Lipid biomarkers in Holocene and glacial sediments from ancient Lake Ohrid (Macedonia, Albania)

Abstract. Organic matter preserved in Lake Ohrid sediments originates from aquatic and terrestrial sources. Its variable composition reflects climate-controlled changes in the lake basin’s hydrology and related organic matter export, i.e. changes in primary productivity, terrestrial plant matter input and soil erosion. Here, we present first results from lipid biomarker investigations of Lake Ohrid sediments from two near-shore settings: site Lz1120 near the southern shore, with low-lying lands nearby and probably influenced by river discharge, and site Co1202 which is close to the steep eastern slopes. Variable proportions of terrestrial n-alkanoic acids and n-alkanols as well as compositional changes of !- hydroxy acids document differences in soil organic matter supply between the sites and during different climate stages (glacial, Holocene, 8.2 ka cooling event). Changes in the vegetation cover are suggested by changes in the dominant chain length of terrestrial n-alkanols. Effective microbial degradation of labile organic matter and in situ contribution of organic matter derived from the microbes themselves are both evident in the sediments. We found evidence for anoxic conditions within the photic zone by detecting epicholestanol and tetrahymanol from sulphur-oxidising phototrophic bacteria and bacterivorous ciliates and for the influence of a settled human community from the occurrence of coprostanol, a biomarker for human and animal faeces (pigs, sheep, goats), in an early Holocene sample. This study illustrates the potential of lipid biomarkers for future environmental reconstructions using one of Europe’s oldest continental climate archives, Lake Ohrid.

The history of subaquatic volcanism recorded in the sediments of Lake Kivu

Subaquatic volcanic activity has been ongoing in Lake Kivu since the early Holocene and has a dynamic effect on the biological productivity in the surface water, and the preservation of carbonate in the deep anoxic water. Groundwater discharge into the lake’s deepwater propels the upward advection of the water column that ultimately supplies nutrients to the surface water for biological production. The amount of nutrients supplied from the deepwater can be increased suddenly by (1) a cold meteorological event that drives deep seasonal mixing resulting in increased nutrients from below and oxygen from above, or (2) subaquatic volcanic activity that induces a buoyant hydrothermal plume, which entrains nutrients from the deepwater and results in anoxia or suboxic conditions in the surface water. Previous sedimentological studies in Lake Kivu have hypothesized that regional climatic changes are responsible for sudden changes in the preservation of carbonates in the Main Basin. Here we reveal that sublacustrine volcanic events most likely induce the abrupt changes to the geochemistry in the sediment in Lake Kivu. An unprecedented look into the sediment stratigraphy and geochemistry from high-resolution seismic-reflection, and 15N-isotope analyses was conducted in the Main Basin. The results reveal that buoyant hydrothermal plumes caused by subaquatic volcanic activity are a possible trigger for increased biological productivity and organic matter preservation, and that ongoing hydrothermal activity increases the alkalinity in the deepwater, leading to carbonate preservation. The onset of carbonate preservation since the 1970s that is currently observed in the sediment could indicate that hydrothermal discharge has recently increased in the lake.

Geochemistry of Cenozoic sediments from the central Artic Ocean

Integrated Ocean Drilling Program (IODP) Expedition 302 (Arctic Coring Expedition, ACEX) recovered a unique sediment record from the central Arctic Ocean, revealing that this region underwent major environmental fluctuations since the Late Cretaceous. Major and trace element composition of 1,300 samples were determined using X-ray fluorescence (XRF). The results show significant compositional variability of the sediments with depth that can be attributed to changes in (a) provenance and pathways of detrital material, (b) paleoenvironmental conditions and depositional processes, and (c) diagenetic overprint of the primary record. In addition to existing lithological units, we introduce new geochemical units for a more process-related approach interpreting the ACEX record. In detail, via the geochemical signature of Siberian flood basalts we are able to reconstruct the discontinuous rifting and deepening of the central Lomonosov Ridge during the Paleogene, accompanied by changing current regimes and the onset of sea ice. Eocene biosiliceous sedimentation took place in a relatively shallow setting under predominantly anoxic bottom water conditions, causing a positive anoxia-productivity feedback, although water column stratification was repeatedly interrupted by ventilation events. Anoxic to sulfidic conditions were even more extreme after biosilica production ceased, and significant amounts of pyrite were deposited on the Lomonosov Ridge. Especially in organic matter-rich Paleogene deposits, diagenetic processes obscured the paleoenvironmental signals. Fundamental environmental changes occurred in the Middle Eocene, but geochemical and micropaleontological proxies point not to the identical sediment depth. After approximately 26 Ma of non-deposition or erosion, the Middle Miocene record shows the transition to dominantly oxic bottom water conditions, although suboxic diagenesis seemingly affected these deposits.

Geochemical and nannofossil analyses of Cenomanian/Turonian sediments of DSDP Hole 75-530A

One of the key objectives of Deep Sea Drilling Project (DSDP) Leg 75 was to shed light on the underlying causes of Cretaceous oceanic anoxia in the South Atlantic by addressing two major hypotheses: productivity productivity-driven anoxia vs. enhanced ocean stratification leading to preservation of organic matter and black shale deposition. Here we present a detailed geochemical dataset from sediments deposited during the Cenomanian/Turonian (C/T) transition and the global oceanic anoxic event 2 (OAE 2) at DSDP Site 530A, located off-shore Namibia (southeast Angola Basin, north of Walvis Ridge). To characterise the succession of alternating black and green shales at this site and to reconstruct the evolution of their paleoenvironmental setting, we have combined data derived from investigations on bulk organic matter, biomarkers and the inorganic fraction. The location of the C/T boundary itself is biostratigraphically not well constrained due to the carbonate-poor (but organic matter-rich) facies of these sediments. The bulk d13Corg record and compound-specific d13C data, in combination with published as well as new biostratigraphic data, enabled us to locate more precisely the C/T boundary at DSDP Site 530A. The compound-specific d13C record is the first of this kind reported from C/T black shales in the South Atlantic. It is employed for paleoenvironmental reconstructions and chemostratigraphic correlation to other C/T sections in order to discuss the paleoceanographic aspects and implications of the observations at DSDP Site 530A in a broader context, e.g., with regard to the potential trigger mechanisms of OAE 2, global changes in black shale deposition and climate. On a stratigraphic level, an approximation and monitoring of the syndepositional degree of oxygen depletion within the sediments/bottom waters in comparison to the upper water column is achieved by comparing normalised concentrations of redox-sensitive trace elements with the abundance of highly source specific molecular compounds. These biomarkers are derived from photoautotrophic and simultaneously anoxygenic green sulphur bacteria (Chlorobiacea) and are interpreted as paleoindicators for events of photic zone euxinia. In contrast to a number of other OAE 2 sections that are characterised by continuous black shale sequences, DSDP Site 530A represents a highly dynamic setting where newly deposited black shales were repeatedly exposed to conditions of subtle bottom water re-oxidation, presumably leading to their progressive alteration into green shales. The frequent alternation between both facies and the related anoxic to slight oxygenated conditions can be best explained by variations in vertical extent of an oxygen minimum zone in response to changes in a highly productive western continental margin setting driven by upwelling.

(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.

Dinoflagellate and other palynomorph abundance in sediments from ODP Leg 189 sites

At Ocean Drilling Program (ODP) Leg 189 Sites 1170-1172, the climatologically critical Eocene-Oligocene (E-O) transition is barren of any calcareous microfossils but contains rich marine organic walled dinoflagellate cyst (dinocyst) and diatom assemblages, suitable for detailed biostratigraphic and paleoenvironmental analysis. The resulting first-ever integrated dinocyst/diatom magnetostratigraphy allows confident correlation of the E-O interval between all Leg 189 sites, including Site 1168. Our correlations indicate that the (deep) opening of the Tasmanian Gateway occurred quasi-synchronously throughout the Tasmanian region, starting at ~35.5 Ma. At Sites 1170-1172, quantitatively, three distinct dinocyst assemblages may be distinguished that reflect the relatively rapid and pronounced stepwise environmental changes associated with the E-O transition in the Tasmanian region, from a pro-deltaic setting to a deep marine pelagic setting. Moreover, synchronous with the deepening of the gateway, at the southern and eastern Sites 1170-1172, typical endemic Antarctic assemblages were replaced by more cosmopolitan dinocyst communities. In marked contrast, at Site 1168 off western Tasmania, endemic Antarctic taxa are virtually absent during the E-O transition. At Sites 1170-1172, the endemic Antarctic dinocyst assemblage (Transantarctic Flora) drastically changes into a more cosmopolitan assemblage at ~35.5 Ma, with a more offshore character, reflecting the arrival of different oceanographic and environmental conditions associated with the deepening of the Tasmanian Gateway. In turn, this assemblage grades at ~34 Ma into one more typical for even more offshore and/or upwelling conditions at Site 1172. In slightly younger deposits at all sites, organic microfossils are virtually absent, reflecting winnowing and oxidation, indicative of a next step of oceanographic development. This phase may be dated as close to the Oceanic Anoxic (Oi)-1 18O (Antarctic glaciation) event (~33.3 Ma). In a single productive sample from the earliest Oligocene the northern Site 1172, a relatively warm-water cosmopolitan assemblage has been recovered. This aspect contrasts findings from coeval deposits from the Ross Sea, where endemic Antarctic species remain dominant. Somewhere between the paleogeographic positions of Site 1172 and the Ross Sea, a strong differentiation of surface waters occurred in the earliest Oligocene, possibly reflecting the onset of the Antarctic Circumpolar Current.

Geochemistry of sediments and kerogenes of ODP Hole

The organic matter contained within a series of Albian to Cenomanian, dark gray to black marls was characterized using pyrolysis techniques and analysis (elemental and carbon isotopes) of isolated kerogens. It was concluded that this material had a marine affinity. Variations in geochemical characteristics reflect differences in the extent of preservation, rather than changes in organic provenance. These changes appear to reflect differences in water depth and the position of the depositional site relative to the oxygen-minimum zone. Sediments displaying the most elevated levels of organiccarbon and hydrogen enrichment probably reflect sedimentation within the oxygen-minimum zone. Waters within the oxygen-minimum zone were probably dysaerobic, rather than anoxic. The presence of at least trace quantities of oxygen at the depositional site explains the poor degree of organic preservation and the material's largely gas-prone characteristics.

Sulphur and iron species in Dvurechenskii mud volcano sediments

The deep Black Sea is known to be depleted in electron-acceptors for sulphide oxidation. This study on depth distributions of sulphur species (S(II), S(0),S(n)**2-,S2O3**2-,SO3**2-,SO4**2-) in the Dvurechenskii mud volcano, a cold seep situated in the permanently anoxic eastern Black Sea basin (Sorokin Trough, 2060 m water depth), showed remarkable concentrations of sulphide oxidation products. Sulphite concentrations of up to 11 µmol L**1-, thiosulphate concentrations of up to 22 µmol L**1-, zero-valent sulphur concentrations of up to 150 µmol L**1- and up to five polysulphide species were measured in the upper 20 cm of the sediment. Electron-acceptors found to be available in the Dvurechenskii mud volcano (DMV) for the oxidation of hydrogen sulphide to sulphide oxidation intermediates are iron-minerals, and probably also reactive manganese phases. Up to 60 µmol g**1- of reactive iron-minerals and up to 170 µmol L**1- dissolved iron was present in the central summit with the highest fluid upflow and fresh mud outflow. Thus, the source for the oxidative power in the DMV are reactive iron phases extruded with the mud from an ancient source in the deeply buried sediments, leading to the formation of various sulphur intermediates in comparably high concentrations. Another possible source of sulphide oxidation intermediates in DMV sediments could be the formation of zero-valent sulphur by sulphate dependent anaerobic microbial oxidation of methane followed by disproportionation of zero-valent sulphur. Sulphide oxidation intermediates, which are produced by these processes, do not reach thermodynamic equilibrium with rhombic sulphur, especially close to the active center of the DMV due to a short equilibration time. Thus, mud volcano sediments, such as in the DMV, can provide oxidizing niches even in a highly reduced environment like the abyssal part of the Black Sea.

Geochemistry on Holocene sediments from the Mediterranean

The enhanced accumulation of organic matter in Eastern Mediterranean sapropels and their unusually low d15N values have been attributed to either enhanced nutrient availability which led to elevated primary production and carbon sequestration or to enhanced organic matter preservation under anoxic conditions. In order to evaluate these two hypothesis we have determined Ba/Al ratios, amino acid composition, N and organic C concentrations and d15N in sinking particles, surface sediments, eight spatially distributed core records of the youngest sapropel S1 (10-6 ka) and older sapropels (S5, S6) from two locations. These data suggest that (i) temporal and spatial variations in d15N of sedimentary N are driven by different degrees of diagenesis at different sites rather than by changes in N-sources or primary productivity and (ii) present day TOC export production would suffice to create a sapropel like S1 under conditions of deep-water anoxia. This implies that both enhanced TOC accumulation and d15N depletion in sapropels were due to the absence of oxygen in deep waters. Thus preservation plays a major role for the accumulation of organic-rich sediments casting doubt on the need of enhanced primary production for sapropel formation.

Electromagnetic, rock magnetic, and geochemical properties of surficial sediments in Eckernförde Bay

Submarine groundwater discharge in coastal settings can massively modify the hydraulic and geochemical conditions of the seafloor. Resulting local anomalies in the morphology and physical properties of surface sediments are usually explored with seismo-acoustic imaging techniques. Controlled source electromagnetic imaging offers an innovative dual approach to seep characterization by its ability to detect pore-water electrical conductivity, hence salinity, as well as sediment magnetic susceptibility, hence preservation or diagenetic alteration of iron oxides. The newly developed electromagnetic (EM) profiler Neridis II successfully realized this concept for a first time with a high-resolution survey of freshwater seeps in Eckernförde Bay (SW Baltic Sea). We demonstrate that EM profiling, complemented and validated by acoustic as well as sample-based rock magnetic and geochemical methods, can create a crisp and revealing fingerprint image of freshwater seepage and related reductive alteration of near-surface sediments. Our findings imply that (1) freshwater penetrates the pore space of Holocene mud sediments by both diffuse and focused advection, (2) pockmarks are marked by focused freshwater seepage, underlying sand highs, reduced mud thickness, higher porosity, fining of grain size, and anoxic conditions, (3) depletion of Fe oxides, especially magnetite, is more pervasive within pockmarks due to higher concentrations of organic and sulfidic reaction partners, and (4) freshwater advection reduces sediment magnetic susceptibility by a combination of pore-water injection (dilution) and magnetite reduction (depletion). The conductivity vs. susceptibility biplot resolves subtle lateral litho- and hydrofacies variations.

Investigations on sediments from Lake Nam Co (Tibetan Plateau)

This study focuses on the analysis of lake sediments retrieved from the deepest part of Lake Nam Co (Tibetan Plateau). One gravity core of 115 cm length, covering the last ~ 4000 cal BP, was analyzed for geochemical and biological parameters. High organic content at ~ 4000 cal BP and the coinciding presence of pyrite framboids until ~ 2000 cal BP point to hampered decomposition of organic material due to anoxic conditions within the lake sediments. At the same time sedimentological and biological proxies suggest a rather high lake level, but still ~ 5 m below the recent one, with less saline lake water due to enhanced monsoonal activity. During this time a change in the source of organic matter to lowered input of terrestrial components is observed. A rather quick shift to a dry environment with less monsoonal influence and a lake level ~ 15 m lower than today at ~ 2000 cal BP lead to the oxygenation of sediment, the degradation of organic matter and the absence of pyrite. Oscillations of the lake level thereafter were of minor amplitude and not able to establish anoxia at the lake bottom again. A wet spell between ~ 1500 cal BP and ~ 1150 cal BP is visible in proxies referring to catchment hydrology and the ostracod-based water depth transfer function gives only a slightly elevated lake level. The last ~ 300 years are characterized by low TOC and rising TN values reflecting enhanced nutrient supply and hence an advancing influence of human activity in the catchment. Decreasing TOC/TN values point to a complete shift to almost solely aquatic biomass production. These results show that hydrological variations in terms of lake level change based on monsoonal strength can be linked to redox conditions at the lake bottom of Nam Co. Comparison with other archives over larger parts of the Tibetan Plateau and beyond exhibits a rather homogeneous climatic pattern throughout the late Holocene.

Organic matter composition of Cretaceous sediments of the central Pacific Ocean

Complete records of organic-carbon-rich Cretaceous strata were continuouslycored on the flanks of the Mid-Pacific Mountains and southern Hess Rise in the central North Pacific Ocean during DSDP Leg 62. Organic-carbon-rich laminated silicified limestones were deposited in the western Mid-Pacific Mountains during the early Aptian, a time when that region was south of the equator and considerably shallower than at present. Organic-carbon-rich, laminated limestone on southern Hess Rise overlies volcanic basement and includes 136 m of stratigraphic section of late Albian to early Cenomanian age. This limestone unit was deposited rapidly as Hess Rise was passing under the equatorial high-productivity zone and was subsiding from shallow to intermediate depths. The association of volcanogenic components with organic-carbon-rich strata on Hess Rise in the Mid-Pacific Mountains is striking and suggests that there was a coincidence of mid-plate volcanic activity and the production and accumulation of organic matter at intermediate water depths in the tropical Pacific Ocean during the middle Cretaceous. Pyrolysis assays and analyses of extractable hydrocarbons indicate that the organic matter in the limestone on Hess Rise is composed mainly of lipid-rich kerogen derived from aquatic marine organisms and bacteria. Limestones from the Mid-Pacific Mountains generally contain low ratios of pyrolytic hydrocarbons to organic carbon and low hydrogen indices, suggesting that the organic matter may contain a significant proportion of land-derived material, possibly derived from numerous volcanic islands that must have existed before the area subsided. The organic carbon in all samples analyzed is isotopically light (d13C -24 to -29 per mil) relative to most modern rine organic carbon, and the lightest carbon is also the most lipid-rich. There is a positive linear correlation between sulfur and organic carbon in samples from Hess Rise and from the Mid-Pacific Mountains. The slopes and intercepts of C-S regression lines however, are different for each site and all are different from regression lines for samples from modern anoxic marine sediments and from Black Sea cores. The organic-carbon-rich limestones on Hess Rise, the Mid-Pacific Mountains, and other plateaus and seamounts in the Pacific Ocean are not synchronous but do occur within the same general middle Cretaceous time period as organic-carbon-rich lithofacies elsewhere in the world ocean, particularly in the Atlantic Ocean. Strata of equivalent age in the deep basins of the Pacific Ocean are not rich in organic carbon, and were deposited in oxygenated environments. This observation, together with the evidence that the plateau sites were considerably shallower and closse to the equator during the middle Creataceous suggests that local tectonic and hydrographic conditions may have resulted in high surface-water productivity and the preservation of organic matter in an oxygen-deficient environment where an expanded mid-water oxygen minimum developed and impinged on elevated platforms and seamounts.

Investigations of Cretaceous and Tertiary kerogens in sediments of ODP Leg 113 holes

Seventy-one samples from nine sites were analyzed for total organic carbon (TOC). Fifty-six samples, containing 0.2% or more TOC, were evaluated by Rock-Eval to assess the nature of their kerogen and its petroleum source potential. Visual kerogen studies were carried out. Petroleum potential was encountered only in Valanginian calcareous claystones at Hole 692B close to the margin of Dronning Maud Land. A section of 44.7 m was penetrated. The unit possesses a revised mean TOC of 9.8% and petroleum potential of 43.2 kg/Mg, relatively high values in comparison to other Cretaceous anoxic oceanic sections and the totality of petroleum source rocks. At Sites 689 and 690, extremely low TOC levels, mean 0.07%, preclude kerogen analysis. Kerogens in Eocene to Pliocene sediments of the central and western Weddell Sea (Sites 694, 695, 696, and 697) are similar everywhere, largely comprising brown to black, granular, amorphous material of high rank, and generally possessing several reflectance populations of vitrinite particles. The latter are interpreted as indicative of the recycling of sediments of a variety of levels of thermal maturity.