Natural remanent magnetization (NRM) from ODP Site 1263 covering magnetochron C20r and C21n and high-resolution bulk carbon isotope (d13C) records from Sites 702 and 1263

To explore cause and consequences of past climate change, very accurate age models such as those provided by the astronomical timescale (ATS) are needed. Beyond 40 million years the accuracy of the ATS critically depends on the correctness of orbital models and radioisotopic dating techniques. Discrepancies in the age dating of sedimentary successions and the lack of suitable records spanning the middle Eocene have prevented development of a continuous astronomically calibrated geological timescale for the entire Cenozoic Era. We now solve this problem by constructing an independent astrochronological stratigraphy based on Earth's stable 405 kyr eccentricity cycle between 41 and 48 million years ago (Ma) with new data from deep-sea sedimentary sequences in the South Atlantic Ocean. This new link completes the Paleogene astronomical timescale and confirms the intercalibration of radioisotopic and astronomical dating methods back through the Paleocene-Eocene Thermal Maximum (PETM, 55.930 Ma) and the Cretaceous-Paleogene boundary (66.022 Ma). Coupling of the Paleogene 405 kyr cyclostratigraphic frameworks across the middle Eocene further paves the way for extending the ATS into the Mesozoic.

Sea surface temperature reconstruction for Mediterranean Sea samples

Alkenone unsaturation ratios and planktonic delta18O records from sediment cores of the Alboran, Ionian and Levantine basins in the Mediterranean Sea show pronounced variations in paleo-temperatures and -salinities of surface waters over the last 16,000 years. Average sea surface temperatures (SSTs) are low during the last glacial (averages prior to 13,000 years: 11-15°C), vary rapidly at the beginning of the Holocene, and increase to 17-18°C at all sites during S1 formation (dated between 9500 and 6600 calendar years). The modern temperature gradient (2-3°C) between the Mediterranean sub-basins is maintained during formation of sapropel S1 in the Eastern Mediterranean Sea. After S1, SSTs have remained uniform in the Alboran Sea at 18°C and have fluctuated around 20°C in the Ionian and Levantine Basin sites. The delta18O of planktonic foraminifer calcite decreases by 2 per mil from the late glacial to S1 sediments in the Ionian Basin and by 2.8 per mil in the Levantine Basin. In the Alboran Sea, the decrease is 1.7 per mil. Of the 2.8 per mil decrease in the Levantine Basin, the effect of global ice volume accounts for a maximum of 1.05 per mil and the temperature increase explains only a maximum of 1.3 per mil. The remainder is attributed to salinity changes. We use the temperature and salinity estimates to calculate seawater density changes. They indicate that a reversal of water mass circulation is not a likely explanation for increased carbon burial during S1 time. Instead, it appears that intermediate and deep water formation may have shifted to the Ionian Sea approximately 2000 years before onset of S1 deposition, because surface waters were as cold, but saltier than surface water in the Levantine Basin during the Younger Dryas. Sapropel S1 began to form at the same time, when a significant density decrease also occurred in the Ionian Sea.

Nitrogen isotope gradients off Peru and Ecuador related to upwelling, productivity, nutrient uptake and oxygen deficiency

We present new nitrogen isotope data from the water column and surface sediments for paleo-proxy validation collected along the Peruvian and Ecuadorian margins between 1°N and 18°S. Productivity proxies in the bulk sediment (organic carbon, total nitrogen, biogenic opal, C37 alkenone concentrations) and 15N/14N ratios were measured at more than 80 locations within and outside the present-day Peruvian oxygen minimum zone (OMZ). Microbial N-loss to N2 in subsurface waters under O2 deficient conditions leaves a characteristic 15N-enriched signal in underlying sediments. We find that phytoplankton nutrient uptake in surface waters within the high nutrient, low chlorophyll (HNLC) regions of the Peruvian upwelling system influences the sedimentary signal as well. How the d15Nsed signal is linked to these processes is studied by comparing core-top values to the 15N/14N of nitrate and nitrite (d15N[NOx]) in the upper 200 m of the water column. Between 1°N and 10°S, subsurface O2 is still high enough to suppress N-loss keeping d15NNOx values relatively low in the subsurface waters. However d15N[NOx] values increase toward the surface due to partial nitrate utilization in the photic zone in this HNLC portion of the system. d15N[sed] is consistently lower than the isotopic signature of upwelled [NO3]-, likely due to the corresponding production of 15N depleted organic matter. Between 10°S and 15°S, the current position of perennial upwelling cells, HNLC conditions are relaxed and biological production and near-surface phytoplankton uptake of upwelled [NO3]- are most intense. In addition, subsurface O2 concentration decreases to levels sufficient for N-loss by denitrification and/or anammox, resulting in elevated subsurface d15N[NOx] values in the source waters for coastal upwelling. Increasingly higher production southward is reflected by various productivity proxies in the sediments, while the north-south gradient towards stronger surface [NO3]- utilization and subsurface N-loss is reflected in the surface sediment 15N/14N ratios. South of 10°S, d15N[sed] is lower than maximum water column d15N[NOx] values most likely because only a portion of the upwelled water originates from the depths where highest d15N[NOx] values prevail. Though the enrichment of d15N[NOx] in the subsurface waters is unambiguously reflected in d15N[sed] values, the magnitude of d15N[sed] enrichment depends on both the depth of upwelled waters and high subsurface d15N[NOx] values produce by N-loss. Overall, the degree of N-loss influencing subsurface d15N[NOx] values, the depth origin of upwelled waters, and the degree of near-surface nitrate utilization under HNLC conditions should be considered for the interpretation of paleo d15N[sed] records from the Peruvian oxygen minimum zone.

Sea surface temperature reconstruction of sediment core GeoB6518-1

Past hydrological changes in Africa have been linked to various climatic processes, depending on region and timescale. Long-term precipitation changes in the regions of northern and southern Africa influenced by the monsoons are thought to have been governed by precessional variations in summer insolation (Kutzbach and Liu, 1997, doi:10.1126/science.278.5337.440; Partridge et al., 1997, doi:10.1016/S0277-3791(97)00005-X). Conversely, short-term precipitation changes in the northern African tropics have been linked to North Atlantic sea surface temperature anomalies, affecting the northward extension of the Intertropical Convergence Zone and its associated rainbelt (Hastenrath, 1990, doi:10.1002/joc.3370100504, Street-Perrott and Perrott, 1990, doi:10.1038/343607a0). Our knowledge of large-scale hydrological changes in equatorial Africa and their forcing factors is, however, limited (Gasse, 2000, doi:10.1016/S0277-3791(99)00061-X). Here we analyse the isotopic composition of terrigenous plant lipids, extracted from a marine sediment core close to the Congo River mouth, in order to reconstruct past central African rainfall variations and compare this record to sea surface temperature changes in the South Atlantic Ocean. We find that central African precipitation during the past 20,000 years was mainly controlled by the difference in sea surface temperatures between the tropics and subtropics of the South Atlantic Ocean, whereas we find no evidence that changes in the position of the Intertropical Convergence Zone had a significant influence on the overall moisture availability in central Africa. We conclude that changes in ocean circulation, and hence sea surface temperature patterns, were important in modulating atmospheric moisture transport onto the central African continent.

Persistent organic pollutants, d13C and d15N in zooplankton, fish and bird species in Kongsfjorden according to season

Seasonality in biomagnification of persistent organic pollutants (POPs; polychlorinated biphenyls, chlorinated pesticides, and brominated flame retardants) in Arctic marine pelagic food webs was investigated in Kongsfjorden, Svalbard, Norway. Trophic magnification factors (TMFs; average factor change in concentration between two trophic levels) were used to measure food web biomagnification in biota in May, July, and October 2007. Pelagic zooplankton (seven species), fish (five species), and seabirds (two species) were included in the study. For most POP compounds, highest TMFs were found in July and lowest were in May. Seasonally changing TMFs were a result of seasonally changing POP concentrations and the d15N-derived trophic positions of the species included in the food web. These seasonal differences in TMFs were independent of inclusion/exclusion of organisms based on physiology (i.e., warm- versus cold-blooded organisms) in the food web. The higher TMFs in July, when the food web consisted of a higher degree of boreal species, suggest that future warming of the Arctic and increased invasion by boreal species can result in increased food web magnification. Knowledge of the seasonal variation in POP biomagnification is a prerequisite for understanding changes in POP biomagnification caused by climate change.

Alkenone composition, UK'37 index, and carbon, sulphur, nitrogen and element oxides of ODP Site 186-1151

Ocean Drilling Program (ODP) Site 1151 (Sacks, Suyehiro, Acton, et al., 2000, doi:10.2973/odp.proc.ir.186.2000) is located in an area where the surface water mass is influenced by both the Kuroshio and Oyashio Currents. The site also receives a relatively high flux of detrital materials from riverine input from Honsyu Island and eolian input from Central and East Asia. We analyzed alkenones and alkenoates in the sediments to reconstruct alkenone unsaturation index (Uk'37)-based sea-surface temperature (SST), total organic carbon, and total nitrogen to estimate the terrigenous contribution by the C/N ratio during the last glacial-interglacial cycle. The major elements were also analyzed to examine the variation in terrigenous composition.

Paleotemperature reconstructions on sediment core GIK161603-3

Different proxies for sea surface temperature (SST) often exhibit divergent trends for deglacial warming in tropical regions, hampering our understanding of the phase relationship between tropical SSTs and continental ice volume at glacial terminations. To reconcile divergent SST trends, we report reconstructions of two commonly used paleothermometers (the foraminifera G. ruber Mg/Ca and the alkenone unsaturation index) from a marine sediment core collected in the southwestern tropical Indian Ocean encompassing the last 37,000 years. Our results show that SSTs derived from the alkenone unsaturation index (UK'37) are consistently warmer than those derived from Mg/Ca by ~2-3°C except for the Heinrich Event 1. In addition, the initial timing for the deglacial warming of alkenone SST started at ~15.6 ka, which lags behind that of Mg/Ca temperatures by 2.5 kyr. We argue that the discrepancy between the two SST proxies reflects seasonal differences between summer and winter rather than post-depositional processes or sedimentary biases. The UK'37 SST record clearly mimics the deglacial SST trend recorded in the North Atlantic region for the earlier part of the termination, indicating the early deglacial warming trend attributed to local summer temperatures was likely mediated by changes in the Atlantic Meridional Overturning Circulation at the onset of the deglaciation, In contrast, the glacial to interglacial SST pattern recorded by G. ruber Mg/Ca probably reflects cold season SSTs. This indicates that the cold season SSTs was likely mediated by climate changes in the southern hemisphere, as it closely tracks the Antarctic timing of deglaciation. Therefore our study reveals that the tropical southwestern Indian Ocean seasonal SST was closely linked to climate changes occurring in both hemispheres. The austral summer and winter recorded by each proxy is further supported with seasonal SST trends modeled by AOGCMs for our core site. Our interpretation that the alkenone and Mg/Ca SSTs are seasonally biased may also explain similar proxy mismatches observed in other tropical regions at the onset of the last termination.

Sulphate and d34S in pore waters and d13C, d18O and mineral composition of carbonate nodules from ODP Leg 188 sites

Carbon and oxygen isotopic compositions of authigenic carbonate nodules or layers reflect the diagenetic conditions at the time of nodule growth. The shallowest samples of carbonate nodules and dissolved inorganic carbon of pore water samples beneath the sulfate reduction zone (0-160 meters below seafloor [mbsf]) at Site 1165 have extremely negative d13C values (-50 per mil and -62 per mil, respectively). These negative d13C values indicate nodule formation in association with anaerobic methane oxidation coupled with sulfate reduction. The 34S of residual sulfate at Site 1165 shows only minor 34S enrichment (+6 per mil), even with complete sulfate reduction. This small degree of apparent 34S enrichment is due to extreme "open-system" sulfate reduction, with sulfate abundantly resupplied by diffusion from overlying seawater. Ten calcite nodules from Site 1165 contain minor quartz and feldspar and have d13C values ranging from -49.7 per mil to -8.2 per mil. The nodules with the most negative d13C values currently are at depths of 273 to 350 mbsf and must have precipitated from carbonate largely derived from subsurface anaerobic methane oxidation. The processes of sulfate reduction coupled with methane oxidation in sediments of Hole 1165B are indicated by characteristic concentration and isotopic (d34S and d13C) profiles of dissolved sulfate and bicarbonate. Three siderite nodules from Site 1166 contain feldspar and mica and one has significant carbonate-apatite. The siderite has d13C values ranging from -15.3 per mil to -7.6 per mil. These siderite nodules probably represent early diagenetic carbonate precipitation during microbial methanogenesis.