生物标记物色谱-质谱-质谱分析及地质应用研究

通过实验研究建立了生物标记物色谱－质谱－质谱（GC／MS／MS）分析方法，通过GC／MS／MS与GC／MS对比分析可知，GC／MS／MS在鉴定极微量生标组分，分离复杂组分及对复杂和未知组分更准确定性，定量方面独具优势，对辽河，塔里木盆地岩石及原油饱和烃样品进行GC／MS／MS分析，对几个系列生物标记物结构进行鉴定，鉴定出了具有时代意义的生标组分，时代意义三环二萜，四环二萜，双杜松烷，五环三萜等多个系列；甲藻甾烷，甲基甾烷系列，C26降胆甾烷系列，以及高碳数五环萜，六环萜等多个系列生物标记物。     

气相色谱-质谱-质谱技术在油源研究中的应用

早期气相色谱质谱质谱技术主要用于分离鉴定更痕量的化合物,对具时代意义的生物标志物研究是其应用领域的新拓展。当原油中检出这些具时代意义的生物标志物时,可由此推测原油生源岩沉积的地质时代。在概述目前已知具时代意义的生物标志物基础上,介绍利用气相色谱质谱质谱技术研究塔里木盆地柯克亚地区原油油源的应用实例。研究认为柯克亚原油主要来源于二叠系烃源岩,但因原油中检测出微量的二萜类化合物,说明侏罗系烃源岩也有一定的贡献。     

色谱／质谱／质谱技术在海上油气勘探中的应用

在琼东南盆地的凝析油和煤系泥岩中发现高丰度的未知物，据GC／MS分析的保留时间和质谱图初步鉴定为树脂化合物W、T，进一步运用GC／MS／MS分析方法获得化合物T的质谱信息与双杜松烷分子结构吻合。并且运用GC／MS／MS手段在珠江口盆地鉴定出双杜松烷型的树脂化合物，排除了对甾烷的干扰。双杜松烷及其同系物对指示这些地区的生源物质及沉积环境有特殊意义。     

生物标志化合物色谱—质谱定量分析研究

在原油或者岩石抽提沥青"A"经过硅胶—氧化铝柱层析后得到的饱和烃馏分中加入内标物,然后进行生物标志化合物GC-MS定量分析研究。实验结果表明甾烷和藿烷化合物的定量分析误差小于10%。应用此定量方法对岩石热模拟排出油中的生物标志化合物进行GC-MS定量分析。结果表明随着模拟温度的增高生物标志化合物含量逐渐降低,但在350℃后基本稳定;Ts/(Ts+Tm)值随着模拟温度的增加而提高。     

裂解气相色谱-质谱联用法在建立润滑油指纹图谱中的应用

润滑油的指纹图谱是润滑油质量控制的有效手段,是其物质组成整体性和模糊性的综合体现。采用裂解气相色谱-质谱联用法建立润滑油的指纹图谱,对样品的前处理方法、裂解方式、气相色谱-质谱条件等影响指纹图谱稳定性的因素进行了研究,利用得到的典型润滑油指纹图谱建立相应的谱库,选择几种润滑油指纹图谱作为校验集在谱库中进行检索,检索结果的准确率达到99%以上,为润滑油质量的有效控制提供了便捷的方法。     

全二维色谱飞行时间质谱在石油地质样品分析中的应用

利用全二维气相色谱—飞行时间质谱技术对石油地质样品进行了分析研究。原油直接进样分析显示原油组分中链烷烃、环烷烃、单环芳烃、双环芳烃和三环芳烃非常有规律地分布在特征区域。化合物鉴别定性准确可靠,能获取原油烃组成的详细特征。和传统色谱分析相比,轻烃分析可实现C₆-C₁₀轻烃组分中的单体烃的分离和识别,能提供更为丰富的轻烃指纹信息。生物标志物多环萜烷的分析可实现高碳数低含量三环萜烷与五环萜烷的分离和识别,伽马蜡烷也得到很好的分离。研究表明全二维气相色谱—飞行时间质谱技术在石油地质勘探研究中有广阔的应用前景。      

色谱／质谱联用仪在原油分析中的应用

针对重质原油采用气相色谱／质谱法(GS/MS)测定新疆克拉玛依九区油田原油组分，并进行条件的优选。原油样品经层析分离后，用气相色谱／质谱法(GC/MS)检测烷烃的28种组分，确定了九区油田原油组成及烃类正构异构体的排列分布情况。并对每一种组分通过谱图的检索及标准样品的对比进行组分定性定量。     

凝析油非正构烷烃色谱-质谱分析及其在石油地质中的应用

色谱-质谱分析技术已发展成为发现油气层的实用技术,在石油地质勘探领域占据重要地位,并在勘探和寻找油气层等方面做出了重要贡献;但对于高成熟凝析油,主要为C10之前的正构烷烃,常规的生物标志化合物含量极低,采用常规饱和烃地球化学分析技术往往不能很好解决诸如油源、油气成熟度、油气运移、油气充注方向及次序等地质问题.应用色谱-质谱分析技术,对正构烷烃之间的异构烷烃进行定性定量,进而应用一些新的轻烃地球化学指标,准确判定油气特征,对提高油气勘探效益具有重要意义.     

全二维气相色谱-飞行时间质谱表征喷气燃料和生物航煤详细烃组成

采用全二维气相色谱-飞行时间质谱(GC×GC-TOFMS)和全二维气相色谱-氢火焰离子化检测器(GC×GC-FID)构建石油基喷气燃料(简称喷气燃料)和生物基航空煤油(简称生物航煤)烃类分子水平表征方法。该方法利用 GC×GC-TOFMS的族分离特性和瓦片效应对喷气燃料和生物航煤的烷烃、环烷烃和芳烃等组分进行定性分析和碳数分布规律研究,将族分类信息由GC×GC-TOFMS转移至GC×GC-FID,并利用保留时间关联方程校正后进行定量。考察了不同来源喷气燃料和生物航煤的烃组成和碳数分布特点。结果表明,喷气燃料和生物航煤的芳烃和异构烷烃含量差异很大,不同来源的喷气燃料和生物航煤碳数分布有很大不同。     

甲基氯硅烷高馏份的色谱-质谱检测

采用色谱-质谱-计算机联用方法,对直接法生产的甲基氯硅烷的高馏份进行了检测。含氯硅烷单体的高馏份,在程序升温条件下,按其沸程差进行分离,并进行检测,获得较为满意的结果。确定了26个组份,为有机硅工业的开发和工艺设计提供了依据。     

GC/MS分析油酸乙二醇单酯的组成

用硅胶玻璃色谱柱吸附样品,采用溶剂梯度洗脱的方法从油酸乙二醇酯添加剂中分离出油酸乙二醇单酯,再用ＧＣ／ＭＳ详细地分析了油酸乙二醇单酯的组成和结构,并通过油酸乙二醇单酯的结构推断出油酸原料中所含酸的种类,从ＧＣ／ＭＳ分析领域给出了分析油酸乙二醇单酯的较好方法     

A monitoring study of glyceroltriheptanoate (GTH) in animal by-products through a validated GC–MS analytical method

According to Commission Regulation (EU) No 142/2011, animal by-products (ABPs) not intended for human consumption should be excluded from the food chain, as they are a potential source of risks to public and animal health. As an example, in recent years an improper use of certain ABPs brought to a spread of bovine spongiform encephalopathy (BSE). Therefore, Commission Regulation (EU) 142/2009 forces producers to mark permanently the ABPs not intended for human consumption (category 1 and category 2), with glyceroltriheptanoate (GTH). All EU Member States have the duty to control the content of GTH in ABPs, which should be present homogenously throughout the substance at a minimum concentration of at least 250 mg GTH per kg fat. Starting from a Joint Research Centre procedure (von Holst, Boix, Bellorini, Androni, & Serano, 2009), a method based on gas chromatography coupled to mass spectroscopy (GC–MS) was studied and validated as stated by Regulation 882/2004, providing an efficient tool for both official and in-house laboratories. Moreover, a monitoring study on seventeen samples collected throughout Italy by the Official Veterinary Service in rendering industries was carried out. Eight samples were not compliant with Commission Regulation (EU) No 142/2011, as their GTH concentration ranged from 224 mg kg⁻¹ to values below the lower range limit. Results found satisfied the requirements of European Union analytical methods validation criteria (Regulation (EC) No 882/2004).     

Multiple reaction monitoring of GC/MS/MS analysis of terpanes and its application to petroleum exploration

A highly sensitive and accurate multiplex gas chromatography–mass spectrometry–mass spectrometry (GC/MS/MS) technique and GC/MS technique are tested for terpanes in a hydrocarbon source rock sample. The terpanes, including tricyclic, tetracyclic, and pentacyclic, were quantified monitoring and identified with the transition m/z (262+14n)→191, 330→191, and (370+14n)→191 by multiple reaction monitoring of GC/MS/MS technique using collision energies of 5–30 eV. Results show that collision energies have great influence on tricyclic and pentacyclic terpanes' ratios. After comparing the analysis results by GC/MS, the collision energy for detecting terpanes using the MRM-MS/MS method is optimized at 23 eV.     

GC/MS法测定工业污水中有机物

采用液-液萃取法对炼油废水中有机物样品进行处理，对分离条件做了探讨。用GC／MS法进行测定并定性分析。     

Nitrogen Compound Determination and Distribution in Three Source Fuels by GC/MS

Three middle distillate fuels from Kenya, Kuwait, and Sweden were studied for the identification and comparison of their nitrogen content. The organic nitrogen compounds were isolated by mild acid extraction, and three extracts were obtained from each source fuel: a basic nitrogen extract in methylene chloride (BNC), a nonbasic nitrogen extract in methylene chloride (NBNC), and a nonbasic nitrogen extract in methanol (NBNC). The major constituents of each extract were determined by gas chromatography/mass spectrometry (GC/MS). The largest number of nitrogen compounds of the BNC extracts were pyridines and pyrroles in the Kuwait fuel, indoles and pyrroles in the Swedish fuel, and pyrroles and quinolines in the Kenya fuel. The Kenya fuel had carbazoles present in the BNC extract, whereas, the other two fuels didn't have this compound. The predominant organic nitrogen compounds in the NBNC extracts in methylene chloride for Kuwait and Kenya were tetrahydroquinolines and quinolines, respectively. The analysis of the NBNC extracts in methanol showed the following prevalent organic nitrogen compounds: indoles for Kuwait, quinolines for Sweden, and pyrroles for Kenya. All three fuels had short chain alkyl substituted indoles. Kenya had the lowest nitrogen content, followed by Kuwait and Sweden.     

Nitrogen Compound Determination and Distribution in Three Source Fuels by GC/MS

Abstract

Three middle distillate fuels from Kenya, Kuwait, and Sweden were studied for the identification and comparison of their nitrogen content. The organic nitrogen compounds were isolated by mild acid extraction, and three extracts were obtained from each source fuel: a basic nitrogen extract in methylene chloride (BNC), a nonbasic nitrogen extract in methylene chloride (NBNC), and a nonbasic nitrogen extract in methanol (NBNC). The major constituents of each extract were determined by gas chromatography/mass spectrometry (GC/MS). The largest number of nitrogen compounds of the BNC extracts were pyridines and pyrroles in the Kuwait fuel, indoles and pyrroles in the Swedish fuel, and pyrroles and quinolines in the Kenya fuel. The Kenya fuel had carbazoles present in the BNC extract, whereas, the other two fuels didn’t have this compound. The predominant organic nitrogen compounds in the NBNC extracts in methylene chloride for Kuwait and Kenya were tetrahydroquinolines and quinolines, respectively. The analysis of the NBNC extracts in methanol showed the following prevalent organic nitrogen compounds: indoles for Kuwait, quinolines for Sweden, and pyrroles for Kenya. All three fuels had short chain alkyl substituted indoles. Kenya had the lowest nitrogen content, followed by Kuwait and Sweden.     

测井资料在汪升地区火山岩相分析中的应用

松辽盆地汪家屯—升平地区火山岩埋藏深、岩石类型多、岩心资料少,岩相分析难度大。通过对取心段火山岩相测井资料的研究,得出了该区火山通道相、爆发相、喷溢相、侵出相中自然伽马和双测向测井的基本特征。以此为参照,对比分析了非取心段火山岩的岩相,最后给出了测井资料在识别火山岩相特殊岩性、气层和岩相界面方面的应用实例。     

Analytical Profile of Organo-nitrogen Compounds in Gulf Coast Refined Fuels by GC/MS

Abstract

This study examines the composition of two samples of crude fuels originating from the Gulf Coastal areas of the United States. Both nitrogen-containing basic compounds as well as non-basic hydrocarbon compounds were evaluated for presence and relative amount in these two samples. The extractions of the basic nitrogenous compounds were achieved with weak acid extractions. The basic nitrogenous compounds, due to emulsification, formed two distinct fractions. The nitrogenous based-compounds were comprised of pyridines, quinolines, tetrahydroquinolines, indoles, and carbazoles to varying amounts. The hydrocarbon content in each of the two fuels analyzed was found to contain mostly naphthols.     

Analytical Profile of Organo-nitrogen Compounds in Gulf Coast Refined Fuels by GC/MS

This study examines the composition of two samples of crude fuels originating from the Gulf Coastal areas of the United States. Both nitrogen-containing basic compounds as well as non-basic hydrocarbon compounds were evaluated for presence and relative amount in these two samples. The extractions of the basic nitrogenous compounds were achieved with weak acid extractions. The basic nitrogenous compounds, due to emulsification, formed two distinct fractions. The nitrogenous based-compounds were comprised of pyridines, quinolines, tetrahydroquinolines, indoles, and carbazoles to varying amounts. The hydrocarbon content in each of the two fuels analyzed was found to contain mostly naphthols.