Rapid settling of nanoparticles due to heteroaggregation with suspended sediment.

Sedimentation of engineered nanoparticles (ENPs) has been studied mainly in artificial media and stagnant systems mimicking natural waters. This neglects the role of turbulence and heteroaggregation with sediment. The authors studied the apparent sedimentation rates of selected ENPs (cerium dioxide [CeO2 ], polyvinylpyrrolidone-capped silver [PVP-Ag], and silica-coated silver [SiO2 -Ag]) in agitated sediment-water systems resembling fresh, estuarine, and marine waters. Experiments were designed to mimic low energy and periodically resuspended sediment water systems (14 d), followed by a long-term aging, resuspension, and settling phase (6 months), as would occur in receiving shallow lakes. The ENPs in systems with periodical resuspension of sediment were removed with sedimentation rates between 0.14 m/d and 0.50 m/d. The sedimentation rates did not vary much among ENP type, salinity, and aging time, which is attributed to the capture of ENPs in sediment flocks. The sedimentation rates were 1 to 2 orders of magnitude higher than those reported for aggregation-sedimentation in stagnant systems without suspended sediment. Heteroaggregation rates were estimated and ranged between 0.151 L/mg/d and 0.547 L/mg/d, which is up to 29 times higher than those reported for natural colloids under quiescent settling conditions. The authors conclude that rapid scavenging and sedimentation drives removal of ENPs from the water column.

Estimation of in situ sediment-to-water fluxes of polycyclic aromatic hydrocarbons, polychlorobiphenyls and polybrominated diphenylethers.

Sediment-water fluxes of hydrophobic organic chemicals (HOC) may affect the quality of surface waters. Here, we present an approach to derive such fluxes from (a) in situ HOC concentration gradients measured with passive samplers and (b) mass transfer coefficients measured with a novel flux method using Empore disks. For eight undisturbed sediments, this method identified whether the sediment acted as a source or as a sink for HOCs. The analysis also identified which type of transport resistance governed sediment water exchange. For seven inland locations, exchange was limited by benthic boundary layer transport, showing no dependencies on sediment or chemical properties other than concentration. For one river mouth location, exchange was limited by slow in-bed intraparticle diffusion. A biphasic dual compartment radial diffusion model adequately described the data for this location. Fast desorption was interpreted as molecular diffusion retarded by microscale dual domain sorption to amorphous as well as black carbon (BC). Slow desorption was invariant with LogK(ow) and consistent with intraorganic matter diffusion through BC particles. Finally, it is discussed how these findings can be translated into a general framework for flux based exposure assessment.

Aquatic ecotoxicity tests of some nanomaterials.

Nanoparticles of TiO2, ZrO2, AL2O3, CeO2, fullerene (C60), single-walled carbon nanotubes, and polymethylmethacrylate were tested for ecotoxic effects using one or more ecotoxicity endpoints: Microtox (bacteria), pulse-amplitude modulation (algae), Chydotox (crustaceans), and Biolog (soil enzymes). No appreciable effects were observed at nominal concentrations of up to 100 mg/L. Dilution of nanoparticle suspensions, either in ultrapure (Milli-Q) water or in natural (pond) water, led to formation of larger particles, which settled easily. (Nano)particles in water were characterized by means of atomic force microscopy, energy-dispersive x-ray analysis, inductively coupled plasma-mass spectrometry, flow cytometry, and spectrophotometry. It is concluded that the absence of ecotoxicity is the result of low concentrations of free nanoparticles in the tests, and it is suggested that colloid (in)stability is of primary importance in explaining ecotoxic effects of nanoparticles in the natural environment.