Étude de la sorption et de la désorption de neuf contaminants émergents dans les boues usées

Des études de sorption/désorption ont été effectuées pour neuf contaminants émergents sélectionnés (caféine, sulfaméthoxazole, déséthylatrazine, carbamazépine, atrazine, estradiol, éthinylestradiol, noréthindrone et diclofénac) dans les boues usées provenant de trois systèmes différents. Les contaminants incluent une variété de classes de composés (pesticides, hormones et pharmaceutiques) qui possèdent des propriétés physicochimiques différentes. L’objectif de ces travaux est de modéliser leur comportement dans une station d’épuration, en présence d’une phase particulaire et d’une phase aqueuse, et du même coup, de mieux comprendre leur devenir lors de leur rejet dans l’environnement. Le coefficient octanol-eau (log Kow) permet de bien interpréter les résultats et nous permet de classer les composés selon deux types de comportements observés : les composés avec un log Kow inférieur à 3 montrent peu ou pas de sorption alors que les composés avec un log Kow supérieur à 3 montrent une sorption variant de 30 à 90 % durant les premières minutes, suivi d’une sorption lente durant les heures suivantes. Une augmentation du contenu organique favorise la sorption des composés hydrophobes alors qu’un changement de pH peut modifier la charge à la surface des particules et également la charge des analytes. Les résultats ont montré que seul le diclofénac était sensible aux variations de pH étudiés. Dans une telle situation, il est nécessaire d’utiliser le facteur d’hydrophobicité corrigé en fonction du pH (log Dow). Le coefficient de distribution solide-eau (log Kd) a été déterminé pour chaque composé à la fin de chaque expérience de sorption et se situe entre -0.3 et 2.6. Avec l’augmentation de l’hydrophobicité, la désorption diminue avec le temps et avec l’étape de rinçage. Pour simuler le relargage dans les systèmes aquatiques, les facteurs de rinçage ont été déterminés pour estimer le nombre de rinçages qui seraient nécessaire pour désorber 50 et 99 % de la concentration initialement sorbée. Les bilans de masse ont été effectués après chaque expérience dans le but de ne pas surestimer les capacités de sorption d’un composé et se situent entre 7 et 25 % pour l’estradiol, la noréthindrone et le sulfaméthoxazole et entre 44 et 103 % pour l’éthinylestradiol, l’atrazine, la déséthylatrazine, la carbamazépine, la caféine et le diclofénac.

Over-parameterised, uncertain 'mathematical marionettes' - How can we best use catchment water quality models? An example of an 80-year catchment-scale nutrient balance

The Integrated Catchment Model of Nitrogen (INCA-N) was applied to the River Lambourn, a Chalk river-system in southern England. The model's abilities to simulate the long-term trend and seasonal patterns in observed stream water nitrate concentrations from 1920 to 2003 were tested. This is the first time a semi-distributed, daily time-step model has been applied to simulate such a long time period and then used to calculate detailed catchment nutrient budgets which span the conversion of pasture to arable during the late 1930s and 1940s. Thus, this work goes beyond source apportionment and looks to demonstrate how such simulations can be used to assess the state of the catchment and develop an understanding of system behaviour. The mass-balance results from 1921, 1922, 1991, 2001 and 2002 are presented and those for 1991 are compared to other modelled and literature values of loads associated with nitrogen soil processes and export. The variations highlighted the problem of comparing modelled fluxes with point measurements but proved useful for identifying the most poorly understood inputs and processes thereby providing an assessment of input data and model structural uncertainty. The modelled terrestrial and instream mass-balances also highlight the importance of the hydrological conditions in pollutant transport. Between 1922 and 2002, increased inputs of nitrogen from fertiliser, livestock and deposition have altered the nitrogen balance with a shift from possible reduction in soil fertility but little environmental impact in 1922, to a situation of nitrogen accumulation in the soil, groundwater and instream biota in 2002. In 1922 and 2002 it was estimated that approximately 2 and 18 kg N ha(-1) yr(-1) respectively were exported from the land to the stream. The utility of the approach and further considerations for the best use of models are discussed. (C) 2008 Elsevier B.V. All rights reserved.

Over-parameterised, uncertain 'mathematical marionettes' - How can we best use catchment water quality models? An example of an 80-year catchment-scale nutrient balance

The Integrated Catchment Model of Nitrogen (INCA-N) was applied to the River Lambourn, a Chalk river-system in southern England. The model's abilities to simulate the long-term trend and seasonal patterns in observed stream water nitrate concentrations from 1920 to 2003 were tested. This is the first time a semi-distributed, daily time-step model has been applied to simulate such a long time period and then used to calculate detailed catchment nutrient budgets which span the conversion of pasture to arable during the late 1930s and 1940s. Thus, this work goes beyond source apportionment and looks to demonstrate how such simulations can be used to assess the state of the catchment and develop an understanding of system behaviour. The mass-balance results from 1921, 1922, 1991, 2001 and 2002 are presented and those for 1991 are compared to other modelled and literature values of loads associated with nitrogen soil processes and export. The variations highlighted the problem of comparing modelled fluxes with point measurements but proved useful for identifying the most poorly understood inputs and processes thereby providing an assessment of input data and model structural uncertainty. The modelled terrestrial and instream mass-balances also highlight the importance of the hydrological conditions in pollutant transport. Between 1922 and 2002, increased inputs of nitrogen from fertiliser, livestock and deposition have altered the nitrogen balance with a shift from possible reduction in soil fertility but little environmental impact in 1922, to a situation of nitrogen accumulation in the soil, groundwater and instream biota in 2002. In 1922 and 2002 it was estimated that approximately 2 and 18 kg N ha(-1) yr(-1) respectively were exported from the land to the stream. The utility of the approach and further considerations for the best use of models are discussed. (C) 2008 Elsevier B.V. All rights reserved.

Insights into redox cycling of sulfur and iron in peatlands using high-resolution diffusive equilibrium thin film (DET) gel probe sampling

High spatial resolution vertical profiles of pore-water chemistry have been obtained for a peatland using diffusive equilibrium in thin films (DET) gel probes. Comparison of DET pore-water data with more traditional depth-specific sampling shows good agreement and the DET profiling method is less invasive and less likely to induce mixing of pore-waters. Chloride mass balances as water tables fell in the early summer indicate that evaporative concentration dominates and there is negligible lateral flow in the peat. Lack of lateral flow allows element budgets for the same site at different times to be compared. The high spatial resolution of sampling also enables gradients to be observed that permit calculations of vertical fluxes. Sulfate concentrations fall at two sites with net rates of 1.5 and 5.0nmol cm− 3 day− 1, likely due to a dominance of bacterial sulfate reduction, while a third site showed a net gain in sulfate due to oxidation of sulfur over the study period at an average rate of 3.4nmol cm− 3 day− 1. Behaviour of iron is closely coupled to that of sulfur; there is net removal of iron at the two sites where sulfate reduction dominates and addition of iron where oxidation dominates. The profiles demonstrate that, in addition to strong vertical redox related chemical changes, there is significant spatial heterogeneity. Whilst overall there is evidence for net reduction of sulfate within the peatland pore-waters, this can be reversed, at least temporarily, during periods of drought when sulfide oxidation with resulting acid production predominates.

Impact of melt ponds on Arctic sea ice simulations from 1990 to 2007

The extent and thickness of the Arctic sea ice cover has decreased dramatically in the past few decades with minima in sea ice extent in September 2007 and 2011 and climate models did not predict this decline. One of the processes poorly represented in sea ice models is the formation and evolution of melt ponds. Melt ponds form on Arctic sea ice during the melting season and their presence affects the heat and mass balances of the ice cover, mainly by decreasing the value of the surface albedo by up to 20%. We have developed a melt pond model suitable for forecasting the presence of melt ponds based on sea ice conditions. This model has been incorporated into the Los Alamos CICE sea ice model, the sea ice component of several IPCC climate models. Simulations for the period 1990 to 2007 are in good agreement with observed ice concentration. In comparison to simulations without ponds, the September ice volume is nearly 40% lower. Sensitivity studies within the range of uncertainty reveal that, of the parameters pertinent to the present melt pond parameterization and for our prescribed atmospheric and oceanic forcing, variations of optical properties and the amount of snowfall have the strongest impact on sea ice extent and volume. We conclude that melt ponds will play an increasingly important role in the melting of the Arctic ice cover and their incorporation in the sea ice component of Global Circulation Models is essential for accurate future sea ice forecasts.

Present state of global wetland extent and wetland methane modelling: methodology of a model inter-comparison project (WETCHIMP)

The Wetland and Wetland CH4 Intercomparison of Models Project (WETCHIMP) was created to evaluate our present ability to simulate large-scale wetland characteristics and corresponding methane (CH4) emissions. A multi-model comparison is essential to evaluate the key uncertainties in the mechanisms and parameters leading to methane emissions. Ten modelling groups joined WETCHIMP to run eight global and two regional models with a common experimental protocol using the same climate and atmospheric carbon dioxide (CO2) forcing datasets. We reported the main conclusions from the intercomparison effort in a companion paper (Melton et al., 2013). Here we provide technical details for the six experiments, which included an equilibrium, a transient, and an optimized run plus three sensitivity experiments (temperature, precipitation, and atmospheric CO2 concentration). The diversity of approaches used by the models is summarized through a series of conceptual figures, and is used to evaluate the wide range of wetland extent and CH4 fluxes predicted by the models in the equilibrium run. We discuss relationships among the various approaches and patterns in consistencies of these model predictions. Within this group of models, there are three broad classes of methods used to estimate wetland extent: prescribed based on wetland distribution maps, prognostic relationships between hydrological states based on satellite observations, and explicit hydrological mass balances. A larger variety of approaches was used to estimate the net CH4 fluxes from wetland systems. Even though modelling of wetland extent and CH4 emissions has progressed significantly over recent decades, large uncertainties still exist when estimating CH4 emissions: there is little consensus on model structure or complexity due to knowledge gaps, different aims of the models, and the range of temporal and spatial resolutions of the models.

Anthropogenic nutrient sources and loads from a Mediterranean catchment into a coastal lagoon: Mar Menor, Spain

The Mar Menor is a coastal lagoon increasingly threatened by urban and agricultural pressures. The main watercourse draining into the lagoon is the Rambla del Albujón. A fortnightly campaign carried out over one annual cycle enabled us to characterize the treated urban sewage effluents and agricultural sources which contribute to the nutrient fluxes in the watercourse. Multivariate analysis provided information for establishing chemical signatures and for assessing the relative influence of the various sources on the water quality at the outlet. Mass balances were used to examine net gains and losses, and cross-correlations with rainfall to analyze climatic influence and control factors in the trends of the nutrient flux. The rainfall pattern was significantly cross-correlated with nitrate and phosphorus fluxes from agricultural sources, while fluctuations in the resident population explained the phosphorus flux trend in urban sources. 50% of dissolved inorganic nitrogen was from agricultural sources, while 70% of total phosphate and 91% of total organic carbon were from urban point sources. The net amounts of all the nutrients fell as a result of plant uptake and/or denitrification in the channel. The control of urban point sources (phosphorus-enriched) is suggested as a promptly action for improving the health of the coastal lagoon.

Respirometric techniques for assessment of biological kinetics in constructed wetland

The aim of this research was the development of a procedure to measure biological kinetics of organic matter oxidation and nitrification in constructed wetland, by using respirometric techniques. Columns simulating cores of vertical subsurface flow systems were investigated. The oxygen uptake rate (OUR) of the columns was calculated on the basis of the difference of DO concentrations measured continuously at the top and at the bottom of the column. From the respirogram, the following kinetic parameters have been evaluated: maximum rate of oxidation of readily biodegradable COD, maximum rate of nitrification, endogenous respiration of the biomass grown inside the bed. In order to improve the interpretation of the respirograms, additional respirometric tests were carried out on the wetland columns by using pure substrates, such as acetate (carbon source) and ammonium (substrate for nitrification). The kinetic parameters obtained from respirograms can be useful for control and design of constructed wetlands or for improving nutrient and carbon mass balances.

Evaluation of a simple alkaline pretreatment for screening of sugarcane hybrids according to their in vitro digestibility

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dextran sulfate/Triton X two-phase micellar systems as an alternative first purification step for clavulanic acid

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Prove di ozonolisi sui fanghi biologici prodotti da impianti di depurazione delle acque reflue urbane

La tecnica di ozonolisi viene applicata ai fanghi biologici derivanti da impianti di depurazione acque reflue urbane, e consiste nell'ottenere, grazie all'ozono, una minor massa fangosa da smaltire e una miglior trattabilità del fango residue. In questo elaborato si prendono in esame le sperimentazioni effettuate a Marina di Ravenna e si estraggono le prime conclusioni gestionali, economiche e ambientali sull'applicabilità del metodo a questo tipo di fango.

Perennial Snow and Ice Variations (2000-2008) in the Arctic Circumpolar Land Area from Satellite Observations

Perennial snow and ice (PSI) extent is an important parameter of mountain environments with regard to its involvement in the hydrological cycle and the surface energy budget. We investigated interannual variations of PSI in nine mountain regions of interest (ROI) between 2000 and 2008. For that purpose, a novel MODIS data set processed at the Canada Centre for Remote Sensing at 250 m spatial resolution was utilized. The extent of PSI exhibited significant interannual variations, with coefficients of variation ranging from 5% to 81% depending on the ROI. A strong negative relationship was found between PSI and positive degree-days (threshold 0°C) during the summer months in most ROIs, with linear correlation coefficients (r) being as low as r = −0.90. In the European Alps and Scandinavia, PSI extent was significantly correlated with annual net glacier mass balances, with r = 0.91 and r = 0.85, respectively, suggesting that MODIS-derived PSI extent may be used as an indicator of net glacier mass balances. Validation of PSI extent in two land surface classifications for the years 2000 and 2005, GLC-2000 and Globcover, revealed significant discrepancies of up to 129% for both classifications. With regard to the importance of such classifications for land surface parameterizations in climate and land surface process models, this is a potential source of error to be investigated in future studies. The results presented here provide an interesting insight into variations of PSI in several ROIs and are instrumental for our understanding of sensitive mountain regions in the context of global climate change assessment.

Early last glacial maximum in the southern Central Andes reveals northward shift of the westerlies at similar to 39 ka

The latitudinal position of the southern westerlies has been suggested to be a key parameter for the climate on Earth. According to the general notion, the southern westerlies were shifted equatorward during the global Last Glacial Maximum (LGM: ~24–18 ka), resulting in reduced deep ocean ventilation, accumulation of old dissolved carbon, and low atmospheric CO2 concentrations. In order to test this notion, we applied surface exposure dating on moraines in the southern Central Andes, where glacial mass balances are particularly sensitive to changes in precipitation, i.e. to the latitudinal position of the westerlies. Our results provide robust evidence that the maximum glaciation occurred already at ~39 ka, significantly predating the global LGM. This questions the role of the westerlies for atmospheric CO2, and it highlights our limited understanding of the forcings of atmospheric circulation.

LGM and Late Glacial glacier advances in the Cordillera Real and Cochabamba (Bolivia) deduced from 10Be surface exposure dating

Surface exposure dating (SED) is an innovative tool already being widely applied for moraine dating and for Late Quaternary glacier and climate reconstruction. Here we present exposure ages of 28 boulders from the Cordillera Real and the Cordillera Cochabamba, Bolivia. Our results indicate that the local Last Glacial Maximum (LGM) in the Eastern Cordilleras occurred at ~22–25 ka and was thus synchronous to the global temperature minimum. We were also able to date several Late Glacial moraines to ~11–13 ka, which likely document lower temperatures and increased precipitation ("Coipasa" humid phase). Additionally, we recognize the existence of older Late Glacial moraines re-calculated to ~15 ka from published cosmogenic nuclide data. Those may coincide with the cold Heinrich 1 event in the North Atlantic region and the pronounced "Tauca" humid phase. We conclude that (i) exposure ages in the tropical Andes may have been overestimated so far due to methodological uncertainties, and (ii) although precipitation plays an important role for glacier mass balances in the tropical Andes, it becomes the dominant forcing for glaciation only in the drier and thus more precipitation-sensitive regions farther west and south.

Present state of global wetland extent and wetland methane modelling: methodology of a model inter-comparison project (WETCHIMP)

The Wetland and Wetland CH4 Intercomparison of Models Project (WETCHIMP) was created to evaluate our present ability to simulate large-scale wetland characteristics and corresponding methane (CH4) emissions. A multi-model comparison is essential to evaluate the key uncertainties in the mechanisms and parameters leading to methane emissions. Ten modelling groups joined WETCHIMP to run eight global and two regional models with a common experimental protocol using the same climate and atmospheric carbon dioxide (CO2) forcing datasets. We reported the main conclusions from the intercomparison effort in a companion paper (Melton et al., 2013). Here we provide technical details for the six experiments, which included an equilibrium, a transient, and an optimized run plus three sensitivity experiments (temperature, precipitation, and atmospheric CO2 concentration). The diversity of approaches used by the models is summarized through a series of conceptual figures, and is used to evaluate the wide range of wetland extent and CH4 fluxes predicted by the models in the equilibrium run. We discuss relationships among the various approaches and patterns in consistencies of these model predictions. Within this group of models, there are three broad classes of methods used to estimate wetland extent: prescribed based on wetland distribution maps, prognostic relationships between hydrological states based on satellite observations, and explicit hydrological mass balances. A larger variety of approaches was used to estimate the net CH4 fluxes from wetland systems. Even though modelling of wetland extent and CH4 emissions has progressed significantly over recent decades, large uncertainties still exist when estimating CH4 emissions: there is little consensus on model structure or complexity due to knowledge gaps, different aims of the models, and the range of temporal and spatial resolutions of the models.