A new method for calibrating a boron isotope paleo‐p<scp>H</scp> proxy using massive <scp><i>P</i></scp><i>orites</i> corals

Kubota, Kaoru; Yokoyama, Yūsuke; Ishikawa, Tsuyoshi; Suzuki, Atsushi

doi:10.1002/2015gc005975

Cited by 22 publications

(11 citation statements)

References 80 publications

(212 reference statements)

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“…Boron is lost from the oceans in a variety of pathways, of which incorporation in carbonates is the best known and the basis for the use of δ 11 B as an indicator of past changes in the pH of seawater [ Vengosh et al ., ; Hemming and Hanson , ]. Numerous attempts have made to calibrate and evaluate the magnitude of the selective 10 B incorporation into biogenic skeletons and its dependence on boron speciation and thus pH [ Spivack et al ., ; Lemarchand et al ., ; Sanyal et al ., ; Hönisch et al ., , ; Hemming and Hönisch , ; Kubota et al ., ]. While the boron isotope ratios of corals correspond to an apparent boron species fractionation magnitude of ~20‰ determined earlier by Kakihana et al .…”

Section: Background Geochemical Cycle For Boronmentioning

confidence: 71%

“…Boron is lost from the oceans in a variety of pathways, of which incorporation in carbonates is the best known and the basis for the use of δ 11 B as an indicator of past changes in the pH of seawater [Vengosh et al, 1991;Hemming and Hanson, 1992]. Numerous attempts have made to calibrate and evaluate the magnitude of the selective 10 B incorporation into biogenic skeletons and its dependence on boron speciation and thus pH Lemarchand et al, 2000;Sanyal et al, 2000;Hönisch et al, 2007Hönisch et al, , 2009Hemming and Hönisch, 2007;Kubota et al, 2015]. While the boron isotope ratios of corals correspond to an apparent boron species fractionation magnitude of~20‰ determined earlier by Kakihana et al [1977], the boron isotopic ratios of benthic foraminifera are consistent with a higher fractionation factor of 26-27‰ [Hönisch et al, 2008;Rae et al, 2011], which is consistent with direct isotopic measurement of boron species through separation by RO membranes [Nir et al, 2015].…”

Section: The Oceansmentioning

confidence: 99%

“…Together with natural decadal variability in seawater pH [Wei et al, 2015], the rise of pCO 2 in the atmosphere and the induced ocean acidification caused by absorption of anthropogenic CO 2 into the ocean Global Biogeochemical Cycles 10.1002/2015GB005266 [Hönisch et al, 2012] is expected to change the boron speciation and the boron isotope ratio of carbonates. A study of Porites corals in areas of subtropical gyres, where surface seawater is close to equilibrium with atmospheric pCO 2 , has shown a slight parallel decrease in pH (8.2 to 8.1) and δ 11 B in corals age dated from 1900 to 2000 [Kubota et al, 2015]. Likewise, a reconstruction of seasonal variability and anthropogenic change in seawater pH and temperature from a long-lived coralline alga has shown a decline in the δ 11 B during the twentieth century [Fietzke et al, 2015].…”

Section: Conclusion and Future Trendsmentioning

confidence: 99%

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Global boron cycle in the Anthropocene

Schlesinger

Vengosh

2016

Global Biogeochemical Cycles

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This paper presents a revised and updated synthesis of the biogeochemical cycle of boron at the Earth's surface, where the largest fluxes are associated with the injection of sea‐salt aerosols to the atmosphere (1.44 Tg B/yr), production and combustion of fossil fuels (1.2 Tg B/yr), atmospheric deposition (3.48 Tg B/yr), the mining of B ores (1.1 Tg B/yr), and the transport of dissolved and suspended matter in rivers (0.80 Tg B/yr). The new estimates show that anthropogenic mobilization of B from the continental crust exceeds the naturally occurring processes, resulting in substantial fluxes to the ocean and the hydrosphere. The anthropogenic component contributes 81% of the flux in rivers. The mean residence time for B in seawater supports the use of δ11B in marine carbonates as an index of changes in the pH of seawater over time periods of > 1 Ma.

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Section: Background Geochemical Cycle For Boronmentioning

confidence: 71%

“…Boron is lost from the oceans in a variety of pathways, of which incorporation in carbonates is the best known and the basis for the use of δ 11 B as an indicator of past changes in the pH of seawater [Vengosh et al, 1991;Hemming and Hanson, 1992]. Numerous attempts have made to calibrate and evaluate the magnitude of the selective 10 B incorporation into biogenic skeletons and its dependence on boron speciation and thus pH Lemarchand et al, 2000;Sanyal et al, 2000;Hönisch et al, 2007Hönisch et al, , 2009Hemming and Hönisch, 2007;Kubota et al, 2015]. While the boron isotope ratios of corals correspond to an apparent boron species fractionation magnitude of~20‰ determined earlier by Kakihana et al [1977], the boron isotopic ratios of benthic foraminifera are consistent with a higher fractionation factor of 26-27‰ [Hönisch et al, 2008;Rae et al, 2011], which is consistent with direct isotopic measurement of boron species through separation by RO membranes [Nir et al, 2015].…”

Section: The Oceansmentioning

confidence: 99%

Section: Conclusion and Future Trendsmentioning

confidence: 99%

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Global boron cycle in the Anthropocene

Schlesinger

Vengosh

2016

Global Biogeochemical Cycles

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“…The isotope ratios of boron show large variations in nature (Fig. 1), and are of great interest to geo-, environmental, and marine scientists (Spivack, & Palmer, Edmond, 1987;Spivack, You, & Smith, 1993;Spivack & You, 1997;Lemarchand et al, 2002b;Kubota et al, 2015). These include studies in hydrology for ground water contamination by sea water (Barth, 1997); to assess the impact of artificial recharge on water sources; to identify mechanisms of adsorption/desorption on clay minerals; and in the environment as potential tracers of contamination of ground water with coal combustion residues, etc.…”

Section: Introductionmentioning

confidence: 99%

A review on the determination of isotope ratios of boron with mass spectrometry

Aggarwal

You

2016

Mass Spectrometry Reviews

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The present review discusses different mass spectrometric techniques-viz, thermal ionization mass spectrometry (TIMS), inductively coupled plasma mass spectrometry (ICPMS), and secondary ion mass spectrometry (SIMS)-used to determine B/ B isotope ratio, and concentration of boron required for various applications in earth sciences, marine geochemistry, nuclear technology, environmental, and agriculture sciences, etc. The details of the techniques-P-TIMS, which uses Cs BO , N-TIMS, which uses BO , and MC-ICPMS, which uses B ions for bulk analysis or B and B ions for in situ micro-analysis with SIMS-are highlighted. The capabilities, advantages, limitations, and problems in each mass spectrometric technique are summarized. The results of international interlaboratory comparison experiments conducted at different times are summarized. The certified isotopic reference materials available for boron are also listed. Recent developments in laser ablation (LA) ICPMS and QQQ-ICPMS for solids analysis and MS/MS analysis, respectively, are included. The different aspects of sample preparation and analytical chemistry of boron are summarized. Finally, the future requirements of boron isotope ratios for future applications are also given. Presently, MC-ICPMS provides the best precision and accuracy (0.2-0.4‰) on isotope ratio measurements, whereas N-TIMS holds the potential to analyze smallest amount of boron, but has the issue of bias (+2‰ to 4‰) which needs further investigations. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 36:499-519, 2017.

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“…Corals calcify from an isolated fluid located between the living tissue and the existing skeleton (Barnes, 1970;Cohen and McConnaughey, 2003;Venn et al, 2011;Tambutté et al, 2012). Up-regulation of pH within this fluid, potentially achieved via proton pumping and/or symbiont photosynthesis, elevates the saturation state with respect to aragonite ( Ar ), contributing to rapid nucleation and growth of aragonite crystals (Gattuso et al, 1999;Cohen and McConnaughey, 2003;Al-Horani et al, 2003;McCulloch et al, 2012;Kubota et al, 2015).…”

Section: Introductionmentioning

confidence: 99%

Coral calcifying fluid aragonite saturation states derived from Raman spectroscopy

DeCarlo¹,

D’Olivo²,

Foster³

et al. 2017

Biogeosciences

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Abstract. Quantifying the saturation state of aragonite ( Ar ) within the calcifying fluid of corals is critical for understanding their biomineralization process and sensitivity to environmental changes including ocean acidification. Recent advances in microscopy, microprobes, and isotope geochemistry enable the determination of calcifying fluid pH and [CO ]/K sp ) has proved elusive. Here we test a new technique for deriving Ar based on Raman spectroscopy. First, we analysed abiogenic aragonite crystals precipitated under a range of Ar from 10 to 34, and we found a strong dependence of Raman peak width on Ar with no significant effects of other factors including pH, Mg/Ca partitioning, and temperature. Validation of our Raman technique for corals is difficult because there are presently no direct measurements of calcifying fluid Ar available for comparison. However, Raman analysis of the international coral standard JCp-1 produced Ar of 12.3 ± 0.3, which we demonstrate is consistent with published skeletal Mg/Ca, Sr/Ca, B/Ca, δ 11 B, and δ 44 Ca data. Raman measurements are rapid (≤ 1 s), high-resolution (≤ 1 µm), precise (derived Ar ± 1 to 2 per spectrum depending on instrument configuration), accurate ( ±2 if Ar < 20), and require minimal sample preparation, making the technique well suited for testing the sensitivity of coral calcifying fluid Ar to ocean acidification and warming using samples from natural and laboratory settings. To demonstrate this, we also show a high-resolution time series of Ar over multiple years of growth in a Porites skeleton from the Great Barrier Reef, and we evaluate the response of Ar in juvenile Acropora cultured under elevated CO 2 and temperature.

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A new method for calibrating a boron isotope paleo‐pH proxy using massive Porites corals

Cited by 22 publications

References 80 publications

Global boron cycle in the Anthropocene

Global boron cycle in the Anthropocene

A review on the determination of isotope ratios of boron with mass spectrometry

Coral calcifying fluid aragonite saturation states derived from Raman spectroscopy

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