The polymer-like organic material in the Orgueil meteorite

The insoluble organic material in the Orgueil (Cl) chondrite was analyzed by combined high vacuum pyrolysis-gas chromatography-mass spectrometry. Stepwise pyrolyses at 150, 300, 450 and 600°C of Orgueil meteorite powder which had been exhaustively extracted with solvents yielded a series of alkenes and alkanes to C₈, an extensive series of alkylbenzene isomers, thiophene, alkylthiophenes, and benzothiophene, together with the nitrogen- and oxygen-containing breakdown products, acetonitrile, acrylonitrile, benzonitrile, acetone and phenol. The Orgueil polymer fragmentation products are very similar both qualitatively and quantitatively to pyrolysis products of solvent-extracted Pueblito de Allende (C3) chondrite described in the literature.Changes in the relative abundances of polymer degradation products between 150 and 600°C imply the preferential loss of aliphatic and certain heteroatomic portions of the polymer at lower temperatures to leave highly condensed aromatic and heteroaromatic portions of the polymer which begin to fragment only at 450–600°C. The Orgueil polymer-like matter thus appears to be a complex mixture of polymerized materials having different thermal stabilities. Similarities between vacuum pyrolyzates of the Orgueil polymer and terrestrial kerogen suggest the possibility that meteorite organic matter may have been subjected on the meteorite parent bodies to diagenetic processes similar to those by which terrestrial kerogen is formed.     

Kerogen of Toarcian shales of the Paris Basin. A study of its maturation by flash pyrolysis techniques

A set of 14 samples—both extracted and unextracted from the Toarcian of the Paris Basin have been investigated using Curie-point pyrolysis-mass spectrometry and Curie-point pyrolysis gas chromatography mass spectrometry. The relative amount of n-alkenes and n-alkanes in the pyrolyzates increases with increasing maximum burial depth of the samples. Comparison of the pyrolysis data of extracted and unextracted samples shows that generation of hydrocarbons from the kerogen starts at a maximum burial depth of ~ 1000m. The increase of pristane and phytane in the extracts of the deeper samples is correlated with the gradual decrease of the characteristic pyrolysis product prist-1-ene. Three samples yield pyrolyzates with high relative amounts of aromatic compounds. This phenomenon probably reflects a different type of contributing organic matter and/or a different environment of sedimentation.     

Evaluating the thermal metamorphism of CM chondrites by using the pyrolytic behavior of carbonaceous macromolecular matter

The degrees of thermal metamorphism of 10 CM chondrites and of the Allende CV3 chondrite were evaluated from the viewpoint of “graphitization” of the carbonaceous macromolecular matter by means of flash pyrolysis-gas chromatography (GC). The unheated chondrites, Yamato- (Y-) 791198, Murray and Cold Bokkeveld, yielded larger amounts and wider varieties of pyrolyzates than the chondrites strongly heated in the parent asteroids, Y-82054, Y-86695, and Belgica- (B-) 7904, and Asuka- (A-) 881334 (more strongly heated than Y-793321, which has been weakly heated, but lesser than the other strongly heated meteorites). The weakly heated chondrites, Y-793321 and A-881458, showed intermediate features. The data indicate that graphitization of the carbonaceous matter is most extreme in the strongly heated chondrites and that during graphitization, the matter has lost its labile portion, which can generate pyrolyzates such as naphthalene. In order to establish a new method for the evaluation of the degree of graphitization of chondritic carbonaceous matter, a diagram was developed to show the relationship between the total amounts of pyrolyzates with retention times later than 5 min (=S_RT>5) and the ratio of the amount of naphthalene, a pyrolysis product, to S_RT>5 (=S_N/S_RT>5). The diagram indicates a possible evolutionary pathway of graphitization of the carbonaceous matter in carbonaceous chondrites.     

Biological markers in bitumens and pyrolyzates of Upper Cretaceous bituminous chalks from the Ghareb Formation (Israel)

The sterane and triterpane distributions of three bituminous chalks from the Upper Cretaceous Ghareb Formation (Israel) were investigated both in the original extractable bitumens and in extracts obtained after pyrolysis of whole rock and isolated kerogen samples at 450°C. Pyrolysis was performed in a closed system under hydrous (whole rock) and anhydrous conditions (isolated kerogens). The carbon number distributions of steranes and triterpanes differ significantly between original bitumen and pyrolyzates. Unlike the bitumens in which diasteranes were not detected, the anhydrous pyrolyzates contain small amounts of diasteranes. The presence of water during pyrolysis leads to an increase of sterane isomerization, the abundant formation of diasteranes and an increase of the $\text{18α(}\text{H}\text{)-}\text{trisnorneohopane}\text{17α(}\text{H}\text{)-}\text{trisnorhopane}$ ratio. Sterane isomerization maturation parameters show a closer match between original bitumen and pyrolyzates after pyrolysis in a closed system when compared with an open system.     

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.     

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.     

Modeling of catagenetic transformation of organic matter from a Riphean mudstone in hydrous pyrolysis experiments: Biomarker data

The catagenesis of organic matter (OM) was modeled by the hydrous pyrolysis of a Riphean mudstone. Microscopic observations of the processes operating during kerogen heating to 600°C were conducted in a diamond anvil cell. The results of pyrolysis in an aqueous environment were used to calculate the activation energies of kerogen cracking and derive chemical kinetic models for OM catagenesis. Isothermal experiments were carried out for 3 days at temperatures of 300, 310, …, 360, and 370°C. The maximum bitumen yield was obtained at 330°C followed by thermal cracking at higher temperatures. The aromatic and saturated hydrocarbons from rock bitumen, hydrous pyrolyzates, and kerogen flash pyrolyzates were analyzed by chromatography-mass spectrometry. We also discuss the problem of extrapolation of high-temperature pyrolysis results to geologic observations under the conditions of regional catagenesis.     

Quantitative chemical characterization of vitrinite concentrates using pyrolysis-gas chromatography. Rank variation of pyrolysis products

A series of hand-picked vitrinite samples from the Lower Kittanning Seam, Pennsylvania have been examined using quantitative pyrolysis-gas chromatography. These vitrinites ranged in rank from 0.59 to 1.71% reflectance, a rank range from high volatile C bituminous to low volatile bituminous. High molecular weight pyrolysis products included alkyl aromatic and phenolic compounds. Attempts have been made to correlate the pyrolysis product composition to rank parameters including vitrinite reflectance, volatile matter yield, carbon content, atomic H/C ratio and Rock-Eval determined T_max. Total yield of phenols was found to be strongly and inversely rank related. A clear relationship between C₈ alkyl-benzene yield and rank was not found for the sample set.     

Heterogeneous organic matter from the surface horizon of a temperate zone marsh

Abundance, bulk chemical composition and sources of the organic matter in the surface horizon of the permanently water-covered part of an intermittently water-covered marsh were investigated. Lipids, insoluble non-hydrolysable macromolecular organic matter and black carbon fractions were isolated and examined via Rock-Eval pyrolysis, elemental analysis, Fourier transform infrared spectroscopy, isotopic (δ¹³C, δ¹⁵N) methods and high resolution transmission electron microscopy. Integration of bulk Rock-Eval data, elemental and isotopic composition, together with spectroscopic features, suggested immature Type III organic matter derived mainly from C₃ vascular plants. The distribution of n-alkanes from the non-aromatic lipid fraction exhibited the importance of emergent macrophytes and terrestrial plants, as well as a moderate input of submerged/floating macrophytes to the source biomass. Mathematical deconvolution of a Rock-Eval pyrogram revealed highly heterogeneous organic matter composed of a mixture of thermally labile biopolymers (36%) at various stages of decomposition, as well as humic substances and highly refractory organic matter (64%) in the whole sample. Markedly lower heterogeneity and aliphaticity, together with a higher proportion of humic substances and highly refractory organic matter (ca. 84%) were observed in the macromolecular fraction. An abundant contribution of black carbon to the macromolecular fraction was indicated by mathematical deconvolution of the Rock-Eval pyrogram and was clearly shown by the isolation of this fraction and chemical oxidation. The black carbon fraction appeared to account for ca. half of the macromolecular fraction, the carbon in these two fractions representing 30% and 14% of the initial carbon, respectively. The electron microscopy observations directly evidenced the presence of black carbon, which was comprised of both amorphous poorly organized particles and highly ordered onion-shaped particles.     

Pyrolysis gas chromatography-mass spectrometry to characterize organic matter and its relationship to uranium content of Appalachian Devonian black shales

Gas Chromatographic analysis of volatile products formed by stepwise pyrolysis of black shales can be used to characterize the kerogen by relating it to separated, identified precursors such as land-derived vitrinite and marine-source Tasmanites. Analysis of a Tasmanites sample shows exclusively $\text{n-}\text{alkane}$ and -alkene pyrolysis products, whereas a vitrinite sample shows a predominance of one- and two-ring substituted aromatics. For core samples from northern Tennessee and for a suite of outcrop samples from eastern Kentucky, the organic matter type and the U content (<10?120ppm) show variations that are related to precursor organic materials. The samples that show a high vitrinite component in their pyrolysis products are also those samples with high contents of U.     

Organic geochemistry of silicified wood,Petrified Forest National Park,Arizona

Lignin derivatives have been isolated for the first time from carbonaceous sections of the silicified (~90% SiO₂) conifer Araucarioxylon arizonicum. The products released by sequential high vacuum pyrolysis and identified by combined gas chromatography-mass spectrometry (GC-MS) include a wide variety of alkyl-substituted, phenolic and condensed aromatic compounds.Brauns spruce lignin was pyrolized and analyzed by GC-MS as a comparison for the fossil wood data. The primary pyrolyzates at the 300°C step were CO₂, H₂O, ethanol and propanol. The main product at 450°C was 4-methyl-2-methoxyphenol (methyl guaiacol), but at 600°C the pyrolyzates were similar both in product composition and in relative abundance to those from silicified wood. The results suggest that the fossil wood experienced a mild thermal event during which the ether bonds were ruptured and loss of oxygen occurred along with the rearrangement of the original wood into a highly stable polymer.     

Investigating the variations in carbon and nitrogen isotopes in carbonaceous chondrites

The carbonaceous chondrites contain significant amounts of carbon- and nitrogen-bearing components, the most abundant of which is organic matter. Stepped combustion data of whole rock and HF/HCl residues of carbonaceous chondrites reveal that the organic material can be subdivided operationally into three components: (1) free organic matter (FOM), which is readily extractable from whole-rock meteorites and is enriched in ¹³C and ¹⁵N; (2) labile organic matter (LOM), which has a macromolecular structure but is liberated by hydrous pyrolysis; LOM is the parent structure for some FOM and is also enriched in ¹³C and ¹⁵N; and (3) refractory organic matter (ROM), which is also macromolecular but is virtually unaffected by hydrous pyrolysis and is relatively depleted in ¹³C and ¹⁵N. The macromolecular entities (LOM and ROM) are by far the most abundant organic components present, and as such, the relative abundances of the ¹³C- and ¹⁵N-enriched LOM and the ¹³C- and ¹⁵N-depleted ROM will have a major influence on the overall isotopic composition of the whole-rock meteorite. Laboratory experiments designed to simulate the effects of parent body aqueous alteration indicate that this form of processing removes LOM from the macromolecular material, allowing ROM to exert a stronger influence on the overall isotopic compositions. Hence, aqueous alteration of macromolecular materials on the meteorite parent body may have a significant control on the stable isotopic compositions of whole-rock carbonaceous chondrites. The enstatite chondrites are also carbon rich but have been subjected to high levels of thermal metamorphism on their parent body. Stepped combustion data of HF/HCl residues of enstatite chondrites indicate, that if they and carbonaceous chondrites inherited a common organic progenitor, metamorphism under reducing conditions appears to incorporate and preserve some of the ¹³C enrichments in LOM during graphitisation. However, when metamorphism is at its most extreme, the ¹⁵N enrichments in LOM are lost.     

Classification of torbanite and cannel coal: II. Insights from pyrolysis-GC/MS and multivariate statistical analysis

Petrographic and megascopic criteria have traditionally been used as the basis for the classification of torbanite and cannel coal. For this study, it was hypothesized that modern analytical organic geochemical and multivariate statistical techniques could provide an alternative approach. Towards this end, the demineralized residues of 14 torbanite (rich in Botryococcus-related alginite) and cannel (essentially, rich in organic groundmass and/or sporinite) coal samples were analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Cluster analysis performed on the Py-GC/MS data clearly distinguished the torbanite from the cannel coal, demonstrating a consistency between the chemical properties and the petrographic composition. All the torbanite samples group into one cluster, their pyrolyzates having an overwhelming predominance of straight chain hydrocarbons, a characteristic typical of Botryococcus. The presence of the C₉–C₂₆ n-α,ω-alkadiene series is the key feature distinguishing the torbanites from the other samples. The cannel coals exhibit more chemical diversity, reflecting their greater variability in petrographic composition. The Breckinridge cannel, dominated by a highly aliphatic lamalginitic groundmass, chemically fits the torbanite category. The bituminitic groundmass-dominated cannel coals fall into a cannel sub-cluster, their pyrolyzates having a characteristic predominance of n-alk-1-enes and n-alkanes (particularly the long-chain homologues), with no detectable alkadienes. The vitrinitic groundmass-dominated Ohio Linton cannel and the sporinite-rich Canadian Melville Island cannel are readily distinguishable from the other cannels by the relatively abundant aromatic and phenolic compounds in their pyrolyzates. The internal distribution patterns of alkylaromatic and alkylphenolic isomers are shown to be less significant in the classification of this sample set. Multivariate statistical analysis of the pyrolysis data not only successfully discriminated torbanites from cannel coals, but recognized subtler differences between the examples of these two coal types, in substantial agreement with the petrographic characterization. As such, these methods can substitute for or supplement the traditional microscope-based approach.     

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.     

Non-combustible suspended matter in surface waters off eastern Asia*

A total of about 1100 well-distributed samples of suspended matter in surface waters off the length of eastern Asia are available. From these samples, 180 were selected for detailed examination of the non-combustible fraction using optical and electron microscopy along with computer methods of particle measurement and counting. The results showed that, generally, all major components of the suspended matter are most abundant in the nearshore belt (combustible fraction, mineral grains of silt size, skeletal debris, and clay minerals), the result of mechanical transport of detrital sediment and chemical transport of nutrients from the land. Mineral grains of silt size average about 2%, skeletal debris plus clay minerals—23%, and combustible organic matter—75% of total sample weights, but the last two categories vary over a wide range depending upon geographical positions of the samples. Most evident is an oceanward decrease in percentage and concentration of the total noncombustible fraction and an oceanward increase in median diameter of the mineral grains.     

Evaluation of on-line pyrolysis two-dimensional gas chromatography time-of-flight mass spectrometry (Py-GC × GC-ToFMS) on whole sediments from a Mediterranean sapropel sequence

Analysis of the molecular composition of the organic matter (OM) from whole sediment samples can avoid analytical bias that might result from isolation of components from the sediment matrix, but has its own analytical challenges. We evaluated the use of GC × GC-ToFMS to analyze the pyrolysis products of six whole sediment samples obtained from above, within and below a 1 million year old OM-rich Mediterranean sapropel layer. We found differences in pyrolysis products <n-C₂₂ between the OM-rich sapropel samples and the OM-poor background marls. The presence of alkyl pyrroles, probably derived from chlorophyll, in pyrolysates of the sapropels but not in those of the marls suggests that higher marine productivity and greater OM preservation accompanied deposition of the sapropels. Detection of tetramethyl benzenes considered to be pyrolysis products of isorenieratene in the sapropel samples is evidence that nitrogen-fixing green sulfur bacteria contributed to the high productivity. Greater abundances of shorter chain aliphatic hydrocarbons, pyrroles, furans and alkyl aromatics in the pyrolysates of sapropel samples relative to the marls confirm better preservation of marine OM in the sapropels. In addition, the presence of greater amounts of thiophenes in the sapropels than in the marls is consistent with the existence of euxinic conditions during sapropel deposition. The combination of whole sediment pyrolysis and GC × GC-ToFMS is promising, but the procedure requires careful selection of its multiple analytical variables, particularly the pyrolysis temperature and the operational features of the GC columns.     

Investigation of catalytic effects of indigenous minerals in the pyrolysis of Aleksinac oil shale organic matter

The catalytic effect of indigenous minerals in the pyrolysis of Aleksinac (Yugoslavia) oil shale was studied in this paper. The substrates were prepared by gradual removal of the mineral constituents (carbonates, silicates, pyrite) and the free and bound bitumens. The substrates were analyzed by chemical methods, X-ray diffraction, porosimetry, thermal analysis, ¹³C NMR, and standard ASTM Micro Activity Test (MAT) designed for the investigation of cracking catalysts. The liquid pyrolysis products were analyzed by organic geochemical techniques as well. Based on the yields of gaseous and liquid products and the coke, conversion degrees, GC analyses (MAT parameters) and weight losses (TG parameter), the catalytic effect of indigenous mineral components in the pyrolysis of Aleksinac oil shale organic matter was found to be very low. The results suggested that principal organic matter changes should be attributed to thermal rather than to catalytic cracking.     

The influence of minerals on the pyrolysis of kerogens

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

Geochemical implications of minerals and environmentally sensitive elements of Giral lignite,Barmer Basin,Rajasthan (India)

The Barmer Basin of Rajasthan is significant for its Paleogene lignite sequences. The lignite seam occurs in Akli Formation of Barmer Basin at the depth of 06–241 m. A total of 57 lignite samples were collected from the working faces of lignite mine and were subjected to proximate analysis (moisture, ash yield, volatile matter, and fixed carbon), ultimate analysis (carbon, hydrogen, nitrogen, oxygen and sulfur), elemental analysis (Fe, Ca, Mg, Cd, Mn, K, Na, Cu, Co, Ni, Cr, Zn, and Pb) and rock-eval pyrolysis for mineral carbon (MINC). Some elements like Cu, Cd, Co, Ni, Zn, Pb, Na, and K occur in high concentration, while Mg and Ca have their concentrations lower than World Clarke average. In addition, various minerals and functional groups present in the lignite samples were analyzed through X-ray diffraction and Fourier transform infrared (FTIR) spectroscopy. The mineral (weight and atomic) percentage has also been analyzed through scanning electron microscopy–energy dispersive spectroscopy (SEM–EDS).     

Formation of methane and hydrocarbons by pyrolysis of immature kerogens

Pyrolysis of sedimentary organic matter under inert atmosphere and by low-rate temperature programming produces solid and liquid pyrolyzates which have been studied by different techniques. The result is a good agreement between such pyrolyzates and samples having undergone natural maturation. For methane such a comparison is not possible, because of the mobility of methane in nature but, on the basis of previous studies, methane formation from different types of organic matter can be studied in the same conditions. The organic matter is studied as kerogen, outside and inside the original rock. No significant difference is seen in methane formation, which always occurs during the main stage of hydrocarbon formation or after it, but never before. The minimum temperature is 250°C. In order to test the likeliness of a catalytic effect, some kerogens are mixed with industrial catalysts and processed as usual. The distribution of hydrocarbons is thereby modified, the temperature of formation of hydrocarbons is lowered by circa 50°C, but the formation of methane is not modified.Thermal cracking mechanisms explain quite well the formation of hydrocarbons and methane as it occurs in our experiment. Catalysts, though inducing other mechanisms, do not modify the methane formation.Other mechanisms should be used to explain the presumed formation of “early”, non biogenic, methane, but, due to the mobility of methane in nature, arguments are only experimental or theoretical, but no direct evidence can be brought.