Marine nitrogen cycling dynamics under altering redox conditions: Insights from deposition of sapropels S1 and the ambiguous S2 in the Eastern Mediterranean Sea

Abstract

The eastern Mediterranean Sea (EMS) sedimentary record is periodically interspersed with organic-rich ‘sapropel’ layers. Sapropels are characteristic of basin-wide anoxic events, triggered by precession-forced insolation maxima. Relatively subdued insolation maxima, however, are not always expressed as distinct sapropel events. The EMS sedimentary record is thus useful to investigate feedbacks between marine anoxia and the nitrogen (N) cycle and offers an analogue for modern deoxygenation and past oceanic anoxic events. To this end, we investigated a ∼68 kyr sedimentary record from the EMS containing the well-established sapropel S1 (deposited in two phases: S1a [∼10.5–8.5 ka BP] and S1b [∼7.8–6.1 ka BP]) and sediments timed to the ambiguous S2 sapropel (∼53 ka BP). We used lipid biomarkers of microorganisms to reconstruct key N-cycle components: (1) anaerobic ammonium oxidation (anammox) using ladderanes and a stereoisomer of bacteriohopanetetrol (BHT-x), (2) dinitrogen gas (N2) fixation using heterocyte glycolipids, and (3) nitrification by Thaumarchaeota using crenarchaeol. Additionally, benthic foraminifera and trace metals (U, Mo, Mn) were used to reconstruct redox conditions. During S1a, abundances of Thaumarchaeota increased, likely promoted by elevated high-nutrient freshwater discharge. At this time, a combination of phosphorus supply and intensified loss of bioavailable N via water column anammox, may have reinforced anoxia by favoring diatom-diazotroph associations. During S1b, anammox is equally intense. Yet, no positive feedback on N2-fixation is observed, likely because diazotrophs were phosphorus limited. Instead, anammox may have provided negative feedback on anoxia by quenching primary production. Ladderanes suggest additional episodes of anammox between ∼69 to 39 cal ka BP, corresponding to brief periods of water column deoxygenation. Anoxia likely occurred at the sediment–water interface in S2-timed sediments (53–51 cal ka BP). During these episodes, ladderanes co-occur with the later eluting BHT-34R stereoisomer. δ13CBHT-34R indicate an anammox source, potentially synthesized by marine sedimentary anammox bacteria. No corresponding increase in diatom-diazotroph associations is observed, likely due to the oligotrophic conditions and the limited effect of sedimentary anammox on N-availability in the euphotic zone. Our results highlight various modes of operation of the N-cycle at different degrees of deoxygenation, which depend amongst others on nutrient-availability and the niche-segregation of N-loss and N2-fixating microorganisms.