Stephen A. Diamond

Ecotoxicity of manufactured ZnO nanoparticles – A review

This report presents an exhaustive literature review on the toxicity of manufactured ZnO nanoparticles (NPs) to ecological receptors across different taxa: bacteria, algae and plants, aquatic and terrestrial invertebrates and vertebrates. Ecotoxicity studies on ZnO NPs are most abundant in bacteria, and are relatively lacking in other species. These studies suggest relative high acute toxicity of ZnO NPs (in the low mg/l levels) to environmental species, although this toxicity is highly dependent on test species, physico-chemical properties of the material, and test methods. Particle dissolution to ionic zinc and particle-induced generation of reactive oxygen species (ROS) represent the primary modes of action for ZnO NP toxicity across all species tested, and photo-induced toxicity associated with its photocatalytic property may be another important mechanism of toxicity under environmentally relevant UV radiation. Finally, current knowledge gaps within this area are briefly discussed and recommendations for future research are made.

Potential Scenarios for Nanomaterial Release and Subsequent alteration in the Environment

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.

Phototoxicity of TiO2 nanoparticles under solar radiation to two aquatic species: Daphnia magna and Japanese medaka

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.

Adapting OECD Aquatic Toxicity Tests for Use with Manufactured Nanomaterials: Key Issues and Consensus Recommendations.

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.

Photocatalytic reactive oxygen species production and phototoxicity of titanium dioxide nanoparticles are dependent on the solar ultraviolet radiation spectrum.

Generation of reactive oxygen species (ROS) by titanium dioxide nanoparticles (nano-TiO(2)) 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-TiO(2), 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-TiO(2). 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-TiO(2) phototoxicity on environmentally realistic variations in solar radiation suggests that risk assessment of these nanomaterials requires careful evaluation of exposure conditions in the environment.

OPTICAL CHARACTERISTICS OF NATURAL WATERS PROTECT AMPHIBIANS FROM UV-B IN THE U.S. PACIFIC NORTHWEST

Increased exposure to ultraviolet-B (UV-B) radiation has been proposed as a major environmental stressor leading to global amphibian declines. Prior experimental evidence from the U.S. Pacific Northwest (PNW) indicating the acute embryonic sensitivity of at least four amphibian species to UV-B has been central to the literature about amphibian decline. However, these results have not been expanded to address population-scale effects and natural landscape variation in UV-B transparency of water at amphibian breeding sites: both necessary links to assess the importance of UV-B for amphibian declines. We quantified the UV-B transparency of 136 potential amphibian breeding sites to establish the pattern of UV-B exposure across two montane regions in the PNW. Our data suggest that 85% of sites are naturally protected by dissolved organic matter in pond water, and that only a fraction of breeding sites are expected to experience UV-B intensities exceeding levels associated with elevated egg mortality. Thus, the spectral characteristics of natural waters likely mediate the physiological effects of UV-B on amphibian eggs in all but the clearest waters. These data imply that UV-B is unlikely to cause broad amphibian declines across the landscape of the American Northwest.

Phototoxicity of TiO2 nanoparticles to a freshwater benthic amphipod: Are benthic systems at risk?

This study investigated phototoxicity of TiO₂ nanoparticles (nano-TiO₂) to a freshwater benthic amphipod (Hyalella azteca) using 48-h and 96-h bioassays. Thorough monitoring of particle interactions with exposure media (Lake Superior water, LSW) and the surface of organisms was performed using dynamic light scattering, UV/Vis spectroscopy, and Scanning Electron Microscopy. Large agglomeration and sedimentation (>77%) in LSW was observed after 0.5h. A simulated solar radiation (SSR)-favored surface attachment of nanoparticles was observed, indicating enhanced phototoxicity with the increased attachment. A 96-h median lethal concentration (LC50) of 29.9 mg/L in H. azteca was calculated, with a daily 4-h UV exposure of 2.2 W/m(2). Phototoxicity of nano-TiO₂ under SSR had a 21-fold increase as compared to that under ambient laboratory light. This phototoxicity was also dependent on UV dose, with calculated LC50s around 22.9 (95% CI, 20.5-23.3)Wh/m(2) when exposed to 20 mg/L nano-TiO₂. Also, H. azteca exhibited negative phototaxis in the presence of shelters, indicating that other factors might play a role in environmental systems. Finally, the environmental implications of nano-TiO₂ to benthic organisms were illustrated, emphasizing the importance of various environmental factors in the ultimate phototoxicity. This increased phototoxicity and its complex interactions with various environmental factors suggest further investigations are needed for future risk assessment of photoactive nanomaterials to benthic organisms.

Ambient Solar UV Radiation Causes Mortality in Larvae of Three Species of Rana Under Controlled Exposure Conditions

Abstract Recent reports concerning the lethal effects of solar ultraviolet-B (UV-B) (290–320 nm) radiation on amphibians suggest that this stressor has the potential to impact some amphibian populations. In this study embryos and larvae of three anuran species, Rana pipiens, Rana clamitans and Rana septentrionalis, were exposed to full-spectrum solar radiation and solar radiation filtered to attenuate UV-B radiation or UV-B and ultraviolet-A (UV-A) (290–380 nm) radiation to determine the effects of each wavelength range on embryo and larval survival. Ambient levels of solar radiation were found to be lethal to all three species under exposure conditions that eliminated shade and refuge. Lethality was ameliorated by filtration of UV-B radiation alone, demonstrating that ambient UV-B radiation is sufficient to cause mortality. Although several studies have qualitatively demonstrated the lethality of UV-B to early life stage amphibians this study demonstrates that the larval life stages of the three species tested are more sensitive than the embryonic stages. This suggests that previous reports that have not included the larval life stage may underestimate the risk posed to some anuran populations by increasing UV-B exposure. Furthermore, this study reports quantitative UV-B dosimetry data, collected in conjunction with the exposures, which can be used to begin the assessment of the impact of environmental changes which increase UV-B exposure of these anurans.

Photoactivated polycyclic aromatic hydrocarbon toxicity in medaka (Oryzias latipes) embryos: Relevance to environmental risk in contaminated sites

The hazard for photoactivated toxicity of polycyclic aromatic hydrocarbons (PAHs) has been clearly demonstrated; however, to our knowledge, the risk in contaminated systems has not been characterized. To address this question, a median lethal dose (LD50) for fluoranthene photoactivated toxicity in medaka (Orvzias latipes) embryos was determined experimentally and then compared with ultraviolet-A (UV-A; 320-400 nm) radiation exposures in a PAH-contaminated field site. The dose metric, J/cm2/ microg fluoranthene/g egg wet weight, provided the means to estimate risk as the depth where the LD50 level would be exceeded at realistic field PAH concentrations, based on estimates of UV-A exposure. The estimates were made using 30 years of solar radiation data for Duluth (MN, USA) and measurements of water-column UV-A transmittance in a PAH-contaminated field site. Medaka embryo failure was strongly related to tissue PAH concentration and UV-A exposure. The LD50 was estimated to be 12.64 J/cm2/ microg fluoranthene/g egg wet weight; the 95% confidence interval was 8.46 to 19.7 J/cm2/microg fluoranthene/g egg wet weight. Embryo failures were characterized by undifferentiated cell proliferation that occurred very early in development. No partial effects or embryo/larval malformations were observed. Estimates of the depth at which the LD50 would be exceeded in the contaminated field site ranged from 10.7 cm (clear-sky conditions and lowest attenuation) to 0.0 cm (cloudy conditions and highest attenuation). Similar calculations were done using water-column attenuation estimates from 12 sites across the Great Lakes (USA). For these, the depths at which the LD50 would be exceeded ranged from 0.00 to 271.6 cm under the conditions described above. These results suggest that PAH phototoxicity may be a risk factor in specific contaminated sites, and they provide a framework for assessing that risk.

Species sensitivity and dependence on exposure conditions impacting the phototoxicity of TiO2 nanoparticles to benthic organisms

Toxicity of titanium dioxide nanoparticles (nano-TiO2 ) to aquatic organisms can be greatly increased after exposure to ultraviolet (UV) radiation. This phenomenon has received some attention for water column species; however, investigations of nano-TiO2 phototoxicity for benthic organisms are still limited. In the present study, bioassays of 3 representative benthic organisms (Hyalella azteca, Lumbriculus variegatus, and Chironomus dilutus) were conducted to evaluate nano-TiO2 phototoxicity. When exposed to 20 mg/L of nano-TiO2 and various light intensities (0-30 W/m(2)), H. azteca was the most sensitive, with a median lethal dose of 40.7 (95% confidence interval, 36.3-44.7) Wh/m(2), and hence is a potential model organism in future toxicological guidelines for photoactive nanomaterials to freshwater benthos. Without the presence of nano-TiO2 , no mortality was observed in L. variegatus and C. dilutus exposed to UV intensity ranging from 0 W/m(2) to 41 W/m(2). However, a sharp drop of H. azteca survival was observed when UV intensity was higher than 9.4 W/m(2), demonstrating the importance of UV-only effects on the ultimate phototoxicity of nanomaterials. Furthermore, both bioavailability and surface attachment of nano-TiO2 onto organisms were affected by the exposure scenario, supported by the exposure scenario-dependent phototoxicity seen in H. azteca and C. dilutus. Overall, the present study demonstrates the importance of species sensitivity and exposure scenarios in future test guidelines of nano-phototoxicity.