Compositions of branched glycerol dialkyl glycerol tetraethers (GDGTs) in sediment samples from Bullenmoor peat bog, Northern Germany

Two types of intact branched glycerol dialkyl glycerol tetraethers (GDGTs) were detected in peat bog samples from Bullenmoor, Northern Germany. Glucuronosyl and glucosyl branched GDGTs comprise on average ca. 4% of the microbial intact polar lipids in the anoxic, acidic peat layer ca. 20 cm below the surface of the bog, suggesting an important ecological role for the source microorganisms. No corresponding phospholipids were detected. Notably, glycosidic branched GDGTs are 5-10 times less abundant than their intact isoprenoid counterparts derived from Archaea, while branched GDGT core lipids exceed their isoprenoid analogues by about an order of magnitude. These contrasting relationships may reflect lower standing stocks of the biomass of producers of branched GDGTs, combined with higher population growth rates relative to soil Archaea. Search strategies for the microbial producers of these conspicuous orphan lipids should benefit from the discovery of their intact polar precursors.

Fractional abundances of isoprenoid and branched glycerol dialkyl glycerol tetraethers (GDGT) of cores SO201-2-12KL and SO201-2-114KL

It has been proposed that North Pacific sea surface temperature (SST) evolution was intimately linked to North Atlantic climate oscillations during the last glacial-interglacial transition. However, during the early deglaciation and the Last Glacial Maximum, the SST development in the subarctic northwest Pacific and the Bering Sea is poorly constrained as most existing deglacial SST records are based on alkenone paleothermometry, which is limited prior to 15 ka B.P. in the subarctic North Pacific realm. By applying the TEXL86 temperature proxy we obtain glacial-Holocene-SST records for the marginal northwest Pacific and the Western Bering Sea. Our TEXL86-based records and existing alkenone data suggest that during the past 15.5 ka, SSTs in the northwest Pacific and the Western Bering Sea closely followed millennial-scale climate fluctuations known from Greenland ice cores, indicating rapid atmospheric teleconnections with abrupt climate changes in the North Atlantic. Our SST reconstructions indicate that in the Western Bering Sea SSTs drop significantly during Heinrich Stadial 1 (HS1), similar to the known North Atlantic climate history. In contrast, progressively rising SST in the northwest Pacific is different to the North Atlantic climate development during HS1. Similarities between the northwest Pacific SST and climate records from the Gulf of Alaska point to a stronger influence of Alaskan Stream waters connecting the eastern and western basin of the North Pacific during this time. During the Holocene, dissimilar climate trends point to reduced influence of the Alaskan Stream in the northwest Pacific.

Concentrations and abundance ratios of long-chain alkenones and glycerol dialkyl glycerol tetraethers in sinking particles south of Java

In this study, we obtained concentrations and abundance ratios of long-chain alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) in a one-year time-series of sinking particles collected with a sediment trap moored from December 2001 to November 2002 at 2200 m water depth south of Java in the eastern Indian Ocean. We investigate the seasonality of alkenone and GDGT fluxes as well as the potential habitat depth of the Thaumarchaeota producing the GDGTs entrained in sinking particles. The alkenone flux shows a pronounced seasonality and ranges from 1 µg m-**2 d**-1 to 35 µg m**-2 d**-1. The highest alkenone flux is observed in late September during the Southeast monsoon, coincident with high total organic carbon fluxes as well as high net primary productivity. Flux-weighted mean temperature for the high flux period using the alkenone-based sea-surface temperature (SST) index UK'37 is 26.7°C, which is similar to satellite-derived Southeast (SE) monsoon SST (26.4°C). The GDGT flux displays a weaker seasonality than that of the alkenones. It is elevated during the SE monsoon period compared to the Northwest (NW) monsoon and intermonsoon periods (approximately 2.5 times), which is probably related to seasonal variation of the abundance of Thaumarchaeota, or to enhanced export of GDGTs by aggregation with sinking phytoplankton detritus. Flux-weighted mean temperature inferred from the GDGT-based TEXH86 index is 26.2°C, which is 1.8 °C lower than mean annual (ma) SST but similar to SE monsoon SST. As the time series of TEXH86 temperature estimates, however, does not record a strong seasonal amplitude, we infer that TEXH86 reflects ma upper thermocline temperature at approximately 50 m water depth.

Glycerol dialkyl glycerol tetraethers (GDGT) abundance in suspended particulate matter from the South-west and Equatorial Atlantic Ocean

The TEX86 paleotemperature proxy is based on archaeal glycerol dibiphytanyl glycerol tetraether (GDGT) lipids preserved in marine sediments, yet both the influence of different physiological factors on the structural distribution of GDGTs, and the mechanism(s) by which GDGTs are exported to marine sediments remain unclear. In particular, TEX86 temperatures derived directly from suspended particulate matter (SPM) in the water column can diverge strongly from corresponding in situ temperatures. Here we investigated the abundance and structural distribution of GDGTs in the South-west and Equatorial Atlantic Ocean by examining SPM collected from four surface 1000 m depth profiles spanning 48 degrees of latitude. The depth distribution of GDGTs was consistent with our current understanding of marine archaeal ecology, and specifically of ammonia-oxidizing Thaumarchaeota. Maximum GDGT concentrations occurred at the base of the primary NO2- maximum. Core GDGTs dominated the structural distribution in surface waters, while intact polar GDGTs - thought to potentially indicate live cells - were more abundant at all depths below the maximum NO2- concentration. When integrated through the upper 1000 m of the water column, > 98% of GDGTs were present in waters at and below the depth of the primary NO2- maximum. TEX86-calculated temperatures showed local minima at the depth of the NO2- maximum, while the ratio of GDGT 2:GDGT 3 [2/3] increased with depth throughout the upper water column. These results were used to model the depth of origin for GDGTs exported to sediments. By comparing our SPM data to published TEX86 values and [2/3] ratios from sediments near our study sites, we conclude that most GDGTs are exported from the depth of maximum GDGT concentrations, near the subsurface NO2- maximum (~80-250 m). This indicates that local ammonia oxidation dynamics are important regional controls on the GDGT ratios preserved in sediments. Predicting the extent to which subsurface variations in archaeal activity may influence the sedimentary TEX86 record will require a better understanding of how site-specific productivity and particle dynamics in the upper water column influence the depth of origin for exported organic matter.

Glycerol dialkyl glycerol tetraethers (GDGT) abundance of sediment core GeoB15103-1

Marine microorganisms adapt to their habitat by structural modification of their membrane lipids. This concept is the basis of numerous molecular proxies used for paleoenvironmental reconstruction. Archaeal tetraether lipids from ubiquitous marine planktonic archaea are particularly abundant, well preserved in the sedimentary record and utilized in several molecular proxies. We here introduce the direct, extraction-free analysis of these compounds in intact sediment core sections using laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). LDI FTICR-MS can detect the target lipids in single sub-mm sized spots on sediment sections, equivalent to a sample mass in the nanogram range, and could thus pave the way for biomarker-based reconstruction of past environments and ecosystems at subannual to decadal resolution. We demonstrate that ratios of selected archaeal tetraethers acquired by LDI FTICR-MS are highly correlated with values obtained by conventional LC/MS protocols. The ratio of the major archaeal lipids, caldarchaeol and crenarchaeol, analyzed in a 6.2-cm intact section of Mediterranean sapropel S1 at 250-µm resolution (~4-year temporal resolution), provides an unprecedented view of the fine-scale patchiness of sedimentary biomarker distributions and the processes involved in proxy signal formation. Temporal variations of this lipid ratio indicate a strong influence of the 200-yr de Vries solar cycle on reconstructed sea surface temperatures with possible amplitudes of several degrees, and suggest signal amplification by a complex interplay of ecological and hydrological factors. Laser-based biomarker analysis of geological samples has the potential to revolutionize molecular stratigraphic studies of paleoenvironments.

Intact and core tetraether lipids in water column profiles of suspended particulate matter and of surface sediment samples off Cape Blanc, NW Africa

In the reconstruction of sea surface temperature (SST) from sedimentary archives, secondary sources, lateral transport and selective preservation are considered to be mainly negligible in terms of influencing the primary signal. This is also true for the archaeal glycerol dialkyl glycerol tetraethers (GDGTs) that form the basis for the TEX86 SST proxy. Our samples represent four years variability on a transect off Cape Blanc (NW Africa). We studied the subsurface production, vertical and lateral transport of intact polar lipids and core GDGTs in the water column at high vertical resolution on the basis of suspended particulate matter (SPM) samples from the photic zone, the subsurface oxygen minimum zone (OMZ), nepheloid layers (NL) and the water column between these. Furthermore we compared the water column SPM GDGT composition with that in underlying surface sediments. This is the first study that reports TEX86 values from the precursor intact polar lipids (IPLs) associated with specific head groups (IPL -specific TEX86). We show a clear deviation from the sea surface GDGT composition in the OMZ between 300 and 600 m. Since neither lateral transport nor selective degradation provides a satisfactory explanation for the observed TEX-derived temperature profiles with a bias towards higher temperatures for both core- and IPL -specific TEX86 values, we suggest that subsurface in situ production of archaea with a distinct relationship between lipid biosynthesis and temperature is the responsible mechanism. However, in the NW-African upwelling system the GDGT contribution of the OMZ to the surface sediments does not seem to affect the sedimentary TEX86 as it shows no bias and still reflects the signal of the surface waters between 0 and 60 m.

A four-year record of UK'37- and TEX86-derived sea surface temperature estimates from sinking particles in the filamentous upwelling region off Cape Blanc, Mauritania

Lipid biomarker records from sinking particles collected by sediment traps are excellent tools to study the seasonality of biomarker production as well as processes of particle formation and settling, ultimately leading to the preservation of the biomarkers in sediments. Here we present records of the biomarker indices UK'37 based on alkenones and TEX86 based on isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs), both used for the reconstruction of sea surface temperatures (SST). These records were obtained from sinking particles collected using a sediment trap moored in the filamentous upwelling zone off Cape Blanc, Mauritania, at approximately 1300 water depth during a four-year time interval between 2003 and 2007. Mass and lipid fluxes are highest during peak upwelling periods between October and June. The alkenone and GDGT records both display pronounced seasonal variability. Sinking velocities calculated from the time lag between measured SST maxima and minima and corresponding index maxima and minima in the trap samples are higher for particles containing alkenones (14-59 m/d) than for GDGTs (9-17 m/d). It is suggested that GDGTs are predominantly exported from shallow waters by incorporation in opal-rich particles. SST estimates based on the UK'37 index faithfully record observed fluctuations in SST during the study period. Temperature estimates based on TEX86 show smaller seasonal amplitudes, which can be explained with either predominant production of GDGTs during the warm season, or a contribution of GDGTs exported from deep waters carrying GDGTs in a distribution that translates to a high TEX86 signal.