Ashley R. Harmon

Characterization of silver nanoparticles using flow-field flow fractionation interfaced to inductively coupled plasma mass spectrometry

The ability to detect and identify the physiochemical form of contaminants in the environment is important for degradation, fate and transport, and toxicity studies. This is particularly true of nanomaterials that exist as discrete particles rather than dissolved or sorbed contaminant molecules in the environment. Nanoparticles will tend to agglomerate or dissolve, based on solution chemistry, which will drastically affect their environmental properties. The current study investigates the use of field flow fractionation (FFF) interfaced to inductively coupled plasma-mass spectrometry (ICP-MS) as a sensitive and selective method for detection and characterization of silver nanoparticles. Transmission electron microscopy (TEM) is used to verify the morphology and primary particle size and size distribution of precisely engineered silver nanoparticles. Subsequently, the hydrodynamic size measurements by FFF are compared to dynamic light scattering (DLS) to verify the accuracy of the size determination. Additionally, the sensitivity of the ICP-MS detector is demonstrated by fractionation of μg/L concentrations of mixed silver nanoparticle standards. The technique has been applied to nanoparticle suspensions prior to use in toxicity studies, and post-exposure biological tissue analysis. Silver nanoparticles extracted from tissues of the sediment-dwelling, freshwater oligochaete Lumbriculus variegatus increased in size from approximately 31-46nm, indicating a significant change in the nanoparticle characteristics during exposure.

Tiered guidance for risk-informed environmental health and safety testing of nanotechnologies

Provided the rapid emergence of novel technologies containing engineered nanomaterials, there is a need to better understand the potential environmental, health, and safety effects of nanotechnologies before wide-scale deployment. However, the unique properties of nanomaterials and uncertainty regarding applicable test methods have led to a lack of consensus regarding the collection and evaluation of data related to hazard and exposure potentials. Often, overly conservative approaches to characterization and data collection result in prolonged, unfocused, or irrelevant testing, which increases costs and delays deployment. In this paper, we provide a novel testing guidance framework for determining whether a nanotechnology has the potential to release material with nano-specific parameters that pose a risk to humans or the environment. The framework considers methods to categorize nanotechnologies by their structure and within their relevant-use scenarios to inform testing in a time- and resource-limited reality. Based on the precedent of dredged sediment testing, a five-tiered approach is proposed in which opportunities are presented to conclude testing once sufficient risk-related information has been collected, or that the technology in question does not require nano-specific scrutiny. A series of screening stages are suggested, covering relevant aspects including size, surface area, distribution, unique behaviors, and release potential. The tiered, adaptive guidance approach allows users to concentrate on collecting the most relevant data, thus accelerating technology deployment while minimizing risk.

Determination of nanosilver dissolution kinetics and toxicity in an environmentally relevant aqueous medium.

Assessing the dissolution of silver nanoparticles (AgNPs) in laboratory test media and in the aquatic environment is critical for determining toxicity. In the present study, the ion-release kinetics for 20-nm, 50-nm, and 80-nm AgNPs in environmentally relevant freshwaters with different electrical conductivity values (30 µS/cm, 150 µS/cm) were examined and related to the associated impact on Daphnia magna. The acute toxicity of the AgNP suspensions to D. magna was assessed after 0 d and 7 d of interaction time between the particles and test media. When 48-h lethal median concentrations were expressed as total silver, D. magna was more sensitive to AgNPs suspended in low ionic strength media relative to higher ionic strength media, with the exception of 50-nm AgNPs suspended in the 150-µS/cm medium. A 3.3-fold increase in hydrodynamic diameter measured by dynamic light scattering and field flow fractionation was observed over time for 20-nm particles in the 150-µS/cm medium, but only a small increase in aggregation size for 50-nm and 80-nm particles (1.4-fold and 1.2-fold increase, respectively) was observed. At a lower conductivity of 30 µS/cm, a 1.7-fold, 1.0-fold, and 1.2-fold increase in aggregation size was observed in the 20-nm, 50-nm, and 80-nm particles, respectively. Thus, the impact of higher conductivity test media on increased aggregation and decreased toxicity (after 7 d) was relatively greater for the smaller (20-nm) AgNP higher compared to the 50-80 nm AgNPs.

Nano-Aluminum Thermite Formulations: Characterizing the Fate Properties of a Nanotechnology during Use

Nano-Aluminum Thermite Formulations: Characterizing the Fate Properties of a Nanotechnology during Use Nanothermites represent an emerging class of highly efficient propellants/explosive materials whose environmental impacts are poorly understood. In this work, several nanothermite formulations (e.g., Fe2O3/Al and Bi2O3/Al) were investigated following material transformation during end use. Combustion products were analyzed by SEM, EDS, and XRD. These products subsist with unique physical and chemical forms as compared to the original materials. The combustion process results in the formation of inert spinel structures in the case of the iron-based formulations, whereas Bi2O3/Al composites react fully, transforming to metallic bismuth and aluminum oxide. These products are largely resistant to wetting and evidence suggests that transport in aqueous environments would be limited. Due to the particle size ranges found, it is speculated that the main transport route for these materials is aerosolization. These data will ultimately establish a baseline for future studies aimed at an accurate determination of the fate of nanothermite formulations after use.

Accumulation of 2,4‐dinitroanisole in the earthworm Eisenia fetida from chemically spiked and aged natural soils

An initiative within the US military is targeting the replacement of traditional munitions constituents with insensitive munitions to reduce the risk of accidental detonation. The bioavailability and bioaccumulative potential of the insensitive munitions compound 2,4-dinitroanisole (DNAN) to Eisenia fetida was assessed in soils with different geochemical characteristics. Prior to exposure, soils were chemically spiked with DNAN and aged for 1 wk or 29 wk. Transformation products 2- and 4-amino-nitroanisole (2A-4NAN and 4A-2NAN) occurred in aged soils and their porewater but never at concentrations higher than the residual DNAN. The sum of DNAN, 2A-4NAN, and 4A-2NAN (sumDNAN) in soil decreased with aging, likely by irreversible binding. Both clay and organic matter contents of the soil appeared to affect the bioavailability of DNAN. The sumDNAN body residues of earthworms approached apparent steady state after 1 d and remained relatively constant through to day 7. Higher concentrations of 2A-4NAN and 4A-2NAN measured in worm tissues relative to those in soil suggest reductive transformation of DNAN in the tissues. Mean bioaccumulation factors (ratio of tissue to soil concentrations) varied from 1.2 to 4.3, whereas mean bioconcentration factors (ratio of tissue to porewater concentrations) ranged from 1.4 to 3.2. Porewater seems to play a significant role in the accumulation of DNAN in earthworms, consistent with equilibrium partitioning theory. The concentration of DNAN in soil porewater could serve as an indicator of bioavailability as well as a predictor of the concentration of that compound in earthworms. Environ Toxicol Chem 2016;35:1835-1842. Publlished 2015 SETAC. This article is a US Government work, and as such, is in the public domain in the United States of America.

Assessing nanomaterial exposures in aquatic ecotoxicological testing: Framework and case studies based on dispersion and dissolution

Abstract The unique behavior of engineered nanomaterials (ENM) in aqueous media and dynamic changes in particle settling, agglomeration and dissolution rates is a challenge to the consistency, reliability and interpretation of standard aquatic hazard bioassay results. While the toxicological endpoints (e.g., survival, growth, reproduction, etc.) in ecotoxicity bioassays are largely applicable to ENMs, the standard methods as written for dissolved substances are confounded by the dynamic settling, agglomeration and dissolution of particulate ENMs during the bioassay. A testing framework was designed to serve as a starting point to identify approaches for the consistent conduct of aquatic hazard tests that account for the behavior of ENMs in test media and suitable data collection to support representative exposure metrology. The framework was demonstrated by conducting three case studies testing ENMs with functionally distinct characteristics and behaviors. Pretests with a temporal sampling of particle concentration, agglomeration and dissolution were conducted on each ENM in test media. Results indicated that a silver nanoparticle (AgNP) powder was not dispersible, a nano-TiO2 powder was dispersible but unstable, and a polyvinylpyrrolidinone-coated AgNP was relatively stable in test media. Based on these functional results, Ceriodaphnia dubia bioassays were conducted to compare different exposure summary methods (nominal, arithmetic average, geometric average, time-weighted average) for calculating and expressing toxicity endpoints. Results indicated that while arithmetic means were effective for expressing the toxicity of more stable materials, time-weighted averaged concentrations were appropriate for the unstable nano-TiO2.

Comparison of acute to chronic ratios between silver and gold nanoparticles, using Ceriodaphnia dubia

Abstract As integration of nanoparticles (NPs) into products becomes more common, the need to address the paucity of chronic hazard information for aquatic environments required to determine risk potential increases. This study generated acute and chronic toxicity reference values for Ceriodaphnia dubia exposed to 20 and 100 nm silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) to generate and evaluate potential differences in acute-to-chronic ratios (ACR) using two different feeding methods. A modified feeding procedure was employed alongside the standard procedures to investigate the influence of food on organism exposure. An 8-h period before food was added allowed direct organism exposure to NP dispersions (and associated ions) without food-to-NP interactions. The AgNPs [chronic lethal median concentrations (LC50) between 18.7 and 31.9 µg/L] were substantially more toxic than AuNPs (LC50 = 21 507 to >26 384 µg/L). The modified chronic testing method resulted in greater sensitivity in AgNPs exposures. However, the modified feeding ration had less of an effect in exposures to the larger (100 nm) AgNPs compared to smaller particles (20 nm). The ACRs for AgNPs using the standard feeding ration were 1.6 and 3.5 for 20 nm and 100 nm, respectively. The ACRs for AgNPs using the modified feeding ration were 3.4 and 7.6 for 20 nm and 100 nm NPs, respectively. This supports that the addition of the standard feeding ration decreases C. dubia chronic sensitivity to AgNPs, although it must also be recognized organisms may be sensitized due to less access to food. The ACRs for 20 nm and 100 nm AuNPs (standard ration only) were 4.0 and 3.0, respectively. It is important to also consider that dissolved Ag+ ions are more toxic than AgNPs, based on both acute toxicity values in the cited literature and chronic toxicity thresholds generated in this study that support existing thresholds that Ag+ are likely protective of AgNPs effects.

Life stage sensitivity of the marine mussel Mytilus edulis to ammonia

Ammonia is an important contaminant to consider in all toxicity tests. It is especially important to consider the impacts of ammonia in test methods that use sensitive water column organisms exposed to sediments or sediment extracts, such as porewater and elutriate toxicity tests. Embryo-larval development toxicity tests, such as the 48-h method using Mytilus mussel species, are particularly sensitive to ammonia. To better understand the effect thresholds across different life stages of these mussels, 6 short-term (48-h) development toxicity tests and 3 21-d toxicity tests with different-sized juvenile mussels were conducted. Two of the juvenile mussel tests involved 21-d continuous chronic exposure to ammonia, whereas the third involved an acute 2-d ammonia exposure, followed by a 19-d recovery period. The embryo-larval development test method (50% effect concentration [EC50] = 0.14-0.18 mg/L un-ionized ammonia) was 2.5 times more sensitive than the juvenile mussel 21-d survival endpoint (50% lethal concentration = 0.39 mg/L un-ionized ammonia) and 2 times more sensitive than the most sensitive sublethal juvenile mussel endpoint (EC50 = 0.26 mg/L un-ionized ammonia). Further, it was found that the juveniles recovered from a 48-h exposure to un-ionized ammonia of up to 1.1 mg/L. The data generated suggest that the embryo development endpoint was sufficiently sensitive to un-ionized ammonia to protect the chronically exposed (21 d) juvenile mussels. Environ Toxicol Chem 2017;36:89-95. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.