Origin of low-molecular-weight alkylthiophenes in pyrolysates of sulphur-rich kerogens as revealed by micro-scale sealed vessel pyrolysis

Micro-scale sealed vessel (MSSV) pyrolysis experiments have been conducted at temperatures of 150, 200, 250, 300, 330 and 350°C for various times on a thermally immature Type II-S kerogen from the Maastrichtian Jurf ed Darawish Oil Shale (Jordan) in order to study the origin of low-molecular-weight (LMW) alkylthiophenes. These experiments indicated that the LMW alkylthiophenes usually encountered in the flash pyrolysates of sulphur-rich kerogens are also produced at much lower pyrolysis temperatures (i.e. as low as 150°C) as the major (apart from hydrogen sulfide) sulphur-containing pyrolysis products. MSSV pyrolysis of a long-chain alkylthiophene and an alkylbenzene indicated that at 300°C for 72 h no β-cleavage leading to generation of LMW alkylated thiophenes and benzene occurs. In combination with the substantial production of LMW alkylthiophenes with a linear carbon skeleton at these conditions, this indicated that these thiophenes are predominantly formed by thermal degradation of multiple (poly)sulfide-bound linear C₅–C₇ skeletons, which probably mainly originate from sulphurisation of carbohydrates during early diagenesis. LMW alkylthiophenes with linear carbon skeletons seem to be unstable at MSSV pyrolysis temperatures of ≥330°C either due to thermal degradation or to methyl transfer reactions. LMW alkylthiophenes with a branched carbon skeleton most likely derive from both multiple (poly)sulfide-bound branched C₅–C₇ skeletons and alkylthiophene units present in the kerogen.     

Possible carotenoid-derived structures in fossil kerogens

The unique KMnO₄ degradation products of β-carotene, previously identified as 2,2-dimethyl succinic acid (C₆) and 2,2-dimethyl glutaric acid (C₇) have been found in the oxidation products of Green River shale (Eocene, 52 × 10⁶yr) and Tasmanian Tasmanite (Permian, 220−274 × 10⁶yr) kerogens. These two compounds were also detected in KMnO₄ degradation products of young kerogens from lacustrine and marine sediments. The results indicate that kerogens incorporated carotenoids (possibly β-carotene) at the time of kerogen formation in surface sediments. Both acids are useful markers to obtain information on biological precursors contributing to the formation of fossil kerogens.     

Comparative studies of the kinetic parameters of various algaenans and kerogens via open-system pyrolyses

Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (E_a) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in E_a distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad E_a distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma⁻¹ and the generation rate curves and cumulative yield curves thus obtained were compared.     

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.     

Sulphur,organic carbon and iron relationships in estuarine and freshwater sediments: effects of sedimentation rate

Concentrations of S, organic C and Fe were investigated in profiles of sediments from two estuarine systems in the SW of Western Australia. In marine-affected sediments, inorganic S dominates total S and concentrations of total S correlate with Fe and not with organic C. In freshwater sediments, organic S dominates total S and concentrations of total S correlate with organic C and not with Fe. Molar Fe/S ratios in the estuarine sediments decrease with increasing salinity and approach unity for marine conditions. Net accumulation rates of S in sediments were estimated with a numerical computer model, calibrated with published data on profiles of marine sediments for diffusion of SO²⁻₄, sedimentation rates and distributions of S. Measured depth-integrated reduction rates of SO²⁻₄ in the marine-affected estuarine sediments approach those obtained for Fe-limited marine conditions at similar rates of sedimentation. Measured concentrations of inorganic S in anoxic freshwater sediments fit a numerically calculated relationship between inorganic S and sedimentation rate.     

Solid state C NMR studies of selected oil shales from Queensland, Australia

Solid state ¹³C NMR techniques of cross polarization with magic-angle spinning, and interrupted decoupling have been employed to examine the nature of the organic matter in eight kerogen concentrates representing five Tertiary deposits in Queensland, Australia. The NMR results show that five of the kerogens have high proportions of aliphatic carbon in their organic matter and correspond to Type I–II algal kerogens. Three of the kerogens, derived from carbonaceous shales, have a high proportion of aromatic carbon in their organic matter and correspond to Type III kerogens. The fractions of aliphatic carbon in all the kerogens, regardless of type, are shown to correlate with the conversion characteristics of the corresponding raw shales during Fischer assay. Interrupted decoupling NMR results show the presence of more oxygen-substituted carbon in the carbonaceous shales, which may account for the greater CO₂ evolution and phenolic materials found in the pyrolysis products of the carbonaceous shales.     

Organic geochemistry of Deep Sea Drilling Project sediments from the Gulf of Calofornia—hydrothermal effects on unconsolidated diatom ooze

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material.The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter.Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (δ¹³C) values of kerogens decrease by 1–1.5‰ near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.     

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.     

TG/plus—a pyrolysis method for following maturation of oil and gas generation zones using Tmax of methane

Thermogravimetric Fourier transform infrared spectroscopy (TG-FTIR) analyses were carried out on two sets of isolated kerogens covering a wide maturity range from low mature (0.46% R_o) through the end of oil and gas generation (maximum R_{o = 5.32%}). Data onweight percent and T_max for evolution of methane, volatile tars, ethylene, SO₂, NH₃, CO₂, and CO are reported. The T_max of methane shows the most consistent response to increasing maturation in both sets of samples. Results are comparable to those of whole rocks from an Alaskan North Slope well analyzed previously. The collective data for both whole rocks and isolated kerogens shows a generally linear correlation between %R_o and T_max of methane, with the exception of R_o of about 2.0% where a dip in the curve occurs. The slope of the correlation line was steeper for the predominantly terrigenous Wilcox kerogen than for more marine Colorado kerogen or for the Alaskan North Slope whole rock samples, probably reflecting differences in the chemical nature of various kerogen sets, which is also reflected by differences in the shapes of the pyrolysis curves of SO₂, CO₂, CO, H₂O, and ethylene. These preliminary data indicate that T_max of methane is a good maturation indicator for whole rocks and isolated kerogens up to an R_o of about 4%, which includes all of the wet gas and a considerable portion of the dry gas generation zones. This correlation was also observed for samples containing migrated bitumen, where it was not possible to obtain a reliable T_max for the volatile tar (S2) peak. The more terrigenous Wilcox kerogens also showed a good correlation of the T_max of ethylene with %R_o. T_max of ammonia evolution did not correlate with maturity and occurred 100–200°C lower than previously found for whole rocks, consistent with a whole-rock source of pyrolytic ammonia for Alaskan whole rock samples. HI and OI indices were calculated in several ways and plotted to reflect kerogen type as well as both the residual oil and gas generation potential. The ratio of pyrolyzable to combustible sulfur (evolved as SO₂) was independent of maturity and showed a clear difference between the more terrigenous Wilcox kerogens and the more marine Colorado kerogens.     

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.     

Kinetics of microbial sulfate reduction in estuarine sediments

Kinetic parameters of microbial sulfate reduction in intertidal sediments from a freshwater, brackish and marine site of the Scheldt estuary (Belgium, the Netherlands) were determined. Sulfate reduction rates (SRR) were measured at 10, 21, and 30 °C, using both flow-through reactors containing intact sediment slices and conventional sediment slurries. At the three sites, and for all depth intervals studied (0-2, 2-4, 4-6 and 6-8 cm), the dependence of potential SRR on the sulfate concentration followed the Michaelis-Menten rate equation. Apparent sulfate half-saturation concentrations, K_m, measured in the flow-through reactor experiments were comparable at the freshwater and marine sites (0.1-0.3 mM), but somewhat higher at the brackish site (0.4-0.9 mM). Maximum potential SRR, R_max, in the 0-4 cm depth interval of the freshwater sediments were similar to those in the 0-6 cm interval of the marine sediments (10-46 nmol cm⁻³ h⁻¹ at 21 °C), despite much lower in situ sulfate availability and order-of-magnitude lower densities of sulfate-reducing bacteria (SRB), at the freshwater site. Values of R_max in the brackish sediments were lower (3.7-7.6 nmol cm⁻³ h⁻¹ at 21 °C), probably due to less labile organic matter, as inferred from higher C_org/N ratios. Inflow solutions supplemented with lactate enhanced potential SRR at all three sites. Slurry incubations systematically yielded higher R_max values than flow-through reactor experiments for the freshwater and brackish sediments, but similar values for the marine sediments. Transport limitation of potential SRR at the freshwater and brackish sites may be related to the lower sediment porosities and SRB densities compared to the marine site. Multiple rate controls, including sulfate availability, organic matter quality, temperature, and SRB abundance, modulate in situ sulfate-reducing activity along the estuarine salinity gradient.     

Characterization of Precambrian kerogens by analytical pyrolysis

A selection of Precambrian kerogens has been characterized by Curie-point pyrolysis combined with gas chromatography and gas chromatography-mass spectrometry. The resulting pyrograms can be classified into two groups. The first group of pyrograms is derived from kerogens whose pyrolysis products are dominated by alkanes, alkenes and alkadienes, whereas the second group contains pyrograms from kerogens that produce complex mixtures of branched hydrocarbons dominated by components at every third carbon number (C₉, C₁₂, C₁₅, C₁₈, C₂₁, and up to C₃₃). It is suggested that these branched hydrocarbons may remotely represent remains of isoprenoid hydrocarbons, or other branched hydrocarbons, of the original organisms.     

Lipids of marine Archaea: Patterns and provenance in the water-column and sediments

We measured archaeal lipid distributions from globally distributed samples of freshwater, marine, and hypersaline suspended particulate matter. Cluster analysis of relative lipid distributions identified four distinct groups, including: (1) marine epipelagic (<100 m) waters, (2) marine mesopelagic (200-1500 m) and upwelling waters, (3) freshwater/estuarine waters, and (4) hypersaline waters. A pronounced difference in lipid composition patterns is the near absence of ring-containing glycerol dialkyl glycerol tetraethers (GDGTs) at high salinity. Different archaeal communities populate marine (mesophilic Crenarchaeota and Euryarchaeota), and hypersaline environments (halophilic Euryarchaeota) and community shifts can regulate differences in lipid patterns between marine and hypersaline waters. We propose that community changes within meosphilic marine Archaea also regulate the lipid patterns distinguishing epipelagic and mesopelagic/upwelling zones. Changes in the relative amounts of crenarchaeol and caldarchaeol and low relative abundances of ringed structures in surface waters differentiate lipids from the epipelagic and mesopelagic/upwelling waters. Patterns of lipids in mesopelagic (and upwelling) waters are similar to those expected of the ammonia-oxidizing Group I Crenarchaeota, with predominance of crenarchaeol and abundant cyclic GDGTs; non-metric multidimensional analysis (NMDS) shows this pattern is associated with high nitrate concentrations. In contrast, limited culture evidence indicates marine Group II Euryarchaeota may be capable of producing mainly caldarchaeol and some, but not all, of the ringed GDGTs and we suggest that these organisms, along with the Crenarchaeota, contribute to lipids in epipelagic marine waters. Calculated TEX₈₆ temperatures in mesopelagic samples (reported here and in published data sets) are always much warmer than measured in situ temperatures. We propose lipids used in the temperature proxy derive from both Euryarchaeaota and Crenarchaeota, and observed values of TEX₈₆ are subject to changes in their ecology as influenced by nutrient fluctuations or other perturbations. Applications of published core-top TEX₈₆-SST correlations require that (1) the surface waters are always composed of similar communities with the same temperature response and (2) that deeper water GDGT production is not transported to the sediments. Our lipid distribution patterns demonstrate both surface-water archaeal community differences (which accompany greater nutrient influxes, shoaling of mesopelagic Crenarchaeota during upwelling periods, and possibly due to an influx of terrestrial Archaea), and changes in organic matter transport through the water column can affect the distribution of lipids recorded in sediments. We therefore suggest that reported temperature shifts in ancient applications indicate TEX₈₆ lipids recorded not only temperature changes, but also changes in archaeal ecology, nutrient concentrations, and possibly oceanographic conditions.     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

Benthic metabolism and nutrient cycling along an estuarine salinity gradient

Benthic metabolism and nutrient exchange across the sediment-water interface were examined over an annual cycle at four sites along a freshwater to marine transect in the Parker River-Plum Island Sound estuary in northeastern Massachusetts, U.S. Sediment organic carbon content was highest at the freshwater site (10.3%) and decreased along the salinity gradient to 0.2% in the sandy sediments at the marine end of the estuary. C:N ratios were highest in the mid estuary (23:1) and lowest near the sea (11:1). Chlorophyll a in the surface sediments was high along the entire length of the estuary (39–57 mg chlorophyll a m⁻²) but especially so in the sandy marine sediments (172 mg chlorophyll a m⁻²). Chlorophyll a to phaeophytin ratios suggested most chlorophyll is detrital, except at the sandy marine site. Porewater sulfide values varied seasonally and between sites, reflecting both changes in sulfate availability as overlying water salinity changed and sediment metabolism. Patterns of sediment redox potential followed those of sulfide. Porewater profiles of inorganic N and P reflected strong seasonal patterns in remineralization, accumulation, and release. Highest porewater NH₄ ⁺ values were found in upper and mid estuarine sediments, occasionally exceeding 1 mM N. Porewater nitrate was frequently absent, except in the sandy marine sediments where concentrations of 8 μM were often observed. Annual average respiration was lowest at the marine site (13 mmol O₂ m⁻² d⁻¹ and 21 mmol TCO₂ m⁻² d⁻¹) and highest in the mid estuary (130 mmol O₂ m⁻² d⁻¹ and 170 mmol TCO₂ m⁻² d⁻¹) where clam densities were also high. N₂O and CH₄ fluxes were low at all stations throughout the year: Over the course, of a year, sediments varied from being sources to sinks of dissolved organic C and N, with the overall spatial pattern related closely to sediment organic content. There was little correlation between PO₄ ³⁻ flux and metabolism, which we attribute to geochemical processes. At the two sites having the lowest salinities, PO₄ ³⁻ flux was directed into the sediments. On average, between 22% and 32% of total system metabolism was attributable to the benthos. The mid estuary site was an exception, as benthic metabolism accounted for 95% of the total, which is attributable to high densities of filter-feeding clams. Benthic remineralization supplied from less than 1% to over 190% of the N requirements and 0% to 21% of the P requirements of primary producers in this system. Estimates of denitrification calculated from stoichiometry of C and N fluxes ranged from 0% for the upper and mid estuary site to 35% for the freshwater site to 100% of sediment organic N remineralization at the marine site. We hypothesize that low values in the upper and mid estuary are attributable to enhanced NH₄ ⁺ fluxes during summer due to desorption of exchangeable ammonium from rising porewater salinity. NH₄ ⁺ desorption during summer may be a mechanism that maintains high rates of pelagic primary production at a time of low inorganic N inputs from the watershed.     

Variations in the carbon isotope composition and production yield of various pyrolysis products under open and closed system conditions

Production rates and carbon isotopic compositions of various pyrolysis products were investigated for three sediments from the Williston Basin under open and closed pyrolysis conditions in the temperature range of 300–600°C.Both parameters do not show any significant differences for kerogens and carbon dioxides with the analytical procedure. Contrary to open system pyrolysis, however, decreasing yields of pyrolysates and higher amounts of gaseous hydrocarbons (C_2–4 compounds) at temperatures of 500 and 600°C, point to their decomposition to give ultimately methane.Moreover, these pyrolysis products display distinct carbon isotopic variations under open and closed pyrolysis conditions. They are due to a kinetic isotope effect, i.e. the preferential cleavage of ¹²C-¹²C over ¹³C-¹²C bonds, but the extent of the shift in isotopic composition seems to depend primarily on the reservoir size and the type of source material.     

Geochemical behavior of Pt and Pd in coastal marine sediments,southeastern margin of the Japan Sea

Eighty-one argillaceous marine sediments collected from the southeastern coastal margin of the Japan Sea were analyzed for Pt and Pd by atomic absorption spectrometry using a graphite furnace atomizer after solvent extraction separation. The average Pt (1.2 ± 0.5 ppb) and Pd(1.6 ± 0.9 ppb) contents are generally similar to those of the published crustal abundances. The Pt or Pd is generally enriched in the fine sediment fraction, and positively correlated with Cu, Pb and water depth. The inverse correlation between the Pt or Pd content and redox potential of the sediment suggests that significant amounts of Pt and Pd are supplied in their dissolved forms, and reduced to their metallic states. It is concluded that the Pt and Pd distributions in the coastal marine sediments are controlled by the geological characteristics of the studied area, grain size and redox potential of sediments, water depths, and dissolved O₂ concentration of sea water.     

Early evolution and transformation of organic matter in the active continental Jordan Rift Valley

A sequence of alternating lacustrine marls, peat and basalts was penetrated in the Notera-3 well in the northern part of the Jordan Rift, Israel. The 2781 m thick sequence, ranges from Upper Miocene to Recent, reflects high sedimentation rate in the active continental rift associated with the Dead Sea Transform. The deep burial and the relatively high geothermal gradient (40°C km⁻¹) compensate for the short time span so that coalification expressed by vitrinite reflectance consistently increases with depth, from about 0.32% Ro at 1040 m to 0.48% Ro at 2495 m.Analysis of the peat reveals that the O/C, S/C and δ¹³C of the humic acids (HA) and the heavy to light normal alkane ratios are the only parameters sensitive enough to express this slight maturation increase with depth. A sharp δ¹³C change from about − 18‰ prevailing in the uppermost meters to an average of − 27.5‰ at 15 m and deeper reflects a change in the higher plant source of the peat (from C4 to C3 plants) rather than an early diagenetic modification.The δ¹³C, O/C, S/C and N/C ratios are usually lower in the kerogens than in the corresponding HA. The decrease in the δ¹³C and the O/C ratios are explained by elimination of oxygen-containing functional groups during transformation and by polymerization effects. The gradual decrease in the ¹²C and the O/C of the HA with depth are attributed to decarboxylation coupled with kinetic effects. The N/C depletion during the transformation from HA to kerogens probably results from the breakdown of amino acids. The S/C ratio which decreases both during this transformation and also with maturation is most readily explained by the breakdown of ester sulfate-containing groups such as sulfated polysaccarids, which formed diagenetically during the humification process.     

Patterns of organic and inorganic sulfur transformations in sediments

Two new methods for analysis of sedimentary sulfur employing sensitive flame photometric detection have been developed and applied to a study of marine, estuarine and freshwater sediments. Volatile organosulfur compounds generated from freeze-dried sediments upon heating in a H₂ atmosphere reflect the distribution and extent of degradation of detrital organic matter. Regions of biogeochemical sulfur transformations, as characterized by the presence of SO₂ progenitors, sulfite and thiosulfate, are also depicted. Scrubbing of sediment slurries treated with the reducing agent, acidic Cr(II) solution, releases H₂S and CH₂SH from their metal-complexed forms. CH₃SH is a common constituent of marine and estuarine sediments at sub-ppm concentrations.     

Organic petrography and geochemistry of inertinite-rich mudstones, Jakobsstigen Formation, Upper Jurassic, northeast Greenland: Indications of forest fires and variations in relative sea-level

The lower-middle Oxfordian Jakobsstigen Formation, Wollaston Forland, northeast Greenland, consists mainly of stacked coarsening-upward successions of offshore to shoreface heteroliths, sandstone and rare foreshore sandstones. The units are separated by thin, laterally extensive sheets of terrigenous carbonaceous mudstones, which have been subjected to organic petrographic and geochemical studies. The mudstones are thermally immature, with maturities corresponding to R₀ in the range 0.35–0.50%. The mudstones contain very high proportions of allochthonous inertinite, subordinate huminite, char and negligible proportions of liptinite. Inertinite reflectance distributions are markedly bimodal, with maxima at approximately 1.73 and 4.91% R_m. Both pyrolysis yields and solvent extract yields are low. The distributions of n-alkanes are markedly light-end skewed and show a pronounced predominance of even-numbered compounds in the lower carbon number range. Biomarker-distributions feature a dominance of C₂₉-steranes, slight enhancement of extended hopanes and αββ-steranes, low proportion of tricyclic triterpanes and very low hopane/sterane ratios. Sedimentological, organic petrographical and geochemical evidence suggests that the regular alternation between marine and terrestrial depositional environments during deposition of the Jakobsstigen Formation was related to low-amplitude, high-frequency changes in relative sea-level and local climate. The mudstones were deposited during early rise of relative sea-level in shallow, flat-bottomed lakes or lagoons on a broad coastal plain. The lakes acted as traps for fine elastic sediment and for predominantly windborne inertinite, generated by wildfires in the hinterland. High rates of evaporation rendered the lakes mildly saline, hampering their colonization by vegetation other than cyanobacteria and halophilic microorganisms. Similarly, saline porewaters excluded higher plant vegetation from emergent areas. Upon continued rise of the relative sea-level, the lakes were gradually flooded and their deposits became covered by sandy shallow marine sediments. The larger areas covered by shallow marine waters during periods of high relative sea-level led to a more humid local climate and to lower frequency of wildfires. During falling relative sea-level, the marine deposits were eroded and partially removed and the cycle subsequently repeated upon renewed rise in relative sea-level. Hence, minor changes in relative sea-level gave rise to the regular alternation of two vastly different depositional environments, as well as to marked variations in local climate.