Karen Tiede

Detection and characterization of engineered nanoparticles in food and the environment.

Nanotechnology is developing rapidly and, in the future, it is expected that increasingly more products will contain some sort of nanomaterial. However, to date, little is known about the occurrence, fate and toxicity of nanoparticles. The limitations in our knowledge are partly due to the lack of methodology for the detection and characterisation of engineered nanoparticles in complex matrices, i.e. water, soil or food. This review provides an overview of the characteristics of nanoparticles that could affect their behaviour and toxicity, as well as techniques available for their determination. Important properties include size, shape, surface properties, aggregation state, solubility, structure and chemical composition. Methods have been developed for natural or engineered nanomaterials in simple matrices, which could be optimized to provide the necessary information, including microscopy, chromatography, spectroscopy, centrifugation, as well as filtration and related techniques. A combination of these is often required. A number of challenges will arise when analysing environmental and food materials, including extraction challenges, the presence of analytical artifacts caused by sample preparation, problems of distinction between natural and engineered nanoparticles and lack of reference materials. Future work should focus on addressing these challenges.

Nanoparticle analysis and characterization methodologies in environmental risk assessment of engineered nanoparticles

Environmental risk assessments of engineered nanoparticles require thorough characterization of nanoparticles and their aggregates. Furthermore, quantitative analytical methods are required to determine environmental concentrations and enable both effect and exposure assessments. Many methods still need optimization and development, especially for new types of nanoparticles in water, but extensive experience can be gained from the fields of environmental chemistry of natural nanomaterials and from fundamental colloid chemistry. This review briefly describes most methods that are being exploited in nanoecotoxicology for analysis and characterization of nanomaterials. Methodological aspects are discussed in relation to the fields of nanometrology, particle size analysis and analytical chemistry. Differences in both the type of size measures (length, radius, aspect ratio, etc.), and the type of average or distributions afforded by the specific measures are compared. The strengths of single particle methods, such as electron microscopy and atomic force microscopy, with respect to imaging, shape determinations and application to particle process studies are discussed, together with their limitations in terms of counting statistics and sample preparation. Methods based on the measurement of particle populations are discussed in terms of their quantitative analyses, but the necessity of knowing their limitations in size range and concentration range is also considered. The advantage of combining complementary methods is highlighted.

Considerations for environmental fate and ecotoxicity testing to support environmental risk assessments for engineered nanoparticles

There is an increasing concern over the safety of engineered nanoparticles (ENPs) to humans and the environment and it is likely that the environmental risks of these particles will have to be tested under regulatory schemes such as REACH. Due to their unique properties and the fact that their detection and characterisation in complex matrices is challenging, existing analytical methods and test approaches for assessing environmental risk may not be appropriate for ENPs. In this article we discuss the challenges associated with the testing of ENPs to generate data on persistence, mobility, bioavailability and ecotoxicity in the environment. It is essential that careful consideration is given to the selection of the test material, the test system (including test vessels and study media) and the test exposure conditions. During a study it is critical that not only the concentration of the ENP is determined but also its characteristics (e.g. size, shape, degree of aggregation and dissolution). A range of analytical techniques is available including microscopy-based approaches (e.g transmission and scanning electron microscopy), dynamic light scattering, and size separation approaches (e.g. field flow fractionation and hydrodynamic chromatography) coupled to detection methods such as inductively coupled plasma MS. All of these have their disadvantages: some are unable to distinguish between ENPs and natural interferences; some techniques require sample preparation approaches that can introduce artefacts; and others are complex and time-consuming. A combination of techniques is therefore needed. Our knowledge in this area is still limited, and co-ordinated research is required to gain a better understanding of the factors and processes affecting ENP fate and effects in the environment as well as to develop more usable, robust and sensitive methods for characterisation and detection of ENPs in environmental systems.

Engineered nanomaterials in soils and water: how do they behave and could they pose a risk to human health?

It is inevitable that, during their use, engineered nanoparticles will be released into soils and waters. There is therefore increasing concern over the potential impacts of engineered nanoparticles in the environment on aquatic and terrestrial organisms and on human health. Once released into the environment, engineered nanoparticles will aggregate to some degree; they might also associate with suspended solids, sediment, be accumulated by organisms and enter drinking water sources and food materials. These fate processes are dependent on the characteristics of the particle and the characteristics of the environmental system. A range of ecotoxicological effects have also been reported, including effects on microbes, plants, invertebrates and fish. Although available data indicate that current risks of engineered nanoparticles in the environment to environmental and human health are probably low, our knowledge of the potential impacts of engineered nanoparticles in the environment on human health is still limited. There is therefore a need for continued work to develop an understanding of the exposure levels for engineered nanoparticles in environmental systems and to begin to explore the implications of these levels in terms of the ecosystem and human health. This will require research in a range of areas, including detection and characterization, environmental fate and transport, ecotoxicology and toxicology.

Nanopesticides: State of Knowledge, Environmental Fate, and Exposure Modeling

Published literature has been reviewed in order to (a) explore the (potential) applications of nanotechnology in pesticide formulation, (b) identify possible impacts on environmental fate, and (c) analyze the suitability of current exposure assessment procedures to account for the novel properties of nanopesticides within the EU regulatory context. The term nanopesticide covers a wide variety of products and cannot be considered to represent a single category. Many nanoformulations combine several surfactants, polymers, and metal nanoparticles in the nanometer size range. The aims of nanoformulations are generally common to other pesticide formulations, these being to increase the apparent solubility of poorly soluble active ingredients, to release the active ingredient in a slow/targeted manner and/or to protect against premature degradation. Nanoformulations are thus expected to (a) have significant impacts on the fate of active ingredients and/or (b) introduce new ingredients for which the environmental fate is still poorly understood (e.g., nanosilver). Therefore, it seems that adaptations of current exposure assessment approaches will be necessary, at least for some nanopesticides. The present analysis provides a useful framework to identify priorities for future research in order to achieve more robust risk assessments of nanopesticides.

Application of hydrodynamic chromatography-ICP-MS to investigate the fate of silver nanoparticles in activated sludge

Detection and characterisation are two of the major challenges in understanding the fate, behaviour and occurrence of engineered nanoparticles (ENPs) in the natural environment. In a previous paper we described the development of hydrodynamic chromatography coupled to plasma mass spectrometry (HDC-ICP-MS) for detecting and characterising ENPs in aqueous matrices. This paper describes the applicability of the approach, to study the behaviour of silver nanoparticles in a much more complex and relevant environmental system i.e. sewage sludge supernatant. Batch sorption studies were performed at a range of nanosilver concentrations. Following completion, the sludge supernatant was characterised by ICP-MS, HDC-ICP-MS and transmission electron microscopy (TEM). It was found that, after a contact time of 6 h, most of the silver had partitioned to the sewage sludge (>90%). However, of the silver remaining in the supernatant, some of this was in the nanoparticle form, implying that closer consideration should be given to the longer-term impact of the release of silver ENPs into aquatic ecosystems. These preliminary data clearly show the utility of HDC-ICP-MS for studying the occurrence and behaviour of ENPs in complex natural environments.

A robust size-characterisation methodology for studying nanoparticle behaviour in ‘real’ environmental samples, using hydrodynamic chromatography coupled to ICP-MS

A hyphenated methodology has been developed and validated, which utilizes the extensive size separation range of hydrodynamic chromatography (here: 5–300 nm) combined with the multi-element selectivity of ICP-MS. This has been applied to the analysis of metal-based nanoparticles in environmental samples. The quality of the particle sizing data obtained from this exercise was enabled through the production of a range of gold nanoparticles (sterically stabilized to prevent aggregation in environmental matrices), which were validated for use as external size calibration standards as well as internal retention time markers, using TEM. The methodology was then successfully applied to a study where nanosilver was spiked into sewage sludge, preliminary data from which showed that a fraction of nanosilver survived as single nanoparticles in the sludge supernatant. The method was also tested on solutions containing other commonly used nanoparticles (TiO2, SiO2, Al2O3 and Fe2O3). Overall, the data showed that, by using ICP-MS with collision cell technology, the methodology would be helpful in investigating the fate of a significant range of nanoparticle types. Other characteristics of HDC-ICP-MS are: rapid analysis time ( 300 nm), and limited sample pre-treatment required.

Nanopesticides: guiding principles for regulatory evaluation of environmental risks

Nanopesticides or nano plant protection products represent an emerging technological development that, in relation to pesticide use, could offer a range of benefits including increased efficacy, durability, and a reduction in the amounts of active ingredients that need to be used. A number of formulation types have been suggested including emulsions (e.g., nanoemulsions), nanocapsules (e.g., with polymers), and products containing pristine engineered nanoparticles, such as metals, metal oxides, and nanoclays. The increasing interest in the use of nanopesticides raises questions as to how to assess the environmental risk of these materials for regulatory purposes. Here, the current approaches for environmental risk assessment of pesticides are reviewed and the question of whether these approaches are fit for purpose for use on nanopesticides is addressed. Potential adaptations to existing environmental risk assessment tests and procedures for use with nanopesticides are discussed, addressing aspects such as analysis and characterization, environmental fate and exposure assessment, uptake by biota, ecotoxicity, and risk assessment of nanopesticides in aquatic and terrestrial ecosystems. Throughout, the main focus is on assessing whether the presence of the nanoformulation introduces potential differences relative to the conventional active ingredients. The proposed changes in the test methodology, research priorities, and recommendations would facilitate the development of regulatory approaches and a regulatory framework for nanopesticides.

Imaging of engineered nanoparticles and their aggregates under fully liquid conditions in environmental matrices.

The increasing industrial production of engineered nanoparticles (ENPs) raises concern over their safety to humans and the environment. There is a lack of knowledge regarding the environmental fate and impact of ENPs and in situ methods are needed to investigate e.g. nanoparticle aggregation and adsorption in the media of concern such as water, sediment and soil. In this study, the application of wet scanning electron microscopy (WetSEM) technology in combination with energy dispersive x-ray spectroscopy (EDS) to visualise and elementally identify metal and metal oxide nanoparticles (Au, TiO(2), ZnO and Fe(2)O(3)) under fully liquid conditions in distilled and lake water as well as in a soil suspension has been investigated. WetSEM capsules comprise an electron transparent membrane enabling the imaging and EDS analysis of liquid samples. Results are compared with conventional SEM images and show that WetSEM/EDS is a promising complementary tool for the in situ investigation of ENPs and their aggregates in natural matrices. In combination with other analytical tools (e.g. HDC- or FFF-ICP-MS, DLS), WetSEM could help to provide a better understanding of the fate and behaviour of ENPs in the environment.

Imaging and Characterization of Engineered Nanoparticles in Sunscreens by Electron Microscopy, Under Wet and Dry Conditions

Abstract There is increasing concern over the risks of nanoparticles to humans and the environment, but little is known about the properties of the nanoparticulate mineral filters, such as titanium dioxide and zinc oxide, in sunscreens. There is an urgent need to develop methods for characterizing nanoparticles in (NPs) such products to provide data for human and environmental risk assessments. This study explored three methods (transmission electron microscopy [TEM], conventional scanning electron microscopy [SEM], and wet-scanning electron microscopy [WetSEM]) for characterizing NPs in sunscreens. Our results showed that these products contained titanium dioxide and zinc oxide particles in the nanometer range; thus, it is likely that consumers and the environment are exposed to engineered NPs through the use of these products. Further, we found that the combination of all three microscopy methods provided the most comprehensive information on size-related properties, which are crucial parameters for risk assessment of NPs in wet matrices.