Polymers of intrinsic microporosity for gas permeation: a molecular simulation study

We report a molecular simulation study for gas permeation in two membranes constructed from polymers of intrinsic microporosity (PIM-1 and PIM-7). With rigid ladder polymer chains, the membranes posses approximately 47.7 and 46.6% fractional free volumes (FFVs) in PIM-1 and PIM-7, respectively. The voids in the membranes have a diameter up to 9 Å and are largely interconnected. The sorption and diffusion of four gases (H₂, O₂, CH₄ and CO₂) were calculated by Monte Carlo and molecular dynamics simulations. The solubility coefficients increase in the order of H₂ < O₂ < CH₄ < CO₂, while the diffusion coefficients increase in the following order: CH₄ < CO₂ < O₂ < H₂. The simulation results agree well with experimental data, particularly for the solubility coefficients. The solubility and diffusion coefficients correlate well separately with the critical temperatures and effective diameters of gases. These molecular-based correlations can be used in the prediction for other gases. As attributed to the microporous structure, PIM-1 and PIM-7 outperform most glassy polymeric membranes in sorption and diffusion. PIM-1 has larger solubility and diffusion coefficients than PIM-7 because the cyano groups in PIM-1 lead to a stronger affinity and a larger FFV. The simulated solubility, diffusivity and permeation selectivities of CO₂/H₂, CO₂/O₂ and CO₂/CH₄ are consistent with experimental data. The quantitative microscopic understanding of gas permeation in the PIM membranes is useful for the new development of high-performance membranes.     

Work Function Evolution in Li Anode Processing

Toward improved understanding and control of the interactions of Li metal anodes with their processing environments, a combined X‐ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT) characterization of the effects that O₂, CO₂, and N₂, the main gases in dry‐atmosphere battery production lines, induced on a reproducibly clean Li surface at room temperature is presented here. XPS measurements demonstrate that O₂ is ten times more effective than CO₂ at oxidizing metal Li. Notably, pure N₂ is shown to not dissociate on clean metal Li. UPS results indicate that decomposition of O₂ (CO₂) reduces the work function of the Li surface by almost 1 eV, therefore increasing the reduction energy drive for the treated substrate by comparison to bare metallic Li. DFT simulations semiquantitatively account for these results on the basis of the effects of dissociative gas adsorption on the surface dipole density of the Li surface.     

Computer simulation of gas adsorption in modified COF-108: the impregnation of C60 into COF-108

Gas adsorption and separation performance of COF-108 framework impregnated by C₆₀ clusters were simulated. The adsorption properties of pure CO₂, the mixtures of CO₂/CH₄, CO₂/N₂ and N₂/O₂ were investigated. The simulated results of the adsorption isotherms, the adsorption quantity, the density fields, the isosteric heats and the selectivity in COF-108s were obtained. It is shown that the impregnation of C₆₀ can enhance the adsorption capacity of CO₂, N₂ and O₂, and the selectivity of CO₂/CH₄, CO₂/N₂ and N₂/O₂ in COF-108. The impregnation of C₆₀ can increase the surface area COF-108 but decrease its free volume and the pore diameter. At low adsorption pressures, the monolayer surface adsorption is dominant. With the increase in adsorption pressure, the dominant factor is changed into the free volume of COF-108 by the multilayer adsorption. The impregnation of C₆₀ plays different roles for the polar or non-polar gases at different pressures.     

中国森林面积变化及其温室气体储量模拟研究

陆地生态系统承载的温室气体对全球碳循环及气候调节服务意义重大,森林生态系统是陆地生态系统的重要组成部分,量化森林对温室气体的储量有利于从生物地球化学角度研究全球变化问题。针对中国森林生态系统承载的温室气体在大尺度上无法有效量化的问题,基于2000与2010年两期土地利用数据和前人的相关研究,通过一个生态系统温室气体值模型,模拟得到中国森林生态系统承载的三大主要温室气体(CO₂,CH₄,N₂O)的量。结果表明:(1)中国森林生态系统的面积从2000年的224.3×10⁶ hm²略增到2010的224.6×10⁶ hm²;其中落叶阔叶林、常绿阔叶林和针叶林的面积减少,而混交林与灌木林的面积增加;(2)对应地,2000和2010年中国森林的温室气体储量分别为154.03和154.37 Pg CO₂当量,10年间增加了0.34 Pg CO₂当量。其中,常绿针叶林、常绿阔叶林、落叶阔叶林在研究时段内的...     

Computational screening of ZIFs for CO2 separations

Using molecular simulations, we studied a diverse collection of zeolite–imidazolate frameworks (ZIFs) to evaluate their performances in adsorption- and membrane-based gas separations. Molecular simulations were performed for both single-component gases (CH₄, CO₂, H₂ and N₂) and binary gas mixtures (CO₂/CH₄, CO₂/N₂, CO₂/H₂ and CH₄/H₂) to predict the intrinsic and mixture selectivities of ZIFs. These two selectivities were compared to discuss the importance of multi-component mixture effects on making predictions about the separation performance of a material. Gas separation performances of ZIFs were compared with other nanoporous materials and our results showed that several ZIFs can outperform well-known zeolites and metal–organic frameworks in CO₂ separations. Several other properties of ZIFs such as gas permeability, working capacity and sorbent selection parameter were computed to identify the most promising materials in adsorption- and membrane-based separation of CO₂/CH₄, CO₂/N₂, CO₂/H₂ and CH₄/H₂.     

Net greenhouse gas balance in response to nitrogen enrichment: perspectives from a coupled biogeochemical model

Increasing reactive nitrogen (N) input has been recognized as one of the important factors influencing climate system through affecting the uptake and emission of greenhouse gases (GHG). However, the magnitude and spatiotemporal variations of N‐induced GHG fluxes at regional and global scales remain far from certain. Here we selected China as an example, and used a coupled biogeochemical model in conjunction with spatially explicit data sets (including climate, atmospheric CO₂, O₃, N deposition, land use, and land cover changes, and N fertilizer application) to simulate the concurrent impacts of increasing atmospheric and fertilized N inputs on balance of three major GHGs (CO₂, CH₄, and N₂O). Our simulations showed that these two N enrichment sources in China decreased global warming potential (GWP) through stimulating CO₂ sink and suppressing CH₄ emission. However, direct N₂O emission was estimated to offset 39% of N‐induced carbon (C) benefit, with a net GWP of three GHGs averaging ?376.3 ± 146.4 Tg CO₂ eq yr^?1 (the standard deviation is interannual variability of GWP) during 2000–2008. The chemical N fertilizer uses were estimated to increase GWP by 45.6 ± 34.3 Tg CO₂ eq yr^?1 in the same period, and C sink was offset by 136%. The largest C sink offset ratio due to increasing N input was found in Southeast and Central mainland of China, where rapid industrial development and intensively managed crop system are located. Although exposed to the rapidly increasing N deposition, most of the natural vegetation covers were still showing decreasing GWP. However, due to extensive overuse of N fertilizer, China's cropland was found to show the least negative GWP, or even positive GWP in recent decade. From both scientific and policy perspectives, it is essential to incorporate multiple GHGs into a coupled biogeochemical framework for fully assessing N impacts on climate changes.     

Benefits of ethylene removal during apple storage

The potential use of an ethylene absorbent in controlled atmosphere storage of two varieties of apple has been investigated. With Golden Delicious, the rise in ethylene concentration during controlled atmosphere storage can be delayed for about 40 days but not prevented by inclusion of potassium permanganate in the storage container. But with Bramley's Seedling, potassium permanganate can delay ethylene accumulation for over 200 days. Ethylene treatment of Bramley's Seedling in a flowing stream of 5% CO₂:3% O₂:92% N₂ caused accelerated softening, accumulation of α-farnesene and earlier onset of superficial scald. Use of potassium permanganate to remove ethylene during storage in static controlled atmosphere conditions retarded all three processes in Bramley's Seedling kept in 5% CO₂:3% O₂ and in 9% CO₂:12% O₂. However, in one experiment, ethylene removal in 5% CO₂:3% O₂, led to external and internal symptoms of CO₂ damage. A subsequent investigation of the combined effects of harvest date, store temperature and ethylene removal in 5% CO₂:3% O₂ did not show any damage or accumulation of succinic acid which is known to be involved in CO₂ injury. This experiment revealed that ethylene removal could be successfully accomplished on Bramley fruit harvested up to a month after the usual date and little α-farnesene accumulated in this fruit. Nevertheless scald did develop on late picked fruit and this raises doubts about the causal role of farnesene in scald.     

A method for equilibration chamber sampling and gas chromatographic analysis of the soil atmosphere

The method includes sampling of gases from an equilibration chamber permanently installed in the soil, transferring the sample to laboratory and subsequent measurement by gas chromatography. The equilibration chamber allows sampling of the gas phase both above and below the groundwater level, which is a major advantage. After significant concentration changes in non-saturated soils, gases in chambers regain equilibrium with the surrounding soils within 1–2 days. In the most unfavourable equilibration situations,i.e. in mineral subsoils with stagnant groundwater and very low biological activity, 90% equilibrium is attained in about 15 days. N₂, O₂+Ar, CO₂, CH₄, N₂O, H₂ and Ne, are measured on a series/bypass multi-column system, followed by a thermal conductivity detector.     

Dynamics of dissolved O2, CO2, CH4, and N2O in a tropical coastal swamp in southern Thailand

We studied the distribution of dissolved O₂, CO₂, CH₄, and N₂O in a coastal swamp system in Thailand with the goal to characterize the dynamics of these gases within the system. The gas concentrations varied spatially and seasonally in both surface and ground waters. The entire system was a strong sourcefor CO₂ and CH₄, and a possible sink for atmospheric N₂O. Seasonal variation in precipitation primarily regulated the redox conditions in the system. However, distributions of CO₂, CH₄, and N₂O in the river that received swamp waters were not always in agreement with redox conditions indicated by dissolvedO₂ concentrations. Sulfate production through pyriteoxidation occurred in the swamp with thin peat layerunder aerobic conditions and was reflected by elevatedSO ₄ ^2– /Cl^– in the river water. When SO ₄ ^2– /Cl^– was high, CO₂ and CH₄ concentrations decreased, whereas the N₂O concentration increased. The excess SO ₄ ^2– in the river water was thus identified as a potential indicator for gas dynamics in this coastal swamp system.     

Influence of carbon availability on the production of NO, N2O, N2 and CO2 by soil cores during anaerobic incubation

Net productions of permanent soil atmosphere gases (N₂, CO₂, O₂) and temporary gases (N₂O, NO) were monitored in soil cores using a non-interfering, fully automated measuring technique allowing highly time resolved measurements over prolonged periods. The influence of changes in available organic carbon on CO₂, N₂O, NO and N₂ production was studied by changing the soil carbon content through aerobic preincubations of different length, up to 21 days.The aerobic preincubation caused an increase in NO₃ ^- concentration and a decrease in available carbon content. Available carbon content dominated both CO₂ and total N gas (N₂+N₂O+NO) production during anaerobiosis. Both CO₂ and total N gas production rates decreased with increasing length of the previous aerobic preincubation, this in spite of the higher initial NO₃ ^- concentration.Total denitrification rates were closely related to the anaerobic CO₂ production rates. No relation was found between water soluble carbon content and total denitrification. The N₂O/N₂ ratio could be explained by an interaction of carbon availability, NO₃ ^- concentration and enzyme status. Net N₂O consumption was monitored. The balance between cumulative total N gas production and NO₃ ^- consumption varied according to the different treatments. Cumulative N₂O production exceeded cumulative N₂ production for 0 up to 5 days.     

Simultaneous numerical representation of soil microsite production and consumption of carbon dioxide,methane, and nitrous oxide using probability distribution functions

Production and consumption of nitrous oxide (N₂O), methane (CH₄), and carbon dioxide (CO₂) are affected by complex interactions of temperature, moisture, and substrate supply, which are further complicated by spatial heterogeneity of the soil matrix. This microsite heterogeneity is often invoked to explain non‐normal distributions of greenhouse gas (GHG) fluxes, also known as hot spots and hot moments. To advance numerical simulation of these belowground processes, we expanded the Dual Arrhenius and Michaelis–Menten model, to apply it consistently for all three GHGs with respect to the biophysical processes of production, consumption, and diffusion within the soil, including the contrasting effects of oxygen (O₂) as substrate or inhibitor for each process. High‐frequency chamber‐based measurements of all three GHGs at the Howland Forest (ME, USA) were used to parameterize the model using a multiple constraint approach. The area under a soil chamber is partitioned according to a bivariate log‐normal probability distribution function (PDF) of carbon and water content across a range of microsites, which leads to a PDF of heterotrophic respiration and O₂ consumption among microsites. Linking microsite consumption of O₂ with a diffusion model generates a broad range of microsite concentrations of O₂, which then determines the PDF of microsites that produce or consume CH₄ and N₂O, such that a range of microsites occurs with both positive and negative signs for net CH₄ and N₂O flux. Results demonstrate that it is numerically feasible for microsites of N₂O reduction and CH₄ oxidation to co‐occur under a single chamber, thus explaining occasional measurement of simultaneous uptake of both gases. Simultaneous simulation of all three GHGs in a parsimonious modeling framework is challenging, but it increases confidence that agreement between simulations and measurements is based on skillful numerical representation of processes across a heterogeneous environment.     

Computational exploration of the gas adsorption on the iron tetracarboxylate metal-organic framework MIL-102

Density functional theory calculations have been combined with forcefield-based grand canonical Monte Carlo simulations to explore the adsorption of CO₂, N₂, CH₄ and H₂ on the small one-dimensional channel MIL-102, a naphthalene tetracarboxylate-based metal-organic framework (MOF) built up from a connection of trimers of trivalent iron. A detailed analysis is provided on the preferential arrangement of the confined adsorbates as well as the energetics of the host/guest interactions. The co-adsorption properties of this solid for the elimination of CO₂ from hydrogen, natural and flue gases are then revealed. The so-predicted performances are further compared with those reported so far for a diverse series of MOFs.     

Fungal community composition and metabolism under elevated CO2 and O3

Atmospheric CO₂ and O₃ concentrations are increasing due to human activity and both trace gases have the potential to alter C cycling in forest ecosystems. Because soil microorganisms depend on plant litter as a source of energy for metabolism, changes in the amount or the biochemistry of plant litter produced under elevated CO₂ and O₃ could alter microbial community function and composition. Previously, we have observed that elevated CO₂ increased the microbial metabolism of cellulose and chitin, whereas elevated O₃ dampened this response. We hypothesized that this change in metabolism under CO₂ and O₃ enrichment would be accompanied by a concomitant change in fungal community composition. We tested our hypothesis at the free-air CO₂ and O₃ enrichment (FACE) experiment at Rhinelander, Wisconsin, in which Populus tremuloides, Betula papyrifera, and Acer saccharum were grown under factorial CO₂ and O₃ treatments. We employed extracellular enzyme analysis to assay microbial metabolism, phospholipid fatty acid (PLFA) analysis to determine changes in microbial community composition, and polymerase chain reaction–denaturing gradient gel electrophoresis (PCR–DGGE) to analyze the fungal community composition. The activities of 1,4-β-glucosidase (+37%) and 1,4,-β-N-acetylglucosaminidase (+84%) were significantly increased under elevated CO₂, whereas 1,4-β-glucosidase activity (−25%) was significantly suppressed by elevated O₃. There was no significant main effect of elevated CO₂ or O₃ on fungal relative abundance, as measured by PLFA. We identified 39 fungal taxonomic units from soil using DGGE, and found that O₃ enrichment significantly altered fungal community composition. We conclude that fungal metabolism is altered under elevated CO₂ and O₃, and that there was a concomitant change in fungal community composition under elevated O₃. Thus, changes in plant inputs to soil under elevated CO₂ and O₃ can propagate through the microbial food web to alter the cycling of C in soil.     

Photoinhibition of photosynthesis in the cyanobacterium Microcystis aeruginosa

We have examined characteristics of the photoinhibition of photosynthesis which occur in the unicellular cyanobacterium Microcystis aeruginosa, following exposure to photon fluence rates in excess of those required for growth. Photoinhibition occurs following exposure of cells to a photon fluence rate of 1,000 μmol m^-2 s^-1, which is manifested as a decrease in either light-limited CO₂ fixation or light-saturated CO₂-dependent O₂ evolution. The extent and rapidity of this photoinhibition is greatly enhanced under CO₂-depleted conditions. Experiments in which cultures were sparged with different gases indicate that photoinhibition is not an obvious consequence of elevated O₂ tensions, unlike the photooxidative bleaching of photosynthetic pigments. Comparative studies on the photoinactivation of CO₂-dependent O₂ evolution and of the methyl viologen-dependent Mehler reaction, in whole cells, indicate that a primary site of light damage is within the photosynthetic electron-transport reactions and that carbon fixation is initially unaffected.     

Diffusion of N2, O2, H2S and SO2 in MFI and 4A zeolites by molecular dynamics simulations

This paper presents diffusion data of N₂, O₂, H₂S and SO₂ in MFI and 4A zeolites obtained by molecular dynamics simulations, especially its dependence on temperature and loading. At high loadings and temperatures, the order of self-diffusivity of guests in two zeolites is O₂ > N₂ > H₂S>SO₂. The diffusion behaviour is different in different zeolites at lower loadings, reflecting different influences from straight channels (MFI) and α-cages (4A). Furthermore, with increasing loading, the self-diffusivity of guest molecules decreases in MFI but generally increases in 4A. The centre of mass (COM) probability densities and diffusion trajectories of guests give insight into molecular-level diffusion process. The simulation results reveal that with increasing loading, the diffusion mechanism would change from the inter-pore to intra-pore diffusion in MFI. However, in 4A, the intra-pore diffusion is predominant at low and high loadings, but inter-pore diffusion is more important at moderate loadings.     

Temporal Dynamics in Soil Oxygen and Greenhouse Gases in Two Humid Tropical Forests

Soil redox plays a key role in regulating biogeochemical transformations in terrestrial ecosystems, but the temporal and spatial patterns in redox and associated controls within and across ecosystems are poorly understood. Upland humid tropical forest soils may be particularly prone to fluctuating redox as abundant rainfall limits oxygen (O₂) diffusion through finely textured soils and high biological activity enhances O₂ consumption. We used soil equilibration chambers equipped with automated sensors to determine the temporal variability in soil oxygen concentrations in two humid tropical forests with different climate regimes. We also measured soil trace gases (CO₂, N₂O, and CH₄) as indices of redox-sensitive biogeochemistry. On average, the upper elevation cloud forest had significantly lower O₂ concentrations (3.0 ± 0.8%) compared to the lower elevation wet tropical forest (7.9 ± 1.1%). Soil O₂ was dynamic, especially in the wet tropical forest, where concentrations changed as much as 10% in a single day. The periodicity in the O₂ time series at this site was strongest at 16 day intervals and was associated with the hourly precipitation. Greenhouse gas concentrations differed significantly between sites, but the relationships with soil O₂ were consistent: O₂ was negatively related to both CO₂ and CH₄ and positively related to N₂O. These results are among the first to quantify the temporal and spatial scale of variability in soil redox in humid tropical forests, and show that the timing of precipitation plays a strong role in biogeochemical cycling on the scale of hours to weeks.     

An evaluation of the recycling in measurements of photorespiration

All measurements of photorespiration and gross photosynthesis in leaves, whether using isotopes or not, are underestimated because of the recycling of O₂ or CO₂. On the basis of a simple diffusion model, we propose a method for the calculation of the recycling and the corresponding underestimation of the measurements. This procedure can be applied when the stomatal resistance is known, and allows for a correction of certain results in the literature. It is found that measurements of the photorespiratory CO₂ release are usually underestimated by 20 to 100%, which sets the estimated rate of CO₂ photorespired at 30 to 50% of the net photosynthesis in C3 plants under normal conditions. In water stress studies, the correction of the photorespiration is still more important (1.5-3.3) because the stomata are closed more. Analysis of the diffusion of O₂ shows that its recycling is low and that the underestimation of photorespiration with ¹⁸O₂ is negligible.     

不同干扰因素对森林和湿地温室气体通量影响的研究进展

森林和湿地是CO2、CH4和N2O等温室气体重要的源、汇和转换器,在全球气候变化过程中起着重要作用。森林和湿地温室气体通量受到诸多因子的作用,其中干扰便是一个重要的因素。不同干扰因素对于森林和湿地生态系统温室气体通量的影响,国际上已经开展了相应的研究。基于人为和自然两大类干扰方式,分别从采伐、施肥、垦殖等人为干扰因素和火烧、台风(飓风)等自然干扰因素综述了干扰对于森林和湿地生态系统CO2、CH4和N2O通量的影响。根据目前研究中存在的不足,提出了今后应需加强的领域,以期更好地揭示干扰对于森林和湿地生态系统温室气体通量的影响及作用机制,为今后深入开展相关研究提供一定的参考价值。     

Mathematical studies of the interaction of respiratory gases with whole blood II. CO2 absorption

Some progress has been made on the problem of the interaction of respiratory gases with whole blood. A working mathematical model for the O₂−CO₂ interaction phenomena has been developed from mathematical studies of the data. The Edsall-Wyman (1958) model for CO₂ absorption is improved upon in this paper by consolidating it with the O₂ absorption model developed in paper I of this set (Bernard, S. R.,Bull. Math. Biophysics,22, 391–415, 1960). This improved model assumed the effect of O₂ on CO₂ absorption is mediated through the electrical charge possessed by the hemoglobin molecule,i.e., O₂ molecules bound to hemoglobin displace protons from the hemoglobin thereby increasing the negative charge on the hemoglobin and at the same time increasing the acidity of the solution. The model is tested against the data.     

Gas adsorption and diffusion in a highly CO2 selective metal–organic framework: molecular simulations

Grand canonical Monte Carlo and equilibrium molecular dynamics simulations were used to assess the performance of an rht-type metal–organic framework (MOF), Cu-TDPAT, in adsorption-based and membrane-based separation of CH₄/H₂, CO₂/CH₄ and CO₂/H₂ mixtures. Adsorption isotherms and self-diffusivities of pure gases and binary gas mixtures in Cu-TDPAT were computed using detailed molecular simulations. Several properties of Cu-TDPAT such as adsorption selectivity, working capacity, diffusion selectivity, gas permeability and permeation selectivity were computed and compared with well-known zeolites and MOFs. Results showed that Cu-TDPAT is a very promising adsorbent and membrane material especially for separation of CO₂ and it can outperform traditional zeolites and MOFs such as DDR, MFI, CuBTC, IRMOF-1 in adsorption-based CO₂/CH₄ and CO₂/H₂ separations.