Adsorption of hydrogen fluoride (HF) onto amorphous solid water films at 50 K is reported to yield a strong absorbance continuum in their reflection-absorption infrared spectra (RAIRS). This and other complex features observed in the RAIRS spectra of stratified binary composite HF:H(2)O nanoscopic films deposited onto Pt(111) are interpreted quantitatively using a classical optics model. Comparison with experimental data allows us to determine that the absorbance continuum is due to absorption within the film (as opposed to trivial optical effects) and that the extent of intermixing and uptake is mostly limited to the first few molecular layers. Furthermore, extensive isotope scrambling is demonstrated by the observation of similar Zundel continua upon codeposition of neat HF, or DF, and H(2)O vapors onto Pt(111) at 50 K. These observations are consistent with those expected from extensive ionic dissociation of HF upon dissolution within, and adsorption onto, ASW at 50 K.
Environmental context
The number of nano-enabled products reaching consumers is growing exponentially, inevitably resulting in their release to the environment. The environmental fate and mobility of nanomaterials will depend on their physicochemical form(s) under natural conditions. For ZnO nanoparticles, determinations of agglomeration and dissolution under environmentally relevant conditions of pH, ionic strength and natural organic matter content will provide insight into the potential environmental risk of these novel products.
Abstract
The increasing use of engineered nanoparticles (ENPs) in industrial and household applications has led to their release into the environment and increasing concern about their effects. Proper assessment of the ecological risks of ENPs will require data on their bioavailability, persistence and mobility over a broad range of physicochemical conditions, including environmentally relevant pH, ionic strength and concentrations of natural organic matter (NOM). In this study, fluorescence correlation spectroscopy was used to determine the agglomeration of a ZnO ENP (nZnO) with a nominal size of 20nm. Particle dissolution was followed using scanned stripping chronopotentiometry. The effects of Suwannee River fulvic acid (SRFA, 0–60mgL–1) and the roles of pH (4–10) and ionic strength (0.005–0.1M) were carefully evaluated. Agglomeration of the bare nZnO increased for pH values near the zero point of charge, whereas the dissolution of the particles decreased. At any given pH, an increase in ionic strength generally resulted in a less stable colloidal system. The role of SRFA was highly dependent upon its concentration with increased agglomeration observed at low SRFA : nZnO mass ratios and decreased agglomeration observed at higher SRFA : nZnO mass ratios. The results indicated that in natural systems, both nZnO dispersion and dissolution will be important and highly dependent upon the precise conditions of pH and ionic strength.
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