ALBERT

Description: In the last few decades and in the near future CO2-induced ocean acidification is potentially a big threat to marine calcite-shelled animals (e.g. brachiopods, bivalves, corals and gastropods). Despite the great number of studies focusing on the effects of acidification on shell growth, metabolism, shell dissolution and shell repair, the consequences for biomineral formation remain poorly understood. Only a few studies have addressed the impact of ocean acidification on shell microstructure and geochemistry. In this study, a detailed microstructure and stable isotope geochemistry investigation was performed on nine adult brachiopod specimens of Magellania venosa (Dixon, 1789). These were grown in the natural environment as well as in controlled culturing experiments under different pH conditions (ranging from 7.35 to 8.15 ± 0.05) over different time intervals (214 to 335 days). Details of shell microstructural features, such as thickness of the primary layer, density and size of endopunctae and morphology of the basic structural unit of the secondary layer were analysed using scanning electron microscopy. Stable isotope compositions (δ13C and δ18O) were tested from the secondary shell layer along shell ontogenetic increments in both dorsal and ventral valves. Based on our comprehensive dataset, we observed that, under low pH conditions, M. venosa produced a more organic-rich shell with higher density of and larger endopunctae, and smaller secondary layer fibres. Also, increasingly negative δ13C and δ18O values are recorded by the shell produced during culturing and are related to the CO2 source in the culture set-up. Both the microstructural changes and the stable isotope results are similar to observations on brachiopods from the fossil record and strongly support the value of brachiopods as robust archives of proxies for studying ocean acidification events in the geologic past.

Description: The loss of carbonate production during the Toarcian Oceanic Anoxic Event (T-OAE, ca. 183 Ma) is hypothesized to have been at least partly triggered by ocean acidification linked to magmatism from the Karoo-Ferrar large igneous province (southern Africa and Antarctica). However, the dynamics of acidification have never been directly quantified across the T-OAE. Here, we present the first record of temporal evolution of seawater pH spanning the late Pliensbachian and early Toarcian from the Lusitanian Basin (Portugal) reconstructed on the basis of boron isotopic composition (δ11B) of brachiopod shells. δ11B declines by ~1‰ across the Pliensbachian-Toarcian boundary (Pl-To) and attains the lowest values (~12.5‰) just prior to and within the T-OAE, followed by fluctuations and a moderately increasing trend afterwards. The decline in δ11B coincides with decreasing bulk CaCO3 content, in parallel with the two-phase decline in carbonate production observed at global scales and with changes in pCO2 derived from stomatal indices. Seawater pH had declined significantly already prior to the T-OAE, probably due to the repeated emissions of volcanogenic CO2. During the earliest phase of the T-OAE, pH increased for a short period, likely due to intensified continental weathering and organic carbon burial, resulting in atmospheric CO2 drawdown. Subsequently, pH dropped again, reaching the minimum in the middle of the T-OAE. The early Toarcian marine extinction and carbonate collapse were thus driven, in part, by ocean acidification, similar to other Phanerozoic events caused by major CO2 emissions and warming.