Naturally occurring nanoparticles (NP) enhance the transport of hydrophobic organic contaminants (HOCs) in porous media. In addition, the debate on the environmental impact of engineered nanoparticles (ENP) has become increasingly important. HOC bind strongly to carbonaceous ENP. Thus, carbonaceous ENP may also act as carriers for contaminant transport and might be important when compared to existing transport processes. ENP bound transport is strongly linked to the sorption behavior, and other carbonaceous ENP-specific properties. In our analysis the HOC-ENP sorption mechanism, as well as ENP size and ENP residence time, was of major importance. Our results show that depending on ENP size, sorption kinetics and residence time in the system, the ENP bound transport can be estimated either as (1) negligible, (2) enhancing contaminant transport, or (3) should be assessed by reactive transport modeling. One major challenge to this field is the current lack of data for HOC-ENP desorption kinetics. Using nanoparticle size, residence time and sorption behavior, it was possible to estimate the relevance of engineered nanoparticle facilitated organic contaminant transport.

In this study, the influence of the co-existence of TiO2 nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO2 nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO2 nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO2 nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO2 nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO2 nanoparticles than in the absence of TiO2 nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO2 nanoparticles. The co-existence of TiO2 nanoparticles could change the speciation of arsenite by adsorption and photo-oxidation, and enhance its bioaccumulation to carp.

Particles from channelled emissions of a battery recycling facility were size-segregated and investigated to correlate their speciation and morphology with their transfer towards lettuce. Microculture experiments carried out with various calcareous soils spiked with micronic and sub-micronic particles (1650 ± 20 mg Pb kg-1) highlighted a greater transfer in soils mixed with the finest particles. According to XRD and Raman spectroscopy results, the two fractions presented differences in the amount of minor lead compounds like carbonates, but their speciation was quite similar, in decreasing order of abundance: PbS, PbSO4, PbSO4·PbO, α-PbO and Pb0. Morphology investigations revealed that PM2.5 (i.e. Particulate Matter 2.5 composed of particles suspended in air with aerodynamic diameters of 2.5 μm or less) contained many Pb nanoballs and nanocrystals which could influence lead availability. The soil-plant transfer of lead was mainly influenced by size and was very well estimated by 0.01 M CaCl2 extraction. The soil-lettuce lead transfer from atmospheric industrial sub-micronic and micronic particles depends on particle size.

Since the discovery of fullerenes in 1985, these carbon nanospheres have attracted attention regarding their physico/chemical properties. Despite little knowledge about their impact on the environment and human health, the production of fullerenes has already reached an industrial scale. However, the toxicity of C60 is still controversially discussed. The aim of this study was to clarify the biological effects of tetrahydrofuran (THF) suspended C60 fullerene in comparison to water stirred C60 fullerene suspensions. Beyond that, we analyzed the effects on the Crustacea Daphnia magna an indicator for ecotoxicological effects and the human lung epithelial cell line A549 as a simplified model for the respiratory tract. We could demonstrate that water-soluble side products which were formed in THF nC60 suspension were responsible for the observed acute toxic effects, whereas fullerenes themselves had no negative effect regardless of the preparative route on either A549 cell in vitro or D. magna in vivo. THF suspended nC60 did not show any toxic effect to Daphnia and lung cells when side products were eliminated by additional washing steps.

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. The ability of metallic nanoparticles to be oxidized, reduced or dissolved in biological media can be used to predict their toxicity in vitro.

Soil humic substances (HS) stabilize carbon nanotube (CNT) dispersions, a mechanism we hypothesized arose from the surfactive nature of HS. Experiments dispersing multi-walled CNT in solutions of dissolved Aldrich humic acid (HA) or water-extractable Catlin soil HS demonstrated enhanced stability at 150 and 300 mg L-1 added Aldrich HA and Catlin HS, respectively, corresponding with decreased CNT mean particle diameter (MPD) and polydispersivity (PD) of 250 nm and 0.3 for Aldrich HA and 450 nm and 0.35 for Catlin HS. Analogous trends in MPD and PD were observed with addition of the surfactants Brij 35, Triton X-405, and SDS, corresponding to surfactant sorption maximum. NEXAFS characterization showed that Aldrich HA contained highly surfactive domains while Catlin soil possessed a mostly carbohydrate-based structure. This work demonstrates that the chemical structure of humic materials in natural waters is directly linked to their surfactive ability to disperse CNT released into the environment. Suspensions of multi-walled carbon nanotubes are stabilized by relatively low concentrations of dissolved humic substances in solution through surfactive mechanisms.

Canopy leaf area index (LAI) is an important structural parameter of the vegetation controlling pollutant uptake by terrestrial ecosystems. This paper presents a computationally efficient algorithm for retrieval of vegetation LAI and canopy clumping factor from satellite data using observed Simple Ratios (SR) of near-infrared to red reflectance. The method employs numerical inversion of a physics-based analytical canopy radiative transfer model that simulates the bi-directional reflectance distribution function (BRDF). The algorithm is independent of ecosystem type. The method is applied to 1-km resolution AVHRR satellite images to retrieve a geo-referenced data set of monthly LAI values for the conterminous USA. Satellite-based LAI estimates are compared against independent ground LAI measurements over a range of ecosystem types. Verification results suggest that the new algorithm represents a viable approach to LAI retrieval at continental scale, and can facilitate spatially explicit studies of regional pollutant deposition and trace gas exchange. The paper presents a physics-based algorithm for retrieval of vegetation LAI and canopy-clumping factor from satellite data to assist research of pollutant deposition and trace-gas exchange. The method is employed to derive a monthly LAI dataset for the conterminous USA and verified at a continental scale.

An integrative passive sampler consisting of a C18 Empore® disk receiving phase saturated with n-octanol and fitted with low-density polyethylene diffusion membrane was calibrated for the measurement of time-weighted average concentrations of hydrophobic micropollutants, including polyaromatic hydrocarbons and organochlorine pesticides, in water. The effect of temperature and water turbulence on kinetic and thermodynamic parameters characterising the exchange of analytes between the sampler and water was studied in a flow-through system under controlled conditions. It was found that the absorption of test analytes from water to the sampler is related to their desorption to water. This allows for the in situ calibration of the uptake of pollutants using offload kinetics of performance reference compounds. The sampling kinetics are dependent on temperature, and for most of the tested analytes also on the flow velocity. Sampler–water partition coefficients did not significantly change with temperature.

The stability of TiO2 nanoparticles in soil suspensions and their transport behavior through saturated homogeneous soil columns were studied. The results showed that TiO2 could remain suspended in soil suspensions even after settling for 10 days. The suspended TiO2 contents in soil suspensions after 24 h were positively correlated with the dissolved organic carbon and clay content of the soils, but were negatively correlated with ionic strength, pH and zeta potential. In soils containing soil particles of relatively large diameters and lower solution ionic strengths, a significant portion of the TiO2 (18.8-83.0%) readily passed through the soils columns, while TiO2 was significantly retained by soils with higher clay contents and salinity. TiO2 aggregate sizes in the column outflow significantly increased after passing through the soil columns. The estimated transport distances of TiO2 in some soils ranged from 41.3 to 370 cm, indicating potential environmental risk of TiO2 nanoparticles to deep soil layers. TiO2 nanoparticles could efficiently suspend in soil suspensions and potentially transport to deeper soil layers.

In previous work we have shown that the toxicity of nanomaterials to Daphnia spp. differs with the type of nanoparticle either due to the core of the particle or to the way in which a particle suspension is prepared. The purpose of this study was to investigate the toxicity and antioxidant response of Daphnia pulex in relation to a change in surface functionalization of nanomaterials with the same core material, nC60. Despite the lack of acute toxicity for various nC60 suspensions up to 100 ppm concentration, there was a significant production of the toxicity biomarkers glutathione-S-transferase and catalase, at lower concentrations indicating changes in reactive oxygen species. Nanoparticle functionalization significantly affected this response. Oxidative stress markers appear to be a good predictor of potential future toxicity of nanomaterials. Functionalization alters both toxicity and oxidative stress in whole organism assays. Antioxidant response of Daphnia to nanoparticles with differing surface functionalization and core structure.