Pore Fluid Research Articles

Bioremediation of contaminated soil by crude oil of Baiji refinery by extraction of the local dominant bacteria

Abstract In most communities, soil contamination is a problem as it affects people and the environment. Because oil spills on soil substantially impact the environment, accidental infusions and spills of ore oils frequently result in a complete or partial exchange of the soil pore fluid by oil-contaminated soils, altering the geotechnical engineering characteristics. Therefore, efficiently removing petroleum hydrocarbon pollutants from contaminated soil is urgently needed. A novel technique that is gaining popularity worldwide to clean up places polluted with petroleum hydrocarbons is known as bioremediation. This study browser the fundamental processes involved in bioremediation and removal efficiency of TPH (Total Petroleum Hydrocarbon) within different periods for (the Baiji refinery) which is polluted with crude oil as a result of numerous oil wells, oil drilling, pipeline, and storage tank damage, natural seepage, and spills during the conflict and Noory channel which content crude oil, waste of refinery process and sludge. The research aims to extract the dominant bacteria in the contaminated soil and use the last in bioremediation and find out the differences in its effectiveness in treating total petroleum hydrocarbons (TPH) later. The result indicates that the dominant bacteria are Stutzerimonas balearica and Bacillus subtilis which are used later in bioremediation and can digest TPH. The removal efficiency of TPH during the study period was 55, 65, 68, 78, 82, 85, and 92% for spilled samples and 50, 62, 66, 70, 80, 84, and 90% for the Noory channel, respectively.

Sorption of 32Si and 45Ca by isotopic exchange during recrystallisation of cement phases

The uptake kinetics of 32Si and 45Ca on cement minerals including C-S-H phases, portlandite, AFm phases, ettringite, and aged hardened cement paste were determined through batch sorption experiments. A two-step uptake kinetics was observed, with a fast initial step during ∼1 day followed by a much slower second step, not yet completed after one year. The working hypothesis that the fast uptake is caused by exchange of the radioisotopes with stable isotopes adsorbed on the mineral surface, whereas the slow uptake step is due to uptake in the crystal lattice during recrystallisation, was tested with the help of phenomenological models that combine surface adsorption and homogeneous recrystallisation. The experimental data could be reproduced satisfactorily using a refined version of the formerly published continuous homogeneous recrystallisation (CHOR) model, supporting the working hypothesis and allowing equilibrium sorption coefficients (Rd; L kg−1) for these radionuclides to be calculated on a mechanistic basis. This provides insight into the intrinsic rates and mechanisms of interaction between cementitious materials and their pore fluids which contain dissolved calcium and silicon.

The Frictional‐Viscous Transition in Experimentally Deformed Granitoid Fault Gouge

AbstractIn crustal faults dominated by granitoid gouges, the frictional‐viscous transition marks a significant change in strength constraining the lower depth limit of the seismogenic zone. Dissolution‐precipitation creep (DPC) may play an important role in initiating this transition, especially within polymineralic materials. Yet, it remains unclear to what extent DPC contributes to the weakening of granitoid gouge materials at the transition. Here we conducted sliding experiments on wet granitoid gouges to large displacement (15 mm), at an effective normal stress and pore fluid pressure of 100 MPa, at temperatures of 20–650°C, and at sliding velocities of 0.1–100 μm/s, which are relevant for earthquake nucleation. Gouge shear strengths were generally ∼75 MPa even at temperatures up to 650°C and at velocities >1 μm/s. At velocities ≤1 μm/s, strengths decreased at temperatures ≥450°C, reaching a minimum of 37 MPa at the highest temperature and lowest velocity condition. Microstructural observations showed that, as the gouges weakened, the strain localized into thin, dense, and ultrafine‐grained (≤1 μm) principal slip zones, where nanopores were located along grain contacts and contained minute biotite‐quartz‐feldspar precipitates. The stress sensitivity exponent n decreased from a large number at 20°C to ∼2.2 at 650°C at the lowest velocities. These findings suggest that high temperature, slow velocity and small grain sizes promote DPC‐accommodated granular flow over cataclastic frictional granular flow, leading to the observed weakening and strain localization. Field observations together with extrapolation suggest that DPC‐induced weakening occurs at depths of 7–20 km depending on geothermal gradient.

Shear Bands Triggered by Solitary Porosity Waves in Deforming Fluid‐Saturated Porous Media

AbstractThe interplay between compaction‐driven fluid flow and plastic yielding within porous media is investigated through numerical modeling. We establish a framework for understanding the dynamics of fluid flow in deforming porous materials that corresponds to the equations describing solitary porosity wave propagation. A concise derivation of the coupled fluid flow and poro‐viscoelastoplastic matrix behavior is presented, revealing a connection to Biot's equations of poroelasticity and Gassmann's theory in the elastic limit. Our findings demonstrate that fluid overpressure resulting from channelized fluid flow initiates the formation of new shear zones. Through three‐dimensional simulations, we observe that the newly formed shear zones exhibit a parabolic shape. Furthermore, plasticity exerts a significant influence on both the velocity of fluid flow and the shape of fluid channels. Importantly, our study highlights the potential of spontaneous channeling of porous fluids to trigger seismic events by activating both new and pre‐existing faults.

Study on the fluidity of the pore-fracture binary system in a tight sandstone reservoir-NMR

Fluid movability in tight sands may not be accurately characterized by pore size-based classification methods solely because of the complex pore structure and heterogeneity in pore size. In this study, on the basis of casting thin slices and scanning electron microscope observation, pore structure was analyzed using mercury injection, NMR, and micron CT to classify and evaluate the tight oil reservoir. The experiment suggest that the quality of tight reservoir is determined by its pore structure, particularly the throat radius, with the microthroat being an essential factor in permeability. Uniquely, we divide the reservoir by Q-cluster with throat radius, displacement pressure, permeability and other parameters. Based on reservoir classification, this study proposed a method for studying the pore size classification of samples on the T2 spectrum by combining CT scanning with mercury intrusion and a NMR experiment. Pore fluids are generally classified into movable fluid and irreducible fluid by one or two NMR T2 cut-offs. The pore size distributions and capillarity boundaries are converted from T2 and mercury injection capillary pressure (MICP). We categorized pores into micropores (T2 < 1), macropores (T2 > 10, with T2 > 300 as fractures), and medium pores (the rest). The saturation of movable fluid and the percentage of micro-fractures can characterize the seepage characteristics of tight reservoirs, which is of great significance for the later periods of oilfield development.

A new approach for identification of dispersivity class of soils by combining physical and chemical tests

The safety and performance of embankment dams after impounding water are highly related to the characteristics of the selected dam material. Impermeability is achieved by using clay soils as the core material in embankment dams. It has been observed that there are many collapsed dams, especially when dispersive soils with very low internal erosion resistance are used in the impermeable zone. For this reason, such soils should be determined at the design stage and not used in the construction of embankment dams. The dispersion mechanism is known to be controlled by clay mineralogy and cations in the pore fluid of soil. The physicochemical behaviour of the clay-water system is crucial to clarify the dispersion mechanism. Physical and chemical tests used for determining the dispersibility potential of soils are extensive and time-consuming methods. An alternative method has been proposed within the scope of this study. Three user-friendly and practical models based on Gene Expression Programming (GEP) were produced using chemical and double hydrometer test results to predict dispersion percentage (D%). In addition, a new classification criteria was proposed to identification of dispersivity class based on pinhole test data. If the dispersion percentage is less than 12% is soil is classified as non-dispersive, the dispersion percentage is between 12% and 30% and greater than 30%, it is defined as intermediate and dispersive, respectively. With this proposed criterion, more consistent and successful results were obtained for the dispersivity class.

Analyzing the seismic response characteristics of P, SV, and SH waves to reservoir parameters using physical modeling

Changes in reservoir parameters cause differences in seismic response characteristics, which can reflect the formation lithology and fluids. We conduct seismic physical modeling and seismic response characteristic analysis of P, SV, and SH wavefields. A seismic physical model is developed in the laboratory, which included several groups of sandstone blocks for simulating reservoir parameters, such as different fluid and clay content. Two-dimensional wavefield data of P-P, SV-SV, and SH-SH waves are acquired and processed in the laboratory. Compared with P waves, SV and SH waves are insensitive to pore fluids, and the SH stack profile is superior to the SV stack profile. The reflection events at the interface are slightly better for the SH-wave section than for the SV-wave section. The reflection coefficient of P waves varies greatly on amplitude variation with angle (AVA) gathers and is significantly influenced by factors such as fluids. The variation in the SV-wave reflection coefficient on AVA gathers is not as significant as that of P waves, and SV and SH waves are more conducive in identifying whether the block contained clay. The SH wave is more reliable for seismic imaging. Overall, this study can assist in combining different seismic wave data for better hydrocarbon identification and reservoir description.

The analytical study of double diffusive convection in a rectangular enclosure bounded by porous lining with thermal radiation

The current analytical study is dedicated to the boundary layer regime where heat and mass transfer rates are ruled by natural convection. A rectangular enclosure filled with a combination of an arbitrary buoyancy ratio has an Oseen-linear solution, and the position of Beavers and Joseph's condition is employed at the porous fluid interface. Thermal radiation's interaction with a porous lining influences overall heat transfer in a system. Porous linings and radiation are employed in many applications, such as furnaces, insulation, heat exchangers, solar energy collecting and storage, and heat control in electronics. The effect of slip and radiation is to increase the flow rate because of the reduction in friction at the surface. It indicates the fact that temperature and concentration are rapidly lowering. As the slip parameter and radiation parameter increase, the heat and mass transport increase due to the rise in velocity. The Nusselt and Sherwood numbers reach their maximum when the radiation parameter, Rayleigh number, and slip parameter are increased. The findings of the Nusslet number and Sherwood numbers are related to the finite situations of the slip parameter tending to infinity, the radiation parameter going to zero and the angle 90°.

TECTONIC AND NON-TECTONIC MESO-STRUCTURES IN THE LISAN FORMATION AND EQUIVALENT RECENT SEDIMENTS OF THE JORDAN RIFT VALLEY-CHARACTERIZATION AND FORMATION MECHANISMS

In this study, the structural elements portrayed in the recent sediments of the Dead Sea, which became exposed at its shores due to the drop in its level are described, and the mechanisms leading to their formation are elaborated. These structures include Plumes and density inversions, subaquatic gliding, seismites, undulations and wavy structures, flexures, and overpressure structures. The formation of these structures is found to be the result of different triggering factors such as Earthquakes, tectonic activity, instability of slopes, density inversion, pore fluids overpressure resulting from gas production by biochemical processes within the sediments (sulfur bacteria reduction of sulfates and oxidation of organic matter (petroleum residues)), submarine groundwater discharge, and volume changes associated with the transformation of gypsum to basinite and anhydrite, and the reversal of that transformation. Each of these triggering factors can produce more than one type of structure, depending on the prevailing composition of the sediments, its layering attitudes, grain-size distribution, porosities, and differential pressure situations within the sediment packages. The main finding of the study is the clarification of the role of gas production within the sediments as a result of sulfur bacteria activity and of the volume change processes associated with the transformation of gypsum to anhydrite and the reversal of that transformation in the formation of the mesostructures of the Dead Sea sediments.

Coupled finite element analysis of the dynamics of poroelastic media considering the relative fluid acceleration

AbstractThis paper mainly discusses the dynamics of poroelastic media using the finite element analysis based on the u‐v‐p full formulation, where , , and p denote the solid displacement, relative fluid velocity with respect to solid velocity, and pore fluid pressure. It incorporates the effect of relative fluid acceleration with respect to solid acceleration on soil dynamic response. The ‐‐p formulation is first verified through the comparison with the analytical solution. After that, the response of one‐dimensional saturated soil column and two‐dimensional partially saturated soil layer subjected to vertical loading with different combinations of soil permeability and loading frequency are investigated using the analyses with the ‐‐p and ‐p formulations, based on which the effect of relative pore fluid motion is discussed and the differences in the soil response between two kinds of analysis approaches are examined. Results reveal that the rapid fluid flow has a pronounced effect on soil dynamics and the soil with a greater degree of saturation is more sensitive to the increase of loading frequency and soil permeability. The soil dynamic response can basically be divided into two main categories that represent insignificant and significant flow motion depending on loading frequency and soil permeability. Furthermore, despite vertical loading, horizontal soil response can also be affected by the large relative pore fluid flow when loading frequency and soil permeability are large. In addition, the simplified formulation can still be applicable to predict dynamics of poroelastic media in cases with high loading frequency and low soil permeability.

Formation mechanism and implication of analcime in the sandstone reservoirs of the Permian Jingjingzigou formation in the Jinan sag, southern Junggar basin, NW China

Analcime plays a significant role in sandstone reservoirs as an authigenic diagenetic mineral in the Junggar Basin (northwestern China). However, the origin and controls on the reservoirs have received remarkably little attention. This study investigates the formation mechanism of analcime in the Middle Permian strata in the Jinan sag (southern Junggar Basin) through petrography and geochemistry. The results show that analcime is formed through early alkaline hydrolysis of volcanic materials under specific temperature and pressure conditions. The reservoir rocks primarily consist of various lithic sandstones, including volcanic debris such as basalt, andesite, and tuff. Analcime is characterized as rich in aluminium and poor in sodium, classified as low-silica analcime with a low Si-Al ratio (1.98–2.38). Furthermore, various other diagenetic minerals, such as glauconite, chlorite, albite, and calcite have been identified. The primary reservoir space chiefly consists of intragranular dissolved pores of analcime, while secondary pores are formed by intragranular pores of feldspar and lithic, along with some remaining intergranular pores. Cementation of analcime during early diagenesis changes primary pore structures and reduces reservoir properties. The low-silica analcime dissolves due to acidic pore fluids associated with three stages of oil and gas charging, transforming into albite and creating numerous secondary pores, thereby enhancing reservoir quality.

Differential evolution of pore fluid pressure in the Sinian carbonate reservoirs of the central and eastern Sichuan Basin, China: Implication for gas preservation and destruction

Trillions of cubic meters of gas reserve have been found in the Sinian Dengying carbonate reservoirs with normal pressure in the central Sichuan Basin, while no industrial gas reservoir have been detected in the Sinian Dengying reservoir with normal pressure in the eastern Sichuan Basin. The pore fluid pressure of gas reservoir is usually closely related to total gas content. To investigate the pore fluid pressure evolution and its implication for gas reserve preservation in the Sinian Dengying reservoir of the central and eastern Sichuan Basin, we conducted a comprehensive analysis including fluid inclusion petrography, microthermometry and Raman spectroscopy. The timings of gas inclusions captured in the central and eastern Sichuan Basin occurred from 175 to 92 Ma and 191 to 183 Ma, respectively. The presence of two‐phase vapour‐solid bitumen inclusions with similar phase proportions in a single fluid inclusion assemblage of fluorite provides direct evidence of in situ oil cracking to gas. The widespread solid bitumen from the Sinian Dengying reservoir in the central Sichuan Basin indicates the existence of massive oil cracking, which results in the formation of overpressure in the reservoir. Pore fluid pressure evolution of the Sinian Dengying reservoir of the central Sichuan Basin experiences normal pressure stage (200–155 Ma), overpressure development stage (155–90 Ma) and overpressure release stage (90–0 Ma). The maximum pore fluid pressure and its corresponding pressure coefficient of the Sinian Dengying reservoir of the central Sichuan Basin are approximately 141.4 MPa and 1.95, respectively. The overpressure development stage reflects the processes of oil cracking and gas accumulation, and the overpressure release stage reflects the dissipation of some natural gas in the Sinian Dengying reservoir of the central Sichuan Basin. The pore fluid pressure of the Sinian Dengying reservoir in the eastern Sichuan Basin has maintained at normal pressure since 200 Ma, indicating that the gas reservoir was small during the oil cracking stage and natural gas completely leaked due to tectonic uplift.

Insight into Fluid Occurrence and Pore Structure of Lacustrine Shale from the Cretaceous Tengger Formation, A’nan Sag, Erlian Basin, China

Insight into Fluid Occurrence and Pore Structure of Lacustrine Shale from the Cretaceous Tengger Formation, A’nan Sag, Erlian Basin, China

Review of the Interfacial Structure and Properties of Surfactants in Petroleum Production and Geological Storage Systems from a Molecular Scale Perspective.

Surfactants play a crucial role in tertiary oil recovery by reducing the interfacial tension between immiscible phases, altering surface wettability, and improving foam film stability. Oil reservoirs have high temperatures and high pressures, making it difficult and hazardous to conduct lab experiments. In this context, molecular dynamics (MD) simulation is a valuable tool for complementing experiments. It can effectively study the microscopic behaviors (such as diffusion, adsorption, and aggregation) of the surfactant molecules in the pore fluids and predict the thermodynamics and kinetics of these systems with a high degree of accuracy. MD simulation also overcomes the limitations of traditional experiments, which often lack the necessary temporal-spatial resolution. Comparing simulated results with experimental data can provide a comprehensive explanation from a microscopic standpoint. This article reviews the state-of-the-art MD simulations of surfactant adsorption and resulting interfacial properties at gas/oil-water interfaces. Initially, the article discusses interfacial properties and methods for evaluating surfactant-formed monolayers, considering variations in interfacial concentration, molecular structure of the surfactants, and synergistic effect of surfactant mixtures. Then, it covers methods for characterizing microstructure at various interfaces and the evolution process of the monolayers' packing state as a function of interfacial concentration and the surfactants' molecular structure. Next, it examines the interactions between surfactants and the aqueous phase, focusing on headgroup solvation and counterion condensation. Finally, it analyzes the influence of hydrophobic phase molecular composition on interactions between surfactants and the hydrophobic phase. This review deepened our understanding of the micro-level mechanisms of oil displacement by surfactants and is beneficial for screening and designing surfactants for oil field applications.

Modelling the rheology of living cell cytoplasm: poroviscoelasticity and fluid-to-solid transition

Eukaryotic cell rheology has important consequences for vital processes such as adhesion, migration, and differentiation. Experiments indicate that cell cytoplasm can exhibit both elastic and viscous characteristics in different regimes, while the transport of fluid (cytosol) through the cross-linked filamentous scaffold (cytoskeleton) is reminiscent of mass transfer by diffusion through a porous medium. To gain insights into this complex rheological behaviour, we construct a computational model for the cell cytoplasm as a poroviscoelastic material formulated on the principles of nonlinear continuum mechanics, where we model the cytoplasm as a porous viscoelastic scaffold with an embedded viscous fluid flowing between the pores to model the cytosol. Baseline simulations (neglecting the viscosity of the cytosol) indicate that the system exhibits seven different regimes across the parameter space spanned by the viscoelastic relaxation timescale of the cytoskeleton and the poroelastic diffusion timescale; these regimes agree qualitatively with experimental measurements. Furthermore, the theoretical model also allows us to elucidate the additional role of pore fluid viscosity, which enters the system as a distinct viscous timescale. We show that increasing this viscous timescale hinders the passage of the pore fluid (reducing the poroelastic diffusion) and makes the cytoplasm rheology increasingly incompressible, shifting the phase boundaries between the regimes.

Biotic and abiotic processes in Ediacaran spheroid formation

Organic-rich shales from the uppermost Doushantuo Fm. (South China) record one of the most negative carbonate carbon isotopic excursions in Earth’s history, known as the Shuram excursion, and contain meter to micro-size spheroids. In this study, we use Raman and energy dispersive spectroscopy to identify and describe the most common diagenetic spheroids to refine our understanding of the profound perturbations of the carbon cycle and the evolution of pore fluid chemistry imprinted in the sedimentary Precambrian record, especially in the late Ediacaran. The presence of 13C-depleted carbonate concretions or organic matter (OM) enclosed by lenticular dolomitic structures within the host shale unit suggests OM remineralisation and anaerobic oxidation, resulting in authigenic carbonate precipitation during the earliest stages of sediment diagenesis. Other mineralogical features, however, point to high levels of primary production, such as apatite bands that host spheroidal microfossils with highly fluorescent quartz and OM within abiotic concretions. These observations highlight the importance of considering co-occurring biotic and abiotic processes in explaining the formation of diagenetic spheroids in ancient sedimentary environments. From an astrobiology perspective, the interplay of biotic and abiotic processes reflects the complexity of early life systems and the environments that may exist on other terrestrial planets. Understanding the signatures of biotic and abiotic interactions in the Doushantuo Fm. is crucial for identifying potential biosignatures in extraterrestrial materials, thereby enhancing our understanding of life’s universality and adaptability in diverse and extreme environments.

Characterization of Carbonate Reservoir Potential in Salawati Basin, West Papua: Analysis of Seismic Direct Hydrocarbon Indicator (DHI), Seismic Attributes, and Seismic Spectrum Decomposition

Carbonate reservoir of Kais Formation in Salawati Basin, West Papua, is the most famous oil and gas reservoir in the eastern part of Indonesian Archipelago since 1970’s. Nowadays, new prospects in this area are more challenging and most relevant near the infrastructure of previous oil and gas fields. In this study, a relatively new seismic dataset was investigated to figure out new prospects in carbonate reservoir rocks in the area of interest. In this preliminary study, where seismic data are not supported by well data, direct hydrocarbon indicator (DHI), seismic attribute, and spectral decomposition (CWT: continuous wavelet transform) allow the authors to characterize the reservoir geometry and to predict pore fluids within the reservoir rocks. The reservoir geometry of carbonate reef of Kais Formation (C1) was identified by seismic reflectors with high amplitude contrast at the top C1. The hydrocarbon indicator was predicted by DHI where dim spots, flat spots, and polarity reversals are indicative of hydrocarbon prospects. From the attribute analysis, the attribute instantaneous amplitude detected the top carbonate C1, whereas pore fluids were predicted from high sweetness attribute. In addition, spectral decomposition CWT method confirms the top C1, identified as saturated rock by the frequency of 10 Hz, 20 Hz, and 30 Hz. Based on a seismic study in the researched area, the target zone is expected to be a very promising hydrocarbon reservoir, specifically a carbonate reservoir. As a result, the preferred well-test location is in a region with access to the Kais Formation limestone reef layer. This study can assist in reservoir characterization, especially in areas with limited well control.

Experimental Study on Edge Water Invasion of Strongly Heterogeneous Carbonate Gas Reservoirs Based on NMR Technology

Controlling the extent of water invasion in the reservoir and mitigating its detrimental effects on gas well production and natural gas recovery have long been a challenging task in the efficient development of strongly heterogeneous edge water gas reservoirs. To elucidate the edge water invasion mechanism of strongly heterogeneous carbonate gas reservoirs, this study investigates the pore throat characteristics and fluid mobility from both qualitative and quantitative aspects, leveraging natural core observations, cast thin sections, scanning electron microscopy (SEM), and nuclear magnetic resonance (NMR) tests with centrifuge experiments. A core-scale edge water invasion simulation experiment was conducted under online NMR monitoring to examine the dynamic gas production characteristics of the three types of reservoirs during the water invasion process and to elucidate the formation mechanism and distribution pattern of water-sealed gas. Research findings indicate that carbonate reservoirs typically exhibit a diverse range of pore types, including various types of fractures and cavities. Fractures significantly enhance reservoir connectivity, thereby increasing fluid mobility, but also lead to strong non-uniform water invasion. In contrast, cavities substantially improve the storage capacity of the reservoir and can retard the advancement of the water invasion front, thereby alleviating the adverse effects of water invasion. The ultimate recovery rates of fracture-type, cavity-type, and fracture-cavity cores in the water invasion simulation experiment were 29.81%, 64.87%, and 53.03%, respectively. Premature water breakthroughs in the reservoir can result in a large number of gases in matrix pores and even cavities being sealed by formation water, rendering them unrecoverable, which seriously impacts the gas recovery rate of the reservoir.

The occurrence of pore fluid in shale-oil reservoirs using nuclear magnetic resonance: The Paleogene Funing Formation, Subei Basin, Eastern China

The occurrence characteristics of pore fluids restrict shale oil recovery. Various approaches have been proposed to analyze the microdistribution of shale oil, but they are limited by the simultaneous characterization of the occurrence of oil and water within shale pore networks. This study conducted a range of nuclear magnetic resonance (NMR) T2 and T1–T2 measurements on the shales at different states, sampled from the Paleogene Funing Formation in the Gaoyou Sag, Subei Basin. A novel water and oil restoration method was introduced to restore pore fluid distributions in shales. The T1–T2 pattern with eight regions was determined for shale oil reservoirs. The pore oil and water in different states were quantitatively calculated using NMR T1–T2 spectra and compared with the results from Rock-Eval. In addition, the occurrence pattern of pore fluids in shales was proposed. The primary results indicated that free oil derived from multistage Rock-Eval is generally lower than that determined using the NMR T1–T2 spectrum. The NMR T1–T2 spectrum specializes in detecting the adsorbed, capillary-bound, and movable oil in pore systems but is limited in quantitatively identifying oil absorbed in organic matter. The occurrences and distributions of pore oil and water in different states can be effectively revealed by the T1–T2 spectrum. Capillary-bound water is predominantly associated with micropores (<100 nm) and, to a lesser extent, with mesopores (100–1000 nm); a similar pattern is observed for adsorbed oil. As a result, adsorbed oil is significantly restricted by pore water. Capillary-bound oil primarily occurs in mesopores, whereas macropores (>1000 nm) are saturated with movable oil. Hence, the distribution of capillary-bound oil is still affected by pore water, whereas movable oil is not. The authors are confident that the results presented in this study offer innovative insights into the occurrence and distribution of pore fluids in shale pore networks.

Biochemically induced diagenesis of Jurassic micrite: evidence from phase analysis, carbon, oxygen, and strontium isotopes (Franconian Alb, Germany)

The marine Upper Jurassic rocks of the Franconian Alb consist largely of micritic carbonate of partly dolomitized reef mounds and bedded basinal limestone. All carbonates were lithified in the shallow (centimeters, meters) subsurface and have a wide range of ∂13C (≤ + 3‰ to − 10‰VPDB) but always negative ∂18O (− 1 to − 6‰VPDB). Dolomite and reef limestone show the highest ∂18O and ∂13C values. The most negative ∂13C (≥ − 10‰) occurs mainly as cement in dolomite of a basinal, partly dolomitic, biostrome interval. Basinal limestone shows intermediate ∂13C values. Because freshwater diagenesis and elevated temperatures cannot explain the observed isotope values, pH is here considered a major factor influencing the isotope signal of micritic limestone. The bulk sediment isotope signal was reset to lower values, from an original lime mud with ∂13C ≥ 3‰ and a ∂18O of ≥ + 1‰, as a result of biochemically induced diagenesis. Carbonate, probably mostly aragonite but occasionally including dolomite, was dissolved in a zone where low pH developed as a result of organic matter degradation. Dissolved carbonate was translocated by diffusion and re-precipitated as cement (ca. 50vol%) in a zone with elevated pH where all in situ lime mud ∂18O was reset. Imported cement carbonate precipitated in equilibrium with the pore fluid with negative isotope values, whereas ∂13C of the in situ lime mud remained unmodified. The negative shift of the bulk ∂13C and ∂18O is variable and depends on pH and the contribution of 12C from anaerobic sulfate reduction in the zone of cement precipitation. This produced an ubiquitous covariance of ∂18O and ∂13C. Incorporation of seawater-derived Mg2+ during recrystallization of carbonate can account for the local dolomitization. Elevated 87Sr/86Sr ratios are explained as a result of interaction of clay minerals with the stationary pore fluids. This study shows that the isotopic signal produced by biochemically induced shallow submarine subsurface carbonate diagenesis can be indistinguishable from freshwater diagenesis, that ∂18O and ∂13C of the bulk rock are always reset, and that carbonates can show, in the presence of clay minerals, elevated 87Sr/86Sr ratios even when the pore fluids were never exchanged.Graphical