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: 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 study of past sedimentary records from coastal margins allows us to reconstruct variations in terrestrial input into the marine realm and to gain insight into continental climatic variability. There are numerous organic proxies for tracing terrestrial input into marine environments but none that strictly reflect the input of river-produced organic matter. Here, we test the fractional abundance of the C32 alkane 1,15-diol relative to all 1,13- and 1,15-long-chain diols (FC32 1, 15) as a tracer of input of river-produced organic matter in the marine realm in surface and Quaternary (0-45 ka) sediments on the shelf off the Zambezi and nearby smaller rivers in the Mozambique Channel (western Indian Ocean). A Quaternary (0-22 ka) sediment record off the Nile River mouth in the eastern Mediterranean was also studied for long-chain diols. For the Mozambique Channel, surface sediments of sites most proximal to Mozambique rivers showed the highest F1, 15 - C32 (up to 10 k%). The sedimentary record shows high (15-35 k%) pre-Holocene F1, 15 - C32 and low (〈 10 k%) Holocene F1, 15 - C32 values, with a major decrease between 18 and 12 ka. F1, 15 - C32 is significantly correlated (r2 = 0.83, p 〈 0.001) with the branched and isoprenoid tetraether (BIT) index, a proxy for the input of soil and river-produced organic matter in the marine environment, which declines from 0.25 to 0.60 for the pre-Holocene to 〈 0.10 for the Holocene. This decrease in both FC32 1, 15 and the BIT is interpreted to be mainly due to rising sea level, which caused the Zambezi River mouth to become more distal to our study site, thereby decreasing riverine input at the core location. Some small discrepancies are observed between the records of the BIT index and FC32 1, 15 for Heinrich Event 1 (H1) and the Younger Dryas (YD), which may be explained by a change in soil sources in the catchment area rather than a change in river influx. Like for the Mozambique Channel, a significant correlation between FC32 1, 15 and the BIT index (r2 = 0.38, p 〈 0.001) is observed for the eastern Mediterranean Nile record. Here also, the BIT index and FC32 1, 15 are lower in the Holocene than in the pre-Holocene, which is likely due to the sea level rise. In general, the differences between the BIT index and FC32 1, 15 eastern Mediterranean Nile records can be explained by the fact that the BIT index is not only affected by riverine runoff but also by vegetation cover with increasing cover leading to lower soil erosion. Our results confirm that FC32 1, 15 is a complementary proxy for tracing riverine input of organic matter into marine shelf settings, and, in comparison with other proxies, it seems not to be affected by soil and vegetation changes in the catchment area.

Description: TS2Diatom-diazotroph associations (DDAs) include marine heterocystous cyanobacteria found as exosymbionts and endosymbionts in multiple diatom species. Heterocysts are the site of N2 fixation and have thickened cell walls containing unique heterocyst glycolipids which maintain a low oxygen environment within the heterocyst. The endosymbiotic cyanobacterium Richelia intracellularis found in species of the diatom genus Hemiaulus and Rhizosolenia makes heterocyst glycolipids (HGs) which are composed of C30 and C32 diols and triols with pentose (C5) moieties that are distinct from limnetic cyanobacterial HGs with predominantly hexose (C6) moieties. Here we applied a method for analysis of intact polar lipids to the study of HGs in suspended particulate matter (SPM) and surface sediment from across the tropical North Atlantic. The study focused on the Amazon plume region, where DDAs are documented to form extensive surface blooms, in order to examine the utility of C5 HGs as markers for DDAs as well as their transportation to underlying sediments. C30 and C32 triols with C5 pentose moieties were detected in both marine SPM and surface sediments. We found a significant correlation between the water column concentration of these long-chain C5 HGs and DDA symbiont counts. In particular, the concentrations of both the C5 HGs (1-(O-ribose)-3,27,29-triacontanetriol (C5 HG30 triol) and 1-(O-ribose)-3,29,31-dotriacontanetriol (C5 HG32 triol)) in SPM exhibited a significant correlation with the number of Hemiaulus hauckii symbionts. This result strengthens the idea that long-chain C5 HGs can be applied as biomarkers for marine endosymbiotic heterocystous cyanobacteria. The presence of the same C5 HGs in surface sediment provides evidence that they are effectively transported to the sediment and hence have potential as biomarkers for studies of the contribution of DDAs to the paleomarine N cycle.

Description: We tested the applicability of the BIT (branched and isoprenoid tetraether) index as a proxy for palaeoflood events in the river-dominated continental margin of the Gulf of Lions (NW Mediterranean). We compared the concentrations of branched glycerol dialkyl glycerol tetraethers (br GDGTs) and crenarchaeol in suspended particulate matter (SPM) collected downstream in the Rhône River, as well as in surface sediments and a ca. 8m piston core from the Rhône prodelta. The core covered the last 400 yr, with four distinct intervals recording the river influence under natural and man-induced shifts in four main channels of the river mouth (Bras de Fer, Grand Rhône, Pégoulier and Roustan). The results indicate that there are mixed sources of br GDGTs and crenarchaeol in the prodelta, complicating application of the BIT index as an indicator of continental organic carbon input and thus as a palaeoflood proxy. However, the sedimentary BIT record for the period when ontinental material was delivered by the river more directly to the core site (Roustan phase; 1892 to the present) mimics the historical paleoflood record. This shows the potential of the BIT index as a palaeoflood proxy, provided that the delivery route of the continental material by rivers to the core sites remains constant over time. The study also highlights the idea that shifts in river channels should be taken into account for the use of the BIT index as a palaeoflood proxy.