Organic Sulfides Research Articles

Characterizing spatio-temporal variations of dimethyl sulfide in the Yellow and East China Sea based on BP neural network

Dimethyl sulfide (DMS), an organic volatile sulfide produced from Dimethylsulfoniopropionate (DMSP), exerts a significant impact on the global climate change. Utilizing published literature data spanning from 2005 to 2020, a BP neural network (BPNN) model of the surface seawater DMS in the Yellow and East China Sea (YECS) was developed to elucidate the influence of various marine factors on the DMS cycle. Results indicated that the six parameters inputted BPNN model, that include the time (month), latitude and longitude, sea-surface chlorophyll a (Chl-a), sea-surface temperature (SST), and sea-surface salinity (SSS), yielded the optimized simulation results (R2 = 0.71). The optimized estimation of surface seawater DMS in the YECS were proved to be closely aligned with the observed data across all seasons, which demonstrated the model’s robust applicability. DMS concentration in surface seawater were found to be affected by multiple factors such as Chl-a and SST. Comparative analysis of the three environmental parameters revealed that Chl-a exhibited the most significant correlation with surface seawater DMS concentration in the YECS (R2 = 0.20). This underscores the pivotal role of chlorophyll in phytoplankton photosynthesis and DMS production, emphasizing its importance as a non-negligible factor in the study of DMS and its sulfur derivatives. Furthermore, surface seawater DMS concentration in the YECS exhibited positive correlations with Chl-a and SST, while displaying a negative correlation with SSS. The DMS concentration in the YECS show substantial seasonal variations, with the maximum value (5.69 nmol/L) in summer followed in decreasing order by spring (3.96 nmol/L), autumn (3.18 nmol/L), and winter (1.60 nmol/L). In the YECS, there was a gradual decrease of DMS concentration from the nearshore to the offshore, especially with the highest DMS concentration concentrated in the Yangtze River Estuary Basin and the south-central coastal part off the Zhejiang Province. Apart from being largely composed by the release of large amounts of nutrients from anthropogenic activities and changes in ocean temperature, the spatial and temporal variability of DMS may be driven by additional physicochemical parameters.

Garlic (Allium sativum L.): A review of varied health benefits

Introduction: Garlic (Allium sativum L.), has been cultivated in various countries and is valued for its medicinal and culinary properties. It contains bioactive compounds such as phenolic compounds, organic sulfides, polysaccharides, and saponins, with allicin being a particularly studied compound. These compounds have been shown to possess antioxidant, antimicrobial, antiviral, anticancer, anti-inflammatory, anti-hyperlipidemic and antihypertensive effects. Garlic has been used for over 5000 years as a curative plant and has potential applications in food science, medicine, and nutraceuticals. Aim of the Study: The aim of the study is to provide a comprehensive review of the overall impact of Allium sativum L. on human health and in order to draw attention to the benefits of regular consumption. Materials and methods: A comprehensive review of scientific and medical literature was conducted utilizing PubMed and Google Scholar databases. Searching terms were: garlic, Allium sativum L., garlic anti-inflammatory, garlic anticancer, garlic health effects. Conclusion: Allium sativum L. is associated with a comprehensive range of beneficial effects on the human body. These include anti-inflammatory and antioxidant properties, positive influence on lipid profile, cardiovascular system, and the anticancer activity among others by stimulation of tumor apoptosis. As a result, garlic and its bioactive compounds hold promise as functional foods or nutraceuticals for the prevention and treatment of various diseases.

Biogeochemical mechanisms of iron (Fe) and manganese (Mn) in groundwater and soil profiles in the Zhongning section of the Weining Plain (northwest China)

High levels of Iron (Fe) and manganese (Mn) in soils may contribute to secondary contamination of groundwater. However, there is limited understanding of the cycling mechanisms of Fe and Mn in groundwater and soil. This study aimed to investigate the biogeochemical processes constituting the Fe and Mn cycle by combining hydrochemistry, sequential extraction and microbiological techniques. The results indicated a similar vertical distribution pattern of Fe and Mn, with lower levels of the effective form (EFC-Fe/Mn) observed at the oxygenated surface, increasing near the groundwater table and decreasing below it. Generally, there was a tendency for accumulation above the water table, with Mn exhibiting a higher release potential compared to Fe. Iron‑manganese oxides (Ox-Fe/Mn) dominated the effective forms, with Fe and Mn in the soil entering groundwater through the reduction dissolution of Ox-Fe/Mn and the oxidative degradation of organic matter or sulfide (OM-Fe/Mn). Correlation analysis revealed that Fe and Mn tend to accumulate in media with fine particles and high organic carbon (TOC) contents. 16S rRNA sequencing analysis disclosed significant variation in the abundance of microorganisms associated with Fe and Mn transformations among unsaturated zone soils, saturated zone media and groundwater, with Fe/Mn content exerting an influence on microbial communities. Furthermore, functional bacterial identification results from the FAPROTAX database show a higher abundance of iron-oxidizing bacteria (9.3 %) in groundwater, while iron and manganese-reducing bacteria are scarce in both groundwater and soil environments. Finally, a conceptual model of Fe and Mn cycling was constructed, elucidating the biogeochemical processes in groundwater and soil environments. This study provides a new perspective for a deeper understanding of the environmental fate of Fe and Mn, which is crucial for mitigating Fe and Mn pollution in groundwater.

Interaction of composite fume suppression and odor elimination agents with crumb rubber modified asphalt: Inhibition behavior of volatile organic compounds (VOCs) and inorganic fume

The production and construction of crumb rubber modified asphalt (RMA) at high temperatures can produce a large amount of toxic fume, which is detrimental to human health and environment. In this study, a series of composite fume suppression and odor elimination agents (CSEAs) with both physical adsorption and chemical capture functions were adopted to reduce the emissions of volatile organic compounds (VOCs) and hydrogen sulfide (H2S). The material composition, microstructure, and specific surface area of CSEA were analyzed by using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and N2 adsorption-desorption isotherm (BET). The inhibitory effects of adding CSEA on toxic fume emissions from RMA at high temperatures were investigated through a combination of fume emission tests, H2S gas detection, gel permeation chromatography (GPC), and gas chromatography–mass spectrometry technology (GC–MS). The adsorption behavior of CSEA on H2S was analyzed through adsorption dynamics. Results showed that the physical and chemical properties of CSEA are stable while chemical adsorption dominates the CSEA's effect on H2S. ZnO and Ca(OH)2 exhibit good crystallization effects on the surface of the carrier by forming mesoporous structures mostly above 3.4 nm in size. The incorporation of CSEA significantly reduced the total emissions of RMA fume and the main components of VOCs in which the average inhibition rate of H2S can reach 44 % at an initial 30 mins.

Lithium fluorosulfonate-induced low-resistance interphase boosting low-temperature performance of commercial graphite/LiFePO4 pouch batteries

The performance of Li-ion batteries (LIBs) at sub-ambient temperatures is limited by the resistive interphases due to electrolyte decomposition, particularly on the anode surface. In this study, lithium fluorosulfonate (LFS) was added to commercial electrolytes to enhance the low-temperature electrochemical performance of LiFePO4 (LFP)/graphite (Gr) pouch cells. The addition of LFS significantly reduced the charge transfer resistance of the anode, substantially extending the cycle life and discharge capacity of commercial LFP/Gr pouch cells at −10 and −30 °C. Compared with the capacity retention rate of the baseline electrolyte at −10 °C (80 % after 25cycles), the capacity retention rate of the LFS electrolyte after 100 cycles under 0.5 C/0.5 C was retained at 94 %. Further mechanistic studies showed that the LFS additive induced the formation of a solid electrolyte interphase (SEI) film comprising inorganic-rich LiF, Li2SO4, and additional organic fluorides and sulfides to maintain good stability at the Gr/electrolyte interface during low-temperature operation. LFS suppressed electrolyte decomposition by forming a robust and low-resistance SEI film on the anode. These results demonstrate that LFS is a promising electrolyte additive for low-temperature LFP/Gr pouch cells.

Single walled carbon nanotubes covalently functionalized by a ruthenium complex for photocatalytic oxidations

The covalent bonding of a ruthenium bipyridine complex derivative with the aromatic network of single walled carbon nanotubes (SWNT) through a stepwise protocol is presented, thus yielding the sample SWNT-Ru. To do that, an-amino decorated phenanthroline is bonded to the nanotube by means of the diazonium chemistry protocol, providing anchoring points for discrete organometallic units as depicted by the solid characterization techniques employed. The hybrid material, able to emit upon excitation, is active in the visible light-driven photocatalytic oxidation of organic sulfides to sulfoxides. SWNT-Ru presents a wide scope being able to convert more than 10 substrates with different characteristics, including added-value chemicals, with a stable performance over more than 6 cycles without metal leaching and enhanced activity compared to related homogeneous complexes. A versatile character is also demonstrated since this hybrid catalyst follows both possible photooxidation mechanisms.

Organic acid and aromatic compounds create distinctive flavor in the blackening process of jujube

Previous studies demonstrated jujube blackening effectively increased cyclic adenosine phosphate and triterpene acid levels, improving its nutritional value. However, compositional changes during this process require further elucidation. The objective aimed to analyze compositional transformations during this process with SEM, TPA, UPLC- MS, E-nose. Results showed decreased hardness, springiness, and chewiness coupled with increased gumminess over blackening durations. Untargeted omics analysis revealed increases of 2-aminooctadec-8-ene-1,3,4-trioland carbendazim. Targeted organic acid analysis showed initial citric acid accumulation (1481.62 to 1645.78 mg/kg) in the first 24 h, then declines to 1072.96 mg/kg. Meanwhile, oxalic and lactic acids steadily rose, peaking at 96–120 h before slightly decreasing. E-nose analysis implied alterations in organic sulfide aromatics engendered the characteristic flavors. Organic acid fluctuations likely resulted from sugar biotransformation and thermal degradation. These comprehensive analyses demonstrate jujube blackening imparts a rich and unique flavor, providing theoretical support for investigating the mechanisms and products underlying this process.

Exceptional functionalized ionic liquid@metal–organic framework: A high-efficiency desulfurization platform for organic sulfide oxidation by reactive oxygen species

There is a challenge with designing catalysts that simultaneously possess active sites for catalyzing the generation of reactive oxygen species (ROSs) and effectively overcoming mass transfer resistance in oil–water biphasic systems. In this study, a novel, highly efficient oxidative desulfurization (ODS) strategy is proposed that uses an ILs-loaded metal–organic framework (MOF) coupled material as a catalyst. The IL@MOF ([Hnmp]HSO4@MIL-125(Ti)) coupled material prepared by loading [Hnmp]HSO4 onto MIL-125(Ti) has catalytic-adsorption synergistic capability. It demonstrated outstanding oxidative desulfurization performance by achieving nearly a 100 % removal of dibenzothiophene (DBT) from model oil with a dosage of 0.04 g IL@MOF per 10 mL of model fuel under mild conditions (50 °C, 10 min). By comparing the experimental results with the characterization data, it is suggested that [Hnmp]HSO4@MIL-125(Ti) converts superoxide radicals (•O2−) into 1O2 through oxygen vacancies (Ov) and that the catalytic action of Ti on the oxidation of DBT is primarily based on a 1O2-driven non-free radical mechanism. [Hnmp]HSO4@MIL-125(Ti) serves as a favorable medium for contact to be made between ROSs and sulfides, which indicates an efficient catalytic-adsorption synergy.

Determination of emission factors from a landfill through an inverse methodology: Experimental determination of ambient air concentrations and use of numerical modelling

The application of numeric modelling for determining the impact of landfills needs for reliable emission source data. In this study, a methodology for the characterization of the emission profiles of the different sources present in landfills for emission factors determination, applying an indirect methodology, is presented. Ambient air concentrations of volatile organic compounds (VOCs), hydrogen sulphide (H2S) and ammonia (NH3) were determined in three potentially emission sources in Can Mata landfill (Hostalets de Pierola, Catalonia, Spain): dumping areas, pre-closed zone and leachate reservoir as well as in biogas, for the determination of emission factors. Multi-sorbent bed and Tenax TA tubes were used for a wide range of VOCs sampling, and analysis was conducted through TD-GC/MS. H2S and NH3 were sampled and analysed using Radiello passive samplers. The highest total VOC (TVOC) concentrations were found in dumping areas (0.7–3.5 mg m−3), followed by leachate reservoir (0.3–0.6 mg m−3) and pre-closed area (77–165 μg m−3). On the other hand, the highest H2S and NH3 concentrations were found in leachate reservoir, presenting values of 0.8–1.1 mg m−3 and 1.7–1.8 mg m−3, respectively. With the application of odour thresholds to the concentrations obtained, the most critical compounds regarding odour annoyances were determined. The highest odour units (O.U.) were found in leachate reservoir due to H2S concentrations, whereas VOCs contributed mainly to O.U. in the dumping areas. The obtained ambient air concentrations were used for the indirect determination of the emission factors through numerical modelling using a Eulerian dispersion model. The emission factors obtained for the landfill for TVOC, H2S and NH3 were in the range of 0.44–10.9 g s-1, 0.16–1.02 g s−1 and 0.23–1.82 g s−1, respectively, depending on the emission source. Reliable emission factors are crucial to obtain landfill impact maps, which are essential for the correct management of these facilities.

Thiazole-linked isomeric covalent organic frameworks for divergent photocatalysis: Selective oxidation of organic sulfides

The photocatalysis of covalent organic frameworks (COFs) is underpinned by their inherent structures in which the linkage plays a vital role in determining the activity. The transformation of imine into thiazole leads to isomeric structures owing to the different orientations of linkages. Here, two thiazole-linked COFs, COF-TZ-1 and COF-TZ-2, are constructed from two imine-linked COFs, COF-IM-1 and COF-IM-2, with the imine N next to the linker triphenylbenzene and triphenyltriazine, respectively. Despite better absorption, COF-TZ-1 possesses inferior optoelectronic properties to COF-TZ-2. Besides, the dipole moment of COF-TZ-2 is twice that of COF-TZ-1. COF-TZ-2 is much better than COF-TZ-1 for blue light photocatalytic selective oxidation of organic sulfides with O2 under blue light irradiation. Furthermore, the facile adsorption sites of O2 are verified by density functional theory calculations, and the generation of superoxide is tracked over COF-TZ-2. This work highlights that subtle variations of COFs can lead to divergent photocatalysis.

Chemical Speciation, Leaching Behavior, and Environmental Risk Assessment of Trace Elements in the Bottom Ash from Biomass Power Plant.

Biomass combustion for power generation stands as a pivotal method in energy utilization, offering a promising approach for renewable energy utilization. However, the substantial volume of slag produced by biomass burning plants poses environmental challenges, impeding sustainable energy practices. This article systematically studies the characteristics of ash generated from typical biomass direct combustion power plant ash and analyzes the chemical composition, trace element content characteristics, leaching characteristics, and chemical forms of biomass bottom ash. Furthermore, it assesses the environmental ecology and bioavailability of trace elements in bottom ash using the ecological risk assessment method and RAC method. The results demonstrate that the biomass bottom ash contains plant nutrients, such as K, Ca, Mg, and P, while the content of harmful trace elements is lower than the relevant Chinese standards. In dissolution experiments, the leaching rate of nearly all elements remains exceptionally low, primarily due to the distribution of trace elements within the lattice structure of stable minerals. Trace elements predominantly exist in the residual phase, Cu and Zn primarily found in organic compounds and sulfide bound states, while other elements mostly exist in the form of iron manganese oxide bound states. Ecological risk assessment indicates a significant risk level for Cd, contrasting with the slight risk associated with other elements. RAC results indicated no ecological risk of all of the trace elements. Consequently, the utilization of bottom ash in agricultural and forestry soils is deemed to be viable. These findings serve as a crucial foundation for biomass bottom ash resource utilization and underpin the sustainable utilization of biomass energy.

Correlation analysis of microbial groups and sensory quality in the fourth round of the stacked fermentation of sauce-flavor liquor

Stacked fermentation is the process of utilizing microorganisms in the environment and further enriching their population in Jiupei. However, the composition of microbial communities in the different layers of Jiupei and their relationship with sensory quality requires more clarity. This study analyzed the microbial composition of the different layers of Jiupei in the fourth round of stacked fermentation using high-throughput sequencing technology. Physicochemical properties and sensory qualities were measured; the correlation between the observed microorganisms and sensory quality was further analyzed. The results showed that there were significant differences in acidity, moisture, starch, reducing sugar, and protein content across the different layers of the Jiupei (P < 0.05). The flavor substances in the entire Jiupei dump primarily included organic sulfides, terpenes, and ethanol, and umami was the most dominant taste indicator. Significant differences in microbial community structure were observed across the layers of the Jiupei, with the main bacterial genera being Thermoactinomyces (63.95%), and Bacillus (11.77%). Meanwhile, the main fungal genera identified were Pichia (28.37%), Saccharomyces (24.42%), and Byssochlamys (17.01%). The correlation between the microorganisms and the sensory indexes in Jiupei was found to be significant (P < 0.05); the presence of the bacterial genera Bacillus and Thermoactinomyces and the fungal genera Saccharomyces, Byssochlamys, and Zygosaccharomyces was found to be related to the sensory quality of Jiupei. This study provides insights into the role of microorganisms in the fourth round of liquor fermentation and provides a theoretical reference for the subsequent optimization of sauce-flavor liquor quality.

Synergistic effect between amorphous ZrO2 modified support and Pd catalyst: Unveiling superlative sulfur resistance and exquisite catalytic hydrogenation performance

The presence of sulfides in the reaction system can seriously affect the stability and activity of the catalysts. In this paper, we compare the impact of introducing varying amounts of the metal oxide ZrO2 on the hydrogenation activity and sulfur resistance of Pd-based catalysts. The study examined the effect of calcination temperature for catalysts and various organic sulfide types on their catalytic performance. We employed multiple techniques to characterize the catalysts, including physical adsorption, TEM, XRD, XPS, H2-TPD, NH3-TPD, and Py-IR. The results revealed that the catalysts achieved 99.9 % conversion and exhibited 99.5 % selectivity towards 4-ethyltoluene when the Pd and Zr molar ratio was 1:5. Furthermore, they could withstand the presence of toxicants for over 10 cycles. The main reason for the difference in activity and stability between catalysts lies in introducing ZrO2 as a promoter. This introduction increases the number of acidic sites and enhances the electronic effect, thereby facilitating the cleavage of H2 by Pd0. The synergistic effect between Pd and ZrO2 decreases the strength of S-Me, impedes sulfide adsorption, and improves the sulfur resistance stability of the catalyst. This work demonstrates that ZrO2-modified Pd-based catalysts have great potential in the anti-sulfur system of olefin hydrogenation.

Effect of various different pretreatment methods on infrared combined hot air impingement drying behavior and physicochemical properties of strawberry slices

In current work, the effect of freezing (F), ultrasound (U), and freeze- ultrasound (FU) pretreatment on infrared combined with hot air impingement drying kinetics, cell ultrastructure, enzyme activity, and physicochemical properties of strawberry slices were explored. Results showed that FU pretreatment enhanced cell membrane permeability via forming micropores, altered water status by transforming bound water into free water and thus promoted moisture diffusivity and decreased drying time by 50% compared to the control group. FU pretreatment also extensively decreased pectin methylesterase enzyme activity and maintained quality. The contents of total phenols, anthocyanins, vitamin C, antioxidant activity, and a* value of dried strawberries pretreated by FU were extensively increased compared to the control group. U and FU pretreatments were beneficial for retaining aromatic components and organic sulfides according to e-nose analyses. The findings indicate that FU is a promising pretreatment technique as it enhances drying process and quality of strawberry slices.

Influence of environmental factors on changes in the speciation of Pb and Cr in sediments of Wuliangsuhai Lake, during the ice-covered period.

Ecological pollution caused by heavy metals released from sediments is a worldwide concern. However, the effect of changes in sediment speciation on their release of heavy metals has not been adequately reported. In this study, the research focused on Pb and Cr in the ice period of Wuliangsuhai. This study analyzed changes in the sediment speciation of Pb and Cr before and after a release experiment using four risk assessment methods while varying the temperature, pH, and salinity of the water column. The results indicated that the total concentration of Pb ranged from 11.17 to 24.25mg/kg, while for Cr it ranged from 42.26 to 69.68mg/kg. Both elements exhibited mild contamination. The release of Pb and Cr from sediments increases with increasing water temperature, mainly due to the conversion of the residual fraction of Pb to the Fe-Mn oxide fraction and Cr converting more residual fraction to the organic matter and sulfide fraction. The release of sediment Pb and Cr decreased with increasing pH, with Pb converting more acid extractable fraction to the residual fraction and Cr converting more organic matter and sulfide fraction to the residual fraction. In contrast, the release of Pb and Cr increased and then decreased with increasing salinity. For Pb, the acid extractable fraction was more susceptible to conversion to the residual fraction by environmental influences, whereas for Cr, the organic matter and sulfide fraction were susceptible to conversion to the residual fraction.

Pseudocyclic Arylbenziodoxaboroles as Water-Triggered Aryne Precursors in Reactions with Organic Sulfides.

Pseudocyclic arylbenziodoxaboroles are unique aryne precursors under neutral aqueous conditions that selectively react with organic sulfides, forming the corresponding sulfonium salts. This reaction is compatible with various substituents (alkyl, halogen, CN, NO2, CHO, and cyclopropyl) in the aromatic ring or alkyl group of the sulfide. Similar reactions of sulfoxides afford o-hydroxy-substituted sulfonium salts. The structures of key products were confirmed by X-ray analysis.

Mild selective photochemical oxidation of an organic sulfide using OxP-polyimide porous polymers as singlet oxygen generators

ABSTRACT A series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen (‘OxP’) has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH 2 Bn) 4 ) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (~530 m2 g−1). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best 1O2 generating capability. Although the starting OxP-tetraamine precursor is a poor 1O2 generator, its incorporation into OxP POPs leads to a significant enhancement of 1O2 productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall 1O2 production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents.

Expanding Olefin-Linked Covalent Organic Frameworks toward Selective Photocatalytic Oxidation of Organic Sulfides.

Olefin-linked covalent organic frameworks (COFs) have exhibited great potential in visible-light photocatalysis. In principle, expanding fully conjugated COFs can facilitate light absorption and charge transfer, leading to improved photocatalysis. Herein, three olefin-linked COFs with the same topology are synthesized by combining 2,4,6-trimethyl-1,3,5-triazine (TMT) with 1,3,5-triformylbenzene (TFB), 1,3,5-tris(4-formylphenyl)benzene (TFPB), and 1,3,5-tris(4-formylphenylethynyl)benzene (TFPEB), namely, TMT-TFB-COF, TMT-TFPB-COF, and TMT-TFPEB-COF, respectively. From TMT-TFB-COF to TMT-TFPB-COF, expanding phenyl rings provides only limited expansion for π-conjugation due to the steric effect of structural twisting. However, from TMT-TFPB-COF to TMT-TFPEB-COF, the insertion of acetylenes eliminates the steric effect and provides more delocalized π-electrons. As such, TMT-TFPEB-COF exhibits the best optoelectronic properties among these three olefin-linked COFs. Consequently, the photocatalytic performance of TMT-TFPEB-COF is much better than those of TMT-TFB-COF and TMT-TFPB-COF on the oxidation of organic sulfides into sulfoxides with oxygen. The desirable reusability and substrate compatibility of the TMT-TFPEB-COF photocatalyst are further confirmed. The selective formation of organic sulfoxides over TMT-TFPEB-COF under blue light irradiation proceeds via both electron- and energy-transfer pathways. This work highlights a rational design of expanding the π-conjugation of fully conjugated COFs toward selective visible-light photocatalysis.

Probing the exchange of CO2 and O2 in the shallow critical zone during weathering of marl and black shale

Abstract. Chemical weathering of sedimentary rocks can release carbon dioxide (CO2) and consume oxygen (O2) via the oxidation of petrogenic organic carbon and sulfide minerals. These pathways govern Earth's surface system and climate over geological timescales, but the present-day weathering fluxes and their environmental controls are only partly constrained due to a lack of in situ measurements. Here, we investigate the gaseous exchange of CO2 and O2 during the oxidative weathering of black shales and marls exposed in the French southern Alps. On six field trips over 1 year, we use drilled headspace chambers to measure the CO2 concentrations in the shallow critical zone and quantify CO2 fluxes in real time. Importantly, we develop a new approach to estimate the volume of rock that contributes CO2 to a chamber, and assess effective diffusive gas exchange, by first quantifying the mass of CO2 that is stored in a chamber and connected rock pores. Both rock types are characterized by similar contributing rock volumes and diffusive movement of CO2. However, CO2 emissions differed between the rock types, with yields over rock outcrop surfaces (inferred from the contributing rock volume and the local weathering depths) ranging on average between 73 and 1108 tCkm-2yr-1 for black shales and between 43 and 873 tCkm-2yr-1 for marls over the study period. Having quantified diffusive processes, chamber-based O2 concentration measurements are used to calculate O2 fluxes. The rate of O2 consumption increased with production of CO2, and with increased temperature, with an average O2:CO2 molar ratio of 10:1. If O2 consumption occurs by both rock organic carbon oxidation and carbonate dissolution coupled to sulfide oxidation, either an additional O2 sink needs to be identified or significant export of dissolved inorganic carbon occurs from the weathering zone. Together, our findings refine the tools we have to probe CO2 and O2 exchange in rocks at Earth's surface and shed new light on CO2 and O2 fluxes, their drivers, and the fate of rock-derived carbon.

The Green Preparation of Mesoporous WO3/SiO2 and Its Application in Oxidative Desulfurization

Recently, supported WO3-based catalysts have been widely used in oxidative desulfurization (ODS) due to their advantages of easy separation, high activity, and being environment-friendly. In this work, supported mesoporous WO3/SiO2 catalysts have been prepared using an incipient-wetness impregnation method with agricultural waste rice husks as both a silicon source and mesoporous template, and phosphotungstic acid as a tungsten source. The effects of different calcination temperatures and WO3 loadings on the ODS performance of samples are studied, and the appropriate calcination temperature and WO3 loading are 923 K and 15.0 wt.%, respectively. The relevant characterization results show that, compared with pure WO3, the specific surface area and mesopore volume of WO3/SiO2 samples are greatly increased. Due to (a) high WO3 loading, (b) high specific surface area, and (c) nanoscale WO3 grains uniformly dispersed on the surface of the mesoporous SiO2 carrier, active sites of WO3/SiO2 catalysts are greatly increased, and their catalytic activities are improved. After the sixth and eighth runs in the ODS of dibenzothiophene and 4,6-dimethyldibenzothiophene, respectively, the WO3/SiO2 catalyst still maintains high catalytic activity (&gt;99.0%) despite the presence of a partial loss of WO3. In addition, with the aid of the UV-Vis technique, the tungsten-peroxo species, the active intermediates in the ODS reaction catalyzed by the WO3/SiO2 catalyst, are captured. Finally, a possible mechanism for the ODS of bulky organic sulfides using the WO3/SiO2 catalyst is proposed.