Harmon, A.; Hull, M.; Mitrano, D. M.; Ranville, J. F.; and Steevens, J., "Characterization of silver nanoparticles using flow-field flow fractionation interfaced to inductively coupled plasma mass spectrometry" (2010 a b s t r a c tThe 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 g/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 31-46 nm, indicating a significant change in the nanoparticle characteristics during exposure.Published by Elsevier B.V.

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As the production and applications of silver nanoparticles (AgNPs) increase, it is essential to characterize fate and effects in environmental systems. Nanosilver materials may settle from suspension; therefore, the authors' objective was to utilize environmentally relevant bioassays and study the impact, bioaccumulation, tissue distribution, uptake, and depuration of AgNPs on a sediment-dwelling invertebrate, Lumbriculus variegatus. Hydrodynamic diameters of uncoated 30-nm, 80-nm, and 1500-nm AgNP powders and a polyvinyl pyrrolidone (PVP) AgNP suspension were measured utilizing dynamic light scattering in freshwater media (0-280 µS/cm). Aggregation for 30 nm, 80 nm, and 1500 nm silver increased with conductivity but was minimal for PVP silver. Lumbriculus variegatus were exposed to AgNPs or silver nitrate (AgNO3 ) spiked into sediment (nominally 100 mg/kg) and water (PVP 30 nm and 70 nm Ag, nominally 5 mg/L). Uptake was assessed through inductively coupled plasma mass spectroscopy (ICP-MS) and hyperspectral imaging. Particle sizes were examined through field flow fractionation-ICP-MS (FFF-ICP-MS) and ICP-MS in single particle mode (SP-ICP-MS). Lumbriculus variegatus were also depurated for 6 h, 8 h, 24 h, and 48 h to determine gut clearance. Bioaccumulation factors of sediment-exposed L. variegatus were similar regardless of particle size or coatings. The FFF-ICP-MS and SP-ICP-MS detected AgNPs for up to 48 h post depuration. The present study provides information on bioaccumulation and interactions of AgNPs within biological systems.

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.

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.