Evaluation of long chain 1,14-alkyl diols in marine sediments as indicators for upwelling and temperature

Long chain alkyl diols form a group of lipids occurring widely in marine environments. Recent studies have suggested several palaeoclimatological applications for proxies based on their distributions, but have also revealed uncertainty about their applicability. Here we evaluate the use of long chain 1,14-alkyl diol indices for reconstruction of temperature and upwelling conditions by comparing index values, obtained from a comprehensive set of marine surface sediments, with environmental factors such as sea surface temperature (SST), salinity and nutrient concentration. Previous studies of cultures indicated a strong effect of temperature on the degree of saturation and the chain length distribution of long chain 1,14-alkyl diols in Proboscia spp., quantified as the diol saturation index (DSI) and diol chain length index (DCI), respectively. However, values of these indices for surface sediments showed no relationship with annual mean SST of the overlying water. It remains unknown as to what determines the DSI, although our data suggest that it may be affected by diagenesis, while the relationship between temperature and DCI may be different for different Proboscia species. In addition, contributions from algae other than Proboscia diatoms may affect both indices, although our data provide no direct evidence for additional long chain 1,14-alkyl diol sources. Two other indices using the abundance of 1,14-diols vs. 1,13-diols and C30 1,15-diols have been applied previously as indicators for upwelling intensity at different locations. The geographical distribution of their values supports the use of 1,14 diols vs. 1,13 diols [C28 + C30 1,14-diols]/[(C28 + C30 1,13-diols) + (C28 + C30 1,14-diols)] as a general indicator for high nutrient or upwelling conditions

The impact of oxic degradation on long chain alkyl diol distributions in Arabian Sea surface sediments

Oxygen exposure has a large impact on lipid biomarker preservation in surface sediments and may affect the application of organic proxies used for reconstructing past environmental conditions. To determine its effect on long chain alkyl diol and keto-ol based proxies, the distributions of these lipids was studied in nine surface sediments from the Murray Ridge in the Arabian Sea obtained from varying water depths (900–3000 m) but in close lateral proximity and, therefore, likely receiving a similar particle flux. Due to substantial differences in bottom water oxygen concentration (<3–77 μmol/L) and sedimentation rate, substantial differences exist in the time the biomarker lipids are exposed to oxygen in the sediment. Long chain alkyl diol and keto-ol concentrations in the surface sediments (0–0.5 cm) decreased progressively with increasing oxygen exposure time, suggesting increased oxic degradation. The 1,15-keto-ol/diol ratio (DOXI) increased slightly with oxygen exposure time as diols had apparently slightly higher degradation rates than keto-ols. The ratio of 1,14- vs. 1,13- or 1,15-diols, used as upwelling proxies, did not show substantial changes. However, the C30 1,15‐diol exhibited a slightly higher degradation rate than C28 and C30 1,13‐diols, and thus the Long chain Diol Index (LDI), used as sea surface temperature proxy, showed a negative correlation with the maximum residence time in the oxic zone of the sediment, resulting in ca. 2–3.5 °C change, when translated to temperature. The UK′37 index did not show significant changes with increasing oxygen exposure. This suggests that oxic degradation may affect temperature reconstructions using the LDI in oxic settings and where oxygen concentrations have varied substantially over time

Long chain alkyl diol distribution in Arabian Sea surface sediments

Oxygen exposure has a large impact on lipid biomarker preservation in surface sediments and may affect the application of organic proxies used for reconstructing past environmental conditions. To determine its effect on long chain alkyl diol and keto-ol based proxies, the distributions of these lipids was studied in nine surface sediments from the Murray Ridge in the Arabian Sea obtained from varying water depths (900 to 3000 m) but in close lateral proximity and, therefore, likely receiving a similar particle flux. Due to substantial differences in bottom water oxygen concentration (<3 to 77 µmol/L) and sedimentation rate, substantial differences exist in the time the biomarker lipids are exposed to oxygen in the sediment. Long chain alkyl diol and keto-ol concentrations in the surface sediments (0-0.5 cm) decreased progressively with increasing oxygen exposure time, suggesting increased oxic degradation. The 1,15-keto-ol/diol ratio (DOXI) increased slightly with oxygen exposure time as diols had apparently slightly higher degradation rates than keto-ols. The ratio of 1,14- vs. 1,13- or 1,15-diols, used as upwelling proxies, did not show substantial changes. However, the C30 1,15-diol exhibited a slightly higher degradation rate than C28 and C30 1,13-diols, and thus the Long chain Diol Index (LDI), used as sea surface temperature proxy, showed a negative correlation with the maximum residence time in the oxic zone of the sediment, resulting in ca. 2-3.5 °C change, when translated to temperature. The UK'37 index did not show significant changes with increasing oxygen exposure. This suggests that oxic degradation may affect temperature reconstructions using the LDI in oxic settings and where oxygen concentrations have varied substantially over time

The impact of oxygen exposure on long-chain alkyl diols and the long chain diol index (LDI) – a long-term incubation study

In recent years, long chain alkyl diols (LCDs) have been used increasingly to study and reconstruct past sea surface temperatures using the long chain diol index (LDI), which is based on changes in the distribution of 1,15-LCDs. However, the impact of diagenesis on LCDs and the LDI is still poorly constrained. Here we studied the impact of oxygen exposure on LCDs and the LDI, by aerobically incubating biomass of the LCD-producing alga Nannochloropsis oculata for 271 days. The concentrations of extractable free- and bound, residually ester-bound and residually-bound glycosidic ether- or amide-bound saturated fatty acids and LCDs were determined. A significant impact of oxygen exposure was observed for C14, C16 and C18 saturated fatty acids and the C20:5 polyunsaturated fatty acid, as their concentration decreased significantly over time, irrespective of their mode of binding. LCDs, in contrast, increased significantly in concentration over incubation time, e.g. up to a 30-fold increase in concentrations for residually ester-bound LCDs at day 125 compared to concentrations at the beginning of the experiment. This increase in concentration most likely represents a release of LCDs from the insoluble biopolymer algaenan due to the impact of oxygen exposure. Values of the LDI differed strongly depending on the mode of occurrence of LCDs in the biomass. However, despite the large changes in concentration of LCDs in response to oxygen exposure, the LDI remained relatively stable after prolonged degradation. This suggests that oxygen exposure may not have a substantial impact on the LDI of extractable LCDs used for its determination

Long-chain alkenones, long-chain diols and GDGTs over the last 90 Myrs for sediment core Bass River Site

We evaluated changes in the distributions of long-chain alkenones, long-chain diols and GDGTs, lipids commonly used for paleothermometry, over the last 90 Myrs for sediments deposited on the New Jersey shelf (the Bass River site) and assessed potential effects of different ancestral producers and diagenesis on their distributions and their impact on the associated temperature proxies. As reported before, the Paleogene distributions of alkenones are generally similar to those in haptophytes, but unusual alkenone distributions, characterized by a dominant di-unsaturated C40 alkenone, are observed for Late Cretaceous sediments, suggesting different ancestral source organisms for alkenones in this interval. The isoprenoid GDGT distributions remained comparable to modern-day distributions, suggesting that the TEX86 can be applied up to ca. 90 Ma. The Miocene long-chain diol distributions are similar to modern-day distributions, but the older sediments reveal unusual distributions, dominated by the C28 1,12- and C26 1,13-diols, suggesting different source organisms before ~30 Ma. Accordingly, the LDI does not match other paleotemperature proxies, suggesting its applicability might be compromised for sediments older than the Miocene. Our results indicate that of the three proxies, the TEX86 seems to be the most applicable for deep time temperature reconstructions