Drastic changes in the distribution of branched tetraether lipids in suspended matter and sediments from the Yenisei River and Kara Sea (Siberia): Implications for the use of brGDGT-based proxies in coastal marine sediment

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-do