Coupled effects of hydrodynamics and biogeochemistry on Zn mobility and speciation in highly contaminated sediments.

Porewater transport and diagenetic reactions strongly regulate the mobility of metals in sediments. We executed a series of laboratory experiments in Gust chamber mesocosms to study the effects of hydrodynamics and biogeochemical transformations on the mobility and speciation of Zn in contaminated sediments from Lake DePue, IL. X-ray absorption spectroscopy (XAS) indicated that the oxidation of surficial sediments promoted the formation of more mobile Zn species. Bulk chemical measurements of porewater, overlying water, and sediment also suggested that this process liberated aqueous metals to porewater and facilitated Zn efflux to the overlying water. In addition, sediment resuspension events increased the release of aqueous metals to both surficial porewater and the overlying water column. XAS analysis indicated that resuspension increased dissolution of Zn-sequestering mineral phases. These results show that both steady slow porewater transport and rapid episodic resuspension are important to the release of metal from fine-grained, low-permeability contaminated sediments. Thus, information on metals speciation and mobility under time-varying overlying flow conditions is essential to understanding the long-term behavior of metals in contaminated sediments.

Influence of monovalent ions on density fluctuations in hydrothermal aqueous solutions by small angle X-ray scattering.

Synchrotron small angle X-ray scattering measurements on water and alkaline bromine aqueous solutions (XBr, with X = Li, Rb, or Cs) were carried out from ambient to supercritical conditions. The temperature was increased from 300 to 750 K along several isobars between 24 and 35 MPa. The correlation length and the structure factor were extracted from the data following the Ornstein-Zernike formalism. We obtained experimental evidence of the shift of the critical point and isochore and their dependence on the ions concentration (0.33 mol/kg and 1.0 mol/kg). We also observed that the size of the density fluctuations and the structure factor increase with the presence of the ions and that this effect is positively correlated with the atomic number of the cation. These behaviors were compared with ZnBr(2) and NaCl systems from the literature.