色谱／光谱联机检测化石燃料中的芳香化合物

色谱／光谱联机检测化石燃料中的芳香化合物８０年代发展起来的毛细管柱气相色谱／傅里叶变换红外光谱（ＣＧＣ／ＦＴＩＲ）是分离和鉴定组成复杂、结构相似的芳香烃混合物的有效工具，其特点是能在高效分离基础上提供未知物的整体结构信息，尤其是对各种官能团和异构体有...     

环境样品中痕量元素的化学形态分析Ⅰ．分析技术在化学形态分析中的应用

文章介绍了形态分析的基本概念,常用的联用分析技术,如气相色谱原子吸收光谱、气相色谱原子荧光光谱、气相色谱微波诱导等离子体原子发射光谱、气相色谱电感耦合等离子体质谱、高效液相色谱电感耦合等离子体质谱等在环境样品(水、土壤、沉积物)中痕量元素化学形态(价态、金属有机化合物等)分析中的应用,土壤和沉积物中污染元素的顺序提取步骤,以形态分析发展动态。引用文献72篇。     

有机地球化学在重建砂岩型铀矿形成物理化学环境方面的应用前景

从铀的活化、迁移、沉淀、成矿以及保存等几方面综述了有利于砂岩型铀形成的物理化学环境。有机质在铀矿富集成矿的各个阶段起着重要的作用,各种有机地球化学方法已被用于揭示铀矿中有机质的特征,如元素分析、Rock-Eval热解、气相色谱和红外光谱分析、色谱-质谱分析、裂解色谱-质谱及显微光谱技术、紫外荧光光谱分析1、3C核磁共振、碳/氢同位素分析等;同时结合鄂尔多斯盆地铀矿富集的有利地质条件阐述了有机地球化学在重建砂岩型铀矿形成条件中的应用前景。     

多氯联苯的环境特性及分析测试进展

由于多氯联苯(PCBs)在环境样品中残留浓度低,基质复杂干扰多,必须对环境样品进行预处理,并且结合先进的分析测试方法进行分析。文章综述了PCBs的性质及其主要来源;近年来分析PCBs的前处理方法,主要包括加速溶剂萃取、超临界流体萃取、微波萃取、固相微萃取、基质分散固相萃取等提取方法和固相萃取小柱、凝胶渗透色谱等净化方法;目前气相色谱和气相色谱-质谱联用技术发展以及一些新技术在分析PCBs方面的应用,包括全二维气相色谱法、快速气相色谱法、气相色谱-离子肼串联质谱法、高分辨气相色谱-高分辨质谱法等。总结了国内外PCBs的研究现状。     

土壤中有机氯农药残留的分析技术研究进展

文章总结了近年来土壤中有机氯农药残留分析的样品前处理和测定方法的研究进展,重点阐述微波萃取法、加速溶剂萃取法、固相萃取法、固相微萃取法、基质固相分散萃取法、超临界流体萃取法等前处理技术及气相色谱技术、气相色谱-质谱联用技术等在土壤中有机氯农药残留分析中的应用,指出了未来的发展趋势。     

泥炭分子化石单体碳氢同位素的古气候意义

为了查明泥炭分子化石记录的古植被状况与古植物学分析结果的差异，并进一步探讨这些分子化石所记录的古气候信息，本文利用气相色谱仪(CC)、气相色谱—质谱联用仪(GC—MS)、气相色谱—燃烧-同位素比质谱仪(GC-C-IRMS)、气相色谱-热转换—同位素比质谱仪(CC—TC—IRMS)详细分析了一个40cm(约220年)长的泥炭岩芯中的分子化石及其单体碳、氢同位素组成。正构烷烃分子化石的主峰化合物(C23)及其碳、氢同位素组成与温度有很好的对应关系，工业革命以来化石燃料的燃烧效应也在单体碳同位素上反映出来。这些结果反映了泥炭分子化石具有很好的古气候和古环境意义。     

丛粒藻烷类非烃化合物的分离、富集与气相色谱纯化、制备

气相制备色谱(pGC)作为分离、纯化高纯度单体化合物的有效手段,被广泛应用于许多领域。国外地球化学方面已有众多关于化石燃料生物标志物的应用实例,而国内这方面的应用相对较少。本文选取富含丛粒藻烷类生物标志物的茂名油页岩特殊样品,尝试对非烃馏分中的目标化合物开展分离、富集和纯化、制备。在经过硅胶/氧化铝柱色谱初次分离后,取非烃组分进行纯硅胶柱色谱二次分离,之后再采用气相制备色谱开展精细分离和纯化,成功制备出非烃组分中3个与丛粒藻烷相关联的目标化合物,纯度高达95%以上。以此为例,介绍了气相制备色谱的使用原理和目标化合物分离、富集、纯化的经验。     

光引发剂残留分析研究进展

光引发剂残留分析起步较晚,由于残留水平低,在分析中更多地使用了较新的高灵敏度分析技术。文章对光引发剂Benzophenone、ITX、Irgacure 184、Irgacure 907、Irgacure 369、TPO和EHA的定义、种类、来源和危害进行了介绍;总结了目前光引发剂残留分析几类检测方法,包括气相色谱-质谱联用、薄层色谱-质谱联用、液相色谱-质谱联用等,由于气相色谱使用范围的限制,液相色谱-质谱在光引发剂分析中应用越来越广泛。比较了常用的样品前处理手段的优缺点,如液-液萃取、加速溶剂萃取、固相萃取等。相对于其他方法,固相萃取更为成熟,普适性更强,便于实现大批量光引发剂中多残留分析。光引发剂的多残留分析甚至与其他农药、兽药残留同时分析是未来发展的方向。     

电感耦合等离子体质谱联用技术在元素形态分析中的应用进展

电感耦合等离子体质谱(ICP-MS)作为一种高灵敏度的分析技术在痕量超痕量无机元素分析方面已被广泛应用,其与色谱分离技术相结合为元素形态分析提供了强有力的检测工具。本文阐述了近年来利用不同ICP-MS联用技术进行元素形态分析的研究进展,主要包括:(1)气相色谱-电感耦合等离子体质谱联用技术(GC-ICP-MS);(2)毛细管电泳-电感耦合等离子体质谱联用技术(CE-ICP-MS);(3)离子色谱-电感耦合等离子体质谱联用技术(IC-ICP-MS);(4)高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)。在此基础上归纳总结了中国元素形态分析领域的主要研究情况,对元素形态分析发展前景作了展望。这些联用技术中,GC-ICP-MS的灵敏度高,样品传输率接近100%,但其适用于易挥发或中等挥发性样品的分离,应用范围相对较窄;CE-ICP-MS的分离效率高,样品和试剂消耗量少,但受到其进样量限制使得最低检出浓度较大;IC-ICP-MS主要分析阴离子和阳离子及小分子极性化合物,是液相色谱的有益补充,具有分离效果好和快速方便等优点,但离子色谱流动相中的盐类会造成ICP-MS进样管和采样锥的堵塞,使得基体效应严重;HPLC-ICP-MS以其广泛的应用范围、简单的接口技术,成为元素形态分析研究中应用最广泛的联用技术。本文认为,元素形态分析研究中开展复杂基体样品前处理方法研究,研制系列元素形态分析标准物质,建立多元素形态同时分析方法是元素形态分析领域的发展方向。     

张强凹陷长北背斜原油分析

采用气相色谱，色谱－质谱，同位素，红外光谱等方法，分析了长北油田原油的来源，母质类型的成熟度的高低。研究结果表明，本区原油具有同源性，母质为陆相沉积腐殖型，原油生成于浅湖相弱还原环境中，热演化处于低成熟－成熟过程。     

Biogenic and abiogenic polynuclear aromatic hydrocarbons in sediments from two remote Adirondack lakes

Sediment cores from Sagamore Lake and Woods Lake in New York State's Adirondack Park, an area remote from industrial activities, were analyzed for polynuclear aromatic hydrocarbons (PAH) by high resolution gas chromatography/mass spectrometry (GC/MS). Their composition and distribution with depth in the sediment indicate that the parental PAH in the surface sediments are primarily produced by anthropogenic combustion of fossil fuels. Perylene in deep sediments is apparently transformed from natural precursors in the reducing environment, however, the exact precursors remain unknown. The rather even sediment distributions of the non-parental PAH differ from the parental, suggesting biogenic origins. Based on their chemical structures, retene and alkylated and partially hydrogenated phenanthrenes are believed to be biogenically converted from abietic acid; hydrochrysenes and hydropicenes, from pentacyclic triterpenes.     

北京市西北城区大气可吸入颗粒物中饱和烃的分布特征

利用气相色谱、气相色谱-质谱分析法从北京市西北城区四个季节大气可吸入颗粒物（PM10）中检测出种类丰富的饱和烃,主要包括正构烷烃、萜烷及甾烷等系列化合物。利用饱和烃的多项参数（如主峰碳数、碳优势指数CPI、藿烷22S/(22S+22R)比值等）对大气PM10中可溶有机物的来源及分布作了探讨。北京市西北城区PM10中正构烷烃的主峰碳数均介于23和27之间,而CPI值介于1和3之间,表明北京市西北城区PM10中的饱和烃均不同程度地受到了高等植物等现代生物和化石燃料（石油、煤等）不完全燃烧产物两种来源的影响,其中在春、夏季以高等植物、花粉、微生物等生物来源占比重较大,而在秋、冬季,尤其在冬季,化石燃料的不完全燃烧造成的污染比较明显。萜烷类物质的检出,表明北京市西北城区四个季节PM10中部分饱和烃来自于石油等化石燃料的不完全燃烧。甾烷类物质的检出,表明北京市西北城区四个季节PM10中部分饱和烃是来自于车辆释放的机油等。     

Sources d'énergie primaires et effet de serre

In the frame of the diminution of fossil energy and climate change, the two most difficult demands to satisfy are providing electricity to megalopolises and fuels for transportation. Renewable energies have to be promoted but will not be able to replace fossil fuels in their current uses before several decades. According to the previsions for this century, carefulness is necessary to preserve the future of humanity and the environment. To cite this article: B. Tissot, C. R. Geoscience 335 (2003).     

Fossil fuels: a crisis of resources or effluents?

Most professional geologists are employed to find oil, gas and coal. They work for a society constantly concerned about future supplies of fossil fuels. Yet now the global atmospheric pollution from burning these fuels threatens to harm society sooner than any shortage of resources. Caught amidst the fossil fuel debate, how should geologists respond?     

Molecular composition and paleobotanical origin of Eocene resin from northeast India

The molecular composition of fossil resins from early to middle Eocene coal from northeast India, has been analyzed for the first time to infer their paleobotanical source. The soluble component of fossil resin was analyzed using gas chromatography–mass spectrometry (GC–MS). The resin extracts are composed of cadalene-based C₁₅ sesquiterpenoids and diagenetically altered triterpenoids. The macromolecular composition was investigated using pyrolysis gas chromatography-mass spectrometry (Py-GC–MS) and Fourier transform infrared (FTIR) spectroscopy. The major pyrolysis products are C₁₅ bicyclic sesquiterpenoids, alkylated naphthalenes, benzenes and a series of C₁₇–C₃₄ n-alkene-n-alkane pairs. Spectroscopic analysis revealed the dominance of aliphatic components. The presence of cadalene-based sequiterpenoids confirms the resin to be Class II or dammar resin, derived from angiosperms of Dipterocarpaceae family. These sesquiterpenoids are often detected in many SE Asian fluvio-deltaic oils. Dipterocarpaceae are characteristic of warm tropical climate suggesting the prevalence of such climate during early Eocene in northeast India.     

From the dawn of organic geochemistry (1933, 1938): Estrogenic substances in bituminous deposits and in the Dead Sea

We describe several pioneering organic geochemical studies from the 1930s on estrogenic substances isolated from various fossil fuels and bituminous materials and from water and sediments of the Dead Sea. The techniques employed were bioanalytical and not chemical. One of the studies, although not done on the same molecular level as his, precedes the work of Alfred Treibs, who is considered the father of organic geochemistry. By shedding light on a relatively unknown chapter of organic geochemistry, the roots of this discipline are shown to extend wider than usually recognized.     

Relationship between surface morphology and chemical composition of spheroidal carbonaceous particles within sediment core samples recovered from Osaka Bay,Japan

Spheroidal carbonaceous particles (SCPs) are produced by the high-temperature combustion of fossil fuels and are emitted to the atmosphere. Previous studies are divided regarding whether SCPs derived from the combustion of various fossil fuels can be identified based on their surface morphologies and chemical compositions. In this study, we examined the surface morphology and chemical composition of SCPs in sediment core samples collected from Osaka Bay, Japan, with the aim of evaluating the usefulness of SCPs morphology in identifying their origin. Scanning electron microscope (SEM) observations reveal three distinct surface morphologies: (1) smooth, (2) rough and irregular, and (3) convoluted and layered. According to a morphological classification scheme proposed previously, the former two morphologies correspond to coal-derived carbon particles, whereas the latter corresponds to oil-derived carbon particles. In terms of the chemical compositions of the particles with different morphologies, as analyzed by energy-dispersive spectroscopy, linear discriminant analysis reveals that the two fuel types can be distinguished. An overall success rate of >90% of reference of morphologically classified material correctly assigned to two groups that are chemically different each other, indicating a relationship between surface morphology and chemical composition. This result suggests that morphological characterization based on conventional SEM observations is useful in identifying the source fuel of SCPs.     

Organic geochemistry of Amynteo lignite deposit,northern Greece: a Multi-analytical approach

Several lignite samples were collected from boreholes of the Amynteo opencast lignite mine, northern Greece. Organic geochemical characteristics were investigated with the help of various analytical techniques, comprising Gas Chromatography (GC) and Gas-chromatography-Mass Spectrometry (GC-MS), Fourier Transform Infrared Spectroscopy (FTIR), solid-state Nuclear Magnetic Resonance (NMR) and Electron Paramagnetic Resonance (EPR) spectroscopy, petrographical measurements as well as determination of bulk parameters. In the low rank (Rr = 0.21%) Amynteo lignites, huminite is the most abundant maceral group, inertinite has relatively low percentages and liptinite concentrations are rather high. Carbon Preference Index (CPI) reveals the predominance of odd-numbered, long-chained aliphatic hydro-carbons, which is related to a higher terrestrial plant input. The Pr/Ph ratio suggests that reducing conditions were persistent during peatification. Gymnosperm biomarkers such as isoprimarane, abietane, phyllocladane and sandaracopimarane, as well as angiosperm indicators (lupane) and hopanoid compounds with bacterial origin were identified. Analyses of the aromatic fractions revealed the presence of naphthalene, alkyl benzenes and phenols, pyrene, cadalene, cadinane, fluoranthene and dibenzofurane. Based on the FTIR analysis, aliphatic and oxygen containing structures were prevailed over the aromatic moieties. The intensity of the mineral bands was preferentially increased in the FTIR spectra of insoluble material. According to NMR analysis, the aliphatic carbons (0–50 ppm) have higher proportions comparing to aromatic carbons (100–160 ppm). The aromaticity fraction is low (fa = 0.32), as expected for these low rank coals. The presence of free organic radicals and Fe³⁺ and Mn²⁺ paramagnetic ions was revealed by EPR. In summary, the combined application of complementary analytical techniques allowed a deep inside into the geochemical characteristics of Amynteo lignites.     

Biomass for energy in developing countries

Biomass, like fossil fuels, can provide cooking and heating energy, electricity, chemicals and liquid fuels. Today about 14% of the worldwide primary energy supply is provided by biomass resources — equivalent to 1000 million tons oil each year. Most of this biomass use occurs in rural areas of developing countries where half the world's population lives. For example Kenya derives about 75%, India 50%, China 33% and Brazil 25% of their total energy from biomass, A number of industrialized countries also derive a considerable amount of energy from biomass, such as Finland 18%, Ireland 16%, Sweden 9% and USA 3%. World ependiture on biomass programmes exceeds S 2 bn/yr; several natioal biomass energy programmes are discussed. Biomass resources and conversion technologies are described, as are the factors necessary for successful regional implementation of biomass energy schemes.     

Self-sedimentation of phytoplankton blooms in the geologic record

Understanding the formation of laminated, organic-rich sediments is an essential topic for researchers interested in fossil fuels, biogeochemical cycles, Earth's environmental history and global change. Biologists have very recently demonstrated that some marine phytoplankton blooms actively govern their own sedimentation by the formation of sticky transparent gels that facilitate rapid aggregation, accelerated sinking and efficient export flux. Here we present fossil evidence of unfragmented, low-diversity phytoplankton assemblages preserved as sedimentary laminae and irregular flocs that are attributable to a similar phytoplankton-driven sedimentary mechanism we term ‘self-sedimentation’. The geological evidence suggests that self-sedimentation precludes significant heterotrophic grazing, propels the formation of some conspicuous hemipelagic sedimentary laminae and results in efficient carbon and opal flux to the sediments. We suggest that the self-sedimentation phenomenon may have broad implications for the geological history of biogeochemical cycling, oceanic ecological dynamics, and abrupt atmospheric/environmental change. Broader recognition of the self-sedimentation phenomenon as explicitly defined here is a prerequisite to testing these unconventional hypotheses.