氨化学电离色谱-质谱法分析原油及岩石抽提物中的咔唑类含氮化合物

利用色谱氨化学电离质谱(GC-NH3CIMS)法分析了原油及烃源岩中的咔唑类含氮化合物,分析结果与普通色谱质谱(GC-MS)进行了对比与评价.结果表明,氨化学电离质谱法对含氮化合物具有较高的灵敏度和选择性,在氮化物含量较低或有芳烃共逸出的情况下,可以进行定量分析.氨化学电离质谱没有碎片离子产生,质量色谱图上同系物间没有碎片离子产生的相互干扰,定量结果比较准确.     

Biomarkers in crude oil revealed by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry: Depositional paleoenvironment proxies

Crude oil samples from two basins were analyzed using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC–TOFMS) to better understand the compositional heterogeneity of branched-cyclic hydrocarbons. GC×GC–TOFMS and conventional GC–MS results were compared. GC×GC–TOFMS revealed a wide range of compounds, including tricyclic, tetracyclic and pentacyclic terpane series, rearranged hopanes, methyl hopanes, secohopanes, onoceranes and steranes. Assignment of methyl hopane and 8,14-secohopane series other than onocerane isomers was only possible due to the high peak capacity and sensitivity of GC×GC. The oils comprised a mixture of two end members: non-biodegraded oil with abundant tricyclic terpanes and hopanes, and severely biodegraded oil with abundant 8,14-secohopane and demethylated tricyclic terpanes. A predominance of two distinct series, 3β-methylhopane and onocerane, was detected only in the lacustrine samples (classification based on biomarker parameters). In contrast, the predominance of a 2α-methylhopane series and lack of onocerane were found only for the marine oil sample. The results suggest that the distribution of 3β- and 2α-methylhopane series and the presence or absence of onocerane isomers reflect genetic differences in the source organic matter and that these compounds are new classes of biomarkers that can used as depositional paleoenvironment proxies.     

Determination of indium in natural waters by flow injection inductively coupled plasma mass spectrometry

Two methods have been developed to measure indium (In) in natural waters by flow injection inductively coupled plasma mass spectrometry (ICPMS). One is the isotope dilution technique using an¹¹³In enriched spike and the other utilizes natural yttrium present in the sample as an internal standard. In the former, optimization of the¹¹³In spike to minimize error is often difficult for samples in which In concentrations are variable, whereas in the latter method, a separate determination of Y in the sample is necessary and hence more sample is required. Using about 1 liter of a water sample, 200 fold preconcentration of In was performed by solvent extraction and back extraction technique and then introduced into the ICPMS to measure the¹¹³In/¹¹⁵In or¹¹⁵In/⁸⁹Y ratios. The detection limits were 0.01–0.02 pmol kg⁻¹ for both methods. Application of the methods to seawater samples yielded the concentrations of 0.06–0.15 pmol kg⁻¹ for the Pacific and 0.6–1.5 pmol kg⁻¹ for the Atlantic. The large inter-oceanic variation of In best resembles that of Al amongst the 3B group of elements in the periodic table. River and estuarine samples gave a more variable range of concentrations of 0.01–15 pmol kg⁻¹. Most of the In supplied by rivers is removed by scavenging in the estuarine mixing zone, suggesting that the fluvial input of In to the ocean is small.     

W同位素高精度负离子热电离质谱(NTIMS)测定方法

W同位素的高精度测定对于研究地球、月球和太阳系其他行星的起源和早期演化、核幔相互作用等领域具有重要意义。本文开展了负离子热电离质谱(NTIMS)高精度W同位素测定方法研究(测定WO_3~-)。采用多接收动态跳扫方式对W同位素进行测定,实时在线测定~(18)O/~(16)O,并利用实验室实时在线氧校正NTIMS Os同位素分析时获得的~(17)O/~(16)O-~(18)O/~(16)O同位素分馏趋势线计算~(17)O/~(16)O,进行氧校正计算。对多接收动态和多接收静态数据处理方式及不同的同位素分馏校正方法进行了详细对比研究。在上述工作基础上,最终建立了以~(186)W/~(184)W=0.92767进行标准化,采用多接收动态方法进行数据处理的在线氧校正W同位素NTIMS测定方法。~(182)W/~(184)W测定结果的外部精度(2RSD)可达3×10~(-6)～6×10~(-6),基本满足地球、月球和行星早期演化等W同位素研究工作的需要。     

光谱样品中银的测定

样品经酸溶后,加碘化钾,银以AgI方式存在,有机试剂萃取分离,用原子吸收分光光度计测定有机相中银的含量,测定范围(1~1 000)×10-9。     

电感耦合等离子体质谱法测定地质样品中的碲

本文采用电感耦合等离子体质谱法,对地质样品中的碲的测定进行了研究,建立了一种快速、准确、简便的测定土壤样品中碲的方法。该方法克服了常规方法的局限性。此方法对6个国家标准物质进行了方法验证,12次测定精密度、准确度均符合标准要求。     

Effect of secondary oil migration distance on composition of acidic NSO compounds in crude oils determined by negative-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry

The acidic and neutral NSO compounds in a series of Duvernay-sourced oils in Canada, which are believed to have migrated extensively over relatively long distances such as along the Rimbey-Meadowbrook reef trends, were characterized by negative-ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Heteroatomic compounds were characterized according to their class (number of nitrogen, oxygen and sulfur heteroatoms), degree of aromaticity [rings plus double bonds (DBE)] and carbon number distribution. The N₁, N₁O₁, N₁O₂, N₁S₁, O₁ and O₂ classes were identified in Duvernay-sourced oils. With increasing migration distance, the relative abundance of O₂, N₁O₁ and N₁O₂ showed a significant decrease, while the O₁ class increased from < 10% to nearly 30% of the total. With increasing migration along the Rimbey-Meadowbrook reef trend, pyrrolic nitrogen compounds (N₁ class) shows an enrichment of alkylcarbazoles (DBE = 9) relative to alkylbenzocarbazoles (DBE = 12), and of higher homologous relative to the lower homologous. O₁ compounds show a relative enrichment of those with low DBE values. Additionally, the N₁O₁ and N₁S₁ compounds show a relative enrichment of those with high DBE values, and of higher homologues compared to the lower homologues, indicating great potential for developing new migration indices.     

氢化物发生原子荧光光度法测定地质样品中的痕量锗

实验选择了最佳仪器工作条件,比较了不同载流酸对荧光强度的影响,用L-半胱氨酸-硫脲-酒石酸混合溶液消除干扰.本法检出限0.08μg/g(n=12),8个土壤标样的RSD为4.8%～9.6%(n=12),ΔtgC为0.002～0.015,此法可满足化探分析的要求.     

电感耦合等离子体质谱法测定黑色页岩中的铂钯

对于黑色页岩中的铂钯元素,试样经过灼烧除去硫以及有机质后,用王水分解,经树脂富集,再将树脂灰化后溶解,采用电感耦合等离子体质谱仪测量,取代比色法,得到了更好的检出限,以及准确度。     

浊点萃取-电感耦合等离子体质谱法测定高矿化度水中的稀土元素

文章采用浊点萃取-电感耦合等离子体质谱法测定高矿化度水中的稀土元素,高矿化度水中的稀土元素与8-羟基喹啉生成疏水性络合物,经水浴加热,稀土元素络合物被萃取到TritonX-114表面活性剂相.对影响浊点萃取效率的主要因素进行分析,发现检出限为0.002~0.005 μg/L,实际水样的加标回收率为93.3%~107.1%,测定结果的相对标准偏差(RSD)为2.12%~3.53%.     

超高效液相色谱串联质谱法快速测定地下水和含水层介质中16种全氟烷基酸

全氟烷基酸(PFAAs)是一种新型的持久有机污染物,在各种环境介质中被频繁检出。目前,PFAAs的检测方法主要包括液相色谱串联质谱法(HPLC-MS/MS)、超高效液相色谱串联质谱法(UPLC-MS/MS)、气相色谱法和光谱类方法。但是,上述方法多存在样品前处理过程复杂、周期长、成本高的问题,不适用于PFAAs的快速检测。为此,本文建立了一种快速测量地下水和含水层介质中16种PFAAs的UPLC-MS/MS方法。水样过0.22μm滤膜后直接测定浓度,土样经过超声离心后,取上清液过滤测量浓度。本方法分别为16种PFAAs建立了低浓度(5~50μg/L)和高浓度(100~500μg/L)两条校准曲线,相关系数R^2>0.99。地下水中16种PFAAs快速检测方法检出限为0.06~1.07μg/L,回收率为75%~120%,精密度(RSD)为2.61%~9.19%(除高浓度时全氟丁烷磺酸和全氟已烷磺酸分别为11.34%和14.70%外)。含水层介质中14种PFAAs(全氟十三酸和全氟十四酸除外)方法检出限为2.69~12.33ng/g,回收率为65%~103%,精密度(RSD)为1.96%~7.22%。     

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。     

应用高分辨率质谱分析苏丹高酸值原油成因

苏丹Muglad和Melut盆地是苏丹乃至整个中、西非剪切带最富含油气的盆地,所发现的原油主要为中质油(重度为20°～34°API),其次为重质油(重度小于20°API),普遍高含沥青质、高含蜡、高酸值、低含硫。为了探讨高酸值原油的成因,选择了苏丹地区18个不同酸值的原油样品,尝试高分辨率质谱分析上述原油有机酸的组成。结果表明,高酸值原油的有机酸主要由环烷酸组成;环烷酸的平均相对分子质量随降解作用程度增加而增大,分子碳原子数分布范围变宽;环烷酸以一环、二环、三环环烷酸为主。生物降解作用是形成高酸值原油的主要原因。     

辽河原油好氧生物降解模拟过程中化学组成及其碳同位素值的变化

对辽河盆地中央凸起南部潜山原油进行了好氧生物降解模拟实验,分析了辽河原油在轻度至中度(PM 1~4级)的好氧生物降解过程中化学组分的变化,以及在此过程中原油族组分和正构烷烃单体的稳定碳同位素值的变化。结果显示,饱和烃组分的消耗速率最快,正构烷烃的消耗速率高于异构烷烃,低碳数正构烷烃的消耗速率高于高碳数正构烷烃。正构烷烃的疏水性及其在原油中的相对浓度可能是影响微生物选择性地消耗正构烷烃的主导因素,即低碳数的正构烷烃由于在油水界面上的表面张力较小而更容易被微生物降解。正构烷烃单体(C_(14)~C_(30))稳定碳同位素值在生物降解过程中较稳定,未产生明显的碳同位素分馏效应。正构烷烃的好氧降解产物主要是脂肪酸、醇和CO_2。辽河原油中正构烷烃组分的δ~(13)C值较饱和烃、芳烃、胶质和沥青质组分都要偏重,降解产物中水溶性较低的高碳数脂肪酸和醇大部分进入胶质中,少部分通过氢键缔合和形成酯键等方式进入到沥青质组分中,造成沥青质组分的δ~(13)C值发生相应的变化,即对沥青质的δ~(13)C值产生"拉动效应";而降解产物中高水溶性的低碳数烷基酸和醇会进入水相而脱离原油,导致残余油的整体δ~(13)C值相应变轻。因此,假如易受生物降解的烃类如正构烷烃等的δ~(13)C值与原油的δ~(13)C值差别比较大,那么生物降解过程中随着原油化学组成的改变,原油本身及其族组分的δ~(13)C值均可能发生明显的变化。     

Determination of hydrocarbon distributions in oils and sediment extracts by gas chromatography—high resolution mass spectrometry

The distributions of steroid and triterpenoid hydrocarbons in crude oils and sedimentary rock extracts can be routinely determined by the direct injection of the sample into a gas chromatograph coupled to a mass spectrometer (GC-MS). The mass spectrometer is operated at a resolution of about 2500 (10% valley), and only the ion intensities at selected accurate mass values, diagnostic of the structural types of interest, are monitored throughout the analysis. The distributions, so obtained, find application in the assessment of the source and thermal maturity of crude oil accumulations in the subsurface. This technique eliminates chromatographic separation steps and combines two analyses in one. Thus, more geological samples and reference mixtures may be analyzed in a given time.     

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.     

Isolation of degraded pentacyclic triterpenoid acids in a Nigerian crude oil and their identification as tetracyclic carboxylic acids resulting from ring A cleavage

Three tetracyclic acids were identified in a Nigerian crude oil, after reduction and deuterium labelling followed by GC/MS investigation. Two of them are identical to 3:4 seco acids previously identified in sediments. The third one is a novel C₂₄ acid that has not been reported up to now. These geochemical markers are assumed to belong to the class of photochemical tetracyclic triterpenes formed by decay of pentacyclic 3-ketoterpenoids.     

Molecular characterization of dissolved black nitrogen via electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Combustion produces a complex mixture of polycondensed aromatic compounds known as black carbon (BC). Such products can become remobilized from char and soil in the form of dissolved BC (DBC). Ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI–FT-ICRMS) analysis of a variety of soil and char leachates showed that a significant proportion of DBC compounds contained one or more nitrogen atoms. While the presence of black nitrogen (DBN) in dissolved organic matter (DOM) has been reported, its molecular features were uncharacterized. Here we present results of FT-ICRMS characterization of DBN, where assigned formulae were validated on the basis on their ¹³C isotope signatures and fragmentation patterns obtained via collision induced dissociation. Possible chemical structures were assigned for several DBN formulae and suggest that nitrogen was incorporated into the core ring system as a pyrrole-type moiety. Most DBN compounds existed as part of homologous series where homologs differed by a mass corresponding to CO₂, suggesting that they were polysubstituted with carboxylic acid groups. The environmental contribution of such novel, aromatic, combustion-derived nitrogen compounds with respect to global nitrogen cycling remains elusive. The biogeochemical implications of the input of such fire-derived products to aquatic ecosystems as part of climate change therefore need to be assessed.