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.

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.

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.

An unbalanced nested sampling design was used to investigate the spatial scale of soil and herbicide interactions at the field scale. A hierarchical analysis of variance based on residual maximum likelihood (REML) was used to analyse the data and provide a first estimate of the variogram. Soil samples were taken at 108 locations at a range of separating distances in a 9 ha field to explore small and medium scale spatial variation. Soil organic matter content, pH, particle size distribution, microbial biomass and the degradation and sorption of the herbicide, isoproturon, were determined for each soil sample. A large proportion of the spatial variation in isoproturon degradation and sorption occurred at sampling intervals less than 60 m, however, the sampling design did not resolve the variation present at scales greater than this. A sampling interval of 20-25 m should ensure that the main spatial structures are identified for isoproturon degradation rate and sorption without too great a loss of information in this field.

Toxicity of nano-scaled aluminum, silicon, titanium and zinc oxides to bacteria (Bacillus subtilis, Escherichia coli and Pseudomonas fluorescens) was examined and compared to that of their respective bulk (micro-scaled) counterparts. All nanoparticles but titanium oxide showed higher toxicity (at 20 mg/L) than their bulk counterparts. Toxicity of released metal ions was differentiated from that of the oxide particles. ZnO was the most toxic among the three nanoparticles, causing 100% mortality to the three tested bacteria. Al2O3 nanoparticles had a mortality rate of 57% to B. subtilis, 36% to E. coli, and 70% to P. fuorescens. SiO2 nanoparticles killed 40% of B. subtilis, 58% of E. coli, and 70% of P. fluorescens. TEM images showed attachment of nanoparticles to the bacteria, suggesting that the toxicity was affected by bacterial attachment. Bacterial responses to nanoparticles were different from their bulk counterparts; hence nanoparticle toxicity mechanisms need to be studied thoroughly. Oxide nanoparticles show higher toxicity than their bulk counterparts.

Surface sediments (0-5 cm) from 59 stations within the Yangtze River intertidal zone (YRIZ) were sampled for metal contamination analysis in April and August 2005. The concentrations ranged (in mg kg-¹ dry weight): Al, 40,803-97,213; Fe, 20,538-49,627; Cd, 0.12-0.75; Cr, 36.9-173; Cu, 6.87-49.7; Mn, 413-1,112; Ni, 17.6-48.0; Pb, 18.3-44.1; and Zn, 47.6-154; respectively. Among the 59 sampling stations, enrichment factors (EF) indicate enrichment of Cd (52 stations), Cr (54 stations), Cu (5 stations), Ni (26 stations), Pb (5 stations) and Zn (5 stations). Geoaccumulation indexes (Igeo) also suggest individual metal contamination in localized areas. This study indicates that Cd, Cr and Ni enrichment in the YRIZ sediment is widespread whereas Cu, Mn, Pb and Zn enrichment is localized or nonexistent. Factor and cluster analyses indicate that Cd is associated with total organic carbon whereas Cu, Cr, Ni, Pb and Zn have a close association with Mn. Surface sediment metal enrichment is evidenced for Cd, Cr and Ni in the Yangtze River intertidal zone.

The Tibetan Plateau (TP) is an ideal place for monitoring the atmospheric environment of low to mid latitudes. In total 54 soil samples from the western TP were analyzed for major and trace elements. Results indicate that concentrations of some typical "pollution" elements (such as As) are naturally high here, which may cause incorrect evaluation for the source region of these elements, especially when upper continental crust values are used to calculate enrichment factors. Because only particles <20 μm are transportable as long distances, elemental concentrations of this fraction of the TP soils are more reliable for the future aerosol related studies over the TP. In addition, REE compositions of the TP soils are unusual, highly characteristic and can be used as an effective index for identifying dust aerosol from the TP. High concentrations of some elements of the Tibetan soils can cause incorrect evaluation for the source region of these elements during aerosol related study.

Particle-size-fractioned transfer of dioxins from sediments to water columns by resuspension process was investigated, using supernatant samples obtained from shaking experiments of sediment-water pairs simulating natural disturbances. The concentrations (dry-matter mass basis) of individual compounds (Cfraction) in two particle size fractions (0.1-1 and 1-10 μm) in the supernatants were generally slightly higher than those in the original sediment (Csed). Cfraction/Csed ratios ranged from 0.45 to 5.9 (median 1.5) without consistent differences among congener groups or consistent correlations against the number of chlorine atoms. The dioxin concentrations in the water column associated with the remaining sediment particles can therefore be estimated by those in the original sediment and by the concentration of suspended sediment particles in the water. The concentration of each compound in the remaining sediment particles (mostly 0.1-10 μm in size) can be roughly estimated by multiplying the concentration in the original sediment by 1.5. Dioxin concentrations (dry-matter mass basis) in sediment particles resuspended in the water column were slightly higher than or comparable to those in the bottom sediment.

The discovery that negatively charged aggregates of C60 fullerene (nC60) are stable in water has raised concerns regarding the potential environmental and health effects of these aggregates. In this work, we show that nC60 aggregates produced by extended mixing in the presence of environmentally relevant carboxylic acids (acetic acid, tartaric acid, citric acid) have surface charge and morphologic properties that differ from those produced by extended mixing in water alone. In general, aggregates formed in the presence of these acids have a more negative surface charge and are more homogeneous than those produced in water alone. Carboxylic acid identity, solution pH, and sodium ion concentration, which are all intricately coupled, play an important role in setting the measured surface charge. Comparisons between particle sizes determined by analysis of TEM images and those obtained by dynamic light scattering (DLS) indicate that DLS results require careful evaluation when used to describe nC60 aggregates. The effects of carboxylic acids on the formation of nC60 aggregates are discussed.

Zerovalent iron powder (ZVI or Fe⁰) and nanoparticulate ZVI (nZVI or nFe⁰) are proposed as cost-effective materials for the removal of aqueous antibiotics. Results showed complete removal of Amoxicillin (AMX) and Ampicillin (AMP) upon contact with Fe⁰ and nFe⁰. Antibiotics removal was attributed to three different mechanisms: (i) a rapid rupture of the β-lactam ring (reduction), (ii) an adsorption of AMX and AMP onto iron corrosion products and (iii) sequestration of AMX and AMP in the matrix of precipitating iron hydroxides (co-precipitation with iron corrosion products). Kinetic studies demonstrated that AMP and AMX (20 mg L⁻¹) undergo first-order decay with half-lives of about 60.3 ± 3.1 and 43.5 ± 2.1 min respectively after contact with ZVI under oxic conditions. In contrast, reactions under anoxic conditions demonstrated better degradation with t1/2 of about 11.5 ± 0.6 and 11.2 ± 0.6 min for AMP and AMX respectively. NaCl additions accelerated Fe⁰ consumption, shortening the service life of Fe⁰ treatment systems. 21Fe⁰ is efficient for the aqueous removal of the β-lactam antibiotics and chlorides enhanced the removal rate by sustaining the process of iron corrosion.