Nickel isotopic compositions of ferromanganese crusts and the constancy of deep ocean inputs and continental weathering effects over the Cenozoic

Abstract

The global variability in nickel (Ni) isotope compositions in ferromanganese crusts is investigated by analysing surface samples of 24 crusts from various ocean basins by MC–ICPMS, using a double-spike for mass bias correction. Ferromanganese crusts have View the MathML source isotopic compositions that are significantly heavier than any other samples thus far reported (−0.1‰ to 0.3‰), with surface scrapings ranging between 0.9‰ and 2.5‰ (relative to NIST SRM986). There is no well resolved difference between ocean basins, although the data indicate somewhat lighter values in the Atlantic than in the Pacific, nor is there any evidence that the variations are related to biological fractionation, presence of different water masses, or bottom water redox conditions. Preliminary data for laterite samples demonstrate that weathering is accompanied by isotopic fractionation of Ni, which should lead to rivers and seawater being isotopically heavy. This is consistent with the slightly heavier than average isotopic compositions recorded in crusts that are sampled close to continental regions. Furthermore, the isotopic compositions of crusts growing close to a hydrothermal source are clustered around ∼1.5‰, suggesting that hydrothermal fluids entering the ocean may have a Ni isotopic composition similar to this value. Based on these data, the heavy Ni isotopic compositions of ferromanganese crusts are likely due to input of isotopically heavy Ni to the ocean from continental weathering and possibly also from hydrothermal fluids. A depth profile through one crust, CD29-2, from the north central Pacific Ocean displays large variations in Ni isotope composition (1.1–2.3‰) through the last 76 Myr. Although there may have been some redistribution of Ni associated with phosphatisation, there is no systematic difference in Ni isotopic composition between deeper, older parts and shallower, younger parts of the crust, which may suggest that oceanic sources and sinks of Ni have largely remained in steady state over the Cenozoic. Additionally, the isotope profile is in agreement with a profile of Mn concentration through the same crust. This implies a link between the Ni isotopic composition recorded in ferromanganese crusts and the release of Ni into the ocean through hydrothermal activity. This supports the conclusions drawn from surface data, that Ni isotope ratios in ferromanganese crusts are largely controlled by the isotopic compositions of the Ni oceanic input sources.