Source Of brGDGTs Research Articles

Environmental controls on the distribution of brGDGTs and brGMGTs across the Seine River basin (NW France): implications for bacterial tetraethers as a proxy for riverine runoff

Abstract. Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial lipids that have been widely used as environmental proxies in continental paleorecords. Another group of related lipids, branched glycerol monoalkyl glycerol tetraethers (brGMGTs), has recently been proposed as a potential paleotemperature proxy. Nevertheless, the sources and environmental dependencies of both brGDGTs and brGMGTs along the river–sea continuum are still poorly understood, complicating their application as paleoenvironmental proxies in some aquatic settings. In this study, the sources of brGDGTs and brGMGTs and the potential factors controlling their distributions are explored across the Seine River basin (NW France), which encompasses the freshwater-to-seawater continuum. BrGDGTs and brGMGTs were analyzed in soils, suspended particulate matter (SPM), and sediments (n=237) collected along the land–sea continuum of the Seine basin. Both types of compounds (i.e., brGDGTs and brGMGTs) are shown to be produced in situ, in freshwater and saltwater, based on their high concentrations and distinct distributions in aquatic settings (SPM and sediments) vs. soils. Redundancy analysis further shows that both salinity and nitrogen dominantly control the brGDGT distributions. Furthermore, the relative abundance of 6-methyl vs. that of 5-methyl brGDGTs (the IR6Me ratio), the total nitrogen (TN), the δ15N, and the chlorophyll a concentration co-vary in a specific geographical zone with low salinity, suggesting that 6-methyl brGDGTs are preferentially produced under low-salinity and high-productivity conditions. In contrast to brGDGTs, the brGMGT distribution appears to be primarily regulated by salinity, with a distinct influence on the individual homologues. Salinity is positively correlated with homologues H1020a and H1020b and negatively correlated with compounds H1020c and H1034b in SPM. This suggests that bacteria living in freshwater preferentially produce compounds H1020c and H1034b, whereas bacteria that primarily grow in saltwater appear to be predominantly responsible for the production of homologues H1020a and H1020b. Based on the abundance ratio of the freshwater-derived compounds (H1020c and H1034b) vs. their saltwater-derived homologues (H1020a and H1020b), a novel proxy, the Riverine IndeX (RIX), is proposed to trace riverine organic matter inputs, with high values (>0.5) indicating a higher riverine contribution. We successfully applied RIX to the Godavari River basin (India) and a paleorecord across the upper Paleocene and lower Eocene from the Arctic Coring Expedition at Lomonosov Ridge, showing its potential applicability to both modern samples and paleorecords.

Distribution of branched glycerol dialkyl glycerol tetraether (brGDGT) lipids from soils and sediments from the same watershed are distinct regionally (central Chile) but not globally

Quantitative reconstructions of past continental climates are vital for understanding contemporary and past climate change. Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are unique bacterial lipids that have been proposed as universal paleothermometers due to their correlation with temperature in modern settings. Thus, brGDGTs may serve as a crucial paleotemperature proxy for understanding past climate variations and improving regional climate projections, especially in critical but under constrained regions. That said, complications can arise in their application due to varying source contributions (e.g., soils vs. peats vs. lacustrine). As such, this study investigates brGDGT distributions in Chilean lake surface sediments and corresponding watershed soils to determine the source of brGDGTs to lake sediments. Global datasets of brGDGTs in lake sediments and soils were additionally compiled for comparison. Distinct brGDGT distributions in Chilean lakes and soils indicate minimal bias from soil inputs to the lacustrine sediments as well as in situ lacustrine production of brGDGTs, which supports the use of brGDGTs in lake sediments as reliable paleotemperature proxies in the region. The ΣIIIa/ΣIIa ratio, initially promising as a brGDGT source indicator in marine settings, shows global complexities in lacustrine settings, challenging the establishment of universal thresholds for source apportionment. That said, we show that the ratio can be successfully applied in Chilean lake surface sediments. Direct comparisons with watershed soils and further research are crucial for discerning brGDGT sources in lake sediments and improving paleotemperature reconstructions on regional and global scales moving forward. Overall, this study contributes valuable insights into brGDGT variability, essential for accurate paleoreconstructions.

Potential influence of bacterial community structure on the distribution of brGDGTs in surface sediments from Yangtze River Estuary to East China Sea

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are special components of bacterial membrane lipids and are ubiquitously found in diverse terrestrial and marine environments. Acidobacteria have been recently evidenced as one of their source microorganisms in terrigenous environments, such as acidic soils and peats. However, the biological sources of brGDGTs, their distributions and ecophysiological responses, and these biotic impacts on the relationships between brGDGT-based proxies and environmental variables (e.g., ambient temperature, pH, and dissolved oxygen content) in the marine realm are poorly understood. In this study, we analyzed C5- and C6-methylated brGDGTs as well as bacterial communities in the surface sediment samples from the Yangtze River Estuary (YRE) to the East China Sea (ECS), aiming to explore the relationship between brGDGT distribution and bacterial composition and to examine how benthic conditions and bacterial communities jointly influence the spatial patterns of brGDGTs from marine sediments. Substantial differences in the spatial distribution of brGDGTs from coast to shelf were observed. The increase in the proportion of brGDGTs with cyclopentyl and C6-methyl moieties (e.g., Ic and IIc’) and #ringstetra values of >0.7 indicate the occurrence of marine-sourced brGDGTs in the shelf. Statistical analyses suggest that the bacterial community structure and the geochemical and environmental variables may contribute 43.56% and 29.97% to the brGDGT distribution, respectively. Multiple significant correlations between bacterial groups at the order level and brGDGT compounds suggest that bacteria such as Gemmatimonadetes, Planctomycetes and Proteobacteria may potentially contribute to the brGDGT production in marine environments. With the consideration of benthic environmental changes, the shift in bacterial community structure could further result in the variations of brGDGT-based proxies incorporating cyclopentyl and C6-methyl moieties that are likely to be produced by benthic marine bacteria. Overall, in addition to environmental conditions of the ocean bottom, the potential influence of bacterial community structure on the distribution of brGDGTs highlights the caution of using brGDGT-based proxies as terrestrial indicators in coastal oceans.

Bacterial glycerol tetraethers as a potential tool to trace marine methane cycling

AbstractBranched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial lipids that can be preserved in sedimentary archives for tens of millions of years and are ubiquitous in diverse environments, including cold seep systems. Their potential implications for detecting methane activity in deep time are, however, hampered by the multiple sources of brGDGTs in cold seeps and the lack of evidence of their stable carbon isotopes. Here, we show that brGDGTs in cold seeps are characterized by depleted stable carbon isotopic compositions of the alkyl moieties (δ13C = −32.9‰ to −82.7‰), indicating a methane metabolizing community origin, which is supported by the association between 16S rRNA genes and brGDGTs. We further identify unique seep‐derived brGDGT signals from the global published dataset by a tree‐based machine‐learning algorithm. This trained model, named light gradient‐boosting machine classification for paleoSEEP (GBM_SEEP), is further applied on a paleorecord across the Paleocene–Eocene Thermal Maximum (PETM), which suggests potential methane emission events during the PETM recovery phase. Collectively, our study links brGDGT production in cold seeps with methane metabolizing communities and provides a potential strategy to capture significant methane emission events using the machine‐learning model, which warrants further investigation.

Enhanced production of highly methylated brGDGTs linked to anaerobic bacteria from sediments of the Mariana Trench

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids that are widely used in terrestrial paleoclimatic reconstructions. Recent studies have reported that brGDGTs can also be produced by marine bacteria. However, the environmental factors influencing marine-derived brGDGTs and their source organisms remain largely unknown. Here, we investigated the distribution and composition of brGDGTs and a suite of their putative derivatives called overly branched GDGTs (obGDGTs) in the Mariana Trench core sediments (water depth 8300 m, core length 320 cm), as well as the composition of bacterial communities. The ratio of the branched over isoprenoid tetraethers (BIT) was 0.03-0.21 (average 0.07; SD = 0.04; n = 21) and the ratio ΣIIIa/ΣIIa of brGDGTs was 0.93-7.47 (average 3.39; SD = 1.73; n = 21), which support the in situ production of brGDGTs. Co-occurrence network analysis revealed that a total of 33 types of bacteria at the order level (e.g., Armatimonadota DG-56, Proteobacteria Rhodospirillales, Chloroflexi SAR202_clade) were closely related to the distribution of brGDGTs and obGDGTs, which could be potential sources for these compounds. The abrupt increase in brGDGT and obGDGT concentrations in deeper oxygen-depleted sediments and their good correlations with anaerobic bacterial abundances suggest that these brGDGTs and obGDGTs may be produced by anaerobic bacteria residing in the anoxic sediments. Considerable variation in the degrees of methylation and cyclization of brGDGTs (obGDGTs) under different redox conditions indicate that sediment oxygen levels may have a profound impact on the presence and abundance of brGDGTs and obGDGTs, which should be considered when applying them for paleo-temperature or pH reconstructions. This study shows that brGDGTs and obGDGTs obtained from the Mariana Trench were probably produced by a variety of bacterial phyla indigenous in the hadal ocean, which are different from Acidobacteria commonly considered to be major terrestrial sources of brGDGTs.

Biomarker-based quantitative constraints on maximal soil-derived brGDGTs in modern lake sediments

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are emerging as a powerful tool for quantifying past terrestrial temperature variations. In lake sediments, mixed lacustrine vs. soil sources of brGDGTs pose a challenge to quantitative application of this paleothermometer, and this effect has not yet been well-constrained. In this work, we analyzed concentrations and distributions of brGDGTs along with two other types of typical lipid biomarkers (isoGDGTs and long-chain n-alkanes) in modern sediments and catchment soils from 26 park lakes across a large climatic gradient in China. BrGDGTs in these lakes may largely represent the lacustrine signal due to the relatively small catchment area and high eutrophic condition. This is confirmed by the combined use of crenarchaeol, its isomer crenarchaeol′, and C33n-alkane as tracers of soil input for brGDGTs. This novel method quantifies the upper limit of soil brGDGT contribution to be less than 10% for most investigated lakes, with an average value of 7% ± 10%. Subsequently, the brGDGT signal of the assumed pure lacustrine origin was constrained by the subtle difference between the original sedimentary brGDGTs and those corrected by the maximum possible soil brGDGT input for those park lakes. A compilation of global freshwater lakes further shows that the correlation between the methylation index of brGDGTs (MBT or MBT′5ME) of their sediments and temperature matches that for the assumed pure lacustrine signals. Hence, soil contribution might be generally minor and may not significantly impact the quantitative application of the brGDGT paleothermometer for worldwide lakes. This study reinforces a foundation for this novel lacustrine paleothermometer to be applied in paleoclimate reconstructions, although factors affecting lacustrine brGDGT distributions within lakes still need to be better constrained.

Intact Polar brGDGTs in Arctic Lake Catchments: Implications for Lipid Sources and Paleoclimate Applications

AbstractPaleotemperature histories derived from lake sediment archives provide valuable context for modern and future climate changes. Branched glycerol dialkyl glycerol tetraether (brGDGT) lipids are a valuable tool in such pursuits due to their empirical correlation with temperature and near ubiquity in nature. However, the relative contributions of terrestrial and lacustrine sources of brGDGTs to lake sediments is site‐dependent and difficult to constrain. Here, we explored the potential for intact brGDGTs—the complete lipids with polar head groups (HGs) still attached—to provide insight into the sources of brGDGTs on the landscape and their contributions to the sedimentary record in a set of Arctic lakes. We measured core and intact brGDGTs in soils, surface and downcore sediments, water filtrates, and sediment traps across five lake catchments in the Eastern Canadian Arctic, with an emphasis on Lake Qaupat (QPT), Baffin Island. Soils were dominated by brGDGTs with a monoglycosyl (1G) HG, while lacustrine samples contained more phosphohexose (PH) brGDGTs, providing evidence for in situ brGDGT production in both settings. Core‐ and PH‐brGDGT‐IIIa were more abundant in sediments than in the soils or water column, implying an additional post‐depositional source of brGDGTs. A hierarchical clustering analysis indicated that core brGDGTs in Lake QPT sediments were largely lacustrine in origin, while 1G‐brGDGTs were primarily soil‐derived. Additionally, we found evidence for preservation of intact brGDGTs—especially 1G‐brGDGTs—downcore on thousand‐year timespans, though in situ production deeper in the sediment column cannot be ruled out. Finally, we explored the possibility of reconstructing 1G‐brGDGT‐derived soil temperatures and core‐brGDGT‐derived lake temperatures in tandem from sedimentary archives.

Branched glycerol dialkyl glycerol tetraethers as indicators for environmental parameters in a subtropical mountainous river, southern China

Indices based on branched glycerol dialkyl glycerol tetraethers (brGDGTs) have been useful in paleo-environmental reconstructions, although their applicability in river-estuarine sediments remains unclear. This study aims to investigate the correlation between brGDGT-based indices and modern environmental parameters, and to discuss possible impact factors. In this study, we discussed the applicability of several brGDGT-based indices, with specific interests on the IRx’ (the relative abundance of 6- vs. 5-methylated brGDGTs) and CBT’ (cyclization index of branched tetraethers based on the separation of 5- and 6-methylated brGDGTs) for pH reconstruction, and MBT’5ME (the methylation index of branched tetraethers based on the separation of 5- and 6-methylated brGDGTs) for MAAT (mean annual air temperature) reconstruction. From the Jiulong River (JLR) catchment, we have analyzed both riverbank soil samples and riverbed surface sediment samples for brGDGTs, with the following main findings: Firstly, for pH reconstruction, the indices CBT’ and IRx’ are useful in soil and fluvial sedimentary settings. Secondly, for MAAT reconstruction, the MBT’5ME index is sensitive to the air temperature, and the BayMBT0 model performs relatively better than other global or regional calibrations in the study area; By employing the BayMBT0 model, MAAT reconstructed from soils are higher than the measured MAAT, but are generally lower than the measured MAAT when reconstructed from riverbed surface sediments. Thirdly, the disagreement between the reconstructed results from the two sedimentary archives suggests that: Signatures of brGDGTs in the aquatic environment are under strong impacts of in situ produced brGDGTs; Impacts of upper-reach brGDGTs input might have resulted in the increasingly negative offset for the reconstructed MAAT downstream; And influences of complex aquatic biogeochemical conditions on sedimentary brGDGT signals are site-dependent in this area. Finally, brGDGT-based indices are sensitive to the source of brGDGTs, e.g., soil vs aquatic in situ brGDGTs; And terrigenous brGDGTs have been exposed to a range of complex biogeochemical processes before their deposition in the estuary. Based on these findings, we suggest that at least the above impact factors need to be taken into consideration when interpreting the brGDGT signals from estuarine archives, and thus, multi-proxy studies are encouraged. The findings of this study provide a better understanding of the correlation between brGDGT-based indices and modern environmental parameters in subtropical river systems, and provide useful information for interpreting the paleo-environmental signals based on brGDGTs from fluvial-estuarine archives.

Source Identification of brGDGTs in the Surface Sediments of the East China Sea

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are components of bacterial membranes in terrestrial soils, which are widely used in paleoenvironmental reconstruction in global terrestrial soils and marine sediments. In marine sediments, the mixed sources of brGDGTs complicate the applications of brGDGT-related indicators in reconstructing terrestrial environments. In this study, we reported the spatial distribution of brGDGT-related indicators (MBTʹ 5ME, CBTʹ 5ME, #Ringstetra, and IIIa/IIa) in surface sediments from the East China Sea (ECS). MBTʹ 5ME and CBTʹ 5ME showed a stepped trend from the inner shelf to the outer shelf, and #Ringstetra and ∑IIIa/∑IIa values in sediments of the ECS are distinct compared with those in the catchment soils, suggesting marine in situ production of brGDGTs. We also examined the existence of marine in situ brGDGTs and quantitatively determined the contributions of terrestrial and in situ production of brGDGTs. This study reported mixed sources of soil-derived brGDGTs were dominant, and marine in situ brGDGTs were overprinted. Our results indicate that there were predominantly marine in situ brGDGTs (avg. 60.5 ± 5.5%) in the outer shelf due to the weak riverine transportation and were characterized by high #Ringstetra and IIIa/IIa.

Identifying marine and freshwater overprints on soil-derived branched GDGT temperature signals in Pliocene Mississippi and Amazon River fan sediments

The fractional abundance of branched glycerol dialkyl glycerol tetraether (brGDGT) membrane lipids in coastal marine sediments has been posited as a proxy for the reconstruction of terrestrial temperatures on the nearby land, based on the assumption that they are produced in soils and delivered to the marine realm by rivers following erosion. Here, we test the suitability of brGDGTs as a continental paleothermometer in Pliocene age sediments from the northern Gulf of Mexico (GoM; speculated Mississippi River input) and the Ceará Rise (speculated Amazon River input). Low branched to isoprenoid tetraether (BIT) index values of 0.00–0.13 and the near absence of pollen and long-chain plant waxes in the GoM sediments suggest that the Mississippi River did not have a strong influence on the delivery of terrestrial organic matter to the site during the Pliocene and soil input was limited. Indeed, the high weighted average of cyclopentane-containing tetramethylated brGDGTs (#ringstetra) in the GoM sediments (0.50 ± 0.09) relative to that of modern soils from the Mississippi catchment (0.25 ± 0.16) indicates that the brGDGTs in the GoM sediments were mostly produced in situ in the marine realm, hampering reliable land temperature reconstruction using the global soil transfer function. In contrast, high BIT index values (0.46 ± 0.21) and low #ringstetra (0.25 ± 0.15) in sediments from the Ceará Rise suggest that these brGDGTs are primarily derived from soils. However, reconstructed temperatures were 11–18 °C lower than modern Amazon catchment temperatures. The relative abundance of 6-methylated brGDGTs (Isomerisation Ratio; IR) in the sediments is 0.82 ± 0.10, which resembles that of suspended particulate matter (SPM) in the modern Amazon River more than that of catchment soils (IR = 0.18 ± 0.18). This reveals that brGDGTs in the Ceará Rise sediments likely have a freshwater, riverine origin. Thus, the majority of the brGDGTs in both the GoM and Ceará Rise sediments are produced in situ, in the marine or river realms, which precludes application of the brGDGT paleothermometer. Our study shows that the sources of brGDGTs in coastal marine sediment archives must be critically evaluated prior to using the proxy for paleoclimate reconstruction.

Different temperature dependence of marine-derived brGDGT isomers in a sediment core from the Chukchi Sea shelf

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are thought to be produced by as yet unknown bacteria on land, and their distribution in soils, peats, and lake sediments has been shown to correlate with mean annual air temperature (MAAT). Recently, an increasing number of studies have shown that in situ production of brGDGT in marine environments is likely. However, the influence of environmental factors on marine-derived brGDGT distributions is still unknown. In this study, we assessed the sources of brGDGTs preserved in a sediment core from the Chukchi Sea shelf using multiple brGDGT-based indices, including the branched and isoprenoid tetraethers (BIT) index, the ratio of IIIa/IIa, cyclization degree of branched tetraethers (CBT), and #rings indices, and discuss the influence of seawater temperature changes over the last 70 years on the distribution of brGDGT isomers. The low BIT and CBT values, high IIIa/IIa ratios, and significant correlations between different #rings indices suggest that these brGDGTs primarily have a marine source. With increasing sea surface temperatures (SSTs), the fractional abundances of 5-Me IIIa (IIIa5) showed an increased trend, while there was no obvious trend in 6-methyl IIIa (IIIa6). This finding indicates different behaviors of 5-Me and 6-Me isomers in marine-derived brGDGTs, similar to what has been observed in soils, peats and lakes. In addition, we found a significant correlation between IIIa5 and IIIa7 (a novel isomer of IIIa), indicating that they might share the same bacterial source and/or are controlled by the same environmental factors (e.g., temperature). Finally, the fractional abundances of IIIa5 and IIIa7 are significantly correlated with SST (r2 = 0.64 and 0.49, respectively), which suggests that marine-derived brGDGTs have the potential to reconstruct seawater temperature.

Sedimentary core brGDGTs in the East China Sea are mainly produced in situ as evidenced by their similar distributions with brGDGTs derived from intact polar lipids

The provenance of brGDGTs in marine sediments was initially thought to be from terrestrial soils, and hence brGDGTs-based proxies have been used for reconstructing terrestrial environments. However, this notion has been challenged by the finding that the distribution of brGDGTs in marine sediments can differ from global surface soils. To constrain the sources of brGDGTs in marine sediments in the East China Sea (ECS), we analyzed brGDGTs occurring as both ‘fossil’ core and in ‘living’ intact polar lipids (core brGDGTs and IPL-derived brGDGTs, respectively). The results showed that the distribution of core brGDGTs was similar to IPL-derived brGDGTs but differed clearly from those in the global soils database. In addition, for both IPL-derived and core brGDGTs, the methylation index, MBT′5ME, decreased with increasing latitude, likely caused by northward decreases of bottom water temperature. The degree of cyclization of tetra-methylated brGDGTs, #Ringstetra, increased with water depth, with highest values >0.7, likely reflecting an increase in seawater pH. Our results indicate that core brGDGTs may be predominantly produced in situ and that the soil contribution is minimal in this setting. Nonetheless, differences in MBT′5ME and #Ringstetra between IPL-derived and core brGDGTs exist, showing increasing offsets offshore. These offsets could be due to decreased sedimentation rates and hence increased age differences between IPL-derived and core brGDGTs offshore, which likely reflects changes in temperature and pH of seawater, most likely the bottom waters, during the past decades.

Branched GDGTs as Proxies in Surface Sediments From the South-Eastern Brazilian Continental Margin

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids produced by bacteria usually ascribed to soil and peat deposits. The presence of brGDGTs in marine sediments can thus be used to track terrigenous organic matter inputs to the continental margin and to infer the local continental mean annual air temperature (MAT) and soil pH. The proxy rationale is based on the degree methylation and cyclization of the brGDGTs from terrestrial bacteria, but recently evidence was found of river and oceanic production of brGDGTs with similar configuration, indicating the necessity to better constrain the applicability of the soil brGDGTs in the marine realm. Here we considered crenarchaeol and brGDGTs obtained in 46 core-top sediments from cross-margin transects in the Campos Basin in the Southwest Atlantic, with the goal to evaluate the effectiveness of the brGDGT-associated proxies in a region in the southeastern tropical Brazilian continental margin influenced by upwelling events and low terrigenous inputs. The separation of the 5- and 6-methyl brGDGTs proved to be essential for a better evaluation of the sources of brGDGTs in the environment. Direct evidence of input of terrigenous organic matter by the medium-sized Paraiba do Sul River and other small rivers in the region were observed. More importantly, the high proportions of ring-containing brGDGTs – and the consequent increased values of the #ringstetra – in the sediments deposited between 75 and 400 m water depths (mid-shelf to upper slope) were clear evidence of marine in situ production of brGDGTs. In some stations deeper than 1900 m, an increase in the acyclic 6-methyl hexamethylated compounds can also be ascribed to in situ production. Our results revealed that the initial soil signal is lost during transport and after river discharge in the Campos Basin, which compromise the use of brGDGTs to reconstruct the soil pH and MAT of the nearby land area.

Holocene mean annual air temperature (MAAT) reconstruction based on branched glycerol dialkyl glycerol tetraethers from Lake Ximenglongtan, southwestern China

Here we investigate the sources of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in Lake Ximenglongtan from southwestern China and present a brGDGTs-based Holocene (∼9.4 cal kyr BP) temperature reconstruction. The similarities in the distributions of brGDGTs between surface sediments and catchment soils indicate that soil is the dominant source of brGDGTs. This contrasts with the recent emphasis on lacustrine GDGTs in other regional studies. Holocene temperature evolution is characterized by an early cool phase (with a mean annual air temperature (MAAT) of 12.5 °C) prior to 7.6 cal kyr BP, followed by a rapid warming towards the local thermal maximum (MAAT = 13.8 °C) from 7.6 to 5.5 cal kyr BP and a subsequent long-term cooling that ended at 1.5 cal kyr BP. Temperature changes after 1.5 cal kyr BP show high variability and low correspondence to global climate events such as the Medieval Warm Period. Overall Holocene temperature variation has been primarily controlled by boreal summer insolation changes. The larger amplitude (1.5–4.0 °C) in annual cooling during the early Holocene in MAAT contrasts with summer temperature records from this region (range of cooling 0.3–1.0 °C) and indicates the likely influence of lower winter temperature on MAAT variation. We suggest that substantial remnants of the Northern Hemisphere ice-sheets during the early Holocene enhanced the winter westerlies and East Asian winter monsoon (EAWM), and decreased the winter temperature in southwestern China, leading to a cold early Holocene climate.

Different temperature dependence of the bacterial brGDGT isomers in 35 Chinese lake sediments compared to that in soils

During the last decade, the distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in lacustrine sediments has been widely used to reconstruct past variations in lake temperature. A prerequisite for the application of brGDGTs to lacustrine paleoclimate reconstructions is to understand the sources of brGDGTs in lake systems and the processes that influence their distribution. In this study, we investigated the distribution of brGDGTs in core-top sediments from 35 lakes across China, with a broad mean annual air temperature (MAAT) range, but a constrained pH range, to explore the effect of temperature. The results reveal a contrasting response of MBT′5ME and MBT′6ME to temperature in lake environments compared to that in soils. The sedimentary distributions of 5- and 6-methyl brGDGTs exhibit different relationships with temperature, with most of the latter being correlated to MAAT while the former responding to temperature by only hexamethylated compounds. In both global and Chinese soils, most 6-methyl brGDGTs have no relationship with MAAT, but the distribution of 5-methyl brGDGTs is correlated with MAAT. The different behaviors suggest that communities producing 5- or 6-methyl brGDGTs might be different in lakes and soils. In addition, in lakes from cold regions (MAAT < 5 °C), the brGDGT distributions correlate only with warm season temperatures (April to October) but exhibit no correlation with cold seasons, suggesting a seasonal bias in brGDGT production in these lakes. This bias towards the warm season is not found in lakes from warmer regions (MAAT > 5 °C). Based on these results we propose new temperature calibrations for paleotemperature reconstructions in Chinese alkaline lakes.

Distribution of branched tetraether lipids in ponds from Inner Mongolia, NE China: Insight into the source of brGDGTs

We examined the distributions of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in surface sediments and associated catchment soils of 11 Inner Mongolian ponds (NE China) that collectively comprise a salinity gradient. We explored the sources of brGDGTs in the surface sediments, specifically the recently identified brGDGT isomers. Comparison of brGDGT distributions between surface sediments and soils indicated that the proportion of brGDGTs produced in situ within ponds was relatively minor compared with that contributed from catchment soils. The sole exception was the recently identified 6-Me hexamethylated brGDGT (IIIa′) isomer which, in the surface sediments, appeared to be significantly produced in situ or in the water column. However the 6-Me pentamethylated brGDGT (IIa′) isomer was derived primarily from the surrounding soils based on the plot of individual brGDGT isomers. By extension, the brGDGT-IIIa′ and -IIa′ components in surface sediments have different biological sources but in soils share a similar biological source.

Distribution of branched GDGTs in surface sediments from the Colville River, Alaska: Implications for the MBT′/CBT paleothermometer in Arctic marine sediments

AbstractSignificant climate fluctuations in the Arctic over the recent past, and additional predicted future temperature changes, highlight the need for high‐resolution Arctic paleoclimate records. Arctic coastal environments supplied with terrigenous sediment from Arctic rivers have the potential to provide annual to subdecadal resolution records of climate variability over the last few millennia. A potential tool for paleotemperature reconstructions in these marine sediments is the revised methylation index of branched tetraethers (MBT′)/cyclization ratio of branched tetraethers (CBT) proxy based on branched glycerol dialkyl glycerol tetraethers (brGDGTs). In this study, we examine the source of brGDGTs in the Colville River, Alaska, and the adjacent Simpson Lagoon and reconstruct temperatures from Simpson Lagoon sediments to evaluate the applicability of this proxy in Arctic estuarine environments. The Colville catchment soils, fluvial sediments, and estuarine sediments contain statistically similar brGDGT distributions, indicating that the brGDGTs throughout the system are soil derived with little alteration from in situ brGDGT production in the river or coastal waters. Temperatures reconstructed from the MBT′/CBT indices for surface samples show good agreement with regional summer (June through September) temperatures, suggesting a seasonal bias in Arctic temperature reconstructions from the Colville system. In addition, we reconstruct paleotemperatures from an estuarine sediment core that spans the last 75 years, revealing an overall warming trend in the twentieth century that is consistent with trends observed in regional instrumental records. These results support the application of this brGDGT‐based paleotemperature proxy for subdecadal‐scale summer temperature reconstructions in Arctic estuaries containing organic material derived from sediment‐laden, episodic rivers.

Interannual and (multi-)decadal variability in the sedimentary BIT index of Lake Challa, East Africa, over the past 2200 years: assessment of the precipitation proxy

Abstract. The branched vs. isoprenoid tetraether (BIT) index is based on the relative abundance of branched tetraether lipids (brGDGTs) and the isoprenoidal GDGT crenarchaeol. In Lake Challa sediments the BIT index has been applied as a proxy for local monsoon precipitation on the assumption that the primary source of brGDGTs is soil washed in from the lake's catchment. Since then, microbial production within the water column has been identified as the primary source of brGDGTs in Lake Challa sediments, meaning that either an alternative mechanism links BIT index variation with rainfall or that the proxy's application must be reconsidered. We investigated GDGT concentrations and BIT index variation in Lake Challa sediments at a decadal resolution over the past 2200 years, in combination with GDGT time-series data from 45 monthly sediment-trap samples and a chronosequence of profundal surface sediments.Our 2200-year geochemical record reveals high-frequency variability in GDGT concentrations, and therefore in the BIT index, superimposed on distinct lower-frequency fluctuations at multi-decadal to century timescales. These changes in BIT index are correlated with changes in the concentration of crenarchaeol but not with those of the brGDGTs. A clue for understanding the indirect link between rainfall and crenarchaeol concentration (and thus thaumarchaeotal abundance) was provided by the observation that surface sediments collected in January 2010 show a distinct shift in GDGT composition relative to sediments collected in August 2007. This shift is associated with increased bulk flux of settling mineral particles with high Ti / Al ratios during March–April 2008, reflecting an event of unusually high detrital input to Lake Challa concurrent with intense precipitation at the onset of the principal rain season that year. Although brGDGT distributions in the settling material are initially unaffected, this soil-erosion event is succeeded by a massive dry-season diatom bloom in July–September 2008 and a concurrent increase in the flux of GDGT-0. Complete absence of crenarchaeol in settling particles during the austral summer following this bloom indicates that no Thaumarchaeota bloom developed at that time. We suggest that increased nutrient availability, derived from the eroded soil washed into the lake, caused the massive bloom of diatoms and that the higher concentrations of ammonium (formed from breakdown of this algal matter) resulted in a replacement of nitrifying Thaumarchaeota, which in typical years prosper during the austral summer, by nitrifying bacteria. The decomposing dead diatoms passing through the suboxic zone of the water column probably also formed a substrate for GDGT-0-producing archaea. Hence, through a cascade of events, intensive rainfall affects thaumarchaeotal abundance, resulting in high BIT index values.Decade-scale BIT index fluctuations in Lake Challa sediments exactly match the timing of three known episodes of prolonged regional drought within the past 250 years. Additionally, the principal trends of inferred rainfall variability over the past two millennia are consistent with the hydroclimatic history of equatorial East Africa, as has been documented from other (but less well dated) regional lake records. We therefore propose that variation in GDGT production originating from the episodic recurrence of strong soil-erosion events, when integrated over (multi-)decadal and longer timescales, generates a stable positive relationship between the sedimentary BIT index and monsoon rainfall at Lake Challa. Application of this paleoprecipitation proxy at other sites requires ascertaining the local processes which affect the productivity of crenarchaeol by Thaumarchaeota and brGDGTs.

Spatial heterogeneity of sources of branched tetraethers in shelf systems: The geochemistry of tetraethers in the Berau River delta (Kalimantan, Indonesia)

The bulk organic matter composition (total organic carbon (TOC) content and δ13CTOC) and composition of isoprenoid and branched glycerol dialkyl glycerol tetraethers (GDGT) in surface sediments from 43 stations in the Berau River delta (east Kalimantan, Indonesia), including two coast-shelf transects and stations within the river mouth, were examined to reveal the spatial heterogeneity in these parameters in order to assess the impact of a tropical river loaded with suspended matter on the sedimentary organic matter in the shelf system. The high-resolution study showed that, despite the extensive transport of eroded soil material by the river to the sea, terrestrial organic matter and brGDGTs are only deposited on a relatively small part of the shelf. The concentrations of brGDGTs are highest (up to 120μgg−1 TOC) in sediments deposited in and close to the mouth of the Berau River and their distribution indicates that they represent a mixture of soil-derived and river in-situ produced brGDGTs. Crenarchaeol concentrations reach 700μgg−1 TOC in sediments deposited on the outer shelf due to Thaumarchaeotal production in shelf waters. This results in a strong gradient (0.93–0.03) in the BIT index, with high values in the river mouth and low values on the shelf. The decline in the BIT index is caused by both decreasing concentrations of the brGDGTs and increasing concentrations of crenarchaeol. The BIT index shows a highly significant but non-linear relationship with δ13CTOC. On the shelf, in the area not under the direct influence of the Berau River, cyclic brGDGTs become relatively dominant, most probably due to in-situ production in the alkaline pore waters of the surface sediments. The spatial heterogeneity of sources of brGDGTs on the Berau shelf complicates the use of brGDGTs as temperature proxies. Application of the global soil calibration to sedimentary mixtures of brGDGTs in the river-influenced area of the shelf results in a severe underestimation of mean annual air temperature (MAT) by 6°C. This is due to the mixed origin of the brGDGTs, which are not only derived from soil erosion but, likely, also from riverine production, as has been observed for other river systems.Comparison of the Berau shelf other shelf systems indicates that in-situ production of brGDGTs in shelf sediments is a widespread phenomenon that is especially pronounced at water depths of ca. 50–300m. It is hypothesized that this is so because benthic in-situ production of heterotrophic brGDGT-producing bacteria is fueled by the higher delivery of fresh organic matter to these sediments as the consequence of higher primary productivity in shelf waters and a decreased mineralization due to the relatively short settling times of particles on the shelf. For palaeoclimatic studies of marine shelf sediments the application of brGDGTs as proxies is severely complicated by the heterogeneity of sources of brGDGTs. Comparison of the brGDGT composition of soils with those of shelf sediments may assist in deciding if sedimentary brGDGTs are predominantly derived from soil erosion. Several methods to do so are discussed.

Tracing tetraether lipids from source to sink in the Rhône River system (NW Mediterranean)

In this study, we investigated soils and river suspended particulate matter (SPM) collected in the Rhone and its tributary basins as well as marine surface sediments taken in the Rhone 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 Rhone 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 Rhone 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 Rhone 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 Rhone prodelta close to the river mouth.