. Furthermore, it did not significantly impact spatial learning and retention memory as measured in the Morris water maze in adult offspring mice (PND 120-123). Our results suggest that perinatal exposure to contaminated eels does not affect spatial cognitive performances, as assessed by the Y-maze and Morris water maze at adult age. Adverse effects of xenobiotics reported earlier might be camouflaged by beneficial eel constituents, such as n-3 fatty acids. However, additional studies are needed to differentiate between potential positive and negative effects following consumption of food items both rich in nutrients and contaminants.