Crystallographic control on the boron isotope paleo-pH proxy

Noireaux, Johanna; Mavromatis, Vasileios; Gaillardet, Jérôme; Schott, Jacques; Montouillout, V.; Louvat, Pascale; Rollion‐Bard, Claire; Neuville, Daniel R.

doi:10.1016/j.epsl.2015.07.063

Cited by 88 publications

(101 citation statements)

References 49 publications

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“…Concerning inorganic calcite precipitated in the laboratory, Hemming et al (1995) found no major δ 11 B value difference between calcite and aragonite with values at about-16.5 ± 1.3 ‰and Sanyal et al (2000) calculatedlower values,at around-19.25 ± 0.35 ‰for inorganic calcite at seawater of pH range=7.9-8.06. Nevertheless, more recent work showed that calcite and aragonite do not have the same fractionation factors with respect to boron isotopes (Noireaux et al, 2015). These authors suggest that this difference could be related to different pathways of boron incorporation in the calcite lattice compared to the aragonite one, such difference having also been shown byUchikawa et al (2015).…”

Section: Impact On δ 11 B B/ca and Reconstructed Phmentioning

confidence: 64%

Intra-skeletal calcite in a live-collected Porites sp.: Impact on environmental proxies and potential formation process

Lazareth

Soares-Pereira

Douville

et al. 2016

Geochimica et Cosmochimica Acta

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Geochemical proxies measured in the carbonate skeleton of tropical coral Porites sp. have commonly been used to reconstruct sea surface temperature (SST) and more recently seawater pH. Nevertheless, both reconstructed SST and pH depend on the preservation state of the skeleton, here made of aragonite; i.e., diagenetic processes and its related effects should be limited. In this study, we report on the impact of the presence of intra-skeletal calcite on the skeleton geochemistry of a live-collected Porites sp..The Porites skeleton preservation state was analyzed using X-ray diffraction and scanning electron microscopy. Sr/Ca, Mg/Ca, U/Ca, Ba/Ca, Li/Mg, and B/Ca ratios were measured at a monthly and yearly resolution using solution ICP-MS and multi-collector ICP-MS. Theδ 11 B signatures and the calcite percentages were acquired at a yearly timescale. The coral colony presents two parts, one with less than 3% calcite (referred to as "no-calcite" skeleton), the other one, corresponding to the skeleton formed during the last 4 yrs. of growth,with calcite percentages varying from 13 to 32% (referred to as "with calcite" skeleton). This intra-skeletal calcite replaces partly or completely numerouscenter of calcification (COCs). All geochemical tracers investigated are significantlyimpacted by the presence of calcite. Thereconstructed SSTdecreasesby about0.1°C per calcite-percent as inferred fromthe Sr/Ca ratio. Such impact reaches up to 0.26°C per calcite-percent for temperature deduced from the Li/Mg ratio. So, less than 5% of such intra-skeletal calcite does not prevent SST reconstructions using Sr/Ca ratio, but the percentage and type of calcite have to be determined before fine SST interpretation. Seawater pH reconstruction inferredfrom boron isotopes drop by about -0.011 pH-unit per calcitepercent. Such sensitivity to calcite presence is particularly dramatic for fine paleo-pH reconstructions. Here we suggest that after being brought to shallow waters following a cyclone, the studied coral was seasonally subjected to rainfall-related water freshening that could have mimicked a vadose environment like can be encountered on raised fossil coral reefs. Nevertheless, the process of calcite precipitation remains to be determined.

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Section: Impact On δ 11 B B/ca and Reconstructed Phmentioning

confidence: 64%

Intra-skeletal calcite in a live-collected Porites sp.: Impact on environmental proxies and potential formation process

Lazareth

Soares-Pereira

Douville

et al. 2016

Geochimica et Cosmochimica Acta

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“…CC-BY 3.0 License. mineralogy was not found to influence boron isotope fractionation (Noireaux et al 2015). Furthermore, because the borate/boric acid ratio is higher in aragonite than in calcite, aragonite-producing species should have a universally lower 335 δ 11 BCaCO3 composition than calcite-producing species (urchins, coralline alga, oyster) if shell mineralogy was the primary driver of the observed interspecific variation in δ 11 BCaCO3 compositions -a trend that is not observed (Fig.…”

Section: The δ 11 Bcaco3 Compositions For a Diverse Range Of Marine Cmentioning

confidence: 84%

“…Although Mavromatis et al (2015) also found that polymorph mineralogy influences both the B/Ca ratio (higher in aragonite than calcite) and speciation of B in inorganic CaCO3 (borate/boric acid ratio higher in aragonite than calcite), polymorph Biogeosciences Discuss., doi:10.5194/bg-2017-154, 2017 Manuscript under review for journal Biogeosciences Discussion started: 15 May 2017 c Author(s) 2017. CC-BY 3.0 License.…”

Section: The δ 11 Bcaco3 Compositions For a Diverse Range Of Marine Cmentioning

confidence: 99%

“…abiogenic) is known to be dependent on solution pH and inorganic CaCO3 precipitation rate, however, the relative abundances of the inorganic B species in solution that are incorporated into inorganic 330 CaCO3 (borate ion and boric acid) have been shown to be independent of the parent solution pH (Mavromatis et al 2015).…”

Section: The δ 11 Bcaco3 Compositions For a Diverse Range Of Marine Cmentioning

confidence: 99%

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δ11B as monitor of calcification site pH in marine calcifying organisms

Sutton

Liu

Ries

et al. 2017

Preprint

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Abstract. The isotope composition of boron (B) in marine biogenic carbonates has been predominantly studied as a proxy 15 for monitoring past changes in seawater pH and carbonate chemistry. In order to derive seawater pH from boron isotope ratio data, a number of assumptions related to chemical kinetics and themodynamic isotope exchange reactions are necessary. Furthermore, the boron isotope composition (

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“…More recently, however, alternative models of boron incorporation into CaCO 3 have been proposed (Balan et al, 2016;Klochko et al, 2009;Noireaux et al, 2015;Uchikawa et al, 2015). These studies present evidence consistent with the incorporation of boric acid, along with borate, into some carbonates (e.g., Noireaux et al, 2015;Uchikawa et al, 2015) and/or the occurrence of trigonal boron in the carbonate lattice due to transformation from borate during carbonate precipitation (e.g., Mavromatis et al, 2015).…”

Section: In Modern Seawater B(oh)mentioning

confidence: 99%

δ11B as monitor of calcification site pH in divergent marine calcifying organisms

et al. 2018

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Abstract. The boron isotope composition (δ 11 B) of marine biogenic carbonates has been predominantly studied as a proxy for monitoring past changes in seawater pH and carbonate chemistry. However, a number of assumptions regarding chemical kinetics and thermodynamic isotope exchange reactions are required to derive seawater pH from δ 11 B biogenic carbonates. It is also probable that δ 11 B of biogenic carbonate reflects seawater pH at the organism's site of calcification, which may or may not reflect seawater pH. Here, we report the development of methodology for measuring the δ 11 B of biogenic carbonate samples at the multicollector inductively coupled mass spectrometry facility at Ifremer (Plouzané, France) and the evaluation of δ 11 B CaCO 3 in a diverse range of marine calcifying organisms reared for 60 days in isothermal seawater (25 • C) equilibrated with an atmospheric pCO 2 of ca. 409 µatm. Average δ 11 B CaCO 3 composition for all species evaluated in this study range from 16.27 to 35.09 ‰, including, in decreasing order, coralline red alga Neogoniolithion sp. (35.89 ± 3.71 ‰), temperate coral Oculina arbuscula (24.12 ± 0.19 ‰), serpulid worm Hydroides crucigera (19.26 ± 0.16 ‰), tropical urchin Eucidaris tribuloides (18.71 ± 0.26 ‰), temperate urchin Arbacia punctulata (16.28 ± 0.86 ‰), and temperate oyster Crassostrea virginica (16.03 ‰). These results are discussed in the context of each species' proposed mechanism of biocalcification and other factors that could influence skeletal and shell δ 11 B, including calcifying site pH, the proposed direct incorporation of isotopically enriched boric acid (instead of borate) into biogenic calcium carbonate, and differences in shell/skeleton polymorph mineralogy. We conclude that the large inter-species variability in δ 11 B CaCO 3 (ca. 20 ‰) and significant discrepancies between measured δ 11 B CaCO 3 and δ 11 B CaCO 3 expected from established relationships between abiogenic δ 11 B CaCO 3 and seawater pH arise primarily from fundamental differences in calcifying site pH amongst the different species. These results highlight the potential utility of δ 11 B as a proxy of calcifying site pH for a wide range of calcifying taxa and underscore the importance of using species-specific seawater-pH-δ 11 B CaCO 3 calibrations when reconstructing seawater pH from δ 11 B of biogenic carbonates.

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Crystallographic control on the boron isotope paleo-pH proxy

Cited by 88 publications

References 49 publications

Intra-skeletal calcite in a live-collected Porites sp.: Impact on environmental proxies and potential formation process

Intra-skeletal calcite in a live-collected Porites sp.: Impact on environmental proxies and potential formation process

δ<sup>11</sup>B as monitor of calcification site pH in marine calcifying organisms

<i>δ</i><sup>11</sup>B as monitor of calcification site pH in divergent marine calcifying organisms

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Crystallographic control on the boron isotope paleo-pH proxy

Cited by 88 publications

References 49 publications

Intra-skeletal calcite in a live-collected Porites sp.: Impact on environmental proxies and potential formation process

Intra-skeletal calcite in a live-collected Porites sp.: Impact on environmental proxies and potential formation process

δ&lt;sup&gt;11&lt;/sup&gt;B as monitor of calcification site pH in marine calcifying organisms

&lt;i&gt;δ&lt;/i&gt;&lt;sup&gt;11&lt;/sup&gt;B as monitor of calcification site pH in divergent marine calcifying organisms

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δ<sup>11</sup>B as monitor of calcification site pH in marine calcifying organisms

<i>δ</i><sup>11</sup>B as monitor of calcification site pH in divergent marine calcifying organisms