Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater

The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO₃. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg²⁺ and Ca²⁺ ions. The increase was 5 times greater for Ca²⁺ than Mg²⁺. The effects ofCa²⁺ and Mg²⁺ are diminished with the addition of SO₄^2- apparently due to the formation of MgSO₄ and CaSO₄ complexes in solution and/or SO₄^2- adsorption on the surface of CaCO₃. The adsorbed Ca²⁺ and Mg²⁺ on CaCO₃ (at carbonate sites) may act as bridges to PO₄^3- ions. The bridging effect of Ca²⁺is greater than Mg²⁺ apparently due to the stronger interactions of Ca²⁺ with PO₄^3-.The apparent effect of salinity on the adsorption of PO₄ was largely due to changes in the concentration of HCO₃^- in the solutions. An increase in the concentration of HCO₃^- caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO₃^- (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO₄]_ad = K_mC_m[PO₄]_T/(1 +K_m [PO₄]_T) , ]where [PO₄]_ad and [PO₄]_T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of C_m (the maximum monolayer adsorption capacity, (mol/g) and K_m (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ C_m = 17.067 + 0.1707t - 0.4693S + 0.0082S² ( = 0.7) ][ ln K_m = - 2.412 + 0.0165t - 0.0004St - 0.0008S² ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO₄]_ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO₄ left on the CaCO₃ is close to the equilibrium adsorption. The release of PO₄ from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.