Theoretical study on rate constants for the reactions of CF3CH2NH2 (TFEA) with the hydroxyl radical at 298 K and atmospheric pressure

Theoretical investigations are carried out on reaction mechanism of the reactions of CF₃CH₂NH₂ (TFEA) with the OH radical by means of ab initio and DFT methods. The electronic structure information on the potential energy surface for each reaction is obtained at MPWB1K/6-31+G(d,p) level and energetic information is further refined by calculating the energy of the species with a Gaussian-2 method, G2(MP2). The existence of transition states on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. Our calculation indicates that the H abstraction from –NH₂ group is the dominant reaction channel because of lower energy barrier. The rate constants of the reaction calculated using canonical transition state theory (CTST) utilizing the ab initio data. The agreement between the theoretical and experimental rate constants is good at the measured temperature. From the comparison with CH₃CH₂NH₂, it is shown that the fluorine substution decreases the reactivity of the C-H bond.     

Kinetic studies on partial oxidation of methane over samarium oxides

Kinetic studies on the oxidative coupling of methane over Sm₂O₃ have been carried out. The experimental rate equation observed could be well explained in terms of the reaction mechanism proposed. The reaction is initiated by abstracting hydrogen atom from the methane adsorbed by the diatomic oxygen on the surface. The coupling of two CH₃· radicals leads to C₂H₆. Deep oxidation of CH₃· produces CO and CO₂. The large activation energy (149 kJ mol⁻¹) needed for the formation of CH₃· explains the sharp increase in the selectivity to C₂-compounds (C₂H₆ + C₂H₄) as raising temperatures. The oxygen species responsible for initiating the reaction was suggested to be O₂²⁻ or O₂⁻ on the surface.     

Hydrogen and methane production from desugared molasses using a two‐stage thermophilic anaerobic process

Hydrogen and methane production from desugared molasses by a two‐stage thermophilic anaerobic process was investigated in a series of two up‐flow anaerobic sludge blanket (UASB) reactors. The first reactor that was dominated with hydrogen‐producing bacteria of Thermoanaerobacterium thermosaccharolyticum and Thermoanaerobacterium aciditolerans could generate a high hydrogen production rate of 5600 mL H₂/day/L, corresponding to a yield of 132 mL H₂/g volatile solid (VS). The effluent from the hydrogen reactor was further converted to methane in the second reactor with the optimal production rate of 3380 mL CH₄/day/L, corresponding to a yield of 239 mL CH₄/g VS. Aceticlastic Methanosarcina mazei was the dominant methanogen in the methanogenesis stage. This work demonstrates that biohydrogen production can be very efficiently coupled with a subsequent step of methane production using desugared molasses. Furthermore, the mixed gas with a volumetric content of 16.5% H_2, 38.7% CO₂, and 44.8% CH₄, containing approximately 15% energy by hydrogen is viable to be bio‐hythane.     

Evaluation and modeling of biochemical methane potential (BMP) of landfilled solid waste: A pilot scale study

The main goal of this study was to present a comparison of landfill performance with respect to solids decomposition. Biochemical methane potential (BMP) test was used to determine the initial and the remaining CH₄ potentials of solid wastes during 27 months of landfilling operation in two pilot scale landfill reactors. The initial methane potential of solid wastes filled to the reactors was around 0.347 L/CH₄/g dry waste, which decreased with operational time of landfill reactors to values of 0.117 and 0.154 L/CH₄/g dry waste for leachate recirculated (R1) and non-recirculated (R2) reactors, respectively. Results indicated that the average rate constant increased by 32% with leachate recirculation. Also, the performance of the system was modeled using the BMP data for the samples taken from reactors at varying operational times by MATLAB program. The first-order rate constants for R1 and R2 reactors were 0.01571 and 0.01195 1/d, respectively. The correlation between the model and the experimental parameters was more than 95%, showing the good fit of the model.     

Methane flux in Peltandra virginica (Araceae) wetlands: comparison of field data with a mathematical model

We present a mathematical model of the diffusive flux of methane through Peltandra virginica. Data on the diurnal changes in both the petiolar [CH₄] gradient and the values of the radial bulk exchange coefficient, E_r, are entirely consistent with this model and the assertion that changes in stomatal conductance regulate the rate of methane efflux in P. virginica. The differences between the values of E_r calculated for daytime and nighttime conditions are -40% for the submerged condition and -54% for the emergent condition. The axial diffusivity of CH₄ through the petiole of P. virginica is estimated in vitro to be 0.771 cm² min^-1. Using our model, we estimate the equilibrium rate of methane efflux under daytime (97 ng CH₄ min ¹ petiole^-1) and nighttime (65 ng CH₄ min^-1 petiole^-1) emergent conditions. Numerical solutions of the model equations in the time domain offer a way of providing a dynamic model of the gas exchange responses of P. virginica to changing environmental conditions.     

Methanogenesis from trimethylamine + H2 by Methanosarcina barkeri is coupled to ATP formation by a chemiosmotic mechanism

Cell suspensions of Methanosarcina barkeri catalyzed the conversion of trimethylamine and molecular hydrogen to methane according to the equation (CH₃)₃NH⁺ + 3 H₂ → 3 CH₄ + NH⁺₄. The onset of methane formation resulted in an increase of the intracellular ATP content from 2 to 4.6 nmol/mg protein and in the generation of a protonmotive force (Δp) of −130 mV, of which the Δψ contributed 90%. The addition of the uncoupler led to a drastic decrease of the intracellular ATP content and the Δψ, but stimulated methanogenesis. The ATPase inhibitor DCCD caused a rapid exhaustion of the ATP pool and inhibited methane formation, whereas Δψ was not affected. The inhibition of methane formation by DCCD could be relieved by addition of TCS, indicating a chemiosmotic coupling between methane formation according to the above equation and ATP synthesis.     

Biogas production from boreal herbaceous grasses – Specific methane yield and methane yield per hectare

The objective of this study was to determine the specific methane yields of four grass species (cocksfoot, tall fescue, reed canary grass and timothy) cultivated under boreal conditions as well as how harvesting time and year of cultivation affects the specific methane yields per ha. The specific methane yields of all grasses and all harvests varied from 253 to 394 Nl CH₄/kg volatile solids (VS) added. The average specific methane yield of the 1st harvest of all grasses was higher than the 2nd harvests. In this study the methane and energy yields from different harvest years were ranged from 1200 to 3600 Nm³ CH₄/ha/a, corresponding from 12 to 36 MWh_CH4${\text{MWh}}_{{\text{CH}}_4}$/ha/a. The methane yield per hectare of the 1st harvest was always higher than that of the 2nd harvest per hectare because of the higher dry matter yield and specific methane yield. High biomass yield per hectare, good digestibility and regrowth ability after harvesting are important factors when choosing grass species for biogas production. If 30% of fallow and the second harvest of grassland were cultivated grasses and harvested for biogas production in Finland, the energy produced could be 4.9 TWh_CH4${\text{TWh}}_{{\text{CH}}_4}$.     

Net methane emissions from grazing sheep

Methane emissions from ruminant livestock are responsible for 45 % of New Zealand’s combined CO₂-equivalent greenhouse gas inventory, and arise principally from sheep. Using a flock of 6-month old sheep (20 ha^–1) grazing abundant pasture, we compare micrometeorological measurements of net methane emission rates with measurements from individual sheep based on a sulphur-hexafluoride tracer technique. Individual sheep emission rates were highly variable and averaged 19.5 ± 4.8 (SD) g CH₄ sheep^–1 d^–1, or 39 ± 9.6 mg CH₄ m^–2 d^–1 on an areal basis. Emission rates were poorly correlated with animal live weight or dry matter intake but represented an average dietary energy loss of 3.6%. Methane fluxes from the surface were determined as half hourly averages by a flux-gradient technique using temperature and methane gradients. Soil methane consumption was measured using chambers and found to be negligible (< 0.09 mg CH₄ m^–2 d^–1) in comparison with the animal contribution. Daily net emission rates averaged 46 mg m^–2 d^–1 and exhibited a broad peak in the early afternoon which corresponded with animal activity patterns. On average, net emisssion rates were 40% higher during the day than at night. Stable nocturnal conditions led to a separation of the micrometeorological measurements from the methane source and hence highly variable results. Based on two corroborating techniques, the average net methane emission rate was c. 43 mg CH₄ m^–2 d^–1 or 155 kg CH₄ ha^–1 y^–1.     

基于过程模型的青藏高原湿地甲烷排放格局评估

甲烷(CH_4)是大气中最丰富的碳氢化合物,是仅次于二氧化碳(CO_2)的温室气体。湿地是甲烷的重要来源,在全球碳循环中发挥着重要作用,其排放的甲烷占所有天然甲烷排放源的70%,占全球甲烷排放总量的24.8%。青藏高原平均海拔4000 m以上,占有中国约三分之一的湿地。近几十年来,由于全球气候变暖和降水增加,该地区甲烷排放率和湿地面积都发生着巨大变化,因此,青藏高原湿地CH_4排放的长期变化在很大程度上仍存在较大的不确定性。利用TRIPLEX-GHG模型模拟了青藏高原湿地1978—2008年CH_4排放的动态特征,研究结果表明:(1)1978—2008年青藏高原湿地CH_4排放速率呈逐渐增加趋势。(2)青藏高原大多数湿地区域CH_4排放速率为0—6.13 g CH_4 m~(-2 )a~(-1);东北部分湿地区域CH_4排放速率为6.14—20.19 g CH_4 m~(-2 )a~(-1);较高的CH_4排放速率分布于青藏高原南部湿地区域,为56.14—74.97 g CH_4 m~(-2 )a~(-1)。(3)青藏高原湿地CH_4排放量在1978、1990、2000年和2008年分别为0.21、0.23、0.27和0.32 Tg CH_4 a~(-1)。在1978—1990年,尽管CH_4排放速率增加,但湿地面积减少,因此这一时期青藏高原湿地CH_4排放量并未发生明显变化。随后由于降水增加和冰川融化,使得湿地面积逐渐增加,青藏高原湿地CH_4排放量也呈现增加趋势。     

Quantification of methane emissions from Chinese rice fields (Zhejiang Province) as influenced by fertilizer treatment

Methane emissions from rice paddies were quantified by using an automatic field system stationed in Zhejiang Province, one of the centres for rice cultivation in China. The data set showed pronouned interannual variations over 5 consecutive vegetation periods; by computing average values of all experimental plots the annual emissions were 177 g CH₄ m⁻² yr⁻¹ in 1987, 50 g CH₄ m⁻² yr⁻¹ in 1988, and 187 g CH₄ m⁻² yr⁻¹ in 1989. The field preparations encompassed 4 different treatments: (1) no fertilizers, (2) mineral fertilizer (KCl, K₂SO₄), (3) organic manure (rape seeed cake, animal manure), (4) mineral fertilizer plus organic manure. The methane emission rates of the different fertilizer treatments did not show significant differences. The mean emission rates, calculated over the entire observation period of 5 seasons, were 30.4 mg CH₄ m⁻² h⁻¹ (non-fertilized plot) and 28.3 mg CH₄ m⁻² h⁻¹ (mineral fertilizers). These values indicate a high level of methane production even without additional input of organic material into the rice-soils. In the other plots, the organic fertilizers were added once per vegetation period at app. 1 t fresh weight per ha, a relatively low application rate by agronomical standards. The mean emission rates were 35.1 mg CH₄ m⁻² h⁻¹ when manure was applied as sole fertilizer and 27.5 mg CH₄ m⁻² h⁻¹ when applied jointly with potassium fertilizers. Based on the results of this study we estimate a range of 18–28 Tg CH₄ yr⁻¹ as the total methane emission from Chinese rice fields. However, more field data from representative sites in China are needed to reduce the uncertainties in this estimate.     

Annual emissions of greenhouse gases from sheepfolds in Inner Mongolia

Sheepfolds represent significant hot spot sources of greenhouse gases (GHG) in semi-arid grassland regions, such as Inner Mongolia in China. However, the annual contribution of sheepfolds to regional GHG emissions is still unknown. In order to quantify its annual contribution, we conducted measurements of carbon dioxide (CO₂), methane (CH₄) and nitrous oxide (N₂O) fluxes at two sheepfold sites in the Baiyinxile administrative region of Inner Mongolia for 1 year, using static opaque chamber and gas chromatography methods. Our data show that, at an annual scale, both sheepfolds functioned as net sources of CO₂, CH₄ and N₂O. Temperatures primarily determined the seasonal pattern of CO₂ emission; 60–84% of the CO₂ flux variation could be explained by temperature changes. High rates of net CH₄ emissions from sheepfold soils were only observed when animals (sheep and goats) were present. While nitrous oxide emissions were also stimulated by the presence of animals, pulses of N₂O emissions were also be related to rainfall and spring-thaw events. The total annual cumulative GHG emissions in CO₂ equivalents (CO₂: 1; CH₄: 25; and N₂O: 298) were quantified as 87.4?±?18.4 t ha^?1 for the sheepfold that was used during the non-grazing period (i.e., winter sheepfold) and 136.7?±?15.9 t ha^?1 used during the grazing period (i.e., summer sheepfold). Of the annual total GHG emissions, CH₄ release accounted for approximately 1% of emissions, while CO₂ and N₂O emissions contributed to approximately 59% and 40%, respectively. The total GHG emission factor (CO₂?+?CH₄?+?N₂O) per animal for the sheepfolds investigated in this study was 30.3 kg CO₂ eq yr^?1 head^?1, which translates to 0.3, 18.8 and 11.2 kg CO₂ eq yr^?1 head^?1 for CH₄, CO₂ and N₂O, respectively. Sheepfolds accounted for approximately 34% of overall N₂O emissions in the Baiyinxile administrative region, a typical steppe region within Inner Mongolia. The contribution of sheepfolds to the regional CO₂ or CH₄ exchange is marginal.     

Theoretical investigation of the gas-phase reactions of CF2ClC(O)OCH3 with the hydroxyl radical and the chlorine atom at 298 K

A Theoretical study on the mechanism of the reactions of CF₂ClC(O)OCH₃ with the OH radical and Cl atom is presented. Geometry optimization and frequency calculations have been performed at the MPWB1K/6-31+G(d,p) level of theory and energetic information is further refined by calculating the energy of the species using G2(MP2) theory. Transition states are searched on the potential energy surface involved during the reaction channels and each of the transition states are characterized by presence of only one imaginary frequency. The existence of transition states on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate (IRC) calculation. Theoretically calculated rate constants at 298 K and atmospheric pressure using the canonical transition state theory (CTST) are found to be in good agreement with the experimentally measured ones. Using group-balanced isodesmic reactions as working chemical reactions, the standard enthalpies of formation for CF₂ClC(O)OCH_3, CF₂ClC(O)OCH₂ and CF₃C(O)OCH₃ are also reported for the first time.     

Decomposition of carbon-bearing compounds and their influence on methane formation in a lignite incubation experiment

Carbon-bearing compounds (glucose, sodium acetate, methanol, yeast extract, and nutrient broth) were added in different proportions to cultures to stimulate methanogenesis in a lignite incubation experiment. Their addition significantly influenced the isotopic composition of methane generated during the fermentation of lignite. Glucose was degraded mainly in the first 2 weeks of incubation, when the atmospheric air was present in the headspace and used for biomass growth. Sodium acetate, methanol, and, presumably, lignite were decomposed in the next phase, in which anaerobic conditions occurred. The simultaneous decomposition of sodium acetate and methanol (as single substrates or as a mixture) with lignite resulted in the formation of methane with δ¹³C(CH₄) values typical for methyl-type fermentation. The identification of decomposed compounds in the mixture of sodium acetate and methanol was accomplished via isotopic analysis of carbon and hydrogen in the methane. The δ²H(CH₄) values in the case of methanol biodegradation were characterized by a negative trend over time, in contrast to a positive trend observed when sodium acetate decomposed. This observation may help to identify a very good tracer for the determination of methane precursors during methyl-type fermentation.     

A Heterogeneous Carbon Nitride–Nickel Photocatalyst for Efficient Low‐Temperature CO2 Methanation

The Sabatier reaction, i.e., the hydrogenation of CO₂ to methane (CH₄) using hydrogen (H₂), constitutes a potentially scalable method to store energy in a product with a high energy density. However, up to today, this reaction has been mainly thermally driven and conducted at high temperatures (typically 400–600 °C). Using light as a renewable energy source will allow for a more sustainable process by lowering the reaction temperature. Here, it is demonstrated that Ni nanoparticles support on graphitic carbon nitride (g‐CN) are a highly efficient and stable photocatalyst for the gas‐phase CO₂ methanation at low temperature (150 °C). Detailed mechanistic studies reveal a very low activation energy for the reaction and high activity under visible light, leading to a remarkable and continuous CH₄ production of 28 µmol g^?1 h^?1 of CH₄ for 24 h.     

Energy recovery from lipid extracted,transesterified and glycerol codigested microalgae biomass

The production of methane (CH₄) via the anaerobic digestion of microalgae biomass residues from the biodiesel production process has the potential to meet some of the energy requirements of the primary biomass to fuel conversion process. This paper investigates the practical CH₄ yields achievable from the anaerobic conversion of the microalgae residues (as well as codigestion with glycerol) after biodiesel production using both the conventional and in situ transesterification methods. Results demonstrate that the type of lipid extraction solvent utilized in the conventional transesterification process could inhibit subsequent CH₄ production. On the basis of actual CH₄ production, a recoverable energy of 8.7–10.5 MJ kg^?1 of dry microalgae biomass residue was obtained using the lipid extracted and transesterified microalgae samples. On codigesting the microalgae residues with glycerol, a 4–7% increase in CH₄ production was observed.     

Acidophilic Methanotrophic Communities from Sphagnum Peat Bogs

Highly enriched methanotrophic communities (>25 serial transfers) were obtained from acidic ombrotrophic peat bogs from four boreal forest sites. The enrichment strategy involved using media conditions that were associated with the highest rates of methane uptake by the original peat samples, namely, the use of diluted mineral medium of low buffering capacity, moderate incubation temperature (20°C), and pH values of 3 to 6. Enriched communities contained a mixture of rod-shaped bacteria arranged in aggregates with a minor contribution of Hyphomicrobium-like cells. The growth stoichiometry of isolates was characteristic of methanotrophic bacteria (CH₄/O₂/CO₂=1:1.1:0.59), with an average apparent yield of 0.41 ± 0.03 g of biomass C/g of CH₄-C. DNA from each enrichment yielded a PCR product of the expected size with primers for both mmoX and mmoY genes of soluble methane monooxygenase. Two types of sequences were obtained for PCR-amplified fragments of mmoX. One of them exhibited high identity to the mmoX protein of the Methylocystis-Methylosinus group, whereas the other showed an equal level of divergence from both the Methylosinus-Methylocystis group and Methylococcus capsulatus (Bath) and formed a distinct branch. The pH optimum for growth and for CH₄ uptake was 4.5 to 5.5, which is very similar to that for the optimum CH₄ uptake observed in the original peat samples. These methanotrophs are moderate acidophiles rather than acidotolerant organisms, since their growth rate and methane uptake were much lower at neutral pH. The growth of the methanotrophic community was enhanced by using media with a very low salt content (20 to 200 mg/liter), more typical of their natural environment. All four enriched communities grew on N-free medium.     

Biomethanation of H2 and CO2 by Methanobacterium thermoautotrophicum in membrane and ceramic bioreactors

Direct conversion of gaseous H₂ and CO₂ to CH₄ was achieved with Methanobacterium thermoautotrophicum ΔH (DSM 1053) cells fixed either on a cellulose acetate membrane or inside a porous silica-alumina ceramic support.In a membrane bioreactor with cellulose acetate (5 μmø), methane production rate increased in proportion to the contact area between the gases and the methanogen cells, giving a methane production rate of 0.75 ml CH₄/cm² contact area/h. The initial fixed-cell mass of 0.2 mg dry cell/cm² of contact area increased to 1 mg/cm² after 12 h of cultivation (steady state).In the ceramic bioreactor (cylindrical, 30 mmø × 70; av. pore size 100 μ, and porosity 79.7%), the methane production rate at steady state was 6 l CH₄/l ceramic/l. The methanogen cells grew homogeneously inside the ceramic up to 7 cm depth, and the cell density ranged from 20 to 30 mg dry cell/cm³ ceramic.     

Stimulation of CO2 reduction to methane by methylcoenzyme M in extracts Methanobacterium.

Addition of methyl-coenzyme M (CH₃SCH₂CH₂SO₃^?) to undialized, anaerobic, cell-extracts of $\text{Methanobacterium thermoautotrophicum}$ under an atmosphere of H₂ and CO₂ (80:20 v/v) stimulates 30-fold the rate of CO₂ reduction to methane. For each mol of CH₃SCH₂CH₂SO₃^? added 12 mol of methane is produced. This stimulation phenomenon requires magnesium ion, ATP, H₂, and CH₃SCH₂CH₂SO₃^?. Neither the reduced form of the cofactor, HSCH₂CH₂SO₃^?, nor the oxidized, disulfide form will replace the methylated coenzyme.     

The carbon and hydrogen stable isotope composition of bacteriogenic methane: A laboratory study using a landfill inoculum

Anaerobic bacterial degradation of landfill waste produces a globally significant source of the greenhouse gas methane. Stable isotopic measurements of methane [δ^I3C(CH₄) and δD(CH₄)] can often fingerprint different sources of methane (natural vs. anthro‐pogenic) and help identify the bacterial processes involved in methane production. Landfill microbial communities are complex and diverse, and hence so too is the biogeochem‐istry of methane formation. To investigate the influence of (l) the methane formation pathway (acetoclastic methanogenesis and CO₂ reduction), and (2) SD of water on the stable isotopic composition of landfill methane, two model butyrate‐degrading landfill systems were established. The systems were inoculated with domestic refuse from a landfill and incubated in the laboratory for 92 days. Both systems were identical except δD of water initially added to system 2 was 118% heavier than system 1. Between days 39 and 72 the systems were resupplemented with butyrate. Production of CH₄ and CO₂ and changes in volatile fatty acid concentration confirmed that active methanogenic populations had been established. CH₄ became ¹³C enriched in both incubations with time. Interpreting changes in acetate, butyrate, and propionate concentration during incubation is complicated, but these observations and other information suggest that the dominant methanogenic substrate changed front CO₂/H₂ to acetate as the experiment progressed. This is also consistent with the observed ¹³C enrichment of CH₄, as ¹³C discrimination during methane production from acetate is less than from CO₂. In contrast, δD(CH₄) remained relatively constant, suggesting that this measurement may not provide a reliable basis for distinguishing between CH₄ from CO₂ reduction and acetoclastic methanogenesis, as has previously been suggested.     

Kinetic Parameters of the Conversion of Methane Precursors to Methane in a Hypereutrophic Lake Sediment

The kinetic parameters K_m, V_max, T_t (turnover time), and v (natural velocity) were determined for H₂ and acetate conversion to methane by Wintergreen Lake sediment, using short-term (a few hours) methods and incubation temperatures of 10 to 14°C. Estimates of the Michaelis-Menten constant, K_m, for both the consumption of hydrogen and the conversion of hydrogen to methane by sediment microflora averaged about 0.024 μmol g⁻¹ of dry sediment. The maximal velocity, V_max, averaged 4.8 μmol of H₂ g⁻¹ h⁻¹ for hydrogen consumption and 0.64 μmol of CH₄ g⁻¹ h⁻¹ for the conversion of hydrogen to methane during the winter. Estimated natural rates of hydrogen consumption and hydrogen conversion to methane could be calculated from the Michaelis-Menten equation and estimates of K_m, V_max, and the in situ dissolved-hydrogen concentration. These results indicate that methane may not be the only fate of hydrogen in the sediment. Among several potential hydrogen donors tested, only formate stimulated the rate of sediment methanogenesis. Formate conversion to methane was so rapid that an accurate estimate of kinetic parameters was not possible. Kinetic experiments using [2-¹⁴C]acetate and sediments collected in the summer indicated that acetate was being converted to methane at or near the maximal rate. A minimum natural rate of acetate conversion to methane was estimated to be about 110 nmol of CH₄ g⁻¹ h⁻¹, which was 66% of the V_max (163 nmol of CH₄ g⁻¹ h⁻¹). A 15-min preincubation of sediment with 5.0 × 10⁻³ atm of hydrogen had a pronounced effect on the kinetic parameters for the conversion of acetate to methane. The acetate pool size, expressed as the term K_m + S_n (S_n is in situ substrate concentration), decreased by 37% and T_t decreased by 43%. The V_max remained relatively constant. A preincubation with hydrogen also caused a 37% decrease in the amount of labeled carbon dioxide produced from the metabolism of [U-¹⁴C]valine by sediment heterotrophs.