Yingkai Xiao

Boron isotope variations and its geochemical application in nature

The high geochemical reactivity of boron and the large relative mass difference between 10B and 11B lead to significant boron isotope fractionation in nature. So far the measured range of boron isotope composition (δ11B) varies between –70 and +75‰. The negative δ11B values are found in non-marine evaporite borate minerals and tourmalines, whereas positive δ11B values are common in salt lake brines and evaporated seawater. Since the 1980s, with improved measurement methods, applications of boron isotope analysis have increased rapidly. At present, boron isotopes are successfully applied to reconstruct ancient marine environments, to determine depositional environments and ore genesis, to trace groundwater pollution and seawater intrusion, and to study continental erosion. This paper summarises the methods for boron isotope analysis, the mechanisms of boron isotope fractionation and the distribution of boron isotopes in nature, reviews the achievements and the problems of boron isotopes in geochemical applications, and proposes research directions of boron isotopes in geochemical fields.

Boron concentration and isotopic composition of halite from experiments and salt lakes in the Qaidam Basin

Abstract The concentration and isotopic abundance of boron in salt can be used to trace paleosalinities and depositional environments for marine and non marine evaporites. However, the mechanism of incorporating boron into halite during evaporation of salt lake brines is subject to dispute, and there have been few studies of boron concentrations and isotopic compositions during this process due to the low boron concentration in halite. A group of evaporation experiments from artificial solutions and salt lake brines have been analyzed in this study. The results of boron concentration and isotopic analyses demonstrate that the boron in halite comes mainly from fluid inclusions, with a lesser amount from coprecipitation. The isotopic fractionation factors between the brine and halite are from 0.9857 to 1.0000 for the evaporation experiments, and 0.9945 to 1.0009 for natural samples from the salt lake. The δ11B values of halite from the Qaidam Basin salt lakes vary from −4.7 to 25.8‰, compared to −4.7 to 31.4‰ in the salt lake brines. These values are controlled by the boron isotopic composition of the boron sources, pH values and Na/Ca ratios in the salt lake brines. The variation of boron isotopes in halite may be used to trace the hydrochemical evolution and paleoevaporation environment in salt lakes.

Precise Determination of the Absolute Isotopic Abundance Ratio and the Atomic Weight of Chlorine in Three International Reference Materials by the Positive Thermal Ionization Mass Spectrometer-Cs2Cl+-Graphite Method

Because the variation in chlorine isotopic abundances of naturally occurring chlorine bearing substances is significant, the IUPAC Inorganic Chemistry Division, Commission on Isotopic Abundances and Atomic Weights (CIAAW-IUPAC) decided that the uncertainty of atomic weight of chlorine (A(r)(Cl)) should be increased so that the implied range was related to terrestrial variability in 1999 (Coplen, T. B. Atomic weights of the elements 1999 (IUPAC Technical Report), Pure Appl. Chem.2001, 73(4), 667-683; and then, it emphasized that the standard atomic weights of ten elements including chlorine were not constants of nature but depend upon the physical, chemical, and nuclear history of the materials in 2009 (Wieser, M. E.; Coplen, T. B. Pure Appl. Chem.2011, 83(2), 359-396). According to the agreement by CIAAW that an atomic weight could be defined for one specified sample of terrestrial origin (Wieser, M. E.; Coplen, T. B. Pure Appl. Chem.2011, 83(2), 359-396), the absolute isotope ratios and atomic weight of chlorine in standard reference materials (NIST 975, NIST 975a, ISL 354) were accurately determined using the high-precision positive thermal ionization mass spectrometer (PTIMS)-Cs(2)Cl(+)-graphite method. After eliminating the weighing error caused from evaporation by designing a special weighing container and accurately determining the chlorine contents in two highly enriched Na(37)Cl and Na(35)Cl salts by the current constant coulometric titration, one series of gravimetric synthetic mixtures prepared from two highly enriched Na(37)Cl and Na(35)Cl salts was used to calibrate two thermal ionization mass spectrometers in two individual laboratories. The correction factors (i.e., K(37/35) = R(37/35meas)/R(37/35calc)) were obtained from five cycles of iterative calculations on the basis of calculated and determined R((37)Cl/(35)Cl) values in gravimetric synthetic mixtures. The absolute R((37)Cl/(35)Cl) ratios for NIST SRM 975, NIST 975a, and ISL 354 by the precise calibrated isotopic composition measurements are 0.319876 ± 0.000067, 0.319768 ± 0.000187, and 0.319549 ± 0.000044, respectively. As a result, the atomic weights of chlorine in NIST 975, NIST 975a, and ISL 354 are derived as 35.45284(8), 35.45272(21), and 35.45252(2) individually, which are consistent with the issued values of 35.453(2) by IUPAC in 1999.

Isotopic compositions of chlorine in brine and saline minerals

ConclusionThe above results indicate that37Cl/35 C1 ratios in saline minerals are higher than those in brine due to chlorine isotopic fractionation during evaporation.37Cl/35 C1 ratios of salt lakes brine reflect the change in hydrochemical condition. The chlorine isotopic composition of saline mineral is associated with environment. Therefore, chlorine isotope may be used to trace evolution of salt lakes and the environment.

Effect of microstructure of graphite on the nonreductive thermal ion emission in thermal ionization mass spectrometry.

The emission behavior of polyatomic ions in the ionization source of thermal ionization mass spectrometry (TIMS) was investigated. The results suggest that the presence of a graphite promoter plays a key role for the formation and stable emission of polyatomic ions, such as M(2)X(+), M(2)BO(2)(+), Cs(2)NO(2)(+), and Cs(2)CNO(+). Our data further implied that the intensity of M(2)X(+) and M(2)BO(2)(+) increases and the emission temperature decreases with increasing cationic and anionic radius. During the boron isotopic measurement using the Cs(2)BO(2)(+)-graphite-PTIMS method, the isobaric interference ion Cs(2)CNO(+) cannot be transformed from nitrate or organic compounds containing an amide group but can be induced by the existence of trace amounts of boron because of its special electron-deficiency property (B(3+)). Characterization on the planar crystalline structure of various graphite samples with SEM, TEM, and Raman spectroscopy confirmed the relationship of the emission capacity of polyatomic ions and the crystal microstructure of graphite and provides direct evidence that graphite with a perfect parallel and equidistant layer orientation shows a beneficial effect on the emission of polyatomic ions in TIMS. The mechanism study on the formation of polyatomic ions opens the possibility to establish high precision methods for isotopic composition analysis of more nonmetal elements with the TIMS technique.

Investigation of characteristics of non-reductive thermal ion emission of various graphites in thermal ionization mass spectrometry

The characteristics of non-reductive thermal ion emission in thermal ionization mass spectrometry for six kinds of graphite with different origins, purity and crystal structure and one high pure carbon powder are studied. The results show that the efficacy of non-reductive thermal ion emission of graphite is weakly related to the purity and particle size of graphite while dependent on the crystal microstructure of graphite. Graphite with a perfect crystal structure has a higher efficiency of non-reductive thermal ion emission.

Correlation between δ 18 O, Sr/Ca and Mg/Ca of coral Acropora and seawater temperature from coral culture experiments

To be used as proxies of seawater surface temperature (SST), the δ18Oc values and Sr/Ca and Mg/Ca ratios of scleractinian coral skeletons must be verified by coral culture experiments in the laboratory. This paper describes a coral culture experiment that was conducted at several seawater temperatures T (21–28°C) using a tandem aquarium system and the new method for depositing coral skeletons grown under controlled conditions. The δ18Oc values and the Sr/Ca and Mg/Ca ratios of the cultured coral were measured. We concluded that the δ18Oc values and Sr/Ca and Mg/Ca ratios of the cultured coral are clearly correlated with T. The linear regression curve is δ18Oc(‰)=−0.1427×T(°C)−0.1495 (n=18, r=0.955, p<0.0001), and the slope of −0.1427‰/°C is at the low end of the range of published values (−0.13- −0.29‰/°C). The Sr/Ca ratio decreases with increasing T, whereas the Mg/Ca ratio increases with increasing T, indicating a negative correlation between Sr/Ca and Mg/Ca. Their linear regression curves are Sr/Ca(mmol/mol)=−0.04156×T+10.59 (n=15, r=0.789, p<0.005) and Mg/Ca (mmol/mol)=0.04974×T+2.339 (n=17, r=0.457, p<0.05), respectively, which demonstrate that when Mg/Ca and Sr/Ca are increased by one unit, T increases by 5.19°C and decreases by 15.62°C, respectively. These variations are significantly lower than published values.

Effective elimination of organic matter interference in boron isotopic analysis by thermal ionization mass spectrometry of coral/foraminifera: micro‐sublimation technology combined with ion exchange

In order to better estimate the effectiveness of micro-sublimation technology on the elimination of organic matter interference during boron isotopic analysis, a series of improved experiments was carried out using simple apparatus. Recovery rates after micro-sublimation were measured for boric acid solutions with different B contents or different B/organic matter ratios. The improved micro-sublimation procedure combined with ion-exchange technology was then used to test natural samples (coral and foraminifera) for the separation of boron. Our results show that the time taken for 100% recovery of different amounts of B differed and that the proportions of B/organic matter within the natural organic matter have little effect on the relationship between the recovery rates of B and the micro-sublimation times. The experiments further confirm that the organic matter does indeed have an effect on boron isotope analyses by positive thermal ionization mass spectrometry and that the use of micro-sublimation can effectively remove interferences from the organic matter during boron isotopic analysis.

Boron isotopic fractionation and trace element incorporation in various species of modern corals in Sanya Bay, South China Sea

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.

Emission mechanism of polyatomic ions Cs2Cl+ and Cs2BO2(+) in thermal ionization mass spectrometry with various carbon materials.

The emission behavior of polyatomic ions Cs(2)Cl(+) and Cs(2)BO(2)(+) in the presence of various carbon materials (Graphite, Carbon, SWNTs, and Fullerenes) in the ionization source of thermal ionization mass spectrometry (TIMS) has been investigated. The emission capacity of various carbon materials are remarkably different as evidenced by the obvious discrepancy in signal intensity of polyatomic ions and accuracy/precision of boron and chlorine isotopic composition determined using Cs(2)Cl(+)-graphite-PTIMS/Cs(2)BO(2)(+)-graphite-PTIMS methods. Combined with morphology and microstructure properties of four selected carbon materials, it could be concluded that the emission behavior of the polyatomic ions strongly depends on the microstructure of the carbon materials used. A surface-induced collision mechanism for formation of such kinds of polyatomic ions in the ionization source of TIMS has been proposed based on the optimized configuration of Cs(2)BO(2)(+) and Cs(2)Cl(+) ions in the gas phase using a molecular dynamics method. The combination of the geometry of the selected carbon materials with the configuration of two polyatomic ions explains the structure effect of carbon materials on the emission behavior of polyatomic ions, where graphite samples with perfect parallels and equidistant layers ensure the capacity of emission to the maximum extent, and fullerenes worsen the emission of polyatomic ions by blocking their pathway.