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1.
Bioresour Technol ; 398: 130480, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38395235

RESUMO

The control of emissions of short-chain hydrocarbons with different structures is critical for the petrochemical industry. Herein, three two-carbon-containing (C2) hydrocarbons, ethane, ethylene, and acetylene, were chosen as pollutants to study the effects of chemical structure of hydrocarbons on removal performance and microbial responses in biotrickling filters. Results showed that the removal efficiency (RE) of C2 hydrocarbons followed the sequence of acetylene > ethane > ethylene. When the inlet loading rate was 30 g/(m3·h) and the empty bed residence time was 60 s, the RE of ethane, ethylene, and acetylene was 57 ± 4.0 %, 49 ± 1.0 %, and 84 ± 2.7 %, respectively. The high water solubility resulted in the high removal of C2 hydrocarbons, while a low surface tension enhanced the removal of C2 hydrocarbons. Additionally, the microbial community, enzyme activity, and extracellular properties of microorganisms also contributed to the difference in C2 hydrocarbon removal. These results could be referred for the effective control of light hydrocarbon emissions.


Assuntos
Filtração , Hidrocarbonetos , Biodegradação Ambiental , Filtração/métodos , Acetileno , Etano , Etilenos
2.
ISME J ; 18(1)2024 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-38365228

RESUMO

The short-chain gaseous alkanes (ethane, propane, and butane; SCGAs) are important components of natural gas, yet their fate in environmental systems is poorly understood. Microbially mediated anaerobic oxidation of SCGAs coupled to nitrate reduction has been demonstrated for propane, but is yet to be shown for ethane or butane-despite being energetically feasible. Here we report two independent bacterial enrichments performing anaerobic ethane and butane oxidation, respectively, coupled to nitrate reduction to dinitrogen gas and ammonium. Isotopic 13C- and 15N-labelling experiments, mass and electron balance tests, and metabolite and meta-omics analyses collectively reveal that the recently described propane-oxidizing "Candidatus Alkanivorans nitratireducens" was also responsible for nitrate-dependent anaerobic oxidation of the SCGAs in both these enrichments. The complete genome of this species encodes alkylsuccinate synthase genes for the activation of ethane/butane via fumarate addition. Further substrate range tests confirm that "Ca. A. nitratireducens" is metabolically versatile, being able to degrade ethane, propane, and butane under anoxic conditions. Moreover, our study proves nitrate as an additional electron sink for ethane and butane in anaerobic environments, and for the first time demonstrates the use of the fumarate addition pathway in anaerobic ethane oxidation. These findings contribute to our understanding of microbial metabolism of SCGAs in anaerobic environments.


Assuntos
Etano , Nitratos , Etano/metabolismo , Nitratos/metabolismo , Propano/metabolismo , Anaerobiose , Bactérias/genética , Bactérias/metabolismo , Oxirredução , Butanos/metabolismo , Gases/metabolismo , Fumaratos/metabolismo
3.
J Chromatogr A ; 1710: 464418, 2023 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-37797421

RESUMO

A composite material was synthesized at room temperature by performing modification of the copper benzene-1,3,5-tricarboxylate (HKUST-1) metal-organic framework material by multilayer fluorinated graphene (FG). The FG-HKUST-1 composite was used as a stationary phase for a micro gas chromatography column (µGCC) fabricated using micro-electro-mechanical system (MEMS) technology. The separation results showed that the µGCC with the FG-HKUST-1 composite stationary phase achieved a baseline separation of C1-C4 in 8 min. The retention factors for C2-C4 were 2.13, 7.14, and 12.04, respectively. The maximum relative standard deviation (RSD) of the retention times was 0.14 %. The difference in the retention time between methane and ethane was 1.11 min, with a resolution of 9.2 for methane and ethane. The retention factor of ethane and the resolution of methane and ethane were increased by 166 % and 114 %. Therefore, this µGCC is promising for separating light hydrocarbons with widely differing concentrations.


Assuntos
Benzeno , Grafite , Grafite/química , Cobre , Cromatografia Gasosa/métodos , Gases , Etano , Metano
4.
Sci Total Environ ; 905: 167323, 2023 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-37742949

RESUMO

Groundwater contamination by chlorinated ethenes is an urgent concern worldwide. One approach for detoxifying chlorinated ethenes is aerobic co-metabilims using ethane (C2H6) as the primary substrate. This study evaluated long-term continuous biodegradation of three chlorinated alkenes in a membrane biofilm reactor (MBfR) that delivered C2H6 and O2 via gas-transfer membranes. During 133 days of continuous operation, removals of dichloroethane (DCE), trichloroethene (TCE), and tetrachloroethene (PCE) were as high as 94 % and with effluent concentrations below 5 µM. In situ batch tests showed that the co-metabolic kinetics were faster with more chlorination. C2H6-oxidizing Comamonadaceae and "others," such as Methylococcaceae, oxidized C2H6 via monooxyenation reactions. The abundant non-ethane monooxygenases, particularly propane monooxygenase, appears to have been responsible for C2H6 aerobic metabolism and co-metabolism of chlorinated ethenes. This work proves that the C2H6 + O2 MBfR is a platform for ex-situ bioremediation of chlorinated ethenes, and the generalized action of the monooxygenases may make it applicable for other chlorinated organic contaminants.


Assuntos
Tricloroetileno , Poluentes Químicos da Água , Biodegradação Ambiental , Etano , Oxigênio , Tricloroetileno/metabolismo , Oxigenases de Função Mista , Biofilmes , Poluentes Químicos da Água/metabolismo
5.
Chem Res Toxicol ; 36(9): 1549-1559, 2023 09 18.
Artigo em Inglês | MEDLINE | ID: mdl-37657424

RESUMO

Sulfur mustard [HD; bis-(2-chloroethyl) sulfide] and other analogues are a kind of highly toxic vesicant and have been prohibited by the Organization for the Prohibition of Chemical Weapons (OPCW) since 1997. Exposures to HD could generate several adducts in the plasma and hydrolysis products in the urine, which are widely applied as biomarkers to identify HD exposure in forensic analysis. Several methods have been developed for the detection of related biomarkers. However, most methods are based on complex derivatization, and not enough attention is paid to HD analogues. A modified and convenient analytical method reported herein includes simultaneous incubation and organic solvent extraction. The biomarkers such as thiodiglycol and 1,2-bis (2-hydroxyethylthio) are transferred to HD and 1,2-bis(2-chloroethylthio) ethane via hydrochloric acid at the appropriate temperature. The analytes are analyzed by gas chromatography tandem mass spectrometry (GC-MS/MS) with 2-chloroethyl ethyl sulfide (2-CEES) applied as the internal standard. The interday and intraday study according to FDA rules has been achieved to evaluate the accuracy and precision of the method. The two targets are detected with a good linearity (R2 > 0.99) in the concentration ranges from 5 to 1000 ng/mL and 10 to 1000 ng/mL, with small relative standard deviations (RSD ≤6.62% and RSD ≤6.93%) and favorable recoveries between 90.3 and 107.3% and between 89.4 and 108.7%, respectively. The established method can be used for retrospective detection of sulfur mustards in biological samples and successfully applied in the biomedical proficiency testing organized by the OPCW.


Assuntos
Sulfetos , Espectrometria de Massas em Tandem , Humanos , Estudos Retrospectivos , Cromatografia Gasosa-Espectrometria de Massas , Biomarcadores , Etano
6.
Environ Sci Technol ; 57(31): 11531-11540, 2023 08 08.
Artigo em Inglês | MEDLINE | ID: mdl-37471133

RESUMO

Photocatalytic oxidative coupling is an effective way of converting CH4 to high-value-added multi-carbon chemicals under mild conditions, where the breaking of the C-H bond is the main rate-limiting step. In this paper, the Ag3PO4-ZnO heterostructure photocatalyst was synthesized for photocatalytic oxidative coupling of methane (OCM) to C2H6. In addition, an excellent C2H6 yield (16.62 mmol g-1 h-1) and a remarkable apparent quantum yield (15.8% at 350 nm) at 49:1 CH4/Air and 20% RH are obtained, which is more than three times that of the state-of-the-art photocatalytic systems. Ag3PO4 improves the adsorption and dissociation ability of O2 and H2O, benefiting the formation of surface hydroxyl species. As a result, the C-H bond activation energy of CH4 on ZnO was obviously reduced. Meanwhile, the improved separation of photogenerated carriers on the Ag3PO4-ZnO heterostructure also accelerates the OCM process. Moreover, Ag nanoparticles (NPs) derived from Ag3PO4 reduction by photoelectrons promote the coupling of *CH3, which can inhibit the overoxidation of CH4 and increase C2H6 selectivity. This research provides a guide for the design of catalyst and reaction systems in the photocatalytic OCM process.


Assuntos
Nanopartículas Metálicas , Óxido de Zinco , Luz , Água , Acoplamento Oxidativo , Oxigênio , Etano , Metano , Prata
7.
Angew Chem Int Ed Engl ; 62(25): e202305041, 2023 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-37101344

RESUMO

Hydrogen-bonded organic frameworks (HOFs) show great potential in energy-saving C2 H6 /C2 H4 separation, but there are few examples of one-step acquisition of C2 H4 from C2 H6 /C2 H4 because it is still difficult to achieve the reverse-order adsorption of C2 H6 and C2 H4 . In this work, we boost the C2 H6 /C2 H4 separation performance in two graphene-sheet-like HOFs by tuning pore polarization. Upon heating, an in situ solid phase transformation can be observed from HOF-NBDA(DMA) (DMA=dimethylamine cation) to HOF-NBDA, accompanied with transformation of the electronegative skeleton into neutral one. As a result, the pore surface of HOF-NBDA has become nonpolar, which is beneficial to selectively adsorbing C2 H6 . The difference in the capacities for C2 H6 and C2 H4 is 23.4 cm3 g-1 for HOF-NBDA, and the C2 H6 /C2 H4 uptake ratio is 136 %, which are much higher than those for HOF-NBDA(DMA) (5.0 cm3 g-1 and 108 % respectively). Practical breakthrough experiments demonstrate HOF-NBDA could produce polymer-grade C2 H4 from C2 H6 /C2 H4 (1/99, v/v) mixture with a high productivity of 29.2 L kg-1 at 298 K, which is about five times as high as HOF-NBDA(DMA) (5.4 L kg-1 ). In addition, in situ breakthrough experiments and theoretical calculations indicate the pore surface of HOF-NBDA is beneficial to preferentially capture C2 H6 and thus boosts selective separation of C2 H6 /C2 H4 .


Assuntos
Etano , Etilenos , Adsorção , Hidrogênio
8.
Angew Chem Int Ed Engl ; 62(25): e202303405, 2023 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-37085959

RESUMO

Photo-driven CH4 conversion to multi-carbon products and H2 is attractive but challenging, and the development of efficient catalytic systems is critical. Herein, we construct a solar-energy-driven redox cycle for combining CH4 conversion and H2 production using iron ions. A photo-driven iron-induced reaction system was developed, which is efficient at selective coupling of CH4 as well as conversion of benzene and cyclohexane under mild conditions. For CH4 conversion, 94 % C2 selectivity and a C2 H6 formation rate of 8.4 µmol h-1 is achieved. Mechanistic studies reveal that CH4 coupling is induced by hydroxyl radical, which is generated by photo-driven intermolecular charge migration of an Fe3+ complex. The delicate coordination structure of the [Fe(H2 O)5 OH]2+ complex ensures selective C-H bond activation and C-C coupling of CH4 . The produced Fe2+ can be used to reduce the potential for electrolytic H2 production, and then turns back into Fe3+ , forming an energy-saving and sustainable recyclable system.


Assuntos
Ferro , Metano , Ferro/química , Metano/química , Etano/química , Oxirredução , Radical Hidroxila
9.
J Phys Chem B ; 127(1): 396-406, 2023 01 12.
Artigo em Inglês | MEDLINE | ID: mdl-36563326

RESUMO

Liquid-vapor interfacial properties of alkane mixtures present a challenge for experimental determination, especially under conditions relevant to the energy industry processes. Molecular dynamics (MD) simulations can accurately predict interfacial tensions (IFTs) for complex alkane mixtures under virtually any conditions, thereby alleviating the need for difficult and costly experiments. MD simulations with the CHARMM force field and empirical corrections for the IFT and pressure were used to obtain the IFT for three binary mixtures of ethane (with n-pentane, n-hexane, and n-nonane) and a ternary system (ethane/n-butane/n-decane) under a variety of conditions. The results were thoroughly validated against experimental data from the literature, and new original IFT data were collected using the pendant drop method. The simulations are able to reproduce the experimental IFT to better than 0.5 mN/m or 5% on average and within 1 mN/m or 10% in the worst case. IFTs for the studied three binary and ternary alkane mixtures were predicted for wide ranges of conditions with no known experimental data. Finally, using the MD simulation data, the reliability of the widely used empirical parachor model for predicting IFT was reaffirmed, and the significance of the empirical parameters examined to establish an optimal balance between the accuracy and broad applicability of the model.


Assuntos
Alcanos , Simulação de Dinâmica Molecular , Tensão Superficial , Reprodutibilidade dos Testes , Gases , Etano
10.
J Am Chem Soc ; 144(48): 22202-22211, 2022 12 07.
Artigo em Inglês | MEDLINE | ID: mdl-36404600

RESUMO

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 C2+ products with respect to adsorbed CO are substantially less than unity, clearly indicating that the coupling of adsorbed CO is not the rate-determining step leading to multicarbon products. The increase in CO coverage can reduce the C affinity on the Cu surface and favor the selectivity towards oxygenates, especially acetate, over ethylene. Uncommon products, including ethane, glycolaldehyde, and ethylene glycol, were detected in appreciable amounts, likely due to a new C-C coupling mechanism taking place at elevated CO pressures.


Assuntos
Etano , Espectrofotometria Infravermelho
11.
J Am Chem Soc ; 144(41): 19186-19195, 2022 10 19.
Artigo em Inglês | MEDLINE | ID: mdl-36194198

RESUMO

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.


Assuntos
Cobalto , Piridinas , Cobalto/química , Cinética , Deutério , Piridinas/química , Alcinos/química , Alcenos , Etano
12.
Sci Rep ; 12(1): 16977, 2022 10 10.
Artigo em Inglês | MEDLINE | ID: mdl-36216955

RESUMO

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.


Assuntos
Substitutos Ósseos , Osteogênese , Materiais Biocompatíveis/farmacologia , Substitutos Ósseos/farmacologia , Fosfatos de Cálcio/farmacologia , Etano , Furanos , Metacrilatos/farmacologia , Polímeros , Impressão Tridimensional , Engenharia Tecidual , Tecidos Suporte
13.
Org Lett ; 24(40): 7355-7360, 2022 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-36190411

RESUMO

Diastereo- and enantioselective kinetic resolution of racemic planar-chiral 1-R-2-vinylferrocenes (rac-1) was attained by the molybdenum-catalyzed asymmetric metathesis dimerization (AMD). Two sequential AMD reactions of rac-1a (R = Br) provided (E)-(S,S)-1,2-di(2-bromoferrocenyl)ethylene in >99% ee, which was converted to (S,S)-1,2-bis[(2-diphenylphosphino)ferrocenyl]ethane (S,S)-5. Planar-chiral bisphosphine (S,S)-5 coordinated to a dichloropalladium(II) fragment in a trans-chelating fashion, which was applied as a chiral ligand in the palladium-catalyzed asymmetric allylic alkylation showing enantioselectivity of up to 90% ee.


Assuntos
Molibdênio , Paládio , Catálise , Dimerização , Etano , Etilenos , Compostos Ferrosos , Ligantes , Estereoisomerismo , Compostos de Vinila
14.
Nat Commun ; 13(1): 6115, 2022 10 17.
Artigo em Inglês | MEDLINE | ID: mdl-36253480

RESUMO

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.


Assuntos
Compostos de Amônio , Nitratos , Alcanos/metabolismo , Anaerobiose , Butanos , Carbono , Dióxido de Carbono , Ecossistema , Etano/metabolismo , Fumaratos , Metano/metabolismo , Nitratos/metabolismo , Oxirredução , Propano/metabolismo , Sulfatos/metabolismo
15.
Nat Commun ; 13(1): 5790, 2022 10 02.
Artigo em Inglês | MEDLINE | ID: mdl-36184637

RESUMO

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 13C-13C clumped-isotope analysis of ethane and demonstrate that the abiotically-synthesized ethane shows distinctively low 13C-13C abundances compared to thermogenic ethane. A collision frequency model predicts the observed low 13C-13C abundances (anti-clumping) in ethane produced from methyl radical recombination. In contrast, thermogenic ethane presumably exhibits near stochastic 13C-13C distribution inherited from the biological precursor, which undergoes C-C bond cleavage/recombination during metabolism. Further, we find an exceptionally high 13C-13C signature in ethane remaining after microbial oxidation. In summary, the approach distinguishes between thermogenic, microbially altered, and abiotic hydrocarbons. The 13C-13C signature can provide an important step forward for discrimination of the origin of organic molecules on Earth and in extra-terrestrial environments.


Assuntos
Etano , Geologia , Isótopos de Carbono , Planeta Terra , Hidrocarbonetos/química , Isótopos
16.
J Am Chem Soc ; 144(40): 18526-18531, 2022 10 12.
Artigo em Inglês | MEDLINE | ID: mdl-36178850

RESUMO

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.


Assuntos
Polietileno , Polipropilenos , Alcenos , Catálise , Etano , Etilenos , Plásticos
17.
Water Res ; 224: 119046, 2022 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-36096026

RESUMO

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 SO4•-, HO•, and O2•-, and improve the oxidation of anisole and nitrobenzene, though suppressing the reduction of hexachloroethane to some extent. Especially, suitable inorganic stabilizers (e.g., trisodium phosphate) can effectively improve TAP oxidation of TCE DNAPL while suppressing peroxydisulfate decomposition. Overall, this study provides the fundamental basis of coupling TAP-ISCO with peroxide stabilizers.


Assuntos
Tricloroetileno , Poluentes Químicos da Água , Anisóis , Ácido Edético , Etano/análogos & derivados , Etilenos , Hidrocarbonetos Clorados , Nitrobenzenos , Oxirredução , Peróxidos/química , Fosfatos , Espécies Reativas de Oxigênio/química , Sódio , Citrato de Sódio , Solo/química , Tricloroetileno/química , Poluentes Químicos da Água/química
18.
J Mol Graph Model ; 117: 108293, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-35988438

RESUMO

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 C3H8/CH4 separation on MIL-127 at low pressure has a selectivity of more than 1000 and the C3H8/CH4 separation on CNT (9,9) is even above 2000. This is due to the strong molecule lattice interaction in narrow channels which leads to large enthalpies of adsorption. The Arrhenius law for the Henry coefficients is analysed in order to show that the effect is due to this enthalpy rather than to steric reasons.


Assuntos
Nanotubos de Carbono , Adsorção , Dióxido de Carbono , Etano , Hidrocarbonetos , Metano , Gás Natural , Propano
19.
Anal Chem ; 94(32): 11134-11143, 2022 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-35920637

RESUMO

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 CO2-N2 binary mixture is also presented.


Assuntos
Dióxido de Carbono , Zeolitas , Dióxido de Carbono/química , Etano , Etilenos , Hélio , Propano , Zeolitas/química
20.
Environ Sci Technol ; 56(18): 13419-13427, 2022 09 20.
Artigo em Inglês | MEDLINE | ID: mdl-35917334

RESUMO

Anaerobic ammonium oxidation (anammox) and nitrification, two common biological ammonium oxidation pathways, are critical for the microbial nitrogen cycle. Short chain alkanes (C2-C8) have been well-known as inhibitors for nitrification through interaction with the ammonia monooxygenase, while whether these alkanes affect anammox is an open question. Here, this work demonstrated significant inhibition of ethane on anammox and revealed the inhibitory mechanism. The acute inhibition of ethane on anammox was concentration-dependent and reversible; 0.86 mM dissolved ethane caused 50% inhibition (IC50), and 1.72 mM ethane almost completely inhibited anammox. After long-term exposure to 0.09 mM ethane for 30 days, the ammonium (nitrite) removal rate dropped from 202 (267) mg N L-1 d-1 to 1 (1) mg N L-1 d-1, and the abundance of anammox bacteria decreased from 61.9% to 9.5%. The intercellular ammonium concentration of anammox bacteria decreased after ethane exposure, while metatranscriptome analysis showed significant upregulation of genes for ammonium transport of anammox bacteria. Thus, ethane could suppress ammonium uptake resulting in the inhibition of anammox activities. As ethane is the second most prevalent alkane after methane in various anoxic environments, ethane may have an important effect on the nitrogen cycle driven by anammox that should be investigated in future research.


Assuntos
Compostos de Amônio , Nitritos , Compostos de Amônio/metabolismo , Anaerobiose , Bactérias/metabolismo , Reatores Biológicos/microbiologia , Desnitrificação , Etano , Metano/metabolismo , Nitritos/metabolismo , Nitrogênio/análise , Oxirredução
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