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Evolutionary or adaptative changes in Noelaerhabdaceae coccolithophores occurred in parallel with major changes in carbonate export and burial during scenarios of low orbital eccentricity, with a ∼400 kyr recurrence, during the Pleistocene. Coeval with these conditions of enhanced proliferation, here we report that the calcification of specimens was enhanced at a global scale and across multiple species or morphotypes within the Gephyrocapsa complex during the Mid-Brunhes (MB) interval. This acme of increased production of organic and inorganic carbon by Gephyrocapsa , suggests that such global changes may originate from a common driver. Increased seawater alkalinity, with an appropriately long residence time, is proposed as environmental trigger on the selection of a wide variety of highly calcified and prolific Gephyrocapsa taxa. This new perspective highlights the role of orbital forcing in phytoplankton evolution or adaptation, via a global environmental driver in the form of seawater carbon chemistry. Our results fit with earlier proposals appealing for an intensified biological pump and respiration dissolution during this interval. We hypothesize that the Gephyrocapsa acme may play a double-edged role, by increasing shallow respiration dissolution rates, limiting the removal of alkalinity by burial, which may help to recycle alkalinity and maintain constant levels at the ∼400 kyr scale. This idea suggests the potential capacity of the Noelaerhabdaceae coccolithophore acmes to modify the typical behaviour of carbonate compensation in the ocean and that the changes in coccolithophore calcification may be indicative of changes in ocean carbonate chemistry and the operation of the global carbon cycle in the past. • The morphological (MDI) record of the Gephyrocapsa acme is coeval at every latitude. • A different array of highly calcified Gephyrocapsa taxa is universally identified. • Size is the main factor controlling the changes in mass in Gephyrocapsa coccoliths. • The Gephyrocapsa complex acted as a sink and source of alkalinity during 400 kyr. • Ocean alkalinity could mediate between orbital forcing and Noelaerhabdaceae acmes. [ABSTRACT FROM AUTHOR]

Abstract: The mismatch between the 100 and 400 k.y. components of Pleistocene climate and the relative power of those terms from the eccentricity of the Earth''s orbit remains a challenge to the Milankovitch hypothesis. Coccolithophores have the potential to respond to parameters of orbital forcing other than insolation, and, as a critical component of the ocean carbon cycle, can act to modify the climate response. The first direct comparison of coccolith fraction Sr/Ca, alkenone abundance and automated coccolithophore counts, shows that CF Sr/Ca is largely driven by changing production of bloom species, with unusually high Sr/Ca ratios. The periods of high CF Sr/Ca and high bloom production mark periods of high global coccolithophore production, which correlate inversely with the low amplitude 100 and higher amplitude 400 k.y. eccentricity orbital frequency. ∼400 k.y. cycles of coccolithophore bloom production correspond to periods of enhanced carbonate accumulation in some parts of the ocean, deep ocean dissolution in others, positive shifts in global ocean δ13C, and acmes of Gephyrocapsa caribbeanica and Emiliania huxleyi. The link between production of coccolithophore blooms and eccentricity may be due to orbital control of silica leakage from the Southern Ocean, to the orbitally defined inverse correlation between insolation and growing season length and the asymptotic growth response to these parameters, or to changes in nutrient input from weathering. During the Pleistocene, the eccentricity induced coccolithophore acmes have no apparent influence on atmospheric carbon dioxide (pCO2) due to the shift towards small bloom coccolithophores, or to coupling with increased diatom productivity, or the ballast effect of the calcium carbonate rain, such that Pleistocene climate has no significant variance at the largest amplitude eccentricity forcing of 400 k.y. Coccolithophores and their influence on the carbon cycle may act as a filter between the incident orbital forcing and resultant climate. [Copyright &y& Elsevier]

The role of El Niño-Southern Oscillation (ENSO) in greenhouse warming and climate change remains controversial. During the warmth of the early-mid Pliocene, we find evidence for enhanced thermocline tilt and cold upwelling in the equatorial Pacific, consistent with the prevalence of a La Nina-like state, rather than the proposed persistent warm El Niño-like conditions. Our Pliocene paleothermometer supports the idea of a dynamic "ocean thermostat" in which heating of the tropical Pacific leads to a cooling of the east equatorial Pacific and a La Nina-like state, analogous to observations of a transient increasing east-west sea surface temperature gradient in the 20th-century tropical Pacific. [ABSTRACT FROM AUTHOR]

Reports on the investigation of the Southern Ocean's nutrient utilization in surface water to determine the relationship between the atmospheric carbon dioxide concentration and the oceanic carbon uptake, using the principles of paleoceanography. Concentration of cadmium and phosphorus that is explained by chemical fractionation; Reconstruction of surface water phosphate concentrations; Results that include information on phosphate utilization during the Last Glacial Maximum.

Coccoliths have dominated the sedimentary archive in the pelagic environment since the Jurassic. The biominerals produced by the coccolithophores are ideally placed to infer sea surface temperatures from their oxygen isotopic composition, as calcification in this photosynthetic algal group only occurs in the sunlit surface waters. In the present study, we dissect the isotopic mechanisms contributing to the “vital effect”, which overprints the oceanic temperatures recorded in coccolith calcite. Applying the passive diffusion model of carbon acquisition by the marine phytoplankton widely used in biogeochemical and palaeoceanographic studies, our results suggest that the oxygen isotope offsets from inorganic calcite in fast dividing species Emiliania huxleyi and Gephyrocapsa oceanica originates from the legacy of assimilated 18 O-rich CO 2 that induces transient isotopic disequilibrium to the internal dissolved inorganic carbon (DIC) pool. The extent to which this intracellular isotopic disequilibrium is recorded in coccolith calcite (1.5 to +3‰ over a 10 to 25 °C temperature range) is set by the degree of isotopic re-equilibration between CO 2 and water molecules before intracellular mineralisation. We show that the extent of re-equilibration is, in turn, set by temperature through both physiological (dynamics of the utilisation of the DIC pool) and thermodynamic (completeness of the re-equilibration of the relative 18 O-rich CO 2 influx) processes. At the highest temperature, less ambient aqueous CO 2 is present for algal growth, and the consequence of carbon limitation is exacerbation of the oxygen isotope vital effect, obliterating the temperature signal. This culture dataset further demonstrates that the vital effect is variable for a given species/morphotype, and depends on the intricate relationship between the environment and the physiology of biomineralising algae. [ABSTRACT FROM AUTHOR]

Abstract: The Mg/Ca ratio of foraminiferal calcite is an important proxy for estimating past ocean temperatures. Used in conjunction with δ18O of foraminiferal calcite it allows deconvolution of temperature and ice-volume signals to infer past ocean temperatures and salinities (assuming the relationship between seawater δ18O and salinity is known). Such work assumes that temperature is the only, or at least the dominant, environmental controller of foraminiferal Mg/Ca. The semi-enclosed Mediterranean Sea, where salinity varies from 36 to 40 psu over a seasonal temperature range of between only 5 °C to 8 °C, provides a relevant setting to test this assumption outside the laboratory. In this study, planktonic foraminifera (O. universa, G. siphonifera, G. bulloides and G. ruber (white) and (pink)) were picked from 11 box core tops spanning the Mediterranean salinity gradient and analysed for their trace-element concentrations. Mg/Ca ratios are higher, for the associated calcification temperatures, than in other regions where calibrations have been conducted and correlate poorly with calcification temperature. Mg/Ca ratios are particularly high for samples from the Eastern Mediterranean where salinity is unusually high. Correlations of Mg/Ca with the calcification salinity are statistically significant with Mg/Ca changing by 15–59% per psu, suggesting that salinity may act as a control on Mg/Ca ratios in addition to the dominant temperature control. We show that contamination by non-carbonate material and diagenetic high-Mg carbonate overgrowths cannot account for the observed trend of increasing Mg/Ca with salinity. A relationship between Mg/Ca and salinity is also suggested by re-analysis of calibrations from open-ocean settings. These new Mediterranean results are from a region with unusually high salinity but suggest that the effects of salinity on the Mg/Ca palaeothermometer should be considered even in open-ocean settings, particularly where large salinity changes occurred in the past. [Copyright &y& Elsevier]

Abstract: In order to achieve reliable and reproducible analysis of biological materials by SIMS, it is critical both that the chosen specimen preparation method does not modify substantially the in vivo chemistry that is the focus of the study and that any chemical information obtained can be calibrated accurately by selection of appropriate standards. In Oxford, we have been working with our new Cameca NanoSIMS50 on two very distinct classes of biological materials; the first where the sample preparation problems are relatively undemanding – human hair – but calibration for trace metal analysis is a critical issue and, the second, marine coccoliths and hyperaccumulator plants where reliable specimen preparation by rapid freezing and controlled drying to preserve the distribution of diffusible species is the first and most demanding requirement, but worthwhile experiments on tracking key elements can still be undertaken even when it is clear that some redistribution of the most diffusible ions has occurred. [Copyright &y& Elsevier]