Description: In this study we have applied different indices based on long chain diols, i.e., the Long chain Diol Index (LDI) as proxy for past SST, the Diol Index as indicator of past upwelling conditions and the Nutrient Diol Index (NDI) as proxy for nitrate and phosphate concentrations in seawater. The proxies were analyzed in marine sediments recovered at ODP Site 1234, located within the Peru-Chile upwelling system, with a 2 kyr resolution, covering the last 150 kyrs. We also generated TEX^H^~86 and U_K'37 temperature and planktonic δ^18^O records, as well as total organic carbon (TOC) and accumulation rates (ARs) of TOC and lipid biomarkers (i.e., C~37~ alkenones, GDGTs, dinosterol and loliolide) to reconstruct past phytoplankton production. The LDI-derived SST record co-varies with TEX^H^86- and UK'37-derived SST records as well as with the planktonic δ^18^O record, implying that the LDI reflects past SST variations at this site. TOC and phytoplankton AR records indicate increased export production during the Last Interglacial (MIS 5), simultaneous with a peak in the abundance of preserved _Chaetoceros diatoms, suggesting intensified upwelling during this period. The Diol Index is relatively low during the upwelling period, but peaks before and after this period, suggesting that Proboscia diatoms were more abundant before and after the period of upwelling. The NDI reveals the same trends as the Diol Index suggesting that the input of nitrate and phosphate was minimal during upwelling, which is unrealistic. We suggest that the Diol Index and NDI should perhaps be considered as indicators for Proboscia productivity instead of upwelling conditions or nutrient concentrations.

Description: Ladderane fatty acids are commonly used as biomarkers for bacteria involved in anaerobic ammonium oxidation (anammox). These lipids have been experimentally shown to undergo aerobic microbial degradation to form short chain ladderane fatty acids. However, nothing is known of the production or the distribution of these oxic biodegradation products in the natural environment. In this study, we analysed marine water column particulate matter and sediment from three different oceanic regimes for the presence of ladderane oxidation products (C14 ladderane fatty acids) and of original ladderane fatty acids (C18 and C20 ladderane fatty acids). We found that ladderane oxidation products, i.e. C14 ladderane fatty acids, are already produced within the water column of the Arabian Sea oxygen minimum zone (OMZ) and thus only low amounts of oxygen (〈 3 µM) are needed for the ?-oxidation of original ladderane fatty acids to proceed. However, no short chain ladderane fatty acids were detected in the Cariaco Basin water column, where oxygen concentrations were below detection limit, suggesting that the beta-oxidation pathway is inhibited by the absence of molecular oxygen, or that the microbes performing the degradation are not proliferating under these conditions. Comparison of distributions of ladderane fatty acids indicates that short chain ladderane fatty acids are mostly produced in the water column and at the sediment surface, before being preserved deeper in the sediments. Short chain ladderane fatty acids were abundant in Arabian Sea and Peru Margin sediments (ODP Leg 201), often in higher concentrations than the original ladderane fatty acids. In a sediment core taken from within the Arabian Sea OMZ, short chain ladderanes made up more than 90% of the total ladderanes at depths greater than 5 cm below sea floor. We also found short chain ladderanes in higher concentrations in hydrolysed sediment residues compared to those freely occurring in lipid extracts, suggesting that they had become bound to the sediment matrix. Furthermore, these matrix-bound short chain ladderanes were found at greater sediment depths than short chain ladderanes in the lipid extract, suggesting that binding to the sediment matrix aids the preservation of these lipids. Though sedimentary degradation of short chain ladderane fatty acids did occur, it appeared to be at a slower rate than that of the original ladderane fatty acids, and short chain ladderane fatty acids were found in sediments from the Late Pleistocene (~ 100 kyr). Together these results suggest that the oxic degradation products of ladderane fatty acids may be suitable biomarkers for past anammox activity in OMZs.

Description: The eastern Mediterranean Sea sedimentary record is characterised by intervals of organic rich sediment (sapropels), indicating periods of severe anoxia triggered by astronomical forcing. It has been hypothesized that nitrogen fixation was crucial in injecting the Mediterranean Sea with bioavailable nitrogen (N) during sapropel events. However, the evolution of the N biogeochemical cycle of sapropels is poorly understood. For example, the role of the complementary removal reaction, anaerobic ammonium oxidation (anammox), has not been investigated because the traditional lipid biomarkers for anammox, ladderane fatty acids, are not stable over long periods in the sedimentary record. The recent development of an alternative lipid biomarker for anammox (bacteriohopanetetrol stereoisomer; BHT isomer) allowed for the investigation of anammox during sapropel deposition in this marginal sea. We present here the first application of a lipid biomarker for N removal throughout the progression (e.g. formation, propagation, and termination) of basin-wide anoxic events. In this study, BHT isomer and ladderanes were analysed in sapropel records taken from three Eastern Mediterranean sediment cores, spanning the most recent (S1) to Pliocene sapropels. Ladderanes were rapidly degraded in sediments, as recently as the S5 sapropel (ca. 125 ka). BHT isomer, however, was present in all sapropel sediments, as far back as the Pliocene (2.97 Ma), and clearly showed the response of anammox bacteria to marine water column redox shifts in high-resolution records. Two different N removal scenarios were observed in Mediterranean sapropels. During S5, anammox experienced Black Sea-like water column conditions, with the peak of BHT isomer coinciding with the core of the sapropel. Under the alternative scenario observed in the Pliocene sapropel, the anammox biomarker peaked at onset and termination of said sapropel, which may indicate sulphide inhibition of anammox during the core of sapropel deposition. This study shows the use of BHT isomer as a biomarker for anammox in the marine sediment record and highlights its potential in reconstructing anammox during past anoxic events that are too old for ladderanes to be applied (e.g. the history of oxygen minimum zone expansion and oceanic anoxic events).