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.     

苦草(Vallisneria spiralis)释放的酚酸类物质对铜绿微囊藻(Microcystis aeruginosa)的化感作用

采用广谱性固相萃取小柱富集以10 g( FW)/L的密度培养三天后的苦草(Vallisneria spiralis)种植水,不同溶剂洗脱得到的各组分对铜绿微囊藻(Microcystis aeruginosa)的生长表现出不同程度的抑制,其中甲醇洗脱组分抑藻活性最强.去除该组分中的酚酸后,其抑藻活性下降了22.8％,表明...     

近地面臭氧研究进展

近地面臭氧是空气中氮氧化物和挥发性有机物发生光化学反应的产物,其浓度与气象条件密切相关。晴天少云、紫外辐射较强、温度较高、相对湿度较低以及风速较小的天气,均有利于臭氧的生成,其中紫外辐射是产生臭氧最关键的因素。臭氧前体物（氮氧化物和挥发性有机物）的浓度及其比值是影响近地面臭氧浓度的另外三个重要因素。我国大多数城市的O3处于VOC控制区,即NOx浓度的增加会引起O3浓度的降低,而VOCs浓度的增加则会使其浓度升高。因而VOC源解析问题成为近年来O3研究的一个热点问题。同时,由于气溶胶可以直接吸收、散射太阳紫外辐射、短波辐射以及大气长波辐射,因此气溶胶的存在会影响大气中光化学反应的进程,从而影响臭氧的光化学生成,气溶胶对近地面臭氧的影响已成为目前大气环境的前沿课题。     

Field investigations and laboratory simulation of clogging in Lixi tailings dam of Jinduicheng,China

Clogging is one of the most important factors affecting the stability of the tailings dams. Firstly, this work investigates the clogging materials of Lixi tailings dam using ICP-AES, X-ray powder diffraction (XRD) and SEM analysis methods. The ICP-AES results indicate that Fe is the dominant element in the clogging materials. The iron contents of clogging samples collected from 2# radial-well pipe and the access hole of the starter dam are 54.35 and 40.24%, respectively. XRD spectra show that ferric hydroxide is the main initial component of the clogging materials. Other compounds such as akaganeite, hematite and goethite are products from ferric hydroxide transformation. Therefore, the clogging materials are a mixture of ferric hydroxide and its converted products. The clogging materials commonly exist in an amorphous form with a cluster microstructure when viewed under SEM. Secondly, this work uses a continuous flow column to simulate clogging in the laboratory, and the clogging materials are analyzed with XRD and SEM. The chemical analysis indicates that the iron content of the clogging materials from the experiment is 45.43%. XRD spectra show that hematite is the only compound detected. The clogging materials generated experimentally are also in amorphous cluster microstructure when viewed under SEM.     

含铁矿物的表面催化氧化作用及其环境意义

了解含铁矿物在环境地球化学和生物地球化学中所起的作用，重点在于介了解含铁矿物表面催化氧化作用对重金属As(Ⅴ)，Cr(Ⅵ)，U(Ⅵ)离子的表面还原反应，以及对有机污染物卤代烷烃、苯、氯苯、硝基苯类等芳香化合物的降解及退氯化作用，进而了解表面催化氧化作用的机制。     

烃源岩生成有机酸过程的高分辨质谱研究

研究石油中有机酸的生成过程对研究储层改造、石油润湿性及页岩油可动性评价具有重要意义。在热压生烃模拟实验基础上,对Ⅲ型烃源岩不同演化阶段生成油中的非烃馏分进行了负离子电喷雾傅立叶变换离子回旋共振质谱分析,研究了烃源岩生成有机酸过程。对样品生成有机酸分析表明,在整个演化过程烃源岩都能生成有机酸,在低演化阶段主要生成脂肪酸,随演化程度的升高,脂肪酸丰度快速减少,芳环酸开始大量生成。随演化程度的增加,芳环上短链取代基发生断裂,并促进了有机酸的缩合,使得生成的有机酸缩合度逐渐提高,高碳数有机酸逐渐减少;烃源岩生成脂肪酸系列中存在偶奇优势,生成的C16、C18脂肪酸存在异常高丰度, C16、C18脂肪酸异常丰度现象可能是污染造成的,是否与烃源岩类型及成熟度有关尚需进一步研究。     

沉积物中NSO杂环芳烃的分布特征及其地球化学意义

对金湖凹陷原油和烃源岩中分子骨架结构相似，分别含N，S，O的三类杂环芳烃－吡咯类，硫芴和氧芴系列的分布特征及其应用进行了初步探讨,烃源岩中这三类杂原子化合物的丰度一般高于原油，其在油，岩中的丰度差异按含N，O和S化合物的顺序依次降低，指示三类化合物吸附性依次降低，原油和烃源岩中三类杂原子化合物丰度具有较好的正相关性，并与芴系列具有良好的多项式关系，暗示三类杂原子化合物在原生和（或）后生作用与干酪根降解方式上可能有某些相似性与相关性，在未熟一低熟阶段，随着成熟度的增加，三类化合物的丰度逐渐增加，指示成熟度对其有一定的控制作用，NSO化合物在油气运移，成熟度评价和指相等方面具有重要意义。     

基于BIF条带状铁建造矿化特征的国际铁矿石盈亏平衡运营成本定量研究

国内外铁矿石价格对标基准多采用离岸价或到岸价,而非盈亏平衡运营成本,难以揭示我国铁矿石所面对的真实市场承压价格。为了厘清国际一线生产商的铁矿石盈亏平衡运营成本价格,本文对世界上最重要的条带状铁建造(BIF)矿产地——西澳哈默斯利盆地高品位赤铁矿矿床的矿化特征及代表性铁矿石产品展开系统研究,同时引入巴西铁四角地区的铁英岩型赤铁矿矿石作为对照,分析全球典型高品位赤铁矿矿石经济指标。结合前人研究成果,将西澳哈默斯利盆地与BIF相关的高品位赤铁矿的富集矿化类型划分为假象赤铁矿-针铁矿、微板状赤铁矿与河道沉积型赤铁矿,巴西铁四角主要为铁英岩型赤铁矿。上述各矿化类型对应的铁矿石产品的铁元素含量均高于56%;在杂质元素含量上,假象赤铁矿-针铁矿的磷含量高,微板状赤铁矿的磷、硫含量较高,河道沉积型赤铁矿的磷、硫含量较低,铁英岩型赤铁矿含锰。经定量估算,西澳力拓、必和必拓、FMG和巴西淡水河谷的铁矿石盈亏平衡运营成本价格分别为34.66、36.76、47.35、38.07美元/干吨,可为中国海外权益铁矿项目开发提供运营成本的参考。     

25-降藿烷系列化合物及其在油藏地球化学研究中的应用

通过阐述烃源岩及原油中25-降藿烷系列化合物的结构、鉴定方法、成因（生物降解作用、原生作用）、降解机理,系统介绍了目前国内外25-降藿烷系列化合物的研究现状。认为25-降藿烷系列化合物在油源对比和油气成藏方面的应用和研究,有助于推动油藏地球化学的发展,同时也存在一些局限性。     

胶束电动毛细管色谱法测定岩屑样品中的苯系化合物

用胶束电动毛细管色谱法测定了同一井位、不同深度岩屑样品中的苯、甲苯、乙苯和二甲苯化合物。采用 50 μm× 57cm毛细管柱 ,以 50mmol/L十二烷基硫酸钠 - 2 0mmol/L四硼酸钠溶液 (pH 9 1 6)作为缓冲溶液 ,电压 2 5kV ,检测波长 2 0 0nm ,1 6min内 ,苯、甲苯、乙苯和二甲苯可获得良好的分离。用峰面积定量 ,线性范围为 2～ 1 0 0mg/L ,最小检测浓度分别为 :0 75mg/L苯 ;0 45mg/L甲苯 ;0 39mg/L乙苯 ;0 1mg/L邻 二甲苯 ;0 31mg/L对 二甲苯。加标回收率分别为 :苯 1 0 1 % ,甲苯 99% ,邻二甲苯 97% ,乙苯 95% ,对二甲苯 1 0 0 %。方法用于实际岩屑样品的测量 ,获得各含量范围在 0 .0x～ 0 .xμg/ g ;3次平行测定的RSD在 3 3%～ 34%。