Effect of orthophosphate on the dissolution kinetics of biogenic magnesian calcites

Abstract

The dissolution behavior of two biogenic Mg-calcites, the echinoid, Tripneustes (12 mol% MgCO 3), and the red alga, Neogoniolithon (18 mol% MgCO 3 plus brucite), was studied using free-drift methods in distilled water and phosphate-spiked solutions at 25°C and P CO2 = 1 atm. Small concentrations of phosphate strongly inhibit dissolution rates. Inhibition increases with increased phosphate levels and with approach toward saturation. Near saturation, dissolution rates are reduced by 10 3 by the presence of 0.6 μmol adsorbed-P/m 2. The magnitude of phosphate inhibition is similar to that observed for low-Mg calcite, and like calcite, the mechanism of inhibition is probably by adsorption of P at surface kink sites. Phosphate appears to inhibit removal of Mg and Ca equally during Mg-calcite dissolution. Rates of brucite dissolution are unaffected by phosphate. Mg-calcites containing >8.5 mol% MgCO 3 should be thermodynamically unstable relative to aragonite in most natural waters. Recent work, however, shows that in contrast to its effect on the behavior of Mg-calcites. phosphate does not inhibit aragonite dissolution. The presence of phosphate might thus reverse the relative stability of these two minerals during diagenesis of shallow marine carbonate sediments.