Search

Water flow and TiO2 nanoparticle (NP) transfer in a fractured hard-rock aquifer were studied in a tracer test experiment at a pilot site in Brittany, France. Results from the Br tracer test show that the schist aquifer can be represented by a two-layer medium comprising i) fractures with low longitudinal dispersivity in which water and solute transport is relatively fast, and ii) a network of small fissures with high longitudinal dispersivity in which transport is slower. Although a large amount of NPs was retained within the aquifer, a significant TiO2 concentration was measured in a well 15m downstream of the NP injection well, clearly confirming the potential for TiO2 NPs to be transported in groundwater. The Ti concentration profile in the downstream well was modelled using a two-layer medium approach. The delay used for the TiO2 NPs simulation compared to the Br concentration profiles in the downstream well indicate that the aggregated TiO2 NPs interacted with the rock. Unlike Br, NPs do not penetrate the entire pore network during transfer because of electrostatic interactions between NP aggregates and the rock and also to the aggregate size and the hydrodynamic conditions, especially where the porosity is very low; NPs with a weak negative charge can be attached onto the rock surface, and more particularly onto the positively charged iron oxyhydroxides coating the main pathways due to natural denitrification. Nevertheless, TiO2 NPs are mobile and transfer within fracture and fissure media. Any modification of the aquifer's chemical conditions is likely to impact the groundwater pH and, the nitrate content and the denitrification process, and thus affect NP aggregation and attachment., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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 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.

The bacterial reverse mutation test, recommended by the Organization for Economic Co-operation and Development (OECD) to determine genotoxicity of chemical compounds, has been recently used by several authors to investigate nanoparticles. Surprisingly, test results have been negative, whereas in vitro mammalian cell tests often give positive genotoxic responses. In the present study, we used the fluctuation test procedure with the Salmonella typhimurium strains TA97a, TA98, TA100 and TA102 to determine the mutagenic potential of TiO(2) nanoparticles (NP-TiO(2)) and showed that, when it is used conventionally, this test is not suitable for nanoparticle genotoxicity assessment. Indeed, the medium used during exposure prevents electrostatic interactions between bacterial cells and nanoparticles, leading to false-negative responses. We showed that a simple pre-exposure of bacteria to NP-TiO(2) in a low ionic strength solution (NaCl 10mM) at a pH below the nanoparticle isoelectric points (pH 5.5) can strongly improve the accuracy of the test. Thus, based on these improvements, we have demonstrated the genotoxicity of the engineered NP-TiO(2) tested and a NP-TiO(2) byproduct from a sunscreen nanocomposite. It was also shown that strain TA102 is more sensitive than the other strains, suggesting an oxidative stress-mediated mechanism of genotoxicity., (Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.)

Mineral sunscreen nanocomposites, based on a nano-TiO(2) core, coated with aluminium hydroxide and dimethicone films, were submitted to an artificial ageing process. The resulting Altered TiO(2) Nanocomposites (ATN) were then tested in the liquid phase on the plant model Vicia faba, which was exposed 48 h to three nominal concentrations: 5, 25 and 50 mg ATN/L. Plant growth, photosystem II maximum quantum yield, genotoxicity (micronucleus test) and phytochelatins levels showed no change compared to controls. Oxidative stress biomarkers remained unchanged in shoots while in roots, glutathione reductase activity decreased at 50 mg ATN/L and ascorbate peroxidase activity decreased for 5 and 25 mg ATN/L. Nevertheless, despite the weak response of biological endpoints, ICP-MS measurements revealed high Ti and Al concentrations in roots, and X-ray fluorescence micro-spectroscopy revealed titanium internalization in superficial root tissues. Eventual long-term effects on plants may occur., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The increasing production of nanomaterials will in turn increase the release of nanosized byproducts to the environment. The aim of this study was to evaluate the behaviour, uptake and ecotoxicity of TiO(2) byproducts in the earthworm Eisenia fetida. Worms were exposed to suspensions containing 0.1, 1 and 10 mg/L of byproducts for 24 h. Size of TiO(2) byproducts showed aggregation of particles up to 700 μm with laser diffraction. Only worms exposed at 10 mg/L showed bioaccumulation of titanium (ICP-AES), increasing expression of metallothionein and superoxide dismutase mRNA (Real-time PCR) and induction of apoptotic activity (Apostain and TUNEL). TiO(2) byproducts did not induce cytotoxicity on cœlomocytes, but a significant decrease of phagocytosis was observed starting from 0.1 mg/L. In conclusion, bioaccumulation of byproducts and their production of reactive oxygen species could be responsible for the alteration of the antioxidant system in worms., (Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.)

Titanium dioxide nanoparticles seem to have a low toxicity to terrestrial organisms, though few studies are published in this area. TiO(2) used in sunscreens are nanocomposites where TiO(2) has been coated with magnesium, silica or alumina, as well as amphiphilic organics like polydimethyl siloxane (PDMS), and these coatings are modified by ageing. We assessed the ecotoxicity and propensity for bioaccumulation of an aged TiO(2) nanocomposite used in sunscreen cosmetics, and its potential effect on the frequency of apoptosis in different earthworm tissues. The earthworm Lumbricus terrestris was exposed to the TiO(2) nanocomposite for 7 days in water or 2-8 weeks in soil with the nanocomposite mixed either into food or soil at concentrations ranging from 0 to 100 mg kg(-1). Apoptosis was then measured by immunohistochemistry and Ti localized by XRF microscopy. Results showed no mortality, but an enhanced apoptotic frequency which was higher in the cuticule, intestinal epithelium and chloragogenous tissue than in the longitudinal and circular musculature. TiO(2) nanoparticles did not seem to cross the intestinal epithelium/chloragogenous matrix barrier to enter the coelomic liquid, or the cuticule barrier to reach the muscular layers. No bioaccumulation of TiO(2) nanocomposites could thus be observed., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

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.)

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.