Does As(III) interact with Fe(II), Fe(III) and organic matter through ternary complexes?

International audienceUp until now, only a small number of studies have been dedicated to the binding processes of As(III) with organic matter (OM) via ionic Fe(III) bridges; none was interested in Fe (II). Complexation isotherms were carried out with As(III), Fe(II) or Fe(III) and Leonardite humic acid (HA). Although PHREEQC/Model VI, implemented with OM thiol groups, reproduced the experimental datasets with Fe(III), the poor fit between the experimental and modeled Fe(II) data suggested another binding mechanism for As(III) to OM. PHREEQC/Model VI was modified to take various possible As(III)-Fe(II)-OM ternary complex conformations into account. The complexation of As(III) as a mononuclear bidentate complex to a bidentate Fe(II)-HA complex was evidenced. However, the model needed to be improved since the distribution of the bidentate sites appeared to be unrealistic with regards to the published XAS data. In the presence of Fe(III), As(III) was bound to thiol groups which are more competitive with regards to the low density of formed Fe(III)-HA complexes. Based on the new data and previously published results, we propose a general scheme describing the various As(III)-Fe-MO complexes that are able to form in Fe and OM-rich waters

Devenir des nanoparticules dans l'environnement : stabilité colloïdale, réactivité chimique et impacts sur le végétal

Engineered Iron Oxide Nanoparticles (IONPs) are specific nanoscale materials that have recently been used into wide environmental applications. The dispersion of IONPs into soils and waters, as well as their interactions with living organisms, raise many scientific issues. The first part of this work is intended to provide a thorough characterization of IONPs in aqueous solution, from their intrinsic physico-chemical properties to their colloidal behavior and chemical reactivity. Surface modifications are applied to evidence the key role of surface chemistry towards most interactions IONPs encounter. In particular, humic acid reduce NPs-Fe aggregation and display a high adsorption capacity for trace metals, especially copper (Cu).On the other hand, the pH of the solution play a critical role towards NPs-Fe interactions. Depending on the pH, the surface charge of the particles are modified and hence pH is involved in the electrostatic forces that drive the particles aggregation state and contribute to metal adsorption. The second part of the study is focused on the interactions occurring with IONPs in presence of plants. Several experiments are conducted in aqueous solution and in soil columns to precise the impacts of IONPs on the growth medium and to assess the effects of IONPs on plants. Results (magnetic susceptibility) show that IONPs manage to penetrate the roots of beans and sunflower plants (57 and 63 days-old) and that they are translocated to the aerial parts in low amounts. Plants respond to IONPs penetration by increasing the plant biomass and the chlorophyll contents and by decreasing the lipid peroxidation.Les nanoparticules de fer manufacturées (NPs-Fe) sont des matériaux de taille nanométrique dont l’utilisation s’est, depuis peu, étendue à des domaines environnementaux. Leur dispersion dans les milieux aqueux et solides, et leurs interactions avec le vivant soulèvent toutefois encore de nombreuses questions. Dans la première partie de cette étude, nous conduisons un travail approfondi de caractérisation des NPs-Fe et précisons comment ces propriétés sont impliquées dans les processus contrôlant la stabilité colloïdale puis la réactivité chimique (capacité d’adsorption du cuivre) des NPs-Fe en solution aqueuse. Des modifications à la fois surfaciques et cristallochimiques sont appliquées afin de mettre en évidence le rôle clés de la chimie de surface des NPs-Fe. Dans cette étude, il est montré que les acides humiques limitent l’agrégation des NPs-Fe et procurent des sites d’adsorption pour les métaux. Les conditions physico-chimiques du milieu s’avèrent également jouer un rôle crucial. Le pH modifie notamment la charge de surface des NPs-Fe et les forces d’interactions électrostatiques qui en résultent. Dans un deuxième temps, nous étudions les interactions entre les NPs-Fe et les végétaux, en solution puis dans un sol. Après 63 et 57 jours, les mesures de susceptibilité magnétique montrent que les NPs-Fe s’accumulent au niveau des racines avant d’être transloquées, en moindre quantité, dans les parties aériennes des plantes. La réponse des plantes à l’exposition aux NPs-Fe se traduit par une augmentation de la biomasse végétale et des teneurs en chlorophylles et une diminution de la peroxydation lipidique

Fate and behavior of iron oxide nanoparticles in the environment : impacts on trace metal mobility and soil-plant systems

Les nanoparticules de fer manufacturées (NPs-Fe) sont des matériaux de taille nanométrique dont l’utilisation s’est, depuis peu, étendue à des domaines environnementaux. Leur dispersion dans les milieux aqueux et solides, et leurs interactions avec le vivant soulèvent toutefois encore de nombreuses questions. Dans la première partie de cette étude, nous conduisons un travail approfondi de caractérisation des NPs-Fe et précisons comment ces propriétés sont impliquées dans les processus contrôlant la stabilité colloïdale puis la réactivité chimique (capacité d’adsorption du cuivre) des NPs-Fe en solution aqueuse. Des modifications à la fois surfaciques et cristallochimiques sont appliquées afin de mettre en évidence le rôle clés de la chimie de surface des NPs-Fe. Dans cette étude, il est montré que les acides humiques limitent l’agrégation des NPs-Fe et procurent des sites d’adsorption pour les métaux. Les conditions physico-chimiques du milieu s’avèrent également jouer un rôle crucial. Le pH modifie notamment la charge de surface des NPs-Fe et les forces d’interactions électrostatiques qui en résultent. Dans un deuxième temps, nous étudions les interactions entre les NPs-Fe et les végétaux, en solution puis dans un sol. Après 63 et 57 jours, les mesures de susceptibilité magnétique montrent que les NPs-Fe s’accumulent au niveau des racines avant d’être transloquées, en moindre quantité, dans les parties aériennes des plantes. La réponse des plantes à l’exposition aux NPs-Fe se traduit par une augmentation de la biomasse végétale et des teneurs en chlorophylles et une diminution de la peroxydation lipidique.Engineered Iron Oxide Nanoparticles (IONPs) are specific nanoscale materials that have recently been used into wide environmental applications. The dispersion of IONPs into soils and waters, as well as their interactions with living organisms, raise many scientific issues. The first part of this work is intended to provide a thorough characterization of IONPs in aqueous solution, from their intrinsic physico-chemical properties to their colloidal behavior and chemical reactivity. Surface modifications are applied to evidence the key role of surface chemistry towards most interactions IONPs encounter. In particular, humic acid reduce NPs-Fe aggregation and display a high adsorption capacity for trace metals, especially copper (Cu).On the other hand, the pH of the solution play a critical role towards NPs-Fe interactions. Depending on the pH, the surface charge of the particles are modified and hence pH is involved in the electrostatic forces that drive the particles aggregation state and contribute to metal adsorption. The second part of the study is focused on the interactions occurring with IONPs in presence of plants. Several experiments are conducted in aqueous solution and in soil columns to precise the impacts of IONPs on the growth medium and to assess the effects of IONPs on plants. Results (magnetic susceptibility) show that IONPs manage to penetrate the roots of beans and sunflower plants (57 and 63 days-old) and that they are translocated to the aerial parts in low amounts. Plants respond to IONPs penetration by increasing the plant biomass and the chlorophyll contents and by decreasing the lipid peroxidation

Surface modifications at the oxide/water interface: implications for Cu binding, solution chemistry and chemical stability of iron oxide nanoparticles

International audienceThe oxidation of magnetite into maghemite and its coating by natural organic constituents are common changes that affect the reactivity of iron oxide nanoparticles (IONP) in aqueous environments. Certain ubiquitous compounds such as humic acids (HA) and phosphatidylcholine (PC), displaying a high affinity for both copper (Cu) and IONP, could play a critical role in the interactions involved between both compounds. The adsorption of Cu onto four different IONP was studied: magnetite nanoparticles (magnNP), maghemite NP (maghNP), HA- and PC-coated magnetite NP (HA-magnNP and PC-magnNP, respectively). According to the results, the percentage of adsorbed Cu increases with increasing pH, irrespective of the IONP. Thus, protonation/deprotonation reactions are likely involved within Cu adsorption mechanism. Contrary to the other studied IONP, HA-magnNP favor Cu adsorption at most of the pH tested including acidic pH (pH = 3), suggesting that part of the active surface sites for Cu2+ were not grabbed by protons. The Freundlich adsorption isotherm of HA-magnNP provides the highest sorption constant KF (bonding energy) and n value which supports a heterogeneous sorption process. The heterogeneous adsorption between HA-magnNP and Cu2+ can be explained by both the diversity of the binding sites HA procured and the formation of multidendate complexes between Cu2+ and some of the HA functional groups. Such favorable adsorption process was neither observed on PC-coated-magnNP nor on maghNP, whose behaviors were comparable to that of magnNP. On another hand, HA and PC coatings considerably reduced iron (Fe) dissolution from magnNP as compared with magnNP. It was suggested that HA and PC coatings either provided efficient shield against Fe leaching or fostered dissolved Fe re-adsorption onto the functional groups at the coated magnNP surfaces. Thus, this study can help to better understand the complex interfacial reactions between cations-organic matter-colloidal surfaces which are relevant in environmental and agricultural contexts.This work showed that magnetite NP properties can be affected by surface modifications, which drive NP chemical stability and Cu adsorption, thereby affecting the global water chemistry

Unravelling Iron Oxide Nanoparticles (IONPs) interactions in the environment

International audienceEither used as nano-carriers in blood, depolluting agents in groundwaters or nanofertilizers in soils engineered nanoparticles (ENPs) are prone to a growing interest that explains their multiple uses as well as their increasing industrial production. The very small size of ENPs (having at least one space dimension <100nm) gives rise to some exceptional physicochemical properties that ensue from their high reactivity. In environmental and agricultural fields, where iron oxide nanoparticles (IONPs) are particularly used, this reactivity is directly related to their adsorption capacity, which is of prime interest regarding soil contamination and soil recovery issues. Considering the peculiar role of copper (Cu) in soils, we investigated the specific relationships that exist between IONPs and Cu. Most particularly, this study aims at understanding how pH, Cu concentration and Fe3O4-NPs natural coatings drive Cu adsorption to IONPs. In a primary step, eight nm-sized Fe3O4-NPs were synthesized using a co-precipitation method and thoroughly characterized with TEM, XRD, FT-IR and BET while in a second stage Cu-adsorption tests were conducted through ultrafiltrations (<2kDa) and monitored with ICP-MS analyses. In these experiments, four types of IONPs were investigated regarding their mineralogy and the nature of their coating. They were tested with four copper concentrations (0.01, 0.05, 0.1 and 0.5mM) and five different pH values (3.5; 5; 6; 7 and 8). According to the results, un-adsorbed Cu decreases with increasing pH values and about 100% of Cu is adsorbed to IONPs at high pH values. Although the trend looks repeatable regardless NPs’ coating and Cu concentrations, each NP-type may have its typical pHpzc value and the amount of Cu adsorbed to IONPs is also likely to be related to the number of available adsorption sites

Investigating the remediation potential of iron oxide nanoparticles in Cu-polluted soil–plant systems: coupled geochemical, geophysical and biological approaches

International audienceAlthough the use of iron oxide nanoparticles (IONPs) has high potential in remediation and agriculture, a major hindrance to their use includes the risk of contamination of soil and water resources with underexplored effects of IONPs on biota. The fate, phytotoxicity and remediation potential of IONPs are investigated with soil column experiments using 7 nm-sized magnetite (Fe 3 O 4) nanoparticles (magnNPs) and sunflower (Helianthus annuus). Control soil, magnNP-containing soil (10 g magnNPs per kg soil), copper-polluted soil (500 mg Cu per kg soil) and copper-polluted soil containing magnNPs (10 g magnNPs per kg soil and 500 mg Cu per kg soil) support sunflower growth for 57 and 95 days. In magnNP-exposed plants, the occurrence of magnNPs does not affect the growth of the vegetative aerial parts and photosynthetic efficiency. Decreased lipid peroxidation indicates an enhanced antioxidant enzymatic response of magnNP-exposed plants. In plants grown in Cu-and magnNP-Cu-soils, the physiological and biochemical impacts of excess copper are clearly identified, resulting in growth retardation, decreased pigment contents and photosynthetic efficiency, and increased lipid peroxidation and peroxidase (POD) activities. Based on magnetic susceptibility, a higher amount of magnNPs is detected after 57 days in the roots of magnNP-exposed plants (1400 mg kg À1) than in the roots of magnNP-Cu-exposed plants (920 mg kg À1). In the latter, magnNP internalization is likely hampered because of the plants' physiological responses to Cu toxicity. At the working Cu and magnNP concentrations, magnNPs neither decrease Cu accumulation in the plant tissues nor alleviate the overall growth retardation of sunflowers and certain phytotoxic effects induced by excess Cu. However, this study highlights several positive environmental aspects relative to magnNP use, including the harmless effects of magnNPs on sunflowers (1% magnNPs in soil) and the ability of magnNPs to influence Cu mobility in the soil (which could be even more pronounced at lower Cu concentration)

Colloidal and chemical stability of iron oxides nanoparticles in aqueous solution

International audienceEither used as nano-carriers in blood, depolluting agents in groundwaters or in soils, engineered iron nanoparticles are prone to a growing interest that explains their multiple uses as well as their increasing industrial production. The very small size of iron oxide nanoparticles (IONPs) having at least one space dimension <100nm gives rise to some exceptional physicochemical properties that ensue from their high reactivity. In environmental and agricultural fields, where IONPs could be particularly used, this reactivity is directly related to their colloidal stability which is of prime interest regarding groundwater- or soil-remediation, allowing IONPs to reach their target. NPs stability in aqueous environments depends on many parameters including the environmental conditions (pH, temperature, soil solution chemistry and ionic strength), NPs concentration, as well as NPs intrinsic and surficial characteristics. In this context, experimentations were investigated to assess the effects of pH, surface modifications and NPs intrinsic physicochemical properties (size, morphology and surface area (SA)) on their colloidal and chemical stability.In a primary step, nm-sized Fe3O4-NPs and ɣ-Fe2O3-NPs were synthesized and their surface were then coated with HA and PC (Phosphatidylcholines) to model natural surface modification. In a second step, these IONPS were characterized with TEM, XRD, FT-IR and BET. Fe(II)/Fe(III) ratio measurements have been conducted on Fe3O4-NPs in aerobic conditions to assess the oxidation kinetics of magnetite to maghemite. Then, the effect of pH on the colloidal stability of these bare-IONPs and surface modified Fe3O4-NPs was studied in a pH range from 3 to 7.5. The results evidenced that pH played a key role in driving IONPs colloidal stability as pH changes affected the size distribution (SD) of all the IONPs investigated, leading at least to two SD configurations: IONPs were either stable or aggregated depending of the closeness of the pH regards to their respective pHzpc. Surface coatings with HA and PC induced surface chemical modifications, which shifted the pHzpc of bare magnetite and modified the ensuing pH-dependent SD through electrosteric interactions. HA turned out to be much more effective than PC in enhancing IONPs colloidal stability as it promoted smaller sized aggregates and widened magnetite pH-stability range (pH=4 to 7.5). The rapid transformation of magnetite into maghemite (five days) resulted in the loss of Fe(II) from its chemical structure and increased magnetite-NPs SA. Maghemite also displayed a higher sensitivity to pH than magnetite and the oxidized NPs formed almost exclusively μm-scaled aggregates in acidic medium (pH=3, 4 and 5). The colloidal stability of magnetite at acidic pH would thus likely be hindered in aerobic environments because of its rapid oxidation into maghemite which lead to higher aggregation at most pH values

Colloidal and chemical stabilities of iron oxide nanoparticles in aqueous solutions: the interplay of structural, chemical and environmental drivers

International audienceNanoparticle (NP) stability in aqueous environments is dependent upon many parameters including environmental conditions, NP concentrations as well as NP intrinsic characteristics. In this study, the effects of pH and surface modifications on the colloidal and chemical stabilities of nanosized magnetite (Fe3O4), maghemite (γ-Fe2O3) and hematite (α-Fe2O3) are investigated. Because changes in surface charge affect the size distribution of NP, pH plays a key role in driving the colloidal stability. More NP aggregation is observed at pH values close to the pH of zero point of charge (pHzpc). Coating of magnetite with humic acid (HA) and phosphatidylcholine (PC) affects the electrostatic interactions and then the colloidal behavior of NP. The rapid transformation of magnetite into maghemite through air oxidation results in significant modification of both surface charge and specific surface area of NP. Because the maghemite almost exclusively formed µm-scale aggregates, the colloidal stability of magnetite is expected to be hindered in oxic environments. For hematite, the particle size distribution data emphasize the influence of both pH and intrinsic surface properties in the colloidal stability. These findings may have strong implications for an accurate prediction of the transformation and mobility of Fe-nanoparticles under environmentally relevant conditions and thus their fate in nature

Experimental evidence of REE size fraction redistribution during redox variation in wetland soil

International audienceThe evolution of rare earth element (REE) speciation between reducing and oxidizing conditions in a riparian wetland soil was studied relative to the size fractionation of the solution. In all size fractions obtained from the reduced and oxidized soil solutions, the following analyses were carried out: organic matter (OM) characterization, transmission electron microscopy (TEM) observations as well as major and trace element analyses. Significant REE redistribution and speciation evolution between the various size fractions were observed. Under reducing conditions, the REEs were bound to colloidal and dissolved OM (2 μm size fraction), colloidal (<2 μm size fraction), organic and Fe-enriched fractions. In the particulate size fraction, the REEs were bound to humic and bacterial OM embedding Fe nano-oxides. The resulting REE pattern showed a strong enrichment in heavy REEs (HREEs) in response to REE binding to specific bacterial OM functional groups. In the largest colloidal size fraction (0.2 μm–30 kDa), the REEs were bound to humic substances (HS). The lowest colloidal size fraction (<30 kDa) is poorly concentrated in the REEs and the REE pattern showed an increase in the middle REEs (MREEs) and heavy REEs (HREEs) corresponding to a low REE loading on HS. A comparison of the REE patterns in the present experimental and field measurements demonstrated that, in riparian wetlands, under a high-water level, reducing conditions are insufficient to allow for the dissolution of the entire Fe nano-oxide pool formed during the oxidative period. Therefore, even under reducing conditions, Fe(III) seems to remain a potential scavenger of REEs