Carbon and energy yields in prebiotic syntheses using atmospheres containing CH4, CO and CO2

Yields based on carbon are usually reported in prebiotic experiments, while energy yields (moles cal^–1) are more useful in estimating the yields of products that would have been obtained from the primitive atmosphere of the earth. Energy yields for the synthesis of HCN and H₂CO from a spark discharge were determined for various mixtures of CH₄, CO, CO₂, H₂, H₂O, N₂ and NH₃. The maximum yields of HCN and H₂CO from CH₄, CO, and CO₂ as carbon sources are about 4×10^–8 moles cal^–1.     

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.     

Land use and season affect fluxes of CO2, CH4, CO,N2O,H2 and isotopic source signatures in Panama: evidence from nocturnal boundary layer profiles

Conversion of tropical rainforests to pastures and plantations is associated with changes in soil properties and biogeochemical cycling, with implications for carbon cycling and trace gas fluxes. The stable isotopic composition of ecosystem respiration (δ¹³C_R and δ¹⁸O_R) is used in inversion models to quantify regional patterns of CO₂ sources and sinks, but models are limited by sparse measurements in tropical regions. We measured soil respiration rates, concentrations of CO₂, CH₄, CO, N₂O and H₂ and the isotopic composition of CO₂, CH₄ and H₂ at four heights in the nocturnal boundary layer (NBL) above three common land‐use types in central Panama, during dry and rainy seasons. Soil respiration rates were lowest in Plantation (average 3.4 μmol m^?2 s^?1), highest in Pasture (8.3 μmol m^?2 s^?1) and intermediate in Rainforest (5.2 μmol m^?2 s^?1). δ¹³C_R closely reflected land use and increased during the dry season where C₃ vegetation was present. δ¹⁸O_R did not differ by land use but was lower during the rainy than the dry season. CO₂ was correlated with other species in approximately half of the NBL profiles, allowing us to estimate trace gas fluxes that were generally within the range of literature values. The Rainforest soil was a sink for CH₄ but emissions were observed in Pasture and Plantation, especially during the wet season. N₂O emissions were higher in Pasture and Plantation than Rainforest, contrary to expectations. Soil H₂ uptake was highest in Rainforest and was not observable in Pasture and Plantation during the wet season. We observed soil CO uptake during the dry season and emissions during the wet season across land‐use types. This study demonstrated that strong impacts of land‐use change on soil–atmosphere trace gas exchange can be detected in the NBL, and provides useful observational constraints for top‐down and bottom‐up biogeochemistry models.     

Effect of temperature on gas composition and char structural features of pyrolyzed agricultural residues

The gases and chars produced during fast pyrolysis of maize stalk, rice straw, cotton straw and rice husk at temperatures ranging from 600 to 1000 °C were studied by Fourier transform infrared spectroscopy, non-dispersive infrared technique, thermal conductivity detection method, ultimate analysis, X-ray diffraction, helium density measurement and N₂ adsorption method. The gas yield increased by more than 80% from 600 to 1000 °C, while the char and liquid yield decreased. The content of CO₂, CO and CH₄ accounted for more than 86%. The CO and CH₄ content increased with temperature, while the CO₂ content decreased. The hydroxyl, aliphatic CH, carbonyl, olefinic CC and ether groups were lost above 800 °C. Carbon skeleton shrinkage increased by more than 23% when the temperature increased from 600 to 1000 °C. Maximum porosity appeared at 900 °C. This study revealed the relationships between gas composition/char properties and pyrolysis temperature under high heating rate conditions.     

Organic acid production from CO2/H2 and CO/H2 by mixed-culture anaerobes

The gases CO, CO₂, and H₂ were used as substrates in anaerobic fermentations producing organic acids. Various mixed bacterial sources were used, including sewage sludge digester effluent, rabbit feces, and soil. Nonsterile microorganism selection was carried out using CO₂/H₂ and CO/H₂ as the primary carbon and energy sources. Cultures were grown in specially designed, high-pressure (to 70 psig) flasks. Methanogenic bacteria were eliminated from the cultures. Liquid products of the fermentations were acetic through caproic acids, with the even-numbered acids predominating. Carbon balances showed conclusively that acetic acid was formed from carbon contained in the CO or CO₂ feed gas. Measurements made included rates of acid product formation, cell density, and degree of gas utilization. Limited characterization of the microorganisms was also performed. Production of organic acids by mixed culture inocula from CO₂/H₂ or CO/H₂ had not been reported previously. Application of this work is to the production of organic chemicals from synthesis gas (SNG), produced by the gasification of fossil fuels (peat, lignite, and various ranks of coals), biomass (agricultural and forest residues, and various biomass crops grown expressly for energy recovery), and municipal solid waste.     

Abiotic synthesis of organic molecules from minerals containing traces of dissolved H2O,CO2 and N2 part II: Experimental data

Even though a given mineral, for instance olivine, may contain only traces of dissolved H₂O, CO₂ and N₂ the gases which evolve from its surface during heating comprise (a) highly reduced molecules such as H₂, CH₄, C_mH_n and more complex hydrocarbons, HCN and other N-bearing compounds (b) oxidized species in various degrees of oxidation from formaldehyde and CO to oxygen. These gases evolve sequentially besides H₂O, CO₂ and possibly N₂, their relative amounts being controlled by experimental parameters such as the rate of heating. Preliminary indications of amino acids have been obtained by liquid extraction. The chemical complexity is a consequence of radical reactions between different solute species in the surface and the bulk of the mineral grains. Data for synthetic MgO and for mantle-derived olivine are presented.     

A simple and rapid GC/MS method for the simultaneous determination of gaseous metabolites

We modified and tuned a commercial model of a gas chromatography/mass spectrometry (GC/MS) instrument to develop a simple and rapid method for the simultaneous quantification of a variety of gas species. Using the developed method with the newly modified instrument, gas species such as H₂, N₂, O₂, CO, NO, CH₄, CO₂, and N₂O, which are common components of microbial metabolism, were accurately identified based on their retention times and/or mass-to-charge ratios (m/z) in less than 2.5 min. By examining the sensitivities and dynamic ranges for the detection of H₂, N₂, O₂, CH₄, CO₂, and N₂O, it was demonstrated that the method developed in this study was sufficient for accurately monitoring the production and the consumption of these gaseous species during microbial metabolism. The utility of the new method was demonstrated by a denitrification study with Pseudomonas aureofaciens ATCC 13985^T. This method will be suitable for a variety of applications requiring the identification of gaseous metabolites in microorganisms, microbial communities, and natural ecosystems.     

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.     

Co-pyrolysis of sunflower-oil cake with potassium carbonate and zinc oxide using plasma torch to produce bio-fuels

This study examined the effects of additives of potassium carbonate (K₂CO₃) and zinc oxide (ZnO) on the pyrolysis of waste sunflower-oil cake using a 60 kW pilot-scale plasma torch reactor. The major gaseous products were CO and H₂. The productions of CO and CH₄ increased while that of H₂ decreased with the addition of K₂CO₃. The use of ZnO reduced while enhanced the formation of CO and H₂, respectively. In order to match the appeal of resource reutilization, one can use the waste K₂CO₃ resulted from the sorption of CO₂ with KOH in greenhouse gas control and the waste ZnO obtained from the melting process as additives for the co-pyrolysis of sunflower-oil cake, yielding fuels rich in CO and H₂, respectively.     

温带针阔混交林土壤碳氮气体通量的主控因子与耦合关系

中高纬度森林地区由于气候条件变化剧烈,土壤温室气体排放量的估算存在很大的不确定性,并且不同碳氮气体通量的主控因子与耦合关系尚不明确。以长白山温带针阔混交林为研究对象,采用静态箱-气相色谱法连续4a(2005—2009年)测定土壤二氧化碳(CO2)、甲烷(CH4)和氧化亚氮(N2O)净交换通量以及温度、水分等相关环境因子。研究结果表明:温带针阔混交林土壤整体上表现为CO2和N2O的排放源和CH4的吸收汇。土壤CH4、CO2和N2O通量的年均值分别为-1.3 kg CH4hm-2a-1、15102.2 kg CO2hm-2a-1和6.13 kg N2O hm-2a-1。土壤CO2通量呈现明显的季节性规律,主要受土壤温度的影响,水分次之;土壤CH4通量的季节变化不明显,与土壤水分显著正相关;土壤N2O通量季节变化与土壤CO2通量相似,与土壤水分、温度显著正相关。土壤CO2通量和CH4通量不存在任何类型的耦合关系,与N2O通量也不存在耦合关系;土壤CH4和N2O通量之间表现为消长型耦合关系。这项研究显示温带针阔混交林土壤碳氮气体通量主要受环境因子驱动,不同气体通量产生与消耗之间存在复杂的耦合关系,下一步研究需要深入探讨环境变化对其耦合关系的影响以及内在的生物驱动机制。     

Chlorobium limicola forma thiosulfatophilum: Biocatalyst in the Production of Sulfur and Organic Carbon from a Gas Stream Containing H2S and CO2

Chlorobium limicola forma thiosulfatophilum (ATCC 17092) was grown in a 1-liter continuously stirred tank reactor (800-ml liquid volume) at pH 6.8, 30°C, saturated light intensity, and a gas flow rate of 23.6 ml/min from a gas cylinder blend consisting of 3.9 mol% H₂S, 9.2 mol% CO₂, 86.4 mol% N₂, and 0.5 mol% H₂. This is the first demonstration of photoautotrophic growth of a Chlorobium sp. on a continuous inorganic gas feed. A significant potential exists for applying this photoautotrophic process to desulfurization and CO₂ fixation of gases containing acidic components (H₂S and CO₂).     

CO2 uptake is offset by CH4 and N2O emissions in a poplar short‐rotation coppice

The need for renewable energy sources will lead to a considerable expansion in the planting of dedicated fast‐growing biomass crops across Europe. These are commonly cultivated as short‐rotation coppice (SRC), and currently poplar (Populus spp.) is the most widely planted. In this study, we report the greenhouse gas (GHG) fluxes of carbon dioxide (CO₂), methane (CH₄) and nitrous oxide (N₂O) measured using eddy covariance technique in an SRC plantation for bioenergy production. Measurements were made during the period 2010–2013, that is, during the first two rotations of the SRC. The overall GHG balance of the 4 years of the study was an emission of 1.90 (±1.37) Mg CO₂eq ha^?1; this indicated that soil trace gas emissions offset the CO₂ uptake by the plantation. CH₄ and N₂O contributed almost equally to offset the CO₂ uptake of ?5.28 (±0.67) Mg CO₂eq ha^?1 with an overall emission of 3.56 (±0.35) Mg CO₂eq ha^?1 of N₂O and of 3.53 (±0.85) Mg CO₂eq ha^?1 of CH₄. N₂O emissions mostly occurred during one single peak a few months after the site was converted to SRC; this peak comprised 44% of the total N₂O loss during the two rotations. Accurately capturing emission events proved to be critical for deriving correct estimates of the GHG balance. The nitrogen (N) content of the soil and the water table depth were the two drivers that best explained the variability in N₂O and CH_4, respectively. This study underlines the importance of the ‘non‐CO₂ GHGs’ on the overall balance. Further long‐term investigations of soil trace gas emissions should monitor the N content and the mineralization rate of the soil, as well as the microbial community, as drivers of the trace gas emissions.     

Biomass Pyrolysis in an Argon/Hydrogen Plasma Reactor

This paper presents the experimental results of biomass pyrolysis in a laboratory argon/hydrogen plasma reactor. The samples tested were wood and rice husk. The gaseous product was found to contain mainly H₂, CO, C₂H₂ and CH₄. The conversion of carbon and oxygen from the biomass feed to gaseous product can reach up to 79 % and 72 %, respectively. The results indicate that plasma pyrolysis of biomass may be a useful way for gaseous fuel production.     

Electron availability in CO2, CO and H2 mixtures constrains flux distribution,energy management and product formation in Clostridium ljungdahlii

Acetogens such as Clostridium ljungdahlii can play a crucial role reducing the human CO₂ footprint by converting industrial emissions containing CO₂, CO and H₂ into valuable products such as organic acids or alcohols. The quantitative understanding of cellular metabolism is a prerequisite to exploit the bacterial endowments and to fine-tune the cells by applying metabolic engineering tools. Studying the three gas mixtures CO₂ + H₂, CO and CO + CO₂ + H₂ (syngas) by continuously gassed batch cultivation experiments and applying flux balance analysis, we identified CO as the preferred carbon and electron source for growth and producing alcohols. However, the total yield of moles of carbon (mol-C) per electrons consumed was almost identical in all setups which underlines electron availability as the main factor influencing product formation. The Wood–Ljungdahl pathway (WLP) showed high flexibility by serving as the key NAD⁺ provider for CO₂ + H_2, whereas this function was strongly compensated by the transhydrogenase-like Nfn complex when CO was metabolized. Availability of reduced ferredoxin (Fd_red) can be considered as a key determinant of metabolic control. Oxidation of CO via carbon monoxide dehydrogenase (CODH) is the main route of Fd_red formation when CO is used as substrate, whereas Fd_red is mainly regenerated via the methyl branch of WLP and the Nfn complex utilizing CO₂ + H₂. Consequently, doubled growth rates, highest ATP formation rates and highest amounts of reduced products (ethanol, 2,3-butanediol) were observed when CO was the sole carbon and electron source.     

Real time monitoring of a biogas digester with gas chromatography, near-infrared spectroscopy, and membrane-inlet mass spectrometry

Four methods of monitoring the anaerobic digestion process were studied at pilot scale. The methods employed were Micro Gas Chromatography (μ-GC) and Membrane Inlet Mass Spectrometry (MIMS) for measurements in the gas phase, Near Infrared Spectroscopy (NIRS) and pH in the liquid phase. Micro Gas Chromatography accurately measured H₂, CH₄, H₂S, N₂ and O₂ in the headspace whereas the MIMS accurately measured CH₄, CO₂, H₂S, reduced organic sulfur compounds and p-cresol, also in the headspace. In the liquid phase, NIRS was found to be suitable for estimating the concentrations of acetate, propionate and total volatile fatty acids (VFA) but the error of prediction was too large for accurate quantification. Both the μ-GC and NIRS were low maintenance methods whereas the MIMS required frequent cleaning and background measurements.     

Study on the chemical evolution of low molecular weight compounds in a highly oxidized atmosphere using electric discharges

The molecular basis for the chemical evolution of low molecular compounds was studied using electric discharges on a higly oxidized atmosphere comprised of CO₂, N₂ and H₂O. In the gas phase, O₂ and CO were formed by the decomposition of CO₂ and their yields were enhanced by the addition of N₂ to the gas mixture. It was demonstrated that H₂O suppressed the reduction of CO₂ while H₂O also had a role in producing organic compounds such as formic acid and formaldehyde. Infrared analysis of the water soluble products and the inner surface of the reaction vessel indicated the production of compounds more complex than formic acid and formaldehyde. These compounds contained the chemical bonds which were identified to be OH, CO, CN and/or CC.     

Greenhouse gas emissions from a Cu-contaminated soil remediated by in situ stabilization and phytomanaged by a mixed stand of poplar,willows, and false indigo-bush

Phytomanagement of trace element-contaminated soils can reduce soil toxicity and restore soil ecological functions, including the soil gas exchange with the atmosphere. We studied the emission rate of the greenhouse gases (GHGs) CO₂, CH₄, and N₂O; the potential CH₄ oxidation; denitrification enzyme activity (DEA), and glucose mineralization of a Cu-contaminated soil amended with dolomitic limestone and compost, alone or in combination, after a 2-year phytomanagement with a mixed stand of Populus nigra, Salix viminalis, S. caprea, and Amorpha fruticosa. Soil microbial biomass and microbial community composition after analysis of the phospholipid fatty acids (PLFA) profile were determined. Phytomanagement significantly reduced Cu availability and soil toxicity, increased soil microbial biomass and glucose mineralization capacity, changed the composition of soil microbial communities, and increased the CO₂ and N₂O emission rates and DEA. Despite such increases, microbial communities were evolving toward less GHG emission per unit of microbial biomass than in untreated soils. Overall, the aided phytostabilization option would allow methanotrophic populations to establish in the remediated soils due to decreased soil toxicity and increased nutrient availability.     

Soil-atmosphere exchange of CH4, CO2, NOx,and N2O in the Colorado shortgrass steppe under elevated CO2

In late March 1997, an open-top-chamber (OTC) CO₂ enrichment study was begun in the Colorado shortgrass steppe. The main objectives of the study were to determine the effect of elevated CO₂ (720 mol mol^–1) on plant production, photosynthesis, and water use of this mixed C₃/C₄ plant community, soil nitrogen (N) and carbon (C) cycling and the impact of changes induced by CO₂ on trace gas exchange. From this study, we report here our weekly measurements of CO₂, CH₄, NO_x and N₂O fluxes within control (unchambered), ambient CO₂ and elevated CO₂ OTCs. Soil water and temperature were measured at each flux measurement time from early April 1997, year round, through October 2000. Even though both C₃ and C₄ plant biomass increased under elevated CO₂ and soil moisture content was typically higher than under ambient CO₂ conditions, none of the trace gas fluxes were significantly altered by CO₂ enrichment. Over the 43 month period of observation NO_x and N₂O flux averaged 4.3 and 1.7 in ambient and 4.1 and 1.7 g N m^–2 hr ^–1 in elevated CO₂ OTCs, respectively. NO_x flux was negatively correlated to plant biomass production. Methane oxidation rates averaged –31 and –34 g C m^–2 hr^–1 and ecosystem respiration averaged 43 and 44 mg C m^–2 hr^–1 under ambient and elevated CO₂, respectively, over the same time period.     

Assessing the performance of the photo‐acoustic infrared gas monitor for measuring CO2, N2O,and CH4 fluxes in two major cereal rotations

Rapid, precise, and globally comparable methods for monitoring greenhouse gas (GHG) fluxes are required for accurate GHG inventories from different cropping systems and management practices. Manual gas sampling followed by gas chromatography (GC) is widely used for measuring GHG fluxes in agricultural fields, but is laborious and time‐consuming. The photo‐acoustic infrared gas monitoring system (PAS) with on‐line gas sampling is an attractive option, although it has not been evaluated for measuring GHG fluxes in cereals in general and rice in particular. We compared N₂O, CO_2, and CH₄ fluxes measured by GC and PAS from agricultural fields under the rice–wheat and maize–wheat systems during the wheat (winter), and maize/rice (monsoon) seasons in Haryana, India. All the PAS readings were corrected for baseline drifts over time and PAS‐CH₄ (PCH₄) readings in flooded rice were corrected for water vapor interferences. The PCH₄ readings in ambient air increased by 2.3 ppm for every 1000 mg cm^?3 increase in water vapor. The daily CO₂, N₂O, and CH₄ fluxes measured by GC and PAS from the same chamber were not different in 93–98% of all the measurements made but the PAS exhibited greater precision for estimates of CO₂ and N₂O fluxes in wheat and maize, and lower precision for CH₄ flux in rice, than GC. The seasonal GC‐ and PAS‐N₂O (PN₂O) fluxes in wheat and maize were not different but the PAS‐CO₂ (PCO₂) flux in wheat was 14–39% higher than that of GC. In flooded rice, the seasonal PCH₄ and PN₂O fluxes across N levels were higher than those of GC‐CH₄ and GC‐N₂O fluxes by about 2‐ and 4fold, respectively. The PAS (i) proved to be a suitable alternative to GC for N₂O and CO₂ flux measurements in wheat, and (ii) showed potential for obtaining accurate measurements of CH₄ fluxes in flooded rice after making correction for changes in humidity.     

H2-CO2 Recirculation and pH Control for Growth of Methanogens in Mass Culture

We modified a fermentor (10-liter liquid volume) for the growth of anaerobic, H₂-CO₂-catabolizing bacteria. Gas in the fermentor (ca. 10% CO₂, 50% H₂, 40% CH₄) was recirculated by a diaphragm pump. During growth, the gas composition was maintained by the addition of a mixture of 80% H₂ and 20% CO₂, and this addition was controlled by a pH auxostat. During gas addition, gas was discharged from the recirculating gas stream and was collected by the displacement of an acidified salt solution.