原油中三芳甾烃的色谱质谱定量分析

三芳甾烃是原油芳烃组分中的常见化合物,其色谱质谱分析结果对寻找油气有着重要的意义.以往原油中芳烃色谱质谱分析大多忽略了各三芳甾烃化合物的绝对含量,而仅得出各化合物的相对量,使三芳甾烃的应用受到了限制.我们采用人工合成的二氘代化合物d2C28三芳甾烃加入原油中作内标,进行三芳甾烃的色谱质谱定量分析,该内标化合物是将原油中自然存在的1种C28三芳甾烃化合物进行氘代反应,合成得到的d2C28三芳甾烃与原油中的三芳甾烃系列化合物有着相似的结构和质谱分裂特征,并在色谱质谱分析时与原油中的化合物不产生共流.该定量分析方法可以为油气勘探提供更多的信息.     

催化加氢热解/气相色谱-质谱研究沉积物中生物标志物

针对地质体中高演化沉积有机质,应用催化加氢热解/气相色谱-质谱方法测定了干酪根中以共价键结合的生物标志物。结果表明,实验样品的催化加氢热解产物收率明显高于二氯甲烷（DCM）索氏抽提,产物色谱图中饱和烃的峰形、保留时间和质谱特征与索氏抽提峰形基本一致;对比两种方法产物中饱和烃主要指标甾烷m/z 217和藿烷m/z 191表明,经过加氢还原,干酪根分子网络中共价键结合着两种生物标志物分子骨架得到印证,为催化加氢热解提取沉积物中生物标志物的方法可靠性提供了依据。催化加氢热解/气相色谱-质谱技术是一种对研究高演化沉积有机质中生物标志化合物有独特作用的有效分析手段。     

准噶尔盆地陆梁油气田原油的生物降解作用与油气成藏

1原油的生物降解现象 陆梁油气田原油可按饱和烃色谱图上正构烷烃的完整程度和m/z 177质量色谱图上25-降藿烷的存在与否,分为3类.第1类:饱和烃分布完整,不存在25-降藿烷,主要分布于中侏罗统西山窑组X4段;第2类:饱和烃分布完整但存在25-降藿烷,主要分布于中侏罗统西山窑组X1段;第3类:饱和烃分布差异较大,从仅缺损部分低碳数正构烷烃到几乎完全缺损正构烷烃,而且存在25-降藿烷,主要分布于下白垩统吐谷鲁群.原油中25-降藿烷的存在,表示了该原油曾经遭受过"严重"级别的生物降解.     

苯二氮卓类新精神活性物质Flubromazolam的快速检测

建立了气相色谱-质谱(GC-MS)和超高效液相色谱-串联四极杆飞行时间质谱(UPLC-Q-TOF MS)技术联合鉴定检材中flubromazolam的方法。未知样品用甲醇和水提取,取上清液,采用GC-MS和UPLC-Q-TOF MS进行分析。经GC-MS检测,保留时间为17.96 min的未知组分的质谱碎片主要特征离子峰有m/z 222,341,343,370,372,111,102,75。经UPLC-QTOF M S检测,保留时间为4.99 min的未知组分的准分子离子峰为m/z 371.0298,碰撞诱导解离(CID)模式下二级质谱主要离子有m/z 343.0114,302.9928,292.1118,263.0982,237.0951,223.0670。经美国缉毒署毒品分析谱库、缴获毒品分析科学工作组(SWGDRUG)分析谱库检索和文献查询获得的信息资料进行比对,确认目标物为flubromazolam。     

快速气相色谱法分析石油饱和烃

提出了一种快速分析原油和岩石抽提物中饱和烃组分的毛细管气相色谱(GC)方法。由于在该方法中采用了细内径毛细管柱,故饱和烃的GC分析周期由原来的80~90 min缩短至15 min,分析速度加快约5倍,大大提高了工作效率和仪器通量,使石油饱和烃得到了很好的分离分析。该方法符合中华人民共和国石油天然气行业标准SY/T5120-1997的要求。20万理论塔板数的细径柱的应用,可供石油中异构烷烃,尤其是甾烷、萜烷类的气相色谱/质谱(GC/MS)快速分析方法及芳烃的GC快速分析方法借鉴。     

气相色谱-质谱联用法测定烟用香精中黄樟素及香豆素

采用气相色谱-质谱(GC-MS)联用分析技术,提出了烟用香精中香豆素、黄樟素的同时测定方法。色谱柱为DB-1 MS石英毛细管柱,电子轰击离子源,选择香豆素质谱图中m/z89,90,118,146;黄樟素m/z104,131,135,162各4个特征离子用于选择离子检测法检测,根据这4个离子的抽出离子色谱图的峰面积比进行目标物确证,以基峰m/z118,162作两成分的定量分析,方法的检出限(3S/N)均为0.1 mg.kg-1。用色谱保留时间、质谱特征离子同时定性,消除了香精样品中复杂基体的干扰,避免了假阳性结果的出现。     

严重生物降解原油GC-MS特征及油源对比

图牧吉油砂位于松辽盆地边缘,搞清它的油源对于该地区的油气勘探有着十分重要的意义。气相色谱-质谱分析表明,该样品受到了严重的生物降解,部分用于对比的甾、萜烷生标标志物受到了降解,使与之有关的参数值发生了变化,给油源对比带来了困难。本研究采用抗生物降解的三环萜烷和四环萜烷等作生标对比参数,将图牧吉油砂与周边已知烃源岩的原油进行对比,确定了该生物降解油来自松辽盆地的嫩江组和青三口组烃源岩。该研究为严重生物降解原油的油源对比提供了有效的方法。     

结合直观推导式演进特征投影法分析原油中非烃结构和含量

提出一种分析原油非烃结构和含量的方法。用直观推导式演进特征投影法分辨有关二维数据以获得非烃的纯色谱和纯质谱,再将所获质谱在标准质谱库中检索,并结合色谱保留指数分析等来进行单个非烃化合物结构鉴定;利用实验数据,根据分辨获得的纯色谱峰面积所建立的规一化模型,进行非烃化合物定量分析。用本法确定了一原油样品中168个含氮化合物和该油样一个馏分中60个其它非烃化合物的结构和含量。本方法具有系统分析原油非烃结构和含量的通用性;标准化合物加标回收实验表明,其准确度很好。     

超声萃取-高效液相色谱-串联质谱法测定大气颗粒物中甾醇类化合物

采用超声萃取与液相色谱-串联质谱联用,建立了快速测定大气颗粒物中甾醇类化合物的方法.甾醇类化合物用甲醇超声萃取,浓缩后使用液相色谱-串联质谱分析.采用Waters公司Atlantis C18色谱柱(100mm× 2.1 mm,3μm),以乙腈和水混合流动相梯度洗脱,实现了胆甾醇、豆甾醇、菜油甾醇及β-谷甾醇的分离.并在APCI-MS/MS MRM模式下定量检测.在选取的实验条件下,方法回收率在80.3％～97.7％之间,检出限0.015 ng/m3,相对标准偏差小于15％,日内及日间测定精密度小于20％.本方法具有较好的准确性及精密度,实际样品的测试结果表明,方法可以满足大气颗粒物中甾醇类化合物的定量分析要求.     

原油中含氧化合物的质谱分析

本文介绍自原油分离含氧化合物,酯化混合酸和用毛细管气相色谱-质谱(GC-MS)鉴定其组分的方法。色谱-质谱分离并鉴定出C_8—C_(30)的脂肪酸、分子量为484和498的二对藿烷酸的立体异构体,烷基酚,邻苯二甲酸酯等,并首次发现石油中含有癸二酸二异辛酯类组分。     

Chromatographic study of the organic matter from Moroccan Rif bituminous rocks

The bituminous rocks of the Upper Cretaceous in the Moroccan Rif have been assessed and characterized in detail using organic geochemical techniques and a variety of organic geochemical parameters. The organic matter from 4 sites was studied in order to determine its thermal maturity and its depositional environments. The organic extracts (bitumens) were fractionated on silica-potassium hydroxide column according to the aliphatic hydrocarbons, acid compounds and polar compounds. Aliphatic hydrocarbons were identified by gas chromatography and mass spectrometry (GC/MS).The distribution of the aliphatic hydrocarbon fractions, and the various organic geochemical parameters (pristane/phytane, isoprenoids/n-alkanes, CPI, C₂₇:C₂₈:C₂₉ regular, C₂₉20S/(20S+20R), C₂₉ββ/(ββ+αα), C₂₉/C₃₀ hopanes and Ts/Tm) showed that the studied samples were generally mature. Two of the 4 samples appeared to be derived from source rocks deposited under anoxic conditions while suboxic to oxic conditions seemed to have been dominant for the remaining two samples. Rock–Eval pyrolysis data in addition to GC results suggested types II, III and IV kerogens for the studied samples.     

搅拌棒吸附子萃取与GC-MS法测定水中20种有机氯农药

建立了搅拌棒吸附子萃取/气相色谱-质谱法(SBSE/GC-MS)同时检测水中α-六六六、γ-六六六、β-六六六、七氯、δ-六六六、艾氏剂、环氧七氯、γ-氯丹、顺-氯丹、硫丹Ⅰ、p,p-滴滴伊、狄氏剂、异狄氏剂、p,p-滴滴滴、硫丹Ⅱ、p,p-滴滴涕、异狄氏剂醛、硫丹硫酸盐、甲氧滴滴涕、异狄氏剂酮20种有机氯农药含量的方法.样品在室温下经拌棒吸附子搅拌吸附,甲醇解吸附后,以J&W DB-35 MS(30 m×0.25 mm×0.25 μm)石英毛细管色谱柱为分析柱,气相色谱-质谱选择离子流模式检测.考察了萃取时间、氯化钠及甲醇加入量等对萃取的影响.实验结果表明:在2.5 ～20.0 μg/L 范围内,20种有机氯农药呈良好的线性关系,检出限(S/N=3)为0.008 ～0.118 μg/L,水样中分别添加2.5、20 μg/L的20种有机氯农药,回收率为 52% ～117%,相对标准偏差小于13%(n= 6).该方法操作简便、快速、灵敏度高,应用于实际样品检测,结果满意.     

硒芳香杂环化合物的GC/MS分析

本文对合成的7种含硒芳香杂环化合物进行了GC／MS分析研究。结果表明：BS、MB、BBS和DBBS等4个化合物在色谱柱内的保留时间与它们的相对分子质量呈线性关系。所有化合物均可获得特征质谱,表现出含单个硒原子的分子离子或碎片离子特征峰簇,硒的两种主要同位素在峰簇中表现为主要峰M与（M-2）的相对丰度比约为2：1,可为鉴定含硒分子离子或碎片离子提供重要信息。新化合物1,2,5-硒二唑并[3,4-d]嘧啶-5,7-（4H,6H）二酮（SPDO）在色谱柱内出现11．83min和7．96min两个具有相同的质谱的色谱峰,被认为是互变异构体的峰。     

色谱-质谱分析在有机地球化学研究中的应用

色谱-质谱分析在有机地球化学领域主要用来检测地质体中的生物标志物和分子化合物。生物标志物(biomarkers)指存在地壳和大气圈中,分子结构与特定天然产物之间具有明确联系,或与特定生物类别的分子结构之间具有相关性的天然有机化合物。从1982年到1992年10年的时间共召开了五届全国有机地球化学会议,每次会议都有生物标志物专题,在五届的全国有机地球化学会议中共有论文摘要1491篇,和生物标志物有关的论文达     

气相色谱-质谱指纹图谱在甄别真假卷烟上的应用

运用固相微萃取／气相色谱-质谱法建立卷烟挥发性和半挥发性物质的指纹图谱。通过指纹图谱相似度评价软件,对12批正品卷烟和1个假冒品卷烟的指纹图谱进行了相似度计算,结果表明：12批样品间相似度很好,而假冒品卷烟与正品卷烟的相似度很低,该方法为探讨卷烟质量稳定和甄别真假卷烟提供了一种简便易行的方法模式。     

Determination of Atenolol in Pharmaceutical Preparations by Gas Chromatography with Flame Ionization and Mass Spectrometric Detection

The present work describes the methodology and validation of gas chromatography with flame ionization (FID) and mass spectrometric (MS) detection after derivatization with N-Methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) for determination of atenolol with an internal standard (metoprolol) in pharmaceutical preparations. The linearity was established over the concentration range of 0.5–20 μg/mL for GC/FID and 12.5–500 ng/mL for GC/MS method. The intra- and inter-day relative standard deviation was less than 4.72 and 5.80%, respectively. Limit of quantification was determined as 500 ng/mL and 12.5 ng/mL for GC/FID and GC/MS, respectively. No interference was found from tablet excipients at the selected assay conditions. Developed GC/FID and GC/MS methods in this study are accurate, sensitive, and precise and can be easily applied to Tensinor tablet as pharmaceutical preparation.     

GC-MS与GC-FTIR联合测定C9烃馏分组成

混合碳九组成复杂,估计为环状烯烃、芳烃、多环烃、烷烃等,目前该产品主要用于生产石油树脂。随着我国乙烯生产能力的不断扩大,其产量也在不断增加,为充分利用碳九资源,研究开拓其新的应用领域非常必要。而此研究的首要条件在于对其组成进行较为全面、准确地分析。传统的分析方法不能对其组成提供详尽的数据资料,直接影响了对碳九进行综合利用研究。GC-MS兼有GC的高效分离能力与MS很好的定性功能,且灵敏度较高,是分析有机混合物十分有效的手段。本文将GC-MS应用于碳九组成的定性分析中。但由于碳九组分中含有较多的同分异构体如三甲苯与二甲苯等,同分异构体的质谱图几乎相同,GC-MS对其不易鉴别,而红外(FTIR)对有机物同分异构体尤其苯系物的异构体具有非常好的鉴别能力。因此本文将GC-MS与GC-FTIR联合使用,对碳九组成进行定性分析,样品定量采用色谱氢火焰检测器峰面积归一化法得到的各组分峰面积相对百分含量,较好地解决了碳九组分的定性定量问题,为开发碳九新的应用领域提供依据。     

Determination of the acaricide fenbutatin oxide in water samples by automated headspace-SPME-GC/MS

The analysis of the acaricide fenbutatin oxide (FBTO) having a molecular weight of 1052.66 g mol(-1) in water samples by capillary GC/MS after in-situ derivatization with sodium tetraethylborate (NaBEt4) and headspace-SPME enrichment is described. Automated SPME is performed at 80 degrees C for 30 min. Detection is carried out in the ion monitoring mode with deuterated triphenyltin (TPhTd15) as internal standard. Good linearity (R2 = 0.9993) was obtained in the dynamic range 20 to 1000 ng L(-1) with a limit of detection of 16 ng L(1) (LOD at 3 S/N) and a limit of quantitation of 50 ng L(-1) (LOQ at 10 S/N). Intra-day RSD% for n=6 was 8.9 at the LOQ level.     

Book Reviews

A gas chromatography/ion trap mass spectrometry method was used for the trace analysis of atrazine and its deethylated degradation product deethylatrazine in environmental water and sediment samples. The isotope dilution technique was applied for the quantitative analysis of atrazine at parts-per-trillion levels. Water samples were pre-concentrated by solid-phase extraction using a C18 cartridge while the sediment samples were extracted by sonication with methanol. The concentrated extracts were analysed by a GC/ion trap MS operated in the MS/MS method. The extraction recoveries for the analytes were better than 83% when 1 L of water or 10 g of sediment was analysed. The method detection limits were 0.75 ng/L and 0.13 ng/g for atrazine and deethylatrazine detected in water and sediment, respectively. The precisions of the method represented by the relative standard deviation were in the range of 3.2-16.1%. The method was successfully applied to analyse surface water and sediment samples collected from Beijing Guanting reservoir. Trace levels of atrazine at 35.9-217.3 ng/L and 2.4-8.4 ng/g were detected in the water and sediment samples, respectively. The levels of deethylatrazine were five to 20 times lower that those of atrazine.     

Use of small diameter WCOT columns for ultra-high resolution GC/MS

For clinical and environmental analyses utilizing capillary gas chromatography/mass spectrometry (GC/MS), increased sensitivity and speed of analysis are highly desirable. These performance advantages are realized using a WCOT column of 100 μm i.d. as compared to the more conventional 200 μm i.d. capillary columns. The improved sensitivity of capillary direct GC/MS with the 100 μm i.d. column for the confirmation of drugs of abuse will be demonstrated. For environmental analysis, the superior efficiency and resolution of the 100 μm i.d. column can be employed for the separation of priority pollutants. This approach is more amenable to capillary direct GC/MS providing a more effective interface to the mass spectrometer. As a result improved sensitivity and a considerable decrease in analysis time is achieved over that obtained with the larger diameter environmental specialty phase columns.