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Biogeosciences An interactive open-access journal of the European Geosciences Union
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https://doi.org/10.5194/bg-2019-424
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/bg-2019-424
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 20 Nov 2019

Submitted as: research article | 20 Nov 2019

Review status
This discussion paper is a preprint. It is a manuscript under review for the journal Biogeosciences (BG).

Distribution of chlorine and fluorine in benthic foraminifera

Anne Roepert1, Lubos Polerecky1, Esmee Geerken2, Gert-Jan Reichart1,2, and Jack J. Middelburg1 Anne Roepert et al.
  • 1Department of Earth Sciences, Utrecht University, PO Box 80021, 3508 TA Utrecht, The Netherlands
  • 2Department of Ocean Systems, NIOZ Royal Netherlands Institute for Sea Research, and Utrecht University, 1790 AB Den Burg, The Netherlands

Abstract. Over the last decades a suite of inorganic proxies based on foraminiferal calcite have been developed, of which some are now widely used for paleoenvironmental reconstructions. Studies of foraminiferal shell chemistry have largely focused on cations and oxyanions, while much less is known about the incorporation of anions. The halogens fluoride and chloride are conservative in the ocean, which makes them candidates for reconstructing paleoceanographic parameters. However, their potential as a paleoproxy has hardly been explored, and fundamental insight in their incorporation is required. Here we used nano-scale secondary ion mass spectrometry (NanoSIMS) to investigate, for the first time, the distribution of Cl and F within shell walls of four benthic species of foraminifera. In the rotaliid species Ammonia tepida and Amphistegina lessonii Cl and F were highly heterogeneous and correlated within the shell walls, forming bands that were co-located with the banded distribution of phosphorus. In the miliolid species Sorites marginalis and Archaias angulatus the distribution of Cl and F was much more homogeneous without discernible bands. In these species Cl and P were correlated, whereas no correlation was observed between Cl and F or between F and P. Additionally, their F content was about an order of magnitude higher than in the rotaliid species. The high variance in the Cl and F content in the studied foraminifera could not be attributed to environmental parameters. Based on these findings we suggest that in the rotaliid species Cl and F are predominately associated with organic linings. We further propose that in the miliolid species Cl may be incorporated as a solid solution of chlorapatite or associated with organic molecules in the calcite. The high F content together with the lack of correlation between Cl and F or P in the miliolid foraminifera suggests a fundamentally different incorporation mechanism. Overall, our data clearly show that the calcification pathway employed by the studied foraminifera governs the incorporation and distribution of Cl, F, P and other elements in their calcite shells.

Anne Roepert et al.
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Anne Roepert et al.
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Supplementary data to "Distribution of Cl and F in benthic foraminifera" A. Roepert https://doi.org/10.4121/uuid:9951e801-5574-498e-b375-fa6941a0f071

Anne Roepert et al.
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Short summary
Here we investigated for the first time the spatial distribution of chlorine and fluorine in shell walls of 4 benthic foraminifera species: Ammonia tepida, Amphistegina lessonii, Archaias angulatus, and Sorites marginalis. Cross sections of specimens were imaged using nanoSIMS. The distribution of Cl and F is co-localized with organics in the rotaliid specimen and rather homogeneously distributed in miliolid specimens. We suggest the incorporation is governed by the biomineralization pathway.
Here we investigated for the first time the spatial distribution of chlorine and fluorine in...
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