The carbon isotopic response of algae, (cyano)bacteria, archaea and higher plants to the late Cenomanian perturbation of the global carbon cycle: Insights from biomarkers in black shales from the Cape Verde Basin (DSDP Site 367)

The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ¹³C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C₃₁ and C₃₂ hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ¹³C_TOC with the δ¹³C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ¹³C values of S-bound phytane and C₃₅ hopane were also used to estimate pCO₂ levels. Before the OAE burial event, pCO₂ levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO₂ levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO₂ levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO₂ levels.     

Thermal stability of ladderane lipids as determined by hydrous pyrolysis

Anaerobic ammonium oxidation (anammox) has been recognized as a major process resulting in loss of fixed inorganic nitrogen in the marine environment. Ladderane lipids, membrane lipids unique to anammox bacteria, have been used as markers for the detection of anammox in marine settings. However, the fate of ladderane lipids after sediment burial and maturation is unknown. In this study, anammox bacterial cell material was artificially matured by hydrous pyrolysis at constant temperatures ranging from 120 to 365 °C for 72 h to study the stability of ladderane lipids during progressive dia- and catagenesis. HPLC-MS/MS analysis revealed that structural alterations of ladderane lipids already occurred at 120 °C. At temperatures >140 °C, ladderane lipids were absent and only more thermally stable products could be detected, i.e., ladderane derivatives in which some of the cyclobutane rings were opened. These diagenetic products of ladderane lipids were still detectable up to temperatures of 260 °C using GC-MS. Thus, ladderane lipids are unlikely to occur in ancient sediments and sedimentary rocks, but specific diagenetic products of ladderane lipids will likely be present in sediments and sedimentary rocks of relatively low maturity (i.e., C₃₁ hopane 22S/(22S + 22R) ratio <0.2 or ββ/(αβ + βα + ββ) ratio of >0.5).     

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

Organic matter of the Mulhouse Basin, France: a synthesis

The lower Oligocene evaporite sequence of the Mulhouse Basin (France) contains organic matter-rich marl deposits. These marls display an overall cyclic variation of sedimentation rate, organic carbon content, hydrogen index and selected molecular parameters over a 30 m thick stratigraphic interval. The integration of all sedimentological and geochemical parameters has allowed the reconstruction and characterization of the paleoenvironment of deposition. The marls were deposited in a perennial lake that was at times connected to the sea. Two organic facies end members could be assigned to a lake stage with a marine connection and a lake stage that received dominantly continental water input. The overall stratigraphic variation in the organic matter content is interpreted to reflect the adaptation of the Oligocene flora to the changing paleoclimate and environmental conditions.     

Identification and occurrence of novel C36–C54 3,4-dialkylthiophenes with an unusual carbon skeleton in immature sediments

A series of novel long-chain 3,4-dialkylthiophenes (C₃₆–C₅₄) was identified in a number of sediments ranging from Pleistocene to Cretaceous. The identifications were based on mass spectral characterisation, desulphurisation and mass spectral data of synthesised model compounds. These organic sulphur compounds are probably formed by sulphur incorporation into mid-chain dimethylalkadienes with two methylenic double bonds. These putative precursor lipids are unprecedented and may be considered rather unusual. The distribution of 3,4-dialkylthiophenes in sediments varies considerably with the depositional palaeoenvironment, indicating that these compounds have a potential as molecular markers reflecting changes in palaeoenvironment.     

Sulphur-containing compounds in sulphur-rich crude oils from hypersaline lake sediments and their geochemical implications

Three sulphur-rich commercial crude oils have been studied, which contain sulphur as high as up to 4–12%. These samples were collected from Tertiary hypersaline lake sediments of the Jianghan Basin, Hubei Province at different depths, but above the oil generation threshold (2200m). FPD-GC and GC-MS data show that aromatic fractions of the crude oils are composed of different homologues of sulphur-containing compounds, including long-chain normal alkyl-thiophenes and-thiolanes, long-chain isoprenoid-thiophenes and -thiolanes, and benzothiophenes. It is worth noting that the distribution patterns of long-chain alkyl-thiophenes and -thiolanes from two shallow-seated crude oils are quite similar to those of normal alkanes showing marked even-odd predominance. It seems that the even-odd predominance of sulphur-containing compounds decreases with increasing burial depth of the crude oils. The major component of aliphatic fraction is phytane, and similarly the major peaks of aromatic fractions also represent C₂₀ isoprenoid thiophenes. Some preliminary conclusions have been drawn from the above discussion: (1) Abundant sulphur-containing compounds may be used as an indicator of low mature or immature crude oils produced from hypersaline lake sediments; (2) Sulphur-containing compounds are considered to be early diagenetic products of reactions between elemental sulphur or sulfides and alkanes or their precursors (phytols, fatty acids, alcohols, etc.), or of bacterial activities, but not direct inputs of organisms.     

Microbial ecology of the stratified water column of the Black Sea as revealed by a comprehensive biomarker study

The stratified water column of the Black Sea is partitioned into oxic, suboxic, and euxinic zones, each characterized by different biogeochemical processes and by distinct microbial communities. In 2003, we collected particulate matter by large volume in situ filtration at the highest resolution to date for lipid biomarker analysis and bacterioplankton for enumeration of major prokaryotic groups. Abundances of several prokaryotic groups were estimated using CARD-FISH probes specific for Bacteria, Archaea (Crenarchaeota and Euryarchaeota), epsilonproteobacteria (mainly sulfide oxidizers) and sulfate reducing bacteria. We also measured a wide range of bacterial and archaeal lipid biomarkers. Depth distributions of diagnostic biomarkers are matched with zonation of microbial processes, including aerobic bacterial oxidation of methane, oxidation of ammonium by bacteria and archaea, metal reduction, and sulfide oxidation at the chemocline, and bacterial sulfate reduction and anaerobic oxidation of methane by archaea in the anoxic zone. Cell densities for archaea and sulfate reducing bacteria are estimated based on water column biomarker concentrations and compared with CARD-FISH results.     

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.     

Constraints on the application of the MBT/CBT palaeothermometer at high latitude environments (Svalbard,Norway)

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are membrane lipids of unknown bacteria that are ubiquitous in soil and peat. Two indices based on the distribution of these lipids in soils, the Cyclization of Branched Tetraethers (CBT) and the Methylation of Branched Tetraethers (MBT) indices have been shown to correlate with soil pH, and mean annual air temperature (MAT) and soil pH, respectively, and can be used to reconstruct MAT in palaeoenvironments. To verify the extent to which branched GDGTs in marine sediments reflect the distribution pattern on land and whether these proxies are applicable for palaeoclimate reconstruction in high latitude environments with a MAT of <0 °C, we compared the branched GDGT distribution in Svalbard soils and nearby fjord sediments. Although branched GDGT concentrations in the soil are relatively low (0.02–0.95 μg/g dry weight (dw)) because of the cold climate and the short growing season, reconstructed MATs based on the MBT/CBT proxy are ca. ?4 °C, close to the measured MAT (ca. ?6 °C). Concentrations of branched GDGTs (0.01–0.20 μg/g dw) in fjord sediments increased towards the open ocean and the distribution was strikingly different from that in soil, i.e. dominated by GDGTs with one cyclopentane moiety. This resulted in MBT/CBT-reconstructed MAT values of 11–19 °C, well above measured MAT. The results suggest that at least part of the branched GDGTs in marine sediments in settings with a low soil organic matter (OM) input may be produced in situ. In these cases, the application of the MBT/CBT palaeothermometer will generate unrealistic MAT reconstructions. The MBT/CBT proxy should therefore only be used at sites with a substantial input of soil OM relative to the amount of marine OM, i.e. at sites close to the mouth of rivers with a catchment area where sufficient soil formation takes place and the soil thus contains substantial amounts of branched GDGTs.     

Identification and distribution of intact polar branched tetraether lipids in peat and soil

Branched glycerol dialkyl glycerol tetraether lipids (GDGTs) are membrane lipids of soil bacteria that occur ubiquitously in soil, but their occurrence as intact polar lipids (IPLs) has not been well studied. Here, we report the identification and distribution of IPL-branched GDGTs throughout a depth profile of a Swedish peat bog. In addition to two reported glycosidic IPL branched GDGTs, we identified IPL branched GDGTs with a hexose-glycuronic acid, phospho-hexose, or hexose-phosphoglycerol head group, based on mass spectrometry. A selected reaction monitoring (SRM) assay was developed to monitor changes in head group distribution with depth. The abundance of the IPL branched GDGTs increased below the water table, suggesting that they were primarily produced in this part of the peat. This was supported by the concentrations of core lipid and IPL-derived branched GDGTs, which also substantially increased below the water table. However, individual IPL trends differed, which may be due to changes in the microbial community composition with depth or to different degradation rates for the different IPL branched GDGTs. The SRM method was also applied to two different soil types, which showed that similar IPL branched GDGTs as those in peat were present, albeit with different distributions.