(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.

The Long chain Diol Index (LDI) is a relatively new organic geochemical proxy for sea surface temperature (SST), based on the abundance of the C30 1,15-diol relative to the summed abundance of the C28 1,13-, C30 1,13-and C30 1,15-diols. Here we substantially extend and reevaluate the initial core top calibration by combining the original dataset with 172 data points derived from previously published studies and 262 newly generated data points. In total, we considered 595 globally distributed surface sediments with an enhanced geographical coverage compared to the original calibration. The relationship with SST is similar to that of the original calibration but with considerably increased scatter. The effects of freshwater input (e.g., river runoff) and long-chain diol contribution from Proboscia diatoms on the LDI were evaluated. Exclusion of core-tops deposited at a salinity < 32 ppt, as well as core-tops with high Probosciaderived C28 1,12-diol abundance, resulted in a substantial improvement of the relationship between LDI and annual mean SST. This implies that the LDI cannot be directly applied in regions with a strong freshwater influence or high C28 1,12-diol abundance, limiting the applicability of the LDI. The final LDI calibration (LDI=0.0.0325×SST+0.1082; R 2 = 0.88; n = 514) is not statistically different from the original calibration of Rampen et al. (2012)

Abstract. Long chain alkyl diols (LCDs) are widespread in the marine water column and sediments, but their biological sources are mostly unknown. Here we combine lipid analyses with 18S rRNA gene amplicon sequencing on suspended particulate matter (SPM) collected in the photic zone of the western tropical North Atlantic Ocean at 24 stations to infer relationships between LCDs and potential LCD producers. The C30 1,15-diol was detected in all SPM samples and accounted for >95 % of the total LCDs, while minor proportions of C28 and C30 1,13-diols, C28 and C30 1,14-diols, as well as C32 1,15-diol were found. The concentration of the C30 and C32 diols was higher in the mixed layer of the water column compared to the deep chlorophyll maximum (DCM), whereas concentrations of C28 diols were comparable. Sequencing analyses revealed extremely low contributions (≈0.1 % of the 18S rRNA gene reads) of known LCD producers, but the contributions from two taxonomic classes with which known producers are affiliated, i.e. Dictyochophyceae and Chrysophyceae, followed a trend similar to that of the concentrations of C30 and C32 diols. Statistical analyses indicated that the abundance of 4 operational taxonomic units (OTUs) of the Chrysophyceae and Dictyochophyceae, along with 23 OTUs falling into other phylogenetic groups, were weakly (r≤0.6) but significantly (p value <0.01) correlated with C30 diol concentrations. It is not clear whether some of these OTUs might indeed correspond to C28−32 diol producers or whether these correlations are just indirect and the occurrence of C30 diols and specific OTUs in the same samples might be driven by other environmental conditions. Moreover, primer mismatches were unlikely, but cannot be excluded, and the variable number of rRNA gene copies within eukaryotes might have affected the analyses leading to LCD producers being undetected or undersampled. Furthermore, based on the average LCD content measured in cultivated LCD-producing algae, the detected concentrations of LCDs in SPM are too high to be explained by the abundances of the suspected LCD-producing OTUs. This is likely explained by the slower degradation of LCDs compared to DNA in the oxic water column and suggests that some of the LCDs found here were likely to be associated with suspended debris, while the DNA from the related LCD producers had been already fully degraded. This suggests that care should be taken in constraining biological sources of relatively stable biomarker lipids by quantitative comparisons of DNA and lipid abundances.