Pyrolytic and spectroscopic study of a sulphur-rich kerogen from the “Kashpir oil shales” (Upper Jurassic, Russian platform)

The kerogen of an organic-rich sample, termed f top, from the Gorodische section (Russian platform) was studied using a combination of microscopic, spectroscopic and pyrolytic methods so as to examine its chemical structure, source organisms and formation pathway(s). This kerogen, which is mainly composed of orange gel-like, nanoscopically amorphous organic matter, exhibits a relatively high aliphatic character; organic sulphur is mainly present as di(poly)sulphides and alkylsulphides. The f top kerogen was chiefly formed via intermolecular incorporation of sulphur in algal or cyanobacterial lipids and carbohydrates. However, its formation also involved oxidative condensation via ether linkages. Comparison of f top sample with other S-rich kerogens points to a closer similarity with Monterey kerogens rather than with a kerogen from the bituminous laminites of Orbagnoux.     

Uranium mineralization in the Alum Shale Formation (Sweden): Evolution of a U-rich marine black shale from sedimentation to metamorphism

The Alum Shale Formation is a metal-rich black shale, deposited on the Baltoscandian platform between Middle Cambrian and Early Ordovician. These black shales may be of particular economic interest for their relatively high uranium content (100–300 ppm) and their wide distribution from Norway to Estonia. Scandinavian Alum Shale may thus constitute a great potential resource of uranium, as a low grade ore. The Alum Shale Formation is particularly interesting to study the mineralogical expression and content of uranium in series submitted to progressive burial and metamorphism. For this purpose, the behavior of U, P, Ti and organic matter was studied on a series of representative samples from most Alum Shale prospection zones. In southern Sweden, where Alum Shale underwent fairly shallow burial, uranium concentrations have no mineralogical expression except a rather high U content of biogenic phosphates. Calcite concretions (beefs) and fractures recorded the migration of hot overpressured hydrocarbons and brines from thermally mature areas to immature Alum Shale. However, thermal maturation and fluid migration did not allow remobilization of uranium and metals. At the opposite, in northern Sweden, where the series were folded, duplicated and submitted to low grade Greenschist metamorphism during Caledonian orogeny, phospho-silicates U-Si-Ca-P (±Ti ±Zr ±Y) and minor amounts of uraninite are identified and indicate that U, P, and Ti were mobile and precipitated as new phases. The effect of metamorphism is therefore important to consider as the leachability of U, especially during (bio)-hydrometallurgical processes, which will be by far different between the two considered areas.     

Possible chemical structures and biological precursors of different vitrinites in coal measure in Northwest China

Chemical structure of Jurassic vitrinites isolated from the coals in basins in NW China have been checked using solid state ¹³C NMR and flash pyrolysis-GC/MS. Study shows some Jurassic collodetrinites are rich in aliphatic products in pyrolysates, consisting with the high amount of methylene carbon in ¹³C NMR spectra. In contrast, pyrolysates of Jurassic collotelinites are rich in phenols and alkylbenzenes. Also one Pennsylvanian and one Permian vitrinite selected from the Ordos basin, NW China have been checked for comparison. The proportion of aliphatics is low in pyrolysates, and aliphatic carbon peak in ¹³C NMR spectrum of Permian vitrinite is mostly composed of gas-prone carbons compared with collodetrinites in those Jurassic basins. But both pyrolysis and ¹³C NMR data shows the Pennsylvanian vitrinite is not only gas-prone but also oil-prone. Relatively high proportion of long chain aliphatic structure of some Jurassic vitrinite in Junggar, Turpan-Hami basins may be due to the contribution of liptodetrinites, which may be included during the formation of vitrinites. And it seems that suberinite is the most possible precursor of long chain aliphatics in the structure of Jurassic collodetrinite.     

Chemical characterization of the kerogen from Moroccan Timahdit oil shale by analysis of oxidation products

A 33 step alkaline permanganate degradation of the kerogen from Moroccan Timahdit oil shale (M-Zone) was carried out. A very high total yield of oxidation products was obtained (95.4% based on original kerogen). Detailed GC-MS analyses of ether-soluble acids, acids isolated from aqueous solutions and soluble products of further controlled permanganate dedradation of precipitated, ether-insoluble acids, served as a basis for the quantitative estimation of the participation of various types of products and for comparison with other kerogens. The most interesting finding was the observed uniquely high yield of aromatic oxidation products from an intermediate type I–II kerogen. Taking into account the almost equally dominant aliphatic (50.2%) and aromatic (43.2%) nature of the acidic oxidation products, the existence of an aliphatic cross-linked nucleus mixed with cross-linked aromatic units in the Timahdit shale kerogen is postulated. Uniform distribution of oxidation products throughout the degradation suggested a similar reactivity of the various kerogen constituents towards alkaline permanganate.     

C and N NMR analysis of some fungal melanins in comparison with soil organic matter

A variety of fungal melanins with natural ¹⁵N abundance are characterized by solid-state ¹³C and ¹⁵N NMR spectroscopy and are compared to solid-state ¹³C and ¹⁵N NMR spectra of organic matter from representative soils. In all solid-state ¹⁵N NMR spectra the peptide/amide region (−220 to −285 ppm) dominates with more than 70% of the total intensity. The region between −285 and −375 ppm, assigned to amino and ammonium groups, always contains more than half of the remaining intensity. The area in the region from −30 to −220 ppm, where aromatic heterocycles would show signals, makes up less than 10% of the total intensity. These findings call into question common structural models for melanins. The solid-state ¹³C NMR spectra, on the other hand, reveal large differences when the melanins are compared to each other, and to composts and soils. The concentration of the aromatic carbon varies from 5 to 40% in the melanin series. The ratio C_aro/N_tot and C_ali/N_tot were calculated, and confirm that nitrogen in these samples is bound in C_a-groups rather than in aromatic heterocyclic structures.     

Isoprenoid constituents in kerogens as a function of depositional environment and catagenesis

The ratio of the abundance of the C_19:1 isoprenoids 1-pristene and 2-pristene to the abundance of (nC_17:1 + nC_17:0) is significantly lower in pyrolysates of kerogens from highly anoxic depositional environments than in pyrolysates of kerogen if similar types and levels of catagenesis from more oxic organic facies. ¹³C-NMR analysis shows that the occurrence of lower relative concentrations of isoprenoid precursors also correlates with the occurrence of low proportions of oxygen-bonded carbon and high proportion of aliphatic carbon in kerogens. The ratio of 1-pristene to (n-C_17:1 + nC_17:0) can be correlated laterally and statigraphically within a basin. There is no clearly discernible dependence of relative isoprenoid concentration of kerogen type for oil-generative kerogens, although immature lignites have high 1-pristene/(nC_17:1 + nC_17:0) ratios.The 1-pristene/(nC_17:1 + nC_17:0) ratios in kerogens pyrolysates from the same organic facies decrease logarithmically with increasing catagenesis and can be correlated directly with measured vitrinite reflectance values. Geologic and experimental data imply that 1-pristene precursors are lost from kerogen more rapidly than the precursors of the C₁₈ isoprenoid.The lower relative isoprenoid concentrations observed in anoxically deposited kerogens appear to be the result of the enhanced preservation of normal alkyl groups and the enhanced formation of free isophrenoids early in the sequence of kerogen alteration. These results are significant to the use of isoprenoids as geochemical marker oils, bitumens, and kerogens and to the determination of the structure and diagenesis of isoprenoid precursors.     

Analyses of insoluble residues of altered organic matter by C CP/MAS nuclear magnetic resonance

Alteration phenomena affecting organic matter during diagenesis frequently lead to the formation of residues almost insoluble. Data from ¹³C CP/MAS nuclear magnetic resonance analyses (NMR) of these residues have been compared to those obtained by other techniques such as elemental analysis, infrared spectroscopy, Rock-Eval pyrolysis or gas chromatography. Three examples of alteration phenomena have been chosen: the artificial and natural oxidation of coals, the biodegradation of oils and solid bitumens, and the radiolytic degradation of organic matter. NMR results and those obtained by other techniques converge on similar general conclusions. Additional information can be extracted from ¹³C NMR data: e.g. definition of the phenol/carbonyl ratio, transformation of the aromatic network and aromatic ring substitution. These comparisons are good evidence for the reliability of non-destructive analysis of the insoluble fraction of altered organic material by ¹³C CP/MAS NMR.     

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.     

Improvement of kerogen structural interpretations based on oxidation products isolated from aqueous solutions

A detailed investigation of kerogen oxidation products remaining in aqueous solutions after the usual isolation of degradation products by extraction with ether or precipitation, was carried out for the first time in kerogen structural studies. Three shale samples were investigated: Green River shale (type I kerogen), Toarcian shale, Paris Basin (type II), and Mannville shale, Canada (type III). The yields of acids from aqueous solutions were noticeable: 12.98, 15.32 and 22.32%, respectively, based on initial kerogens. Qualitative and quantitative capillary GC/MS analysis showed that the ratios of different kinds of identified acids depended much on the type of precursor kerogen. Some of the acids identified in aqueous solutions have not been found earlier among the degradation products of the same kerogen samples, or were obtained in different ranges and yields. Consequently, slight modifications were suggested of the image on the nature of various types of kerogens based on examination of ether-soluble acids only. Namely, slightly higher proportions of aromatic and alkane-polycarboxylic acids in the total oxidation products of both type I and type II kerogens indicated larger participation of aromatic and alicyclic and/or heterocyclic structures in these two kerogens. On the other hand, for type III Mannville shale kerogen, a somewhat larger share of aliphatic type structures was demonstrated.     

Chemical structural models for coalified wood (vitrinite) in low rank coal

Examination of a series of coalified gymnospermous woods ranging in rank from brown coal to subbituminous coal by solid-state ¹³C NMR and analytical pyrolysis has provided sufficient information to construct structural models depicting the changes that occur to lignin, the primary precursor of vitrinite, during coalification. Progressive changes in the chemistry of coalified wood suggest the following series of reactions: (1) demethylation to form catechol-like structures that are dominant components of brown coal and lignite A; (2) cleavage of aryl ether linkages to form phenols and reactive carbocations that alkylate the catechol rings; (3) dehydration of the catechol rings; (3) dehydration of the catechol-like structures to form the structures of subbituminous coal dominated by alkylphenols; and (4) reduction of the 3-carbon alkyl side chain derived from lignin to form propyl substituents. The models developed for each stage of coalification are derived from chemical modifications of the structure of lignin.     

Pyrolysis of immature Torbanite and of the resistant biopolymer (PRB A) isolated from extant alga Botryococcus braunii. Mechanism of formation and structure of torbanite

Immature Torbanite and the resistant biopolymer (PRB A) isolated from extant B. braunii were previously compared using bulk spectroscopic methods. In the present work, analysis of 400°C pyrolysis products and pyrolysis residues provided further information on their structure and possible relationships. It appears that such polymers are based upon unbranched, saturated, cross-linked hydrocarbon chains up to C₃₁. In addition to these bridging structures, a substantial part of the alkyl chains is singly bound, as esters of unbranched, saturated or cis unsaturated, even fatty acids. These esters are sterically protected, against chemical degradations, by the network of the bioand geopolymer.Quantitative and qualitative observations derived from 400°C pyrolysis confirm that the chemical structure of PRB A and immature Torbanite are closely related. The pyrolysis residues show a similar evolution and numerous common features are noted, with respect to the nature and the distribution of the major constituents of the pyrolysates (hydrocarbons and fatty acids). Accordingly, Botryococcus provides what seems to be the first example of a close structural relationship between a biopolymer produced in large amounts by an extant alga and the geopolymer of an immature kerogen. The essential role of PRB A in Torbanite formation is ascertained. Moreover, it is found that the resistant biopolymer does not undergo important structural changes during the first stages of diagenesis. Thus, owing to steric protection, the esters of immature Torbanite show a distribution quite close to the one of PRB A esters, with exclusively even constituents and a large contribution of unsaturated acids.Recent observations pointed to the possible genesis of some algal kerogens principally by selective preservation of resistant macromolecules. Such a type of formation is clearly predominant in Torbanite, where the bulk of the fossil organic matter corresponds to a selectively preserved and weakly altered, resistant biopolymer, while incorporation of lipids into the kerogen structure during diagenesis seems to play a minor role.     

Controls, variation, and a record of climate change in detailed stable isotope record in a single bryozoan skeleton

The long-lived (about 20 yr) bryozoan Adeonellopsis sp. from Doubtful Sound, New Zealand, precipitates aragonite in isotopic equilibrium with seawater, exerting no metabolic or kinetic effects. Oxygen isotope ratios (δ¹⁸O) in 61 subsamples (along three branches of a single unaltered colony) range from −0.09 to +0.68‰ PDB (mean = +0.36‰ PDB). Carbon isotope ratios (δ¹³C) range from +0.84 to +2.18‰ PDB (mean = +1.69‰ PDB). Typical of cool-water carbonates, δ¹⁸O-derived water temperatures range from 14.2 to 17.5 °C. Adeonellopsis has a minimum temperature growth threshold of 14 °C, recording only a partial record of environmental variation. By correlating seawater temperatures derived from δ¹⁸O with the Southern Oscillation Index, however, we were able to detect major events such as the 1983 El Niño. Interannual climatic variation can be recorded in skeletal carbonate isotopes. The range of within-colony isotopic variability found in this study (0.77‰ in δ¹⁸O and 1.34 in δ¹³C) means that among-colony variation must be treated cautiously. Temperate bryozoan isotopes have been tested in less than 2% of described extant species — this highly variable phylum is not yet fully understood.     

Paleoclimate reconstruction based on the timing of speleothem growth and oxygen and carbon isotope composition in a cave located in the rain shadow in Israel

High-resolution ²³⁰Th/²³⁴U ages and δ¹⁸O and δ¹³C compositions of speleothems in Ma’ale Efrayim Cave located to the east of the central mountain ridge of Israel enable us to examine the nature of the rain shadow aridity during glacial and interglacial intervals. Speleothem growth occurred during marine glacial isotopic periods, with no growth during the two last marine isotope interglacial intervals and during the peak of the Last Glacial Maximum. This contrasts with speleothem growth in caves located on the western flank of the central mountain ridge, in the Eastern Mediterranean semiarid climatic zone, which continued throughout the last 240,000 yr. Thus, during glacial periods water reached both sides of the central mountain ridge. A comparison of the present-day rain and cave water isotopic compositions and amounts at the Ma’ale Efrayim Cave site with those on the western flank shows that evaporation and higher temperatures on the eastern flank are major influences on isotopic composition and the lack of rainfall. The δ¹⁸O and δ¹³C profiles of the speleothems deposited between 67,000 and 25,000 yr B.P. match the general trends of the isotopic profiles of Soreq Cave speleothems, suggesting a similar source (eastern Mediterranean Sea) and similar climatic conditions. Thus, during glacial periods the desert boundary effectively migrated further south or east from its present-day location on the eastern flank, whereas interglacial periods appear to have been similar to the present, with the desert boundary at the same position. The decrease in overall temperature and a consequent reduction in the evaporation to precipitation ratios on the eastern flank are viewed as the major factors controlling the decay of the rain shadow effect during glacial periods.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es₂, the second member of the Shahejie Formation, showed values of δ¹³C and δ¹⁸O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ¹³C and δ¹⁸O values than in a meteoric environment. The values of δ¹³C and δ¹⁸O preserved within the carbonates of the overlying lower Shahejie I (Es₁) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ¹³C and δ¹⁸O were controlled by salinity. The high δ¹³C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ¹³C and δ¹⁸O from carbonates in upper Es₁ ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ¹³C values resulted from biochemical fermentation. The positive δ¹³C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.     

Palaeogeography and tectonic structure of allochthonous units in the German part of the Rheno-Hercynian Belt (Central European Variscides)

New information on palaeogeography, orogenic evolution, tectonic structure, and boundaries of allochthonous units in the Rheno-Hercynian Belt is based on provenance analyses of clastic sediments and field studies. ⁴⁰K/⁴⁰Ar dating of detrital muscovites proved to be a particularly useful method because Cadomian, Caledonian and Early Variscan provenances of detrital material can be distinguished. Cadomian muscovite cooling ages are restricted to allochthonous units whereas Caledonian ages dominate within par-autochthonous and shortly displaced allochthonous units. The largest and uppermost preserved nappe, the Gießen-Harz Nappe, is derived from an oceanic flysch basin, which was not reached by Caledonian detritus. The other allochthonous units form a duplex-like structure sandwiched between the Gießen-Harz Nappe and par-autochthonous units at its base. The thick and heterogeneous roof- and floor-thrusts of this structure were previously often misinterpreted as olistostromes. The northern margin of allochthonous units is the steeply dipping Hörre-Gommern Zone. It consists of three sub-units derived from deep-water areas between the shelf at the southern margin of the Old Red Sandstone Continent and an oceanic basin to the south. The southeastern part of the duplex-structure (Harzgerode Zone) shows close affinities to Armorican terranes.     

The Variation of Soil Organic Matter in a Forest-Cultivation Sequence Traced by Stable Carbon Isotopes

On the basis of different photosynthetic pathways.there is an obvious difference in δ^13C values between C3 and C4 plants,In terms of this characteristic,we analyzed the organic carbon content (forestlands:1.81%-16.00%;farmland:0.45%-2.22%) and δ^13C values(forestlands:-23.86‰--27.12‰;farmland:-19.66‰--23.26‰)of three profile-soil samples either in farmland or in forestland near the Maolan Karst virgin forest,where there were developed plant C3 plants previously and now are C4 plants.Results showed that the deforestation has accelerated the decomposition rate of soil organic matter and reduced the proportion of active components in soil organic matter and thus soil fertility.     

Late Holocene δC and pollen records of paleosalinity from tidal marshes in the San Francisco Bay estuary, California

Records of stable carbon isotopes (δ¹³C) are presented from cores collected from four San Francisco Bay marshes and used as a proxy for changes in estuary salinity. The δ¹³C value of organic marsh sediments are a reflection of the relative proportion of C₃ vs. C₄ plants occupying the surface, and can thus be used as a proxy for vegetation change on the marsh surface. The four marshes included in this study are located along a natural salinity gradient that exists in the San Francisco Bay, and records of vegetation change at all four sites can be used to infer changes in overall estuary paleosalinity. The δ¹³C values complement pollen data from the same marsh sites producing a paleoclimate record for the late Holocene period in the San Francisco Bay estuary. The data indicate that there have been periods of higher-than-average salinity in the Bay estuary (reduced fresh water inflow), including 1600-1300 cal yr B.P., 1000-800 cal yr B.P., 300-200 cal yr B.P., and ca. A.D. 1950 to the present. Periods of lower-than-average salinity (increased fresh water inflow) occurred before 2000 cal yr B.P., from 1300 to 1200 cal yr B.P. and ca. 150 cal yr B.P. to A.D. 1950. A comparison of the timing of these events with records from the California coast, watershed, and beyond the larger drainage of the Bay reveals that the paleosalinity variations reflected regional precipitation.     

Carbon isotope characteristics of the diaromatic carotenoid, isorenieratene (intact and sulfide-bound) and a novel isomer in sediments

Messinian marls from evaporitic cycle IV of the Gessoso-solfifera formation (Italy) are known to contain in high abundance the diaromatic carotenoid isorenieratene of green sulfur bacterial (Chlorobiaceae) origin along with a second diaromatic carotenoid. The previous tentative assignment of the latter as a cis diastereomer of isorenieratene has now been confirmed; this indicates that double bond isomerization occurs during early diagenesis and provides further evidence for the pathway proposed previously to link isorenieratene to a number of aromatic isoprenoid hydrocarbon biomarkers. Stable carbon isotopic data confirm the Chlorobiaceae origin of the intact all-trans isorenieratene isomer and indicate that the isomerization is accompanied by little or no kinetic isotope effect. Comparison of the δ¹³C values of each of the isolated carotenoids (measured as isorenieratane after hydrogenation) with those of their sulfide-bound counterpart in the polar fraction of the extracts (also measured as isorenieratane) indicates that sulfurization resulted in little depletion in ¹³C.     

New data on Sr-and C-isotopic chemostratigraphy of the Upper Riphean type section (Southern Urals)

New data on Sr-and C-isotopic systematics of carbonate rocks from the Upper Riphean stratotype (Karatau Group of the southern Urals) are obtained for several southwestern sections of the Bashkirian meganticlinorium, which have not been studied before. The results obtained supplement the Sr-and C-isotopic information for the group upper horizons thus detailing chemostratigraphic characterization of the entire succession. Limestone and dolostone samples used to analyze the Sr isotope composition satisfy strict geochemical criteria of the isotopic system retentivity and have been subjected to preliminary treatment in ammonium acetate to remove secondary carbonate phases. Data on 255 samples of carbonate rocks (171 studied for the first time) show that δ¹³C value varies in the Karatau Group succession from ?2.8 to +5.9 ‰ V-PDB with several in-phase excursions from the general trend in all the sections studied in the area 90 × 130 km. The δ¹³C variation trend demarcates several levels in the carbonate succession of the Karatau Group suitable for objectives of regional stratigraphy and for C-isotope chemostratigraphic subdivision of the Upper Riphean. The results of Sr isotopic analysis of 121 samples (51 unstudied before) from the Karatau Group imply that rocks in its lower part (the Katav Formation and basal horizon of the Inzer Formation) experienced considerable secondary alterations, while limestones and dolostones of the overlying interval of the group are frequently unaltered. In the “best” samples satisfying geochemical criteria of the isotopic system retentivity, the ⁸⁷Sr/⁸⁶Sr initial ratio increases from 0.70521–0.70532 in the lower Inzer deposits to 0.70611 in the upper Min’yar carbonates, decreasing to <0.70600 near the top of the latter. Above the regional hiatus separating the Min’yar and Uk formation, this ratio grows from 0.70533 to 0.70605–0.70609 in the limestone succession of the last formation.     

Late Holocene environmental reconstruction using cave sediments from Belize

Cave sediments collected from Reflection Cave on the Vaca Plateau, Belize show variations in the δ¹³C values of their fulvic acids (FAs), which indicate periods of vegetation change caused by climatic and Maya influences during the late Holocene. The δ¹³C values range from − 27.11‰ to − 21.52‰, a shift of ∼ 5.59‰, which suggests fluctuating contributions of C₃ and C₄ plants throughout the last 2.5 ka, with C₄ plant input reflecting periods of Maya agriculture. Maya activity in the study area occurred at different intensities from ∼ 2600 cal yr BP until ∼ 1500 cal yr BP, after which agricultural practices waned as the Maya depopulated the area. These changes in plant assemblages were in response to changes in available water resources, with increased aridity leading to the eventual abandonment of agricultural areas. The Ix Chel archaeological site, located in the study area, is a highland site that would have been among the first agricultural settlements to be affected during periods of aridity. During these periods, minimal water resources would have been available in this highly karstified, well-drained area, and supplemental groundwater extraction would have been difficult due to the extreme depth of the water table.