Chemical composition and palaeobotanical origin of Miocene resins from Kerala-Konkan Coast,western India

The terpenoid composition of resins from the Miocene lignite horizons from the Kerala-Konkan Coast, western India was analyzed by Curie-point pyrolysis-gas chromatography-mass spectrometry (Cupy-GC-MS). The major pyrolysates were cadalene-based bicyclic sesquiterpenoids including some C₃₀-C₃₁ bicadinenes and bicadinanes typical of dammar resin from angiosperm plants of Dipterocarpaceae family. These plants are typically supported by tropical climates which the western Indian region was known to have experienced during early Tertiary period. The present study suggests that these palaeoclimatic conditions persisted until at least the Miocene epoch. These sesquiterpenoids which are commonly detected in many SE Asian crude oils may be utilised as useful biomarkers for petroleum exploration in the western Indian region.     

Mineralogy of fossil resins in Northern Eurasia

The investigation is focused on identification and origin of fossil resins from the Cretaceous, Tertiary, and Quaternary sediments of Northern Eurasia on the basis of detailed study of their physical and chemical characteristics: morphology; size; mass; density; optical, mechanical, and thermal properties; chemical composition; etc. The composition of amorphous organic minerals with polymeric structure, fossil resins included, is studied with IR spectrometry, the EPR method, derivatography at low heating rates, XRD, chemical analysis, emission spectrometry, etc. The results of investigation summarized for the Baltic-Dnieper, North Siberian, and Far East amber-bearing provinces show some similarity of fossil resins in combination with specific features inherent to each province. Resins from the Baltic-Dnieper province should be termed as amber (succinite). Their variety is the most characteristic of Northern and Eastern Europe. Amber-like fossil resins from the North Siberian and Far East provinces are irrelevant to succinite. They usually occur as brittle resins, namely, retinite and gedanite, without jewelry value. Viscous fossil resin rumänite with an expected high economic value occurs in the Far East, on the shore of Sakhalin Island.     

The nature and fate of natural resins in the geosphere XIII: a probable pinaceous resin from the early Cretaceous (Barremian), Isle of Wight

Terpenoid resin is produced by all families and most genera of the order Coniferales (the conifers), and the distribution of terpenes present in most conifer resins is characteristic of the originating family. Analyses of early Cretaceous (Barremian) amber (fossil resin) from the English Wealden, Isle of Wight, southern England, by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), indicate a terpene distribution dominated by abietane- and labdane-type terpenes. Similar distributions are observed in some species of the extant family Pinaceae. The Pinaceae are well represented within the Wealden deposits of southern England, by only one (known) species, Pityites solmsii (Seward) Seward, whereas the macro-fossil record of these deposits is dominated by the extinct conifer family Cheirolepidiaceae, for which no resin chemistry has been reported. By analogy with modern materials, it is probable that the ambers found in these deposits are derived from an extinct member of the Pinaceae, but given the absence of evidence concerning the chemotaxonomy of the Cheirolepidiaceae, this family cannot be excluded a priori as a possible paleobotanical source. These ambers may therefore be assigned to either the Pinaceae or to the Cheirolepidiaceae. These samples are the oldest ambers to date to yield useful chemotaxonomic data.     

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.     

The diagenetic production of α-keto acids in heated and fossil Chione shells

Both pyruvic and α-ketobutyric acids are formed during heating experiments with modern Chione shells. These α-keto acids are also present in fossil specimens. These findings provide additional evidence that the dehydration reaction of free serine and threonine or the β-elimination reaction of peptide bound serine and threonine occurred in fossil materials. These experiments suggest that the formation of α-keto acids occurs early in protein diagenesis. A large fraction of the α-keto acids which were formed have been lost either by subsequent reactions or by diffusion out of the shell matrix.     

Molecular composition and chemosystematic aspects of Cretaceous amber from the Amazonas,Araripe and Recôncavo basins,Brazil

Amber occurrences in Brazil are rare. In this regard, the molecular composition of three such fossil resin samples from Brazilian Cretaceous sedimentary basins has been analyzed to determine the botanical origin of the resins. The samples were collected from the Amazonas (Alter do Chão Formation), Araripe (Santana Formation, Crato Member) and Recôncavo (Maracangalha Formation, Caruaçu Member) basins. The mono-, sesqui- and diterpenoids in the extracts were used as chemosystematic markers when compared with terpenoids in extant conifers. The compounds were mainly diterpenoids and their degradation products from the labdane, podocarpane, pimarane and isopimarane classes, in addition to paraffins, methoxyphenols and carboxylic acids. Tetracyclic diterpenoids such as phyllocladane, kaurenol and kauranol were also present. The biomarker compositions are certainly typical for conifers and, given the absence of triterpenoids and diterpenoids such as ozic acid, angiosperms can be excluded as a botanical source. The absence of phenolic diterpenoids (ferruginol, totarol) and their derivatives excludes podocarpaceous affinities for the ambers from the Amazonas and Araripe basins. The fossil records of the embedding sediments (e.g. Araucariaceae pollen and leaves) support the proposal of an Araucariacae origin for these ambers, but Cupressaceae and Cheirolepidiaceae cannot be excluded. On the other hand, the presence of phyllocladane and kaurane derivatives is evidence for Araucariaceae or Podocarpaceae origins for the amber from the Recôncavo basin, but Cupressaceae cannot be excluded.     

Analysis of modern and fossil plant cuticles by Curie point Py-GC and Curie point Py-GC-MS: Recognition of a new, highly aliphatic and resistant biopolymer

This paper investigates to what extent the chemical constituents of plant cuticles (waxes and cutin) can survive diagenesis. Recent and fossil plant cuticles were analyzed by means of Curie point pyrolysis-gas chromatography and Curie point pyrolysis-gas chromatography-mass spectrometry. Recent cuticles were analyzed without treatment, after solvent extraction and after cutin depolymerization. Extensive series of straight-chain alkanes, alk-1-enes and α,ω)-alkadienes dominate the pyrolysates, especially after removal of the wax and cutin. ¹³C-NMR spectroscopy of the residue after removal of the cutin confirmed the presence of a new, highly aliphatic biopolymer and a polysaccharide fraction.The abundance of straight-chain alkanes, alk-1-enes and α,ω-alkadienes in the fossil plant cuticles indicates the chemical resistence of the biopolymer to diagenesis and may explain the occurrence of straight-chain aliphatic moieties in organic-matter-rich sediments and coals as revealed by “C-NMR spectroscopy and flash pyrolysis methods. The highly aliphatic biopolymer may function as an important oil precursor.     

分子有机地球化学与古气候、古环境研究

分子有机地球化学可以从分子级水平研究地质体中有机分子化合物的演化规律。本文报道了应用生物标志化合物指标探讨古气候和古环境,例如探讨古生物(含古植物)的输入,淡水、半咸水和高盐度水古环境的判识以及大气飘尘的来源和成因等。     

A resin nodule in the Cretaceous Garschella Formation from Langer Köchel (Bavaria, S Germany): possible origin and palaeogeographic provenance

A resin nodule was found in glauconite-rich detrital sediments of the Cretaceous Garschella Formation (Aptian to Albian) outcropping at Langer Köchel (Bavaria, S Germany). Gas chromatographic and mass spectrometric analyses of the fossil resin revealed dealkylation and the total defunctionalisation of its polycyclic constituents. Besides many unspecific components a specific one, agathalene, has survived. Agathalene also presents a strongly degraded product, but may have been derived from its natural precursor agathic acid, which is a very specific constituent (biomarker) of recent and fossil kauri resin. Although agathalene is a far less specific secondary biomarker, it indicates the botanic origin of the fossil resin nodule. Besides other potential producers of agathic acid, precursors of the present-day conifer species Agathis dammara and A. australis were distributed in a wider palaeophytogeographic range than today and might have been the botanical source of kauri resin. In view of the east–west directed Early Cretaceous surface current system of the Tethys ocean, the palaeogeographic provenance of the Werdenfels resin nodule probably was a mainland positioned further to the east or southeast of the Helvetic shelf, to where it was transported probably by driftwood of the resin-producing Agathis sp.     

Mineral matter in triassic and tertiary low-rank coals from South Australia

The minerals and non-mineral inorganic constituents in Triassic and Tertiary low-rank coals from various coal deposits in South Australia were studied using selective chemical leaching and oxygen-plasma ashing techniques. Although gypsum may be present in some samples, most of the sodium, calcium and magnesium, as well as part of the sulphur, appears to occur as a combination of dissolved ions in pore water and exchangeable ions attached to carboxylate groups. Significant concentrations of iron and aluminium occur in acid-soluble form, probably as organometallic complexes within the hydrocarbon structure.Quartz is the dominant mineral in the Tertiary coal samples. It appears to be mainly detrital, but doubly terminated euhedral crystals suggest an authigenic origin in one of the deposits. Well crystallized kaolinite is common in the Triassic coals, while poorly crystallized kaolinite occurs in the Tertiary samples. Siderite, calcite and possibly collophane occur in the Triassic coals; sparse pyrite is present in both the Tertiary and the Triassic samples.The differences in minerals and other inorganic constituents between the Tertiary and Triassic deposits can be explained partly by variations in the composition of the pore waters permeating the strata, and partly by mobility of silica and alumina from different sources within the peat deposit. The relative mobility of the different inorganic constituents is also significant in beneficiation of the coal for use in combustion processes.     

Polar constituents of organic matter rich marls from evaporitic series of the Mulhouse basin

A suite of marl samples from the evaporitic series of the Mulhouse basin (France; Lower Oligocene) was studied for its biomarker content, in particular its polar constituents. Novel series of 3-carboxyalkyl steranes and 15-oxo triaromatic ketones were identified by synthesis. The 3-carboxyalkyl steranes probably originate from highly polar precursors yet unreported in living organisms. Our data suggest that micro-algae could be the major source of these compounds which seem to be indicators of high algal input rather than characteristic of evaporitic environments. The 15-oxo triaromatic ketones could be oxidation products of triaromatic steroid hydrocarbons formed during diagenesis, although their formation during work-up procedure could not be excluded.     

Organic geochemical studies of a recent Inner Great Barrier Reef sediment—I. Assessment of input sources

The concentration of solvent-extractable (SE) and bound hydrocarbons, ketones, alcohols, sterols, monocarboxylic acids, hydroxyacids and α,ω-dicarboxylic acids of a surface sample (0–2.5 cm) from a recent carbonate tropical sediment taken at 60ft (18m) depth north-west of the Low Isles, North Queensland, are reported in detail. n-Alkanes are a minor constituent in the SE and bound hydrocarbon fractions with the major component being unresolved complex hydrocarbon material which is not an anthropogenic input. 6,10,14-Trimethylpentadecan-2-one derived from chlorophyll, as well as phytol, were identified as major components of the ketone and alcohol constituents. No chlorophyll pigments or pigmented degradation products were present, implying degradation before incorporation into the sediment. This conclusion is consistent with evidence for higher-plant input in which all sensitive lipids have been degraded before incorporation. SE and bound fractions have been studied in detail and show considerable differences probably arising from the importance of viable biomass in the SE fraction. Inputs to the sediment are determined as higher plants, algae, bacteria, fungi and meiofauna in descending order of importance.     

Diterpenoid compounds and other lipids in deep-sea sediments and their geochemical significance

Cyclic diterpenoid compounds have been found by various investigators in the geosphere (e.g. fossil resins, coals, soil, shale and deep-sea sediments). These compounds occur in significant amounts only in higher plants and are therefore potential markers of terrigenous plant lipids.Diterpenoids with the abietane skeleton (mainly dehydroabietic acid) have been identified in the lipids of sediment samples from the northeast Pacific Ocean, Black Sea and North Atlantic Ocean. The presence of these resin-derived compounds correlated with the terrigenous clay components and with the presence of pollen. The presence of polycyclic diterpenoids was also correlated with the distribution patterns and inferred sources of other sediment lipid constituents (e.g. n-alkanes, n-fatty acids, etc.).Potamic transport, followed by turbidite redistribution are the probable input mechanisms of these resin-derived compounds to the deep-sea sediments. These diterpenoids appear to be excellent biological markers of resinous higher plants.     

Biomarker lipids of the freshwater fern Azolla and its fossil counterpart from the Eocene Arctic Ocean

Eocene sediments recovered from the Lomonosov Ridge in the central Arctic Ocean during Integrated Ocean Drilling Program Expedition 302 contain high amounts of fossil remains of the free floating freshwater fern Azolla. Both extant Azolla and the sediments from the Arctic Azolla interval were found to contain relatively high quantities of compounds identified as 1,ω20 C₃₀–C₃₆ diols. Furthermore, structurally related mid-chain hydroxy fatty acids, long chain n-alkanols and keto-ols were discovered. The different series have a common feature: there is always a hydroxy group at the ω20 position. In addition, structurally related C₂₉ ω20,ω21 diols, C₂₉ 1,20,21 triols, C₂₉ dihydroxy fatty acids as well as a series of wax esters containing these mono- and dihydroxy lipids are reported. Selective extraction of Azolla surface lipids revealed that these compounds are most likely present in the leaf waxes of the fern. The suite of long-chain, mid-chain ω20 hydroxy wax constituents is described for the first time. As they are well preserved in the Eocene sediments, these lipids may serve as palaeo-environmental indicators of the Arctic Azolla interval and as markers for the past occurrence of Azolla in general.     

18O and 34S in the Upper Bartonian gypsum deposits of the Paris basin

Isotopic analyses (¹⁸O and ³⁴S) of the Eocene gypsum from the Paris basin show a range beyond the normal Tertiary marine values. The possibility of a reduction process during diagenesis is discussed.A hypothesis of continental origin by leaching of Permotriassic deposits is proposed for this formation on the basis of a comparison of the isotopic contents recorded from Germany and eastern France.     

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.     

Geochemical Characterization and Origin of High-Sulfur, Heavy Oils in Jiyang Sub-Basin, East China

High-sulfur,heavy petroleum is widely occurring in the Tertiary lacustrine Jiyang sub-basin, Bohai Bay Basin.They are differentiated into two families based on the bulk properties and biomarker compositions.Family 1 is characterized by high resins(40%-71%)and sulfur(2%-4%),and low wax (l%-6%),with n-alkanes removed by biodegradation,whereas family 2 is characterized by extremely abundant sulfur(3%-10%),and high asphaltenes(7%-31%)and wax(2%-19%),with no evidence of microbial attack.The oils of family 1 a...     

Possibilities of palaeopedology

Although fossil hydromorphic soils are very abundant in both Tertiary and older deposits in Western Europe, they are either not recognized or their study is not undertaken. A short account is given on the pedogenetical processes in hydromorphic soils and some of the features that can be traced and others that cannot are discussed. Two examples illustrate conclusions that can be drawn from the study of fossil hydromorphic soils.     

内蒙古商都地区CO2气藏地质条件研究

本文以商都盆地第三系CO2气成藏条件研究为目的，通过对区域构造（断裂、火山活动、岩浆作用）和地层特征及沉积相研究，结合地震勘探成果、CO2碳同位素、氦同位素分析成果，系统探讨了商都盆地CO2气源、运移通道、储集条件、圈闭及盖层条件，并对CO2气成藏模式进行了分析。认为：该区CO2气为幔源成因气，通过包兰哈达－高勿素深断裂运移到第三系储集层中富集成藏。第三系河流或冲积扇沉积的粗碎屑岩广泛分布，而且厚度较大，成岩程度低，具有良好的储集条件。新第三纪晚期的湖泛沉积，形成了巨厚的泥页岩盖层。沉积期后的差异压实作用、断裂、火山及岩浆活动等多因素作用，使这一地区局部构造发育，形成岩性－构造圈闭或构造性圈闭，有利于CO2气成藏。     

Polar aromatic biomarkers of Miocene-aged Chukurovo resinite and correlation with a progenitor macrofossil

Functionalised aromatic constituents of Chukurovo resinite are compared here with the chemical composition of a macrofossil assigned paleobotanically as Taxodium dubium (Sternb.) Heer. Terpenoids and lipids of fossil wood tissue embedded in a clay sediment were extracted and analyzed for comparison. The information was interpreted in relation to the biomarker compositions of different conifer families, as well as to the effects of contamination by inward migration of organic matter from the adjacent sediments.Many of identified geolipids, i.e., alkanes, alkanols, alkan-2-ones, and steranes/triterpanes have no chemosystematic value because they are ubiquitous in the plant kingdom. Ferruginol, sugiol, and products of their diagenetic transformations were identified as the dominant specific biomarkers in the resinite. Ferruginol and its analogues were the most abundant diterpenoids in Taxodium dubium sample. Thus, the biomarker composition of the extractable matter of the resinite strongly suggests that species of Cupressaceae contributed significantly to the Chukurovo paleoenvironment.