[Departement_IRSTEA]Ecotechnologies [TR1_IRSTEA]TED | International audience | Constructed wetlands for combined sewer overflow treatment (CSO CWs) are variably saturated vertical flow filters in France. The design-support software Orage aims to facilitate engineering work by optimizing filter area and material sitespecifically which was otherwise encumbered by the stochasticity of CSO flows and concentrations. The optimization process relies on measured or simulated CSO series and a low number of input parameters. The iterative shell calls the core model repetitively. During the process, effluent flows and concentrations are simulated from a range of CW domains and compared to legislative thresholds. The iterative shell was tested both with measured and simulated inflows. First, key parameters of the hydraulic optimization were fixed. Large and underscaled designs are excluded this way and succeeding optimizations for pollutant removal are more efficient. Then, the optimization functions were verified using inflow and available land from an existing CSO CW. At third, the automatizations were used to test model predictions in the function of legislative thresholds. Zeolite-enriched media ensures high NH4-N removal at hydraulic loads exceeding the recommendations of present guidelines, marking clogging as an issue for further research. In summary, the demonstrated simulation experiments verified the optimization approach of the dynamic design tool Orage.

[Departement_IRSTEA]Ecotechnologies [TR1_IRSTEA]TED | International audience | The French Overseas Territories experience big sanitations problems and have to comply with both French and EU regulations. Vertical flow constructed wetland (VFCW) appear well adapted to the context of these regions, but their adaptation to tropical climate requires new guidelines to be defined (area needed, number of filters, species of plants, material to be used …). To this end ATTENTIVE project was build up in the French Antilles with local water offices and supported by the national water authorities. Three different VFCW fed with raw wastewater were built in Martinique and Guadeloupe and are now under monitoring. While the 3 plants are actually in operation, this paper will focus on Taupinière plant (Martinique), sized for 900 p.e., in operation since October 2014. The treatment plant is composed of aunsaturated/saturated vertical flow constructed wetland, receiving raw domestic wastewaters, followed by a simplified trickling filter.The first stage is 0,8m²/p.e. with two filters in parallel (360 m² each), with a 40 cm unsaturated first layer of 2/4 mm gravel, a 15 cm transition layer of 11/22 with intermediate passive aeration pipes and a 60 cm saturated layer at the bottom made of 20/40 pea gravel. The trickling filter(116 m²)is composed of 150 cm of pumice stones. The sludge accumulated at the bottom of the trickling filter is sent back to the first stage.A recirculation loop is implemented on the trickling filter. Before the outlet, effluent passes through UV. The regulationobjectives is to achieve 90% removal for COD, BOD5 and TSS, 80% for TKN, and less than 1000 unit per 100 mL for E.coli and intestinal streptococcus. Nevertheless, the monitoring look after optimal operation to increase TN removal rates as well as the maximum loads that can be treated. The monitoring consists on classical daily composite samples at each treatment stages (30 campaigns) as well as online measurements. The later aim at measuring flows, climatic conditions, and COD, BOD5, and Nitrate (UV/visible analysis) at each treatment stages. Three different loading phases has been implemented from 30 % of the nominal load to 150 %. The paper will present performances of this compact (less than 1 m²/p.e.) treatment system in both dry and rainy season and discuss the optimization of TN removal as well as the footprint reduction with the high loads that can be implemented.

1H-HRMAS NMR-based metabolomics was used to better understand the toxic effects on maize root tips of organochlorine pesticides (OCPs), namely lindane (γHCH) and chlordecone (CLD). Maize seedlings were exposed to 2.5 μM γHCH (mimicking basic environmental contaminations) for 7 days and compared to 2.5 μM CLD and 25 μM γHCH for 7 days (mimicking hot spot contaminations). The 1H-HRMAS NMR-based metabolomic profiles provided details of the changes in carbohydrates, amino acids, tricarboxylic acid (TCA) cycle intermediates and fatty acids with a significant separation between the control and OCP-exposed root tips. First of all, alterations in the balance between glycolysis/gluconeogenesis were observed with sucrose depletion and with dose-dependent fluctuations in glucose content. Secondly, observations indicated that OCPs might inactivate the TCA cycle, with sizeable succinate and fumarate depletion. Thirdly, disturbances in the amino acid composition (GABA, glutamine/glutamate, asparagine, isoleucine) reflected a new distribution of internal nitrogen compounds under OCP stress. Finally, OCP exposure caused an increase in fatty acid content, concomitant with a marked rise in oxidized fatty acids which could indicate failures in cell integrity and vitality. Moreover, the accumulation of asparagine and oxidized fatty acids with the induction of LOX3 transcription levels under OCP exposure highlighted an induction of protein and lipid catabolism. The overall data indicated that the effect of OCPs on primary metabolism could have broader physiological consequences on root development. Therefore, 1H-HRMAS NMR metabolomics is a sensitive tool for understanding molecular disturbances under OCP exposure and can be used to perform a rapid assessment of phytotoxicity.

Urban and peri-urban forests provide a multitude of Ecosystem Services to the citizens. While the capacity of removing carbon dioxide and gaseous compounds from the atmosphere has been tested, their capacity to sequestrate particles (PM) has been poorly investigated. Mediterranean forest ecosystems are often located nearby or inside large urban areas. This is the case of the city of Rome, Italy, which hosts several urban parks and is surrounded by forested areas. In particular, the Presidential Estate of Castelporziano is a 6000 ha forested area located between the Tyrrhenian coast and the city (25 km downtown of Rome). Under the hypothesis that forests can ameliorate air quality thanks to particle deposition, we measured fluxes of PM1, 2.5 and 10 with fast optical sensors and eddy covariance technique. We found that PM1 is mainly deposited during the central hours of the day, while negligible fluxes were observed for PM 2.5 and 10. A Hybrid Single–Particle Lagrangian Integrated Trajectory model (HYSPLIT v4) simulated PM emission from traffic areas in the city of Rome and showed that a significant portion of PM is removed by vegetation in the days when the plume trajectory meets the urban forest.

More than a decade ago, the Stockholm Convention on Persistent Organic Pollutants (POPs), one of the multilateral environmental agreements administered by the United Nations Environment Programme (UNEP), entered into force. The objective of this Convention is to protect human health and the environment by controlling the releases of POPs. According to its Article 16, the effectiveness of the Stockholm Convention shall be evaluated using comparable monitoring data on the presence of POPs as well as their regional and global environmental transport. Here, we present a time series analysis on atmospheric POP concentrations from 15 monitoring stations in North America and Europe that provide long-term data and have started operations between 1990 and 2003. We systematically searched for temporal trends and significant structural changes in temporal trends that might result from the provisions of the Stockholm Convention. We find that such structural changes do occur, but they are related mostly to effects of national regulations enforced prior to the implementation of the Stockholm Convention, rather than to the enforcement of the provisions laid out in the Convention. One example is that concentrations of polychlorinated biphenyls, many of which started to decrease rapidly during the 1990s. Also effects of chemical transport and fate, for instance the re-volatilization of POPs from secondary sources, are thought to be a cause of some of the observed structural changes. We conclude that a decade of air monitoring data has not been sufficient for detecting general and statistically significant effects of the Stockholm Convention. Based on these lessons, we present recommendations for the future operation of existing monitoring programs and advocate for a stricter enforcement of the provisions of the Stockholm Convention, in the current absence of proof for its effectiveness.

Difenoconazole is a widely used triazole fungicide and has been reported to have negative impacts on zebrafish embryos. To investigate the mechanism of its developmental toxicity, zebrafish embryos were exposed to 0.5 and 2.0 mg/L difenoconazole for 96 h. The morphological and physiological indicators of embryo development were tested. The total cholesterol (TCHO) level, triglyceride (TG) level and malondialdehyde (MDA) content were measured at 96 hpf (hours post-fertilization). In addition, the transcription of genes related to embryo development, the antioxidant system, lipid synthesis and metabolism was quantified. Our results showed that a large suite of symptoms were induced by difenoconazole, including hatching regression, heart rate decrease, growth inhibition and teratogenic effects. 0.5 mg/L difenoconazole could significantly increase the TG content of zebrafish embryos at 96 hpf, while no apparent change in the TCHO and MDA level was observed post 96 h exposure. Q-PCR (quantitative real-time polymerase chain reaction) results showed that the transcription of genes related to embryonic development was decreased after exposure. Genes related to hatching, retinoic acid metabolism and lipid homeostasis were up-regulated by difenoconazole.

In recent years, phosphorus-containing flame retardants (PFRs) have been frequently detected in various environmental media and biota - and in humans - as the result of steady increase in global usage of PFRs. However, studies on the potential health and ecological risks of PFRs are still scarce. In this study, we investigated the thyroid hormone-disrupting activity and ecological risk of nine frequently detected PFRs by in vitro, in vivo and in silico approaches. Results from the dual-luciferase reporter gene assay showed that tributyl phosphate (TNBP), tricresyl phosphate (TMPP), tris(2-chloroisopropyl)phosphate (TCIPP) and tris(2-chloro-1-(chloromethyl)ethyl)phosphate (TDCIPP) exerted thyroid receptor β (TRβ) antagonistic activity, with the values of RIC20 of 5.2 × 10−7, 2.7 × 10−7, 1.2 × 10−6 and 6.8 × 10−6 M, respectively. Molecular docking platform simulations suggested that the observed effects may be attributed to direct binding of PFRs to TR. Results from the T-screen assay indicated that TNBP and TMPP showed T3 antagonistic activity and thus significantly decreased the viability of GH3 cell lines in the presence of T3. The exposure assay using Xenopus tropicalis embryos revealed the potential teratogenic effect of TNBP, TMPP, TCIPP and TDCIPP. In conclusion, our studies revealed that some PFRs were potential thyroid hormone disruptors and may cause health and ecological risks. However, the mode of action of PFRs on TR remains uncertain. The correlation between the predicted affinity and the amplitude of the effect observed in cell based assay is encouraging, but not decisive. Further in vitro binding experiments of TR and PFRs are required. At the same time, the results provided here also demonstrated that multi-model approaches are of great importance to comprehensively evaluate the potential risks of emerging contaminants.

Deposition of dissolved organic nitrogen (DON) in both bulk precipitation (BD) and canopy throughfall (TF) has been measured for the first time in the western Mediterranean. The study was carried out over a year from 2012 to 2013 at four evergreen holm oak forests located in the Iberian Peninsula: two sites in the Province of Barcelona (Northeastern Spain), one in the Province of Madrid (central Spain) and the fourth in the Province of Navarra (Northern Spain). In BD the annual volume weighted mean (VWM) concentration of DON ranged from 0.25 mg l−1 in Madrid to 1.14 mg l−1 in Navarra, whereas in TF it ranged from 0.93 mg l−1 in Barcelona to 1.98 mg l−1 in Madrid. The contribution of DON to total nitrogen deposition varied from 34% to 56% in BD in Barcelona and Navarra respectively, and from 38% in Barcelona to 72% in Madrid in TF. Agricultural activities and pollutants generated in metropolitan areas were identified as potential anthropogenic sources of DON at the study sites. Moreover, canopy uptake of DON in Navarra was found in spring and autumn, showing that organic nitrogen may be a supplementary nutrient for Mediterranean forests, assuming that a portion of the nitrogen taken up is assimilated during biologically active periods.

Aquatic sediments serve as an important sink for engineered nanomaterials (ENMs), such as metal oxide nanoparticles (MeO NPs) and carbon nanotubes (CNTs). Owing to their remarkable properties, ENMs demonstrate significant potential to disturb the adsorption behavior of other contaminants in aquatic sediments, thereby altering the bioavailability and toxicity of these contaminants. Thus far, most studies have investigated the effect of CNTs on the adsorption of other contaminants on sediments. Cerium dioxide nanoparticles (CeO2 NPs), as one of the important MeO NPs, are also inevitably discharged into aquatic sediments because of their widespread use. In this study, we investigated the adsorption behavior of Pb2+ on sediments spiked with CeO2 NPs at a weight ratio of 5.0%. The results showed that the adsorption rates at three stages occurring during adsorption clearly increase for sediments contaminated with CeO2 NPs. Moreover, the results obtained from the adsorption isotherms indicated that the Langmuir isotherm model best fits the isotherm data for both sediments and those contaminated with CeO2 NPs. After spiking the sediments with CeO2 NPs, the theoretical maximum monolayer adsorption capacity (Qmax) for Pb2+ increased from 4.433 to 4.995 mg/g and the Langmuir isotherm coefficient (KL) decreased from 8.813 to 7.730 L/g. The effects of CeO2 NPs on the surface charge and pore surface properties of sediments were also studied as these properties affect the adsorption of several chemicals in sediments. The results showed that pHzpc, SBET, Sext, and average pore size of sediments clearly decrease for sediments contaminated with CeO2 NPs. Hence, the strong adsorption capacity of CeO2 NPs and the changes of sediment surface charge and pore surface properties caused by CeO2 NPs are important factors affecting the adsorption behavior of Pb2+. The potential risk of Pb2+ in aquatic environment may increase with CeO2 NPs buried in sediments.