Effect of an environmental microplastic mixture from the Seine River and one of the main associated plasticizers, dibutylphthalate, on the sentinel species Hediste diversicolor.

The aim of this study was to explore the adverse effects of a microplastic (MP) mixture obtained from litter accumulated in the Seine River (France) compared to those of their major co-plasticizer, dibutylphthalate (DBP), on the sentinel species Hediste diversicolor. A suite of biomarkers has been investigated to study the impacts of MPs (100 mg kg-1 sediment), DBP (38 µg kg-1 sediment) on worms compared to non-exposed individuals after 4 and 21 days. The antioxidant response, immunity, neurotoxicity and energy and respiratory metabolism were investigated using biomarkers. After 21 days, worms exposed to MPs showed an increasing aerobic metabolism, an enhancement of both antioxidant and neuroimmune responses. Energy-related biomarkers demonstrated that the energy reallocated to the defence system may come from proteins. A similar impact was depicted after DBP exposure, except for neurotoxicity. Our results provide a better understanding of the ecotoxicological effects of environmental MPs and their associated-contaminants on H. diversicolor.

Occurrence and fate of an emerging drug pollutant and its by-products during conventional and advanced wastewater treatment: Case study of furosemide.

Conventional wastewater treatment systems are not designed to remove pharmaceutical compounds from wastewater. These compounds can be degraded into many other transformation products which are hardly, if at all, studied. In this context, we studied the occurrence and degradation of furosemide, a very frequently detected diuretic, along with its known degradation products in several types of wastewater. Influent and effluent from the Seine-Centre Wastewater Treatment Plant (WWTP) (Paris, France) as well as outlet of residential care homes (Dordogne, France) were analyzed by Ultra-Performance Liquid Chromatography-tandem Mass Spectrometry (UPLC-MS/MS) to quantify furosemide and its known degradation products, saluamine and pyridinium of furosemide. Oxidation experiments (chlorination, ozonation and UV photolysis with hydrogen peroxide) were then performed on furosemide solutions and on water from residential care facilities to study the degradation of furosemide by potential advanced processes, and also to identify unknown oxidation products by high-resolution mass spectrometry. Furosemide was well degraded in Seine-Centre WWTP (>75%) but did not increase the concentrations of its main degradation products. Saluamine and pyridinium of furosemide were already present at similar concentrations to furosemide in the raw wastewater (∼2.5-3.5 µg.L-1), and their removal in the WWTPs were very high (>80%). Despite their removal, the three compounds remained present in treated wastewater effluents at concentrations of hundreds of nanograms per liter. Chlorination degraded furosemide without pyridinium production unlike the other two processes. Chlorination and ozonation were also effective for the removal of furosemide and pyridinium in residential care home water, but they resulted in the production of saluamine. To our knowledge this is the first evidence of saluamine and pyridinium of furosemide in real water samples in either the particulate or dissolved phase.

Evaluation of Sample Preparation Methods for Non-Target Screening of Organic Micropollutants in Urban Waters Using High-Resolution Mass Spectrometry.

Non-target screening (NTS) has gained interest in recent years for environmental monitoring purposes because it enables the analysis of a large number of pollutants without predefined lists of molecules. However, sample preparation methods are diverse, and few have been systematically compared in terms of the amount and relevance of the information obtained by subsequent NTS analysis. The goal of this work was to compare a large number of sample extraction methods for the unknown screening of urban waters. Various phases were tested for the solid-phase extraction of micropollutants from these waters. The evaluation of the different phases was assessed by statistical analysis based on the number of detected molecules, their range, and physicochemical properties (molecular weight, standard recoveries, polarity, and optical properties). Though each cartridge provided its own advantages, a multilayer cartridge combining several phases gathered more information in one single extraction by benefiting from the specificity of each one of its layers.

Innovative combination of tracing methods to differentiate between legacy and contemporary PAH sources in the atmosphere-soil-river continuum in an urban catchment (Orge River, France).

Polycyclic aromatic hydrocarbons (PAH) have been released by human activities during more than a century, contaminating the entire atmosphere - soil - river continuum. Due to their ubiquity in the environment and their potential severe biological impacts, PAH became priority pollutants and were targeted by environmental public agencies. To better manage PAH pollution, it is necessary to identify unambiguously the sources and pathways of those compounds at the catchment scale, and to evaluate the persistence of historical PAH pollution in the environment especially in those urban contexts concentrating multiple PAH sources. Accordingly, the current research monitored the contamination in atmospheric fallout, soils and rivers of a 950-km2 catchment (Orge River) characterized by an increasing urban gradient in downstream direction, and located in the Seine River basin characterized by a high level of PAH legacy contamination. A combination of various approaches was used, including the widely used PAH diagnostic ratios, together with innovative methods such as PAH correlations and sediment fingerprinting using fallout radionuclides to clearly identify both the origin of PAH and their main PAH pathways to the river. The results demonstrated the persistence of legacy PAH contamination in the catchment, responsible for the signature of the suspended particulate matter currently transiting in the Orge River. They underlined the conservation of PAH through the soil - river continuum. Finally, urban runoff was demonstrated to provide the main PAH source to the river in the densely urbanized area by both PAH correlations and sediment fingerprinting. These results were used to model PAH concentrations in those particles supplied from urban areas to the river.

Retention and transport processes of particulate and dissolved micropollutants in stormwater biofilters treating road runoff.

Road runoff is contaminated by various micropollutants and may be treated using low impact development techniques, such as stormwater biofilters. Better understanding the processes, such as filtration, sorption and leaching, which affect pollutants in these systems is essential to reliably predicting treatment performance and optimizing system design. Field data from an in situ monitoring campaign, wherein dissolved and particulate concentrations of a wide range of micropollutants (trace metals, polycyclic aromatic hydrocarbons, bisphenol-A, alkylphenols and phthalates) were characterized in untreated road runoff and biofilter outlets for 19 rain events, are used to explore transport and retention processes. Although retention of the particulate phase of pollutants was generally quite effective, unusually high particle concentrations were observed at biofilter outlets for three winter events. Particle characterization in road runoff and outlet waters revealed that this degraded performance was due to poor filtration rather than particle erosion, which was attributed to the relative abundance of small (<10 µm) particles during this period, along with possible preferential flows. Dissolved pollutants were less effectively removed in general. To better understand this behavior, field results were combined with laboratory sorption and leaching tests. Dissolved concentrations of trace metals were shown to be influenced by organic carbon; leaching from road-originated particles may also influence their transport. Removal of the dissolved phase of organic micropollutants was limited by the contamination of the filter media, either before installation or during the first period of operation, due to emissions from construction materials.

Impact of urban pressure on the spatial and temporal dynamics of PAH fluxes in an urban tributary of the Seine River (France).

Polycyclic aromatic hydrocarbons (PAHs) produced by numerous anthropogenic activities are ubiquitous in the environment and have become a priority concern due to their potential severe biological impacts. A better understanding of PAH transfer at the catchment scale is therefore necessary to improve the management of PAH contaminants and protect rivers. Furthermore, the impact of changes in hydrological regimes and land uses on PAH fluxes should be specifically investigated. Accordingly, the current research monitors the contamination in atmospheric fallout, soils and rivers in a 950-km2 catchment (Orge River) characterized by an increasing urban gradient in downstream direction. During an entire hydrological year, river water contamination was quantified through regular sampling of both particulate and dissolved material at four river-monitoring stations, reflecting the increasing urbanization gradient. The significant input of PAHs from urban areas in downstream river sections corresponded to a specific PAH flux that reached 23 g km-2 y-1 despite the low sediment yield. Moreover, the comparison with runoff-specific fluxes reported in the literature underlined the major impact of urban runoff on the Orge River water and sediment quality. Nevertheless, the annual PAH load exported by the river (21 kg y-1) remained lower than the PAH inputs from atmospheric fallout (173 kg y-1), demonstrating the continuous accumulation of PAH from atmospheric fallout in the catchment soils. Consequently, the notably large PAH stock (close to 1000 tons) resulting from historical contamination of this early-industrialized region continues to increase due to ongoing atmospheric inputs.

Field performance of two biofiltration systems treating micropollutants from road runoff.

The treatment efficiency of a vegetative filter strip and a biofiltration swale treating heavily loaded road runoff are evaluated. Concentrations measured in water drained from the two systems are compared to those in untreated road runoff collected from a reference catchment for a wide range of contaminants including organic carbon, nutrients (N and P), trace metals, and organic micropollutants (polycyclic aromatic hydrocarbons (PAH), total petroleum hydrocarbons (TPH), alkylphenols, bisphenol-A, phthalates), in both total and dissolved phases. Predominantly particulate pollutants, including Pb, Zn and PAH, were very efficiently removed (around 90%) for most events. However, poor particulate removal was observed during a winter period. Relatively few pollutants were significantly removed in the dissolved phase and observed concentration reductions tended to be lower than those of suspended solids and associated pollutants; as such, lower removals were observed for total concentrations of moderately particulate micropollutants, including bisphenol-A, alkylphenols and phthalates. In addition, some pollutants appear to be emitted from various biofilter components (filter media, drainage and lining materials), as low or negative concentration removals were observed during the first months of operation of the biofiltration swale.

Alkylphenol and bisphenol A contamination of urban runoff: an evaluation of the emission potentials of various construction materials and automotive supplies.

Alkylphenol (AP) and bisphenol A (BPA) contamination of urban runoff has already been established. Potential sources of these contaminants in runoff are endogenous to the urban watershed and are mainly related to traffic and leaching from construction materials. This article summarizes the results of experimental work carried out on a selection of building materials, automotive materials, and consumables, which can be in contact with rain, to assess their potential emission of alkylphenols, alkylphenol ethoxylates, and bisphenol A into runoff. 36 samples of materials, new and used, across 7 major families of building materials (PVC, concrete, polycarbonate, SBS-modified bitumen, drainage materials) and automotive materials (body, tires) were subjected to leaching tests with methanol and then, for a selection of them, with water. Automotive fluids were also directly analyzed. The results demonstrate the ubiquitous presence of APs and BPA in urban materials and their extractable character with water. The compounds with the strongest emission rates were bisphenol A and nonylphenol. The most important BPA emissions into water (10 to 300 ng/g) were measured for polycarbonate, tires, some car bodies, and PVC. Nonylphenol was leached in large quantities (1 to 10 ng/g) from PVC, some concretes, SBS-modified bitumen, and body samples. The tires were the only materials having a strong emission in octylphenol (1 to 10 ng/g). The analysis of automotive fluids confirmed the presence of BPA (0.3 to 5.5 g/L) and nonylphenol (2.3 to 2.9 mg/L) in brake fluids, while APs and BPA were found at trace levels in coolants and windscreen washer. Graphical abstract ᅟ.

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.

Cosmet'eau-Changes in the personal care product consumption practices: from whistle-blowers to impacts on aquatic environments.

The Cosmet'eau project (2015-2018) investigates the "changes in the personal care product (PCP) consumption practices: from whistle-blowers to impacts on aquatic environments." In this project, the example of PCPs will be used to understand how public health concerns related to micropollutants can be addressed by public authorities-including local authorities, industries, and consumers. The project aims to characterize the possible changes in PCP consumption practices and to evaluate the impact of their implementation on aquatic contamination. Our goals are to study the whistle-blowers, the risk perception of consumers linked with their practices, and the contamination in parabens and their substitutes, triclosan, and triclocarban from wastewater to surface water. The project investigates the following potential solutions: modifications of industrial formulation or changes in consumption practices. The final purpose is to provide policy instruments for local authorities aiming at building effective strategies to fight against micropollutants in receiving waters.

Partitioning of the pesticide trifluralin between dissolved organic matter and water using automated SPME-GC/MS.

Solid-phase microextraction (SPME) was used to determine the equilibrium association constant for a pesticide, trifluralin (TFR), with dissolved organic matter (DOM). After optimization of the SPME method for the analysis of TFR, partition coefficients (K DOM) with three different sources of DOM were determined in buffered solutions at pH 7. Commercial humic acids and DOM fractions isolated from two surface waters were used. The values of log K DOM varied from 4.3 to 5.8, depending on the nature of the organic material. A good correlation was established between log K DOM and DOM properties (as measured with the H/O atomic ratio and UV absorbance), in agreement with literature data. This is consistent with the effect of polarity and aromaticity for governing DOM-pollutant associations, regardless of the origin of DOM. This association phenomenon is relevant to better understand the behavior of pesticides in the environment since it controls part of pesticide leaching and fate in aquatic systems.

Photodegradation of estrone enhanced by dissolved organic matter under simulated sunlight.

In the present work the degradation of estrone (E1) a natural estrogenic hormone has been studied under simulated solar irradiation. The photodegradation of E1 has been investigated in the absence and in the presence of 7.7-8.9 mg L(-1) of dissolved organic carbon (DOC), under solar light simulation with irradiance approximating that of the sun. DOC extracts from different origins have been used. Half-lives ranging between 3.9 h and 7.9 h were observed. Results indicated that E1 was photodegraded even in the absence of DOC. The presence of DOC was found to enhance the degradation of E1. Experiments performed with the addition of reactive species scavengers (azide ions and 2-propanol) have shown that these two species play a significant role in the photodegradation. Some experiments have been performed with a DOC previously submitted to solar irradiation. Changes in optical and physico-chemical properties of DOC strongly affect its photoinductive properties, and hence its efficiency on E1 degradation. A part of the study consisted in the investigation of photoproducts structures. Five photoproducts were shown by chromatographic analysis: one arising from direct photolysis and the four others from DOC photoinduced degradation.

Optimization of large-volume injection for the determination of polychlorinated biphenyls in children's fast-food menus by low-resolution mass spectrometry.

This study includes the determination of five indicator polychlorinated biphenyls (PCBs) (52, 101, 153, 138, and 180), six non-ortho PCBs (35, 80, 81, 77, 126, and 169), and two mono-ortho PCBs (28 and 118) in fast food for children. A freeze-dried sample of 10 g is extracted by using pressurized n-hexane in two 5 min cycles at 120 degrees C and 100 mbar. Fatty extracts were cleaned up by means of acetonitrile/n-hexane partitioning and gel-permeation chromatography. The fractionation of non-ortho, mono-ortho, and indicator PCBs was made on graphitized carbon solid-phase extraction cartridges by using n-hexane, n-hexane/toluene (99:1, v/v), and toluene as elution solvents. Gas chromatography coupled to tandem mass spectrometry and large-volume injections with a programmed-temperature vaporizer (PTV-LV) were used to increase sensitivity and selectivity of the PCB determination. The PTV-LV injection settings, that is, vaporizing temperature, vaporizing time, and purge flow, were optimized by using a central composite design. A 15-40 times increased sensitivity was reached as compared with that obtained with the conventional 1 microL splitless injection. The limits of detection achieved were between 0.3 and 1.2 pg/g, and repeatability data, as relative standard deviation varied, ranged from 2 to 9% for the 0.05 ng/mL PCB level.