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Hydrogen is not only an important industrial chemical but also an energy carrier with increasing demand. However, the current production techniques are based on technologies that result in massive CO2 emissions. In contrast, the pyrolysis of alkanes in a liquid metal bubble column reactor does not lead to direct CO2 emissions. In order to transfer this technology from lab-scale to industrial applications, it has to be scaled up and the influences of the most common constituent of natural gas on the pyrolysis process have to be determined. For this study, the liquid metal bubble column technology developed at the KIT was scaled up by a factor of 3.75, referred to as the reactor volume. In this article, the experimental setup containing the reactor is described in detail. In addition, new methods for the evaluation of experimental data will be presented. The reactor, as well as the experimental results from pure methane pyrolysis (PM), will be compared to the previous generation of reactors in terms of methane conversion. It could be proven that scaling up the reactor volume did not result in a decrease in methane conversion. For part II of this publication, methane-ethane (MEM) gas mixtures and high calorific natural gas (nGH) were pyrolyzed, and the results were discussed on the basis of the present part I.

Although polyethylene (PE) and polypropylene (PP) are by far the world's largest volume plastics, only a tiny fraction of these energy-rich polyolefins are currently recycled. Depolymerization of PE to its constituent monomer, ethylene, is highly endothermic and conventionally accessible only through unselective, high-temperature pyrolysis. Here, we provide experimental demonstrations of our recently proposed tandem catalysis strategy, which uses ethylene to convert PE to propylene, the commodity monomer used to make PP. The approach combines rapid olefin metathesis with rate-limiting isomerization. Monounsaturated PE is progressively disassembled at modest temperatures via many consecutive ethenolysis events, resulting selectively in propylene. Fully saturated PE can be converted to unsaturated PE starting with a single transfer dehydrogenation to ethylene, which produces a small amount of ethane (1 equiv per dehydrogenation event). These principles are demonstrated using both homogeneous and heterogeneous catalysts. While selectivity under batch conditions is limited at high conversion by the formation of an equilibrium mixture of olefins, high selectivity to propylene (≥94%) is achieved in a semicontinuous process due to the continuous removal of propylene from the reaction mixture.

Numerical computations comprising of Grand Canonical-Monte Carlo (GCMC) and Canonical Statistical Ensemble (NVT) Molecular Dynamics (MD) simulations were used to study the diffusion and sorption characteristics primarily for methane, ethane, and ethene molecules and for their ternary mixtures at different temperatures in ZIF-8 porous material. Methane as pure component or in mixture proved to be the sorbed hydrocarbon with the higher molecular mobility at the temperature range of 273-373 K among alkanes and alkenes. In addtion, alkenes were the hydrocarbons with the higher self-diffusion coefficients compared to the respective alkanes. In the ternary mixtures ethane was preferentially sorbed in ZIF-8 at all temperatures studied. Direct comparisons of the self-diffusivity data obtained from the NVT-MD simulations with recently reported Magic Angle Spinning Pulsed Field Gradient Nuclear Magnetic Resonance (MAS PFG NMR) measurements showed reasonable agreement. Furthermore, the NVT-MD self-diffusivity coefficients in conjunction with the aforementioned MAS PFG NMR experimental measurements, and sorption thermodynamic data obtained from the present GCMC simulations were utilized for the development of individual Artificial Neural Networks (ANNs) predictive modeling procedures in order to provide additional quantitative and qualitative information regarding the diffusion and sorption of small alkanes, alkenes in ZIF-8. The ANNs predictions were in good agreement with the experimental measurements and with the molecular simulation data. The modeling and analysis capabilities of ANNs along with their fast computations using moderate computer resources can significantly assist the irreplaceable molecular simulation and experimental approaches to cope with complicated problems at the molecular level.

The photocatalytic reduction of carbon dioxide (CO

This project investigated passive adsorbent sampling of light (C2-C5) hydrocarbons which are the sensitive tracers of fugitive emissions from oil and natural gas (ON under the worst case relative humidity level of 95% RH, VOCs uptake rates dropped to 27-39% of those in dry air. This effect potentially causes results to be biased low when cartridges are deployed at high RH, including overnight when RH is often elevated over daytime levels. Nonetheless, representative sampling results were obtained under ambient conditions during three field studies where cartridges were evaluated alongside whole air sample collection in canisters. Agreement varied by compound: Ethane and alkenes correlated poorly and could not be analyzed with satisfactory results; results for C3-C5 alkanes were much better: i-butane correlated with R2 > 0.5, and propane, n-butane, i-pentane, and n-pentane with R2 > 0.75, which demonstrates the feasibility of the passive sampling of these latter O&NG tracers.

This thesis discusses the binding of alkanes (saturated hydrocarbons) to transition metal complexes. The thesis describes: (i) the first direct Nuclear Magnetic Resonance (NMR) spectroscopic observation of alkane coordination to group 8 transition metal centres; (ii) the only complete group of analogous transition metal alkane σ-complexes (Fe, Ru and Os); and (iii) the first set of methane σ-complexes, formed from molecular methane, that are sufficiently stable to analyse using NMR spectroscopy. Chapter 1 is a general introduction for the non-specialist, introducing the concepts of coordination chemistry and in particular the formation of σ-complexes including complexes of molecular hydrogen and alkanes. Chapter 2 contains an introduction to methane in organometallic chemistry and describes results from low temperature NMR spectroscopic and computational investigations into the methane σ-complexes [η5-CpM(CO)2(CH4)][Al(OC(CF3)3)4] (M = Os (5), Ru (13), Fe (17)) that were produced using an improved in situ NMR sample photolysis apparatus. The bound methane fragments in 5, 13 and 17 have 1H resonances at δ −2.16, δ −2.10 and δ −4.27; 13C resonances at δ −56.3, δ −48.8, and δ −53.0; and 1J C-H couplings of 127 Hz, 126 Hz, and 126 Hz respectively. Of these three species, 13 is the least stable and 5 is the most stable. DFT and ab initio calculations provide further insight into the structures of the [η5-CpM(CO)2(CH4)]+ (M = Os (5), Ru (13) and Fe (17)) complexes and find that the binding free energies of 5, 13 and 17 are -13.6 kcal mol- 1, -10.5 kcal mol-1 and -11.7 kcal mol-1 respectively. Chapter 3 describes results from the low temperature NMR spectroscopic and computational investigations into the ethane σ-complex [η5-CpOs(CO)2(C2H6)][Al(OC(CF3)3)4] (19). The proton resonances, at δ −2.39 (for the osmium-bound CH3) and δ 1.32 (for and the non-bound CH3) were correlated to 13C resonances at δ −30.7 and δ 11.1 respectively. DFT calculations support the observation that there is no exchange observed between the bound and non-bound methyl groups at temperatures as high as -75 ℃, with calculations predicting the barrier to exchange to be a relatively high value of 13.7 kcal mol-1. NMR data show that 19 is more stable than the methane analogue 5, discussed in Chapter 2, consistent with the free energy of binding being calculated to be higher in the case of the ethane complex (-16.6 kcal mol-1). Chapter 4 describes results from the low temperature NMR spectroscopic investigations into the cyclopentane σ-complexes [η5-CpM(CO)2(c-C5H10)][Al(OC(CF3)3)4] (M = Os (20), Ru (22), Fe (23)). The cyclopentane σ-complexes show the same trend in stability as was reported for the methane complexes (20 > 23 > 22). The osmium centred cyclopentane σ-complex (20) is the most stable of the cyclopentane σ-complexes studied here and is sufficiently stable to be observed in solution for a short period (t1/2 = 7.8 mins) at temperatures as high as -50 ℃, making it one of the most stable alkane σ-complexes to be studied in the solution state. Chapter 5 describes preliminary results from the low temperature NMR spectroscopic investigation into the n -pentane σ- complexes [η5-CpM(CO)2(n -C5H12)][Al(OC(CF3)3)4] (M = Os (24) and Ru (25)). NMR data show that the osmium complex preferentially binds methyl groups during UV irradiation, but in the dark the methyl-bound species isomerises to preferentially bind the methylene groups. The ruthenium complex (25) shows a preference to bind via methylene groups under all conditions examined. Chapter 6 draws some overarching conclusions from the investigations presented in this thesis and gives some suggestions to direct future studies in this field. Chapter 7 describes the design and production of an improved experimental apparatus for conducting in situ photolysis of NMR samples with added gaseous reagents and describes the experimental procedures and synthesis of precursor compounds.

The preparation, characterization and application of hydroxyapatite silica propyl bis aminoethoxy ethane cuprous complex (HASPBAEECC) as a novel hybrid nano-catalyst for synthesis of new benzimidazole-1,2,3-triazole hybrid analogues as promising antifungal agents have been described. HASPBAEECC is fully characterized by different microscopic, spectroscopic and physical techniques, including scanning electron microscopy (SEM), transmission, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA) and FT-IR. The 'Click̕ Huisgen cycloaddition reaction of N-propargyl benzimidazole with diverse azidoalkyls in a THF-water media at ambient temperature provides the products in good-to-excellent yields using HASPBAEECC. HASPBAEECC is proved to be a stable, low cost, reusable and environmentally benign nanohybrid catalyst. The target compounds were screened against some pathogenic fungal comprising Candida albicans, Candida krusei, Candida parapsilosis, Aspergillus fumigatus and Aspergillus flavus in which it was determined that compounds 11f and 11 h have displayed promising antifungal activity similar to fluconazole as a reference drug. HASPBAEECC is a novel hybrid nano-catalyst for highly efficient synthesis of new benzimidazole-1,2,3- triazole hybrid analogues as antifungal agents.

The absolute coverage of CO has been a missing piece in the mechanistic puzzle of the CO reduction reaction (CORR) on Cu. For the first time, we revealed the upper bound of the CO coverage under electrocatalytic conditions to be 0.05 monolayer at atmospheric pressure and the saturation CO coverage to be ∼0.25 monolayer by conducting surface enhanced infrared spectroscopy at CO pressures up to 60 barg in a custom-designed spectroelectrochemical cell. CORR activities on Cu were also determined in the same pressure range. Calculated reaction orders of C

At a time of unpredictable challenges for health, one trend is certain: there is an exceedingly high demand for functional implants, particularly bone grafts. This has encouraged the emergence of bone tissue engineering substitutes as an alternative method to conventional bone grafts. However, the current approaches in the field face several limitations that have prevented the ultimate translation into clinical settings. As a result, many attempts have been made to fabricate synthetic bone implants that can offer suitable biological and mechanical properties.Light curable methacrylate-based polymers have ideal properties for bone repair. These materials are also suitable for 3D printing which can be applicable for restoration of both function and aesthetics. The main objective of this research was to investigate the role of calcium phosphate (CaP) incorporation in a mechanically stable, biologically functional and 3D printable polymer for the reconstruction of complex craniofacial defects. The experimental work initially involved the synthesis of (((((((((((3R,3aR,6S,6aR)- hexahydrofuro[3,2-b]furan-3,6-diyl)bis(oxy))bis(ethane-2,1- 48 diyl))bis(oxy))bis(carbonyl))bis(azanediyl))bis(3,3,5-trimethylcyclohexane-5,1- 49 diyl))bis(azanediyl))bis(carbonyl))bis(oxy))bis(ethane-2,1-diyl) bis(2-methylacrylate) referred to as CSMA and fabrication of composite discs via a Digital Light Printing (DLP) method. The flow behaviour of the polymer as a function of CaP addition, surface remineralisation potential, in vitro cell culture, using MC3T3 and Adipose-Derived Mesenchymal Stem Cells (ADSCs) and ex ovo angiogenic response was assessed. Finally, in vivo studies were carried out to investigate neo-bone formation at 4- and 8-weeks post-implantation. Quantitative micro-CT and histological evaluation did not show a higher rate of bone formation in CaP filled CSMA composites compared to CSMA itself. Therefore, such polymeric systems hold promising features by allowing more flexibility in designing a 3D printed scaffold targeted at the reconstruction of maxillofacial defects.

Five- and six-coordinate cationic bis(phosphine) cobalt(III) metallacycle complexes were synthesized with the general structures, [(depe)Co(cycloneophyl)(L)(L′)][BArF4] (depe = 1,2-bis(diethylphosphino)ethane; cycloneophyl = [κ-C:C-(CH2C(Me)2)C6H4]; L/L′ = pyridine, pivalonitrile, or the vacant site, BAr4F = B[(3,5-(CF3)2)C6H3]4). Each of these compounds promoted facile directed C(sp2)–H activation with exclusive selectivity for ortho-alkylated products, consistent with the selectivity of reported cobalt-catalyzed arene-alkene-alkyne coupling reactions. The direct observation of C–H activation by cobalt(III) metallacycles provided experimental support for the intermediacy of these compounds in this class of catalytic C–H functionalization reaction. Deuterium labeling and kinetic studies provided insight into the nature of C–H bond cleavage and C–C bond reductive elimination from isolable cobalt(III) precursors.

Diastereo- and enantioselective kinetic resolution of racemic planar-chiral 1-iR/i-2-vinylferrocenes (irac/i-b1/b) was attained by the molybdenum-catalyzed asymmetric metathesis dimerization (AMD). Two sequential AMD reactions ofirac/i-b1a/b(R = Br) provided (iE/i)-(iS/i,iS/i)-1,2-di(2-bromoferrocenyl)ethylene ingt;99% ee, which was converted to (iS/i,iS/i)-1,2-bis[(2-diphenylphosphino)ferrocenyl]ethane (iS/i,iS/i)-b5/b. Planar-chiral bisphosphine (iS/i,iS/i)-b5/bcoordinated to a dichloropalladium(II) fragment in aitrans/i-chelating fashion, which was applied as a chiral ligand in the palladium-catalyzed asymmetric allylic alkylation showing enantioselectivity of up to 90% ee.

Aromatization of light hydrocarbons can contribute to a secure supply of aromatics for the chemical industry. In this work, we investigate the influence of modification of zeolite ZSM-5 with Ga and Mo on the reaction mechanism underlying the activation and aromatization of ethane. Well-defined Mo/ZSM-5 and Ga/ZSM-5 zeolites efficiently promote ethane aromatization to benzene-toluene-xylene mixtures. Both catalysts suffer from coke formation, which leads to rapid deactivation. From catalytic tests, temperature-programmed surface reaction and pulsed reaction experiments, we infer that ethane conversion on Ga/ZSM-5 follows a conventional sequential dehydrogenation-oligomerization-aromatization mechanism, while the reaction over Mo/ZSM-5 involves reactive surface carbon (hydrocarbon pool) species.

The novel binuclear η

This paper describes an experimental system for simultaneous permeation of a pressurized test gas through different gas permeable membranes and provides a proof of concept for a novel approach for gas identification/fingerprinting for potential construction of electronic noses. The design, construction, and use of a six-channel system which allows simultaneous gas permeation from a single pressurized gas compartment through six different parallel membranes are presented. The permeated gas is accumulated in confined spaces behind the respective membranes. The rate of gas pressure accumulation behind each membrane is recorded and used as a measure of the gas permeation rate through the membrane. The utilized gas permeable membranes include Teflon AF, silicone rubber, track-etch hydrophilic polycarbonate, track-etch hydrophobic polycarbonate, track-etch polyimide, nanoporous anodic aluminum oxide, zeolite ZSM-5, and zeolite NaY. An analogy between the rate of pressure accumulation of the permeating gas behind the membrane and the charging of an electric capacitor in a single series RC circuit is proposed and thoroughly validated. The simultaneous permeation rates through different membranes demonstrated a very promising potential as characteristic fingerprints for 10 test gases, that is, helium, neon, argon, hydrogen, nitrogen, carbon dioxide, methane, ethane, propane, and ethylene, which are selected as representative examples of mono-, di-, tri-, and polyatomic gases and to include some homologous series as well as to allow testing the potential of the proposed system to discriminate between closely related gases such as ethane and ethylene or carbon dioxide and propane which have almost identical molecular masses. Finally, a preliminary investigation of the possibility of applying the developed gas permeation system for semiquantitative analysis of the CO

Anaerobic ammonium oxidation (anammox) and nitrification, two common biological ammonium oxidation pathways, are critical for the microbial nitrogen cycle. Short chain alkanes (C

We use global airborne observations of propane (C₃H₈) and ethane (C₂H₆) from the Atmospheric Tomography (ATom) and HIAPER Pole-to-Pole Observations (HIPPO), as well as U.S.-based aircraft and tower observations by NOAA and from the NCAR FRAPPE campaign as tracers for emissions from oil and gas operations. To simulate global mole fraction fields for these gases, we update the default emissions’ configuration of C₃H₈ used by the global chemical transport model, GEOS-Chem v13.0.0, using a scaled C₂H₆ spatial proxy. With the updated emissions, simulations of both C₃H₈ and C₂H₆ using GEOS-Chem are in reasonable agreement with ATom and HIPPO observations, though the updated emission fields underestimate C₃H₈ accumulation in the arctic wintertime, pointing to additional sources of this gas in the high latitudes (e.g., Europe). Using a Bayesian hierarchical model, we estimate global emissions of C₂H₆ and C₃H₈ from fossil fuel production in 2016–2018 to be 13.3 ± 0.7 (95% CI) and 14.7 ± 0.8 (95% CI) Tg/year, respectively. We calculate bottom-up hydrocarbon emission ratios using basin composition measurements weighted by gas production and find their magnitude is higher than expected and is similar to ratios informed by our revised alkane emissions. This suggests that emissions are dominated by pre-processing activities in oil-producing basins.

For bottom-up proteomics, peptide separation with high peak capacity under MS-compatible conditions is of vital significance to increase proteome coverage. Herein, a surface-charged ethane-bridged hybrid monolithic column was prepared based on the efficient ring-opening reaction of

Scatter plot analyses for 14,169 phenylethanes of the substructure C

Author(s): Liu, J; He, N; Zhang, Z; Yang, J; Jiang, X; Zhang, Z; Su, J; Shu, M; Si, R; Xiong, G; Xie, HB; Vile, G | Abstract: We report herein the preparation, characterization, and catalytic performance of a series of heterogeneous catalysts featuring highly dispersed zinc sites on zeolitic SSZ-13 and ZSM-5 frameworks. The materials are evaluated in the CO2-assisted oxidative ethane dehydrogenation, a very important reaction for the synthesis of platform chemicals. In particular, we find that Zn2.92/SSZ-13 exhibits high reactivity in the conversion of C2H6 and CO2 and high ethene selectivity. In line with the experimental results, we show that the selective character of the catalyst is due to the characteristic compositional structure of the support and its topology that can effectively confine CO2 molecules. An in-depth molecular analysis via operando studies and DFT calculations shows that the rate-limiting step of the reaction with CO2 is the second C-H bond dissociation to give C2H4. The addition of CO2 effectively reduces the energy barrier of this step, favoring desorption of C2H4 while limiting byproduct formation. Overall, this work demonstrates the breakthrough potential of catalysts made of highly dispersed zinc species on zeolites in relevant transformations.

The methane emission intensity (methane emitted/gas produced or methane emitted/methane produced) of individual unconventional oil and gas production sites in the United States has a characteristic temporal behavior, exhibiting a brief period of decrease followed by a steady increase, with intensities after 10 years of production reaching levels that are 2-10 times the 10 year production-weighted average. Temporal patterns for methane emission intensity for entire production regions are more complex. Historical production data and facility data were used with a detailed basin-wide methane emission model to simulate the collective behavior of tens of thousands of wells and associated midstream facilities. For production regions with few to no new wells being brought to production, and existing wells having reached a mature stage, as in the Barnett Shale production region in north central Texas, the methane emission intensity gradually increases, as natural gas production decreases faster than emissions decrease, following the general pattern exhibited by individual wells. In production regions that are rapidly evolving, either with large numbers of new wells being put into production or with the introduction of source-specific regulations, the behavior is more complex. In the Eagle Ford Shale, which has had both a large number of new wells and the introduction of source-specific regulations, the methane emission intensity stays within relatively narrow bounds but the distribution of sources varies. As source distributions vary, basin-wide propane-to-methane and ethane-to-methane emission ratios vary, impacting methods used in source attribution.

Previous studies demonstrated that methane can be used as an electron donor to microbially remove various oxidized contaminants in groundwater. Natural gas, which is more widely available and less expensive than purified methane, is potentially an alternative source of methane. However, natural gas commonly contains a considerable amount of ethane (C2H6) and propane (C3H8), in addition to methane. It is important that these gaseous alkanes are also utilized along with methane to avoid emissions. Here, we demonstrate that perchlorate (ClO4-), a frequently reported contaminant in groundwater, can be microbially reduced to chloride (Cl-) driven by C2H6 or C3H8 under oxygen-limiting conditions. Two independent membrane biofilm reactors (MBfRs) supplied with C2H6 and C3H8, respectively, were operated in parallel to biologically reduce ClO4-. The continuous ClO4- removal during long-term MBfR operation combined with the concurrent C2H6/C3H8 consumption and ClO4- reduction in batch tests confirms that ClO4- reduction was associated with C2H6 or C3H8 oxidation. Polyhydroxyalkanoates (PHAs) were synthesized in the presence of C2H6 or C3H8 and were subsequently utilized for supporting ClO4- bio-reduction in the absence of gaseous alkanes. Analysis by reverse transcription-quantitative polymerase chain reaction (RT-qPCR) showed that transcript abundance of bmoX (encoding alpha hydroxylase subunit of C2H6/C3H8 monooxygenase) was positively correlated to the consumption rates of C2H6/C3H8, while pcrA (encoding a catalytic subunit of perchlorate reductase) was positively correlated to the consumption of ClO4-. High-throughput sequencing targeting 16S rRNA, bmoX, and pcrA indicated that Mycobacterium was the dominant microorganism oxidizing C2H6/C3H8, while Dechloromonas may be the major perchlorate-reducing bacterium in the biofilms. These findings shed light on microbial ClO4- reduction driven by C2H6 and C3H8, facilitating the development of cost-effective strategies for ex situ groundwater remediation.

Porous solids with channel sizes that are not much above the size of small hydrocarbons can yield extremely large adsorption selectivity. Our Grand Canonical Monte-Carlo simulations indicate exceptionally high selectivity for the separation of methane, ethane and propane from natural gas. At 250 K the C

Distinguishing biotic compounds from abiotic ones is important in resource geology, biogeochemistry, and the search for life in the universe. Stable isotopes have traditionally been used to discriminate the origins of organic materials, with particular focus on hydrocarbons. However, despite extensive efforts, unequivocal distinction of abiotic hydrocarbons remains challenging. Recent development of clumped-isotope analysis provides more robust information because it is independent of the stable isotopic composition of the starting material. Here, we report data from a

Top-down proteomics is challenged by the high complexity of biological samples. The coelution of intact proteins results in overlapped mass spectra, and hence, an increased peak capacity for protein separation is needed. Herein, ethane-bridged hybrid monoliths with well-defined large mesopores were successfully prepared based on the sol-gel condensation of 1,2-bis(trimethoxysilyl)ethane and tetramethoxysilane, followed by two-step base etching of the Si-O-Si domain while maintaining the Si-C-C-Si domain in the structure. Relatively homogeneous macropores of 1.1 μm and large mesopores of 24 nm were obtained, permitting fast mass transfer of large molecules and efficient diffusion without obstruction. The use of less hydrophobic C1 ligand further sharpened the peak shape and improved peak capacity. A 120 cm-long capillary column was used for top-down proteomic analysis of

Anaerobic microorganisms are thought to play a critical role in regulating the flux of short-chain gaseous alkanes (SCGAs; including ethane, propane and butane) from terrestrial and aquatic ecosystems to the atmosphere. Sulfate has been confirmed to act as electron acceptor supporting microbial anaerobic oxidation of SCGAs, yet several other energetically more favourable acceptors co-exist with these gases in anaerobic environments. Here, we show that a bioreactor seeded with biomass from a wastewater treatment facility can perform anaerobic propane oxidation coupled to nitrate reduction to dinitrogen gas and ammonium. The bioreactor was operated for more than 1000 days, and we used 13C- and 15N-labelling experiments, metagenomic, metatranscriptomic, metaproteomic and metabolite analyses to characterize the microbial community and the metabolic processes. The data collectively suggest that a species representing a novel order within the bacterial class Symbiobacteriia is responsible for the observed nitrate-dependent propane oxidation. The closed genome of this organism, which we designate as ‘Candidatus Alkanivorans nitratireducens’, encodes pathways for oxidation of propane to CO2 via fumarate addition, and for nitrate reduction, with all the key genes expressed during nitrate-dependent propane oxidation. Our results suggest that nitrate is a relevant electron sink for SCGA oxidation in anaerobic environments, constituting a new microbially-mediated link between the carbon and nitrogen cycles.

Abiotic transformation of trichloroethene (TCE) in fractured porous rock such as sandstone is challenging to characterize and quantify. The objective of this study was to estimate the pseudo first-order abiotic reaction rate coefficients in diffusion-dominated intact core microcosms. The microcosms imitated clean flow through a fracture next to a contaminated rock matrix by exchanging uncontaminated groundwater, unamended or lactate-amended, in a chamber above a TCE-infused sandstone core. Rate coefficients were assessed using a numerical model of the microcosms that were calibrated to monitoring data. Average initial rate coefficients for complete dechlorination of TCE to acetylene, ethene, and ethane were estimated as 0.019 y-1 in unamended microcosms and 0.024 y-1 in lactate-amended microcosms. Moderately higher values (0.026 y-1 for unamended and 0.035 y-1 for lactate-amended) were obtained based on 13C enrichment data. Abiotic transformation rate coefficients based on gas formation were decreased in unamended microcosms after ∼25 days, to an average of 0.0008 y-1. This was presumably due to depletion of reductive capacity (average values of 0.12 ± 0.10 μeeq/g iron and 18 ± 15 μeeq/g extractable iron). Model-derived rate coefficients and reductive capacities for the intact core microcosms aligned well with results from a previous microcosm study using crushed sandstone from the same site.

[EN] A comparative study of the catalytic properties for the oxidation of C2-C3 alkanes and olefins has been carried out over unpromoted and M-promoted NiO catalysts (Me¿=¿K, La, Ce, al, Zr, Sn, Nb). The catalysts have been characterized by several physico-chemical techniques (UV Raman, Visible Raman, FTIR of adsorbed CO and XPS). The characteristics of promoter elements are of paramount importance, since they are able to modify both the nature of the active nickel and the concentration of electrophilic O2¿/O¿ oxygen species. Thus, a relatively high acidity and valence of the promoter oxide (with oxidation state higher than¿+¿3) are necessary to achieve high selectivity to olefins during the oxidative dehydrogenation (ODH) of C2¿C3 alkanes. In addition, an inverse correlation between the selectivity to the corresponding olefin and the concentration of electrophilic oxygen species has been observed, although the selectivity to propene during propane ODH is lower than the selectivity to ethylene achieved during ethane ODH. On the other hand, a very low influence of alkane conversion on the selectivity to the corresponding olefins is observed. This behaviour can be explained by considering that the reaction rate for olefin combustion is lower than the reaction rate for alkane oxidation. However, the comparative study of the oxidation of alkanes and olefins suggest that the differences observed between the ODH of propane and ethane are not related to the reactivity of olefins, but to the different number and reactivity of C¿H bonds in both alkanes. A discussion on the importance of the concentration of active sites and the characteristics of the alkanes fed on the selectivity to olefin during the alkane ODH is also presented., The authors would like to acknowledge the Ministerio de Ciencia, Innovacion y Universidades of Spain (RTl2018-099668-B-C21 and MAT2017-84118-C2-1-R projects) and FEDER. Authors from ITQ also thank Project SEV-2016-0683 for supporting this research. D.D. thanks MINECO and Severo Ochoa Excellence Program for his fellowship (SVP-2014-068669).

A comprehensive experimental and kinetic modeling study of the ignition delay time (IDT) characteristics of some binary blends of C1–C2 gaseous hydrocarbons such as methane/ethylene, methane/ethane, and ethane/ethylene was performed over a wide range of composition (90/10, 70/30, 50/50%), temperature (∼800–2000 K), pressure (∼1–40 bar), equivalence ratio (∼0.5–2.0), and dilution (∼75–90%). An extensive literature review was conducted, and available data were extracted to create a comprehensive database for our simulations. Based on the existing literature data, an experimental matrix was designed using the Taguchi approach (L9) in order to identify and complete the experimental matrix required to generate a comprehensive experimental IDT set necessary for the validation of a chemical kinetic model. The required high- and low-temperature IDTs were collected using low-/high-pressure shock tubes and rapid compression machines, respectively. The predictions of NUIGMech1.0 are examined versus all of the available experimental data, including those taken in the current study using the IDT simulations and a correlation technique. Moreover, the individual effect of the studied parameters, including mixture composition, pressure, equivalence ratio, and dilution on IDT, is investigated over the studied temperature range. Correlations that were developed based on NUIGMech1.0 are presented for each specific blended fuel over the conditions studied. These correlations show an acceptable performance versus the experimental data. The authors would like to express their gratitude to Shell Research Ltd. and Science Foundation Ireland (SFI) for funding via project numbers 15/IA/3177 and 16/SP/3829. The authors from PCFC, RWTH Aachen University, would like to recognize the funding support from the German Research Foundation (Deutsche Forschungsgemeinschaft, DFG) through the project number – 322460823 (HE7599/2-1). peer-reviewed 2021-06-03

Multi-elemental C-Br-Cl compound-specific isotope analysis was applied for characterizing abiotic and biotic degradation of the environmental pollutant 1-bromo-2-chloroethane (BCE). Isotope effects were determined in the model processes following hydrolytic dehalogenation and dihaloelimination pathways as well as in a microcosm experiment by the microbial culture from the contaminated site. Hydrolytic dehalogenation of BCE under alkaline conditions and by DhaA enzyme resulted in similar dual isotope slopes (ɅC/Br 21.9 ± 4.7 and 19.4 ± 1.8, respectively, and ɅC/Cl ~ ∞). BCE transformation by cyanocobalamin (B12) and by Sulfurospirillum multivorans followed dihaloelimination and was accompanied by identical, within the uncertainty range, dual isotope slopes (ɅC/Br 8.4 ± 1.7 and 7.9 ± 4.2, respectively, and ɅC/Cl 2.4 ± 0.3 and 1.5 ± 0.6, respectively). Changes over time in the isotope composition of BCE from the contaminated groundwater showed only a slight variation in δ13C values and were not sufficient for the elucidation of the BCE degradation pathway in situ. However, an anaerobic microcosm experiment with the enrichment cultures from the contaminated groundwater presented dual isotope slopes similar to the hydrolytic pathway, suggesting that the potential for BCE degradation in situ by the hydrolytic dehalogenation pathway exists in the contaminated site.

Shipboard measurements of offshore oil and gas facilities were conducted in the Gulf of Mexico in February 2018. Species measured at 1 s include methane, ethane, carbon-13 (13C) and deuterium (D) i...

A quartz enhanced photoacoustic spectroscopy (QEPAS) sensor capable to detect high concentrations of methane (C1) and ethane (C2) is here reported. The hydrocarbons fingerprint region around 3 µm was exploited using an interband cascade laser (ICL). A standard quartz tuning fork (QTF) coupled with two resonator tubes was used to detect the photoacoustic signal generated by the target molecules. Employing dedicated electronic boards to both control the laser source and collect the QTF signal, a shoe-box sized QEPAS sensor was realized. All the generated mixtures were downstream humidified to remove the influence of water vapor on the target gases. Several natural gas-like samples were generated and subsequently diluted 1:10 in N

A team at WPI-MANA has demonstrated that methane can be efficiently and selectively oxidized to ethane with oxygen under light irradiation over an Au-ZnO/TiO₂ hybrid. This achievement opens the door to cheaper and more efficient production of valuable chemicals using methane as a feedstock., MANA E-BULLETIN. 76 (2022)

Photocatalytic nonoxidative coupling of CH 4 to multicarbon (C 2+ ) hydrocarbons (e.g., C 2 H 4 ) and H 2 under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource. However, as the methyl intermediates prefer to undergo self-coupling to produce ethane, it is a challenging task to control the selective conversion of CH 4 to higher value-added C 2 H 4 . Herein, we adopt a synergistic catalysis strategy by integrating Pd-Zn active sites on visible light-responsive defective WO 3 nanosheets for synergizing the adsorption, activation, and dehydrogenation processes in CH 4 to C 2 H 4 conversion. Benefiting from the synergy, our model catalyst achieves a remarkable C 2+ compounds yield of 31.85 μ mol·g -1 ·h -1 with an exceptionally high C 2 H 4 selectivity of 75.3% and a stoichiometric H 2 evolution. In situ spectroscopic studies reveal that the Zn sites promote the adsorption and activation of CH 4 molecules to generate methyl and methoxy intermediates with the assistance of lattice oxygen, while the Pd sites facilitate the dehydrogenation of methoxy to methylene radicals for producing C 2 H 4 and suppress overoxidation. This work demonstrates a strategy for designing efficient photocatalysts toward selective coupling of CH 4 to higher value-added chemicals and highlights the importance of synergistic active sites to the synergy of key steps in catalytic reactions.

The reactions here explored are microscopic analogs of Newton cradle: left thing attack, right thing leaves and central thing remains unaffected. We have studied symmetric S2 reactions, X = N or E, where the attacking and leaving molecules are the same: HN, HB, HC and the central molecules are HB (S2@B), HN (S2) or HC (S2@C). Non-symmetric reactions with different initial and final complexes were also studied and examples where the elements of the lateral molecules differ, P vs N., This work was carried out with financial support from the Ministerio de Ciencia, Innovación y Universidades of Spain (Project No. PID2021- 125207NB-C32) and Comunidad Autónoma de Madrid (P2018/EMT4329 AIRTEC-CM).

We use the newly introduced spanning stress tensor trajectory $U_{\sigma}$-space construction within next generation quantum theory of atoms in molecules (NG-QTAIM) for a chirality investigation of singly and doubly substituted ethane with halogen substituents: F, Cl, Br. A lack of achiral character in $U_{\sigma}$-space was discovered for singly substituted ethane. The resultant axial bond critical point (BCP) sliding responded more strongly to the increase in atomic number of the substituted halogen than the chirality. The presence of the very light F atom was found responsible for a very high degree of achiral character of the doubly substituted ethane., Comment: arXiv admin note: substantial text overlap with arXiv:2203.09750

Understanding the behaviour of short-chain hydrocarbons confined to porous solids informs the targeted extraction of natural resources from geological features, and underpins rational developments in separation, storage and catalytic conversion processes. Herein, we report the application of low-field (12.7 MHz)

In search of a more effective process of ethane oxidative hydrogenation, different operation modes (thermal and microwave heating) are compared. The catalyst Mo1-V0.3-Te0.13-Nb0.11-Ox was prepared by hydrothermal synthesis and characterized by a set of physicochemical methods (XRD, N2 adsorption, SEM, EDX). The direct microwave heating of the catalyst layer is proposed as an alternative way of energy-saving ethane-to-ethylene oxidation by a Mo-V-Te-Nb-Ox system. A substantial decrease in the reactor temperature upon the microwave-assisted process is accompanied by extremely high catalyst selectivity, which remains at a very high level of 98+%.

The current study presents a periodic mesoporous organosilica (PMO) with a high surface area and uniform-porosity material. The PMO materials were successfully synthesized and modified. The resultant material was characterized by different characterization techniques. The prepared PMO was immobilized on a stainless steel wire surface and was evaluated for headspace solid-phase microextraction of the ultra-trace amount of phthalate esters from saliva and polyethylene terephthalate containers which were in contact with hot and cold water. Separation and determination of the phthalate esters (PEs) were performed by the GC-FID and GC-MS instruments. The key parameters affecting the extraction efficiencies, including extraction temperature, extraction time, ionic strength, and desorption temperature and time, were investigated and optimized. Under optimum conditions, the repeatability for one fiber (n = 7) was 4.8-8.7%, and fiber-to-fiber reproducibility (n = 3) was 7.5-10.6% for the extracted compounds. The limits of detection of the developed method for the studied compounds were between 0.01 and 1 μg L

Natural gas seeps release significant amounts of methane and other gases including ethane and propane contributing to global climate change. In this study, bacterial actively consuming short-chain alkanes were identified by cultivation, whole-genome sequencing, and stable-isotope probing (SIP)-metagenomics using

The X-ray structure of racemic tris(ethane-1,2-diamine-κ

Excessive molybdenum (Mo) and cadmium (Cd) are toxic environmental pollutants. Our previous research confirmed excessive Mo and Cd co-induced calcium homeostasis disorder and autophagy in duck kidneys, but how calcium ion (Ca

Thermally activated peroxydisulfate In Situ Chemical Oxidation (TAP-ISCO) is often applied for the remediation of soil-sorbed hydrophobic organic contaminants (HOCs) and nonaqueous phase liquids (NAPLs), which act as long-term sources of groundwater contamination. TAP-ISCO benefits from improved desorption/dissolution of organic contaminants into the aqueous phase and efficient activation of peroxydisulfate at elevated temperatures, but the primary limitation of TAP-ISCO is the short lifetime of peroxydisulfate (therefore the availability of reactive radical species). To resolve this problem, coupling of peroxide stabilizers with TAP were tested. The compatibility of seven representative commercial organic and inorganic peroxide stabilizers, including sodium stannate, trisodium phosphate, sodium pyrophosphate, sodium silicate, sodium citrate, ethylene diamine tetra methylene phosphonic acid and ethylenediaminetetraacetic acid disodium salt, with TAP in aqueous solutions and solutions containing goethite or soil particles were first studied. The effects of stabilizers on the formation, distribution and reactivity of reactive oxygen species were then investigated through electron paramagnetic resonance (EPR) spin-trapping experiments using 5,5-dimethyl-1-pyrroline-N-oxide, chemical probe experiments using anisole, nitrobenzene and hexachloroethane, and biphasic trichloroethylene (TCE) dense nonaqueous phase liquids (DNAPLs) TAP-ISCO mimicking experiments. The results indicate that organic stabilizers significantly accelerate peroxydisulfate decomposition at both ambient and elevated temperatures. In contrast, inorganic stabilizers can markedly increase peroxydisulfate longevity by suppressing the acid-catalyzed peroxydisulfate decomposition, quenching radical-chain acceleration, and sequestering transition metal species. In addition, TAP systems containing inorganic stabilizers can effectively generate a variety of reactive radical species, including SO

Geochemical studies of gases from low-permeability reservoirs have raised new questions regarding the chemical and stable isotope systematics of gas hydrocarbons. For instance, the possibility of thermodynamic equilibrium is recurrently in discussion. However, it is not clear whether there is anything “unconventional” in the way these systems continue to be studied. Using molecular and stable carbon isotope data from North American unconventional and conventional reservoirs, this research has applied two parameters that well describe key transformation stages during gas generation. The δ13C of ethane and the C2/C3 ratio increase from baseline values (

This study highlights the role of seaweed as important indicators of pollutants as they respond immediately to change in water chemistry and have high survival capabilities. Concentration and risk assessment of 13 polycyclic aromatic hydrocarbons (PAHs), as well as 20 organochlorine pesticides (OCPs), were examined in the seaweed from El-Mex Bay, Mediterranean Sea during spring and autumn seasons. The green alga Ulva compressa had a maximum ability to accumulate both PAHs and OCPs. In general, the content of the tested micropollutants in the collected seaweed is correlated to their species, morphology, concentration, and nature of pollutant. Naphthalene (NAP) and benzo a pyrene were the predominant polycyclic aromatic hydrocarbons in all species with mean concentrations of 68.57 and 56.14 ng g−1, respectively. The results of the current study showed that the contribution of the different fractions of PAHs from the total concentration was as follows: fossil-fuel derived polycyclic aromatic hydrocarbons (∑PAHF; 49.32%) > combustion-derived polycyclic aromatic hydrocarbons (PAHCOMB; 30.83%) > carcinogenic fractions (PAHCARC; 19.86%). A maximum PAHCARC (30.38%) was recorded in Ulva fasciata. For OCPs, the presence of 1,1-dichloro-2, 2-bis (4-chlorophenyl) ethane (DDD) (ND-27.8 ng g−1) rather than DDT; 1,1,1-trichloro-2, 2-bis (4-chlorophenyl) ethane was an indication for biotransformation involving the reductive dichlorination of DDT to more recalcitrant and toxic DDD. Endrin ketone has the highest mean hazard quotient (0.376). The cancer risk values of most PAHs and OCPs were in the range from 10−4 to 10−3 recommending precautionary measures. The results explained that the present algal species play a vital role in the uptake of organic pollutants and act as biomarkers for micropollutants in the ecosystem.

We investigate the distribution of volatile organic compounds (VOCs) over Indian subcontinent during a winter month of January 2011 combining the regional model WRF-Chem (Weather Research and Forecasting model coupled with Chemistry) with ground- and space-based observations and chemical reanalysis. WRF-Chem simulated VOCs are found to be comparable with ground-based observations over contrasting environments of the Indian subcontinent. WRF-Chem results reveal the elevated levels of VOCs (e. g. propane) over the Indo-Gangetic Plain (16 ppbv), followed by the Northeast region (9.1 ppbv) in comparison with other parts of the Indian subcontinent (1.3–8.2 ppbv). Higher relative abundances of propane (27–31%) and ethane (13–17%) are simulated across the Indian subcontinent. WRF-Chem simulated formaldehyde and glyoxal show the western coast, Eastern India and the Indo-Gangetic Plain as the regional hotspots, in a qualitative agreement with the MACC (Monitoring Atmospheric Composition and Climate) reanalysis and satellite-based observations. Lower values of RGF (ratio of glyoxal to formaldehyde

International audience; Production of coal and natural gas is responsible for one third of anthropogenic methane (CH4) emissions in the United States. Here we examine CH4 emissions from coal and natural gas production in southwestern Pennsylvania. Using a top-down methodology combining measurements of CH4 and ethane, we conclude that while Environmental Protection Agency inventories appear to report emissions from coal accurately, emissions from unconventional natural gas are underreported in the region by a factor of 5 (±3). However, production-scaled CH4 emissions from unconventional gas production in the Marcellus remain small compared to other basins due to its large production per well. After normalizing emissions by energy produced, total greenhouse gas emissions from Pennsylvania unconventional natural gas production produce half the carbon footprint compared to regionally produced coal, with carbon dioxide emissions from combustion being the dominant source of greenhouse gas emissions for both sources.

Nitrogenous classes of disinfection by-products (DBPs), such as haloacetamides (HAAms), haloacetonitriles (HANs) and halonitromethanes (HNMs), while generally present at lower concentrations in disinfected waters than carbonaceous DBPs, such as trihalomethanes or haloacetic acids, have been shown to be more detrimental to human health. While several methods have been shown to be suitable for the analysis of some nitrogenous DBPs (N-DBPs) in disinfected waters, many are unable to quantify HAAms, the most detrimental to health of these three N-DBP classes. Here, we report the first method for the simultaneous analysis of twenty-five N-DBPs (nine HANs, nine HNMs and seven HAAms) in disinfected waters using liquid-liquid extraction followed by gas chromatography-mass spectrometry. The use of a programmable temperature vaporiser injector minimises degradation of the thermally labile HNMs, while avoiding the concomitant decreases in HANs and HAAms which occur when using lower injector temperatures. Extraction parameters, including sample pH, solvent volume, salt addition and sample pre-concentration, were investigated to determine the optimal conditions across all target N-DBPs. Good detection limits were achieved for all analytes (0.8–1.7 μg L−1) and both laboratory and instrumental runtimes were significantly reduced compared to previous methods. The method was validated for the analysis of N-DBPs in drinking, swimming pool and spa waters, and concentrations of up to 41 μg L−1 of some N-DBPs were measured in some pools.

Spatially resolved emission inventories were used with an atmospheric dispersion model to predict ambient concentrations of methane, ethane, and propane in the Eagle Ford oil and gas production region in south central Texas; predicted concentrations were compared to ground level observations. Using a base case inventory, predicted median propane/ethane concentration ratios were 106% higher (95% CI: 83% higher-226% higher) than observations, while median ethane/methane concentration ratios were 112% higher (95% CI: 17% higher-228% higher) than observations. Predicted median propane and ethane concentrations were factors of 6.9 (95% CI: 3-15.2) and 3.4 (95% CI: 1.4-9) larger than observations, respectively. Predicted median methane concentrations were 7% higher (95% CI: 39% lower-37% higher) than observations. These comparisons indicate that sources of emissions with high propane/ethane ratios (condensate tank flashing) were likely overestimated in the inventories. Because sources of propane and ethane emissions are also sources of methane emissions, the results also suggest that sources of emissions with low ethane/methane ratios (midstream sources) were underestimated. This analysis demonstrates the value of using multiple light alkanes in attributing sources of methane emissions and evaluating the performance of methane emission inventories for oil and natural gas production regions.

Hydrocarbon detection in the gas phase represents a powerful tool to guide oil exploration and production operations for the oil & gas industry. This application requires highly sensitive, selective and robust spectroscopic techniques. In this work, a quartz-enhanced photoacoustic sensor system designed to detect methane (C1), ethane (C2) and propane (C3), employing a single interband cascade laser emitting in the spectral range 3.342–3.349 μm, is reported. Detection levels in the part-per billion concentration range for C1 and C2 and a few parts per million for C3 were achieved. Measurements at both low and atmospheric pressures were carried out for mixtures simulating typical downhole hydrocarbon concentrations.