Concentration Of Functional Groups Research Articles

A metal–organic frameworks-imprinted emulsion interface with dynamic size- and site-selective recognition for significantly enhanced flavoniods extraction

The boronic acid suspended Cr based MIL-100 (MIL-100-B) sorbents have been widely used to separation of cis-diol containing molecules. However, it’s still challenging in fabrication of high performance metal organic frameworks (MOFs) due to its irregular size and low content of functional groups. For improving identification efficiency, the emulsion microreactor were firstly designed to purify MIL-100-B prior to their use. Herein, a highly ordered MOFs-imprinted polymer microsphere was synthesized by O/W Pickering emulsion template, which can highly selective separation of MIL-100-B via the synergistic effect of boronic acid sites and imprinted cavities. The obtained purified H-MIL-100-B exhibited the uniform size and abundant boronic acid groups (B elements ratio up to 27.37 %). The emulsion imprinted microsphere (EIMs) showed the good selectivity towards MIL-100-B. Additionally, the obtained MOF-imprinted microsphere exhibited green, convenient, sustainable separation process towards the purification and recycle of MIL-100-B. The purified MOFs (H-MIL-100-B) were used to specific bind with cis-diol flavoniods naringin (NRG). Satisfactorily, H-MIL-100-B show high adsorption amount (43.69μmol/g at 308 K), fast capture kinetics (160 min), high selectivity and excellent regenerability (up to seven cycles). Remarkably, the purified NRG solutions displayed lasting antibacterial activity against Staphylococcus aureus (S. aureus) with inhibition zone of 13.47 mm. More importantly, the H-MIL-100-B could effectively promote the specific recognition ability of NRG by reducing matrix interference and improving purification efficiency (93.93 %) from complex natural extracts. A high score (0.75) was predicted via analytical GREEnness (AGREE) approaches, demonstrating environmentally friendly and greenness of separation process. The MOFs-imprinted emulsion microspheres possessed dynamic recognition properties towards target MOFs, thus opening new direction for the development of convenient and efficient microreactor for the purification of other functional MOFs.

Investigation of the sorption activity of native coals to air oxygen

The influence of the gaseous medium during sample preparation, the granulometric composition, the duration of contact with air and the stage of metamorphism on the process of oxygen sorption from the air was established. It is shown that conducting sample preparation in an air atmosphere leads to primary oxidation of the outer surface of the coals, which introduces an error in determining the oxygen sorption rate constant. Fine coal fractions (0-0.2 mm) with a more developed outer surface have increased oxygen absorption activity. The rate of oxygen sorption is maximal at the initial moment of the interaction of active carbons with air and decreases with the duration of contact. The least metamorphosed hard coals of the D brand with a high content of reactive functional groups and a developed porous structure are characterized by the greatest chemisorption activity.

Plasma Functionalization for Enhanced Natural Dye Affinity on Bioplastics: A Novel Approach

ABSTRACTBioplastics offer biodegradability and reduced environmental impact but often use nondegradable synthetic dyes. This study introduces a novel application of glow discharge plasma (GDP) technology to modify cassava starch‐based bioplastic sheets, specifically optimizing conditions to enhance their hydrophilicity and adhesion for natural dyes. This research systematically tailors plasma treatment parameters to maximize the interaction between bioplastics and eco‐friendly natural dyes. Optimal conditions, identified as 30 W for 3 min using oxygen, air, and nitrogen plasma treatments, demonstrate significant advancement in sustainable material development. Analyses (ATR‐FTIR, EDX, XPS) showed increased concentration of polar functional groups and oxygen content, with FE‐SEM and water contact angle measurements revealing improved surface roughness and wettability, respectively. Oxygen plasma treatment yielded the highest hydrophilicity and crystallinity of the polymer. Tensile tests indicated increased strength and decreased elongation. UV‐Vis spectroscopy confirmed enhanced dye retention and reduced leaching. This study demonstrates GDP's potential to incorporate eco‐friendly natural dyes into bioplastics, thereby contributing to the development of more sustainable materials.

Thermodynamic properties and structure of interfacial boundaries in nonionic fluids from the multilayer quasichemical model

The interfacial properties and structure of nonuniform fluids containing complex chainlike molecules and associating species are very much needed in a variety of different fields, including enhanced oil recovery, drug delivery, pharmacy, cosmetics, food processing, etc.Recently, we described the Multilayer Quasichemical Model (MQuM) of a nonuniform fluid that provides a remarkably detailed structural information, including the local concentration and orientation of functional groups of the molecules, the orientation profiles of the chemical bonds in molecular chains and the orientation profiles of the hydrogen bonds in the mixture.In this work, we focus on the description of thermodynamic properties with the aid of MQuM, including the interfacial tension and the profiles of normal and transverse pressures. Before proceeding to more complex systems, a test is performed through comparison with the previously known results from the Scheutjens-Fleer theory for the planar liquid–vapor interface and spherical droplet in one-component fluid of nonpolar monomeric molecules. The model is applied then for planar interfaces between the liquid phases in mixtures of water with n-alkanes of different chain length and for spherical drops in model systems that contain an associating solvent, a nonpolar chain and a nonionic amphiphile. Our theoretical results are compared with experiment, predictions from iSAFT and MD simulation data from the literature. For the spherical droplets, we discuss the model description of the dependence of the interfacial tension on the curvature and estimate the Tolman length. For the planar interface between the equilibrium liquid phases in water – n-alkane mixtures, the interfacial tensions predicted from the model are in good agreement with experiment.

Enhanced Removal of Chlorpyrifos, Cu(II), Pb(II), and Iodine from Aqueous Solutions Using Ficus Nitida and Date Palm Biochars

This study explores the adsorption efficiency of biochar derived from palm trees and Ficus nitida for the removal of various contaminants, including Cu(II), Pb(II), iodine, and chlorpyrifos from aqueous solutions. Biochar was prepared using a two-step pyrolysis process for date palm biochar and single-step pyrolysis for Ficus nitida biochar. Characterization techniques such as SEM, EDX, and FTIR revealed a significant surface area and a variety of functional groups in both types of biochar, essential for effective adsorption. The date palm biochar exhibited superior adsorption capacities for Cu(II) and Pb(II) ions, achieving efficiencies up to 99.9% and 100%, respectively, due to its high content of oxygen-containing functional groups that facilitated strong complexation and ion exchange mechanisms. Conversely, Ficus nitida biochar demonstrated a higher adsorption capacity for iodine, reaching 68% adsorption compared to 39.7% for date palm biochar, owing to its greater surface area and microporosity. In the case of chlorpyrifos, Ficus nitida biochar again outperformed date palm biochar, achieving a maximum adsorption efficiency of 87% after 24 h of incubation, compared to 50.8% for date palm biochar. The study also examines the effect of incubation time on adsorption efficiency, showing that the adsorption of chlorpyrifos by date palm biochar increased significantly with time, reaching a maximum of 62.9% after 48 h, with no further improvement beyond 12 h. These results highlight the importance of biochar characteristics, such as surface area, pore structure, and functional groups, in determining adsorption efficiency. The findings suggest that optimizing pyrolysis conditions and surface modifications could further enhance the performance of biochar as a cost-effective and sustainable solution for water purification and environmental remediation.

Achievement of biochar photocatalytic performance by synergistic oxidation of sulfuric acid/hydrogen peroxide: Towards revealing the mechanism of synergistic oxidation on photocatalytic performance

The oxygen-containing functional groups of biochar have great potential in tailoring photochemical properties, but the content of oxygen-containing functional groups of pristine biochar is insufficient to support photocatalytic reactions. In this study, a synergistic oxidation of H2SO4 and H2O2 was innovatively proposed to prepare biochar photocatalysts (OGPC400). The results showed that the synergistic oxidation of H2SO4 and H2O2 increased the contents of hydroxyl and carboxyl groups of biochar with the degree of oxidation, and the total concentration of acidic functional groups was about 4 mmol/g higher than that of the oxidation with H2SO4 or H2O2 alone, which was attributed to the synergistic oxidation to promote the conversion of CH and C-OH on the benzene ring. The achievement of electron exchange among hydroxyl and carboxyl groups and internal electron transfer within biochar by the benzene ring as a medium resulted in 100 % degradation of rhodamine b (RhB) and 25 times reaction rate constant higher than that of pristine biochar, as compared to only 45 % or 37 % degradation by oxidation with H2SO4 or H2O2 alone. The exciting results confirmed the positive availability of H2SO4 and H2O2 synergistic oxidation on biochar photocatalysts, which is expected to be applied in environmental remediation.

Kinetic analysis of coal oxidative pyrolysis before and after immersion effect

The oxidative pyrolysis kinetics of coal before and after immersion effect was studied by thermogravimetric experiments. Non-isothermal thermogravimetric analysis data were analyzed at four heating rates of 5, 10, 20 and 30 K/min. Furthermore, temperature-programmed experiments and Fourier-transform infrared (FTIR) spectroscopy were employed to understand the oxidation activity and chemical structure of raw coal and soaked coal. After coal immersion effect, the increase in the content of active functional groups, the increase in the concentration of gaseous products, and the decrease in crossing point temperature during oxidation process all indicate that soaked coal is easier to oxidize and spontaneously combust. Lastly, four model-free methods such as Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Friedman and Kissinger methods are employed to calculate the activation energy (Eα). Kinetic analysis reveals that Eα value obtained by the former three methods significantly depends on the conversion of coal oxidative pyrolysis process, and the average Eα value of soaked coal obtained by four methods is lower than that of raw coal. For the kinetic analysis of coal oxygen adsorption and combustion stages, it is more reliable to adopt the FWO and KAS methods in turn. This research helps to better understand the mechanism of enhanced oxidation activity of soaked coal and optimizes the calculation method of kinetic parameters in different oxidation stages of coal.

Renewable Resources as Promising Materials for Obtaining Graphene Oxide-like Structures.

Currently, one of the topical directions in the field of production and application of graphene-like nanostructures is the use of renewable natural raw materials, which have unlimited resources for an economically efficient large-scale yield of a product with environmental safety. In this regard, we present the production of graphene oxide (GO) from a renewable natural raw material of plant biomass, birch activated carbon (BAC), and a comparison of the obtained physicochemical, mechanical, and electrical properties of birch activated carbon-graphene oxide (BAC-GO) and graphite-graphene oxide (G-GO) synthesized from the initial materials, BAC and graphite (G). Results obtained from this study confirm the successful oxidation of BAC, which correlates well with the physical-chemical dates of the G-GO and BAC-GO samples. Change in data after the oxidation of graphite and BAC was facilitated by the structure of the starting materials and, presumably, the location and content of functional oxygen-containing groups in the G-GO and BAC-GO chains. Based on the results, the application of a cost-effective, eco-friendly colloidal solution of nanodispersed BAC-GO from a plant biomass-based high-quality resource for producing large-scale nanostructured graphene is validated which has potential applicability in nanoelectronics, medicine, and other fields.

Phosphorus-loaded coconut biochar: A novel strategy for cadmium remediation and soil fertility enhancement

The management of cadmium (Cd) contamination in soils poses a significant environmental challenge. This study investigates the effectiveness of phosphorus (P)-loaded coconut biochar, synthesized at various pyrolysis temperatures (450°C, 500°C, 550°C, and 600°C), in immobilizing Cd and enhancing P availability in soil environments. The biochar underwent a series of treatments including activation and P enrichment, followed by incubation trials to evaluate its performance in Cd immobilization and P bioavailability enhancement across varying soil concentrations (0.5 %, 1.0 %, and 2.0 %) over time periods of 15, 30, and 45 days. Remediation progress was monitored using phytotoxicity assessments with radish (Raphanus sativus) root length as a bioindicator, supplemented by urease activity analyses. Notably, the activation process increased the P loading capacity of biochar produced at 450°C, 500°C, and 550°C by 54.6 %, 72.4 %, and 51.8 %, respectively, while reducing the P retention capacity of biochar prepared at 600°C by 31.0 %. The biochar activated at 550°C presented the highest efficiency in remediating Cd-contaminated soils. Key findings indicate that the enhanced specific surface area and oxygenated functional group content of the activated biochar facilitated Cd adsorption and P uptake. The P-loaded biochar exhibited a substantial adsorption capacity for Cd, particularly effective at lower concentrations, rendering it highly suitable for soil remediation purposes. Additionally, the study revealed that the application of biochar led to an increase in soil pH, resulting in precipitation of Cd as hydroxide species and formation of insoluble complexes with phosphate ions, thereby reducing its bioavailability. In summary, incorporating P-loaded biochar into soil significantly improved soil quality and enhanced Cd passivation in contaminated soils. The utilization of biochar produced at 550°C, which exhibited optimal performance, suggests a practical and sustainable approach for soil remediation. Future research endeavors should prioritize the refinement of the biochar production process to enhance cost-effectiveness while maintaining high P loading efficiency.

Catalytic ethanolysis of Xiaojihan subbituminous coal to platform chemicals enhanced by pre-oxidation with ozone

Xiaojihan subbituminous coal (XSBC) was pre-oxidized by ozone to prepare oxidized XSBC (OXSBC). Then, the ethanolysis was conducted on OXSBC at 300 °C under an initial nitrogen pressure (INP) of 1 MPa for 2 h. On this basis, the influences of pre-oxidation conditions on the content of oxygen-containing functional groups and the yield of soluble portion (SP) from the ethanolysis of XSBC and OXSBC were explored. The research results show that the yield of SP from the OXSBC ethanolysis is higher than that from the XSBC ethanolysis, and the highest yield of SP from the OXSBC ethanolysis reaches 24.9 wt% at 50 °C for 3 h, an increase of 80.4 % compared to the yield of SP from the XSBC ethanolysis. Besides, the magnetic nanosphere Co-CuFe2O4 catalyst, prepared by adopting the one-pot hydrothermal method, was applied to the catalytic ethanolysis (CE) of OXSBC3 at 300 °C, 1 MPa INP, and 2 h. The catalyst is noticeably active in the CE of OXSBC3, as it promotes the yields of SP and oxygen-containing organic compounds obtained from the OXSBC3 ethanolysis from 24.9 wt% and 76.25 mg g−1 to 42.8 wt% and 204.16 mg g−1, respectively. The CE of the model compound demonstrates that ethanol is activated by Co-CuFe2O4 to release H+, H-, and +CH2CH3, which play a crucial role in the conversion of benzyloxybenzene. This study provides a novel approach for acquiring value-added organic chemicals from low-rank coals.

Influence of accelerated aging on mechanical properties and aging behavior of glass fiber reinforced pipe

In this work, the accelerated aging test of GFRP in two thermal environments was conducted. The accelerated aging test was conducted at a constant temperature of 95°C for periods of 3000h to analyze and study the aging behaviors and mechanism under two environments. Resin defects caused by aging were found in the SEM images, and degradation of the fiber/resin interface was observed. Both the hoop tensile test and uniaxial compression test showed brittle fracture characteristics, and the strength of hydrothermal aging specimens decreased more significantly. Due to matrix degradation, uniaxial compression fracture after hydrothermal aging was observed that the resin exhibited poor adhesion. The decrease in the hardness of the outer resin layer was attributed to the development of the degree of molecular chain breakage. ATR-FTIR results showed that the accelerated aging process is accompanied by changes in the concentration of functional groups. The change in C-H intensity was attributed to the post-curing phenomenon. Accelerated aging resulted in the formation of carboxylic acids or esters and the introduction of hydroxyl groups. Thermogravimetric tests showed that accelerated aging did not change the thermal decomposition temperature of epoxy resins, but caused a decrease in resin content.

Turning coal hydrogenation liquefaction residue into high conductivity carbon black with magnesium citrate-assisted steam activation followed by high temperature treatment

The high conductivity carbon black was prepared using coal hydrogenation liquefaction residue as raw material, through a combination methods of solvent extraction purification, magnesium citrate-assisted carbonization, steam activation, and high-temperature treatment. The effects of carbonization and activation process parameters, heat treatment temperatures, and other factors on the microstructure, specific surface area, degree of graphitization, and conductivity of the carbon black were studied. The coal direct liquefaction residue was firstly purified using a xylene and tetrahydrofuran solution with a volume ratio of 1:1 by centrifugal separation method to obtain coal liquefaction asphalt. Then, the coal liquefaction asphalt was mixed with magnesium citrate in a mass ratio of 3:7 and ball-milled for 90 min. After carbonizing at 950 °C for 120 min, magnesium ions were leached out with hydrochloric acid. The obtained sample was activated with steam at 900 °C for 100 min and then underwent high-temperature treatment at 1500 °C under a N2 atmosphere for 120 min. The microstructure of the conductive carbon black exhibited an irregular blocky structure with an average particle size of 2–10 μm. The specific surface area of carbon material was 579.69 m2/g, with the pore distribution predominantly microporous, accounting for 69.81 % of the total pore volume. It featured a higher degree of graphitization (ID/IG=1.06) and fewer surface oxygen-containing functional groups compared with coal direct liquefaction residue. Electrochemical testing showed that the electrical resistance of the carbon material was only 1.55 Ω, and the reversible capacity under a current density of 1 A/g was 96 mAh/g, which are superior to those of the existing commercial conductive carbon black. The microporous structure and higher degree of graphitization facilitate efficient electron transmission, while the lower content of surface oxygen functional groups effectively reduces electron transfer resistance. This work offers new insights into the structural design and performance enhancement of coal liquefaction residue-derived conductive carbon black functional materials. Furthermore, it has significant implications for the future development of conductive carbon black in energy saving and energy storage.

Plastic film from the source of anaerobic digestion: Surface degradation, biofilm and UV response characteristics

This study simulates a major environmental scenario involving “organic fertilizer source” plastics, by exploring the key factors influencing the changes in plastic-films during anaerobic digestion (AD), as well as the responses of the anaerobically digested plastics to ultraviolet (UV) radiation exposure. The results demonstrate that the degradation effect of AD on plastics is reflected by their yellowish and ruptured appearance, slightly worn surfaces, hardening and opacity, and fragmentation. AD significantly increases the content of oxygen-containing functional groups and the degree of unsaturation in plastic films, with thermophilic temperature processes proving more effective than those conducted at mesophilic temperatures. Exposure to UV light has been found to amplify the degradative effects, suggesting the potential cumulative impact of AD and UV. Both AD and UV irradiation reduced the hydrophilicity of plastics. In particular, the hydrophobicity of polylactic acid films was completely disrupted under overlay-exposure. Furthermore, microbial populations on plastic surfaces were mainly bacterial. These bacterial populations were primarily influenced by temperature, and moderately by the plastic types. In contrast, archaea were predominantly affected by both temperature and digested substrate. This study offers a theoretical foundation for strategies aimed at preventing and controlling plastic pollution derived from organic fertilizers.

Dewatering promoting of carbon-rich coal gasification coarse slag by size reduction with surface modification

ABSTRACT Coal gasification coarse slag (CGCS) has become a bulk coal-based solid waste that threatens the ecological environment. The high moisture content of carbon-rich coal coarse gasification slag (CR-CGCS) seriously limits its utilization. In this study, a pore water releasing method was proposed to promote the dewatering of CR-CGCS through size reduction with surface modification. Hexadecyl trimethyl ammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and kerosene were added during the grinding process, respectively. The results showed that kerosene can significantly improve the dewatering efficiency of CR-CGCS more than CTAB and SDS. The final moisture content of the CR-CGCS could be reduced from 47.50% to 33.01%. The SEM and FTIR results illustrated that kerosene could effectively reduce the content of oxygen-containing functional groups on the surface of CR-CGCS more than CTAB and SDS. Meanwhile, the PVM results showed that CR-CGCS modified by kerosene tended to form hydrophobic agglomerates. The LF-NMR results indicated that only the water in the macropores of CR-CGCS could be released in grinding process, but the water in micropores could be reduced when kerosene, CTAB, or SDS was added in grinding. This study provides new insight into enhancing the dewatering of CR-CGCS and theoretical support for the efficient utilization of CR-CGCS.

Impact of ultraviolet radiation energy curing UV primer on adhesion of bamboo lumber surfaces and colorimetry of UV inkjet coatings

ABSTRACT The application of UV digital inkjet printing technology in the home furnishing industry has greatly enriched the diversity of decorative panels. Controlling the UV radiation energy curing UV primers process has a significant impact on the performance of UV printing coatings on bamboo surfaces. The results showed that the UV radiation energy is in the range of 60∼300 mJ cm−2, the adhesion of the UV primer on the surface of bamboo is the best when it is controlled at 180 mJ cm−2, which reaches the standard of 0 level; when the radiation energy reaches 240 mJ cm−2, the content of oxygen-containing functional groups on the surface of the primer is higher, the surface wettability is the best, and the roughness is also relatively high. When the radiation energy reaches 360 mJ cm−2, radiation energy that is too high would reduce the adhesion performance of the UV primer on the surface of bamboo lumber. In addition, the gloss difference of the UV ink coatings between adjacent parameter samples is small, while the color difference is more obvious. The energy of UV radiation should be controlled in the range of 180∼240 mJ cm−2 in the actual production application.

Changes in Soil Aggregate Carbon Components and Responses to Plant Input during Vegetation Restoration in the Loess Plateau, China.

Vegetation restoration is an effective measure to cope with global climate change and promote soil carbon sequestration. However, during vegetation restoration, the turnover and properties of carbon within various aggregates change. The effects of plant source carbon input on surface soil and subsurface soil may be different. Thus, the characteristics of carbon components in aggregates are affected. Therefore, the research object of this study is the Robinia pseudoacacia forest located in 16-47a of the Loess Plateau, and compared with farmland. The change characteristics of organic carbon functional groups in 0-20 cm, 20-40 cm, and 40-60 cm soil layers were analyzed by Fourier near infrared spectroscopy, and the relationship between the chemical structure of organic carbon and the content of organic carbon components in soil aggregates was clarified, and the mechanism affecting the distribution of organic carbon components in soil aggregates was revealed in the process of vegetation restoration. The results show the following: (1) The stability of surface aggregates is sensitive, while that of deep aggregates is weak. Vegetation restoration increased the surface soil organic carbon content by 1.97~3.78 g·kg-1. (2) After vegetation restoration, the relative contents of polysaccharide functional groups in >0.25 mm aggregates were significantly reduced, while the relative contents of aromatic and aliphatic functional groups of organic carbon were significantly increased. The opposite is true for aggregates smaller than 0.25 mm. (3) With the increase in soil depth, the effect of litter on organic carbon gradually decreased, while the effect of root input on the accumulation of inert carbon in deep soil was more lasting.

Differences in humic acid structure extracted from different types of peat

ABSTRACT Peat is an organic mineral resource. Peat contains a large amount of humic acid, and extracting humic acid from peat is a way to efficiently utilize peat. This article mainly studies the effects of using woody, herbaceous, and mossy peat as raw materials on the yield, content, and especially molecular structure of humic acid extraction, including that the oxygen-containing functional groups of humic acids, aromatic carbon content, microcrystalline structure, carbon chain structure, and degree of aromatization. The results showed that the highest yield of humic acid in woody peat was 54.33%, the yield of humic acid in herbaceous peat and mossy peat are relatively low, at 44.67% and 15.00%, respectively. while the woody peat humic acid has the lowest content, that is 38.38%. The content of humic acid in herbaceous peat was 77.33%. and the content of humic acid in mossy peat is 57.85%. Through comprehensive consider, herbaceous peat is more suitable for extracting humic acid. At the same time, this article studies the molecular structures of three peat humic acids and concludes as follows. Woody peat humic acid has the highest degree of aromatization, the highest content of benzene ring, and more functional groups such as methyl, phenol, aromatic ether, carbonyl, and hydroxyl groups. The content of methoxy and methylene groups in herbaceous peat humic acid is relatively high. Through XPS characterization analysis, it was found that the main forms of oxygen element in humic acid are C = O, C-O, and -COOH, without inorganic oxygen. The humic acid extracted from different types of peat has significant differences in yield, purity, and functional group content. Compared to woody peat and mossy peat, herbaceous peat is the most suitable raw material for extracting humic acid from peat.

Analysis of Rheological Properties and Regeneration Mechanism of Recycled Styrene-Butadiene-Styrene Block Copolymer (SBS) Modified Asphalt Binder Using Different Rejuvenators.

The regeneration performance of an aged styrene-butadiene-styrene block copolymer (SBS) will be significantly influenced by different rejuvenators. The objective of this study was to comparatively investigate the regeneration effect of different SBS-modified asphalt regenerators on aged SBS-modified asphalt. Four types of different regenerant formulations were selected. The optimal rejuvenator content was determined firstly using conventional performance tests. The rheological properties of the aged SBS-modified asphalt binder were evaluated by multiple stress creep recovery (MSCR) experiments. Subsequently, the regeneration mechanism of the SBS-modified asphalt binder was investigated using thin-layer chromatography-flame ionization detection (TLC-FID) and Fourier transform infrared spectroscopy (FTIR). The results showed that the rejuvenator had a certain recovery effect on the penetration, softening point, and ductility of the SBS-modified asphalt binder after aging. The SBS-modified rejuvenating agent was the most favorable among the four types of rejuvenators, where a rejuvenator dosage of 12% showed the optimal rejuvenation effect. The addition of regenerators could appropriately improve the elastic deformation capacity of the aged asphalt binder. The epoxy soybean oil in the regenerant reacted with the aging SBS-modified asphalt binder, supplementing the lost oil in the aged SBS-modified asphalt binder, dispersing the excessive accumulation of asphaltene, and making the residual SBS swell again. The viscoelastic properties of the aging asphalt binder were improved by adjusting the content of components and functional groups to achieve the purpose of regeneration.

Formation and radiolytic alteration of uraniferous solid bitumen related to hydrothermal base-metal mineralization in the Bytíz deposit, Příbram district, Czech Republic

The Bytíz deposit is a part of the Příbram uranium and base-metal ore district. It is an example of a vein-type deposit with polyphase hydrothermal mineralization. Samples of uraniferous solid bitumen from Bytíz with U content up to 38 wt% are characterized petrologically, geochemically, and mineralogically using EPMA, Raman and infrared microspectroscopy. The bitumen-bearing samples consist of base-metal sulfides: galena, sphalerite, pyrite, chalcopyrite, and also minor amounts of tetrahedrite, stibnite, and acanthite, associated with Mn-bearing calcite, quartz and silicates (chlorite, muscovite). Solid bitumens were found in the form of small veins and droplets, and roundish to irregular accumulations, in association with uraninite and carbonate veins.U-bearing minerals in the studied samples are represented by uraninite and more rarely by coffinite. Three generations of uraninite in association with solid bitumen were distinguished: 1. spherulites and large grains, filled with organic phase in the cracks; 2. as a part of complex textures inside areas with organic matter; in this case, the uraninite was assumed to have been remobilized; and 3. small inclusions in the latest calcite veins.More than 80 vol% of the solid bitumen from the vein fillings appeared to be radiolytically altered. Radiolytic alteration results in changes in optical properties and in composition, and in the formation of various textures around uraninite grains: halos, and irregular textures from simple massive to flow, dendritic, and fractured to a very complex morphology. The random reflectance values of unaltered mineral-free bitumen range from 0.45% to 0.99%, while in the radiolytically altered bitumen the average reflectance values are higher, from approximately 1.72% to 3.44%.The degree of graphitization of the organic matter was assessed by infrared micro-spectroscopy. Spectral maps show significant destruction changes of the aliphatic CH bonds and an increase in the content of oxygen functional groups in the vicinity of U minerals.On the element distribution maps, obtained by EPMA, the distribution of S, U, Pb and other elements across solid bitumen in the vicinity of uraninite and coffinite has a very heterogeneous character. An elevated content of sulfur in bitumen was also found, as well as a clear interdependence between S and C. It is suggested that the presence of sulfur in solid bitumen may result in ‘clouding’ of the solid bitumen with tiny stibnite grains. The dark rims of the halos observed under the optical microscope may be due to an elevated U content at the rims around the uraninite.Based on analysis of complex textural relationships of the solid bitumens with coexisting minerals, the formation of solid bitumen in association with uraninite is therefore assumed to relate to several stages of the influx of hydrothermal fluid. The temperature of the fluid, associated with bitumen formation was estimated to be up to 270 °C, according to chlorite thermometry.

Experimental investigation of kerogen structure and heterogeneity during pyrolysis

Kerogen in shale microstructure plays a vital role in hydrocarbon generation, retention and accumulation. However, characterization of kerogen structure is challenging arguably due to a complex microporous structure and chemical heterogeneity. Thus, the role of kerogen molecular structure in controlling porosity and its heterogeneity, as well as its evolutionary processes, remains unclear. In this study, we investigate the chemical and pore structure of heated kerogen samples by employing a range of characterization tools including gas adsorption experiments, high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared (FTIR) spectroscopy, and laser Raman experiments for a broad range of pyrolysis temperatures (420–850 °C). Multifractal theory and peak fitting techniques were used to evaluate the controlling mechanisms of kerogen pore structure and heterogeneity. The results suggest that with increasing thermal maturity, the content of oxygen functional groups and long-chain aliphatic groups in kerogen significantly decreases, while the length of aromatic fringes increases and gradually becomes oriented. Furthermore, with increasing thermal maturity, the pore volume of kerogen exhibits a non-monotonic trend, i.e., a decrease, followed by an increase, and then finally a decrease. This is primarily influenced by processes such as hydrocarbon production weakening, secondary hydrocarbon cracking, and carbonization. The heterogeneity and dispersion of meso to macro-sized pores in kerogen increase with temperature, while the connectivity gradually decreases. The chemical structure and spatial distribution of kerogen significantly affect the heterogeneity, connectivity, and dispersion of meso to macro-sized pores. Specifically, high aromaticity, structural disorder, and short aliphatic chains result in enhanced heterogeneity and dispersion of meso to macro-sized pores, reducing pore connectivity. This study thus contributes to a deeper understanding of the evolution of organic matter pores.