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Abstract Iron (Fe) availability impacts marine primary productivity, potentially influencing the efficiency of the biological carbon pump. Stable Fe isotope analysis has emerged as a tool to understand how Fe is sourced and cycled in the water column; however its application to sediment records is complicated by overlapping isotope signatures of different sources and uncertainties in establishing chronologies. To overcome these challenges, we integrate Fe and osmium isotope measurements with multi‐element geochemical analysis and statistical modeling. We apply this approach to reconstruct the history of Fe delivery to the South Pacific from three pelagic clay sequences spanning 93 million years. Our analysis reveals five principal Fe sources—dust, distal background, two distinct hydrothermal inputs, and a magnesium‐rich volcanic ash. Initially, hydrothermal inputs dominated Fe deposition, but as the sites migrated away from their respective mid‐ocean ridges, other sources became prominent. Notably, from 66 to 40 million years ago (Ma), distal background Fe was the primary source before a shift to increasing dust dominance around 30 Ma. This transition implies that Fe in South Pacific seawater has been dust‐dominated since ≈30 Ma, despite extremely low dust deposition rates today. We speculate that the shift to episodic and low Fe fluxes in the South Pacific and Southern Ocean over the Cenozoic helped shape an ecological niche that favored phytoplankton that adapted to these conditions, such as diatoms. Our analysis highlights how Fe delivery to the ocean is driven by large‐scale tectonic and climatic shifts, while also influencing climate through its integral role in marine phytoplankton and Earth's biogeochemical cycles.more » « lessFree, publicly-accessible full text available July 1, 2026
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The ratio of atmosphere-derived10Be to continent-derived9Be in marine sediments has been used to probe the long-term relationship between continental denudation and climate. However, its application is complicated by uncertainty in9Be transfer through the land-ocean interface. The riverine dissolved load alone is insufficient to close the marine9Be budget, largely due to substantial removal of riverine9Be to continental margin sediments. We focus on the ultimate fate of this latter Be. We present sediment pore-water Be profiles from diverse continental margin environments to quantify the diagenetic Be release to the ocean. Our results suggest that pore-water Be cycling is mainly controlled by particulate supply and Mn-Fe cycling, leading to higher benthic fluxes on shelves. Benthic fluxes may help close the9Be budget and are at least comparable to, or higher (~2-fold) than, the riverine dissolved input. These observations demand a revised model framework, which considers the potentially dominant benthic source, to robustly interpret marine Be isotopic records.more » « less
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null (Ed.)Cadmium is a trace metal of interest in the ocean partly because its concentration mimics that of phosphate. However, deviations from the global mean dissolved Cd/PO 4 relationship are present in oxygen deficient zones, where Cd is depleted relative to phosphate. This decoupling has been suggested to result from cadmium sulphide (CdS) precipitation in reducing microenvironments within sinking organic matter. We present Cd concentrations and Cd isotope compositions in organic-rich sediments deposited at several upwelling sites along the northeast Pacific continental margin. These sediments all have enriched Cd concentrations relative to crustal material. We calculate a net accumulation rate of Cd in margin settings of between 2.6 to 12.0 × 10 7 mol/yr, higher than previous estimates, but at the low end of a recently published estimate for the magnitude of the marine sink due to water column CdS precipitation. Cadmium in organic-rich sediments is isotopically light ( δ 114/110 Cd NIST-3108 = +0.02 ± 0.14‰, n = 26; 2 SD) compared to deep seawater (+0.3 ± 0.1‰). However, isotope fractionation during diagenesis in continental margin settings appears to be small. Therefore, the light Cd isotope composition of organic-rich sediments is likely to reflect an isotopically light source of Cd. Non-quantitative biological uptake of light Cd by phytoplankton is one possible means of supplying light Cd to the sediment, which would imply that Cd isotopes could be used as a tracer of past ocean productivity. However, water column CdS precipitation is also predicted to preferentially sequester light Cd isotopes from the water column, which could obfuscate Cd as a tracer. We also observe notably light Cd isotope compositions associated with elevated solid phase Fe concentrations, suggesting that scavenging of Cd by Fe oxide phases may contribute to the light Cd isotope composition of sediments. These multiple possible sources of isotopically light Cd to sediments, along with evidence for complex particle cycling of Cd in the water column, bring into question the straightforward application of Cd isotopes as a paleoproductivity proxy.more » « less
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