An unusual isotopic fractionation of boron in synthetic calcium carbonate precipitated from seawater and saline water  

作　　者：XIAO Yingkai1,2,LI Shizhen1,WEI Haizhen1,SUN Aide1,ZHOU Weijian2 & LIU Weiguo2 1. Qinghai Institute of Salt Lakes,Chinese Academy of Sciences,Xining 810008,China 2. State Key Laboratory of Loess and Quaternary Geology,Institute of Earth Environment,Chinese Academy of Sciences,Xi’an 710075,China 

出　　处：《Science China Chemistry》2006年第5期454-465,共12页中国科学（化学英文版）

基　　金：This project was supported by the National Natural Science Foundation of China (Grant No. 40373006) ; State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, Chinese Academy of Sciences (Grant No. SKLLQG0502).

摘　　要：Inorganic calcium carbonate precipitation from natural seawater and salinewater at various pH values was carried out experimentally. The results show the clear positiverelationships between boron concentration and δ^(11)B of inorganic calcium carbonate with the pH ofnatural seawater and saline water. However, the variations of boron isotopic fractionation betweeninorganic calcite and seawater/saline water with pH are inconsistent with the hypothesis thatB(OH)_4^- is the dominant species incorporated into the biogenic calcite structure. The isotopicfractionation factors a between synthetic calcium carbonate precipitate and parent solutionsincrease systematically as pH increases, from 0.9884 at pH 7.60 to 1.0072 at pH 8.60 for seawaterand from 0.9826 at pH 7.60 to 1.0178 at pH 8.75 for saline water. An unusual boron isotopicfractionation factor of larger than 1 in synthetic calcium carbonate precipitated fromseawater/saline water at higher pH is observed, which implies that a substantial amount of theisotopically heavier B(OH)_3 species must be incorporated preferentially into synthetic inorganiccarbonate. The results propose that the incorporation of B(OH)_3 is attributed to the formation ofMg(OH)_2 at higher pH of calcifying microenvironment during the synthetic calcium carbonateprecipitation. The preliminary experiment of Mg(OH)_2 precipitated from artificial seawater showsthat heavier ^(11)B is enriched in Mg(OH)_2 precipitation, which suggests that isotopically heavierB(OH)_3 species incorporated preferentially into Mg(OH)_2 precipitation. This result cannot beapplied to explain the boron isotopic fractionation of marine bio-carbonate because of thepossibility that the unusual environment in this study appears in formation of marine bio-carbonateis infinitesimal. We, however, must pay more attention to this phenomenon observed in this study,which accidentally appears in especially natural environment.Inorganic calcium carbonate precipitation from natural seawater and saline water at various pH values was carried out experimentally. The results show the clear positive relationships between boron concentration and δ11B of inorganic calcium carbonate with the pH of natural seawater and saline water. However, the variations of boron isotopic fractionation between inorganic calcite and seawater/saline water with pH are inconsistent with the hypothesis that B(OH)4- is the dominant spe-cies incorporated into the biogenic calcite structure. The isotopic fractionation factors α between synthetic calcium carbonate precipitate and parent solutions increase systematically as pH increases, from 0.9884 at pH 7.60 to 1.0072 at pH 8.60 for seawater and from 0.9826 at pH 7.60 to 1.0178 at pH 8.75 for saline water. An unusual boron isotopic fractionation factor of larger than 1 in synthetic calcium carbonate precipitated from seawater/saline water at higher pH is observed, which implies that a substantial amount of the isotopically heavier B(OH)3 species must be incorporated preferentially into synthetic inorganic carbonate. The results propose that the incorporation of B(OH)3 is attributed to the formation of Mg(OH)2 at higher pH of calcifying microenvironment during the synthetic calcium carbonate precipitation. The preliminary experiment of Mg(OH)2 precipitated from artificial seawater shows that heavier 11B is enriched in Mg(OH)2 precipitation, which suggests that isotopically heavier B(OH)3 species incorporated preferentially into Mg(OH)2 precipitation. This result cannot be applied to explain the boron isotopic fractionation of marine bio-carbonate because of the possibility that the unusual environment in this study appears in formation of marine bio-carbonate is infinitesimal. We, however, must pay more attention to this phenomenon observed in this study, which accidentally appears in especially natural environment.

关 键 词：boron  ISOTOPIC fractionation  calcium carbonate precipitate  seawater  SALINE water. 

分 类 号：TQ128.1[化学工程—无机化工]