Synchronous Scan and Excitation-Emission Matrix Fluorescence Spectroscopy of Water-Soluble Organic Compounds in Atmospheric Aerosols

Three-dimensional excitation–emission matrix (EEM) fluorescence spectra of water-soluble organic compounds (WSOC) from aerosol samples were measured and compared with those reported in the literature for natural dissolved organic matter. The EEM profiles of the WSOC presented three characteristic excitation/emission (_Exc/_Em) peaks: 240/405 nm, 310/405 nm and 280/340 nm. The fluorescence intensities at _Exc/_Em240/405 nm and _Exc/_Em310/405 nm are located at wavelengths shorter than those reported for aquatic humic substances, indicating a smaller content of both aromatic structures and condensed unsaturated bond systems in the WSOC fraction. The EEM profiles of fractions obtained by the isolation procedure of the WSOC by the XAD resins showed that a fractionation has occurred and the XAD-8 eluate is highly representative of the total WSOC of collected aerosol. Synchronous scan spectra were more detailed than conventional fluorescence emission spectra, appearing more suitable for studying multicomponent samples such as the WSOC from atmospheric aerosols.     

西藏罗布莎铁族元素金属互化物矿物及其成因探讨

对西藏罗布莎铬铁矿中的铁族元素金属及金属互化物矿物进行了X射线衍射测定,结果显示其归属于镍纹石、自然铁、钴铁矿及铁镍矿4种矿物。它们与超高压矿物方铁矿、铂族元素矿物等连生,形成于深部的高还原环境,矿物的化学成分与地核十分相近,故认为它们可能来自于地幔及地核。     

Research on the direction of secondary migration of oil by making use of nitrogen compounds as tracers in the No. 6 area of the Melut Basin

1 IntroductionThe application of isomeric-nitrogen compounds astracers to oil-migration research is a piece of innovatorywork, and also a newbreakthrough made in non-hydro-carbon geochemistry research. At present, a lot ofwork has been done on nitrogen co…     

Advances in Air Sparging Technology of Saturated Zone

In situ air sparging involves injecting atmospheric air, under pressure, into the saturated zone to remove those volatile and semi-volatile organic groundwater contaminants and to promote their biodegradation by increasing subsurface oxygen concentrations. Due to the advantages of low cost, high efficiency and in situ constructability, groundwater Air Sparging (AS) technology has been quickly developed in the world recently. Based on the explanation of its remediation principle, literature review is done on the research advancement of air sparging technology mainly from three aspects. First, various methods for determination of the zone of influence and visualization techniques of air flow forms during air sparging are summarized. Then the influence of environmental geological conditions and construction technology parameters on the remediation effect of air sparging is systematically analyzed. Thereafter, two main types of air sparging theoretical models including lumped-parameter model and multiphase fluid flow model are discussed respectively in detail. Finally, based on the problems and difficulties existing in present research and engineering practice, several future tasks such as the enhancement remediation techniques in complex geological sites, microscopic intrinsic mechanisms, and establishment of related design and construction standards which require to be done are briefly analyzed.     

马朗凹陷断裂-烃源岩空间配置关系与石油垂向运移特征

马朗凹陷的原油类型可以划分为3大类,Ⅰ类原油来自二叠系芦草沟组,Ⅱ类原油来自石炭系哈尔加乌组,Ⅲ类原油为Ⅰ与Ⅱ类原油的混源油。通过断裂活动强度、垂向输导断裂与烃源岩的匹配关系的研究,结合原油含氮化合物的分析资料,分析了马朗凹陷油气的垂向运移特征。研究表明,断层的断裂活动强度控制着油气的垂向运移能力,垂向输导断裂与烃源岩相匹配时,烃源岩生成的油气才能向上运移至上覆地层聚集成藏。二叠系芦草沟组烃源岩厚度中心附近的垂向输导断裂断穿侏罗系,所以,芦草沟组烃源岩生成的Ⅰ类原油可以运移至侏罗系聚集成藏,而石炭系哈尔加乌组烃源岩附近的断裂大都未断至二叠系和侏罗系,所以哈尔加乌组烃源岩生成的Ⅱ类原油未能运移到侏罗系聚集成藏,而主要在石炭系成藏。与断裂输导分析相配合,含氮化合物可以很好示踪油气的垂向运移方向,沿断裂从深层到浅层,原油含氮化合物总浓度逐渐降低,1,8DMC/1,3 DMC或1,8DMC/2,4 DMC值增大。     

土壤样品中挥发性有机物的提取方法研究

挥发性有机物(VOCs)在土壤样品中残留浓度低且极易挥发,因此测定时选择合适的提取方法十分重要。文章研究优化了土壤样品中包括卤代烷烃、卤代烯烃和苯类的53种VOCs的提取方法。通过比较酸化、甲醇提取剂浓度和提取体积对土壤中挥发性有机物提取效率的影响,建立了使用4 mL 100%甲醇不酸化提取,顶空-气相色谱-质谱联用测定的分析方法,结果表明,0.10μg/g加标土壤53种VOCs的平均回收率为40.45%～119.73%,精密度(RSD,n=7)为1.26%～9.14%;1,1,2,2-四氯乙烷、三氯乙烯的回收率欠佳,主要是由于在碱性土壤条件下1,1,2,2-四氯乙烷分解造成的。该方法简便、快速,提取效果较好。但对土壤标准样品CRM 628-030进行提取,烯烃的回收率偏低,达不到给定区间浓度,且无法控制1,1,2,2-四氯乙烷的分解问题,有待于进一步研究。     

The impact of thermal maturity level on the composition of crude oils,assessed using ultra-high resolution mass spectrometry

We have examined, using a 12 Tesla FTICR-MS instrument, the impact of varying thermal maturity level on a suite of 9 related crude oils charged from source rocks covering most of the liquid petroleum generating portion of the oil window (0.68–1.11% vitrinite reflectance equivalent (%Re)). The sample suite was analyzed as whole oils under three different conditions, electrospray ionization (ESI) in positive and negative ion mode to analyze basic and acidic components, respectively, and atmospheric pressure photoionization (APPI) in positive ion mode, for sulfur and hydrocarbon species.Increasing oil maturity level had a strong influence on the composition of all compound classes in the oils with several major observations evident:The relative apparent abundances of all heteroatom containing compound classes detected in this study, using all ionization modes, decrease systematically with increasing oil maturation levels. Both aromatic hydrocarbons, detectable in APPI mode, and NSO compound classes (detectable in both ESI and APPI modes), as broad classes, are becoming more aromatic (shift to a greater predominance of higher DBE group members) and dealkylated (decreasing average molecular mass of individual compound groups), with increasing maturation level in the oil suite. Several putative oil maturity level dependent, molecular ratios were identified in the study. Of particular note, the relative abundance ratios of heteroatom compound classes tentatively identified as alkylated carbazoles, quinolines and benzothiophenes, compared to their benzannulated homologues are very sensitive to maturation level. Several groups of compounds show interesting and specific carbon number distributions, suggesting there may be hints of specific molecular markers in the FTICR-MS data. One observation of note is the strong increase in the relative abundance of protonated hydrocarbon components with DBE 5. We speculate this might reflect the presence of previously unreported higher molecular weight diamondoid (diamantane) species in oils with up to 40 carbon atoms or more, at advanced maturity levels. Such species may prove very valuable as molecular markers in highly mature fluids, such as those currently being produced from some shale reservoirs. Covariation of quantitative GC–MS data for alkylated hetero aromatic sulfur and nitrogen compounds in this oil suite, together with the corresponding FTICR-MS data from compounds believed to be, based on accurate mass, alkylated sulfur and alkylated nitrogen compounds, suggests that FTICR-MS already has some very rudimentary quantitation capabilities.     

Applicability of Carbazole Migration Indices in Continental Rift Basins: A Case Study of Western Lujiapu Depression in Kailu Basin, NE China

<正>Kailu Basin in which the Western Lujiapu Depression is located is a typical continental rift basin.Biomarker parameters of the oils indicate that depositional facies and environments vary between the Bao 1 and Bao 14 fault blocks with a higher saline environment in the Bao 1 fault block, but such difference has no significant impact on carbazole abundance and distribution.Maturity and migration distance are the main controls on carbazole abundance and distribution in the Western Lujiapu Depression.The commonly used migration indices,such as ratios of nitrogen shield isomers to nitrogen exposed isomers(1-/4-methylcarbazole ratio,1,8-/2,4-dimethylcarbazole(DMC) ratio and half-shield/exposed-DMC ratio),absolute concentrations of alkylated carbazoles and BC ratio(=benzo [a]carbazole/(benzo[a]carbazole+benzo[c]carbazole)) increase at the low mature range and decrease at a higher mature range with increasing maturity.At relatively low maturity stage(Rc0.77%), maturation has reversal effects with migration on the ratios of nitrogen shield isomers to nitrogen exposed isomers,which may cover migration influence and makes these parameters fail to indicate migration effects.Valid migration indicators at this maturity stage are concentrations of alkylated carbazoles and BC ratios,which can provide ideal tools for migration direction assessment even within short migration distance.Maturity effects should be taken into account when carbazole compounds are applied to indicate migration direction,and at different maturity stages,these commonly used parameters have different validity in tracing migration direction.Coupled with our previous study in the Eastern Lujiapu Depression,a conceptual model of the variation of nitrogen migration indices can be established for terrestrial rifted basins,that is,strong fractionation lateral migration model through sandy beds,weak fractionation vertical migration model along faults,and maturity impacts on migration assessment.     

吹扫捕集-气相色谱/质谱联用同时测定饮用水源地水中痕量挥发性有机物

为满足饮用水源地监测要求,采用吹扫捕集-气相色谱/质谱法同时测定饮用水源地水中乙醛、环氧氯丙烷、丙烯醛、苯系物等27种挥发性有机物。实验中运用程序升温,在26 min内完成检测,采用全扫描(SCAN)方式扫描,提高了化合物的定性能力。方法检出限均低于我国饮用水源地标准限值,回收率为75.6%~111.0%。