Deborah Oughton

Aging and soil organic matter content affect the fate of silver nanoparticles in soil.

Sewage sludge application on soils represents an important potential source of silver nanoparticles (Ag NPs) to terrestrial ecosystems, and it is thus important to understand the fate of Ag NPs once in contact with soil components. Our aim was to compare the behavior of three different forms of silver, namely silver nitrate, citrate stabilized Ag NPs (5nm) and uncoated Ag NPs (19nm), in two soils with contrasting organic matter content, and to follow changes in binding strength over time. Soil samples were spiked with silver and left to age for 2h, 2 days, 5 weeks or 10 weeks before they were submitted to sequential extraction. The ionic silver solution and the two Ag NP types were radiolabeled so that silver could be quantified by gamma spectrometry by measuring the (110m)Ag tracer in the different sequential extraction fractions. Different patterns of partitioning of silver were observed for the three forms of silver. All types of silver were more mobile in the mineral soil than in the soil rich in organic matter, although the fractionation patterns were very different for the three silver forms in both cases. Over 20% of citrate stabilized Ag NPs was extractible with water in both soils the first two days after spiking (compared to 1-3% for AgNO(3) and uncoated Ag NPs), but the fraction decreased to trace levels thereafter. Regarding the 19nm uncoated Ag NPs, 80% was not extractible at all, but contrary to AgNO(3) and citrate stabilized Ag NPs, the bioaccessible fraction increased over time, and by day 70 was between 8 and 9 times greater than that seen in the other two treatments. This new and unexpected finding demonstrates that some Ag NPs can act as a continuous source of bioaccessible Ag, while AgNO(3) is rapidly immobilized in soil.

Radionuclide mobility and bioavailability in Norwegian and Soviet soils

A sequential extraction procedure has been applied to study the speciation of Chernobyl-derived radionuclides (137Cs and 90Sr) in soils from Norway, and from Byelorussia and the Chernobyl region in the USSR. Most 137Cs (greater than 80%) was strongly associated with soil components, whereas 90Sr was more mobile, up to 70% being found in the easily extractable fractions. The 90Sr: 137Cs ratio decreased with the distance from the reactor, reflecting the higher proportion of hot particles deposited in the regions close to the reactor, and the easily extractable fraction of 90Sr was significantly lower in the soils collected from the Chernobyl area. The distribution of stable Cs and stable Sr in the extraction fractions was similar for the various sites. Therefore, the location-specific differences in the distribution of 90Sr and, to a lesser extent, 137Cs arise because of fallout speciation rather than because of local environmental factors.

Hot particles in accidental releases from Chernobyl and Windscale nuclear installations

Fuel particles released during the accident at the Chernobyl reactor (1986) and during the operation at the Windscale (UK) pile (1952–57) were investigated with respect to structure using scanning electron microscopy and composition using X-ray microanalysis and γ-, β- and α-spectrometry. Particles from Chernobyl released at a relatively high temperature have in general a compact crystalline-like structure with a relatively uniform surface layer of uranium. Aggregates consisting of small-sized (1–2 µm) spherical uranium granulates were also identified. These granulates were similar to particles identified in Norway. About 25% of the particles investigated were covered by lead, which is attributed to a release during the last stage of the accident. Particles from Windscale released under low-temperature conditions have a flake-like layered structure, varying in size (10–250 µm) and activity levels. Thus the travelling distance for these particles may be substantially longer than previously anticipated for spheres. The surfaces of these particles were also composed of uranium. The mobility of radionuclides associated with fuel particles of different structure is believed at least initially to be low when compared with those associated with condensed particles or with ionic tracers. However, mobilization of especially 90Sr due to weathering of hot particles should be expected in the years to come.

Issues and practices in the use of effects data from FREDERICA in the ERICA Integrated Approach

The ERICA Integrated Approach requires that a risk assessment screening dose rate is defined for the risk characterisation within Tiers 1 and 2. At Tier 3, no numerical screening dose rate is used, and the risk characterisation is driven by methods that can evaluate the possible effects of ionising radiation on reproduction, mortality and morbidity. Species sensitivity distribution has been used to derive the ERICA risk assessment predicted no-effect dose rate (PNEDR). The method used was based on the mathematical processing of data from FRED (FASSET radiation effects database merged with the EPIC database to form FREDERICA) and resulted in a PNEDR of 10 microGy/h. This rate was assumed to ascribe sufficient protection of all ecosystems from detrimental effects on structure and function under chronic exposure. The value was weighed against a number of points of comparison: (i) PNEDR values obtained by application of the safety factor method, (ii) background levels, (iii) dose rates triggering effects on radioactively contaminated sites and (iv) former guidelines from literature reviews. In Tier 3, the effects analysis must be driven by the problem formulation and is thus highly case specific. Instead of specific recommendations on numeric values, guidance on the sorts of methods that may be applied for refined effect analysis is provided and illustrated.

Ecotoxicological effects of an aged TiO2 nanocomposite measured as apoptosis in the anecic earthworm Lumbricus terrestris after exposure through water, food and soil.

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.

Acute and sub-lethal effects in juvenile Atlantic salmon exposed to low μg/L concentrations of Ag nanoparticles

Silver nanoparticles (Ag-NP) are components in numerous commercial products and are discharged into the environment in quantities that are largely unknown. In the present study, juvenile Atlantic salmon were exposed to 1, 20, and 100 μg/L (48 h, static renewal) of a commercially available Ag-NP colloidal suspension in natural (soft) lake water. A solution of AgNO(3) containing 20 μg/L Ag(I) ions was also included to discriminate the effect of NPs from that of ionic silver. Furthermore, the commercial Ag-NP suspension was compared to an in-house synthesised colloidal NP suspension prepared from AgNO(3) and NaBH(4) in citrate buffer. The size distribution of Ag in all exposure solutions was characterised by 0.22 μm filtration and 10 kDa hollow fibre cross-flow ultrafiltration in combination with ICP-MS. All exposures were characterised by a relatively high proportion of Ag-NP in the colloidal size fraction 3-220 nm. For assessment of biological effects, acute toxicity, gill histopathology, blood plasma parameters (Na, Cl, glucose, haemoglobin), and gene expression of a selection of gill biomarkers were measured. Results showed that the gills accumulated Ag in all exposure groups apart from the fish exposed to 1 μg/L Ag-NP. Accumulated Ag caused concentration-dependent response increases in general stress markers such as plasma glucose and gill gene expression of heat shock protein 70. Furthermore, induction of the metallothionein A gene indicated that Ag had been internalized in the gills, whereas a concentration-dependant inhibition of Na/K ATPase expression indicated impaired osmoregulation at as low as 20 μg/L concentrations of Ag-NP. The commercial Ag-NP suspension caused acute gill lamellae necrosis at high concentrations (100 μg/L), potentially giving rise to the substantial (73%) fish mortality at this concentration. The two different Ag-NP preparations gave comparable results for several endpoints measured, but differed in MT-A induction and mortality, thus emphasising the variation in effects that may arise from different Ag-NP preparations.

Silver nanoparticle exposure causes apoptotic response in the earthworm Lumbricus terrestris (Oligochaeta).

In terrestrial ecotoxicology there is a serious lack of data for potential hazards posed by engineered nanoparticles (ENPs). This is partly due to complex interactions between ENPs and the soil matrix, but also to the lack of suitable toxicological end points in organisms that are exposed to ENPs in a relevant manner. Earthworms are key organisms in terrestrial ecosystems, but so far only physiological end points of low sensitivity have been used in ecotoxicity studies with ENPs. We exposed the earthworm Lumbricus terrestris to silver nanoparticles and measured their impact on apoptosis in different tissues. Increased apoptotic activity was detected in a range of tissues both at acute and sublethal concentrations (down to 4 mg/kg soil). Comparing exposure in water and soil showed reduced bioavailability in soil reflected in the apoptotic response. Apoptosis appears to be a sensitive end point and potentially a powerful tool for quantifying environmental hazards of ENPs.

Neutron activation of engineered nanoparticles as a tool for tracing their environmental fate and uptake in organisms.

Studies regarding the environmental impact of engineered nanoparticles (ENPs) are hampered by the lack of tools to localize and quantify ENPs in water, sediments, soils, and organisms. Neutron activation of mineral ENPs offers the possibility of labeling ENPs in a way that avoids surface modification and permits both localization and quantification within a matrix or an organism. Time-course experiments in vivo also may be conducted with small organisms to study metabolism and exposure, two aspects currently lacking in ecotoxicological knowledge about ENPs. The present report explains some of the prerequisites and advantages of neutron activation as a tool for studying ENPs in environmental samples and ecologically relevant organisms, and it demonstrates the suitability of neutron activation for Ag, Co/Co3O4, and CeO2 nanoparticles. In a preliminary experiment with the earthworm Eisenia fetida, the dietary uptake and excretion of a Co nanopowder (average particle size, 4 nm; surface area, 59 m2/g) were studied. Cobalt ENPs were taken up to a high extent during 7 d of exposure (concentration ratios of 0.16-0.20 relative to the ENP concentration in horse manure) and were largely retained within the worms for a period of eight weeks, with less than 20% of absorbed ENPs being excreted. Following dissection of the worms, 60Co was detected in spermatogenic cells, cocoons, and blood using scintillation counting and autoradiography. The experimental opportunities that neutron activation of ENPs offer are discussed.

Bioavailability of cobalt and silver nanoparticles to the earthworm Eisenia fetida

Abstract Due to difficulties in tracing engineered nanoparticles (ENPs) in complex media, there are few data on the exposure of soil biota to ENPs. This study used neutron activated cobalt (Co NPs) and silver (Ag NPs) nanoparticles, as well as soluble cobalt and silver salts, to assess the uptake, excretion and biodistribution in the earthworm Eisenia fetida. Concentrations of cobalt in worms after four weeks exposure reached 88% and 69% of the Co ions and Co NPs concentrations in food, respectively, while corresponding values for Ag ions and Ag NPs were 2.3% and 0.4%. Both Ag ions and Ag NPs in earthworms were excreted rapidly, while only 32% of the cobalt accumulated from Co ions and Co NPs were excreted within four months. High accumulation of cobalt was found in blood and in the digestive tract. Metal characterization in the exposure medium was assessed by sequential extraction and ultrafiltration. The Co NPs showed significant dissolution and release of ions, while Ag ions and particularly Ag NPs were more inert.

Protection of the environment from ionising radiation in a regulatory context—an overview of the PROTECT coordinated action project

The outcome of the PROTECT project (Protection of the Environment from Ionising Radiation in a Regulatory Context) is summarised, focusing on the protection goal and derivation of dose rates which may detrimentally affect wildlife populations. To carry out an impact assessment for radioactive substances, the estimated dose rates produced by assessment tools need to be compared with some form of criteria to judge the level of risk. To do this, appropriate protection goals need to be defined and associated predefined dose rate values, or benchmarks, derived and agreed upon. Previous approaches used to estimate dose rates at which there may be observable changes in populations or individuals are described and discussed, as are more recent derivations of screening benchmarks for use in regulatory frameworks. We have adopted guidance and procedures used for assessment and regulation of other chemical stressors to derive benchmarks. On the basis of consultation with many relevant experts, PROTECT has derived a benchmark screening dose rate, using data on largely reproductive effects to derive species sensitivity distributions, of 10 microGy h(-1) which can be used to identify situations which are below regulatory concern with a high degree of confidence.