Patterns of Element Incorporation in Calcium Carbonate Biominerals Recapitulate Phylogeny for a Diverse Range of Marine Calcifiers.

Elemental ratios in biogenic marine calcium carbonates are widely used in geobiology, environmental science, and paleoenvironmental reconstructions. It is generally accepted that the elemental abundance of biogenic marine carbonates reflects a combination of the abundance of that ion in seawater, the physical properties of seawater, the mineralogy of the biomineral, and the pathways and mechanisms of biomineralization. Here we report measurements of a suite of nine elemental ratios (Li/Ca, B/Ca, Na/Ca, Mg/Ca, Zn/Ca, Sr/Ca, Cd/Ca, Ba/Ca, and U/Ca) in 18 species of benthic marine invertebrates spanning a range of biogenic carbonate polymorph mineralogies (low-Mg calcite, high-Mg calcite, aragonite, mixed mineralogy) and of phyla (including Mollusca, Echinodermata, Arthropoda, Annelida, Cnidaria, Chlorophyta, and Rhodophyta) cultured at a single temperature (25°C) and a range of pCO2 treatments (ca. 409, 606, 903, and 2856 ppm). This dataset was used to explore various controls over elemental partitioning in biogenic marine carbonates, including species-level and biomineralization-pathway-level controls, the influence of internal pH regulation compared to external pH changes, and biocalcification responses to changes in seawater carbonate chemistry. The dataset also enables exploration of broad scale phylogenetic patterns of elemental partitioning across calcifying species, exhibiting high phylogenetic signals estimated from both uni- and multivariate analyses of the elemental ratio data (univariate: λ = 0-0.889; multivariate: λ = 0.895-0.99). Comparing partial R 2 values returned from non-phylogenetic and phylogenetic regression analyses echo the importance of and show that phylogeny explains the elemental ratio data 1.4-59 times better than mineralogy in five out of nine of the elements analyzed. Therefore, the strong associations between biomineral elemental chemistry and species relatedness suggests mechanistic controls over element incorporation rooted in the evolution of biomineralization mechanisms.

A coastal coccolithophore maintains pH homeostasis and switches carbon sources in response to ocean acidification.

Ocean acidification will potentially inhibit calcification by marine organisms; however, the response of the most prolific ocean calcifiers, coccolithophores, to this perturbation remains under characterized. Here we report novel chemical constraints on the response of the widespread coccolithophore species Ochrosphaera neapolitana (O. neapolitana) to changing-CO2 conditions. We cultured this algae under three pCO2-controlled seawater pH conditions (8.05, 8.22, and 8.33). Boron isotopes within the algae's extracellular calcite plates show that this species maintains a constant pH at the calcification site, regardless of CO2-induced changes in pH of the surrounding seawater. Carbon and oxygen isotopes in the algae's calcite plates and carbon isotopes in the algae's organic matter suggest that O. neapolitana utilize carbon from a single internal dissolved inorganic carbon (DIC) pool for both calcification and photosynthesis, and that a greater proportion of dissolved CO2 relative to HCO3- enters the internal DIC pool under acidified conditions. These two observations may explain how O. neapolitana continues calcifying and photosynthesizing at a constant rate under different atmospheric-pCO2 conditions.