Fluorescence spectral analysis of resinite macerals from coals of the Hanna Formation, Wyoming, U.S.A.

Flourescence spectral analysis indicates that resinite macerals from Tertiary Hanna Formation coals (Hanna Coal Field, southcentral Wyoming, U.S.A.) can be separated into five distinct groups. The first resinite group fluoresces a a medium green (in blue light); its average spectral maximum occurs at or below 440 mm with a red/green quotient of 0.22. The second resinite group fluoresces yellow-green with an average spectral maximum of 500 nm and a red/green quotient of 0.53. The third resinite group displays a yellow fluorescence having an average spectral maximum of 580 nm and a red/green quotient of 0.86. The fourth resinite group fluorescence orange-brown having an average spectral maximum of 610 nm and a red/green quotient of 1.20. These four groups mostly occur as primary globular resinites exhibiting scratches and fractures, indicating that they are brittle, solid substances. Primary cell-filling and secondary fracture-filling resinites also occur in these four groups. The fifth group only occurs as a secondary void-filling material and lacks evidence of br of brittle properties. It fluoresces a reddish-brown, has a spectral maximum at 690 nm, and a red/green quotient of 1.54. The fifth group has properties resembling exsudatinite. The five resinite groups can be separated on the basis of their nine spectral properties alone, without qualitative petrographic interpretation.The relative quantities of the five resinite groups vary among Hanna Formation coals. The origins of these five resinite groups are probably related to their botanical properties and pre- and post-depossitional conditions. Overall, Hanna Formation resinites have petrographic characteristics similar to other North American resinites; however, only four resinite groups have been distinguished in in certain coals from Utah and New Mexico (U.S.A.), and western Canada.     

Tertiary deltaic and lacustrine organic facies: comparison of biomarker and kerogen distributions

Biological marker and kerogen compositional data in Tertiary deltaic and lacustrine settings were compared and contrasted. The two settings are represented by (a) coals and organic-carbon-rich shales in a ick deltaic sequence from the Far East, constituting three distinct organic facies, and (b) humic coals and spropelic oil shales in a restricted intermontane (freshwater) lacustrine sequence from western Montana (U.S.A.), constituting two distinct organic facies. Wedistinguish the organic facies in each depositional setting by systematic differences in gross compound class distributions, kerogen and infrared spectral characteristics, molecular character of pyrolyzates, sterane carbon number distribution and sterane/hopane ratios. The kerogens of the three deltaic organic facies are characterized by varying quantities of vitrinite, resinite, sporinite, cutinite and fluorescent amorphinite. Triterpane distributions reveal numerous terrigenous compounds, including oleanane, oleanenes and unidentified C₃₀ (presumably) resin-derived components. The two organic facies of the freshwater lacustrine setting are distinguishedased upon either a vitrinite or an alganite/fluorescent amorphinite predominance in the kerogen. Numerous characteristics facies-related markers are also present, including dehydroabietane (land plant resins) and 4-methylsteranes (perhaps from freshwater dinoflagellate input). The available molecular and petrographic data are evaluated, and characteristics are proposed for distinguishing five organic facies of these two depositional settings. The successful simultaneous use of molecular geochemistry and organic petrography in this study provides a format for refining the organic facies concept.     

Inside amber: New insights into the macromolecular structure of Class Ib resinite

Class Ib resinites are the most common subclass of amber and are found throughout the world. They have a macromolecular structure based on co-polymerized communic acid, communol and biformenes. Because this class of resinite does not contain succinic acid, crosslinking of the polymer through esterification of communol moieties has never been theorized. Analysis of Class Ib resinites from Grassy Lake and Cedar Lake in western Canada was performed using pyrolysis–gas chromatography–mass spectrometry with in situ hexamethyldisilazane derivatization, using a thermal separation probe to perform the pyrolysis and sample introduction. This has allowed larger, more complex fragments to be released from the polymer matrix than previously possible using instantaneous pyrolysis methodologies. The results show for the first time that Class Ib resinite can undergo self-crosslinking between the communol and communic acid moieties in the polylabdane matrix. The chromatographic results also show that a portion of the monoterpenes and non-polymerizable diterpenes in the resinite are bound to the polymer matrix and not fully occluded as was previously theorized. Fourier transform infrared (FTIR) spectra of the resinites are presented and a more accurate spectral interpretation is proposed, based on the chromatographic results.     

Simulation of the fluorescence evolution of “live” oils from kerogens in a diamond anvil cell: Application to inclusion oils in terms of maturity and source

The evolution of fluorescence has been measured for “live” oils generated from 14 oil-prone kerogens or coals from varying depositional environments during closed system pyrolysis in a diamond anvil cell at three heating rates (3, 8, and 25 °C/min), and temperatures up to 600 °C. The measured fluorescence intensities of the samples, employing using violet excitation at 405 nm, increases significantly during maturation intervals within the oil window, while the fluorescence spectra of oils generated from all studied kerogens exhibit progressive blue-shift of peak wavelengths (λ_max) and red/green quotients (I₆₅₀/I₅₀₀) upon increasing maturity. The observed trend is consistent with a maturity dependence of the spectral shift, which is widely recognized in natural hydrocarbon inclusions and crude oils using ultraviolet (UV) excitation (365 nm). The data presented herein suggest that the λ_max of spectra for inclusion oils shift in similar direction despite differences in composition or source kerogen. This implies that the reverse or anomalous trends reported for inclusion oils in nature may be attributed to other processes, which significantly alters the fluorescence properties of oils subsequent to their generation. Oils with the similar color (λ_max or I₆₅₀/I₅₀₀) can be derived from diverse kerogens with maturities that vary by ±0.3% Ro, suggesting that the fluorescent colors of crude and inclusion oils are both maturity- and source-dependent, and therefore cannot be used as universal maturity indicators. In addition, the blue-shifts observed for cumulative oils generated from all kerogens approaches similar minima λ_max values around the green-yellow wavelength (564 nm) and at I₆₅₀/I₅₀₀ values around 0.6, at maturities close to the middle or late stage of oil generation. This suggests that most late-stage cumulative oils will exhibit similar colors. Oils generated during late-stage maturity intervals, however, can exhibit colors with shorter wavelengths.     

Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and Recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.     

煤岩组分化学结构随热演化变化与生烃性研究

应用显微傅立叶红外光谱分析,研究了胜利油田附近的石炭系太原组煤烃源岩中主要生烃有机组分化学结构特征。结果表明,荧光镜质体富含芳烃结构和含氧有机结构,而树脂体和角质体富含脂肪烃结构,荧光镜质体和树脂体烷基烃碳链短或支化程度高。随热演化程度增高,荧光镜质体和树脂体红外光谱参数(CH₂+CH₃) C=C和CH₂ CH₃比值逐渐减小,而孢子体和角质体的这两个参数先增后减,反映出荧光镜质体与树脂体具早期生烃特点,而孢子体与角质体生烃演化具弱—强—弱特性,具生烃高峰期。     

6种不同产地柯巴树脂的谱学特征探究

收集了来自俄罗斯、新西兰、婆罗洲、马达加斯加、哥伦比亚和苏门答腊6个不同产地的柯巴树脂,采用宝石显微镜、红外光谱、紫外荧光观察和三维荧光光谱等测试方法对柯巴树脂谱学特征进行了对比研究。婆罗洲、苏门答腊柯巴树脂的红外光谱主要特征为存在3000~2800 cm^-1范围内4个吸收峰,1732 cm^-1肩峰和1708 cm^-1吸收峰,888 cm^-1处的弱吸收峰。新西兰柯巴树脂红外光谱主要特征为存在3000~2800 cm^-1范围内3个吸收峰,1642 cm^-1和888 cm^-1处的弱吸收峰。马达加斯加、哥伦比亚和俄罗斯柯巴树脂的红外光谱相似,主要特征为存在与C=C相关的3处组合特征吸收峰以及1270 cm^-1和1180 cm^-1处的2个吸收峰。在长波紫外荧光下,婆罗洲和新西兰柯巴树脂荧光强度明显强于其他产地样品,马达加斯加柯巴树脂荧光强度最弱。由三维荧光光谱可知,婆罗洲和苏门答腊柯巴树脂中存在445、474、505 nm 3个发射峰,可被416、447 nm波长有效激发;新西兰柯巴树脂的最强发射峰位于385 nm,其最佳激发波长352 nm;俄罗斯柯巴树脂最强发射峰在399 nm,可被354 nm波长最佳激发;哥伦比亚柯巴树脂的最强发射峰为470 nm,被400 nm波长最佳激发;马达加斯加柯巴树脂的最强荧光峰在465 nm,被378 nm波长最佳激发。综合分析认为,三维荧光光谱特征和红外光谱特征可为柯巴树脂的鉴别和分类提供依据。     

Observations on Indian Permian Gondwana Coals Under Fluorescence Microscopy: An Overview

Macerals like sporinite, cutinite, suberinite and resinite of the liptinite group have been insufficiently recorded in Indian Permian Gondwana coals, until the fluorescence microscopy came into existence. With the introduction of this technique, macerals like bituminite, fluorinite and exsudatinite were convincingly recognized and alginite and liptodetrinite, normally mistaken for mineral matter under normal reflected light in routine coal petrographic analysis, were identified with certainty. Thus, fluorescence microscopy has added certain new macerals to the tally of the liptinite group and has increased their overall proportion in Indian Gondwana coals.In addition to the liptinite group, collodetrinite (=desmocollinite) and a certain fraction of collotelinite (=telocollinite) macerals of the vitrinite group were found to be fluorescing with dull reddish-brown to dark brown colours. Certain semifusinite and inertodetrinite macerals of inertinite group were also found to fluoresce with almost identical intensity and colour as that of the associated perhydrous (fluorescing) vitrinite. Contributions of degraded resinite, algal matter and bitumen in the formation of perhydrous vitrinite have been established. The fluorescence behaviour of inertinite appears to be related with its genesis from partial oxidation of resin/bitumen-impregnated cell walls.     

Characteristics of amorphous kerogens fractionated from terrigenous sedimentary rocks

A preliminary attempt to fractionate amorphous kerogens from terrigenous bulk kerogen by a benzene-water two phase partition method under acidic condition was made. Microscopic observation revealed that amorphous kerogens and structured kerogens were fractionated effectively by this method. Characteristics of the amorphous and structured kerogens fractionated by this method were examined by some chemical analyses and compared with those of the bulk kerogen and humic acid isolated from the same rock sample (Haizume Formation, Pleistocene, Japan). The elemental and infrared (IR) analyses showed that the amorphous kerogen fraction had the highest atomic$\text{H}\text{C}$ ratio and the lowest atomic $\text{N}\text{C}$ ratio and was the richest in aliphatic structures and carbonyl and carboxyl functional groups. Quantities of fatty acids from the saponification products of each geopolymer were in agreement with the results of elemental and IR analyses. Distribution of the fatty acids was suggestive that more animal lipids participate in the formation of amorphous kerogens because of the abundance of relatively lower molecular weight fatty acids (such as C₁₆ and C₁₈ acids) in saponification products of amorphous kerogens. On the other hand, although the amorphous kerogen fraction tends to be rich in aliphatic structures compared with bulk kerogen of the same rock samples, van Krevelen plots of elemental compositions of kerogens from the core samples (Nishiyama Oil Field, Tertiary, Japan) reveal that the amorphous kerogen fraction is not necessarily characterized by markedly high atomic $\text{H}\text{C}$ ratio. This was attributed to the oxic environment of deposition and the abundance of biodegraded terrestrial amorphous organic matter in the amorphous kerogen fraction used in this work.     

沉积有机质的成烃热模拟实验研究

作者采用小玻管热模拟方法研究了煤及碳质泥岩中藻类体、基质镜质体、沥青质体、运移沥青、角质体、树脂体、孢子体、现代栓皮栎的木栓层,水生植物蓝藻(粘球藻)和水生动物虾蛄的成烃规律。并根据有机组分的荧光特性和显微傅利叶红外光谱特征初步建立了我国煤系源岩生油组分及现代海生生物蓝藻和虾蛄的生油模式。研究结果表明:结构藻类体生油晚,结束晚;不同类型的基质镜质体和沥青质体的成烃过程存在差异,且基质镜质体可早期生油;现代木栓组织的成烃模拟支持了木栓质体早期生油的观点;角质体、基质镜质体B的成烃具多阶段性的特点;现代粘球藻具生油晚,结束晚,且成烃范围宽;水生动物虾蛄具成烃早,结束早,且成烃范围窄的特点。     

珠江口盆地番禺低隆起-白云凹陷北坡干酪根热演化模拟与生烃

通过密封金管-高压釜体系对珠江口盆地番禺低隆起-白云凹陷北坡恩平组炭质泥岩的干酪根(PY),在24.1 MPa压力、20℃/hr(373.5~526℃)和2℃/h(343~489.2℃)两个升温速率条件下进行热模拟生烃实验,分析气态烃(C1 5)和液态烃(C6 14和C14+)的产率,以及沥青质和残余有机质碳同位素组成。同时与Green River页岩(GR)和Woodford泥岩(WF)的干酪根,分别代表典型的I型和II型干酪根进行对比研究。结果显示PY热演化产物中总油气量明显低于GR和WF干酪根,且气态烃(C1 5)最高产率是液态烃的1.5倍,揭示恩平组炭质泥岩主要以形成气态烃为主。在热演化过程中,有机质成熟度和母质类型是控制油气比的主要因素,气态烃和轻烃的产率比值主要受热演化成熟度的影响。干酪根残余有机质碳同位素和沥青质碳同位素在热演化过程中受有机质成熟度的影响较小,δ13C残余和δ13C沥青质可以间接反映原始母质的特征,为高演化烃源岩油气生成提供依据。     

The influence of minerals on the pyrolysis of kerogens

The effect of mineral matter on the laboratory pyrolysis of sediments, kerogens and coals, and of coal macerals mixed with either alumina, bentonite, kaolinite, or calcium carbonate has been investigated. Some minerals are more active than others in effecting changes in the composition of the pyrolysate. The relative content of low molecular weight pyrolysis products is higher for kerogens pyrolyzed in a mineral matrix than for isolated kerogens. Our limited data suggests that this is due to both condensation and gasification of higher molecular weight constituents in the ‘primary’ pyrolysate. Differences in the content of aromatic versus aliphatic compounds have been noted when pyrograms from coal macerals are compared with pyrograms from coal maceral-mineral mixtures. We conclude that mineralogy is important in controlling the composition of kerogen pyrolysis products.     

Distribution and geochemical significance of trace elements in shale rocks and their residual kerogens

There is a dearth of information about the distribution of trace elements in kerogen from shale rocks despite several reports on trace element composition in many shale samples. In this study, trace elements in shale rocks and their residual kerogens were determined by inductively coupled plasma–mass spectrometry. The results from this study show redox-sensitive elements relatively concentrated in the kerogens as compared to the shales. This may be primarily due to the adsorption and complexation ability of kerogen, which enables enrichment in Ni, Co, Cu, and Zn. For the rare earth elements (REEs), distinct distribution characteristics were observed for shales dominated by terrigenous minerals and their kerogen counterparts. However, shales with less input of terrigenous minerals showed similar REE distribution patterns to their residual kerogen. It is speculated that the distribution patterns of the REEs in shales and kerogens may be source-related.     

An unusual non-fluorescing algal kerogen from the Canadian Arctic

Bituminous cobbles collected from the Fossil Forest site (Geodetic Hills, Axel Heiberg Island, Canadian Arctic) have been subjected to petrographic and geochemical characterization. Transmitted light microscopy and pyrolytic analyses indicate that these samples are derived from algal biomass and are in most ways, generally comparable with other boghead coals and torbanites. However, fluorescence microscopy results in the surprising observation that these samples do not fluoresce under normal blue-light excitation conditions. Strong fluorescence is generally considered to be characteristic of alginites and Type I (and II) kerogens, and the absence of this property in these samples suggests that even petrographic analyses with blue-light excitation (fluorescence) may underestimate the occurrence of algal-derived materials in some samples.     

Geochemical studies on the organic matter from the Douala Basin (Cameroon)—II. Evolution of kerogen

Optical examinations, elemental analysis, i.r. spectroscopy and thermogravimetric analysis have been used to characterize the kerogens from the Logbaba (Upper Cretaceous) cores from the Douala Basin (Cameroon). It is shown that those kerogens are derived from the same type of organic matter, having mainly a land-plant origin. This conclusion fits very well that obtained from the examination of the soluble organic matter (see Part I). Thus the evolution of the properties of kerogens during burial is not due to a change in the nature of organic matter and can be related mainly to catagenesis. Owing to the existence of a high geothermal gradient in the basin and a sampling along a 4000 m thick sedimentary column, this evolution can be followed over a large range and correlated to the formation of petroleum and gas.     

海相成熟干酪根生气潜力评价方法研究

高成熟阶段干酪根热解氢指数（HI）非常低,在热成熟度指标镜质组反射率Ro为2.0%以上的Ⅰ或Ⅱ型有机质,一般都在20 mg/gTOC以下,甚至接近0 mg/gTOC,因此,一般认为这种干酪根生烃能力极低。本文通过对不同成熟阶段的干酪根采用元素分析和热解模拟实验相结合的方法,发现HI指数很低的高过成熟阶段干酪根仍然具有一定的生气能力,生气潜力是HI指数的数倍,如HI指数为12 mg/gTOC的样品,H/C原子比为046,生气能力仍然为65 mg/gTOC,占总生烃能力的15%左右,说明成熟—过成熟有机质HI指数不适合衡量生气潜力。同时发现,干酪根生气能力与H/C原子比具有极好相关性,相关系数达到096,通过回归公式所获得有效生气干酪根H/C原子比下限为026。     

Solid state C NMR studies of selected oil shales from Queensland, Australia

Solid state ¹³C NMR techniques of cross polarization with magic-angle spinning, and interrupted decoupling have been employed to examine the nature of the organic matter in eight kerogen concentrates representing five Tertiary deposits in Queensland, Australia. The NMR results show that five of the kerogens have high proportions of aliphatic carbon in their organic matter and correspond to Type I–II algal kerogens. Three of the kerogens, derived from carbonaceous shales, have a high proportion of aromatic carbon in their organic matter and correspond to Type III kerogens. The fractions of aliphatic carbon in all the kerogens, regardless of type, are shown to correlate with the conversion characteristics of the corresponding raw shales during Fischer assay. Interrupted decoupling NMR results show the presence of more oxygen-substituted carbon in the carbonaceous shales, which may account for the greater CO₂ evolution and phenolic materials found in the pyrolysis products of the carbonaceous shales.     

沥青质傅里叶变换红外光谱 (FT IR)分析及其在有机地球化学研究中的应用

沥青质傅里叶变换红外光谱（FT－IR）分析可以反映出其分子结构上的特征，红外吸收因子Z[I(1380cm^-1)/I(720cm^-1）]能指示不同来源沥青质的母质类型；吸收因子Y[I(1600cm^-1)/I(1450cm^-1)]可以较好地讨论沥青质的成熟度演化状况；沥青质的红外研究认为，所有的沥青质都具有较好的再生烃潜力，其中Ⅲ型母质来源的沥青质具有较好的再生气潜力。而Ⅰ和Ⅱ型母质来源的沥青质具有高的再生油潜力。     

四川盆地海、陆相烃源岩有机质稳定碳同位素组成变化及其地球化学意义

采用质谱和色谱-同位素质谱技术,测定了500余个干酪根及饱和烃、芳烃组份、正构烷烃的δ13C值,以此揭示了四川盆地海、陆相烃源岩有机碳同位素组成随地质时代的变化特点及其在高成熟阶段的演化特征,并结合其他相关分析资料,应用碳同位素剖析了不同类型海、陆相烃源岩的有机质生源及沉积环境。研究结果表明,该盆地从震旦系灯影组到中三叠统雷口坡组的海相地层中,干酪根的碳同位素组成随层位变新呈逐渐变重的趋势,可能的原因之一是浮游植物的进化作用;而上三叠统须家河组至中侏罗统千佛崖组的陆相有机质碳同位素组成则有反向的年代变化,主要与生源构成和沉积环境性质有关。这些海、陆相烃源岩的有机源难以用干酪根δ13C值进行区分,而可用饱和烃与芳烃组份的δ13C及其CV值来区别。海洋和湖泊不同沉积相带烃源岩的干酪根具有明显不同的δ13C值,结合其他相关资料可识别其有机质来源。煤系地层中煤与泥岩在干酪根碳同位素组成上没有可区分性,而两者有不同的正构烷烃碳同位素分布曲线。从成熟晚期到高-过成熟阶段,海、陆相干酪根的碳同位素均变重1~2‰,煤系泥岩的正构烷烃碳同位素分布曲线由负向线型分布向平直型演变。这些碳同位素的变化特征为油气源对比和烃源识别提供了依据。