Investigating pathways of diagenetic organic matter sulfurization using compound-specific sulfur isotope analysis

We present the results of compound-specific sulfur isotope analyses performed on organic sulfur compounds (OSCs) isolated from sediments deposited in the euxinic Cariaco Basin, Venezuela. Individual OSCs (sulfurized highly branched isoprenoids and malabaricatriene) have sulfur isotope compositions of ca. −15‰, which is ³⁴S enriched by 5-15‰ relative to coeval bulk organic and inorganic sulfur pools. These observed differences in the sulfur isotope composition of bulk organic sulfur in the kerogen and bitumen pools and individual OSCs demonstrate that there are multiple pathways of organic sulfur formation operating simultaneously in marine sediments. Comparison of our measured compound-specific sulfur isotope data with values predicted using simple isotopic mass balance assumptions suggests that the sulfurization process likely involves multiple sources of inorganic sulfur. Further, the isotopic composition of these various precursor inorganic sulfur species and the specific pathway of sulfur incorporation into organic matter (OM) impart distinct isotopic compositions to the resulting organic sulfur compounds. These data represent the first compound-specific sulfur isotope measurements made in marine sediments, and demonstrate the utility of compound-specific sulfur isotope analysis in identification of inorganic sulfur sources for OM sulfurization and tracking pathways of sulfur incorporation, which will lead to a more complete understanding of diagenetic sulfurization of OM.     

Under pressure: clastic dykes in glacial settings

Clastic dykes are widespread in glacial settings, and we provide examples from Switzerland, Patagonia, Iceland and the Antarctic, ranging in age from Tertiary to recent. On the basis of these examples we establish the general characteristics of clastic dykes and proceed to establish the direction of propagation on sedimentological grounds. Micromorphological analysis reveals that sedimentation in the dykes is ruled by pressure gradients and that ordinary sedimentological rules do not apply. Clastic dykes act like safety valves in the subglacial hydraulic system. Their development depends on specific subglacial conditions like water volume and pressure, the nature of the bed, sediments or bedrock, and the hydraulic properties of the bed. A number of scenarios for clastic dyke development are presented as there is not just one set of conditions under which they form. Development of clastic dykes affects glaciodynamics, like velocity and surging and landform formation, like till thickness and bedrock disruption.     

Metripol birefringence imaging of unconsolidated glaciotectonized and ice keel scoured sediments: identification of unistrial plasmic fabric

In unconsolidated sediments subject to strain, clays and silts are realigned into particular optical birefringent arrangements (plasmic fabrics), which provide information on the style and intensity of sediment deformation. A relatively new, non‐destructive, optical microscopy technique for automatically recording and quantifying birefringence (previously commercialized under the name ‘Metripol’) is pioneered in this study as a valuable and innovative micromorphological tool with which to examine deformation in unconsolidated sediments. Metripol is applied to unistrial plasmic fabric in glaciotectonized and ice keel scoured sediment from the Netherlands and former Glacial Lake Agassiz (Manitoba, Canada) respectively. Colour‐coded images are produced in which colour represents relative optical retardation and thus optical anisotropy through the quantity |sinδ| and optical orientation of anisotropy through the angle Ø (also indicated by linear azimuths). In this study Metripol typically demonstrates that the better developed the unistrial plasmic fabric is, the higher the |sinδ| values, the larger the areas of high |sinδ| values, and the longer and more densely populated the azimuths. In addition, some unistrial plasmic fabrics under Metripol demonstrate lower |sinδ| than previous examples and the surrounding sediment, despite being ‘perceived’ as demonstrating higher birefringence under a standard petrographic microscope. This is particularly true in clay‐rich sediments and has implications for the way we currently describe and interpret unistrial plasmic fabrics in unconsolidated sediment. Finally, the identification and quantification of additional structures that would otherwise have gone undetected using a standard petrographic microscope (e.g. linear and circular structures that are likely to represent discrete shears and skelsepic plasmic fabric, respectively) highlight the potential for Metripol to gather information on the deformation history of unconsolidated sediments that is unavailable to standard techniques.     

Bacterial tetraether membrane lipids in peat and coal: Testing the MBT-CBT temperature proxy for climate reconstruction

Peatlands are widespread and important natural archives of environmental change. Here we explore the potential of the recently introduced MBT-CBT proxy (methylation index and cyclisation ratio of branched tetraethers) to estimate past annual mean air temperature (MAT) based on the distribution of bacterially-derived branched glycerol dialkyl glycerol tetraether (GDGT) membrane lipids in peat and coal. To this end, branched GDGTs in an ombrotrophic peat bog from Switzerland and three coal deposits of increasing maturity were analysed.For the surface of the bog, reconstructed annual MAT is higher than both measured annual MAT and measured in situ pore water temperature. Changes in the CBT ratio, considered a proxy for pH, with depth in the bog do not match with present day in situ pore water pH, but coincide with a peat stratigraphic boundary. This indicates that GDGTs down the bog profile are predominantly fossil and not derived from extant biomass. The MBT-CBT derived annual MAT record also shows a large drop at this stratigraphic boundary, which likely relates to past change in trophic status of the bog. Branched GDGTs are abundant in an immature lignite (vitrinite reflectance, R_o 0.25%), but occur in low amount in a slightly more mature coal (R_o 0.32%). Annual MAT could be reconstructed for the lignite alone and is higher than other proxy-based estimates from approximately the same time and location.Our results indicate potential for the application of the MBT-CBT proxy in peat and immature coals, but improved constraints on the effects of different types of peat on branched GDGT distributions as well as improved calibration of MAT estimates are needed before the method can be confidently applied.     

Separation of core and intact polar archaeal tetraether lipids using silica columns: Insights into living and fossil biomass contributions

Intact polar lipids (IPLs) are frequently used as biomarkers for living microbial cells and can be separated from core lipids (i.e. lipids without polar headgroups), which are mainly derived from fossil (i.e. dead) cell material, using column chromatography. We have compared the effect of various silica column conditions on the separation and recovery of archaeal glycerol dialkyl glycerol tetraether (GDGT) core lipids, glycolipids and phosphoglycolipids using authentic standards and direct analysis with various high performance liquid chromatography-mass spectrometry (HPLC-MS) techniques. The commonly used procedure to separate these compound classes using dichloromethane, acetone and methanol as eluents, respectively, did not separate core GDGTs from glyco- and phosphoglyco-GDGTs. In contrast, a recently described procedure using hexane:ethyl acetate (3:1, v:v), ethyl acetate and methanol achieved both high recovery and successful separation of core GDGTs from the other IPLs. Application of the method to a geothermally heated soil and suspended particulate matter from the North Sea showed that it separates most of the core GDGTs from the other IPLS and that considerable qualitative and quantitative differences can occur between core and IPL-GDGTs. We conclude that the method is therefore appropriate for the separation of intact archaeal IPLs and their fossil analogues.     

Glacier extent in a Novaya Zemlya fjord during the "Little Ice Age" inferred from glaciomarine sediment records

Glacier activity at Russkaya Gavan', north-west Novaya Zemlya (Arctic Russia), is reconstructed by particle size analysis of three fjord sediment cores in combination with ¹⁴C and ²¹⁰Pb dating. Down-core logging of particle size variation reveals at least two intervals with sediment coarsening during the past eight centuries. By comparing them with reconstructions of summer temperature and atmospheric circulation, these intervals are interpreted to represent two cycles of glacier advance and retreat sometime during ca. AD 1400–1700 and AD 1700–present. Sediment accumulation thus appears to be sensitive to century-scale fluctuations of the Barents Sea climate. The identification of two glacier cycles in the glaciomarine record from Russkaya Gavan' demonstrates that during the "Little Ice Age" major glacier fluctuations on Novaya Zemlya occurred in broad synchrony with those in other areas around the Barents Sea.     

Resistant biomacromolecules in marine microalgae of the classes Eustigmatophyceae and Chlorophyceae: Geochemical implications

Non-hydrolysable macromolecular constituents (i.e. algaenans) were isolated from two out of seven marine microalgae investigated. Nannochloropsis salina and Nannochloropsis sp. from the class of Eustigmatophyceae produce highly aliphatic algaenans. Flash pyrolysis and chemical degradations with HI and RuO₄ allowed for the identification of their chemical structure, which is mainly composed of polyether-linked long-chain (up to C₃₆) n-alkyl units. The building blocks of this polymer were also recognized in lipid fractions. The green microalgae (Chlorophyceae) Chlorella spaerckii, Chlorococcum sp. and Nannochloris sp. were earlier thought to biosynthesize algaenans comprising aliphatic and/or aromatic moieties. However, a new isolation method utilizing trifluoroacetic acid (TFA) prior to the other hydrolyses revealed that the macromolecular material isolated from these three chlorophytes was either hydrolysable with TFA or artefacts from the former method. Similar to algaenans from fresh water green microalgae, the aliphatic eustigmatophyte algaenans are likely to be selectively preserved in depositional environments and might ultimately serve as source rock organic matter of marine crude oils. Furthermore, they may play an important role in the cycling of carbon.