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.     

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.     

n-Alkan-2-ones in peat-forming plants from the Roñanzas ombrotrophic bog (Asturias, northern Spain)

We determined the distribution of lipids (n-alkanes and n-alkan-2-ones) in present-day peat-forming plants in the Roñanzas Bog in northern Spain. Consistent with the observation of others, most Sphagnum (moss) species alkanes maximized at C₂₃, whereas the other plants maximized at higher molecular weight (C₂₇ to C₃₁). We show for the first time that plants other than seagrass and Sphagnum moss contain n-alkan-2-ones. Almost all the species analysed showed an n-alkan-2-one distribution between C₂₁ and C₃₁ with an odd/even predominance, maximizing at C₂₇ or C₂₉, except ferns, which maximized at lower molecular weight (C₂₁-C₂₃). We also observed that microbial degradation can be a major contributor to the n-alkan-2-one distribution in sediments as opposed to a direct input of ketones from plants.     

Distribution of n-alkan-2-ones in Qionghai Lake sediments,southwest China,and its potential for late Quaternary paleoclimate reconstruction

Studies on long-chain n-alkan-2-ones from lake sediments remain sparse. In this study, we present an n-alkan-2-one record from Qionghai Lake, southwest China, to assess the paleoclimate significance of variations in their compositions. A homologous series of n-alkan-2-ones ranging from C₂₁ to C₃₅ were identified, with maximum concentrations of the C₂₉ or C₃₁ chain lengths and a strong odd-over-even predominance. This type of n-alkan-2-one is considered to derive mainly from microbial oxidation of the corresponding n-alkanes, and partial inputs from plants. The n-alkan-2-one-derived average chain length (ACL) and carbon preference index (CPI) values changed significantly over the past 28k cal a bp , consistent with the sediment grain size and n-alkane proxies from the same core. Generally, the high CPI_27-33-ket and low ACL_27-33-ket values indicated cold and dry climates such as for the Last Glacial Maximum (23.2–19.7k cal a bp ), Heinrich 1 event (17.6–15.6k cal a bp ) and Younger Dryas (12.8–11.6k cal a bp ), but low CPI_27-33-ket and high ACL_27-33-ket values denoted a warm and humid Holocene Climatic Optimum (7.0–4.3k cal a bp ). Therefore, n-alkan-2-ones have great paleoclimatic potential and can be applied together with other biomarkers to reconstruct a reliable paleoclimate record in lake sediments.     

The lipid chemistry of an interfacial sediment from the Peru Continental Shelf: Fatty acids,alcohols, aliphatic ketones and hydrocarbons

A sample of the sediment-water column interface which lies on the continental shelf under the Peru upwelling regime, has been examined for fatty acids, fatty alcohols, ketones and hydrocarbons. Fatty acids were the most abundant compound class, ranging from C₁₂-C₂₄, with 16:0 as the major component (765.5 μg/g dry sediment). The alcohols were dominated by 3,7,11,15-tetramethylhexadeca-2-en-ol (phytol), with even-chain n-alcohols in the range C₁₄-C₂₀. The ketones consisted of C₃₇-C₃₉ di- and tri-unsaturated alken-2-ones and alken-3-ones. Both alkanes and alkenes were present in the hydrocarbon fraction; the alkanes ranging from C₁₃ — C₂₀ and comprising both straight chain and isoprenoid compounds; the alkenes consisting of isomeric pairs of C₂₅ branched trienes and tetraenes. The data indicate that the organic content has been contributed very largely from marine sources (probably mainly from phytoplankton and bacteria), showing little terrigenous influence. The presence of labile compounds such as polyunsaturated fatty acids (with two to six double bonds), implies that the sediment has undergone very little diagenetic alteration, and the lipids are probably largely unchanged from the state in which they actually reached the sediment. They may therefore serve as a useful baseline in assessing diagenesis in older sediments, where diagenetic transformations are more advanced.     

n-Alkan-2-one distributions in a northeastern China peat core spanning the last 16 kyr

Most research on long chain methyl ketones has focused on their origins and distributions. Their application in paleoclimate studies is less common than that of other n-alkyl lipids. The goal of this research was to explore this potential by studying n-alkan-2-ones from the Hani peat sequence in northeastern China. They were identified using gas chromatography-mass spectrometry (GC-MS) and showed a distribution ranging from C₁₉ to C₃₁ with a strong odd/even predominance. This type of distribution is considered to derive from Sphagum and microbial oxidation of n-alkanes. Comparison with climate sensitive indicators and macrofossil analysis shows that microbial oxidation of n-alkanes derived from higher plants was enhanced during the warm early Holocene period. This led us to develop three n-alkan-2-one proxies - C₂₇/ΣC_23-31 (C₂₇/HMW-KET), carbon preference index (CPI_H-KET) and average chain length (ACL_(27-31)-KET) - as possible indicators of paleoclimate in the peat-forming environment. These proxies, in combination with C₂₇n-alkane δD values and peat cellulose δ¹⁸O records, might allow examination of paleo-ecosystem behavior during climatic evolution in northeastern China over the past 16,000 yr.     

Molecular and isotopic stratigraphy in an ombrotrophic mire for paleoclimate reconstruction

A 40 cm deep Sphagnum-dominated peat monolith from Bolton Fell Moss in Northern England was systematically investigated by lipid molecular stratigraphy and compound-specific δ¹³C and δD analysis using gas chromatography (GC), GC-mass spectrometry (GC-MS), GC-combustion-isotope ratio-MS (GC-C-IRMS) and GC-thermal conversion-IRMS (GC-TC-IRMS) techniques. ²¹⁰Pb dating showed the monolith accumulated during the last ca. 220 yr, a period encompassing the second part of Little Ice Age. While the distributions of lipids, including n-alkan-1-ols, n-alkan-2-ones, wax esters, sterols, n-alkanoic acids, α,ω-alkandioic acids and ω-hydroxy acids, display relatively minor changes with depth, the cooler climate event was recorded in the concentrations of n-alkanes and organic carbon, CPI values of n-alkanes and n-alkanoic acids, and the ratio of 5-n-alkylresorcinols/sterols. Superimposed on the fossil fuel effect, the relatively cooler climate event was also recorded by δ¹³C values of individual hydrocarbons, especially the C₂₃n-alkane, a major compound in certain Sphagnum spp. The δD values of the C₂₉ and C₃₃n-alkanes correlated mainly with plant composition and were relatively insensitive to climatic change. In contrast the C₂₃n-alkane displayed variation that correlated strongly with recorded temperature for the period represented by the monolith, agreeing with previously reported deuterium records in tree ring cellulose spanning the same period in Scotland, Germany and the USA, with more negative values occurring during the second part of Little Ice Age. These biomarker characteristics, including the compound-specific δ¹³C and δD records, provide a new set of proxies of climatic change, potentially independent of preserved macrofossils which will be of value in deeper sections of the bog where the documentary records of climate are unavailable and humification is well advanced.     

Environmental evolution recorded by lipid biomarkers from the Tawan loess–paleosol sequences on the west Chinese Loess Plateau during the late Pleistocene

This study provides a reconstruction of the environmental evolution since 128 ka recorded by the lipid biomarkers of the C₁₅–C₃₅ n-alkanes, the C₁₃–C₃₃ n-alkan-2-ones and the C₁₂–C₃₀ n-alkanols isolated from the Tawan loess section, Northwest China. Variations in paleoenvironment are reconstructed from the values of the carbon preference index (CPI), the average chain length (ACL), the L/H (ratio of lower-molecular-weight to higher-molecular-weight homologues), the n-alkane C₂₇/C₃₁ ratios, and the n-alkan-2-one C₂₇/C₃₁ ratio. These parameters indicate the dominance of grasses over the west Chinese Loess Plateau (CLP) during the late Pleistocene. Lower values of the CPI and the ACL values, respectively, indicate stronger microbial reworking of organic matter and changes in plant species, which are both indicative of a warmer-wetter environment. Furthermore, the fluctuations of environment recorded in the Tawan section exhibit ten phases that show obvious cycles between warm periods and cold intervals. This study reveals that changes in the biomarker proxies agree well with changes in the magnetic susceptibility and grain size, and it indicates a huge potential for paleoenvironmental reconstructions by using the n-alkan-2-one and n-alkanol proxies.     

Origin of organic matter in early solar system—V. Further studies of meteoritic hydrocarbons and a discussion of their origin

The Murchison meteorite contains aliphatic and aromatic hydrocarbons similar to those made in static Fischer-Tropsch-type syntheses. Principal compound classes above C₈ are n-alkanes, mono- and dimethylalkanes, alkenes, alkylbenzenes and -naphthalenes. Below C₈, n-alkanes are virtually absent; instead, benzene, toluene, branched alkanes dominate. The CH₄/C₂H₆ ratio is greater than 30, possibly greater than 700. Isoprenoids from C₁₇ to C₂₀ occur in a surface rinse but not in subsequent extracts and appear to be terrestrial contaminants. Thiophenes, porphyrin-like pigments and chlorobenzenes were also found; the latter appear to be contaminants. In the Allende meteorite, only methane, benzene, toluene and an aromatic polymer seem to be indigenous.     

Lipids of aquatic organisms as potential contributors to lacustrine sediments—II

The relationship between the lipid composition of organisms in the water column of an eutrophic lake and the lipid composition of underlying sediments, previously examined for n-alkanols and steroids, is now reported for hydrocarbons, ketones and carboxylic acids.The n-C₇ alkane and alkenoic acids from two primary sources are rapidly metabolized in the water column and surficial sediment. Bacterial biomarkers, including hopenes and fatty acids, were detected in the photosynthetic bacterial layer occurring just above the sediment-water interface.Within the sediment the apparent conversion of free n-alkanes, alkan-2-ones and ω-hydroxy acids to the corresponding bound form is noted; microbiological oxidation of n-alkanes to alkan-2-ones is supported by the detection of the intermediate alkan-2-ols with a distribution similar to that of the ketones. The geochemistry of sediment deposited c. 1900, prior to biological study of the site, was interpreted from stable biomarkers and the diagenetic changes recognised in the study of contemporary deposition. A qualitative difference in algal input to the older sediment is inferred from the low Δ⁷-sterol content and presence of 2,6,10-trimethyl-7-(3-methylbutyl)-dodecane. However, there was still significant dinoflagellate input, as indicated by the presence of 4α-methylsterols. A difference in higher-plant input to the older sediment, indicated from the n-alkane, alkene and triterpenoid ketone distributions, is consistent with the recent development of tree cover.     

Origin of organic sulphur compounds and sulphur-containing high molecular weight substances in sediments and immature crude oils

The distribution patterns of Organic Sulphur Compounds (OSC), occurring in certain sediments and immature crude oils, were compared with those of the corresponding hydrocarbons. Because of the complexity of the OSC mixtures, they were desulphurized to hydrocarbons (n-alkanes, isoprenoid alkanes, steranes, triterpanes and branched alkanes). The hydrocarbons produced by desulphurization of the OSC exhibited distribution patterns different from those of the hydrocarbons originally present. Therefore reaction of elemental sulphur with these hydrocarbons at elevated temperatures must be considered as an unlikely origin for these OSC. Sulphur incorporation reactions on an intramolecular basis with suitable functionalized precursors at the early stages of diagenesis are probably the major origin for these OSc. Desulphurization of high molecular weight fractions also produced hydrocarbons, dominated by n-alkanes up to C₄₀. Therefore it is assumed that these substances contain n-alkanes, 2,5-dialkyl-thiophenes and -thiolanes linked to each other by sulphur briddges. These findings stronly suggest that sulphur-containing high molecular weight substances are formed by the same sulphur incorporation reactions as OSC, but in an intermolecular fashion.     

Lipid distribution in a subtropical southern China stalagmite as a record of soil ecosystem response to paleoclimate change

Lipid extracts from a 61.7-cm-long subtropical stalagmite in southern China, spanning the period of ca. 10,000–21,000 yr ago as constrained by U–Th dating, were analyzed using gas chromatography–mass spectrometry. The higher plants and microorganisms in the overlying soils contribute a proportion of n-alkanes identified in the stalagmite. The occurrence of LMW (lower molecular weight) n-alkanols and n-alkan-2-ones in the stalagmite was mainly related to the soil microorganisms. We suggest that HMW (higher molecular weight) n-alkanols and n-alkan-2-ones identified in the stalagmite originate from soil organics and reflect input from contemporary vegetation. Shifts in the ratio of LMW to HMW n-alkanols or n-alkan-2-ones indicative of the variation of soil ecosystems (e.g., microbial degradation of organic matter and/or the relative abundance of soil microorganisms to higher plants) are comparable with the subtropical alkenone-SST (sea surface temperature) record of the same period. The similar trends seen in the δ¹³C data and the lipid parameters in this stalagmite imply that the overlying soil ecosystem response to climate might be responsible for the variation of δ¹³C values.     

Effect of climate change on delivery and degradation of lipid biomarkers in a Holocene peat sequence in the Eastern European Russian Arctic

Lipid biomarkers from a peat plateau profile from the Northeast European Russian Arctic were analyzed. The peat originated as a wet fen ca. 9 ka BP and developed into a peat bog after the onset of permafrost ca. 2.5 ka BP. The distributions and abundances of n-alkanols, n-alkanoic acids, n-alkanes, n-alkan-2-ones and sterols were determined to study the effect of degradation on their paleoclimate proxy information. Plant macrofossil analysis was also used in combination with the lipid distributions. The n-alkanol and n-alkanoic acid distributions in the upper part of the sequence generally correspond to compositions expected from plant macrofossil assemblages. Their carbon preference index (CPI) values increase with depth and age, whereas those of the n-alkanes decrease. The different CPI patterns suggest that n-alkanoic acids and n-alkanols deeper in the sequence may be produced during humification through alteration of other lipids. Excursions in the n-alkanoic acid content also suggest an important contribution of invasive roots to the lipid biomarker composition. The CPIs associated with these compounds show that under permafrost conditions organic material from Sphagnum is better preserved than material from vascular plants. Increasing stanol/stenol ratio values and decreasing n-alkane CPI values indicate progressive degradation of organic matter (OM) with depth. The n-alkan-2-one/n-alkane and n-alkan-2-one/n-alkanoic acid ratios were shown to be useful proxies that can reflect the degree of OM preservation and suggest that both microbial oxidation of n-alkanes and decarboxylation of n-alkanoic acids produce n-alkan-2-ones in this peat sequence.     

Using GC-MS/Combustion/IRMS to determine the C/C ratios of individual hydrocarbons produced from the combustion of biomass materials--application to biomass burning

Simultaneous mass spectral detection and stable carbon isotope analysis was performed on individual indigenous n-alkanes isolated from single C₄ and C³ plant species and on a series of aliphatic and polycyclic aromatic hydrocarbons (PAH) produced from the combustion of these same biomass materials. The analysis technique used a combined gas chromatograph-mass spectrometer/combustion/isotope ratio mass spectrometer (GC-MS/C/IRMS). Precision (2σ) for replicate measurements of individual compounds in standard solutions using this novel configuration ranged between 0.2 and 0.5‰ for n-alkanes and 0.3 and 0.8‰ for PAH. Accuracy of the n-alkane measurements ranged between 0.1 and 0.4‰ and that of the PAH measurements ranged between 0.2 and 0.9‰. Replicate GC-MS/C/IRMS measurements on the combustion-derived n-alkene/alkane pairs were performed to within a precision of between 0.1 and 1.1‰ and the precision for the combustion PAH was similar to the standard PAH solution. No notable isotopic effects were observed when altering the temperature of the combustion process from 900 to 700°C, or as a result of the individual n-alkenes/alkanes partitioning between the gaseous and condensate fractions. Combustion-derived n-alkenes/alkanes ranged from C₁₁ to C₃₁, and the C₄-derived n-alkenes/alkanes were approx. 8‰ more enriched in ¹³C than the C₃-derived compounds. Both the C₄ and C₃-derived n-alkenes/alkanes (C₂₀-C₃₀) were isotopically similar to the indigenous n-alkanes and were 2-3‰ more depleted in ¹³C than the lower mol. wt (C₁₁₁₁-C₁₉) n-alkenes/alkanes, suggesting an independent origin for the lower mol. wt compounds. Combustion-generated C₄ and C₃-derived 2-, 3-, and 4-ring PAH were also isotopically distinct (Δδ = 10‰). Unlike the n-alkenes/alkanes, no compound-to-compound variations were observed between the low and high mol. wt PAH. This study demonstrates that the isotopic composition of original plant biomass material is mainly preserved in the aliphatic hydrocarbons and PAH generated by its combustion. Consequently, analyses of these compounds in sediments impacted by fire occurrences may provide useful information about paleo-fire activity that may help elucidate the impact biomass burning may have had and could have on climate-biosphere interactions.     

n-alkane distribution coupled with organic carbon isotope composition in the shell bar section, Qarhan paleolake, Qaidam basin, NE Tibetan Plateau

Lipids extracted from lacustrine deposits in the paleolake Qarhan of the Qaidam basin in the northeastern Tibetan Plateau were determined by conventional gas chromatography-mass spectrometry. Several series of biomarkers were identified, mainly including n-alkanes, n-alkan-2-ones, n-alkanoic acids, branched alkanes, triterpenoids and steroids, indicative of various biogenic contributions. On the basis of cluster analysis, the n-C₁₅, n-C₁₇, n-C₁₉ alkanes were proposed to be derived from algae and/or photosynthetic bacteria, the n-C₂₁, n-C₂₃, n-C₂₅ homologues from aquatic plants, and the n-C₂₉, n-C₃₁ homologues from vascular plants. In contrast, the n-C₂₇ alkane is not categorized in the n-C₂₉ and n-C₃₁ group of alkanes, probably due to more complex origins including both aquatic and vascular plants, and/or differential biodegradation. Stratigraphically, layers-2, 4 and 5 were found to show a close relationship in n-alkane distribution, associated with a positive shift in carbon isotope composition of bulk organic matter (δ¹³C_org), inferring a cold/dry period. Layers-1 and 6 were clustered together in association with a negative δ¹³C_org, excursion, probably indicating a relatively warm/humid climate. The potential coupling between the n-alkane distributions and δ¹³C_org, suggests a consequence of vegetation change in response to climate change, with the late MIS3 being shown to be unstable, thought to be the climatic optimum in the Tibetan Plateau. Our results suggest that the cluster analysis used in this study probably provides an effective and authentic method to investigate the n-alkane distribution in paleolake sediments.     

Hydrocarbons of the hypersaline basins of Shark Bay,Western Australia

Shark Bay is an 8000 sq. km shallow marine embayment on the western coast of Western Australia. The waters exhibit a well established salinity gradient from oceanic to hypersaline. The chemical assemblage of sediment hydrocarbons along the salinity gradient may be classified into two distinct chemogeographic types. Firstly, oceanic sediments contain n-alkanes and a suite of highly branched and branched/cyclic C₂₅ alkenes. Hypersaline sediments are characterised by a high relative abundance of a C₂₅H₅₀ alkene together with an analogous C₂₀H₄₀ alkene and its parent C₂₀H₄₂ alkene (2,6,10-trimethyl-7-(3-methylbutyl)-dodecane). A pair of alkanes C₂₁H₄₂ and C₂₂H₄₄ increase in concentration and relative abundance with depth. The hydrocarbons of the hypersaline basins are found in only trace amounts in oceanic sediments. These chemical signals are overlain by further input indicative of the immediate biotic community.     

The use of high temperature gas chromatography to study the biodegradation of high molecular weight hydrocarbons

A consequence of the biodegradation of petroleum is that lower molecular weight compounds are removed preferentially to higher molecular weight (HMW) compounds greater than triacontane (n-C₃₀). The extent to which the latter compounds are biodegraded has rarely been studied. Reasons for this include the technical difficulties associated with carrying out biodegradability tests with solid, water-insoluble substances and the limits of the analytical techniques, such as gas chromatography (GC).A quantitative high temperature GC (HTGC) method was developed to monitor the biodegradation of the aliphatic fraction of a waxy Indonesian oil by Pseudomonas fluorescens. Recoveries of over 90% were obtained for n-alkanes up to hexacontane (C₆₀) using liquid-liquid continuous extraction. After only 14 days, 80% of the aliphatic hydrocarbons had been degraded. At the end of the 136-day study, 14% of the original fraction remained. This comprised mainly C₄₀₊ compounds. No decrease in the concentrations of compounds above C₄₅ was observed. However, the use of a rapid screening biodegradation method provided tentative proof that Pseudomonas fluorescens was capable of utilising n-alkanes up to C₆₀ once the bacteria had acclimated to HMW alkanes.     

Hydrocarbon geochemistry of the Puget Sound region—I. Sedimentary acyclic hydrocarbons

Hydrocarbon compositions have been determined for ²¹⁰Pb-dated sediment cores collected at 23 sites within the inland marine waters of northwestern Washington State, U.S.A. Concentrations of total aliphatic hydrocarbons (TAH) and an unresolved complex mixture (UCM) are significantly higher in surface sediments near urban areas than at all other locations with a chronology that indicates a predominantly anthropogenic origin. Concentrations of chromatographically resolvable alkanes are comparatively uniform; the major constituents are plant wax n-alkanes and a naturally-occurring suite of fossil isoprenoid and n-alkanes. Pristane concentrations decrease sharply near the sea-sediment interface suggesting rapid degradation of a plankton-derived component. A saturated multibranched, but nonisoprenoid, C₂₀ hydrocarbon and two novel mono-olefinic analogs have been isolated along with a previously unreported suite for four acyclic multibranched C₂₅ polyenes. Structural and distributional similarities between the C₂₀ and C₂₅ multibranched hydrocarbons suggest that they may be structurally homologous and share a common source.     

Biomarkers in surface sediments from the Cross River and estuary system,SE Nigeria: Assessment of organic matter sources of natural and anthropogenic origins

Herein, lipid biomarker analysis is applied to surface sediments from the southeastern Niger Delta region for the quantitative determination of aliphatic lipids, steroids and triterpenoids in order to differentiate between natural (autochthonous vs. allochthonous) and anthropogenic organic matter (OM) inputs to this deltaic environment. This ecosystem, composed of the Cross, Great Kwa and Calabar Rivers, is receiving new attention due to increased human and industrial development activities and the potential effects of these activities impacting its environmental health. While the presence of low molecular weight n-alkanes (<C₂₂) and the fossil biomarkers pristane and phytane in all samples, are indicative of a minor petroleum related input, the total extractable organic component of the surface sediments of these rivers remains predominantly of a natural origin as characterized by the variety and predominance of lipid classes that are mainly derived from the epicuticular waxes of vascular plants and include n-alkanes, n-alkanols, n-alkan-2-ones, n-alkanoic acids, steroids and triterpenoids. In addition, recent OM inputs from microorganisms are indicated by the presence of lower molecular weight n-alkanoic acids (C_max = 16), while the major triterpenoids of the sediments, taraxerol and friedelin, and the major sterol, sitosterol, indicate recent OM inputs from vascular plants. Plankton-derived sterols, such as fucosterol and dinosterol, are also found in sediments from the Cross and Great Kwa Rivers and likely originate from autochthonous primary productivity. Furthermore, the coprosterols coprostanol and 24-ethylcoprostanol are present in most samples and indicate measurable anthropogenic contributions from domestic untreated sewage inputs and agricultural run-off, respectively. Of the three rivers studied, the Cross River system was excessively influenced by human and industrial development activities, including drivers such as urbanization and population center growth, land-use change to support agricultural production and animal husbandry, and petroleum exploration and production. These influences were found to be regionally specific as controlled by point sources of pollution based on the relative distributions measured and on the fact that the molecular characteristics of sedimentary OM were not distributed smoothly along a gradient.     

Characterization of high molecular weight biomarkers in crude oils

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C₁₂₀ in crude oils. As a result, hydrocarbons in waxes (> C₂₀) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C₄₀ were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C₄₀) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes.