Oxygen depletion in the upper ocean is commonly associated with poor ventilation and storage of respired carbon, potentially linked to atmospheric CO2 levels. Iodine to calcium ratios (I/Ca) in recent planktonic foraminifera suggest that values less than ∼2.5 μmol mol−1 indicate the presence of O2-depleted water. Here we apply this proxy to estimate past dissolved oxygen concentrations in the near surface waters of the currently well-oxygenated Southern Ocean, which played a critical role in carbon sequestration during glacial times. A down-core planktonic I/Ca record from south of the Antarctic Polar Front (APF) suggests that minimum O2 concentrations in the upper ocean fell below 70 μmol kg−1 during the last two glacial periods, indicating persistent glacial O2 depletion at the heart of the carbon engine of the Earth's climate system. These new estimates of past ocean oxygenation variability may assist in resolving mechanisms responsible for the much-debated ice-age atmospheric CO2 decline.
Rising oceanic and atmospheric oxygen levels through time have been crucial to enhanced habitability of surface Earth environments. Few redox proxies can track secular variations in dissolved oxygen concentrations around threshold levels for metazoan survival in the upper ocean. We present an extensive compilation of iodine-to-calcium ratios (I/Ca) in marine carbonates. Our record supports a major rise in the partial pressure of oxygen in the atmosphere at ~400 million years (Ma) ago and reveals a step change in the oxygenation of the upper ocean to relatively sustainable near-modern conditions at ~200 Ma ago. An Earth system model demonstrates that a shift in organic matter remineralization to greater depths, which may have been due to increasing size and biomineralization of eukaryotic plankton, likely drove the I/Ca signals at ~200 Ma ago.
Iron released from Asian desert dust may be an important source of bioavailable iron for the North Pacific Ocean and thereby may stimulate primary productivity. However, the Fe species of the fine dusts from this source region are poorly characterized. Here we investigate iron species and mineralogy in the clay‐sized fractions (<2 μm), the size fraction most prone to long‐distance transport as dust. Samples were analyzed by sequential chemical extraction, X‐ray diffraction, and diffuse reflectance spectrometry. Our results show that Fe dissolved from easily reducible iron phases (ferrihydrite and lepidocrocite) and reducible iron oxides (dominated by goethite) are 0.81 wt % and 2.39 wt %, respectively, and Fe dissolved from phyllosilicates extracted by boiling HCl (dominated by chlorite) is 3.15 wt %. Dusts originating from deserts in northwestern China, particularly the Taklimakan desert, are relatively enriched in easily reducible Fe phases, probably due to abundant Fe contained in fresh weathering products resulting from the rapid erosion associated with active uplift of mountains to the west. Data about Fe speciation and mineralogy in Asian dust sources will be useful for improving the quantification of soluble Fe supplied to the oceans, especially in dust models.
The Neoproterozoic Bitter Springs Anomaly (BSA; 810-800 Ma) is characterised by an 8 ‰ negative δ 13 C excursion and is coeval with multiple indicators of increasing oxygenation of the ocean and atmosphere. Here, we use carbonate iodine contents to provide the first constraints on the evolution of local upper ocean redox conditions spanning the BSA. Iodine speciation in seawater is strongly redox sensitive, and carbonates precipitated proximal to O 2 -depleted water record low I/(Ca + Mg). Data from the Akademikerbreen Group of Svalbard show a major rise of I/(Ca + Mg) during the recovery phase of the BSA. Other relatively high I/(Ca + Mg) values are also associated with rising δ 13 C throughout the section. Combined with existing palaeoredox proxies (e.g., Cr and S isotopes), our new iodine data most likely reflect an oxygenation event.
Profound changes in upper ocean oxygenation have taken place in recent decades and are expected to continue in the future, but the complexity of the processes driving these changes has yet to be fully unraveled. Planktic foraminiferal I/Ca is a promising tool to reconstruct the extent of past upper ocean oxygenation, but a thorough assessment is necessary to evaluate both its potential and its limitations. We used foraminifers from Holocene core-tops (Southeast Atlantic Ocean) to document planktic I/Ca across a range of oceanographic conditions. Subsurface O 2 concentrations may be the dominant control on planktic foraminiferal I/Ca and planktic I/Ca decreases rapidly at low O 2 conditions (O 2 < ~70-100 µmol/kg). We thus document that low planktic I/Ca can be used empirically to indicate hypoxia in the upper water column, but questions remain as to the mechanistic understanding of the relation between seawater iodine speciation change, its O 2 threshold and foraminiferal I/Ca. Planktic I/Ca records from core *Manuscript 2 GeoB1720-2 (Benguela Upwelling System, SE Atlantic) suggest that hypoxic waters were present near the site persistently during the last 240 ka, without clear glacial-interglacial variability.
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