S-containing Compounds Research Articles

Investigation of SDS on Corrosion Behavior and Discharge Performance of AZ31B Magnesium Alloys in Aqueous Magnesium Air Batteries

To address the issue of high self-corrosion rate of Mg anodes in seawater batteries leading to low discharge efficiency, the green inhibitor, sodium dodecyl sulfate (SDS), was utilized to enhance the discharging performance of AZ31B alloy. The addition of SDS in a 3.5% NaCl solution led to a reduction in the corrosion rate of AZ31B alloy due to the formation of S-containing compounds. During the continuous-discharging period, the addition of 0.05 M SDS increased the anodic utilization efficiency from 64% to 81% and the specific energy density of the entire battery elevated from 1280 to 1912 mAh g−1 (an increase of 49%). The enhancement of the discharge performance of AZ31B Mg alloy in a 3.5% NaCl solution by SDS can be attributed to three aspects: reducing the negative difference effect of the Mg alloy, decreasing the accumulation of corrosion products on the surface of the Mg alloy, and promoting a more uniform dissolution of the Mg alloy.

Prediction of Nernst coefficient of S-containing compounds between fuel and ionic liquid phases in the extractive desulfurization using linear and supported vector machine (SVM) methods: QSPR-based machine learning

BackgroundThe presence of sulfur-containing compounds (SCCs) in the refinery streams has significant economic and environmental implications. Great attention has been focused on finding the proper green solvents like ionic liquids (ILs11Ionic liquids) with efficient extraction performance as a matter of concern of environmental issues. MethodsThe research aimed to develop a predictive model using QSPR to forecast the partition coefficient of dibenzothiophene by ILs from n-dodecane. Utilizing a dataset of 54 ILs and their partition coefficients for DBT, the study employed two methods to optimize ILs structures and compared linear (GA-MLR) and non-linear (LS-SVM) models, with non-linear models showing higher accuracy. After initial modeling and assessing the primary dataset of 54 ILs, yielding an R2 parameter of 0.39 for the test set, the dataset was divided into smaller clusters for further analysis. Three additional clusters were investigated. The second cluster comprised 14 ILs with identical cations and varying anions, modeled with two descriptors. The third cluster, consisting of 21 ILs with imidazolium cations and diverse anions, was modeled with three descriptors. Lastly, the fourth cluster, comprising 26 ILs with different cations but the same anion, was also modeled with three descriptors. Significant findingsThe MLR model yielded R2 values of 0.98, 0.85, and 0.93 for the test sets of the second, third, and fourth clusters respectively. Effective descriptors, including cation polarizability and alkyl branch length, were examined for their impact on partition coefficient and desulfurization efficiency. This research aids in enhancing EDS processes with ILs, advancing more efficient desulfurization technologies.

Different impacts of natural and anthropogenic factors on dissolved organic matter chemistry in coastal rivers: Implications for water management

The chemical composition of dissolved organic matter (DOM) exerts significant influence on aquatic energy dynamics, pollutant transportation, and carbon storage, thereby playing pivotal roles in the local water quality and regional-global biogeochemical cycling. However, the effects of natural climate change and local human activities on watershed characteristics and in-river processes have led to uncertainties regarding their contributions to DOM chemistry in coastal rivers, creating challenges for effective water management and the study of organic matter cycling. In this investigation, we employed a combination of stable isotopic analysis, optical techniques, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to elucidate the sources, optical properties, and molecular composition of DOM in three South China coastal rivers. Our results suggest that terrestrial DOM entering the three rivers through natural or anthropogenic pathways is gradually diluted by in situ primary production as it moves downstream, ultimately being influenced by seawater intrusion near the estuary. Additionally, terrestrial processes influenced by temperature likely govern DOC concentration, while seawater intrusion promotes the natural production of S-containing organic compounds. In contrast, human-altered landcover significantly impacts DOM molecular composition. Increased water areas lead to the enrichment of lignins with high disinfection byproduct formation potential, and agricultural residue burning appears to be the dominant source of pyrogenic DOM in these coastal rivers. Our distinct results suggest that the development of specific water management plans that consider the combined effects of temperature, seawater intrusion, landcover changes, and agricultural practices will be essential to ensure sustainable water resource.

Insight into the inhibition mechanisms of Ca-, N-, S-containing compounds on persistent organic pollutant formation from the thermal reaction of anthracene on copper chloride

Four inhibitors (CaO, CaS, CH4N2S, and (NH4)2SO4) were employed to inhibit the formation of multiple unintentional persistent organic pollutants (POPs) and environmentally persistent free radicals (EPFRs) using anthracene as a precursor, with CuCl2 serving as both a transition metal catalyst and chlorine source. The inhibition mechanisms were elucidated in terms of chlorine immobilization, catalyst deactivation, and free radical regulation. The inhibition efficiency of the four inhibitors on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) ranged from 64.7 % to 98.4 %, with the corresponding inhibition rates on toxic equivalency quantity ranging from 86.3 % to 99.7 %. The distribution of homologs shifted towards less chlorinated species, indicating effective suppression of chlorination. Calcium- and nitrogen-containing compounds consumed chlorine sources by forming CaCl2, CaClOH, and NH4Cl, while sulfur-containing compounds deactivated catalysts by forming CuSO4. EPFRs derived from anthracene were identified as carbon-centered anthracene-type and anthraquinone-type radicals. Positive correlations were observed between POPs and EPFRs concentrations, suggesting the pivotal role of organic free radicals as intermediates in POPs formation. Anthraquinones derived from anthracene underwent decomposition, recombination and chlorination, leading to the formation of PCDD/Fs and PCBs. The addition of inhibitors reduced EPFRs concentrations by 74.2–95.1 %. Sulfur- and nitrogen-containing inhibitors generated radicals that attacked POPs precursors and intermediates, forming heteroatomic compounds and inhibiting POPs formation. These findings enhanced the understanding of the source control mechanisms of POPs and provided theoretical and technical support for the synergistic inhibition of POPs and EPFRs in industrial thermal processes.

Size-resolved molecular characterization of water-soluble organic matter in atmospheric particulate matter from northern China

Atmospheric particulate matter (PM) affects visibility, climate, biogeochemical cycles and human health. Water-soluble organic matter (WSOM) is an important component of PM. In this study, PM samples with size-resolved measurements at aerodynamic cut-point diameters (Dp) of 0.01–18 μm were collected in the rural area of Baoding and the urban area of Dalian, Northern China. Non-targeted analysis was adopted for the characterization of the molecule constitutes of WSOM in different sized particles using Fourier transform-ion cyclotron resonance mass spectrometry. Regardless of the location, the composition of WSOM in Aitken mode particles (aerodynamic diameter <0.05 μm) was similar. The WSOM in accumulation mode particles (0.05–2 μm) in Baoding was predominantly composed of CHO compounds (84.9%), which were mainly recognized as lignins and lipids species. However, S-containing compounds (64.2%), especially protein and carbohydrates species, accounted for most of the WSOM in the accumulation mode particles in Dalian. The CHO compounds (67.6%–79.7%) contributed the most to the WSOM in coarse mode particles (>2 μm) from both sites. Potential sources analysis indicated the WSOM in Baoding were mainly derived from biomass burning and oxidation reactions, while the WSOM in Dalian arose from coal combustion, oxidation reactions, and regional transport.

Sustainable and Safe N-alkylation of N-heterocycles by Propylene Carbonate under Neat Reaction Conditions.

A new, eco-friendly process utilising the green solvent propylene carbonate (PC) has been developed to perform N-alkylation of N-, O- and/or S-containing heterocyclic compounds. PC in these reactions served as both the reagent and solvent. Importantly, no genotoxic alkyl halides were required. No auxiliary was necessary when using anhydrous PC. Product formation includes nucleophilic substitution with the concomitant loss of water and carbon dioxide. Substrates prepared, including the newly invented PROTAC drugs, are widely used.

Novel use of the electrocatalytic oxidation process with Fe-DSA dual anode configuration for leachate treatment: Significance of in situ ferrate generation

The leachate produced by waste transfer stations (WTSs) contains substantial amounts of refractory organic matter and ammonia, necessitating on-site treatment. In this study, a novel electrocatalytic oxidation (ECO) process with Fe-DSA dual anode configuration was established for leachate pretreatment. In this configuration, chloride in the leachate was converted to active chlorine by the DSA anode, while ferric hydroxide (Fe(OH)3) was produced from Fe anode. As a result, Fe (VI) was in situ formed through the reactions between active chlorine and Fe(OH)3. Simultaneous and efficient removal of COD and NH4+-N in the ECO process with Fe-DSA dual anode configuration was achieved, significantly improving leachate biodegradability compared with the Fe–Fe and DSA-DSA dual anode configurations. The transformation characteristics of organic compounds in the ECO process were investigated through the electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) analysis. The ECO process with Fe-DSA dual anode configuration promoted the removal and transformation of lignins/carboxylic rich alicyclic molecules (CRAM)-like and tannins compounds with biologically refractory properties, as well as S-containing compounds with biological toxicity. Further X-ray photoelectron spectroscopy (XPS) analysis revealed that iron oxides, amorphous Fe-(oxy) hydroxide, and amorphous Fe(OH)3 produced by Fe (VI) decomposition in the ECO process with Fe-DSA dual anode configuration enhanced removal performance through coagulation. In addition, the contribution of different active species to organic matter removal in the ECO process was quantified by quenching experiments. High-valent iron oxidation dominated the ECO process with Fe-DSA dual anode configuration, while active chlorine oxidation, •OH oxidation and coagulation synergistically contributed to organic matter removal.

Impact of crystal and molecular structure of three novel thiosulfonate crystals on their vibrational and NMR parameters

Due to antimicrobial potential of S-containing compounds, the current study explores experimentally the crystal and molecular structure of three new thiosulfonates at 100 K, notably S-ethyl 4-aminobenzene-1-sulfonothioate (1), S-ethyl 4-acetamidobenzene-1-sulfonothioate (2), and S-methyl 4-acetamidobenzene-1-sulfonothioate (3). Theoretical analysis between their molecular structure and vibrational IR, Raman, as well as NMR parameters is given. The details of -SO2-S- structural motif are analyzed theoretically using HOOH, HS-SH and H3CS-SCH3, as model molecules. The experimental structural parameters, as determined by low temperature X-ray diffraction method are accurately predicted using DFT-B3LYP combined with large and flexible aug-cc-pVTZ basis set. In case of C-S-S-C dihedral angle the crystal forces are responsible for larger difference with respect to isolated molecules, predicted in the gas phase. In addition, electronic properties of the title compounds are explored using theoretical calculations of their geometric and magnetic aromaticity indexes and substituent push-pull effect. The obtained results provide a deeper insight into their molecular structure and IR/Raman and NMR spectroscopic properties. Finally, these compounds could be directly used in future in vitro investigation of therapeutic potential of the studied and structurally similar compounds.

Non-equilibrium electronic structure of Fe-based bulk catalysts: Dual-channel electron transfer behavior among Fe, Zn, and P species and its impact on hydrodesulfurization reaction pathway

Regulation of electronic structure of metal active phase for catalysts has been known as efficient in promoting its catalytic activity; however, manipulating the activity of catalysts via controllable metal active phase electronic structure is still challenging. A non-equilibrium electronic structure Fe-based bulk catalyst has been developed via controllably adding P species, where the non-equilibrium electronic structure of Fe species is formed through the electron transfer from the Zn species through the P electronic channel. As a result, the catalytic activity of the modified Fe-based bulk catalysts has increased by 24.4–50.4%. Meanwhile, the sulfurization degree (SD) of the modified Fe-based bulk catalysts has increased by 5.6–25.9%. In addition, the HDS reaction rate constant (kHDS) has increased by about 2.0 times, and the DDS reaction rate constant (kDDS) has increased by about 2.4 times. The P modifying can regulate the directional transfer of unpaired free electrons between Fe and Zn species to form a more non-equilibrium electronic structure of Fe species, which can reduce the energy barrier of the C–S bond adsorbed on the P-modified Fe-based bulk catalysts. Importantly, the P species can be used as an active site to adsorb S-containing compounds in the modified Fe-based bulk catalysts, which is conducive to generating more coordinatively unsaturated sites (CUSs). The former can promote the formation of the more non-equilibrium electronic structure of Fe species, and the latter can adjust the adsorption active site of S-containing on the catalyst surface. Therefore, an electron transfer channel is formed among Fe, Zn, and P species, and another one is formed among Fe, P, and S-containing compounds, which form a dual-channel electron transfer behavior. Furthermore, the specific surface area, total pore volume, and reducibility of the modified Fe-based bulk catalysts have also shown varying degrees of improvement via the controllable addition of P species.

Characteristics of polar organic compounds from diesel truck emissions measured by FT-ICR MS

Water-soluble organic compounds (WSOC) and dichloromethane: methanol-soluble organic compounds (DMSOC) in polar organic compounds (POCs) present in emissions from a diesel truck were characterized by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The main compositions and molecular structures of WSOC and DMSOC were investigated and classified into three groups based on their elemental compositions: CHO, CHON, and S-containing compounds (CHONS and CHOS) (namely WSOCCHO; WSOCCHON; WSOCOS; DMSOCCHO; DMSOCCHON and DMSOCOS). The main results are as follows. (1) The order of groups in WSOC and DMSOC in terms of peak response was CHO (WSOC: 52.2% and DMSOC: 64.5%), CHON (WSOC: 43.4% and DMSOC:25.9%), and S-containing compounds (WSOC: 4.35% and DMSOC: 9.57%). (2) The relative response of compounds with low H/C and O/C ratios and double-bond equivalents (DBE) > 10 in WSOCCHO was twice that of DMSOCCHO, indicating that the WSOC emitted by diesel trucks might contain many highly condensed benzene rings. Compounds with H/C = 2 and DBE = 1 in DMSOCCHO showed a strong relative response, presumably due to a fatty-acid structure, which might be used as a tracer to distinguish emissions from diesel trucks and other pollution sources. (3) The strongest relative response in WSOCCHON was for C11H7O5N2 with an aromaticity equivalent (Xc) = 2.5 and DBE = 9, suggesting that dinitrophenol or methyl nitrophenol might be present. Moreover, C39H76O8N1 with Xc = 0 and DBE = 2 was dominant in DMSOCCHON, suggesting the presence of carboxylic acids. (4) In both WSOC and DMSOC, long-chain aliphatic and organic sulfate compounds accounted for the largest proportion of S-containing compounds. However, the contents of condensed hydrocarbons and aromatic rings in DMSOCOS were higher than those in WSOCOS, which suggests that DMSOCOS has a strong optical absorption ability. Thus, this study effectively determined the POC compounds of diesel truck emissions and their possible structures, providing data for assessing the environmental effects of using diesel trucks.

Biogeochemical and microscopic studies of soil and Phragmites australis (Cav.) Trin. ex Steud. plants affected by coal mine dumps.

Developed areas of the coal industry are subjected to long-term anthropogenic impacts from the input and accumulation of overburdened coal material, containing potentially toxic heavy metals and metalloids (HMM). For the first time, comprehensive studies of soils and plants in the territory of the Donetsk coal basin were carried out using X-ray fluorescence, atomic absorption analysis, and electron microscopy. The observed changes in the soil redox conditions were characterized by a high sulfur content, and formations of new microphases of S-containing compounds: FeS2, PbFe6(SO4)4(OH)12, ZnSO4·nH2O, revealed the presence of technogenic salinization, increased Сorg content, and low pH contents. Exceedances of soil maximum permissible concentrations of Pb, Zn, Cu, and As in areas affected by coal dumps were apparent. As a consequence of long-term transformation of the environment with changes in properties and chemical pollution, a phytotoxic effect was revealed in Phragmites australis (Cav.) Trin. ex Steud, accompanied by changes in ultrastructural and organization features of roots and leaves such as increases in root diameters and thickness of leaf blades. The changes in the ultrastructure of cell organelles: a violation of the grana formation process, an increase in the number of plastoglobules, a decrease in the number of mitochondrial cristae, and a reduction in the electron density of the matrix in peroxisomes were also observed. The accumulation of large electron-dense inclusions and membrane fragments in cell vacuoles was observed. Such ultrastructural changes may indicate the existence of a P. australis ecotype due to its long-term adaptation to the disturbed environment.

Similarities and differences in the physiological adaptation to water salinity between two life forms of aquatic plants in alpine and arid wetlands

Aquatic plants play a crucial role in freshwater ecosystems as primary producers, but their survival is threatened by salinization. Understanding the physiological responses of aquatic plants to increasing water salinity is important for predicting their adaptive strategies under future climate change scenarios. In this study, we measured 15 physiological traits of 49 aquatic plant species along a large environmental gradient in alpine and arid regions of western China to explore their physiological adaptations and compare the similarities and differences in adaptive strategies between emergent and submerged life forms. We found that water salinity and low temperature were key factors affecting aquatic plants in these regions. Aquatic plants adapted to saline habitats by accumulating proline and sulfur (S) concentrations, and to cold habitats by increasing ascorbate peroxidase activity. Plant trait network analysis revealed that S was the hub trait in emergent plants, while proline was the hub trait in submerged plants, indicating that emergent plants balanced osmoregulation and reactive oxygen metabolism through S-containing compounds, while submerged plants prioritized the regulation of osmotic balance through proline.

Foliar Application of Sulfur-Containing Compounds-Pros and Cons.

Sulfate is taken up from the soil solution by the root system; and inside the plant, it is assimilated to hydrogen sulfide, which in turn is converted to cysteine. Sulfate is also taken up by the leaves, when foliage is sprayed with solutions containing sulfate fertilizers. Moreover, several other sulfur (S)-containing compounds are provided through foliar application, including the S metabolites hydrogen sulfide, glutathione, cysteine, methionine, S-methylmethionine, and lipoic acid. However, S compounds that are not metabolites, such as thiourea and lignosulfonates, along with dimethyl sulfoxide and S-containing adjuvants, are provided by foliar application-these are the S-containing agrochemicals. In this review, we elaborate on the fate of these compounds after spraying foliage and on the rationale and the efficiency of such foliar applications. The foliar application of S-compounds in various combinations is an emerging area of agricultural usefulness. In the agricultural practice, the S-containing compounds are not applied alone in spray solutions and the need for proper combinations is of prime importance.

Three-dimensional porous carbon materials as catalysts for upgrading coal pyrolysis volatiles to boost light tar

The large proportion of heavy components in volatiles from coal pyrolysis is liable to entrain dust and form coke, resulting in the difficulty of separating oil from dust, which thus causes the blocking of technical pipelines. Carbon-based catalysts (BC and BHC) and metal-modified carbon-based catalysts (Fe-BC, Ni-BC, Fe-BHC and Ni-BHC) were prepared for the upgrading of volatiles from coal pyrolysis. This three-dimensional interconnected macroporous carbon material is primarily derived from the pyrolysis of the blend of a biochar and a caking coal. The results show that the metal-modified carbon-based catalysts aid in activating small molecules, such as CH4, CO2, and H2O, increasing in-situ hydrogen donation while cracking polycyclic aromatics, macromolecular oxygen-containing compounds, and N, S-containing heterocyclic compounds. This thus increases the selective catalysis of benzene, naphthalene, biphenyl, and anthracene and improves tar quality. The unactivated Fe-BC and Ni-BC catalysts exhibit high selectivity for light oil with a boiling point below 170 °C. In contrast, the activated Fe-BHC and Ni-BHC catalysts have a stronger ability to crack heavy tar due to the synergistic effect of metal and carbon defect structures. However, the micropores within the catalysts prevent mass transfer of macromolecular compounds, drastically lowering the tar yield with coke formation. Overall, the unactivated metal modified catalyst with three-dimensional porous structure allows for the synergistic effect of dust removal and upgrading of volatiles while maintaining the tar yield, especially the Fe-BC catalyst with a lower price.

Reductive Transformation of O-, N-, S-Containing Aromatic Compounds under Hydrogen Transfer Conditions: Effect of the Process on the Ni-Based Catalyst.

The influence of the reaction medium on the surface structure and properties of a Ni-based catalyst used for the reductive transformations of O-, N-, and S-containing aromatic substrates under hydrogen transfer conditions has been studied. The catalysts were characterized by XRD, XPS, and IR spectroscopy and TEM methods before and after the reductive reaction. It has been shown that the conversion of 1-benzothiophene causes irreversible poisoning of the catalyst surface with the formation of the Ni2S3 phase, whereas the conversion of naphthalene, 1-benzofuran, and indole does not cause any phase change of the catalyst at 250 °C. However, after the indole conversion, the catalyst surface remains enriched with N-containing compounds, which are evenly distributed over the surface.

Activation of peroxymonosulfate by biochar-supported Fe3O4 derived from oily sludge to enhance the oxidative degradation of tetracycline hydrochloride

Carbon materials used for catalysis in advanced oxidation processes tend to be obtained from cheap and readily available raw materials. We constructed a carbon material, OSC@Fe3O4, by loading Fe3O4 onto the pyrolyzed hazardous waste oily sludge. OSC@Fe3O4 was then used to activate peroxymonosulfate (PMS) for the removal of tetracycline hydrochloride (TTCH) from water. At 298 K, 0.2 g⋅L−1 of catalyst and 0.3 g⋅L−1 of PMS, the reaction rate constant of the OSC@I-2/PMS system reached 0.079 min−1, with a TTCH removal efficiency of 92.6%. The degradation efficiency of TTCH remained at 81% after five cycles. The specific surface area and pore volume of OSC@I-2 were 263.9 m2⋅g−1 and 0.42 cm3⋅g−1, respectively, which improved the porous structure of the carbon material and provided more active points, thus improving the catalytic performance. N and S were doped into the oily sludge carbon due to the presence of N- and S-containing compounds in the raw oily sludge. N and S doping led to more electron-rich sites with higher negative charges in OSC@I-2 and gave the oily sludge carbon a higher affinity to PMS, thereby promoting its ability to activate PMS. Sulfate radicals (SO4•‾) played a dominant role in the degradation of TTCH, with demethylation and the breaking of double bonds being a possible degradation pathway. A biotoxicity test showed that the microbial toxicity of the degradation intermediates was significantly reduced. This work provides a strategy for the application of PMS-based catalysts derived from waste carbon resources.

NO/SO2/HCl emissions from solid waste combustion via oxygen-carrier-aided combustion in rotary kiln

Rotary kiln incineration technology has become an important approach to achieve the harmless, reduced, and resourceful solid waste (SW) due to its wide range of fuel adaptability and high treatment efficiency. SW incineration through oxygen carrier (OC) aided combustion in the rotary kiln shows significant advantages in improving SW conversion and reducing CO emission. However, the impacts of introducing OC into the rotary kiln on the emissions of NO, SO2, and HCl, are still unknown. This research objective was to investigate the effects of OCs on the emission characteristics of NO, SO2, and HCl. Natural manganese and ilmenite ores as OCs, are added to a continuous-feeding rotary kiln during the combustion of biomass SW and hazardous SW. The results show that the introduction of OCs can significantly improve the uniformity of oxygen distribution in the furnace, and promotes the conversion of fuel N to NO. At high temperatures and low oxygen concentrations range, the reduction rate of NO by high-concentration CO or catalytic reduction by char and ash is faster than the oxidation of fuel N by OCs, which decreases NO concentration. Moreover, at high temperatures, when OCs are distributed in the bed of the rotary kiln, the fuel in the oxygen-poor zone can obtain O2 or lattice oxygen from the OCs, which promotes the decomposition and oxidation of S-containing compounds in fuels and increase the SO2 concentration. In addition, OCs in the bed provide more reaction sites for fuel conversion and promote the release of Cl as HCl at high temperatures. Specifically, during the oil sludge combustion at 900 °C, compared with the inert reference case, the addition of ilmenite ore increased the concentrations of NO, SO2, and HCl by 47.44%, 64.87%, and 20.28%, respectively, which is attributed to the better reactivity and redox cycle stability of ilmenite ore. This study highlights the potential of OC-aided combustion in rotary kilns as an approach to regulate SW combustion and offers a foundation for the future related research.

Characteristics of dissolved organic matter in point-source wastewaters at a petrochemical plant: Molecular constituents and contributions to the influent of wastewater treatment plant

Dissolved organic matter (DOM) in point-source petrochemical wastewaters (PCWs) from different operating units is closely linked to the efficiency of wastewater treatment plant (WWTP). However, systematic studies on DOM characters of point-source PCWs and their influences on WWTP influents were seldom conducted. In this study, DOM in three low-salinity point-source PCWs and four high-salinity point-source PCWs at a typical petrochemical plant were comprehensively characterized at a molecular level. Orbitrap mass spectrometry results indicated that point-source PCWs had diverse DOM constituents tightly related to the corresponding petrochemical processes. Phenols in oily wastewaters (OW), phenols and N-containing compounds in coal partial oxidation wastewater (POXW), and naphthenic acids (NAs) and aromatic acids in crude oil electric desalting unit wastewater (EDW) were characteristic DOM constituents for low-salinity point-source PCWs. While S-containing compounds (mercaptans, thiophenes) and NAs in spent caustic liquors (SCL), alcohols and esters in butanol-octanol plant wastewater (BOW), high molecular weight aromatic ketones in phenol-acetone plant wastewater (PAW), and oxygenated NAs as well as short chain N-containing compounds in concentrate from reverse osmosis unit (ROC) were characteristic DOM constituents for high-salinity point-source PCWs. Spearman correlation analysis indicated that though with relative low pollutant contents (OW) and discharge volume (EDW), N/O/S-containing compounds of OW and EDW greatly contributed to the polar DOM constituents of low-salinity influent in WWTP (R > 0.5, P < 0.001). While N-containing compounds of ROC mainly contributed to the polar DOM of high-salinity influent (R > 0.5, P < 0.001). Though N-/S-containing species in PAW had low contents, they also posed obvious impacts on DOM constituents of high-salinity influent. Interestingly, some O-/S-containing species were newly formed during the confluent process of high-salinity point-source PCWs. The results strengthened the combined contributions of pollutants contents, discharge emission and DOM constituents of point-source PCWs to the water matrix of WWTP influents, which would provide reference for the management of PCW streams.

Ceramic membrane reactor integrated with UV/O3/Catalyst Beads for treating real textile wastewater: Enhanced effluent quality, fouling control and molecular transformations of DOM

A ceramic membrane reactor (CMR) was employed to treat real textile wastewater with the simultaneous use of UV, O3, and photocatalytic beads for dissolved organic matter (DOM) transformation and membrane fouling control. The O3 treatment exhibited high performance in color removal. Simultaneous use of UV and ozonation (UV/O3) resulted in 91% and 64% color and chemical oxygen demand (COD) removal, respectively, and delayed (3-fold) fouling time compared to UV alone. A combination of TiO2-loaded polymeric beads with UV/O3 (UV/O3/Beads) further enhanced the color (96%) and COD (86%) removal as well as improved fouling control by 9-folds compared to the control (Air alone) experiment. Three-dimensional excitation-emission matrix (3-D EEM) fluorescence spectra revealed minimum DOM and synergistic effects of UV, O3, and photocatalytic beads (UV/O3/Beads) in the degradation of fluorescent DOM. The •OH radicals were leading in degrading organic pollutants during the treatment. Transformations of heteroatomic DOMs were confirmed by the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). S-containing compounds in the treated samples appeared in a reduced state (lower H/C and O/C ratios), indicating the transformation of R–SO3 to R–S–R. Whereas N-containing DOM was mostly oxidized. UV/O3 rapidly transformed dye molecules to colorless, creating suitable conditions for photocatalytic beads for accelerated degradation of pollutants. Also, the PTR-TOF-MS analysis revealed the successful removal of toxic VOCs (Methanethiol, Allylamine, Cyclohexenes, Butanes, Propanes, and Hydrazines) from wastewater by the UV/O3/Beads treatment. Based on these findings, DOM transformations could be better understood, and the simultaneous application of heterogeneous photocatalysis and UV/O3 could be safely recommended as a promising technology for treating industrial wastewater.

Al-modified yolk-shell silica particle-supported NiMo catalysts for ultradeep hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene: Efficient accessibility of active sites and suitable acidity

Yolk-shell SiO2 particles (YP) with center-radial meso-channels were fabricated through a simple and effective method. Al-containing YP-supported NiMo catalysts with different Al amounts (NiMo/AYP-x, x = Si/Al molar proportion) were prepared and dibenzothiophene (DBT) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT) were employed as the probes to evaluate the hydrodesulfurization (HDS) catalytic performance. The as-prepared AYP-x carriers and corresponding catalysts were characterized by some advanced characterizations to obtain deeper correlations between physicochemical properties and the HDS performance. The average pore sizes of series AYP-x supports are above 6.0 nm, which favors the mass transfer of organic sulfides. The cavity between the yolk and the shell is beneficial for the enrichment of S-containing compounds and the accessibility between reactants and active metals. Aluminum embedded into the silica framework could facilitate the formation of Lewis (L) and Brønsted (B) acid sites and adjust the metal-support interaction (MSI). Among all the as-synthesized catalysts, NiMo/AYP-20 catalyst shows the highest HDS activities. The improved HDS activity of NiMo/AYP-20 catalyst is attributed to the perfect combination of excellent structural properties of the yolk-shell mesoporous silica, enhanced acidity, moderate MSI, and good accessibility/dispersion of active components.