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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. Full article

Glaucony is a significant green marine facies in the northwestern passive margin of the Guadalquivir Basin (Spain), where glauconite formed authigenically on a sediment-starved continental shelf, with fecal pellets and benthic foraminiferal tests being the main glauconitized substrates. Results from a study using XRD, TGA-DSC, SEM-EDS, and EPMA have revealed that glauconite is remarkably heterogeneous in mineral composition and chemical maturity, even in a single grain, reflecting a complex interaction of micro-environmental factors, substrate influences and post-depositional alterations. In its early stage, the glauconitization process is consistent with the slow precipitation of a Fe-rich smectite phase, most likely intergrade between nontronite and Fe-montmorillonite end-members, which evolved to a regularly interstratified glauconite-smectite (Gl/S). The Fe-smectite-to-Gl/S transformation is interpreted as a diffusion-controlled reaction, involving sufficient Fe availability in pore water and the constant diffusive transport of seawater K⁺ and Mg²⁺ ions towards the substrate. The pelletal glauconite is actually a highly evolved Gl/S consisting almost totally of mica layers, with 0.74 ± 0.05 apfu of K⁺ in the interlayer, while the Gl/S occurring as replacements of foraminiferal tests contains a mean of 7% of expandable layers in the walls and 16% in the chamber fillings, due to rate-limited ion diffusion. Full article