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Global variability in seawater Mg:Ca and Sr:Ca ratios in the modern ocean.

ABSTRACT: Seawater Mg:Ca and Sr:Ca ratios are biogeochemical parameters reflecting the Earth-ocean-atmosphere dynamic exchange of elements. The ratios' dependence on the environment and organisms' biology facilitates their application in marine sciences. Here, we present a measured single-laboratory dataset, combined with previous data, to test the assumption of limited seawater Mg:Ca and Sr:Ca variability across marine environments globally. High variability was found in open-ocean upwelling and polar regions, shelves/neritic and river-influenced areas, where seawater Mg:Ca and Sr:Ca ratios range from ∼4.40 to 6.40 mmol:mol and ∼6.95 to 9.80 mmol:mol, respectively. Open-ocean seawater Mg:Ca is semiconservative (∼4.90 to 5.30 mol:mol), while Sr:Ca is more variable and nonconservative (∼7.70 to 8.80 mmol:mol); both ratios are nonconservative in coastal seas. Further, the Ca, Mg, and Sr elemental fluxes are connected to large total alkalinity deviations from International Association for the Physical Sciences of the Oceans (IAPSO) standard values. Because there is significant modern seawater Mg:Ca and Sr:Ca ratios variability across marine environments we cannot absolutely assume that fossil archives using taxa-specific proxies reflect true global seawater chemistry but rather taxa- and process-specific ecosystem variations, reflecting regional conditions. This variability could reconcile secular seawater Mg:Ca and Sr:Ca ratio reconstructions using different taxa and techniques by assuming an error of 1 to 1.50 mol:mol, and 1 to 1.90 mmol:mol, respectively. The modern ratios' variability is similar to the reconstructed rise over 20 Ma (Neogene Period), nurturing the question of seminonconservative behavior of Ca, Mg, and Sr over modern Earth geological history with an overlooked environmental effect.

SUBMITTER: Lebrato M

PROVIDER: S-EPMC7486706 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Acesta excavata (Fabricius, 1779) is a slow growing bivalve from the Limidae family and is often found associated with cold-water coral reefs along the European continental margin. Here we present the compositional variability of frequently used proxy elemental ratios (Mg/Ca, Sr/Ca, Na/Ca) measured by laser-ablation mass spectrometry (LA-ICP-MS) and compare it to in-situ recorded instrumental seawater parameters such as temperature and salinity. Shell Mg/Ca measured in the fibrous calcitic shell section was overall not correlated with seawater temperature or salinity; however, some samples show significant correlations with temperature with a sensitivity that was found to be unusually high in comparison to other marine organisms. Mg/Ca and Sr/Ca measured in the fibrous calcitic shell section display significant negative correlations with the linear extension rate of the shell, which indicates strong vital effects in these bivalves. Multiple linear regression analysis indicates that up to 79% of elemental variability is explicable with temperature and salinity as independent predictor values. Yet, the overall results clearly show that the application of Element/Ca (E/Ca) ratios in these bivalves to reconstruct past changes in temperature and salinity is likely to be complicated due to strong vital effects and the effects of organic material embedded in the shell. Therefore, we suggest to apply additional techniques, such as clumped isotopes, in order to exactly determine and quantify the underlying vital effects and possibly account for these. We found differences in the chemical composition between the two calcitic shell layers that are possibly explainable through differences of the crystal morphology. Sr/Ca ratios also appear to be partly controlled by the amount of magnesium, because the small magnesium ions bend the crystal lattice which increases the space for strontium incorporation. Oxidative cleaning with H2O2 did not significantly change the Mg/Ca and Sr/Ca composition of the shell. Na/Ca ratios decreased after the oxidative cleaning, which is most likely a leaching effect and not caused by the removal of organic matter.

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Global variability in seawater Mg:Ca and Sr:Ca ratios in the modern ocean.

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