The influence of competing, similarly charged, inorganic ions on the size and charge behavior of suspended titanium-dioxide (nTiO(2)), silver (nAg) and fullerene (nC(60)) nanoparticles (NPs) was investigated. Under pH and ionic conditions similar to natural water bodies, Ca(2+) induced aggregation of nTiO(2) and nAg NPs more strongly than K(+) and Na(+). Although K(+) and Na(+) had a similar effect on aggregation, K(+) provided better screening of the particle surface charge presumably because of its small hydrated radius. These effects were decidedly more prominent for TiO(2) than Ag. Anions (co-ions), SO(4)(2-) and Cl(-), affected the surface charge behavior of nTiO(2) but not of nAg NPs. The zeta potential (ZP) of nTiO(2) NPs was more negative at higher SO(4)(2-)/Cl(-) ratios than lower. When Mg(2+) was the counterion, charge inversion and rapid aggregation of nC(60) NPs occurred under alkaline conditions, with a more pronounced effect for Cl(-) than SO(4)(2-). Response dissimilarities suggest fundamental differences in the interfacial-interaction characteristics of these NPs in the aquatic environment with corresponding differences in transport of these particles. Our study also shows the important role played by the iso-electric point pH (pH(iep)) of the NPs in determining their aggregation kinetics in the environment.
In this study, we investigated the influence of inorganic ions on the aggregation and deposition (adsorption) behavior of human adenovirus (HAdV). Experiments were conducted to determine the surface charge and size of HAdV and viral adsorption capacity of sand in different salt conditions. The interfacial potential energy was calculated using extended Derjaguin and Landau, Verwey and Overbeek (XDLVO) and steric hindrance theories to interpret the experimental results. Results showed that different compositions of inorganic ions have minimal effect on varying the iso-electric point pH (pH(iep)) of HAdV (ranging from 3.5 to 4.0). Divalent cations neutralized/shielded virus surface charge much more effectively than monovalent cations at pH above pH(iep). Consequently, at neutral pH the presence of divalent cations enhanced the aggregation of HAdV as well as its adsorption to sand. Aggregation and adsorption behaviors generally agreed with XDLVO theory; however, in the case of minimal electrostatic repulsion, steric force by virus' fibers can increase the energy barrier and distance of secondary minimum, resulting in limited aggregation and deposition. Overall, our results indicated that subsurface water with low hardness residing in sandy soils may have a higher potential of being contaminated by HAdV.
Effects of natural organic matter (NOM) on the photoreaction kinetics of fullerenes (i.e., C60 and fullerenol) were investigated using simulated sunlight and monochromatic radiation (365 nm). NOM from several sources quenched (slowed) the photoreaction of C60 aggregates in water (aqu/nC60), but sensitized (accelerated) photoreaction of fullerenol. Kinetic studies indicated that the quenching occurred through a static mechanism involving NOM molecules adsorbed on the aqu/nC60 surface. Quenching constants for the photoreaction of aqu/nC60 correlated approximately with optical parameters related to the aromaticity and molecular size of the NOM. Association of aqu/nC60 particles with NOM was investigated indirectly via the study of the aggregation kinetics of colloidal C60 in the presence and absence of NOM as a function of NaCl strength at pH 7. In contrast to aqu/nC60, the photoreaction efficiencies of the hydrophilic fullerene, fullerenol, increased linearly with increasing NOM concentrations and kinetic parameters for the sensitized photoreactions increased as the spectral slope coefficients and ratio of absorption coefficients at 254 to 365 nm (E2:E3) of the NOM increased. The results indicate that triplet excited states of the NOM are key intermediates in the photosensitized reactions.
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