Description: Boron isotopic and elemental systematics are used to define the vital effects for the temperate shallow water Mediterranean coral Cladocora caespitosa. The corals are from a range of seawater pH conditions (pHT ~ 7.6 to ~ 8.1) and environmental settings: (1) naturally living colonies harvested from normal pH waters offshore Levanto, (2) colonies transplanted nearby a subsea volcanic vent system, and (3) corals cultured in aquaria exposed to high (700 µatm) and near present day (400 µatm) pCO2 levels. B/Ca compositions measured using laser ablation inductively coupled mass spectrometry (LA-ICPMS) show that boron uptake by C. caespitosa cultured at different pCO2 levels is independent of ambient seawater pH being mainly controlled by temperature-dependent calcification. In contrast, the boron isotope compositions (delta11Bcarb) of the full suite of corals determined by positive thermal ionisation mass spectrometry (PTIMS) shows a clear trend of decreasing delta11Bcarb (from 26.7 to 22.2 %o) with decreasing seawater pH, reflecting the strong pH dependence of the boron isotope system. The delta11Bcarb compositions together with measurements of ambient seawater parameters enable calibration of the boron pH proxy for C. caespitosa, by using a new approach that defines the relationship between ambient seawater pH (pHsw) and the internally controlled pH at the site of calcification (pHbiol). C. caespitosa exhibits a linear relationship between pHsw and the shift in pH due to physiological processes (deltapH = pHbiol - pHsw) giving the regression deltapHClad = 4.80 - 0.52* pHsw for this species. We further apply this method ("deltapH-pHsw") to calibrate tropical species of Porites, Acropora, and Stylophora reported in the literature. The temperate and tropical species calibrations are all linearly correlated (r2 〉 0.9) and the biological fractionation component (deltapH) between species varies within ~ 0.2 pH units. Our "deltapH-pHsw" approach provides a robust and accurate tool to reconstruct palaeoseawater pHsw for both temperate and tropical corals, further validating the boron fractionation factor (alphaB3-B4 = 1.0272) determined experimentally by Klochko et al. (2006) and the boron isotope pH proxy, both of which have been the foci of considerable debate.

Description: The formation of Eastern Mediterranean sapropels has periodically occurred during intensification of northern hemisphere monsoon precipitation over North Africa. However, the large-scale response of the Eastern Mediterranean thermohaline circulation during these monsoon-fuelled freshening episodes is poorly constrained. Here, we investigate the formation of the youngest sapropel (S1) along an across-slope transect in the Adriatic Sea. Foraminifera-based oxygen index, redox-sensitive elements and biogeochemical parameters reveal - for the first time - that the Adriatic S1 was synchronous with the deposition of south-eastern Mediterranean S1 beds. Proxies of paleo thermohaline currents indicate that the bottom-hugging North Adriatic Dense Water (NAdDW) suddenly decreased at the sapropel onset simultaneously with the maximum freshening of the Levantine Sea during the African Humid Period. We conclude that the lack of the "salty" Levantine Intermediate Water hampered the preconditioning of the northern Adriatic waters necessary for the NAdDW formation prior to the winter cooling. Consequently, a weak NAdDW limited in turn the Eastern Mediterranean Deep Water (EMDWAdriatic) formation with important consequences for the ventilation of the Ionian basin as well. Our results highlight the importance of the Adriatic for the deep water ventilation and the interdependence among the major eastern Mediterranean water masses whose destabilization exerted first-order control on S1 deposition.

Description: We present the neodymium isotopic composition (epsilon-Nd) of mixed planktonic foraminifera species from a sediment core collected at 622 m water depth in the Balearic Sea, as well as epsilon-Nd of scleractinian cold-water corals (CWC; Madrepora oculata, Lophelia pertusa) retrieved between 280 and 442 m water depth in the Alboran Sea and at 414 m depth in the southern Sardinian continental margin. The aim is to constrain hydrological variations at intermediate depths in the western Mediterranean Sea during the last 20 kyr. Planktonic (Globigerina bulloides) and benthic (Cibicidoides pachyderma) foraminifera from the Balearic Sea were also analyzed for stable oxygen (d18O) and carbon (d13C) isotopes. The foraminiferal and coral epsilon-Nd values from the Balearic and Alboran seas are comparable over the last ~13 kyr, with mean values of -8.94 ± 0.26 (1 Sigma; n = 24) and -8.91 ± 0.18 (1 Sigma; n = 25), respectively. Before 13 ka BP, the foraminiferal epsilon-Nd values are slightly lower (-9.28 ± 0.15) and tend to reflect higher mixing between intermediate and deep waters, which are characterized by more unradiogenic epsilon-Nd values. The slight epsilon-Nd increase after 13 ka BP is associated with a decoupling in the benthic foraminiferal d13C composition between intermediate and deeper depths, which started at ~16 ka BP. This suggests an earlier stratification of the water masses and a subsequent reduced contribution of unradiogenic epsilon-Nd from deep waters. The CWC from the Sardinia Channel show a much larger scatter of epsilon-Nd values, from -8.66 ± 0.30 to 5.99 ± 0.50, and a lower average (-7.31 ± 0.73; n = 19) compared to the CWC and foraminifera from the Alboran and Balearic seas, indicative of intermediate waters sourced from the Levantine basin. At the time of sapropel S1 deposition (10.2 to 6.4 ka), the epsilon-Nd values of the Sardinian CWC become more unradiogenic (-8.38 ± 0.47; n = 3 at ~8.7 ka BP), suggesting a significant contribution of intermediate waters originated from the western basin. We propose that western Mediterranean intermediate waters replaced the Levantine Intermediate Water (LIW), and thus there was a strong reduction of the LIW during the mid-sapropel (~8.7 ka BP). This observation supports a notable change of Mediterranean circulation pattern centered on sapropel S1 that needs further investigation to be confirmed.