Methane retrieval from Atmospheric Infrared Sounder using EOF-based regression algorithm and its validation

This paper presents a rapid regression algorithm for the retrieval of methane(CH4)profile from Atmospheric Infrared Sounder(AIRS)based on empirical orthogonal functions(EOF)and its validation.This algorithm was trained using the simulated radiance from an assemble of atmospheric profiles and can be utilized to derive the CH4profile rapidly with the input of the AIRS cloud-clear radiance.Validation using hundreds of aircraft profiles demonstrates that the root mean square error(RMSE)is about 1.5%in the AIRS sensitive region of359–596 hPa,which is smaller than AIRS-V5 product(except in high latitudes).Comparison with the groundbased solar Fourier transform spectrometry observations showed that the RMSE of the retrieved CH4total column amount is less than 3%.This EOF-based regression method can be easily applied to other thermal infrared sounders for deriving CH4and some other gases,and the derived profiles can be used as the first guess for further physical retrieval.     

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.     

F,Cl原子与臭氧和甲烷反应机理和反应动力学的理论研究

用量子化学从关计算UMP2（full)方法研究F和Cl原子与甲烷分子和臭氧之间的反应机理，优化了反应物、产物、中间体和过渡态的几何构型，在Gaussian-3(G3)和G3MP2水平计算了它们的能量，研究结果表明：F原子与Cl原子一样与臭氧之间有很强的反应活性，而F原子与甲烷分子反应过程中有氢键生成，键能为3.71KJ/MOL，F原子与甲烷分子之间反应活性比与臭氧分子之间反应活性强。F原子易与甲烷分子生成含有氢键的化合物，且很快分解生成化学性质非常稳定的HF，能同F O3反应竞争，而CL原子甲烷分子反应过程中则无氢键生成现象，且在CL原子与臭氧和甲烷之间竞争反应时，CL原子与臭氧之间反应优先，同时我们还对F和CL原子与甲烷分子臭氧之间反应动力学速率常数进行了计算，我们的理论计算结果能合理地解释大气中CL原子是损耗臭氧的主要化学物质，而活性更强的F原子为什么对臭氧损耗较小的原因。     

Detection and classification of atmospheric methane oxidizing bacteria in soil

Well-drained non-agricultural soils mediate the oxidation of methane directly from the atmosphere, contributing 5 to 10% towards the global methane sink. Studies of methane oxidation kinetics in soil infer the activity of two methanotrophic populations: one that is only active at high methane concentrations (low affinity) and another that tolerates atmospheric levels of methane (high affinity). The activity of the latter has not been demonstrated by cultured laboratory strains of methanotrophs, leaving the microbiology of methane oxidation at atmospheric concentrations unclear. Here we describe a new pulse-chase experiment using long-term enrichment with 12CH4 followed by short-term exposure to 13CH4 to isotopically label methanotrophs in a soil from a temperate forest. Analysis of labelled phospholipid fatty acids (PLFAs) provided unambiguous evidence of methane assimilation at true atmospheric concentrations (1.8-3.6 p.p.m.v.). High proportions of 13C-labelled C18 fatty acids and the co-occurrence of a labelled, branched C17 fatty acid indicated that a new methanotroph, similar at the PLFA level to known type II methanotrophs, was the predominant soil micro-organism responsible for atmospheric methane oxidation.     

水稻品种以及施肥措施对稻田甲烷排放的影响

１９９４年４月至１０月，在北京稻田试验田研究了不同水稻品种对甲烷排放的影响以及施肥措施对降低甲烷排放和提高水稻产量的匹配关系。实验表明稻田甲烷排放在品种之间存在着明显差异，实验中品种间甲烷排放通量最大差异可达到五倍。以有机肥混合硫酸铵作底肥并配合不同时间和不同用量的硫酸铵作追肥与仅施混合底肥不施施硫酸铵作追肥的相比较可减少甲烷排放约５８％，水稻产量提高３１．７％。可明显地抑制水稻生长期的甲烷排放高     

矿井抽放煤层气中甲烷的变压吸附提浓

变压吸附(PSA)技术提浓矿井抽放煤层气中的甲烷(CH4)对解决煤层气对环境的污染、得到高效能源和化工原料具有重要意义.为此,介绍了以活性炭作吸附剂,PSA提浓抽放煤层气中CH4的国内外研究和应用状况,系统地从理论和实验上探讨了PSA分离煤层气的热力学关系、动力学过程以及PSA操作参数对浓缩CH4效果的影响,并对存在的问题提出了相应的建议.     

二氧化碳置换甲烷试验中渗透率变化研究

为研究煤层注CO2置换CH4过程中煤样对气体的吸附特性及渗透率变化特征,利用沁水盆地圆柱体原煤试样,在恒定体积应力(36 MPa)及不同注入压力(1~5 MPa)条件下,进行CO2置换CH4试验。结果表明:煤体对CO2的渗透率高于CH4气体;置换试验中,随注入压力的降低,煤体中CO2吸附相浓度逐渐升高,而CH4气体吸附相浓度呈相反变化趋势;在试验压降范围内,煤体对CO2、CH4气体的吸附量分别降低了48.73%、68.04%,煤体解吸CH4能力强于CO2气体。同时,在置换过程中,煤样置换渗透率受有效应力效应、基质收缩效应及滑脱效应等作用影响,其随注入压力的降低呈现先降低再增大的变化关系,且渗透率最低值出现在压力3.25 MPa时;在体积应力36 MPa条件下,注入压力下降后期渗透率相对于初期提高了17.03%。     

基于过渡金属氧化物载氧体的煤矿通风瓦斯处理性能

采用反应管对基于过渡金属氧化物载氧体的煤矿通风瓦斯(VAM)处理性能展开了研究.结果表明,经活化后的三种载氧体均能将CH4完全转化为CO2,其活性顺序为CuO60/γ-Al2 O3>NiO60/γ-Al2 O3>Fe2 O360/γ-Al2 O3;基于CuO60/γ-Al2 O3的CH4转化率随空速的增加而减小,随CuO负载量和床层温度的升高而增大;煤矿通风瓦斯中的CH4浓度越低,CH4转化率达到90%所需的床层温度就越低;对活性物质低分散高负载的CuO60/γ-Al2 O3和活性物质高分散低负载的CuO5.5/γ-Al2 O3两种CuO/γ-Al2 O3系载氧体进行了比较,发现两种载氧体的CH4转化机理均包含有化学链燃烧和催化燃烧两种机理,基于催化燃烧机理的CH4转化率在一定温度下存在极大值,当床层温度高于该极大值温度时,化学链燃烧对CH4转化率的贡献明显大于催化燃烧对CH4转化率的贡献;相同条件下,CuO5.5/γ-Al2 O3的初期活性优于Cu60/γ-Al2 O3,但CuO60/γ-Al2 O3的活性稳定性优于CuO5.5/γ-Al2 O3.     

等离子体催化转化甲烷合成C2烃的研究进展

甲烷是天然气的主要成份,由于其化学性质稳定。因而将甲烷直接转化合成C2烃难度很大。本文论述了利用等离子体活化及等离子体与催化剂协同活化甲烷转化的国内外研究进展。同时对其反应机理进行了讨论,分析了当前利用等离子体活化甲烷所存在的问题。并提出了今后的研究方向。     

甲烷在直流放电等离子体中形成自由基研究

采用发射光谱分析法对直流辉光放电等离子体裂解甲烷所产生的自由基H·(656.3nm),CH3·(724.6nm),CH2·(341.9nm)及CH·(431.42nm)的发射光谱强度进行了在线测量和分析描述.结果表明:在甲烷等离子体空间存在激发态的甲基、亚甲基、次甲基、氢自由基,各自由基的形成规律具有相似性,即其光谱强度都有一个开始时大幅上升,达到峰值后下降或稳定,最后伴有强度的小波动逐渐进入准动态平衡过程,但各自由基的成分比例在放电的不同时间是不同的,且随放电条件而异;各自由基的形成规律受进料量(气压)的影响是不同的.     

D to H ratio and the origin and evolution of Titan's atmosphere

A value of 1.7 x 10(-3) has been reported for the ratio of CH3D to CH4 in the stratosphere of the saturnian moon Titan. A lower value of 6 x 10(-4) for this ratio in the deeper part of Titan's atmosphere was reported by de Bergh et al. For comparison we note that the CH3D to CH4 ratio on Saturn and Jupiter is 8.7 x 10(-5) and 6.7 x 10(-5), respectively. We estimate the uncertainties in all these observations and data reduction to be about a factor of 2. Despite these uncertainties it appears that Titan's atmosphere is enriched in deuterium by a factor of > or = 3 relative to Jupiter and Saturn. Potential causative factors examined here for this enrichment are condensation to form tropospheric methane clouds, fractionation occurring over a hypothetical CH4-C2H6 ocean and between the ocean and the clathrate crust beneath, fractionation which occurred during the formation of Titan and fractionation occurring as a result of the evolution of Titan's atmosphere. We conclude that the greater part of the observed fractionation is probably derived from the formation of Titan and the subsequent evolution of Titan's atmosphere driven by photochemistry.     

CH4、CO2与O2制合成气的研究(V)--催化剂床层的热波分布

采用微型固定床反应装置,研究了甲烷、二氧化碳和氧气制氧化重整合成气时Ni-Ce-Cu-Li／Al2O3催化剂床层的热波分布,考察了炉温和进料配比对催化剂床层热波分布的影响．研究结果表明：在甲烷、二氧化碳和氧气的氧化重整反应中,催化剂床层存在明显的热波现象;在相同的炉温下,甲烷部分氧化反应的热波强度最大,甲烷、二氧化碳和氧气的氧化重整反应次之;甲烷、二氧化碳的重整反应没有热波现象．热波现象进一步印证了甲烷、二氧化碳和氧气制氧化重整合成气的反应遵从燃烧-重整的反应机理．     

玉米芯活性炭的制备及储气性能

天然气、氢气、二氧化碳等气体的吸附研究在洁净气体代油燃料的强化存储、温室气体减排、大气治理等方面具有重要意义,其重点内容是高效吸附材料的开发．以玉米芯为原料,采用磷酸活化法制备了含有较高中孔比例的活性炭,其比表面积达到1,610,m2/g,孔容为1.72,cm3/g,中孔体积达到1.14,cm3/g,占孔容的66％．测定了H2、N2、CH4和 CO2在该吸附剂上的吸附等温线．在0.4,MPa 时,CO2对 CH4的选择性达到2.76,对 N2的选择性达到7.63,对 H2的选择性达到42.31,具有良好的分离应用前景．测定了水存在条件下甲烷在该活性炭上的吸附等温线,由于孔尺寸有利于甲烷水合物的生成,因此甲烷吸入量较在干燥吸附剂上提高了82％．根据克劳修斯-克拉佩龙方程计算了甲烷水合物的生成焓为-64.37,kJ/mol．     

人工免疫分类器多类问题研究

AIRS是一种基于资源有限人工免疫原理的分类器，已经在许多标准数据集合上与其他传统性能较好的分类器进行了比较．但这些测试问题涉及的数据类别比较少，一般仅是2类问题．对AIRS在多类问题上的性能进行研究，与传统的分类器Kohonens LVQ在仿真和实际数据集合卜进行了比较，结果表明，AIRS在多类问题上具有良好的性能．     

不可采煤层CO2封存的数值模拟

将CO2注入不可采煤层进行封存(CO2-ECBM)能在封存CO2的同时回收甲烷,因而是一项具有良好前景的CO2处置技术。CO2或者CO2/N2混合气注入煤层后在煤层中运移涉及到多组分气体在煤中的吸附、多组分气体以及气、水两相在煤层中的扩散渗流等过程。基于上述过程,建立了考虑煤基质吸附气体后的膨胀效应、能够描述多组分气体在煤层中吸附/解吸扩散渗流过程的数学模型,并采用数值解法对模型进行了求解,与已有的模拟结果比较表明建立的模型是可靠的;利用该模型研究了煤层渗透率、不同气体差异性吸附膨胀系数、煤对CO2/CH4的吸附比、以及注入气体组成对于CO2封存以及煤层气生产的影响,研究结果可以为CO2-ECBM项目的场地条件选择以及工艺参数的优化提供依据。     

电磁辐射作用下煤中自由基影响瓦斯突出的研究

目前煤与瓦斯突出灾害仍时有发生,非常严重。本文着重从突出煤的微观分子结构方面寻找瓦斯的来源。理论分析化学变化和粒子相互作用在煤与瓦斯突出过程中的影响,并建立一套电磁辐射实验方案力求通过实验研究含瓦斯煤岩在电磁辐射作用下其物质粒子移动或相互作用,研究煤的大分子结构中部分烷基(CH3-、CH2=CH-)和氢(H-)发生断裂和结合生成新的甲烷或瓦斯的可能性,创新煤层瓦斯灾害防治基础理论。     

用从头计算研究煤表面与甲烷分子相互作用

依据所提出的煤表面原子簇模型,量子化学从头计算（ＳＴＯ－４－３１Ｇ）表明甲烷分子与煤表面相互作用是各向异性的,最大作用势（吸附势）为２．６５ＫＪ／ｍｏｌ,旋转势垒为１．３４ＫＪ／ｍｏｌ。结果表明甲烷在煤粒表面上的吸附属物理过程（表面凝聚）。     

N_2/CO_2/H_2O抑制甲烷燃烧数值分析

建立了CH4-O2预混气体等容绝热燃烧、爆炸的零维数学模型,并以此为基础对惰性气体抑制CH4点火、燃烧和爆炸的微观化学动力学过程进行数值模拟.数值计算结果表明,N2,CO2和H2O的加入,大大延长了CH4-O2预混气体的点火延迟时间,同时降低了燃烧反应系统温度.N2,CO2和H2O能有效抑制CH4点火、燃烧和爆炸,一方面源于CH4和O2在混合气体中的摩尔浓度被降低,致使离解出的H,O,OH和CH3自由基减少;另一方面则源于N2,CO2和H2O作为第三体稳定分子参与三元碰撞反应,使高活性的自由基转变成了低活性的稳定分子.相同条件下,CO2和H2O除了重点参与三元碰撞反应外,还不同程度地参与其他链式反应,而N2则是完全不参与其他链式反应.这就导致N2,CO2和H2O的抑燃、抑爆的能力和效果存在差异.     

Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H2

Molecular hydrogen (H2) is the second most abundant trace gas in the atmosphere after methane (CH4). In the troposphere, the D/H ratio of H2 is enriched by 120 per thousand relative to the world's oceans. This cannot be explained by the sources of H2 for which the D/H ratio has been measured to date (for example, fossil fuels and biomass burning). But the isotopic composition of H2 from its single largest source--the photochemical oxidation of methane--has yet to be determined. Here we show that the D/H ratio of stratospheric H2 develops enrichments greater than 440 per thousand, the most extreme D/H enrichment observed in a terrestrial material. We estimate the D/H ratio of H2 produced from CH4 in the stratosphere, where production is isolated from the influences of non-photochemical sources and sinks, showing that the chain of reactions producing H2 from CH4 concentrates D in the product H2. This enrichment, which we estimate is similar on a global average in the troposphere, contributes substantially to the D/H ratio of tropospheric H2.     

微波ECR等离子体化学汽相沉积金刚石膜的研究

本文利用微波电子回旋共振（ＥＣＲ）等离子体化学气相沉积（ＣＶＤ）法在较低气压下进行了金刚膜的沉积工艺研究，发现ＣＨ４气体的浓度可适当提高至ＣＨ４／Ｈ２＝０．８。所得的Ｒａｍａｎ谱图证实在该条件下得到的膜比在ＣＨ４／Ｈ２较小情况下得到的膜含有更多的金刚石相。