Sedimentary lipids and palynomorphs of sediment core ABC26 from the Eastern Mediterranean

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.

Temperature proxies of sediment cores from the Sea of Marmara

Reconstructing ocean temperature values is a major target in paleoceanography and climate research. However, most temperature proxies are organism-based and thus suffer from an "ecological bias". Multiproxy approaches can potentially overcome this bias but typically require more investment in time and resources, while being susceptible to errors induced by sample preparation steps necessary before analysis. Three lipid-based temperature proxies are widely used: UK'37 (based on long chain alkenones from phytoplanktonic haptophytes), TEX86 [based on glycerol dialkyl glycerol tetraethers (GDGTs) from pelagic archaea] and LDI (based on long chain diols from phytoplanktonic eustigmatophytes). So far, separate analytical methods, including gas chromatography (GC) and liquid chromatography (LC), have been used to determine these proxies. Here we present a sensitive method for determining all three in a single normal phase high performance LC-atmospheric pressure chemical ionization mass spectrometry (NP-HPLC-APCI-MS) analysis. Each of the long chain alkenones and long chain diols was separated and unambiguously identified from the accurate masses and characteristic fragmentation during multiple stage MS analysis (MS2). Comparison of conventional GC and HPLC-MS methods showed similar results for UK'37 and LDI, respectively, using diverse environmental samples and an Emiliania huxleyi culture. Including the three sea surface temperature (SST) proxies; the NP-HPLC-APCI-MS method in fact allows simultaneous determination of nine paleoenvironmental proxies. The extent to which the ecology of the source organisms (ecological bias) influences lipid composition and thereby the reconstructed temperature values was demonstrated by applying the new method to a sediment core from the Sea of Marmara, covering the last 21 kyr BP. Reconstructed SST values differed considerably between the proxies for the Last Glacial Maximum (LGM) and the period of Sapropel S1 formation at ca. 10 kyr BP, whereas the trends during the late Holocene were similar. Changes in the composition of alkenone-producing species at the transition from the LGM to the Bølling/Allerød (B/A) were inferred from unreasonably high UK'37-derived SST values (ca. 20 °C) during the LGM. We ascribe discrepancies between the reconstructed temperature records during S1 deposition to habitat change, e.g. a different depth due to changes in nutrient availability.

Coccolithosphores and fossil organic compounds of sediment core MD01-2444

This study analyzes coccolithophore abundance fluctuations (e.g., Emiliania huxleyi, Gephyrocapsa specimens, and Florisphaera profunda) in core MD01-2444 sediment strata retrieved at the Iberian Margin, northeastern Atlantic Ocean. Coccolithophores are calcareous nannofossils, a major component of the oceanic phytoplankton, which provide information about past ecological and climatological variability. Results are supported by data on fossil organic compounds (sea surface temperatures, alkenones, and n-hexacosan-1-ol index) and geochemical analyses (benthic d13Ccc and planktonic d18Occ isotopes). Three scenarios are taken into account for this location at centennial-scale resolution over the last 70,000 years: the Holocene and the stadial and interstadial modes. The different alternatives are described by means of elements such as nutrients; upwelling phenomena; temperatures at surface and subsurface level; or the arrival of surface turbid, fresh, and cold waters due to icebergs, low sea level, increased aridity, and dust. During the Holocene, moderate primary productivity was observed (mainly concentrated in E. huxleyi specimens); surface temperatures were at maxima while the water column was highly ventilated by northern-sourced polar deep waters and warmer subsurface, nutrient-poor subtropical waters. Over most of the last glacial stadials, surface productivity weakened (higher F. profunda and reworked specimen percentages and lower diunsaturated and triunsaturated C37 alkenones); the arrival of cold Arctic surface waters traced by tetraunsaturated C37 peaks and large E. huxleyi, together with powerful ventilated southern-sourced polar deep waters, disturbed, in all likelihood, the delicate vertical equilibrium while preventing significant upwelling mixing. Finally, during the last glacial interstadials (lower F. profunda percentages, nonreworked material, and higher diunsaturated and triunsaturated C37 alkenones) a combined signal is observed: warm surface temperatures were concurrent with generally low oxygenation of the deep-sea floor, moderate arrival of northern-sourced deep waters, and subsurface cold, nutrient-rich, recently upwelled waters, probably of polar origin; these particular conditions may have promoted vertical mixing while enhancing surface primary productivity (mainly of Gephyrocapsa specimens).

Stable isotope ratios of foraminifera and sea surface temperature estimation of sediment core W2804A-14

Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C (epsilon p) in a central equatorial Pacific sediment core that spans the last ~255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic compostion of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon p, derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 (c e) based on a new, site-specific calibration of the relationship between epsilon p and c e. The calibration was based on reassessment of existing epsilon p versus c e data, which support a physiologically based model in which epsilon p is inversely related to c e. Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index UK 37. Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon p and 1/c e. These are discussed in detail and it is concluded that the observed record of epsilon p most probably reflects significant variations in Delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from ~110 µatm during glacial intervals (ocean > atmosphere) to ~60 µatm during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial intervals. If this were characteristic of large areas of the equatorial Pacific, then greater glacial sinks for the equatorially evaded CO2 must have existed elsewhere. Statistical analysis of air-sea pCO2 differences and other parameters revealed significant (p < 0.01) inverse correlations of Delta pCO2 with sea surface temperature and with the mass accumulation rate of opal. The former suggests response to the strength of upwelling, the latter may indicate either drawdown of CO2 by siliceous phytoplankton or variation of [CO2]/[Si(OH)4] ratios in upwelling waters.

Organic matter preservation in turbidites on the Madeira Abyssal Plain

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.

Pollen and spores record, and paleotemperature reconstructions for mid-Holocene sediments of the Northwest Pacific

Sannai-Maruyama is one of the most famous and best-researched mid-Holocene (mid-Jomon) archaeological sites in Japan, because of a large community of people for a long period. Archaeological studies have shown that the Jomon people inhabited the Sannai-Maruyama site from 5.9-4.2 +/- 0.1 cal. kyr B.P. However, a continuous record of the terrestrial and marine environments around the site has not been available. Core KT05-7 PC-02, was recovered from Mutsu Bay, only 20 km from the site, for the reconstruction of high-resolution time series of environmental records, including sea surface temperature (SST). C37 alkenone SSTs showed clear fluctuations, with four periods of high (8.4-7.9, 7.0-5.9, 5.1-4.1, and 2.3-1.4 cal. kyr B.P.) and four of low (-8.4, 7.9-7.0, 5.9-5.1, and 4.1-2.3 cal. kyr B.P.) SST. Thus, each SST cycle lasted 1.0-2.0 kyr, and the amplitude of fluctuation was about 1.5-2.0 °C. Total organic carbon (TOC) and C37 alkenone contents, and the TOC/total nitrogen ratio indicate that marine biogenic production was low before 7.0 cal. kyr B.P., but was clearly increased between 5.9 and 4.0 cal. kyr B.P., because of stronger vertical mixing. During the period when the community at the site prospered (between 5.9 and 4.2 +/- 0.1 cal. kyr B.P.), the terrestrial climate was relatively warm. The high relative abundance of pollen of both Castanea and Quercus subgen. Cyclobalanopsis supports the interpretation that the local climate was optimal for human habitation. Between 5.9 and 5.1 cal. kyr B.P., in spite of warm terrestrial climates, the C37 alkenone SST was low; this apparent discrepancy may be attributed to the water column structure in the Tsugaru Strait, which differed from the modern condition. The evidence suggests that at about 5.9 cal. kyr B.P, high productivity of marine resources such as fish and shellfish and a warm terrestrial climate led to the establishment of a human community at the Sannai-Maruyama site. Then, at about 4.1 +/- 0.1 cal. kyr B.P., abrupt marine and terrestrial cooling, indicated by a decrease of about 2 °C in the C37 alkenone SST and an increase in pollen of taxa of cooler climates, led to a reduced terrestrial food supply, causing the people to abandon the site. The timing of the abandonment is consistent with the timing (around 4.0-4.3 cal. kyr B.P.) of the decline of civilizations in north Mesopotamia and along the Yangtze River. These findings suggest that a temperature rise of ~2 °C in this century as a result of global warming could have a great impact on the human community and especially on agriculture, despite the advances of contemporary society.

Determination of millennial-scale climate variability based on alkenones in the western Atlantic Ocean

High-resolution records of alkenone-derived sea surface temperatures and elemental Ti/Ca ratios from a sediment core retrieved off northeastern Brazil (4° S) reveal short-term climate variability throughout the past 63,000 a. Large pulses of terrigenous sediment discharge, caused by increased precipitation in the Brazilian hinterland, coincide with Heinrich events and the Younger Dryas period. Terrigenous input maxima related to Heinrich events H6-H2 are characterized by rapid cooling of surface water ranging between 0.5 and 2° C. This signature is consistent with a climate model experiment where a reduction of the Atlantic meridional overturning circulation (AMOC) and related North Atlantic cooling causes intensification of NE trade winds and a southward movement of the Intertropical Convergence Zone, resulting in enhanced precipitation off northeastern Brazil. During deglaciation the surface temperature evolution at the core site predominantly followed the Antarctic warming trend, including a cooling, prior to the Younger Dryas period. An abrupt temperature rise preceding the onset of the Bølling/Allerød transition agrees with model experiments suggesting a Southern Hemisphere origin for the abrupt resumption of the AMOC during deglaciation caused by Southern Ocean warming and associated with northward flow anomalies of the South Atlantic western boundary current.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.

Alkenone variations, total organic carbon and stable oxygen isotope ratios of the western Arabian Sea

We here present records of total organic carbon (TOC) and C37 alkenones, used as indicators for past primary productivity, from the western (WAS) and eastern Arabian Sea (EAS). New data from an open ocean site of the WAS upwelling area are compared with similar records from Ocean Drilling Program (ODP) Site 723 from the continental margin off Oman and MD 900963 from the EAS. These records together with other proxies used to reconstruct upwelling intensity, indicate periods of high productivity in tune with precessional forcing. On the basis of their phase relationship to boreal summer insolation they can be divided into three groups: in the WAS differences between monsoonal proxies (1) and productivity (2) document a combined signal of moderate SW monsoon winds and of strengthened and prolonged NE monsoon winds, whereas in the EAS phasing indicates maximum productivity (3) at times of stronger NE monsoon winds associated with precession-related maxima in ice volume.