Description: Branched glycerol dialkyl glycerol tetraethers (brGDGTs), which are thought to be transported from soil to marine sediment by rivers, have been used to reconstruct the mean annual air temperature (MAAT) and soil pH of the drainage basin using the methylation index of branched tetraethers (MBT, recently refined as MBT') and cyclization index of branched tetraethers (CBT) from coastal marine sediment records. In this study we are tracing the brGDGTs from source to sink in the Tagus River basin, the longest river system on the Iberian Peninsula, by determining their concentration and distribution in soils, river suspended particulate matter (SPM), riverbank sediments, marine SPM, and marine surface sediments. The concentrations of brGDGTs in river SPM were substantially higher and their distributions were different compared to those of the drainage basin soils. This indicates that brGDGTs are mainly produced in the river itself. In the marine environment, the brGDGT concentrations rapidly decreased with increasing distance from the Tagus estuary. At the same time, the brGDGT distributions in marine sediments also changed, indicating that marine in-situ production also takes place. These results show that there are various problems that complicate the use of the MBT'/CBT for paleoreconstructions using coastal marine sediments in the vicinity of a river. However, if the majority of brGDGTs are produced in the river, it might be possible to reconstruct the environmental (temperature and pH) conditions of the river water using appropriate aquatic calibrations, provided that marine core locations are chosen in such a way that the brGDGTs in their sediments are predominantly derived from riverine in-situ production.

Description: Branched glycerol dialkyl glycerol tetraethers (GDGTs) are membrane lipids of unknown bacteria that are ubiquitous in soil and peat. Two indices based on the distribution of these lipids in soils, the Cyclization of Branched Tetraethers (CBT) and the Methylation of Branched Tetraethers (MBT) indices have been shown to correlate with soil pH, and mean annual air temperature (MAT) and soil pH, respectively, and can be used to reconstruct MAT in palaeoenvironments. To verify the extent to which branched GDGTs in marine sediments reflect the distribution pattern on land and whether these proxies are applicable for palaeoclimate reconstruction in high latitude environments with a MAT of 〈0 °C, we compared the branched GDGT distribution in Svalbard soils and nearby fjord sediments. Although branched GDGT concentrations in the soil are relatively low (0.02-0.95 µg/g dry weight (dw)) because of the cold climate and the short growing season, reconstructed MATs based on the MBT/CBT proxy are ca. -4 °C, close to the measured MAT (ca. -6 °C). Concentrations of branched GDGTs (0.01-0.20 µg/g dw) in fjord sediments increased towards the open ocean and the distribution was strikingly different from that in soil, i.e. dominated by GDGTs with one cyclopentane moiety. This resulted in MBT/CBT-reconstructed MAT values of 11- 19 °C, well above measured MAT. The results suggest that at least part of the branched GDGTs in marine sediments in settings with a low soil organic matter (OM) input may be produced in situ. In these cases, the application of the MBT/CBT palaeothermometer will generate unrealistic MAT reconstructions. The MBT/CBT proxy should therefore only be used at sites with a substantial input of soil OM relative to the amount of marine OM, i.e. at sites close to the mouth of rivers with a catchment area where sufficient soil formation takes place and the soil thus contains substantial amounts of branched GDGTs.

Description: The distributions of branched glycerol dialkyl glycerol tetraethers (brGDGTs), which are transported from the soils where they are predominantly produced to marine sediments via rivers, have been applied in reconstructing mean annual air temperature (MAT) and pH of soils. However, paleoclimate reconstructions using sedimentary brGDGTs have proven difficult in arid regions, including the Iberian Peninsula. Recently, six novel 6-methyl brGDGTs have been described using new analytical methods (in addition to the nine 5-methyl brGDGTs previously used for climate reconstructions), and so new pH and MAT calibrations have been developed that were shown to improve the accuracy of reconstructions in a set of global soil samples, especially in arid regions. Because of this we decided to apply the new method to separate the 5- and 6-methyl isomers along with the novel calibrations to a sample set from the Iberian Peninsula to determine whether it improves paleoclimate reconstructions in this area. This set includes samples that run in a transect from source to sink along the Tagus River and out to the deep ocean off the Portuguese margin spanning the last 6000 years. We found that although pH reconstructions in the soils were improved using the new calibration, MAT reconstructions were not much better even with the separation of the 5- and 6-methyl brGDGTs. This confirmed the conclusion of previous studies that the amount of aquatically produced brGDGTs is overwhelming the soil-derived ones in marine sediments and complicating MAT reconstructions in the region. Additionally, the newseparation revealed a strong and until now unseen relationship between the new degree of cyclization (DC') of the brGDGTs and MAT that could be making temperature reconstructions in this and other arid regions difficult

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

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

Description: The branched vs. isoprenoid tetraethers (BIT) index, which is based on the relative abundance of non-isoprenoidal, so-called branched glycerol dialkyl glycerol tetraethers (brGDGTs) versus a structurally related isoprenoid GDGT "crenarchaeol", has been used to trace soil organic carbon (OC) from the continent to the ocean. However, it has been found in some locations that the BIT index can be primarily influenced by crenarchaeol concentrations and brGDGT production in fresh water rather than by soil-derived brGDGT concentrations. This may hamper the application of this proxy as an indicator for the input of soil OC. Here we examined the concentration and distribution of brGDGTs as well as variations in the BIT index in marine surface sediments from five transects (Douro, Mondego, Estremadura, Tagus, and Sado) along the southern Portuguese continental margin and in marine suspended particulate matter (SPM) from the Douro and Tagus transects. Higher BIT values and brGDGT concentrations (normalized to OC content) were found close to the river mouths and coast than in deep offshore sites. This clearly indicated the continental input of brGDGTs and revealed that, at least in this setting, the BIT index was primarily influenced by the delivery of brGDGTs from the rivers. However, the BIT index was also, to a minor extent, influenced by crenarchaeol concentrations. This shows that the brGDGT concentration may provide a more straightforward indication of continental OC input than the BIT index. BrGDGT concentrations and distributions in sediments and SPM close to the rivers were similar to those of SPM in the Tagus River. This indicates that degradation processes in the estuaries had no significant effect on the riverine brGDGTs. Therefore, brGDGTs should be a good indicator for the rigid OC fraction transported from the continent to the ocean. Our results also indicate that there are multiple sources of brGDGTs in the marine environment, which complicates the use of the brGDGT distribution as an indicator for terrestrial vs. marine produced brGDGTs.

Description: Suspended particulate matter (SPM) was collected along the Amazon River in the central Amazon basin and in three tributaries during the risingwater (RW), high water (HW), falling water (FW) and low water (LW) season. Changes in the concentration and the distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs), i.e., the methylation index of branched tetraethers (MBT) and the cyclization of brGDGTs (CBT), were seen in the Amazon main stem. The highest concentration of core lipid (CL) brGDGTs normalized to particulate organic carbon (POC) was found during the HW season. During the HW season the MBT and CBT in the Amazon main stem was also most similar to that of lowland Amazon (terra firme) soils, indicating that the highest input of soil-derived brGDGTs occurred due to increased water runoff. During the other seasons the MBT and CBT indicated an increased influence of in situ production of brGDGTs even though soils remained the main source of brGDGTs. Our results reveal that the influence of seasonal variation is relatively small, but can be clearly detected. Crenarchaeolwasmostly produced in the river. Its concentration was lower during the HW season compared to that of the other seasons. Hence, our study shows the complexity of processes that influence the GDGT distribution during the transport from land to ocean. It emphasizes the importance of a detailed study of a river basin to interpret the MBT/CBT and BIT records for paleoreconstructions in adjacent marine setting.

Description: Branched glycerol dialkyl glycerol tetraethers (brGDGTs) in river fan sediments have been used successfully to reconstruct mean annual air temperature (MAAT) and soil pH of the Congo River drainage basin. However, in a previous study of Amazon deep-sea fan sediments the reconstructed MAATs were ca. 10°C colder than the actual MAAT of the Amazon basin. In this study we investigated this apparent offset, by comparing the concentrations and distributions of brGDGTs in Amazon River suspended particulate matter (SPM) and sediments to those in marine SPM and surface sediments. The riverine brGDGT input was evident from the elevated brGDGT concentrations in marine SPM and surface sediments close to the river mouth. The distributions of brGDGTs in marine SPM and sediments varied widely, but generally showed a higher relative abundance of methylated and cyclic brGDGTs than those in the river. Since this difference in brGDGT distribution was also found in intact polar lipid (IPL)-derived brGDGTs, which were more recently produced, the change in the marine brGDGT distribution was most likely due to marine in-situ production. Consequently, the MAATs calculated based on the Methylation of Branched Tetraethers (MBT) and the Cyclisation of Branched Tetraethers (CBT) were lower and the CBT-derived pH values were higher than those of the Amazon basin. However, SPM and sediments from stations close to the river mouth still showed MBT/CBT values that were similar to those of the river. Therefore, we recommend caution when applying the MBT/CBT proxy, it should only be used in sediment cores that were under high river influence. The influence of riverine derived isoprenoid GDGT (isoGDGT) on the isoGDGT-based TEX86 temperature proxy was also examined in marine SPM and sediments. An input of riverine isoGDGTs from the Amazon River was apparent, but its influence on the marine TEX86 was minor since the TEX86 of SPM in the Amazon River was similar to that in the marine SPM and sediments.

Description: Recently, four bacteriohopanepolyols (BHPs), adenosylhopane, and structurally similar adenosylhopane-type 1, 2-methyl adenosylhopane, and 2-methyl adenosylhopane-type 1, have been suggested to be characteristic of soil microbial communities and therefore can serve as molecular markers for soil organic matter (OM) supply in river, lake, and marine sediments. In this study, we analyzed BHPs in peats and soils collected in the Têt watershed (southern France) and compared them with branched glycerol dialkyl glycerol tetraethers (GDGTs), a more established molecular tracer of soil OM. Adenosylhopane-type I is identified in all of the samples from the study area except one collected near the Têt River mouth with up to three of the related compounds also frequently present, particularly in the surface samples. The concentrations of soil-specific BHPs in peat environments have been shown to increase with lower d15N values, providing evidence that N2-fixing bacteria are probably a major source of soil-specific BHPs in acidic environments. It seems likely that soil pH is a major factor controlling BHP occurrence based on statistical analysis of environmental parameters and BHP concentration data. The comparison of the soil-specific BHP concentrations with those of branched GDGTs shows no clear relationship in the Têt River system, supporting the concept that these two groups of soil-specific compounds are synthesized by different microbial organisms living in different niches in the soil profile (e.g., oxic top versus anoxic deep).

Description: The TEX86H paleothermometer based on isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs) has widely been applied in various marine settings to reconstruct past sea surface temperatures (SSTs). However, it still remains uncertain how well this proxy reconstructs annual mean SSTs. Here, we assess environmental factors governing the TEX86H paleothermometer in the Mediterranean Sea, by studying the distribution of isoGDGTs in surface sediments, suspended particulate matter (SPM), and two sediment cores. A redundancy analysis using the fractional abundance of the six major isoGDGTs indicates that the sedimentary isoGDGTs are mostly influenced by three environmental factors explaining a large part (74%) of the variance in isoGDGT distribution. In order of decreasing significance, these factors are annual mean SST, continental organic matter input as indicated by the BIT index, and water depth. However, when considering only the four isoGDGTs that are used for the TEX86H proxy, water depth is the most significant parameter, explaining 63% of the variance. Indeed, a strong positive relationship between water depth and TEX86H is observed in both surface sediments and SPM from the Mediterranean Sea. This is driven by an increase in fractional abundances of GDGT-2 and crenarchaeol regio-isomer and a decrease in the fractional abundances of GDGT-1 and GDGT-3 with increasing water depth, leading to a bias to higher temperatures of TEX86H in deep-water surface sediments. The fact that the water-depth trend is also apparent in SPM suggests that this change might be due to a change in thaumarchaeotal community thriving below surface mixed-layer waters and that this signal is, at least partly, incorporated into sedimentary isoGDGTs. Interestingly, surface-sediment TEX86H values from 〉1000 m water depth do not show a correlation with water depth anymore and instead are correlated to annual mean SSTs. A composite deep-water TEX86H dataset of surface sediments from both the Mediterranean Sea and the Red Sea, interconnected regional restricted basins with relatively high bottom-water temperatures and high salinity, forms a distinctive correlation line, statistically distinct from that of the general global correlation. Application of this correlation on two sedimentary records from the western Mediterranean Sea covering the last deglaciation yields SSTs nearly identical to those obtained with the UK'37 paleothermometer, whereas the global calibration substantially overestimates SSTs. Our results show that the warm bias of the TEX86H proxy in the Mediterranean Sea is not due to seasonality, as previously suggested. Further research is needed to elucidate the mechanism behind the strong water depth trend of TEX86H in the Mediterranean Sea which is not apparent in open ocean settings.