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.     

Micromorphological Analysis of Coastal Sediments from Willapa Bay, Washington, USA: A Technique for Analysing Inferred Tsunami Deposits

Tsunami deposits are provisionally distinguished in the field on the basis of anomalous sand horizons, fining-up and fining-landward, coupled with organic-rich, fragmented `backwash' sediments. In this paper, micromorphological features of a sediment sequence previously interpreted as being of tsunami origin are described. These characteristics are shown to be consistent with the macro-scale features used elsewhere, but show additional details not seen in standard stratigraphies, including possible evidence for individual waves, possibly wave-magnitude progression, organic fragment alignment and intraclast microstructures. Although replication and more complete studies are needed, this analysis confirms the identification of a tsunami in Willapa Bay in ca.1700 AD, while demonstrating a widely applicable technique for confirming or refuting possible tsunami deposits.     

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.     

A review of EU bio-economic models for fisheries: The value of a diversity of models

The lessons learned from a review of thirteen existing European bio-economic models used in the evaluation of EU policies are presented. How these models compare and differ in terms of their biological and economic components, the integration between the components, which indicators are selected and how they are used, are described and analysed. The article concludes that the multitude of construction differences reflects the necessity of adapting the modelling approach to answer different questions. Since real life questions in fisheries are so diverse, answering them requires a diversity of models.     

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.     

Diapirism synchronous with regional deformation and gold mineralisation,a new concept for granitoid emplacement in the Southern Cross Province,Western Australia

The Southern Cross Province in the Archean Yilgarn Block of Western Australia comprises large dome-shaped granitoid bodies surrounded by narrow greenstone belts. Determination of the emplacement mechanism of these domes is fundamental for understanding the tectonic history of this region. Many structures in the greenstone belts show trends which reflect their tectonic relationships with the granitoid domes. Some of these structures host large gold occurrences. The domes have concentric foliation patterns, both within the granitoids themselves, and in the neighbouring greenstone belts. The smaller domes only have radial mineral lineation patterns in their wall rocks, but the largest dome, the Ghooli Dome, has also a tangential pattern. The prevailing gentle dip of the foliation in the centre of this dome and the abundance of greenstone xenoliths suggest that the present exposures are close to its roof. Geothermometry and geobarometry on mineral assemblages in the Ghooli granitoid and its xenoliths show that its crystallisation temperature was just above 700 °C at a relatively high pressure of 4.3 to 6.2 kbar. These P-T conditions are higher than those inferred for peak metamorphism in the greenstones. Therefore, this granitoid must have been emplaced initially at crustal levels deeper than the maximum burial of the greenstones which flank the dome. The Ghooli Dome has a SHRIMP U-Pb zircon age of 2691 ± 7 Ma. Diapiric rise of the granitoid plutons taking place in a regional compressive tectonic regime is considered to be the most likely mechanism for the final emplacement of these bodies into their host rock at about 2636–2620 Ma. This concept is preferred over the alternatives because it best reconciles the calculated P-T data, the observed structural patterns, the presence of pegmatites and aplites in the host rock, and the orientation of the mineral-bearing structures.     

The impact of climate change on the river rhine: A scenario study

This paper concerns the impact of human-induced global climate change on the River Rhine discharge. For this purpose a model for climate assessment, named ESCAPE, is coupled to a water balance model, named RHINEFLOW. From climate scenarios, changes in regional annual water availability and seasonal discharge in the River Rhine Basin are estimated. The climate scenarios are based on greenhouse gases emissions scenarios. An assessment is made for best guess seasonal discharge changes and for changes in frequencies of low and high discharges in the downstream reaches of the river. In addition, a quantitative estimation of the uncertainties associated with this guess is arrived at.The results show that the extent and range of uncertainty is large with respect to the best guess changes. The uncertainty range is 2–3 times larger for the Business-as-Usual than for the Accelerated Policies scenarios. This large range stems from the doubtful precipitation simulations from the present General Circulation Models. This scenario study showed the precipitation scenarios to be the key-elements within the present range of reliable climate change scenarios.For the River Rhine best guess changes for annual water availability are small according to both scenarios. The river changes from a present combined snow-melt-rain fed river to an almost entirely rain fed river. The difference between present-day large average discharge in winter and the small average discharge in autumn should increase for all scenarios. This trend is largest in the Alpine part of the basin. Here, winter discharges should increase even for scenarios forecasting annual precipitation decreases. Summer discharge should decrease. Best guess scenarios should lead to increased frequencies of both low and high flow events in the downstream (Dutch) part of the river. The results indicate changes could be larger than presently assumed in worst case scenarios used by the Dutch water management authorities.