Contaminants organiques en milieux aquatiques : développements analytiques, techniques et applications

Large varieties of organic micro-pollutants are currently used in domestic and industrial products. The massive use of these products leads to the release of micro-pollutants into the environment and in different stages of the water cycle. Consequently, they present a major health and environmental risk. Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), pesticides, phthalates from plastics, bisphenols, pharmaceuticals and personal care products (PPCPs) are among the toxic, emerging and/or priority organic micro-pollutants. Present in surface and ground waters, these organic micro-pollutants threaten drinking water resources; disrupt the functioning of ecosystems and can also impact human health via water resources or food chains. The adoption of Water Directive (OJEC, December 2000) involves a national action for the detection and reduction of releases of dangerous substances in water. Pollution induced by organic micro-pollutants in aquatic environments has become a very serious concern; requiring further studies to better understand the behavior, origin, fate and the impact of this kind of pollution and thus finding the appropriate solutions. Nevertheless, while the need to protect quantitatively and qualitatively water resources and ecosystems, the tools allowing to evaluate the current state of contamination of the environment or to provide less costly and more effective technologies to eliminate these micro-pollutants remain to be defined and/or deepened. The research presented in this work is focused on organic micro-pollutants in aquatic environments. A presentation of the problem of environmental pollution related to organic micro-pollutants, the adequate methods of their detection and quantification are developed. Some case studies of contamination levels in natural aquatic environment, and elimination possibilities are given mainly in the northern French and some abroad sites in Lebanon, Tunisia and Senegal.A ce jour, de nombreux polluants organiques entrent dans la composition de produits domestiques et industriels. Suite à des utilisations massives et variées, ces micropolluants sont émis et dispersés dans l’environnement et dans différentes étapes du cycle de l’eau. Ils présentent ainsi un risque sanitaire et environnemental majeur. Les hydrocarbures aromatiques polycycliques (HAP), les polychlorobiphényles (PCB), les pesticides, les phtalates issus des matières plastiques, les bisphénols, les produits pharmaceutiques et d’hygiènes corporels (PPCP) figurent parmi les micropolluants organiques toxiques, émergents et/ou prioritaires. Présents dans les eaux de surface et souterraines, ces micropolluants menacent les ressources en eau potable, perturbent le fonctionnement des écosystèmes et impactent la santé humaine via la ressource en eau ou la chaine trophique. L’adoption de la directive cadre sur l’eau (JOCE, 2000) implique une action nationale de recherche et de réduction des Rejets de Substances Dangereuses dans les Eaux (RSDE). La pollution induite par les micropolluants dans les milieux aquatiques est devenue une source de préoccupations très sérieuses qui nécessite la réalisation des études afin de mieux appréhender le comportement, l’origine, le devenir et l’impact de cette pollution, et d’y apporter des réponses appropriées. Néanmoins, si la nécessité de protéger la ressource en eau et les écosystèmes, les outils permettant d’apporter un diagnostic sur l’état actuel de contamination des milieux ou d’apporter des technologies moins coûteuses et efficaces pour éliminer ces micropolluants restent à définir et/ou approfondir. Les travaux de recherches présentés dans le cadre de cette HDR se focalisent sur cette thématique des « micropolluants organiques en milieu aquatique ». Il s’agit d’une présentation de la problématique de la pollution environnementale liée aux micropolluants organiques, des méthodes adéquates de détection et de quantification. Des études de cas dans les milieux aquatiques naturels et des possibilités d’élimination, principalement dans la région Hauts de France et sur quelques sites à l’étranger (Liban, Tunisie, Sénégal,…) sont présentées

Overview of sediments pollution by PAHs and PCBs in mediterranean basin: Transport, fate, occurrence, and distribution

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Light-induced heterogeneous ozone processing on organic coated particles: Kinetics and condensed-phase products

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Photoenhanced degradation of veratraldehyde upon the heterogeneous ozone reactions

International audienceLight-induced heterogeneous reactions between gas-phase ozone and veratraldehyde adsorbed onsilica particles were performed. At an ozone mixing ratio of 250 ppb, the loss of veratraldehydelargely increased from 1.81 106 s1 in the dark to 2.54 105 s1 upon exposure to simulatedsunlight (l 4 300 nm). The observed rates of degradation exhibited linear dependence with theozone in the dark ozonolysis experiments which change in the non-linear Langmuir-Hinshelwooddependence in the experiments with simultaneous ozone and light exposure of the coated particles.When the coated silica particles were exposed only to simulated sunlight in absence of ozone theloss of veratraldehyde was about three times higher i.e. 5.97 106 s1 in comparison to theozonolysis experiment under dark conditions at 250 ppb ozone mixing ratio, 1.81 106 s1.These results clearly show that the most important loss of veratraldehyde occurs undersimultaneous ozone and light exposure of the coated silica particles. The main identifiedproduct in the heterogeneous reactions between gaseous ozone and adsorbed veratraldehydeunder dark conditions and in presence of light was veratric acid.Carbon yields of veratric acid were calculated and the obtained results indicated that at lowozone mixing ratio (250 ppb) the carbon yield obtained under dark conditions is 70% whereasthe carbon yield obtained in the experiments with simultaneous ozone and light exposure of thecoated particles is 40%. In both cases the carbon yield of veratric acid exponentially decayed leadingto the plateau (B35% of carbon yield) at an ozone mixing ratio of 6 ppm. Two reaction productsi.e. 3-hydroxy-4-methoxybenzoic acid and 4-hydroxy-3-methoxybenzoic acid were identified(confirmed with the standards) only in the experiments performed under simultaneousozonolysis and light irradiation of the particles

A review of the most popular systems for greywater treatment

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Heterogeneous ozonation kinetics of 4-phenoxyphenol in the presence of photosensitizer

International audienceIn this work we have quantitatively measured the degradation of 4-phenoxyphenol adsorbed on silica particles following oxidative processing by gas-phase ozone. This was performed under dark conditions and in the presence of 4-carboxybenzophenone under simulated sunlight irradiation of the particles surface. At the mixing ratio of 60 ppb which corresponds to strongly polluted ozone areas, the first order of decay of 4-phenoxyphenol is k 1 =9.95×10 −6 s −1. At a very high ozone mixing ratio of 6 ppm the first order rate constants for 4-phenoxyphenol degradation were the following: k 1 =2.86×10 −5 s −1 under dark conditions and k 1 =5.58×10 −5 s −1 in the presence of photosensitizer (4-carboxybenzophenone) under light illumination of the particles surface. In both cases, the experimental data follow the modified Langmuir-Hinshelwood equation for surface reactions. The Langmuir-Hinshelwood and Langmuir-Rideal mechanisms for bimolecular surface reactions are also discussed along with the experimental results. Most importantly, the quantities of the oligomers such as 2-(4-Phenoxyphenoxy)-4-phenoxyphenol and 4-[4-(4-Phenoxyphenoxy)phenoxy]phenol formed during the heterogeneous ozonolysis of adsorbed 4-phenoxyphenol were much higher under solar light irradiation of the surface in comparison to the dark conditions

Heterogeneous reactions of ozone with methoxyphenols, in presence and absence of light

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Occurrence of phthalate acid esters (PAEs) in the northwestern Mediterranean Sea and the Rhone River

Phthalate acid esters (PAEs) which are mainly anthropogenic molecules with endocrine disrupting effects in animals and humans, have been detected in terrestrial and aquatic environments. However, little is known about their distribution in the Mediterranean Sea, mainly because of analytical difficulties and the high possibility of ambient sample contamination. Here, we report the optimization of an existing protocol for the determination of PAEs in seawater and freshwater samples, as well as the first estimation of the source and distribution of phthalates acid esters (PAEs) in coastal waters from the NW Mediterranean Sea. By passing 1 L of sample through glass cartridges packed with 200 mg of Oasis HLB and eluted with 6 mL of ethyl acetate, the recoveries for DMP, DEP, DPP, DiBP, DnBP, BzBP, DEHP and DnOP were 101, 98, 115, 110, 99, 98, 103 and 95%, respectively, with acceptable blank values (below 0.4-4.0% of the masses measured in different seawater samples). By using this method, we detected PAEs in the Marseilles coastal area, offshore (2000 m depth) and in the Rhone River with total concentrations ranging from 75.3 ng/L offshore in surface water to 1207.1 ng/L a few meters above the bottom of the Marseilles Bay. High concentrations were also observed in deep waters offshore (310.2 ng/L) as well as in the Rhone River (615.1 ng/L). These results suggest that Marseilles urban area, Rhone River and sediment are potential sources of PAEs in the areas studied. In the Rhone River, DEHP was the most abundant PAE (66.1%) followed by DiBP (20.5%) and DnBP (6.6%), whereas a gradual change was observed in the plume of the river with increasing salinity. In the Marseilles Bay, DiBP was the most abundant PAE at the surface (47.3% of total PAEs) followed by DEHP (22.7%) and DnBP (19.1%), whereas DnBP was predominant (38.6%) a few meters above the bottom. By contrast, DEHP was the dominant species in the first 50 m (66.9-76.7%) offshore followed by DnBP (10.9-15.2%), whereas DnBP was the most abundant (57.0-72.6%) followed by DEHP (20.1-33.1%) in the deepest waters. This study suggests that in addition to direct PAEs injection in marine waters, different processes regulate PAE distribution in Mediterranean Sea including photochemical oxidation reactions, bacterial degradation and possible diffusion following release from marine litter near the bottom

Occurrence, fate, behavior and ecotoxicological state of phthalates in different environmental matrices

International audienceBecause of their large and widespread application,phthalates or phthalic acid esters (PAEs) are ubiquitous in all the environmental compartements. They have been widely detected throughout the worldwide environment. Indoor air where people spend 65!90% of their time is also highly contaminated by various PAEs released from plastics, consumer products as well as ambient suspended particulate matter. Because of their widespread application, PAEs are the most common chemicals that humans are in contact with daily. Based on various exposure mechanisms, including the ingestion of food, drinking water, dust/soil, air inhalation and dermal exposure the daily intake of PAEs may reach values as high as 70 μg/kg/day. PAEs are involved in endocrine disrupting effects, namely, upon reproductive physiology in different species of fish and mammals. They also present a variety of additional toxic effects for many other species including terrestrial and aquatic fauna and flora. Therefore, their presence in the environment has attracted considerable attention due to their potential impacts on ecosystem functioning and on public health. This paper is a synthesis of the extensive literature data on behavior, transport, fate and ecotoxicological state of PAEs in environmental matrices: air, water, sediment, sludge, wastewater, soil, and biota. First, the origins and physicochemical properties of PAEs that control the behavior, transport and fate in the environment are reviewed. Second, the compilation of data on transport and fate, adverse environmental and human health effects, legislation, restrictions, and ecotoxicological state of the environment based on PAEs is presented

Reliable quantification of phthalates in environmental matrices (air, water, sludge, sediment and soil): A review

International audienceBecause of their widespread application, phthalates or phthalic acid esters (PAEs) are ubiquitous in the environment. Their presence has attracted considerable attention due to their potential impacts on ecosystem functioning and on public health, so their quantification has become a necessity. Various extraction procedures as well as gas/liquid chromatography and mass spectrometry detection techniques are found as suitable for reliable detection of such compounds. However, PAEs are ubiquitous in the laboratory environment including ambient air, reagents, sampling equipment, and various analytical devices, that induces difficult analysis of real samples with a low PAE background. Therefore, accurate PAE analysis in environmental matrices is a challenging task. This paper reviews the extensive literature data on the techniques for PAE quantification in natural media. Sampling, sample extraction/pretreatment and detection for quantifying PAEs in different environmental matrices (air, water, sludge, sediment and soil) have been reviewed and compared. The concept of “green analytical chemistry” for PAE determination is also discussed. Moreover useful information about the material preparation and the procedures of quality control and quality assurance are presented to overcome the problem of sample contamination and these encountered due to matrix effects in order to avoid overestimating PAE concentrations in the environment.