Dominant Reaction Pathway Research Articles

A detailed analysis of the key steps of the cyclopentene autoignition mechanism from calculated RRKM rate constants associated with ignition delay time simulations

Cyclopentene, a prototype for studying the combustion chemistry of cyclic olefins, appears in the oxidation of cyclic hydrocarbons and can provide key information in the understanding of the formation of polycyclic aromatic hydrocarbons. The ▪ addition to the double-bond is one of the main steps in low-temperature oxidation mechanisms of unsaturated organic compounds. In the case of cyclopentene, addition of ▪ yields a hydroxycyclopentyl radical, that can further react with O2. In this work, we studied the potential energy surface and reaction rates for the subsequent reactions of O2 with the hydroxycyclopentyl radical. The temperature and pressure dependence of the rate constants were determined using master equation simulations, with microcanonical rate coefficients calculated by RRKM theory. The potential energy surface was extracted from high-level electronic structure theory, based on geometries and frequencies obtained using density functional theory. Our results indicate that a Waddington-type mechanism, which produces glutaraldehyde and regenerates ▪ , is the dominant reaction pathway. However, at low-temperatures, a secondary pathway leading to the formation of epoxycyclopentanol and ▪ becomes equally significant. The thermochemistry of all ▪ radicals involved were also evaluated. The kinetic and thermodynamic data were incorporated into a comprehensive mechanism of cyclopentene autoignition, in order to simulate the associated ignition delays. The updated reaction mechanism resulted in shorter ignition delays compared to the non-updated mechanism. Sensitivity analysis was performed to identify the primary contributors.Novelty and Significance StatementCyclopentene is an important intermediate in the oxidation of cyclic olefins and serves as a precursor in the formation of polycyclic aromatic hydrocarbons. Kinetic modeling studies require detailed information on elementary reactions, much of which is typically unavailable from experiments. The novelty and significance of this study lie in the theoretical calculations of rate constants for key reactions in the oxidation of cyclopentene and their evaluation within the comprehensive mechanism proposed by Lokachari et al. The results demonstrate that the studied reactions significantly influence the ignition delays of cyclopentene at low temperatures. Furthermore, the data presented here can be applied in future studies focusing on the oxidation of cyclic olefins.

Bioleaching of lithium from jadarite, spodumene, and lepidolite using Acidiothiobacillus ferrooxidans

Lithium (Li) is becoming increasingly important due to its use in clean technologies that are required for the transition to net zero. Although acidophilic bioleaching has been used to recover metals from a wide range of deposits, its potential to recover Li has not yet been fully explored. In this study, we used a model Fe(II)- and S-oxidising bacterium, Acidiothiobacillus ferrooxidans (At. Ferrooxidans), to extract Li from three different minerals and kinetic modelling to predict the dominant reaction pathways for Li release. Bioleaching of Li from the aluminosilicate minerals lepidolite (K(Li,Al)3(Al,Si,Rb)4O10(F,OH)2) and spodumene (LiAl(Si2O6)) was slow, with only up to 14% (approximately 12 mg/L) of Li released over 30 days. By contrast, At. ferrooxidans accelerated Li leaching from a Li-bearing borosilicate clay (jadarite, LiNaB3SiO7OH) by over 50% (over 120 mg/L) in 21 days of leaching, and consistently enhanced Li release throughout the experiment compared to the uninoculated control. Biofilm formation and flocculation of sediment occurred exclusively in the experiments with At. ferrooxidans and jadarite. Fe(II) present in the jadarite-bearing clay acted as an electron donor. Chemical leaching of Li from jadarite using H2SO4 was most effective, releasing approximately 75% (180 mg/L) of Li, but required more acid than bioleaching for pH control. Kinetic modelling was unable to replicate the data for jadarite bioleaching after primary abiotic leaching stages, suggesting additional processes beyond chemical leaching were responsible for the release of Li. A new crystalline phase, tentatively identified as boric acid, was observed to form after acid leaching of jadarite. Overall, the results demonstrate the potential for acidophilic bioleaching to recover Li from jadarite, with relevance for other Li-bearing deposits.

Concentrated C2+ Alcohol Production Enabled by Post-Intermediate Modulation and Augmented CO Adsorption in CO Electrolysis.

The electrocatalytic synthesis of multicarbon products from CO2/CO feedstock represents a sustainable method for chemical production with a reduced carbon footprint. Traditional copper catalysts predominantly produce alkenes, but generating valuable and versatile C2+ alcohols, especially high-energy-density C3 alcohols, has been challenging due to issues with selectivity, activity, and stability. Here, we present the construction of Ru-doped Cu nanowires that enhance the selectivity of n-PrOH and C2+ alcohols. In situ Raman spectroscopy shows that our approach promotes both *CO binding and availability, particularly facilitating the formation of high-frequency-bound *CO (*COHFB) and maintaining multiple *CO adsorption modes on Ru-modified and bare low-coordinated Cu nanowires. Density-functional theory (DFT) simulations illustrate that introducing Ru species onto a low-coordinated Cu step surface simultaneously stabilizes CO and alcohol-related intermediates, shifting the dominant reaction pathway toward alcohols and facilitating CO-C2 coupling at the expense of ethylene selectivity. In an alkaline gas-diffusion electrolyzer, we attained a maximum Faradaic efficiency (FE) of 35.9% for n-PrOH and 62.4% for the total C2+ alcohols. Optimizing parameters in the membrane electrode assembly (MEA) system enabled the one-pot generation and separation of C2+ alcohols, achieving a record concentration of 18.8 wt % (4.2 wt % n-PrOH and 14.6 wt % EtOH) with nearly 100% purity at 200 mA/cm2 over 100 h. This work not only provides new insights and guidance for the development of future catalysts from the perspectives of surface science and mechanisms but also highlights the importance of coupling material engineering with reactor engineering to optimize the production process of high-value alcohol products.

Uncertainty Qualification for Deep Learning-Based Elementary Reaction Property Prediction.

The prediction of the thermodynamic and kinetic properties of elementary reactions has shown rapid improvement due to the implementation of deep learning (DL) methods. While various studies have reported the success in predicting reaction properties, the quantification of prediction uncertainty has seldom been investigated, thus compromising the confidence in using these predicted properties in practical applications. Here, we integrated graph convolutional neural networks (GCNN) with three uncertainty prediction techniques, including deep ensemble, Monte Carlo (MC)-dropout, and evidential learning, to provide insights into the uncertainty quantification and utility. The deep ensemble model outperforms others in accuracy and shows the highest reliability in estimating prediction uncertainty across all elementary reaction property data sets. We also verified that the deep ensemble model showed a satisfactory capability in recognizing epistemic and aleatoric uncertainties. Additionally, we adopted a Monte Carlo Tree Search method for extracting the explainable reaction substructures, providing a chemical explanation for DL predicted properties and corresponding uncertainties. Finally, to demonstrate the utility of uncertainty qualification in practical applications, we performed an uncertainty-guided calibration of the DL-constructed kinetic model, which achieved a 25% higher hit ratio in identifying dominant reaction pathways compared to that of the calibration without uncertainty guidance.

Heteroatom-Controlled Three-Component [4 + 3] or [3 + 2] Annulation of Isatin-Derived Azomethine Ylide with Azadiene: Selective Synthesis of Spirooxindole-diazepines and Density Functional Theory Studies.

A novel three-component [4 + 3] annulation reaction of isatin-derived azomethine ylides with azadienes was developed for the first time to efficiently synthesize spirooxindole-diazepines incorporating a benzothiophene moiety under catalyst-free conditions. Effects of the heteroatom of azadiene on the chemoselectivity was investigated. With the use of the azadiene bearing a benzofuran moiety as a substrate, the dominant reaction pathway was changed to an α-[3 + 2] annulation. When azadiene bearing an indenone moiety was used, a distinct γ-[3 + 2] annulation was observed. Density functional theory calculations revealed that a delicate balance between kinetic accessibility and the thermodynamic driving force controlled the competition of different annulation reactions.

Oxidation of butane-2,3-dione at high pressure: Implications for ketene chemistry

Ketene (CH2CO) mechanism is a building block for developing combustion kinetic models of practical fuels. To revisit the combustion chemistry related to ketene, oxidation experiments of butane-2,3‑dione (diacetyl, CH3COCOCH3), considered as an effective precursor of CH2CO, are conducted in a jet-stirred reactor (JSR) at 10 bar and temperatures ranging from 650 to 1160 K. Identification and quantification of intermediates are achieved by Fourier transform infrared spectrometry, gas chromatography, and mass spectrometry. A kinetic model of diacetyl is constructed based on recent theoretical and modeling studies on diacetyl and ketene, which has been validated against the present data and experimental data of diacetyl and CH2CO in literature. Generally, the present model can adequately predict most of them, and better predict the methyl-related intermediates under wide pyrolysis and combustion conditions than previous models. Based on modeling analyses, the unimolecular decomposition reaction of diacetyl is the dominant reaction pathway for fuel consumption under different equivalence ratio conditions, especially at high temperatures. Under lean conditions, both the H-atom abstraction reactions by methyl (i.e. CH3COCOCH3 + CH3 = CH4 + CH2CO + CH3CO, R3) and by OH (i.e. CH3COCOCH3 + OH = H2O + CH2CO + CH3CO, R5) are important for diacetyl consumption, while under rich conditions R5 becomes negligible. As the most important intermediates in diacetyl oxidation, the main consumption pathways of CH2CO and CH3 are dependent on the equivalence ratio conditions. Under lean conditions, CH2CO mainly reacts with OH to produce CH2OH and CO (i.e. CH2CO + OH = CH2OH + CO, R10), while methyl reacts with HO2 to produce CH3O and OH (i.e. CH3 + HO2 = CH3O + OH, R20). In contrast, under rich conditions, the addition-elimination reaction between CH2CO and H becomes competitive with R10, while the CH3 self-combination producing C2H6 plays a more important role than the CH3 oxidation pathway R20. Sensitivity analysis of CH2CO shows that not only the reactions of CH2CO, but also those of CH3 are sensitive to CH2CO formation. This is because CH3 related reactions influence the distribution of radical pool, which determines the oxidation reactivity of the reaction system.

Reactivity, Pathways, and Iodinated Disinfection Byproduct Formation during Chlorination of Iodotyrosines Derived from Edible Seaweed.

Iodine derived from edible seaweed significantly enhances the formation of iodinated disinfection byproducts (I-DBPs) during household cooking. Reactions of chlorine with monoiodotyrosine (MIT) and diiodotyrosine (DIT) derived from seaweed were investigated. Species-specific second-order rate constants (25 °C) for the reaction of hypochlorous acid with neutral and anionic MIT were calculated to be 23.87 ± 5.01 and 634.65 ± 75.70 M-1 s-1, respectively, while the corresponding rate constants for that with neutral and anionic DIT were determined to be 12.51 ± 19.67 and 199.12 ± 8.64 M-1 s-1, respectively. Increasing temperature facilitated the reaction of chlorine with MIT and DIT. Based on the identification of 59 transformation products/DBPs from iodotyrosines by HPLC/Q-Orbitrap HRMS, three dominant reaction pathways were proposed. Thermodynamic results of computational modeling using density functional theory revealed that halogen exchange reaction follows a stepwise addition-elimination pathway. Among these DBPs, 3,5-diiodo-4-hydroxy-benzaldehyde and 3,5-diiodo-4-hydroxy-benzacetonitrle exhibited high toxic risk. During chlorination of MIT and DIT, iodinated trihalomethanes and haloacetic acids became dominant species at common cooking temperature (80 °C). These results provide insight into the mechanisms of halogen exchange reaction and imply important implications for the toxic risk associated with the exposure of I-DBPs from household cooking with iodine-containing food.

Numerical investigation of vacuum ultra-violet emission in Ar/O2 inductively coupled plasmas

Abstract Controlling fluxes of vacuum ultraviolet (VUV) radiation is important in a number of industrial and biomedical applications of low pressure plasma sources because, depending on the process, VUV radiation may be desired, required to a certain degree, or unwanted. In this work, the emission of VUV radiation from O atoms is investigated in low-pressure Ar/O2 inductively coupled plasmas via numerical simulations. For this purpose, a self-consistent Ar/O2 plasma-chemical reaction scheme has been implemented in a zero dimensional plasma chemical kinetics model and is used to investigate VUV emission from excited O atoms (3s 5S 2 0 and 3s 3S 1 0 ) at 130 and 135 nm. The model is extensively compared with experimental measurements of absolute VUV emission intensities, electron densities and Ar excited state densities. In addition, oxygen VUV emission intensities are investigated as a function of pressure, Ar/O2 mixture, and power deposition and the dominant reaction pathways leading to oxygen VUV emission are identified and described. In general terms, absolute oxygen VUV emission intensities increase with power and oxygen fraction over the ranges investigated and peak emission intensities are found for pressures between 5–50 Pa. The emission is dominated by the 130 nm resonance line from the decay of the O(3s 3S 1 0 ) state to the ground state. Besides, at low pressure (0.3–1 Pa), the flux of oxygen VUV photons to surfaces is much lower than that of positive ions, whereas oxygen VUV fluxes dominate at higher pressure, ≳ 5–50 Pa depending on O2 fraction. Finally, oxygen atom fluxes to surfaces are, in general, larger than those of VUV photons for the parameter space investigated.

Selective Synthesis of Organonitrogen Compounds via Electrochemical C-N Coupling on Atomically Dispersed Catalysts.

The C-N coupling reaction demonstrates broad application in the fabrication of a wide range of high value-added organonitrogen molecules including fertilizers (e.g., urea), chemical feedstocks (e.g., amines, amides), and biomolecules (e.g., amino acids). The electrocatalytic C-N coupling pathways from waste resources like CO2, NO3-, or NO2- under mild conditions offer sustainable alternatives to the energy-intensive thermochemical processes. However, the complex multistep reaction routes and competing side reactions lead to significant challenges regarding low yield and poor selectivity toward large-scale practical production of target molecules. Among diverse catalyst systems that have been developed for electrochemical C-N coupling reactions, the atomically dispersed catalysts with well-defined active sites provide an ideal model platform for fundamental mechanism elucidation. More importantly, the intersite synergy between the active sites permits the enhanced reaction efficiency and selectivity toward target products. In this Review, we systematically assess the dominant reaction pathways of electrocatalytic C-N coupling reactions toward various products including urea, amines, amides, amino acids, and oximes. To guide the rational design of atomically dispersed catalysts, we identify four key stages in the overall reaction process and critically discuss the corresponding catalyst design principles, namely, retaining NOx/COx reactants on the catalyst surface, regulating the evolution pathway of N-/C- intermediates, promoting C-N coupling, and facilitating final hydrogenation steps. In addition, the advanced and effective theoretical simulation and characterization technologies are discussed. Finally, a series of remaining challenges and valuable future prospects are presented to advance rational catalyst design toward selective electrocatalytic synthesis of organonitrogen molecules.

Investigation of ultrafast intermediate states during singlet fission in lycopene H-aggregate using femtosecond stimulated Raman spectroscopy.

The singlet fission process involves the conversion of one singlet excited state into two triplet states, which has significant potential for enhancing the energy utilization efficiency of solar cells. Carotenoid, a typical π conjugated chromophore, exhibits specific aggregate morphologies known to display singlet fission behavior. In this study, we investigate the singlet fission process in lycopene H-aggregates using femtosecond stimulated Raman spectroscopy aided by quantum chemical calculation. The experimental results reveal two reaction pathways that effectively relax the S2 (11Bu+) state populations in lycopene H-aggregates: a monomer-like singlet excited state relaxation pathway through S2 (11Bu+) → 11Bu- → S1 (21Ag-) and a dominant sequential singlet fission reaction pathway involving the S2 (11Bu+) state, followed by S* state, a triplet pair state [1(TT)], eventually leading to a long lifetime triplet state T1. Importantly, the presence of both anionic and cationic fingerprint Raman peaks in the S* state is indicative of a substantial charge-transfer character.

Combined Strategies Enable Highly Selective Light Olefins and para-Xylene Production on Single Catalyst Bed.

Achieving multiple high-value-added chemical production through novel reaction processes and shape-selective catalytic strategy is the key to realizing efficient low-carbon catalytic processes. In this work, a methanol-toluene coreaction system was developed, and combined control strategies of reaction pathway guidance and shape-selective catalysis were applied for the successful production of light olefins and para-xylene on single HZSM-5 catalyst bed. Cofeeding toluene additionally provides reactive and flowing aromatic hydrocarbon pool species that change the dominant reaction pathway in the complex network of the methanol reaction on HZSM-5 and promote the formation of ethylene. For the first time, the key reaction intermediates methylmethylenecyclodiene are directly captured and identified by experimental and theoretical techniques. This helps to propose the catalytic cycle for the dominant generation of ethylene and, more importantly, enriches the methanol-to-hydrocarbons (MTH) chemistry and hydrocarbon pool mechanism. Furthermore, 0.4HZSM-5@S-1-CLD, an optimized HZSM-5 catalyst modified by the silicalite-1 epitaxial growth followed by silanization approach, realizes highly selective production of light olefins (especially ethylene) and para-xylene, while excellent reactant activity is maintained. This highly efficient coreaction route gives an important leading significance in synthesizing the raw materials for the polyolefin and polyester industries. The establishment of the combined control strategies provides a model for the joint production of multiple target chemicals in complex catalytic processes.

Enhanced levofloxacin degradation through efficient activation of peroxymonosulfate using N-doped bulged multilayer Graphene: Harnessing interface structure to regulate carrier concentration and transport speed

Nitrogen (N)-doped carbon materials are regarded as potential catalysts for advanced oxidation procedures due to their efficiency and environmentally friendly nature. Nevertheless, the low carrier concentration, slow charge transfer, and limited mass transfer efficiency hinder satisfactory catalytic performance. Herein, we present the novel use of graphite nanosheets as precursors to synthesize nanoporous N-doped mesoporous expanded and bulged multilayer graphene (EG@N-x) with varying proportions for peroxydisulfate (PMS) activation. The EG@N-2.5 catalyst demonstrates a degradation rate of 0.140 min−1, and over 90 % of LEVO (24 mg/L) was decomposed in 10 min. Additionally, the EG@N-2.5/PMS system possessed a broad pH range of efficiency (1.0–7.0), exceptional anti-interference performance against anions and humic acid (HA), and marvelous reusability, which can be attributed to the superior PMS activation performance of EG@N-x by lowering the EHOMO − ELUMO (EPD = 0.014433) gap, and reducing the adsorption binding energy (Eads = -2.33 eV), enhancing the amount of charge transfer (Q = 0.6190 e) in the EG@N-x/PMS system. The removal of LEVO is primarily attributed to the mechanism of singlet oxygen (1O2) mechanism and the metastable reactive complexes in electron transfer. Decarboxylation, defluorination, and depiperazinylation are three dominant reaction pathways. Moreover, the EG@N-x/PMS system demonstrates adequate mineralization of LEVO under various organic and environmental conditions, reducing effluent biotoxicity.

Assessment of Cryogenic Coring to Preserve Vertical Distributions of Trichloroethylene and Reaction Products in an Aquitard

AbstractThere is not a clear understanding of the extent by which naturally occurring reactions can attenuate trichloroethene (TCE) and its daughter products within low permeability zones (LPZs), and addressing this knowledge gap requires advancement of methods to accurately measure in situ volatile chemical concentrations. In this study, a soil coring method that freezes the soil in‐situ (a.k.a., cryogenic coring) was utilized to measure depth‐discrete distributions of TCE and its volatile reaction products through a TCE‐impacted silty clay aquitard, and results were compared with those from adjacent soil cores taken using a conventional coring approach. Vertical concentration profiles of TCE, cis‐1,2‐dichloroethylene (DCE), vinyl chloride (VC), ethane, and methane were all compared between the two coring methods, and results indicate the two coring methods recovered statistically equivalent concentrations of volatiles across most depths of the fine‐grained cohesive clayey soil at the study site. Biotic reductive dechlorination was the dominant TCE reaction pathway at the site; several reduced gasses that are possible markers for abiotic reduction were detected, but their concentrations and intervals of occurrence were not sufficiently consistent to indicate whether they were from abiotic TCE reduction or unrelated biological processes. Overall, cryogenic coring yielded improved recovery of sand lenses compared to conventional coring, but offered no apparent benefits for improved recovery of TCE and its volatile reaction products in the low permeability aquitard material at the site.

A numerical study of NOX and soot emissions in ethylene-ammonia diffusion flames with oxygen enrichment

Blending ammonia with hydrocarbon fuels is gaining interest due to its potential to significantly reduce carbon emissions from the combustion of these blends. Additionally, studies have provided strong evidence of oxygen enhanced combustion to reduce soot emissions and improve flame stability. The present work attempts to leverage the benefits of both strategies, ammonia doping and oxygen enhanced combustion, by considering ethylene diffusion flames. Simulations are performed using the CHEMKIN-Pro software. A reaction mechanism with 372 species and 13,847 reactions is developed by combining gas phase chemistries for ethylene, NH3 and NOX, along with a detailed soot mode. The mechanism is extensively validated for a range of fuel blends in terms of flame structure, intermediate hydrocarbons, soot precursors and soot. Oxygen enrichment is achieved by removing certain amount of nitrogen from oxidizer stream and adding it to fuel stream, and thereby maintaining a nearly constant flame temperature. Extensive analysis is carried out to characterize the chemical and dilution effects of ammonia doping on flame structure, soot precursors, soot, and NOX in ethylene flames with varying levels of oxygenation. Further, dominant reaction pathways for several soot precursors and NOx are identified through detailed rate of production analyses. Results indicate that ammonia doping in ethylene flames leads to substantial increase in NOX emissions, while oxygenation has negligible influence on NOX emissions. In contrast, both NH3 doping and oxygenation provide significant reduction in the formation of soot precursors and soot. Oxygenation achieves this reduction through both hydrodynamic and flame structure effects, as the flame shifts from oxidizer side to fuel side. On the other hand, NH3 doping reduces the rates of important reactions for the formation of soot precursors, as the concentrations of relevant species (C2H2, C3H3, C3H3-P, C3H3-A etc.) decrease due to their consumption through reactions with species like NCO and CN formed from NH3. Moreover, the effectiveness of NH3 doping is further enhanced when combined with oxygenation. Hence, NH3 doping and oxygenation are found to be effective and synergistic strategies in reducing soot emissions, and their proper combination could provide near zero soot emissions.

Theoretical study on the concerted catalysis of Ir/Ni for amino radical transfer for C(sp2)-C(sp3) bond formation.

Thomas C. Maier's group has reported a synergistic Ir/Ni catalysis method for the synthesis of C(sp2)-C(sp3) bonds through an amino radical transfer (ART) strategy to generate alkyl radicals. This work employed density functional theory (DFT) to investigate the reaction mechanism, including the redox mechanism of Ir complexes in the generation process of amino radicals, analyzed the role and rationale behind alkyl boronic esters becoming dominant reaction pathways in the ART process, and discussed the competitive reaction mechanisms between oxidative addition and radical capture during C(sp2)-C(sp3) cross-coupling with Ni complexes. Through this theoretical calculation study, we aim to provide a theoretical foundation for constructing key carbon radical intermediates using ART and Ni-complex catalyzed free-radical-involved C(sp2)-C(sp3) cross-coupling reactions.

Auto-ignition characteristics of oxygenated aromatic compounds: Benzyl alcohol, benzaldehyde, and phenol

The growing attention towards biomass and biomass-derived fuels for transportation, energy production, forest fire prevention, and safety applications stimulated significant research activities focused on understanding the chemical kinetics of oxygenated aromatic hydrocarbons, which represent important reference components for biofuels. This motivates the current investigation of the ignition behavior of benzyl alcohol, benzaldehyde, and phenol, which exhibit intertwined reaction pathways. Novel ignition delay time data were measured in a shock tube and a rapid compression machine covering pressures from 10 to 40 bar and temperatures from 860–1250 K. In addition, a kinetic model was developed and used to analyze critical reaction pathways in comparison to models from literature. It is shown that the phenyl-phenoxy-phenyl peroxy subsystem plays a key role not only in the oxidation of benzaldehyde, but also in the oxidation of benzene and phenol. Comparison of the current model with a recent version of the CRECK mechanism reveals that differences are present with respect to the dominant reaction pathways that have a strong influence on the formation of Ö radicals. Further investigations are required to resolve this discrepancy reconciling theory, modelling, and the unfortunately limited number of systematic experimental data to which this work significantly contributes.

Products and yields for the NO3 radical initiated atmospheric degradation of 2-methylfuran (2-MF, CH3–C4H3O)

Furans represent a group of oxygenated, heterocyclic, organic compounds that are emitted during biomass burning (BB). Notably, these compounds undergo rapid oxidation, a process observed both during the day and at night. Methylated furanoids comprise a large fraction of total furan emissions. Recent kinetic studies suggest that the NO3 initiated degradation of methylated furans is the dominant reaction pathway during nighttime, and with significant contribution on daytime. The aim of this study is to investigate the degradation products and the reaction mechanism of 2-methylfuran (2-MF) reaction with NO3 radicals using two atmospheric simulation chambers: CHARME (Chamber for the Atmospheric Reactivity and the Metrology of the Environment, Dunkerque, France) and THALAMOS (Thermally Regulated Atmospheric Simulation Chamber, Douai, France). All experiments were carried out at ambient temperature, (294 ± 2) K and atmospheric pressure (760 Torr, zero air). Oxidation products were qualitatively and quantitatively characterized using multiple, complementary detection techniques. Gas phase major and minor products were detected via offline GC-EI-MS (Gas chromatography - Electronic Impact - Mass Spectrometry) after trapping the gas-phase mixture on different adsorption media. PTR-ToF-MS (Proton Transfer Mass Reaction – Time of Flight – Mass Spectrometer, CHARME) and SIFT-MS (Selected Ion Flow Tube Mass Spectrometry, THALAMOS) were used on-line to monitor reactants and major products and to determine the end-product yields. 4-Oxo-2-pentenal (H(O)CCHCHC(O)CH3), and 2(5H)-furanone, 5-methyl, 5-nitrooxy ((CH3)C(ONO2)(C4H2O2)) were detected as major products with yields (62 ± 15) % and (26 ± 3) %, respectively. In-situ FTIR (Fourier Transform Infrared Spectroscopy) along with quantum mechanical molecular calculations revealed that organic nitrates and dinitrates were also formed. Secondary organic aerosols (SOA) formation, in the presence of ammonium sulfate seed, was also monitored using SMPS-CPC (Scanning Mobility Particle Sizer-Condensation Particle Counter). The size distribution and the mass concentration of the particles were determined for 2-MF concentration between 80 and 531 ppbv leading to SOA yields 1.03–2.23 %. Finally, SOA formed were chemically characterized using ESI-LC-QToF-MS/MS (Electrospray Ionization Liquid Chromatography – Quadrupole - Time of Flight - Tandem Mass Spectrometer) revealing that oligomers, e.g. highly oxygenated molecules (HOMs) were also formed. Based on our experimental observations, a reaction mechanism is proposed. NO3 radical is predominately added to the C2/C5 double bond of 2-MF, while the H atom abstraction channel, is estimated to be of minor importance. Results from this work provide detailed information about the NO3 radical initiated oxidation of 2-MF that can be used in chemical transport models to simulate the ageing processes occurring in biomass burning plumes.

Oxidation of selected fluoroquinolones by ferrate(VI) in water: Kinetics, mechanism, effects of constituents, and reaction pathways

In this work, the oxidation of gatifloxacin (GAT), fleroxacin (FLE) and enoxacin (ENO) in aqueous solution by ferrate (Fe(VI)) was systemically investigated. Weak alkaline and high oxidant doses were favorable for the reaction. The pseudosecond-order rate constants were 0.18055, 0.29162, and 0.05476 L/(mg·min), and the activation energies were 25.13, 15.25, and 11.30 kJ/mol at pH = 8.00 and n(Fe(VI)):n(GAT) = 30:1, n(Fe(VI)):n(FLE) = 20:1, n(Fe(VI)):n(ENO) = 40:1 and a temperature of 25 °C. The maximum degradation rates of the GAT, FLE and ENO were 96.72%, 98.48% and 94.12%, respectively, well simulated by Response Surface Methodology. During the oxidation, the contribution of hydroxyl radicals (HO•) varied with time, whereas the final contribution was approximately 20% at 30 min. The removal efficiency was inhibited by anions by less than 10%, and cations by less than 25%, and significantly inhibited by high concentrations of humic acid. Moreover, two or three dominant reaction pathways were predicted, and the ring cleavages of quinolone and piperazine were mainly achieved through decarboxylation, demethlation and hydroxylation, and some pathways ended up with monocyclic chemicals, which were harmless to aquatic animals and plants. Theoretical calculations further proved that the reactions between FeO4− and neutral fluoroquinolone antibiotics were the major reactions. This work illustrates that Fe(VI) can efficiently remove fluoroquinolone antibiotics (FQs) in aqueous environments, and the results may contribute to the treatment of wastewater containing trace antibiotics and Fe(VI) chemistry.

Effect of industrial alkene ozonolysis on atmospheric H2SO4 formation

This study has employed the master chemical mechanism (MCM) to investigate the influence of the ozone oxidation pathways in the atmospheric formation of H2SO4 from short-chain olefins in industrialized areas. In-situ H2SO4 formation data were obtained using a high-resolution chemical ionization time-of-flight mass spectrometer, and the simulated H2SO4 concentrations calculated using updated parameters for the MCM model exhibited good agreement with observations. In the simulation analysis of different reaction pathways involved in H2SO4 formation, hydroxyl radicals were found to dominate H2SO4 production during the daytime, while olefin ozone oxidation contributed up to 65% of total H2SO4 production during the night-time. A sensitivity analysis of the H2SO4 production parameters has revealed a high sensitivity to changes in sulfur dioxide, and a relatively high sensitivity to olefins with fast ozonolysis reaction rates and bimolecular reaction rates of resulting stabilized Criegee Intermediates. A high relative humidity promotes daytime H2SO4 formation, but has an inhibiting effect during the night-time due to the different dominant reaction pathways.

Pyrolysis of plastics-free refuse derived fuel derived from municipal solid waste and combustion of the char products in lab and pilot scales: A comparative study

Pyrolysis of refuse derived fuel (RDF) has great potential for energy recovery from municipal solid waste (MSW), while chlorine-related plastics issue was one major barrier for scale up. After screening out plastics, the RDF pyrolysis and char products combustion were evaluated in lab and pilot scales. Thermogravimetry with Fourier-transform infrared spectroscopy results suggest that the main RDF pyrolysis reaction occurred in 190–410 °C, involving decomposition, decarboxylation, demethylation, and dehydration reactions, with CO2, CH4, H2O, CO, and organic compounds as the main gaseous products. Impacts of temperature and residence time on char yield and proximate composition were evaluated in lab, and a lower temperature was favored. The pilot-scale char had a comparable proximate composition to the lab-scale ones, but a lower heating value, lower H/C ratio, higher O/C ratio, which may due to different dominant reaction pathways during pyrolysis: apparent demethanation versus dehydration. Thermogravimetry data infers that the combustion performance of pilot-scale char, including combustion stage, weight loss, and kinetic parameters, were close to chars made in lab. Pilot-scale combustion tests show relief of flue gas pollution after upgrading RDF to char, while particulate matter and heavy metals were still main concerns. Lab- and pilot-scale investigations highlight scale up of plastics-free RDF pyrolysis and combustion as a promising and economic alternative for materials and energy recoveries from MSW.