Ether lipids in deep sea and swamp sediments

Methanogen ether lipids have been quantified in sediments from a Florida swamp and the Atlantic ocean. Swamp cores containing acyclic and monocyclic isopranyl ethers are clearly differentiated from deep sea sediments which also contain bicyclic compounds. A concentration maximum near the bottom of the sulfate reducing zone in deep sea sediments may reflect a biogeochemical system in which methanogenesis and sulfate reduction are coupled by the process of methane oxidation. Lipid diagenesis is evident in the deep sea sediments. Species zonation, possibly caused by oxygen sensitivity, is detected in the relative lipid abundances in swamp sediments.

Organic matter based proxies from surface sediments along three transects on the Pakistan continental margin

A valid assessment of selective aerobic degradation on organic matter (OM) and its impact on OM-based proxies is vital to produce accurate environmental reconstructions. However, most studies investigating these effects suffer from inherent environmental heterogeneities. In this study, we used surface samples collected along two meter-scale transects and one longer transect in the northeastern Arabian Sea to constrain initial OM heterogeneity, in order to evaluate selective aerobic degradation on temperature, productivity and alteration indices at the sediment-water interface. All of the studied alteration indices, the higher plant alkane index, alcohol preservation index, and diol oxidation index, demonstrated that they are sensitive indicators for changes in the oxygen regime. Several export production indices, a cholesterol-based stanol/stenol index and dinoflagellate lipid- and cyst-based ratios, showed significant (more than 20%) change only over the lateral oxygen gradients. Therefore, these compounds do not exclusively reflect surface water productivity, but are significantly altered after deposition. Two of the proxies, glycerol dibiphytanyl glycerol tetraether-based TEX86 sea surface temperature indices and indices based on phytol, phytane and pristane, did not show any trends related to oxygen. Nevertheless, unrealistic sea surface temperatures were obtained after application of the TEX86, TEX86L, and TEX86H proxies. The phytol-based ratios were likely affected by the sedimentary production of pristane. Our results demonstrate the selective impact of aerobic organic matter degradation on the lipid and palynomorph composition of surface sediments along a short lateral oxygen gradient and suggest that some of the investigated proxies may be useful tracers of changing redox conditions at the sediment-water interface.

Organic and inorganic geochemistry and archaeal community composition of hypersaline sediments from Orca Basin, RV Atlantis Expedition AT18-02

Among the most extreme habitats on Earth, dark, deep, anoxic brines host unique microbial ecosystems that remain largely unexplored. As the terminal step of anaerobic degradation of organic matter, methanogenesis is a potentially significant but poorly constrained process in deep-sea hypersaline environments. We combined biogeochemical and phylogenetic analyses as well as incubation experiments to unravel the origin of methane in hypersaline sediments of Orca Basin in the northern Gulf of Mexico. Substantial concentrations of methane (up to 3.4 mM) coexisted with high concentrations of sulfate (16-43 mM) in two sediment cores retrieved from the northern and southern parts of Orca Basin. The strong depletion of 13C in methane (-77 to -89 per mill) pointed towards a biological source. While low concentrations of competitive substrates limited the significance of hydrogenotrophic and acetoclastic methanogenesis, the presence of non-competitive methylated substrates (methanol, trimethylamine, dimethyl sulfide, dimethylsulfoniopropionate) supported the potential for methane generation through methylotrophic methanogenesis. Thermodynamic calculations demonstrated that hydrogenotrophic and acetoclastic methanogenesis were unlikely to occur under in situ conditions, while methylotrophic methanogenesis from a variety of substrates was highly favorable. Likewise, carbon isotope relationships between methylated substrates and methane supported methylotrophic methanogenesis as the major source of methane. Stable isotope tracer and radiotracer experiments with 13C bicarbonate, acetate and methanol as well as 14C-labeled methylamine indicated that methylotrophic methanogenesis was the predominant methanogenic pathway. Based on 16S rRNA gene sequences, halophilic methylotrophic methanogens related to the genus Methanohalophilus dominated the benthic archaeal community in the northern basin but also occurred in the southern basin. High abundances of methanogen lipid biomarkers such as intact polar and polyunsaturated hydroxyarchaeols were detected in sediments from the northern basin, with lower abundances in the southern basin. Strong 13C-depletion of saturated and monounsaturated hydroxyarchaeol were consistent with methylotrophic methanogenesis as the major methanogenic pathway. Collectively, the availability of methylated substrates, thermodynamic calculations, experimentally determined methanogenic activity as well as lipid and gene biomarkers strongly suggested methylotrophic methanogenesis as predominant pathway of methane formation in the presence of sulfate in Orca Basin sediments.

14C concentrations of algal and archaeal lipids and their associated sea surface temperature proxies in the Black Sea

Understanding the preservation and deposition history of organic molecules is crucial for the understanding of paleoenvironmental information contained in their abundance ratios such as Uk'37 and TEX86 used as proxies for sea surface temperature (SST). Based on their relatively high refractivity, alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) can survive postdepositional processes like lateral transport, potentially causing inferred SSTs to be misleading. Likewise, selective preservation of alkenones and GDGTs may cause biases of the SST proxies themselves and can lead to decoupling of both proxy records. Here we report compound-specific radiocarbon data of marine biomarkers including alkenones, GDGTs, and low molecular weight (LMW) n-fatty acids from Black Sea sediments deposited under different redox regimes to evaluate the potentially differential preservation of both biomarker classes and its effect on the SST indices Uk'37 and TEX86 . The decadal D14C values of alkenones, GDGTs, and LMW n-fatty acids indicate similar preservation under oxic, suboxic, and anoxic redox regimes and no contribution of pre-aged compounds, e.g., by lateral supply. Moreover, similar 14C concentrations of crenarchaeol, alkenones, and LMW n-fatty acids imply that the thaumarchaeotal GDGTs preserved in these sediments are produced in the euphotic zone rather than in subsurface/thermocline waters. However, we observe biomarker-based SSTs that strongly deviate (deltaSST up to 8.4 °C) from in situ measured mean annual SSTs in the Black Sea. This is not due to redox-dependent differential biomarker preservation as implied by their D14C values and spatial SST pattern. Since contributions from different sources can largely be excluded, the deviation of the Uk'37 and TEX86 proxy-derived SSTs from in situ SSTs requires further study of phylogenetic and other yet unknown environmental controls on alkenone and GDGT lipid distributions in the Black Sea.

Sediment core-top GDGT data from the Arctic, the North Pacific and the Southern Ocean

TEX86 (TetraEther indeX of tetraethers consisting of 86 carbon atoms) is a sea surface temperature (SST) proxy based on the distribution of archaeal isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs). In this study, we appraise the applicability of TEX86 and TEX86L in subpolar and polar regions using surface sediments. We present TEX86 and TEX86L data from 160 surface sediment samples collected in the Arctic, the Southern Ocean and the North Pacific. Most of the SST estimates derived from both TEX86 and TEX86L are anomalously high in the Arctic, especially in the vicinity of Siberian river mouths and the sea ice margin, plausibly due to additional archaeal contributions linked to terrigenous input. We found unusual GDGT distributions at five sites in the North Pacific. High GDGT-0/crenarchaeol and GDGT-2/crenarchaeol ratios at these sites suggest a substantial contribution of methanogenic and/or methanotrophic archaea to the sedimentary GDGT pool here. Apart from these anomalous findings, TEX86 and TEX86L values in the surface sediments from the Southern Ocean and the North Pacific do usually vary with overlaying SSTs. In these regions, the sedimentary TEX86-SST relationship is similar to the global calibration, and the derived temperature estimates agree well with overlaying annual mean SSTs at the sites. However, there is a systematic offset between the regional TEX86L-SST relationships and the global calibration. At these sites, temperature estimates based on the global TEX86L calibration are closer to summer SSTs than annual mean SSTs. This finding suggests that in these subpolar settings a regional TEX86L calibration may be a more suitable equation for temperature reconstruction than the global calibration.