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To trace the origin of branched glycerol dialkyl glycerol tetraethers (brGDGTs), their distribution in soils and suspended particulate matter (SPM) of Amazonian rivers and floodplain lakes (várzeas) was studied. Differences in distribution between river SPM and surrounding (lowland) soils suggests an additional brGDGT source to eroded soils in the lowland drainage basin. Erosion of high Andean soils (above 2500 m in altitude) has no major influence because its brGDGT distribution differs substantially from that in river SPM. Furthermore, SPM in the Tapajó s River, a tributary that does not derive from the Andes, has a virtually identical brGDGT distribution to that of the Amazon main stem. The higher proportion of phospholipid-derived brGDGTs in river SPM compared to soils indicates that in situ production in the Amazon is an additional source for riverine brGDGTs. This affects the methylation and cyclization index of brGDGTs (MBT-CBT), resulting in slightly lower MBT-CBT-derived temperatures and slightly higher CBT-derived pH values, i.e., between the pH of the basin soil and that of the river. Since the difference between MBT-CBT-derived temperatures of Amazon River SPM and the surrounding soils is relatively small (2uC) compared to other aquatic systems (for lakes a difference of , 10uC has been observed), it might still be possible to trace large climate changes in the Amazon basin with the MBT-CBT using river fan cores. However, variations in in situ production of brGDGTs in the Amazon River over time and space have to be evaluated in the future. Likewise, in situ production may affect the application of the MBT-CBT paleothermometer in other river systems. Our results also show that crenarchaeol is primarily produced in the Amazon River and that its varying production influences the branched vs. isoprenoid tetraether (BIT) index. This indicates that the BIT index not only represents the input of soil organic carbon to the river but is also affected by in situ production of brGDGTs and crenarchaeol.

(2017). The C32 alkane-1,15-diol as a tracer for riverine input in coastal seas. Geochimica et Cosmochimica Acta, 202,[146][147][148][149][150][151][152][153][154][155][156][157][158] The NIOZ Repository gives free access to the digital collection of the work of the Royal Netherlands Institute for Sea Research. This archive is managed according to the principles of the Open Access Movement, and the Open Archive Initiative. Each publication should be cited to its original source -please use the reference as presented. When using parts of, or whole publications in your own work, permission from the author(s) or copyright holder(s) is always needed. 1The C 32 alkane-1,15-diol as a tracer for riverine input in coastal seas ABSTRACTLong chain alkyl diols are lipids that occur ubiquitously in marine sediments and are used as a proxy for sea surface temperature (SST), using the Long chain Diol Index (LDI), and for upwelling intensity/high nutrient conditions. The distribution of 1,13-and 1,15-diols has been documented in open marine and lacustrine sediments and suspended particulate matter, but rarely in coastal seas receiving a significant riverine, and thus continental organic matter, input. Here we studied the distribution of diols in four shelf seas with major river outflows: the Gulf of Lion, the Kara Sea, the Amazon shelf and the Berau delta, covering a wide range of climate conditions. The relative abundance of the C 32 1,15-diol is consistently higher close to the river mouth and particularly in the suspended particulate matter of the rivers suggesting a terrigenous source. This is supported by statistical analysis which points out a significant positive correlation between the C 32 1,15-diol and the Branched and Isoprenoid Tetraether index, a proxy reflecting soil and riverine input in marine environments. However, the C 32 1,15-diol was not detected in soils and is unlikely to be derived from vegetation, suggesting that the C 32 1,15-diol is mainly produced in rivers. This agrees with the observation that it is a dominant diol in most cultivated freshwater eustigmatophyte algae. We, therefore, suggest that the relative abundance of the C 32 1,15-diol can potentially be used as a proxy for riverine organic matter input in shelf seas. Our results also show that long chain alkyl diols delivered by rivers can substantially affect LDI-reconstructed SSTs in coastal regions close to river mouths.

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The volatiles released by Phaeobacter gallaeciensis, Oceanibulbus indolifex and Dinoroseobacter shibae have been investigated by GC-MS, and several MeSH-derived sulfur volatiles have been identified. An important sulfur source in the oceans is the algal metabolite dimethylsulfoniopropionate (DMSP). Labelled [2H6]DMSP was fed to the bacteria to investigate the production of volatiles from this compound through the lysis pathway to [2H6]dimethylsulfide or the demethylation pathway to [2H3]-3-(methylmercapto)propionic acid and lysis to [2H3]MeSH. [2H6]DMSP was efficiently converted to [2H3]MeSH by all three species. Several DMSP derivatives were synthesised and used in feeding experiments. Strong dealkylation activity was observed for the methylated ethyl methyl sulfoniopropionate and dimethylseleniopropionate, as indicated by the formation of EtSH- and MeSeH-derived volatiles, whereas no volatiles were formed from dimethyltelluriopropionate. In contrast, the dealkylation activity for diethylsulfoniopropionate was strongly reduced, resulting in only small amounts of EtSH-derived volatiles accompanied by diethyl sulfide in P. gallaeciensis and O. indolifex, while D. shibae produced the related oxidation product diethyl sulfone. The formation of diethyl sulfide and diethyl sulfone requires the lysis pathway, which is not active for [2H6]DMSP. These observations can be explained by a shifted distribution between the two competing pathways due to a blocked dealkylation of ethylated substrates.

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