Rare earth elements in clay-sized fractions: Implications for weathering fingerprint from parent materials to soils

Rare earth elements (REEs) have gained attention as tracers of pedogenic processes over the last few decades. Clay-sized fractions (CSFs, < 2 mu m) may play a crucial role in hosting REEs. To better understand the pedochemical signals of REEs in clay-sized phases, such as iron oxides and phyllosilicates, we analyzed REE speciation in CSFs of carbonate rocks (limestone), clastic rocks (sandstone and shale), and their derived saprolites. Our results quantified the REE content (41.2-144.6 mg kg(-1)) and speciation in CSFs of parent materials, revealing that REEs were primarily hosted in amorphous iron oxides (Fe-ox1), followed by crystalline iron oxides (Fe-ox2) and phyllosilicates. Compared to parent materials, saprolites derived from carbonate rocks exhibited more than a two-fold enrichment of REEs in major clay-sized phases, confirming the role of CSFs as REE sinks during carbonate rock weathering. Furthermore, the initial REE patterns of CSFs of carbonate rocks underwent alteration throughout the weathering process, likely due to water-mineral interactions. Our findings suggest that REEs in CSFs record the weathering fingerprint for soils derived from carbonate rocks, while they are indicative of provenance for soils originating from clastic rocks.