Stable isotopes and Mg/Ca measurements of two sediment cores in the northeastern tropical Atlantic

Two SST records based on Mg/Ca of G. ruber (pink) from the continental slope off West Africa at 15°N and 12°N shed new light on the thermal bipolar seesaw pattern in the northeastern tropical Atlantic during periods of reduced Atlantic Meridional Overturning Circulation (AMOC) associated with Heinrich stadials H1 to H6. The two records indicate that the latitudinal position of the bipolar seesaw's zero-anomaly line, between cooling in the North and warming in the South, gradually shifted southward from H6 to H1. A conceptual model is presented that aims to provide a physically consistent mechanism for the southward migration of the seesaw's fulcrum. The conceptual model suggests latitudinal movements of the Intertropical Convergence Zone, driven by a combination of orbital-forced changes in the meridional temperature gradient within the realm of the Hadley cell and the expansion of the Northern Hemisphere cryosphere, as a major factor.

Mg/Ca variability in Globigerinoides ruber tests

Laser ablation inductively coupled plasma-mass spectrometry microanalysis of fossil and live Globigerinoides ruber from the eastern Indian Ocean reveals large variations of Mg/Ca composition both within and between individual tests from core top or plankton pump samples. Although the extent of intertest and intratest compositional variability exceeds that attributable to calcification temperature, the pooled mean Mg/Ca molar values obtained for core top samples between the equator and >30°S form a strong exponential correlation with mean annual sea surface temperature (Mg/Ca mmol/mol = 0.52 exp**0.076SST°C, r**2 = 0.99). The intertest Mg/Ca variability within these deep-sea core top samples is a source of significant uncertainty in Mg/Ca seawater temperature estimates and is notable for being site specific. Our results indicate that widely assumed uncertainties in Mg/Ca thermometry may be underestimated. We show that statistical power analysis can be used to evaluate the number of tests needed to achieve a target level of uncertainty on a sample by sample case. A varying bias also arises from the presence and varying mix of two morphotypes (G. ruber ruber and G. ruber pyramidalis), which have different mean Mg/Ca values. Estimated calcification temperature differences between these morphotypes range up to 5°C and are notable for correlating with the seasonal range in seawater temperature at different sites.

B/Ca ratios in planktonic foraminifera

Boron isotope systematics indicate that boron incorporation into foraminiferal CaCO3 is determined by the partition coefficient, KD = [B/Ca](CaCO3)/[B(OH)4**-/HCO3**-](seawater), and [B(OH)4?/HCO3?](seawater), providing, in principle, a method to estimate seawater pH and PCO2. We have measured B/Ca ratios in Globigerina bulloides and Globorotaliainflata for a series of core tops from the North Atlantic and the Southern Ocean and in Globigerinoides ruber (white) from Ocean Drilling Program (ODP) site 668B on the Sierra Leone Rise in the eastern equatorial Atlantic. B/Ca ratios in these species of planktonic foraminifera seem unaffected by dissolution on the seafloor. KD shows a strong species-specific dependence on calcification temperature, which can be corrected for using the Mg/Ca temperature proxy. A preliminary study of G. inflata from Southern Ocean sediment core CHAT 16K suggests that temperature-corrected B/Ca was ~30% higher during the last glacial. Correspondingly, pH was 0.15 units higher and aqueous PCO2 was 95 ?atm lower at this site at the Last Glacial Maximum. The covariation between reconstructed PCO2 and the atmospheric pCO2 from the Vostok ice core demonstrates the feasibility of using B/Ca in planktonic foraminifera for reconstructing past variations in pH and PCO2.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

Radiocarbon dataing, stable oxygen isotopes, and Mg/Ca ratios in surface sediment samples of the tropical eastern Indian Ocean

Shell chemistry of planktic foraminifera and the alkenone unsaturation index in 69 surface sediment samples in the tropical eastern Indian Ocean off West and South Indonesia were studied. Results were compared to modern hydrographic data in order to assess how modern environmental conditions are preserved in sedimentary record, and to determine the best possible proxies to reconstruct seasonality, thermal gradient and upper water column characteristics in this part of the world ocean. Our results imply that alkenone-derived temperatures record annual mean temperatures in the study area. However, this finding might be an artifact due to the temperature limitation of this proxy above 28°C. Combined study of shell stable oxygen isotope and Mg/Ca ratio of planktic foraminifera suggests that Globigerinoides ruber sensu stricto (s.s.), G. ruber sensu lato (s.l.), and G. sacculifer calcify within the mixed-layer between 20 m and 50 m, whereas Globigerina bulloides records mixed-layer conditions at ~50 m depth during boreal summer. Mean calcifications of Pulleniatina obliquiloculata, Neogloboquadrina dutertrei, and Globorotalia tumida occur at the top of the thermocline during boreal summer, at ~75 m, 75-100 m, and 100 m, respectively. Shell Mg/Ca ratios of all species show a significant correlation with temperature at their apparent calcification depths and validate the application of previously published temperature calibrations, except for G. tumida that requires a regional Mg/Ca-temperature calibration (Mg/Ca = 0.41 exp (0.068*T)). We show that the difference in Mg/Ca-temperatures of the mixed-layer species and the thermocline species, particularly between G. ruber s.s. (or s.l.) and P. obliquiloculata, can be applied to track changes in the upper water column stratification. Our results provide critical tools for reconstructing past changes in the hydrography of the study area and their relation to monsoon, El Niño-Southern Oscillation, and the Indian Ocean Dipole Mode.