原油中常见化合物的全二维气相色谱-飞行时间质谱分析

全二维气相色谱-飞行时间质谱分析是近年来发展起来的一项全新的复杂混合物分离分析技术,该技术在分离石油烃类化合物方面显示出比传统一维色谱-四极杆质谱分析更强的优越性。通过不同类型原油的全二维气相色谱-飞行时间质谱分析,建立生物解降原油饱和烃组分和轻质原油烃类组分(饱和烃与芳烃)的分析方法,得到了甾烷、萜烷和芳烃化合物的二维平面点阵图和三维立体图。结果表明,该方法在原油的萜类化合物和轻质原油的饱和烃与芳烃同时分离方面取得了良好的结果,许多在普通一维色谱分析中不能分离或分离效果不佳的共馏化合物得到了很好的分离。     

加速溶剂提取-气相色谱-质谱法分析土壤和沉积物中15种有机磷酸酯类阻燃剂

有机磷酸酯类阻燃剂广泛存在于环境中,长期接触会对生物体的生殖系统、免疫系统造成破坏,进而对人类健康产生影响,调查研究其在环境中的污染水平非常有必要,而多组分、同时、准确的分析技术是研究的基础,目前已有的分析方法在化合物种类和提取效率方面还有待提高。本文建立了一种分析土壤和沉积物中15种有机磷酸酯类阻燃剂的方法。新鲜样品采用加速溶剂萃取(ASE)直接提取,提取液用复合填料的固相萃取柱进行净化,再采用气相色谱-质谱(GC-MS)进行定性、定量分析。为了改善提取效率和净化效果等问题,针对土壤和沉积物样品基质的复杂性,实验中主要优化了样品的提取、净化条件：针对磷酸三(2-氯乙基)酯提取回收率低的问题,改进了样品制备方式,新鲜样品在有少量水的存在下直接提取,使得有机溶剂更好地与样品颗粒进行接触,显著提高了该化合物的提取效率;采用石墨化碳和氨基硅胶复合填料的固相萃取小柱对样品提取液进行净化,保障了复杂沉积物样品净化效果的有效性,同时选用5%甲苯的洗脱溶剂体系,能够提高磷酸三甲苯酯(TCP)在石墨化碳固相萃取柱上的洗脱效率,保证了净化过程的回收率。结果表明,目标化合物浓度在10.0～500.0ng/...     

高压液相色谱-电感耦合等离子体发射光谱联用技术在元素化学形态分析中的应用

介绍了高压液相色谱与等离子体光谱仪的联用技术及其应用于元素化学形态分析的现状、前景和存在问题。着重叙述了联用接口的作用和几种接口的结构性能。     

气相色谱-质谱法分析某阻燃剂生产厂周边淡水鱼中的多溴联苯醚及其累积特征

近年来多溴联苯醚(PBDEs)的研究集中在电子行业发达地区、电子废物处置区、塑料制品生产区等重点污染区域。对阻燃剂生产厂周边PBDEs的研究有助于更好地理解PBDEs的累积特征和环境过程。本文选择江苏某PBDEs生产厂周边的淡水河流,采用气相色谱-质谱法(GC-MS)分析该河流5种淡水鱼中13种PBDEs同族体的浓度。结果显示,淡水鱼样品肌肉、肝脏和鱼卵组织中∑_(13)PBDEs(BDE17、28、71、47、66、100、99、85、154、153、138、183、190)的浓度平均值分别为34.5 ng/g.lip、41.5 ng/g.lip和18.2 ng/g.lip。研究水域不同种类淡水鱼的食性、习性和代谢能力等是影响鱼体中PBDEs浓度的主要因素。鱼体中BDE47是主要的同族体,但是与大多数已报道的研究数据相比,鱼体中含有的六溴(BDE153、154)和七溴同族体(BDE183)比例较高,这与河流附近工厂生产八溴联苯醚工业品(以六溴、七溴和八溴同族体为主)相符。工厂生产的八溴联苯醚工业品以及河流上游径流带来的其他区域生产和使用的多溴联苯醚工业品释放到环境中,被河流中的淡水鱼类选择性地积累和代谢,形成了本研究区淡水鱼体中PBDEs特殊的同族体分布。     

Determination of naphthenic acids in crude oil by chemical ionization mass spectrometry

Naphthenic acids in petroleum are considered a class of biological markers. Their potential use in source correlation and as an indicator of biodegradation was reported in the past ( Dzidic et al. ,1988 ; Behar and Albrecht, 1984). Due to their highly complicated properties, detailed characterization of the acids is difficult. A method based on positive ion CI (chemical ionization) mass spectrometry using isobutane reagent gas to produce ( M 15)^ ions was applied to the analysis of naphthenic acid esters. Since the complex mixture of naphthenic acids cannot be separated into individual components, only the determination of relative distribution of acids classified in terms of hydrogen deficiency was possible. The identities and relative distribution of fatty and mono-, di-, tri-, and higher polycyclic acids were obtained from the intensities of the ( M 15 )^ ions according to z-series formula CπH2π 2 O2 of naphthenic acids. The components are characterized on the basis of group type and carbon number distributions. A comparison of the FAB and CI results showed that the group type distributions obtained bv both methods agree surprisingly well.The results indicated this method is simple, rapid and easy to operate. The geochemical implication of naphthenic acids was investigated by using a set of well-characterized crude oil samples. It is found that the naphthenic acid distribution can be used as a fingerprint for oil-oil and oil-source correlations.     

An invariance in the carbazoles of petroleum

A remarkable invariance in the ratio of 1,3-dimethylcarbazole （DMC） to 1,6-DMC was discovered in crude oils from the Pearl River Mouth Basin, South China Sea. The remarkably invariant ratio is kept at a constant of about unity regardless of their concentrations, sources or maturities for the sampies. In combination with the molecular structures of 1,3- and 1,6-DMCs, the invariance might indicate that the nitrogen compounds share a common precursor with a skeleton of 1-methylcarbazole and are formed through methylation at C3 and C6 with an essentially identical rate.     

直接熔融热电离质谱法测定硼硅玻璃中硼同位素比值

硼硅玻璃是目前压水堆应用最多的可燃毒物材料,产品中硼同位素组成的准确测定对燃耗预估及产品质量判定具有重要意义。文章基于直接熔融热电离质谱法,首先探讨了硅元素对硼酸中硼同位素测量结果的影响,结果表明:Si/B质量比小于9时,硅对NIST 951a硼酸标准物质测量结果无显著干扰,采用直接熔融热电离质谱法测定核电用硼硅玻璃中硼同位素比值具有可行性;随后,详细分析了Na/B摩尔比、甘露醇和石墨加入量3个参数对测试结果的影响,得到的最佳参数为Na/B摩尔比9、加入甘露醇及3μL石墨发射剂;最后,采用优化测试参数,对实际硼硅玻璃样品进行了测试,并以NIST 951a硼酸标准物质为外标对测量结果进行分馏校正,结果发现分馏校正后样品的不确定度来源主要是标准物质。研究成果可满足硼硅玻璃的燃耗预估及产品质量的快速判定需要。     

热电离质谱铀系法测定碳酸盐标样

用高精度热电离质谱（ＴＩＭＳ）铀系法测定碳酸盐标样的年龄,测定结果与α谱仪铀系法进行比较,铀含量和年龄值均吻合。方法对Ｕ的回收率可达９５％,Ｔｈ为９２％。ＴＩＭＳ铀系法具有样品用量少、测试时间短、精度高的优点。     

银额盆地居延海坳陷原油物理化学特征与油源探讨

居延海坳陷的吉格达、天草、路井等次级凹陷原油物理、化学特征分析表明,原油物理特征以轻质-挥发性原油为主,个别井产凝析油,具有低粘度、中凝固点的特点。原油化学特征具有饱和烃含量高（78.06%~92.95%）,全油碳同位素轻（δ13CPDB为-33.7‰~-32.0‰）,轻烃/重烃（∑nC21-/∑nC22+）显著大于1（1.28~2.94）等特点。原油物理、化学特征指示其母质以低等水生生物为主,热演化程度为成熟-高成熟。在对钻井揭示的烃源岩及邻区地表剖面烃源岩分析的基础上,以吉格达凹陷蒙额参3井晚石炭世侵入岩和中—下二叠统2个产层为代表,开展了油-源生物标志化合物及碳同位素分布对比。结果表明,原油与上石炭统—下二叠统干泉组上段烃源岩具有良好的亲缘关系,与白垩系烃源岩无关,原油母岩为石炭系—二叠系烃源岩。依据原油指示的母岩演化程度显著高于钻井揭示的烃源岩演化程度,认为区内油气存在深层（干泉组下段）烃源岩的贡献。综合分析认为,居延海坳陷已揭示的油气藏为石炭系—二叠系含油系统,应将其作为主要勘探目的层。     

基于GSI值量化和修正方法的岩体力学参数确定

为了准确确定岩体力学参数,通过综合分析多种地质强度指标(GSI)量化方法,提出了一种改进的GSI值量化和修正方法。首先,利用测线法估算结构面平均间距(d)和岩体块度指数(RBI)的改进型岩体块度率(RBR),根据岩体三维结构面网络,获得岩体体积节理数(Jv)和岩体结构等级(SR),然后采用上述参数和结构表面条件(SCR)及结构表面特性参数(Jc)进行了GSI值的定量化处理。为了克服GSI体系的缺点,考虑结构面产状和地下水对岩体力学性质的影响,提出了GSI值的修正方法和公式。以某铅锌矿体的矿岩体为例,根据改进的GSI值量化和修正方法及Hoek-Brown强度准则来确定矿岩体力学参数,通过与原位变形试验的对比分析,验证了该方法的精确性和可行性。该方法为从室内岩石力学试验合理地获取节理岩体力学参数提供了理论及实现的依据。     

Accurate quantification of melt inclusion chemistry by LA-ICPMS: a comparison with EMP and SIMS and advantages and possible limitations of these methods

Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) has recently emerged as a powerful in situ microanalytical technique for major to trace elements in heterogeneous samples such as fluid and melt inclusions. Here, a rigorous comparison of melt inclusion (MI) data acquired by electron microprobe (EMP), ion microprobe (the secondary ion mass spectrometry, SIMS) and LA-ICPMS is used to evaluate the applicability and advantages/drawbacks of these approaches. We are specifically interested in determining if LA-ICPMS data on entire, unexposed, crystallized MI that cannot be homogenized in the lab are accurate and of a useful precision.

Quantification of LA-ICPMS MI signals requires the use of an internal standard, i.e., the concentration of one element, or an element ratio, at the time of MI entrapment must be known independently, in order to derive the pure MI composition from the MI plus host mixed signal. Analysis of plagioclase-hosted glassy MI of a mid-ocean ridge basalt (MORB) sample from the East Pacific Rise illustrates that melt inclusion chemistry can be accurately quantified by LA-ICPMS, including the correction for postentrapment sidewall crystallisation of the host mineral without prior reheating in the lab.

The LA-ICPMS data obtained on crystallized MI demonstrate agreement with the EMP and SIMS data on exposed glassy MI at the 1 standard deviation uncertainty level except for a few elements close to their limits of detection. LA-ICPMS data reduction schemes include the quantification of analytical uncertainty on each element of single MI. Therefore, weighted average element concentrations can be obtained for MI assemblages, at precisions that compare well with those of average element concentrations obtained by EMP and SIMS.

Simple sample preparation minimizing inclusion loss through polishing combined with the analytical efficiency of 50 inclusions plus neighbouring host mineral at up to 40 elements per day enable the collection of statistically relevant datasets by LA-ICPMS. These allow to recognize nonrepresentative MI (e.g., heterogeneous entrapment). Application to individual clinopyroxene crystals from the AD79 pumice horizon of Mt. Somma-Vesuvius reveals chemical variability that exceeds the analytical precision on single melt inclusions. This variability was not obvious from the limited data set obtained by SIMS and EMP.

The largest source of nonquantifiable error for EMP and SIMS data stems from the requirement of reheating the melt inclusions in the lab in order to reverse postentrapment crystallisation onto inclusion walls or growth of crystallites. For LA-ICPMS analysis of unexposed MI, the reliability with which the internal standard (IS) element concentration is known determines the quality of the data. LA-ICPMS, however, cannot analyse H₂O, F, S and Cl reliably, has higher limits of detection (LODs) than SIMS for some elements for MI below 25 μm, has lower spatial resolution than both EMP and SIMS and consumes much more sample per analysis. Therefore, EMP, SIMS and LA-ICPMS are complementary in MI research, and the type of application will determine the analytical method or methods of choice.     

纺织品中偶氮染料还原液内芳香胺的电喷雾电离质谱分析

在优化的条件下,用电喷雾电离质谱(ESI-MS)检测了多种纺织品中由偶氮染料还原获得的芳香胺。当毛细管温度为100℃、鞘气流速为25单位、进样流速为10μL/min、电压为5kV时,信号的总离子流强度高且较稳定。实验分析了19种致癌芳香胺标准溶液的二级质谱,获得了相应物质的特征碎片离子;在此基础上,建立了基于ESI-MS对毛巾、棉布等样品中芳香胺进行快速定性分析的方法,具有灵敏度高、特异性好、检测速度快等优点。     

Laser Ablation (193 nm), Purification and Determination of Very Low Concentrations of Solar Wind Nitrogen Implanted in Targets from the GENESIS Spacecraft

The GENESIS space mission recovered ions emitted by the Sun during a 27 month period. In order to extract, purify and determine the very low quantities of solar nitrogen implanted in the GENESIS targets, a new installation was developed and constructed at the CRPG (Nancy, France). It permitted the simultaneous determination of nitrogen and noble gases extracted from the target by laser ablation. The extraction procedure used a 193 nm excimer laser that allowed for surface contamination in the outer 5 nm to be removed, followed by a step that removed 50 nm of the target material, extracting the solar nitrogen and noble gases implanted in the target. Following purification using Ti and Zr getters for noble gases and a Cu-CuO oxidation cycle for N₂, the extracted gases were analysed by static mode (pumps closed) mass spectrometry using electron multiplier and Faraday cup detectors. The nitrogen blanks from the purification section and the static line (30 minutes) were only 0.46 picomole and 0.47 picomole, respectively.     

纺织品中致癌性芳香胺电喷雾解吸电离质谱法测定

用甲醇-水-乙酸(体积比49∶49∶2)混合溶液作为喷雾溶剂,在优化实验条件下,将电喷雾解吸电离质谱(DESI-MS)用于各种质地纺织品中24种致癌性芳香胺的非破坏性快速检测,均获得满意结果。分析实际样品时,由于该方法无需样品预处理,单个样品单一指标的检测不到30 s,大大节省了分析时间,提高了分析效率。同时借助串联质谱的特异性,能够有效地避免实验结果的假阳性。方法对大部分芳香胺具有较高的灵敏度,二级质谱中特征离子的检出限一般为10-9g/kg。建立的方法能灵敏、快速、无损检测纺织品中的致癌芳香胺,精密度较好,对同一样品10次测量结果的相对标准偏差为5%~10%。