Mélanie Davranche

How does organic matter constrain the nature, size and availability of Fe nanoparticles for biological reduction?

Few studies have so far examined the kinetics and extent of the formation of Fe-colloids in the presence of natural organic ligands. The present study used an experimental approach to investigate the rate and amount of colloidal Fe formed in presence of humic substances, by gradually oxidizing Fe(II) at pH 6.5 with or without humic substances (HS) (in this case, humic acid--HA and fulvic acid--FA). Without HS, micronic aggregates (0.1-1 μm diameter) of nano-lepidocrocite is obtained, whereas, in a humic-rich medium (HA and FA suspensions at 60 and 55 ppm of DOC respectively), nanometer-sized Fe particles are formed trapped in an organic matrix. A proportion of iron is not found to contribute to the formation of nanoparticles since iron is complexed to HS as Fe(II) or Fe(III). Humic substances tend to (i) decrease the Fe oxidation and hydrolysis, and (ii) promote nanometer-sized Fe oxide formation by both inhibiting the development of hydroxide nuclei and reducing the aggregation of Fe nanoparticles. Bioreduction experiments demonstrate that bacteria (Shewanella putrefaciens CIP 80.40 T) are able to use Fe nanoparticles associated with organic matter about eight times faster than in the case of nano-lepidocrocite. This increase in bioreduction rate appears to be related to the presence of humic acids that (i) indirectly control the size, shape and density of oxyhydroxides and (ii) directly enhance biological reduction of nanoparticles by electron shuttling and Fe complexation. These results suggest that, in wetlands but also elsewhere where mixed organic matter-Fe colloids occur, Fe nanoparticles closely associated with organic matter represent a bioavailable Fe source much more accessible for microfauna than do crystallized Fe oxyhydroxides.

Rare earth element sorption onto hydrous manganese oxide: A modeling study

Manganese oxides are important scavengers of rare earth elements (REE) in hydrosystems. However, it has been difficult to include Mn oxides in speciation models due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), as well as discrepancies between published sorption data and predictions using the available models. Surface complexation reactions for hydrous Mn oxide were described using a two surface site model and the diffuse double layer SCM. The specific surface area, surface side density, and pH(zpc) were fixed to 746 m2/g, 2.1 mmol/g, and 2.2, respectively. Two site types (≡XOH and ≡YOH) were also used with pK(a2) values of 2.35 (≡XOH) and 6.06 (≡YOH). The fraction of the high affinity sites was fixed at 0.36. Published REE sorption data were subsequently used to determine the equilibrium surface complexation constants, while considering the influence of pH, ionic strength, and metal loading. LogK increases from light REE to heavy REE and, more specifically, displays a convex tetrad effect. At low metal loading, the ≡YOH site type strongly expresses its affinity toward REE, whereas at higher metal loading, the same is true for the ≡XOH site type. This study thus provides evidence for heterogeneity in the distribution of the Mn oxide binding sites among REE.

Dynamic structure of humic substances: Rare earth elements as a fingerprint

Whereas humic substances are known to play a key role in controlling metal speciation and trace element mobility within soils and waters, the understanding of their structure is still unclear and remains a matter of debate. Several models of humic substance structure have been proposed, where humic substances were composed of either: (i) macromolecular polyelectrolytes that can form molecular aggregates or (ii) supramolecular assemblies (molecular aggregates) of small molecules without macromolecular character, joined together by weak attraction forces. This experimental study was designed and dedicated: (i) to follow the size of organic molecules versus ionic strength or pH by the combined means of ultrafiltration and aromaticity data and rare earth element (REE) fingerprinting, and (ii) to investigate the pH and ionic strength effect on the distribution of associated rare earth elements in soil solution. This study supports the presence of supramolecular associations of small molecules and probably the presence of macromolecules in the bulk dissolved organic matter. By contrast to ionic strength, pH appeared to be the major parameter playing on the stability of the humic substance structure. Humic substances displayed dynamic structures, which evolved with regard to pH. Low pH led to a destabilization of the humic substance conformation. This destabilization had an impact on the trace element distribution in soil solution, as assessed by REE data, and conversely, the destabilization degree of humic substances seemed to be influenced by the metal ion charge.

Double pH control on humic substance-borne trace elements distribution in soil waters as inferred from ultrafiltration

Colloidal dissolved organic carbon (DOC) is an important carrier phase for trace elements (TE) in subsurface environments. As suggested by previously published field observations, preferential sorption of DOC onto mineral surfaces tends to enrich the solid phase in humic acids. This DOC fractionation may affect the mobility of TE. pH is known to play an important role in the stability of colloids. This study was therefore dedicated to identifying the influence of DOC fractionation on TE mobility. Sequential extraction has been used to provide information on the possible TE carriers within soil (as exchangeable, weak acid soluble, reducible, oxidizable, and nonextractible metal fractions). Batch experiments were carried out to investigate the influence of pH on the detachment of colloids and associated TE. Different groups of elements were identified according to TE behavior during pH changes. Several elements displayed increasing concentrations with decreasing pH. These concentrations can represent an important fraction of the total soil concentration. By contrast, other elements showed increasing concentrations following increasing pH, in association with an increasing amount of colloids in soil solution. Concerning this latter group, two colloidal carrier phases were identified during the pH increase: (i) the first one concerned the majority of elements, which were associated with humic substances remaining in solution, and (ii) the second one involved several TE rather associated with nanooxides. Therefore, DOC fractionation plays a key role in the TE concentration in soil solution during pH changes.

Interactions between natural organic matter, sulfur, arsenic and iron oxides in re-oxidation compounds within riparian wetlands: NanoSIMS and X-ray adsorption spectroscopy evidences

Arsenic (As) is a toxic and ubiquitous element which can be responsible for severe health problems. Recently, Nano-scale Secondary Ions Mass Spectrometry (nanoSIMS) analysis has been used to map organomineral assemblages. Here, we present a method adapted from Belzile et al. (1989) to collect freshly precipitated compounds of the re-oxidation period in a natural wetland environment using a polytetrafluoroethylene (PTFE) sheet scavenger. This method provides information on the bulk samples and on the specific interactions between metals (i.e. As) and the natural organic matter (NOM). Our method allows producing nanoSIMS imaging on natural colloid precipitates, including (75)As(-), (56)Fe(16)O(-), sulfur ((32)S(-)) and organic matter ((12)C(14)N) and to measure X-ray adsorption of sulfur (S) K-edge. A first statistical treatment on the nanoSIMS images highlights two main colocalizations: (1) (12)C(14)N(-), (32)S(-), (56)Fe(16)O(-) and (75)As(-), and (2) (12)C(14)N(-), (32)S(-) and (75)As(-). Principal component analyses (PCAs) support the importance of sulfur in the two main colocalizations firstly evidenced. The first component explains 70% of the variance in the distribution of the elements and is highly correlated with the presence of (32)S(-). The second component explains 20% of the variance and is highly correlated with the presence of (12)C(14)N(-). The X-ray adsorption near edge spectroscopy (XANES) on sulfur speciation provides a quantification of the organic (55%) and inorganic (45%) sulfur compositions. The co-existence of reduced and oxidized S forms might be attributed to a slow NOM kinetic oxidation process. Thus, a direct interaction between As and NOM through sulfur groups might be possible.

Biogeochemical Factors Affecting Rare Earth Element Distribution in Shallow Wetland Groundwater

Wetlands are specific areas able to regulate metals mobility in the environment. Among metals, rare earth elements (REE) appear to be particularly interesting because of the information that could be provided by the REE patterns. Moreover, as REE are becoming a matter of great economic interest, their significant release into the environment may be expected over the next few decades. Wetlands would then play a key role in the regulation of their concentration in the environment. This review demonstrated that REE are released in wetland bound to colloidal organic matter. During the flood season, the released REE concentrations are largely higher than those released during the wet period. This solubilization is related to the organic matter desorption caused by the pH rise imposed by the reducing reactions. The resulting REE patterns depend on the heterogeneity of the humic acid (HA) binding sites and the presence of potential competitive cations, such as Fe(III) and Al(III). At high REE loading, REE are bound to HA carboxylic groups and the pattern exhibit a MREE downward concavity. At low loading, REE are bound to phenolic and chelate groups and the pattern exhibits a lanthanide contraction. At low loading, REE seem to act as cationic bridges between two organic molecules, whereas at high loading they seem to be engaged in strong multidentate bonding. Moreover, the REE patterns can be modified with the competitive cations amount and speciation. The prime factor governing all these processes is pH, which drives the organic colloid production, REE loading and solubility of competitive cations.

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.

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.

Characterization of iron–organic matter nano-aggregate networks through a combination of SAXS/SANS and XAS analyses: impact on As binding

Nanoparticles play an important role in controlling the mobility of pollutants such as arsenic (As) in the environment. In natural waters, aggregates of nanoparticles can be constituted of organic matter (OM) associated with iron (Fe). However, little is known about their network structure, especially the role of each component in the resulting aggregate morphology. This network structure can be of major importance for the metal and metalloid sorption processes. We synthesized an aggregate model of nanoparticles by varying the Fe/organic carbon (OC) ratio (R). By coupling small-angle neutron and X-ray scattering (SANS, SAXS), dynamic light scattering (DLS), transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS), we revealed the fractal organization of Fe (i.e. primary beads forming a nanoparticle called an intermediate aggregate and then forming a secondary aggregate of nanoparticles). As the aggregate size increases with R, the As adsorption rate increases at a constant As/Fe ratio. Two hypotheses were considered: with increasing R, i) the repulsion interactions between the nanoparticles increase, inducing a structure opening, and ii) the Fe part size increases more strongly and is more ramified than the OM part, leading to a decrease of the coating by OM. Both hypotheses involve an increase in the number of available As binding sites. This study offers new perspectives on the impact of the network structure of heterogeneous nano-aggregates on their sorption capacity and could explain some metal/metalloid sorption variations observed in natural samples with variations in Fe/OC ratios.