International audience | The cocktail of pesticides sprayed to protect crops generates a miscellaneous and generalized contamination of water bodies. Sorption, especially on soils, regulates the spreading and persistence of these contaminants. Fine resolution sorption data and knowledge of its drivers are needed to manage this contamination. The aim of this study is to investigate the potential of Mid-Infrared spectroscopy (MIR) to predict and specify the adsorption and desorption of a diversity of pesticides. We constituted a set of 37 soils from French mainland and West Indies covering large ranges of texture, organic carbon, minerals and pH. We measured the adsorption and desorption coefficients of glyphosate, 2,4-dichlorophenoxyacetic acid (2,4-D) and difenoconazole and acquired MIR Lab spectra for these soils. We developed Partial Least Square Regression (PLSR) models for the prediction of the sorption coefficients from the MIR spectra. We further identified the most influencing spectral bands and related these to putative organic and mineral functional groups. The prediction performance of the PLSR models was generally high for the adsorption coefficients Kdads (0.4 < R 2 < 0.9 & RPIQ > 1.8). It was contrasted for the desorption coefficients and related to the magnitude of the desorption hysteresis. The most significant spectral bands in the PLSR differ according to the pesticides indicating contrasted interactions with mineral and organic functional groups. Glyphosate interacts primarily with polar mineral groups (OH) and difenoconazole with hydrophobic organic groups (CH2, C=C, COO-, CO , CO -C). 2,4-D has both positive and negative interactions with these groups. Finally, this work suggests that MIR combined with PLSR is a promising and cost-effective tool. It allows both the prediction of adsorption and desorption parameters and the specification of these mechanisms for a diversity of pesticides including polar active ingredients.

International audience | The nanoscale size of plastic debris makes them potential efficient vectors of many pollutants and more especially of metals. In order to evaluate this ability, nanoplastics were produced from microplastics collected on a beach exposed to the North Atlantic Gyre. The nanoplastics were characterized using multi-dimensional methods: asymmetrical flow field flow fractionation and dynamic light scattering coupled to several detectors. Lead (II) adsorption kinetics, isotherm and pH-edge were then carried out. The sorption reached a steady state after around 200 min. The maximum sorption capacity varied between 97% and 78.5% for both tested Pb concentrations. Lead (II) adsorption kinetics is controlled by chemical reactions with the nanoplastics surface and to a lesser extent by intraparticle diffusion. Adsorption isotherm modeling using Freundlich model demonstrated that NPG are strong adsorbents equivalent to hydrous ferric oxides such as ferrihydrite (log against 11.76 for NPG and ferrihydrite, respectively). The adsorption is dependent upon pH, in response to the Pb(II) adsorption by the oxygenated binding sites developed on account of the surface UV oxidation under environmental conditions. They could be able to compete with Fe or humic colloids for Pb binding regards to their amount and specific areas. Nanoplastics could therefore be efficient vectors of Pb and probably of many other metals as well in the environment.

International audience | The nanoscale size of plastic debris makes them potential efficient vectors of many pollutants and more especially of metals. In order to evaluate this ability, nanoplastics were produced from microplastics collected on a beach exposed to the North Atlantic Gyre. The nanoplastics were characterized using multi-dimensional methods: asymmetrical flow field flow fractionation and dynamic light scattering coupled to several detectors. Lead (II) adsorption kinetics, isotherm and pH-edge were then carried out. The sorption reached a steady state after around 200 min. The maximum sorption capacity varied between 97% and 78.5% for both tested Pb concentrations. Lead (II) adsorption kinetics is controlled by chemical reactions with the nanoplastics surface and to a lesser extent by intraparticle diffusion. Adsorption isotherm modeling using Freundlich model demonstrated that NPG are strong adsorbents equivalent to hydrous ferric oxides such as ferrihydrite (log against 11.76 for NPG and ferrihydrite, respectively). The adsorption is dependent upon pH, in response to the Pb(II) adsorption by the oxygenated binding sites developed on account of the surface UV oxidation under environmental conditions. They could be able to compete with Fe or humic colloids for Pb binding regards to their amount and specific areas. Nanoplastics could therefore be efficient vectors of Pb and probably of many other metals as well in the environment.

In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces. © 2005 Elsevier Ltd. All rights reserved.

Phosphorus removal from wastewater has been of growing interest for some decades to avoid eutrophication in surface water. In subsurface constructed wetlands precipitation and adsorption are the main mechanisms responsible of P uptake. The use of calcareous media is attractive because of p-ca interactions. Two media (calcite and recycled crushed concrete (rcc)) were examined in batch and continuous systems. They show attractive sorption capacities using batch experiments, however experiments carried out in open reactors pointed out some limitation in retention capacities and effluent quality. rcc was sensitive to a strong dissolution leading to a quick phosphorus precipitation but induced high conductivity and ph values in the treated water. Calcite efficiency depended on the material dissolution rate, directly linked to the carbonate equilibrium of the solution. Microscopic observations of the calcite surface show crystal making of phosphorus precipitate. Crystal growth seems to be the main P uptake once materials surfaces are covered. No experimental condition allows to reach an effluent concentration below 2 mgp.l-1.

Competing ions strongly affect heavy metal sorption onto the solid surfaces of soil. This study evaluated competitive sorption of Cd, Cu, Ni, Pb and Zn on three soils: Calcixerollic Xerochrept, Paralithic Xerorthent and Lithic Haplumbrept. Monometal and competitive sorption isotherms were obtained at 25°C. The individual effect of ions on retention of the others was ascertained by a fractional factorial analysis design. Most of the sorption isotherms belonged to type L subtype 2 in the classification of Giles. In competitive sorption the initial linear part was shorter and the knee sharper when compared with monometal sorption isotherms. Parameters related to sorptive capacity, such as Point B, Langmuir monolayer and Freundlich distribution coefficient, were higher in monometal than in competitive sorption, and in basic soils than in acidic soil. Calcium desorbed at different points of the sorption isotherms indicated that cationic exchange with Ca was the main retention mechanism in calcareous soils. For Pb, the ratio Ca desorbed/Pb sorbed was close to one; for Cu, Ni and Zn the ratio ranged from 1.20 to 1.37, probably due to partial dissolution of calcium carbonates by hydrolytic processes during retention. On the other hand, Cd had a ratio around 0.6 reflecting another additional retention mechanism, probably surface complexation. Fractional factorial design confirmed that the presence of the cations investigated reduced the amount of the five metals retained, but the presence of Cu and Pb in the system depressed Ni, Cd and Zn sorption more than the inverse. Cation mobility was enhanced when equilibrium concentration increased and the effect was higher in Ca-saturated soils.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]ARCEAU | International audience | Pesticide pollution is one of the main current threats on water quality. This paper presents the potential and functioning principles of a "Wet" forest buffer zone for reducing concentrations and loads of glyphosate, isoproturon, metazachlor, azoxystrobin, epoxiconazole, and cyproconazole. A tracer injection experiment was conducted in the field in a forest buffer zone at Bray (France). A fine time-scale sampling enabled to illustrate that interactions between pesticides and forest buffer substrates (soil and organic-rich litter layer), had a retarding effect on molecule transfer. Low concentrations were observed for all pesticides at the forest buffer outlet thus demonstrating the efficiency of "Wet" forest buffer zone for pesticide dissipation. Pesticide masses injected in the forest buffer inlet directly determined concentration peaks observed at the outlet. Rapid and partially reversible adsorption was likely the major process affecting pesticide transfer for short retention times (a few hours to a few days). Remobilization of metazachlor, isoproturon, desmethylisoproturon, and AMPA was observed when non-contaminated water flows passed through the forest buffer. Our data suggest that pesticide sorption properties alone could not explain the complex reaction mechanisms that affected pesticide transfer in the forest buffer. Nevertheless, the thick layer of organic matter litter on the top of the forest soil was a key parameter, which enhanced partially reversible sorption of pesticide, thus retarded their transfer, decreased concentration peaks, and likely increased degradation of the pesticides. Consequently, to limit pesticide pollution transported by surface water, the use of already existing forest areas as buffer zones should be equally considered as the most commonly implemented grass buffer strips.

[Departement_IRSTEA]Ecotechnologies [TR1_IRSTEA]TED [Axe_IRSTEA]TED-EPURE | International audience | Xenobiotics such as pesticides and pharmaceuticals are an increasingly large problem in aquatic environments. A fixed-bed adsorption filter, used as tertiary stage of sewage treatment, could be a solution to decrease xenobiotics concentrations in wastewater treatment plants (WWTPs) effluent. The adsorption efficiency of two mineral adsorbent materials (expanded clay (EC) and zeolite (ZE)), both seen as a possible alternative to activated carbon (AC), was evaluated in batch tests. Experiments involving secondary treated domestic wastewater spiked with a cocktail of ten xenobiotics (eight pharmaceuticals and two pesticides) known to be poorly eliminated in conventional biological process were carried out. Removal efficiencies and partitions coefficientswere calculated for two levels of initial xenobiotic concentration, i.e, concentrations lower to 10 microg/L and concentrations ranged from 100 to 1,000 microg/L. While AC was the most efficient adsorbent material, both alternative adsorbent materials showed good adsorption efficiencies for all ten xenobiotics (from 50 to 100 % depending on the xenobiotic/adsorbent material pair). For all the targeted xenobiotics, at lower concentrations, EC presented the best adsorption potential with higher partition coefficients, confirming the results in terms of removal efficiencies. Nevertheless, Zeolite presents virtually the same adsorption potential for both high and low xenobiotics concentrations to be treated. According to this first batch investigation, ZE and EC could be used as alternative absorbent materials to AC in WWTP.