15Long chain diols are lipids that have gained interest over the last years due to their high potential to 16 serve as biomarkers and diol indices have been proposed to reconstruct upwelling conditions and sea 17 surface temperature (SST). However, little is known about the sources of the diols and the mechanisms 18 impacting their distribution. Here we studied the factors controlling diol distributions in the Iberian 19Atlantic margin, which is characterized by a dynamic continental shelf under the influence of upwelling 20 of nutrient-rich cold deep waters, and fluvial input. We analyzed suspended particulate matter (SPM) of 21 the Tagus river, marine SPM and marine surface sediments along five transects off the Iberian margin, 22 as well as riverbank sediments and soil from the catchment area of the Tagus river. Relatively high 23 fractional abundances of the C32 1,15-diol (normalized with respect to the 1,13-and 1,15-diols) were 24 observed in surface sediments in front of major river mouths and this abundance correlates strongly with 25 the BIT index, a tracer for continental input of organic carbon. Together with an even higher fractional 26 abundance of the C32 1,15-diol in the Tagus river SPM, and the absence of long chain diols in the 27 watershed riverbank sediments and soils, we suggest that this long chain diol is produced in-situ in the 28 river. Further support for this hypothesis comes from the small but distinct stable carbon isotopic 29 difference of 1.3‰ with the marine C28 1,13-diol. The 1,14-diols are relatively abundant in surface 30

Suspended particulate matter (SPM) was collected along the Amazon River in the central Amazon basin and in three tributaries during the rising water (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. Crenarchaeol was mostly 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 paleo reconstructions in adjacent marine setting.

Abstract. Branched glycerol dialkyl glycerol tetraethers (brGDGTs), which are 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.

Abstract. 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 trace 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.