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Abstract-The risks associated with exposure to engineered nanomaterials (ENM) will be determined in part by the processes that control their environmental fate and transformation. These processes act not only on ENM that might be released directly into the environment, but more importantly also on ENM in consumer products and those that have been released from the product. The environmental fate and transformation are likely to differ significantly for each of these cases. The ENM released from actual direct use or from nanomaterial-containing products are much more relevant for ecotoxicological studies and risk assessment than pristine ENM. Released ENM may have a greater or lesser environmental impact than the starting materials, depending on the transformation reactions and the material. Almost nothing is known about the environmental behavior and the effects of released and transformed ENM, although these are the materials that are actually present in the environment. Further research is needed to determine whether the release and transformation processes result in a similar or more diverse set of ENM and ultimately how this affects environmental behavior. This article addresses these questions, using four hypothetical case studies that cover a wide range of ENM, their direct use or product applications, and their likely fate in the environment. Furthermore, a more definitive classification scheme for ENM should be adopted that reflects their surface condition, which is a result of both industrial and environmental processes acting on the ENM. The authors conclude that it is not possible to assess the risks associated with the use of ENM by investigating only the pristine form of the ENM, without considering alterations and transformation processes. Environ. Toxicol. Chem. 2012;31:50-59. # 2011 SETAC

The unique or enhanced properties of manufactured nanomaterials (MNs) suggest that their use in nanoenabled products will continue to increase. This will result in increased potential for human and environmental exposure to MNs during manufacturing, use, and disposal of nanoenabled products. Scientifically based risk assessment for MNs necessitates the development of reproducible, standardized hazard testing methods such as those provided by the Organisation of Economic Cooperation and Development (OECD). Currently, there is no comprehensive guidance on how best to address testing issues specific to MN particulate, fibrous, or colloidal properties. This paper summarizes the findings from an expert workshop convened to develop a guidance document that addresses the difficulties encountered when testing MNs using OECD aquatic and sediment test guidelines. Critical components were identified by workshop participants that require specific guidance for MN testing: preparation of dispersions, dose metrics, the importance and challenges associated with maintaining and monitoring exposure levels, and the need for reliable methods to quantify MNs in complex media. To facilitate a scientific advance in the consistency of nanoecotoxicology test results, we identify and discuss critical considerations where expert consensus recommendations were and were not achieved and provide specific research recommendations to resolve issues for which consensus was not reached. This process will enable the development of prescriptive testing guidance for MNs. Critically, we highlight the need to quantify and properly interpret and express exposure during the bioassays used to determine hazard values.

One target of development and application of TiO(2) nanoparticles (nano-TiO(2) ) is photochemical degradation of contaminants and photo-killing of microbes and fouling organisms. However, few ecotoxicological studies have focused on this aspect of nano-TiO(2) , specifically whether this photoreactivity might significantly increase hazard and risk of the materials in the natural environment. In the present study, we evaluated acute phototoxicity of nano-TiO(2) under simulated solar radiation (SSR) to two aquatic species-Daphnia magna and Japanese medaka, using 48-h and 96-h assays, respectively. A thorough characterization of the exposure system was performed by measuring particle agglomeration and TiO(2) concentration in suspension in a time-course manner. Sedimentation and loss of bulk concentration of nano-TiO(2) particles occurred at all concentrations above 2 mg/L and was more significant as concentration increased. Phototoxicity of nano-TiO(2) under SSR was enhanced by two to four orders of magnitude as compared to toxicity under ambient laboratory light, with a 48-h median lethal concentration (LC50) of 29.8 µg/L in D. magna and a 96-h LC50 of 2.2 mg/L in medaka. Our results also indicate that these effects are dependent on simultaneous exposure of the organisms to nanoparticles and SSR. This dramatic increase in toxicity of nano-TiO(2) at environmentally realistic levels of SSR indicates the need to incorporate this mode of action into risk assessment for nano-TiO(2) and other photoreactive nanomaterials.

Generation of reactive oxygen species (ROS) by titanium dioxide nanoparticles (nano‐TiO2) and its consequent phototoxicity to Daphnia magna were measured under different solar ultraviolet (UV) spectra by applying a series of optical filters in a solar simulator. Removing UV‐B (280–320 nm) from solar radiation had no significant impact on photocatalytic ROS production of nano‐TiO2, whereas removal of UV‐A (320–400 nm) decreased ROS production remarkably. Removal of wavelengths below 400 nm resulted in negligible ROS production. A linear correlation between ROS production and D. magna immobilization suggests that photocatalytic ROS production may be a predictor of phototoxicity for nano‐TiO2. Intracellular ROS production within D. magna was consistent with the immobilization of the organism under different solar UV spectra, indicating that oxidative stress was involved in phototoxicity. The dependence of nano‐TiO2 phototoxicity on environmentally realistic variations in solar radiation suggests that risk assessment of these nanomaterials requires careful evaluation of exposure conditions in the environment. Environ. Toxicol. Chem. 2012; 31: 2099–2107. © 2012 SETAC