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11B As Monitor of Calcification Site Ph in Divergent Marine Calcifying Organisms Jill Sutton, Yi-Wei Liu, Justin B

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11B As Monitor of Calcification Site Ph in Divergent Marine Calcifying Organisms Jill Sutton, Yi-Wei Liu, Justin B δ11B as monitor of calcification site pH in divergent marine calcifying organisms Jill Sutton, Yi-Wei Liu, Justin B. Ries, Maxence Guillermic, Emmanuel Ponzevera, Robert A. Eagle To cite this version: Jill Sutton, Yi-Wei Liu, Justin B. Ries, Maxence Guillermic, Emmanuel Ponzevera, et al.. δ11B as monitor of calcification site pH in divergent marine calcifying organisms. Biogeosciences, European Geosciences Union, 2018, 15 (5), pp.1447-1467. 10.5194/bg-15-1447-2018. hal-02651007 HAL Id: hal-02651007 https://hal.archives-ouvertes.fr/hal-02651007 Submitted on 29 May 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Distributed under a Creative Commons Attribution| 4.0 International License Biogeosciences, 15, 1447–1467, 2018 https://doi.org/10.5194/bg-15-1447-2018 © Author(s) 2018. This work is distributed under the Creative Commons Attribution 3.0 License. δ11B as monitor of calcification site pH in divergent marine calcifying organisms Jill N. Sutton1, Yi-Wei Liu1,2, Justin B. Ries3, Maxence Guillermic2, Emmanuel Ponzevera4, and Robert A. Eagle1,5,6 1Université de Brest, UMR 6539 CNRS/UBO/IRD/Ifremer, LEMAR, IUEM, 29280, Plouzané, France 2Université de Brest, UMR 6539 CNRS/UBO/IRD/Ifremer, LGO, IUEM, 29280, Plouzané, France 3Department of Marine and Environmental Sciences, Marine Science Center, Northeastern University, 430 Nahant Rd, Nahant, MA 01908, USA 4Unité de Recherche Géosciences Marines, Ifremer, 29280, Plouzané, France 5Institute of the Environment and Sustainability, University of California, Los Angeles, LaKretz Hall, 619 Charles E Young Dr E no. 300, Los Angeles, CA 90024, USA 6Atmospheric and Oceanic Sciences Department, University of California, Los Angeles, Math Sciences Building, 520 Portola Plaza, Los Angeles, CA 90095, USA Correspondence: Jill N. Sutton ([email protected]) and Robert A. Eagle ([email protected]) Received: 20 April 2017 – Discussion started: 15 May 2017 Revised: 8 December 2017 – Accepted: 14 December 2017 – Published: 8 March 2018 Abstract. The boron isotope composition (δ11B) of marine cification and other factors that could influence skeletal and biogenic carbonates has been predominantly studied as a shell δ11B, including calcifying site pH, the proposed direct proxy for monitoring past changes in seawater pH and car- incorporation of isotopically enriched boric acid (instead of bonate chemistry. However, a number of assumptions re- borate) into biogenic calcium carbonate, and differences in garding chemical kinetics and thermodynamic isotope ex- shell/skeleton polymorph mineralogy. We conclude that the 11 change reactions are required to derive seawater pH from large inter-species variability in δ BCaCO3 (ca. 20 ‰) and 11 11 11 δ B biogenic carbonates. It is also probable that δ B of significant discrepancies between measured δ BCaCO3 and 11 biogenic carbonate reflects seawater pH at the organism’s site δ BCaCO3 expected from established relationships between 11 of calcification, which may or may not reflect seawater pH. abiogenic δ BCaCO3 and seawater pH arise primarily from Here, we report the development of methodology for mea- fundamental differences in calcifying site pH amongst the suring the δ11B of biogenic carbonate samples at the multi- different species. These results highlight the potential utility collector inductively coupled mass spectrometry facility at of δ11B as a proxy of calcifying site pH for a wide range 11 Ifremer (Plouzané, France) and the evaluation of δ BCaCO3 of calcifying taxa and underscore the importance of using 11 in a diverse range of marine calcifying organisms reared for species-specific seawater-pH–δ BCaCO3 calibrations when 60 days in isothermal seawater (25 ◦C) equilibrated with an reconstructing seawater pH from δ11B of biogenic carbon- 11 atmospheric pCO2 of ca. 409 µatm. Average δ BCaCO3 com- ates. position 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 1 Introduction Hydroides crucigera (19.26 ± 0.16 ‰), tropical urchin Euci- daris tribuloides (18.71 ± 0.26 ‰), temperate urchin Arba- The ability to monitor historical changes in seawater pH on cia punctulata (16.28 ± 0.86 ‰), and temperate oyster Cras- both short and long timescales is necessary to understand the sostrea virginica (16.03 ‰). These results are discussed in influence that changes in the partial pressure of atmospheric the context of each species’ proposed mechanism of biocal- CO2 (pCO2/ have had on the carbonate chemistry of seawa- ter. The recent anthropogenic increase in pCO2 has already Published by Copernicus Publications on behalf of the European Geosciences Union. 1448 J. N. Sutton et al.: δ11B as monitor of calcification site pH than the mixing time of oceans (ca. 1000 years), suggest- (a) ) ing that it is conservatively distributed throughout the ocean –1 400 11 [B(OH)3] (Foster et al., 2010) – making δ B a potentially attractive proxy for paleo-seawater pH. 300 Boron exists in aqueous solutions as either trigonal boric ] (µmol kg - − 4 acid [B(OH)3] or as the tetrahedral borate anion [B(OH)4 ], 200 with the proportions of these two chemical species varying as a function of pH (Fig. 1) pursuant to the following equi- ]/[B(OH) 3 100 librium reaction: - [B(OH)4 ] − C [B(OH) B.OH/3 C H2O $ B.OH/ C H : 0 4 70 (b) B(OH)3 − In modern seawater, B(OH)4 represents ca. 24.15 % of 60 dissolved boron, assuming that the dissociation constant ◦ (pKB/ between the two species of boron is 8.597 (at 25 C, 50 pH D 8.1, 35 psu (practical salinity units); Dickson, 1990). Boron has two stable isotopes, 10B and 11B, with relative B (‰) 40 11 Seawater abundances of 19.9 and 80.1 %, respectively. B(OH)3 is en- δ - − 30 B(OH)4 11 riched in B relative to B(OH)4 due to differences in the ground state energy of molecular vibration of these chemi- 20 cal species in solution. The isotopic composition of boron is 10 expressed following standard convention: 7.0 8.0 9.0 10.0 11 pH Bsample 10 Bsample δ11B D − 1 × 1000 .‰/; (1) Figure 1. (a) Speciation of dissolved inorganic boron, B(OH) and 11 3 Bstandard − 11 10 B(OH)4 , as a function of seawater pH. (b) δ B of dissolved inor- Bstandard ganic boron species as a function of seawater pH. The pKB is 8.6 ◦ at 25 C and 35 psu (practical salinity units; Dickon, 1990), α is where the reference standard is NIST SRM (Standard Refer- 11 1.0272 (Klochko et al., 2006), and δ BSW is 39.61 (Foster et al., ence Materials) 951 (Catanzaro et al., 1970). 2010). The δ11B of modern seawater is 39.61 ± 0.20 ‰ (Foster et al., 2010) and a large (> 20 ‰) and constant isotope frac- tionation exists between the two aqueous species described resulted in a significant decrease in seawater pH (Bates, above. The fractionation factor (α) for boric acid and borate 2007; Byrne et al., 2010; Dore et al., 2009; Feely et al., 2008, ion is defined as follows: 2016; Gonzalez-Davlia et al., 2010; IPCC, 2014), which affects the ability of marine calcifying organisms to pro- 11B=10B α D Boric acid : duce their shells and skeletons (CaCO3; IPCC, 2014). Ex- 11 10 B= B Borate ion perimental studies have revealed that organismal responses to ocean acidification vary widely amongst taxa, highlight- A range of theoretical and empirical values for α has been ing the complexity of biological responses to global change suggested (Byrne et al., 2006; Kakihana et al., 1977; Klochko stressors (e.g., Kroeker et al., 2010, 2013; Ries et al., 2009) et al., 2006; Nir et al., 2015; Palmer et al., 1987). For exam- and necessitating a more thorough understanding of how an ple, α of 1.0194 was calculated from theory by Kakihana organism’s mechanism of biocalcification governs its spe- et al. (1977) and was widely applied in reconstructions of cific response to ocean acidification. paleo-seawater pH (Hönisch et al., 2004; Kakihana et al., 1977; Sanyal et al., 1995). Zeebe (2005) used analytical tech- 1.1 Theoretical model of δ11B variation with pH niques and ab initio molecular orbital theory to calculate α ranging from 1.020 to 1.050 at 300 K. Zeebe (2005) provided 11 The boron isotope composition (δ B) of biogenic CaCO3 several arguments in support of α ≥ 1:030, ultimately con- 11 (δ BCaCO3 / has been primarily used as a paleoceanographic cluding that experimental work was required to determine proxy for seawater pH (Hönisch and Hemming, 2004; the α for dissolved boric acid and the borate ion. Subsequent Hönisch et al., 2004; Montagna et al., 2007; Palmer, 1998; to the work by Zeebe (2005), significant error was identified Pearson et al., 2009; Penman and Hönisch, 2014; Rae et al., for the borate vibrational spectrum term used in Kakihana 2011; Trotter et al., 2011; Vengosh et al., 1991; Wei et al., et al.’s (1977) theoretical calculation of α (Klochko et al., 2009). Boron has a residence time in seawater of ca. 14 mil- 2006; Rustad and Bylaska, 2007). An empirical α of 1.0272 lion years (Lemarchand et al., 2000), which is much longer (Klochko et al., 2006), using a corrected borate vibrational Biogeosciences, 15, 1447–1467, 2018 www.biogeosciences.net/15/1447/2018/ J.
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