Organic Heterogeneities in Foraminiferal Calcite Traced Through the Distribution of N, S, and I Measured With NanoSIMS: A New Challenge for Element-Ratio-Based Paleoproxies?

Glock, Nicolaas; Liebetrau, Volker; Vogts, Angela; Eisenhauer, Anton

doi:10.3389/feart.2019.00175

Cited by 17 publications

(18 citation statements)

References 84 publications

(149 reference statements)

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“…To the best of our knowledge, the spatial distribution of F has not been investigated yet, while Cl was previously found at the location of organic linings in shell walls of A. lobifera (Szafranek and Erez, 1993;Erez, 2003). Recently, also the iodine micro-distribution in shell walls of U. striata was found to spatially correlate with organics (Glock et al, 2019).…”

mentioning

confidence: 93%

Distribution of chlorine and fluorine in benthic foraminifera

Roepert¹,

Polerecký²,

Geerken³

et al. 2019

Preprint

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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.

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mentioning

confidence: 93%

Distribution of chlorine and fluorine in benthic foraminifera

Roepert¹,

Polerecký²,

Geerken³

et al. 2019

Preprint

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“…In foraminiferal shells, the presence of sulphur was reported in the calcite lattice (as sulphate) and organic matter within the shell (i.e., glycosaminoglycans and proteins) (Paris et al 27 ; Glock et al 32 ; Van Dijk et al 45 ; Geerken et al 46 ). Thus, the high variability in the C. neoteretis δ 34 S dataset ( Fig.…”

Section: Discussionmentioning

confidence: 99%

The benthic foraminiferal δ34S records flux and timing of paleo methane emissions

Borrelli

Gabitov

Liu

et al. 2020

Sci Rep

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In modern environments, pore water geochemistry and modelling simulations allow the study of methane (cH 4) sources and sinks at any geographic location. However, reconstructing CH 4 dynamics in geological records is challenging. Here, we show that the benthic foraminiferal δ 34 S can be used to reconstruct the flux (i.e., diffusive vs. advective) and timing of CH 4 emissions in fossil records. We measured the δ 34 S of Cassidulina neoteretis specimens from selected samples collected at Vestnesa Ridge, a methane cold seep site in the Arctic Ocean. Our results show lower benthic foraminiferal δ 34 S values (∼20‰) in the sample characterized by seawater conditions, whereas higher values (∼25-27‰) were measured in deeper samples as a consequence of the presence of past sulphate-methane transition zones. The correlation between δ 34 S and the bulk benthic foraminiferal δ 13 C supports this interpretation, whereas the foraminiferal δ 18 O-δ 34 S correlation indicates cH 4 advection at the studied site during the Early Holocene and the Younger-Dryas-post-Bølling. This study highlights the potential of the benthic foraminiferal δ 34 S as a novel tool to reconstruct the flux of CH 4 emissions in geological records and to indirectly date fossil seeps.

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“…5) that have developed during the evolution of foraminifera (Debenay et al, 1996;Bentov and Erez, 2006). Hyaline (including the rotaliid) foraminifera precipitate calcite onto organic templates within an extracellular but confined space, and they add a new lamella to the entire shell each time they produce a new chamber (Hemleben et al, 1986;de Nooijer et al, 2014). For some intermediate-Mg calcite-producing foraminifera (like A. lobifera or A. lessonii), the transport of vesicles to the site of calcification has been observed, suggesting controlled biomineralization (at least partly) from internal Ca and carbonate pools (e.g.…”

Section: And F Incorporation In Foraminifera Is Primarily Controllmentioning

confidence: 99%

“…Miliolid foraminifera precipitate calcium crystals in intracellular vesicles prior to arranging them in the shape of the new chamber wall (a; Angell, 1980;Hemleben et al, 1986;Debenay et al, 1996Debenay et al, , 1998Debenay et al, , 2000Bentov and Erez, 2006). Rotaliid foraminifera precipitate calcite onto organic templates within an extracellular but confined space, and they add a new lamella to the entire shell each time they produce a new chamber Hemleben et al, 1986;de Nooijer et al, 2014). In intermediate-Mg calcite-producing rotaliid foraminifera (like A. lessonii), the transport of vesicles to the site of calcification has been observed, suggesting controlled biomineralization (at least partly) from internal Ca and carbonate pools (b; e.g.…”

Section: And F Incorporation In Foraminifera Is Primarily Controllmentioning

confidence: 99%

Distribution of chlorine and fluorine in benthic foraminifera

et al. 2020

View full text Add to dashboard Cite

Abstract. Over the last few decades, a suite of inorganic proxies based on foraminiferal calcite have been developed, some of which are now widely used for palaeoenvironmental 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 palaeoceanographic parameters. However, their potential as a palaeoproxy has hardly been explored, and fundamental insight into their incorporation is required. Here we used nanoscale 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 distributed highly heterogeneously within the shell walls, forming bands that were co-located with the bands observed in the distribution of phosphorus (significant positive correlation of both Cl and F with P; p<0.01). 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 spatially positively correlated (p<0.01), 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 specimens could not be attributed to environmental parameters. Based on these findings, we suggest that Cl and F are predominately associated with organic linings in the rotaliid species. We further propose that Cl may be incorporated as a solid solution of chlorapatite or may be associated with organic molecules in the calcite in the miliolid species. The high F content and the lack of a correlation between Cl and F or P in the miliolid foraminifera suggest 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.

show abstract

Organic Heterogeneities in Foraminiferal Calcite Traced Through the Distribution of N, S, and I Measured With NanoSIMS: A New Challenge for Element-Ratio-Based Paleoproxies?

Cited by 17 publications

References 84 publications

Distribution of chlorine and fluorine in benthic foraminifera

Distribution of chlorine and fluorine in benthic foraminifera

The benthic foraminiferal δ34S records flux and timing of paleo methane emissions

Distribution of chlorine and fluorine in benthic foraminifera

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