The Behavior of Rare Earth Elements during Green Clay Authigenesis on the Congo Continental Shelf

Clay mineral authigenesis at continental margins plays an important role in global marine element cycles. However, despite being increasingly used as tracers for both modern and past oceanographic conditions, the behavior of the rare earth elements (REEs) and their isotopes during marine clay authigenesis still remains poorly known. In this study, we report on a detailed geochemical investigation of glauconite from the West African continental shelf, near the mouth of the Congo River. Elemental, neodymium, and hafnium isotope analyses were conducted on both acid leachate and separated clay-size fractions of glauconite pellets, in order to investigate the behavior of REE during the formation of authigenic clays. Our data indicate that kaolinite dissolution and subsequent Fe-bearing clay authigenesis act as a net source of REEs to seawater. We show that enhanced glauconitization, as inferred from increasing Fe and K contents, is accompanied by significant decoupling of the REE toward markedly LREE-enriched shale-normalized patterns in neoformed clay separates. Using both Nd and Hf isotopes and SEM observations, we rule out any seawater influence and argue that this shift primarily reflects the progressively overwhelming presence of insoluble nanocrystals of detrital LREE-rich phosphates, which are known to occur in close association with kaolinite in tropical soils. Due to their marked insolubility in surface environments, such nanocrystals can be preserved during kaolinite dissolution and subsequently incorporated into the aggregates of authigenic green clays forming the peloids. Most strikingly, we show that the combined influence of net REE loss (due to kaolinite dissolution) and decoupling (due to subsequent entrapment of inherited LREE-bearing accessory phases into neoformed clay minerals) is accompanied by preferential release of a dissolved REE fraction characterized by seawater-like distribution patterns. These findings reinforce the emerging view that clay mineral dissolution and authigenesis at continental margins possibly play a major role in marine REE cycling.