Elemental composition and geochemical characteristics of iron-manganese nodules from nine main soils in China were studied by chemical and multivariate statistical analyses to better understand the reactions and functions of iron-manganese nodules in soils and sediment. Compared to the corresponding soils, Mn, Ba, Cd, Co and Pb had strong accumulation, Ni had moderate accumulation, while Ca, Cu, Fe, Na, P, Sr and Zn accumulated to a minor degree in the iron-manganese nodules. In contrast, Si, Al, K, Mg and Ti were reduced in the iron-manganese nodules. The contents of Ba, Cd, Co, Cu, Ni, Pb and Zn were positively and significantly correlated with that of MnO2 in the iron-manganese nodules, while the contents of Cr, Cu, Ni, Pb and Zn were positively and significantly correlated with that of Fe2O3 in soils. Based on a principle component analysis, the elements of iron-manganese nodules were divided into four groups: 1) Mn, Ba, Cd, Co, Cu, Li, Ni, Pb and Zn that were associated with Mn oxides, 2) Fe, Cr and P that were associated with Fe oxides, 3) Si, K, and Mg that were included in the elemental composition of phyllosilicate, and 4) Ca, Na, Al and Ti that existed in todorokite, birnessite, lithiophorite and phyllosilicate. It was suggested that accumulation, mineralization and specific adsorption were involved in the formation processes of soil iron-manganese nodules.
TAN Wen-FengLIU FanLI Yong-HuaHU Hong-QingHUANG Qiao-Yun
Birnessite is a common weathering and oxidation product of manganese-bearing rocks. An O2 oxidation procedure of Mn(OH)2 in the alkali medium has been used to synthesize birnessite. Fast and powder X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), energy dispersed X-ray analysis (EDAX), infrared spectroscopy (IR) techniques and chemical composition analysis, Eh-pH equilibrium diagram approaches were employed to investigate the reaction process and pathways of birnessite formation. Results showed that the process of the birnessite formation could be divided into four stages: (1) forma- tion stage for hausmannite and feitknechtite, (2) stage of transformation of hausmannite and feitknechtite to buserite, (3) buserite crystal growing stage, and (4) stage of conversion of buser- ite into birnessite. Mn(OH)2 was mainly present as amorphous state only for a short initial time of oxidation reaction. In the oxidation process, buserite formed following two pathways by recrys- tallization after dissolution of the intermediates, and the transformations of the minerals de- pended on the Eh determined by the dissolved O2 concentration on their surfaces. The results are fundamental in further exploration on the mechanism of birnessite formation in the alkali medium. A great practical significance would also be expected with respect to the areas of mate- rial sciences.
FENG Xionghan1, TAN Wenfeng1, LIU Fan1, HUANG Qiaoyun1 & LIU Xiangwen2 1. College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, China
