Sedimentology, organic geochemistry, and stable isotopes of core PS2138-1

We studied variations in terrigenous (TOM) and marine organic matter (MOM) input in a sediment core on the northern Barents Sea margin over the last 30 ka. Using a multiproxy approach, we reconstructed processes controlling organic carbon deposition and investigated their paleoceanographic significance in the North Atlantic-Arctic Gateways. Variations in paleo-surface-water productivity are not documented in amount and composition of organic carbon. The highest level of MOM was deposited during 25-23 ka as a result of scavenging on fine-grained, reworked, and TOM-rich material released by the retreating Svalbard/Barents Sea ice sheet during the late Weichselian. A second peak of MOM is preserved because of sorptive protection by detrital and terrigenous organic matter, higher surface-water productivity due to permanent intrusion of Atlantic water, and high suspension load release by melting sea ice during 15.9-11.2 ka.

Age determinations, biomarker analyses, and accumulation rates of three sediment cores from the Fram Strait

A reconstruction of Holocene sea ice conditions in the Fram Strait provides insight into the palaeoenvironmental and palaeoceanographic development of this climate sensitive area during the past 8,500 years BP. Organic geochemical analyses of sediment cores from eastern and western Fram Strait enable the identification of variations in the ice coverage that can be linked to changes in the oceanic (and atmospheric) circulation system. By means of the sea ice proxy IP25, phytoplankton derived biomarkers and ice rafted detritus (IRD) increasing sea ice occurrences are traced along the western continental margin of Spitsbergen throughout the Holocene, which supports previous palaeoenvironmental reconstructions that document a general cooling. A further significant ice advance during the Neoglacial is accompanied by distinct sea ice fluctuations, which point to short-term perturbations in either the Atlantic Water advection or Arctic Water outflow at this site. At the continental shelf of East Greenland, the general Holocene cooling, however, seems to be less pronounced and sea ice conditions remained rather stable. Here, a major Neoglacial increase in sea ice coverage did not occur before 1,000 years BP. Phytoplankton-IP25 indices ("PIP25-Index") are used for more explicit sea ice estimates and display a Mid Holocene shift from a minor sea ice coverage to stable ice margin conditions in eastern Fram Strait, while the inner East Greenland shelf experienced less severe to marginal sea ice occurrences throughout the entire Holocene.

Biomarker proxies on ODP Holes 151-912A and 151-912B

A novel and promising biomarker proxy for reconstruction of Arctic sea ice conditions was developed and is based on the determination of a highly branched isoprenoid with 25 carbons (IP25). IP25 records have been restricted to the last 150 kyr BP. We present a biomarker record from Ocean Drilling Program (ODP) Site 912, going back to the Pliocene-Pleistocene boundary and indicating that sea ice of variable extent occurred in the Fram Strait/southern Yermak Plateau area at least since about 2.2 Ma. Furthermore, our data support the idea that a combination of IP25 and open water, phytoplankton biomarker data ("PIP25 index") may give a more reliable and quantitative estimate of past sea ice cover (at least for the study area). The study reveals that the novel IP25/PIP25 biomarker approach has potential for semi-quantitative paleo-sea ice studies covering the entire Quaternary and could motivate further detailed high resolution research on ODP/IODP material using this proxy.

Biomarker distributions in surface sediments from the Kara and Laptev Seas (Arctic Ocean)

Studies of spatial and temporal changes in modern and past sea-ice occurrence may help to understand the processes controlling the recent decrease in Arctic sea-ice cover. Here, we determined concentrations of IP25, a novel biomarker proxy for sea ice developed in recent years, phytoplankton-derived biomarkers (brassicasterol and dinosterol) and terrigenous biomarkers (campesterol and ß-sitosterol) in the surface sediments from the Kara and Laptev seas to estimate modern spatial (seasonal) sea-ice variability and organic-matter sources. C25-HBI dienes and trienes were determined as additional paleoenvironmental proxies in the study area. Furthermore, a combined phytoplankton-IP25 biomarker approach (PIP25 index) is used to reconstruct the modern sea-ice distribution more quantitatively. The terrigenous biomarkers reach maximum concentrations in the coastal zones and estuaries, reflecting the huge discharge by the major rivers Ob, Yenisei and Lena. Maxima in phytoplankton biomarkers indicating increased primary productivity were found in the seasonally ice-free central part of the Kara and Laptev seas. Neither IP25 nor PIP25, however, show a clear and simple correlation with satellite sea-ice distribution in our study area due to the complex environmental conditions in our study area and the transportation process of sea-ice diatom in the water column. Differences in the diene/IP25 and triene/IP25 ratios point to different sources of these HBIs and different environmental conditions. The diene/IP25 ratio seems to correlate positively with sea-surface temperature, while negatively with salinity distributions.

Organic compounds in surface sediments from the Pakistan continental margin

In order to assess whether the oxygen-minimum zone (OMZ) in the Arabian sea has an effect on the preservation and composition of organic matter in surface sediments we investigated samples from three different transects on the Pakistan continental margin across the OMZ. In addition to determining the total amount of organic carbon (TOC), we analyzed the extractable lipids by gas chromatography, combined gas chromatography/mass spectrometry, and compound-specific stable carbon isotope measurements. The extractable lipids are dominated by marine organic matter as indicated by the abundance of lipids typical of marine biota and by the bulk and molecular isotopic composition. Sediments from within the OMZ are enriched in organic carbon and in several extractable lipids (i.e. phytol, n-alcohols, total sterols, n-C35 alkane) relative to stations above and below this zone. Other lipid concentrations, such as those of total n-fatty acids and total n-alkanes fail to show any relation to the OMZ. Only a weak correlation of TOC with mineral surface area was found in sediments deposited within the OMZ. In contrast, sediments from outside the OMZ do not show any relationship between TOC and surface area. Among the extractable lipids, only the n-alkane concentration is highly correlated with surface area in sediments from the Hab and Makran transects. In sediments from outside the OMZ, the phytol and sterol concentrations are also weakly correlated with mineral surface area. The depositional environment of the Indus Fan offers the best conditions for an enhanced preservation of organic matter. The OMZ, together with the undisturbed sedimentation at moderate rates, seems to be mainly responsible for the high TOC values in this area. Overall, the type of organic matter and its lability toward oxic degradation, the mineral surface area, the mineral composition, and possibly the secondary productivity by (sedimentary) bacteria also appear to have an influence on organic matter accumulation and composition.

Biomarker distributions in surface sediments from the Central Arctic Ocean and adjacent marginal seas

Records of the spatial and temporal variability of Arctic Ocean sea ice are of significance for understanding the causes of the dramatic decrease in Arctic sea-ice cover of recent years. In this context, the newly developed sea-ice proxy IP25, a mono-unsaturated highly branched isoprenoid alkene with 25 carbon atoms biosynthesized specifically by sea-ice associated diatoms and only found in Arctic and sub-Arctic marine sediments, has been used to reconstruct the recent spatial sea-ice distribution. The phytoplankton biomarkers 24S-brassicasterol and dinosterol were determined alongside IP25 to distinguish ice-free or permanent ice conditions, and to estimate the sea-ice conditions semi-quantitatively by means of the phytoplankton-IP25 index (PIP25). Within our study, for the first time a comprehensive data set of these biomarkers was produced using fresh and deep-frozen surface sediment samples from the Central Arctic Ocean proper (>80°N latitude) characterised by a permanent ice cover today and recently obtained surface sediment samples from the Chukchi Plateau/Basin partly covered by perennial sea ice. In addition, published and new data from other Arctic and sub-Arctic regions were added to generate overview distribution maps of IP25 and phytoplankton biomarkers across major parts of the modern Arctic Ocean. These comprehensive biomarker data indicate perennial sea-ice cover in the Central Arctic, ice-free conditions in the Barents Sea and variable sea-ice situations in other marginal seas. The low but more than zero values of biomarkers in the Central Arctic supported the low in-situ productivity there. The PIP25 index values reflect modern sea-ice conditions better than IP25 alone and show a positive correlation with spring/summer sea ice. When calculating and interpreting PIP25 index as a (semi-quantitative) proxy for reconstructions of present and past Arctic sea-ice conditions from different Arctic/sub-Arctic areas, information of the source of phytoplankton biomarkers and the possible presence of allochthonous biomarkers is needed, and the records of the individual biomarkers always should be considered as well.

Organic geochemistry of sediments from sapropel 94 of ODP Hole 161-974C

Analysis of the molecular composition of the organic matter (OM) from whole sediment samples can avoid analytical bias that might result from isolation of components from the sediment matrix, but has its own analytical challenges. We evaluated the use of GC * GC-ToFMS to analyze the pyrolysis products of six whole sediment samples obtained from above, within and below a 1 million year old OM-rich Mediterranean sapropel layer. We found differences in pyrolysis products

Biomarkers in turbidites at ODP Sites 157-951 and 157-952

Free and ester-bound lipid biomarkers were analysed in oxidised and unoxidised parts of four distinct turbidites from the Madeira Abyssal Plain (MAP), which contained 1 to 2% organic carbon homogeneously distributed throughout the turbidites at the time they were deposited. These turbidites are well suited to study the effects of oxic degradation on lipid biomarkers without the complicating influence of varying organic matter sources, sedimentation rates, or bioturbation. One sample from the oxidised turbidite was compared with two samples from the unoxidised part of each turbidite. Postdepositional oxic degradation decreased concentrations of biomarkers by several orders of magnitude. The ester-bound lipids were degraded to a far lesser extent than their free counterparts were. The extent of degradation of different compounds differed substantially. Within a specific class of biomarkers, degradation also took place to a different extent, altering their distributions. This study shows that oxic degradation of the organic matter may have a profound effect on the biomarker fingerprint and may result in a severe bias in, for example, the interpretation of organic matter sources and the estimation of the palaeoproductivity of specific groups of phytoplankton.

Biomarker distributions in sediment core PS2767-4

Here, we present a first (low-resolution) biomarker sea-ice proxy record from the High Arctic (southern Lomonosov Ridge), going back in time to about 60 ka (MIS 3 to MIS 1). Variable concentrations of the sea-ice diatom specific highly branched isoprenoid (HBI) with 25 carbon atoms ("IP25"), in combination with the phytoplankton biomarker brassicasterol, suggest variable seasonal sea-ice coverage and open-water productivity during MIS 3. During most of MIS 2, the spring to summer sea-ice margin significantly extended towards the south, resulting in a drastic decrease in phytoplankton productivity. During the Early Holocene Climate Optimum, brassicasterol reached its maximum, interpreted as signal for elevated phytoplankton productivity due to a significantly reduced sea-ice cover. During the mid-late Holocene, IP25 increased and brassicasterol decreased, indicating extended sea-ice cover and reduced phytoplankton productivity, respectively. The HBI diene/IP25 ratios probably reached maximum values during the Bølling-Allerød warm period and decreased during the Holocene, suggesting a correlation with sea-surface temperature.

Organic geochemical parameters (biomarker) in sedimentary sequences and sediment traps

For the reconstruction of sea-ice variability, a biomarker approach which is based on (1) the determination of sea-ice diatom-specific highly-branched isoprenoid (IP25) and (2) the coupling of phytoplankton biomarkers and IP25 has been used. For the first time, such a data set was obtained from an array of two sediment traps deployed at the southern Lomonosov Ridge in the central Arctic Ocean at water depth of 150 m and 1550 m and recording the seasonal variability of sea ice cover in 1995/1996. These data indicate a predominantly permanent sea ice cover at the trap location between November 1995 and June 1996, an ice-edge situation with increased phytoplankton productivity and sea-ice algae input in July/August 1996, and the start of new-ice formation in late September. The record of modern sea-ice variability is then used to better interpret data from sediment core PS2458-4 recovered at the Laptev Sea continental slope close to the interception with Lomonosov Ridge and recording the post-glacial to Holocene change in sea-ice cover. Based on IP25 and phytoplankton biomarker data from Core PS2458-4, minimum sea-ice cover was reconstructed for the Bølling/Allerød warm interval between about 14.5 and 13 calendar kyr BP, followed by a rapid and distinct increase in sea-ice cover at about 12.8 calendar kyr BP. This sea-ice event was directly preceded by a dramatic freshwater event and a collapse of phytoplankton productivity, having started about 100 years earlier. These data are the first direct evidence that enhanced freshwater flux caused enhanced sea-ice formation in the Arctic at the beginning of the Younger Dryas. In combination with a contemporaneous, abrupt and very prominent freshwater/meltwater pulse in the Yermak Plateau/Fram Strait area these data may furthermore support the hypothesis that strongly enhanced freshwater (and ice) export from the Arctic into the North Atlantic could have played an important trigger role for the onset of the Younger Dryas cold reversal. During the Early Holocene, sea-ice cover steadily increased again (ice-edge situation), reaching modern sea-ice conditions (more or less permanent sea-ice cover) probably at about 7-8 calendar kyr BP.

Sedimentology on core MSM05/05_723-2

Two high-resolution sediment cores from eastern Fram Strait have been investigated for sea subsurface and surface temperature variability during the Holocene (the past ca 12,000 years). The transfer function developed by Husum and Hald (2012) has been applied to sediment cores in order to reconstruct fluctuations of sea subsurface temperatures throughout the period. Additional biomarker and foraminiferal proxy data are used to elucidate variability between surface and subsurface water mass conditions, and to conclude on the Holocene climate and oceanographic variability on the West Spitsbergen continental margin. Results consistently reveal warm sea surface to subsurface temperatures of up to 6 °C until ca 5 cal ka BP, with maximum seawater temperatures around 10 cal ka BP, likely related to maximum July insolation occurring at that time. Maximum Atlantic Water (AW) advection occurred at surface and subsurface between 10.6 and 8.5 cal ka BP based on both foraminiferal and dinocyst temperature reconstructions. Probably, a less-stratified, ice-free, nutrient-rich surface ocean with strong AW advection prevailed in the eastern Fram Strait between 10 and 9 cal ka BP. Weakened AW contribution is found after ca 5 cal ka BP when subsurface temperatures strongly decrease with minimum values between ca 4 and 3 cal ka BP. Cold late Holocene conditions are furthermore supported by high planktic foraminifer shell fragmentation and high d18O values of the subpolar planktic foraminifer species Turborotalita quinqueloba. While IP25-associated indices as well as dinocyst data suggest a sustained cooling due to a decrease in early summer insolation and consequently sea-ice increase since about 7 cal ka BP in surface waters, planktic foraminiferal data including stable isotopes indicate a slight return of stronger subsurface AW influx since ca 3 cal ka BP. The observed decoupling of surface and subsurface waters during the later Holocene is most likely attributed to a strong pycnocline layer separating cold sea-ice fed surface waters from enhanced subsurface AW advection. This may be related to changes in North Atlantic subpolar versus subtropical gyre activity.