Rare Earth Partition Characteristics and Sedimentary Diagenetic Response in Layered Argillaceous Limestone: Taking the Shale of Upper Es4 in the Nx55 Well Area as an Example

Abstract

Taking the layered argillaceous limestone in the upper Es4 in the Dongying Sag as the research object, the geochemical analysis of major, trace, and rare earth elements (REEs) established the response relationship between REE distribution characteristics and sedimentary diagenesis. The average values of total light REE ( $\Sigma \text{LREE}$ )/total heavy REE ( $\Sigma \text{HREE}$ ) of micrite calcite and argillaceous laminae are 6.75 and 4.06, respectively. The LREEs and HREEs are differentiated, consistent with the distribution pattern of REEs in the crust. Th and U elements are more enriched in the sediments in the lacustrine sedimentary environment than in the diagenetic calcite veins. In primary sediments (argillaceous clay and micrite calcite laminae), LREEs are more enriched, HREEs are depleted, and Eu shows positive anomaly-enrichment characteristics. The LREEs and HREEs of the sparry calcite veins are lower than those of the original sediment argillaceous clay and micrite calcite, showing characteristics of a negative anomaly depletion. Sparry calcite veins originate from diagenetic fluid crystallization and precipitation and have the characteristics of low Th and U, evident positive anomalies of Sr and Eu, and substantial depletion of La. The distribution patterns of REEs within the four components of the laminated argillaceous sparry limestone reflect the order of REE distribution from primary sediment laminae (argillaceous clay and micrite calcite) to diagenetic laminae (calcite veins). Compared with the North American shale, the four components of the contact surface between the argillaceous and bright crystalline laminae, the micrite calcite, the calcite veins, and the argillaceous laminae all showed weak negative $\delta \text{Ce}$ anomalies and positive $\delta \text{Eu}$ anomalies. The fractionation degree between LREEs and HREEs reflected by ${\left(\text{La}/\text{Sm}\right)}_{\text{cn}}$ and ${\left(\text{Gd}/\text{Yb}\right)}_{\text{cn}}$ is in descending order: the interface between the argillaceous lamina and sparry calcite lamina, micritic calcite, calcite vein, and argillaceous lamina. The argillaceous laminar material has the characteristics of basalt REEs, indicating that the terrestrial debris and argillaceous lacustrine shale in the upper Es4 member of the Niuzhuang subsag are primarily derived from the basic extrusive rocks of the Qingtuozi bulge. REE differentiation is most noticeable at the interface between the argillaceous lamina and calcite vein, proving the directionality of REE differentiation from the original sedimentary lamina to the diagenetic lamina. Shale in the study area is primarily deposited below the redox interface of water at a certain depth, and the deposition rate is stable and slow, providing good conditions for preserving organic matter.