Modelling the fate of nonylphenolic compounds in the Seine River -- part 1: Determination of in-situ attenuation rate constants

International audienceAssessing the fate of endocrine disrupting compounds (EDCs) in the environment is currently a key issue for determining their impacts on aquatic ecosystems. The 4-nonylphenol (4-NP) is a well known EDC and results from the biodegradation of surfactant nonylphenol ethoxylates (NPnEOs). Fate mechanisms of NPnEO are well documented but their rate constants have been mainly determined through laboratory experiments. This study aims at evaluating the in-situ fate of 4-NP, nonylphenol monoethoxylate (NP1EO) and nonylphenolic acetic acid (NP1EC). Two sampling campaigns were carried out on the Seine River in July and September 2011, along a 28 km-transect downstream Paris City. The field measurements are used for the calibration of a sub-model of NPnEO fate, included into a hydro-ecological model of the Seine River (ProSe). The timing of the sampling is based on the Seine River velocity in order to follow a volume of water. Based on our results, in-situ attenuation rate constants of 4-NP, NP1EO and NP1EC for both campaigns are evaluated. These rate constants vary greatly. Although the attenuation rate constants in July are especially high (higher than 1 d− 1), those obtained in September are lower and consistent with the literature. This is probably due to the biogeochemical conditions in the Seine River. Indeed, the July sampling campaign took place at the end of an algal bloom leading to an unusual bacterial biomass while the September campaign was carried out during common biogeochemical status. Finally, the uncertainties on measurements and on the calibration parameters are estimated through a sensitivity analysis. This study provides relevant information regarding the fate of biodegradable pollutants in an aquatic environment by coupling field measurements and a biogeochemical model. Such data may be very helpful in the future to better understand the fate of nonylphenolic compounds or any other pollutants at the basin scale

Determination of in-situ biodegradation rate constants of nonylphenolic compounds in the Seine River

Assessing the fate of endocrine disrupting compounds (EDC) in the environment is currently a key issue for determining their impacts on aquatic ecosystems. The 4 nonylphenol (4-NP) is a well known EDC. It results from the biodegradation of surfactant nonylphenol ethoxylates (NPEO). Biodegradation mechanisms of NPEO are well documented (Giger et al. 2009) but their rate constants have been mainly determined through laboratory experiments. To our knowledge only Jonkers et al. (2005) evaluate NPEO biodegradation rate constants according to field measurements. Their study was carried out in an estuary (salt water) and has to be confirmed for freshwater. This study aims at evaluating the in-situ biodegradation of 4-NP, nonylphenol monoethoxylate (NP1EO) and nonylphenolic acetic acid (NP1EC). Two innovative sampling campaigns were carried out on the Seine River in July and September 2011, from Maisons-Laffitte to Triel-sur-Seine (along a 40km-transect downstream of Paris City). Their results were used for calibrating a sub-model of NPEO biodegradation of the hydrodynamic-biogeochemical model of the Seine River (PROSE, Even et al. 1998). Sampling times were estimated according to the Seine River velocity in order to follow the same volume of water. Simultaneously, during the September sampling campaign, small scale spatial and temporal variabilities of nonylphenolic compounds concentrations were assessed. Biodegradation rate constants of 4-NP, NP1EO and NP1EC between July and September varied greatly. Although the biodegradation rate constants in July were especially high (higher than 1 d 1), those obtained in September were smaller but consistent with the literature. This variability is probably linked to the biogeochemical behaviour of the Seine River. Indeed, the July sampling campaign took place at the end of an algal bloom leading to an unusual bacterial biomass while the September campaign was carried out during an "usual" biogeochemical state. This study provides relevant information regarding biodegradation rate constants of alkylphenols in an aquatic environment. Such data may be very helpful in the future to better understand the fate and transfer of nonylphenolic compounds at the catchment basin scale

Inland Waters Increasingly Produce and Emit Nitrous Oxide

Nitrous oxide (N 2O) is a long-lived greenhouse gas and currently contributes ∼10% to global greenhouse warming. Studies have suggested that inland waters are a large and growing global N 2O source, but whether, how, where, when, and why inland-water N 2O emissions changed in the Anthropocene remains unclear. Here, we quantify global N 2O formation, transport, and emission along the aquatic continuum and their changes using a spatially explicit, mechanistic, coupled biogeochemistry-hydrology model. The global inland-water N 2O emission increased from 0.4 to 1.3 Tg N yr -1 during 1900-2010 due to (1) growing N 2O inputs mainly from groundwater and (2) increased inland-water N 2O production, largely in reservoirs. Inland waters currently contribute 7 (5-10)% to global total N 2O emissions. The highest inland-water N 2O emissions are typically in and downstream of reservoirs and areas with high population density and intensive agricultural activities in eastern and southern Asia, southeastern North America, and Europe. The expected continuing excessive use of nutrients, dam construction, and development of suboxic conditions in aging reservoirs imply persisting high inland-water N 2O emissions

Modélisation du fonctionnement biogéochimique de la Seine de l'agglomération parisienne à l'estuaire à différentes échelles temporelles

Hydro-ecological models are essential to complete our knowledge of the functioning of aquatic systems. They can moreover be used to forecast the impact of new management strategies on the future water quality. The aim of this thesis is to use the hydro-ecological ProSe model to improve our understanding of the biogeochemical functioning of the Seine River downstream the Paris urban area. Simulated biogeochemical processes are first implemented, calibrated, and validated independently for the 2007-2012 period. For each one of these processes, appropriate methodologies are used. These methodologies include the direct use of experimentally obtained parameters, the upscaling of results from coupled laboratory experiments and stand-alone biogeochemical modelling, or the analysis of high frequency in-situ measurements. Different datasets, which are available at various time steps, allow the validation of these processes along the whole 220 km simulated stretch (from Paris to the entrance of the Seine River estuary). Once validated, the ProSe model is then used to assess the biogeochemical functioning of the Seine River along this highly anthropized stretch. The impact of pelagic and benthic processes on the different biogeochemical cycles (carbon, nitrogen, and phosphorus) is quantified for different hydrological conditions, up- and downstream the major waste water treatment plant of the Paris urban area, which treats the effluents of over 5 million population equivalent. The model is then used to assess the effect of the monitoring frequency on the estimation of the water quality as defined by the European Water Framework Directive. The results highlight the importance of a detailed representation of physical processes in hydro-ecological models for a reliable simulation of in-river biogeochemical fluxes and of exchanges at the sediment-water interface. Having in mind the present targets of the improvement of the quality of water bodies, this work illustrates the importance of hydro-ecological modelling as an essential complement to water quality monitoring strategies.Dans le contexte des nouvelles exigences en termes de qualité des eaux du surface, les modèles hydro-écologiques s'avèrent être des outils indispensables pour compléter notre compréhension du fonctionnement du milieu ou prévoir l'impact sur la qualité de l'eau de nouvelles mesures. L'objectif de cette recherche est de tirer parti de l'outil de modélisation ProSe, et de le faire évaluer afin de compléter la compréhension du fonctionnement biogéochimique de la Seine. Dans une première étape, différents processus biogéochimiques sont implémentés, calibrés et validés indépendamment, grâce à des jeux de données disponibles sur un linéaire de 220 km (de Paris jusqu'à l'estuaire), à différents pas de temps, pour la période 2007-2012. Ces améliorations sont réalisées grâce à l'utilisation directe de résultats expérimentaux, à l'extrapolation de résultats de couplage entre expériences de laboratoire et modélisation biogéochimique, ou encore grâce à l'analyse de mesures haute fréquence in-situ. Le modèle ProSe est ensuite utilisé pour établir un bilan du fonctionnement biogéochimique de la Seine dans cette zone fortement anthropisée. L'effet des processus pélagiques et benthiques sur les différents cycles biogéochimiques (carbone, azote, phosphore) est quantifié, pour différentes conditions hydrologiques, en amont et en aval de la plus grosse station d'épuration de l'agglomération parisienne, qui traite les effluents de plus de 5 millions équivalent habitants. La précision spatio-temporelle du modèle est ensuite utilisée pour évaluer l'effet de la fréquence d'échantillonnage sur l'estimation des critères de qualité de l'eau au sens de la Directive Cadre sur l'Eau. Les résultats soulignent l'importance d'une représentation précise des processus physiques (hydrodynamique et processus hydro-sédimentaires) dans les modèles de qualité de l'eau pour parvenir à une simulation fiable des flux biogéochimiques dans le milieu et des échanges entre compartiment benthique et colonne d'eau. Ce travail illustre enfin toute l'utilité des modèles hydro-écologiques pour venir en appui au suivi du milieu dans le cadre des objectifs actuels d'amélioration de la qualité des milieux aquatiques

Modelling the biogeochemical functioning of the Seine River from Paris to the estuary at different temporal scales

Dans le contexte des nouvelles exigences en termes de qualité des eaux du surface, les modèles hydro-écologiques s'avèrent être des outils indispensables pour compléter notre compréhension du fonctionnement du milieu ou prévoir l'impact sur la qualité de l'eau de nouvelles mesures. L'objectif de cette recherche est de tirer parti de l'outil de modélisation ProSe, et de le faire évaluer afin de compléter la compréhension du fonctionnement biogéochimique de la Seine. Dans une première étape, différents processus biogéochimiques sont implémentés, calibrés et validés indépendamment, grâce à des jeux de données disponibles sur un linéaire de 220 km (de Paris jusqu'à l'estuaire), à différents pas de temps, pour la période 2007-2012. Ces améliorations sont réalisées grâce à l'utilisation directe de résultats expérimentaux, à l'extrapolation de résultats de couplage entre expériences de laboratoire et modélisation biogéochimique, ou encore grâce à l'analyse de mesures haute fréquence in-situ. Le modèle ProSe est ensuite utilisé pour établir un bilan du fonctionnement biogéochimique de la Seine dans cette zone fortement anthropisée. L'effet des processus pélagiques et benthiques sur les différents cycles biogéochimiques (carbone, azote, phosphore) est quantifié, pour différentes conditions hydrologiques, en amont et en aval de la plus grosse station d'épuration de l'agglomération parisienne, qui traite les effluents de plus de 5 millions équivalent habitants. La précision spatio-temporelle du modèle est ensuite utilisée pour évaluer l'effet de la fréquence d'échantillonnage sur l'estimation des critères de qualité de l'eau au sens de la Directive Cadre sur l'Eau. Les résultats soulignent l'importance d'une représentation précise des processus physiques (hydrodynamique et processus hydro-sédimentaires) dans les modèles de qualité de l'eau pour parvenir à une simulation fiable des flux biogéochimiques dans le milieu et des échanges entre compartiment benthique et colonne d'eau. Ce travail illustre enfin toute l'utilité des modèles hydro-écologiques pour venir en appui au suivi du milieu dans le cadre des objectifs actuels d'amélioration de la qualité des milieux aquatiques.Hydro-ecological models are essential to complete our knowledge of the functioning of aquatic systems. They can moreover be used to forecast the impact of new management strategies on the future water quality. The aim of this thesis is to use the hydro-ecological ProSe model to improve our understanding of the biogeochemical functioning of the Seine River downstream the Paris urban area. Simulated biogeochemical processes are first implemented, calibrated, and validated independently for the 2007-2012 period. For each one of these processes, appropriate methodologies are used. These methodologies include the direct use of experimentally obtained parameters, the upscaling of results from coupled laboratory experiments and stand-alone biogeochemical modelling, or the analysis of high frequency in-situ measurements. Different datasets, which are available at various time steps, allow the validation of these processes along the whole 220 km simulated stretch (from Paris to the entrance of the Seine River estuary). Once validated, the ProSe model is then used to assess the biogeochemical functioning of the Seine River along this highly anthropized stretch. The impact of pelagic and benthic processes on the different biogeochemical cycles (carbon, nitrogen, and phosphorus) is quantified for different hydrological conditions, up- and downstream the major waste water treatment plant of the Paris urban area, which treats the effluents of over 5 million population equivalent. The model is then used to assess the effect of the monitoring frequency on the estimation of the water quality as defined by the European Water Framework Directive. The results highlight the importance of a detailed representation of physical processes in hydro-ecological models for a reliable simulation of in-river biogeochemical fluxes and of exchanges at the sediment-water interface. Having in mind the present targets of the improvement of the quality of water bodies, this work illustrates the importance of hydro-ecological modelling as an essential complement to water quality monitoring strategies

Estimation of the water quality of a large urbanized river as defined by the European WFD: what is the optimal sampling frequency?

International audienceAssessment of the quality of freshwater bodies is essential to determine the impact of human activities on water resources. The water quality status is estimated by comparing indicators with standard thresholds. Indicators are usually statistical criteria that are calculated on discrete measurements of water quality variables. If the time step of the measured time series is not sufficient to fully capture the variable’s variability, the deduced indicator may not reflect the system’s functioning. The goal of the present work is to assess, through a hydro-biogeochemical modeling approach, the optimal sampling frequency for an accurate estimation of 6 water quality indicators defined by the European Water Framework Directive (WFD) in a large human-impacted river, which receives large urban effluents (the Seine River across the Paris urban area). The optimal frequency depends on the sampling location and on the monitored variable. For fast varying compounds that originate from urban effluents, such as PO3−4, NH+4 and NO−2, a sampling time step of one week or less is necessary. To be able to reflect the highly transient character of bloom events, chl a concentrations also require a short monitoring time step. On the contrary, for variables that exert high seasonal variability, as NO−3 and O 2, monthly sampling can be sufficient for an accurate estimation of WFD indicators in locations far enough from major effluents. Integrative water quality variables, such as O 2, can be highly sensitive to hydrological conditions. It would therefore be relevant to assess the quality of water bodies at a seasonal scale rather than at annual or pluri-annual scales. This study points out the possibility to develop smarter monitoring systems by coupling both time adaptative automated monitoring networks and modeling tools used as spatio-temporal interpolators

Pluri-annual sediment budget in a navigated river system: The Seine River (France)

International audienceThis study aims at quantifying pluri-annual Total SuspendedMatter (TSM) budgets, and notably the share of river navigation in total re-suspension at a long-term scale, in the Seine River along a 225 km stretch including the Paris area. Erosion is calculated based on the transport capacity concept with an additional term for the energy dissipated by river navigation. Erosion processes are fitted for the 2007–2011 period based on i) a hydrological typology of sedimentary processes and ii) a simultaneous calibration and retrospective validation procedure.The correlation between observed and simulated TSM concentrations is higher than 0.91 at all monitoring stations. A variographic analysis points out the possible sources of discrepancies between the variabilities of observed and simulated TSM concentrations at three time scales: sub-weekly, monthly and seasonally. Most of the error on the variability of simulated concentrations concerns sub-weekly variations and may be caused by boundary condition estimates rather than modeling of in-river processes. Once fitted, the model permits to quantify that only a small fraction of the TSM flux sediments onto the river bed (b0.3‰). The river navigation contributes significantly to TSM re-suspension in average (about 20%) and during low flow periods (over 50%).Given the significant impact that sedimentary processes can have on the water quality of rivers, these results highlight the importance of taking into account river navigation as a source of re-suspension, especially during low flow periods when biogeochemical processes are the most intense

Forms and subannual variability of nitrogen and phosphorus loading to global river networks over the 20th century

Nitrogen (N) and phosphorus (P) play a major role in the biogeochemical functioning of aquatic systems. N and P transfer to surface freshwaters has amplified during the 20th century, which has led to widespread eutrophication problems. The contribution of different sources, natural and anthropogenic, to total N and P loading to river networks has recently been estimated yearly using the Integrated Model to Assess the Global Environment - Global Nutrient Model (IMAGE-GNM). However, eutrophic events generally result from a combination of physicochemical conditions governed by hydrological dynamics and the availability of specific nutrient forms that vary at subyearly timescales. In the present study, we define for each simulated nutrient source: i) its speciation, and ii) its subannual temporal pattern. Thereby, we simulate the monthly loads of different N (ammonium, nitrate + nitrite, and organic N) and P forms (dissolved and particulate inorganic P, and organic P) to global river networks over the whole 20th century at a half-degree spatial resolution. Results indicate that, together with an increase in the delivery of all nutrient forms to global rivers, the proportion of inorganic forms in total N and P inputs has risen from 30 to 43% and from 56 to 65%, respectively. The high loads originating from fertilized agricultural lands and the increasing proportion of sewage inputs have led to a greater proportion of DIN forms (ammonium and nitrate), that are usually more bioavailable. Soil loss from agricultural lands, which delivers large amounts of particle-bound inorganic P to surface freshwaters, has become the dominant P source, which is likely to lead to an increased accumulation of legacy P in slow flowing areas (e.g., lakes and reservoirs). While the TN:TP ratio of the loads has remained quite stable, the DIN:DIP molar ratio, which is likely to affect algal development the most, has increased from 18 to 27 globally. Human activities have also affected the timing of nutrient delivery to surface freshwaters. Increasing wastewater emissions in growing urban areas induces constant local pressure on the quality of aquatic systems by delivering generally highly bioavailable nutrient forms, even in periods of low runoff

Developments in Dynamic Modelling of Meandering Fluvial Systems

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Modélisation du fonctionnement hydro-écologique de la Seine: Impact des vases sur la qualité de l'eau

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