Increased soil emissions of potent greenhouse gases under increased atmospheric CO2

Increasing concentrations of atmospheric carbon dioxide (CO(2)) can affect biotic and abiotic conditions in soil, such as microbial activity and water content. In turn, these changes might be expected to alter the production and consumption of the important greenhouse gases nitrous oxide (N(2)O) and methane (CH(4)) (refs 2, 3). However, studies on fluxes of N(2)O and CH(4) from soil under increased atmospheric CO(2) have not been quantitatively synthesized. Here we show, using meta-analysis, that increased CO(2) (ranging from 463 to 780 parts per million by volume) stimulates both N(2)O emissions from upland soils and CH(4) emissions from rice paddies and natural wetlands. Because enhanced greenhouse-gas emissions add to the radiative forcing of terrestrial ecosystems, these emissions are expected to negate at least 16.6 per cent of the climate change mitigation potential previously predicted from an increase in the terrestrial carbon sink under increased atmospheric CO(2) concentrations. Our results therefore suggest that the capacity of land ecosystems to slow climate warming has been overestimated.     

Orbital and millennial-scale features of atmospheric CH4 over the past 800,000 years

Atmospheric methane is an important greenhouse gas and a sensitive indicator of climate change and millennial-scale temperature variability. Its concentrations over the past 650,000 years have varied between approximately 350 and approximately 800 parts per 10(9) by volume (p.p.b.v.) during glacial and interglacial periods, respectively. In comparison, present-day methane levels of approximately 1,770 p.p.b.v. have been reported. Insights into the external forcing factors and internal feedbacks controlling atmospheric methane are essential for predicting the methane budget in a warmer world. Here we present a detailed atmospheric methane record from the EPICA Dome C ice core that extends the history of this greenhouse gas to 800,000 yr before present. The average time resolution of the new data is approximately 380 yr and permits the identification of orbital and millennial-scale features. Spectral analyses indicate that the long-term variability in atmospheric methane levels is dominated by approximately 100,000 yr glacial-interglacial cycles up to approximately 400,000 yr ago with an increasing contribution of the precessional component during the four more recent climatic cycles. We suggest that changes in the strength of tropical methane sources and sinks (wetlands, atmospheric oxidation), possibly influenced by changes in monsoon systems and the position of the intertropical convergence zone, controlled the atmospheric methane budget, with an additional source input during major terminations as the retreat of the northern ice sheet allowed higher methane emissions from extending periglacial wetlands. Millennial-scale changes in methane levels identified in our record as being associated with Antarctic isotope maxima events are indicative of ubiquitous millennial-scale temperature variability during the past eight glacial cycles.     

Spatiotemporal variations in mid-upper tropospheric methane over China from satellite observations

Spaceborne measurements by the Atmospheric Infrared Sounder (AIRS) on the EOS/Aqua satellite provide a global view of methane (CH 4 ) distribution in the mid-upper troposphere (MUT-CH 4 ). The focus of this study is to analyze the spatiotemporal varia- tions in MUT-CH 4 over China from 2003 to 2008. Validation of AIRS CH 4 products versus Fourier transform infrared profiles demonstrates that its RMS error is mostly less than 1.5%. A typical atmospheric methane profile is found that shows how concentrations decrease as height increases because of surface emissions. We found that an important feature in the seasonal variation in CH 4 is the two peaks that exist in summer and winter in most parts of China, which is also observed in in-situ measurements at Mt. Waliguan, Qinghai Province, China (36.2879°N 100.8964°E, 3810 m). Also, in the summer, only one peak existed in western and southern China since there are no more significant anthropogenic sources in winter than at any other time of the year. Further analysis of the deseasonalized time-series of AIRS CH 4 in three fixed pressure layers of AIRS from 2003 to 2008 indicates that CH 4 in the Northern Hemisphere has increased abruptly since 2007, with no significant increase occurring before 2007. The increase in China is generally more significant than in other areas around the world, which again correlates with in-situ measurements at Mt. Waliguan.     

Methane oxidation by an extremely acidophilic bacterium of the phylum Verrucomicrobia

Aerobic methanotrophic bacteria consume methane as it diffuses away from methanogenic zones of soil and sediment. They act as a biofilter to reduce methane emissions to the atmosphere, and they are therefore targets in strategies to combat global climate change. No cultured methanotroph grows optimally below pH 5, but some environments with active methane cycles are very acidic. Here we describe an extremely acidophilic methanotroph that grows optimally at pH 2.0-2.5. Unlike the known methanotrophs, it does not belong to the phylum Proteobacteria but rather to the Verrucomicrobia, a widespread and diverse bacterial phylum that primarily comprises uncultivated species with unknown genotypes. Analysis of its draft genome detected genes encoding particulate methane monooxygenase that were homologous to genes found in methanotrophic proteobacteria. However, known genetic modules for methanol and formaldehyde oxidation were incomplete or missing, suggesting that the bacterium uses some novel methylotrophic pathways. Phylogenetic analysis of its three pmoA genes (encoding a subunit of particulate methane monooxygenase) placed them into a distinct cluster from proteobacterial homologues. This indicates an ancient divergence of Verrucomicrobia and Proteobacteria methanotrophs rather than a recent horizontal gene transfer of methanotrophic ability. The findings show that methanotrophy in the Bacteria is more taxonomically, ecologically and genetically diverse than previously thought, and that previous studies have failed to assess the full diversity of methanotrophs in acidic environments.     

Reduced methane growth rate explained by decreased Northern Hemisphere microbial sources

Atmospheric methane (CH(4)) increased through much of the twentieth century, but this trend gradually weakened until a stable state was temporarily reached around the turn of the millennium, after which levels increased once more. The reasons for the slowdown are incompletely understood, with past work identifying changes in fossil fuel, wetland and agricultural sources and hydroxyl (OH) sinks as important causal factors. Here we show that the late-twentieth-century changes in the CH(4) growth rates are best explained by reduced microbial sources in the Northern Hemisphere. Our results, based on synchronous time series of atmospheric CH(4) mixing and (13)C/(12)C ratios and a two-box atmospheric model, indicate that the evolution of the mixing ratio requires no significant change in Southern Hemisphere sources between 1984 and 2005. Observed changes in the interhemispheric difference of (13)C effectively exclude reduced fossil fuel emissions as the primary cause of the slowdown. The (13)C observations are consistent with long-term reductions in agricultural emissions or another microbial source within the Northern Hemisphere. Approximately half (51?±?18%) of the decrease in Northern Hemisphere CH(4) emissions can be explained by reduced emissions from rice agriculture in Asia over the past three decades associated with increases in fertilizer application and reductions in water use.     

Geochemistry: biosignatures and abiotic constraints on early life

Ueno et al. contend that methane found in fluid inclusions within hydrothermally precipitated quartz in the Dresser Formation of western Australia (which is roughly 3.5 Gyr old) provides evidence for microbial methanogenesis in the early Archaean era. The authors discount alternative origins for this methane, suggesting that the range of delta(13)C(CH(4)) values that they record (-56 to -36 per thousand) is attributable to mixing between a primary microbial end-member with a delta(13)C(CH(4)) value of less than -56 per thousand and a mature thermogenic gas enriched in (13)C (about -36 per thousand). However, abiotic methane produced experimentally and in other Precambrian greenstone settings has (13)C-depleted delta(13)C(CH(4)) values, as well as Delta(13)C(CO(2)-CH(4)) relationships that encompass the range measured for the inclusions by Ueno et al. - which suggests that an alternative, abiotic origin for the methane is equally plausible. The conclusions of Ueno et al. about the timing of the onset of microbial methanogenesis might not therefore be justified.     

Triassic-Jurassic atmospheric CO2 spike.

I question the claim by Tanner et al. that atmospheric CO2 levels remained constant across the Triassic-Jurassic boundary on the grounds of problems with stratigraphic completeness and contamination with atmospheric methane. Because methanogenic CH4 has a light isotope composition and oxidizes readily to CO2, methane-clathrate dissociation and oxidation events cannot be detected by palaeobarometers that use the carbon-isotope composition of palaeosol carbonate.     

Fatty-acids and their <Emphasis Type="Italic">δ</Emphasis><Superscript>13</Superscript>C characteristics of seep carbonates from the northern continental slope of Gulf of Mexico

Here we reported the fatty-acids and their δ¹³C values in seep carbonates collected from Green Canyon lease block 185 (GC 185; Sample GC-F) at upper continental slope (water depth: ~540 m), and Alaminos Canyon lease block 645 (GC 645; Sample AC-E) at lower continental slope (water depth: ~2200 m) of the Gulf of Mexico. More than thirty kinds of fatty acids were detected in both samples. These fatty acids are maximized at C₁₆. There is a clear even-over-odd carbon number predominance in carbon number range. The fatty acids are mainly composed of n-fatty acids, iso-/anteiso-fatty acids and terminally branched odd-numbered fatty acids (iso/anteiso). The low δ¹³C values (−39.99‰ to −32.36‰) of n-C₁₂:0, n-C₁₃:0, i-C₁₄:0 and n-C₁₄:0 suggest that they may relate to the chemosynthetic communities at seep sites. The unsaturated fatty acids n-C_18:2 and C_18:1△⁹ have the same δ¹³C values, they may originate from the Beggiatoa/Thioploca. Unlike other fatty acids, the terminally branched fatty acids (iso/anteiso) show lower δ¹³C values (as low as −63.95‰) suggesting a possible relationship to sulfate reducing bacteria, which is common during anaerobic oxidation of methane at seep sites.     

土壤因素对填埋场终场覆盖层甲烷氧化的影响

以填埋场三种不同性质的终场覆土为对象,考察了其各自的甲烷氧化速率,并采用其中氧化速率最大的土壤进行柱培养,进而通过对出柱土样进行含水率与氨氮投加量的双因素正交实验,考察它们对土壤甲烷氧化能力的影响.实验结果表明：不同土壤的甲烷氧化能力存在显著差异,这与土壤的理化性质及其覆盖龄有关;氨氮的投加对甲烷氧化的抑制作用并不明显;低含水率（5%）下土壤的甲烷氧化几乎停止,而甲烷氧化最适含水率为15%;含水率相对氨氮而言,是影响填埋场覆土甲烷氧化的主要因素.     

Methanotrophy below pH 1 by a new Verrucomicrobia species

Mud volcanoes, mudpots and fumaroles are remarkable geological features characterized by the emission of gas, water and/or semi-liquid mud matrices with significant methane fluxes to the atmosphere (10(-1) to 10(3) t y(-1)). Environmental conditions in these areas vary from ambient temperature and neutral pH to high temperatures and low pH. Although there are strong indications for biological methane consumption in mud volcanoes, no methanotrophic bacteria are known that would thrive in the hostile conditions of fumaroles (temperatures up to 70 degrees C and pH down to 1.8). The first step in aerobic methane oxidation is performed by a soluble or membrane-bound methane mono-oxygenase. Here we report that pmoA (encoding the beta-subunit of membrane-bound methane mono-oxygenase) clone libraries, made by using DNA extracted from the Solfatara volcano mudpot and surrounding bare soil near the fumaroles, showed clusters of novel and distant pmoA genes. After methanotrophic enrichment at 50 degrees C and pH 2.0 the most distant cluster, sharing less than 50% identity with any other described pmoA gene, was represented in the culture. Finally we isolated an acidiphilic methanotrophic bacterium Acidimethylosilex fumarolicum SolV belonging to the Planctomycetes/Verrucomicrobia/Chlamydiae superphylum, 'outside' the subphyla of the Alpha- and Gammaproteobacteria containing the established methanotrophs. This bacterium grows under oxygen limitation on methane as the sole source of energy, down to pH 0.8--far below the pH optimum of any previously described methanotroph. A. fumarolicum SolV has three different pmoA genes, with two that are very similar to sequences retrieved from the mudpot. Highly homologous environmental 16S rRNA gene sequences from Yellowstone Park show that this new type of methanotrophic bacteria may be a common inhabitant of extreme environments. This is the first time that a representative of the widely distributed Verrucomicrobia phylum, of which most members remain uncultivated, is coupled to a geochemically relevant reaction.     

Novel microbial communities of the Haakon Mosby mud volcano and their role as a methane sink

Mud volcanism is an important natural source of the greenhouse gas methane to the hydrosphere and atmosphere. Recent investigations show that the number of active submarine mud volcanoes might be much higher than anticipated (for example, see refs 3-5), and that gas emitted from deep-sea seeps might reach the upper mixed ocean. Unfortunately, global methane emission from active submarine mud volcanoes cannot be quantified because their number and gas release are unknown. It is also unclear how efficiently methane-oxidizing microorganisms remove methane. Here we investigate the methane-emitting Haakon Mosby Mud Volcano (HMMV, Barents Sea, 72 degrees N, 14 degrees 44' E; 1,250 m water depth) to provide quantitative estimates of the in situ composition, distribution and activity of methanotrophs in relation to gas emission. The HMMV hosts three key communities: aerobic methanotrophic bacteria (Methylococcales), anaerobic methanotrophic archaea (ANME-2) thriving below siboglinid tubeworms, and a previously undescribed clade of archaea (ANME-3) associated with bacterial mats. We found that the upward flow of sulphate- and oxygen-free mud volcano fluids restricts the availability of these electron acceptors for methane oxidation, and hence the habitat range of methanotrophs. This mechanism limits the capacity of the microbial methane filter at active marine mud volcanoes to <40% of the total flux.     

一株噬甲烷菌的分离鉴定及其消除煤矿瓦斯能力的初步研究

借鉴滚管法,从煤矿矿井及甲烷处理水稻田土壤中分离纯化,获得一株可在以甲烷为唯一碳源的培养基上正常生长且具有较高甲烷氧化活性的噬甲烷细菌,暂命名为ZD4,经对该菌进行形态观察、Biolog生理生化分析、G Cmol%含量分析和16SrDNA序列同源性比较,鉴定该菌为甲烷甲基单胞菌(Methylomonas capsulatus),并对ZD4菌株进行了生长量、对甲烷消除作用的分析。试验结果表明,该菌株可以使甲烷含量在一周内比初始甲烷浓度降低85%以上。利用其良好的甲烷消除能力,用于煤矿瓦斯治理是可行的。     

甲烷氧化偶联催化剂和部分氧化反应机理的原位及非原位谱学表征

采用原痊红外和原位显微Raman光谱技术及XPS、吡啶（Py)吸附的漫反射UV谱、Py-TPD、CO2-TPD等方法对含氟稀土基催化剂上甲烷氧化偶联（OCM）反应活性氧物种、催化剂表面酸碱性进行了考察。在O2预处理和/或工作条件下的SrF2/La2O3,SrF2/Nd2O3,LaOF,BaF2/LaOF和BaF2/CeO2等催化剂上原位观测到超氧物种（O2^-),并在其中前4种催化剂上检测到O2^-物种与CH4反应生成的气相C2H4,CO2和表面碳酸盐等OCM反应主、副产物。这些结果为O2^-是相应催化剂上OCM反应的活性氧物种首次提供了直接的光谱证据。研究结果表明,催化剂的OCM反应性能与其表面酸碱性的强弱并无简单的对应关系。采用原拉时间分辨红外光谱和原位显微Raman光谱技术对SiO2和γ-Al2O3负载的Rh、Ru催化剂上甲烷部分氧化（POM）制合成气反应的研究表明,由CH4直接氧化生成CO和H2是Rh/SiO2上POM反应的主要途径,而燃烧-重整机理是Ru/γ-Al2O3和Ru/SiO2上CO和H2生成的主要途径,反应条件下催化剂表面氧（O^2-)物种浓度的差异很可能是导致这两种催化剂体系上POM反应机理不同的主要原因,其本质可能源于Rh和Ru对氧的亲合力的不同。     

Methanotrophic symbionts provide carbon for photosynthesis in peat bogs

Wetlands are the largest natural source of atmospheric methane, the second most important greenhouse gas. Methane flux to the atmosphere depends strongly on the climate; however, by far the largest part of the methane formed in wetland ecosystems is recycled and does not reach the atmosphere. The biogeochemical controls on the efficient oxidation of methane are still poorly understood. Here we show that submerged Sphagnum mosses, the dominant plants in some of these habitats, consume methane through symbiosis with partly endophytic methanotrophic bacteria, leading to highly effective in situ methane recycling. Molecular probes revealed the presence of the bacteria in the hyaline cells of the plant and on stem leaves. Incubation with (13)C-methane showed rapid in situ oxidation by these bacteria to carbon dioxide, which was subsequently fixed by Sphagnum, as shown by incorporation of (13)C-methane into plant sterols. In this way, methane acts as a significant (10-15%) carbon source for Sphagnum. The symbiosis explains both the efficient recycling of methane and the high organic carbon burial in these wetland ecosystems.     

Catalytic combustion properties of nanocomplex oxide for natural gas

The catalysts of copper oxide supported on cerium dioxide were prepared by different methods for methane catalytic combustion. The effects of copper content in the catalysts and calcination temperatures of the catalysts on the catalytic activity are investigated. Results show that the complex oxide catalyst exhibits high catalytic activity for methane combustion due to the synergistic effect of CuO and CeO₂. The catalyst prepared by impregnation is more active than that prepared by controlled coprecipitation even if CuO content is the same. When W(CuO)<13%, the light-off temperature and full conversion temperature for the CH₄ reaction decrease with the increasing of CuO content in the catalysts. However, when the copper content is above 13%, the excess CuO has a negative effect on the catalytic activity owing to the formation of bulk CuO particles. A proper calcinations temperature of 650 ℃ can lead to a high dispersion of CuO and accordingly can enhance the catalytic activity of the composites.     

森林土壤温室气体通量对森林管理和全球大气变化的响应

森林土壤是温室气体重要的源和汇。探讨不同森林管理和全球大气变化下土壤温室气体通量特征,为有效减少温室气体排放及森林可持续管理等提供参考。笔者从森林土壤温室气体(forest soil green house gases)、森林管理(forest mangement)和全球大气变化(global atmospheric change)3个关键研究点,查阅近年来相关研究成果,归纳森林管理和全球大气变化下土壤温室气体通量的一般性模式。CO₂、CH₄和N₂O是3种重要温室气体,其通量间存在协同、消长和随机型耦合关系。森林管理如火烧、采伐和造林等显著影响土壤温室气体通量。一般情况下,火烧导致土壤N₂O通量降低,CH₄吸收量增加,CO₂通量因火烧类型、火烧强度、生态系统类型不同出现增加、减低和无影响3种结果; 采伐通常导致土壤CO₂、CH₄和N₂O排放增加; 造林可使土壤CO₂排放减少,对N₂O和CH₄通量的影响随生态系统类型、造林树种等而改变。全球大气变化如CO₂浓度升高、氮沉降和气温升高影响森林土壤温室气体通量。通常,CO₂浓度升高导致土壤CO₂和N₂O排放量增加,CH₄吸收量降低; 氮沉降促进土壤N₂O排放、抑制CH₄吸收。气温升高导致土壤CO₂和N₂O排放增加。森林管理和全球大气变化对土壤温室气体通量的综合影响是非叠加的,有效的森林管理可能改变土壤温室气体通量对全球大气变化的响应。     

A hydrothermal origin for isotopically anomalous cap dolostone cements from south China

The release of methane into the atmosphere through destabilization of clathrates is a positive feedback mechanism capable of amplifying global warming trends that may have operated several times in the geological past. Such methane release is a hypothesized cause or amplifier for one of the most drastic global warming events in Earth history, the end of the Marinoan 'snowball Earth' ice age, ～635?Myr ago. A key piece of evidence supporting this hypothesis is the occurrence of exceptionally depleted carbon isotope signatures (δ(13)C(PDB) down to -48‰; ref. 8) in post-glacial cap dolostones (that is, dolostone overlying glacial deposits) from south China; these signatures have been interpreted as products of methane oxidation at the time of deposition. Here we show, on the basis of carbonate clumped isotope thermometry, (87)Sr/(86)Sr isotope ratios, trace element content and clay mineral evidence, that carbonates bearing the (13)C-depleted signatures crystallized more than 1.6?Myr after deposition of the cap dolostone. Our results indicate that highly (13)C-depleted carbonate cements grew from hydrothermal fluids and suggest that their carbon isotope signatures are a consequence of thermogenic methane oxidation at depth. This finding not only negates carbon isotope evidence for methane release during Marinoan deglaciation in south China, but also eliminates the only known occurrence of a Precambrian sedimentary carbonate with highly (13)C-depleted signatures related to methane oxidation in a seep environment. We propose that the capacity to form highly (13)C-depleted seep carbonates, through biogenic anaeorobic oxidation of methane using sulphate, was limited in the Precambrian period by low sulphate concentrations in sea water. As a consequence, although clathrate destabilization may or may not have had a role in the exit from the 'snowball' state, it would not have left extreme carbon isotope signals in cap dolostones.     

CH4/O2/CO2层流预混火焰传播速度实验研究

采用本生灯法,测量了CH4/O2/CO2混合气在不同工况下的层流预混火焰传播速度.采用基于火焰图像的全面积法计算本生灯火焰的传播速度.主要研究了化学当量比(08~12)、氧气体积分数(25%~35%)和稀释剂种类(N2,CO2)对火焰传播速度的影响规律.结果表明:当化学当量比为1时火焰传播的速度达到最大值,在其两侧火焰传播速度逐渐下降;火焰传播速度随着氧气体积分数的增加而增加,且火焰传播速度与氧气体积分数呈二次函数关系;与N2相比,高浓度CO2降低了火焰传播速度,CH4在O2/CO2气氛下的火焰传播速度约为O2/N2气氛下的五分之一.     

Recent decreases in fossil-fuel emissions of ethane and methane derived from firn air

Methane and ethane are the most abundant hydrocarbons in the atmosphere and they affect both atmospheric chemistry and climate. Both gases are emitted from fossil fuels and biomass burning, whereas methane (CH(4)) alone has large sources from wetlands, agriculture, landfills and waste water. Here we use measurements in firn (perennial snowpack) air from Greenland and Antarctica to reconstruct the atmospheric variability of ethane (C(2)H(6)) during the twentieth century. Ethane levels rose from early in the century until the 1980s, when the trend reversed, with a period of decline over the next 20?years. We find that this variability was primarily driven by changes in ethane emissions from fossil fuels; these emissions peaked in the 1960s and 1970s at 14-16 teragrams per year (1?Tg = 10(12)?g) and dropped to 8-10?Tg yr(-1) by the turn of the century. The reduction in fossil-fuel sources is probably related to changes in light hydrocarbon emissions associated with petroleum production and use. The ethane-based fossil-fuel emission history is strikingly different from bottom-up estimates of methane emissions from fossil-fuel use, and implies that the fossil-fuel source of methane started to decline in the 1980s and probably caused the late twentieth century slow-down in the growth rate of atmospheric methane.     

双（二苯氧膦）甲烷的卤代和烃基化合物合成

本文报导将双(二苯基)甲烷(1)溴化水解制备双(二苯氧膦)甲烷(2),利用3的自由基反应合成相应的溴代物(4)和氯代物(5),利用3的阴离子反应合成相应的碘代物(6)和烯丙基化合物(8)(新化合物)及苄基化物(9),并对这些化合物的~(31)p和~(13)C核磁共振谱数据作了报导。