RESUMEN
RATIONALE: Information on the temperature of formation or alteration of carbonate minerals can be obtained by measuring the abundance of the isotopologues 47 and 48 (Δ47 and Δ48 values) of CO2 released during acid dissolution. The combination of these two proxies can potentially provide a greater insight into the temperature of formation, particularly if the carbonate minerals form by non-equilibrium processes. METHODS: We have precipitated calcium carbonates at seven temperatures between 5 and 65°C and measured their δ48 values using a Thermo-253 plus isotope ratio mass spectrometer. The values were transformed to Δ48 values in the conventional manner and then converted to the carbon dioxide equilibrium scale. RESULTS: Using the Δ48 values, we have established an empirical calibration between temperature and Δ48 values: [Formula: see text] CONCLUSIONS: The calibration line produced allows the determination of the temperature of natural carbonates using the Δ48 values and agrees with the measurements of the Δ47 and Δ48 values of some carbonates assumed to have formed under equilibrium conditions.
RESUMEN
Marine bony fish are important participants in Earth's carbon cycle through their contributions to the biological pump and the marine inorganic carbon cycle. However, uncertainties in the composition and magnitude of fish contributions preclude their integration into fully coupled carbon-climate models. Here, we consider recent upwards revisions to global fish biomass estimates (2.7-9.5×) and provide new stable carbon isotope measurements that show marine fish are prodigious producers of carbonate with unique composition. Assuming the median increase (4.17×) in fish biomass estimates is linearly reflected in fish carbonate (ichthyocarbonate) production rate, marine fish are estimated to produce between 1.43 and 3.99 Pg CaCO3 yr-1, but potentially as much as 9.03 Pg CaCO3 yr-1. Thus, marine fish carbonate production is equivalent to or potentially higher than contributions by coccolithophores or pelagic foraminifera. New stable carbon isotope analyses indicate that a significant proportion of ichthyocarbonate is derived from dietary carbon, rather than seawater dissolved inorganic carbon. Using a statistical mixing model to derive source contributions, we estimate ichthyocarbonate contains up to 81 % dietary carbon, with average compositions of 28-56 %, standing in contrast to contents <10 % in other biogenic carbonate minerals. Results also indicate ichthyocarbonate contains 5.5-40.4 % total organic carbon. When scaled to the median revised global production of ichthyocarbonate, an additional 0.08 to 1.61 Pg C yr-1 can potentially be added to estimates of fish contributions to the biological pump, significantly increasing marine fish contributions to total surface carbon export. Our integration of geochemical and physiological analyses identifies an overlooked link between carbonate production and the biological pump. Since ichthyocarbonate production is anticipated to increase with climate change scenarios, due to ocean warming and acidification, these results emphasize the importance of quantitative understanding of the multifaceted role of marine fish in the global carbon cycle.