Aggregation of nanoscale iron oxyhydroxides and corresponding effects on metal uptake, retention, and speciation: I. Ionic-strength and pH

作者：Dale J G; Stegemeier J P; Kim C S^*

来源：Geochimica et Cosmochimica Acta, 2015, 148: 100-112.

DOI：10.1016/j.gca.2014.08.029

The capacity of nanosized particles to adsorb and sequester dissolved metals can be significantly impacted by the mechanism and extent of aggregation the particles have undergone, which in turn can affect the long-term fate and transport of potentially toxic metals in natural aqueous systems. Suspensions of monodisperse nanoscale iron oxyhydroxides were synthesized and subjected to increased pH (pH 8.0, 10.0) or ionic strength (0.1, 1.0 M NaNO3) conditions to induce various states of aggregation prior to conducting macroscopic adsorption/desorption experiments with dissolved Cu(II) or Zn(II). The metal adsorption and retention capacities of the nanoparticle aggregates were compared to one another and to non-aggregated control nanoparticles, while the mode(s) of metal sorption to the nanoparticle surfaces were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy analysis.
With increasing aggregation by both pH and ionic strength, the proportion of introduced zinc adsorbed to the iron oxyhydroxide nanoparticles progressively decreased from 45% on the monodispersed control particles to as low as 16% on the aggregates, while the proportion of introduced zinc retained upon desorption (obtained by lowering the suspension pH) increased from 7% on the control particles to as much as 17% on the aggregated particles. Copper exhibited a subtler trend of only slightly declining uptake (from 43% to 36%) and retention (from 35% to 30%) with increasing aggregation state. EXAFS analysis was consistent with the macroscopic results, showing relatively little change in Cu speciation between samples analyzed before and after the desorption step but significant increases in Zn-Fe interatomic distances and coordination numbers after desorption. This suggests the presence of both strongly- and weakly-bound zinc ions; the latter are likely affiliated with less stable, more distorted surface sorption sites and are thus more readily desorbed, resulting in the retention of zinc that is bound to more stable, less-distorted sorption sites. For both metals, inner-sphere bidentate sorption appears to dominate the sorption process to the nanoparticle aggregates, with potential structural incorporation into the aggregates themselves.

• 出版日期2015-1-1