Structural modifications of vitrinite and alginite concentrates during pyrolitic maturation at different heating rates. A combined infrared, C NMR and microscopical study

Immature vitrinite samples from a Miocene lignite seam of western Germany (H/C = 1.14, O/C = 0.41) and alginite concentrates from a Tasmanite deposit of Australia (H/C = 1.60, O/C = 0.10) were pyrolyzed in a stream of argon at heating rates of 0.1 and 2.0°C/min up to temperatures varying from 200 to 670°C. The solid maceral residues were subjected to elemental and microscopical analysis and studied by IR and ¹³C CP/MAS NMR spectroscopy with respect to structural modifications.The maximum pyrolytic weight loss amounts to 60% of the initial organic matter in the case of vitrinite and to 85% for alginite, the onset of degradation reactions being shifted to higher temperatures with increasing rate of heating. Both infrared and NMR spectra of the vitrinite samples indicate a rapid decomposition of the cellulose component upon heating whereas lignin related structures such as aromatic ether linkages remain remarkably stable. The main hydrocarbon release from vitrinite occurs at very early evolution stages (T_max = 296°C, R_m = 0.20% at 0.1°C/min; T_max = 337°C, R_m = 0.23 at 2.0°C/min). Hydrocarbon generation from alginite requires higher temperatures (T_max = 388 and 438°C) and is completed within a distinctly narrower temperature range.The pronounced increase of vitrinite reflectance between 350 and 670°C seems to be associated with a rather time-consuming reorganization of the residual organic material. The concomitant growth of polyaromatic units is illustrated by the increasing intensity ratio of the aromatic ring stretching vibration bands at 1600 and 1500 cm⁻¹. These reactions are moreover marked by increasing loss of phenolic oxygen and by increasing conversion of aliphatic carbon into fixed aromatic carbon.     

Correlation between local structure and molar ratio of Au (III) complexes in aqueous solution: An XAS investigation

The local and geometrical structure around gold (III) e.g., Au³⁺ ions in aqueous solution with different OH⁻/Cl⁻ molar ratios, has been investigated by X-ray absorption spectroscopy (XAS). X-ray absorption near-edge structure (XANES) spectra of [AuCl_n(OH)_4−n]⁻ solutions have been calculated and the multiple-scattering spectral features have been attributed to Cl d-states, axial water molecules and the replacement of Cl⁻ ligands by OH⁻ ligands. A square–planar geometry for [AuCl_n(OH)_4−n]⁻ with two axial water molecules has been identified. Moreover, a spectral correlation between XANES features and the type of planar atoms has been identified. By extended X-ray absorption fine structure spectra (EXAFS), the planar Au bond distances in the solutions have also been determined, e.g., 2.28 Å for Au–Cl and 1.98 Å for Au–O, respectively. The same EXAFS analysis provides evidence that the peak at about 4.0 Å in solutions with the lowest OH⁻/Cl⁻ molar ratio arises from collinear Cl–Au–Cl multiple-scattering contributions. For the first time, a complete detailed reconstruction of the hydration structure of an Au ion at different pH values has been achieved.     

Geochemistry and occurrence of inorganic gas accumulations in Chinese sedimentary basins

Inorganic gases are commonly seen in eastern China and occasionally in southern China from the shallow water columns above hot and cold springs. The gases contain 68% to nearly 100% CO₂, with δ¹³C_CO2 and δ¹³C₁ values in the range of −1.18‰ to −6.00‰ and −19.48‰ to −24.94‰, respectively. All of the 34 large inorganic CO₂ and one inorganic methane accumulations discovered in China are distributed in eastern parts of the country, from both onshore and continental shelf basins. No commercial inorganic gas accumulation has been found in central and western China. This is a review of the occurrence and geochemical characteristics of inorganic gas accumulations in Chinese sedimentary basins. A detailed study of gas samples collected from four representative inorganic CO₂ pools and one possible inorganic methane pool indicates that inorganic alkane gases typically show δ¹³C₁ values greater than −10‰ versus PDB (mostly −30‰), with a positive stable carbon isotope sequence of δ¹³C₁ < δ ¹³C₂ < δ¹³C₃ < δ ¹³C₄. In contrast, the δ¹³C₁ values of biogenic alkane gases are lighter than −30‰, with a negative isotope sequence (i.e. δ¹³C₁ > δ¹³C₂ > δ ¹³C₃ > δ¹³C₄). Inorganic gases also tend to show less negative δ¹³C_CO2 values (−10‰) than biogenic gases (<−10‰).     

Isotopic fractionation associated with biosynthesis of fatty acids by a marine bacterium under oxic and anoxic conditions

Shewanella putrefaciens (Strain MR-4), a gram negative facultative marine bacterium, was grown to stationary phase under both aerobic and anaerobic conditions using lactate as the sole carbon source. Aerobically-produced cells were slightly enriched in ¹³C (+1.5‰) relative to the lactate carbon source, whereas those from anaerobic growth were depleted in ¹³C (−2.2‰). The distribution of fatty acids produced under aerobic conditions was similar to that resulting from anaerobic growth, being dominated by C_16:1 ω7 and C_16:0 fatty acids with a lesser amount of the C_18:1 ω7 component. Low concentrations of saturated even numbered normal fatty acids in the C₁₄ to C₁₈ range, and iso-C_15:0 were synthesized under both conditions. Fatty acids from anaerobic cultures (average δ¹³C=−37.8‰) were considerably depleted in ¹³C relative to their aerobically-synthesized counterparts (−28.8‰). The distinct differences in isotopic composition of both whole cells and individual fatty acid components result from differences in assimilation pathways. Under aerobic conditions, the primary route of assimilation involves the pyruvate dehydrogenase enzyme complex which produces acetyl-CoA, the precursor to lipid synthesis. In contrast, under anaerobic conditions formate, and not acetate, is the central intermediate in carbon assimilation with the precursors to fatty acid synthesis being produced via the serine pathway. Anaerobically-produced bacterial fatty acids were depleted by up to 12‰ relative to the carbon source. Therefore, detection of isotopically depleted fatty acids in sediments may be falsely attributed to a terrestrial origin, when in fact they are the result of bacterial resynthesis.     

Molecular and carbon isotopic analysis of individual biological markers: evidence for sources of organic matter and paleoenvironmental conditions in the Upper Ordovician Maquoketa Group, Illinois Basin, U.S.A.

Variations in the carbon isotopic composition (δ¹³C) of pristane, phytane, n-heptadecane (n-C₁₇), C₂₉ ααα 20R sterane, and aryl isoprenoids provide evidence for a diverse community of algal and bacterial organisms in organic matter of the Upper Ordovician Maquoketa Group of the Illinois Basin. Carbon isotopic compositions of pristane and phytane from the Maquoketa are positively covariant (r = 0.964), suggesting that these compounds were derived from a common source inferred to be primary producers (algae) from the oxygenated photic zone. A variation of 3‰ in δ¹³C values (−31 to −34‰) for pristane and phytane indicates that primary producers utilized variable sources of inorganic carbon. Average isotopic compositions of n-C₁₇ (−32‰) and C₂₉ ααα 20R sterane (−31‰) are enriched in ¹³C relative to pristane and phytane (−33‰) suggesting that these compounds were derived from a subordinate group of primary producers, most likely eukaryotic algae. In addition, a substantial enrichment of ¹³C in aryl isoprenoids (−14 to −18‰) and the identification of tetramethylbenzene in pyrolytic products of Maquoketa kerogen indicate a contribution from photosynthetic green sulfur bacteria to the organic matter. The presence of anaerobic, photosynthetic green sulfur bacteria in organic matter of the Maquoketa indicates that anoxic conditions extended into the photic zone.The δ¹³C of n-alkanes and the identification of an unusual suite of straight-chain n-alkylarenes in the m/z 133 fragmentograms of Ordovician rocks rich in Gloeocapsomorpha prisca (G. prisca) indicate that G. prisca did not contribute to the organic matter of the Maquoketa Group.     

Middle Pleistocene climate and habitat change at Zhoukoudian, China, from the carbon and oxygen isotopic record from herbivore tooth enamel

The Pleistocene deposits at Zhoukoudian, often referred to as the “Peking Man” site, contain dental remains from a diverse group of herbivores, including Equus sanmeniensis, Cervus elaphus, Cervus nippon, Megaloceros pachyosteus, Sus lydekkeri, and Dicerorhinus choukoutienensis. The carbon and oxygen isotopic compositions of structural carbonate within the enamel of these teeth are used to reconstruct the paleodiet and paleoenvironment of the mammals. The δ¹³C values of enamel from Zhoukoudian range from −2.3‰ to −13.0‰, indicating that these mammals consumed between 25% and 100% C₃ plants. The presence of significant amounts of C₄ plants in the diets of some herbivore species indicates that at the onset of the Middle Pleistocene local habitats included mixed C₃/C₄ vegetation. By approximately 470,000 yr ago, C₃ plants dominated the diets of herbivores studied, suggesting that the abundance of C₄ flora had decreased in the area. For all deer analyzed in this study, the values of δ¹³C and δ¹⁸O decrease substantially from about 720,000 to 470,000 yr ago. This trend may be due to a strengthening of the winter monsoon during the Middle Pleistocene.     

Ammonium ion behaviour in feldspar: variable-temperature infrared and 2H NMR studies of synthetic buddingtonite, N(D,H)4AlSi3O8

The behaviour of the ammonium ion in synthetic buddingtonite, N(D,H)₄AlSi₃O₈, has been studied by infrared (IR) spectroscopy from 20 K to 298 K and by ²H NMR spectroscopy from 120 K to 298 K. IR spectra were collected from 500 to 3500 cm^–1. Static ²H NMR spectra collected at 298 K and 120 K are very similar, consisting of a single sharp isotropic resonance, indicating complete averaging of quadrupolar interactions and implying that at these temperatures the ammonium ion is in rapid (<1 s) randomised motion within the M-site cavity of the feldspar framework. NMR spectroscopy indicates that the splitting of the internal modes of the ammonium ion observed by IR spectroscopy is not due to freezing in of the ammonium ion. This observation rules out the formation of a preferred N–H...O hydrogen bond, with precession of the ion about it, as proposed by Kimball and Megaw (1978), because any N–H...O hydrogen bond must be very weak and transient in nature. Contraction of the cavity site upon cooling imposes a distortion upon the ammonium ion that affects vibrational modes. This distortion does not affect the motion of the ammonium ion as observed on the NMR time-scale.     

Stable carbon isotope compositions and source rock geochemistry of the giant gas accumulations in the Ordos Basin, China

Ordos Basin, the second largest sedimentary basin in China, contains enormous natural gas resources. Each of the four giant gas fields discovered so far in this basin (i.e., Sulige, Yulin, Wushenqi and Jingbian) has over 100 billion cubic meters (bcm) or 3.53 trillion cubic feet (tcf) of proven gas reserves. This study examines the stable carbon isotope data of 125 gas samples collected from the four giant gas fields in the Ordos Basin. Source rocks in the Upper Paleozoic coal measures are suggested by the generally high δ¹³C values of C₁–C₄ gaseous hydrocarbons in the gases from the Sulige, Yulin and Wushenqi gas fields. While the δ¹³C_iC4 value is higher than that of the δ¹³C_nC4, the dominant ranges for the δ¹³C₁, δ¹³C₂, and δ¹³C₃ values in these Upper Paleozoic reservoired gases are −34 to −32‰, −27 to −23‰, and −25 to −24‰, respectively. The δ¹³C values of methane, benzene and toluene in gases from the Lower Paleozoic reservoirs of the Jingbian field indicate a significant contribution from humic source rocks, as they are similar to those in the Upper Paleozoic reservoirs of the Sulige, Yulin and Wushenqi gas fields. However, the wide variation and reversal in the δ¹³C₁, δ¹³C₂ and δ¹³C₃ values in the Jinbian gases cannot be explained using a single source scenario, thus the gases were likely derived dominantly from the Carboniferous-Permian coal measures with some contribution from the carbonates in the Lower Permian Taiyuan Formation. The gas isotope data and extremely low total organic carbon contents (<0.2% TOC) suggest that the Ordovician Majiagou Formation carbonates are unlikely to be a significant gas source rock, thus almost all of the economic gas accumulations in the Ordos Basin were derived from Upper Paleozoic source rocks.     

C NMR, micro-FTIR and fluorescence spectra, and pyrolysis-gas chromatograms of coalified foliage of late Carboniferous medullosan seed ferns, Nova Scotia, Canada: Implications for coalification and chemotaxonomy

The cuticles and cuticle-free compressions of three Carboniferous medullosan seed-fern leaf species (Macroneuropteris scheuchzeri, Neuropteris ovata var. simonii and Alethopteris lesquereuxii) were analyzed by elemental, ¹³C nuclear magnetic resonance (NMR), micro-FTIR (Fourier transform infrared) and coal petrographic techniques. The 13C NMR spectra of the cuticle-free compressions and the associated whole coal (high volatile A/B bituminous coal rank) are generally similar and consist of a large aromatic carbon peak, a smaller aliphatic carbon peak and a shoulder on the aromatic peak, representing phenolic carbons. In contrast, the ¹³C NMR spectra of the cuticles from the same leaves have a predominant peak for aliphatic carbons and a much smaller aromatic carbon peak. This difference in aromaticity between the cuticles and the cuticle-free compressions is also reflected in the higher atomic H/C ratios of the cuticles. Micro-FTIR spectra of the cuticles show oxygenated functional groups (carboxyl and ketone) similar to those in modern cuticles but their most characteristic feature is very strong bands in the aliphatic stretching region. The cuticle-free compressions (mainly vitrinite), in turn, show the absence or significant reduction in oxygenated functional groups, reduction in aliphatic stretching bands and, usually, increased absorbance of aromatic out-of-plane deformation in the 700–900 cm⁻¹ region. Fluorescence spectra for the cuticles from all three species show a great similarity with a λ_max at 580–590 nm, probably reflecting a similardegree of coalification, which is consistent with the similar vitrinite reflectance (R_r) and H/C and O/C ratios of the cuticlefree compressions.These results indicate that leaf cuticle-free compressions, which were initially cellulose rich ( 90% cellulose and hemicellulose, < 10% lignin), can alter, during peatification and coalification, to a macromolecular structure similar to that of coalified wood (initially 50% cellulose and hemicellulose, 30%–50% lignin). Thus, a lignin-enriched structure is not a prerequisite for the formation of the macromolecular structure of vitrinite. In addition, the micro-FTIR spectra reveal the complexity of the molecular structure in coalified seed-fern leaves. The micro-FFIR data reveal some significant differences among the cuticles that may be of chemotaxonomic value. Clearly, a combination of macro- and micro-techniques offers a better basis for the interpretation of the molecular structure of pre-macerals and their alteration during peatification and coalification. Also, the data presented in this paper provide important new information that extends the data from morphological and cuticular taxonomic studies of some seed ferns. The data are encouraging preliminary advances in the chemotaxonomy of medullosan seed fern species.Pyrolysis-gas chromatography (PY-GC) data for the cuticles of three seed-fern leaves indicate distinct chemical signatures for the two neuropterid leaves as compared to the Alethopteris leaf. This perhaps indicates a chemotaxomic factor, or it could be related to the greater thickness of the cuticle of Alethopteris. Mass spectrometric data are needed to identify individual components in the PY-GC chromatograms.     

The nature of olefins and carboxyl groups in an Australian brown coal resin

The chemical structure of the resin from an Australian soft brown coal (Yallourn) has been investigated by cross-polarization nuclear magnetic resonance spectroscopy with magic angle spinning (¹³C CP MAS NMR). Some additional solution ¹H and ¹³C data were also obtained. Solid-state experiments were performed with and without a delay period before data acquisition. The resulting free induction decays were Fourier transformed with respect to acquisition time and delay period to produce two-dimensional solid-state spectra. Assignments made from the spectra clearly demonstrate that the gross chemical structure of the Yallourn resin is best described as a polymerized diterpenoid with one axial carboxylic group and two double bonds. One double bond is trisubstituted, the other is monosubstituted. After consideration of various mechanisms for polymerization of diterpenoid units during biogenesis and coalification, it was concluded that polymerization occurs at the C₁₅ carbon atoms in the diterpenoids without cyclization of the methylene units at C₈.     

Micro-FTIR spectroscopy of liptinite macerals in coal

Reflectance FTIR microspectroscopy has been used to investigate the chemical structure of the liptinite macerals, alginite, bituminite, sporinite, cutinite and resinite in bituminous coals of Carboniferous to Tertiary age. In comparison with the spectra of vitrinite in the same coals, the micro-FTIR spectra of liptinite macerals are characterized by stronger aliphatic CH_x absorptions at 3000–2800 and 1460–1450 cm⁻¹, less intense aromatic C=C ring stretching vibration and aromatic CH out of plane deformation at 1610–1560 and 900–700 cm⁻¹ respectively and various intense acid C=O group absorptions at 1740–1700 cm⁻¹. The peaks at 1000–900 cm⁻¹ due to aliphatic CH₂ wagging vibrations in olefins and at 730–720 cm⁻¹ due to CH₂ rocking vibration in long chain aliphatic substances ([CH₂]_n, n≥4), are characteristic of liptinite macerals. Collectively the micro-FTIR spectral characteristics indicate that liptinite is composed of greater numbers of long chain aliphatics, fewer aromatics and a broader range of oxygen-containing groups than other macerals. Marked differences exist in micro-FTIR spectra within the liptinite maceral group. Alginite has the strongest aliphatic and least aromatic absorptions followed by bituminite, resinite, cutinite and sporinite. The aliphatic components in alginite are the longest chained and least branched whereas those in sporinite are the shortest chained and most branched. Bituminite, resinite and cutinite are intermediate. Notable differences in micro-FTIR spectra of individual liptinite macerals, such as intensities and peak locations of aromatic C=C in alginite, C=O groups in bituminite and resinite and substituted aromatic CH and C–O–C groups in cutinite and sporinite, also exist, which are attributed to differences in depositional environments or biotaxonomy.     

Carbon isotopes of Middle–Lower Jurassic coal-derived alkane gases from the major basins of northwestern China

Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ¹³C values are found in the Tarim and Qaidam basins (δ¹³C₁: − 19.0 to − 29.9‰; δ¹³C₂: − 18.8 to − 27.1‰), and those with lowest δ¹³C values occur in the Turpan-Harmi and Junggar basins (δ¹³C₁: − 40.1 to − 44.0‰; δ¹³C₂: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C_5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ¹³C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.     

Detection of tannins in modern and fossil barks and in plant residues by high-resolution solid-state C nuclear magnetic resonance

Bark samples isolated from brown coal deposits in Victoria, Australia, and buried wood from Rhizophora mangle have been studies by high-resolution solid-state nuclear magnetic resonance (NMR) techniques. Dipolar dephasing ¹³C NMR appears to be a useful method of detecting the presence of tannins in geochemical samples including barks, buried woods, peats and leaf litter. It is shown that tannins are selectively preserved in bark during coalification to the brown coal stage.     

Environmental control of carbon isotope variations in Pennsylvania black-shale sequences, Midcontinent, U.S.A.

A reversal of the conventional carbon isotope relationship, “terrestrial-lighter-than-marine” organic matter, has been documented for two Pennsylvanian (Desmoinesian) cyclothemic sequence cores from the Midcontinent craton of the central United States. “Deep” water organic-rich phosphatic black shales contain a significant proportion of algal-derived marine organic matter (as indicated by organic petrography, Rock-Eval hydrogen index and ratios) and display the lightest δ¹³C-values (max −27.80‰ for kerogen) while shallower water, more oxic facies (e.g. fossiliferous shales and limestones) contain dominantly terrestrial organic matter and have heavier δ¹³C_kerogen-values (to −22.87‰ for a stratigraphically adjacent coal). δ¹³C-values for extract fractions were relatively homogeneous for the organic-rich black shales with the lightest fraction (often the aromatics) being only 1‰, or less, more negative than the kerogen. Differences between extract fractions and kerogens were much greater for oxic facies and coals (e.g. saturates nearly 5‰ lighter than the kerogen).A proposed depositional model for the black shales calls upon a large influx of nutrients and humic detritus to the marine environment from the laterally adjacent, extremely widespread Pennsylvanian (peat) swamps which were rapidly submerged by transgression of the epicontinental seas. In this setting marine organisms drew upon a CO₂-reservoir which was in a state of disequilibrium with the atmosphere, being affected by isotopically light “recycled-CO₂” derived from the decomposition of peaty material in the water column and possibly from the anoxic diagenesis of organic matter in the sediments.     

Origins and accumulation of organic matter in expanded Albian to Santonian black shale sequences on the Demerara Rise, South American margin

Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian–Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, δ¹³C_org values lie mostly between −30‰ and −27‰, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C₃ land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low δ¹³C_org values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian–Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.     

Carbon isotope chemostratigraphy of a Precambrian/Cambrian boundary section in the Three Gorge area, South China: Prominent global-scale isotope excursions just before the Cambrian Explosion

Carbon isotope chemostratigraphy has been used for worldwide correlation of Precambrian/Cambrian (Pc/C) boundary sections, and has elucidated significant change of the carbon cycle during the rapid diversification of skeletal metazoa (i.e. the Cambrian Explosion). Nevertheless, the standard δ¹³C curve of the Early Cambrian has been poorly established mainly due to the lack of a continuous stratigraphic record. Here we report high-resolution δ¹³C chemostratigraphy of a drill core sample across the Pc/C boundary in the Three Gorge area, South China. This section extends from an uppermost Ediacaran dolostone (Dengying Fm.), through a lowermost Early Cambrian muddy limestone (Yanjiahe Fm.) to a middle Early Cambrian calcareous black shale (Shuijingtuo Fm.). As a result, we have identified two positive and two negative isotope excursions within this interval. Near the Pc/C boundary, the δ¹³C_carb increases moderately from 0 to + 2‰ (positive excursion 1: P1), and then drops dramatically down to − 7‰ (negative excursion 1: N1). Subsequently, the δ¹³C_carb increases continuously up to about + 5‰ at the upper part of the Nemakit–Daldynian stage. After this positive excursion, δ¹³C_carb sharply decreases down to about − 9‰ (N2) just below the basal Tommotian unconformity. These continuous patterns of the δ¹³C shift are irrespective of lithotype, suggesting a primary origin of the record. Moreover, the obtained δ¹³C profile, except for the sharp excursion N2, is comparable to records of other sections within and outside of the Yangtze Platform. Hence, we conclude that the general feature of our δ¹³C profile best represents the global change in seawater chemistry. The minimum δ¹³C of the N1 (− 7‰) is slightly lower than carbon input from the mantle, thus implying an enhanced flux of ¹³C-depleted carbon just across the Pc/C boundary. Hence, the ocean at that time probably became anoxic, which may have affected the survival of sessile or benthic Ediacaran biota. The subsequent δ¹³C rise up to + 5‰ (P2) indicates an increase of primary productivity or an enhanced rate of organic carbon burial, which should have resulted in lowering pCO₂ and following global cooling. This scenario accounts for the cause of the global-scale sea-level fall at the base of the Tommotian stage. The subsequent, very short-term, and exceptionally low δ¹³C (− 9‰) in N2 could have been associated with the release of methane from gas hydrates due to the sea-level fall. The inferred dramatic environmental changes (i.e., ocean anoxia, increasing productivity, global cooling and subsequent sea-level fall with methane release) appear to coincide with or occur just before the Cambrian Explosion. This may indicate synchronism between the environmental changes and rapid diversification of skeletal metazoa.     

Gas maturity and alteration systematics across the Western Canada Sedimentary Basin from four mud gas isotope depth profiles

Carbon isotope and molecular compositions of Mississippian to Upper Cretaceous mud gases have been examined from four depth profiles across the Western Canada Sedimentary Basin (WCSB). The profiles range from the shallow oil sands in the east (R₀ = 0.25) to the very mature sediments in the overthrust zone to the west (R₀ = 2.5). In the undisturbed WCSB, δ¹³C₁–δ¹³C₂ and δ¹³C₂–δ¹³C₃ cross-plots show three maturity and alteration trends: (1) pre-Cretaceous gas sourced from type II kerogen; (2) Cretaceous Colorado Group gas; and (3) Lower Cretaceous Mannville Group biodegraded gas. A fourth set of distinctly different maturity trends is recognized for Lower Cretaceous gas sourced from type III kerogen in the disturbed belt of the WCSB. Displacement of these latter maturity trends to high δ¹³C₂ values suggests that the sampled gas was trapped after earlier formed gas escaped, probably as a result of overthrusting. Unusually ¹³C-enriched gas (δ¹³C₁ = −34‰, δ¹³C₂ = −13‰, and δ¹³C₃ = 0‰), from the Gething Formation in the disturbed belt, is the result of late stage gas cracking in a closed system. In general, gas maturity is consistent with the maturity of the host sediments in the WCSB, suggesting that migration and mixing of gases was not pervasive on a broad regional and stratigraphic scale. The ‘Deep Basin’ portion of the WCSB is an exception. Here extensive cross-formational homogenization of gases has occurred, in addition to updip migration along the most permeable stratigraphic units.     

Isotopic and molecular composition of coal-bed gas in the Amasra region (Zonguldak basin—western Black Sea)

Previous studies on the coal-bed methane potential of the Zonguldak basin have indicated that the gases are thermogenic and sourced by the coal-bearing Carboniferous units. In this earlier work, the origin of coal-bed gas was only defined according to the molecular composition of gases and to organic geochemical properties of the respective source rocks, since data on isotopic composition of gases were not available. Furthermore, in the western Black Sea region there also exist other source rocks, which may have contributed to the coal-bed gas accumulations. The aim of this study is to determine the origin of coal-bed gas and to try a gas-source rock correlation. For this purpose, the molecular and isotopic compositions of 13 headspace gases from coals and adjacent sediments of two wells in the Amasra region have been analyzed. Total organic carbon (TOC) measurements and Rock-Eval pyrolysis were performed in order to characterize the respective source rocks. Coals and sediments are bearing humic type organic matter, which have hydrogen indices (HI) of up to 300 mgHC/gTOC, indicating a certain content of liptinitic material. The stable carbon isotope ratios (δ¹³C) of the kerogen vary from −23.1 to −27.7‰. Air-free calculated gases contain hydrocarbons up to C₅, carbon dioxide (<1%) and a considerable amount of nitrogen (up to 38%). The gaseous hydrocarbons are dominated by methane (>98%). The stable carbon isotope ratios of methane, ethane and propane are defined as δ¹³C₁: −51.1 to −48.3‰, δ¹³C₂: −37.9 to −25.3‰, δ¹³C₃: −26.0 to −19.2 ‰, respectively. The δD₁ values of methane range from −190 to −178‰. According to its isotopic composition, methane is a mixture, partly generated bacterially, partly thermogenic. Molecular and isotopic composition of the gases and organic geochemical properties of possible source rocks indicate that the thermogenic gas generation took place in coals and organic rich shales of the Westphalian-A Kozlu formation. The bacterial input can be related to a primary bacterial methane generation during Carboniferous and/or to a recent secondary bacterial methane generation. However, some peculiarities of respective isotope values of headspace gases can also be related to the desorption process, which took place by sampling.     

Origin of methane in high-arsenic groundwater of Taiwan – Evidence from stable isotope analyses and radiocarbon dating

Groundwaters in the confined aquifers of the Chianan and Ilan coastal plains of Taiwan are rich in dissolved methane (CH₄). Serious endemic “blackfoot disease”, which occurred in the Chianan plain, especially during AD1950-1970, has been demonstrated to have arisen from drinking highly reducing groundwater with abnormal arsenic and humic substance levels. In order to explore the origin of CH₄ and its hydrological implications, stable carbon isotope ratios (δ¹³C) and radiocarbon (¹⁴C) ages of exsolved CH₄, dissolved inorganic carbon (DIC), and sedimentary biogenic sediments from a total of 34 newly completed water wells at 16 sites were determined. The main results obtained are as follows: (1) The δ¹³C_CH4 (−65‰ to −75‰) values indicate that, except for one thermogenic sample (δ¹³C_CH4=38.2‰) from the Ilan plain, all CH₄ samples analyzed were produced via microbially mediated CO₂ reduction. Many δ¹³C_DIC values are considerably greater than −10‰ and even up to 10‰ due to Rayleigh enrichment during CO₂ reduction. (2) Almost all the ¹⁴C ages of CH₄ samples from the shallow aquifer (I) (<60 m depth) are greater than the ¹⁴C ages of coexisting DIC and sediments, suggesting the presence of CH₄ from underlying aquifers. (3) The ¹⁴C ages of coexisting CH₄, DIC and sediments from aquifer (II) of the Chianan plain are essentially equal, reflecting in-situ generation of CH₄ and DIC from decomposition of sedimentary organic matter and sluggishness of the groundwater flow. On the other hand, both CH₄ and DIC from each individual well of the relatively deep aquifers (III) and (IV) in the Chianan plain are remarkably younger than the deposition of their coexisting sediments, indicating that current groundwaters entered these two aquifers much later than the deposition of aquifer sediments. (4) Each CH₄ sample collected from the Ilan plain is older than coexisting DIC, which in turn is distinctly older than the deposition of respective aquifer sediments, demonstrating the presence of much older CO₂ and CH₄ from underlying strata.     

Structural identification of the C25 highly branched isoprenoid pentaene in the marine diatom Rhizosolenia setigera

2,6,10,14-tetramethyl-7-(3-methylpent-4-enyl)-pentadeca-2,5E,9E,13-tetraene I possessing a C₂₅ highly branched isoprenoid skeleton has been isolated from the marine diatom Rhizosolenia setigera and identified by ¹H and ¹³C NMR spectroscopy.