An official website of the United States government
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.
more »
« less
Planktic foraminifera iodine/calcium ratios from plankton tows
Planktic foraminifera test iodine to calcium ratios represent an emerging proxy method to assess subsurface seawater oxygenation states. Several core-top studies show lower planktic foraminifera I/Ca in locations with oxygen depleted subsurface waters compared to well oxygenated environments. The reasoning behind this trend is that only the oxidized species of iodine, iodate, is incorporated in foraminiferal calcite. The I/Ca of foraminiferal calcite is thought to reflect iodate contents in seawater. To test this hypothesis, we compare planktic foraminifera I/Ca ratios, obtained from plankton tows, with published and new seawater iodate concentrations from 1) the Eastern North Pacific with extensive oxygen depletion, 2) the Benguela Current System with moderately depleted oxygen concentrations, and 3) the well oxygenated North and South Atlantic. We find the lowest I/Ca ratios (0.07 µmol/mol) in planktic foraminifera retrieved from the Eastern North Pacific, and higher values for samples (up to 0.72 µmol/mol) obtained from the Benguela Current System and North and South Atlantic. The I/Ca ratios 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. This would suggest that planktic foraminifera gain iodine post-mortem, either when sinking through the water column, or during burial.
more »
« less
- Award ID(s):
- 2154081
- PAR ID:
- 10415186
- Date Published:
- Journal Name:
- Frontiers in Marine Science
- Volume:
- 10
- ISSN:
- 2296-7745
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The iodine to calcium ratio in carbonate (I/Ca) has been widely used to indicate ocean oxygenation level in the past. Given the volatility of iodine, I/Ca has been measured in alkaline solutions in previous studies. However, this limits the application of I/Ca with other element/Ca (El/Ca) proxies at the same time and in the same foraminifera because other El/Ca data are preferably analyzed in acidic solutions. This study assesses the reliability of I/Ca measurements in acidic solutions measured with other El/Ca as well as the effects of different sample pre‐treatments on measured foraminiferal I/Ca. Our results show that when samples are measured within hours of prepaparation, the pH of the final solution has an insignificant effect on I/Ca measurements of a carbonate reference material JCp‐1 and a multi‐element standard solution, consistent with the slow kinetics of iodine volatilization. We find, however, that low pH possibly reduces the measured I/Ca in foraminiferal tests in some samples. Our experiments also suggest a resolvable effect of reductive cleaning, yielding lower foraminiferal I/Ca compared to without reductive cleaning. The HNO3concentration used to dissolve foraminiferal shells has a negligible effect. Despite the different solution pHs and cleaning and dissolving methods, our core top planktic I/Ca data are able to differentiate well‐oxygenated from oxygen‐depleted waters in the upper ocean, and after correcting for cleaning effect, our data are generally consistent with the published studies that analyzed I/Ca without reductive cleaning and in basic solutions. This study shows that measurements of I/Ca within hours of sample dissolutions yield reliable planktic I/Ca data, while also allowing the acquisition of other El/Ca values for paleoceanographic studies.more » « less
-
Abstract. The close association between planktic foraminiferal assemblages and local hydrography make foraminifera invaluable proxies for environmental conditions. Modern foraminiferal seasonality is important for interpreting fossil distributions and shell geochemistry as paleoclimate proxies. Understanding this seasonality in an active upwelling area is also critical for anticipating which species may be vulnerable to future changes in upwelling intensity and ocean acidification. Two years (2012–2014) of plankton tows, along with conductivity–temperature–depth profiles and carbonate chemistry measurements taken along the north-central California shelf, offer new insights into the seasonal dynamics of planktic foraminifera in a seasonal coastal upwelling regime. This study finds an upwelling affinity for Neogloboquadrina pachyderma as well as a seasonal and upwelling associated alternation between dominance of N. pachyderma and Neogloboquadrina incompta, consistent with previous observations. Globigerina bulloides, however, shows a strong affinity for non-upwelled waters, in contrast to findings in Southern California where the species is often associated with upwelling. We also find an apparent lunar periodicity in the abundances of all species and document the presence of foraminifera even at very low saturation states of calcite.more » « less
-
To use planktic foraminiferal tests as paleoproxy substrates, it is necessary to delineate environmental versus biological controls on trace element incorporation. Here we utilize laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to explore interspecies, chamber-to-chamber, and intratest trace element (i.e., Mg, Na, Sr, Ba, Mn, Zn) variability in thickly-calcified specimens of the polar and subpolar planktic foraminifera Neogloboquadrina incompta, N. pachyderma, and Turborotalita quinqueloba collected from plankton tows in the Northern California Current. Among the study taxa, test Mg/Ca, Na/Ca, and Sr/Ca are likely dominantly controlled by depth habitat. The neogloboquadrinids record higher Ba/Ca and Mn/Ca, and also show positive covariance between these elements, possibly due to calcifying in an oxygen-depleted marine snow microhabitat. Trace elements are found to be more enriched in the lamellar calcite than the outer chamber wall dominated by gametogenic crust. The data presented herein provide insight into potential vital effects, paleoproxy considerations, ontogeny, and biomineralization processes.more » « less
-
Abstract The distributions of iodate (IO3−), iodide (I−), nitrite (NO2−), and oxygen (O2) were determined on two zonal transects and one meridional transect in the Eastern Tropical North Pacific (ETNP) in 2018. Iodine is a useful tracer of in situ redox transformations and inputs within the water column from continental margins. In oxygenated waters, iodine is predominantly present as oxidized iodate. In the oxygen deficient zone (ODZ) in the ETNP, a substantial fraction is reduced to iodide, with the highest iodide concentrations coincident with the secondary nitrite maxima. These features resemble ODZs in the Arabian Sea and Eastern Tropical South Pacific (ETSP). Maxima in iodide and nitrite were associated with a specific water mass, referred to as the 13 °C Water, the same water mass that contains the highest concentrations of iodide within the ETSP. Physical processes leading to patchiness in the 13 °C Water relative to other water masses could account for the patchiness frequently observed in iodide and nitrite, probably reflecting subsurface mesoscale features such as eddies. Throughout much of the ETNP ODZ, iodine concentrations were higher than the mean oceanic value. This “excess iodine” is attributed to lateral inputs from sedimentary margins. Excess iodine maxima are centered within a potential density of 26.2–26.6 kg/m3, a density range that intersects with reducing shelf sediments and is almost identical to the ETSP. Evidently, margin input processes are significant throughout the basin and can influence the nitrogen and iron cycles as well, as in the ETSP.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3389/fmars.2023.1095570
