Class Id resinite from Canada: A new sub-class containing succinic acid

This paper describes a new sub-category of Class I resinites based on labdanoid diterpenes having an enantiomeric configuration, including ozic acid, ozol and enantio biformenes, and incorporating succinic acid. This hitherto unnamed resinite sub-class, now designated as Class Id, has been identified in three distinct deposits in Canada: two sites in Nunavut and one site in British Columbia. The composition of Class Id resinites was determined using pyrolysis-gas chromatography–mass spectrometry with in situ trimethylsilylation with hexamethyldisilazane, Py(HMDS)-GC–MS. Fourier transform infrared spectroscopy (FTIR) of the resinites was also carried out and provided evidence of partial esterification of the ozol with succinic acid.     

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.     

The geochemistry of exinites—1. Evaluation of spectral fluorescence of a series of modern resins and fossil resinites

A series of six fossil resins and four modern resins have been analysed using microscope-based spectral fluorescence methods, in addition to a preliminary study of the chemical composition of these samples using infrared spectroscopy and pyrolysis-gas chromatography. This study illustrates problems encountered during the measurement of spectral fluorescence of resins and resinite kerogens using conventional microscopy methods. Most notable, alteration of fluorescence significantly influences spectral measurements. Further, fossilized resins within rocks are complex mixtures of resinite and bitumen. Pre-extraction of resinites prior to petrographic analysis resulted in somewhat more uniform spectral fluorescence results.Spectral fluorescence of recent resins used in this study could be used to distinguish angiosperm from gymnosperm derived resinite kerogens. Distinction of plant class source of resinite kerogens, however, is more difficult using this method and is considered genarally unreliable.     

Molecular composition and chemotaxonomic aspects of Eocene amber from the Ameki Formation,Nigeria

The molecular composition of fossil resin from the Eocene Ameki Formation, southern Nigeria has been analyzed by infrared spectroscopy, pyrolysis–gas chromatography–mass spectrometry and thermochemolysis gas chromatography–mass spectrometry to determine the structural class and botanical source of the resin. The pyrolysis products were dominated by bicyclic products derived from regular labdatriene structure and lacked succinic acid indicating Class Ib type amber. The biomarker compositions in the pyrolysates are dominated by sesquiterpenoids of the cadinane and bisabolane classes that are common constituents of higher plants and labdane type diterpenoids. The exclusive presence of labdane type diterpenoids and the absence of higher plant triterpenoids strongly suggest that the amber was derived from a gymnosperm (conifer) botanical source. This observation contrasts with the angiosperm source previously suggested for the resin based on the palaeobotanical studies of the host sediments. The specific family source within the conifers could not be ascertained based on the molecular composition of the resin. However, the presence of methyl-16,17-dinor-callitrisate pointed to the Cupressaceae family although other Cupressaceae biomarker indicators were not detected in the resin.     

The nature and fate of natural resins in the geosphere Part XI.† Ruthenium tetroxide oxidation of a mature Class Ib amber polymer‡

The results of ruthenium tetroxide (RuO₄) oxidation of a mature Class Ib amber polymer are reported and discussed. These data indicate that the residual double bond present in mature Class I ambers is not located in the A/B ring structure of these materials and that C17 of the original labdanoid precursors is retained in mature Class I ambers as a methyl group. These data also suggest that the reaction which results in formation of the residual unsaturated structure in mature ambers also results in a second covalent connection between the A/B ring system and the polymer backbone, probably through C8 of the original labdanoid structure.     

The nature and fate of natural resins in the geosphere--VIII. NMR and Py-GC-MS characterization of soluble labdanoid polymers, isolated from Holocene class I resins

Soluble polylabdanoids isolated by sequential solvent extraction have been characterized by liquid-state ¹³C- and ¹H NMR and ¹³C-¹H HMQC (heteronuclear correlation) NMR spectroscopy in addition to solid-state NMR and Py-GC-MS techniques. Two Holocene resins originating from Santander, Colombia and Mombasa, Kenya were analyzed. Soluble polymers were isolated by extraction with a 1:1 (v/v) methylene chloride-methanol mixture following sequential extractions with methylene chloride and methanol. The molecular weight of polymer extracts was shown by GPC analyses to exceed that of non-polymeric occluded terpenoids. Py-GC-MS, solid-state ¹³C CP/MAS and ¹³C cross-polarization/depolarization NMR spectroscopy results indicated that chemical compositions of soluble polymers isolated from immature resins are highly representative of the structure of corresponding insoluble polymers, i.e. polylabdatrienes. These data provide evidence for cross-linking or cyclization of side-chain olefinic carbons during or shortly after polymerization. Generally, the characterization of soluble resin polymers by liquid-state NMR spectroscopy has proven to be an excellent means for investigating the maturation mechanism of polylabdanoid resinites, and has potential for furthering the application of Class I resinites as geothermal indicators.     

沉积有机质激光热裂解色谱质谱探针分析技术的尝试及其前景探讨

激光热裂解－色谱－质谱分析方法具有从技术层面上融合分子地球化学方法和有机岩石学方法的潜能。通过抚顺煤镜质组分和树脂体的研究实例，介绍了激光热裂解－色谱－质谱探针分析的基本原理及测试方法。抚顺煤显微组分的微区热裂解产物特征中，镜质组和树脂体热解产物的正烷烃、烷基萘和四氢化萘的总体面貌相似，但树脂体中正烷烃含量较低，而烷基四氢化萘明显较高，这可能反映显微组分形成过程中发生过低分子烃类在各显微组分之间的混合作用。除此之外，还把激光热裂解－色谱－质谱探针技术与传统的分子地球化学方法、有机岩石学方法进行比较。探讨了激光热裂解－色谱－质谱探针技术的应用前景以及尚待解决的技术问题。落射到样品表面的激光束能量（温度）和控制和激光辐射时间的，激光束斑大小、热解产物量、色谱－质谱检验灵敏度极限三者关系等，都是限制新技术应用的技术问题。     

Pyrolysis of transvaal kerogens I. Diagenesis of kerogen in a stromatolite near Zeerust,South Africa: One possible chemical evolution process

This study represents an attempt to understand some of the many post-lithification chemical processes which affect the evolution of kerogen. Kerogens separated from four carbonate stromatolites, collected over a horizontal distance of ～ 350 km from the Malmani Dolomite of the Olifants River Group in the Transvaal Supergroup, were characterized by combined vacuum pyrolysis—gas chromatography-mass spectrometry. The relative profiles of the gas chromatographic peak distributions and intensities (·finger print patterns’) of three of the kerogen pyrolyzates were closely similar. The Zeerust stromatolite kerogen yielded a different pattern, showing a greater abundance of higher molecular weight aliphatic and alkyl aromatic hydrocarbon moieties than the other three samples. Many of the stromatolites near the Zeerust area contain epigenetic fluorite introduced by aqueous solutions. Fluid inclusion homogenization analysis showed that the emplacement temperature of fluorite in the sample studied was 100–200°C. Fluoride ion initiated base catalyzed condensations may have been a feasible cause for the production of higher molecular weight aliphatic and (indirectly) some alkyl aromatic moieties in this stromatolite, as compared to those in the other three samples. Acid-catalyzed condensations may also achieve similar results in aqueous diagenetic environments.     

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。     

Molecular composition and paleobotanical origin of Eocene resin from northeast India

The molecular composition of fossil resins from early to middle Eocene coal from northeast India, has been analyzed for the first time to infer their paleobotanical source. The soluble component of fossil resin was analyzed using gas chromatography–mass spectrometry (GC–MS). The resin extracts are composed of cadalene-based C₁₅ sesquiterpenoids and diagenetically altered triterpenoids. The macromolecular composition was investigated using pyrolysis gas chromatography-mass spectrometry (Py-GC–MS) and Fourier transform infrared (FTIR) spectroscopy. The major pyrolysis products are C₁₅ bicyclic sesquiterpenoids, alkylated naphthalenes, benzenes and a series of C₁₇–C₃₄ n-alkene-n-alkane pairs. Spectroscopic analysis revealed the dominance of aliphatic components. The presence of cadalene-based sequiterpenoids confirms the resin to be Class II or dammar resin, derived from angiosperms of Dipterocarpaceae family. These sesquiterpenoids are often detected in many SE Asian fluvio-deltaic oils. Dipterocarpaceae are characteristic of warm tropical climate suggesting the prevalence of such climate during early Eocene in northeast India.     

A comparison of results from two different flash pyrolysis methods on a solid bitumen sample

A Cambrian solid bitumen from northwestern Sichuan Basin, southern China was analyzed using two different flash pyrolysis methods coupled with gas chromatography–mass spectrometry analysis, including Pyroprobe® and analytical laser micropyrolysis. Results show that pyrolysis products from a Pyroprobe® (model 5000) analysis are dominated by mono-, di- and tricyclic aromatic hydrocarbons, whilst those from laser micropyrolysis are dominated by aliphatic hydrocarbons (n-alk-1-ene/n-alkane doublets), which is consistent with the results from an FT-IR spectrum of the solid bitumen. According to the molecular compositions of the pyrolysates from two types of pyrolysis, results from a 532 nm continuous wave laser may be more suitable for pyrolysis research of bitumen/asphaltene. Thus, differences in pyrolysis techniques must be considered when used to characterize oil asphaltenes or source rock kerogens.     

Strain distribution across an experimental single-layer fold

Experiments have been carried out to study the effects of progressive deformation on the shape of folds and the variation in two-dimensional strains on cross-sections of singlelayer folds in a less competent matrix, in a pure-shear plane-strain deformation box with no volume change. The layer shortening continues after buckling has set in, leading to thickening of the fold hinge and with progressive buckling the layer elongates. During the layer elongation stage of folding the hinges continue to thicken, whereas the limbs thin out. Concentric folds are a combination of Class 1a type in the outer arc which gradually change to Class Ib type and then to Class 3 folds of Ramsay (1967) in the inner arc. Tangential longitudinal strains and shearing strains predominate in the fold-hinge zone and in the fold limbs of the buckling layer, respectively. Initially, uniform layer-flattening strains perpendicular to the layering develop which become extensive strains in the outer fold arc and compressive strains in the inner fold arc with progressive buckling. In the outer fold arc the extensive strains are distributed laterally over a wider zone and are of a lower magnitude than the compressive strains which are restricted to a narrow zone in the inner fold arc. The neutral surface first appears when the initial layer-flattening strains are removed due to extensive strains on the outer arc and with progressive buckling migrates towards the inner fold arc and extends laterally on the outer fold arc.     

Terpenoid composition and origin of amber from the Cape York Peninsula,Australia

The terpenoid composition of fossil resin from the Cape York Peninsula, Australia has been analysed by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) to determine its origin. The pyrolysis products were dominated by cadalene-based C₁₅ bicyclic sesquiterpenoids including some C₃₀–C₃₁ bicadinanes and bicadinenes typical of Class II resin derived from angiosperm plants of Dipterocarpaceae. This observation contrasts with the Araucariaceae (Agathis sp.) source previously suggested for the resin based on Fourier transform infrared (FTIR) analyses. Dipterocarpaceae are not known in Australian vegetation but grow abundantly in Southeast Asia including New Guinea, indicating that the geological origin of the amber is not the Australian mainland but could be traced to Southeast Asia.     

New pyrolytic and spectroscopic data on Orgueil and Murchison insoluble organic matter: A different origin than soluble?

Pyrolysis with and without tetramethylammonium hydroxide (TMAH), vacuum pyrolysis, and solid state ¹⁵N nuclear magnetic resonance (NMR) were used to examine the macromolecular insoluble organic matter (IOM) from the Orgueil and Murchison meteorites. Conventional pyrolysis reveals a set of poorly functionalized aromatic compounds, ranging from one to four rings and with random methyl substitutions. These compounds are in agreement with spectroscopic and pyrolytic results previously reported. For the first time, TMAH thermochemolysis was used to study extraterrestrial material. The detection of aromatics bearing methyl esters and methoxy groups reveals the occurrence of ester and ether bridges between aromatic units in the macromolecular network.No nitrogen-containing compounds were detected with TMAH thermochemolysis, although they are a common feature in terrestrial samples. Along with vacuum pyrolysis results, thermochemolysis shows that nitrogen is probably sequestered in condensed structures like heterocyclic aromatic rings, unlike oxygen, which is mainly located within linkages between aromatic units. This is confirmed by solid state ¹⁵N NMR performed on IOM from Orgueil, showing that nitrogen is present in pyrrole, indole, and carbazole moieties.These data show that amino acids are neither derived from the hydrolysis of IOM nor from a common precursor. In order to reconcile the literature isotopic data and the present molecular results, it is proposed that aldehydes and ketones (1) originated during irradiation of ice in space and (2) were then mobilized during the planetesimal hydrothermalism, yielding the formation of amino acids. If correct, prebiotic molecules are the products of the subsurface chemistry of planetesimals and are thus undetectable through astronomical probes.     

Generation of isoprenoid compounds,notably prist-1-ene,via photo- and autoxidative degradation of vitamin E

In order to mimic the photodegradation of vitamin E during phytoplankton senescence and study the behaviour of the resulting photoproducts during cell lysis, vitamin E dispersed in seawater was irradiated with solar light in the presence of hematoporphyrin as sensitizer. Under these conditions, singlet oxygen-mediated photooxidation and free radical oxidation (autoxidation) acted simultaneously on the substrate, affording 4,8,12-trimethyltridecanal, 4,8,12-trimethyltridecanoic acid, 6,10,14-trimethylpentadecan-2-one, α-tocopherylquinone, 4,8,12,16-tetramethylheptadecan-4-olide, 2,3-epoxy-α-tocopherylquinone and 5,6-epoxy-α-tocopherylquinone as minor products. Different mechanisms were proposed to explain the formation of these different isoprenoids. The main products (85% of the degraded substrate) appeared to be previously described diastereoisomeric trimeric oxidation products of vitamin E, whose pyrolysis during gas chromatography–mass spectrometry (GC–MS) afforded 2,6,10,14-tetramethylpentadec-1-ene (prist-1-ene). On the basis of their greater ability to produce prist-1-ene during pyrolysis than intact vitamin E and their highly favoured production in phytoplanktonic cells, these trimers are proposed as likely sources of this isoprenoid alkene, previously identified in many pyrolysates from immature kerogens.     

Class I and Class II Rocks: Implication of Self-sustaining Fracturing in Brittle Compression

Tests to determine the complete stress–strain curve of rocks indicate whether the rocks can be classified a Class I or Class II. Class II rocks exhibits the potential for self-sustained failure in the post-peak region. The purpose of the research described in this paper was to investigate whether or not this self-sustained failure characteristic is related to the fragmentation of the rock. The aim of the research was, therefore, to determine possible relationships between fragmentation and various properties of several rocks types, including the influence of the Class II characteristic. Fragmentation of rock depends on its self-sustaining failure behaviour and the energy available in the post-peak region to shatter the rock. The correlation of static and dynamic rock properties with size of fragments resulting from compression tests demonstrate clear relationships of Class II rocks, but the same cannot be said for Class I rocks. Analyses of test results show that fragmentation increases with an increase in rock strength, and is explosive for Class II rocks. Probability density distributions were constructed to show the overall comparison of fragment sizes produced during failure of Class II and Class rocks. The calculated probability of passing at X₅₀ and X₁₀ sieve sizes show that Class II rocks as a group are more finely fragmented. It can therefore be concluded that, when breaking rocks under the same steady loading conditions, Class II rocks will show greater fragmentation than Class I rocks.     

Igneous and metamorphic geochronologic evolution of granitoids in the central Eastern Segment,southern Sweden

The Eastern Segment abutting the Transscandinavian Igneous Belt (TIB) mostly consists of rocks with overlapping igneous ages. In the Eastern Segment west of Lake Vättern, granitoids of clear TIB affinity exhibit strong deformational fabrics. This article presents U–Pb zircon ages from 21 samples spanning the border zone between these deformed TIB rocks in the east, and more thoroughly reworked rocks in the west. Magmatic ages fall in the range 1710–1660 million years, irrespective of the degree of deformation, confirming the overlapping crystallization ages between deformed TIB rocks and orthogneisses of the Eastern Segment. A common history is further supported by leucocratic rocks of similar ages. Prolonged orogenic (magmatic) activity is suggested by continued growth of zircon at 1.66–1.60 Ga. Six of the weakly gneissic rocks show zircons with cathodoluminescence-dark patches and embayments, possibly partly replacing metamict parts of older magmatic crystals, with ²⁰⁷Pb/²⁰⁶Pb ages dominantly between 1460 and 1400 million years, whereas three of the gneisses have zircon rims with calculated ages of 1440–1430 million years. Leucosome formation took place at 1443 ± 9 and 1437 ± 6 Ma. The minimum age of SE–NW folds was determined by an undeformed 1383 ± 4 million years crosscutting aplitic dike. Sveconorwegian zircon growth was not found in any of the samples from the studied area. To our knowledge, 1.46–1.40 Ga metamorphism affecting the U–Pb zircon system has not previously been reported this far northeast in the Eastern Segment. We suggest that the E–W- to SE–NW-trending deformation fabrics in our field area were produced during the Hallandian–Danopolonian orogeny and escaped later, penetrative Sveconorwegian reworking.     

Composition of estuarine colloidal material: organic components

Colloidal material in the size range 1.2 nm to 0.4 μm was isolated by ultrafiltration from Chesapeake Bay and Patuxent River waters (U.S.A.). Temperature controlled, stepwise pyrolysis of the freeze-dried material, followed by gas chromatographic-mass spectrometric analyses of the volatile products indicates that the primary organic components of this polymer are carbohydrates and peptides. The major pyrolysis products at the 450°C step are acetic acid, furaldehydes, furoic acid, furanmethanol, diones and lactones characteristic of carbohydrate thermal decomposition. Pyrroles, pyridines, amides and indole (protein derivatives) become more prevalent and dominate the product yield at the 600°C pyrolysis step. Olefins and saturated hydrocarbons, originating from fatty acids, are present only in minor amounts. These results are consistent with the composition of Chesapeake phytoplankton (approximately 50% protein, 30% carbohydrate, 10% lipid and 10% nucleotides by dry weight). The pyrolysis of a cultured phytoplankton and natural particulate samples produced similar oxygen and nitrogencontaining compounds, although the proportions of some components differ relative to the colloidal fraction. There were no lignin derivatives indicative of terrestrial plant detritus in any of these samples. The data suggest that aquatic microorganisms, rather than terrestrial plants, are the dominant source of colloidal organic material in these river and estuarine surface waters.     

Sedimentary evidence and luminescence and ESR dating of Early Pleistocene high lake levels of Megalake Tengger,northwestern China

The timing of high lake-level stands during the Late Pleistocene in western China remains controversial. Here we report new results from Megalake Tengger based on a study of palaeo-shorelines and a drill core from Baijian Lake in the northwestern Tengger Desert. Multiple dating methods, based on luminescence signals (quartz optically stimulated luminescence, K-feldspar post infrared-infrared stimulated luminescence) and electron spin resonance signals of quartz, were used to date beach sands from palaeo-shoreline profiles at altitudes of ~1310 m (+20 m above lake level), ~1320 m (+30 m) and ~1350 m (+60 m), and from the top 20 m of sandy sediments from the drill core obtained from the modern beach of Baijian Lake. The dating results show that high lake-level stands associated with the previously reported Megalake Tengger (~1310–1320 m) occurred during the late Early to Middle Pleistocene, which is much earlier than previously reported. In addition, no geomorphological evidence of shorelines and sedimentary evidence from the drill core profile were found to support the previously reported Late Pleistocene lake levels. Our results indicate that the exact age of the previously reported ‘high lake level event’ in a large part of northwestern China during the Late Pleistocene needs to be re-evaluated.     

A multi-facetted study of a cretaceous coal with algal affinities. I. Provenance of the coal samples and basic compositional data

This coal, of Cretaceous age and from southwest Utah, attracted attention because a lithobody from it showed a high hydrogen content and excellent behavior in liquefaction. The seam is 230 cm thick and consists of an upper and lower lithobody of a clarodurainic type, extensively weathered, surrounding two lithobodies of canneloid-boghead character. The petrography of the canneloid-boghead lithobodies is complex; the vitrinite content is only about 25%, and the bulk of the material appears to consist of a matrix of what may be bituminite. Appreciable amounts of resinite and liptodetrinite are also present. If the suggested affinity to canneloid-boghead coal types is correct, the lithobodies would be regarded as saprohumolithic in character and were probably formed in an open body of water. Ultimate analysis shows hydrogen contents of 7% (dmmf) or greater. Fourier Transform Infrared spectroscopy shows that the samples have a high degree of aliphatic character, methylene chains being abundant. Carboxylic acid groups are present, presumably as a result of weathering. Subtraction of spectra shows that one canneloid-boghead lithobody is appreciably more weathered than others.