Neogen carbonate and stable isotope record of ODP Hole 120-751A

Lower Miocene through upper Pleistocene benthic foraminifer assemblage records from Ocean Drilling Program Site 751 on the Southern Kerguelen Plateau (57°44'S, water depth 1634 m) were combined with benthic and planktonic foraminifer oxygen and carbon isotope records and high-resolution CaCO3 data from the same site. Implications for the Neogene productivity and paleoceanography of the southern Indian Ocean are discussed. We used distinctive features of the Miocene d18O and d13C curves for stratigraphic correlation. Coinciding with a lower middle Miocene hiatus from 14.2 to 13.4 Ma, there was a rapid increase in benthic d18O values by 1.2 per mil. This distinct increase occurs in middle Miocene benthic foraminifer oxygen isotope curves from all oceans. No major change, however, in benthic foraminifer faunal composition occurred in this period of growth of the Antarctic ice cap and cooling of deep ocean waters (14.9-14.2 Ma). A drastic change in benthic foraminifer faunas coincided with a hiatus from 8.4 to 5.9 Ma. Shortly after this hiatus, in the latest Miocene, the CaCO3 content of the sediments dropped from 75% to 0%. From that time ( 5.8 Ma) through the early Pliocene, Site 751 has been situated beneath a high biogenic siliceous productivity zone. Carbonate contents of upper Pliocene and Pleistocene sediments vary between 20% and 70%. The benthic foraminifer faunas in the uppermost Pliocene and lower Pleistocene reflect strong bottom current conditions, in contrast to those in the upper Pleistocene, which indicate calm sedimentation and high food supply. High d13C values of planktonic foraminifers compared with low values of benthic foraminifers suggest high primary productivity in the late Pleistocene. The changes in productivity were probably a result of latitudinal migration and meandering of the Polar Frontal Zone.

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.

Benthic stable-isotope records of ODP Site 208-1262, South Atlantic

The Late Paleocene and Early Eocene were characterised by warm greenhouse climates, punctuated by a series of rapid warming and ocean acidification events known as "hyperthermals", thought to have been paced or triggered by orbital cycles. While these hyperthermals, such as the Paleocene Eocene Thermal Maximum (PETM), have been studied in great detail, the background low-amplitude cycles seen in carbon and oxygen-isotope records throughout the Paleocene-Eocene have hitherto not been resolved. Here we present a 7.7 million year (myr) long, high-resolution, orbitally-tuned, benthic foraminiferal stable-isotope record spanning the late Paleocene and early Eocene interval (~52.5 - 60.5 Ma) from Ocean Drilling Program (ODP) Site 1262, South Atlantic. This high resolution (~2-4 kyr) record allows the changing character and phasing of orbitally-modulated cycles to be studied in unprecedented detail as it reflects the long-term trend in carbon cycle and climate over this interval. The main pacemaker in the benthic oxygen-isotope (d18O) and carbon-isotope (d13C) records from ODP Site 1262, are the long (405 kyr) and short (100 kyr) eccentricity cycles, and precession (21 kyr). Obliquity (41 kyr) is almost absent throughout the section except for a few brief intervals where it has a relatively weak influence. During the course of the Early Paleogene record, and particularly in the latest Paleocene, eccentricity-paced negative carbon-isotope excursions (d13C, CIEs) and coeval negative oxygen-isotope (d18O) excursions correspond to low carbonate (CaCO3) and coarse fraction (%CF) values due to increased carbonate dissolution, suggesting shoaling of the lysocline and accompanied changes in the global exogenic carbon cycle. These negative CIEs and d18O events coincide with maxima in eccentricity, with changes in d18O leading changes in d13C by ~6 (±5) kyr in the 405-kyr band and by ~3 (±1) kyr in the higher frequency 100-kyr band on average. However, these phase lags are not constant, with the lag in the 405-kyr band extending from ~4 (±5) kyr to ~21 (±2) kyr from the late Paleocene to the early Eocene, suggesting a progressively weaker coupling of climate and the carbon-cycle with time. The higher amplitude 405-kyr cycles in the latest Paleocene are associated with changes in bottom water temperature of 2-4ºC, while the most prominent 100 kyr-paced cycles can be accompanied by changes of up to 1.5ºC. Comparison of the 1262 record with a lower resolution, but orbitally-tuned benthic record for Site 1209 in the Pacific allows for verification of key features of the benthic isotope records which are global in scale including a key warming step at 57.7 Ma.

Stable carbon and oxygen isotope record of Cretaceous planktonic foraminifera from DSDP (Table 1)

The Cretaceous Heterohelix moremani (Cushman) was the only biserial planktonic foraminiferal species from its first appearance in the late Albian up to the Cenomanian/Turonian boundary. Within that time, it increased gradually in abundance relative to other planktonic foraminifera in five Circum-North Atlantic sections. It is generally rare in upper Albian sediments, common in most of the Cenomanian and very abundant in sediments representing the latest Cenomanian Oceanic Anoxic Event. Short-term variations on the overall abundance trend correlate with positive excursions in the bulk carbonate delta13C record. Maximum rain rates of H. moremani during OAE2 show that this species was an opportunist that did well in extreme conditions, but its overall distribution indicates that it is not necessarily a marker for very high palaeoproductivity environments. Stable oxygen and carbon isotope measurements on foraminiferal species indicate that H. moremani was a surface water dweller at least in part of its geographic range, but incorporated 13C out of equilibrium with ambient seawater. It is depleted in delta13C relative to other planktonic foraminifera, which is attributed to vital effects related to its opportunistic character.

Stable carbon and oxygen isotope ratios for different test sizes of live benthic foraminifera from the Arabian Sea

We determined the stable oxygen and carbon isotopic composition of live (Rose Bengal stained) tests belonging to different size classes of two benthic foraminiferal species from the Pakistan continental margin. Samples were taken at 2 sites, with water depth of about 135 and 275 m, corresponding to the upper boundary and upper part of the core region of the oxygen minimum zone (OMZ). For Uvigerina ex gr. U. semiornata and Bolivina aff. B. dilatata, delta13C and delta18O values increased significantly with increasing test size. In the case of U. ex gr. U. semiornata, delta13C increased linearly by about 0.105 per mil for each 100-µm increment in test size, whereas delta18O increased by 0.02 to 0.06 per mil per 100 µm increment. For B. aff. B. dilatata the relationship between test size and stable isotopic composition is better described by logarithmic equations. A strong positive linear correlation is observed between delta18O and delta13C values of both taxa, with a constant ratio of delta18O and delta13C values close to 2:1. This suggests that the strong ontogenetic effect is mainly caused by kinetic isotope fractionation during CO2 uptake. Our data underline the necessity to base longer delta18O and delta13C isotope records derived from benthic foraminifera on size windows of 100 µm or less. This is already common practice in down-core isotopic studies of planktonic foraminifera.

Stable carbon and oxygen isotope ratios of Planulina wuellerstorfi from sediments of the Sierra Leone Rise

Causes of change in deep water delta13C can be either global or local in extent. Global causes include (1) climatically-induced changes in the amount of terrestrial biomass which alter the average carbon isotopic composition of the oceanic reservoir (Shackleton, 1977), and (2) erosion and deposition of organic-rich, continental shelf sediments during sea level fluctuations which change the mean oceanic carbon: phosphorus ratio (Broecker, 1982 doi:10.1016/0079-6611(82)90007-6). Regional gradients of delta13C are created by remineralization of organic detritus within the deep ocean itself thus reflecting the distribution of water masses and modern thermohaline flow. Changes in a single geological record of benthic foraminiferal delta13C can result from any combination of these global and abyssal circulation effects. By sampling a large number of cores collected over a wide bathymetric range yet confined to a small geographical region we have minimized the ambiguity. We can assume that each delta13C record was equally affected by global causes of delta13C variation. The differences seen between the delta13C records must, therefore, reflect changes in the distribution of delta13C in the deep ocean. We interpret these differences in distribution in terms of changes in the ocean's abyssal circulation. Benthic foraminiferal carbon isotopic evidence from a suite of Sierra Leone Rise cores indicates that the deeper parts of the eastern Atlantic basins underwent a reduction in [O2] during the maximum of the last glaciation. Reduced advection of O2-rich deep water through low-latitude fracture zones, associated with increased delivery of organic matter to the deep ocean, lowered the delta13C of deep water SumCO2 at all depths below the sill separating the eastern and western Atlantic basins (Metcalf et al., 1964 doi:10.1016/0011-7471(64)91078-2). This decreased advection into the eastern Atlantic Ocean coincides with the overall decrease in deep water production in the North Atlantic during the last glacial maximum (Curry and Lohmann, 1982 doi:10.1016/0033-5894(82)90071-0; Boyle and Keigwin, 1982 doi:10.1126/science.218.4574.784; Schnitker, 1979 doi:10.1016/0377-8398(79)90020-3; Streeter and Shackleton, 1979 doi:10.1126/science.203.4376.168).

Biomass and stable isotope composition of plankton in five size fractions along a zonal transect (24°N) from the Canary Islands to Florida in January-March 2011

The spatial variability of biomass and stable isotopes in plankton size fractions in the upper 200 m was studied in a high spatial resolution transect along 24°N from Canary Islands to Florida (January - March 2011) during Leg 8 of the Malaspina-2010 expedition (http://www.expedicionmalaspina.es) to determine nitrogen and carbon sources. Plankton samples were collected by vertical tows of a microplankton net (40 mm mesh size) and a mesoplankton net (200 mm mesh size) through the upper 200 m of the water column. Sampling was between 10:00 and 16:00 h GMT. Plankton was separated into five size fractions (40 - 200, 200 - 500, 500 - 1000, 1000 - 2000 and > 2000 mm) by gentle filtration of the samples by a graded series of nylon sieves (2000, 1000, 500, 200 and 40 mm). Large gelatinous organisms were removed before filtration. Aliquots for each size fraction were collected on pre-weighed glass-fibre filters, dried (60°C, 48 h) and stored in a desiccator before determination of biomass (dry weight), carbon and nitrogen content and natural abundance of stable carbon and nitrogen isotopes ashore. Vertical advection of waters predominated in lateral zones while the central Atlantic (30-70°W) was characterized by a strong stratification and oligotrophic surface waters. Plankton biomass was low in the central zone and high in both eastern and western sides, with most of the variability due to either large (>2000 µm) and small plankton (<500 µm). Carbon isotopes reflected mainly the advection the deep water in lateral zones. Stable nitrogen isotopes showed a nearly symmetrical spatial distribution in all fractions, with the lowest values (delta15N <1per mill) in the central zone, and were inversely correlated to carbon stable isotopes (delta13C) and to the abundance of the nitrogen-fixer Trichodesmium. Diazotrophy was estimated to account for >50% of organic nitrogen in the central zone, and even >30% in eastern and western zones. The impact of diazotrophy increased with the size of the organisms, supporting the wide participation of all trophic levels in the processing of recently fixed nitrogen. These results indicate that atmospheric sources of carbon and nitrogen prevail over deep water sources in the subtropical North Atlantic and that the zone influenced by diazotrophy is much larger than reported in previous studies.

Geochemistry and stable carbon isotope composition of kerogen of DSDP Site 124-767

Celebes Basin sediments from Ocean Drilling Program Site 767 (Leg 124) containing both marine and terrestrial organic matter have been investigated through palynofacies and geochemical analyses. The main degradation processes affecting or having affected organic matter are recorded in the sedimentary column as shown by ammonium, phosphate and sulfate pore-water profiles, and by petrographic and geochemical analyses of sediments. In the upper part of the sedimentary section (down to 200 mbsf), the decrease of the ratio of total organic carbon to sulfur (TOC/S) with depth, generally related to the sulfate reduction process, is accompanied by an increase of framboidal pyrite content in the marine organic matter, and by an increasing amount of amorphous marine organic matter relative to the total organic matter. However, as the terrestrial organic input also varies with depth, dilution effects are superimposed on diagenesis. This continental supply affects the TOC/S ratio by increasing total organic carbon and decreasing the ability of the bulk organic matter to be metabolized through sulfate reduction. A positive relationship between the TOC/P ratio and the amount of degraded organic matter of marine origin clearly displays the effect of an organic source on the composition of the sediment. Each lithostratigraphic unit possesses its own characteristics in terms of composition and preservation of organic matter. The effects of diagenesis can only be appreciated within a single lithostratigraphic unit and mainly affect the less-resistant marine organic matter.