Seasonal variation of Mn adsorption on to calcareous surfaces in the English Channel, and its implication on the manganese distribution coefficient

Dissolved and particulate manganese in seawater samples derived from the English Channel has been analyzed using graphite furnace atomic absorption (GFAAS), and inductively coupled plasma atomic emission (ICP—AES) spectroscopies. Because of the high contents of carbonate minerals found in the suspended matter samples, the English Channel constitutes an ideal field area for the study of the Mn²⁺/Ca²⁺/CaCO₃ system. Owing to the chemical speciation of particulate manganese and the combined use of the X-ray diffraction and electron spin resonance spectroscopy we have shown the importance of the carbonate phase in the stabilization of manganese (II). This has been confirmed by p-pH measurements in the field. All these studies have also indicated that: (1) manganese is associated with calcite in the form of a solid solution, Mn_xCa_1−xCO₃; and (2) significant increases in the concentrations of particulate manganese, especially in offshore waters, occur in summer. This seasonal phenomenon has been attributed to the proliferation of coccolithophorids, which are known to be covered with calcified skeletons at high specific surface areas. To appraise the implication of the coccolithophorid-blooms phenomenon on the Mn²⁺/Ca²⁺/CaCO₃ system, we have used the manganese distribution coefficient, D_i, between the liquid phase and CaCO₃ particles. Overall we have shown that: (1) D_i in summer (i.e. when coccoliths considered as very fine-grained calcite are abundant) is much higher than that obtained in winter; and (2) in the vicinity of the French coast, D_i does not vary significantly even in summer. This is because of the high content of chalk-derived particles found in the near-shore waters.