ALBERT

Description: Soil-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs) in marine river fan sediments have a potential use for determining changes in the mean annual temperature (MAT) and pH of the river watershed soils. Prior to their incorporation in marine sediments, the compounds are transported to the marine system by rivers. However, emerging evidence suggests that the brGDGTs in freshwater systems can be derived from both soil run-off and in situ production. The production of brGDGTs in the river system can complicate the interpretation of the brGDGT signal delivered to the marine system. Therefore, we studied the distribution of brGDGT lipids in suspended particulate matter (SPM) of the Yenisei River. Chromatographic improvements allowed quantification of the recently described hexamethylated brGDGT isomer, characterized by having two methyl groups at the 6/6' instead of the 5/5' positions, in an environmental dataset for the first time. This novel compound was the most abundant brGDGT in SPM from the Yenisei. Its fractional abundance correlated well with that of the 6-methyl isomer of the hexamethylated brGDGT that contains one cyclopentane moiety. The Yenisei River watershed is characterized by large differences in MAT (〉11 °C) as it spans a large latitudinal range (46-73°N), which would be expected to be reflected in brGDGT distributions of its soils. However, the brGDGT distributions in its SPM show little variation. Furthermore, the reconstructed pH values are high compared to the watershed soil pH. We, therefore, hypothesize that the brGDGTs in the Yenisei River SPM are predominantly produced in situ and not primarily derived from erosion of soil. This accounts for the absence of a change in the temperature signal, as the river water temperature is more stable. Using a lake calibration, the reconstructed temperature values agree with the mean summer temperatures (MST) recorded. The brGDGTs delivered to the sea by the Yenisei River during this season are thus not soil-derived, possibly complicating the use of brGDGTs in marine sediments for palaeoclimate reconstructions.

Description: The distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in soils has been shown to correlate with pH and mean annual air temperature. Because of this dependence brGDGTs have found an application as palaeoclimate proxies in coastal marine sediments, based on the assumption that their distribution is not altered during the transport from soils to marine systems by rivers. To study the processes acting on the brGDGT distributions, we analysed the full suite of brGDGTs, including the recently described 6-Me brGDGTs, in both the suspended particulate matter (SPM) of the Siberian Yenisei River and the SPM and sediments of its outflow in the Kara Sea. The brGDGT distribution in the SPM of the Yenisei River was fairly constant and characterized by high abundances of the 6-Me brGDGTs, reflecting their production at the neutral pH of the river water. However, the brGDGT distribution showed marked shifts in the marine system. Firstly, in the Yenisei River Mouth, the fractional abundance of the 6-Me brGDGTs decreases sharply. The brGDGT signature in the Yenisei River Mouth possibly reflects brGDGTs delivered during the spring floods that may carry a different distribution. Also, coastal cliffs were shown to contain brGDGTs and to influence especially those sites without major river inputs (e.g. Khalmyer Bay). Further removed from the river mouth, in-situ production of brGDGTs in the marine system influences the distribution. However, also the fractional abundance of the tetramethylated brGDGT Ia increases, resulting in a distribution that is distinct from in-situ produced signals at similar latitudes (Svalbard). We suggest that this shift may be caused by preferential degradation of labile (riverine in-situ produced) brGDGTs and the subsequent enrichment in less labile (soil) material. The offshore distribution indeed agrees with the brGDGT distribution encountered in a lowland peat. This implies that the offshore Kara Sea sediments possibly carry a soil-dominated signal, indicating potential for palaeoclimate reconstructions at this site. Both in the river system and coastal cliffs, brGDGTs were much more abundant than crenarchaeol, an archaeal isoprenoid GDGT, resulting in high (〉0.93) Branched and Isoprenoid Tetraether (BIT) index values. Moving downstream in the marine sediments, a decrease in brGDGT concentrations, coeval with an increase in crenarchaeol, resulted in decreasing BIT index values. This decrease correlates with changes in bulk proxies for terrigenous input (d13Corg, C/N), confirming the use of the BIT index to trace the delivery of river-transported and coastal cliff-derived terrigenous organic matter.

Description: Bacteriohopanepolyols (BHPs) are ubiquitous bacterial membrane lipids, encountered in soils, river and marine suspended particulate matter (SPM) and sediments. Their abundance and distribution provides a direct means to identify bacterial inputs and can be used to trace soil-derived bacterial organic matter (OM) and in some cases the presence of bacterial groups and their activities in aquatic systems. We have studied the BHP distribution in the SPM of a major Siberian River (Yenisei River) that crosses a large latitudinal gradient, draining a large part of Mongolia and Siberian Russia. The Yenisei River is the main river to flow into the Kara Sea, a shelf sea of the Arctic Ocean. We show that the BHP distribution and concentration of SPM and surface sediments of the Yenisei Outflow in the Kara Sea allow to trace soil-marker BHPs and evaluate the performance of the R'soil index, a proxy developed to trace bacterial soil-derived OM. Soil-marker BHPs are present in the Yenisei River, and their concentration decreases from the Yenisei River Outflow into the offshore marine sediments. The R'soil correlates well with an independent proxy for bacterial OM, the BIT-index (r**2 = 0.82) and has a moderate correlation with the d13Corg values, a bulk OM proxy for terrigenous input (r**2 = 0.44). Consequently, the R'soil index performs well in the Kara Sea, strengthening its application for tracing bacterial OM in the Arctic Ocean, both in modern and downcore sediments. Furthermore, a suite of BHPs that are characteristic for methanotrophic bacteria, i.e. 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol) and 35-aminobacteriohopane-31,32,33,34-tetrol (aminotetrol), is encountered in the Yenisei Outflow sediments. These components are partly sourced from terrigenous sources, but are likely also produced in-situ in the marine sediments. The distribution of the pentafunctionalized cyclitol ether BHP in the marine systems is noteworthy, and indicates that it can possibly be applied as a marker for cyanobacterial biomass in marine sediments.

Description: Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids found in several environments, including soils, rivers and lakes, whose distribution varies with temperature and pH, although this dependence is apparently not the same for the different environments. Mixing of brGDGT sources may thus complicate palaeoenvironmental reconstruction. The extent to which brGDGTs in a lake outflow reflect the distribution delivered by upstream rivers was studied for Lake Baikal (Russia), one of the largest freshwater lakes worldwide. Fifteen brGDGTs in suspended particulate matter (SPM) of the Selenga River and its outflow from the lake were quantified. The river and lake SPM had rather different distributions. The riverine distribution was still apparent in the SPM of the lake surface water 5 km from the river mouth, but shifts in the distribution were already apparent in the SPM of the surface water after 1 km. Based on the brGDGT distributions of the SPM of the Selenga outflow and that of the lake, conservative mixing between the river and the lake brGDGT distributions could not fully explain the observed shifts in distributions. Both preferential degradation and in situ production of brGDGTs in the surface and, especially, bottom water of the river outflow were potentially responsible. This implies that a riverine lipid distribution delivered to a lake can be modified prior to being transported downstream. The lacustrine brGDGT distribution, that possibly could have reflected a mixture of mountainous and Selenga River SPM, was not recognized in downstream Yenisei River SPM. The watershed of Lake Baikal thus does not seem to contribute to the brGDGTs transported to the marine system. As many large rivers have major lakes in their watershed, this has implications for palaeoclimate reconstruction from river fan sediments globally.

Description: Sediments (spanning a minimum of 13.3 ka) from the St. Anna Trough (Northern Kara Sea). The site has experienced extensive fluctuation in the delivery of river-derived organic matter (OM), caused by a eustatic change in sea level. This is in line with the record of the concentration of the isoprenoid GDGT, crenarchaeol, produced by marine Thaumarchaota, which was low at the bottom of the core, increasing gradually in the most shallow unit. The concentration of branched (br)GDGTs showed an opposite trend and a marked shift in distribution. The deepest sediments (〉10 ka), with a distribution currently encountered in surface sediments in front of the Yenisei River, are characterized by terrigenous brGDGTs, whereas the distribution in the shallowest unit (〈10 ka) is strongly influenced by marine, in-situ brGDGTs. During the shift from terrigenous to marine-sourced brGDGTs, there was one horizon where a pronounced shift in the brGDGT distribution was observed and the brGDGT concentration significantly decreased. As the brGDGTs delivered to the current Kara Sea system are derived from several sources, we postulate that a temporary change in the relative importance of the brGDGT sources happened during this interval. Both in-situ production and changing brGDGT provenance have implications for paleoclimate reconstruction using brGDGTs. In-situ production of marine brGDGTs results in a higher reconstructed pH. However, these in-situ produced brGDGTs did not influence the reconstructed mean annual air temperature (MAT), when the MATmrs calibration was used. Changes in the relative contribution of brGDGT sub-pools were shown, however, to influence both soil pH reconstruction and MAT reconstruction.