Contamination of soils by metals and organic micropollutants: case study of the Parisian conurbation.

Soils are playing a central role in the transfer and accumulation of anthropogenic pollutants in urbanized regions. Hence, this study aimed at examining the contamination levels of selected soils collected within and around the Paris conurbation (France). This also evaluated factors controlling contamination. Twenty-three trace and major elements as well as 82 organic micropollutants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalates (PAEs), polybrominated diphenyl ethers (PBDEs), alkylphenols (APs), and perfluoroalkylated substances (PFASs) were analyzed. Results reinforced the concern raised by the occurrence and levels of metals such as Zn, Pb, Cu, and Hg, identified as metallic markers of anthropogenic activities, but also pointed out the ubiquitous contamination of soils by organic micropollutants in the 0.2-55,000-µg/kg dw range. For well-documented compounds like PAHs, PCBs, and to a lesser extent PBDEs, contents were in the range of background levels worldwide. The pollutant stock in tested soil was compared to the annual atmospheric input. For PAHs; Pb; and to a lesser extent Zn, Cu, Cd, Hg, Sb, PAEs, and APs, a significant stock was observed, far more important than the recent annual atmospheric fluxes. This resulted from both (i) the persistence of a fraction of pollutants in surface soils and (ii) the cumulative atmospheric inputs over several decades. Regarding PBDEs and PFASs, stronger atmospheric input contributions were observed, thereby highlighting their recent dispersal into the environment.

A new analytical protocol for the determination of 62 endocrine-disrupting compounds in indoor air.

The objective of this study was to develop and validate a new analytical protocol for simultaneous determination of 62 semi-volatile organic compounds in both phases of indoor air. Studied compounds belong to several families: polybrominated diphenyl ethers, polychlorinated biphenyls, hexachlorobenzene, pentachlorobenzene, phthalates, polyaromatic hydrocarbons, parabens, tetrabromobisphenol A, bisphenol A, hexabromocyclododecane, triclosan, alkylphenols, alkylphenol ethoxylates, synthetic musks (galaxolide and tonalide) and pesticides (lindane and cypermethrin). A medium volume sampling system was used to collect simultaneously these endocrine-disrupting compounds (EDCs) from the gaseous and particulate phases. An accelerated solvent extraction method was optimized to obtain all EDCs in a single extract by atmospheric phase. Their extraction from the sorbents and their analysis by liquid and gas chromatography-mass spectrometry (LC/MS/MS, GC/MS and GC/MS/MS) was validated using spiked sorbents (recovery study and analytical uncertainty analysis by fully nested design). The developed protocol achieved low limits of quantification (<0.5ng m(-3)) and low uncertainty values (<5ng m(-3)) for all compounds. Once validated, the method was applied to indoor air samples from four locations (a house, an apartment, a day nursery and an office) and compared to literature to confirm its efficiency. All target EDCs were quantified in the samples and were primarily present in the gaseous phase. The major contaminants found in indoor air were, in descending order, phthalates, synthetic musks, alkylphenols and parabens.

Bioaccumulation of polybrominated diphenyl ethers by the freshwater benthic amphipod Gammarus pulex.

This study reports on the relationship between polybrominated diphenyl ether (PBDE) levels in water, sediment, and the benthic macroinvertebrate Gammarus pulex, which plays a major ecological role in freshwater ecosystems. Samples were taken in a periurban watershed (near Paris, France), and PBDEs were systematically detected in sediment (≤727 ng g(-1) OC) and G. pulex (≤264 ng g(-1) lipids). PBDEs were also occasionally detected in the water column at low levels (∑ PBDEs < 1.5 ng L(-1)). The log values of bioaccumulation factors were in the range 7.8 ± 0.1-8.3 ± 0.4 L kg(-1) for tetra- and penta-BDEs, which were the only ones quantified in the dissolved phase of river water. Meanwhile, levels of individual tri- to hepta-PBDE congeners in G. pulex generally positively correlated with sediment levels, suggesting an equilibrium situation. Biota-to-sediment accumulation factors (BSAFs) of tri-hepta BDEs were congener specific and were in the range 0.5 ± 0.3-2.6 ± 1.2. For several PBDEs, BSAF values deviated from the expected range, likely because of in vivo metabolism.

Influence of hydrological parameters on organohalogenated micropollutant (polybrominated diphenyl ethers and polychlorinated biphenyls) behaviour in the Seine (France).

The temporal dynamics of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were investigated in a heavily urbanized river (Seine River, Paris, France) from November 2009 to May 2010. Pollutant concentrations were in the range of 0.2 to 3.8 ng l(-1) (median 1.1) and 0.4 to 3.6 ng l(-1) (median 1.1) for ∑ tri-deca BDEs and ∑ 7PCBs, respectively. In addition, for both PBDEs and PCBs, the partitioning between the particulate and dissolved phases was investigated. Due to their low water solubility, PBDEs were mainly (>70%) bound to particles. In contrast, only 54% of ∑ 7PCBs occurred in the particulate phase, and their partitioning was influenced by the degree of chlorination. During the sampling period, PBDE/PCB fluxes were quite similar and ranged from 3 to 128 and from 6 to 125 g day(-1), respectively. The annual mass flow of PBDEs and PCBs was estimated to 10 kg for both. Contrary to PCBs and BDE-209, the temporal evolution of ∑ tri-hepta BDEs was related to particulate organic matter content, which is controlled by river flow variations. This suggests that they exhibit different sources or behavior in the Seine River.

Determination of polybrominated diphenyl ethers in fish tissues by matrix solid-phase dispersion and gas chromatography coupled to triple quadrupole mass spectrometry: case study on European eel (Anguilla anguilla) from Mediterranean coastal lagoons.

This paper describes the development and validation of an analytical methodology to determine 28 polybrominated diphenyl ethers (PBDEs) in European eel (Anguilla anguilla) tissues using matrix solid-phase dispersion (MSPD) and gas chromatography coupled to triple quadrupole mass spectrometry (GC-QQQ-MS/MS). A total of 28 PBDEs were targeted, including tri- to deca-brominated congeners. The robustness and effectiveness of the proposed sample preparation procedure was demonstrated in lipid-rich eel tissues. The use of batch MSPD with activated silica gel and H(2)SO(4)-impregnated silica gel, followed by H(2)SO(4) digestion and multilayer cartridge clean-up allowed for complete lipid removal and eliminated matrix effects during GC-QQQ-MS/MS analysis. The average PBDE recoveries from eel muscle samples spiked with PBDEs at two levels were in the range 56.2-119.0%. Precision was satisfactory since relative standard deviations were lower than 19.6%, regardless of spike level, and method quantification limits ranged between 1 and 170 pg g(-1) (wet weight). The method demonstrated its successful application for the analysis of eel samples from two coastal lagoons located on the western French Mediterranean coast. All samples tested positive, but for tri- to hexa-brominated congeners only and total PBDE levels observed in this study were in the range 0.08-1.80 ng g(-1) wet weight.

Development of analytical procedures for trace-level determination of polybrominated diphenyl ethers and tetrabromobisphenol A in river water and sediment.

The aim of this work was to develop procedures for the simultaneous determination of selected brominated flame retardants (BFRs) in river water and in river bed sediment. The target analytes were polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA). To determine dissolved BFRs, a novel mixed-mode solid-phase extraction procedure was developed by combining a hydrophobic sorbent (C(18)) with a silica-based anion exchange sorbent, so as to overcome the negative artefact induced by dissolved organic carbon. Extraction recoveries exceeded 73% for most analytes, except for BDE-183 and BDE-209 (57%). As regards suspended sediment and river bed sediment, extraction was carried out by means of ultrasonication (recoveries: 73-94%). These procedures, combined to gas chromatography coupled to negative chemical ionisation mass spectrometry (GC-NCI-MS), enabled the determination of BFRs at trace level: 3-160 pg L(-1) in river water, 5-145 pg g(-1) in bed sediment. These methods were applied to the determination of PBDEs and TBBPA in a suburban river (near Paris, France). PBDEs were systematically detected in the water column (SigmaBDEs, 2,300-4,300 pg L(-1)); they partitioned between the dissolved and particulate phases and BDE-209 was the dominant congener, followed by BDE-99 and BDE-47. TBBPA was detected in the dissolved phase only (<35-68 pg L(-1)). All selected BFRs were ubiquitous in bed sediments and levels ranged from 3,100 to 15,100 pg g(-1) and from 70 to 280 pg g(-1) (dry weight), for SigmaBDEs and TBBPA, respectively.