International audience | 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.

9 pages | International audience | The influence of different organic amendments on diuron leaching was studied through undisturbed vineyard soil columns. Two composts (A and D), the second at two stages of maturity, and two soils (VR and Bj) were sampled. After 1 year, the amount of residues (diuron þ metabolites) in the leachates of the VR soil (0.19e0.71%) was lower than in the Bj soil (4.27e8.23%), which could be explained by stronger diuron adsorption on VR. An increase in the amount of diuron leached through the amended soil columns, compared to the blank, was observed for the Bj soil only. This result may be explained by the formation of mobile complexes between diuron and water-extractable organic matter (WEOM) through the Bj soil, or by competition between diuron and WEOM for the adsorption sites in the soil. For both soils, the nature of the composts and their degree of maturity did not significantly influence diuron leaching.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | International audience | This study focuses on spatiotemporal variations in the type of dissolved organic matter (DOM) and copper binding ability both upstream and downstream of Paris. It also compares the relative influence of both natural DOM upstream of Paris and effluent dissolved organic matter (EfDOM) output from a wastewater treatment plant (WWTP) on trace metal speciation and bioavailability in aquatic systems. In addition to the typical high- and low-affinity binding sites, a third family of very high-affinity binding sites has been highlighted for EfDOM. In receiving waters downstream of Paris during low-flow periods, the percentage of high- and very high-affinity sites originating from EfDOM reaches nearly 60 %. According to the speciation computation, the free copper concentration upstream of Paris exceeds the downstream Paris concentration by a factor of 2 to 4. As regards copper bioavailability, the highest EC50<inf>tot</inf> values were observed for EfDOM and downstream DOM, with a very low aromaticity and low UV absorbance. This finding suggests that specific ultraviolet absorbance (SUVA) is unlikely to be useful in assessing metal speciation and toxicity in aquatic systems subject to strong urban pressures. These results also highlight that the copper speciation computation for surface water exposed to considerable human pressures should include not only the humic and/or fulvic part of dissolved organic carbon but more hydrophilic fractions as well, originating for example from EfDOM. © 2015 Springer-Verlag Berlin Heidelberg

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA | International audience | This study focuses on spatiotemporal variations in the type of dissolved organic matter (DOM) and copper binding ability both upstream and downstream of Paris. It also compares the relative influence of both natural DOM upstream of Paris and effluent dissolved organic matter (EfDOM) output from a wastewater treatment plant (WWTP) on trace metal speciation and bioavailability in aquatic systems. In addition to the typical high- and low-affinity binding sites, a third family of very high-affinity binding sites has been highlighted for EfDOM. In receiving waters downstream of Paris during low-flow periods, the percentage of high- and very high-affinity sites originating from EfDOM reaches nearly 60 %. According to the speciation computation, the free copper concentration upstream of Paris exceeds the downstream Paris concentration by a factor of 2 to 4. As regards copper bioavailability, the highest EC50<inf>tot</inf> values were observed for EfDOM and downstream DOM, with a very low aromaticity and low UV absorbance. This finding suggests that specific ultraviolet absorbance (SUVA) is unlikely to be useful in assessing metal speciation and toxicity in aquatic systems subject to strong urban pressures. These results also highlight that the copper speciation computation for surface water exposed to considerable human pressures should include not only the humic and/or fulvic part of dissolved organic carbon but more hydrophilic fractions as well, originating for example from EfDOM. © 2015 Springer-Verlag Berlin Heidelberg

International audience | Solid-phase microextraction (SPME) was used to determine the equilibrium association constant for a pesticide, trifluralin (TFR), with dissolved organic matter (DOM). After optimization of the SPME method for the analysis of TFR, partition coefficients (KDOM) with three different sources ofDOM were determined in buffered solutions at pH 7. Commercial humic acids and DOM fractions isolated from two surface waters were used. The values of log KDOM varied from 4.3 to 5.8, depending on the nature of the organic material. A good correlation was established between log KDOM and DOMproperties (as measured with the H/O atomic ratio and UV absorbance), in agreement with literature data. This is consistent with the effect of polarity and aromaticity for governing DOM-pollutant associations, regardless of the origin of DOM. This association phenomenon is relevant to better understand the behavior of pesticides in the environment since it controls part of pesticide leaching and fate in aquatic systems.

Persulfate-based advanced oxidation process is considered as a promising technology for the degradation of phenol, where efficient, cost effective, and green methods with high peroxydisulfate (PS) activation capacity is of increasing demand. In this work, an in-situ liquid phase precipitation combined with ball milling method was applied for the synthesized of α-FeOOH/biochar, as be the PS activator for phenol degradation. Results showed that the ball-milled α-FeOOH and red pine wood biochar prepared at 700 °C (BM-α-FeOOH/PBC700) exhibited the highest catalytic property with PS for phenol oxidation (a phenol removal rate of 100%), compared with the BM-α-FeOOH (16.0%) and BMPBC700 (66.3%). The presence of intermediate products such as hydroquinone and catechol, and total organic carbon (TOC) removal rate (88.9%) proved the oxidation of phenol in the BM-α-FeOOH/PBC700+PS system. The characterization results showed that the functional groups (e.g., CO, C–O, Fe–O, and Si–O), the dissolved organic matter (DOM) in biochar, the loading of Fe element, and higher degree of graphitization and defect structures, contributed to the activation of PS to form free radicals (i.e., SO₄·⁻, ·OH, ·O₂⁻, and hVB⁺) for phenol oxidation, of which, SO₄·⁻ and ·OH account for 72.1% of the phenol removal rate. The specific contribution to the PS activation for phenol oxidation by each part of the materials was calculated based on the “whole to part” experiment. The contribution of DOM, acid-soluble substance, and carbon matrix and basal part in BM-α-FeOOH/PBC700 were 6.0%, 40.9%, and 53.1%, respectively. The reusability experiments of BM-α-FeOOH/PBC700 demonstrated that the composite was relatively stable after four cycles of reuse. Among three co-existing anions (NO₃⁻, Cl⁻, and HCO₃⁻), HCO₃⁻ played the most significant inhibition effects on phenol removal through reducing the phenol removal rate from 89.6% to 77.9%. This work provides guidance for the design of high active and stable carbon materials that activate PS to remove phenol.

The properties and metal-binding abilities of dissolved organic matter (DOM) rely on its molecular weight (MW) structure. In this study, the spatial differences of DOM in compositions, MW structures, and binding mechanisms with copper (Cu²⁺) in Dongping Lake were investigated by applying excitation-emission matrix combining parallel factor analysis (EEM-PARAFAC), synchronous fluorescence (SF) spectra, two-dimensional correlation spectra (2D-COS), and Fourier transform infrared (FTIR) spectra. The EDOM for the entrance of the Dawen River and PDOM for the macrophyte-dominated region were divided from DOM of Dongping Lake based on hierarchical clustering analysis (HCA) and principal component analysis (PCA) and were size-fractioned into MW < 500 kDa and <100 kDa fractions. According to EEM-PARAFAC, Dongping Lake was dominated by tryptophan-like substances with MW < 500 kDa. The concentration of PDOM was higher than that of EDOM (p < 0.05). 2D-COS showed that protein-like components preceded humic-like components binding to Cu²⁺ regardless of sample type (215 nm > 285 nm > 310–360 nm). The Cu²⁺ binding capacity of DOM exhibited specific differences in space, components, and molecular weights. The humic-like component 1 (C1) and tryptophan-like component 4 (C4) of PDOM showed stronger binding abilities than those of EDOM. Endogenous tryptophan-like component 4 (C4) had a higher binding affinity for Cu²⁺ than humic-like components (logKₐ: C4 > C1 > C2) in PDOM irrespective of MW. Humic-like components with MW < 500 kDa displayed higher binding potentials for Cu²⁺. FTIR spectra showed that the main participants of DOM-Cu complexation included aromatic hydrocarbons, aliphatic groups, amide Ⅰ bands, and carboxyl functional groups. This study provides spatial-scale insights into the molecular weight structure of DOM in influencing the behavior, fate, and bioavailability of heavy metals in lakes.

Dissolved organic matter (DOM) plays a significant role in the photochemical behavior of nano- and micro-plastic particles (NPs/MPs). We investigated the influence of DOM on the mechanism on the photoaging of NPs/MPs with different molecular structures under UV₃₆₅ irradiation in water. DOM components used in this study are mainly humic acid and fulvic acid. The results showed that DOM promoted the weathering of aliphatic NPs/MPs (polypropylene (PP)), but inhibited or had only a minor effect on the photoaging of aromatic NPs/MPs (polystyrene (PS) NPs/MPs, carboxyl-modified PS NPs, amino-modified PS NPs, and polycarbonate MPs). NPs with a large surface area may adsorb sufficient DOM on the particle surfaces through π-π interactions, which competes with NPs for photon absorption sites, thus, can delay the photoaging of PS NPs. Aromatic MPs may release phenolic compounds that quench •OH, thereby weakening the photoaging process. For aliphatic MPs, the detection of peracid, aldehyde, and ketone groups on the polymer surface indicated that DOM promoted weathering of PP MPs, which was primarily because the generation of •OH due to DOM photolysis may attack the polymer by C–C bond cleavage and hydrogen extraction reactions. This study provides insight into the UV irradiation weathering process of NPs/MPs of various compositions and structures, which are globally distributed in water.

Iron (III) co-precipitation with dissolved organic matter (DOM) is pervasive in many natural environments. However, the effects of DOM on the formation of Fe(III) hydroxysulfate (FHS) and its environmental implications are poorly understood. In this study, fulvic acid (FA) was used as a model DOM compound, and experiments were devised to investigate the effects of FA on the formation of FHS. In addition, the Pb(II) adsorption capabilities of FHSs biosynthesized under various FA dosages, including kinetics and sorption isotherm experiments, were conducted. These experiments showed that co-precipitation of FA promoted the formation of Fe-FA composites, FA-doped schwertmannite, and small particles of jarosite. Co-precipitates are more enriched in carboxyl (–COOH) functional groups due to their preferential binding with FHS. The adsorption kinetics, isotherms and mechanisms of Pb onto the biosynthesized FHSs were then comprehensively characterized and modeled. Though the specific surface area decreased with increasing FA loading, the introduction of FA into FHSs increased Pb(II) adsorption, with the highest concentration of FA addition improving the removal capacity of Pb(II) to 91.54%. Kinetics studies and intra-particle diffusion models indicated that the adsorption of Pb(II) onto the FHSs was correlated with the number of active sites, and two adsorption steps: surface adsorption and the diffusion of Pb(II) in channels inside the biosynthesized FHSs, are suggested. The adsorption mechanism was attributed to cation exchange between Pb(II) and –OH and –COOH functional groups, and the co-precipitated FA provided additional sites for Pb(II) adsorption by FHS.

Rare earth elements (REE) have become essential in high- and green-technologies. Their increasing use lead to the release of anthropogenic REE into the environment including aquatic systems. The limited data available on the aquatic ecotoxicology of REE indicate their biological effects are highly dependent on their speciation, posing challenges for a reliable environmental risk assessment (ERA). The current study assessed the influence of speciation on the toxicity of neodymium (Nd), gadolinium (Gd) and ytterbium (Yb) in the Daphnia magna mobility inhibition test (ISO 6341:2012). REE toxicity was assessed individually and in ternary mixture, in the absence and presence of dissolved organic matter (DOM). Speciation was predicted by modeling and REE bioaccumulation by D. magna was measured to better understand the relationship between REE speciation and toxicity. DOM decreased significantly the toxicity of Nd, Gd and the mixture towards this freshwater crustacean. This was explained by a lower REE bioaccumulation in the presence of DOM due to REE-DOM complexation, which reduced REE bioavailability. DOM effects on Yb toxicity and bioaccumulation were limited because of Yb precipitation. We show that the way of expressing EC50 values (based on nominal, measured or predicted REE concentrations in solution) drastically changed REE toxicity assessment and that these changes were influenced by REE speciation. This study demonstrates for the first time that REE speciation, and especially REE-DOM complexation, significantly influences REE bioaccumulation and toxicity towards D. magna. Our results have implications for the subsequent ERA of REE.