Iron oxide nanoparticles improving multimetal phytoextraction in Helianthus annuus.

This study assessed the phytotoxicity of a mixture of five different trace elements (TEs) frequently found as pollutants in soils: arsenic, cadmium, copper, lead and zinc. On the other hand, the plant response to a magnetite (Fe3O4) nanoparticle amendment on this mixture as well as nanomagnetite remediation potential has been tested. Sunflower (Helianthus annuus) plants were grown for 90 days in soil contaminated with the five mentioned TEs at the limit levels of TEs in soils likely to receive sludge established by French legislation. Depending on the conditions, experimental set-ups were amended or not with 1% dry weight nanomagnetite (NPsMagn), citric acid-coated nanomagnetite (NPsMagn@CA) or micro-sized magnetite (µPs) in order to assess the behavior of nanomagnetites in a TEs-contaminated water-soil-plant system under repeated water-deficiency stress. The mixture of TEs did not induce phytotoxicity as estimated by plant growth, pigment content, maximum quantum yield of photosynthesis, oxidative impact and antioxidant response. Furthermore, both nanomagnetites treatments in a TEs-contaminated soil significantly increased biomass production by 64 % compared to control and antioxidant enzyme activities compared to control and TEs-treated plants. NPsMagn and NPsMagn@CA particularly enhance phytoextraction of Cd and Cu, increasing the amounts of TEs in aerial parts from 1.5 to 4.5 times compared to set-ups without nanomagnetites. Based on Cd, Cu, Pb and Zn contents in soil solutions, both nanomagnetites treatments improved TEs phytoextraction without increasing groundwater contamination. On the contrary, nanomagnetites significantly reduce arsenic uptake by plants and solubilization in dissolved phase. Our results show that modifying surface physicochemical properties of NPsMagn with citric acid coating does not improve their effects compared to bare NPsMagn. NPsMagn and NPsMagn@CA also appear to mitigate the effects of drought stress. This work highlights several positive environmental aspects related to the use of nanomagnetites in phytoremediation.

More than redox, biological organic ligands control iron isotope fractionation in the riparian wetland.

Although redox reactions are recognized to fractionate iron (Fe) isotopes, the dominant mechanisms controlling the Fe isotope fractionation and notably the role of organic matter (OM) are still debated. Here, we demonstrate how binding to organic ligands governs Fe isotope fractionation beyond that arising from redox reactions. The reductive biodissolution of soil Fe(III) enriched the solution in light Fe isotopes, whereas, with the extended reduction, the preferential binding of heavy Fe isotopes to large biological organic ligands enriched the solution in heavy Fe isotopes. Under oxic conditions, the aggregation/sedimentation of Fe(III) nano-oxides with OM resulted in an initial enrichment of the solution in light Fe isotopes. However, heavy Fe isotopes progressively dominate the solution composition in response to their binding with large biologically-derived organic ligands. Confronted with field data, these results demonstrate that Fe isotope systematics in wetlands are controlled by the OM flux, masking Fe isotope fractionation arising from redox reactions. This work sheds light on an overseen aspect of Fe isotopic fractionation and calls for a reevaluation of the parameters controlling the Fe isotopes fractionation to clarify the interpretation of the Fe isotopic signature.

How crucial is the impact of calcium on the reactivity of iron-organic matter aggregates? Insights from arsenic.

Environmental iron-organic matter (Fe-OM) aggregates play a major role in the dynamic of pollutants. Nowadays, there is a lack of information about the control exerted by their structural organization on their reactivity towards metal(loid)s and in particular, the impact of major ions, such as calcium. The sorption capacity of mimetic environmental Fe-OM-Ca aggregates was investigated relative to the Fe/organic carbon (OC) and Ca/Fe ratios using As as a probe. It was shown that Fe speciation is the key factor controlling the reactivity of Fe-OM-Ca aggregates regarding the high affinity of Fe(III)-oligomers towards As and the high sorption capacity of ferrihydrite-like nanoparticles. Moreover, when it occurs at high concentration, Ca competes with Fe for OM binding leading to an increase in the amount of ferrihydrite-like nanoparticles and binding site availability. As a consequence, Ca not only impacts the ionic strength but it also has a dramatic impact on the structural organization of Fe-OM aggregates at several scales of organization, resulting in an increase of their sorption capacity. In the presence of high amounts of Ca, Fe-OM-Ca aggregates could immobilize pollutants in the soil porous media as they form a micrometric network exhibiting a strong sorption capacity.

How can interspecific interactions in freshwater benthic macroinvertebrates modify trace element availability from sediment?

This study aimed to assess how bioturbation by freshwater benthic macroinvertebrates with different biological traits alone or in combination could modify trace elements (TE) fate between sediment and water, and if water TE concentration and animal TE content impair their body stores. Three macroinvertebrate species were exposed to TE contaminated sediment for 7 days: the omnivorous Echinogammarus berilloni (Amphipoda), the sediment feeding Tubifex tubifex (Oligochaeta) and the filter feeding Pisidium sp. (Bivalvia). Treatments were one without invertebrates (control), two with amphipods or mussels alone, and the combinations amphipod-mussel, and amphipod-mussel-worms. Water TE concentration increased significantly in 2 or 3 species mesocosms, concerning mainly Rare Earth Elements, Cr, U and Pb, known to be associated to the colloidal phase. By contrast, water soluble TE were not affected by animals. For both, amphipods and mussels, TE body content increased with the number of coexisting species. For amphipods, this increase concerned both, soluble and colloid-associated TE, possibly due to intense contact and feeding from sediment and predation on tubificids. TE bioaccumulation in mussel was less important and characterized by soluble TE, with water filtration as most plausible uptake route. Protein, triglyceride and Whole Body Energy Budget increased in amphipods with the number of coexisting species (probably by feeding on mussels' feces and tubificids) whereas triglycerides declined in mussels (presumably filtration was disturbed by amphipods). This study highlights interspecific interactions as key drivers explaining both: TE bioturbation, depending on their water solubility or colloidal association, and the exposure/contamination of species through another species activity.

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

The 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.

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

The 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 (<2µm size fractions). By contrast, under oxidizing conditions, they were distributed in particulate (>2µm size fraction), colloidal (<2µm 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 (0.2µm-30kDa), the REEs were bound to humic substances (HS). The lowest colloidal size fraction (<30kDa) 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.

Nano-litter from cigarette butts: Environmental implications and urgent consideration.

Cigarette butts (CGB) are equivalent to plastic litter in terms of number of pieces released directly into the environment. Due to their small size and social use, CGB are commonly found in natural systems, and several questions have been raised concerning the contaminants that are released with CGB, including metals, organic species, and nanoparticles. The aim of the present study is to investigate the release of nanoscale particles from CGB by leaching with rainwater. After seven days of passive stirring of both smoked and unsmoked CGB in synthetic rainwater, the solutions were treated and analyzed by specific nano-analytical methods. Our results demonstrate the release of 4.12 ± 0.24% (w/CGB) organic carbon in the range of 10 nm up to 400 nm and with a z-average diameter of 202.4 ± 74.1 nm. The fractal dimension (Df) of the nanoscale particles ranges from 1.14 to 1.52 and suggests a soot (carbon)-based composition. The analysis of some metallic species (As, Pb, Cd, Cu, Ni, Cr, Co, Al, Mn, Zn, and Fe) shows that these species are essentially attached to the nanoscale particles per gram of carbon released. By considering the diffusion of the nanomaterials into different environmental compartments, our results suggest a new emerging and global contamination of the environment by cigarette butts, comparable to plastic litter, which urgently needs to be considered.

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

Up 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.

Robust Method Using Online Steric Exclusion Chromatography-Ultraviolet-Inductively Coupled Plasma Mass Spectrometry To Investigate Nanoparticle Fate and Behavior in Environmental Samples.

The foundation of nanoscience is that the properties of materials change as a function of their physical dimensions, and nanotechnology exploits this premise by applying selected property modifications for a specific benefit. However, to investigate the fate and effect of the engineered nanoparticles on toxic metal (TM) mobility, the analytical limitations in a natural environment remain a critical problem to overcome. Recently, a new generation of size exclusion chromatography (SEC) columns developed with spherical silica is available for pore sizes between 5 and 400 nm, allowing the analysis of nanoparticles. In this study, these columns were applied to the analysis of metal-based nanoparticles in environmental and artificial samples. The new method allows quantitative measurements of the interactions among nanoparticles, organic matter, and metals. Moreover, because of the new nanoscale SEC, our method allows the study of these interactions for different size ranges of nanoparticles and weights of organic molecules with a precision of 1.2 × 10(-2) kDa. The method was successfully applied to the study of nanomagnetite spiked in complex matrixes, such as sewage sludge, groundwater, tap water, and different artificial samples containing Leonardite humic acid and different toxic metals (i.e., As, Pb, Th). Finally, our results showed that different types of interactions, such as adsorption, stabilization, and/or destabilization of nanomagnetite could be observed using this new method.

Thiol groups controls on arsenite binding by organic matter: new experimental and modeling evidence.

Although it has been suggested that several mechanisms can describe the direct binding of As(III) to organic matter (OM), more recently, the thiol functional group of humic acid (HA) was shown to be an important potential binding site for As(III). Isotherm experiments on As(III) sorption to HAs, that have either been grafted with thiol or not, were thus conducted to investigate the preferential As(III) binding sites. There was a low level of binding of As(III) to HA, which was strongly dependent on the abundance of the thiols. Experimental datasets were used to develop a new model (the modified PHREEQC-Model VI), which defines HA as a group of discrete carboxylic, phenolic and thiol sites. Protonation/deprotonation constants were determined for each group of sites (pKA=4.28±0.03; ΔpKA=2.13±0.10; pKB=7.11±0.26; ΔpKB=3.52±0.49; pKS=5.82±0.052; ΔpKS=6.12±0.12 for the carboxylic, phenolic and thiols sites, respectively) from HAs that were either grafted with thiol or not. The pKS value corresponds to that of single thiol-containing organic ligands. Two binding models were tested: the Mono model, which considered that As(III) is bound to the HA thiol site as monodentate complexes, and the Tri model, which considered that As(III) is bound as tridentate complexes. A simulation of the available literature datasets was used to validate the Mono model, with logKMS=2.91±0.04, i.e. the monodentate hypothesis. This study highlighted the importance of thiol groups in OM reactivity and, notably, determined the As(III) concentration bound to OM (considering that Fe is lacking or at least negligible) and was used to develop a model that is able to determine the As(III) concentrations bound to OM.

Insights into colloid-mediated trace element release at the soil/water interface.

Organic or inorganic colloids play a major role in the mobilization of trace elements in soils and waters. Environmental physicochemical parameters (pH, redox potential, temperature, pressure, ionic strength, etc.) are the controlling factors of the colloidal mobilization. This study was dedicated to follow the colloid-mediated mobilization of trace elements through time at the soil/water interface by means of an experimental approach. Soil column experiments were carried out using percolating synthetic solutions. The percolated solutions were ultrafiltrated with various decreasing cutoff thresholds to separate the different colloidal phases in which the dissolved organic carbon and trace element concentrations were measured. The major results which stem from this study are the following: (i) The data can be divided into different groups of organic compounds (microbial metabolites, fulvic acids, humic acids) with regard to their respective aromaticity and molecular weight. (ii) Three groups of elements can be distinguished based on their relationships with the colloidal phases: the first one corresponds to the so-called "truly" dissolved group (Li, B, K, Na, Rb, Si, Mg, Sr, Ca, Mn, Ba, and V). The second one can be considered as an intermediate group (Cu, Cd, Co, and Ni), while the third group gathers Al, Cr, U, Mo, Pb, Ti, Th, Fe, and rare earth elements (REE) carried by the organic colloidal pool. (iii) The data demonstrate that the fulvic acids seem to be a major organic carrier phase for trace elements such as Cu, Cd, Co, and Ni. By contrast, the trace elements belonging to the so-called colloidal pool were mostly mobilized by humic acids containing iron nanoparticles. Lead, Ti, and U were mobilized by iron nanoparticles bound to these humic acids. Thus, humic substances allowed directly or indirectly a colloidal transport of many insoluble trace elements either by binding trace elements or by stabilizing a ferric carrier phase. (iv) Finally, the results demonstrated also that REE were mostly mobilized by humic substances. The REE normalized patterns showed a middle REE downward concavity. Therefore, as previously shown elsewhere humic substances are a major control of REE speciation and REE fractionation patterns as well since the humic substance/metal ratio was the key parameter controlling the REE pattern shape.