Bernard Angeletti

Transfer, Transformation, and Impacts of Ceria Nanomaterials in Aquatic Mesocosms Simulating a Pond Ecosystem

Mesocosms are an invaluable tool for addressing the complex issue of exposure during nanoecotoxicological testing. This experimental strategy was used to take into account parameters as the interactions between the NPs and naturally occurring (in)organic colloids (heteroaggregation), or the flux between compartments of the ecosystems (aqueous phase, sediments, biota) when assessing the impacts of CeO2 NPs in aquatic ecosystems. In this study, we determine the transfer, redox transformation, and impacts of 1 mg L(-1) of bare and citrate coated CeO2-NPs toward an ecologically relevant organism (snail, Planorbarius corneus) exposed 4 weeks in a complex experimental system mimicking a pond ecosystem. Over time, CeO2-NPs tend to homo- and heteroaggregate and to accumulate on the surficial sediment. The kinetic of settling down was coating-dependent and related to the coating degradation. After 4 weeks, Ce was observed in the digestive gland of benthic organisms and associated with 65-80% of Ce(IV) reduction into Ce(III) for both bare and coated CeO2 NPs. A transitory oxidative stress was observed for bare CeO2-NPs. Coated-NPs exposed snails did not undergo any lipid peroxidation nor change in the antioxidant contents, while Ce content and reduction in the digestive gland were identical to bare CeO2-NPs. We hypothesized that the presence of citrate coating enhanced the defense capacity of the cells toward the oxidative stress induced by the CeO2 core.

Pulmonary exposure to metallic nanomaterials during pregnancy irreversibly impairs lung development of the offspring

Abstract Due to the growing commercial applications of manufactured nanoparticles (NPs), toxicological studies on NPs, especially during the critical window of development, are of major importance. The aim of the study was to assess the impact of respiratory exposure to metallic and metal oxide NPs during pregnancy on lung development of the offspring and to determine the key parameters involved in lung alterations. Pregnant mice were exposed to weekly doses of 100 μg (total dose 300 μg) of titanium dioxide (TiO2), cerium oxide (CeO2), silver (Ag) NPs or saline solution by nonsurgical intratracheal instillation. The offspring lungs were analyzed at different stages of lung development: fetal stage (gestational day 17.5), pulmonary alveolarization (post-delivery day 14.5) and lung maturity (post-delivery day 49.5). Regardless of the type of NP, maternal exposure during gestation induced long-lasting impairment of lung development of the offspring. This effect was accompanied by: i) decreased placental efficiency together with the presence of NPs in placenta, ii) no increase of inflammatory mediators present in amniotic fluid, placenta or offspring lungs and iii) decreased pulmonary expression of vascular endothelial growth factor-α (VEGF-α) and matrix metalloproteinase 9 (MMP-9) at the fetal stage, and fibroblast growth factor-18 (FGF-18) at the alveolarization stage. Respiratory exposure to metallic NPs during pregnancy induces stereotyped impairment of lung development with a lasting effect in adult mice, independently of the chemical nature of the NP.

Organic carbon, and major and trace element dynamic and fate in a large river subjected to poorly-regulated urban and industrial pressures (Sebou River, Morocco)

An annual-basis study of the impacts of the anthropogenic inputs from Fez urban area on the water geochemistry of the Sebou and Fez Rivers was conducted mostly focusing on base flow conditions, in addition to the sampling of industrial wastewater characteristic of the various pressures in the studied environment. The measured trace metals dissolved/particulate partitioning was compared to the ones predicted using the WHAM-VII chemical speciation code. The Sebou River, upstream from Fez city, showed a weakly polluted status. Contrarily, high levels of major ions, organic carbon and trace metals were encountered in the Fez River and the Sebou River downstream the Fez inputs, due to the discharge of urban and industrial untreated and hugely polluted wastewaters. Trace metals were especially enriched in particles with levels even exceeding those recorded in surface sediments. The first group of elements (Al, Fe, Mn, Ti, U and V) showed strong inter-relationships, impoverishment in Fez particles/sediments and stable partition coefficient (Kd), linked to their lithogenic origin from Sebou watershed erosion. Conversely, most of the studied trace metals/metalloids, originated from anthropogenic sources, underwent significant changes of Kd and behaved non-conservatively in the Sebou/Fez water mixing. Dissolved/particulate partitioning was correctly assessed by WHAM-VII modeling for Cu, Pb and Zn, depicting significant differences in chemical speciation in the Fez River when compared to that in the Sebou River. The results of this study demonstrated that a lack of compliance in environmental regulations certainly explained this poor status.

Biological Fate of Fe3O4 Core-Shell Mesoporous Silica Nanoparticles Depending on Particle Surface Chemistry

The biological fate of nanoparticles (NPs) for biomedical applications is highly dependent of their size and charge, their aggregation state and their surface chemistry. The chemical composition of the NPs surface influences their stability in biological fluids, their interaction with proteins, and their attraction to the cell membranes. In this work, core-shell magnetic mesoporous silica nanoparticles (Fe3O4@MSN), that are considered as potential theranostic candidates, are coated with polyethylene glycol (PEG) or 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayer. Their biological fate is studied in comparison to the native NPs. The physicochemical properties of these three types of NPs and their suspension behavior in different media are investigated. The attraction to a membrane model is also evaluated using a supported lipid bilayer. The surface composition of NPs strongly influences their dispersion in biological fluids mimics, protein binding and their interaction with cell membrane. While none of these types of NPs is found to be toxic on mice four days after intravenous injection of a dose of 40 mg kg−1 of NPs, their surface coating nature influences the in vivo biodistribution. Importantly, NP coated with DMPC exhibit a strong accumulation in liver and a very low accumulation in lung in comparison with nude or PEG ones.

Using DET and DGT probes (ferrihydrite and titanium dioxide) to investigate arsenic concentrations in soil porewater of an arsenic-contaminated paddy field in Bangladesh

Arsenic concentration in the pore water of paddy fields (Csoln) irrigated with arsenic-rich groundwater is a key parameter in arsenic uptake by rice. Pore water extracts from cores and in situ deployment of DET and DGT probes were used to measure the arsenic concentration in the pore water. Ferrihydrite (Fe) and titanium dioxide (Ti) were used as DGT binding agents. Six sampling events during different growing stages of the rice, inducing different biogeochemical conditions, were performed in one rice field. A time series of DGT experiments allow the determination of an in situ arsenic diffusion coefficient in the diffusive gel (3.34×10(-6) cm(2) s(-1)) needed to calculate the so-called CDGT(Fe) and CDGT(Ti) concentrations. Over 3 days of a given sampling event and for cores sampled at intervals smaller than 50 cm, great variability in arsenic Csoln concentrations between vertical profiles was observed, with maxima of concentrations varying from 690 to 2800 μg L(-1). Comparisons between arsenic measured Csol and CDET and calculated CDGT(Fe) and CDGT(Ti) concentrations show either, in a few cases, roughly similar vertical profiles, or in other cases, significantly different profiles. An established iron oxyhydroxide precipitation in the DET gel may explain why measured arsenic CDET concentrations occasionally exceeded Csoln. The large spread in results suggests limitations to the use of DET and type of DGT probes used here for similarly representing the spatio-temporal variations of arsenic content in soil pore water in specific environmental such as paddy soils.

Evidence that Soil Properties and Organic Coating Drive the Phytoavailability of Cerium Oxide Nanoparticles

The ISO-standardized RHIZOtest is used here for the first time to decipher how plant species, soil properties, and physical-chemical properties of the nanoparticles and their transformation regulate the phytoavailability of nanoparticles. Two plants, tomato and fescue, were exposed to two soils with contrasted properties: a sandy soil poor in organic matter and a clay soil rich in organic matter, both contaminated with 1, 15, and 50 mg·kg-1 of dissolved Ce2(SO4)3, bare and citrate-coated CeO2 nanoparticles. All the results demonstrate that two antagonistic soil properties controlled Ce uptake. The clay fraction enhanced the retention of the CeO2 nanoparticles and hence reduced Ce uptake, whereas the organic matter content enhanced Ce uptake. Moreover, in the soil poor in organic matter, the organic citrate coating significantly enhanced the phytoavailability of the cerium by forming smaller aggregates thereby facilitating the transport of nanoparticles to the roots. By getting rid of the dissimilarities between the root systems of the different plants and the normalizing the surfaces exposed to nanoparticles, the RHIZOtest demonstrated that the species of plant did not drive the phytoavailability, and provided evidence for soil-plant transfers at concentrations lower than those usually cited in the literature and closer to predicted environmental concentrations.

Environmental imprints of landscape evolution and human activities during the Holocene in a small catchment of the Calanques Massif (Cassis, southern France)

This paper is based on a multidisciplinary study using both paleoenvironmental methods (biological, sedimentological, magnetic and geochemical) and archaeological data in order to characterize landscape and hydrological network changes as well as human impact on a littoral catchment in the Western Mediterranean area. Sedimentary records obtained around a coastal alluvial plain (Cassis, Southeastern France) reveal local environmental changes and human activities since the Neolithic (ca. 6000 cal. BP). Anthropogenic impact is already noticeable in the earliest record, and we follow its evolution through time. According to biological markers, the Holocene landscape of the Calanques is dominated by a mosaic of open herbaceous formations partly generated by human activity. The prevalence of Cernuella virgata in malacofauna successions and of coprophilous fungal spores in the pollen record testifies to the spread of agro-pastoral activities. Two increases of anthropogenic impact are highlighted during the Roman (ca. 2000 cal. BP) and Modern (from ca. 1450 to today) periods. Lead isotope analyses indicate an anthropogenic release of lead, possibly originating from the Greek Cyclades (ca. 2000 cal. BP). Hydrographic and agricultural work is also enhanced during the Roman period. Magnetic parameters and lead isotopes indicate that the Modern anthropogenic impact may be associated with high temperature activities (e.g. lime kiln, fossil fuel).

Non-linear release dynamics for a CeO 2 nanomaterial embedded in a protective wood stain, due to matrix photo-degradation

The release of CeO2-bearing residues during the weathering of an acrylic stain enriched with CeO2 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.

Stealth Biocompatible Si-Based Nanoparticles for Biomedical Applications

A challenge regarding the design of nanocarriers for drug delivery is to prevent their recognition by the immune system. To improve the blood residence time and prevent their capture by organs, nanoparticles can be designed with stealth properties using polymeric coating. In this study, we focused on the influence of surface modification with polyethylene glycol and/or mannose on the stealth behavior of porous silicon nanoparticles (pSiNP, ~200 nm). In vivo biodistribution of pSiNPs formulations were evaluated in mice 5 h after intravenous injection. Results indicated that the distribution in the organs was surface functionalization-dependent. Pristine pSiNPs and PEGylated pSiNPs were distributed mainly in the liver and spleen, while mannose-functionalized pSiNPs escaped capture by the spleen, and had higher blood retention. The most efficient stealth behavior was observed with PEGylated pSiNPs anchored with mannose that were the most excreted in urine at 5 h. The biodegradation kinetics evaluated in vitro were in agreement with these in vivo observations. The biocompatibility of the pristine and functionalized pSiNPs was confirmed in vitro on human cell lines and in vivo by cytotoxic and systemic inflammation investigations, respectively. With their biocompatibility, biodegradability, and stealth properties, the pSiNPs functionalized with mannose and PEG show promising potential for biomedical applications.

Structural and physical-chemical behavior of a CeO2 nanoparticle based diesel additive during combustion and environmental release

The colloidal and chemical stability of CeO2 nanoparticles used in a diesel additive (viz. Envirox™) was studied at different stages of their lifecycle (formulation, use, end of life). After combustion at a temperature close to that of diesel engines, the size of the CeO2 crystallites increased significantly without detectable Ce(III) in the structure and remaining organic compounds at the surface. Regardless of the aging conditions (salinity, light, pH), the dissolution kinetics of the combusted particles were slowed down compared to that of the initial CeO2 nanoparticles. After 2 days at 0.1 g L−1 of salts, no more than 0.01% of the total Ce was released from the 850 °C-combusted Envirox™ versus 1.5% for the uncombusted Envirox™. Both the crystal growth during combustion and the degradation of the organic matrix will govern the aggregation and dissolution kinetics/mechanisms once the CeO2 particles are released into the environment at different stages of their lifecycle. Such a study is a prerequisite needed before any assessment of the environmental risks of CeO2 nanoparticle-based diesel additives is performed.