An official website of the United States government
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
Simultaneous Determination of I/Ca and Other Elemental Ratios in Foraminifera: Comparing Results From Acidic and Basic Solutions
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
- Award ID(s):
- 1919716
- PAR ID:
- 10378571
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Geochemistry, Geophysics, Geosystems
- Volume:
- 23
- Issue:
- 11
- ISSN:
- 1525-2027
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
ABSTRACT RationaleCorals are continuous, time‐resolved archives of ambient seawater geochemistry and can extend climate records beyond direct monitoring. The iodine‐to‐calcium (I/Ca) ratio may be a proxy for local oxygen depletion in corals, but the current solution‐based ICP‐MS protocol limits sampling resolution. A protocol was developed for rapid analysis of coral I/Ca using laser ablation ICP‐MS. MethodsTwo reference materials, a powdered coral (JCp‐1) and a synthetic carbonate (MACS‐3), were compared for precision in measuring Sr, Mg, I, Ba, and U. Then, the influence of laser parameters (spot size, fluence, repetition rate, and scan speed) on iodine sensitivity from the reference material was evaluated to optimize laser settings for accurate and reproducible I/Ca calibration. Then, I/Ca was measured in line scans along and across the ambulacrum in aDiploria labyrinthiformiscoral. ResultsWe find that JCp‐1 has greater precision in measuring iodine, as well as other traces, compared to MACS‐3. At a 10 Hz repetition rate, spot sizes from 150 to 85 μm obtained concentrations in agreement with certified values, but higher repetition rates overestimated iodine concentrations from JCp‐1. Certain scan speeds and fluence can introduce noise, likely due to matrix effects, but the signal‐to‐noise ratio can be improved by adjacent‐average filtering. Using this simple data filtering routine and optimized laser settings, the highest resolution for accurate I/Ca analysis is < 100 μm. While the fine‐scale (< 250 μm) I/Ca variabilities in parallel transects in a coral sample likely resulted from biomineralization processes, large ‐scale features (> 500 μm) along the ambulacrum tend to correlate. ConclusionsLA‐ICP‐MS has great potential for accurate, high‐resolution I/Ca profiling in corals using JCp‐1 as a calibration standard. Because of compositional variability near centers of calcification, it is important to pay attention to how the laser transect is aligned relative to skeletal elements, which may incorporate iodine differently.more » « less
-
Abstract The minor and trace element compositions of biogenic carbonates such as foraminifera are important tools in paleoceanography research. However, most studies have focused primarily on samples with element to calcium (El/Ca) ratios higher than the El/Ca range often found in benthic foraminifera. Here, we systematically assess the precision and accuracy of foraminifera elemental analysis across a wide range of El/Ca especially at relatively low ratios, using a method on a Thermo Scientific iCAP Qc quadrupole Inductively Coupled Plasma Mass Spectrometer (ICP‐MS). We focus on two benthic foraminifera species,Hoeglundina elegansandCibicidoides pachyderma, and prepared a suite of solution standards based on their typical El/Ca ranges to correct for signal drift and matrix effects during ICP‐MS analysis and to determine analytical precision. We observe comparable precisions with published studies at high El/Ca, and higher relative standard deviations for each element at lower El/Ca, as expected from counting statistics. The overall long‐term analytical precision (2σ) of theH. elegans‐like consistency standard solutions was 6.5%, 4.6%, 5.0%, for Li/Ca, Mg/Ca, Mg/Li, and 6.4%, 10.0%, 4.2% for B/Ca, Cd/Ca, Sr/Ca. The precision forH. elegans‐like Mg/Li is equivalent to a temperature uncertainty of 0.5–1.1°C. Measurement precisions were also assessed based on three international standards (one solution and two powder standards) and replicate measurements ofH. elegansandC. pachydermasamples. We provide file templates and program scripts that can be used to design calibration and consistency standards, prepare run sequences, and convert the raw ICP‐MS data into molar ratios.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
