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.

Occurrence of antibiotics in rural catchments.

The transfer of 23 antibiotics from domestic and hospital sources was investigated in two elementary river watersheds receiving wastewater treatment plant (WWTP) discharges, in relation with the hydrological cycle and seasonal conditions. Antibiotic concentrations in the effluent of a WWTP treating wastewaters from both hospital and domestic sources (18-12 850 ng L-1) were far higher than those from domestic sources exclusively (3-550 ng L-1). In rivers, upstream of the WWTP discharges, fluoroquinolones only were found at low concentrations (≤10 ng L-1). Their presence might be explained by transfer from contaminated agricultural fields located on the river banks. Immediately downstream of the WWTP discharge, antibiotic occurrence increased strongly with mean concentrations up to 1210 ng L-1 for ofloxacin and 100% detection frequencies for vancomycin, sulfamethoxazole, trimethoprim and three fluoroquinolones. Dilution processes during high-flow periods led to concentrations 14 times lower than during low-flow periods. Downstream of the discharge, the antibiotic dissipation rate from the water column was higher for fluoroquinolones, in relation with their high sorption upon suspended matter and sediment. Only five antibiotics (vancomycin and four fluoroquinolones ciprofloxacin, norfloxacin, ofloxacin and enoxacin) were partly distributed (11%-36%) in the particulate phase. Downstream of the discharge, antibiotic contents in sediment ranged from 1700 to 3500 ng g-1 dry weight, fluoroquinolones accounting for 97% of the total.

Fate of antibiotics from hospital and domestic sources in a sewage network.

Investigation of domestic and hospital effluents in a sewage system of an elementary watershed showed that antibiotics belonging to eight classes were present with concentrations ranging from

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.

Endocrine disrupting compounds in gaseous and particulate outdoor air phases according to environmental factors.

This study investigated, for the first time in France, the spatial and temporal patterns of 55 endocrine disrupting chemicals (EDCs) in ambient air at three sites (urban, suburban and forest) under two climatic periods (warm/cold) for 2 successive years. All EDCs, except tetrabromobisphenol A (TBBPA), were encountered with various frequencies of up to 100%. Phthalate diesters (PAEs) were the most abundant chemicals with total concentrations as the sum of compounds, ranging from 10 to 100 ng m(-3) of total air, followed by alkylphenols (APs) and polycyclic aromatic hydrocarbons (PAHs), which were both approximately 1 ng m(-3). Polychlorinated biphenyl (PCBs) and bisphenol A (BPA) concentrations were notably lower (approximately 0.1 ng m(-3)). Air concentrations, depending on the considered compounds, were from 1.2 to 2 times higher in the urban than the suburban area and from 2 to 5 times higher in the urban than the forest site. PAH emissions were higher in the cold period, due to combustion processes. This finding is contrary to the other EDCs that are more abundant in the summer and governed by volatilisation. Most of the EDCs were largely distributed in the gaseous phase (>80% in the summer). The octanol/air partition coefficient (KOA) and vapour pressure (Vp) were relevant parameters for predicting EDC partitioning and direct relationships (p < 0.001) were observed i) between log K particle/gas partitioning (log Kp) and log KOA and ii) between EDC ratios in the gaseous phase and log vapour pressure (log Vp).

Combining measurements and modelling to quantify the contribution of atmospheric fallout, local industry and road traffic to PAH stocks in contrasting catchments.

Various sources supply PAHs that accumulate in soils. The methodology we developed provided an evaluation of the contribution of local sources (road traffic, local industries) versus remote sources (long range atmospheric transport, fallout and gaseous exchanges) to PAH stocks in two contrasting subcatchments (46-614 km²) of the Seine River basin (France). Soil samples (n = 336) were analysed to investigate the spatial pattern of soil contamination across the catchments and an original combination with radionuclide measurements provided new insights into the evolution of the contamination with depth. Relationships between PAH concentrations and the distance to the potential sources were modelled. Despite both subcatchments are mainly rural, roadside areas appeared to concentrate 20% of the contamination inside the catchment while a local industry was found to be responsible for up to 30% of the stocks. Those results have important implications for understanding and controlling PAH contamination in rural areas of early-industrialized regions.

Mass balance and decontamination times of Polycyclic Aromatic Hydrocarbons in rural nested catchments of an early industrialized region (Seine River basin, France).

Accumulation of Polycyclic Aromatic Hydrocarbons (PAHs) in soils and their subsequent release in rivers constitute a major environmental and public health problem in industrialized countries. In the Seine River basin (France), some PAHs exceed the target concentrations, and the objectives of good chemical status required by the European Water Framework Directive might not be achieved. This investigation was conducted in an upstream subcatchment where atmospheric fallout (n=42), soil (n=33), river water (n=26) and sediment (n=101) samples were collected during one entire hydrological year. PAH concentrations in atmospheric fallout appeared to vary seasonally and to depend on the distance to urban areas. They varied between 60 ng·L(-1) (in a remote site during autumn) and 2,380 ng·L(-1) (in a built-up area during winter). PAH stocks in soils of the catchment were estimated based on land use, as mean PAH concentrations varied between 110 ng·g(-1) under woodland and 2,120 ng·g(-1) in built-up areas. They ranged from 12 to 220 kg·km(-2). PAH contamination in the aqueous phase of rivers remained homogeneous across the catchment (72 ± 38 ng·L(-1)). In contrast, contamination of suspended solid was heterogeneous depending on hydrological conditions and population density in the drainage area. Moreover, PAH concentrations appeared to be higher in sediment (230-9,210 ng·g(-1)) than in the nearby soils. Annual mass balance calculation conducted at the catchment scale showed that current PAH losses were mainly due to dissipation (biodegradation, photo-oxidation and volatilization) within the catchments (about 80%) whereas exports due to soil erosion and riverine transport appeared to be of minor importance. Based on the calculated fluxes, PAHs appeared to have long decontamination times in soils (40 to 1,850 years) thereby compromising the achievement of legislative targets. Overall, the study highlighted the major role of legacy contamination that supplied the bulk of PAHs that are still found nowadays in the environment.

Measurement of trace levels of antibiotics in river water using on-line enrichment and triple-quadrupole LC-MS/MS.

This study presents the development of an automated on-line solid phase extraction (SPE)-liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the determination of 23 antibiotics in environmental water samples. After optimisation of LC-MS/MS conditions, SPE parameters such as sorbent type, sample pH or sample volume were optimised. Antibiotic recoveries ranged from 64% to 98% and compared favourably with those achieved using off-line SPE. Limits of detection were in the range 0.5-13.7 ng L(-1). This on-line SPE-LC-MS/MS procedure was applied to the analysis of water samples taken in three rivers within the Seine River basin, near Paris (France). The obtained results revealed the occurrence of 12 antibiotics, including tylosin, erythromycin, tetracycline, amoxicillin, trimethoprim, sulfamethoxazole, oxolinic acid, flumequine, norfloxacin, ciprofloxacin, ofloxacin, and vancomycin (2-1435 ng L(-1)).

Transfer of glyphosate and its degradate AMPA to surface waters through urban sewerage systems.

A study of glyphosate and aminomethyl phosphonic acid (AMPA) transfer in the Orge watershed (France) was carried out during 2007 and 2008. Water samples were collected in surface water, wastewater sewer, storm sewer and wastewater treatment plant (WWTP). These two molecules appeared to be the most frequently detected ones in the rivers and usually exceeded the European quality standard concentrations of 0.1microg L(-1) for drinking water. The annual glyphosate estimated load was 1.9 kg year(-1) upstream (agricultural zone) and 179.5 kg year(-1) at the catchment outlet (urban zone). This result suggests that the contamination of this basin by glyphosate is essentially from urban origin (road and railway applications). Glyphosate reached surface water prevalently through storm sewer during rainfall event. Maximum concentrations were detected in storm sewer just after a rainfall event (75-90 microg L(-1)). High concentrations of glyphosate in surface water during rainfall events reflected urban runoff impact. AMPA was always detected in the sewerage system. This molecule reached surface water mainly via WWTP effluent and also through storm sewer. Variations in concentrations of AMPA during hydrological episodes were minor compared to glyphosate variations. Our study highlights that AMPA and glyphosate origins in urban area are different. During dry period, detergent degradation seemed to be the major AMPA source in wastewater.

Vertical and temporal distribution of persistent organic pollutants in Toronto. 1. Organochlorine pesticides.

From May to September 2005, five passive air samples were deployed over five, 1-month periods at five elevations on the CN Tower in Toronto, Canada, to investigate the vertical distribution, seasonality, and sources of organochlorine pesticides. A strong seasonality was observed between spring and the end of summer. Vertical profiles differed for different pesticide classes. For instance, alpha- and gamma-hexachlorocyclohexane exhibited higher concentrations (60-80 pg m(-3), respectively) near the ground during the spring and early summer, suggesting that surface-air exchange within the city or nearby Lake Ontario may be important sources. The vertical profile for chlordane isomers was variable, suggesting that both advective and local inputs are important. For dieldrin, no obvious trend with elevation was observed, suggesting that concentrations could reflect a regional air mass contamination. Strongest seasonality was observed for the endosulfans, a widely used pesticide in North America, that reached peak concentrations of 750-850 pg m(-3) during June/July. Advective inputs of endosulfan from regional or more distant agricultural regions can explain the relatively uniform concentrations with elevation throughout the study period. The approach used in this study demonstrates that monthly average vertical concentration profiles differ between pesticide groups and reflect their use as well as the relative magnitude of input from local versus regional sources.