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.

The objective of this study is to obtain information on the behaviour of carbon nanotubes (CNTs) as potential carriers of pollutants in the case of accidental CNT release to the environment and on the properties of CNTs as a potential adsorbent material in water purification. The effects of acid treatment of CNTs on (i) the surface properties, (ii) the colloidal stability and (iii) heavy metal sorption are investigated, the latter being exemplified by uranium(VI) sorption. There is a pronounced influence of surface treatment on the behaviour of the CNTs in aqueous suspension. Results showed that acid treatment increases the amount of acidic surface groups on the CNTs. Therefore, acid treatment has an increasing effect on the colloidal stability of the CNTs and on their adsorption capacity for U(VI). Another way to stabilise colloids of pristine CNTs in aqueous suspension is the addition of humic acid. Acid treatment of carbon nanotubes has an increasing effect on their colloidal stability and on their adsorption capacity for U(VI).

A region-wide data analysis on polychlorinated biphenyls (PCBs) in the sediment of the Great Lakes reveals a total accumulation of approximately 300 ± 50 tonnes, representing a >30% reduction from the 1980s. Evidence of in situ degradation of sediment PCB was found, with estimated t1/2 of 11 and 17 years, at two open water locations in Lake Ontario. The relative abundance of heavy homologs as well as para-chlorines decreases with increasing depth, while the opposite is true for medium and light homologs and ortho-chlorines. In Lake Michigan, the vertical pattern features enrichment of heavier congeners and reduction of ortho-chlorines in deeper sediment layers, opposite to the trend in Lake Ontario. PCBs decrease log-linearly with increasing latitude and longitude. Air deposition of PCBs to lake sediment decreases at about 0.077 ng cm-2 yr-1 per degree latitude (N) for the geographic region extending from the Great Lakes to within the Arctic Circle. Data analysis on PCBs in the Great Lakes sediments reveals decline of overall burden, occurrence of in situ degradation, and the geographic gradient in the region and beyond.

Paddy rice may contribute considerably to the human intake of As. The knowledge of soil characteristics affecting the As content of the rice plant enables the development of agricultural measures for controlling As uptake. During field surveys in 2004 and 2006, plant samples from 68 fields (Italy, Po-area) revealed markedly differing As concentration in polished rice. The soil factors total As(aqua regia), pH, grain size fractions, total C, plant available P(CAL), poorly crystalline Fe(oxal.) and plant available Si(Na-acetate) content that potentially affect As content of rice were determined. A multiple linear regression analysis showed a significant positive influence of the total As(aqua regia) and plant available P(CAL) content and a negative influence of the poorly crystalline Fe(oxal.) content of the soil on the As content in polished rice and rice straw. Si concentration in rice straw varied widely and was negatively related to As content in straw and polished rice. Field selection for total As, poorly crystalline Fe and plant available P in soil might contribute to control As content of paddy rice.

Spent shotgun pellets may contaminate terrestrial ecosystems. We examined the fate of elements originating from shotgun pellets in pasture and woodland ecosystems. Two source-receptor pathways: i) soil-soil pore water-plant and ii) whole earthworm/worm gut contents - washed and unwashed small mammal hair were investigated. Concentrations of Pb and associated contaminants were higher in soils from shot areas than controls. Arsenic and lead concentrations were positively correlated in soils, soil pore water and associated biota. Element concentrations in biota were below statutory levels in all locations. Bioavailability of lead to small mammals, based on concentrations in washed body hair was low. Lead movement from soil water to higher trophic levels was minor compared to lead adsorbed onto body surfaces. Lead was concentrated in earthworm gut and some plants. Results indicate that managed game shooting presents minimal risk in terms of element transfer to soils and their associated biota.

Gannet (Morus bassanus) eggs from Bass Rock (North Sea) and Ailsa Craig (eastern Atlantic) were monitored for PCB congeners (1990-2004) and total mercury (1974-2004). Congener profiles for both colonies were dominated by PCBs 153, 138, 180, 118 and 170. All declined in concentration at Ailsa Craig but some (153, 170, 180) remained stable or increased slightly at Bass Rock. Egg congener concentrations at Bass Rock were typically 10-fold higher than at Ailsa Craig by 2002, and Principal Component Analysis indicated that colony differences were driven by the dominant congeners. Egg mercury concentrations were significantly lower at Bass Rock than at Ailsa Craig and temporal trends differed, there being a significant decline at Ailsa Craig but a marginal increase at Bass Rock. Our results suggest there may be differences in contamination between the eastern Atlantic and North Sea and/or there are colony differences in prey selection and associated contaminant loads. Monitoring of PCBs and Hg in gannet eggs reveals contrasting temporal patterns between colonies on the eastern Atlantic and North Sea coasts of Britain.

In this study, three river floodplain soils with different compositions of carbonaceous materials and a reference coal sample were extracted with water using the accelerated solvent extraction (ASE) method. The desorption enthalpy values for 2-ring PAHs were highest in the coal sample, with values in the soil samples decreasing with decrease in coal content. The values for the higher condensed PAHs showed that the highest desorption enthalpies were from the samples with the largest amount of coalderived particles. Elevated desorption enthalpies indicated a strong bonding between PAHs and geosorbents. Moreover, with the application of ASE this study was able to conclude that the PAHs in the samples were preferentially adsorbed to carbonaceous materials with high surface areas.

Industrial activity such as burning of fossil fuels produces magnetically enhanced particulates. These particulates consist of coarse-grained multidomain and stable single domain magnetic minerals. Two threshold values of low field magnetic susceptibility (XLF) and frequency dependent susceptibility percentage (XFD%) discriminate ferrimagnetic minerals of these sizes and can act as a tracer of magnetic pollution. Application of the thresholds to a magnetic topsoil data set (n = 5656 across England and Wales) revealed 637 samples potentially dominated by pollution particulates. The magnetic parameters of these samples display a negative correlation with distance to urban areas and positive correlations with metals associated with anthropogenic activity (Cu, Pb, and Zn). Results of experimentation with threshold values and modelling of magnetic anomalies suggest that regional factors such as geology and potential for pedogenic secondary magnetic enhancement should be considered when setting threshold values.

The degradation of 17b-estradiol (E2) in sterile soil and Mn-free soil slurries was determined. In 0.075 g ml⁻¹ soil slurry, E2 with an initial concentration of 0.0267 mmol g⁻¹ was rapidly degraded and near equimolar estrone (E1) accumulated. A mass balance involving E2 and E1 existed throughout the reaction. The E2 degradation was thus an oxidation process and E1 was the only product. The concurrent release of Mn(II) during E2 oxidation and a lack of E2 oxidation in Mn-free soil slurry together demonstrated that soil manganese oxides were responsible for E2 oxidation. The degree of E2 oxidation was higher at high pH than at low pH, consistent with the fact that the reaction released protons. This study suggests that manganese oxides may be used as soil amendments to effectively oxidize E2 to less potent E1 in soil.

Energy use in urbanization has fundamentally changed the pattern and fluxes of carbon cycling, which has global and local environmental impacts. Here we have investigated organic carbon (OC) and black carbon (BC) in six soil profiles from two contrast zones in an ancient city (Nanjing) in China. BC in soils was widely variable, from 0.22 to 32.19 g kg⁻¹. Its average concentration in an ancient residential area (Zone 1) was, 0.91 g kg⁻¹, whereas in Zone 2, an industrial and commercial area, the figure was 8.62 g kg⁻¹. The ratio of BC/OC ranged from 0.06 to 1.29 in soil profiles, with an average of 0.29. The vertical distribution of BC in soil is suggested to reflect the history of BC formation from burning of biomass and/or fossil fuel. BC in the surface layer of soils was mainly from traffic emission (especially from diesel vehicles). In contrast, in cultural layers BC was formed from historical coal use. The contents of BC and the ratio of BC/OC may reflect different human activities and pollution sources in the contrasting urban zones. In addition, the significant correlation of heavy metals (Cu, Pb, and Zn) with BC contents in some culture layers suggests the sorption of the metals by BC or their coexistence resulted from the coal-involved smelting. Soil black carbon can reflect the pollution history of a city during urbanization.