Carbon nanotubes (NTs) may be among the most useful engineered nanomaterials for structural applications but could be difficult to study in ecotoxicological evaluations using existing tools relative to nanomaterials with a lower aspect ratio. Whereas the hydrophobicity and van der Waals interactions of NTs may suggest aggregation and sedimentation in aquatic systems, consideration regarding how engineered surface modifications influence their environmental fate and toxicology is needed. Surface modifications (e.g., functional groups and coatings) are intended to create conditions to make NTs dispersible in aqueous suspension, as required for some applications. In the present study, column stability and settling experiments indicated that raw, multiwalled NTs (MWNTs) settled more rapidly than carbon black and activated carbon particles, suggesting sediment as the ultimate repository. The presence of functional groups, however, slowed the settling of MWNTs (increasing order of stability: hydroxyl > carboxyl > raw), especially in combination with natural organic matter (NOM). Stabilized MWNTs in high concentrations of NOM provided relevance for water transport and toxicity studies. Aqueous exposures to raw MWNTs decreased Ceriodaphnia dubia viability, but such effects were not observed during exposure to functionalized MWNTs (> 80 mg/L). Sediment exposures of the amphipods Leptocheirus plumulosus and Hyalella azteca to different sizes of sediment-borne carbon particles at high concentration indicated mortality increased as particle size decreased, although raw MWNTs induced lower mortality (median lethal concentration [LC50], 50 to >264 g/kg) than carbon black (LC50, 18-40 g/kg) and activated carbon (LC50, 12-29 g/kg). Our findings stress that it may be inappropriate to classify all NTs into one category in terms of their environmental regulation.
This investigation applied novel techniques for characterizing and fractionating nanosilver particles and aggregates and relating these measurements to toxicological endpoints. The acute toxicity of eight nanosilver suspensions of varying primary particle sizes (10-80 nm) and coatings (citrate, polyvinylpyrrolidone, EDTA, proprietary) was assessed using three aquatic test organisms (Daphnia magna, Pimephales promelas, Pseudokirchneriella subcapitata). When 48-h lethal median concentrations (LC50) were expressed as total silver, both D. magna and P. promelas were significantly more sensitive to ionic silver (Ag(+)) as AgNO(3) (mean LC50 = 1.2 and 6.3 μg/L, respectively) relative to a wide range in LC50 values determined for the nanosilver suspensions (2 -126 μg/L). However, when LC50 values for nanosilver suspensions were expressed as fractionated nanosilver (Ag(+) and/or <4 nm particles), determined by ultracentrifugation of particles and confirmed field-flow-fractograms, the LC50 values (0.3-5.6 μg/L) were comparable to the values obtained for ionic Ag(+) as AgNO(3). These results suggest that dissolved Ag(+) plays a critical role in acute toxicity and underscores the importance of characterizing dissolved fractions in nanometal suspensions.
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