Single-Element and Competitive Metal Mobility Measured with Column Infiltration and Batch Tests

The distribution coefficient, K-d, is often used to quantify heavy metal mobility in soils. Batch sorption or column infiltration tests may be used to measure K-d. The latter are closer to natural soil conditions, but are difficult to conduct in clays. This difficulty can be overcome by using a laboratory centrifuge. An acceleration of 2600 gravities was applied to columns of London Clay, an Eocene clay sub-stratum, and Cu, Ni, and Zn mobility was measured in centrifuge infiltration tests, both as single elements and in dual competition. Single-element K-d values were also obtained from batch sorption tests, and the results from the two techniques were compared. It was found that K-d values obtained by batch tests vary considerably depending on the metal concentration, while infiltration tests provided a single K-d value for each metal. This was typically in the lower end of the range of the batch test K-d values. For both tests, the order of mobility was Ni > Zn > Cu. Metals became more mobile in competition than when in single-element systems: Ni K-d decreased 3.3 times and Zn K-d 3.4 times when they competed with Cu, while Cu decreased only 1.2 times when in competition with either Ni or Zn. Our study showed that competitive sorption between metals increases the mobility of those metals less strongly bound more than it increases the mobility of more strongly bound metals.

Nonharmonic transverse vibration of the H-bonded molecules and the THz spectra in ice and water

A nonlinear equation of motion is found for the dimer comprising two charged H2O molecules. The THz dielectric response to nonharmonic vibration of a nonrigid dipole, forming the hydrogen bond (HB), is found in the direction transverse to this bond. An explicit expression is derived for the autocorrelator that governs the spectrum generated by transverse vibration (TV) of such a dipole. This expression is obtained by analytical solution of the truncated set of recurrence equations. The far infrared (FIR) spectra of ice at the temperature - 7 degrees C are calculated. The wideband, in the wavenumber (frequency) v range 0... 100.0 cm(-1), spectra are obtained for liquid water at room temperature and for supercooled water at -5.6 degrees C. All spectra are represented in terms of the complex permittivity epsilon(v) and the absorption coefficient alpha(v). The obtained analytical formula for epsilon comprises the term epsilon(perpendicular to) pertinent to the studied TV mechanism with three additional terms Delta epsilon(q), Delta epsilon(mu), and epsilon(or) arising, respectively, from: elastic harmonic vibration of charged molecules along the H-bond; elastic reorientation of HB permanent dipoles; and rather free libration of permanent dipoles in 'defects' of water/ice structure. The suggested TV-dielectric relaxation mechanism allows us: (a) to remove the THz 'deficit' of loss epsilon" inherent in previous theoretical studies; (b) to explain the THz loss and absorption spectra in supercooled (SC) water; and (c) to describe, in agreement with the experiment, the low- and high-frequency tails of the two bands of ice H2O located in the range 10...300 cm(-1). Specific THz dielectric properties of SC water are ascribed to association of water molecules, revealed in our study by transverse vibration of HB charged molecules. (C) 2006 Published by Elsevier B.V.