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。     

烃源岩中4β—甲基甾烷的鉴定与研究

用TSQ70GC－MS－MS仪器分析我国珠江口盆地、北部湾盆地下第三系烃源岩的大量样品中，均检测出丰富的40甲基甾烷。通过质谱鉴定确定化合物的构型，在成熟岩样中多为4α－甲基甾烷，在未成熟生油岩中又鉴定出丰富的4β－甲基甾烷（包括C28－C30），其质谱特征以M／Z123为基峰。4β－甲基甾烷的热稳定性差，随着热成熟度的增加，很快向4α－甲基构型转化，直至消失，4β－甲基甾烷是未成熟烃源岩的重要标志，在我国近海陆架盆地多发现于下第三系淡水半深水－深水湖相沉积岩中，有一定的普遍意义。     

4β—甲基甾烷的确认及其地质意义

经用TSQ－70 GC／MS／MS仪器分析，从北部湾盆地不同埋深的生油岩样品中，检测出4－甲基甾烷系列。根据质谱特征、标样共注、献对照，确认其结构为4α－甲基甾烷和4β－甲基甾烷系列。对该区4β－甲基甾烷的分布及热演化规律进行了讨论，提出4α-Me ααα（20R）/（4α-Me ααα 4β-Meααα)(20R）甾烷是一个成熟度参数。     

GC-MS-MS 方法检测时代相关生物标志物及地质意义

利用色谱-质谱-质谱(GC-MS-MS)方法在辽河与塔里木盆地源岩和原油样品中,检测出了多个系列时代相关及特定种属生物标志物,包括:降胆甾烷系列、甲基甾烷及甲藻甾烷系列、三环二萜烷及四环二萜烷系列、六环藿烷及甲基藿烷系列等等,这些化合物很难用常规GC-MS方法检测到。以往认识的许多中生代以后才出现的生物标志物却在塔里木盆地寒武系源岩中有高含量分布,其先驱物的繁盛时代有可能推至更古老的寒武纪生物大爆发时代,GC-MS-MS方法检测出的特定种属和时代意义生物标志物参数提供了分子证据,并很好地区分了塔里木盆地寒武系与中-上奥陶统原油,在争议已久的塔里木油源问题研究中发挥了重要作用。     

东海盆地西湖凹陷煤系烃源岩及凝析油中的二萜化合物

经用GC／MS、GC／MS／MS分析东海西部凹陷煤系烃源岩及凝析油样品，检测出12个二萜烷生物标志化合物。根据色谱保留时间、质谱特征及与献资料对比，进一步确认其结构为：1个8β（H）－半日花烷，4个降海松烷，1个朽松木烷，1个异海松烷和5个四环二萜烷（即：ent-白叶烷，16α（H）－扁枝烷和16β（H）－扁枝烷，16α（H）－贝壳杉烷和16β（H）－贝壳杉烷）。异常丰富的二萜类化合物的检出，标志着树脂二萜对该区成烃的特殊贡献。     

色谱-质谱-质谱分析方法在生物标记物研究中的应用

介绍了色谱-质谱-质谱分析方法及其在生物标记化合物研究中的应用,通过对比可以看到色谱-质谱．质谱在检测痕量生物标记化合物、分析复杂甾、萜类化合物定性、定量方面具有独特优势。色谱-质谱-质谱由于是两级质谱串联比色谱．质谱增加了选择性,有了更强的分离能力,提高了对复杂混合物如甾、萜类化合物定性和定量的可靠性。色谱-质谱-质谱可以检测到通常色谱-质谱检测不到的含量低,又被C27甾烷掩盖的具有应用价值的C26甾烷和轻质油中痕量生物标记化合物。     

生物标志化合物热成熟度参数演化规律及意义——以Ⅲ型烃源岩HTHP生排烃热模拟液态烃产物为例

为了探究烃源岩不同热演化阶段生物标志化合物成熟度参数的演化规律及其专属指示意义。通过对辽河盆地桃10井Ⅲ型烃源岩进行HTHP生排烃热模拟实验,获取的液态烃产物饱和烃组分进行GC/MS分析,以模拟温度为成熟度标尺,检测出正构烷烃、类异戊二烯类烷烃、三环二萜烷、藿烷及甾烷系列中对热成熟度演化具有一定指示意义的生物标志化合物,并计算出参数指标。依据不同生物标志化合物对热作用的敏感程度不同,利用不同热敏感性的生标化合物比值指示热演化阶段。结果发现,随着模拟温度的升高,藿烷会受热作用影响形成三环萜烷,Tm会转化为Ts,20R型生物型异构体会向20S型地质异构体转化,所以∑三环萜烷／∑藿烷、Ts/Tm和C₃₁-藿烷22S／（22S+22R）参数对有机质热演化阶段可以起到较好的指示作用。而受热作用的差异性影响,参数C₂₄-四环萜烷／∑藿烷、C₃₀βα-莫烷／C₃₀αβ-藿烷和C₂₉-甾烷ββ／（αα+ββ）则在成熟至过成熟阶段具有更强的指示意义。由此可见,样品不同热演化阶段均有其最佳适用的生标参数组合,这为正确利用成熟度参数判识该地区烃源岩成熟度演化阶段提供了一定的理论依据。     

辽东湾地区C30甲藻甾烷的检出及其地质意义

用GC／MS分析辽东湾地区下第三系烃源岩及原油样品，检测出丰富的C30甲藻甾烷和C28－304－甲基甾烷。根据色谱保留时间、质谱特征及与文献对比，确认出4α、23，24（R）－三甲基胆甾烷（20R）与4β，23，24（R）－三甲基胆甾烷（20R）结构及6个相应的C30甲藻甾烷异构件。研究表明，甲藻甾烷不仅是海相环境的生物标志物，而且也是湖相咸水～半咸水沉积环境的生物标志物，在研究有机质的生源、沉积环境及油源对比中有特殊意义。     

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。      

中国西北地区侏罗纪煤系油气形成（之二）

西北地区已发现的侏罗纪煤系原油绝大多数为低密度、低硫、中含蜡，饱和烃含量一般为７０％～９０％，并且以Ｃ２１以前的低碳数正构烷烃为主，全油δ１３Ｃ值多为－２９‰～－２４‰。成熟度分析表明，绝大多数煤系原油为正常成熟原油，少数为低成熟原油，没有未成熟原油。天然气中的重烃含量高，Ｃ２以上组分平均达２０％，δ１３Ｃ１值一般为－４５‰～－３５‰，多属接近油型气的混合气。在侏罗纪煤系有机质和原油生物标志物分布中，类异戊二烯烷烃中姥鲛烷占明显优势，即具有较高的Ｐｒ／Ｐｈ值；含有较高的二环倍半萜烷，而三环萜烷含量较低、三环二萜烷含量很低；五环萜烷含量丰富，约占萜烷总量的８０％以上；煤和炭质泥岩中Ｔｓ、Ｃ２９Ｔｓ、Ｃ３０重排藿烷和伽马蜡烷含量很低，而煤系原油和泥岩中这些化合物相对较高；甾烷含量明显较低，且以Ｃ２９甾烷为主，占４０％～８０％；重排甾烷含量相对较高，也以Ｃ２９为主。总体上，煤系原油与泥岩的生物标志物特征较相似，而与煤和炭质泥岩有较大差异。煤系泥岩是西北地区侏罗纪煤系地层中的主力油源岩，煤和炭质泥岩是次要油源岩。这一结论在西北地区侏罗纪煤系含油气盆地具有普遍性。     

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.     

Solubility of a Russia vacuum residue and group composition of the soluble fractions in different solvents

Abstract

A Russia vacuum residue (RVR) was ultrasonically extracted with 15 organic solvents, respectively. The soluble fractions (SFs) were analyzed with a gas chromatography/mass spectrometer (GC/MS). The results show that the extract yields of RVR largely increased with the decrease in the dielectric constant of solvents, i.e., RVR tends to dissolve in weakly polar and non-polar solvents. Most of GC/MS-detectable components in the SFs are chain alkanes and cyclanes.     

THE BIOMARKER HYDROCARBONS AND THE ORGANIC GEOCHEMICAL CHARACTERISTICS OF FU-SHUN BITUMINOUS COAL

Biomarker hydrocarbons, such as C16-C31 n-alkanes, C19, C20, C22 isoprenoids, C14-C26 dicyclic and tricyclic terpanes, C27-C33 pentacyclic triterpanes, C27-C29 n-steranes, rearranged steranes and C19-norpregnane, have been identified as being present in Fu-shun Bituminous Coal by GC/MS. The carbon distribution of these biomarker hydrocarbons and the ratio of steranes and terpanes with different stereo-configuration show that although metamorphism of Fu-shun bituminous coal has progressed to higher rank coalification stage, it is still a relatively young bituminous coal. Moreover, it has amounts of resin and is a humus continental deposit formed by higher plants, which is consistent with the results obtained by routine coal analysis and coal petrography. This method of organic geochemical analysis provides significant information about coal genesis, coal maturation and its depositional environment.     

国产灯用煤油中芳烃的分析

利用ＳＱ－２０６气相色谱议和ＨＰ５８９０Ⅱ／５９７１Ａ色质联用分析仪（ＧＣ／ＭＳ）对国产灯用煤油进行了分析，检测出煤油中的各类芳烃，并用校正归一法求出大庆煤油中烷基苯含量为３．６％，萘的衍生物为４％，总芳烃含量１０．６％，为灯用煤油脱除芳烃制备无芳烃煤油的研究提供了试验依据。     

THE BIOMARKER HYDROCARBONS AND THE ORGANIC GEOCHEMICAL CHARACTERISTICS OF FU-SHUN BITUMINOUS COAL

ABSTRACT

Biomarker hydrocarbons, such as C16-C31 n-alkanes, C19, C20, C22 isoprenoids, C14-C26 dicyclic and tricyclic terpanes, C27-C33 pentacyclic triterpanes, C27-C29 n-steranes, rearranged steranes and C19-norpregnane, have been identified as being present in Fu-shun Bituminous Coal by GC/MS. The carbon distribution of these biomarker hydrocarbons and the ratio of steranes and terpanes with different stereo-configuration show that although metamorphism of Fu-shun bituminous coal has progressed to higher rank coalification stage, it is still a relatively young bituminous coal. Moreover, it has amounts of resin and is a humus continental deposit formed by higher plants, which is consistent with the results obtained by routine coal analysis and coal petrography. This method of organic geochemical analysis provides significant information about coal genesis, coal maturation and its depositional environment.     

混合苯中芳烃组分的气相色谱/质谱分析

利用 GC/ MS和毛细管气相色谱法对混合苯进行了分析。从至少 1 30种组分中准确鉴定出 2 9种芳烃。并对各芳烃组分进行了定量分析。本法适用于出口混合苯品质检验 ,也可用于炼油厂同类产品质量控制分析。     

The rapid selecting of precursor ions and product ions of thirty-four kinds of pesticide for content determination by GC–EI/MS/MS

Pesticide residues caused great threat to human body health, and all countries protected the health of human body by specifying its upper limit. However, pesticide residues were generally very low, similar to trace analysis and as low as millionth or less, the content determination of pesticide residues was a troublesome problem. With the application and promotion of tandem mass spectrometry, it was able to do trace analysis. GC–EI/MS/MS was a common method for the determination of pesticide residues. The multiple reaction monitoring (MRM) mode was the most common quantitative method used in GC–EI/MS/MS. It has the characteristics of high sensitivity, good reproducibility, high accuracy, strong anti-interference and high ion flux. Multiple-twin precursor ions, product ions and collision energy of thirty-four pesticides were provided for MRM. It could play an important role in developing MRM method for the quantifying of 34 kinds of pesticide. Meanwhile, the development of MRM method for the quantifying of other compounds could also refer to this paper.     

A Study on NMR and GC/MS Spectra of the Isomers of Linear Hexyl Naphthalene

The GC/MS and NMR analysis of the reaction products of naphthalene with 1-bromohexane were reported. The products obtained were suggested to have six isomers of linear hexylnaphthalene and the structure of each isomer was determined by GC/MS and NMR spectra. For the first time, the unique chemical shift data were obtained. The content of each isomer calculated by ¹H NMR and ¹³C NMR spectra was consistent with that by GC/MS spectra, which confirmed the accuracy of NMR data.     

芳烃生产新工艺中原料和产物的GC／MS分析

利用ＧＣ／ＭＳ联用法对芳烃生产新工艺中的原料和产物进行了分析，其中原料定出２６个组份，产物定出２４个组份，并用面积归一化法对原料和产物中的各个组份的含量进行了定量计算，为芳烃生产新工艺中的新型芳构化催化剂ＡＦ－５的推广运用提供了科学依据。