Intercomparison of Boron Isotope and Concentration Measurements. Part I: Selection, Preparation and Homogeneity Tests of the Intercomparison Materials

In 1999 the Istituto di Geoscienze e Georisorse (IGG), with the support of the International Atomic Energy Agency (IAEA), undertook the collection, preparation and distribution of eight geological materials intended for a blind interlaboratory comparison of measurements of boron isotopic composition and concentration. The materials came from Italian sources and consist of three natural waters (Mediterranean seawater and two groundwaters) and five rocks and minerals (tourmaline, basalt, obsidian, limestone and clay). The solid materials were crushed, milled and mixed, in preparation for distribution. Extensive assays performed at the IGG on these materials demonstrated that their boron isotopic and chemical compositions are homogeneous.
Additional homogeneity tests were carried out on solid material fragments at the GeoForschungsZentrum Potsdam, with the specific objective of investigating the suitability of some of them for the calibration in situ of micro-analytical techniques. Two materials, B4 (tourmaline) and B6 (obsidian), proved to be isotopically homogeneous and may become excellent references for in situ microanalyses of boron isotopes.
The materials described here were used as the basis of a major laboratory intercomparison study and are now available for further distribution from either the IAEA (solid materials) or the IGG (waters).     

Accurate and High‐Precision Determination of Boron Isotopic Ratios at Low Concentration by MC‐ICP‐MS (Neptune)

We report an approach for the accurate and reproducible measurement of boron isotope ratios in natural waters using an MC‐ICP‐MS (Neptune) after wet chemistry sample purification. The sample matrix can induce a drastic shift in the isotopic ratio by changing the mass bias. It is shown that, if no purification is carried out, the direct measurement of a seawater diluted one hundred times will induce an offset of ?7‰ in the isotopic ratio, and that, for the same concentration, the greater the atomic mass of the matrix element, the greater the bias induced. Whatever the sample, it is thus necessary to remove the matrix. We propose a method adapted to water samples allowing purification of 100 ng of boron with a direct recovery of boron in 2 ml of 3% v/v HNO₃, which was our working solution. Boron from the International Atomic Energy Agency IAEA‐B1 seawater reference material and from the two groundwater reference materials IAEA‐B2 and IAEA‐B3, was chemically purified, as well as boron from the certified reference material NIST SRM 951 as a test. The reproducibility of the whole procedure (wet chemistry and MC‐ICP‐MS measurement) was ± 0.4‰ (2s). Accuracy was verified by comparison with positive‐TIMS values and with recommended values. Seawater, being homogeneous for boron isotope ratios, is presently the only natural water material that is commonly analysed for testing accuracy worldwide. We propose that the three IAEA natural waters could be used as reference samples for boron isotopes, allowing a better knowledge of their isotopic ratios, thus contributing to the certification of methods and improving the quality of the boron isotopic ratio measurements for all laboratories.     

硼及其同位素对水体污染物的示踪研究

硼的易溶性和硼化合物的广泛使用 ,以及污水处理过程中除硼的困难 ,最终导致地表地下水体富集硼及有关污染物。海滨地下水受到海水入侵 ,硼含量及 ρ(B) / ρ(Cl)比值发生明显变化。混合、吸附、水岩等作用使得硼同位素发生分馏 ,显著区别于区域背景值。因此 ,结合其它同位素、水化学等信息 ,硼及其同位素作为良好示踪剂为研究水圈中物质的地球化学循环过程提供了新的手段。文中总结了部分天然水体的硼含量和硼同位素组成特征 ,综述了近年来用硼同位素示踪水体的污染物来源、程度和范围等方面新的研究成果。     

Boron Isotopic Analysis of Proposed Borosilicate Mineral Reference Samples

This brief contribution presents new boron isotopic data for a set of proposed borosilicate reference minerals, most of which are described in the companion paper by Dyar et al.²⁰⁰¹. The results for a variety of minerals (tourmalines, danburite, prismatine, serendibite, ferroaxinite and a Li mica) show that it is generally possible to reproduce the ¹¹ B/¹⁰ B ratio within ± 0.5 per mil with replicate chemistry and mass spectrometry over long time spans. Because the accuracy of boron isotopic analysis is commonly determined by reference to secondary standards, it is suggested that some of the samples used in this study be adopted for interlaboratory comparisons and for quality control on boron isotopic analyses produced by a variety of analytical methods.     

Production and Certification of a Unique Set of Isotope and Delta Reference Materials for Boron Isotope Determination in Geochemical,Environmental and Industrial Materials

Isotopic reference materials are essential to enable reliable and comparable isotope data. In the case of boron only a very limited number of such materials is available, thus preventing adequate quality control of measurement results and validation of analytical procedures. To address this situation a unique set of two boron isotope reference materials (ERM‐AE102a and ‐AE104a) and three offset δ¹¹B reference materials (ERM‐AE120, ‐AE121 and ‐AE122) were produced and certified. The present article describes the production and certification procedure in detail. The isotopic composition of all the materials was adjusted by mixing boron parent solutions enriched in ¹⁰B or ¹¹B with a boron parent solution having a natural isotopic composition under full gravimetric control. All parent solutions were analysed for their boron concentration as well as their boron isotopic composition by thermal ionisation mass spectrometry (TIMS) using isotope dilution as the calibration technique. For all five reference materials the isotopic composition obtained on the basis of the gravimetric data agreed very well with the isotopic composition obtained from different TIMS techniques. Stability and homogeneity studies that were performed showed no significant influence on the isotopic composition or on the related uncertainties. The three reference materials ERM‐AE120, ERM‐AE121 and ERM‐AE122 are the first reference materials with natural δ¹¹B values not equal to 0‰. The certified δ¹¹B values are ?20.2‰ for ERM‐AE120, 19.9‰ for ERM‐AE121 and 39.7‰ for ERM‐AE122, each with an expanded uncertainty (k = 2) of 0.6‰. These materials were produced to cover about three‐quarters of the known natural boron isotope variation. The ¹⁰B enriched isotope reference materials ERM‐AE102a and ERM‐AE104a were produced for industrial applications utilising ¹⁰B for neutron shielding purposes. The certified ¹⁰B isotope abundances are 0.29995 for ERM‐AE102a and 0.31488 for ERM‐AE104a with expanded uncertainties (k = 2) of 0.00027 and 0.00028, respectively. Together with the formerly certified ERM‐AE101 and ERM‐AE103 a unique set of four isotope reference materials and three offset δ¹¹B reference materials for boron isotope determination are now available from European Reference Materials.     

NIST RM 8301 Boron Isotopes in Marine Carbonate (Simulated Coral and Foraminifera Solutions): Inter‐laboratory δ11B and Trace Element Ratio Value Assignment

The boron isotopic ratio of ¹¹B/¹⁰B (δ¹¹B_SRM951) 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 δ¹¹B_SRM951 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 δ¹¹B_SRM951 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.     

Instrumental Neutron Activation Analysis of Estuarine Sediment as a Proposed Reference Material for Environmental Studies

The International Atomic Energy Agency (IAEA) Marine Environmental Studies Laboratory (MEL) organised an intercomparison exercise, through its Analytical Quality Control Services (AQCS), for the determination of trace elements in estuarine sediment IAEA-405, well suited for the characterisation of sediments. The instrumental neutron activation analysis technique (INAA) was developed using a 27 kW low power research reactor. Forty elements in the sediment were determined with a measurement precision varying from 1.8% to 12.3%. IAEA reference materials SL-1 and SD-M-2/TM were analysed throughout this work as quality assurance samples.     

Barium Isotopic Compositions of Geological Reference Materials

The interest in variations of barium (Ba) stable isotope amount ratios in low and high temperature environments has increased over the past several years. Characterisation of Ba isotope ratios of widely available reference materials is now required to validate analytical procedures and to allow comparison of data obtained by different laboratories. We present new Ba isotope amount ratio data for twelve geological reference materials with silicate (AGV‐1, G‐2, BHVO‐1, QLO‐1, BIR‐1, JG‐1a, JB‐1a, JR‐1 and JA‐1), carbonate (IAEA‐CO‐9) and sulfate matrices (IAEA‐SO‐5 and IAEA‐SO‐6) relative to NIST SRM 3104a. In addition, two artificially fractionated in‐house reference materials BaBe12 and BaBe27 (δ^137/134Ba = ?1.161 ± 0.049‰ and ?0.616 ± 0.050‰, respectively) are used as quality control solutions for the negative δ‐range. Accuracy of our data was assessed by interlaboratory comparison between the University of Bern and the United States Geological Survey (USGS). Data were measured by MC‐ICP‐MS (Bern) and TIMS (USGS) using two different double spikes for mass bias correction (¹³⁰Ba–¹³⁵Ba and ¹³²Ba–¹³⁶Ba, respectively). MC‐ICP‐MS measurements were further tested for isobaric and non‐spectral matrix effects by a number of common matrix elements. The results are in excellent agreement and suggest data accuracy.     

Intercomparison of tritium and noble gases analyses, 3H/3He ages and derived parameters excess air and recharge temperature

Groundwater age dating with the tritium–helium (³H/³He) method has become a powerful tool for hydrogeologists. The uncertainty of the apparent ³H/³He age depends on the analytical precision of the ³H measurement and the uncertainty of the tritiogenic ³He component. The goal of this study, as part of the groundwater age-dating interlaboratory comparison exercise, was to quantify the analytical uncertainty of the ³H and noble gas measurements and to assess whether they meet the requirements for ³H/³He dating and noble gas paleotemperature reconstruction.Samples for the groundwater dating intercomparison exercise were collected on 1 February, 2012, from three previously studied wells in the Paris Basin (France). Fourteen laboratories participated in the intercomparison for tritium analyses and ten laboratories participated in the noble gas intercomparison. Not all laboratories analyzed samples from every borehole.The reproducibility of the tritium measurements was 13.5%. The reproducibility of the ³He/⁴He ratio and ⁴He, Ne, Ar, Kr and Xe concentrations was 1.4%, 1.8%, 1.5%, 2.2%, 2.9%, and 2.4% respectively.The uncertainty of the tritium and noble gas measurements results in a typical ³H/³He age precision of better than 2.5 years in this case. However, the measurement uncertainties for the noble gas concentrations are insufficient to distinguish the appropriate excess air model if the measured helium concentration is not included. While the analytical uncertainty introduces an unavoidable source of uncertainty in the ³H/³He apparent age estimate, other sources of uncertainty are often much greater and less well defined than the analytical uncertainty.     

硼同位素分馏的实验理论认识和矿床地球化学研究进展

硼是一种中等挥发性元素,具有¹¹B和¹⁰B两个稳定同位素。两个同位素间高达10%的相对质量差使其在地质过程中引起高达-70‰至+75‰的硼同位素变化。硼在自然界主要与氧键合形成三配位(BO₃)和四配位(BO₄)结构,因而¹¹B和¹⁰B间同位素分馏主要受控于三配体(BO₃)和四面体(BO₄)间配分。本文综述了低温和高温地质过程的硼同位素分馏的理论和实验研究进展。在溶液中B(OH)₃和${B(OH)^{-}_{4}}$间硼同位素分馏受pH和热力学p-T条件控制,实验和理论表征获得常温常压条件下的B(OH)₃和$B(OH)^{-}_{4}$间同位素分馏系数(α_3-4)变化范围为1.019 4至1.033 3。低温条件下矿物(如碳酸盐、黏土矿物(蒙脱石和伊利石)、针铁矿、水锰矿、硼酸盐)与溶液间硼同位素分馏行为除了受p-T-pH影响外,矿物表面吸附引起的分馏效应十分显著。在中高温过程(蒙脱石伊利石化、富硼电气石和白云母矿物与热液流体,以及硅酸盐熔体与流体)中硼同位素分馏行为受到硼配位构型、化学成分以及物理化学条件的控制。随着硼同位素分馏机理研究的深入以及越来越完善的地质储库硼同位素端员特征表征,硼同位素地球化学指标可以灵敏示踪成矿物质来源、探究成矿作用与成因模式和重建成矿过程物理化学条件。目前矿床硼同位素地球化学研究的难点在于实现不同赋存相(如流体、矿物和熔体)中硼配位键合结构和硼同位素组成的精细化表征。     

陆相断陷盆地的构造层序地层分析

海洋浮游有孔虫中的硼同位素能够反映海水酸碱度的变化,从而为重建大气二氧化碳浓度的变化提供了一种新的手段,有望提供目前极地冰心记录所无法企及的百万年甚至千万年时间尺度上的大气二氧化碳浓度的变化。最近,海洋浮游有孔虫硼同位素的研究在实验分析技术(负热电离质谱法)、实验室偏差、同位素分馏系数、海水硼同位素长期变化以及各种次要因素等方面都取得了长足的进步,尤其是全蒸发负热电离质谱法的建立使硼同位素分析的样品需求量降到纳克级以下。不过,尽管海洋浮游有孔虫中的硼同位素作为大气二氧化碳浓度的替代指标很具有潜力,但还需要进行更加深入地研究。     

IAGC and IAEA Interlaboratory Comparisons of Geothermal Water Chemistry: The Propagation of Uncertainty in the Reservoir pH Calculation

A statistical evaluation of the results of geochemical analyses of geothermal waters during interlaboratory comparison programmes of the International Association of Geochemistry and Cosmochemistry (IAGC) and International Atomic Energy Agency (IAEA) was performed to estimate the uncertainty of measurement of pH, electrical conductivity, Na⁺, K⁺, Ca2⁺, Mg²⁺, Li⁺, Cl^?, HCO₃^?, SO₄^2?, SiO₂ and B. The uncertainty of measurement was found to increase exponentially with decrease in value (concentration) for all the parameters except for pH, electrical conductivity and SiO₂ and was of the same order of magnitude as the concentrations for values of less than 1 μ ml^?1. There was an overall uncertainty of ± 2.5% in the measurement of pH and ± 30% in SiO₂. For all the other chemical species the uncertainty data were modelled by exponential curves. The sample IAEA14 was prepared by dissolving commercial reagents (i.e., represents a solution of known composition). Thus, the calculated values are considered to be the conventional true values for each chemical parameter. The difference between the measured mean of the data submitted by participating laboratories and the conventional true value for each parameter (i.e., bias of submitted measurements) for the species Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl^? and SO₄^2? was ‐3.5, ‐1.1, ‐13.3, ‐53.6, ‐12.6 and ‐86.6%, respectively. The observed bias was of the same order of magnitude as statistical fluctuations (1s) for Na⁺ and K⁺, but significantly higher for Ca²⁺, Mg²⁺, Cl^? and SO₄^2?. Two methods, uncertainty interval and GUM (“guide to the expression of uncertainty of measurement”) were used to propagate uncertainty in the pH calculation of geothermal reservoir fluid. The application of the methods is illustrated by considering the IAEA10 and IAEA11 samples analysed in the interlaboratory comparisons as separated geothermal waters at atmospheric pressure.     

硼及硼同位素地球化学在地质研究中的应用

总结了硼及硼同位素的地球化学特征：（１）硼是易溶元素,主要赋存在地球表层,尤其是海水、海相沉积物及海水交代岩石中。其同位素组成δ１１Ｂ值按顺序变化,封闭盐湖卤水（＞４０‰）＞海水（３９５‰）＞海相硼矿物（１８２‰～３１７３‰）＞海相沉积物（１３９‰～２５２‰）＞海水交代岩石（４５１‰～１０８５‰）。大陆水及陆相沉积物硼含量及硼同位素组成变化极大,并多以负值为主。海陆过渡构造带则具有过渡的硼丰度值和硼同位素组成。（２）１１Ｂ较１０Ｂ具有更活跃的地球化学性质,因此在水岩作用中具有明显的同位素交换。硅化交代作用中,岩石被硅化交代,释放硼,并优先释放重硼,同位素组成变轻;在脱硅反应中,岩石释放硅吸收硼,并优先吸收重硼,同位素组成变重。在封闭体系中,水溶液淋滤岩石中部分的硼,即可大量富集,并富集１１Ｂ;在开放体系中,岩石硼被大量淋滤流失,δ１１Ｂ值明显降低。由于水岩作用的结果,从新鲜海底玄武岩到正常海水,硼同位素值从－２９５‰到３９５‰逐渐升高。（３）变质脱水反应中硼被大量排出,并优先排出重硼同位素,进入流体相,因此随着变质程度由低到高,岩石中硼含量及同位素组成δ１１Ｂ值由高变低。（４）在成矿研究中?     

Calcium Isotopic Compositions of Sixteen USGS Reference Materials

Calcium isotopic compositions of sixteen Ca‐bearing USGS geological reference materials including igneous and sedimentary rocks are reported. Calcium isotopic compositions were determined in two laboratories (GPMR, State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan; and CIG, Centre for Isotope Geochemistry, University of California, Berkeley) using the ⁴²Ca‐⁴⁸Ca double‐spike technique by thermal ionisation mass spectrometry. As opposed to common cation exchange resin, a micro‐column filled with Ca‐selective resin (DGA resin) was used in order to achieve high recovery (> 96%) and efficient separation of Ca from the sample matrix. The intermediate measurement precision was evaluated at 0.14‰ (2s) for δ^44/40Ca_SRM915a at GPMR, based on replicate measurements of pure Ca reference material NIST SRM 915a, NIST SRM 915b and seawater. Overall, the measurement uncertainties in both laboratories were better than 0.15‰ at the 2s level. Result validation was carried out for all available data sets. The Ca isotopic compositions of USGS reference materials are not only in agreement between GPMR and CIG, but also in agreement with previously published data within quoted uncertainties. The comprehensive data set reported in this study serves as a reference for both quality assurance and interlaboratory comparison of high precision Ca isotopic study.     

Summary findings of the fourth international radiocarbon intercomparison (FIRI)(1998–2001)

Interlaboratory comparisons have been widely used in applied radiocarbon science. These are an important part of ongoing quality assurance (QA) programmes, which are vital to the appropriate interpretation of the evidence provided by the ¹⁴C record in Quaternary applications (including climate change and environmental reconstruction). International comparisons of laboratory performance are an essential component of the quality assurance process in radiocarbon dating. If the user community is to have confidence in radiocarbon results, it needs to be assured that laboratories world wide are producing measurements that are reliable and in accordance with ‘good practice’. The findings from the most recent (completed in 2001) and extensive (more than 90 participating laboratories) radiocarbon intercomparison (FIRI) are reported here. This study was designed (i) to assess comparability, or otherwise, of the results from different laboratories and (ii) to quantify the extent and possible causes of any interlaboratory variation. The results demonstrate that there are no significant differences amongst the main measurement techniques (gas proportional counting, liquid scintillation counting and accelerator mass spectrometry (AMS)) but there is evidence of small laboratory offsets relative to known age samples for some laboratories. There is also evidence in some cases of underestimation of measurement precision. Approximately 10% of all results were classified as extreme (outliers) and these results were generated by 14% of the laboratories. Overall, the evidence supports the fact that radiocarbon laboratories are generally accurate and precise but that, notwithstanding internal QA procedures, some problems still occur, which can best be detected by participation in independent intercomparisons such as FIRI, where the results allow individual laboratories to assess their performance and to take remedial measures where necessary. The results from FIRI are significant in that they show a broad measure of agreement between measurements made in different laboratories on a wide range of materials and they also demonstrate no statistically significant difference between measurements made by radiometric or AMS techniques. Copyright © 2002 John Wiley & Sons, Ltd.     

Boron Determination in Twenty One Silicate Rock Reference Materials by Isotope Dilution ICP-MS

The concentration of boron was determined in twenty one geochemical reference materials (silicate rocks) by isotope dilution inductively coupled plasma-mass spectrometry. Boron was extracted from the rocks using HF digestion, suppressing boron volatilisation through boron-mannitol complexation. Sample solutions, in a diluted HCl matrix, were analysed by ICP-MS without any separation of boron from the matrix elements. The results obtained were in agreement with the literature data and indicate that using the described procedure, trace amounts of boron can be very easily determined in complex matrices with rapidity and precision. With the instrumentation and reagents used in this study, this procedure can be used for the determination of 0.5 μg g⁻¹ boron in a 15 0 mg silicate rock sample. Replicate analyses of the twenty one geochemical reference materials (GRM), ranging in boron concentration from 1.35 to 15 7 μg g⁻¹, yielded precisions (relative standard deviation) varying between 0.9 and 9.8%.     

Sub‐Permil Interlaboratory Consistency for Solution‐Based Boron Isotope Analyses on Marine Carbonates

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.     

有孔虫中硼的分离及其同位素组成测定的初步研究

本文初步建立了一种用硼特效树脂和阴、阳混和离子交换树脂相结合进行有孔虫中硼的分离和同位素测定的方法。该方法适用低硼含量 (纳克级 )的微体古生物中的硼的分离和同位素测定 ,分离过程不产生同位素分馏 ,满足了正热电离质谱法测定硼同位素的要求。     

Molybdenum Mass Fractions and Isotopic Compositions of International Geological Reference Materials

The double‐spike method with multi‐collector inductively coupled plasma‐mass spectrometry was used to measure the Mo mass fractions and isotopic compositions of a set of geological reference materials including the mineral molybdenite, seawater, coral, as well as igneous and sedimentary rocks. The long‐term reproducibility of the Mo isotopic measurements, based on two‐year analyses of NIST SRM 3134 reference solutions and seawater samples, was ≤ 0.07‰ (two standard deviations, 2s, n = 167) for δ^98/95Mo. Accuracy was evaluated by analyses of Atlantic seawater, which yielded a mean δ^98/95Mo of 2.03 ± 0.06‰ (2s, n = 30, relative to NIST SRM 3134 = 0‰) and mass fraction of 0.0104 ± 0.0006 μg g^?1 (2s, n = 30), which is indistinguishable from seawater samples taken world‐wide and measured in other laboratories. The comprehensive data set presented in this study serves as a reference for quality assurance and interlaboratory comparison of high‐precision Mo mass fractions and isotopic compositions.     

硼掺入Mg(OH)2形式及机理

采用pH=9.5～13.0的无镁合成海水进行了Mg(OH)₂沉积时B的掺入实验,证实了B(OH)₃优先掺入Mg(OH)₂的硼同位素分馏特征。在所研究的pH范围内,Mg(OH)₂沉积的δ11B均高于无镁合成海水的δ11B,它们之间的硼同位素分馏系数α沉积/海水为1.017 7~1.056 9,平均为1.032 9±0.009 32(SD)。硼同位素的这种分馏特征与无机碳酸盐沉积时的硼同位素分馏存在明显差异,表明B掺入Mg(OH)₂沉积具有不同的机理。B在Mg(OH)₂沉积上的吸附以及B(OH)₃与Mg(OH)₂的沉积反应同时存在并相互制约是其主要特征,造成了B(OH)₃优先掺入的总结果,这并不意味B(OH)₃在掺入的分数上占有优势,相反在所研究的pH范围内,Mg(OH)₂沉积的B(OH)₃/B(OH)-₄大都小于1,因此吸附作用决定了Mg(OH)₂沉积中B浓度的变化特征。采用这种模型能很好地解释沉积中B浓度、B在沉积和海水间的分配系数Kd以及沉积与海水间的分馏系数α随海水pH的变化特征。石珊瑚中Mg(OH)₂的普遍存在和Mg(OH)₂中B(OH)₃的优先掺入也许会影响珊瑚的硼同位素组成与海水pH的定量对应关系,给δ11B作为古海水pH的代用指标带来一定的不确定性。