Stable boron isotope fractionation between dissolved B(OH)3 and B(OH)4−

Zeebe, Richard E.

doi:10.1016/j.gca.2004.12.011

Cited by 157 publications

(127 citation statements)

References 46 publications

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“…However, the observed relationships between biogenic 11 BCaCO3 and seawater pH vary widely amongst taxa (Fig. 2), and generally differ from that 140 measured or derived theoretically for B(OH)4 -in seawater Klochko et al, 2006;Liu and Tossell, 2005;Zeebe, 2005) and from that observed in abiotically precipitated CaCO3 (Sanyal et al, 2000).…”

Section: The Role Of Calcification Site Ph In Calcareous Biomineralizmentioning

confidence: 69%

“…For example, α = 1.0194 was calculated from theory by Kakihana et al (1977) and has been widely applied in palaeoreconstructions of seawater pH Kakihana et al, 1977;Sanyal et al, 1995). Zeebe (2005) used 65 analytical techniques and ab initio molecular orbital theory to calculate ranging from 1.020 to 1.050 at 300 K. Zeebe (2005) provided several arguments in support of α 1.030, ultimately concluding that experimental work was required to determine the between dissolved boric acid and the borate ion. Subsequent to the work by Zeebe (2005), significant error was identified for the borate vibrational spectrum term used in Kakihana et al's (1977) theoretical calculation of Rustad and Bylaska, 2007).…”

Section: B(oh)3 + H2o B(oh)4 -+ H +mentioning

confidence: 99%

“…Zeebe (2005) used 65 analytical techniques and ab initio molecular orbital theory to calculate ranging from 1.020 to 1.050 at 300 K. Zeebe (2005) provided several arguments in support of α 1.030, ultimately concluding that experimental work was required to determine the between dissolved boric acid and the borate ion. Subsequent to the work by Zeebe (2005), significant error was identified for the borate vibrational spectrum term used in Kakihana et al's (1977) theoretical calculation of Rustad and Bylaska, 2007). An empirical of 1.0272 , using a corrected borate vibrational 70 spectrum term, is now considered to best describe the boron isotope fractionation between dissolved boric acid and borate ion in seawater (Rollion-Bard and Erez, 2010;Xiao et al, 2014).…”

Section: B(oh)3 + H2o B(oh)4 -+ H +mentioning

confidence: 99%

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δ<sup>11</sup>B 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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Section: The Role Of Calcification Site Ph In Calcareous Biomineralizmentioning

confidence: 69%

Section: B(oh)3 + H2o B(oh)4 -+ H +mentioning

confidence: 99%

Section: B(oh)3 + H2o B(oh)4 -+ H +mentioning

confidence: 99%

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

Sutton

Liu

Ries

et al. 2017

Preprint

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“…Except for pH 9.5, δ 11 B d values are lower than δ 11 B isw3 calculated using α 4−3 = 0.9600 (Fig. 4), so that the true α 4−3 would have to be lower than 0.9600, which is a little lower than the currently expected value between 0.983 (Sanchez-Valle et al, 2005) and 0.952 (Zeebe, 2005). The pH values used in previous carbonate precipitation experiments are lower than 9.0, while that of our experiments are between 9.5 and 13.0.…”

Section: Isotopic Fractionation Of Boron Between Deposited Brucite Anmentioning

confidence: 63%

Boron isotope fractionation during brucite deposition from artificial seawater

2011

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Abstract. Experiments involving boron incorporation into brucite (Mg(OH) 2 ) from magnesium-free artificial seawater with pH values ranging from 9.5 to 13.0 were carried out to better understand the incorporation behavior of boron into brucite and the influence of it on Mg/Ca-SST proxy and δ 11 B-pH proxy. The results show that both the concentration of boron in deposited brucite ([B] d ) and its boron partition coefficient (K d ) between deposited brucite and final seawater are controlled by the pH of the solution. The incorporation capacity of boron into brucite is almost the same as that into corals, but much stronger than that into oxides and clay minerals. The isotopic compositions of boron in deposited brucite (δ 11 B d ) are higher than those in the associated artificial seawater (δ 11 B isw ) with fractionation factors ranging between 1.0177 and 1.0569, resulting from the preferential incorporation of B(OH) 3 into brucite. Both boron adsorptions onto brucite and the precipitation reaction of H 3 BO 3 with brucite exist during deposition of brucite from artificial seawater. The simultaneous occurrence of both processes determines the boron concentration and isotopic fractionation of brucite. The isotopic fractionation behaviors and mechanisms of boron incorporated into brucite are different from those into corals. The existence of brucite in corals can affect the δ 11 B and Mg/Ca in corals and influences the Mg/Ca-SST proxy and δ 11 B-pH proxy negatively. The relationship between δ 11 B and Mg/Ca in corals can be used to judge the existence of brucite in corals, which should provide a reliable method for better use of δ 11 B and Mg/Ca in corals to reconstruct paleo-marine environment.

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“…During the last several years, there has been notable success in first-principles calculation of equilibrium fractionation factors in a variety of geochemical environments ranging from silicon in the Earth's core (13) to boron isotopes in seawater (14,15) to chlorophyll populations in higher plants (16). Recently these methods have been applied to carbonate minerals (17,18).…”

mentioning

confidence: 99%

Calculation of site-specific carbon-isotope fractionation in pedogenic oxide minerals

Rustad

Zarzycki²

2008

Proc. Natl. Acad. Sci. U.S.A.

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atmospheric carbon dioxide ͉ electronic structure calculations ͉ paleosols ͉ goethite ͉ gibbsite T he paleosol carbon-isotope method is one of the major techniques for reconstructing the composition of the ancient atmosphere (1, 2). The depth-dependent mixing of respirative CO 2 from soil ( 13 C-depleted) with atmospheric CO 2 ( 13 Cenriched) can be preserved in soil minerals and has been used to infer atmospheric PCO 2 and respiration rates in paleosols (3). The idea was directed originally at soil carbonate minerals (4) and later applied to the CO 2 component of pedogenic goethite (␣-FeOOH) (5-7) and gibbsite (Al(OH) 3 ) (8, 9). The fractionation between mineral-dissolved CO 2 [CO 2 (m)] and CO 2 (g) is a key factor in the technique because it determines how the respired CO 2 vs. atmospheric CO 2 mixing profile is imprinted onto the soil mineralogy. Direct measurements of the CO 2 (m)-CO 2 (g) fractionation factors for (oxy)hydroxide soil minerals have thus far been elusive. The small values (0 to ϩ2.5 per mil) that have been provisionally implied are surprising because, by analogy with carbonate minerals, a 13 C-enriched fractionation factor (close to ϩ10 per mil) might be expected (10,11).In carbonate minerals with the calcite and aragonite structure, the overwhelming majority of carbonate ions are in a single crystallographic site that governs the equilibrium isotope fractionation. In contrast, occlusion of CO 2 in oxide soil minerals at trace concentrations could involve multiple sites with varying populations, possibly depending on the kinetics and conditions of soil formation. For goethite, it has commonly been assumed that the open pseudochannels parallel to the c crystallographic axis are the major host for CO 2 (m) (12), but this has not been definitively demonstrated, and it is possible that other types of sites could be involved in the uptake of CO 2 (m). An important question is then whether the various kinds of CO 2 (m) sites would have large differences in their equilibrium 12/13 C isotope fractionation factors. Little attention has been given to the possibility of heterogeneous chemical speciation of CO 2 (m) within the host mineral. Site heterogeneity would complicate the interpretation of the carbon isotope records preserved in these minerals. At the same time, a better understanding of the crystal chemistry of CO 2 (m) defects in oxide/oxhydroxide minerals and their isotopic fractionations could serve as a foundation for a much more sensitive paleoclimate indicator than would be possible with knowledge of only the overall isotopic composition. Knowledge of site-specific isotopic signatures in minerals could have much wider applicability than the CO 2 -Fe,Al(oxy)hydroxide system.Although the experimental difficulties of sampling these individual sites might be daunting, accurate theoretical calculation of the potential fractionations is now feasible by using methods of quantum chemistry. During the last several years, there has been notable success in first-principles calculation of equilibriu...

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Stable boron isotope fractionation between dissolved B(OH)3 and B(OH)4−

Cited by 157 publications

References 46 publications

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

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

Boron isotope fractionation during brucite deposition from artificial seawater

Calculation of site-specific carbon-isotope fractionation in pedogenic oxide minerals

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Stable boron isotope fractionation between dissolved B(OH)3 and B(OH)4−

Cited by 157 publications

References 46 publications

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

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

Boron isotope fractionation during brucite deposition from artificial seawater

Calculation of site-specific carbon-isotope fractionation in pedogenic oxide minerals

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Product

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

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