Evolution Of Organic Matter Research Articles

Characteristics of middle-deep reservoirs and the genesis of pore development in the southern slope of the Nanpu sag in the Bohai Bay Basin, China

To clarify the distribution of favorable reservoirs in the middle and deep layers of the southern slope of the Nanpu sag and identify relatively high-quality reservoir sections, the characteristics of the reservoirs in the middle and deep layers of the southern slope of the Nanpu sag were studied by means of core analysis, thin section casting, scanning electron microscopy, and analytical tests. Research shows that the middle and deep reservoirs on the southern slope of the Nanpu sag are mainly lithic feldspathic sandstone and that the debris is mainly magmatic rock. The diagenesis processes are mainly compaction, cementation, and dissolution. The deformation of plastic particles, brittle microcracks on the surface of rigid clastic particles, calcareous cementation, quartz overgrowth, and feldspar dissolution are common. The pores are co-developed by primary pores and secondary pores, in which the primary pores are more common in the third member of the Dongying Formation and the first member of the Shahejie Formation, whereas the secondary pores are more common in the first member of the Shahejie Formation. The genesis of pore development is discussed. It is considered that the anticompaction components, chlorite film, and hydrocarbon filling play major roles in the formation of primary pores, whereas atmospheric water leaching, diagenetic evolution, thermal evolution of organic matter, and clay mineral transformation play major roles in the formation of secondary pores.

Effects of Microplastics and Organic Fertilizer Regulation on Soil Dissolved Organic Matter Evolution.

Microplastics are pollutants of global concern nowadays. However, the effects of microplastics addition to soil as a carbon source and the combined effects of microplastics and organic fertilizer on soil-dissolved organic matter (DOM) evolution are still unclear. This study focused on the evolution of DOM in soil with the addition of microplastics and investigated the variations in the content and composition of DOM in unfertilized and fertilized soil with different particle sizes of microplastics. It was observed that the TOC concentration of the soil DOM in the treatment with organic fertilizer and microplastics increased more (129.97-161.43 mg kg-1) than that in the treatment with microplastics alone (117.17-131.87 mg kg-1) and was higher than that in the original soil (95.65 mg kg-1). According to the humic acid relative abundance in DOM after 40 days of incubation, the humic acid relative abundance in DOM of the soil samples with microplastics and organic fertilizers addition was found to be higher than that in those with microplastic addition alone, reaching more than 80% in a short time. In conclusion, the TOC concentration of the soil DOM increased with the addition of microplastics, and the increase was more pronounced when organic fertilizers and microplastics were added together. Moreover, the soil humification increased to a higher level in the short term with the combined addition of microplastics and organic fertilizers, which was maintained during the long-term incubation process.

Impact of environmental conditions on organic matter in astrophysical ice analogues

ABSTRACT The existence of organic matter presenting a high molecular diversity in extraterrestrial environments is well documented. To understand the origin of this organic diversity, laboratory experiments were developed and showed that irradiation and thermal alteration of simple molecules such as methanol, water, and ammonia in conditions mimicking astrophysical ice environments. Ices containing water, methanol, and ammonia (H2O: MeOH: NH3) photolyzed and monitored by infrared spectroscopy, while the organic matter formed at room temperature was analyzed in situ with infrared spectroscopy and ex situ with high-resolution mass spectrometry. Those ices irradiated at 77 K and 10−8 mbar shows a significant organic molecular diversity: residual organic compounds contain up to 78 C, 188 H, 123 N, and 37 O. Most of them contains all four CHNO atoms (76–86 per cent), followed by CHO (11–17 per cent), and CHN compounds (5–6 per cent). CHNO and CHO compounds are more aliphatic (34–53 per cent), while CHN compounds are mostly condensed aromatics (83–90 per cent). In this work, our objective is to investigate impacts of environment on this organic molecular diversity by focusing on three parameters: photon dose, pressure, and heating rate during the warming process. Analyses of the residue formed showed that the heating rate and pressure weakly alter the abundance of the final organic material, while the irradiation rate reduced its abundance at high photon doses by a factor of 8. These results give insights on the impact of icy environment conditions in the evolution of astrophysical organic matter.

First direct detection of large polycyclic aromatic hydrocarbons on asteroid (162173) Ryugu samples: An interstellar heritage

AbstractPolycyclic aromatic hydrocarbons (PAHs) are considered major players in the physics and chemistry of star‐ and planet‐forming regions. The interstellar PAH hypothesis is based on our understanding of the origin of the aromatic infrared bands (AIBs), a set of bright emission features that are now the focus of observations by the James Webb telescope. While AIB carriers are expected to be large free PAHs (50 carbon atoms or more), laboratory analysis of primitive carbonaceous chondrites (CCs) has mainly revealed relatively small PAHs, up to 24 carbon atoms. In this study, we present a comprehensive analysis of aromatic species in bulk samples from the carbonaceous asteroid Ryugu using a surface mass spectrometry technique provided by two‐step laser desorption ionization. The resulting molecular distribution differs significantly from that obtained for a sample from the CC Orgueil, revealing aromatic species extending up to 61 carbon atoms. The species identified are composed of both peri‐condensed PAHs and non‐condensed aromatics. These results directly support the interstellar PAH hypothesis and open up new perspectives on the formation and evolution of organic matter in star‐forming regions and in the solar nebula.Key Points First direct detection of free aromatic species of large sizes with up to 61 carbon atoms in primitive extraterrestrial matter by applying a highly sensitive two‐step laser mass spectrometry analysis to grain samples from the carbonaceous asteroid Ryugu (Hayabusa2 mission). First direct support for the interstellar polycyclic aromatic hydrocarbon (PAH) hypothesis, according to which large free PAHs are responsible for the aromatic emission bands that are major infrared features currently observed by the James Webb Space Telescope. The large aromatic species detected are present in trace amounts and future research is needed to develop sensitive techniques for studying these compounds in sample return missions and meteorites.

Influence of thermal intrusion on the Alum Shale from south central Sweden

This study investigates the geochemical and petrological characteristics of solid bitumen in the DBH15/73 core from the Furongian (upper Cambrian) and Miaolingian (middle Cambrian) Alum Shale in Billingen, south central Sweden. At Billingen a > 30 m thick Permian diabase (dolerite sill) intruded approximately 100 m above the Alum Shale that promoting the formation of solid bitumen in the uppermost half of the Alum Shale due to enhanced heat flow. The bitumen has been classified into bituminite/diagenetic solid bitumen (DSB), initial-oil solid bitumen (IOSB), and primary-oil solid bitumen (POSB) based on their genesis, morphology and random solid bitumen reflectance (BRo). The Miaolingian shale, constituting the lower part of the Alum Shale, is immature and contains solely bituminite and DSB, with measured BRo ranging from 0.40% to 0.48%. In contrast, the Furongian shale exhibits enrichment in IOSB and POSB and range from marginally mature to peak oil generation with towards the top of the section. Characteristics of uneven heating is seen in the IOSB (BRo: 0.97–1.08%) including oxidation rims and abnormally high maturity surrounding fractures. The POSB (BRo: 0.63–2.01%) is present not only in the Alum Shale but also in the overlying Ordovician Latorp limestone and the underlying Kakeled Limestone Bed, and shows flow structures which is further evidence for migration. The abundance of POSB and IOSB is determined through maceral point counting, revealing POSB as the dominant bitumen type (1.54–7.13 vol%), while IOSB constitutes the minority (0.05–0.31 vol%) within the Furongian shale. This distribution suggests rapid thermal evolution of organic matter within the oil generation window. Additionally, a reduction in free hydrocarbons (Rock-Eval S1), potential hydrocarbons (Rock-Eval S2), and unexpectedly low Tmax was observed in the Furongian shale. Results indicate that hydrocarbon generation resulting from thermal intrusion contributes to the relatively low S2. Migration of POSB and generated oil to adjacent layers leads to the loss of S1, while the reduced Tmax may be attributed to high uranium content which weakens carbon chain bond energy. These anomalies result in an underestimation when evaluating thermal maturity and kerogen type conversion based on Rock Eval data alone.

Molecular Composition Evolution of Dissolved Organic Matter With Water Depth in Prydz Bay of East Antarctic: Carbon Export Implications

AbstractThis study analyzes the molecular composition of dissolved organic matter (DOM) in Prydz Bay by Fourier Transform Ion Cyclotron Resonance mass spectrometry to probe the carbon sequestration capacity in the continental shelf system. Concentrations of particulate organic carbon (POC), particulate nitrogen and dissolved organic carbon (DOC) with water depth show that POC could be mainly decomposed into DOC and/or microbially degraded. Highly labile DOC is further degraded and remineralized by microorganisms within the upper 200 m, as evidenced by a downward enrichment of 13CPOC and increases in the average molecular weight, oxygen atom number (O) and double bond equivalents of DOM molecules, indicating that biodegradation is the main driver for particulate organic matter and DOM evolution with water depth. Semi‐quantitative calculation demonstrates that ∼83% of POC was transformed to DOC as well as dissolved inorganic carbon (DIC), and ∼30% of DOC further to DIC via microbial degradation within the upper 200 m in summer, resulting in a relatively low total organic carbon content in sediments of Prydz Bay. The newly transformed DIC and residue DOC can be preserved in the deep layer due to the formation of well stratified and stable water body in summer of Prydz Bay, ultimately entering the regional circulation system instead of being released back into the atmosphere. This could be one of the most important processes determining the atmosphere CO2 uptake in the continental shelf system of Southern Ocean.

The H2 potential of the Colombian coals in natural conditions

Coal gasification to manufacture dihydrogen (H2) has long been known as a surface process. Recent works have also highlighted the H2 generating potential of the Organic Matter (OM). The evolution of OM generates H2 all along the process but this gas is only expected to remain as free H2 after the maturation and expulsion of the hydrocarbons (HC) which means at a high temperature of above 200 °C. In this paper we studied the potential of three different tertiary coals from Amaga, La Jagua de Ibirico and Barrancas, all located in Colombia. Their H2 yields were studied using a pyrolyser and the kinetic of the H2 generation were quantified. All the studied coals are immature to early mature as source rock (SR) with large TOC content, between 66 and 83%, and good H2 potential. The highest values were found for the Barrancas area where the potential reached 25 mg H2/g TOC. The temperature corresponding to the peak of H2 generation is between 740 and 800 °C depending of the heating rate. This corresponds to the 200–300 °C for the H2 kitchen, even if the H2 generation starts before as already observed for continental organic rich source rock. Comparison with the other coals shows that H2 potential is linear with TOC. In the Colombian coals, the H2 yield in mg H2/g of rock is around 1/4 of the TOC content. In average, these coals have so a H2 yield about 10 000 mmol H2/kg of rock, two orders of magnitude above the “best” olivines. It should nevertheless be kept in mind that the extrapolation of these laboratory data to sedimentary basins remains unconstrained and will need to be refined when well data and modelling tools are available.

Post-drainage vegetation, microtopography and organic matter in Arctic drained lake basins

Wetlands in Arctic drained lake basins (DLBs) have a high potential for carbon storage in vegetation and peat as well as for elevated greenhouse gas emissions. However, the evolution of vegetation and organic matter is rarely studied in DLBs, making these abundant wetlands especially uncertain elements of the permafrost carbon budget. We surveyed multiple DLB generations in northern Alaska with the goal to assess vegetation, microtopography, and organic matter in surface sediment and pond water in DLBs and to provide the first high-resolution land cover classification for a DLB system focussing on moisture-related vegetation classes for the Teshekpuk Lake region. We associated sediment properties and methane concentrations along a post-drainage succession gradient with remote sensing-derived land cover classes. Our study distinguished five eco-hydrological classes using statistical clustering of vegetation data, which corresponded to the land cover classes. We identified surface wetness and time since drainage as predictors of vegetation composition. Microtopographic complexity increased after drainage. Organic carbon and nitrogen contents in sediment, and dissolved organic carbon (DOC) and dissolved nitrogen (DN) in ponds were high throughout, indicating high organic matter availability and decomposition. We confirmed wetness as a predictor of sediment methane concentrations. Our findings suggest moderate to high methane concentrations independent of drainage age, with particularly high concentrations beneath submerged patches (up to 200 μmol l−1) and in pond water (up to 22 μmol l−1). In our DLB system, wet and shallow submerged patches with high methane concentrations occupied 54% of the area, and ponds with high DOC, DN and methane occupied another 11%. In conclusion, we demonstrate that DLB wetlands are highly productive regarding organic matter decomposition and methane production. Machine learning-aided land cover classification using high-resolution multispectral satellite imagery provides a useful tool for future upscaling of sediment properties and methane emission potentials from Arctic DLBs.

Asteroidal Organics from the Sample Return Mission Hayabusa2 and their Implication for Understanding our Origins

The C-type asteroid Ryugu samples returned by the Hayabusa2 spacecraft are the chemically most pristine material in the Solar System, as they have not been exposed to terrestrial environments. The organic matter in Ryugu records the molecular evolution from the Sun’s parent molecular cloud chemistry to asteroidal aqueous alteration. In this article, we review the results of Ryugu sample analysis and discuss the evolution of organic matter in the early Solar System by comparing these results with recent radio and infrared observations of protostars and protoplanetary disks.

The influence of hydrocarbon generation on the sealing capability of mudstone caprock rich in organic matter

To investigate the sealing capability of mudstone caprock during the evolution of organic matter (OM)-rich mudstone, a series of hydrous pyrolysis experiments were first conducted to examine the impact of hydrocarbon generation. The pore type, pore structure, porosity, and gas breakthrough pressure of pyrolytic residual samples were analyzed by field emission scanning electron microscopy, low pressure nitrogen adsorption measurements, porosimetry, and gas breakout core experiments. To model the environment at different depths, these six experiments on hydrous pyrolysis were performed at different temperatures, lithostatic pressures, and hydrodynamic pressures, while other experimental factors such as the original sample, heating time, and rate were kept constant. The results showed that during the thermal evolution process, hydrocarbons were generated from OM in mudstone, resulting in the formation of pores within the OM. Organic acids produced by hydrocarbon generation effectively dissolved minerals, leading to the creation of numerous dissolution pores. Changes in pore type led to changes in pore structure and porosity. The volume of micropores and macropores showed an increasing trend before reaching a Ro value of 1.41%. However, after passing this threshold, they began to decrease. The volume of mesopores showed a decreasing trend before reaching a Ro value of 1.32%. After 1.32%, they began to increase. The porosity was mainly affected by the pore volumes of the mesopores and macropores. The porosity exhibited two peaks: the first occurred at a Ro value of 0.72%, with a porosity level of 4.6%. The second occurred at a Ro value of 1.41% and a porosity level of 10.3%. The breakthrough pressure was a comprehensive reflection of these influences, and its trend exhibited a negative correlation with porosity (R2 = 0.886). For two high values of porosity, the breakthrough pressure corresponded to two low values. Smaller values of the breakthrough pressure indicated a poorer sealing capability of the mudstone caprock. Overall, hydrocarbon generation in the mudstone affected the sealing capability. The mudstone in the studied area exhibited good sealing at Ro below 1.32%. However, once above the 1.32% threshold, the fluctuations of the breakthrough pressure values exhibited considerable variability, requiring a comprehensive evaluation to assess its sealing capability.

Assessment of Phytotoxicity in Untreated and Electrochemically Treated Leachates through the Analysis of Early Seed Growth and Inductively Coupled Plasma-Optical Emission Spectroscopy Characterization

The treatment of stabilized leachates with high refractory organic matter content, which are over 10 years old, presents a challenge. This study explored the potential of electro-coagulation (EC) and electro-oxidation (EO) treatment systems to address this issue. The objective of this study was to investigate the phytotoxicity of the proposed treatment system on seed growth and examine possible relationships between phytotoxicity results and the characterization of leachates, effluents, soil, and radicles. Phytotoxicity tests were conducted on seeds of Lactuca sativa, Cucumis sativus, and Phaseolus vulgaris, using Inductively Coupled Plasma-Optical analysis. The evolution of organic matter was monitored by fractionating the chemical oxygen demand (COD) and humic substances. The biodegradability index increased from 0.094 in raw leachate to 0.26 and 0.48 with EC and EO, respectively. Removal rates of 82%, 86%, 99%, and 81% were achieved for COD, dissolved organic carbon, color, and ammoniacal nitrogen, respectively. The biodegradable COD increased from 26% in raw leachate to 39% in the EC process and 58% in the EO process effluent. The proposed treatment system successfully broke the aromatic structures of the humic substances present in the raw leachate, thereby increasing the content of biodegradable material. Phytotoxicity tests revealed that the proposed treatment system significantly reduced the phytotoxicity of the generated effluents.

Diagenetic alterations induced by lamina-scale mass transfer and the impacts on shale oil reservoir formation in carbonate-rich shale of the Permian Lucaogou Formation, Jimusar Sag

Diagenesis plays a crucial role in shale oil reservoir formation. However, complex organic-inorganic interactions result in pore system formation and heterogeneity changes at the centimeter, or even micrometer scale, which controls the evolution of shale oil reservoirs. In this paper, an integrated approach including core observation, thin section observation, cathodoluminescence thin section observation, scanning electron microscope, μ-XRF analysis, electron microprobe analysis, AMICS analysis, LA-ICP-MS analysis, and isotope analysis was used to clarify the laminae combination carbonate-rich shale, diagenetic alterations in different types of shale laminae and the controls on shale oil reservoir formation. According to the lamina combination, the carbonate-rich shale in the Permian Lucaogou Formation can be divided into three types. They are shale consists of dolomitic lamina and terrigenous felsic lamina (Type A shale), shale consists of calcite-rich tufaceous lamina and terrigenous felsic lamina (Type B shale) and shale consists of calcareous lamina and tufaceous lamina (Type C shale). Dolomite cementation is the major diagenesis in terrigenous felsic lamina of Type A shale. The dolomite can be identified as the early stage forming from recrystallization of micrite dolomite, and the late stage precipitate from adjacent dolomitic lamina. In the terrigenous felsic lamina of Type B shale, however, the calcite cementation is the dominated diagenesis, which was sourced from adjacent calcite-rich tufaceous lamina. Also, some feldspar dissolutions occurred in terrigenous felsic lamina during organic matter evolution. For the Type C shale, the main diagenetic alteration is micrite calcite recrystallization in calcareous lamina. The dissolution and precipitation of carbonate minerals between different laminae of carbonate-rich shale reveal that the organic matter evolution significantly influence the diagenetic alterations of inorganic minerals. Particularly, the diagenetic mass transfer and redistribution at the micro-scale in a relatively diagenetic system were confirmed by organic-inorganic interactions in laminated shale. In this process, dissolution pores and recrystallization pores have provided considerable reservoir pores for shale oil.

Vacuum-ultraviolet irradiation of pyridine:acetylene ices relevant to Titan astrochemistry.

Nitrogen-containing polycyclic aromatic hydrocarbons (NPAHs) are important molecules for astrochemistry and prebiotic chemistry, as their occurrence spans from interstellar molecular clouds to planetary systems. Their formation has been previously explored in gas phase experiments, but the role of solid-state chemical reactions in their formation under cryogenic conditions remains elusive. Here, we explore the formation of NPAHs through vacuum ultraviolet (VUV) irradiation of pyridine:acetylene ices in amorphous and co-crystalline phases, with the aim to simulate conditions relevant to the interstellar medium and Titan's atmosphere. Our results show that the synthesis of ethynylpyridines from VUV-irradiated pyridine:acetylene amorphous ices is achievable at 18 K. In the co-crystal phase, photolysis at 110 K leads to the formation of NPAHs such as quinolizinium+ and precursors, reflecting a dynamical system under our conditions. In contrast, irradiation at 90 K under stable conditions did not produce volatile photoproducts. These results suggest that such chemical processes can occur in Titan's atmosphere and potentially in its stratosphere, where the co-condensation of these molecules can form composite ices. Concurrently, the formation of stable co-crystals can influence the depletion rates of pyridine, which suggests that these structures can be preserved and potentially delivered to Titan's surface. Our findings provide insights into the molecular diversity and chemical evolution of organic matter on Titan, crucial for future space exploration missions, such as the Dragonfly mission, which may uncover higher-order organics derived from pyridine precursors on Titan's surface.

Olivine-catalyzed glycolaldehyde and sugar synthesis under aqueous conditions: Application to prebiotic chemistry

The presence of minerals in the prebiotic environment likely shaped the evolution of organic matter, thereby contributing to the emergence of prebiotic systems. Records of such systems are lacking and the interactions between abiotic organic matter and primary minerals remain poorly understood. Here, we demonstrate the ability of olivine silicates, in simulated early Earth or planetary aqueous environments, to catalyse glycolaldehyde formation from only formaldehyde, and help producing sugars that are essential components for life, through the formose reaction. By combining comprehensive gas chromatography analyses on experimental samples with quantum chemical simulations, we provide a mechanism for an olivine-catalyzed glycolaldehyde formation. Our findings suggest that olivine plays a triple role in the formose chemical network: maintaining an alkaline pH, enabling the initiation step towards the formation of glycoladehyde (which is typically the most challenging step) and promoting the autocatalytic cycle. These results open-up new scenarios on the impact of primary minerals on the evolution of chemical pathways in aqueous environments that were probably essential for the emergence of the first biomolecules.

Diagenetic evolution of tight sandstone and the formation of an effective reservoir in the lower member 3 of the Shahejie Formation, Bohai Bay Basin, East China

Heterogeneity in the physical properties of tight sandstones is mainly caused by complex diagenetic interactions in various combinations during the burial process. The tight sandstone oil in the Linnan Sag of Bohai Bay Basin has great development potential but it is unclear how effective reservoirs were formed, and this is a significant reason why exploration in the deep reservoir is so difficult. Here we studied the diagenetic evolution of the tight sandstone of Lower Member 3 of the Shahejie Formation, Linnan Sag, Bohai Bay Basin, by using cores, thin sections, XRD, SEM, grain-size analysis, high-pressure mercury intrusion porosimetry, fluid inclusions, and carbon and oxygen stable isotopes. Compaction, replacement, cementation and dissolution diagenesis are identified; all four processes mainly occur in the A phase of mesodiagenesis. The interaction of formation burial, thermal evolution of organic matter and dehydration of gypsum leads to the alternating presence of three stages of alkaline fluids and two stages of acidic fluids. The average dissolution porosity of the dissolution sandstone facies is greater than the lower limit of the porosity for the effective reservoir in the study area, which is key to the formation of effective reservoirs. By determining differential diagenetic evolution sequences of tight sandstone reservoirs under the constraints of different lithologies where sandstone is interbedded with mudstone, we are able to elucidate the formation of the effective reservoir as follows: (1) In the eodiagenetic stage, a large amount of early carbonate cement developed in the sandstone adjacent to the mudstone, filling the primary pores and forming a cementation sandstone facies. Smaller amounts of early carbonate cement developed in the interior of the sandstone, which “fixed” the primary pores, and has a positive effect on the formation of a large number of secondary pores in the dissolution stage. (2) In the early stage of mesodiagenesis (A1), due to the filling of primary pores, it is difficult for acidic fluids to enter the cementation sandstone facies adjacent to mudstone, and the dissolution is weak. But dissolution within the sand body was strong, producing a large number of dissolution pores and forming a dissolution sandstone facies that clearly enhanced the physical properties. (3) In a second early stage of mesodiagenesis (A2), dissolution still played a dominant role in the dissolution sandstone facies, due to the development of dissolution pores in the previous stage (it is easy for acidic fluids to enter the dissolution sandstone facies). The physical properties of the dissolution sandstone facies were once again enhanced and an effective reservoir gradually began to form. (4) At the end of mesodiagenesis stages A1 and A2 (26.2–24.6 Ma; 7.5–2.8 Ma), the reservoir experienced two phases of petroleum charging. The charging of the cementation sandstone facies developed at the margins of the sandstones was difficult due to the filling of primary pores. The dissolution sandstone facies are oil-bearing, with higher porosity, which indicates an effective reservoir. By coupling the thermal evolution of organic matter and the dehydration of gypsum with differential diagenetic evolution and the porosity evolution of reservoir, we are able to establish a reservoir genetic model that involves alternating seepage of organic acids and alkaline brines.

Образование углеводородных газов доманиковым сланцем при пиролизе в автоклаве в присутствии воды

A sample of Domanik shale from a stratotype section along the river Chut (Ukhta District, Komi Republic, Russia) was affected to temperatures of 250—375 °C in an autoclave in the presence of water. The composition and yield of the resulting hydrocarbon gases was studied by gas chromatography. The yield of all C1—C5 hydrocarbons grew exponentially with increasing temperature in the autoclave. The total yield of gaseous hydrocarbons C1—C5 at 375 °C was 71 mg/g Corg and reached 18 mg/g Corg for methane. The increasing temperature in the autoclave resulted in decreasing ratio of methane/C2+ gases, which reflected a changing mechanism of methane formation at the corresponding stage of the thermal evolution of the Domanik organic matter.

Further study on the genesis of lamellar calcite veins in lacustrine black shale—A case study of Paleogene in Dongying Depression, China

Lamellar calcite veins are prevalent in carbonate-rich, lacustrine dark shale. The formation mechanisms of these veins have been extensively debated, focusing on factors such as timing, depth, material source, and driving forces. This paper examines dark lacustrine shale lamellar calcite veins in the Paleogene strata of Dongying Depression, using various analytical techniques: petrography, isotope geochemistry, cathodoluminescence, inclusion thermometry, and electron probe micro-analysis. Two distinct types of calcite veins have been identified: granular calcite veins and sparry calcite veins. These two types differ significantly in color, grain structure, morphology, and inclusions. Through further investigation, it was observed that vein generation occurred from the shallow burial period to the maturation of organic matter, with a transition from granular calcite veins to sparry calcite veins. The granular calcite veins exhibit characteristics associated with the shallow burial period, including plastically deformed laminae and veins, the development of strawberry pyrite, the absence of oil and gas, weak fractionation in oxygen isotopes, and their contact relationship with sparry calcite veins. These granular calcite veins were likely influenced by the reduction of sulfate bacteria. On the other hand, sparry calcite veins with fibrous grains are antitaxial and closely linked to the evolution and maturation of organic matter. They contain oil and gas inclusions and show a distribution range of homogenization temperature between 90 °C and 120 °C and strong fractionation in oxygen isotopes, indicating formation during the hydrocarbon expulsion period. The carbon isotope analysis of the surrounding rocks and veins suggests that the material for vein formation originates from the shale itself, specifically authigenic micritic calcite modified by the action of methanogens. The opening of horizontal fractures and vein formation is likely driven by fluid overpressure resulting from undercompaction and hydrocarbon expulsion. Veins may form rapidly or through multi-stage composite processes. Early veins are predominantly formed in situ, while late veins are a result of continuous fluid migration and convergence. Furthermore, the veins continue to undergo modification even after formation. This study emphasizes that the formation of lamellar calcite veins in shale is a complex diagenetic process influenced by multiple factors: biology, organic matter, and inorganic processes, all operating at various stages throughout the shale's diagenetic history.

Evolution processes and diagenetic response of paleo-pore fluids in continental rift basin: A case study of Bonan Sag

Evolution and transport processes of pore fluids are accompanying with the burial process of sedimentary basins. Those processes lead to redistribution of materials and energies, and control the distribution of favorable reservoirs in sedimentary basins too. For petroliferous basins, confirming the evolution processes of pore fluids is useful for favorable reservoirs prediction. In this study, formation waters chemistry characteristics, skeleton particle compositions, and diagenetic products of sandstones were all take into consideration. It is to invert the evolution processes of pore fluids in continental rift basin. This study shows the changes of formation waters, diagenetic products and skeleton particle compositions are regularly with depth. The evolution processes of pore fluids are mainly controlled by basin sinking and uplifting, fluids concentration, mudstones compaction, organic matter evolution, diagenesis. The evolution of pore fluids in Bonan Sag have experienced seven stage: firstly, primary lake water; and then alkaline fluids from mudstone, which is caused by compaction; and then acidic fluids with organic acids; and then the alkaline fluids, which is caused by basin uplifting and water-rock interactions; and then acidic fluids with CO2, which is from cracking of organic matters; and then acidic fluids with CO2/H2S which caused by TSR; at last, alkaline fluids caused by deep buried and water-rock interactions. Changes of pore fluids (physical or chemical) lead parts of minerals in sandstones be unstable, and then dissolved by pore fluids. At the same time, part of dissolved particles in pore fluids reacted with each other, and then precipitated as diagenetic products.

Promoted micropollutant degradation and structural evolution of natural organic matter by a novel S(IV)-based water treatment strategy

The ubiquity of various organic micropollutants in global water and wastewater has raised considerable concern about their cost-efficient elimination. This study reported that the novel UV365/FeTiOX/S(IV) system could accomplish superior abatement of different micropollutants (e.g., carbamazepine, CMZ) in 30–45 min with excellent reusability and stability of FeTiOX. In addition, this system functioned effectively to remove roxarsone and As(III)/As(V) by catalytic oxidation and adsorption, respectively. Mechanistic investigations suggested the dual roles of S(IV) in enhancing pollutant oxidation, i.e., promoted Fe(II)/Fe(III) cycle and photocatalysis. These processes facilitated the continuous generation of multiple oxidizing intermediates (e.g., hydroxyl radicals, sulfate radicals, and singlet oxygen), in which the last one was first proposed as the main contributor in iron-mediated S(IV)-based oxidation processes. Based on the product identification, the transformation pathways of four different micropollutants were tentatively unraveled. The in silico prediction suggested the lower environmental risks of the final reaction products than the precursors. Particularly, the structural alteration of humic acid was analyzed, indicating an increased O/C ratio after oxidative treatment. Overall, this study has implications for developing an efficient oxidation technique for removing multiple micropollutants in water and facilitating the mechanistic reactivity modulation of the S(IV)-based oxidation strategies in water treatment.

Evidence of Potential Organo-Mineral Interactions during the First Stage of Mars Terraforming

Future space missions to Mars will depend on the development of bioregenerative life support systems. Mars regolith contains most of the nutrients needed for plant growth, but not organic matter (OM). Although Mars simulants have been deeply characterized and tested as growing media, no data are available about their possible modification occurring during terraforming, including the interaction of exogeneous OM with iron (Fe) oxides, particularly abundant in Mars regolith. The aim of this study was to investigate the mineral transformation and the OM evolution occurring in the early stages of the terraforming process. Potato was grown for 99 days on Mojave Mars Simulant MMS-1, alone (R100) and mixed with a compost 70:30 v:v (R70C30), and on a fluvial sand, alone (S100) and mixed with compost (S70C30), for comparison. Bulk (BK) and potato tubero/rhizo-sphere (RH) soils were fractionated to obtain particulate OM (POM) and mineral-associated OM (MAOM). Bulk samples and corresponding fractions were characterized for total nitrogen and organic carbon (C) and analyzed by Fe K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Organic C increased by 10 and 25 times in S70C30 and R70C30, respectively, compared to S100 and R100. Most of the organic C accumulated in the POM fraction of both growing substrates, while its content in the MAOM was 3 times higher in R70C30 than in S70C30. No significant differences between BK and RH were found. Finally, ferrihydrite mediated exogenous OM stabilization in regolith-based substrates, while Fe(III)-OM complexes were detected exclusively in sand-based growing media. Understanding mechanisms and testing potential sustainable practices for creating Mars regolith similar to terrestrial soil will be fundamental to sustain food crop production on Mars.