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.     

Characterization of Estonian Kukersite by spectroscopy and pyrolysis: Evidence for abundant alkyl phenolic moieties in an Ordovician, marine, type II/I kerogen

The kerogen of a sample of Estonian Kukersite (Ordovician) was examined by spectroscopic (solid state ¹³C NMR, FTIR) and pyrolytic (“off-line”, flash) methods. This revealed an important contribution of long, linear alkyl chains in Kukersite kerogen. The hydrocarbons formed upon pyrolysis are dominated by n-alkanes and n-alk-1-enes and probably reflect a major contribution of selectivity preserved, highly aliphatic, resistant biomacromolecules from the outer cell walls of Gloeocapsomorpha prisca. This is consistent with the abundant presence of this fossilized organism in Kukersite kerogen. In addition high amounts of phenolic compounds were identified in the pyrolysates. Series of non-methylated, mono-, di- and trimethylated 3-n-alkylphenols, 5-n-alkyl-1,3-benzenediols and n-alkylhydroxybenzofurans were identified. All series of phenolic compounds contain long (up to C₁₉), linear alkyl side-chains. Kukersite kerogen is, therefore, an aliphatic type II/I kerogen, despite the abundance of free phenolic moieties. This study shows that phenol-derived moieties are not necessarily associated with higher plant-derived organic matter.The flash pyrolysate of Kukersite kerogen was also compared with that of the kerogen of the Guttenberg Oil Rock (Ordovician) which is also composed of accumulations of fossilized G. prisca. Similarities in the distributions of hydrocarbons and sulphur compounds were noted, especially for the C₁–C₆ alkylbenzene and alkylthiophene distributions. However, no phenolic compounds were detected in the flash pyrolysate of the Guttenberg kerogen. Possible explanations for the observed similarities and differences are discussed.     

Carbon isotopic composition of individual n-alkanes in asphaltene pyrolysates of biodegraded crude oils from the Liaohe Basin, China

Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C₁₆–C₂₉ range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.     

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

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

Experimental investigation of the compositional variation of acyclic paraffins during expulsion from source rocks

Anhydrous non-isothermal heating experiments were conducted under controlled compressive stress on cylindrical plugs of six oil shales from Permian through Eocene age. The objective of this study was to compare the distribution of acyclic paraffins in initial, residual and expelled organic matter and to highlight causes of compositional differences resulting from expulsion. Pristane generation from kerogen is highest in the Eocene Messel shale and affects the pristane / phytane (pr / ph) ratio commonly used as a redox proxy. The isoprenoid to n-alkane ratios (pr / n-C₁₇, ph / n-C₁₈) decrease during generation and are lowest in the residual bitumen due to preferential generation and retention of n-alkanes. The n-alkane distribution shows that only lacustrine shales produce high wax oils. Evaporative fractionation leads to loss of n-alkanes up to n-C₂₀ with boiling points below 350 °C. This demonstrates that lacustrine and marine shales may lead to accumulation of low wax oils due to evaporative fractionation after expulsion.     

Biomarker distributions in asphaltenes and kerogens analysed by flash pyrolysis-gas chromatography-mass spectrometry

Biomarker distributions in a suite of asphaltenes and kerogens have been analysed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the “free” biomarkers in the corresponding saturated hydrocarbon fractions.The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C₃₀ (free compounds) to C₂₇/C₂₉ is observed. Furthermore, the pyrolysates contain a set of triterpenes (not present among the free compounds), and there is a selective loss of “non-regular” triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilisation of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes).Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis.Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent. This different behaviour appears to be the result of coprecipitation of a part of the maltene fraction with the oil asphaltenes.     

Carbon isotopes of organic matter from the upper Jurassic oil shales from the Volgian-Pechora shale province and its accumulation mechanisms

The isotopic composition of carbon from the organic matter of late Jurassic oil shales from the Volgian-Pechora shale province is studied. The existence of a dependence between C_org content in the rock and the isotopic composition of kerogen carbon is ascertained. The content of the heavy carbon isotope increases with increasing C_org. This dependence is accounted for by the progressive accumulation of isotopically heavy hydrocarbons of the initial organic matter due to sulfurization. The data on the isotopic composition of individual n-alkanes of bitumen in the rocks and the data on the absence of isotopic fractionation between thermobitumen and the residual kerogen from oil shales from the Volgian-Pechora shale province obtained by treating shale in an autoclave in the presence of water are presented first in this paper.     

A molecular and carbon isotope biogeochemical study of biomarkers and kerogen pyrolysates of the Kimmeridge Clay Facies: palaeoenvironmental implications

Structures and carbon isotopic compositions of biomarkers and kerogen pyrolysis products of a dolomite, a bituminous shale and an oil shale of the Kimmeridge Clay Formation (KCF) in Dorset were studied in order to gain insight into (i) the type and extent of water column anoxia and (ii) changes in the concentration and isotopic composition of dissolved inorganic carbon (DIC) in the palaeowater column. The samples studied fit into the curve of increasing δ¹³C of the kerogen (δ¹³C_TOC) with increasing TOC, reported by Huc et al. (1992). Their hypothesis, that the positive correlation between TOC and δ¹³C_TOC is the result of differing degrees of organic matter (OM) mineralisation in the water column, was tested by measuring the δ¹³C values of primary production markers. These δ¹³C values were found to differ on average by only 1‰ among the samples, implying that differences in the extent of OM mineralisation cannot fully account for the 3‰ difference in δ¹³C_TOC. The extractable OM in the oil shale differs from that in the other sediments due to both differences in maturity, and differences in the planktonic community. These differences, however, are not likely to have significantly influenced δ¹³C_TOC either. All three sediments contain abundant derivatives of isorenieratene, indicating that periodically euxinia was extending into the photic zone. The sediments are rich in organic sulfur, as revealed by the abundant sulfur compounds in the pyrolysates. The prominence of C₁-C₃ alkylated thiophenes over n-alkanes and n-alkenes is most pronounced in the pyrolysate of the sediment richest in TOC. This suggests that sulfurisation of OM may have played an important role in determining the TOC-δ¹³C_TOC relationship reported by Huc et al. (1992).     

Organic matter in a low productivity anoxic intraplatform basin in the Triassic Tethys

This paper presents isotopic, bulk geochemical and biomarker data measured on organic matter accumulated in a narrow extensional basin developed at the oceanward margin of the huge Triassic carbonate platform in the Alps–Appenines domain. The integration of isotope signatures, organic petrographical and biomarker evidence together with the composition of kerogen pyrolysates suggests immature organic matter predominantly of algal origin with a minor, but not negligible, higher plant derived and moderate bacterial contribution for the entire sequence. The mineral sources are dominated by platform-derived subtidal Dachstein limestone with a minor palaeosol input and a moderate contribution of autochtonous quartz. Nevertheless, parallel variations observed in the mineral content, as well as in the amount and the quality of the organic matter reflect variations in the palaeoenvironment. The increased humidity, existing in the period of the accumulation of the upper section of the sequence, led to the restriction of dolomitization. A slightly greater higher plant derived contribution, in this section, is evidenced by the composition of bitumen and the results on GC and GC/MS analyses on the non-aromatic hydrocarbon fraction of bitumen. Moreover, the climate-induced weathering enchanced the primary productivity and resulted in a pronounced increase in the TOC content. The average estimated value of the planktonic productivity is about three times higher for the calcite-rich sequence than the dolomite-rich one, being 44.2 and 15.3 tC_org/m²/Ma, respectively. The low to moderate planktonic productivity shows that anoxic conditions, observed for the entire succession, are a consequence of the stagnant water stratification rather than high planktonic productivity. Depth trends in the data measured on kerogens (HI, OI, δ¹³Corg values, composition of pyrolysate) together with the δ¹⁸O excursions and Δδ¹³C values appear to be controlled by sea-level fluctuations. Consistent with the high abundance of alkyltiophenes in kerogen pyrolysates, the high S_org/C ratios (ranging between 0.05 and 0.10) suggest the importance of natural sulfurization in the formation of the sulfur-rich type-II-S kerogen occurring in all of the samples.     

Laboratory sulfurisation of the marine microalga Nannochloropsis salina

To understand more fully the mode of preservation of organic matter in marine sediments, laboratory sulfurisation of intact cells of the cultured microalga Nannochloropsis salina was performed using inorganic polysulfides in seawater at 50°C. Solvent extractable and non-extractable materials were analysed by GC–MS and Py–GC–MS, respectively, to study the incorporation of sulfur into the microalgal organic matter. No GC-amenable sulfur-containing compounds were found in the extracts apart from some minor thiophenes with a phytanyl carbon skeleton. The residue after extraction and hydrolysis contained abundant macromolecular sulfur-containing moieties as revealed by the presence of dominant C₂₈–C₃₂ thiols, thiophenes, thianes and thiolanes in the flash pyrolysates. These products are thought to be formed from moieties derived from sulfurisation of C₂₈–C₃₂ diols and alkenols, characteristic lipids of N. salina. C₁–C₂ alkylated thiophenes were also found in the pyrolysates and probably result from moieties formed upon sulfurisation of carbohydrates. The highly resistant biomacromolecule (algaenan) synthesised by N. salina remains unaffected by sulfurisation. The non-hydrolysable residue isolated from the sulfurised N. salina thus comprises algaenan and (poly)sulfide-bound long alkyl chains. The sulfurisation experiments show that both selective preservation of algaenans and lipid and carbohydrate “vulcanisation” can be involved in the preservation of algal organic matter in marine environments.     

Geochemical characterisation of organic matter in Keg River Formation (Elk point group, Middle Devonian), La Crete Basin, Western Canada

Carbonates from the Keg River Formation, La Crete Basin, Alberta, western Canada were examined in order to define: (a) oil source rock potential; (b) bulk maceral composition; (c) extract yield; and finally (d) facies variations using PY-GC-MS. Thirty samples from 6 different wells were examined from the lower Keg River member and 4 from the upper Keg River member using conventional geochemical methods. As maturity differences are absent within the sample set, variations in TOC, T_max, hydrogen index, organic petrography and extract yields are caused by variability in organic matter input, which is revealed by molecular characterisation using PY-GC-MS. Lower Keg River member bituminous wackestones are excellent potential source rocks containing Types I–II and Type II organic matter. Types I–II organic matter contains large well preserved (up to 200μm in diameter) thick-walled Tasmanites (10–15% of sample) and akinete algal cells indicative of algal blooms within an amorphous bituminite. Type II organic matter contains a higher proportion of degraded alginites/bituminite relative to well-preserved alginites. Extract yields (mg/g TOC) were seen to increase from Types I–II to Type II organic matter. PY-GC-MS revealed that 1,2,3,4-tetramethylbenzene was a major peak in most samples. This is a pyrolysis product arising from β-cleavage of C₄₀ diaromatic carotenoids incorporated within the kerogen during diagenesis. The source of this compound is thought to be from an unknown diaromatic compound with a 2,3,6-/3,4,5-trimethyl substitution pattern and isorenieratene, which is specific to photosynthetic green sulphur bacteria (Chlorobiaceae) suggesting that the photic zone was at least partially anoxic during deposition of these samples. The relative abundance of this compound/n-C11-alkene and organic sulphur (calculated from the thiophene ratio) both increase from Types I–II to Type II organic matter. This trend was grossly similar to the trend seen in the variability of extract yield with hydrogen index. A similar trend for HI and T_max indicates samples containing a higher proportion of degraded alginites/bituminite relative to well-preserved alginite are more labile than Type I–II organic matter. Upper Keg River member marls contain Type II organic matter, which is characterised by heavily degraded algal material within a bituminous groundmass. Pyrolysates of two of the marl samples contain only low amounts of 1,2,3,4-tetramethylbenzene, in contrast to the bituminous wackestones, indicating that the depositional environment/source input was different during deposition of the marl samples. Although both marls contain similar organic matter, their pyrolysates were significantly different. One marl (1141.9 m) was highly paraffinic containing dominantly short-chain alkene/alkane doublets, while the other marl (1137.6 m) contained a bimodal n-alkane/alkene distribution and high amounts of alkylphenols, which may be derived from preservation of resistant algal polyphenolic molecules or suggest a terrestrial input.     

Investigation of the pyrolytic liberation of molecular nitrogen from Palaeozoic sedimentary rocks

Open-system non-isothermal pyrolysis up to 1,200°C in combination with elemental analysis was used to study the thermal liberation of molecular nitrogen (N₂) from sedimentary rocks and kerogen concentrates of Palaeozoic age from the Central European Basin system and an Eocene shale (Liaohe Basin, China) with a high content (36%) of ammonium feldspar (buddingtonite). The N/C_org (atomic) ratios of the kerogen concentrates ranged from 0.005 to 0.014, which represents the range commonly observed for coals. Bulk N/C_org ratios of the Palaeozoic shales extended from 0.035 to 0.108, indicating the presence of significant amounts of inorganic nitrogen. Namurian A and A-B (CnA; CnA-B) samples typically exhibited the earliest onset of N₂ generation with intense, characteristic peaks around 600°C. N₂ liberation from the buddingtonite-rich sample occurred at higher temperatures, with a broad peak around 700°C. Pyrograms of the kerogen concentrates showed no or strongly reduced N₂ generation in the 500–700°C range. On-line isotope-specific analysis of the pyrolytically liberated N₂ on one sample revealed a variability of ∼10‰ in the δ¹⁵N values and a steady increase in δ¹⁵N with temperature during the main phase of N₂ generation.     

Atmospheric weathering of Scandinavian alum shales and the fractionation of C,N and S isotopes

Subaerial exposure and oxidation of organic carbon (C_org)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial C_org oxidation are expected to shift new biomass δ¹³C_org composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ¹³C_org at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, C_org-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, C_org-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of C_org without producing a δ¹³C shift between acid rock drainage precipitates and shale. Moreover, ¹³C enrichment in inorganic carbon of precipitates does not support microbial C_org oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ³⁴S = δ³⁴S_shale − δ³⁴S_precipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ¹⁵N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of C_org, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.     

Precise indices based on n-alkane distribution for quantifying sources of sedimentary organic matter in coastal systems

Precise indices based on n-alkane signatures were developed in order to determine the sources and composition of sedimentary organic matter (SOM) in coastal systems. The Arcachon Bay (France), a well-studied temperate lagoon, was used as an example of a complex coastal system sheltering a wide diversity of OM sources. Three main groups of sources were well discriminated from their n-alkane signatures: seagrass (Zostera sp.) produced mainly n-C₁₇, n-C₁₉, n-C₂₁, n-C₂₃ and n-C₂₅ alkanes, algae (Rhodophyta, Chlorophyta) produced n-C₁₅ and n-C₁₇ and the terrigenous input [Quercus sp., Spartina sp. and river suspended particulate OM (SPOM)] was characterized by n-C₂₅, n-C₂₇, n-C₂₉, n-C₃₁ and n-C₃₃. From the above and literature n-alkane fingerprints, we developed a set of indices (n-alkane ratios) to quantify the contribution of these three major sources of the SOM. At the Arcachon Bay scale, they indicated that SOM was composed mainly of seagrass (ca. 53 ± 19%) and terrestrial (ca. 41 ± 17%) material, followed by algae (ca. 6 ± 9%). Moreover, the new n-alkane indices exhibited more relevant spatial patterns than classical ones – the TAR (C₂₇ + C₂₉ + C₃₁/C₁₅ + C₁₇ + C₁₉; terrestrial to aquatic ratio) and the P_aq (C₂₃ + C₂₅/C₂₃ + C₂₅ + C₂₉ + C₃₁; aquatic plant %) – with a greater contribution from marine sources in the central part of the lagoon where a high density of Zostera seagrass was observed. Therefore, the development of precise indices adapted to the local diversity of OM sources is needed when using n-alkanes for quantifying the source composition of SOM in complex coastal systems.     

Palaeoceanographic controls on geochemical characteristics of organic-rich Exshaw mudrocks: role of enhanced primary production

Organic-rich source rocks have generally been attributed to enhanced preservation of organic matter under anoxic bottom waters. Here, geochemical analysis of kerogen and whole rock samples of organic-rich (lithofacies B₁) and organic-lean (lithofacies B₂) laminated mudrocks of the Devonian–Carboniferous Exshaw Formation, Alberta, highlight the importance of primary production in governing the quantity and quality of organic matter. Lower Si/Al, K/Al, Ti/Al and quartz/clay ratios in lithofacies B₂, similar maceral types and the laminated fabric of the two lithofacies indicate that the quality and quantity of organic matter are not related to grain size, redox or organic matter source changes. High Total Organic Carbon (TOC) and Hydrogen Index (HI), low Oxidation Index (Ox.I. ratio of oxygen functional groups to aliphatic groups derived by FTIR), lighter δ¹⁵N_tot and heavier δ¹³C_org isotopes indicate that kerogen of lithofacies B₁ accumulated during periods of high organic-carbon production and delivery of relatively fresh, labile, well-preserved organic matter to the sea floor. In contrast, low TOC, HI, high Ox.I., heavier δ¹⁵N_tot and lighter δ¹³C_org isotopes indicate low primary productivity and delivery, high recycling and poor preservation of organic matter during accumulation of lithofacies B₂.     

Molecular and carbon isotopic analysis of individual biological markers: evidence for sources of organic matter and paleoenvironmental conditions in the Upper Ordovician Maquoketa Group, Illinois Basin, U.S.A.

Variations in the carbon isotopic composition (δ¹³C) of pristane, phytane, n-heptadecane (n-C₁₇), C₂₉ ααα 20R sterane, and aryl isoprenoids provide evidence for a diverse community of algal and bacterial organisms in organic matter of the Upper Ordovician Maquoketa Group of the Illinois Basin. Carbon isotopic compositions of pristane and phytane from the Maquoketa are positively covariant (r = 0.964), suggesting that these compounds were derived from a common source inferred to be primary producers (algae) from the oxygenated photic zone. A variation of 3‰ in δ¹³C values (−31 to −34‰) for pristane and phytane indicates that primary producers utilized variable sources of inorganic carbon. Average isotopic compositions of n-C₁₇ (−32‰) and C₂₉ ααα 20R sterane (−31‰) are enriched in ¹³C relative to pristane and phytane (−33‰) suggesting that these compounds were derived from a subordinate group of primary producers, most likely eukaryotic algae. In addition, a substantial enrichment of ¹³C in aryl isoprenoids (−14 to −18‰) and the identification of tetramethylbenzene in pyrolytic products of Maquoketa kerogen indicate a contribution from photosynthetic green sulfur bacteria to the organic matter. The presence of anaerobic, photosynthetic green sulfur bacteria in organic matter of the Maquoketa indicates that anoxic conditions extended into the photic zone.The δ¹³C of n-alkanes and the identification of an unusual suite of straight-chain n-alkylarenes in the m/z 133 fragmentograms of Ordovician rocks rich in Gloeocapsomorpha prisca (G. prisca) indicate that G. prisca did not contribute to the organic matter of the Maquoketa Group.     

Distribution of n-alkanes in lacustrine sediments from subtropical lake in Brazil

The geochemical composition of lake bed sediments of a tropical reservoir in Brazil have been investigated. The C, N, P composition showed almost no variation between the different sampling points. All samples contained inorganic phosphorus (IP) ranging from 52 to 70%. The Redfield ratios show that the lake is without significant anthropogenic inputs. Most of the organic matter is composed by higher plants decomposition revealed in the total organic carbon (TOC):nitrogen (N) ratio ranging from 15.4 to 57.2. Also, TOC:organic phosphorus (OP) ranged from 265.3 to 933.6, suggesting that most of the organic matter has terrestrial origin from wood plants. The ratios suggest that most organic matter is influenced by the terrestrial characteristics of the watershed. Furthermore, the relative abundance of n-alkane homologues in the sediments was investigated. All samples have been analyzed for the n-alkanes C₈ to C₄₀. The sediments were dominated by n-alkanes C₂₅–C₃₈. It is concluded that n-alkane in sediments mainly come from terrestrial plants, however there is a contribution of submerged aquatic plants, especially in those sites in deeper areas of the lake. On the basis of P_aq index the n-alkanes in sediments comes from terrestrial plants, however there is a contribution from emerged/floating plants.The investigated lake seems to be considered as meso to eutrophic. Because of the relatively high primary productivity in the lakes, there is a substantial organic-matter flux to the sediments, which rapidly becomes anoxic. According to the pristine/phytane ratio the sediments represent an anoxic environment with values found between 0.38 and 1.72.     

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.     

Mathematical modeling of the aquatic macrophyte inputs of mid-chain n-alkyl lipids to lake sediments: Implications for interpreting compound specific hydrogen isotopic records

We present a systematic study of chain-length distributions and D/H ratios of n-alkyl lipids (both n-alkanes and n-alkanoic acids) in a wide range of terrestrial and aquatic plants around and in Blood Pond, Massachusetts, USA. The primary goal is to establish a model to quantitatively assess the aquatic plant inputs of the mid-chain length n-alkyl lipids to lake sediments and to determine the average hydrogen isotopic ratios of these lipids in different plants. Our results show that middle-chain n-alkyl lipids (C₂₁-C₂₃n-alkanes and C₂₀-C₂₄n-alkanoic acids) are exceptionally abundant in floating and submerged aquatic plants, in contrast to the dominance of long-chain n-alkyl lipids (C₂₇-C₃₁n-alkanes and C₂₆-C₃₂n-alkanoic acids) in other plant types, which are consistent with previously published data from Mountain Kenya and the Tibetan Plateau. Combining available data in different environmental settings allows us to establish statistically robust model distributions of n-alkyl lipids in floating/submerged macrophytes relative to other plant types. Based on the model distributions, we established a multi-source mixing model using a linear algebra approach, in order to quantify the aquatic inputs of mid-chain n-alkyl lipids in lake sediments. The results show that ∼97% of the mid-chain n-alkyl lipids (C₂₃n-alkane and C₂₂n-acid (behenic acid)) in Blood Pond sediments are derived from floating and submerged macrophytes. In addition, D/H ratios of C₂₂n-acid and C₂₃n-alkane in the floating and submerged plants from Blood Pond display relatively narrow ranges of variation (−161 ± 16‰ and −183 ± 18‰, respectively). Our study demonstrates that mid-chain n-alkyl lipids such as C₂₃n-alkane and C₂₂n-acid could be excellent recorders of past lake water isotopic ratios in lakes with abundant floating and submerged macrophyte inputs.