Description: 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.

Description: There is increasing evidence that nitrifying Thaumarchaeota in the deep ocean waters may contribute to the sedimentary composition of isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs), impacting TEX86 paleothermometry. We inves- tigated the potential effect of deep-water dwelling Thaumarchaeota in the warm and saline Mediterranean Outflow Water (MOW) on the distribution of isoGDGTs by analysing suspended particulate matter (SPM) and surface sediments collected along five land-ocean transects along the southern Portuguese continental margin. To this end, we directly compared for the first time the composition of intact polar lipid (IPL)-derived isoGDGTs of SPM with the diversity, abundance, and activity of Thaumarchaeota based on the genetic analysis of the genes coding for the archaeal ammonia monooxygenase (amoA) and the geranylgeranylglyceryl phosphate (GGGP) synthase involved in the isoGDGT biosynthetic pathway. Our results revealed a strong positive relationship between water depth and TEXH86 values for both SPM and surface sediments. The increasing TEXH86 trends for both core lipid (CL) and IPL-derived fractions were accompanied by increasing fractional abundances of GDGT-2 and crenarchaeol regio-isomer and decreasing fractional abundances of GDGT-1 and GDGT-3 with increasing water depth. Phylogenetic analyses based on the archaeal amoA and the GGGP synthase proteins showed that Thaumarchaeota populations detected at 1m and 50 m water depth were different from those detected in 200 m and 1000 m water depth, which had an increased contribution of so-called 'deep water' Thaumarchaeota. The differences in the fractional abundances of isoGDGTs with water depth were compatible with the increasing contribution of 'deep water' Thaumarchaeota harboring a different GGGP synthase enzyme which has been suggested to relate to changes in the relative proportion of synthesized isoGDGTs. Accordingly, it appears that the sedimentary distribution of CL isoGDGTs used in TEXH86 along the Portuguese margin is primarily influenced by water depth due to the increasing contribution of the deep-water population of Thaumarchaeota residing in the MOW. Our study also reveals that the effect of deep water Thaumarchaeotal communities on sedimentary isoGDGT distributions should be considered globally.

Description: In this study, we investigated soils and river suspended particulate matter (SPM) collected in the Rhône and its tributary basins as well as marine surface sediments taken in the Rhône prodelta (Gulf of Lions, NW Mediterranean). Thereby, we traced the signal of branched glycerol dialkyl glycerol tetraethers (brGDGTs) from the source to sink via the Rhône River and its tributaries and identified sources of brGDGTs in rivers and marine sediments. Soil pH rather than the mean annual air temperature (MAAT) explains most of the observed variances of the brGDGT distribution in our soil dataset. The observed changes in the distribution of brGDGTs in the river SPM indicate that brGDGTs brought by the river to the sea are primarily derived from the lower Rhône and its tributary soils, even though in situ production in the river itself cannot be excluded. In marine surface sediments, it appears that the input of riverine brGDGTs is the primary source of brGDGTs in the Rhône prodelta, although the brGDGT composition may be further modified by the in situ production in the marine environment. More work is required to assess fully whether brGDGTs can be used to reconstruct the terrestrial paleoenvironmental changes using marine sediment cores taken in the Rhône prodelta close to the river mouth.

Description: The TEX86 is a widely used paleotemperature proxy based on isoprenoid glycerol dibiphytanyl glycerol tetraethers (GDGTs) produced by Thaumarchaeota. Archaeal membranes are composed of GDGTs with polar head groups (IPL-GDGTs), most of which are expected to be degraded completely or transformed into more recalcitrant core lipid (CL)-GDGTs upon cell lysis. Here, we examined the differences in concentration and distribution of core lipid (CL)- and intact polar lipid (IPL)-GDGTs in surface sediments at different deposition depths, and different oxygen bottom water concentrations (〈3-83 µmol L-1). Surface sediments were sampled from 900 to 3000 m depth on a seamount (Murray Ridge), whose summit protrudes into the oxygen minimum zone of the Arabian Sea. Concentrations of organic carbon, IPL- and CL-GDGTs decreased linearly with increasing maximum residence time in the oxic zone of the sediment (tOZ), suggesting increasing sedimentary degradation of organic matter and GDGTs. IPL-GDGT-0 was the only exception and increased with tOZ, indicating that this GDGT was probably produced in situ in the surface sediment. Concentrations of crenarchaeol with glycosidic headgroups decreased with increasing tOZ, while crenarchaeol with a hexose, phosphohexose head (HPH) group, in contrast, showed an increase with increasing tOZ, indicating that the concentration of HPH crenarchaeol was primarily determined by in situ production in surficial sediments. TEX86 values of both IPL-derived GDGTs and CL-GDGTs decreased by ~0.08 units with increasing water depth, in spite of the sea surface temperatures being identical for the restricted area studied. In situ production in sediments could be excluded as the main cause, due to the slow production rates of GDGTs in sediments, and previous observations of the same trends in TEX86 in sediment trap material. Instead, the incorporation of GDGTs produced in the oxygen minimum zone (with high TEX86 values) and their preferential degradation during the sinking through the water column, or differential degradation of IPL-GDGTs per head group could be the causes for the observed change in TEX86 values. The effect of differential degradation might cause differences between oxic and anoxically deposited sediments, and, together with a potential deep water contribution on TEX86 values, could translate into changes in reconstructed temperature of 〈3 °C, which might have to be accounted for in TEX86 calibration and paleotemperature studies of deep water sedimentary records.

Description: The study of past sedimentary records from coastal margins allows us to reconstruct variations in terrestrial input into the marine realm and to gain insight into continental climatic variability. There are numerous organic proxies for tracing terrestrial input into marine environments but none that strictly reflect the input of river-produced organic matter. Here, we test the fractional abundance of the C32 alkane 1,15-diol relative to all 1,13- and 1,15-long-chain diols (FC32 1, 15) as a tracer of input of river-produced organic matter in the marine realm in surface and Quaternary (0-45 ka) sediments on the shelf off the Zambezi and nearby smaller rivers in the Mozambique Channel (western Indian Ocean). A Quaternary (0-22 ka) sediment record off the Nile River mouth in the eastern Mediterranean was also studied for long-chain diols. For the Mozambique Channel, surface sediments of sites most proximal to Mozambique rivers showed the highest F1, 15 - C32 (up to 10 k%). The sedimentary record shows high (15-35 k%) pre-Holocene F1, 15 - C32 and low (〈 10 k%) Holocene F1, 15 - C32 values, with a major decrease between 18 and 12 ka. F1, 15 - C32 is significantly correlated (r2 = 0.83, p 〈 0.001) with the branched and isoprenoid tetraether (BIT) index, a proxy for the input of soil and river-produced organic matter in the marine environment, which declines from 0.25 to 0.60 for the pre-Holocene to 〈 0.10 for the Holocene. This decrease in both FC32 1, 15 and the BIT is interpreted to be mainly due to rising sea level, which caused the Zambezi River mouth to become more distal to our study site, thereby decreasing riverine input at the core location. Some small discrepancies are observed between the records of the BIT index and FC32 1, 15 for Heinrich Event 1 (H1) and the Younger Dryas (YD), which may be explained by a change in soil sources in the catchment area rather than a change in river influx. Like for the Mozambique Channel, a significant correlation between FC32 1, 15 and the BIT index (r2 = 0.38, p 〈 0.001) is observed for the eastern Mediterranean Nile record. Here also, the BIT index and FC32 1, 15 are lower in the Holocene than in the pre-Holocene, which is likely due to the sea level rise. In general, the differences between the BIT index and FC32 1, 15 eastern Mediterranean Nile records can be explained by the fact that the BIT index is not only affected by riverine runoff but also by vegetation cover with increasing cover leading to lower soil erosion. Our results confirm that FC32 1, 15 is a complementary proxy for tracing riverine input of organic matter into marine shelf settings, and, in comparison with other proxies, it seems not to be affected by soil and vegetation changes in the catchment area.

Description: Sea surface salinity is an essential environmental parameter necessary to understand past changes in global climate. However, reconstructing absolute salinity of the surface ocean with high enough accuracy and precision remains a complicated task. Hydrogen isotope ratios of long-chain alkenones (δ2HC37) have been shown to reflect salinity in culture studies and have been proposed as a tool to reconstruct sea surface salinity in the geological record. The correlation between δ2HC37 - salinity in culture is prominently caused by the relationship between δ2HH2O and salinity, as well as the increase in fractionation factor α with increasing salinity. The δ2HC37 - salinity relationship in the natural environment is poorly understood. Here, surface sediments from a variety of environments that cover a wide range of salinities were analyzed to constrain the environmental relationship between salinity and hydrogen isotopes of alkenones. δ2HC37 correlates significantly (R2 =0.55, p 〈 0.0001, n = 95) with annual mean salinity, but interestingly, the biological hydrogen isotope fractionation (αC37) seems independent of salinity. These findings are different from what has previously been observed in culture experiments, but align with other environmental datasets and suggest that the salinity effect on biological hydrogen isotope fractionation observed in culture is not apparent in sediments. The absence of a correlation between αC37 and salinity for marine surface sediments might be best explained by a mixing of multiple alkenone-producing species that fractionate in distinct ways contributing to the sedimentary alkenone signal. Nevertheless, sedimentary δ2HC37 ratios still correlate with salinity and δ2HH2O, suggesting that δ2HC37 ratios are useful for paleosalinity reconstructions. Our surface sediment calibration presented here can be used when different species contribute to the sedimentary alkenone pool and substantial changes in salinity are expected.

Description: Benthic Archaea comprise a significant part of the total prokaryotic biomass in marine sediments. Recent genomic surveys suggest they are largely involved in anaerobic processing of organic matter but the distribution and abundance of these archaeal groups is still largely unknown. Archaeal membrane lipids composed of isoprenoid diethers or tetraethers (glycerol dibiphytanyl glycerol tetraether, GDGT) are often used as archaeal biomarkers. Here, we compare the archaeal diversity and intact polar lipid (IPL) composition in both surface (0-0.5 cm) and subsurface (10-12 cm) sediments recovered within, just below, and well below the oxygen minimum zone (OMZ) of the Arabian Sea. Archaeal 16S rRNA gene amplicon sequencing revealed a predominance of Thaumarchaeota (Marine Group I, MG-I) in oxygenated sediments. Quantification of archaeal 16S rRNA and ammonia monoxygenase (amoA) of Thaumarchaeota genes and their transcripts indicated the presence of an active in situ benthic population, which coincided with a high relative abundance of hexose phosphohexose crenarchaeol, a specific biomarker for living Thaumarchaeota. On the other hand, anoxic surface sediments within the OMZ and all subsurface sediments were dominated by archaea belonging to the Miscellaneous Crenarchaeota Group (MCG), the Thermoplasmatales and archaea of the DPANN superphylum. Members of the MCG were diverse with a dominance of subgroup MCG-12 in anoxic surface sediments. This coincided with a high relative abundance of IPL GDGT-0 with an unknown polar head group. Subsurface anoxic sediments were characterized by higher relative abundance of GDGT-0, 2 and 3 with dihexose IPL-types, as well as GDGT-0 with a cyclopentanetetraol molecule and a hexose, as well as the presence of specific MCG subgroups, suggesting that these groups could be the biological sources of these archaeal lipids.

Description: TS2Diatom-diazotroph associations (DDAs) include marine heterocystous cyanobacteria found as exosymbionts and endosymbionts in multiple diatom species. Heterocysts are the site of N2 fixation and have thickened cell walls containing unique heterocyst glycolipids which maintain a low oxygen environment within the heterocyst. The endosymbiotic cyanobacterium Richelia intracellularis found in species of the diatom genus Hemiaulus and Rhizosolenia makes heterocyst glycolipids (HGs) which are composed of C30 and C32 diols and triols with pentose (C5) moieties that are distinct from limnetic cyanobacterial HGs with predominantly hexose (C6) moieties. Here we applied a method for analysis of intact polar lipids to the study of HGs in suspended particulate matter (SPM) and surface sediment from across the tropical North Atlantic. The study focused on the Amazon plume region, where DDAs are documented to form extensive surface blooms, in order to examine the utility of C5 HGs as markers for DDAs as well as their transportation to underlying sediments. C30 and C32 triols with C5 pentose moieties were detected in both marine SPM and surface sediments. We found a significant correlation between the water column concentration of these long-chain C5 HGs and DDA symbiont counts. In particular, the concentrations of both the C5 HGs (1-(O-ribose)-3,27,29-triacontanetriol (C5 HG30 triol) and 1-(O-ribose)-3,29,31-dotriacontanetriol (C5 HG32 triol)) in SPM exhibited a significant correlation with the number of Hemiaulus hauckii symbionts. This result strengthens the idea that long-chain C5 HGs can be applied as biomarkers for marine endosymbiotic heterocystous cyanobacteria. The presence of the same C5 HGs in surface sediment provides evidence that they are effectively transported to the sediment and hence have potential as biomarkers for studies of the contribution of DDAs to the paleomarine N cycle.

Description: In this study we have analyzed sediment trap time series from five tropical sites to assess seasonal variations in concentrations and fluxes of long-chain diols (LCDs) and associated proxies with emphasis on the Long chain Diol Index (LDI). For the tropical Atlantic, we observe that generally less than 2 % of LCDs settling from the water column are preserved in the sediment. The Atlantic and Mozambique Channel traps reveal minimal seasonal variations in the LDI, similar to the TEX86 and UK'37. However, annual mean LDI-derived temperatures are in good agreement with the annual mean satellite-derived sea surface temperatures (SSTs). In the Cariaco Basin the LDI shows larger seasonal variation, as do the TEX86 and UK'37. Here, the LDI underestimates SST during the warmest months, which is likely due to summer stratification and the habitat depth of the diol producers deepening to around 20 to 30 m. Surface sediment LDI temperatures in the Atlantic and Mozambique Channel compare well with the average LDI-derived temperatures from the overlying sediment traps, as well as with decadal annual mean SST. Lastly, we observed large seasonal variations in the Diol Index, as indicator of upwelling conditions, at three sites, potentially linked to Guinea Dome upwelling (Eastern Atlantic), seasonal upwelling (Cariaco Basin) and seasonal upwelling and/or eddy migration (Mozambique Channel).

Description: Long chain n-alkanes are terrestrial higher plant biomarkers used to reconstruct continental paleoclimatic and paleohydrological conditions with marine sedimentary archives. Latitudinal variation in their concentration and distribution in marine sediments relatively close to the continent has been widely studied, but little is known on how far this continental signal extends into the ocean. Furthermore, no studies have examined the seasonal variation in the deposition of these biomarkers in marine sediments. Here we studied longitudinal variation in the composition of long chain n-alkanes and two other terrestrial higher plant biomarkers (long chain n-alkanols and long chain fatty acids) in atmospheric particles, as well as longitudinal and seasonal variation in long chain n-alkanes in sinking particles in the ocean at different water depths and in surface sediments, all collected along a 12°N transect across the tropical North Atlantic Ocean. The highest abundance of all three biomarker classes was closest to the African coast, as expected, because they are transported with Saharan dust and the largest part of the dust is deposited close to the source. At this proximal location, the seasonal variability in long chain n-alkane flux and the chain length distribution of the n-alkanes in sinking particles was most pronounced, due to seasonal change in the dust source or due to change in vegetation composition in the source area, related to the position of the Intertropical Convergence Zone (ITCZ). In contrast, in the open ocean the seasonal variability in both the long chain n-alkane flux and chain length distribution of the n-alkanes was low. The abundance of the alkanes was also lower, as expected because of the larger source-to-sink distance. At the western part of the transect, close to South America, we found an additional source of the alkanes in the sinking particles during spring and autumn in the year 2013. The d13C of the alkanes in the surface sediment closest to the South American continent indicated that the isotope signal is likely derived from C3 vegetation from the Amazon, implying an input from the Amazon River, as there is no significant aeolian input from South America there since the prevailing wind direction is from the east. Finally, the concentration of the alkanes was similar in the material collected from the atmosphere, the particles collected while settling through the marine water column, and in the surface sediments, providing evidence that degradation of long chain n-alkanes from the atmosphere to settling at the sediment-water interface at deep open ocean sites is minimal.