Organic matter and deposition conditions of the Kashpir oil shales

The composition of organic matter was investigated in the oil shales and country rocks of the Kashpir deposit. The analysis of the aromatic fraction of bitumen showed the presence of isorenieratene derivatives, which indicates the accumulation of the sequence under anoxic conditions in the bottom waters of a paleobasin. Special attention was given to the composition of organosulfur compounds from the bitumen of rocks and products of kerogen pyrolysis. The concentrations of hydrocarbon structures occurring in the bitumen in a free state and in sulfur-bearing derivatives are comparable. The composition of the pyrolysis products of kerogen depends on the concentration of organic carbon in the rock: carbon-rich rock varieties contain kerogen whose pyrolysis yields relatively high concentrations of organosulfur compounds and low total contents of n-alkanes/n-alkenes-1.     

Effects of base catalysis on the product distribution from pyrolysis of woody biomass in the presence of water

Previous work has shown that woody biomass can generate oil-like products during hydrous pyrolysis. However, the yield of extractable organic matter is rather small, and the proportion of coke is high. In order to increase the oil yield and decrease the coke generation, experiments with added base catalysts have been made. NaOH was chosen as the catalyst. Experimental design is used to investigate the effects of variable experimental conditions during pyrolysis. The results are compared with similar experiments without a catalyst, and show a general decrease in coke formation and increase in the extractable organic matter with a dominance of polar compounds. The variable with the largest effect on yields is the amount of water, while pyrolysis temperature and the amount of starting material have minor effects.     

Hydrothermal petroleum of Lake Chapala,Citala Rift,western Mexico: Bitumen compositions from source sediments and application of hydrous pyrolysis

Hydrothermal simulation experiments were performed with contemporary sediments from Lake Chapala to assess the source of the lake tars. The precursor-product relationships of the organic compounds were determined for the source sediments and their hydrous pyrolysis products. The pyrolysis products contained major unresolved complex mixtures of branched and cyclic hydrocarbons, low amounts of n-alkanes, dinosterane, gammacerane, and immature and mature hopane biomarkers derived from lacustrine biomass sources. The results support the proposal that the tar manifestations in the lake are not biodegraded petroleum, but were hydrothermally generated from lacustrine organic matter at temperatures not exceeding about 250 °C over brief geological times.     

Hydrothermal pyrolysis of organic matter in Riphean mudstone

The catagenesis of organic matter (OM) was modeled by the hydrothermal pyrolysis of a source rock (Riphean mudstone from eastern Siberia). Isothermal experiments 72-h long were carried out in an aqueous environment in autoclaves at temperatures of 300, 310, 320,..., 370°. The pyrolysis products were analyzed for yield of extract, organic carbon, and parameters of Rock-Eval pyrolysis. The amount of the generated liquid hydrocarbon (HC) compounds increased to a temperature of 340°C and then decreased. The experimental trend of the hydrogen index (HI) dependence on the T _Max temperature generally coincided with that for natural OM maturation. The carbon isotopic composition of the insoluble (in organic solvents) OM remained practically unchanged in the course of the experiments. The carbon structure of the solid remnants of the experimental samples was ordered (after the experiments) with the origin of turbostratic graphite with a spacing of d ₀₀₂≈3.5 A°. We also conducted pyrolysis in a diamond anvil cell equipped with a digital camera in order to obtain additional qualitative and quantitative information on oil generation and emigration in the source rock and isolated kerogen. Chemical kinetic parameters of kerogen cracking were calculated for pyrolysis in an open system. The extrapolation of the high-temperature experimental results is discussed with reference to natural OM maturation.     

Release of organic nitrogen compounds from Kerogen via catalytic hydropyrolysis

High hydrogen pressure pyrolysis (hydropyrolysis) was performed on samples of solvent extracted Kimmeridge Clay Formation source rock with a maturity equivalent to ca. 0.35% vitrinite reflectance. We describe the types and distributions of organic nitrogen compounds in the pyrolysis products (hydropyrolysates) using GC-MS. Compounds identified included alkyl-substituted indoles, carbazoles, benzocarbazoles, quinolines and benzoquinolines. The distributions of the isomers of methylcarbazoles, C₂-alkylcarbazoles and benzocarbazoles in the hydropyrolysates were compared to a typical North Sea oil. The hydropyrolysates compared to the North Sea oil, showed increased contributions from alkylcarbazole isomers where the nitrogen group is "exposed" (no alkyl substituents adjacent to the nitrogen functionality) and appreciable levels of benzo[b]carbazole relative to benzo[a]- and benzo[c]carbazoles. Hydropyrolysis is found to be an ideal technique for liberating appreciable quantities of heterocyclic organic nitrogen compounds from geomacromolecules. The products released from the immature Kimmeridge Clay are thought to represent a potential source of nitrogen compounds in the bound phase (kerogen) able to contribute to the free bitumen phase during catagenesis.     

Composition of estuarine colloidal material: organic components

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

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.     

Analysis of organic matter by flash pyrolysis-gas chromatography–mass spectrometry in the presence of Na-smectite: When clay minerals lead to identical molecular signature

Different studies have already pointed out the influence of clays during the analysis of pure organic compounds (especially alkanols, alkanoic acids) as well as macromolecules (humic acids) by flash pyrolysis-gas chromatography–mass spectrometry (PyGC–MS). Especially, the occurrence of clay minerals favors the generation of aromatic units such as alkylbenzenes and polycyclic aromatic hydrocarbons. So as to better identify the nature of the organic compounds which are sensitive to the presence of clays during flash pyrolysis, a humic acid mixed in variable proportions of a Na-homoionic clay was tested. The smectite/humic acid mixtures containing from 10% to 100% humic acid allowed us to identify the progressive disappearance or appearance of specific compounds after PyGC–MS.n-Alk-1-enes disappear when the clay proportion is higher than 67%. For higher contents of Na-smectite, n-alkanes become less and less abundant with a preferential consumption of high molecular weight n-alkanes, whereas the aromatic hydrocarbon proportion increases. Moreover, the distribution of each aromatic hydrocarbon family (alkylbenzenes and alkylnaphthalenes) has been investigated. The pyrogram of pure humic acid exhibits a specific distribution of alkylbenzenes and alkylnaphthalenes reflecting the structure of the organic macromolecule. With the increase in clay proportion, these distributions are modified and lead to other distributions with a preferential predominance of thermally stable isomers.Pyrograms of humic acid and undecanoic acid in the presence of 90% of Na-smectite are similar, especially concerning alkylbenzene and alkylnaphthalene distributions. Therefore, clays (Na-smectite in our experiments) in high proportion modify initial organic products by recombination reactions and lead to the generation of new compounds of very similar distribution, whatever the nature of the initial organic matter. Such results underline the very important catalytic properties of clay minerals on functionalized organic matter during flash pyrolysis.     

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.     

Lignin pyrolysis products: Their structures and their significance as biomarkers

Pyrolysis in combination with gas chromatography and mass spectormetry was used to characterize softwood, hardwood and grass lignins as well as the corresponding synthetic dehydro-polymers. The method permitted differentiation of the three types of lignins. Softwood lignins yielded exclusively guaiacyl derivatives, coniferaldehyde and coniferyl alcohol being major compounds. Hardwood lignins gave rise to guaiacyl and syringyl derivatives, among which syringaldehyde, coniferyl alcohol and sinapyl alcohol were the most prominent. Grass lignins, represented by bamboo lignin, yielded p-vinylphenol as major compound. In addition, other guaiacyl and syringyl pyrolysis products were identified. The results indicate that guaiacyl and syringyl compounds are unique pyrolysis products of lignins and woods. Because of the relatively high resistance of lignins these pyrolysis products can be considered as characteristic biomarkers for terrestrial plant input.     

Relative contribution of foliar and fine root pine litter to the molecular composition of soil organic matter after in situ degradation

The influence of litter quality on soil organic matter (SOM) stabilization rate and pathways remains unclear. We used ¹³C/¹⁵N labeled litter addition and Curie-point pyrolysis gas chromatography–mass spectrometry combustion-isotope ratio mass spectrometry (Py–GC–MS–C–IRMS) to explore the transformation of litter with different composition and decay rate (ponderosa pine needle vs. fine root) to SOM during 18 months in a temperate conifer forest mineral (A horizon) soil. Based on ¹³C Py–GC–MS–C–IRMS the initial litter and bulk soil had ∼1/3 of the total pyrolysis products identified in common. The majority was related either to carbohydrates or was non-specific in origin. In bulk soil, carbohydrates had similar levels of enrichment after needle input and fine root input, while the non-specific products were more enriched after needle input. In the humin SOM fraction (260 yr C turnover time) we found only carbohydrate and alkyl C-derived compounds and greater ¹³C enrichment in the “carbohydrate” pool after fine root decomposition. ¹⁵N Py–GC–MS–C–IRMS of humic substances showed that root litter contributed more than needle litter to the enrichment of specific protein markers during initial decomposition.We found little evidence for the selective preservation of plant compounds considered to be recalcitrant. Our findings suggest an indirect role for decomposing plant material composition, where microbial alteration of fine root litter seems to favor greater initial stabilization of microbially derived C and N in SOM fractions with long mean turnover times, such as humin, compared to needles with a faster decay rate.     

Thermal reactions of kerogen with added water, heavy water and pure organic substances

Finely divided samples of the Messel shale that had first been extracted with organic solvents were subjected to pyrolysis at 330°C for 3 days in the presence of excess water or heavy water and also with added pure organic substances. About 8% of the organic carbon was converted into an assemblage of saturated hydrocarbons that closely resembled petroleum hydrocarbons. No olefins were observed in the products. When the reaction was performed in heavy water, extensive deuteration occurred. The extent of substitution and the position of heavy hydrogen in a variety of hydrocarbon structural types were measured by mass spectrometry. A control experiment in which a saturated hydrocarbon was added showed that this deuterium substitution was not due to simple homogeneous exchange.A mechanism for the production of polydeuterated hydrocarbons is advanced, based on a model wherein the molecular fossils that are chemically bonded into kerogen matrix are released as free radicals. During the subsequent chain reactions, migration of olefinic bonds in intermediates and attack by deuterium free radicals result in multiple deuteration with retention of the carbon skeleton of the molecular fossil.     

High temperature simulation of petroleum formation—IV. Stable carbon isotope studies of gaseous hydrocarbons

Laboratory simulations of petroleum formation were examined by stable carbon isotope studies of five cryogenic distillation fractions of the gases produced by thermal treatment of organic substrates. Simple heat treatment (pyrolysis) of substrates was contrasted with heat treatment in the presence of nickel and vanadium sulfides, ammonia, and water (catalysis). The effect of substrate/catalyst ratio on the isotopic composition of gases was also examined. All reactions were carried out at 440°C, and ambient pressure. Plots of stable carbon isotope ratio versus distillation temperature, for substrates representing marine and terrestrial organic matter, were compared to literature values for natural petroleum accumulations, and to the pyrolysis of Green River oil shale.     

Compositional and source characterization of base progressively extracted humic acids using pyrolytic gas chromatography mass spectrometry

Cyclic base extraction is a commonly used method for the isolation of humic acids from soils and sediments. However, every extract may differ in chemical composition due to the complex nature of humic acids. To better understand the chemical composition of each extract, the heterogeneous property of humic acids and their speciation in environmental samples, eight fractions of humic acids were obtained in the present work by progressive base-extraction of Pahokee peat, and their chemical composition was characterized using two complementary pyrolytic techniques, namely conventional pyrolysis and methylation pyrolysis (TMAH) GC/MS. These quick and effective procedures provide an insight into the structure of macromolecules. The work shows that the lignin-derived aromatic compounds are major components of pyrolysates in both pyrolytic techniques, while aliphatic compounds originating from microorganisms and plants are minor components. Other compounds derived from proteins and carbohydrates at lower concentrations were also detected. Fatty acids were found in the pyrolysis without methylation, indicating their association with humic acid in a free state. These compounds are different from those formed during pyrolysis with in situ methylation, where fatty acids are generally believed to be the cleavage products of carboxylic groups bound to humic acids. A relative decreasing abundance of aromatic components and increasing abundance of aliphatic components in the pyrolysates as the peat was progressively extracted was also observed in this work, suggesting that the extraction of more hydrophobic aliphatics may be delayed in comparison to the aromatic components. Speciation and origin differences may also be important particularly considering that the contribution from lignin organic matter decreased with extraction number, as the contribution of microbial organic matter increased. The observed change in chemical composition with the extracted fractions indicates again that the humic acid distribution and their speciation are complex, and complete extractions are necessary to obtain a representative humic acid sample.     

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.     

Pyrolysis of Transvaal kerogens. II. An evaluation of vacuum pyrolysis with polyethylene,polystyrene and their mixtures with minerals

A series of experiments have been conducted with polyethylene and polystyrene standards in an attempt to define the advantages and limitations of a vacuum pyrolysis—gas chromatography—mass spectrometry procedure for the characterization of kerogen and other macromolecular substances. Effects of variations in pyrolysis temperatures and times, sample sizes (weights) and thickness were evaluated together with the reproducibility of the nature and abundances of pyrolyzates. The effects of minerals (illite and quartz) admixed in the polymers were also considered with reference to the nature of the breakdown products. Optimal pyrolysis conditions, where primary pyrolyzates were sufficiently abundant and secondary products did not hinder characterization, were attained at 450°C and 60–90 min. The reproducibility of the nature and quantities of pyrolyzates was rather satisfactory at this temperature and pyrolysis time. However, relatively large samples of macromolecular matter, which is considerably volatile at this temperature, led to the synthesis of an abundant yield of secondary products, but sample thickness does not affect the nature of pyrolyzates. Admixed mineral matter affected the nature and relative abundances of the pyrolyzates but did not impede characterization of samples, as primary breakdown products were discernible. Macromolecular substances of limited volatility, heterogeneous chemical composition and containing intractable mineral matter, such as many kerogens, need to be pyrolyzed as relatively large samples. The vacuum procedure used in these studies may be to advantage, as compared with some other methods, to pyrolyze such samples. This method seems to be also suitable for the pyrolysis of volatile macromolecular matter, provided that small samples are employed.     

Comparison between natural and artificial maturation series of humic coals from the Mahakam delta,Indonesia

Type III (humic) organic matter from the Mahakam delta (Indonesia) was chosen to compare artificial and natural coal series. Powdered and concentrated immature organic matter was heated in sealed gold tubes for 24 hr at temperatures ranging from 250 to 550°C and under pressures ranging from 0.5 to 4 kb, with and without water. Both elemental and Rock-Eval analyses were used to characterize the products. A comparison between our results, published data and the natural model shows that, quantitatively, natural maturation is simulated better when pyrolysis is performed under confined conditions (no free volume, no diluting inert gas). Thus, pyrolysis in a medium swept by an inert gas, vacuum pyrolysis and some pyrolysis in sealed glass tubes must be considered to be poor simulation tools. The presence of water does not seem to have an essential effect. Allowing the hydrocarbons formed to reach a certain value of partial pressure seems to be important. Results are unchanged when external pressure varies from 0.5 to 4 kb.     

Identification and emission factors of molecular tracers in organic aerosols from biomass burning: Part 3. Grasses

Smoke particulate matter from grasses (Gramineae, temperate, tropical and arctic) subjected to controlled burning, both under smoldering and flaming conditions, was sampled by high volume air filtration on pre-cleaned quartz fiber filters. The filtered particles were extracted with dichloromethane/methanol and the crude extracts were methylated for separation by thin layer chromatography into hydrocarbon, carbonyl, carboxylic acid ester and polar fractions. Then, the total extract and individual fractions were analyzed by GC–MS. The major organic components directly emitted in grass smoke particles were the homologous series of n-alkanoic acids from plant lipids, n-alkanes from epicuticular wax, and sterols and triterpenols. The major natural products altered by combustion included pyrolysis products from cellulose and lignin biopolymers, and oxidation products from triterpenoids and sterols. Polycyclic aromatic hydrocarbons (PAH) were also present; however, only as minor components. Although the concentrations of organic compounds in smoke aerosols are highly variable and dependent on combustion temperature, the biomarkers and their combustion alteration products are in these cases source specific. The major components are adsorbed on or trapped in smoke particulate matter and thus may be utilized as molecular tracers in the atmosphere for determining fuel type and source contributions from grass burning.     

Field-ionization mass spectrometry: application to geochemical analysis

The thiourea adduct, thiourea non-adduct and aromatic fractions from a series of Alberta oil sand bitumens have been subjected to field ionization mass spectrometric analyses. Field ionization mass spectra feature little fragmentation and the molecular weight distributions of compounds in the fractions are readily obtained. Using this method, the various acyclic and cyclic saturated hydrocarbons and the hydrocarbon and thiophenic aromatic materials may be distinguished by compound type and number of carbon atoms. The effect of biodegradation on crude oils is illustrated in the results from the series of oil sand bitumens and their asphaltene pyrolysis products. Field ionization mass spectrometry is potentially an important new analytical tool in organic geochemistry.     

Single carbon surface reactions of 1-octadecene and 2,3,6-trimethylphenol on activated carbon: Implications for methane formation in sediments

The reactions of a terminal alkene (1-octadecene) and a polymethyl phenol (2,3,6-trimethylphenol) on activated carbon have been investigated in closed system pyrolysis experiments in the temperature range 170-340 °C. The reaction products of 1-octadecene included methane, isomeric octadecenes, methyl substituted alkanes, alkyl aromatics and an homologous series of n-alkanes with carbon numbers indicative of progressive single carbon depletion of the reactant. The reaction products of 2,3,6-trimethylphenol also contained methane, as well as C₁-C₄ methyl phenols produced by demethylation and methyl transfer reactions. A carbon surface reaction involving the formation of a reactive single carbon intermediate (i.e. methylene/carbene) is proposed. This reaction accounts for the products observed from the pyrolysis experiments and also is consistent with liquid hydrocarbon distributions found in petroleum basins. Methane was the dominant (ca. 85% of C₁-C₄) gaseous hydrocarbon product of 2,3,6-trimethylphenol but accounted for only ca. 17% of the C₁-C₄ hydrocarbons from 1-octadecene. These findings suggest that single carbon surface reactions may play an important role in the geochemical formation of crude oil and natural gas and that the composition of the source material and therefore the type of organic compounds undergoing such reactions, influences the hydrocarbon gas composition in sedimentary basins.