The influence of biofilms on the mobility of bare and capped zinc oxide nanoparticles in saturated sand and glass beads.

Biofilms are a common constituent of the subsurface and are known to influence contaminant transport; however only a few studies to date have addressed microbial controls on nanoparticle mobility in porous media. The impact of a 3-day Pantoea agglomerans biofilm on the mobility of zinc oxide (ZnO) nanoparticles was studied in column experiments containing sand and glass beads at near-neutral pH and constant ionic strength. Bare ZnO nanoparticles (bZnO-NPs) and ZnO nanoparticles capped with tri-aminopropyltriethoxysilane (cZnO-NPs) were used in the experiments. Breakthrough curves demonstrate that the biofilm particularly slowed nanoparticle migration of bZnO-NPs in glass bead columns and cZnO-NPs in sand columns. With the exception of bZnO-NPs in sand columns, biofilm-coated porous media retained more nanoparticles than those of controls without biofilm. The biofilm may bear an impact on the surface charge of the porous medium, nullifying porous medium-specific effects. Although viable cell counts (VCCs) decreased after the introduction of electrolyte and before nanoparticle transport experiments, SEM and CLSM imaging of porous medium samples taken from columns after nanoparticle transport experiments, as well as total organic carbon (TOC) measurements reveal that biofilm was present in the columns throughout the experiments. Hence, it can be concluded that even a thin amount of biofilm can hinder nanoparticle migration in small-scale porous medium experiments. Moreover, nanoparticle mobility is dependent on the binding capacity of biofilms, rather than the type of porous media.

Transport of bare and capped zinc oxide nanoparticles is dependent on porous medium composition.

Zinc oxide (ZnO) nanoparticles are one of the most frequently used nanoparticles in industry and hence are likely to be introduced to the groundwater environment. The mobility of these nanoparticles in different aquifer materials has not been assessed. While some studies have been published on the transport of ZnO nanoparticles in individual porous media, these studies do not generally account for varying porous medium composition both within and between aquifers. As a first step towards understanding the impact of this variability, this paper compares the transport of bare ZnO nanoparticles (bZnO-NPs) and capped ZnO nanoparticles, coated with tri-aminopropyltriethoxysilane (cZnO-NPs), in saturated columns packed with glass beads, fine grained sand and fine grained calcite, at near-neutral pH and groundwater salinity levels. With the exception of cZnO-NPs in sand columns, ZnO nanoparticles are highly immobile in all three types of studied porous media, with most retention taking place near the column inlet. Results are in general agreement with DLVO theory, and the deviation in experiments with cZnO-NPs flowing through columns packed with sand is linked to variability in zeta potential of the capped nanoparticles and sand grains. Therefore, differences in surface charge of nanoparticles and porous media are demonstrated to be key drivers in nanoparticle transport.

Quantum chemical modeling of electrochromism of tungsten oxide films.

A cluster model is proposed to describe the excitations in solid tungsten oxide. The density-functional theory approach is used to calculate the ground-state electronic structure of the model cluster and its optimum geometry; subsequently, time-dependent density-functional theory calculations are performed to obtain the oscillator strengths and energies of the excited states. The results are reported both for the electrically neutral cluster and for the cluster with an extra electron (mimicking the effect of electron injection from the cathode). They correctly locate the electrochemically active transition. The corresponding wave functions are delocalized, suggesting that electron localization at one tungsten center is rather unlikely, thereby shedding doubt as to the validity of the polaron model. Local lattice distortions presumably created at the stage of sample preparation are found to affect the excitation energies to a considerable extent, which explains the experimentally observable large width of optical absorption responsible for electrochromism.