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This study focuses on understanding the association of rare earth elements (REE; lanthanides + yttrium + scandium) with organic matter from the Middle Devonian black shales of the Appalachian Basin. Developing a better understanding of the role of organic matter (OM) and thermal maturity in REE partitioning may help improve current geochemical models of REE enrichment in a wide range of black shales. We studied relationships between whole rock REE content and total organic carbon (TOC) and compared the correlations with a suite of global oil shales that contain TOC as high as 60 wt.%. The sequential leaching of the Appalachian shale samples was conducted to evaluate the REE content associated with carbonates, Fe–Mn oxyhydroxides, sulfides, and organics. Finally, the residue from the leaching experiment was analyzed to assess the mineralogical changes and REE extraction efficiency. Our results show that heavier REE (HREE) have a positive correlation with TOC in our Appalachian core samples. However, data from the global oil shales display an opposite trend. We propose that although TOC controls REE enrichment, thermal maturation likely plays a critical role in HREE partitioning into refractory organic phases, such as pyrobitumen. The REE inventory from a core in the Appalachian Basin shows that (1) the total REE ranges between 180 and 270 ppm and the OM-rich samples tend to contain more REE than the calcareous shales; (2) there is a relatively higher abundance of middle REE (MREE) to HREE than lighter REE (LREE); (3) there is a disproportionate increase in Y and Tb with TOC likely due to the rocks being over-mature; and (4) the REE extraction demonstrates that although the OM has higher HREE concentration, the organic leachates contain more LREE, suggesting it is more challenging to extract HREE from OM than using traditional leaching techniques.

Miocene tuffs preserved in argillaceous sediment interbedded with lacustrine successions are commonly encountered throughout the Dinarides Lake System (DLS) in south-eastern Europe. In this contribution the volcanic glass degradation and co-genetic Mn-Fe precipitation were studied in a 14.68 Ma felsic tuff from DLS Livno-Tomislavgrad Basin. Microbial activity has been involved in both reactions thus adding the interest of revealing effects of biotic and abiotic processes taking place during tuff eogenesis. X-ray diffraction and electron microbeam analysis with energy-dispersive X-ray spectroscopy revealed the pitting or granular structures developed at glass rims along with smectite flakes protruding from a degrading glass. Mn-Fe mineralization emerges in the form of Mn-Fe coatings, an initial step to micronodule formation, where traces of biogenetic influence included a high content of phases rich in structural Mn (IV) (i.e., ranciéite and jacobsite) and presence of microbial microfossils. Co-genetic ties between glass degradation and Mn-Fe precipitation were established through the report of dioctahedral smectite formed out of altered glass; which then served as nuclei of the ongoing biotic and abiotic Mn-Fe mineralization. These processes manifest on a continuous involvement of microbial life in the course of eogenesis of pyroclastic material in lacustrine environments.

The use of mineral diagenetic indices and organic matter maturity is useful for reconstructing the evolution of sedimentary basins and critical assessments for potential source rocks for petroleum exploration. In this study, the relationship of clay mineral diagenesis and organic matter thermal indices (Rock-Eval Tmax) and calculated vitrinite reflectance (%Ro) were used to constrain the maximum burial depths and temperatures of three distinct intervals within the northern Permian Basin, USA. X-ray diffraction of clay fractions (o within the early to peak oil maturation window. Evaluation of the potential for oil generation is relatively good throughout the Tonya 401 and JP Chilton wells. Organic maturation indices (Tmax, %Ro) and peak burial temperatures correlate well with clay mineral diagenesis (R0–R1 I-S), indicating that maximum burial depths and temperatures were between 2.5 and 4 km and o equations and thus should be further investigated for use in the Permian Basin. Accordingly, these findings show that clay mineral diagenesis, combined with other paleothermal proxies, can considerably improve the understanding of the complex burial history of the Permian Basin in the context of the evolution of the southern margin of Laurentia.

In the southern U.S. states, expansive soils are frequently encountered, presenting an important hazard in geotechnical engineering. This research relies on mineralogical and geochemical clues to explain the swelling behavior of smectite-rich, high-plasticity soils, documented in a series of geomechanical swelling tests that were performed on the soils stabilized with the metakaolin (MKG) and fly ash (FAG) based geopolymers. These geopolymers were mixed with the soil at several concentration levels. The lowest swelling percentage was shown to correspond to the sample stabilized with 12% FAG and was attributed to the neoformation of calcium silicate hydrates that acted as a cementitious material, preventing the soil from expanding by occupying the pore space, thus binding the clay particles together. Conversely, the 12% MKG-stabilized soil exhibited enormous expansion, which was explained by montmorillonite swelling to the point that it gradually began to lose its structural periodicity. The relatively high abundance of the newly formed feldspathoids in MKG-treated samples is believed to have greatly contributed to the overall soil expansion. Finally, the cation exchange capacity tests showed that the percentage of Na+ and Ca2+, as well as the pH value, exercised strong control on the swelling behavior of smectitic soils.