Impact of carboxymethyl cellulose coating on iron sulphide nanoparticles stability, transport, and mobilization potential of trace metals present in soils and sediment.

The stability and transport behaviour of carboxymethyl cellulose (CMC) stabilized iron sulphide (FeS) engineered nanoparticles (ENPs) as well as their concurrent scavenging and mobilization of trace metal contaminants from field-contaminated soils and sediment was studied through a series of batch and column experiments. The synthesized CMC-FeS ENPs were shown to have a hydrodynamic diameter of 154.5 ± 5.8 nm and remained stable in suspension for a prolonged period of time (several weeks) when kept under anaerobic conditions. In the absence of CMC, much larger FeS particles were formed, which quickly aggregated and precipitated within minutes. Batch experiments indicated that the CMC-FeS ENPs have a high affinity for metal contaminants (e.g., Cd, Cr, Cu, Hg, Ni, Pb, and Zn), as high amounts of these trace metals could be retrieved in the aqueous phase after treatment of the soils with the nanoparticles (i.e., up to 29 times more compared to the water-leachable metal contents). Furthermore, batch retention of the nanoparticles by the solid soil phase was low (<37%), also suggesting a high stability and potential mobility. Nanoparticle treatment of the soils also affected the CaCl2-, TCLP-, and SPLP-leachability of trace metals, although no clear trend could be observed and metal leaching appeared to depend on the specific element under consideration, the type of extraction liquid, as well as on soil properties. Column breakthrough tests demonstrated that the CMC-FeS ENPs were highly mobile in the tested soil, even without the use of an external pressure (i.e., just via gravitational percolation). Maximal breakthrough of the nanoparticles was observed after approximately 10 or 16 pore volumes (PVs) for 83.3 or 500 mg L(-1) CMC-FeS ENPs, respectively, and only about 7% of the nanoparticles were retained by the soil after 22.7 PVs. Simultaneous elution of trace elements showed that up to 19, 8.7, or 11% of the respective Cd, Pb, or Zn content originally present in the soil was extracted after 22.7 PVs, with initial peaking occurring during the first 5 PVs. Moreover, filtration of the percolates over 0.10 µm (which was shown to be able to retain ca. 98% of the CMC-FeS ENPs) indicated that the vast majority of these extracted metals were associated with the nanoparticles and thus did not occur as "dissolved" species. Therefore, the high affinity of CMC-FeS ENPs for metals together with their high stability and mobility, suggests that association of trace metals with the nanoparticles could potentially lead to particle-facilitated contaminant transport in the environment, in case conditions favouring colloidal transport are prevailing.

Stability of engineered nanomaterials in complex aqueous matrices: Settling behaviour of CeO2 nanoparticles in natural surface waters.

The stability of engineered nanoparticles (ENPs) in complex aqueous matrices is a key determinant of their fate and potential toxicity towards the aquatic environment and human health. Metal oxide nanoparticles, such as CeO2 ENPs, are increasingly being incorporated into a wide range of industrial and commercial applications, which will undoubtedly result in their (unintentional) release into the environment. Hereby, the behaviour and fate of CeO2 ENPs could potentially serve as model for other nanoparticles that possess similar characteristics. The present study examined the stability and settling of CeO2 ENPs (7.3±1.4 nm) as well as Ce(3+) ions in 10 distinct natural surface waters during 7d, under stagnant and isothermal experimental conditions. Natural water samples were collected throughout Flanders (Belgium) and were thoroughly characterized. For the majority of the surface waters, a substantial depletion (>95%) of the initially added CeO2 ENPs was observed just below the liquid surface of the water samples after 7d. In all cases, the reduction was considerably higher for CeO2 ENPs than for Ce(3+) ions (<68%). A first-order kinetics model was able to describe the observed time-dependant removal of both CeO2 ENPs (R(2)≥0.998) and Ce(3+) ions (R(2)≥0.812) from the water column, at least in case notable sedimentation occurred over time. Solution-pH appeared to be a prime parameter governing nanoparticle colloidal stability. Moreover, the suspended solids (TSS) content also seemed to be an important factor affecting the settling rate and residual fraction of CeO2 ENPs as well as Ce(3+) ions in natural surface waters. Correlation results also suggest potential association and co-precipitation of CeO2 ENPs with aluminium- and iron-containing natural colloidal material. The CeO2 ENPs remained stable in dispersion in surface water characterized by a low pH, ionic strength (IS), and TSS content, indicating the eventual stability and settling behaviour of the nanoparticles was likely determined by a combination of physicochemical parameters. Finally, ionic release from the nanoparticle surface was also examined and appeared to be negligible in all of the tested natural waters.

Partitioning of Ag and CeO2 nanoparticles versus Ag and Ce ions in soil suspensions and effect of natural organic matter on CeO2 nanoparticles stability.

This study examined the solid-liquid distribution of 14.8-nm Ag and 6.2-nm CeO2 nanoparticles in soil suspensions and compared it to that of Ag+ and Ce3+ ions, to better understand their environmental behaviour and fate. After 24 h incubation, more than 51% or 29% of the spiked amounts of Ag or CeO2 nanoparticles, respectively, can be retrieved in the liquid phase of (re)suspended soils. The Ag or Ce concentration remaining in solution depends on the incubation time and was influenced by soil properties. Significant correlations are obtained between, on the one hand, the relative amounts of Ag or CeO2 nanoparticles in suspension and the soil-pH, CEC, texture, suspended matter, nitrogen, phosphorus, TOC and main and trace elements content on the other hand. The presence of dissolved natural organic matter stabilizes CeO2 nanoparticles in the aqueous phase. In soil suspensions, Ag+ and Ce3+ ions seemingly interact more strongly with soil constituents compared to their nanoparticle counterparts, rendering the Ag and CeO2 nanoparticles to be more stable and potentially bioavailable.

Use of filtration techniques to study environmental fate of engineered metallic nanoparticles: Factors affecting filter performance.

We examined the filtration of aqueous suspensions of negatively charged (citrate-stabilized) Ag (14.5±1.1nm) and positively charged CeO2 (7.3±1.4nm) engineered nanoparticles (ENPs) via different filtration techniques such as paper filtration, micro- and ultrafiltration, and evaluated the impact of initial concentration, matrix composition, and filter type and (pre-)treatment, on nanoparticle retention. Solutions of Ag+ and Ce3+ ions were tested in the same way. Significant retention of nanoparticles was observed even for filters having considerably larger pore sizes than the ENPs size. Retention also seemingly increased with decreasing initial concentration, but generally decreased upon preconditioning of the paper or membrane filters with diluted nitric acid or 0.1M Cu(NO3)2, respectively. In ultrapure water, retention appeared to depend more on particle characteristics than on a membrane type. However, in 2mM KNO3, NaCl, or CaCl2, more significant differences in recovery were observed between different membrane materials. Additionally, background electrolytes might reduce nanoparticle or ionic retention, but could also affect their (colloidal) stability, e.g., resulting in enhanced retention of Ag ENPs and Ag+ ions in chloride-containing matrices. Results from centrifugal ultrafiltration recommend using 10kDa filters for nanoparticle removal from the solution, and suggest these filters might potentially be suitable to differentiate between (nano)particulate and dissolved species.

Impact of water composition on association of Ag and CeO2 nanoparticles with aquatic macrophyte Elodea canadensis.

In this study, the potential association of (citrate-stabilized) Ag (14.1 ± 1.0 nm) and CeO2 (6.7 ± 1.2 nm) engineered nanoparticles (ENPs), or their ionic counterparts, with the submerged aquatic plant Elodea canadensis, was examined and, in particular, parameters affecting the distribution of the nanoparticles (or metal ions) between plant biomass and the water phase were assessed using five distinct aqueous matrices (i.e. tap water, 10 % Hoagland's solution and three natural surface water samples). Individual plants were exposed to varying concentrations of Ag and CeO2 ENPs or Ag(+) and Ce(3+) ions during 72-h-lasting batch experiments. A dose-dependent increase of silver or cerium in plant biomass was observed for both the nanoparticles and the ions, whereby exposure to the latter systematically resulted in significantly higher biomass concentrations. Furthermore, the apparent plant uptake of CeO2 ENPs appeared to be higher than that for Ag ENPs when comparing similar exposure concentrations. These findings suggest that association with E. canadensis might be affected by particle characteristics such as size, composition, surface charge or surface coating. Moreover, the stability of the ENPs or ions in suspension/solution may be another important aspect affecting plant exposure and uptake. The association of the nanoparticles or ions with E. canadensis was affected by the physicochemical characteristics of the water sample. The silver biomass concentration was found to correlate significantly with the electrical conductivity (EC), dry residue (DR) and Cl(-), K, Na and Mg content in the case of Ag ENPs or with the EC, inorganic carbon (IC) and Cl(-), NO3 (-), Na and Mg content in the case of Ag(+) ions, whereas significant relationships between the cerium biomass concentration and the EC, DR, IC and Ca content or the pH, EC, DR, IC and Cl(-), Ca and Mg content were obtained for CeO2 ENPs or Ce(3+) ions, respectively. Results also indicated that the Ag ENPs and Ag(+) ions might potentially be toxic towards E. canadensis whereas no evidence of phytotoxicity was noted in the case of CeO2 ENPs or Ce(3+) ions.