Sapropel Formation Research Articles

Multiple Ba Phases in Marine Sediments elucidate environmental processes and conditions for the Holocene Mediterranean

Mediterranean sediments are known for their major shifts in sedimentary composition associated with dramatic changes in environmental and climate conditions. A typical expression for this in Holocene sediments is the occurrence of a distinctly organic-rich unit, sapropel S1, thought to be related with humid climate conditions. The S1 is accompanied by major changes in Ba content and in other elemental composition, respectively related to biological upper water column productivity and shifts in detrital sediment provenance. Here, we focus on changes in Ba and in its various phases to unravel shifts in environmental conditions around S1.Using selective extractions for sediments in cores MP37PC, MP39PC and MP50PC, respectively at 1908, 1359 and 775m water depth, we distinguish different Ba-phases: detrital Ba (Ba-det), barite Ba (Ba-bar), Mn-oxide-related Ba (Ba-ox), carbonate- and pyrite-associated Ba (Ba-carb and Ba-pyr). The predominant Ba-phase during S1 is Ba-bar (∼70%), whereas before and after S1 it is Ba-det (>90%). All other phases are mostly relatively small but have diagnostic value for environmental conditions and processes.The detrital (Ba/Al) is distinctly lower during S1 than before and after. The (Ba/Al). det variability, and enhanced values for Ba-carb and Ba-ox may have substantial influence on the traditional way to derive barite-Ba or excess-Ba content.The steep gradients in Ba-bar at onset and ending of S1and its high level during S1, clearly identify this period. In addition, and due to the exclusive nature of extraction results, we unequivocally demonstrate for the first time that there is a small gradual ‘early onset’ Ba-bar preceding the major increase in sapropel S1 formation sensu stricto.The ending of S1 formation is relatively abrupt with a well-defined reventilation event (’6 ka reventilation event’). This reventilation is associated with a rapid change in environmental conditions such as oxygenation and related remineralization of organic matter and recrystallization of carbonate. This rapid change and associated diagenetic processes are authentically recorded in Ba-carb and Ba-ox. For the period during sapropel S1 formation, the Ba-carb and Ba-ox results point to different levels of ventilation in the Eastern Mediterranean, i.e. a relatively mixed water mass down to ∼800m, a moderately mixed water mass from ∼800-to ∼1500 m, and a more stagnant water mass below 1500 m.

Humid climate phases on the Island of Rhodes (Greece) during the late Pliocene at times of sapropel formation

The Island of Rhodes, located in the Eastern Mediterranean Sea, is affected by an active convergent plate boundary. In this context, marine sediments of Plio-Pleistocene age have been uplifted and are outcropping along the eastern coast of Rhodes. These archives provide an excellent opportunity to unravel the hydrological and climatic changes of the region during the late Pliocene. Our results provide new evidence for a more humid climate and an increased precipitation on the island during times of Northern Hemisphere summer insolation maxima and related sapropel formation in the Mediterranean deep sea. The periodic occurrence of eutrophic conditions at the shelf and upper slope off Rhodes is indicated by the recurrent dominance of eutrophic indicator species (of the genera Bolivina, Eubuliminella and Rectuvigerina), simultaneously with a decline in diversity and oligotrophic indicator species. These conditions resulted from higher primary productivity, triggered by local effects, such as enhanced precipitation and river run-off, which consequently favors the appearance of eutrophic taxa. The ∆δ13C records of the epibenthic foraminifera Cibicidoides pseudoungerianus and the shallow infaunal species Uvigerina peregrina indicate a slight productivity decrease towards younger times.

Monsoon-driven changes in aeolian and fluvial sediment input to the central Red Sea recorded throughout the last 200 000 years

Abstract. Climatic and associated hydrological changes controlled the transport processes and composition of the sediments in the central Red Sea during the last ca. 200 kyr. Three different source areas for mineral dust are identified. The dominant source is located in the eastern Sahara (Sudan and southernmost Egypt). We identify its imprint on Red Sea sediments by high smectite and Ti contents, low 87Sr / 86Sr, and high εNd. The availability of deflatable sediments was controlled by the intensity of tropical rainfall and vegetation cover over North Africa linked to the African monsoon. Intense dust input to the Red Sea occurred during arid phases, and low input occurred during humid phases. A second, less significant source indicated by palygorskite input is probably located on the eastern Arabian Peninsula and/or Mesopotamia, while the presence of kaolinite suggests an additional minor dust source in northern Egypt. Our grain size data reflect episodes of fluvial sediment discharge to the central Red Sea and document the variable strength in response to all of the precession-paced insolation maxima during our study interval including both those that were strong enough to trigger sapropel formation in the eastern Mediterranean Sea and those that were not. The African humid period most strongly expressed in our Red Sea record was the one during the Eemian last interglacial at ca. 125 ka (when the Baraka River was far more active than today), followed by those at 198, 108, 84, and 6 ka.

Impact of hydrological changes and vertical motions on Pleistocene marine environments of the eastern coast of the island of Rhodes (Greece)

The island of Rhodes in the eastern Mediterranean Sea is situated in an area affected by an ongoing plate convergence, and its Pleistocene marine environments were influenced by recurring hypoxia and changes in organic matter fluxes. This makes the island an important site to study the influence of orbital-driven climate changes and tectonic-induced vertical motions on the marine benthic ecosystems in near-coastal areas at local and regional scales. We investigated the Early and Late Pleistocene sediment sections at Agathi Beach and Lardos, located on the middle-eastern coast of the island. Our results show variations in oxygen and food levels at the sea floor, including transient phases of enhanced fresh-water and nutrient input to near-coastal environments. These phases occurred at times of Northern Hemisphere summer insolation maxima, simultaneously to the formation of sapropels in the deep-sea basins of the eastern Mediterranean Sea. The application of a benthic foraminiferal transfer function revealed that both sections were influenced by tectonic-driven long-term and short-term vertical motions with higher rates than expected on the island of Rhodes. While Agathi Beach underwent two short-term cycles of uplift and subsidence, Lardos indicates at least three cycles with average rates of vertical motion as high as 8.6 mm/a.

Sedimentary response to current and nutrient regime rearrangement in the Eastern Mediterranean during the early to middle Miocene (Southwestern Cyprus)

During the early and middle Miocene, the Mediterranean had become a restricted marginal marine sea with diminishing and ultimate loss of connectivity to the Indian Ocean. This dramatically changed the heat, energy, freshwater and nutrient budgets across the Mediterranean and most notably in its eastern basin. While one of the most prominent lines of evidence of this change in the Eastern Mediterranean is the onset of sapropel formation, many other aspects of the sedimentary system changed in response to this rearrangement. Here we present a detailed analysis of a hemipelagic succession from southwestern Cyprus dated to the late Aquitanian to the early Serravallian (22.5–14.5 Ma). This sequence is carbonate-dominated and formed during the decoupling of the Mediterranean Sea and the Indian Ocean. It exhibits sedimentation with mass transport contribution from shallow water carbonates to deeper facies with phosphatization and bottom current (at intermediate depth) interactions. This succession traces both local subsidence and loss of a local carbonate factory. Additionally, it records a shift in bottom current energy and seafloor ventilation, which are an expected outcome of connectivity loss with the Indian Ocean. • A new continuous section from the late Oligocene to the middle Miocene was studied in southern Cyprus. • A multi-proxies approach trace paleoenvironmental changes in the east Mediterranean across its the Indian Ocean decupling. • These changes include changes in the carbonate factories, nutrient state and local subsidence. • Evolving nutrient load and sedimentary composition shades light on events leading to emplacement of precursor sapropels.

Assessment of the Physiological Groups of Bacteria from Salt Lakes and Euxinic Sediments Involved in Sulfur Cycle, Therapeutical Mud Formation, and Regeneration

The biogeochemical cycle of sulfur is important in the diagenesis of organic matter sedimented in saline and euxinic lakes leading to sapropel formation. The study aimed to determine the numerical densities of physiological groups of sulfur bacteria in water and sediment samples from five Romanian saline and euxinic lakes with therapeutical properties in order to assess their peloidogen regeneration potential. Bacterial communities that metabolize sulfur compounds were monitored in lakes with different salinity values: Techirghiol, Amara, Sovata-Black Lake, Ursu Lake, and Braila Salt Lake by multiple tube method. Statistical results revealed the interdependence between sulfoxidizing bacteria/SO42- in sediments, while the reductive microorganisms fraction/metabolic products (H2S/Corg./Norg) separately evolved in the economy of peloidogenic ecosystems. In the lakes, Techirghiol, Amara, and Braila Salt Lake, the dominant role in the specific microbiota belonged to sulfate/sulfur-reducing bacteria, and the formed peloid was sulfurous-sapropelic in Techirghiol Lake or sulfurous-mineral in Amara Lake and Braila Salt Lake. In the hypersaline, meromictic, and heliothermal lakes of Sovata, the sulfur metabolism was predominantly oxidative, made by sulfoxidizing bacteria in higher numerical densities, with the accumulation of SO42- ions in the strongly hydrated aqueous phase of mineral sediments.

Middle-late Holocene climate and hydrologic changes in the Gulf of Saros (NE Aegean Sea)

A multi-proxy analyses was applied on the sediment core from the Gulf of Saros (GoS) to identify and characterize climate and hydrological changes during the middle-to-late Holocene. The formation of two discrete Holocene sapropel layers in the GoS sediments was documented for the first time in the sediment core based on total organic carbon analysis. According to our paleo-proxy records, the lower Holocene sapropel was deposited under warm and humid climate conditions that gave rise to high delivery of terrestrial organic matter by numerous rivers in the northern catchment of the GoS. Biomarker and μ-XRF data were used to decipher climate variations during the middle to late Holocene. The general trends of sea-surface temperature records from the GoS and Sea of Marmara (SoM) at the beginning of late Holocene are in good agreement, underlying the influence of the Black Sea inflow. A relatively warm and wet climate together with a high sedimentation rate during the mid-Holocene Climatic Optimum resulted in high organic productivity and ensuing formation of the younger Holocene sapropel between 5.4 and 3.0 cal ka BP. Late Holocene European climate periods are evident in the Saros core records. The Roman Humid Period is represented by high variation in climate, indicating an earlier (2.5–2.3 cal ka BP) dry and a later (2.3–1.55 cal ka BP) wet periods. The abrupt return to drier condition during the Dark Ages Cold Period (1.6–1.3 cal ka BP) was followed by a wetter Medieval Climate Anomaly (1.1–0.7 cal ka BP). The paleo-proxy record of the core indicates a passage from a wetter to drier climate during the cold Little Ice Age period (730–110 cal yr BP), and highlights the influence of deforestation in the catchment of the GoS as a result of human activities during the last three centuries.

A river flowing through a desert: late Quaternary environments in the Nile basin – current understanding and unresolved questions

Late Quaternary environments in the Nile Basin reflect the influence of the African summer monsoon upon plant cover, sediment yield and flood discharge in the Ethiopian and Ugandan headwaters of the Nile. Intervals of prolonged and very high Nile flow coincide with times of stronger summer monsoon and have been dated using a combination of 14C, OSL and 10Be methods. Periods of high Nile flow into the eastern Mediterranean coincide with the formation of highly organic sedimentary layers termed sapropels. Ages obtained so far for these times of sustained middle to late Pleistocene high flow in the Blue and White Nile are broadly coeval with sapropel beds S8 (ca 217 ka), S7 (ca 195 ka), S6 (ca 172 ka), S5 (ca 124 ka), S4 (ca 102 ka) S3 (ca 81 ka), S2 (ca 55–50 ka) and S1 (10–6.5 ka). Sapropel 5 (ca 124 ka) was synchronous with extreme Blue Nile floods and the formation of the 386 m lake in the lower White Nile Valley, as well as with a prolonged wet phase in the eastern Sahara. Fluctuations in Nile flow and sapropel formation reflect the influence of the precessional cycle upon the East African monsoon. Between 75 ka and 19 ka the climate in the Nile headwaters region became progressively colder and drier. During the Last Glacial Maximum, Lake Tana in Ethiopia and Lake Victoria in Uganda became dry, flow in the White Nile was reduced to a trickle, and the Blue Nile and Atbara became highly seasonal bed–load rivers. The return of the summer monsoon at 14.5 ka ushered in extreme Blue Nile floods, widespread flooding across the Nile Basin and the formation of the 382 m lake in the lower White Nile Valley. There was a brief return to aridity during the Younger Dryas (12.8–11.5 ka), after which the climate again became wetter and widespread flooding in the Nile Valley resumed. The early Holocene floods were later followed by incision and creation of the modern relatively narrow flood plain.

Surface hydrographic changes at the western flank of the Sicily Channel associated with the last sapropel

In the eastern Mediterranean Sea, the early Holocene was characterized by major climatic and oceanographic changes that led to the formation of the last sapropel (S1) between 10.8 and 6.1 kyr cal. BP. These hydrographic changes might have altered the water exchange between the eastern and western Mediterranean sub-basins through the Strait of Sicily, but the existing evidences are inconclusive. In the present study we show new evidence from sediment core NDT-6-2016 located at the western flank of the Sicily channel, a key location to monitor the surface/intermediate water exchange between the two Mediterranean sub-basins. We perform paleo-hydrographic reconstructions based on planktic foraminifera ecology for the last 15 kyr cal. BP, including the S1 deposition interval. In addition, δ 18 O measurements in both Globigerina bulloides and Globigerinoides ruber and also major elements analyses in bulk sediment are presented. Our results show that significant changes in surface water properties occurred in W-Sicily characterized by a strong contrast in the seasonal hydrographic conditions during the S1 interval. This study proposes that the oceanographic changes in the eastern Mediterranean associated with the surface freshening promoted by the African monsoon likely triggered a restricted water exchange through the Strait of Sicily. This situation led to limited influence of the surface Atlantic waters into the studied area that favored the development of intense summer stratification and vertical winter mixing. This situation changed at about 7 kyr cal. BP when a decrease in the summer stratification probably reflected the influence of the eastward path of the surface Atlantic Waters. This situation would suggest a reinforcement of the water exchange through the Strait of Sicily that marked the end of the extreme conditions that prevailed in the eastern Mediterranean during the S1 formation. • Surface hydrographic reorganization related to the sapropel S1 is observed for the first time in the central Mediterranean. • The acquired data provide new evidences of a restricted sea surface water exchange during the S1 across the Strait of Sicily. • Paleo-hydrographic reconstructions are based on planktic foraminifera ecology, major element analyses and δ 18 O measurements.

Black Sea paleosalinity evolution since the last deglaciation reconstructed from alkenone-inferred Isochrysidales diversity

The Black Sea underwent dramatic changes in salinity from the last glacial maximum to Holocene as it evolved from a large inland lake to become a part of the global ocean due to post-glacial sea level rise. However, the detailed history of the re-connection of the Black Sea to the Mediterranean and the resulting Black Sea salinity variations have been heavily debated. We take advantage of our recent study on alkenones from phylogenetically classified haptophyte groups and their association with variable salinity levels in modern environments to reconstruct detailed salinity changes in the Black Sea over the past 16,000 years. We report the first discovery and documentation of alkenones from Group I Isochrysidales in relation to past salinity changes in the Unit III sediment. Our data indicate that the Black Sea surface salinity gradually increased from near fresh at ∼16 ka (∼1-2 psu) to oligohaline (∼ 5-6 psu) at ∼ 9.4 ka, the time of initial marine inflow, suggesting a negative regional hydrological balance. Although the IMI (initial marine inflow) occurred at 9.4 ka, the relatively low surface water salinity levels persisted to the beginning of sapropel formation at 7.6 ka, suggesting a strongly positive regional hydrological balance. Alkenone profiles also indicate a period of significantly reduced salinity between 3.5 and 1.6 ka, differing from the previous proposed peak salinity at 2.7 ka based on alkenone hydrogen isotope values. We demonstrate that the mismatch originates from the predominance of previously unidentified Group II Isochrysidales over E. huxleyi during this time interval, and when species-specific hydrogen isotopic fractionation of alkenones is taken into consideration, the isotope-inferred salinity between 3.5 and 1.6 ka is consistent with our proposal. Our new assessment of the Black Sea salinity evolution since the last glacial shows broad agreement with other regional records and provides a new basis for evaluating the impact of regional hydrological changes on Neolithic human migrations to Europe.

Nannofossil palaeoecology of Lower Miocene sapropels from IODP Expedition 359, the Maldives

During IODP expedition 359 multiple holes recovered Modern to Middle Miocene sediments from the Kardiva Drift which is strongly influenced by monsoonally-driven currents. Two holes continued below the drift into Lower Miocene sediments that were deposited under rather different conditions following Oligocene subsidence of the Maldives Ridge. These sediments are characterised by marked alternation between dark organic-rich sapropelic sediments and pale nannofossil oozes. This interval is also characterised by generally good to excellent nannofossil preservation. Nannofossil assemblages from the sapropel and non-sapropel intervals are broadly similar; both sediment types contain diverse normal marine assemblages and no taxa are confined to either sediment type. In the sapropels nannofossil abundance and diversity tends to be lower and Cyclicargolithus floridanus specimens are smaller. In addition Umbilicosphaera abundances are higher in the non-sapropel layers whilst Discoaster abundance is higher in most sapropels. These differences are more marked in the better developed sapropels. The nannofossil evidence supports the interpretation from geochemistry that sapropel formation was primarily driven by changes in bottom water ventilation linked to sea-level change rather than surface water productivity.

New insights into source and dispersal of Mediterranean S1 tephra, an early Holocene marker horizon erupted at Mt. Erciyes (Turkey)

Deposition of early Holocene Eastern Mediterranean S1 tephra and a Black Sea cryptotephra coincides with cultural transitions in the Fertile Crescent termed the Neolithic Revolution as well as sapropel formation during climate variability of the African humid period, classifying them as paramount regional marker horizons for archaeology as well as paleoclimatology. Their correlations with specific eruptions of the Mt. Erciyes stratovolcanic complex (Central Anatolia) remained inconclusive though. Here, we use zircon double-dating by (U–Th)/He and U–Th disequilibrium methods, major and trace element tephra glass geochemistry, and probabilistic modeling of tephra dispersal in an attempt to characterize all major late Quaternary proximal tephras of Mt. Erciyes, and to correlate them with distal deposits. Furthermore, we discuss contrasting proximal and distal tephra dispersal.Three nearly-coeval rhyolitic satellite domes (Dikkartın, Perikartın, and Karagüllü) erupted at Mt. Erciyes in the early Holocene, and their dome extrusions were all preceded by explosive phases producing pyroclastic material that formed tephra fall and pyroclastic flow deposits. The new eruption age of 9.03 ± 0.55 ka (1σ uncertainty here and elsewhere) for proximal Dikkartın pumice is consistent with 14C-based S1 tephra chronologies in distal locations averaging 8.92 ± 0.03 cal ka BP. Perikartın pyroclastic flow deposits predate S1 tephra by ca. 0.8 ka according to a pair of published 14C ages, and stratigraphically overlie Karagüllü fall-out, here dated to 8.2 ± 1.8 ka. Previously undated proximal tephras of Mt. Erciyes erupted in the Late (85.2 ± 4.9 ka) and Middle Pleistocene (154.5 ± 5.3 ka). S1 tephra glass is chemically similar to that of Dikkartın fall-out, but also indistinguishable from that of Perikartın fall-out. Karagüllü pumice is characterized by a distinct glass chemical composition, which correlates with that of unnamed cryptotephra reported for the southeastern Black Sea instead, where these results call for a re-evaluation of existing age models.Maximum lithic clast size isopleths for proximal Dikkartın fall-out indicate eastward dispersal of a 20 ± 5 km high eruption plume by stratospheric winds, in agreement with results of probabilistic tephra dispersal modeling. This azimuth contrasts with the known distribution of S1 tephra at distal locations that are all south of Mt. Erciyes. Significant tephra occurrences at up to 1300 km distance and orthogonal to prevalent stratospheric wind directions either result from very atypical wind conditions (probability ≪10 %), or are caused by tephra transport by prevailing low altitude winds. Two scenarios are proposed for low altitude transport: eolian reworking of primary fall-out (more likely from the more widespread Dikkartın deposits), or co-ignimbrite ash cloud dispersal (more likely from the Perikartın eruption which predominantly produced pyroclastic flows). Because S1 tephra is chemically indistinguishable from both Dikkartın and Perikartın by major and trace element glass compositions, its exact source and dispersal mechanism remain ambiguous, although existing 14C ages for Perikartın predating those for S1 tephra favor Dikkartın as its source.

Algal biomarkers as a proxy for pCO2: Constraints from late quaternary sapropels in the eastern Mediterranean

Records of carbon dioxide concentrations (partial pressure expressed as pCO2) over Earth’s history provide trends that are critical to understand our changing world. To better constrain pCO2 estimations, here we test organic pCO2 proxies against the direct measurements of pCO2 recorded in ice cores. Based on the concept of stable carbon isotopic fractionation due to photosynthetic CO2 fixation (Ɛp), we use the stable carbon isotopic composition (δ13C) of the recently proposed biomarker phytol (from all photoautotrophs), as well as the conventionally used alkenone biomarkers (from specific species) for comparison, to reconstruct pCO2 over several Quaternary sapropel formation periods (S1, S3, S4, and S5) in the eastern Mediterranean Sea. The reconstructed pCO2 values are within error of the ice core values but consistently exceed the ice core values by ca. 100 µatm. This offset corresponds with atmospheric disequilibrium of present day CO2[aq] concentrations in the Mediterranean Sea from global pCO2, equivalent to ca. 100 µatm, although pCO2 estimates derived from individual horizons within each sapropel do not covary with the ice core values. This may possibly be due to greater variability in local CO2[aq] concentration changes in the Mediterranean, as compared with the global average pCO2, or possibly due to biases in the proxy, such as variable growth rate or carbon-concentrating mechanisms. Thus, the offset is likely a combination of physiological or environmental factors. Nevertheless, our results demonstrate that alkenone- and phytol-based pCO2 proxies yield statistically similar estimations (P-value = 0.02, Pearson’s r-value = 0.56), and yield reasonable absolute estimations although with relatively large uncertainties (±100 µatm).

Factors controlling accumulation of organic carbon in a rift-lake, Oligocene Vietnam

Understanding of the processes of petroleum source rock (SR) accumulation in lacustrine rift basins and the behavior of lake systems as long-term carbon sinks is fragmentary. Investigation of an 800 m thick (500 m core and ~ 300 m outcrop), deep-lacustrine, Oligocene section in Vietnam, provides a rare insight into the controls and deposition of organic carbon (OC) and SR formation in continental rift basins. A multidisciplinary dataset, combining elemental data, inorganic and organic geochemistry with sedimentology, shows that the richest alginite-prone, sapropelic SR developed during periods of relative tectonic quiescence characterized by moderate primary productivity in a mainly dysoxic lacustrine basin. Increased rift activity and further development of graben morphology intensified water column stratification and anoxia, which hindered nutrient recycling. Sapropelic organic matter (OM) continued to accumulate, but with increasing amorphous OM content and decreasing total OC values. Periods of increased seasonality were characterized by thermocline weakening, enhanced mixing of water columns, increased primary productivity and diatom blooming. The results suggest that a change from dysoxia towards anoxia or extreme primary productivity does not necessarily enhance OC burial and SR quality. External nutrient input from a phosphate-rich hinterland is sufficient for sapropel formation, whereas the main limiting factor is methanogenesis.

“Continuous” Backstepping of Holocene Coastal Barrier Systems into Incised Valleys: Insights from the Ofanto and Carapelle-Cervaro Valleys

Two recently recognised incised valleys in the Manfredonia Gulf are described. The first (CCV) is correlated with the current Carapelle and Cervaro streams. The second (OSFV) is correlated mostly with the current Ofanto River. Six seismic facies and seven unconformity-bounded seismic units have been identified, which infilled CCV and OSFV. In CCV, during the sea-level ranges from −29 to −18 and from −18 to −4.7 m b.s.l., two barrier/spit-backbarrier systems formed in the most landward sector of the valley. The lower system was attributed to a time interval between 9.2 ka BP and ca. 8.3 ka BP, chronologically constrained by the ZS2 borehole. In OSFV, during the sea level ranges from −39 to −29, and from −29 and to −18 m b.s.l., two beach/spit-backbarrier systems, arranged in a “continuous” landward backstepping pattern, formed. The phase that contributed most to the beach/spit-backbarrier systems formation is that which is coeval with the formation of the sapropel S1 in the Mediterranean. The conservation of barrier/spit-backbarrier systems arranged in a “continuous” landward backstepping pattern, is due to a strong and continued sediment supply that occurred during the sapropel S1 formation, coupled with low-gradient settings and a regime of slow sea-level rise.

The mechanism of sapropel formation in the Mediterranean Sea: insight from long-duration box model experiments

Abstract. Periodic bottom-water oxygen deficiency in the Mediterranean Sea led to the deposition of organic-rich sediments during geological history, so-called sapropels. Although a mechanism linking the formation of these deposits to orbital variability has been derived from the geological record, physics-based proof is limited to snapshot and short-time-slice experiments with (oceanic) general circulation models. Specifically, previous modelling studies have investigated atmospheric and oceanographic equilibrium states during orbital extremes (minimum and maximum precession). In contrast, we use a conceptual box model that allows us to focus on the transient response of the Mediterranean Sea to orbital forcing and investigate the physical processes causing sapropel formation. The model is constrained by present-day measurement data, while proxy data offer constraints on the timing of sapropels. The results demonstrate that it is possible to describe the first-order aspects of sapropel formation in a conceptual box model. A systematic model analysis provides new insights on features observed in the geological record, such as the timing of sapropels as well as intra-sapropel intensity variations and interruptions. Moreover, given a scenario constrained by geological data, the model allows us to study the transient response of variables and processes that cannot be observed in the geological record. The results suggest that atmospheric temperature variability plays a key role in sapropel formation and that the timing of the midpoint of a sapropel can shift significantly with a minor change in forcing due to nonlinearities in the system.

Tracing water column euxinia in Eastern Mediterranean Sapropels S5 and S7

Sapropels S5 and S7 formed in the semi-enclosed Eastern Mediterranean Sea (EMS) during peak interglacial periods MIS5e and MIS7a, respectively, are considered among the most strongly developed Quaternary sapropels. This study investigates the redox dynamics of the water column during their formation, via Fe isotope and Fe speciation studies of cores taken at 2550 m depth at site ODP-967. Both sapropels show an inverse correlation between δ56Fe and FeT/Al, with slopes mostly matching that found for the Black Sea, pointing to a benthic shelf to basin shuttle of Fe and subsequent precipitation of Fe sulphides in euxinic bottom waters. An exception to these Black Sea-type trends occurs during the later, peak, stages of S7, where the negative δ56Fe - FeT/Al slope shallows. Fe speciation studies reveal that the dominant highly reactive Fe phase (FeHR) in the sapropels is pyrite, with Fe (oxyhydr)oxides forming the second major mineral component. Correspondingly, FeHR/FeT plots show increased strengthening of anoxic water conditions during the passage from pre-sapropel sediment into the sapropel. Nevertheless, despite the evidence for euxinic conditions from both Fe isotopes and high Mo concentrations in the sapropel, Fepy/FeHR ratios remain below values commonly used to identify water column euxinia. This apparent contradiction is ascribed to the sedimentary preservation of a high flux of crystalline Fe (oxyhydr)oxide minerals to the basin, which resulted in a relatively low degree of sulphidation, despite the presence of euxinic bottom waters. Thus, the operationally defined ferruginous/euxinic boundary for EMS sapropels is better placed at Fepy/FeHR = 0.6, which is somewhat below the usually ascribed lower limit of 0.7. Consistent with the significant presence of crystalline Fe (oxyhydr)oxides, the change in the δ56Fe - FeT/Al slope during peak S7 is ascribed to an enhanced monsoon-driven flux of detrital Fe(III) oxides from the River Nile into the EMS basin and comcomitant diagenetic sulphidation. Euxinic water column conditions in sapropel S5 and S7 are interpreted here to reflect the positive balance between dissolved sulphide formation and rates of reductive dissolution of Fe (oxyhydr)oxide minerals. Both of these parameters in turn depend on the extent to which water overturn times are reduced and export productivity increased during sapropel formation.

Dynamic surface-water alterations during sapropel S1 preserved in high-resolution shallow-water sediments of Taranto Gulf, central Mediterranean

The high sedimentation rate and shallow-water depositional depth of the sediments at site DP 30 in the Gulf of Taranto (central Mediterranean) provide unique biogenic signals that are usually not preserved in deeper records. This permits the reconstruction of long and short-term surface water modifications across the sapropel S1 period (10–6.5 ka), including calcareous nannofossil data at centennial-scale resolution.The peculiar patterns of key taxa allowed the recognition of distinct long to short-term surface water changes that provide valuable evidence on climate conditions leading to sapropel deposition. As a long-term pattern, S1 is marked by a distinct increase of Helicosphaera carteri, thought to reflect increased detrital input/land-derived nutrients in the surface water, related to a higher influence of the Western Adriatic Current. A concomitant pattern of increased black organic particles in the sediments supports a connection between organic matter preservation at the seafloor and nutrient availability in the surface water. Decreased salinity in the surface water, testified by an increase of Braurudosphaera bigelowii, develops from 9.2 up to 6.5 ka.At higher frequencies, additional changes occurred in surface-subsurface waters during the formation of S1 at shallow depths. Starting from 11 ka, the relative abundance pattern of Florisphaera profunda indicates a gradual nutrient enrichment in the subsurface waters and the development of a deep chlorophyll maximum (DCM), which becomes well established at the onset of sapropel S1, between 10 and 9 ka. A further change in the plankton ecosystem occurs between 9 and 8.2 ka, when reduced coccolithophore production is concomitant with diatom occurrence and enhanced Br/Ti level, implying a productivity increase. From 8 to 6.5 ka, coccolithophore productivity is re-established in relation to a reduction both in surface-water stratification and turbidity/nutrient availability, characterizing the final phase of sapropel formation. The turbidity in the surface waters was briefly reduced at 8.2 and 7.3 ka, when also oxygen conditions at the seafloor improved. A centennial variability in turbidity/low light conditions in surface waters is evident across S1 and is illustrated by the abundance patterns of H. carteri and Gladiolithus flabellatus. The occurrence of ascidian spicules also represents a distinct biotic signal across the S1 layer, indicating an increase of shallow-water biogenic carbonate or an aragonitic near-coastal source. Surface-water modifications at longer and shorter time scales, accompanying the deposition of sapropel S1 in the Gulf of Taranto, occurred nearly simultaneously and with a magnitude that is comparable to changes observed in S1 deposits in the central and eastern Mediterranean basin and slope settings.

Biomarker evidence for the occurrence of anaerobic ammonium oxidation in the eastern Mediterranean Sea during Quaternary and Pliocene sapropel formation

Abstract. The eastern Mediterranean Sea sedimentary record is characterised by intervals of organic-rich sapropel sediments, indicating periods of severe anoxia triggered by astronomical forcing. It has been hypothesised 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 reactions like 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. Using an alternative lipid biomarker for anammox, bacteriohopanetetrol stereoisomer (BHT isomer), we present here for the first time N removal throughout the progression, e.g. formation, propagation, and termination, of basin-wide anoxic events. BHT isomer and ladderanes were analysed in sapropel records taken from three eastern Mediterranean sediment cores, spanning S1 to Pliocene sapropels. Ladderanes were rapidly degraded in sediments, as recently as the S5 sapropel. BHT isomer, however, was present in all sapropel sediments, as far back as the Pliocene, 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-type 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 sulfide 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.

Paleo-ecologic and neotectonic evolution of a marine depositional environment in SE Rhodes (Greece) during the early Pleistocene

We have studied benthic foraminiferal assemblages in a marine sediment section (Pefka E section) from the Lindos Bay Formation deposited during the early Pleistocene to provide new insights into the paleo-ecologic and neotectonic evolution of the SE part of the island of Rhodes (NE Mediterranean Sea). Relatively high amounts of eutrophic/low oxygen tolerant species and a comparatively high foraminiferal diversity indicate generally mesotrophic conditions at the sea floor and the presence of well-oxygenated bottom waters. These conditions are attributed to generally elevated surface water productivity and related organic matter fluxes during the early Pleistocene, which is in contrast to the modern oligotrophic conditions in this region. The abundance of individual species shows orbital-driven variability in the obliquity (41 kyr) and precessional (∼23 kyr) bands. Obliquity-driven changes in food availability are indicated by increased percentages of Cassidulina carinata s.l. during marine isotope stages (MIS) 44 and 42, reflecting enhanced food fluxes under glacial conditions. Precession-driven changes are observed for Ca. carinata s.l., Cibicidoides pseudoungerianus s.l., Cibicidoides mundulus and Gyroidinoides altiformis. These changes likely reflect prolonged near-coastal phytoplankton blooms triggered by local fresh-water runoff at times of Northern-Hemisphere insolation maxima, coeval to the formation of sapropels in the adjacent deep-sea basins. The application of a benthic foraminiferal transfer function allowed for the identification of a number of short-term subsidence-uplift cycles, superimposed by overall long-term subsidence of the SE coast of Rhodes. Estimated average uplift and subsidence rates vary between ∼4.2 and ∼10.3 mm/yr. These rates of tectonic motions are distinctly higher compared to most other estimates from Rhodes and suggest a complex neotectonic history of the island during the early Pleistocene, involving both large-scale and local motions associated with alternating compressional and extensional regimes.