Can pyrolysis-GC/MS be used to estimate the degree of thermal alteration of black carbon?

Very little is known about the macromolecular properties of biomass combustion residues referred to as black carbon (BC). Pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS) was performed on: (i) peat from Spain at 400–1200 °C to investigate the effect of charring on pyrolysis fingerprint and (ii) natural charcoal from Laos in order to link molecular information to published chemical and reactivity parameters. Confirming earlier Py-GC/MS studies, the BC in the artificially charred peat and the natural charcoal produced predominantly benzene, toluene, C₂-benzenes, PAHs and benzonitriles. Furthermore, some charcoal samples produced significant amounts of phenols, methoxyphenols, carbohydrate markers, n-alkanes and n-alkenes upon pyrolysis, reflecting non-charred and weakly charred biomass. A series of pyrolysis product ratios related to the degree of dealkylation of the pyrolysis products (benzene/toluene, naphthalene/C₁-naphthalenes, C₁-naphthalenes/C₂-naphthalenes, benzofuran/C₁-benzofurans and benzonitrile/C₁-benzonitrile) increased with increasing artificial charring (peat) and, for the natural charcoal, these ratios were in accordance with established chemical and reactivity parameters related to charring intensity from other methods: proportion of aromatic C obtained from solid state ¹³C nuclear magnetic resonance spectroscopy (NMR), the proportion of charred material as estimated from NMR in conjunction with a molecular mixing model (NMR–MMM) and the resistance to acid dichromate oxidation. The alkyl side chains of aromatic pyrolysis products are probably inherited from short chain aliphatic C chains that cross link the predominantly aromatic building blocks of BC, and these linkages seem to disappear with increasing charring intensity. Thus, the degree of thermal alteration of BC can be discerned from the pyrolysis fragmentation pattern.     

Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbon and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin,Pakistan

The stable hydrogen isotopic compositions (δD) of selected aliphatic hydrocarbons (n-alkanes and isoprenoids) in eight crude oils of similar source and thermal maturity from the Upper Indus Basin (Pakistan) were measured. The oils are derived from a source rock deposited in a shallow marine environment. The low level of biodegradation under natural reservoir conditions was established on the basis of biomarker and aromatic hydrocarbon distributions. A plot of pristane/n-C₁₇ alkane (Pr/n-C₁₇) and/or phytane/n-C₁₈ alkane (Ph/n-C₁₈) ratios against American Petroleum Institute (API) gravity shows an inverse correlation. High Pr/n-C₁₇ and Ph/n-C₁₈ values and low API gravity values in some of the oils are consistent with relatively low levels of biodegradation. For the same oils, δD values for the n-alkanes relative to the isoprenoids are enriched in deuterium (D). The data are consistent with the removal of D-depleted low molecular weight (LMW) n-alkanes (C₁₄–C₂₂) from the oils. The δD values of isoprenoids do not change with progressive biodegradation and are similar for all the samples. The average D enrichment for n-alkanes with respect to the isoprenoids is found to be as much as 35‰ for the most biodegraded sample. For example, the moderately biodegraded oils show an unresolved complex mixture (UCM), loss of LMW n-alkanes (<C₁₅) and moderate changes in the alkyl naphthalene distributions. The relative susceptibility of alkyl naphthalenes at low levels of biodegradation is discussed. The alkyl naphthalene biodegradation ratios were determined to assess the effect of biodegradation. The dimethyl, trimethyl and tetramethyl naphthalene biodegradation ratios show significant differences with increasing extent of biodegradation.     

Occurrence and distribution of long-chain acyclic ketones in immature coals

Seven coal and carbonaceous mudstone samples were collected from outcropping Jurassic coal beds, on the margin of the Dingxi Basin, Northwestern China. The n-alkane distributions in all of the samples are characterised by high concentrations of the C₁₉–C₂₉ homologues, and very much lower amounts outside of this range. C₂₃ or C₂₄ are usually the most abundant n-alkanes. Straight chain n-alkanes from C₂₃ to C₂₉ show moderate odd-to-even C number predominances (CPI range: 1.26–2.70). Long-chain acyclic n-alkan-2-ones, n-alkan-3-ones and n-alkan-4-ones ranging from C₁₅ to C₃₃ with moderate odd-to-even C number predominances, were detected together with one isoprenoid methyl ketone (6,10,14-trimethylpentadecan-2-one) in all of the samples. The C number distributions of the three series of alkanones show a similar distribution to that of the n-alkanes, but the correspondence is not sufficient to substantiate a product–precursor relationship. It can be concluded that the n-alkan-2-ones are a mixture of the products of microbially-mediated β-oxidation of corresponding n-alkanes in the sediments and from the microbial oxidation of higher plant-derived n-alkanes prior to incorporation in the sediments. The n-alkan-3-ones and n-alkan-4-ones were formed from microbially mediated oxidation of the corresponding n-alkanes in the γ and δ positions, respectively. Generation of the ketones from higher plant n-fatty alcohols and n-alkanoic acids could be a possible way to form some of the ketones observed, but it can only play a minor role in the samples analysed.     

Distributions of n-alkanes and their hydrogen isotopic composition in plants from Lake Qinghai (China) and the surrounding area

Various aquatic plants from Lake Qinghai, the largest inland saline lake in China, and terrestrial plants from the surrounding area were investigated for the distribution of n-alkanes and their δD values. The n-alkanes in the samples range from C₁₅ to C₃₃ with C preference index (CPI) values of 4.0–29.7. The n-C₂₃ or n-C₂₅ alkane is the dominant compound in the aquatic submerged plants. The aquatic emergent and terrestrial plants have an abundance maximum at n-C₂₇, n-C₂₉ or n-C₃₁. The average chain length (ACL) values, ranging from 26.0 to 29.6, are closely related to the plant species. The n-alkanes from the aquatic plants have mean δD values of −169‰ to −121‰ and those from the terrestrial plants values of −173‰ to −109‰. The H isotopic composition (δD) and fractionation differ significantly among the plants studied. Comparison shows that additional evaporative enrichment of the lake water associated with saline lakes and humidity influence the δD values of the n-alkanes in aquatic and terrestrial plants, respectively. The mean δD values of n-alkanes in the plants decrease with increasing ACL value. The n-alkanes from the different types of plants are more depleted in D relative to environmental water and those from aquatic plants (with a mean value of −143‰) have a greater isotopic fractionation than terrestrial plants (mean value −113‰).     

Hydrocarbons and fatty acids in the Evergreen Shale,Surat Basin,Queensland, Australia

Alkane hydrocarbon and n-fatty acid distributions have been examined in cores taken over a 550 ft thickness through the lower Jurassic, largely non-marine Evergreen Shale, Surat Basin, Queensland, Australia. No depth trends in compound abundances or carbon preference indices are discernible. There is no evidence for significant generation of n-alkanes from kerogen nor for cracking of long-chain n-alkanes. The present distribution patterns of the biochemicals probably reflect closely the nature of the original organic matter. The general strong dominance of long-chain (C₂₀₊) n-alkanes; the lack of evidence for diagenetic change; and the absence of correlation between abundances of n-alkanes and n-fatty acids (among both the longer- and shorter-chain compounds), lead to the conclusion that at least the long-chain n-alkanes were largely deposited as such in the sediment, having originated in land-plant material, remains of which are abundant in the samples. In the upper 170 ft. (possibly marine), n-alkanes with chain lengths below C₂₀ become important, suggesting greater significance of aquatic life as a source of organic matter at the time of deposition, a conclusion which is in general accord with the geological history of the basin, although this history is not well known.     

Different source of n-alkanes and n-alkan-2-ones in a 6000 cal. yr BP Sphagnum-rich temperate peat bog (Roñanzas,N Spain)

The most widely accepted origin of n-alkan-2-ones in peats is the microbial oxidation of the related n-alkanes and/or oxidative decarboxylation of fatty acids derived from plant input. The distributions of n-alkanes and n-alkan-2-ones in 48 samples from the Roñanzas 6000 cal. yr BP peat bog profile (N Spain) do not justify a single source. The n-alkan-2-ones typically dominate the n-alkanes, maximizing at C₁₉ or C₂₅/C_27, whereas the n-alkanes maximized either at C₂₃ or at C₃₁/C₃₃. The averaged δ¹³C values of the n-alkanes ranged from −32.3‰ to −33.1‰, but those of the n-alkan-2-ones were consistently higher (−29.2‰ to −29.9‰), suggesting a different, probably bacterial, source for the ketones.     

Possible ecological and environmental significance of the predominance of even-carbon number C20-C30n-alkanes

Even-carbon number C₂₂-C₂₈n-alkanes, are present in higher concentrations than their C₂₁-C₂₉ odd-carbon number homologs in an organic-rich rock of Mississippian (ca. 310 × 10⁶-yr-old) age, which contains algae-like remnants. Environmental indicators associated with this organic-rich rock permitted environmental comparison with ancient and modern environments that contain n-alkanes which exhibit similar distributions. The results of these comparisons suggest that even-carbon number n-alkanes are preferentially produced in highly saline, carbonate environments where aerobic and anaerobic bacteria have subsisted on the remains of blue-green algae.     

Sources and occurrence of C12C22n-alkane distributions with even carbon-number preference in sedimentary environments

The occurrence of C₁₂C₂₂n-alkanes with a strong even carbon-number preference is reported in recent and Miocene sediments, encompassing marine and freshwater systems, deposited under oxic and anoxic conditions. It is therefore shown that these n-alkanes can be found in a wider type of sedimentary environment than those previously described. The occurrence in some cases of a parallel distribution of C₁₄C₂₀n-alk-1-enes is also illustrated. A variety of biological sources, including both marine and freshwater bacteria as well as fungi and yeast species is suggested to account for such distributions.     

Thermal degradation of rye and maize straw: Lipid pattern changes as a function of temperature

Future climatic conditions may coincide with an increased potential for wildfires in grassland and forest ecosystems, whereby charred biomass would be incorporated into soils. Molecular changes in biomass upon charring have been frequently analysed with a focus on black carbon. Aliphatic and aromatic hydrocarbons, known to be liberated during incomplete combustion of biomass have been preferentially analysed in soot particles, whereas determinations of these compounds in charred biomass residues are scarce. We discuss the influence of increasing charring temperature on the aliphatic and aromatic hydrocarbon composition of crop grass combustion residues. Straw from rye, representing C₃ grasses and maize, representing C₄ grasses, was charred in the presence of limited oxygen at 300, 400 and 500 °C. Typical n-alkane distribution patterns with a strong predominance of long chain odd-numbered n-alkanes maximising at C₃₁ were observed in raw straw. Upon combustion at 300 °C aliphatic hydrocarbons in char were dominated by sterenes, whereas at 400 °C sterenes disappeared and medium chain length n-alkanes, maximising around n-C₂₀, with a balanced odd/even distribution were present. At a charring temperature of 500 °C n-alkane chain length shifted to short chain homologues, maximising at C₁₈ with a pronounced predominance of even homologues. Even numbered, short chain n-alkanes in soils may thus serve as a marker for residues of charred biomass. Aromatic hydrocarbons indicate an onset of aromatization of biomass already at 300 °C, followed by severe aromatization upon incomplete combustion at 400–500 °C. The diagnostic composition of aliphatic and aromatic hydrocarbons from charred biomass affords potential for identifying residues from burned vegetation in recent and fossil soils and sediments.     

Hydrocarbons in 60 northeast Gulf of Mexico shelf sediments: a preliminary survey

Hydrocarbon results from gas chromatography of 60 recent sediment and 10 benthic algae samples delineate two distinct shelf environments in the northeastern Gulf of Mexico.Sediments off Florida (shell hashes and sands) have moderate amounts of lipids/total sediment (average 113ppm ± 80%) but low hydrocarbon levels (average 3.06 ppm ± 41%). Aliphatic hydrocarbons are dominated by a series of branched or cyclic, unsaturated C₂₅ isomers. The major n-alkane is n-C₁₇. The n-alkane and isoprenoid patterns are consistent with a marine hydrocarbon source.Sediments closer to the Mississippi River (silts and clays) contain large amounts of lipids (average 232 ppm ± 53%) and hydrocarbons (average 11.7 ppm ± 55%) to total sediment. Aliphatic hydrocarbons are mainly odd carbon number high molecular weight n-alkanes, indicating a terrigenous hydrocarbon source. Isoprenoids are present in greater abundance than in sediments off Florida (n-C₁₇/ pristane and n-C₁₈/phytane ratios ~2to 3). Relatively large amounts of n-C₁₆, together with an even distribution of n-alkanes in the range C₁₄–C₂₀ and a substantial unresolved envelope all point to a fossil fuel input to the Mississippi samples.Samples off the Alabama coast show intermediate characteristics.     

Carbon isotope composition of long chain leaf wax n-alkanes in lake sediments: A dual indicator of paleoenvironment in the Qinghai-Tibet Plateau

The carbon isotope composition (δ¹³C values) of long chain n-alkanes in lake sediments has been considered a reliable means of tracking changes in the terrigenous contribution of plants with C₃ and C₄ photosynthetic pathways. A key premise is that long chain leaf wax components used for isotope analysis are derived primarily from terrigenous higher plants. The role of aquatic plants in affecting δ¹³C values of long chain n-alkanes in lacustrine sediments may, however, have long been underestimated. In this study, we found that a large portion of long chain n-alkanes (C₂₇ and C₂₉) in nearshore sediments of the Lake Qinghai catchment was contributed by submerged aquatic plants, which displayed a relatively positive carbon isotope composition (e.g. −26.7‰ to −15.7‰ for C₂₉) similar to that of terrestrial C₄ plants. Thus, the use of δ¹³C values of sedimentary C₂₇ and C₂₉ n-alkanes for tracing terrigenous vegetation composition may create a bias toward significant overestimation/underestimation of the proportion of terrestrial C₄ plants. For sedimentary C₃₁, however, the contribution from submerged plants was minor, so that the δ¹³C values for C₃₁ n-alkane in surface sediments were in accord with those of the modern terrestrial vegetation in the Lake Qinghai region. Moreover, we found that changes in the δ¹³C values of sedimentary C₂₇ and C₂₉ n-alkanes were closely related to water depth variation. Downcore analysis further demonstrated the significant influence of endogenous lipids in lake sediments for the interpretation of terrestrial C₄ vegetation and associated environment/climate reconstruction. In conclusion, our results suggest that the δ¹³C values of sedimentary long chain n-alkanes (C₂₇, C₂₉ and C₃₁) may carry different environmental signals. While the δ¹³C values of C₃₁ were a reliable proxy for C₄/C₃ terrestrial vegetation composition, the δ¹³C values of C₂₇ and C₂₉ n-alkanes may have recorded lake ecological conditions and sources of organic carbon, which might be affected by lake water depth.     

Organic geochemistry across the Permian–Triassic transition at the Idrijca Valley,Western Slovenia

Bulk and molecular stable C isotopic compositions and biomarker distributions provide evidence for a diverse community of algal and bacterial organisms in the sedimentary organic matter of a carbonate section throughout the Permian–Triassic (P/Tr) transition at the Idrijca Valley, Western Slovenia. The input of algae and bacteria in all the Upper Permian and Lower Scythian samples is represented by the predominance of C₁₅–C₂₂ n-alkanes, odd C-number alkylcyclohexanes, C₂₇ steranes and substantial contents of C₂₁–C₃₀ acyclic isoprenoids. The occurrence of odd long-chain n-alkanes (C₂₂–C₃₀) and C₂₉ steranes in all the samples indicate a contribution of continental material. The decrease of C_org and C_carb contents, increase of Rock-Eval oxygen indices, and ¹³C-enrichment of the kerogen suggest a decrease in anoxia of the uppermost Permian bottom water. The predominance of odd C-number alkylcycloalkanes, C₂₇ steranes, and C₁₇ n-alkanes with δ¹³C values ∼−30‰, and ¹³C-enrichment of the kerogens in the lowermost Scythian samples are evidence of greater algal productivity. This increased productivity was probably sustained by a high nutrient availability and changes of dissolved CO₂ speciation associated to the earliest Triassic transgression. A decrease of C_org content in the uppermost Scythian samples, associated to a ¹³C-depletetion in the carbonates (up to 4‰) and individual n-alkanes (up to 3.4‰) compared to the Upper Permian samples, indicate lowering of the primary productivity (algae, cyanobacteria) and/or higher degradation of the organic matter.     

Chemical and carbon isotopic evolution of hydrocarbons during prograde metamorphism from 100°C to 550°C: Case study in the Liassic black shale formation of Central Swiss Alps

Hydrocarbon distributions and stable isotope ratios of carbonates (δ¹³C_car, δ¹⁸O_car), kerogen (δ¹³C_ker), extractable organic matter (δ¹³C_EOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C_<20n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C₁₂ and C₁₃n-alkanes, C₁₄, C₁₆ and C₁₈n-alkylcyclopentanes and to a lesser extend C₁₅, C₁₇ and C₂₁n-alkylcyclohexanes. The progressive ¹³C-enrichment (up to 3.9‰) with metamorphism of the C_>17n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6‰) C_<17n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C₁ and C₂ radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C_>13n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C₂₉ to C₃₁ range and 5α(H),14α(H),17α(H)-20R C₂₇, C₂₉ steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C₂₉Ts) vs. 17α(H),21β(H)-30-norhopane [C₂₉Ts/(C₂₉Ts + C₂₉)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples.The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism.     

Effect of leaf litter degradation and seasonality on D/H isotope ratios of n-alkane biomarkers

During the last decade, compound-specific hydrogen isotope analysis of plant leaf-wax and sedimentary n-alkyl lipids has become a promising tool for paleohydrological reconstructions. However, with the exception of several previous studies, there is a lack of knowledge regarding possible effects of early diagenesis on the δD values of n-alkanes. We therefore investigated the n-alkane patterns and δD values of long-chain n-alkanes from three different C3 higher plant species (Acer pseudoplatanus L., Fagus sylvatica L. and Sorbus aucuparia L.) that have been degraded in a field leaf litterbag experiment for 27 months.We found that after an initial increase of long-chain n-alkane masses (up to ∼50%), decomposition took place with mean turnover times of 11.7 months. Intermittently, the masses of mid-chain n-alkanes increased significantly during periods of highest total mass losses. Furthermore, initially high odd-over-even predominances (OEP) declined and long-chain n-alkane ratios like n-C₃₁/C₂₇ and n-C₃₁/C₂₉ started to converge to the value of 1. While bulk leaf litter became systematically D-enriched especially during summer seasons (by ∼8‰ on average over 27 months), the δD values of long-chain n-alkanes reveal no systematic overall shifts, but seasonal variations of up to 25‰ (Fagus, n-C₂₇, average ∼13‰).Although a partly contribution by leaf-wax n-alkanes by throughfall cannot be excluded, these findings suggest that a microbial n-alkane pool sensitive to seasonal variations of soil water δD rapidly builds up. We propose a conceptual model based on an isotope mass balance calculation that accounts for the decomposition of plant-derived n-alkanes and the build-up of microbial n-alkanes. Model results are in good agreement with measured n-alkane δD results. Since microbial ‘contamination’ is not necessarily discernible from n-alkane concentration patterns alone, care may have to be taken not to over-interpret δD values of sedimentary n-alkanes. Furthermore, since leaf-water is generally D-enriched compared to soil and lake waters, soil and water microbial n-alkane pools may help explain why soil and sediment n-alkanes are D-depleted compared to leaves.     

Selective enrichment of steroid and triterpenoid hydrocarbons from crude oil using gel permeation chromatography for stable carbon isotope analysis

Gel permeation chromatography (GPC) using a high performance liquid chromatography (HPLC) system was studied for the separation and enrichment of steroid and hopanoid hydrocarbons from crude oil for stable carbon isotope analysis. A crude oil sample was pretreated using silica gel chromatography and 5A molecular sieve to remove polycyclic aromatic hydrocarbons and n-alkanes. The GPC behavior of both the pretreated saturated hydrocarbon fraction of the oil and standard steroid [5α(H), 14α(H), 17α(H) C₂₇–C₂₉ steranes], hopanoid [17α(H) C₂₇ trisnorhopane, 17α(H), 21β(H) C₂₉–C₃₂ hopanes] and triterpenoid [18α(H)-oleanane, gammacerane] mixtures were examined. The results indicate that 17α(H), 21β(H) hopanes as well as steranes could be enriched efficiently using GPC and that they could be obtained without removing n-alkanes from the oil saturated hydrocarbon fraction. The GPC behavior of steroid and triterpenoid hydrocarbons was controlled by molecular size and shape.     

Organic geochemistry of the Dongsheng sedimentary uranium ore deposits,China

Organic matter (OM) associated with the Dongsheng sedimentary U ore hosting sandstone/siltstone was characterized by Rock-Eval, gas chromatography–mass spectrometry and stable C isotope analysis and compared to other OM in the sandstone/siltstone interbedded organic matter-rich strata. The OM in all of the analyzed samples is Type III with Ro less than 0.6%, indicating that the OM associated with these U ore deposits can be classified as a poor hydrocarbon source potential for oil and gas. n-Alkanes in the organic-rich strata are characterized by a higher relative abundance of high-molecular-weight (HMW) homologues and are dominated by C₂₅, C₂₇ or C₂₉ with distinct odd-to-even C number predominances from C₂₃ to C₂₉. In contrast, in the sandstone/siltstone samples, the n-alkanes have a higher relative abundance of medium-molecular-weight homologues and are dominated by C₂₂ with no or only slight odd-to-even C number predominances from C₂₃ to C₂₉. Methyl alkanoates in the sandstone/siltstone extracts range from C₁₄ to C₃₀, maximizing at C₁₆, with a strong even C number predominance, but in the organic-rich layers the HMW homologues are higher, maximizing at C₂₄, C₂₆ or C₂₈, also with an even predominance above C₂₂. n-Alkanes in the sandstone/siltstone sequence are significantly depleted in ¹³C relative to n-alkanes in most of the organic-rich strata. Diasterenes, ββ-hopanes and hopenes are present in nearly all the organic-rich sediments but in the sandstone/siltstone samples they occur as the geologically mature isomers. All the results indicate that the OM in the Dongsheng U ore body is derived from different kinds of source materials. The organic compounds in the organic-rich strata are mainly terrestrial, whereas, in the sand/siltstones, they are derived mainly from aquatic biota. Similar distribution patterns and consistent δ¹³C variations between n-alkanes and methyl alkanoates in corresponding samples suggest they are derived from the same precursors. The OM in the organic-rich strata does not appear to have a direct role in the precipitation of the U ore in the sandstone, but an indirect role cannot be excluded. The OM in the U hosting sandstone shows a relatively low hydrogen index, presumably due to oxidation or radiolytic damage.     

Volatile C1-C7 organic compounds in surface sediments from Walvis Bay

C₁-C₇ volatile organic compounds were analyzed in three gravity cores taken from Walvis Bay shelf. The compounds detected included alkanes (methane, ethane, propane, i- and n-butane, and i- and n-pentane, and heptane), alkenes (2-methyl-2-butene, dimethylcyclopentenes, cyclohexene), oxygen containing compounds (2- and 3-methylfuran, 2,5-dimethylfuran, 2- and 3-methylbutanal and 3-pentanone), sulfur compounds (dimethylsulfide, thiophene, 2- and 3-methylthiophene) and aromatic compounds (benzene and toluene). In situ biological and low temperature chemical (less than 15°C) formation processes are proposed, possibly from marine terpene precursors. Subsequent to this work, these compounds were found to be widely distributed in surface gravity cores from other areas. Many of these compounds do not survive deeper burial. Furans, ketocompounds, and alkenes are generally not found in more than trace quantities in deeper (?10m subbottom) DSDP cores we have examined from other areas.     

The source and paleoclimatic implication of hydrogen isotopic composition of n-alkanes in sediments from the Yixian Formation,western Liaoning Province,NE China

Hydrogen isotopic composition of n-alkanes was measured in sediments from an excavated profile of the Early Cretaceous Yixian Formation in Liaoning Province, NE China, aiming to assess the significance of the δD value of n-alkanes in ancient lacustrine sediments as the indicator for determining the source inputs of organic matters and paleoclimatic conditions. The δD values of n-alkanes are in the range of − 250‰ to − 85‰ and display an obvious three-stage variation pattern through the profile, which is consistent with the distribution of the dominated n-alkanes and the profile of their δ¹³C values. The δD and δ¹³C values of n-alkanes suggest that short-chain n-alkanes are primarily derived from photosynthetic bacteria and algae; n-C₂₉ and n-C₃₁ are mainly originated from terrestrial higher plants; n-C₂₈ and n-C₃₀ may be derived from the same precursor but via the different biological mechanism of hydrogen isotopic fractionation; while the source inputs of medium-chain n-alkanes are more complicated, with n-C₂₃ being derived from some specific algae or biosynthesized by various aquatic organisms. The paleoclimatic conditions are reconstructed via two approaches. The reconstructed hydrogen isotopic values of lake water and meteoric water (expressed as δD_LW and δD_MW, respectively) were at the intervals of − 51.8‰ to 17.0‰ and − 118.1‰ to − 43.5‰, respectively, indicating a general climate transition from semi-arid to arid. The calculated ΔδD_LW-MW values vary from 37.0‰ to 89.1‰ and display a similar but a significant large-scale variation trend with the ΔδD_{C23 ‐ long} (− 28.8‰ to 85.0‰; long represents long-chain n-alkanes) and ΔδD_mid-long (− 15.4‰ to 43.4‰; mid represents medium-chain n-alkanes) values. The discrepancy may be attributed to the source input overlap for n-alkanes and the uncertainties of ε_water/lipid values. The coupling of ΔδD_{C23 ‐ long}, ΔδD_mid-long and ΔδD_LW-MW values with the paleoclimatic evidence indicates that the δD values of n-alkanes could be more sensitive to the change of paleoclimatic conditions.     

Analysis of some aromatic hydrocarbons in a benzene-soluble bitumen from Green River shale

The hydrocarbon content of an aromatic fraction, isolated from the bitumen of Green River shale, was studied by mass spectrometry, infra-red spectrometry, gas chromatography and a dehydrogenation technique. The hydrocarbon types and their distribution in this aromatic fraction, as determined by mass spectrometry, include the following: C_nH_2n?6(10%), C_nH_{2n?8 (31 %)}, C_nH_2n?10(18%), C_nH_2n?12(12%), C_nH_2n?14(8%) and a series of alkenylbenzenes (20%). The carbon-number range, empirical formulae and quantity of each compound in the major types are reported. Mass spectra of several compounds and homologous mixtures of compounds isolated from the aromatic fraction are also given.     

Compound specific δD values of long chain n-alkanes derived from terrestrial higher plants are indicative of the δD of meteoric waters: Evidence from surface soils in eastern China

The stable carbon and hydrogen isotope composition of higher plant-derived long chain n-alkanes (δ¹³C_n-alkanes and δD_n-alkanes) from 45 surface soil samples (within well characterized vegetation zones) from eastern China (18°N–50°N) are reported. The weighted average δD_n-alkanes value for n-C₂₇, n-C₂₉ and n-C₃₁ in the samples and the annual average δD of meteoric water recorded at 12 weather stations proximal to the sampling sites show similar spatial variations. The δD of n-alkanes shows a gradual depletion in value with increasing latitude. The results demonstrate that, on a large spatial scale, the δD values of long chain n-alkanes derived from higher plants have the potential to record the δD of meteoric water, although many other factors can also influence the isotope values. There appears to be no apparent relationship between the δD of the n-alkanes extracted from the surface soil and the overlying vegetation type (i.e. forest/grassland or C₃/C₄ composition). Therefore, palaeoenvironmental studies utilizing δD_n-alkanes from higher plant-derived material in geological samples have the potential to provide additional information with regard to the past hydrological cycle.