地质封存二氧化碳与深地微生物相互作用研究进展

地质封存将工业和能源相关领域生产活动产生的二氧化碳（CO₂）进行捕集并注入到深部地下岩石构造中,以实现长期储存的目标,是降低温室气体排放、实现CO₂长期封存的重要可行性手段之一。向深部地下地质构造中注入大量CO₂会导致深地环境发生显著变化,进而引起原生微生物活性及群落结构发生明显改变。因此,地质封存CO₂能够直接或间接影响深地微生物驱动的生物地球化学过程。同时,微生物在短期和长期的超临界CO₂（scCO₂）胁迫作用下,也会通过不同的适应性进化方式影响CO₂在地下环境中的迁移、转化和赋存形态。本文介绍了国内外二氧化碳捕获与封存发展现状以及地质封存CO₂影响条件下的scCO₂-水-微生物-矿物的相互作用领域的最新科研进展,并展望了利用深地微生物强化CO₂固定以及将其转化为高附加值产物的潜力。     

Microbial Growth under Supercritical CO2

Growth of microorganisms in environments containing CO₂ above its critical point is unexpected due to a combination of deleterious effects, including cytoplasmic acidification and membrane destabilization. Thus, supercritical CO₂ (scCO₂) is generally regarded as a sterilizing agent. We report isolation of bacteria from three sites targeted for geologic carbon dioxide sequestration (GCS) that are capable of growth in pressurized bioreactors containing scCO₂. Analysis of 16S rRNA genes from scCO₂ enrichment cultures revealed microbial assemblages of varied complexity, including representatives of the genus Bacillus. Propagation of enrichment cultures under scCO₂ headspace led to isolation of six strains corresponding to Bacillus cereus, Bacillus subterraneus, Bacillus amyloliquefaciens, Bacillus safensis, and Bacillus megaterium. Isolates are spore-forming, facultative anaerobes and capable of germination and growth under an scCO₂ headspace. In addition to these isolates, several Bacillus type strains grew under scCO₂, suggesting that this may be a shared feature of spore-forming Bacillus spp. Our results provide direct evidence of microbial activity at the interface between scCO₂ and an aqueous phase. Since microbial activity can influence the key mechanisms for permanent storage of sequestered CO₂ (i.e., structural, residual, solubility, and mineral trapping), our work suggests that during GCS microorganisms may grow and catalyze biological reactions that influence the fate and transport of CO₂ in the deep subsurface.     

2D Assembly of Confined Space toward Enhanced CO2 Electroreduction

Rational design of electrocatalysts toward efficient CO₂ electroreduction has the potential to reduce carbon emission and produce value‐added chemicals. In this work, a strategy of constructing 2D confined‐space as molecular reactors for enhanced electrocatalytic CO₂ reduction selectivity is demonstrated. Highly ordered 2D nanosheet lamella assemblies are achieved via weak molecular interaction of atomically thin titania nanosheets, a variety of cationic surfactants, and SnO₂ nanoparticles. The interlayer spacings can be tuned from 0.9 to 3.0 nm by using different surfactant molecules. These 2D assemblies of confined‐space catalysts exhibit a strong size dependence of CO₂ electroreduction selectivity, with a peak Faradaic efficiency of 73% for formate production and excellent electrochemical stability at an optimal interspacing of ≈2.0 nm. This work suggests great potential for constructing new molecular‐size reactors, for highly selective electrocatalytic CO₂ reduction.     

Effects of modifiers on the supercritical CO<Subscript>2</Subscript> extraction of glycyrrhizin from licorice and the morphology of licorice tissue after extraction

Optimal conditions for the supercritical carbon dioxide (scCO₂) extraction of glycyrrhizin from licorice (Glycyrrhiza glabra) were investigated, with an emphasis on the types and levels of modifiers. The morphology of the licorice tissue remaining after the scCO₂ extraction of glycyrrhizin was examined by scanning electron microscopy, coupled with measurements of absolute density. Conventional organic solvent extraction was also carried out for purpose of quantitative comparison. At 50 MPa and 60°C glycyrrhizin could not be extracted with pure scCO₂, while a considerable amount of glycyrrhizin was extracted when water was added to scCO₂ as a modifier. The highest recovery was found to be about 97% when 70% aqueous methanol was added to scCO₂ at a concentration of 15%. The optimal pressure and temperature for the supercritical fluid extraction of glycyrrhizin were observed to be 30 MPa and 60°C, respectively. Under these conditions, the percentage recovery of glycyrrhizin attained a maximum value of 102.67±1.13% within 60 min. Furthermore, in the case of scCO₂ modified with 70% aqueous methanol, the licorice tissue obtained after extraction was found to be severely degraded by excessive swelling, and the absolute density of the licorice residues was observed to be the highest.     

Molecular Dynamics Simulations of The Swelling of Terephthalate Containing Anionic Clays

Abstract

We report on molecular simulations of the swelling of terephthalate containing anionic clays. We find good agreement with experimentally derived interlayer spacings, and models for the structure and dynamics of the interlayer water. We predict a swelling profile which suggests that at high water content a sharp increase in interlayer spacing will occur. The corresponding swelling curve for methanol incorporation, however, indicates a more continuous expansion.     

On the assessment of root and soil respiration for soils of different textures: interactions with soil moisture contents and soil CO2 concentrations

Estimates of root and soil respiration are becoming increasingly important in agricultural and ecological research, but there is little understanding how soil texture and water content may affect these estimates. We examined the effects of soil texture on (i) estimated rates of root and soil respiration and (ii) soil CO₂ concentrations, during cycles of soil wetting and drying in the citrus rootstock, Volkamer lemon (Citrus volkameriana Tan. and Pasq.). Plants were grown in soil columns filled with three different soil mixtures varying in their sand, silt and clay content. Root and soil respiration rates, soil water content, plant water uptake and soil CO₂ concentrations were measured and dynamic relationships among these variables were developed for each soil texture treatment. We found that although the different soil textures differed in their plant-soil water relations characteristics, plant growth was only slightly affected. Root and soil respiration rates were similar under most soil moisture conditions for soils varying widely in percentages of sand, silt and clay. Only following irrigation did CO₂ efflux from the soil surface vary among soils. That is, efflux of CO₂ from the soil surface was much more restricted after watering (therefore rendering any respiration measurements inaccurate) in finer textured soils than in sandy soils because of reduced porosity in the finer textured soils. Accordingly, CO₂ reached and maintained the highest concentrations in finer textured soils (> 40 mmol CO₂ mol⁻¹). This study revealed that changes in soil moisture can affect interpretations of root and soil measurements based on CO₂ efflux, particularly in fine textured soils. The implications of the present findings for field soil CO₂ flux measurements are discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Interrelationship between water film thicknesses and contact angles and a model for CO2 adhesion

Thermodynamics of contact angle phenomena is strongly affected by the presence of thin liquid films. However, at present, studies for CO₂/brine/mineral systems only consider the films apart from contact angles. In this paper, molecular dynamics (MD) simulations have been performed to simultaneously investigate the interrelationship between water film thicknesses and water contact angles. Two types of contact angles were considered namely Young’s contact angle (no water film is present) and contact angle with film (a stable film is present). The results showed that as Young’s contact angle increased, film thickness decreased which leading to increasing of contact angle with film. The effects of CO₂-mineral pre-contact have also been investigated and it has been found that on mediate hydrophilic surfaces (Q³), water films were present when CO₂ droplets were placed above the surfaces, however, water films were absent when CO₂ droplets directly contact with the surfaces. This phenomenon implies that water films on mineral surfaces have a possibility to rupture and a film rupture mechanism for CO₂ adhesion on hydrated mineral surfaces was proposed. These results may provide new information on interactions among CO₂, water/brine and mineral to better understand the behaviour of CO₂ during geologic sequestration.     

自养微生物同化CO_2的分子生态研究及同化碳在土壤中的转化

大气中CO2浓度持续升高和全球气候变暖是亟待解决的重大环境问题。自养微生物在环境中广泛分布,能直接参与CO2的同化,因此研究自养微生物同化CO2的分子生态学机制具有重大的科学意义。以往对自养微生物的研究多针对基因组DNA,从DNA水平揭示了不同生态系统中碳同化自养微生物的种群结构和多样性,但这些微生物在生态系统中的具体功能有待进一步的研究。近年来,随着转录组学研究技术和稳定同位素探针技术(SIP)的发展,自养微生物同化CO2的生态机理研究不断深入,这些研究明确揭示了碳同化自养微生物是河流、湖泊和海洋生态系统中CO2固定作用的驱动者,并新发现了一些具有CO2同化功能的微生物群落。基于国内外有关研究进展,从DNA和RNA水平上对自养微生物同化CO2的分子机理以及稳定同位素探针技术(SIP)在碳同化微生物研究中的应用进行了分析和总结,初步展望了RNA-SIP技术在陆地生态系统碳同化微生物分子生态学研究中的前景。同时,探讨了陆地生态系统同化碳的转化和稳定性机理,以期为深入了解生态系统碳循环过程和应对气候变化提供理论依据。     

Long-term effects of elevated atmospheric CO2 on below-ground biomass and transformations to soil organic matter in grassland

We determined the effects of elevated [CO₂] on the quantity and quality of below-ground biomass and several soil organic matter pools at the conclusion of an eight-year CO₂ enrichment experiment on native tallgrass prairie. Plots in open-top chambers were exposed continuously to ambient and twice-ambient [CO₂] from early April through late October of each year. Soil was sampled to a depth of 30 cm beneath and next to the crowns of C4 grasses in these plots and in unchambered plots. Elevated [CO₂] increased the standing crops of rhizomes (87%), coarse roots (46%), and fibrous roots (40%) but had no effect on root litter (mostly fine root fragments and sloughed cortex material >500 μm). Soil C and N stocks also increased under elevated [CO₂], with accumulations in the silt/clay fraction over twice that of particulate organic matter (POM; >53 μm). The mostly root-like, light POM (density ≤1.8 Mg m^-3) appeared to turn over more rapidly, while the more amorphous and rendered heavy POM (density >1.8 Mg m^-3) accumulated under elevated [CO₂]. Overall, rhizome and root C:N ratios were not greatly affected by CO₂ enrichment. However, elevated [CO₂] increased the C:N ratios of root litter and POM in the surface 5 cm and induced a small but significant increase in the C:N ratio of the silt/clay fraction to a depth of 15 cm. Our data suggest that 8 years of CO₂ enrichment may have affected elements of the N cycle (including mineralization, immobilization, and asymbiotic fixation) but that any changes in N dynamics were insufficient to prevent significant plant growth responses. This revised version was published online in June 2006 with corrections to the Cover Date.     

Amphiphiles for supercritical CO2

A semi-fluorinated hybrid amphiphile, pentadecafluoro-5-dodecyl (F7H4) sulfate, has been shown to form reversed micelles in dense CO₂; the aggregates evolve to form water-in-CO₂ (w/c) microemulsion droplets on addition of water. Aggregation structures in these w/c phases have been characterised by small-angle neutron scattering (SANS), showing the presence of cylindrical droplets, which change into dispersed lamellar phases at even higher water loadings. Other systems are also introduced, being high internal phase emulsions (HIPEs) with brine, and liquid and supercritical CO₂, stabilized by certain commercially available nonylphenol ethoxylates (Dow Tergitol NP-, and Huntsman Surfonic N- amphiphiles). These dispersions have been characterised by SANS for the first time. Quantitative analyses of the HIPEs SANS profiles show that they behave similarly to hydrocarbon-water emulsion analogues, with regard to total interfacial areas and the effects of amphiphile concentration on the underlying structures. Finally, the advantages and disadvantages of both approaches for controlling the physico-chemical properties of liquid/supercritical CO₂ in potential applications are compared and contrasted. These results highlight the importance of using specially designed CO₂-philic amphiphiles for generating self-assembly structures in dense CO₂.     

The impact of long-term elevated CO2 on C and N retention in stable SOM pools

Elevated atmospheric CO₂ frequently increases plant production and concomitant soil C inputs, which may cause additional soil C sequestration. However, whether the increase in plant production and additional soil C sequestration under elevated CO₂ can be sustained in the long-term is unclear. One approach to study C–N interactions under elevated CO₂ is provided by a theoretical framework that centers on the concept of progressive nitrogen limitation (PNL). The PNL concept hinges on the idea that N becomes less available with time under elevated CO₂. One possible mechanism underlying this reduction in N availability is that N is retained in long-lived soil organic matter (SOM), thereby limiting plant production and the potential for soil C sequestration. The long-term nature of the PNL concept necessitates the testing of mechanisms in field experiments exposed to elevated CO₂ over long periods of time. The impact of elevated CO₂ and ¹⁵N fertilization on L. perenne and T. repens monocultures has been studied in the Swiss FACE experiment for ten consecutive years. We applied a biological fractionation technique using long-term incubations with repetitive leaching to determine how elevated CO₂ affects the accumulation of N and C into more stable SOM pools. Elevated CO₂ significantly stimulated retention of fertilizer-N in the stable pools of the soils covered with L. perenne receiving low and high N fertilization rates by 18 and 22%, respectively, and by 45% in the soils covered by T. repens receiving the low N fertilization rate. However, elevated CO₂ did not significantly increase stable soil C formation. The increase in N retention under elevated CO₂ provides direct evidence that elevated CO₂ increases stable N formation as proposed by the PNL concept. In the Swiss FACE experiment, however, plant production increased under elevated CO₂, indicating that the additional N supply through fertilization prohibited PNL for plant production at this site. Therefore, it remains unresolved why elevated CO₂ did not increase labile and stable C accumulation in these systems.     

Improved Sterilization of Sensitive Biomaterials with Supercritical Carbon Dioxide at Low Temperature

The development of bio-resorbable implant materials is rapidly going on. Sterilization of those materials is inevitable to assure the hygienic requirements for critical medical devices according to the medical device directive (MDD, 93/42/EG). Biopolymer-containing biomaterials are often highly sensitive towards classical sterilization procedures like steam, ethylene oxide treatment or gamma irradiation. Supercritical CO₂ (scCO₂) treatment is a promising strategy for the terminal sterilization of sensitive biomaterials at low temperature. In combination with low amounts of additives scCO₂ treatment effectively inactivates microorganisms including bacterial spores. We established a scCO₂ sterilization procedure under addition of 0.25% water, 0.15% hydrogen peroxide and 0.5% acetic anhydride. The procedure was successfully tested for the inactivation of a wide panel of microorganisms including endospores of different bacterial species, vegetative cells of gram positive and negative bacteria including mycobacteria, fungi including yeast, and bacteriophages. For robust testing of the sterilization effect with regard to later application of implant materials sterilization all microorganisms were embedded in alginate/agarose cylinders that were used as Process Challenge Devices (PCD). These PCD served as surrogate models for bioresorbable 3D scaffolds. Furthermore, the impact of scCO₂ sterilization on mechanical properties of polysaccharide-based hydrogels and collagen-based scaffolds was analyzed. The procedure was shown to be less compromising on mechanical and rheological properties compared to established low-temperature sterilization methods like gamma irradiation and ethylene oxide exposure as well as conventional steam sterilization. Cytocompatibility of alginate gels and scaffolds from mineralized collagen was compared after sterilization with ethylene oxide, gamma irradiation, steam sterilization and scCO₂ treatment. Human mesenchymal stem cell viability and proliferation were not compromised by scCO₂ treatment of these materials and scaffolds. We conclude that scCO₂ sterilization under addition of water, hydrogen peroxide and acetic anhydride is a very effective, gentle, non-cytotoxic and thus a promising alternative sterilization method especially for biomaterials.     

A comparison of field methods for measuring soil carbon dioxide evolution: Experiments and simulation

Three widely used methods for measuring total soil CO₂ evolution are evaluated, including the dynamic CO₂ absorption method, the static CO₂ absorption method and the closed chamber method. The study covers laboratory experiments. numerical experiments with a simulation model and field measurements. The results are used to perform an error analysis. The aim of this error analysis is to indicate the impact of each method on the CO₂ dynamics during the measurement, and to select the most suitable method for frequent field usage.Laboratory experiments and simulation results show that the dynamic CO₂ absorption method has the potential to absorb all CO₂ evolving at the soil surface. The results also prove that the method has only a minor impact on the CO₂ concentration-depth gradient and the CO₂ efflux. The static CO₂ absorption method underestimates the soil CO₂ evolution, because the absorption velocity is too low, due to slow diffusion processes. Measurements with the closed-chamber method are based on an increasing concentration with time under a closed cover. However, the accumulation of gas alters the concentration gradient in the soil profile and thus causes a rapidly decreasing efflux during the measurement. A commonly used mathematical procedure, which corrects for the altered concentration gradient, does not yield the exact surface efflux, because the effect of increasing storage in the soil profile is not incorporated. Field measurements of CO₂ evolution, using the closed-chamber method and the dynamic CO₂ absorption method confirm the trends that have been predicted by the simulation model. The results of this study indicate that the dynamic CO₂ absorption method is accurate. As it is cheap and simple, it is suitable for the study of temporal and spatial dynamics of CO₂ evolution from the soil.     

Canopy CO2 concentrations and Crassulacean acid metabolism in Hoya carnosa in a subtropical rain forest in Taiwan: consideration of CO2 availability and the evolution of CAM in epiphytes

The potential importance of CO₂ derived from host tree respiration at night as a substrate for night time CO₂ uptake during CAM was investigated in the subtropical and tropical epiphytic vine Hoya carnosa in a subtropical rainforest in north-eastern Taiwan. Individuals were examined within the canopies of host trees in open, exposed situations, as well as in dense forests. Although night time CO₂ concentrations were higher near the epiphytic vines at night, relative to those measured during the day, presumably the result of CO₂ added to the canopy air by the host tree, no evidence for substantial use of this CO₂ was found. In particular, stable carbon isotope ratios of H. carnosa were not substantially lower than those of many other CAM plants, as would be expected if host-respired CO₂ were an important source of CO₂ for these CAM epiphytes. Furthermore, laboratory measurements of diel CO₂ exchange revealed a substantial contribution of daytime CO₂ uptake in these vines, which should also result in lower carbon isotope values than those characteristic of a CAM plant lacking daytime CO₂ uptake. Overall, we found that host-respired CO₂ does not contribute substantially to the carbon budget of this epiphytic CAM plant. This finding does not support the hypothesis that CAM may have evolved in tropical epiphytes in response to diel changes in the CO₂ concentrations within the host tree canopy.     

Pulse-modulated photoacoustic measurements reveal strong gas-uptake component at high CO2-concentrations

The effect of high CO₂-concentration on photoacoustic signals from tobacco leaves is studied by means of a recently developed pulse modulation method which provides simultaneous information on photothermal and photobaric components in the millisecond time domain. High CO₂-concentrations are found to induce large gas-uptake signals. Simultaneous measurements of chlorophyll fluorescence suggest that the uptake signals are correlated with energy-dependent fluorescence quenching. Very similar CO₂-concentration dependencies are found in the absence and presence of methylviologen, which is known to catalyze O₂-reduction, and in the presence of glyceraldehyde, which blocks Calvin cycle and photorespiration. It is suggested that the CO₂-enhanced uptake signal is likely to reflect O₂-uptake in the Mehler reaction. However, it is not ruled out that also rapid CO₂-solubilisation or CO₂-binding caused by light-induced stroma alkalisation are involved. Strong uptake is also induced when the CO₂-concentration in the closed photoacoustic chamber increases due to dark-respiration. The consequences of these findings with respect to the interpretation of photoacoustic data (e.g., low-light effect) and to the regulatory role of O₂-dependent electron flow are discussed.     

二氧化碳储存通量对森林生态系统碳收支的影响

涡度相关系统观测高度以下的CO₂储存通量对准确评价森林生态系统与大气间净CO₂交换量（NEE）有着重要的影响.本研究以长白山阔叶红松林为研究对象,利用2003年的涡度相关观测数据以及CO₂浓度廓线数据,分析了CO₂储存通量的变化规律及其对碳收支过程的影响.结果表明：涡度相关观测高度以下的CO₂储存通量具有典型的日变化特征,其最大变化量出现在大气稳定与不稳定层结转换期.利用涡度相关系统观测的单点CO₂浓度变化方法与利用CO₂浓度廓线方法计算的CO₂储存通量差异不显著.忽略CO₂储存通量,在半小时尺度上会造成对夜间和白天的NEE分别低估25%和19%,在日和年尺度上,会对NEE低估10%和25%;忽略CO₂储存通量,会低估Michaelis-Menten光响应方程及Lloyd-Taylor呼吸方程的参数,并且对表观初始量子效率α和参考呼吸R_ref的低估最大;忽略CO₂储存通量,在半小时、日及年尺度上,均会对总光合作用（GPP）和生态系统呼吸（R_e）低估约20%.     

Insights in starch acetylation in sub- and supercritical CO2

An in-depth study on the acetylation of starch with acetic anhydride (Ac₂O) and sodium acetate (NaOAc) as the catalyst in pressurized carbon dioxide (scCO₂) in a broad pressure range (8–25 MPa) and a temperature of 90 °C is provided. Highest degrees of substitution (DS) of 0.29 (1 h reaction time) and 0.62 (24 h reaction time) were found near the critical point of the mixture (15 MPa). The phase behavior of the system CO₂, starch and acetic anhydride (Ac₂O) was studied in a high pressure view cell. The critical points were a clear function of the temperature and increased from the range of 9.4–10 MPa to 14.5–14.8 MPa when going from 50 to 90 °C (Ac₂O mole fraction at the critical point in the range of 0.08–0.09). Acetylation experiments with a range of starch particles sizes showed a clear relation between the DS and the particle size.     

Interactive effects of atmospheric CO2 enrichment,salinity and flooding on growth of C3 (Elymus athericus) and C4 (Spartina anglica) salt marsh species

The growth response of Dutch salt marsh species (C₃ and C₄) to atmospheric CO₂ enrichment was investigated. Tillers of the C₃ speciesElymus athericus were grown in combinations of 380 and 720 11^-1 CO₂ and low (O) and high (300 mM NaCl) soil salinity. CO₂ enrichment increased dry matter production and leaf area development while both parameters were reduced at high salinity. The relative growth response to CO₂ enrichment was higher under saline conditions. Growth increase at elevated CO₂ was higher after 34 than 71 days. A lower response to CO₂ enrichment after 71 days was associated with a decreased specific leaf area (SLA). In two other experiments the effect of CO₂ (380 and 720 11^-1) on growth of the C₄ speciesSpartina anglica was studied. In the first experiment total plant dry weight was reduced by 20% at elevated CO₂. SLA also decreased at high CO₂. The effect of elevated CO₂ was also studied in combination with soil salinity (50 and 400 mM NaCl) and flooding. Again plant weight was reduced (10%) at elevated CO₂, except under the combined treatment high salinity/non-flooded. But these effects were not significant. High salinity reduced total plant weight while flooding had no effect. Causes of the salinity-dependent effect of CO₂ enrichment on growth and consequences of elevated CO₂ for competition between C₃ and C₄ species are discussed.     

Interactive effects of elevated CO2 and temperature on the anatomical characteristics of leaves in eleven species

The anatomical features of leaves in 11 species of plants grown in a temperature gradient and a temperature + CO₂ gradient were studied. The palisade parenchyma thickness, the spongy parenchyma thickness and the total leaf thickness were measured and analyzed to investigate the effects of elevated temperature and CO₂ on the anatomical characteristics of the leaves. Our results show that with the increase of temperature, the leaf thickness of C₄ species increased while the leaf thickness of C₃ species showed no constant changes. With increased CO₂, seven out of nine C₃ species exhibited increased total leaf thickness. In C₄ species, leaf thickness decreased. As for the trend on the multi-grades, the plants exhibited linear or non-linear changes. With the increase of temperature or both temperature and CO₂ for the 11 species investigated, leaf thickness varied greatly in different plants (species) and even in different branches on the same plant. These results demonstrated that the effect of increasing CO₂ and temperature on the anatomical features of the leaves were species-specific. Since plant structures are correlated with plant functions, the changes in leaf anatomical characteristics in elevated temperature and CO₂ may lead to functional differences. Translated from Acta Ecologica Sinica, 2006, 26(2): 326–333 [译自: 生态学报]