Polychlorinated Naphthalenes in Foods from the French Market: Occurrence, Dietary Exposure, and Evaluation of Relative Contributions to Dioxin-like Contaminants.

Despite the growing interest in PCNs and the dioxin-like toxicity exhibited by a number of congeners, a comprehensive assessment of their contribution to the cocktail of dioxin-like contaminants is still lacking. To address such a shortcoming, this study investigated the PCN contamination in foodstuffs recently acquired in France, together with that of the regulatory polychlorinated dibenzodioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs). PCNs were ubiquitous at levels (∑70 PCNs = 2.5-150 pg g-1 wet weight) similar to those reported in other countries, with maximum concentrations observed in fish and fishery products from the North-East Atlantic Ocean. Their congener patterns further suggested unintentional releases of PCNs, while those of the other foodstuffs were correlated to the historical PCN profiles. Low risk from dietary exposure was estimated (∑70 PCNs-EDIs of 60-360 pg kg-1 bw d-1, ∑24 PCNs-TEQ-EDIs of 8 × 10-3-2.2 × 10-2 pg TEQ kg-1 bw d-1), with milk and dairy products being the highest contributors, followed by meat and meat products. Finally, the rather high contributions of PCNs to the total PCNs+PCDD/Fs+PCBs concentrations (0.9-50%, average of 9%) and the toxic equivalents (0.2-24%, average of 5%) show that these substances are not minor components of the PCNs+PCDD/Fs+PCBs cocktail.

Health risk assessment to polychlorinated naphthalenes dioxin-like compounds in French sea food consumers.

There has been a recent revival of interest in some historical contaminants such as polychlorinated naphthalenes (PCNs). However, occurrence data are still lacking in some countries although industrial production of PCNs has been reported. This observation led to the first ever assessment of their presence in fish and seafood products in France in the present work. Their analysis was integrated in an already validated method applied for polychlorinated dibenzodioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs), based on the structural similarity existing between these POPs. Performances of the method (LODs in the range 0.10-0.28 pg g-1 wet weight (ww), LOQs in the range 0.33-0.93 pg g-1 ww), enabled monitoring 69 di-to octachlorinated congeners in a large representative set of fish and seafood samples collected in 2005 in four coastal areas of the French mainland (n > 30). Their systematic presence was demonstrated in all the investigated seafood products, with levels (ΣPCNs in the range 2-440 pg g-1 wet weight) close to those already reported in other European fish and seafood sampled at a similar period. In addition, the robust measurement of almost all possible PCNs (69/75) allowed a fine interpretation of the observed profiles, highlighting in particular the specificities between species and fishing areas. Compared to the PCDD/Fs, PCBs, and polybrominated diphenylethers levels also measured for this set of samples, PCNs were observed as minor contributors to total concentrations (0.05-3.2%). The specific PCN related dietary dioxin-like exposure could be evaluated at 0.028-0.051 pg of toxic equivalent (TEQ) per kg of body weight per week for an adult, based on fish and seafood consumption only. Overall, this study provides the first baseline data on the occurrence of a large number of PCNs in France, which will allow future evaluation of temporal trends and associated risks.

Passive sampling of chlorinated paraffins by silicone: Focus on diffusion and silicone-water partition coefficients.

Short-chain chlorinated paraffins (SCCPs) are under regulation through the European Water Framework Directive and were recently classified as POPs. Consecutively, the increasing use of middle-chain chlorinated paraffins (MCCPs) becomes of growing concern. Knowledge on the occurrence of chlorinated paraffins (CPs) is still scarce particularly in water phase. To achieve sufficient method sensitivity, the passive sampling approach, acting as a relevant alternative to usual grab sampling, has been considered only very recently for the monitoring of CPs in water. The present work aimed at determining the diffusion coefficients in silicone (Ds) and the silicone-water partition coefficients (Ksw) of various CP groups, having different chlorine contents and carbon chain lengths, in four commercial CP mixtures. Log Ds (-10.78 to -10.21) was found to vary little and to be high for the groups of CPs studied. Thus, their uptake in silicone is controlled by the water boundary layer, which allows to consider the release of performance and reference compounds for in-field estimation of the sampling rate. Moreover, CPs partitioned strongly towards silicone rubbers. Both the chlorination degree and the carbon chain length of CPs cause large uncertainties in the partitioning between silicone and water (log Ksw between 4.85 and 6.30), indicating that instead of an average value, differentiated Ksw should be used to estimate aqueous CPs more accurately. Even so, the probable influence of chlorine atoms position on polarity and partitioning may be an argument for favoring sampling in the kinetic stage.

First study of passive sampling to monitor short-chain chlorinated paraffins in water: Comparing capabilities of Chemcatcher® and silicone rubber samplers.

Short-chain chlorinated paraffins (SCCPs) are high-volume chemicals raising concerns because of their classification as priority hazardous substances by the European Water Framework Directive (WFD) and their recent inclusion in the persistent organic pollutants' (POPs) list by the Stockholm convention. As this group cover up to 5000 isomers, their measurement is still challenging. Hence the SCCPs occurrence in the environment is poorly documented in comparison with other POPs, especially in matrices where they are present at ultratrace levels such as waters. In the two-past decades, passive sampling has been increasingly used as it overcomes some major drawbacks associated to the conventional grab sampling. This study constitutes the first work aiming to examine the passive sampling's applicability for the monitoring of such complex analytes' mixtures in waters. Optimization and calibration of two proven passive samplers, namely silicone rubbers and Chemcatcher®, were performed through batch and laboratory pilot experiments. Despite the thousands of molecules present in the SCCPs mixture, the resulting global kinetic uptakes fitted well with the theorical model, for both samplers. Sampling rates of 8.0 L d-1 for silicone rubbers and 0.53 L d-1 for Chemcatcher® were found, and logKsw determined for silicone rubbers equaled 4.24 to 4.95. These values are in complete agreement with published data for other HOCs. A field trial carried out in marine coastal environments provided further evidence to demonstrate the applicability of the passive samplers to measure CPs amounts in water bodies. All these results unveil that passive sampling using silicone rubbers or Chemcatcher® can be a relevant approach to track traces of such complex mixtures in water.