Christian Micheletti

Analysis of currently available data for characterising the risk of engineered nanomaterials to the environment and human health--lessons learned from four case studies.

Production volumes and the use of engineered nanomaterials in many innovative products are continuously increasing, however little is known about their potential risk for the environment and human health. We have reviewed publicly available hazard and exposure data for both, the environment and human health and attempted to carry out a basic risk assessment appraisal for four types of nanomaterials: fullerenes, carbon nanotubes, metals, and metal oxides (ENRHES project 2009(1)). This paper presents a summary of the results of the basic environmental and human health risk assessments of these case studies, highlighting the cross cutting issues and conclusions about fate and behaviour, exposure, hazard and methodological considerations. The risk assessment methodology being the basis for our case studies was that of a regulatory risk assessment under REACH (ECHA, 2008(2)), with modifications to adapt to the limited available data. If possible, environmental no-effect concentrations and human no-effect levels were established from relevant studies by applying assessment factors in line with the REACH guidance and compared to available exposure data to discuss possible risks. When the data did not allow a quantitative assessment, the risk was assessed qualitatively, e.g. for the environment by evaluating the information in the literature to describe the potential to enter the environment and to reach the potential ecological targets. Results indicate that the main risk for the environment is expected from metals and metal oxides, especially for algae and Daphnia, due to exposure to both, particles and ions. The main risks for human health may arise from chronic occupational inhalation exposure, especially during the activities of high particle release and uncontrolled exposure. The information on consumer and environmental exposure of humans is too scarce to attempt a quantitative risk characterisation. It is recognised that the currently available database for both, hazard and exposure is limited and there are high uncertainties in any conclusion on a possible risk. The results should therefore not be used for any regulatory decision making. Likewise, it is recognised that the REACH guidance was developed without considering the specific behaviour and the mode of action of nanomaterials and further work in the generation of data but also in the development of methodologies is required.

Weight of Evidence approach for the relative hazard ranking of nanomaterials

Abstract In assessing hazard for human health posed by newly engineered nanomaterials (ENM), approaches such as Weight of Evidence (WOE) and expert judgment are required to develop conclusions about the hazard of ENM. This is because all factors affecting hazard are not currently well defined and are often subject to different interpretation. Here we report the application of a WOE procedure to assess the potential of ENM to cause harm for human health, by integrating and combining physicochemical properties of NM and toxicity data obtained within the EU-funded Particle Risk project. The procedure was applied to carbon black (CB), single-walled carbon nanotubes (SWNT), C60 fullerene and quantum dots (QD) ENM tested during the Particle Risk project. The results show that some of the investigated ENM present a relatively higher hazardousness level on the basis of the integration of their physicochemical properties and toxicological effects, and that their hazard may be ranked as follow: QD >> C60 > SWNT > CB. This case study shows the utility of WOE approach to obtain a hazard ranking of ENM.

Limitations and information needs for engineered nanomaterial-specific exposure estimation and scenarios: recommendations for improved reporting practices

The aim of this paper is to describe the process and challenges in building exposure scenarios for engineered nanomaterials (ENM), using an exposure scenario format similar to that used for the European Chemicals regulation (REACH). Over 60 exposure scenarios were developed based on information from publicly available sources (literature, books, and reports), publicly available exposure estimation models, occupational sampling campaign data from partnering institutions, and industrial partners regarding their own facilities. The primary focus was on carbon-based nanomaterials, nano-silver (nano-Ag) and nano-titanium dioxide (nano-TiO2), and included occupational and consumer uses of these materials with consideration of the associated environmental release. The process of building exposure scenarios illustrated the availability and limitations of existing information and exposure assessment tools for characterizing exposure to ENM, particularly as it relates to risk assessment. This article describes the gaps in the information reviewed, recommends future areas of ENM exposure research, and proposes types of information that should, at a minimum, be included when reporting the results of such research, so that the information is useful in a wider context.

Approaches and Frameworks for Managing Contaminated Sediments - A European Perspective

Sediment is an essential, integral and dynamic part of the hydrologic system. In natural and agricultural basins, sediment is derived from the weathering and erosion of minerals, organic material and soils in upstream areas and from the erosion of river banks and other in-stream sources. As surface-water flow rates decline in lowland areas, transported sediment settles along the river bed and banks by sedimentation. However, because sediments are the ultimate reservoir for the numerous potential chemical and biological contaminants that may be contained in effluents originating from urban, agricultural, and industrial lands and recreational activities, contaminated sediments in rivers and streams, lakes, coastal harbors, and estuaries have the potential to pose ecological and human health risks. The management of sediment quality and quantity in support of ecological and socioeconomic goals is a cause of extensive research, investment and regulatory and public scrutiny, both in Europe and internationally. This chapter examines the management of sediment from a European perspective. The first section discusses the role of sediment management in achieving European ecosystem objectives. Section two summarizes the findings of the EC-funded, demand driven European Sediment Research Network (SedNet). Section three describes a framework risk assessment and management in a major European region, the Venice Lagoon. The next three sections describe aspects of sediment management in an EC accession country, and the host country for this workshop - Slovakia. Section four describes river and lake sediment contamination and related legislation in Slovakia. Section five discusses the assessment and management of Persistent Organic Pollutants (POPs), a major risk driver in Slovakia. Section six discusses a specific class of POPs - PCBS in sediments of a specific region of Slovakia. Finally, Section seven discusses some barriers to successful sediment risk assessment and management, and lists science and infrastructure needs to address these barriers. Whilst all the authors of this chapter are living and/or working in Europe, and the focus is on European perspectives, much work has benefited from international collaborations and we feel that many of the observations and recommendations will have relevance to a broader audience.

Analytical and environmental chemistry in the framework of risk assessment and management: The lagoon of Venice as a case study

Prevention of toxic pollutant discharge and remediation of contaminated sediments and soils are topics increasingly addressed by the scientific community and the stakeholders. The research activity carried out on the lagoon of Venice highlights the crucial role played by analytical and environmental chemistry in assessing the environmental behavior of chemicals (i.e. occurrence level, transformation, ultimate fate) and exposure of human and environmental targets to pollutants. The extrapolation from analytical data to decisional steps was accomplished by data treatment (descriptive and multivariate statistics, spatial statistics), environmental modeling (e.g. partitioning bioaccumulation models and linear regression models), environ- mental risk assessment (ERA), and a GIS-based Decision Support System (DSS). Results obtained by this integrated approach supported analytical and environmental chemistry by improving the selection of priority pollutants, optimizing sampling design, and identifying critical environmental pathways. Both uncertainty minimization and cost saving of the overall decision process could be achieved. Selected results are presented here on the application of the proposed approach to the contaminated sediments of the lagoon of Venice and to the brownfield of the Porto Marghera industrial district. Both well-known persistent pollutants (e.g. polychlorinated dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), metals and metalloids, and aromatic surfactants and their metabolites), as well as new classes of pollutants (e.g. endocrine disrupting compounds, EDCs) were investigated. The analytical data indicated that the most persistent and toxic organic and inorganic chemicals were found mainly in bottom sediments (especially those near the Porto Marghera industrial district), while substances such as surfactants and their metabolites and EDCs occurred mainly in water and were redistributed over the whole lagoon. Ex- posure characterization allowed Environmental Risk Assessment (ERA) to be undertaken, including the estimation of risk for both human and environmental health. The ERA procedure, developed according to a tiered approach, was applied to contaminated soils of the Porto Marghera industrial district. The ecological risk associated with contaminated lagoon sediments for the benthic community and aquatic food web was also assessed, resulting in a significant risk posed especially by mercury, cadmium and PAHs. Finally, a risk-based decision support system (DSS) for the rehabilitation of the Porto Marghera contaminated site was developed, which included environmental risk and remediation technologies.

Ecological risk assessment of persistent toxic substances for the clam Tapes philipinarum in the lagoon of venice, italy

Because of contamination of sediments of the Lagoon of Venice, Italy, by inorganic pollutants (e.g., arsenic, cadmium, chromium, copper, lead, mercury, nickel, and zinc) and organic pollutants (e.g., polychlorobiphenyls), as well as the ecological and economical relevance of the edible clam Tapes philipinarum, an ecological risk assessment was undertaken to ascertain the extent of bioaccumulation that would pose a significant risk. Risk was estimated by means of toxic units and hazard quotient approaches, by comparing the exposure concentration with the effect concentration. Clam exposure was estimated by applying previous results based on bioaccumulation spatial regression models. In addition, a comparison was made between sum of dioxin-like polychlorinated biphenyl (PCB) congeners and total PCB bioaccumulation provided by spatial regression models and by a partitioning model. The effect concentrations were calculated as tissue screening concentrations, as the product of pollutant sediment quality criteria and the bioaccumulation factor. Finally, the cumulative risk posed by selected inorganic pollutants and total PCBs was estimated and a map of risk was drawn. The resulting chemicals of potential ecological concern were mercury, cadmium, arsenic, and nickel, as well as, to a lesser extent, total PCBs.

Spatially distributed ecological risk for fish of a coastal food web exposed to dioxins

The ecological risk posed by 2,3,7,8-polychlorodibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorobiphenyl (PCB) congeners to five edible fish species of the aquatic food web of Venice Lagoon, Italy, was estimated by applying a state-of the-art kinetic bioaccumulation model. Site-specific data were used to define a representative food web. The experimental data set for model validation and application included PCB and PCDD/F congener concentrations in sediments, in water, and in five organisms (both invertebrates and fish). The spatial distribution of risk was evaluated by dividing the lagoon into six homogeneous areas, and for each area, sediment, water, and organism dioxins concentrations were calculated. The bioaccumulation model was calibrated for both nonmetabolizing and metabolizing congeners, the metabolic elimination rates of which were estimated. The model validation showed an acceptable bioaccumulation estimation, evaluated using the model bias parameter. The calibrated model was applied to the six areas of the lagoon to estimate the fish predicted exposure concentration as 2,3,7,8-tetrachlorodibenzo-p-dioxin toxicity equivalents from sediment concentration. Internal no-effect concentrations were calculated for each fish species from literature data. Risk was estimated by applying the hazard quotient (HQ) approach, obtaining the ecological risk for each fish species on the basis of 90 and 99% protection levels, in each of the six lagoon areas. The sediment dioxins concentration does not pose a significant risk to the selected fish species at the 90% protection target (HQ<1), whereas risk is significant (HQ>1) at the 99% protection target. Risk results were higher near the Porto Marghera industrial district, Italy, and in lagoon zones characterized by a low water-exchange rate and freshwater basin inputs.

Spatial analysis in ecological risk assessment: Pollutant bioaccumulation in clams Tapes philipinarum in the Venetian lagoon (Italy)

Exposure characterization is a central step in Ecological Risk Assessment (ERA). Exposure level is a function of the spatial factors linking contaminants and receptors, yet exposure estimation models are traditionally non-spatial. Non-spatial models are prone to the adverse effects of spatial dependence: inflated variance and biased inferential procedures, which can result in unreliable and potentially misleading models. Such negative effects can be amended by spatial regression modelling: we propose an integration of geostatistics and multivariate spatial regression to compute efficient spatial regression parameters and to characterize exposure at under-sampled locations. The method is applied to estimate bioaccumulation models of organic and inorganic micropollutants in the tissues of the clam Tapes philipinarum. The models link bioaccumulation of micropollutants in clam tissue to a set of environmental variables sampled in the lagoon sediment. The Venetian lagoon case study exemplifies the problem of multiple variables sampled at different locations or spatial units: we propose and test an effective solution to this common and serious problem in environmental as well as socio-economic multivariate analysis.

Review of Decision Support Systems Devoted to the Management of Inland and Coastal Waters in the European Union

One of the most important policies in the European Union concerns the management of water resources, including rivers, lagoons and coastal areas. Within this strategic and holistic approach to water resources management, contamination issues are relevant aspects of concern.