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ArticleMarine sedimentary uranium to barium ratios as a potential quantitative proxy for Pleistocene bottom water oxygen concentrations(Elsevier, 2023-02-15) Costa, Kassandra M. ; Nielsen, Sune G. ; Wang, Yi ; Lu, Wanyi ; Hines, Sophia K.V. ; Jacobel, Allison W. ; Oppo, Delia W.Oxygen is essential for marine ecosystems, and it is linked by respiration to carbon storage in the deep ocean. Reconstructing oxygen concentrations in the past has been limited by the absence of quantitative, rather than qualitative, proxies, but several new (semi-) quantitative oxygen proxies have recently been developed. In this study we explore the possibility of adding bulk sedimentary uranium (U) to this list by normalizing it to barium (Ba). First, U/Ba and bottom water oxygen concentrations are compared on a global scale, using a core top database, in pelagic environments greater than 200 m water depth. Then, the relationships between U/Ba and bottom water oxygen are examined on smaller spatial scales: within each ocean basin and regionally within the Eastern Equatorial Pacific, the Arabian Sea, and Western Equatorial Atlantic. At this regional scale, where secondary influences on the behavior of both U and Ba may be more spatially uniform, empirical piecewise linear calibrations are developed and subsequently tested on downcore records. U/Ba-based oxygen reconstructions generally agree with those derived from previously published alkenone preservation and benthic foraminiferal surface porosity records. Several limitations to the utility of U/Ba as a proxy for oxygen have also been identified. The proxy should only be applied in the uppermost sedimentary intervals that contain porewater sulfate to minimize barite diagenesis, and phosphorus contents should be monitored for the potential influence of apatite on uranium content. U/Ba is more successful at recording oxygen concentrations during mean glacial and interglacial periods than during climate transitions, when the timing and amplitude may be more sensitive to burndown and smoothing. Conservative errors on the calibrations result in the greatest utility of U/Ba in regions with relatively high oxygen concentrations (e.g., >50 μmol/kg) and large oxygen variability (±10 s of μmol/kg). Even with these caveats, U/Ba is only one of two quantitative oxygen proxies potentially capable of recording variability above 50 μmol/kg, and further investigation into its functionality in different environmental settings is worthwhile in the endeavor to reconstruct the full marine range of oxygen concentrations in the past. All data are available in Supplementary Data 1 and 2.
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PreprintOrganically bound iodine as a bottom-water redox proxy : preliminary validation and application( 2017-03-15) Zhou, Xiaoli ; Jenkyns, Hugh C. ; Lu, Wanyi ; Hardisty, Dalton S. ; Owens, Jeremy D. ; Lyons, Timothy W. ; Lu, ZunliCarbonate-associated iodine (I/Ca) has been used as a proxy of local, upper-ocean redox conditions, and has successfully demonstrated highly dynamic spatial and temporal patterns across different time scales of Earth history. To further explore the utility of iodine as a paleo-environmental proxy, we present here a new method of extracting organically bound iodine (Iorg) from shale using volumes of samples on the order of tens of milligrams, thus offering the potential for high-resolution work across thin shale beds. The ratio of Iorg to total organic carbon (I/TOC) in modern surface and subsurface sediments decreases with decreasing bottom-water oxygen, which may be used to reconstruct paleo-redox changes. As a proof of concept, we evaluate the I/TOC proxy in Holocene sediments from the Baltic Sea, Landsort Deep (IODP 347) and discuss those data within a framework of additional independent redox proxies, e.g., iron speciation and [Mo]. The results imply that I/TOC may be sensitive to hypoxic–suboxic conditions, complementary to proxies sensitive to more reducing, anoxic–euxinic conditions. Then, we test the usage of I/TOC in sediments deposited during Late Cretaceous, Cenomanian–Turonian Oceanic Anoxic Event (OAE) 2 from ~ 94 million years ago (Ma). We generated I/TOC and Iorg records from six OAE 2 sections: Tarfaya (Morocco), Furlo (central Italy), Demerara Rise (western equatorial Atlantic), Cape Verde Basin (eastern equatorial Atlantic), South Ferriby (UK), and Kerguelen Plateau (southern Indian Ocean), which provide a broad spatial coverage. Generally, I/TOC decreases over the interval recorded by the positive carbon-isotope excursion, the global signature of OAE 2, suggesting an expansion of more reducing bottom-water conditions and consistent with independent constraints from iron speciation and redox-sensitive trace-metals (e.g., Mo). Relatively higher I/TOC values (thus more oxic conditions) are recorded at two high latitude sites for OAE 2, supporting previous model simulations (cGENIE) that indicated higher bottom water oxygen concentrations in these regions. Our results also indicate that organic-rich and oxygenated seafloors are likely a major sink of iodine and correspondingly influence its global seawater inventory.
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ArticleReconstructing the Oxygen Depth Profile in the Arabian Sea During the Last Glacial Period(American Geophysical Union, 2023-06-16) Lu, Wanyi ; Costa, Kassandra M. ; Oppo, Delia W.Reconstructing the strength and depth boundary of oxygen minimum zones (OMZs) in the glacial ocean advances our understanding of how OMZs respond to climate changes. While many efforts have inferred better oxygenation of the glacial Arabian Sea OMZ from qualitative indices, oxygenation and vertical extent of the glacial OMZ is not well quantified. Here we present glacial-Holocene oxygen reconstructions in a depth transect of Arabian Sea cores ranging from 600 to 3,650 m water depths. We estimate glacial oxygen concentrations using benthic foraminiferal surface porosity and benthic carbon isotope gradient reconstructions. Compared to the modern Arabian Sea, glacial oxygen concentrations were approximately 10–15 μmol/kg higher in the shallow OMZ (<1,000 m), and 5–80 μmol/kg lower at greater depths (1,500–3,650 m). Our results suggest that the OMZ in the glacial Arabian Sea was slightly better oxygenated but remained in the upper 1,000 m. We propose that the small increase in oxygenation of the Arabian Sea OMZ during the last glacial period was due to weaker upper ocean stratification induced by stronger winter monsoon winds coupled with an increase in oxygen solubility due to lower temperatures, counteracting the effects of more oxygen consumption resulting from higher primary productivity. Large-scale changes in ocean circulation may have also contributed to better ventilation of the glacial Arabian Sea OMZ.
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ArticleCommentary: Planktic foraminifera iodine/calcium ratios from plankton tows(Frontiers Media, 2023-07-11) Lu, Zunli ; Thomas, Ellen ; Rickaby, Rosalind E. M. ; Lu, Wanyi ; Prow, Ashley N.I/Ca in planktic foraminiferal shells is one of the few proxies proposed for reconstructing past upper ocean oxygenation. Foraminiferal I/Ca values have been measured in globally distributed core-top samples, with low I/Ca values generally indicative of low-oxygen water (Lu et al., 2020a; Lu et al., 2020b). Winkelbauer et al. (2023) observed that “I/Ca values of plankton tow foraminifera from environments with well oxygenated subsurface waters, however, are an order of magnitude lower compared to core-tops from similarly well-oxygenated regions,” and concluded that “planktic foraminifera gain iodine post-mortem, either when sinking through the water column, or during burial.” These tow-derived low I/Ca values add to the information needed to mechanistically understand the planktic I/Ca proxy. However, we highlight the fact that tow-specimens do not represent the same populations as those present in core tops, and we think that further evidence is needed before reinterpreting the core-top and down-core planktic I/Ca records.
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ArticleDeglacial temperature and carbonate saturation state variability in the tropical Atlantic at Antarctic Intermediate Water Depths(Wiley, 2023-08-26) Oppo, Delia W. ; Lu, Wanyi ; Huang, Kuo-Fang ; Umling, Natalie E. ; Guo, Weifu ; Yu, Jimin ; Curry, William B. ; Marchitto, Thomas M. ; Wang, ShouyiThe Atlantic Meridional Overturning Circulation (AMOC) is characterized by northward flow in the upper ocean and southward flow in the deep ocean. Understanding how the AMOC has changed in the past, and how such changes have affected surface climate and the distribution of ocean heat, carbon, and nutrients is important but challenging, as reconstructions of subsurface ocean properties are sometimes ambiguous. Here, we use the chemical composition of seafloor shells from a site in the western tropical Atlantic Ocean at ∼950 m water depth, within the northward-flowing limb of the AMOC, to reconstruct temperature, nutrients, and carbon content during the end of the last Ice Age, an interval when AMOC strength is believed to have varied. Our results support a link between AMOC strength and tropical Atlantic nutrient content, and further suggest that both rising atmospheric CO2 and AMOC variations influenced temperatures and carbon in the subsurface tropical Atlantic Ocean.
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ArticleIodine-to-calcium ratios in deep-sea scleractinian and bamboo corals(Frontiers Media, 2023-11-06) Sun, Yun-Ju ; Robinson, Laura F. ; Parkinson, Ian J. ; Stewart, Joseph A. ; Lu, Wanyi ; Hardisty, Dalton S. ; Liu, Qian ; Kershaw, James ; LaVigne, Michele ; Horner, Tristan J.The distribution of dissolved iodine in seawater is sensitive to multiple biogeochemical cycles, including those of nitrogen and oxygen. The iodine-to-calcium ratio (I/Ca) of marine carbonates, such as bulk carbonate or foraminifera, has emerged as a potential proxy for changes in past seawater oxygenation. However, the utility of the I/Ca proxy in deep-sea corals, natural archives of seawater chemistry with wide spatial coverage and radiometric dating potential, remains unexplored. Here, we present the first I/Ca data obtained from modern deep-sea corals, specifically scleractinian and bamboo corals, collected from the Atlantic, Eastern Pacific, and Southern Oceans, encompassing a wide range of seawater oxygen concentrations (10–280 μmol/kg). In contrast to thermodynamic predictions, we observe higher I/Ca ratios in aragonitic corals (scleractinian) compared to calcitic corals (bamboo). This observation suggests a strong biological control during iodate incorporation into deep-sea coral skeletons. For the majority of scleractinian corals, I/Ca exhibits a covariation with local seawater iodate concentrations, which is closely related to seawater oxygen content. Scleractinian corals also exhibit notably lower I/Ca below a seawater oxygen threshold of approximately 160 μmol/kg. In contrast, no significant differences in I/Ca are found among bamboo corals across the range of oxygen concentrations encountered (15–240 μmol/kg). In the North Atlantic, several hydrographic factors, such as temperature and/or salinity, may additionally affect coral I/Ca. Our results highlight the potential of I/Ca ratios in deep-sea scleractinian corals to serve as an indicator of past seawater iodate concentrations, providing valuable insights into historical seawater oxygen levels.
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ArticleGlobal oceanic oxygenation controlled by the Southern Ocean through the last deglaciation(American Association for the Advancement of Science, 2024-01-19) Wang, Yi ; Costa, Kassandra M. ; Lu, Wanyi ; Hines, Sophia K. V. ; Nielsen, Sune G.Ocean dissolved oxygen (DO) can provide insights on how the marine carbon cycle affects global climate change. However, the net global DO change and the controlling mechanisms remain uncertain through the last deglaciation. Here, we present a globally integrated DO reconstruction using thallium isotopes, corroborating lower global DO during the Last Glacial Maximum [19 to 23 thousand years before the present (ka B.P.)] relative to the Holocene. During the deglaciation, we reveal reoxygenation in the Heinrich Stadial 1 (~14.7 to 18 ka B.P.) and the Younger Dryas (11.7 to 12.9 ka B.P.), with deoxygenation during the Bølling-Allerød (12.9 to 14.7 ka B.P.). The deglacial DO changes were decoupled from North Atlantic Deep Water formation rates and imply that Southern Ocean ventilation controlled ocean oxygen. The coherence between global DO and atmospheric CO2 on millennial timescales highlights the Southern Ocean’s role in deglacial atmospheric CO2 rise.