Branched Glycerol Dialkyl Glycerol Tetraethers Research Articles

Biomarker proxy records of Arctic climate change during the Mid-Pleistocene transition from Lake El'gygytgyn (Far East Russia)

Abstract. The Mid-Pleistocene Transition (MPT) is a widely recognized global climate shift occurring between approximately 1250 and 700 ka. At this time, Earth's climate underwent a major transition from dominant 40 kyr glacial–interglacial cycles to quasi-100 kyr cycles. The cause of the MPT remains a puzzling aspect of Pleistocene climate. Presently, there are few, if any, continuous MPT records from the Arctic, yet understanding the role and response of the high latitudes to the MPT is required to better evaluate the causes of this climatic shift. Here, we present new continental biomarker records of temperature and vegetation spanning 1142 to 752 ka from Lake El'gygytgyn (Far East Russia). We reconstruct warm-season temperature variations across the MPT based on branched glycerol dialkyl glycerol tetraethers (brGDGTs). The new Arctic temperature record does not display an overall cooling trend during the MPT but does exhibit strong glacial–interglacial cyclicity. Spectral analysis demonstrates persistent obliquity and precession pacing over the study interval and reveals substantial sub-orbital temperature variations at ∼900 ka during the first “skipped” interglacial. Interestingly, Marine Isotope Stage (MIS) 31, which is widely recognized as a particularly warm interglacial, does not exhibit exceptional warmth in the Lake El'gygytgyn brGDGT record. Instead, we find that MIS 29, 27, and 21 were as warm or warmer than MIS 31. In particular, MIS 21 (∼870 to 820 ka) stands out as an especially warm and long interglacial in the continental Arctic while MIS 25 is a notably cold interglacial. Throughout the MPT, Lake El'gygytgyn pollen data exhibit a long-term drying trend, with a shift to an increasingly open landscape noted after around 900 ka (Zhao et al., 2018), which is also reflected in our higher plant leaf wax (n-alkane) distributions. Although the mechanisms driving the MPT remain a matter of debate, our new climate records from the continental Arctic exhibit some similarities to changes noted around the North Pacific region. Overall, the new organic geochemical data from Lake El'gygytgyn contribute to expanding our knowledge of the high-latitude response to the MPT.

The influence of soil chemistry on branched tetraether lipids in mid- and high latitude soils: Implications for brGDGT- based paleothermometry

Branched glycerol dialkyl glycerol tetraethers (BrGDGTs) are a suite of orphan bacterial membrane lipids commonly used as paleo-environmental proxies for mean annual air temperature (MAT) and pH. Recent calibrations between the Methylation of Branched Tetraethers index (MBT′5ME) and MAT, based on modern surface soils (including peats), show a considerable amount of scatter, especially in mid- and high latitude soils, suggesting that brGDGT signals are influenced by additional environmental and/or biological controls at these sites. Here we test the impact of soil chemical gradients and bacterial community changes (16S rDNA sequence-based) on brGDGT distributions at two grasslands sites (Ossenkampen [NL], ForHot [IS]), and one agricultural site (Craibstone [UK]). In addition to the variation in soil chemistry, the ForHot site experiences belowground warming. Of the studied edaphic parameters, soil pH is the primary factor that explains simultaneous changes in both the bacterial community composition and the brGDGT distribution. Variations in the MBT′5ME at two sites without soil warming indeed correlate strongly to soil pH (r = 0.9–1.0, pH = 4.5–7.3), whereas pH explains part of the variation in the MBT′5ME at the site with soil warming (mean soil temperature ranging between 5 and 14 °C). At all sites, soil pH is positively related with the same brGDGTs (Ib, IIb, IIIb, IIIc, IIa′, IIb′, IIc′, IIIa′, IIb′, IIIc′) and influences the ratio between main brGDGT compounds Ia, IIa and IIIa, impacting the MBT′5ME values. This change in brGDGT distributions coincides with a change in the composition of the bacterial community at all sites. The bacterial clades that vary at the three experimental sites (specifically Acidobacteria subgroups 1, 2, 3, 6, 22) have previously been shown to also respond to soil pH on a global scale. As soil pH changes on geological timescales, the impact of changing pH on the MBT′5ME paleothermometer should be considered when performing paleoclimate studies.

Late Paleocene–early Eocene Arctic Ocean sea surface temperatures: reassessing biomarker paleothermometry at Lomonosov Ridge

Abstract. A series of papers published shortly after the Integrated Ocean Drilling Program Arctic Coring Expedition (ACEX, 2004) on Lomonosov Ridge indicated remarkably high early Eocene sea surface temperatures (SSTs; ca. 23 to 27 ∘C) and land air temperatures (ca. 17 to 25 ∘C) based on the distribution of isoprenoid and branched glycerol dialkyl glycerol tetraether (isoGDGT and brGDGT) lipids, respectively. Here, we revisit these results using recent analytical developments – which have led to improved temperature calibrations and the discovery of new temperature-sensitive glycerol monoalkyl glycerol tetraethers (GMGTs) – and currently available proxy constraints. The isoGDGT assemblages support temperature as the dominant variable controlling TEX86 values for most samples. However, contributions of isoGDGTs from land, which we characterize in detail, complicate TEX86 paleothermometry in the late Paleocene and part of the interval between the Paleocene–Eocene Thermal Maximum (PETM; ∼ 56 Ma) and the Eocene Thermal Maximum 2 (ETM2; ∼ 54 Ma). Background early Eocene SSTs generally exceeded 20 ∘C, with peak warmth during the PETM (∼ 26 ∘C) and ETM2 (∼ 27 ∘C). We find abundant branched GMGTs, likely dominantly marine in origin, and their distribution responds to environmental change. Further modern work is required to test to what extent temperature and other environmental factors determine their distribution. Published Arctic vegetation reconstructions indicate coldest-month mean continental air temperatures of 6–13 ∘C, which reinforces the question of whether TEX86-derived SSTs in the Paleogene Arctic are skewed towards the summer season. The exact meaning of TEX86 in the Paleogene Arctic thus remains a fundamental issue, and it is one that limits our assessment of the performance of fully coupled climate models under greenhouse conditions.

Seasonal variability and sources of in situ brGDGT production in a permanently stratified African crater lake

Abstract. Lake sediments are important archives of continental climate history, and their lipid biomarker content can be exploited to reconstruct paleoenvironmental conditions. Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids widely used in paleoclimate studies to reconstruct past temperature. However, major gaps still exist in our understanding of the environmental controls on in situ (i.e. aquatic) production in lake systems. In Lake Chala, a permanently stratified tropical crater lake in East Africa, we determined the concentrations and fractional abundances of individual brGDGTs along depth profiles of suspended particulate matter collected monthly from September 2013 to January 2015 and in settling particles collected monthly at 35 m water depth from August 2010 to January 2015 and compared these brGDGT distributions with those in surficial lake bottom sediments and catchment soils. We find that brGDGTs are primarily produced within the water column and that their concentrations and distributions vary greatly with depth and over time. Comparison with concentration–depth profiles of the monthly distribution and abundance of bacterial taxa, based on 16S rRNA gene amplicon sequencing and quantification, indicates that Acidobacteria are likely not the main producers of brGDGTs in Lake Chala. Shallowing of the oxic–anoxic boundary during seasonal episodes of strong water column stratification promoted production of specific brGDGTs in the anoxic zone. BrGDGT distributions in the water column do not consistently relate with temperature, pH, or dissolved-oxygen concentration but do respond to transitions between episodes of strong stratification and deep (but partial) lake mixing, as does the aquatic bacterial community. Hence, the general link between brGDGT distributions and temperature in brGDGT-based paleothermometry is more likely driven by a change in bacterial community composition than by membrane adaptation of specific members of the bacterial community to changing environmental conditions. Although temperature is not the principal driver of distributional changes in aquatic brGDGTs in this system, at least not during the 17-month study period, abundance-weighted and time-integrated averages of brGDGT fractional abundance in the 53-month time series of settling particles reveal systematic variability over longer timescales that indirectly relates to temperature. Thus, although we do not as yet fully understand the drivers of modern-day brGDGT fluxes and distributions in Lake Chala, our data do support the application of brGDGT paleothermometry to time-integrated archives such as sediments. Highlights. BrGDGTs in the tropical African lake Chala are produced in situ. Acidobacteria are not the dominant source of aquatic brGDGTs. Stratification and mixing drive aquatic brGDGT production and their signature.

Peatland GDGT records of Holocene climatic and biogeochemical responses to the Asian Monsoon

Branched and isoprenoidal glycerol dialkyl glycerol tetraether (GDGT) membrane lipids have been widely used to reconstruct past climate and environmental change. They are not, however, widely applied to peat deposits and the controls on their distributions in peats remain unclear. Here, we present a high resolution record of branched and isoprenoid GDGT concentrations and distributions from a peat core from the Tibetan Plateau that spans the last 13kyr, a period characterised by distinct dry and wet periods in the region. The lowest concentrations of total branched glycerol dialkyl glycerol tetraethers (brGDGTs) occurred during a presumably dry interval in the mid-Holocene, suggesting that brGDGTs-producing bacteria are less productive under such conditions, perhaps reflecting their putative anaerobic ecology. The mean annual air temperature (MAT) estimates derived from the methylation index of brGDGTs and cyclisation ratio of brGDGTs (MBT′/CBT) are higher than present mean annual temperature in the region and closer to summer temperatures, perhaps due to seasonal production of brGDGTs. The downcore distributions of isoprenoidal and branched GDGTs are dominated by GDGT-0 and brGDGT II, respectively. The high fractional abundances of GDGT-0 in warm and especially wet intervals suggest that these conditions are favourable for some groups of methanogenic archaea. The mid-Holocene dry interval is associated with an increase in the fractional and absolute abundance of crenarchaeol, which could be indicative of enhanced ammonia-oxidising archaeal-mediated nitrogen cycling under these conditions. Taken together, variations of GDGT concentrations in peats appear to document the response of microbial processes to climate change and variations in the biogeochemical environment.

Distribution, source and transportation of glycerol dialkyl glycerol tetraethers in surface sediments from the western Arctic Ocean and the northern Bering Sea

Isoprenoid and branched glycerol dialkyl glycerol tetraethers (GDGTs) and grain size distribution were investigated in surface sediments from the western Arctic Ocean including the Chukchi Sea and the adjacent northern Bering Sea to understand their source and transportation in the Arctic region and test environmental proxies derived from the GDGT composition.Coarse sediments such as sand and silty sand are distributed in the Yukon and Mackenzie River estuaries, the northern Bering Sea near Bering Strait, and some areas of the outer shelf of the Bering Sea. In the Chukchi Sea, silt, grading from sandy to clayey silt, predominates and becomes finer northward towards the deep Arctic OceanIsoprenoid GDGTs are abundant on the outer shelf and slope of the Chukchi Sea and the upper slope of the Bering Sea. The higher abundances are attributed to a combination of higher production of marine Archaea (Thaumarchaeota) at the shelf edge, redeposition of GDGT-carrying fine particles, and better preservation of GDGTs at sites with higher sedimentation rates. The TEX86- and TEX86L-derived temperatures are not consistent with sea surface temperatures in the study area, with unrealistically high TEX86- and TEX86L-derived temperatures in samples north of 73 °N probably biased by factors other than temperature.Branched GDGTs are abundant on the Chukchi shelf and in the Yukon and Mackenzie River estuaries. At the shelf edge of the Chukchi Sea, both branched and isoprenoid GDGTs are abundant, indicating common concentration processes such as sediment redeposition and efficient preservation at sites with high sedimentation rates. Sediments from the western Arctic Ocean north of 75 °N, the Yukon and Mackenzie River estuaries, and the Yukon River have higher cyclization ratio of branched tetraethers (CBT) than sediments from the Chukchi and Bering Seas, suggesting two different sources of branched GDGTs inferred as soil and marine bacteria.

Distribution of glycerol ether lipids in the oxygen minimum zone of the Eastern Tropical North Pacific Ocean

The distributions of microbial glycerol ether lipids in suspended particulate matter in the oxygen minimum zone (OMZ) of the Eastern Tropical North Pacific Ocean (ETNP) were investigated. Nine groups of glycerol ether core lipids were detected and quantified: isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs) (iso-GDGTs), isoprenoid glycerol dialkanol diethers (iso-GDDs) and hydroxylated isoprenoid GDGTs and GDDs (OH-GDGTs and OH-GDDs) of archaeal origin; branched glycerol dialkyl glycerol tetraethers (br-GDGTs) of bacterial origin and overly branched GDGTs (OB-GDGTs), sparsely branched GDGTs (SB-GDGTs), hybrid isoprenoid/branched GDGTs (IB-GDGTs) and a tentatively assigned H-shaped GDGT (H-1020) of unknown biological origin. The archaeal iso-GDGTs were the most abundant core lipids (89% of total), followed by iso-GDDs (4%), br-GDGTs (2%) and OH-GDGTs (1%). Archaeal intact polar GDGTs (IP GDGTs), including both mono- and diglycosidic iso-GDGTs, had depth profiles similar to OH-GDGTs and OH-GDDs, with a maximum concentration in the upper OMZ and secondary peaks in the mid and lower OMZ, suggesting similar but multiple planktonic sources. Core lipids of iso-GDGTs and other glycerol ethers showed deviating concentration profiles compared with IP GDGTs and OH-GDGTs and were most abundant in the mid OMZ. This is the first report of OH-GDDs, OB-GDGTs, SB-GDGTs, IB-GDGTs and H-1020 in the marine water column and the distribution patterns of these “orphan lipids” suggest that anaerobic planktonic microbes are their main source.

Glacial and Holocene terrestrial temperature variability in subtropical east Australia as inferred from branched GDGT distributions in a sediment core from Lake McKenzie

Branched glycerol dialkyl glycerol tetraether (GDGT) distributions observed in a sediment core from Lake McKenzie were utilized to quantitatively reconstruct the pattern of mean annual air temperature (MAAT) from coastal subtropical eastern Australia between 37 and 18.3calkaBP and 14.0calkaBP to present. Both the reconstructed trend and amplitude of MAAT changes from the top of the sediment core were nearly identical to a local instrumental MAAT record from Fraser Island, providing confidence that in this sediment core branched GDGTs could be used to produce a quantitative record of past MAAT. The reconstructed trend of MAAT during 37 to 18.3calkaBP and timing of the Last Glacial Maximum (LGM) in the Lake McKenzie record were in agreement with previously published nearby marine climate records. The amplitude of lower-than-present MAAT during the LGM potentially provides information on the latitude of separation of the Tasman Front from the East Australian current in the subtropical western Pacific. The Lake McKenzie record shows an earlier onset of near modern day warm temperatures in the early Holocene compared to marine records and the presence of a warmer than present day period during the mid-Holocene.

A mineralogical and organic geochemical overview of the effects of Holocene changes in Amazon River flow on three floodplain lakes

A synthesis of the impacts of the Amazon River hydrological changes on the sedimentation process of organic matter (OM) in three different floodplain lakes (Santa Ninha, Maracá, and Comprido lakes) is presented in this study. Today the Santa Ninha and Maracá lakes are directly and permanently connected with the main channel of the Amazon River, in contrast to Comprido Lake, which is indirectly and periodically influenced by the Amazon River due to its greater distance from the main channel. All three lake sediment records showed a reduced river inflow due to dry climatic conditions during the early and middle Holocene followed by an increased fluvial input during the wetter late Holocene. In Santa Ninha and Maraca Lakes, the reduced river inflow period was recorded by sediments with a low abundance of smectite (on average ~20wt.%), a clay mineral mainly transported by the fluvial system, high total organic carbon (TOC) contents (on average ~8.2wt.%), and a predominantly acidic soil OM input evidenced by high concentrations (on average 180μggTOC−1) of branched glycerol dialkyl glycerol tetraethers (GDGT). During the late Holocene, a higher smectite abundance (on average ~43 wt.%) and a lower TOC content (on average ~1.4 wt.%) pointed to greater dilution by riverine lithogenic matter. This change was accompanied by a proportional increase in the aquatically produced crenarchaeol, suggesting a higher lake water level. In Comprido Lake, a sedimentation gap occurred during the early and middle Holocene. The wetter late Holocene, since 3000calyears BP, was characterized by high TOC values (on average ~9wt.%) and a sharp increase in soil OM input as recorded by an increase in branched GDGT concentrations (on average ~81μggTOC−1), but the smectite content was low (on average ~14%). This combination suggests that the soil OM input to Comprido Lake from the local catchment area became dominant during the wet-climate late Holocene due to the large distance of the lake from the Amazon River main channel. Consequently, our study shows that the sedimentation processes of OM in Amazonian floodplain lakes were strongly influenced by variations in the hydrodynamic regime of the Amazon River during the Holocene. However, the impacts of the variations on the three floodplain lakes were different depending on the distance of each lake from the main channel of the Amazon River.

Root-associated branched tetraether source microorganisms may reduce estimated paleotemperatures in subsoil

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are complex lipids of high molecular weight, recently discovered in soils and suggested to be produced by still unknown bacteria. The relative distribution of these compounds was shown to depend on environmental parameters, mainly temperature and pH. Over the last years, an increasing number of studies have focused on the application of branched GDGTs as paleoclimate proxies, but only a few were performed in terrestrial archives. In this study, branched GDGTs were analyzed in calcified and non-calcified living and dead roots, in surrounding soil and sediment and in reference material distant from the roots. Samples were mainly collected from subsoil of two forest sites near Sopron (Hungary), where soils developed on fluvial sand and loess deposits, respectively. Branched GDGTs were more abundant in root samples and/or surrounding rhizosphere compared to reference material, suggesting that branched GDGT source microorganisms are closely associated with the root surface. In subsoil, the GDGT-based temperature estimates from former roots and surrounding sediments were mainly lower than those from reference material in both loess and sand profiles. This is likely due to the post-sedimentary incorporation of branched GDGTs deriving from microorganisms that fed on root organic matter in terrestrial sediments. In contrast, branched GDGT-derived temperatures do not seem to be influenced by the presence of roots in topsoil, which may be related to the much higher density of recent roots in topsoil than in subsoil. This argues for a more homogeneous distribution of root-associated microorganisms especially in densely rooted topsoils. In addition, we show that sample pre-treatment may have an effect on the abundance and distribution of branched GDGTs. Indeed, washing root samples with ultrapure water might lead to a decrease in GDGT abundance and an increase in temperature estimates, likely due to the removal of particles adhering to the root surface. Decarbonatization of root and surrounding sediment had only a limited effect on GDGT-derived parameters. Taken together, these results suggest that paleoenvironmental data obtained from branched GDGTs in terrestrial archives might depend on the way the samples were collected and prepared and should be interpreted with caution, especially in loess-paleosol sequences where the frequency of calcified roots can be locally very high.

Flooding impact on the distribution of microbial tetraether lipids in paddy rice soil in China

Isoprenoid and branched glycerol dialkyl glycerol tetraethers (GDGTs) lipids were studied in flooded and non-flooded paddy soil in Wuhan, central China, to examine the response of the GDGTs distribution to the soil flooding. Samples were collected before and after the soil flooding in four specific months. Both core (CL) and intact polar (IPL) GDGTs were quantified. Increase in the abundance of archaeol and caldarchaeol may be indicative of the occurrence of methanogens in the flooded soil. A negative correlation was observed between the ratio of IPL branched GDGT-IIa to GDGT-Ia and the soil pH. The rise of the soil pH in the acid soil is known to be controlled by the redox conditions resulting from flooding. Thus, the branched GDGTs distribution may be controlled by the water content in the paddy soil. In addition, we suggest that the anoxic conditions resulting from flooding may also control the abundance of branched GDGTs relative to crenarchaeol, which in turn results in the increase of branched and isoprenoidal tetraethers (BIT) values, the index for the terrestrial input to the marine sediments.

Influence of lake water pH and alkalinity on the distribution of core and intact polar branched glycerol dialkyl glycerol tetraethers (GDGTs) in lakes

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are bacterial membrane lipids, ubiquitously present in soils and peat bogs, as well as in rivers, lakes and lake sediments. Their distribution in soil is controlled mainly by pH and mean annual air temperature, but the controls on their distribution in lake sediments are less well understood. Several studies have found a relationship between the distribution of branched GDGTs in lake sediments and average lake water pH, suggesting an aquatic source for them, besides that for soil transported to the lake via erosion. We sampled the surface water suspended particulate matter (SPM) from 23 lakes in Minnesota and Iowa (USA), that vary widely in pH, alkalinity and trophic state. The SPM was analyzed for the concentration and distributions of core lipid (presumed fossil origin) and intact polar lipid (IPL, presumed to derive from living cells) branched GDGTs. The presence of substantial amounts (18–48%) of IPL-derived branched GDGTs suggests that branched GDGTs are likely of autochthonous origin. Temperature estimates based on their distribution using lake-specific calibrations agree reasonably with water temperature at time of sampling and average air temperature of the season of sampling. Importantly, a strong correlation between the distribution of branched GDGTs and lake water pH was found (r2 0.72), in agreement with a predominant in situ production. An stronger correlation was found with lake water alkalinity (r2 0.83), although the underlying mechanism that controls the relationship is not understood. Our results raise the potential for reconstructing pH/alkalinity of past lake environments, which could provide important knowledge on past developments in lake water chemistry.

Effects of a short-term experimental microclimate warming on the abundance and distribution of branched GDGTs in a French peatland

Branched glycerol dialkyl glycerol tetraethers (GDGTs) are complex lipids of high molecular weight, recently discovered in soils and increasingly used as palaeoclimate proxies. Their degree of methylation, expressed in the MBT, was shown to depend on mean annual air temperature (MAAT) and to a lesser extent on soil pH, whereas the relative abundance of cyclopentyl rings of branched GDGTs, expressed in the CBT, was related to soil pH. To date, only a few studies were interested in the application of the MBT and CBT proxies in peatlands. In order to validate the applicability of branched GDGTs as temperature proxies in these environments, it is essential to investigate the effect of temperature on branched GDGT-producing bacteria and especially on the speed of adaptation of these microorganisms to temperature changes. The aim of this work was to study the effects of in situ experimental climate warming on the abundance and distribution of branched GDGTs in a Sphagnum-dominated peatland (Jura Mountains, France). Branched GDGTs either present as core lipids (CLs; presumed of fossil origin) or derived from intact polar lipids (IPLs, markers for living cells) were analysed. Air temperature was experimentally increased using a passive warming system consisting of open mini-greenhouses (open-top chamber – OTC). The effect of the OTCs was especially apparent in spring and summer, with (i) an increase in maximal air temperature of ca. 3°C during these two seasons and (ii) an increase in average air temperature of ca. 1°C in summer. Despite the short duration of the climate experiment (26months), branched GDGT distribution was significantly affected by this temperature rise, with higher MBT values in the OTCs than in the control plots, supporting the empirical relationship between MBT and MAAT established from a large range of soils. The difference in branched GDGT-derived temperatures between control and OTC plots (2–3°C) was in the same range as the increase in maximal (daytime) temperature induced by the OTCs in spring and summer, suggesting that branched GDGT-producing bacteria might be more active during the warmest months of the year. The OTC treatment had no significant effect on the abundance of branched GDGTs, which were mainly present as “fossil” CLs (70–85% of the total branched GDGT pool). Furthermore, no significant differences in branched GDGT distribution were observed between the CLs and IPLs, which both provided higher MBT and MAAT values for the OTCs. This suggests that the fossil pool of branched GDGTs has a very fast turnover (less than the 2year duration of the experiment) at the peat surface and that branched GDGT distribution may rapidly reflect changes in environmental conditions (at least air temperature) occurring in peat environments.

Distribution of tetraether lipids in the 25-ka sedimentary record of Lake Challa: extracting reliable TEX86 and MBT/CBT palaeotemperatures from an equatorial African lake

The distribution of isoprenoid and branched glycerol dialkyl glycerol tetraether (GDGT) lipids was studied in the sedimentary record of Lake Challa, a permanently stratified, partly anoxic crater lake on the southeastern slope of Mt. Kilimanjaro (Kenya/Tanzania), to examine if the GDGTs could be used to reconstruct past variation in regional temperature. The study material comprised 230 samples from a continuous sediment sequence spanning the last 25 ka with excellent age control based on high-resolution AMS 14C dating. The distribution of GDGTs showed large variation through time. In some time intervals (i.e., from 20.4 to 15.9 ka BP and during the Younger Dryas, 12.9–11.7 ka BP) crenarchaeol was the most abundant GDGT, whereas at other times (i.e., during the Early Holocene) branched GDGTs and GDGT-0 were the major GDGT constituents. In some intervals of the sequence the relative abundance of GDGT-0 and GDGT-2 was too high to be derived exclusively from lacustrine Thaumarchaeota, suggesting a sizable contribution from methanogens and other archaea. This severely complicated application of TEX86 palaeothermometry in this lake, and limited reliable reconstruction of lake water temperature to the time interval 25–13 ka BP, i.e. the Last Glacial Maximum and the period of post-glacial warming. The TEX86-inferred timing of this warming is similar to that recorded previously in two of the large African rift lakes, while its magnitude is slightly or much higher than that recorded at these other sites, depending on which lake-based TEX86 calibration is used. Application of calibration models based on distributions of branched GDGTs developed for lakes inferred temperatures of 15–18 °C for the Last Glacial Maximum and 19–22 °C for the Holocene. However, the MBT/CBT palaeothermometer reconstructs temperatures as low as 12 °C for a Lateglacial period centred on 15 ka BP. Variation in down-core values of the BIT index are mainly determined by the varying production rate of crenarchaeol relative to in-situ produced branched GDGTs. The apparent relationship of the BIT index with climatic moisture balance can be explained either by the direct influence of lake level and wind strength on nutrient recycling, or by influx of soil nutrients promoting aquatic productivity and nitrification. This study shows that GDGTs can aid in obtaining climatic information from lake records but that the obtained data should be interpreted with care.

Multi-proxy reconstruction of terrigenous input and sea-surface temperatures in the eastern Gulf of Guinea over the last ~ 35 ka

The tight coupling between the atmospheric and oceanic circulation in the equatorial Atlantic region makes this area an important region for paleoclimatic research. Previous studies report the occurrence of large amounts of terrigenous material and soil organic carbon (SOC) within the marine sediments of the eastern Gulf of Guinea. We use the accumulation rates (AR) of branched glycerol dialkyl glycerol tetraethers (GDGTs) to identify variations in SOC delivery to the Niger Fan over the last 35ka, and compare these records to long-chain n-alkanes as a proxy for higher plant material, to an inorganic proxy for terrigenous input (aluminum AR) and to indicators for the marine productivity (AR of carbonate and crenarchaeol). In addition, sea surface temperatures (SSTs) are calculated based on the TEX86H index and environmental factors affecting the SST-reconstructions are discussed.Our results indicate that Al AR are closely connected to the rate of mean sea level change after 15kaBP, with an additional influence of the increased monsoonal precipitation and extended vegetation cover corresponding to the African Humid Period (14.8–5.5kaBP). Branched GDGT AR appears to be determined by shelf erosion in addition to the interplay of monsoonal precipitation and vegetation cover controlling soil erosion. Long-chain n-alkane concentrations clearly show a different trend than the other proxies, which might be due to their predominant eolian transport.Paleo-SSTs show a clear shift from colder temperatures during the last glacial period (20–22°C) to warmer temperatures during the Holocene (24–26°C). However, TEX86H-based SSTs are cold-biased compared to recent SSTs and Mg/Ca-based SST reconstructions, which is probably caused by a high seasonality of the Thaumarchaeota, with a maximum productivity of these organisms during the cold summer months. However, a sub-surface production of GDGTs and/or a potential bias of SST reconstruction by terrestrial input could not be completely excluded.

Tracing soil organic carbon in the lower Amazon River and its tributaries using GDGT distributions and bulk organic matter properties

In order to trace the transport of soil organic carbon (OC) in the lower Amazon basin, we investigated the distributions of crenarchaeol and branched glycerol dialkyl glycerol tetraethers (GDGTs) by analyzing riverbed sediments and river suspended particulate matter (SPM) collected in the Solimões-Amazon River mainstem and its tributaries. The Branched and Isoprenoid Tetraether (BIT) index, a proxy for river-transported soil OC into the ocean, was determined from the distributions of these GDGTs. The GDGT-derived parameters were compared with other bulk geochemical data (i.e. C:N ratio and stable carbon isotopic composition). The GDGT-derived and bulk geochemical data indicate that riverine SPM and riverbed sediments in the lower Amazon River and its tributaries are a mixture of C3 plant-derived soil OC and aquatic-derived OC. The branched GDGTs in the SPM and riverbed sediments did not predominantly originate from the high Andes soils (>2500m in altitude) as was suggested previously. However, further constraint on the soil source area of branched GDGTs was hampered due to the deficiency of soil data from the lower montane forest areas in the Andes. Our study also revealed seasonal and interannual variation in GDGT composition as well as soil OC discharge, which was closely related to the hydrological cycle. By way of a simple binary mixing model using the flux-weighted BIT values at Óbidos, the last gauging station in the Amazon River, we estimated that 70–80% of the POC pool in the river was derived of soil OC. However, care should be taken to use the BIT index since it showed a non-conservative behaviour along the river continuum due to the aquatic production of crenarchaeol. Further investigation using a continuous sampling strategy following the full hydrological cycle is required to fully understand how soil-derived GDGT signals are transformed in large tropical river systems through their transport pathway to the ocean.

Branched tetraether membrane lipids associated with rhizoliths in loess: Rhizomicrobial overprinting of initial biomarker record

Loess–palaeosol sequences are considered important terrestrial archives for studying Quaternary climate. Recent studies have shown that calcified roots (rhizoliths) can be significantly younger than surrounding terrestrial sediment (loess) and that loess organic matter may be contaminated with root-derived carbon from post-sedimentary deep rooting plants. Branched glycerol dialkyl glycerol tetraethers (GDGTs) are membrane lipids produced by unknown bacteria in soil and are increasingly being used as palaeoclimate proxies. The aim of this work was to examine the impact of the temporal decoupling between rhizoliths and loess on the abundance and composition of branched GDGTs, and consequently on the application of branched GDGTs as proxies in loess deposits. Branched GDGTs in rhizoliths and the surrounding sediment from a loess–palaeosol sequence in Nussloch (SW Germany) were examined. Their composition varied between the rhizolith and loess, which may reflect the fact that branched GDGTs were biosynthesized at different times (late Pleistocene for loess and Holocene for rhizoliths) and therefore under different environmental conditions. A large difference (ca. 7 °C) in branched GDGT-reconstructed palaeotemperature was observed between rhizoliths and loess. In addition, the reconstructed temperatures were the opposite from those expected from the assumed depositional ages of branched GDGTs. This might be explained by the post-sedimentary input of root-associated, microorganism-derived branched GDGTs to loess, which might have led to an overprint of the initial branched GDGT signal in the sediment. Our results suggest that post-sedimentary penetration of deep-rooting plants in loess might entail uncertainty regarding the application of branched GDGT palaeoproxies and that caution should be exercised in interpreting temperature estimates derived from branched GDGTs in loess–palaeosol sequences. This is of special importance for loess, where rhizoliths are abundant, and where non-calcified root remains of different age from that of the sediment are possible. In addition, the GDGT concentration in rhizoliths and surrounding loess supports the hypothesis of a heterotrophic lifestyle for branched GDGT-producing bacteria.

Constraints in the application of the Branched and Isoprenoid Tetraether index as a terrestrial input proxy

[1] Determination of the relative inputs of aquatic autochthonous and terrestrial allochthonous organic matter into marine and lacustrine environments is essential to understanding the global carbon budget. A variety of proxies are used for this purpose, including the Branched and Isoprenoid Tetraether (BIT) index. This is calculated from the concentrations of branched glycerol dialkyl glycerol tetraethers (GDGTs), derived from unidentified terrestrial bacteria, and crenarchaeol, a marker for aquatic mesophile Thaumarchaeota (Crenarchaeota group I). As the index is a ratio, its value depends on both the crenarchaeol aquatic in situ production and the soil-derived branched GDGT input. Therefore, the BIT index reflects not only changes in the input of terrestrial or soil organic matter but also relative variations in aquatic Thaumarchaeota abundance in the water column. In fact, we show that in oceanic and lacustrine settings, the BIT index can be dominated by the aquatic end-member of the ratio. Consequently, the BIT index by itself can be an unreliable proxy to compare the input of terrestrial matter between sites and over time, and we propose that the quantification of branched GDGT fluxes or concentrations may instead be a better indicator of soil terrestrial inputs.

Distributions of branched GDGTs in soils and lake sediments from western Uganda: Implications for a lacustrine paleothermometer

Bacterially produced branched glycerol dialkyl glycerol tetraethers (GDGTs) are ubiquitous in soils and lake sediments and can potentially be used to reconstruct past temperatures. In lakes, however, it is still unclear if these compounds are derived from eroded soils or if they are produced in situ. To better understand environmental controls on the distributions of these compounds and the sources of branched GDGTs to lake sediments, we compare branched GDGT distributions and concentrations in lake sediments and catchment soils within a 3600m altitudinal transect in western Uganda. Reconstructed mean annual air temperature (MAAT), determined from the degree of methylation (MBT) and cyclisation (CBT) of branched GDGTs in soils, decreases with increasing altitude, as is expected from the air temperature gradient in our transect. However, we observe significant offsets between observed and reconstructed temperatures in soils from wet, high elevation soils but not in most dry, low elevation soils. Branched GDGT distributions differ significantly between lake sediments and soils at all elevations, with greater differences at low elevations than at high elevations. These data support previous hypotheses that branched GDGTs are produced in situ in lakes and suggest that the abundance of water in soil environments may play a role in controlling the distribution of branched GDGTs. While branched GDGTs in lacustrine sediments can be used to reconstruct temporal temperature variations in lakes, we urge caution in utilizing this proxy in lacustrine systems with high soil loadings, especially if there is evidence of changing clastic fluxes through time.

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.