Pulleniatina obliquiloculata shells from 16 core-top samples from the tropical Indo-Pacific Oceans are analyzed for the ratios of boron and cadmium to calcium(B/Ca and Cd/Ca). The B/Ca ratios show a very weak positive...Pulleniatina obliquiloculata shells from 16 core-top samples from the tropical Indo-Pacific Oceans are analyzed for the ratios of boron and cadmium to calcium(B/Ca and Cd/Ca). The B/Ca ratios show a very weak positive relationship with [B(OH)_4^-] and the dissolved carbonate species at the apparent calcification depth of P.obliquiloculata. The boron partition coefficients(K_D) between P. obliquiloculata B/Ca and seawater[B(OH)_4^-]/[HCO_3^-] distribute around 1.1×10^(-3)-1.3×10^(-3) with a mean value of(1.19±0.12)×10^(-3),and are significantly related to the nutrient concentration, especially phosphate. The lack of any clear correlation between the P. obliquiloculata B/Ca and seawater carbonate chemical parameters suggests that the physiochemical controls on boron incorporation are masked by the complexity of natural seawater condition. But the significant dependence of Ku on nutrient may likely be explained by a nutrient related growth-rate effect. Cd/Ca of P.obliquiloculata shows significant correlation with seawater phosphate concentration, and its partition coefficients(D_(cd)) are significantly related to temperature. A first-principle methodology of P. obliquiloculata B/Ca is applied;with the aid of Cd/Ca as a phosphate proxy and a constraint on K_D, to estimating sea water carbonate chemistry(e.g., pH). The results are fairly promising and allow us to propose the possibility to apply the combination of B/Ca and Cd/Ca proxies(and also Mg/Ca and δ^(18)O for estimating temperature and salinity) for the paleoreconstruction of seawater carbonate chemistry.展开更多
The boron isotope paleo-pH proxy has been extensively studied due to its potential for understanding past climate change, and further calibrations were considered for accurate applications of the proxy because of sign...The boron isotope paleo-pH proxy has been extensively studied due to its potential for understanding past climate change, and further calibrations were considered for accurate applications of the proxy because of significant variability related to biocarbonate microstructure. In this work, we studied the boron isotopic fractionation between modern marine corals and their coexisting seawater collected along shallow area in Sanya Bay, South China Sea. The apparent partition coefficient of boron（KD） ranged from 0.83×10-3 to 1.69×10-3, which are in good agreement with previous studies. As the analyzed coral skeleton（~5 g） spanned the growth time period of 1–2 years, we discussed the boron isotopic fractionation between pristine corals and modern seawater using the annual mean seawater pH of 8.12 in this sea area. Without taking the vital effect into account,（11B/10B）coral values of all living corals spread over the curves of（11B/10B）borate vs.（11B/10B）sw with the α4-3 values ranging from 0.974 to 0.982. After calibrating the biological effect on the calcifying fluid pH, the field-based calcification on calcifying fluid pH（i.e., Δ（pHbiol-pHsw）） for coral species of Acropora, Pavona, Pocillopora, Faviidae, and others including Proites are 0.42, 0.33, 0.36, 0.19, respectively, and it is necessary to be validated by coral culturing experiment in the future. Correlations in B/Ca vs. Sr/Ca and B/Ca vs. pHbiol approve temperature and calcifying fluid pH influence on skeletal B/Ca. Fundamental understanding of the thermodynamic basis of the boron isotopes in marine carbonates and seawater will strengthen the confidence in the use of paleo-pH proxy as a powerful tool to monitor atmospheric CO2 variations in the past.展开更多
基金The National Natural Science Foundation of China(NSFC)and NSFC-Shandong Joint Fund for Marine Science Research Centers under contract Nos 41606049,U1606401 and 41376054the China Postdoctoral Science Foundation under contract No.2015M581658
文摘Pulleniatina obliquiloculata shells from 16 core-top samples from the tropical Indo-Pacific Oceans are analyzed for the ratios of boron and cadmium to calcium(B/Ca and Cd/Ca). The B/Ca ratios show a very weak positive relationship with [B(OH)_4^-] and the dissolved carbonate species at the apparent calcification depth of P.obliquiloculata. The boron partition coefficients(K_D) between P. obliquiloculata B/Ca and seawater[B(OH)_4^-]/[HCO_3^-] distribute around 1.1×10^(-3)-1.3×10^(-3) with a mean value of(1.19±0.12)×10^(-3),and are significantly related to the nutrient concentration, especially phosphate. The lack of any clear correlation between the P. obliquiloculata B/Ca and seawater carbonate chemical parameters suggests that the physiochemical controls on boron incorporation are masked by the complexity of natural seawater condition. But the significant dependence of Ku on nutrient may likely be explained by a nutrient related growth-rate effect. Cd/Ca of P.obliquiloculata shows significant correlation with seawater phosphate concentration, and its partition coefficients(D_(cd)) are significantly related to temperature. A first-principle methodology of P. obliquiloculata B/Ca is applied;with the aid of Cd/Ca as a phosphate proxy and a constraint on K_D, to estimating sea water carbonate chemistry(e.g., pH). The results are fairly promising and allow us to propose the possibility to apply the combination of B/Ca and Cd/Ca proxies(and also Mg/Ca and δ^(18)O for estimating temperature and salinity) for the paleoreconstruction of seawater carbonate chemistry.
基金supported by the National Natural Science Foundation of China (Nos. 40973002, 41073002 and 41173049) the Fundamental Research Funds for the Central Universities (No. 020614330005)
文摘The boron isotope paleo-pH proxy has been extensively studied due to its potential for understanding past climate change, and further calibrations were considered for accurate applications of the proxy because of significant variability related to biocarbonate microstructure. In this work, we studied the boron isotopic fractionation between modern marine corals and their coexisting seawater collected along shallow area in Sanya Bay, South China Sea. The apparent partition coefficient of boron（KD） ranged from 0.83×10-3 to 1.69×10-3, which are in good agreement with previous studies. As the analyzed coral skeleton（~5 g） spanned the growth time period of 1–2 years, we discussed the boron isotopic fractionation between pristine corals and modern seawater using the annual mean seawater pH of 8.12 in this sea area. Without taking the vital effect into account,（11B/10B）coral values of all living corals spread over the curves of（11B/10B）borate vs.（11B/10B）sw with the α4-3 values ranging from 0.974 to 0.982. After calibrating the biological effect on the calcifying fluid pH, the field-based calcification on calcifying fluid pH（i.e., Δ（pHbiol-pHsw）） for coral species of Acropora, Pavona, Pocillopora, Faviidae, and others including Proites are 0.42, 0.33, 0.36, 0.19, respectively, and it is necessary to be validated by coral culturing experiment in the future. Correlations in B/Ca vs. Sr/Ca and B/Ca vs. pHbiol approve temperature and calcifying fluid pH influence on skeletal B/Ca. Fundamental understanding of the thermodynamic basis of the boron isotopes in marine carbonates and seawater will strengthen the confidence in the use of paleo-pH proxy as a powerful tool to monitor atmospheric CO2 variations in the past.
