The rare earth element (REE) content of the Tunisian Permian–Neogene shales have been studied to determine the origins of the clay minerals in these shales. The Permian–Neogene series overlies the Palaeozoic basement that has been studied via oil-drilling cores. This study of REEs was performed in various palaeogeographical domains of Tunisia, from the ‘Saharan Platform’ in the south to the ‘Nappes Zone’ in the north. In this work, those levels rich in illite (Palaeozoic, Triassic and Jurassic), smectite (Campanian–Maastrichtian) and palygorskite (continental Eocene) as well as some Miocene levels rich in halloysite are examined. The distribution of REEs in the Tunisian margin sediments is generally homogeneous, except for the Miocene levels containing halloysites. The normalization curves of REEs vs North American shale composite characterize the inherited clays regardless of the dominant minerals, except for a few cases of neoformation. The flat REE curves indicate a detrital origin of the studied clay levels.

This study evaluates the rare earth element (REE) geochemistry in altered trachyandesitic ignimbrites, tuff and lava flows in the Hashtjin area by assessing chondrite-normalized REE patterns and Y/Ho geochemical ratios. Modifications in the REE patterns took place along altered fault zones that were affected by hypogene and supergene alterations. The precursor volcanic and pyroclastic rocks contain phenocrysts of plagioclase accompanied by augite, zircon, apatite and pyrite. Based on X-ray diffraction analysis, the main mineral assemblages of the altered units consist of kaolinite as the main clay mineral, SiO2 polymorphs (quartz and cristobalite) and anatase as a minor constituent. The chondrite-normalized REE patterns of argillic samples reveal fractionation of light REEs (LREEs) compared to heavy REEs (HREEs), together with a marked Eu anomaly and a weak W-type tetrad effect related to the weak non-charge radius control (CHARAC) behaviour of REEs and slightly higher Y/Ho and Zr/Hf ratios. The relationship between the Y/Ho and Zr/Hf ratios and recognizable T3 and T4 effects (tetrad effect) suggests that an increasing degree of water–rock interaction occurred during hypogene alteration processes by acidic hydrothermal fluids that were overprinted by supergene alteration. Water–rock interaction and adsorption by Mn-oxides and clay minerals are considered to have played important roles in determining the close to non-CHARAC behaviour of REEs during the argillic alteration of the pyroclastic rocks in the Hashtjin area.

Manganese (Mn) and rare-earth elements (REEs) in a stalagmite (SJ3) collected from Central China were analyzed, using an ICP-MS method for the precise determination of > 40 trace elements in geological samples by enriched-isotope internal standardization. Unlike speleothem Mn and REEs investigated by cathodoluminescence, which may be incorporated into crystal lattice, the Mn and REEs analyzed in SJ3 should come largely from colloidal and particle phases in groundwater and may be associated with non-carbonate inclusions. The Mn and REEs in SJ3 vary significantly during the period between 20 and 10 ka. These elements show remarkable increases since ∼ 14.5 ka, suggesting enhanced weathering of the overlying soil layer and the host rock since the onset of the last deglaciation and the strengthening of the Asian summer monsoon. In addition, the Mn and REEs in SJ3 display significant centennial fluctuations which may reflect groundwater dynamics.