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.

Moleculare composition of sediments from ODP Hole 116-717C

We describe the molecular composition of a portion of the solvent-soluble organic material (lipid extract), from three organic rich muds (samples 116-717C-22X-1, 80-86 cm, 116-717C-34X-3, 130-135 cm, and 116-717C-55X-1, 65-70 cm). These samples were taken from Hole 717C, located on the Bengal Fan at a position of 0°55.8'S and 81°23.4'E. Both the palaeoenvironmental and digenetic significance of these lipid distributions have been assessed and found to be consistent with their suspected origins, i.e., turbidites from the upper slope of the western Bay of Bengal and the Ganges-Brahmaputra delta.

(Table 2) Distribution of alkenone unsaturation index UK37 of the eastern North Atlantic

This paper reports the concentrations and within-class distributions of long-chain alkenones and alkyl alkenoates in the surface waters (0-50 m) of the eastern North Atlantic, and correlates their abundance and distribution with those of source organisms and with water temperature and other environmental variables. We collected these samples of >0.8 µm particulate material from the euphotic zone along the JGOFS 20°W longitude transect, from 61°N to 24°N, during seven cruises of the UK-JGOFS Biogeochemical Ocean Flux Study (BOFS) in 1989-1991; the biogeographical range of our 53 samples extends from the cold (<10°C), nutrient-rich and highly productive subarctic waters of the Iceland Basin to the warm (>25°C) oligotrophic subtropical waters off Africa. Surface water concentrations of total alkenone and alkenoates ranged from <50 ng/l in oligotrophic waters below 40°N to 2000-4500 ng/l in high latitude E. huxleyi blooms, and were well correlated with E. huxleyi cell densities, supporting the assumption that E. huxleyi is the predominant source of these compounds in the present day North Atlantic. The within-class distribution of the C37 and C38 alkenones and C36 alkenoates varied strongly as a function of temperature, and was largely unaffected by nutrient concentration, bloom status and other surface water properties. The biosynthetic response of the source organisms to growth temperature differed between the cold (<16°C) waters above 47°N and the warmer waters to the south. In cold (<16°C) waters above 47°N, the relative amounts of alkenoates and C38 alkenones synthesized was a strong function of growth temperature, while the unsaturation ratio of the alkenones (C37 and C38) was uncorrelated with temperature. Conversely, in warm (>16°C) waters below 47°N, the relative proportions of alkenoates and alkenones synthesized remained constant with increasing temperature while the unsaturation ratios of the C37 and C38 methyl alkenones (Uk37 and Uk38Me, respectively) increased linearly. The fitted regressions of Uk37 and Uk38Me versus temperature for waters >16°C were both highly significant (r**2 > 0.96) and had identical slopes (0.057) that were 50% higher than the slope (0.034) of the temperature calibration of Uk37 reported by Prahl and Wakeham (1987; doi:10.1038/330367a0) over the same temperature range. These observations suggest either a physiological adjustment in biochemical response to growth temperature above a 16-17°C threshold and/or variation between different E. huxleyi strains and/or related species inhabiting the cold and warm water regions of the eastern North Atlantic. Using our North Atlantic data set, we have produced multivariate temperature calibrations incorporating all major features of the alkenone and alkenoate data set. Predicted temperatures using multivariate calibrations are largely unbiased, with a standard error of approximately ±1°C over the entire data range. In contrast, simpler calibration models cannot adequately incorporate regional diversity and nonlinear trends with temperature. Our results indicate that calibrations based upon single variables, such as Uk37, can be strongly biased by unknown systematic errors arising from natural variability in the biosynthetic response of the source organisms to growth temperature. Multivariate temperature calibration can be expected to give more precise estimates of Integrated Production Temperatures (IPT) in the sedimentary record over a wider range of paleoenvironmental conditions, when derived using a calibration data set incorporating a similar range of natural variability in biosynthetic response.

Carbon, hydrocarbon and alkenone composition and indices of ODP Hole 167-1016C sediments

Total organic carbon (TOC) and calcium carbonate (CaCO3) concentrations were determined for 304 samples, and biomarkers were analyzed for 101 samples from Core 167-1016C-1H. TOC varies between 1% and 2%, and CaCO3 is typically 1%-4%, with peaks reaching 14%. Paleotemperature estimated from Uk'37 varies from 8.5° to 17.5°C. The Uk'37 variation implies that Core 167-1016C-1H covers oxygen isotope Stages 1-6. Peaks of diatom-derived C25:1 HBI alkene concentrations occur during warming intervals, suggesting intensified upwelling during deglaciation. The concentrations of haptophyte-derived alkenones and diatom-derived C25:1 HBI alkene vary out of phase, which presumably resulted from the changes in the mode of nutrient supply to surface mixed layer. Maximal CaCO3 contents (>10%) were observed in both warming and cooling intervals. The peak in cooling interval relates to an alkenone maximum, whereas the peaks in warming intervals do not. This implies that carbonate production is not the only factor controlling carbonate compensation depth at this site, and it suggests considering the changes in North Pacific deep-water chemistry. Petroleum-type compounds are present in Site 1016 sediments. Their concentrations are maximized in the warming intervals that correspond to the timing of destruction of a huge tar mound off Point Conception. The tarry material was presumably transported by the Arguello Fan system to Site 1016.

High-resolution sedimentological and paleontological record of ODP Site 167-1019

Holocene and latest Pleistocene oceanographic conditions and the coastal climate of northern California have varied greatly, based upon high-resolution studies (ca. every 100 years) of diatoms, alkenones, pollen, CaCO3%, and total organic carbon at Ocean Drilling Program (ODP) Site 1019 (41.682°N, 124.930°W, 980 m water depth). Marine climate proxies (alkenone sea surface temperatures [SSTs] and CaCO3%) behaved remarkably like the Greenland Ice Sheet Project (GISP)-2 oxygen isotope record during the Bølling-Allerod, Younger Dryas (YD), and early part of the Holocene. During the YD, alkenone SSTs decreased by >3°C below mean Bølling-Allerod and Holocene SSTs. The early Holocene (ca. 11.6 to 8.2 ka) was a time of generally warm conditions and moderate CaCO3 content (generally >4%). The middle part of the Holocene (ca. 8.2 to 3.2 ka) was marked by alkenone SSTs that were consistently 1-2°C cooler than either the earlier or later parts of the Holocene, by greatly reduced numbers of the gyre-diatom Pseudoeunotia doliolus (<10%), and by a permanent drop in CaCO3% to <3%. Starting at ca. 5.2 ka, coastal redwood and alder began a steady rise, arguing for increasing effective moisture and the development of the north coast temperate rain forest. At ca. 3.2 ka, a permanent ca. 1°C increase in alkenone SST and a threefold increase in P. doliolus signaled a warming of fall and winter SSTs. Intensified (higher amplitude and more frequent) cycles of pine pollen alternating with increased alder and redwood pollen are evidence that rapid changes in effective moisture and seasonal temperature (enhanced El Niño-Southern Oscillation [ENSO] cycles) have characterized the Site 1019 record since about 3.5 ka.

Sea surface temperature reconstruction for sediment core KNO5103-0029GGC

We present a 15 kyr sea surface temperature (SST) record for a high sedimentation rate core (KNR51-29GGC) from the Feni Drift off of Ireland, based on an organic geochemical technique for paleotemperature estimation, U37 K'. We compare the U37 K' temperature record to planktonic foraminiferal delta18O and foraminiferal assemblage SST estimates from the same sample horizons. U37 K' gives SST estimates of 13°C for the early deglacial and 18°C for the Holocene and Recent, whereas assemblages give estimates of 9°C and 13°C, respectively. As in nearby core V23-81, we find Ash Zone 1, the Younger Dryas increase in Neogloboquadrina pachyderma sinistral abundance, and maximum abundance of this species during glaciation. N. pachyderma dextral oxygen isotopic analyses have a late glacial to interglacial range of 1.5 per mil. A reduction of about 1 per mil in delta18O occurred at about 12 ka, whereas U37 K' and the foraminiferal fauna indicate a 2°C warming. This implies a 0.9 per mil salinity effect on delta18O which we attribute to meltwater freshening. All three parameters indicate cooling during the Younger Dryas. U37 K' SST estimates show that the major shift from deglacial to interglacial temperatures occurred after the Younger Dryas in termination 1b, in contrast to the assemblage data, which show this jump in SST at the end of the glaciation during termination Ia. Differences between the two SST estimators, which may result from their different (floral versus faunal) sources, are more pronounced between transitions Ia and Ib. This may reflect different habitats under the unusual sea surface conditions of the deglaciation.

Salinity estimation from Gulf of Guinea, sediment core MD03-2707

The isotopic composition of surface seawater is widely used to infer past changes in sea surface salinity using paired foraminiferal Mg/Ca and d18O from marine sediments. At low latitudes, paleosalinity reconstructions using this method have largely been used to document changes in the hydrological cycle. This method usually assumes that the modern seawater d18O (d18Osw)/salinity relationship remained constant through time. Modelling studies have shown that such assumptions may not be valid because large-scale atmospheric circulation patterns linked to global climate changes can alter the seawater d18Osw/salinity relationship locally. Such processes have not been evidenced by paleo-data so far because there is presently no way to reconstruct past changes in the seawater d18Osw/salinity relationship. We have addressed this issue by applying a multi-proxy salinity reconstruction from a marine sediment core collected in the Gulf of Guinea. We measured hydrogen isotopes in C37:2 alkenones (dDa) to estimate changes in seawater dD. We find a smooth, long-term increase of ~10 per mil in dDa between 10 and 3 kyr BP, followed by a rapid decrease of ~10 per mil in dDa between 3 kyr BP and core top to values slightly lighter than during the early Holocene. Those features are inconsistent with published salinity estimations based on d18Osw and foraminiferal Ba/Ca, as well as nearby continental rainfall history derived from pollen analysis. We combined dDa and d18Osw values to reconstruct a Holocene record of salinity and compared it to a Ba/Ca-derived salinity record from the same sedimentary sequence. This combined method provides salinity trends that are in better agreement with both the Ba/Ca-derived salinity and the regional precipitation changes as inferred from pollen records. Our results illustrate that changes in atmospheric circulation can trigger changes in precipitation isotopes in a counter-intuitive manner that ultimately impacts surface salinity estimates based on seawater isotopic values. Our data suggest that the trends in Holocene rainfall isotopic values at low latitudes may not uniquely result from changes in local precipitation associated with the amount effect.

Sea surface temperature reconstruction of ODP Site 175-1087

Successful application of the alkenone palaeothermometer, the UK'37 index, relies upon the assumption that fossil alkenone synthesisers responded to growth-temperature changes in a similar manner to the modern producers, chiefly the coccolithophores Emiliania huxleyi and Gephyrocapsa oceanica. We compare coccolith and UK'37 data from ODP Site 1087 in the south-east Atlantic between 1500 and 500 ka, and show that evolutionary events and changes in species dominance within the coccolithophore populations had little impact on the UK'37 record. The relative abundances of the C37 and C38 alkenones also closely resembled those found in modern populations, and suggest a similar temperature sensitivity of UK'37 during the early and mid-Pleistocene to that found at present. These results support the application of the UK'37 index to reconstruct sea-surface temperatures (SSTs) throughout the Quaternary. The UK'37 record at ODP Site 1087 contains an SST signal that documents the emergence of the 100-kyr cycles that characterise the late Quaternary ice volume records. This is preceded by significant cooling at ODP Site 1087, marked by a negative shift in SSTs and a positive shift in the planktonic delta18O some 250-kyr earlier, at ca 1150-1000 ka. This results in a permanent fall in average SSTs of around 1.5 °C. The predicted increase in aridity onshore as a result of this cooling can be identified in a number of published records from southern Africa, and may have played a role in some important evolutionary events of the mid-Pleistocene.

Sea surface temperature reconstruction from biomarker in sediments off Portugal

High resolution reconstructions of sea surface temperature (Uk'37-SST), coccolithophore associations and continental input (total organic carbon, higher plant n-alkanes, n-alkan-1-ols) in core D13882 from the shallow Tagus mud patch are compared to SST records from deep-sea core MD03-2699 and other western Iberian Margin cores. Results reveal millennial-scale climate variability over the last deglaciation, in particular during the LGIT. In the Iberian margin, Heinrich event 1 (H1) and the Younger Dryas (YD) represent two extreme episodes of cold sea surface condition separated by a marine warm phase that coincides with the Bølling-Allerød interval (B-A) on the neighboring continent. Following the YD event, an abrupt sea surface warming marks the beginning of the Holocene in this region. SSTs recorded in core D13882 changed, however, faster than those at deep-sea site MD03-2699 and at the other available palaeoclimate sequences from the region. While the SST values from most deep-sea cores reflect the latitudinal gradient detected in the Iberian Peninsula atmospheric temperature proxies during H1 and the B-A, the Tagus mud patch (core D13882) experienced colder SSTs during both events. This is most certainly related to a supplementary input of cold freshwater from the continent to the Tagus mud patch, a hypothesis supported by the high contents of terrigenous biomarkers and total organic carbon as well as by the dominance of tetra-unsaturated alkenone (C37:4) observed at this site. The comparison of all western Iberia SST records suggests that the SST increase that characterizes the B-A event in this region started 1000 yr before meltwater pulse 1A (mwp-1A) and reached its maximum values during or slightly after this episode of substantial sea-level rise. In contrast, during the YD/ Holocene transition, the sharp SST rise in the Tagus mud patch is synchronous with meltwater pulse IB. The decrease of continental input to the mud patch conflrms a sea level rise in the region. Thus, the synchronism between the maximum warming in the mid-latitudes off the western Iberian margin, the adjacent landmasses and Greenland indicates that mwp-lB and the associated sea-level rise probably initiated in the Northern Hemisphere rather than in the South.

Stable carbon isotopic composition of biomarker lipids of DSDP Hole 31-302

The middle Paleocene through early Eocene long-term gradual warming was superimposed by several transient warming events, such as the Paleocene-Eocene Thermal Maximum (PETM) and Eocene Thermal Maximum 2 (ETM2). Both events show evidence for extreme global warming associated with a major injection of carbon into the ocean-atmosphere system, but the mechanisms of carbon injection and many aspects of the environmental response are still poorly understood. In this study, we analyzed the concentration and stable carbon isotopic (d13C) composition of several sulfur-bound biomarkers derived from marine photoautotrophs, deposited in the Arctic Ocean at ~85°N, during ETM2. The presence of sulfur-bound biomarkers across this event points toward high primary productivity and anoxic bottom water conditions. The previously reported presence of isorenieratene derivatives indicates euxinic conditions in the photic zone, likely caused by a combination of enhanced primary productivity and salinity stratification. The negative carbon isotope excursion measured at the onset of ETM2 for several biomarkers, ranges between 3 per mil and 4.5 per mil, much larger than the ~1.4 per mil recorded in marine carbonates elsewhere, suggesting substantial enhanced isotopic fractionation by the primary producers likely due to a significant rise in pCO2. In the absence of biogenic carbonates in the ETM2 section of our core we use coeval planktonic d13C from elsewhere to estimate surface water d13C in the Arctic Ocean and then apply the relation between isotopic fractionation and pCO2, originally calibrated for haptophyte alkenones, to three selected organic biomarkers (i.e., S-bound phytane, C35 hopane, and a C25 highly branched isoprenoid). This yields pCO2 values potentially in the range of four times preindustrial levels. However, these estimates are uncertain because of a lack of knowledge on the importance of pCO2 on photosynthetic isotopic fractionation.

Carbon contents of lower Cretaceous sediments from ODP Hole 198-1213B (Table 1)

ODP Leg 198 drilling on Shatsky Rise recovered a lower Aptian porcellanite (~120.5 Ma) deposited during oceanic anoxic event (OAE) 1a that contains C36-C39 alkadienones: C37:2 and C39:2 alkadien-2-ones and C36:2 and C38:2 alkadien-3-ones. This alkenone distribution differs from that typical of contemporary sediments and haptophyte algae, but resembles that of Cretaceous sediments from the Blake-Bahama basin. The discovery of alkenones in the early Aptian extends their sedimentary record by 15 M.y. to 120.5 M.y. and demonstrates the potential for long-term survival of these diagnostic functional lipids under favorable depositional conditions and subsequent shallow burial. It also contributes to the understanding and reconstruction of evolutionary developments in alkenone distributions and biosynthesis over geologic time.