Description: Selective degradation of organic matter in sediments is important for reconstructing past environments and understanding the carbon cycle. Here, we report on compositional changes between and within lipid classes and kerogen types (represented by palynomorph groups) in relation to the organic matter flux to the sea floor and oxidation state of the sediments since the early Holocene for central Eastern Mediterranean site ABC26. This includes the initially oxic but nowadays anoxic presapropelic interval, the still unoxidised lower part of the organic rich S1 sapropel, its postdepositionally oxidised and nowadays organic-poor upper part as well as the overlying postsapropelic sediments which have always been oxic. A general ~ 2.3 times increase in terrestrial and marine input during sapropel formation is estimated on the basis of the total organic carbon (TOC), pollen, spore, dinoflagellate cyst, n-alkane, n-alkanol and n-alkanoic acid concentration changes in the unoxidised part of the sapropel. The long-chain alkenones, 1,15 diols and keto-ols, loliolides and sterols indicate that some plankton groups, notably dinoflagellates, may have increased much more. Apart from the terrestrial and surface water contributions to the sedimentary organic matter, anomalous distributions and preservation of some C23-C27 alkanes, alkanols and alkanoic acids have been observed, which are interpreted as a contribution by organisms living in situ. Comparison of the unoxidised S1 sapropel with the overlying oxidised sapropel and the organic matter concentration profiles in the oxidised postsapropelic sediments demonstrates strong and highly selective aerobic degradation of lipids and palynomorphs. There seems to be a fundamental difference in degradation kinetics between lipids and pollen which may be possibly related with the absence of sorptive preservation as a protective mechanism for palynomorph degradation. The n-alkanes, Impagidinium, and Nematosphaeropsis are clearly more resistant than TOC. The n-alkanols and n-carboxylic acids are about equally resistant whereas the pollen, all other dinoflagellate cysts and other lipids appear to degrade considerably faster, which questions the practice of normalising to TOC without taking diagenesis into account. Selective degradation also modifies the relative distributions within lipid classes, whereby the longer-chain alkanes, alcohols and fatty acids disappear faster than their shorter-chain equivalents. Accordingly, interpretation of lipid and palynomorph assemblages in terms of pre- or syndepositional environmental change should be done carefully when proper knowledge of the postdepositional preservation history is absent. Two lipid-based preservation proxies are tested the diol-keto-ol oxidation index based on the 1,15C30 diol and keto-ols (DOXI) and the alcohol preservation index (API) whereby the former seems to be the most promising.

Description: The evolution of productivity, redox conditions, temperature, and ventilation during the deposition of an Aegean sapropel (S1) is independently constrained using bulk sediment composition and high-resolution single specimen benthic foraminiferal trace metal and stable isotope data. The occurrence of benthic foraminifer, Hoeglundina elegans (H. elegans), through a shallow water (260 m) sapropel, permits for the first time a comparison between dissolved and particulate concentrations of Ba and Mn and the construction of a Mg/Ca-based temperature record through sapropel S1. The simultaneous increase in sedimentary Ba and incorporated Ba in foraminiferal test carbonate, (Ba/Ca)H. elegans, points to a close coupling between Ba cycling and export productivity. During sapropel deposition, sedimentary Mn content ((Mn/Al)sed) is reduced, corresponding to enhanced Mn2+ mobilization from sedimentary Mn oxides under suboxic conditions. The consequently elevated dissolved Mn2+ concentrations are reflected in enhanced (Mn/Ca)H. elegans levels. The magnitude and duration of the sapropel interruption and other short-term cooling events are constrained using Mg/Ca thermometry. Based on integrating productivity and ventilation records with the temperature record, we propose a two-mode hysteresis model for sapropel formation.

Description: Oxidized intervals of five organic-rich Madeira Abyssal Plain (MAP) turbidites deposited during the Miocene, Pliocene, and Pleistocene all displayed comparable major loss of total organic carbon (TOC) (84 ± 3.1%) accompanied by a negative isotopic (d13C) shift ranging from -0.3 to -2.9 per mil. Major but significantly lower loss of total nitrogen (Ntot, 61 ± 7.1%) also occurred, leading to a decrease in TOC relative to Ntot (C/Ntot) and a +1.3 to 2.7 per mil Ntot isotopic (d15N) shift. Compound specific isotopic measurements on plant wax n-alkanes indicate the terrestrial organic component in the unoxidized deposits is 13C-enriched owing to significant C4 contribution. Selective preservation of terrestrial relative to marine organic carbon could account for the d13C behavior of TOC upon oxidation but only if a 13C-depleted component of the bulk terrestrial signal is selectively preserved in the process. Although the C/Ntot decrease and positive d15N shift seems inconsistent with selective terrestrial organic preservation, results from analysis of a Modern eolian dust sample collected in the vicinity indicate these observations are compatible. Regardless of the specific explanation for these isotopic observations, however, our findings provide evidence that paleoreconstruction of properties such as pCO2 using the d13C of TOC is a goal fraught with uncertainty whether or not the marine sedimentary record considered is 'contaminated' with significant terrestrial input. Nonetheless, despite major and selective loss of both marine and terrestrial components as a consequence of postdepositional oxidation, intensive organic geochemical proxies such as the alkenone unsaturation index, UK'37, appear resistant to change and thereby retain their paleoceanographic promise.

Description: We compare geochemical and pollen data of several well-dated, high-resolution cores to provide an integral Holocene overview of Nile outflow, sedimentation, and vegetation in and around the Nile delta. We show that the focus point of the Nile plume varied considerably, as indicated by planktonic foraminifer Globigerinoides ruber oxygen isotopes tracing Nile discharge differences in an east-west delta transect. At 13-11.5 cal kyr BP, Nile discharge was low and runoff was predominantly directed to the western part of the delta. Sediment arriving in the delta during that period was dominated by Ethiopian Highland (~Blue Nile) material, shown by high Ti/Al values of the bulk sediment, indicating dry conditions in the source area of the Blue Nile. Nile discharge increased from ~11.5 cal kyr BP, and was high across the whole delta from ~10-6.5 cal kyr BP. During this time, the Ti/Al values decreased within most Nile-delta sediments, suggesting that the relative contribution of Blue-Nile sediment decreased. This was likely due to an increased vegetation cover causing diminished erosion in the Ethiopian Highlands. Nile discharge gradually decreased from ~6.5 cal kyr BP to present. This decrease was more abrupt in the Western Province of the delta and became more gradual towards the east as the shrinking Nile runoff was directed there. The gradual decrease in precipitation in the Nile catchment area seems not to be matched by a gradual response in vegetation growing around the river plain in the lower Nile catchment. Our findings suggest a nonlinear response of northeast African vegetation to precipitation from the middle to late Holocene.

Description: Eastern Mediterranean thermohaline circulation is directly influenced by mid- and low-latitude climate systems. The dramatic paleoclimate changes during the last African Humid Period (~10-6ka BP) were captured in Mediterranean sediments as the distinctly organic-rich unit sapropel S1. Here, deep-water formation variability during S1 deposition, is reconstructed. We use geochemical records of three cores along a bathymetric transect (775-1359-1908m water depth), at the transition between the Adriatic deep-water formation area and the Eastern Mediterranean. In all three cores, sedimentation rates are distinctly higher during S1, corresponding with enhanced run-off emanating from the Adriatic hinterland. Hence, major run-off did not only come from southern, but also from northern borderlands in this period. During sapropel formation, enhanced levels of primary productivity occurred in the surface waters and oxygen-depleted conditions in the bottom-waters for all sites. Conditions for sediment and bottom-water below ~1.4km water depth were sulphidic throughout S1, but for intermediate depth (775m) were anoxic only during the first part (S1a). Bottom-water oxygenation interrupted S1 formation at water depths down to ~1.4km, during two brief episodes, at 8.2 and 7.4 cal.ka BP. From the 7.4 cal.ka BP ventilation onward, the transition to more oxygenated bottom-water conditions was more progressive for the intermediate water depth site (775m) than for the deeper sites. Conditions remained fully oxic for all water depths following the S1-MarkerBed ventilation event. Possibly the onset of continuously oxic conditions started slightly earlier at intermediate depth (775m; 6.6±0.3 cal.ka BP) than at greater depths (1358m, 1908m; 6.0±0.3 cal.ka BP).