Chemical speciations of elements in the Fe-Mn crusts by sequential extraction

Abstract

Sequential extraction was carried out on twenty two subsamples of three ferromanganese crusts from three seamounts (Lemkein, Lomilik, and Litakpooki) near the Marshall Islands in the western Pacific. The extraction was designed to fractionate Fe-Mn crust forming elements into four defined groups: (1) exchangeable and carbornate, (2) Mn-oxide, (3) Fe-oxyhydroxide, and (4) residual fraction. X-ray diffraction result shows that target material were well removed by each extraction step except for CFA in phosphatized crusts generation. According to chemical analysis of each leachate, most of elements in the Fe-Mn crusts are bound with two major phases. Mn, Ba, Co, Ni, Zn, (Fe, Sr, Cu, and V) are strongly bounded with Mn-oxide (δ-MnO2) phase, whereas Fe, Ti, Zr, Mo, Pb, Al, Cu, (V, P, and Zn) show chemical affinity with Fe-oxyhydroxide phase. This result indicates that significant amount of Al, Ti, and Zr can not be explained by detrital origin. Ca, Mg, K, and Sr mainly occur as exchangeable elements and/or carbonate phase. Outermost layer 1 and innner layer 2 which are both young crusts generations are similar in chemical speciations of elements. However, some of Fe-oxyhydroxide bounded elements (Pb, Y, Mo, Ba, Al, and V) in phosphatized innermost layer 3 are released during phosphatization and incorporated into phosphate (Pb, Y, Mo, and Ba) or Mn-oxide phase (Al and V). Our sequential extraction results reveal that chemical speciations of elements in the hydrogenetic crusts are more or less different from interelemental relationship calculated by statistical method based on bulk chemistry.