Amino-acid synthesis in carbonaceous meteorites by aqueous alteration of polycyclic aromatic hydrocarbons

It has been suggested that amino acids and other organic compounds found in carbonaceous meteorites formed by aqueous alteration in the meteorite parent bodies. Observations of carbonaceous material in interstellar grains and interplanetary dust particles indicate that condensed organic compounds may have been present in meteorite parent bodies at the time of aqueous alteration. One group of compounds thought to be representative of this carbonaceous material is the polycyclic aromatic hydrocarbons (PAHs). Recently it was proposed that PAHs condense on SiC grains in the molecular envelopes of carbon-rich red-giant stars, which would allow for their subsequent incorporation into meteorite parent bodies during accretion. This incorporation mechanism is supported by the identification of SiC grains in carbonaceous chondrites. The possibility therefore exists that PAHs, and/or other condensed organic compounds, represent the starting material for aqueous alteration which leads to the formation of amino acids and other water-soluble organic compounds. Here we present calculations of the distribution of aqueous organic compounds in metastable equilibrium with representative PAHs as functions of the fugacities of O2, CO2 and NH3. The results reported here for pyrene and fluoranthene, two PAHs with different structures but the same stoichiometry, differ greatly but indicate that the formation of amino and carboxylic acids is energetically favourable at probable parent-body alteration conditions. The actual reaction mechanisms involved could be revealed by consideration of isotope data for PAHs, amino acids, other organic compounds and carbonates in carbonaceous chondrites.     

Carbon isotope composition of individual amino acids in the Murchison meteorite

A significant portion of prebiotic organic matter on the early Earth may have been introduced by carbonaceous asteroids and comets. The distribution and stable-isotope composition of individual organic compounds in carbonaceous meteorites, which are thought to be derived from asteroidal parent bodies, may therefore provide important information concerning mechanistic pathways for prebiotic synthesis and the composition of organic matter on Earth before living systems developed. Previous studies have shown that meteorite amino acids are enriched in 13C relative to their terrestrial counterparts, but individual species were not distinguished. Here we report the 13C contents of individual amino acids in the Murchison meteorite. The amino acids are enriched in 13C, indicating an extraterrestrial origin. Alanine is not racemic, and the 13C enrichment of its D- and L-enantiomers implies that the excess of the L-enantiomer is indigenous rather than terrestrial contamination, suggesting that optically active materials were present in the early Solar System before life began.     

Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite

Much effort has been directed to analyses of organic compounds in carbonaceous chondrites because of their implications for organic chemical evolution and the origin of life. We have determined the isotopic composition of hydrogen, nitrogen and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite. The unusually high D/H and 15N/14N ratios in the amino acid fraction (delta D = 1,370% after correction for isotope exchange; delta 15N = 90) are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower (377%), but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound, and provide the first evidence suggesting a direct relationship between the massive organo-synthesis occurring in interstellar clouds and the presence of pre-biotic compounds in primitive planetary bodies. The isotope data also bear on the historical problem of distinguishing indigenous material from terrestrial contaminants.     

The specific carbon isotopic compositions of branched and cyclic hydrocarbons from Fushun oil shale

Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from n-alkanes by 5 A molecular-sieve adduction using long time and cold solvent. The branched and cyclic hydrocarbon fraction obtained by this method is able to satisfy the analytic requests of GC-IRMS. The carbon isotopic compositions of these branched and cyclic hydrocarbons obtained from the sample indicate that they are derived from photoautotrophic algae, chemoautotrophic bacteria (-33.4‰— -39.0‰) and methanotrophic bacteria (-38.4‰— -46.3‰). However the long-chain 2-methyl-branched alkanes indicate that their carbon isotopic compositions reflect biological origin from higher plants. The carbon isotopic composition of C30 4-methyl sterane (-22.1‰) is the heaviest in all studied steranes, showing that the carbon source or growth condition for its precursor, dinoflageilate, may be different from that of regular steranes. The variation trend of δ^13C ValUes between isomers of hopanes shows that ^13C-enriched precursors take precedence in process of their epimerization. Methanotrophic hopanes presented reveal the processes of strong transformation of organic matter and cycling of organic carbon in the water column and early diagenesis of oil shale.     

Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs

Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.     

列车餐车油烟雾的采集及化学成分分析

本文采用气相色谱质谱联用仪(GC/MS)对采集于列车餐车的食用油烟雾样品进行全谱分析,发现样品有66种化合物,包括烃类、卤代烃类、醇酚醚类、醛酮类、羧酸及衍生物类、芳稠环杂环类和胺类等七类,其中一些化合物如芳杂环化合物、卤代烃和胺类等具有毒性作用     

三维电极-电Fenton法去除垃圾渗滤液中有机物

采用三维电极-电Fenton法处理垃圾渗滤液,考察了垃圾渗滤液中有机物去除的影响因素及处理效果,优化了实验条件,并探讨了有机物的降解机理。结果表明,电流密度、极板间距、初始pH、Fe²⁺投加量、曝气量等参数对垃圾渗滤液中化学需氧量(COD)和总有碳量(TOC)的去除率均有一定的影响,其最佳运行参数为：电流密度57.1mA/cm²、极板间距10cm、初始pH为4.0、Fe²⁺ 投加量1mmol/L、曝气量0.2m³/h,在此条件下,COD和TOC的去除率分别达80.80%和73.26%。气相色谱-质谱联用仪(GC-MS)定性分析结果显示,电解对垃圾渗滤液中芳烃、烷烃、羧酸、酯类等主要有机物具有很好的去除效果,可生化性(BOD5/COD)从电解前的0.125增大到0.486,有利于后续的生化处理。     

黄县褐煤高锰酸钾碱液分步氧化的研究

用高锰酸钾碱性溶液对黄县褐煤进行了九步氧化,按先后次序将产物分为两个馏份进行分析鉴定。有机酸碳收率达76.5％。对两个馏份酸用乙醚抽提并经甲酯化后分别进行了色-质谱分析,鉴定出六十多种单体化合物,主要有脂肪二元酸及一元酸、芳香二元酸及一元酸,多官能团酸,此外还有一些非酸化合物,如酮、醇、胺、含氮和硫的杂环化合物以及烃类等。配合元素分析及红外光谱分析等对产物进行了较为全面的分析鉴定。     

噻吩在有机合成中的应用

噻吩及其衍生物是重要的有机合成中间体，通过还原脱硫反应，可将其转变成开链化合物，本文综合其在合成烃，芳烃，酮，醇，羧酸以及氨基酸等方面的应用。     

Pre-biotic organic matter from comets and asteroids

Several authors have suggested that comets or carbonaceous asteroids contributed large amounts of organic matter to the primitive Earth, and thus possibly played a vital role in the origin of life. But organic matter cannot survive the extremely high temperatures (>10(4) K) reached on impact, which atomize the projectile and break all chemical bonds. Only fragments small enough to be gently decelerated by the atmosphere--principally meteors of 10(-12)-10(-6) g--can deliver their organic matter intact. The amount of such 'soft-landed' organic carbon can be estimated from data for the infall rate of meteoritic matter. At present rates, only approximately 0.006 g cm-2 intact organic carbon would accumulate in 10(8) yr, but at the higher rates of approximately 4 x 10(9) yr ago, about 20 g cm-2 may have accumulated in the few hundred million years between the last cataclysmic impact and the beginning of life. It may have included some biologically important compounds that did not form by abiotic synthesis on Earth.     

Evidence from the Pacific troposphere for large global sources of oxygenated organic compounds

The presence of oxygenated organic compounds in the troposphere strongly influences key atmospheric processes. Such oxygenated species are, for example, carriers of reactive nitrogen and are easily photolysed, producing free radicals-and so influence the oxidizing capacity and the ozone-forming potential of the atmosphere-and may also contribute significantly to the organic component of aerosols. But knowledge of the distribution and sources of oxygenated organic compounds, especially in the Southern Hemisphere, is limited. Here we characterize the tropospheric composition of oxygenated organic species, using data from a recent airborne survey conducted over the tropical Pacific Ocean (30 degrees N to 30 degrees S). Measurements of a dozen oxygenated chemicals (carbonyls, alcohols, organic nitrates, organic pernitrates and peroxides), along with several C2-C8 hydrocarbons, reveal that abundances of oxygenated species are extremely high, and collectively, oxygenated species are nearly five times more abundant than non-methane hydrocarbons in the Southern Hemisphere. Current atmospheric models are unable to correctly simulate these findings, suggesting that large, diffuse, and hitherto-unknown sources of oxygenated organic compounds must therefore exist. Although the origin of these sources is still unclear, we suggest that oxygenated species could be formed via the oxidation of hydrocarbons in the atmosphere, the photochemical degradation of organic matter in the oceans, and direct emissions from terrestrial vegetation.     

Carbon isotope kinetics of gaseous hydrocarbons generated from different kinds of vitrinites

Kinetics study of gaseous hydrocarbons generated from vitrinites based on pyrolysis of gold tube closed system shows that the activation energies of methane generated from telocollinite are higher than that from desmocol-linite due to structure differences. But carbon isotope ratios of generated methane in pyrolysates of vitrinites at the same temperature points are similar. Carbon isotope ratio of methane may decrease in the early stage of gas generation and then increase in the later stage. But at higher temperature, δ13C1 decreases slightly or almost keeps stable with increasing temperature. Since it is known that carbon isotope distillation is controlled by time, temperature and carbon isotope ratio of bulk organic matter, the character of side chains connected to macromolecule of vitrinite and distribution of activation energies have no obvious effect on carbon isotope fraction. Decreasing trend of δ13C1 in the early stage may be caused by contagious structure of vitrinite or differences of activation energies between 12C-12C and 12C-13C are not strictly constant at different ranges of activation energy area.     

Plant biomarkers in aerosols record isotopic discrimination of terrestrial photosynthesis

Carbon uptake by the oceans and by the terrestrial biosphere can be partitioned using changes in the (12)C/(13)C isotopic ratio (delta(13)C) of atmospheric carbon dioxide, because terrestrial photosynthesis strongly discriminates against (13)CO(2), whereas ocean uptake does not. This approach depends on accurate estimates of the carbon isotopic discrimination of terrestrial photosynthesis (Delta; ref. 5) at large regional scales, yet terrestrial ecosystem heterogeneity makes such estimates problematic. Here we show that ablated plant wax compounds in continental air masses can be used to estimate Delta over large spatial scales and at less than monthly temporal resolution. We measured plant waxes in continental air masses advected to Bermuda, which are mainly of North American origin, and used the wax isotopic composition to estimate Delta simply. Our estimates indicate a large (5 6 per thousand) seasonal variation in Delta of the temperate North American biosphere, with maximum discrimination occurring in late spring, coincident with the onset of production. We suggest that the observed seasonality arises from several factors, including seasonal shifts in the proportions of production by C(3) and C(4) plants, and environmentally controlled adjustments in the photosynthetic discrimination of C(3)-plant-dominated ecosystems.     

Natural gas geochemistry of low evolutionary stage of medium- and small-sized basins in Yunnan Province, southwestern China

The biogenic gas and premature-low mature associated gases in some medium and small-sized basins of Yannan Province, such as Luliang, Yanglin, Baoshan and Jinggu basins, have beed researched. The results show that the biogenic-gas consists mainly of methane which is more than 99% in gasous hydrocarbons and of lighter carbon isotopic composition with δ13C1 values from -60.0‰ to - 75.4‰. The methane carbon isotopic compositions in the Baoshan Basin is relatively heavy (δ13C1 - 60‰- - 65‰), but those in Luliang and Yanglin basins are lighter (δ13C1, less than -70‰), which implies that the gas field of the Baoshan Basin formed earlier than the others. In the Jinggu Basin, where crude oil is premature-lower mature, the natural gas of associated oil relatively wet and the relative content of methane about 58%-95% in gasous hydrocarbons. Constituently the gas composition is much similar to associated one, but the methane carbon isotopic compositions from - 53.8‰ to - 57.8‰ are obviously richer in 12C than those of general oil fields and similarly characterize the biothermo-catalytic transitional zone gas. Their ethane carbon isotopic compositions from - 34.6‰ to -29.0‰ show that they may be derived from type Ⅰ or Ⅱ source rock. But for the associated gas from lower evolutionary stage, the heavier ethane carbon isotopic composition as well as the reversed order among the carbon isotopic composition of ethane, propylane and butane also implies that some gases from the type Ⅲ organic matter are mixed. The δ13CCo2 of the samples essentially less than - 10‰ may be generated from organic matter.     

羧酸在油水相中的分布

研究了甲酸和乙酸于水中和不同有机介质中的分配系数,重点研究了含21、24和27碳原子的三烷基叔胺对甲酸和乙酸的成盐萃取作用。同时,在不同稀释剂及其用量、温度以及甲酸和乙酸浓度的条件下,确定了小分子羧酸的分配系数及其变化规律,最后,根据有机羧酸叔胺盐的热分解行为获得了纯度达90％的甲酸和乙酸,从而为重有机工业的酸回收提供了工艺技术设计的依据。     

Multi-origin alkanes related to CO2-rich, mantle-derived fluid in Dongying Sag, Bohai Bay Basin

With the newly obtained carbon isotope data for the natural gas, a pilot study of multiple-sourced alkanes related to the mantled-derived fluid is presented. The carbon isotope values of alkanes in the Dongying Sag possess thefea tures indicating a general organic origin. However, there are two sub-populations in the isotopic data set, which reflect two specific types of origins. In gene ral, the sub-population with high δ13CCH4 values is related to the CO2-rich, mantle-derived fluid, and it is distributed in the belts where mantle-derived fluid flow and basic volcanic activities have occurred. Geological and geochemical studies demonstrate that this variation of methane carbon isotope values in the Dongying Sag is unrelated with the basin bury and thermal histories, types of source rocks, and reactions between basin fluid and rocks. Mixing of mantle-derived fluid and organic sourced hydrocarbons is probably the cause for the variation .     

The synthesis of organic and inorganic compounds in evolved stars

Recent isotopic analysis of meteorites and interplanetary dust has identified solid-state materials of pre-solar origin. We can now trace the origin of these inorganic grains to the circumstellar envelopes of evolved stars. Moreover, organic (aromatic and aliphatic) compounds have been detected in proto-planetary nebulae and planetary nebulae, which are the descendants of carbon stars. This implies that molecular synthesis is actively happening in the circumstellar environment on timescales as short as several hundred years. The detection of stellar grains in the Solar System suggests that they can survive their journey through the interstellar medium and that they are a major contributor of interstellar grains.     

富有机质页岩有机质孔发育差异性探讨——以四川盆地五峰组-龙马溪组笔石页岩为例

探讨富有机质页岩有机质孔发育的差异性,为页岩气勘探开发提供理论依据。在1 500倍和25 000倍电镜下,对四川盆地南部上奥陶统五峰组-下志留统龙马溪组富有机质笔石页岩进行观察。结果表明,页岩中笔石、干酪根、固体沥青等有机显微组分丰富,有机质孔总体发育;但不同有机显微组分、同一有机显微组分的有机质孔发育均存在差异,个体较大的固体沥青有机质孔最为发育,干酪根有机质孔较为发育,笔石碎片有机质孔不发育。有机质孔是随着有机碳向烃类和碳质残渣转化而形成的,笔石富碳贫氢的特征导致其有机质孔不发育;不同母质来源的干酪根生烃潜力存在差异决定了其有机质孔发育存在差异;固体沥青有机质孔是在原油裂解过程中形成的,其发育程度可能主要与原油赋存的粒间孔隙空间大小相关。     

鄱阳湖湿地洲滩前缘浅层土壤碳-氮-磷的时空特征

湿地洲滩土壤碳、氮、磷是重要的营养元素,其分布特征直接影响湿地生态系统的生产力和生态系统服务功能.通过2014-2017年对鄱阳湖湿地洲滩前缘浅层土壤(0～20 cm)有机碳、全氮、全磷观察实验分析,结果表明:鄱阳湖湿地洲滩前缘浅层土壤有机碳、全氮、全磷的年际变化特征不同,有机碳变化不显著,全氮、全磷变化显著; 浅层土壤有机碳、全磷、全氮的高程梯度变化极显著; 浅层土壤碳氮比、碳磷比年际变化极显著,氮磷比不显著; 浅层土壤碳氮比高程梯度变化不显著,碳磷比、氮磷比的高程梯度变化极显著.浅层土壤氮磷含量较其他     

Uncovering the Neoproterozoic carbon cycle

Interpretations of major climatic and biological events in Earth history are, in large part, derived from the stable carbon isotope records of carbonate rocks and sedimentary organic matter. Neoproterozoic carbonate records contain unusual and large negative isotopic anomalies within long periods (10-100 million years) characterized by δ(13)C in carbonate (δ(13)C(carb)) enriched to more than +5 per mil. Classically, δ(13)C(carb) is interpreted as a metric of the relative fraction of carbon buried as organic matter in marine sediments, which can be linked to oxygen accumulation through the stoichiometry of primary production. If a change in the isotopic composition of marine dissolved inorganic carbon is responsible for these excursions, it is expected that records of δ(13)C(carb) and δ(13)C in organic carbon (δ(13)C(org)) will covary, offset by the fractionation imparted by primary production. The documentation of several Neoproterozoic δ(13)C(carb) excursions that are decoupled from δ(13)C(org), however, indicates that other mechanisms may account for these excursions. Here we present δ(13)C data from Mongolia, northwest Canada and Namibia that capture multiple large-amplitude (over 10 per mil) negative carbon isotope anomalies, and use these data in a new quantitative mixing model to examine the behaviour of the Neoproterozoic carbon cycle. We find that carbonate and organic carbon isotope data from Mongolia and Canada are tightly coupled through multiple δ(13)C(carb) excursions, quantitatively ruling out previously suggested alternative explanations, such as diagenesis or the presence and terminal oxidation of a large marine dissolved organic carbon reservoir. Our data from Namibia, which do not record isotopic covariance, can be explained by simple mixing with a detrital flux of organic matter. We thus interpret δ(13)C(carb) anomalies as recording a primary perturbation to the surface carbon cycle. This interpretation requires the revisiting of models linking drastic isotope excursions to deep ocean oxygenation and the opening of environments capable of supporting animals.