THE CATALYTIC EFFECT OF SODIUM AND LITHIUM IONS ON COUPLED SORPTION-REDUCTION OF CHROMATE AT THE BIOTITE EDGE-FLUID INTERFACE

Abstract

Large single crystals of biotite and near-endmember phlogopite were reacted with aqueous solutions bearing 20 μM Cr(VI) and different concentrations of NaCl, LiCl, RbCl, CsCl, NaClO4, and Na2SO4. Solutions were maintained at 25 +/- 0.5°C, 1 atm, and pH = 4.00 +/- 0.02. Samples were extracted from the reaction chamber at 1, 3, 5, 10, and 20 h. The edges and basal planes of the reacted micas were analyzed by X-ray photoelectron spectroscopy (XPS) for major elements and Cr. XPS analyses of biotite show trivalent chromium on edge surfaces but no detectable chromium on the basal plane. XPS analyses of near-endmember phlogopites that were reacted in the same experiments as biotite showed no detectable Cr on either the basal plane or edge surfaces. Increasing Na and Li salt concentrations increased the rate of coupled sorption-reduction of chromate at the biotite edge-fluid interface, where the order of effectiveness was NaCl # NaClO4 > Na2SO4 > LiCl. In contrast, no Cr was detected on mica edges after reaction in RbCl and CsCl solutions. Comparison of equimolar NaCl and LiCl experiments indicate that the active agent is Na and Li, not ionic strength or the anion. Sulfate tends to block the reaction more so than chloride. We conclude that it is the substitution of hydrated cations for interlayer K in biotite that enhances the heterogeneous reduction of chromate at the biotite edge-fluid interface.