Interactions between organic matter (OM) and clay minerals have received considerable attention in previous studies. The influence of OM on smectite illitization has been analyzed primarily in simulation experiments rather than in diagenetic studies. The present study explores the influence of OM on smectite illitization during diagenesis. Thirty red and dark mudstone samples from the Dongying Depression were analyzed. X-ray diffraction (XRD) analyses revealed that the illite percentages in mixed-layer illite-smectite (I-S) of both types of samples were dispersive above 3100 m and more convergent below this depth. The stacking mode of I-S in dark mudstones above 3100 m remained primarily at R0–R0.5 ordering with the average number of layers (N_ave) dispersively distributed between 2 and 4.5. In red mudstones, the I-S changed from the R0 to R0.5 mode with the N_ave increasing from 2 to 5. Over this range, the smectite illitization in dark mudstones was slower than that in red mudstones. Below 3100 m, the I-S stacking mode of dark mudstones changed from R0.5 to R3 ordering with the N_ave increasing sharply from 4 to 8. In red mudstones, the I-S displayed R1.5 and R3 ordering with the N_ave varying between 4.5 and 6.5. Over this range, the smectite illitization in dark mudstones accelerated rapidly, whereas the process in red mudstones was retarded. Additionally, the red mudstone samples contained little OM, whereas the dark mudstone samples contained abundant total organic carbon (0.17–4.43%). Thermo-XRD, near-infrared (NIR) as well as mid-infrared (MIR) spectroscopy analyses suggested that the OM in dark mudstones exhibited a significant transition at 3100 m, coincident with the illitization change. Above 3100 m, the smectite illitization in dark mudstones was delayed due to the OM pillar effect in the interlayer spaces of smectite. Below 3100 m, the interlayer OM became varied and desorbed, discharging organic acid. This led to the dissolution of smectite structural layers. Consequently, illitization in the dark mudstone was accelerated. This study revealed that the existence and occurrence of OM could influence the smectite illitization in diagenesis. Further study on the interactions between OM and clay minerals is needed to facilitate our understanding on the mechanism of smectite illitization as well as its geological applications.

Types of organic matter and mineral associations and microstructures of shales can reflect the depositional mechanism and sedimentary environment. Therefore, analysis of organic matter and mineral associations is a prerequisite for research on fine-grained sedimentary rocks. Shales from the Eocene Shahejie Formation in the Dongying Sag of China were selected to classify their lithofacies and to investigate the characteristics of their organic matter and mineral associations. This analysis identified six lithofacies (e.g., laminated shales and massive mudstones); in all the lithofacies, clay minerals exhibit a positive correlation with detrital minerals, thus indicating that they were derived from the same source. The comprehensive analysis of mineral and organic matter associations reveals that detrital minerals were deposited with low-hydrogen index (HI) OM. The deposition of detrital minerals was mainly a physical process. Clay minerals can undergo deposition in one of two ways due to their surface charge: they can either aggregate with high-HI OM via chemical deposition, thus forming organic-rich laminae, or they can be deposited together with low-HI OM via physical deposition, thus forming clay-rich laminae or a massive matrix. Carbonate minerals, which often coexist with high-HI OM, are biological sediments. The analysis of the sedimentary characteristics of these organic matter and mineral associations indicates that the sedimentary processes differ between various lithofacies: e.g., the discontinuous laminated shale represents the product of biophysical processes. Differences in depositional mechanisms are also present in each sub-member. Therefore, it is important to analyze the properties of minerals and organic matter, as well as their associations, to more deeply understand the classification of lithofacies and the depositional processes of shales and mudstones.

Organic-inorganic interactions of clay minerals and organic matter: Action mechanism and analysis techniques

The variation in mineral composition will affect the rock brittleness, thus the change of mineral assemblages during diagenesis has a potential control on the brittleness of mudstones. In this study, thin section, X-ray diffraction (XRD), and Scanning Electron Microscope (SEM) analyses were used to investigate compositional and microscopic features of mudstones. With the enhancement of diagenesis, three mineral assemblages were divided due to the diagenetic evolution of minerals. Quartz, feldspar, dolomite, chlorite, and illite were regarded as brittle minerals and (quartz + feldspar + dolomite + illite + chlorite)/(detrital mineral + carbonate + clay mineral) was defined as the brittleness evaluation index The mudstone brittleness changed slightly during early diagenesis but increased gradually with enhancement of diagenesis in the late diagenesis stage. Quartz and feldspar were scattered above the clay matrix and the contact of grains was limited, therefore, the contribution of detrital minerals to the brittleness was affected by the properties of clay minerals. The diagenetic transformation of clay minerals resulted in the reduction of ductile components (smectite/I-Sm and kaolinite) and increase of brittle components (illite and chlorite), leading to the enhancement of integral rigidity of the mudstones. Meanwhile, the improved crystallization of carbonate in late diagenesis stage enlarged the carbonate grains which resulted in rigid contact between grains. These results highlighted the influence of diagenesis on mudstone brittleness. Therefore, for evaluation of mudstone brittleness, attention should be paid to the diagenesis process besides mineral composition.