Lanthanide tetrad effect in ferromanganese concretions and terra rossa overlying dolomite during weathering

The lanthanide tetrad effect was investigated in a 5.4 m thick terra rossa profile overlying dolomite on the Yunnan-Guizhou Plateau, China. The results demonstrate that the chondrite-normalized rare earth element pattern of dolomite bedrock displays a W-type tetrad effect. The insoluble residue from the dolomite bedrock does not exhibit any significant tetrad effect. In contrast, some ferromanganese concretions and the terra rossa show tetrad effect. It is worth noting that the conjugate M- and W-types of the tetrad effect are observed in some terra rossa samples. The tetrad effect in the ferromanganese concretions and the terra rossa possibly originates from redistribution of dissolved rare earth elements during their downwards movement in the profile and not only from water/rock interaction. Within the dolomite weathering system, the ferromanganese concretions and surrounding terra rossa present similar correlations of Eu/Eu*, Y/Ho, Sm/Nd, Ce/Ce*, with the size of the tetrad effect. The ferromanganese concretions and the terra rossa with tetrad effect are characterized by a reduced, non-chondritic Y/Ho ratio. Also the Y/Ho ratio exhibits a clear negative correlation with the size of the tetrad effect in the ferromanganese concretions and the terra rossa. In addition, the Eu/Eu* tends to increase with increasing size of the tetrad effect in the ferromanganese concretions and the terra rossa, as does the Sm/Nd ratio. The regular variation for Eu/Eu*, Y/Ho and Sm/Nd is likely a result of the fractionation of rare earth elements and yttrium with the tetrad effect. On the other hand, the correlation of the Ce/Ce* with the size of the tetrad effect in the ferromanganese concretions and the terra rossa is random. This likely indicates that the Ce behavior within weathering system is mainly controlled by redox condition, rather than tetrad effect. Comparative study indicates that the correlations of Eu/Eu*, Y/Ho, Ce/Ce*, with the size of the tetrad effect in the ferromanganese concretions and the terra rossa, are not similar to those found in a highly evolved igneous system. Nevertheless, the correlation of Sm/Nd with the size of tetrad effect in weathering system is similar to that in igneous system. In general, it appears to indicate that the tetrad effect occurrence in granitic rocks is not associated with weathering.