The impact of redox conditions on the rare earth element signature of redoximorphic features in a soil sequence developed from limestone

Abstract

Redox processes, which are widespread in soils, need to be quantified for an improved comprehension of the dynamics of Fe- and Mn-oxides and their associated trace elements. The classical methodology used to study these redox processes generally relies on the quantification of all mineral species in the various pedological features that can be related to different redox stages. However, this approach usually encounters the difficulty of precisely quantifying the different forms of poorly crystallised Fe- and Mn-oxides.In this study, we use the signature of rare earth elements (REEs) to visualise and, eventually, quantify the importance of redox processes in soils. Our approach relies on that developed by Laveuf et al. (2008) and the idea that the relative contribution to the mobilisation of REEs that is made by the primary minerals reactive to redox conditions depends on the following factors: (i) their initial proportion in the different pedological features that can be related to various redox processes, (ii) their relative mobilisation during the redox process in question, and (iii) their initial REE signatures.The catena studied is characterised by two stages of redox conditions: the first is related to the formation and subsequent dissolution of Fe–Mn concretions, and the second is related to the bleaching of the soil matrix due to morphological degradation. In this soil, the main minerals reactive to redox conditions are Mn-oxides, ferrihydrite, goethite and (fluor)apatite. The results indicate that the primary redox conditions can be characterised by a positive Ce anomaly on the REE pattern, which has been attributed to a preferential immobilisation of this element, due to its association with Mn-oxides. The results also indicate that the secondary redox conditions can be characterised by depletion in medium REEs (MREEs) in the REE pattern, which has been attributed to a preferential release of these elements during the dissolution of (fluor)apatite and, to a lesser extent, of ferrihydrite.These results emphasise the potential of REE signatures of the visualisation of the various redox processes that have been active in a soil. Additionally, REE signatures are a proxy of the frequency and intensity of the redox conditions.