Alkenone and foraminifera records from sediment samples off Namibia

Radiocarbon stratigraphy is an essential tool for high resolution paleoceanographic studies. Age models based on radiocarbon ages of foraminifera are commonly applied to a wide range of geochemical studies, including the investigation of temporal leads and lags. The critical assumption is that temporal coupling between foraminifera and other sediment constituents, including specific molecular organic compounds (biomarkers) of marine phytoplankton, e.g. alkenones, is maintained in the sediments. To test this critical assumption in the Benguela upwelling area, we have determined radiocarbon ages of total C37-C39 alkenones in 20 samples from two gravity cores and three multicorer cores. The cores were retrieved from the continental shelf and slope off Namibia, and samples were taken from Holocene, deglacial and Last Glacial Maximum core sections. The alkenone radiocarbon ages were compared to those of planktic foraminifera, total organic carbon, fatty acids and fine grained carbonates from the same samples. Interestingly, the ages of alkenones were 1000 to 4500 yr older than those of foraminifera in all samples. Such age differences may be the result of different processes: Bioturbation associated with grain size effects, lateral advection of (recycled) material and redeposition of sediment on upper continental slopes due to currents or tidal movement are examples for such processes. Based on the results of this study, the age offsets between foraminifera and alkenones in sediments from the upper continental slope off Namibia most probably do not result from particle-selective bioturbation processes. Resuspension of organic particles in response to tidal movement of bottom waters with velocities up to 25 cm/s recorded near the core sites is the more likely explanation. Our results imply that age control established using radiocarbon measurements of foraminifera may be inadequate for the interpretation of alkenone-based proxy data. Observed temporal leads and lags between foraminifera based data and data derived from alkenone measurements may therefore be secondary signals, i.e. the result of processes associated with particle settling and biological activity.

Shell flux and oxygen isotope data of North Atlantic foraminifera

We present an almost 3 year long time series of shell fluxes and oxygen isotopes of left-coiling Neogloboquadrina pachyderma and Turborotalita quinqueloba from sediment traps moored in the deep central Irminger Sea. We determined their response to the seasonal change from a deeply mixed water column with occasional deep convection in winter to a thermally stratified water column with a surface mixed layer (SML) of around 50 m in summer. Both species display very low fluxes during winter with a remnant summer population holding out until replaced by a vital population that seeds the subsequent blooms. This annual population overturning is marked by a 0.7 per mill increase in d18O in both species. The shell flux of N. pachyderma peaks during the spring bloom and in late summer, when stratification is close to its minimum and maximum, respectively. Both export periods contribute about equally and account for >95% of the total annual flux. Shell fluxes of T. quinqueloba show only a single broad pulse in summer, thus following the seasonal stratification cycle. The d18O of N. pachyderma reflects temperatures just below the base of the seasonal SML without offset from isotopic equilibrium. The d18O pattern of T. quinqueloba shows a nearly identical amplitude and correlates highly with the d18O of N. pachyderma. Therefore T. quinqueloba also reflects temperature near the base of the SML but with a positive offset from isotopic equilibrium. These offsets contrast with observations elsewhere and suggest a variable offset from equilibrium calcification for both species. In the Irminger Sea the species consistently show a contrast in their flux timings. Their flux-weighted delta d18O will thus dominantly be determined by seasonal temperature differences at the base of the SML rather than by differences in their depth habitat. Consequently, their sedimentary delta d18O may be used to infer the seasonal contrast in temperature at the base of the SML.

(Table A1) Diatom isotope measurements from ODP Hole 145-882A

In comparison to other sectors of the marine system, the palaeoceanography of the subarctic North Pacific Ocean is poorly constrained. New diatom isotope records of d13C, d18O, d30Si (d13Cdiatom, d18Odiatom, and d30Sidiatom) are presented alongside existing geochemical and isotope records to document changes in photic zone conditions, including nutrient supply and the efficiency of the soft-tissue biological pump, between Marine Isotope Stage (MIS) 4 and MIS 5e. Peaks in opal productivity in MIS 5b/c and MIS 5e are both associated with the breakdown of the regional halocline stratification and increased nutrient supply to the photic zone. Whereas the MIS 5e peak is associated with low rates of nutrient utilisation, the MIS 5b/c peak is associated with significantly higher rates of nutrient utilisation. Both peaks, together with other smaller increases in productivity in MIS 4 and 5a, culminate with a significant increase in freshwater input which strengthens/re-establishes the halocline and limits further upwelling of sub-surface waters to the photic zone. Whilst d30Sidiatom and previously published records of diatom d15N (d15Ndiatom) (Brunelle et al., 2007, 2010) show similar trends until the latter half of MIS 5a, the records become anti-correlated after this juncture and into MIS 4, suggesting a possible change in photic zone state such as may occur with a shift to iron or silicon limitation.

(Table 1) Isotopic composition of organic compinents of DSDP Hole 24-231

Plant leaf wax hydrogen isotope (dDwax) reconstructions are increasingly being used to reconstruct hydrological change. This approach is based upon the assumption that variations in hydroclimatic variables, and in particular, the isotopic composition of precipitation (dDP), dominate dDwax. However modern calibration studies suggest that offsets between plant types may bias the dDwax hydrological proxy at times of vegetation change. In this study, I pair leaf wax analyses with published pollen data to quantify this effect and construct the first vegetation-corrected hydrogen isotopic evidence for precipitation (dDcorrP). In marine sediments from Deep Sea Drilling Program Site 231 in the Gulf of Aden spanning 11.4-3.8 Ma (late Miocene and earliest Pliocene), I find 77 per mil swings in dDwax that correspond to pollen evidence for substantial vegetation change. Similarities between dDP and dDcorrP imply that the hydrological tracer is qualitatively robust to vegetation change. However, computed vegetation corrections can be as large as 31 per mil indicating substantial quantitative uncertainty in the raw hydrological proxy. The resulting dDcorrP values quantify hydrological change and allow us to identify times considerably wetter than modern at 11.09, 7.26, 5.71 and 3.89 Ma. More generally, this novel interpretative framework builds the foundations of improved quantitative paleohydrological reconstructions with the dDwax proxy, in contexts where vegetation change may bias the plant-based proxy. The vegetation corrected paleoprecipitation reconstruction dDcorrP, represents the best available estimate as proof-of-concept, for an approach that I hope will be refined and more broadly applied.

Standing stocks and carbon isotopes of live benthic foraminifera from the South Atlantic

Live (Rose Bengal stained) and dead benthic foraminifera of surface and subsurface sediments from 25 stations in the eastern South Atlantic Ocean and the Atlantic sector of the Southern Ocean were analyzed to decipher a potential influence of seasonally and spatially varying high primary productivity on the stable carbon isotopic composition of foraminiferal tests. Therefore, stations were chosen so that productivity strongly varied, whereas conservative water mass properties changed only little. To define the stable carbon isotopic composition of dissolved inorganic carbon (d13CDIC) in ambient water masses, we compiled new and previously published d13CDIC data in a section running from Antarctica through Agulhas, Cape and Angola Basins, via the Guinea Abyssal Plain to the Equator. We found that intraspecific d13C variability of all species at a single site is constantly low throughout their distribution within the sediments, i.e. species specific and site dependent mean values calculated from all subbottom depths on average only varied by +/-0.09 per mil. This is important because it makes the stable carbon isotopic signal of species independent of the particular microhabitat of each single specimen measured and thus more constant and reliable than has been previously assumed. So-called vital and/or microhabitat effects were further quantified: (1) d13C values of endobenthic Globobulimina affinis, Fursenkoina mexicana, and Bulimina mexicana consistently are by between -1.5 and -1.0 per mil VPDB more depleted than d13C values of preferentially epibenthic Fontbotia wuellerstorfi, Cibicidoides pachyderma, and Lobatula lobatula. (2) In contrast to the Antarctic Polar Front region, at all stations except one on the African continental slope Fontbotia wuellerstorfi records bottom water d13CDIC values without significant offset, whereas L. lobatula and C. pachyderma values deviate from bottom water values by about -0.4 per mil and -0.6 per mil, respectively. This adds to the growing amount of data on contrasting cibicid d13C values which on the one hand support the original 1:1-calibration of F. wuellerstorfi and bottom water d13CDIC, and on the other hand document severe depletions of taxonomically close relatives such as L. lobatula and C. pachyderma. At one station close to Bouvet Island at the western rim of Agulhas Basin, we interpret the offset of -1.5 per mil between bottom water d13CDIC and d13C values of infaunal living Bulimina aculeata in contrast to about -0.6 +/- 0.1 per mil measured at eight stations close-by, as a direct reflection of locally increased organic matter fluxes and sedimentation rates. Alternatively, we speculate that methane locally released from gas vents and related to hydrothermal venting at the mid-ocean ridge might have caused this strong depletion of 13C in the benthic foraminiferal carbon isotopic composition. Along the African continental margin, offsets between deep infaunal Globobulimina affinis and epibenthic Fontbotia wuellerstorfi as well as between shallow infaunal Uvigerina peregrina and F. wuellerstorfi, d13C values tend to increase with generally increasing organic matter decomposition rates. Although clearly more data are needed, these offsets between species might be used for quantification of biogeochemical paleogradients within the sediment and thus paleocarbon flux estimates. Furthermore, our data suggest that in high-productivity areas where sedimentary carbonate contents are lower than 15 weight %, epibenthic and endobenthic foraminiferal d13C values are strongly influenced by 13C enrichment probably due to carbonate-ion undersaturation, whereas above this sedimentary carbonate threshold endobenthic d13C values reflect depleted pore water d13CDIC values.

Bulk sediment and diatom silica carbon isotope composition from Antarctic coastal marine sediments

Organic carbon occluded in diatom silica is assumed to be protected from degradation in the sediment. d13C from diatom carbon (d13C(diatom)) therefore potentially provides a signal of conditions during diatom growth. However, there have been few studies based on d13C(diatom). Numerous variables can influence d13C of organic matter in the marine environment (e.g., salinity, light, nutrient and CO2 availability). Here we compare d13C(diatom) and d13C(TOC) from three sediment records from individual marine inlets (Rauer Group, East Antarctica) to (i) investigate deviations between d13C(diatom) and d13C(TOC), to (ii) identify biological and environmental controls on d13C(diatom) and d13C(TOC), and to (iii) discuss d13C(diatom) as a proxy for environmental and climate reconstructions. The records show individual d13C(diatom) and d13C(TOC) characteristics, which indicates that d13C is not primarily controlled by regional climate or atmospheric CO2 concentration. Since the inlets vary in water depths offsets in d13C are probably related to differences in water column stratification and mixing, which influences redistribution of nutrients and carbon within each inlet. In our dataset changes in d13C(diatom) and d13C(TOC) could not unequivocally be ascribed to changes in diatom species composition, either because the variation in d13C(diatom) between the observed species is too small or because other environmental controls are more dominant. Records from the Southern Ocean show depleted d13C(diatom) values (1-4 per mil) during glacial times compared to the Holocene. Although climate variability throughout the Holocene is low compared to glacial/interglacial variability, we find variability in d13C(diatom), which is in the same order of magnitude. d13C of organic matter produced in the costal marine environment seems to be much more sensitive to environmental changes than open ocean sites and d13C is of strongly local nature.

Mg/Ca and stable oxygen isotope ratios of Uvigerina spp. from the Southern Ocean

The sensitivity to temperature of Mg/Ca ratios in the shallow-infaunal benthic foraminifera Uvigerina spp. has been assessed. Core-top calibrations over ~1-20 °C show a range in sensitivity of 0.065-0.084 mmol/mol/°C but few data are available spanning the temperature range anticipated in deep-sea records over glacial-interglacial cycles. In contrast to epibenthic foraminiferal species, carbonate ion saturation appears not to affect Mg/Ca significantly. A method based on estimating the ratio of the temperature sensitivity of foraminiferal Mg/Ca to that of d18Ocalcite shows that sensitivity for Mg/Ca at the high end of the observed core-top range (~0.1 mmol/mol/°C) is required for consistency with LGM-Holocene differences in each property as constrained by independent proxy data. This is supported by a Mg/Ca record for Uvigerina spp. generated for the Southern Ocean over the past 440,000 years from Ocean Drilling Program Site 1123 (Chatham Rise, New Zealand). The record shows variability that correlates with climate oscillations. The LGM deep ocean temperature derived from the Mg/Ca record is -1.1 ± 0.3 °C. Transformation to temperature allows estimates to be made of changes in bottom water temperature and seawater d18O and comparison made with literature records. Analysis reveals a ~2.5-kyr lead in the record of temperature over calcite d18O and a longer lead over seawater d18O. This is a reflection of larger phase offsets at eccentricity periods; phase offsets at tilt and precession are within error zero.