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1.
Dissolved boron in modern seawater occurs in the form of two species, trigonal boric acid B(OH)3 and tetrahedral borate ion . One of the key assumption in the use of boron isotopic compositions of carbonates as pH proxy is that only borate ions, , are incorporated into the carbonate. Here, we investigate the speciation of boron in deep-sea coral microstructures (Lophelia pertusa specimen) by using high field magic angle spinning nuclear magnetic resonance (11B MAS NMR) and electron energy-loss spectroscopy (EELS). We observe both boron coordination species, but in different proportions depending on the coral microstructure, i.e. centres of calcification versus fibres. These results suggest that careful sampling is necessary before performing boron isotopic measurements in deep-sea corals. By combining the proportions of B(OH)3 and determined by NMR and our previous ion microprobe boron isotope measurements, we propose a new equation for the relation between seawater pH and boron isotopic composition in deep-sea corals.  相似文献   

2.
Boron isotope composition of marine carbonates has been proposed as a paleo-pH proxy and potential tool to reconstruct atmospheric pCO2. The precise knowledge of the boron isotopic composition of ancient seawater represents the fundamental prerequisite for any paleo-pH reconstruction. This contribution presents boron isotope values for Silurian to Permian brachiopod calcite that might be used to reconstruct pH or boron isotope composition of past oceans. All brachiopod shells were screened for diagenetic recrystallization by means of cathodoluminescence microscopy, trace element geochemistry (B, Fe, Mn, Sr) as well as SEM. Only nonluminescent shells revealing well-preserved microstructures, high strontium and boron concentrations as well as low iron and manganese contents were accepted for boron isotope analysis. The boron isotope ratios of Silurian, Devonian, Pennsylvanian and Permian brachiopod calcite range from 6.8 to 11.0‰, 7.3 to 14.9‰, 12.4 to 15.8‰ and 10.1 to 11.7‰, respectively. These δ11B values are significantly lower in comparison to δ11B values of modern biogenic carbonates and indicate that the Paleozoic oceans were depleted in 11B by up to 10‰. Box modeling of the boron geochemical cycle suggests that the significant depletion of 11B in the oceanic reservoir may have been initiated by an enhanced continental boron discharge. Our data support the earlier made conclusion that boron isotopes may not be used in the geological past as reliable paleo-pH proxy unless the boron isotopic composition of ancient oceans can be constrained by further studies.  相似文献   

3.
《Chemical Geology》2006,225(1-2):61-76
The boron geochemical cycle has been simulated using a time-dependent geochemical box model that was coupled to a one-dimension model of seawater–oceanic crust interactions. Boron elemental and isotopic compositions of oceanic rocks as a function of depth were calculated by mass balance, using the temperature and porosity profiles of the crust as well as the available experimental and empirical distribution coefficients and fractionation factors between mineral and water. Ranges of boron elemental and isotopic variations of seawater were calculated for crust–seawater interactions that take place from the ridge-axis to the off-axis closure of the hydrothermal system. The present-day δ11B of seawater (40‰) could represent a steady-state value. However, depending on crustal permeability, lifetime of water–rock interactions, and expansion rate of the oceanic ridge, the δ11B of seawater may vary from 30‰ to 50‰ at the 10 million year scale.Some boron isotope compositions of Cretaceous biogenic carbonates and ophiolitic serpentinites from Oman are comparable to modern rock samples, suggesting that the δ11B of Cretaceous seawater was close to the present-day value. Low δ11B values of some biogenic carbonates cannot be attributed to low pH values of past seawater, but more probably to δ11B variations of seawater or diagenetic alteration by crustal aqueous fluids. Boron isotope composition of hydrothermally altered serpentines could be considered as a promising proxy of the seawater composition.  相似文献   

4.
古海水pH值代用指标——海洋碳酸盐硼同位素研究进展   总被引：1，自引：0，他引：1  
仪器测量的海水pH记录太短，无法评估海水pH自然变化的频率和幅度,并预测未来大气CO2急剧增加后海水酸度的响应。海相碳酸盐的硼同位素是目前恢复古海洋pH的有效途径，倍受古气候—环境学家的重视。评述了近年来海洋碳酸盐的硼同位素的最新研究成果和研究现状，重点探讨了海相碳酸盐的硼同位素的测定方法、硼同位素—pH模型和古海水pH恢复等前沿内容，旨在提供一个系统的海洋碳酸盐硼同位素—pH系统的基本概念及研究思路，以利于气候学、地质学界了解这一交叉领域的发展动态。  相似文献   

5.
Pagani et al. [Pagani M., Lemarchand D., Spivack A., and Gaillardet J. (2005). A critical evaluation of the boron isotope-pH proxy: the accuracy of ancient ocean pH estimates. Geochim. Cosmochim. Acta69(4), 953-961] use data from previous boron isotope studies to suggest that the fractionation between boric acid and borate in seawater as well as the history of δ11B in seawater are poorly understood, thus limiting our ability to capture realistic ocean pH with this proxy. Although we agree with the authors that the long recognized uncertainty in the secular variation of δ11Bseawater imposes a temporal limit on paleo-pH reconstructions, their evaluation of the δ11B/pH relationship in carbonates is flawed. Potential complications from vital, temperature and dissolution effects reported in that paper are based on studies that are experimentally and/or analytically poorly constrained. Using published validation studies we will demonstrate that many of the problems outlined by Pagani et al. have already been addressed, or are based on misinterpretations of previous work. Most importantly, statistical evaluation suggests empirical data are best described by a fractionation of ∼20‰. Recent paleoreconstructions confirm that the boron isotope proxy can be used with confidence, if sample selection and analyses are done carefully.  相似文献   

6.
The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ11B has some limitations such as the knowledge of the fractionation factor (α4-3) between boric acid and the borate ion and the amplitude of “vital effects” on this proxy that are not well constrained. Using secondary ion mass spectrometry (SIMS) we have examined the internal variability of the boron isotope ratio in the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24 ± 0.1 °C) in seawater with pH ranging between 7.90 and 8.45. Intra-shell boron isotopes showed large variability with an upper limit value of ≈30‰. Our results suggest that the fractionation factor α4-3 of 0.97352 (Klochko et al., 2006) is in better agreement with our experiments and with direct pH measurements in seawater vacuoles associated with the biomineralization process in these foraminifera. Despite the large variability of the skeletal pH values in each cultured specimen, it is possible to link the lowest calculated pH values to the experimental culture pH values while the upper pH limit is slightly below 9. This variability can be interpreted as follows: foraminifera variably increase the pH at the biomineralization site to about 9. This increase above ambient seawater pH leads to a range in δ11B (Δ11B) for each seawater pH. This Δ11B is linearly correlated with the culture seawater pH with a slope of −13.1 per pH unit, and is independent of the fractionation factor α4-3, or the δ11Bsw through time. It may also be independent of the pKB (the dissociation constant of boric acid) value. Therefore, Δ11B in foraminifera can potentially reconstruct paleo-pH of seawater.  相似文献   

7.
Boron isotopic fractionation during adsorption onto Ca-flocculated Aldrich humic acid (HA) has been investigated experimentally as a function of solution pH at 25°C and I = 0.15 M. Boron aqueous concentration and isotopic composition were determined by Cs2BO2+ Positive Thermal Ionization Mass Spectrometry analysis, while the structure of B surface complexes on HA was characterized using 11B Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Significant B sorption on HA was observed at 6 < pH < 12 with a maximum value of Kd, the partition coefficient between adsorbed and aqueous boron, equal to 40 at pH = 9.5-10. Combined 11B MAS NMR analysis and FITEQL modeling of B sorption on HA showed that this element forms tetrahedrally coordinated five- or six-membered ring chelates, most likely 1,2-diol and 1,3-diol complexes at alkaline pH (8 < pH < 11) and dicarboxylic complexes at near neutral conditions (6 < pH < 9). Results of this study demonstrate for the first time that boron sorption on HA induces a strong pH-dependent isotope fractionation—with 11B depleted at the surface of HA—that reaches a maximum at 5 < pH < 9 (α = 0.975, Δ = −25‰) and decreases sharply at pH >9. The measured isotope fractionation cannot be modeled assuming that the isotopic composition of the sorbed borate species is identical to that of B(OH)4- species in the parent solution. It is shown that the extent of isotopic fractionation depends not only on B aqueous speciation but also on the distribution and structure of the borate surface complexes formed. In agreement with energetic constrains, calculation of the isotope fractionation factors between aqueous boric acid and boron surface complexes suggests that the formation of the strained six-membered ring 1,3-diol complex yields a much higher fractionation (αBLP1−III = 0.954-0.960, Δ = −41/-47‰) than that of the very stable five-membered ring 1,2-diol (αBLP2−III = 0.983, Δ = −18‰). The results of this study open new perspectives to understand and model boron biogeochemical cycle. It is predicted that boron sorption onto organic matter can have important consequences for the boron isotopic composition of surface water reservoirs (seawater, groundwater, soil waters) in which either abundant organic surfaces or significant boron concentrations are available. In addition, the large isotope fractionation between aqueous boric acid and surface boron-organic complexes found in the present work makes boron a promising tracer of biologic activity.  相似文献   

8.
Significant boron isotope fractionation occurs in nature (?70 ‰ to +75 ‰) due to the high geochemical reactivity of boron and the large relative mass difference between 10B and 11B. Since the 1990s, reconstruction of ancient seawater pH using the isotopic composition of boron in bio-carbonates (δ 11Bcarb), and then calculation of the past pCO2 have become important issues for the international isotope geochemistry community, and are called the δ 11B-pH proxy. Although many achievements have been made by this proxy, various aspects of boron systematics require rigorous evaluation. Based on the previous researches, mechanism of boron isotope fractionation, variation of boron isotope (δ 11B) in nature (especially in bio-carbonates) and controlling factors of the δ 11B-pH proxy, such as the dissociation constant of B(OH)3 in seawater (pKa), the δ 11B of seawater (δ 11BSW), the boron isotopic fractionation factor between B(OH) 4 ? and B(OH)3 (α 4–3), and the incorporated species of boron into bio-carbonates, are reviewed in detail and the research directions of this proxy are proposed. Generally, the controversy about pKa, δ 11Bsw, and α 4–3 is relatively less, but whether boron incorporated into bio-carbonates only in the form of B(OH) 4 ? remains doubtful. In the future, it is required that the physicochemical processes that control boron incorporation into carbonates be rigorously characterized and that the related chemical and isotopic fractionation be quantified. It is also necessary and important to establish a “best-fit empirically equation” between δ 11Bcarb and pH of seawater based on the precipitation experiments of inorganic or culture experiments of corals or foraminifera. In addition, extended application of the δ 11B-pH proxy to the earlier part of the Phanerozoic relying on the Brachiopods is worthy of studying. Like other geochemical indicators, there are limiting factors of δ 11B; however, it remains a very powerful tool in the reconstruction of past seawater pH at present.  相似文献   

9.
The stable boron isotope ratio (11B/10B) in marine carbonates is used as a paleo-pH recorder and is one of the most promising paleo-carbonate chemistry proxies. Understanding the thermodynamic basis of the proxy is of fundamental importance, including knowledge on the equilibrium fractionation factor between dissolved boric acid, B(OH)3, and borate ion, B(OH)4− (, hereafter α(B3-B4)). However, this factor has hitherto not been determined experimentally and a theoretically calculated value (Kakihana and Kotaka, 1977, hereafter KK77) has therefore been widely used. I examine the calculations underlying this value. Using the same spectroscopic data and methods as KK77, I calculate the same α(B3−B4) = 1.0193 at 300 K. Unfortunately, it turns out that in general the result is sensitive to the experimentally determined vibrational frequencies and the theoretical methods used to calculate the molecular forces. Using analytical techniques and ab initio molecular orbital theory, the outcome for α(B3-B4) varies between ∼1.020 and ∼1.050 at 300 K. However, several arguments suggest that α(B3-B4) ? 1.030. Measured isotopic shifts in various 10B-, 2D-, and 18O-labeled isotopomers do not provide a constraint on stable boron isotope fractionation. I conclude that in order to anchor the fundamentals of the boron pH proxy, experimental work is required. The critics of the boron pH proxy should note, however, that uncertainties in α(B3-B4) do not bias pH reconstructions provided that organism-specific calibrations are used.  相似文献   

10.
Equilibrium boron isotopic fractionations between trigonal B(OH)3 and tetragonal B(OH)4− aqueous species have been calculated at high P-T conditions using measured vibrational spectra (Raman and IR) and force-field modeling to compute reduced partition function ratios for B-isotopic exchange following Urey’s theory. The calculated isotopic fractionation factor at 300 K, α3/4 = 1.0176(2), is slightly lower than the formerly calculated value of α3/4 = 1.0193 (Kakihana and Kotaka, 1977), due to differences in the determined vibrational frequencies. The effect of pressure on α3/4 up to 10 GPa and 723 K is shown to be negligible relative to temperature or speciation (pH) effects. Implications for the interpretation of boron fractionation in experimental and natural systems are discussed. We also show that the relationship between seawater-mineral B isotope fractionation and pH can be expressed using two variables, α3/4 on one hand, and the pKa of the boric acid-borate equilibrium on the other hand. This latter value is given by the equilibrium of boron species in water for the carbonate-water exchange, but could be governed by mineral surface properties in the case of clays. This may allow defining intrinsic paleo-pHmeters from B isotope fractionation between carbonate and authigenic minerals. Finally, it is shown that fractionation of boron isotopes can be rationalized in terms of the changes in 1) coordination of B from trigonal to tetrahedral in both fluids and minerals; and 2) the ligand nature around B from OH− in the fluid and some hydrous minerals to non-hydrogenated O in many minerals. Relationships are established that allow predicting the isotopic fractionation factor of B between minerals and fluid.  相似文献   

11.
The carbonates in martian meteorite ALH84001 preserve a record of aqueous processes on Mars at 3.9 Ga, and have been suggested to contain signatures of ancient martian life. The conditions of the carbonate formation environment are critical for understanding possible evidence for life on Mars, the history of water on Mars, and the evolution of the martian atmosphere. Despite numerous studies of petrographic relationships, microscale oxygen isotope compositions, microscale chemical compositions, and other minerals associated with the carbonates, formation models remain relatively unconstrained. Microscale carbon isotope analyses of ALH84001 carbonates reveal variable δ13C values ranging from +27 to +64‰. The isotopic compositions are correlated with chemical composition and extent of crystallization such that the Mg-poor, early-formed carbonates are relatively 13C depleted and the Mg-rich, later forming carbonates, are 13C enriched. These data are inconsistent with many of the previously proposed environments for carbonate formation, and a new set of hypotheses are proposed. Specifically, two new models that account for the data involve low temperature (<100°C) aqueous processes: (1) the carbonates formed during mixing of two fluids derived from separate chemical and isotopic reservoirs; or (2) the carbonates formed from high pH fluids that are exposed to a CO2-rich atmosphere and precipitate carbonate, similar to high pH springs on Earth.  相似文献   

12.
The boron isotopic ratio of 11B/10B (δ11BSRM951) and trace element composition of marine carbonates are key proxies for understanding carbon cycling (pH) and palaeoceanographic change. However, method validation and comparability of results between laboratories requires carbonate reference materials. Here, we report results of an inter‐laboratory comparison study to both assign δ11BSRM951 and trace element compositions to new synthetic marine carbonate reference materials (RMs), NIST RM 8301 (Coral) and NIST RM 8301 (Foram) and to assess the variance of data among laboratories. Non‐certified reference values and expanded 95% uncertainties for δ11BSRM951 in NIST RM 8301 (Coral) (+24.17‰ ± 0.18‰) and NIST RM 8301 (Foram) (+14.51‰ ± 0.17‰) solutions were assigned by consensus approach using inter‐laboratory data. Differences reported among laboratories were considerably smaller than some previous inter‐laboratory comparisons, yet discrepancies could still lead to large differences in calculated seawater pH. Similarly, variability in reported trace element information among laboratories (e.g., Mg/Ca ± 5% RSD) was often greater than within a single laboratory (e.g., Mg/Ca < 2%). Such differences potentially alter proxy‐reconstructed seawater temperature by more than 2 °C. These now well‐characterised solutions are useful reference materials to help the palaeoceanographic community build a comprehensive view of past ocean changes.  相似文献   

13.
Boron isotopes in marine carbonates are increasingly used to reconstruct seawater pH and atmospheric pCO2 through Earth’s history. While isotope ratio measurements from individual laboratories are often of high quality, it is important that records generated in different laboratories can equally be compared. Within this Boron Isotope Intercomparison Project (BIIP), we characterised the boron isotopic composition (commonly expressed in δ11B) of two marine carbonates: Geological Survey of Japan carbonate reference materials JCp‐1 (coral Porites) and JCt‐1 (giant clam Tridacna gigas). Our study has three foci: (a) to assess the extent to which oxidative pre‐treatment, aimed at removing organic material from carbonate, can influence the resulting δ11B; (b) to determine to what degree the chosen analytical approach may affect the resultant δ11B; and (c) to provide well‐constrained consensus δ11B values for JCp‐1 and JCt‐1. The resultant robust mean and associated robust standard deviation (s*) for un‐oxidised JCp‐1 is 24.36 ± 0.45‰ (2s*), compared with 24.25 ± 0.22‰ (2s*) for the same oxidised material. For un‐oxidised JCt‐1, respective compositions are 16.39 ± 0.60‰ (2s*; un‐oxidised) and 16.24 ± 0.38‰ (2s*; oxidised). The consistency between laboratories is generally better if carbonate powders were oxidatively cleaned prior to purification and measurement.  相似文献   

14.
The effects of phosphate speciation on both rates of isotopic exchange and oxygen isotope equilibrium fractionation factors between aqueous phosphate and water were examined over the temperature range 70 to 180°C. Exchange between phosphate and water is much faster at low pH than at high pH, an observation that is similar to what has been observed in the analogous sulfate-water system. Oxygen isotope fractionations between protonated species like H3PO4 and H2PO4− that are dominant at relatively low pH and species like PO43− and ion pairs like KHPO4− that are dominant at relatively high pH, range between 5 and 8‰ at the temperatures of the experiments. In aqueous phosphate systems at equilibrium, 18O/16O ratios increase with increasing degree of protonation of phosphate. This effect can be explained in part by the relative magnitudes of the dissociation constants of the protonated species. Under equilibrium conditions, carbonate in solution or in solid phases concentrates 18O relative to orthophosphate in solution or in solid phases at all temperatures, supporting the traditional view that biogenic phosphate is precipitated in near oxygen isotope equilibrium with body/ambient aqueous fluids with no attendant vital effects.  相似文献   

15.
The reliability of δ13C trends in Neoproterozoic carbonate-dominated successions for regional and global chemostratigraphic correlation is discussed. In the light of recent findings of a predominantly non-marine rare earth element and yttrium signature in most Neoproterozoic carbonates and a comparatively short oceanic residence time of carbon, trends towards enrichment in 13C seen in many of these carbonates are considered to reflect facies variations rather than temporal signals of ocean chemistry. Positive δ13CCarb excursions are explained by elevated bioproductivity and/or increased evaporation in shallow marine, near-coastal, temporarily restricted depositional environments. Examples are provided that illustrate that C isotope trends can be highly ambiguous temporal markers and are in the absence of other chemostratigraphic data, such as Sr isotope ratios, and radiometric age control of only limited use for stratigraphic correlation. The overall enrichment in 13C recorded by most Neoproterozoic carbonates, except for those in close stratigraphic proximity to glacial deposits, is suggested to reflect a dominance of microbially mediated carbonate formation in the Neoproterozoic. This might explain why C isotope chemostratigraphy in Neoproterozoic successions is less reliable than in Phanerozoic successions in which carbonates are, with only few exceptions, biogenic products of shelly fossils.  相似文献   

16.
Laboratory experiments on the branching, symbiont-bearing coral genus Porites and Acropora have been carried out to determine the dependence of the skeletal boron isotopic composition (δ11B) on the pH of seawater. The results show a clear relationship similar to previously established empirical calibrations for planktonic foraminifera and inorganic calcite. A −0.6‰ offset exists between P. cylindrica and A. nobilis which is systematic over the pH range of 7.7-8.2. To test whether the δ11B of coral skeletons changes with physiological processes such as photosynthesis and respiration, corals were grown along a depth transect in their natural environment and under controlled conditions in the laboratory at varying light intensities and food supply. Although we also observe an isotopic offset between P. compressa and Montipora verrucosa, neither experimental treatment systematically changed the δ11B of the two species. These findings are encouraging for using the boron isotope paleo-pH proxy in corals, because it appears that seawater pH is the dominant control on the boron isotopic composition in corals.  相似文献   

17.
Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater. Mg isotopes are significantly (up to 5‰) fractionated during carbonate precipitation by preferential incorporation of 24Mg, while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of 26Mg. Thus, the marine Mg cycle could be reflected by seawater Mg isotopic composition (δ26Mgsw), which might be recorded in marine carbonate. However, carbonates are both texturally and compositionally heterogeneous, and it is unclear which carbonate component is the most reliable for reconstructing δ26Mgsw. In this study, we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China. Based on petrographic studies, four carbonate components were recognized: micrite, marine cement, brachiopod shell, and mixture. The four components had distinct δ26Mg: (1) micrite samples ranged from ?2.86‰ to ?2.97‰; (2) pure marine cements varied from ?3.40‰ to ?3.54‰, while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range (?3.27‰ to ?3.75‰); (3) values for the mixture component were ?3.17‰ and ?3.49‰; and (4) brachiopod shells ranged from ?2.20‰ to ?3.07‰, with the thickened hinge area enriched in 24Mg. Due to having multiple carbonate sources, neither the micrite nor the mixture component could be used to reconstruct δ26Mgsw. In addition, the marine cement was homogenous in Mg isotopes, but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ26Mgsw. Furthermore, brachiopod shells had heterogeneous C and Mg isotopes, suggesting a significant vital effect during growth. Overall, the heterogeneous δ26Mg of the Huangjin limestone makes it difficult to reconstruct δ26Mgsw using bulk carbonate/calcareous sediments. Finally, δ26Mgsw was only slightly affected by the faunal composition of carbonate-secreting organisms, even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range (0.2‰–4.8‰) of fractionation during biogenic carbonate formation.  相似文献   

18.
为了深入了解黄土地层中丰富的陆生蜗牛壳体碳酸盐化石氧同位素组成的气候环境指示意义,文章对黄土高原典型气候带的现生蜗牛壳体文石氧同位素进行了测量。结果显示:高原半干旱地区蜗牛壳体氧同位素组成相对于半湿润地区显著富集δ18 O;壳体δ18 O值与夏季降水量具有密切负相关关系。对照黄土高原气候特征以及夏季风降水氧同位素组成和降水量的关系,认为:1)夏季风降水δ18 O丰度是影响蜗牛壳体氧同位素组成变化的主要因素;2) 进一步研究黄土沉积物中蜗牛壳体化石氧同位素组成对重建黄土高原夏季风强度变化的历史具有重要的意义。  相似文献   

19.
The boron isotope-pH technique is founded on a theoretical model of carbonate δ11B variation with pH that assumes that the boron isotopic composition of carbonates mirrors the boron isotopic composition of borate in solution (δ11Bcarb = δ11Bborate). Knowledge of the fractionation factor for isotope exchange between boric acid and borate in solution (α4-3), the equilibrium constant for the dissociation of boric acid (pKB*), as well as the isotopic composition of boron in seawater (δ11Bsw) are required parameters of the model.The available data suggests that both the value of α4-3 and the history of δ11Bsw are poorly constrained. However, if one assumes that δ11Bcarb = δ11Bborate, an empirical value for α4-3 can be estimated from the results of inorganic carbonate precipitation experiments. This exercise yields an α4-3 value of ∼0.974 in accordance with recent theoretical estimates, but substantially deviates from the theoretical value of 0.981 often used to estimate paleo-ocean pH. Re-evaluation of ocean pH using an α4-3 value of 0.974 and published foraminiferal δ11B values for the Cenozoic yield pH estimates that are relatively invariant, but unrealistically high (∼8.4-8.6). Uncertainty increases as foraminiferal ‘vital effects’ are considered and different models for secular changes in seawater δ11B are applied.The inability to capture realistic ocean pH possibly reflects on our understanding of the isotopic relationship between carbonate and borate, as well as the mechanism of boron incorporation in carbonates. Given the current understanding of boron systematics, pH values estimated using this technique have considerable uncertainty, particularly when reconstructions exceed the residence time of boron in the ocean.  相似文献   

20.
This paper is focused on the role of boron coordination in determining the 11B/10B isotopic fractionation between melt/glass and biotite at magmatic temperatures. For this purpose, three evolved volcanic rocks from Roccastrada, Mt. Amiata, and Mt. Cimini belonging to the Neogene-Quaternary magmatism of central Italy were studied. In these samples, the measured boron biotite-glass partition coefficient ranges between 0.004 and 0.011, indicating that boron behaves as an incompatible element during biotite crystallization. The 11B magic-angle spinning nuclear magnetic resonance (NMR) spectra reveal the presence of trigonal BO3/2 units, tetrahedral BO4/2− sites, and three-coordinated BO2/2O− species containing one nonbridging oxygen. The relative contributions of these different boron sites were estimated by spectral deconvolution, and it was observed that the fraction of trigonally coordinated boron decreases with increasing K2O concentration in the glass. The 11B/10B isotopic fractionation between biotite and melt/glass was observed to be large even at magmatic temperatures and was found to be 1.0066 (Roccastrada sample), 1.00535 (Mt. Amiata sample), and 1.00279 (Mt. Cimini sample). Fractionation is mostly related to the relative amount of trigonal and tetrahedral boron sites in the glass network rather than to other processes, including the speciation of hydrous species in the glass structure. The measured α values are significantly higher than the calculated ones obtained using the reduced partition function ratios (RPFRs) for B(OH)3 and B(OH)4− as reported by Kakihana et al. (1977) and the abundance of trigonal and tetrahedral boron obtained by 11B NMR spectra. Furthermore, a nonlinear relationship is observed between the percentage of BO4 in the glass structure and the measured 1000lnα, suggesting that the approximation of monomeric B(OH)3 and B(OH)4− species contributions through ideal mixing in calculating the RPFRs in polyanions (Oi et al., 1989) probably does not apply to silicate glasses.The large B isotopic fractionation measured between glass and biotite and its dependence on the boron coordination in the glass are a limitation to the use of δ11B in the mineral to characterize magmas. Nonetheless, the high incompatible behavior of boron in the most common magmatic minerals rules out that fractional crystallization significantly modified the B isotopic composition of the melt.  相似文献   

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