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The release of CeO 2 -bearing residues during the weathering of an acrylic stain enriched with CeO 2 nanomaterial designed for wood protection (Nanobyk brand additive) was studied under two different scenarios: (i) a standard 12-weeks weathering protocol in climate chamber, that combined condensation, water spraying and UV-visible irradiation and (ii) an alternative accelerated 2-weeks leaching batch assay relying on the same weathering factors (water and UV), but with a higher intensity of radiation and immersion phases. Similar Ce released amounts were evidenced for both scenarios following two phases: one related to the removal of loosely bound material with a relatively limited release, and the other resulting from the degradation of the stain, where major release occurred. A non-linear evolution of the release with the UV dose was evidenced for the second phase. No stabilization of Ce emissions was reached at the end of the experiments. The two weathering tests led to different estimates of long-term Ce releases, and different degradations of the stain. Finally, the photo-degradations of the nanocomposite, the pure acrylic stains and the Nanobyk additive were compared. The incorporation of Nanobyk into the acrylic matrix significantly modified the response of the acrylic stain to weathering., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this study, we assessed the transportability of zero valent iron nanoparticles (nano-Fe 0 ) coated with different organics (carboxy methyl cellulose (CMC), poly acrylic acid (PAA), and xanthan gum) in standard porous sand and in real aquifer sediments. Our results suggest that the organic surface coatings optimized for nano-Fe 0 in porous sand media do not necessarily reflect the same transportability in real field aquifer sediment. Xanthan gum-coated nano-Fe 0 showed highest transportability in standard porous sand, but the performance was much lower in real aquifer sediment, whereas the PAA-coated nano-Fe 0 particle showed better transportability both in aquifer sediment and in porous sand media. Nano-Fe 0 without organic surface coating exhibited very low transportability and was largely retained by the porous medium. Our results suggest that the molecular weight and surface charge density of the organic may play a role in transportability of these nanoparticles. To assess the impact of organic coating on the nanoparticle reactivity with contaminants, we also conducted batch tests to follow TCE degradation using different surface coatings and found no significant difference albeit a minor delay in kinetics. Using theoretical calculations, we also estimated the potential distance traveled by nanoparticles in porous sand as well as in aquifer sediment. Our results suggest that using xanthan gum and PAA as surface coating, nano-Fe 0 could travel up to 9.8 and 4.1 m, respectively, in the porous sand media as compared to 0.2 and 0.9 m in real aquifer sediment, respectively. Graphical abstract Nanoparticle mobility in porous sand vs and aquifer sediment.

The influence of inorganic anions on the photoreactivity and aggregation of titanium dioxide nanoparticles (NPs) was assessed by dosing carbonate, chloride, nitrate, phosphate, and sulfate as potassium salts at multiple concentrations. NP stability was monitored in terms of aggregate morphology and electrophoretic mobility (EPM). Aggregate size and fractal dimension were measured over time by laser diffraction, and the isoelectric point (IEP) as a function of anion and concentration was obtained by measuring EPM versus pH. Phosphate, carbonate, and to a lesser extent, sulfate decreased the IEP of TiO 2 and stabilized NP suspensions owing to specific surface interactions, whereas this was not observed for nitrate and chloride. TiO 2 NPs were exposed to UV-A radiation, and the photoreactivity was assessed by monitoring the production of reactive species over time both at the NP surface (photogenerated holes) and in the bulk solution (hydroxyl radicals) by observing their reactions with the selective probe compounds iodide and terephthalic acid, respectively. The generation of photogenerated holes and hydroxyl radicals was influenced by each inorganic anion to varying degrees. Carbonate and phosphate inhibited the oxidation of iodide, and this interaction was successfully described by a Langmuir-Hinshelwood mechanism and related to the characteristics of TiO 2 aggregates. Chloride and nitrate do not specifically interact with TiO 2 , and sulfate creates relatively weak interactions with the TiO 2 surface such that no decrease in photogenerated hole reactivity was observed. A decrease in hydroxyl radical generation was observed for all inorganic anions. Quenching rate constants for the reaction of hydroxyl radicals with each inorganic anion do not provide a comprehensive explanation for the magnitude of this decrease, which arises from the interplay of several physicochemical phenomena. This work shows that the reactivity of NPs will be strongly influenced by the makeup of the waters they are released into. The impact of anion species on hydroxyl radical inhibition was as follows: carbonate > chloride > phosphate > nitrate > sulfate.

Soils act as nanoceria sinks via agricultural spreading and surface waters. Canola plants were grown for one month in soil spiked with nanoceria (1 mg·kg(-1)). To define the role of nanomaterials design on environmental impacts, we studied nanoceria with different sizes (3.5 or 31 nm) and coating (citrate). We measured microbial activities involved in C, N, and P cycling in the rhizosphere and unplanted soil. Bacterial community structure was analyzed in unplanted soil, rhizosphere, and plant roots by 454-pyrosequencing of the 16S rRNA gene. This revealed an impact gradient dependent on nanomaterials design, ranging from decreased microbial enzymatic activities in planted soil to alterations in bacterial community structure in roots. Particle size/aggregation was a key parameter in modulating nanoceria effects on root communities. Citrate coating lowered the impact on microbial enzymatic activities but triggered variability in the bacterial community structure near the plant root. Some nanoceria favored taxa whose closest relatives are hydrocarbon-degrading bacteria and disadvantaged taxa frequently associated in consortia with disease-suppressive activity toward plant pathogens. This work provides a basis to determine outcomes of nanoceria in soil, at a dose close to predicted environmental concentrations, and to design them to minimize these impacts.

Due to their catalytic and oxidative properties, cerium dioxide nanoparticles (CeO2NPs) are widely used as diesel additive or as promising therapy in cancerology; yet, scarce data are available on their toxicity, and none on their reproductive toxicity. We showed a significant decrease of fertilization rate, assessed on 1272 oocytes, during in vitro fertilization (IVF) carried out in culture medium containing CeO2NP at very low concentration (0.01 mg.l(-1)). We also showed significant DNA damage induced in vitro by CeO2NP on mouse spermatozoa and oocytes at 0.01 mg.l(-1) using Comet assay. Transmission Electron Microscopy did not detect any nanoparticles in the IVF samples at 0.01 mg.l(-1), but showed, at high concentration (100 mg.l(-1)), their endocytosis by the cumulus cells surrounding oocytes and their accumulation along spermatozoa plasma membranes and oocytes zona pellucida. We did not observe any nanoparticles in the cytoplasm of spermatozoa, oocytes or embryos. This study demonstrates for the first time the impact of CeO2NP on in vitro fertilization, as well as their genotoxicity on mouse spermatozoa and oocytes, at low nanoparticle concentration exposure. Decreased fertilization rates may result from: (1) CeO2NP's genotoxicity on gametes; (2) a mechanical effect, disrupting gamete interaction and (3) oxidative stress induced by CeO2NP. These results add new and important insights with regard to the reproductive toxicity of nanomaterials requesting urgent evaluation, and support several publications on metal nanoparticles reprotoxicity. Our data highlight the need for in vivo studies after low-dose exposure.

Wastewater Treatment Plants (WWTPs) are a key pathway by which nanoparticles (NPs) enter the environment following release from NP-enabled products. This work considers the fate and exposure of CeO2 NPs in WWTPs in a two-step process of heteroaggregation with bacteria followed by the subsequent reduction of Ce(IV) to Ce(III). Measurements of NP association with solids in sludge were combined with experimental estimates of reduction rate constants for CeO2 NPs in Monte Carlo simulations to predict the concentrations and speciation of Ce in WWTP effluents and biosolids. Experiments indicated preferential accumulation of CeO2 NPs in biosolids where reductive transformation would occur. Surface functionalization was observed to impact both the distribution coefficient and the rates of transformation. The relative affinity of CeO2 NPs for bacterial suspensions in sludge appears to explain differences in the observed rates of Ce reduction for the two types of CeO2 NPs studied., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The economic and societal impacts of nano-materials are enormous. However, releasing such materials in the environment could be detrimental to human health and the ecological biosphere. Here we demonstrate that gold and quantum dots nanoparticles bio-accumulate into mucus materials coming from natural species such as jellyfish. One strategy that emerges from this finding would be to take advantage of these trapping properties to remove nanoparticles from contaminated water.

To better understand and predict the fate of engineered nanoparticles in the water column, we assessed the heteroaggregation of TiO2 nanoparticles with a smectite clay as analogues for natural colloids. Heteroaggregation was evaluated as a function of water salinity (10(-3) and 10(-1) M NaCl), pH (5 and 8), and selected nanoparticle concentration (0-4 mg/L). Time-resolved laser diffraction was used, coupled to an aggregation model, to identify the key mechanisms and variables that drive the heteroaggregation of the nanoparticles with colloids. Our data show that, at a relevant concentration, nanoparticle behavior is mainly driven by heteroaggregation with colloids, while homoaggregation remains negligible. The affinity of TiO2 nanoparticles for clay is driven by electrostatic interactions. Opposite surface charges and/or high ionic strength favored the formation of primary heteroaggregates via the attachment of nanoparticles to the clay. The initial shape and dispersion state of the clay as well as the nanoparticle/clay concentration ratio also affected the nature of the heteroaggregation mechanism. With dispersed clay platelets (10(-3) M NaCl), secondary heteroaggregation driven by bridging nanoparticles occurred at a nanoparticle/clay number ratio of greater than 0.5. In 10(-1) M NaCl, the clay was preaggregated into larger and more spherical units. This favored secondary heteroaggregation at lower nanoparticle concentration that correlated to the nanoparticle/clay surface area ratio. In this latter case, a nanoparticle to clay sticking efficiency could be determined.

The use of nano-enabled materials in industry and consumer products is increasing rapidly and with it, the more imperative it becomes to understand the consequences of such materials entering the environment during production, use or disposal. The novel properties of engineered nanomaterials (ENMs) that make them desirable for commercial applications also present the possibility of impacting aquatic and terrestrial environments in ways that may differ from materials in bulk format. Modeling techniques are needed to proactively predict the environmental fate and transport of nanomaterials. A model for nanoparticle (NP) separation and transformation in water treatment was parameterized for three metal and metal-oxide NPs. Functional assays to determine NP specific distribution and transformation were used to parameterize the model and obtain environmentally relevant concentrations of NPs and transformation byproducts leaving WWTPs in effluent and biosolids. All three NPs were predicted to associate >90% with the solid phase indicating significant accumulation in the biosolids. High rates of transformation for ZnO and Ag NPs resulted in ~97% transformation of the NPs that enter the plant despite differences in transformation rate in aerobic versus anaerobic environments. Due to high insolubility and negligible redox transformation, the only process predicted to impact TiO2 NP fate and transport in WWTPs was distribution between the solid and liquid phases. Subsequent investigation of ZnO NP species fate and transport when land applied in biosolids indicated that steady state concentrations of ZnO phases would likely be achieved after approximately 150days under loading conditions of biosolids typical in current practice., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The growing use of nanomaterials and their associated risks necessitate the emergence of efficient decontamination systems. The main objective of this study is to develop a new prototype based on artificial supramolecular hydrogel capable of removing nanoparticle (NP) waste and nanomaterial by-products from aqueous suspensions. We demonstrate the high trapping efficacy of the low-molecular-weight gelators (LMWG) for very small particles (quantum dots (QDs), gold nanoparticles (AuNPs), TiO2 nanoparticles (TiO2-NPs), below 50 nm in diameter) from aqueous suspensions. The performance levels of removing nanoparticles from contaminated effluents could lead to a competitive alternative to filtration and dialysis devices.

The broad range of applications of cerium oxide (CeO2) nanoparticles (nano-CeO2) has attracted industrial interest, resulting in greater exposures to humans and environmental systems in the coming years. Their health effects and potential biological impacts need to be determined for risk assessment. The aims of this study were to gain insights into the molecular mechanisms underlying the genotoxic effects of nano-CeO2 in relation with their physicochemical properties. Primary human dermal fibroblasts were exposed to environmentally relevant doses of nano-CeO2 (mean diameter, 7 nm; dose range, 6 × 10(-5)-6 × 10(-3) g/l corresponding to a concentration range of 0.22-22 µM) and DNA damages at the chromosome level were evaluated by genetic toxicology tests and compared to that induced in cells exposed to micro-CeO2 particles (mean diameter, 320 nm) under the same conditions. For this purpose, cytokinesis-blocked micronucleus assay in association with immunofluorescence staining of centromere protein A in micronuclei were used to distinguish between induction of structural or numerical chromosome changes (i.e. clastogenicity or aneuploidy). The results provide the first evidence of a genotoxic effect of nano-CeO2, (while not significant with micro-CeO2) by a clastogenic mechanism. The implication of oxidative mechanisms in this genotoxic effect was investigated by (i) assessing the impact of catalase, a hydrogen peroxide inhibitor, and (ii) by measuring lipid peroxidation and glutathione status and their reversal by application of N-acetylcysteine, a precusor of glutathione synthesis in cells. The data are consistent with the implication of free radical-related mechanisms in the nano-CeO2-induced clastogenic effect, that can be modulated by inhibition of cellular hydrogen peroxide release.

Nanoparticles (NPs) are sized between 1 and 100nm. Their size allows new nanoscale properties of particular interest for industrial and scientific purpose. Over the past twenty years, nanotechnology conquered many areas of use (electronic, cosmetic, textile…). While, human is exposed to an increasing number of nanoparticles sources, health impacts and, particularly on reproductive function, remains poorly evaluated. Indeed, traceability of nanoparticles use is lacking and nanotoxicology follows different rules than classical toxicology. This review focuses on the impact of NPs on health and particularly on fertility and addresses potential risks of chronic exposure to NPs on human fertility., (Copyright © 2014 Elsevier Masson SAS. All rights reserved.)

Oxidation behavior of nano-Fe(0) particles in an anoxic environment was determined using different state-of-the-art analytical approaches, including high resolution transmission electron microscopy (HR-TEM) combined with energy filtered transmission electron microscopy (EFTEM), X-ray absorption spectroscopy (XAS), and magnetic measurements. Oxidation in controlled experiments was compared in standard double distilled (DD) water, DD water spiked with trichloroethene (TCE), and TCE contaminated site water. Using HR-TEM and EFTEM, we observed a surface oxide layer (∼3 nm) formed immediately after the particles were exposed to water. XAS analysis followed the dynamic change in total metallic iron concentration and iron oxide concentration for the experimental duration of 35 days. The metallic iron concentration in nano-Fe(0) particles exposed to water, was ∼40% after 35 days; in contrast, the samples containing TCE were reduced to ∼15% and even to nil in the case of TCE contaminated site water, suggesting that the contaminants enhance the oxidation of nano-Fe(0). Frequency dependence measurements confirmed the formation of superparamagnetic particles in the system. Overall, our results suggest that nano-Fe(0) oxidized via the Fe(0) - Fe(OH)2 - Fe3O4 - (γ-Fe2O3) route and the formation of superparamagnetic maghemite nanoparticles due to disruption of the surface oxide layer.

The heteroaggregation of engineered nanoparticles (ENPs) with natural colloids (NCs), which are ubiquitous in natural surface waters, is a crucial process affecting the environmental transport and fate of ENPs. Attachment efficiencies for heteroaggregation, α hetero, are required as input parameters in environmental fate models to predict ENP concentrations and contribute to ENP risk assessment. Here, we present a novel method for determining α hetero values by using a combination of laser diffraction measurements and aggregation modeling based on the Smoluchowski equation. Titanium dioxide nanoparticles (TiO2 NPs, 15 nm) were used to demonstrate this new approach together with larger silicon dioxide particles (SiO2, 0.5 μm) representing NCs. Heteroaggregation experiments were performed at different environmentally relevant solution conditions. At pH 5 the TiO2 NPs and the SiO2 particles are of opposite charge, resulting in α hetero values close to 1. At pH 8, where all particles are negatively charged, α hetero was strongly affected by the solution conditions, with α hetero ranging from <0.001 at low ionic strength to 1 at conditions with high NaCl or CaCl2 concentrations. The presence of humic acid stabilized the system against heteroaggregation.

We assessed the biodistribution and in situ speciation of sub-lethal concentrations of citrate-coated silver nanoparticles and dissolved silver within Fundulus heteroclitus embryos. Using a thorough physico-chemical characterization, we studied the role of salinity on both uptake and in situ speciation. The Ag uptake or adsorption on the chorion was reduced by 2.3-fold for Ag NPs, and 2.9-fold for AgNO3 in estuarine water (10‰ ASW) compared to deionized water (0‰ ASW). Between 58% and 85% of the silver was localized on/in the chorion and formed patches between 20 and 80 µm. More than a physical barrier, the chorion was found to be a chemically reactive membrane controlling the in situ speciation of silver. A strong complexation of the Cit-Ag NPs with the thiolated groups of proteins or enzymes of the chorion was responsible for the oxidation of 48 ± 5% of the Ag(0) into Ag((I))-S species at 0‰ ASW. However, at 10‰ ASW, the presence of Cl(-) ions at the surface of Ag NPs slow down this oxidation. For the dissolved silver, we observed that in deionized water 69 ± 7% of Ag(+) taken up by the chorion was complexed by the thiolated molecules while the others 30 ± 3% were reduced into Ag(0) likely via interaction with the hemiacetal-reducing ends of polysaccharides of the chorion.

Physical-chemists, (micro)biologists, and ecologists need to conduct meaningful experiments to study the environmental risk of engineered nanomaterials with access to relevant mechanistic data across several spatial and temporal scales. Indoor aquatic mesocosms (60L) that can be tailored to virtually mimic any ecosystem appear as a particularly well-suited device. Here, this concept is illustrated by a pilot study aimed at assessing the distribution of a CeO₂-based nanomaterial within our system at low concentration (1.5 mg/L). Physico-chemical as well as microbiological parameters took two weeks to equilibrate. These parameters were found to be reproducible across the 9-mesocosm setup over a 45-day period of time. Recovery mass balances of 115 ± 18% and 60 ± 30% of the Ce were obtained for the pulse dosing and the chronic dosing, respectively. This demonstrated the relevance of our experimental approach that allows for adequately monitoring the fate and impact of a given nanomaterial.

Engineered nanomaterials (ENMs) are used to enhance the properties of many manufactured products and technologies. Increased use of ENMs will inevitably lead to their release into the environment. An important route of exposure is through the waste stream, where ENMs will enter wastewater treatment plants (WWTPs), undergo transformations, and be discharged with treated effluent or biosolids. To better understand the fate of a common ENM in WWTPs, experiments with laboratory-scale activated sludge reactors and pristine and citrate-functionalized CeO2 nanoparticles (NPs) were conducted. Greater than 90% of the CeO2 introduced was observed to associate with biosolids. This association was accompanied by reduction of the Ce(IV) NPs to Ce(III). After 5 weeks in the reactor, 44 ± 4% reduction was observed for the pristine NPs and 31 ± 3% for the citrate-functionalized NPs, illustrating surface functionality dependence. Thermodynamic arguments suggest that the likely Ce(III) phase generated would be Ce2S3. This study indicates that the majority of CeO2 NPs (>90% by mass) entering WWTPs will be associated with the solid phase, and a significant portion will be present as Ce(III). At maximum, 10% of the CeO2 will remain in the effluent and be discharged as a Ce(IV) phase, governed by cerianite (CeO2).

A multi-scale methodology was used to characterize the long-term behavior and chemical stability of a CeO2-based nanocomposite used as UV filter in wood stains. ATR-FTIR and (13)C NMR demonstrated that the citrate coated chelates with Ce(IV) through its central carboxyl- and its α-hydroxyl- groups at the surface of the unaged nanocomposite. After 42 days under artificial daylight, the citrate completely disappeared and small amount of degradation products remained attached to the surface even after 112 days. Moreover, the release/desorption of the citrate layer led to a surface reorganization of the nano-sized CeO2 core observed by XANES (Ce L3-edge). Such a surface and structural transformation of the commercialized nanocomposite could have implications in term of fate, transport, and potential impacts towards the environment., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The CeO₂ NPs are increasingly used in industry but the environmental release of these NPs and their subsequent behavior and biological effects are currently unclear. This study evaluates for the first time the effects of CeO₂ NPs on the survival and the swimming performance of two cladoceran species, Daphnia similis and Daphnia pulex after 1, 10 and 100 mg.L⁻¹ CeO₂ exposures for 48 h. Acute toxicity bioassays were performed to determine EC₅₀ of exposed daphnids. Video-recorded swimming behavior of both daphnids was used to measure swimming speeds after various exposures to aggregated CeO₂ NPs. The acute ecotoxicity showed that D. similis is 350 times more sensitive to CeO₂ NPs than D. pulex, showing 48-h EC₅₀ of 0.26 mg.L⁻¹ and 91.79 mg.L⁻¹, respectively. Both species interacted with CeO₂ NPs (adsorption), but much more strongly in the case of D. similis. Swimming velocities (SV) were differently and significantly affected by CeO₂ NPs for both species. A 48-h exposure to 1 mg.L⁻¹ induced a decrease of 30% and 40% of the SV in D. pulex and D. similis, respectively. However at higher concentrations, the SV of D. similis was more impacted (60% off for 10 mg.L⁻¹ and 100 mg.L⁻¹) than the one of D. pulex. These interspecific toxic effects of CeO₂ NPs are explained by morphological variations such as the presence of reliefs on the cuticle and a longer distal spine in D. similis acting as traps for the CeO₂ aggregates. In addition, D. similis has a mean SV double that of D. pulex and thus initially collides with twice more NPs aggregates. The ecotoxicological consequences on the behavior and physiology of a CeO₂ NPs exposure in daphnids are discussed.

As all arthropods, microcrustaceans shed their chitinous exoskeleton (cuticule, peritrophic membrane) to develop and grow. While the molting is the most crucial stage in their life cycle, it remains poorly investigated in term of pollutant biodistribution within the organisms. In this paper, we used optical, electronic, and X ray-based microscopies to study the uptake and release of CeO2 nanoparticles by/from Daphnia pulex over a molting stage. We measured that D. pulex molts every 59 ± 21 h (confidence interval) with growth rates about 1.1 or 1.8 μm per stage as a function of the pieces measured. Ingestion via food chain was the main route of CeO2 nanoparticles uptake by D. pulex. The presence of algae during the exposure to nanoparticles (sub-lethal doses) enhanced by a factor of 3 the dry weight concentration of Ce on the whole D. pulex. Nanoparticles were localized in the gut content, in direct contact with the peritrophic membrane, and on the cuticle. Interestingly, the depuration (24 h with Chlorella pseudomonas) was not efficient to remove the nanoparticles from the organisms. From 40% to 100% (depending on the feeding regime during exposure) of the CeO2 taken up by D. pulex is not release after the depuration process. However, we demonstrated for the first time that the shedding of the chitinous exoskeleton was the crucial mechanism governing the released of CeO2 nanoparticles regardless of the feeding regime during exposure., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Nanoparticles (NPs) entering a biological fluid undergo surface modification due to dynamic, physicochemical interactions with biological components, especially proteins. In this work we used complementary bio-physico-chemical approaches to characterize the effects of interactions between CeO(2) NPs, immunoglobulins (IgGs) and bovine serum albumin (BSA) of a similar size on protein structural evolution as well as formation of (hetero-) aggregates. Using circular dichroism we showed that IgGs and BSA underwent significant structural changes after interaction with NPs. The NPs and protein-NPs were observed after size exclusion chromatography, highlighting the fact that few aggregates were stable enough to pass this mild separation step. X-ray absorption spectroscopy suggested that the surface chemistry of NPs was not affected by these proteins, also implying weak interactions. Competitive experiments revealed that, while the serum was more concentrated for BSA, IgG-NP aggregates were more stable. Altogether, our results indicate that, under our experimental conditions, the formation of a "protein corona" is an unstable and reversible mechanism. This indicates that, when NPs and proteins are similar in size, the adsorption concept (i.e. protein corona concept) cannot be applied to model the NP-protein interaction, and a heteroaggregation model is more appropriate.

Physical-chemical parameters such as purity, structure, chemistry, length, and aspect ratio of nanoparticles (NPs) are linked to their toxicity. Here, synthetic imogolite-like nanotubes with a set chemical composition but various sizes and shapes were used as models to investigate the influence of these physical parameters on the cyto- and genotoxicity and cellular uptake of NPs. The NPs were characterized using X-ray diffraction (XRD), small angle X-ray scattering (SAXS), and atomic force microscopy (AFM). Imogolite precursors (PR, ca. 5 nm curved platelets), as well as short tubes (ST, ca. 6 nm) and long tubes (LT, ca. 50 nm), remained stable in the cell culture medium. Internalization into human fibroblasts was observed only for the small particles PR and ST. None of the tested particles induced a significant cytotoxicity up to a concentration of 10(-1) mg·mL(-1). However, small sized NPs (PR and ST) were found to be genotoxic at very low concentration 10(-6) mg·mL(-1), while LT particles exhibited a weak genotoxicity. Our results indicate that small size NPs (PR, ST) were able to induce primary lesions of DNA at very low concentrations and that this DNA damage was exclusively induced by oxidative stress. The higher aspect ratio LT particles exhibited a weaker genotoxicity, where oxidative stress is a minor factor, and the likely involvement of other mechanisms. Moreover, a relationship among cell uptake, particle aspect ratio, and DNA damage of NPs was observed.

This study investigates the issue of nanoparticles/pollutants cocontamination. By combining viability assays, physicochemical and structural analysis (to probe the As speciation and valence), we assessed how γFe(2)O(3) nanoparticles can affect the cytotoxicity, the intra- and extracellular speciation of As(III). Human dermal fibroblasts were contaminated with γFe(2)O(3) nanoparticles and As(III) considering two scenarios: (i) a simultaneous coinjection of the nanoparticles and As, and (ii) an injection of the nanoparticles after 24 h of As adsorption in water. In both scenarios, we did not notice significant changes on the nanoparticles surface charge (zeta potential ∼ -10 mV) nor hydrodynamic diameters (∼950 nm) after 24 h. We demonstrated that the coinjection of γFe(2)O(3) nanoparticles and As in the cellular media strongly affects the complexation of the intracellular As with thiol groups. This significantly increases at low doses the cytotoxicity of the As nonadsorbed at the surface of the nanoparticles. However, once As is adsorbed at the surface the desorption is very weak in the culture medium. This fraction of As strongly adsorbed at the surface is significantly less cytotoxic than As itself. On the basis of our data and the thermodynamics, we demonstrated that any disturbance of the biotransformation mechanisms by the nanoparticles (i.e., surface complexation of thiol groups with the iron atoms) is likely to be responsible for the increase of the As adverse effects at low doses.

The synthesis protocol for Ge-imogolite (aluminogermanate nanotubes) consists of 3 main steps: base hydrolysis of a solution of aluminum and germanium monomers, stabilization of the suspension and heating at 95 °C. The successful synthesis of these nanotubes was found to be sensitive to the hydrolysis step. The impact of the hydrolysis ratio (from n(OH)/n(Al) = 0.5 to 3) on the final product structure was examined using a combination of characterization tools. Thus, key hydrolysis ratios were identified: n(OH)/n(Al) = 1.5 for the formation of nanotubes with structural defects, n(OH)/n(Al) = 2 for the synthesis of a well crystallized Ge imogolite and n(OH)/n(Al) > 2.5 where nanotube formation is hindered. The capability of controlling the degree of the nanotube's crystallinity opens up interesting opportunities in regard to new potential applications.

Nanoparticles resistant to salt-induced aggregation are continually being developed for biomedical and industrial applications. Because of their colloidal stability these functionalized nanoparticles are anticipated to be persistent aquatic contaminants. Here, we show that Corbicula fluminea, a globally distributed clam that is a known sentinel of aquatic ecosystem contamination, can uptake and biodeposit bovine serum albumin (BSA) stabilized gold nanoparticles. Nanoparticle clearance rates from suspension were dictated by diameter and concentration, with the largest particles cleared most quickly on a mass basis. Particle capture facilitates size-selective 'biopurification' of particle suspensions with nanoscale resolution. Nanoparticles were retained either within the clam digestive tract or excreted in feces. Our results suggest that biotransformation and biodeposition will play a significant role in the fate and transport of persistent nanoparticles in aquatic systems.

This work investigates the physical-chemical evolution during artificial aging in water of four commercialized sunscreens containing TiO₂-based nanocomposites. Sunscreens were analyzed in terms of mineralogy and TiO₂ concentration. The residues formed after aging were characterized in size, shape, chemistry and surface properties. The results showed that a significant fraction of nano-TiO₂ residues was released from all sunscreens, despite their heterogeneous behaviors. A stable dispersion of submicronic aggregates of nanoparticles was generated, representing up to 38 w/w% of the amount of sunscreen, and containing up to 30% of the total nano-TiO₂ initially present in the creams. The stability of the dispersion was tested as a function of salt concentration, revealing that in seawater conditions, a major part of these nano-TiO₂ residues will aggregate and sediment. These results were put in perspective with consumption and life cycle of sunscreens to estimate the amount of nano-TiO₂ potentially released into AQUATIC environment., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Aging in water of a TiO(2)-based nanocomposite used in sunscreen cosmetics has been studied as a function of light and time. It consisted initially in a TiO(2) core, coated with Al(OH)(3) and polydimethylsiloxane (PDMS) layers. Size measurement, coating alteration, and surface charge were followed by laser diffraction, TEM/EDS, ICP-AES and electrophoretic mobility measurement. The nanocomposite rapidly underwent progressive dispersion in the aqueous phase, enabled by the dissolution of the PDMS layer. A stable suspension of colloidal byproducts from 50 to 700nm in size was formed. Their positively charged Al(OH)(3) surface was evidenced with an isoelectric point around 7-8, controlling the dispersion stability. The critical coagulation concentrations measured with NaCl and CaCl(2) was 2 × 10(-2) and 8 × 10(-3)M respectively. The presence of natural organic matter affected the colloidal stability according to the NOM/byproduct ratio. A 2 wt% ratio favored bridging flocculation, whereas a 20 wt% ratio induced sterical stabilization., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

It is now well-known that copper (Cu) can accumulate on the surface of soils upon which pig slurry has been applied. This is due to the high quantity of Cu in pig slurry resulting from its use as a growth promoter in animal feeds. The mobility and bioavailability of Cu from pig slurry spreading can be better predicted by determining the speciation of this element in addition to its total concentration. The aim of this study was to present a multitechnique approach to investigate Cu speciation in pig slurry. First, size fractionation and chemical characterization of each size fraction were performed to complement results obtained in raw samples. Micro X-ray fluorescence spectroscopy (μXRF) highlighted the colocalization of Cu and sulfur (S). Finally, X-ray absorption near-edge structure spectroscopy (XANES) showed that Cu speciation in raw pig slurry and size fractions could be described by Cu(2)S and that its oxidation state is Cu(I). In addition, geochemical calculation demonstrated that chalcocite (Cu(2)S) was the major Cu species present under pig slurry lagoon physical-chemical conditions. This Cu speciation in pig slurry may be the main reason for the observed Cu accumulation at the soil surface.

Among all environmental contaminants, those emerging from nanotechnologies constitute one of the most critical challenges for the coming years. The new properties of nanoparticles are at the heart of current scientific advances and the growing interest in harnessing them brings awareness of potential impacts that we cannot ignore. To date, scientists and industrialists have focused on the manufacture of nanomaterials more than on the assessment of the risks for humans and ecosystems. Few databases exist regarding the amounts released within ecosystems and no specific procedure of recycling has yet been established. However, nanoparticles cannot be considered as molecular pollutants or larger particles, and careful consideration is needed to establish a legal system that is specific. Their novel properties, surface energy and reactivity make it impossible to simply transfer our physicochemical, thermodynamic and toxicological knowledge from the micronscale to the nanoscale. This article highlights, nonexhaustively, the strong relationship existing between the unique properties of metallic and metal oxide nanoparticles and their biological effects on aquatic organisms.

Nanomaterials and the technologies they enable are often presented as important innovations that will play a critical role in solving problems that range from energy, water and food supply to improved medical treatments. Ironically, many of the more 'media-genic' nanomaterial-enabled products making their way to consumers address considerably more humble objectives, such as making socks cleaner or reducing wrinkles. This very broad range of nanomaterial applications suggests an equally broad range of scenarios for nanomaterial use, incorporation into products and disposal, which characterizes the lifecycle of these novel materials. Nanomaterials introduced to environmental and physiological systems will most likely undergo significant transformations, complicating any effort to related underlying nanoparticle with observed effects. This article discusses several dimensions of nanoparticle reactivity and the potential for environmental transformation of the nanoparticle properties, in particular focusing on metallic nanoparticles.

Theory is developed that relates the reactivity of nanoparticles to the structure of aggregates they may form in suspensions. This theory is applied to consider the case of reactive oxygen species (ROS) generation by photosensitization of C(60) fullerenes. Variations in aggregate structure and size appear to account for an apparent paradox in ROS generation as calculated using values for the photochemical kinetics of fullerene (C(60)) and its hydroxylated derivative, fullerol (C(60)(OH)(22-24)) and assuming that structure varies between compact and fractal objects. A region of aggregation-suppressed ROS production is identified where interactions between the particles in compact aggregates dominate the singlet oxygen production. Intrinsic kinetic properties dominate when aggregates are small and/or are characterized by low fractal dimensions. Pseudoglobal sensitivity analysis of model input variables verifies that fractal dimension, and by extension aggregation state, is the most sensitive model parameter when kinetics are well-known. This theoretical framework qualitatively predicts ROS production by fullerol suspensions 2 orders of magnitude higher compared with aggregates of largely undifferentiated C(60) despite nearly an order of magnitude higher quantum yield for the undifferentiated C(60) based on measurements for single molecules. Similar to C(60), other primary nanoparticles will exist as aggregates in many environmental and laboratory suspensions. This work provides a theoretical basis for understanding how the structure of nanoparticle aggregates may affect their reactivity.

The possibility of simultaneous particle aggregation and deposition in a porous medium was examined for the case of TiO(2) nanoparticles (NPs). While potential for particle aggregation is typically assumed to be negligible in porous media due to favored interactions with porous media surfaces (collectors), we show that nanoscale particle dimensions may favor aggregation kinetics, thus altering the transport and retention of these materials in saturated porous media. When surface chemistry favors nanoparticle-nanoparticle attachment (alpha(pp)) over nanoparticle-collector attachment (alpha(pc)), the rate of particle aggregation within pores may be comparable to that of deposition at ratios of collector to nanoparticle surface areas as high as 40. Aggregation of NPs in the porous media enhances NP deposition, however aggregates that are not removed will sample a smaller portion of the available pore network within the column due to size exclusion.

A number of commercialized nanomaterials incorporate TiO(2) nanoparticles. Studying their structural stability in media mimicking the environment or the conditions of use is crucial in understanding their potential eco-toxicological effects. We focused here on a hydrophobic TiO(2) nanoparticle-based formulation used in cosmetics: T-Lite SF. It is composed of a TiO(2) core, coated with two successive protective layers of Al(OH)(3), and polydimethylsiloxane. Soon after contact with water (pH = 5, low ionic strength), the T-Lite SF becomes hydrophilic and form aggregates. During this aging, 90%wt of the total Si of the organic layer is desorbed, and the PDMS remaining at the surface is oxidized. The Al(OH)(3) layer is also affected but remains sorbed at the surface. This remaining Al-based layer still protects from the production of superoxide ions from the photoactive/phototoxic TiO(2) core in our experimental conditions.

Zinc occurs in high quantity in pig slurry since it is used as an essential micronutrient at high concentrations in animal feeds despite the low Zn assimilation by pigs. Zinc accumulation was measured in soil surface layers that had been amended with pig slurry, while also determining the phytotoxicity as well as the extent of groundwater quality degradation. To accurately predict the mobility and bioavailability of Zn derived from pig slurry spreading, the speciation of this element has to be assessed since the total concentration is not sufficient. This study involved a combination of techniques to investigate Zn speciation in pig slurry. Size fractionation was first performed to account for the complexity of pig slurry, and 75% of total Zn was detected in the 0.45- to 20-mum particle-size range. Then X-ray diffraction, scanning electron microscopy, coupled with energy dispersive spectrometer, and extended X-ray absorption fine structure analyses were combined to assess Zn speciation. The findings highlighted the presence of 49% Zn bound to organic matter, 37% amorphous Zn hydroxides [Zn(OH)(2)], and 14% sphalerite (ZnS).

To date, the successful low-temperature synthesis of the aluminosilicate imogolite nanotubes always involved initial concentrations of the reagents in the millimolar range, higher concentrations being reported to lead to the formation of the less well characterized allophane phase. The present work shows that reaction kinetics and not initial concentration control the formation of the nanotubes: substantial amounts of well formed imogolite were obtained from a decimolar initial concentration, i.e. 100 times higher than the "standard" protocol. The allophane-like spheroids expected from the high reagent concentration were not observed in this work, and proto-imogolite was obtained instead.

The nature of fullerene-water interactions and the role that they play in the fate of C60 in aqueous systems is poorly understood. This work provides spectroscopic evidence for the surface hydroxylation of the initially hydrophobic C60 molecule when immersed in water. This mechanism appears to be the basis for stabilizing the hydrophilic nC60 aggregates in suspension. It is remarkable that such a chemical transformation and dispersion are achieved under mild conditions that are readily produced in an aquatic environment. This acquired affinity for water is likely to play a subsequent role in the reactivity, mobility, and bioavailability of fullerenes in aqueous media.

The regulation of engineered nanoparticles requires a widely agreed definition of such particles. Nanoparticles are routinely defined as particles with sizes between about 1 and 100 nm that show properties that are not found in bulk samples of the same material. Here we argue that evidence for novel size-dependent properties alone, rather than particle size, should be the primary criterion in any definition of nanoparticles when making decisions about their regulation for environmental, health and safety reasons. We review the size-dependent properties of a variety of inorganic nanoparticles and find that particles larger than about 30 nm do not in general show properties that would require regulatory scrutiny beyond that required for their bulk counterparts.

The level of production of nanoparticles will inevitably lead to their appearance in air, water, soils, and organisms. A theoretical framework that relates properties of nanoparticles to their biological effects is needed to identify possible risks to human health and the environment. This paper considers the properties of dispersed metallic nanoparticles and highlights the relationship between the chemical stability of these nanoparticles and their in vitro toxicity. Analysis of published data suggests that chemically stable metallic nanoparticles have no significant cellular toxicity, whereas nanoparticles able to be oxidized, reduced or dissolved are cytotoxic and even genotoxic for cellular organisms.

Iron-based nanoparticles have been proposed for an increasing number of biomedical or environmental applications although in vitro toxicity has been observed. The aim of this study was to understand the relationship between the redox state of iron-based nanoparticles and their cytotoxicity toward a Gram-negative bacterium, Escherichia coli. While chemically stable nanoparticles (gammaFe2O3) have no apparent cytotoxicity, nanoparticles containing ferrous and, particularly, zerovalent iron are cytotoxic. The cytotoxic effects appear to be associated principally with an oxidative stress as demonstrated using a mutant strain of E. coli completely devoid of superoxide dismutase activity. This stress can result from the generation of reactive oxygen species with the interplay of oxygen with reduced iron species (Fe(II) and/or Fe(0)) or from the disturbance of the electronic and/or ionic transport chains due to the strong affinity of the nanoparticles for the cell membrane.

A simple aqueous synthesis yielded about 100 times more structurally well-organized single-walled aluminogermanate nanotubes than previously reported "standard" procedures. The structure analyses using XRD, IRTF, TEM, and XAS were greatly facilitated by the high concentrations available, and they ascertained the imogolite-like structure of the nanotubes. Simplicity and yield of the synthesis protocol are likely to favor commercial applications of theses materials as well as simplified syntheses of other nanophases.

When normalized per unit of surface area, the quantity of arsenic adsorbed at the maghemite surface remains constant for particles between 300 and 20 nm. However, nanoparticles smaller than 20 nm exhibit enhanced adsorption capacity. The origin of this observed size-dependence for adsorption or "nano effect" is unclear. Arsenic was chosen as a probe of the surface structure to explore adsorption mechanisms occurring at the surface of maghemite nanoparticles (6 nm). Two factors contributing to the enhanced reactivity of nanoscale maghemites were determined. The first is related to a size-dependent structural modification of the surface of particles and the decrease of the occupancy of the tetrahedral site that leaves vacant, highly reactive adsorption sites. In particular, there is a site localized in a six-membered iron octahedral ring. This site is the only one for which an oxidation of As(III) occurs. The second factor relates to the thermodynamics of a decrease of the surface free energy. The high density of As adsorbed at the saturation of the surface can be related to crystal growth.

This paper presents a comparison between several methods dedicated to the interpretation of V K-edge X-ray absorption near-edge structure (XANES) features. V K-edge XANES spectra of several V-bearing standard compounds were measured in an effort to evaluate advantages and limits of each method. The standard compounds include natural minerals and synthetic compounds containing vanadium at various oxidation state (from +3 to +5) and in different symmetry (octahedral, tetrahedral, and square pyramidal). Correlations between normalized pre-edge peak area and its centroid position have been identified as the most reliable method for determining quantitative and accurate redox and symmetry information for vanadium. This methodology has been previously developed for the Fe K edge. It is also well adapted for the V K edge and is less influenced by the standard choice than other methods. This methodology was applied on an "environmental sample," i.e., a well-crystallized leached steel slag containing vanadium as traces. Micro-XANES measurements allowed elucidating the microdistribution of vanadium speciation in leached steel slag. The vanadium exhibits an important evolution from the unaltered to the altered phases. Its oxidation state increases from +3 to +5 together with the decrease of its symmetry (from octahedral to tetrahedral).

Basic oxygen furnace (BOF) steel slag is a residue from the basic oxygen converter in steel-making operations, and is partially reused as an aggregate for road constructions. Although BOF slag is an attractive building material, its long-term behaviour and the associated environmental impacts must be taken into account. Indeed BOF slag is mainly composed of calcium, silicon and iron but also contains trace amounts of potential toxic elements, specifically chromium and vanadium, which can be released. The present research focuses (i) on the release of Cr and V during leaching and (ii) on their speciation within the bearing phase. Indeed the mobility and toxicity of heavy metals strongly depend on their speciation. Leaching tests show that only low amounts of Cr, present at relatively high concentration in steel slag, are released while the release of V is significantly high. X-ray absorption near-edge structure (XANES) spectroscopy indicates that Cr is present in the less mobile and less toxic trivalent form and that its speciation does not evolve during leaching. On the contrary, V which is predominantly present in the 4+ oxidation state seems to become oxidized to the pentavalent form (the most toxic form) during leaching.

Studying speciation of heavy metals instead of their total concentration in a complex matrix such as soil is a scientific challenge that requires a combination of different analytical techniques. We compared the speciation of Cr within an andosol (island of Réunion) by using X-ray absorption spectroscopy (XAS) and sequential extraction. Contradictory results were obtained since the fraction of Cr bound to organic matter was detected only with the latter method. As bulk soil is rather complex, its fractionation by a densimetric method decreased its heterogeneity. We found that 60% Cr was within chromite-type primary minerals. Weathering of these phases led to Fe and Cr release, eventually resulting in either coprecipitation as mixed FeCr oxyhydroxide (16% total Cr) or precipitation of a Cr oxyhydroxide (5% total Cr). Our results also revealed that 13% Cr was bound to organic matter. The organic matter was complexed with mineral phases to form organomineral complexes with a density ranging from 1.9 to 2.6. The use of an original density fractionation-based sample preparation allowed identification of the role of organic matter in chromium speciation within an andosol and to overcome the difficulties of EXAFS to detect light elements in the vicinity of heavy elements.