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1.
The Istituto di Geoscienze e Georisorse (IGG), on behalf and with the support of the International Atomic Energy Agency (IAEA), prepared eight geological materials (three natural waters and five rocks and minerals), intended for a blind interlaboratory comparison of measurements of boron isotopic composition and concentration. The materials were distributed to twenty seven laboratories - virtually all those performing geochemical boron isotope analyses in the world -which agreed to participate in the intercomparison exercise. Only fifteen laboratories, however, ultimately submitted the isotopic and/or concentration results they obtained on the intercomparison materials. The results demonstrate that interlaboratory reproducibility is not well reflected by the precision values reported by the individual laboratories and this observation holds true for both boron concentration and isotopic composition. The reasons for the discrepancies include fractionations due to the chemical matrix of materials, relative shift of the zero position on the δ11B scale and a lack of well characterized materials for calibrating absolute boron content measurements. The intercomparison materials are now available at the IAEA (solid materials) and IGG (waters) for future distribution.  相似文献   

2.
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.  相似文献   

3.
Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ11B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ11B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO2 and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).  相似文献   

4.
硼及其同位素对水体污染物的示踪研究   总被引：2，自引：0，他引：2  
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。  相似文献   

5.
We report in this paper a series of experiments whose purpose is to test the long held idea of boron volatility when neutral to acidic solutions containing traces of boron are evaporated. Boron recoveries have been measured precisely by isotopic dilution and boron isotopic ratios have also been determined. Most of the evaporations have been conducted at 60-65 °C. It was found that no loss of boric acid occurs when c. 1 μg of B is evaporated in water, HCl, HF and acetone solutions. At the same time, we did not observe any associated B isotopic fractionation. In contrast to previous studies on B volatilisation, it was not found necessary to use mannitol to prevent B losses during the evaporation of acidic solutions. Important losses of boron were observed from solutions of methanol, ethanol and organic-rich natural solutions. In the presence of methanol and ethanol, a volatile methyl (or ethyl) borate is likely to be formed. In contrast to these studies, we show that boron is highly volatile when the dried residues of an evaporation are heated further. The sublimation of boron that then occurs can be moderated by the use of mannitol, but a slight increase of the temperature allows B volatilisation. Despite the substantial losses of B by sublimation, no B isotopic fractionation was observed at 60-65 C. The property of boron to sublime was used to separate B from an organic matrix. A miniaturized sublimation apparatus, comprising a 5 ml Teflon beaker, and the associated microsublimation technique are described. The 100% boron recovery and the absence of B isotopic fractionation make this method suitable for extracting B from organic-rich samples.  相似文献   

6.
对比分析了太平洋(Site 806)、大西洋(Site 664)和加勒比海地区(Site 999)末次冰期最盛期和全新世钻孔顶部不同尺寸大小的浮游有孔虫Globigerinoides sacculifer(500～600μm和300～355μm)和Globi-gerinoides ruber(300～355μm和250～300μm)的硼同位素组分变化,发现个体相对较小的有孔虫样品由于受到样品量以及样品前处理过程的影响,其硼同位素在末次冰期最盛期出现异常,浮游有孔虫硼同位素分析,尤其是冰期-间冰期时间尺度上的硼同位素分析,适合用个体相对较大的有孔虫。末次冰期最盛期太平洋和加勒比海地区溶解作用可能加强,其G.sacculifer的硼同位素偏低,但G.ruber的硼同位素不受溶解作用的影响,能够反映末次冰期海水pH值的变化。三个钻孔末次冰期最盛期G.ruber的硼同位素比全新世的硼同位素平均高(1.3±1.2)‰(2s.e.),与理论预测值1.6‰一致。  相似文献   

7.
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.  相似文献   

8.
硼及硼同位素地球化学在地质研究中的应用   总被引：17，自引：0，他引：17  
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?  相似文献   

9.
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。  相似文献   

10.
Tourmaline geochemical and boron(B)isotopic compositions in two-mica granites(TMG),tourmaline-bearing leucogranites(Tou-LG),tourmalites and metapelites from the Gyirong-Malashan areas of the Himalayan orogen provide evidence for country rock assimilation during the intrusion of Himalayan leucogranite.The schorls in Gyirong leucogranitic plutons show low contents of MgO(0.238%-1.160%)and δ11B values(-12.1‰--11.2‰),while dravites gathered in the contact zone between the leucogranitic veins and metapelites show high contents of MgO(4.815%-6.755%)and δ11B values(-10.7‰--9.3‰).This geochemical and isotopic variation of tourmalines can also be identified in the Malashan gneiss dome.As a result,three types of tourmaline were identified in the Himalayan orogen:(1)Tou-Ⅰ in the TMG and Tou-LG,which is the most common tourmaline type of schorl;(2)Tou-Ⅱ(dravite and high-Mg schorl)in the Tou-LG and tourmalite at the margins of the leucogranite;and(3)Tou-Ⅲ(mainly dravite,with minor high-Mg schorl)in metapelites of the High Himalayan Crystalline Sequence.The lenses and veins of Tou-LG may have experienced metasomatism and assimilation as a result of interaction with the High Himalayan Crystalline Sequence metasedimentary country rocks,which can be traced by the geochemical and isotopic characteristics of the tourmaline therein.  相似文献   

11.
 In order to investigate the application of the elemental abundance of boron and its stable isotopes, 10B and 11B, for tracing anthropogenic contamination of variably mineralized thermal and mineral waters, B concentrations and isotopic compositions (δ11B) were determined for sample pairs collected during surveys in 1984–1986 and 1995 from representative wells discharging water from deep crustal reservoirs within the central European crystalline basement and sedimentary cover (SW Germany and N Switzerland). The data presented show that natural temporal variations in the total B contents of thermal and mineral waters are a common feature, which makes it difficult to recognize admixture of extraneous (anthropogenic) components from B concentrations alone. Delineation of the natural versus anthropogenic origin of solutes and quantification of the relative mixing proportions may thus benefit considerably from the utilization of boron isotopes as an additional parameter. Hypothetical mixing scenarios involving various thermal waters and municipal wastewater effluents from the study area, with the latter being characterized by conspicuously light boron isotopic compositions, reveal that, in certain cases, δ11B values provide a superior diagnostic tool for detection of objectionable substances derived from the discharge of man-made boron products. Received: 14 September 1999 · Accepted: 8 March 2000  相似文献   

12.
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(α3-4)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。  相似文献   

13.
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。  相似文献   

14.
The importance of obsidian from the northern Patagonian source at Las Cargas is reflected in its early use (∼8000 years B.P.) and extensive geographic diffusion but is nonetheless surprising in light of the source's high altitude (located in the Andes Cordillera), which makes it both difficult to access under ideal conditions and inaccessible for much of the year. Prehistoric use of the Las Cargas source can inform us about mobility, subsistence choices, economics of stone consumption, trade, and territoriality. Here we present the results of various lines of evidence (surface survey, X‐ray fluorescence and instrumental neutron activation analyses, artifact morphometry, and obsidian hydration dating) used to characterize obsidian from Las Cargas and its prehistoric use during the Holocene. Results indicate that Las Cargas obsidian occurs at the source as blocks and nodules, which are chemically homogeneous and of variable quality. Use of the source was nearly continuous through time, and the primary knapping activities performed there were the production of blanks and preparation of cores.  相似文献   

15.
Boron Isotopic Analysis of Proposed Borosilicate Mineral Reference Samples   总被引：2，自引：0，他引：2  
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.  相似文献   

16.
硼同位素在矿床学中的应用研究   总被引：2，自引：0，他引：2       下载免费PDF全文
硼在自然界有两种稳定同位素11B和10B,常采用δ(11B)/10-3来表示不同地质体的同位素组成。由于硼同位素在不同地质体中的分馏作用大,在较大温度范围内岩浆-热液流体中的高活动性和化学性质稳定等方面的优势,使硼同位素在地球科学研究中的作用越来越广泛。控制硼同位素分馏的主要因素是硼源。一般情况下,非海相的硼酸盐矿物和与之相关的电气石的δ(11B)值为负值,而在某些盐湖卤水和与海相环境有关的硼酸盐矿物的δ(11B)值则为正值。目前,硼同位素示踪主要应用于块状硫化物矿床、与花岗岩有关的热液矿床以及盐湖矿床的研究。随着硼同位素分馏机制及其在不同环境地质样品中分布特征的深入研究,硼同位素在解决矿床的成矿物质来源、矿床成因和成矿作用等方面将发挥更大的作用。  相似文献   

17.
The isotopic composition of dissolved boron, in combination with the elemental concentrations of B, Cl and salinities in freshwater-seawater mixed samples taken from the estuary of the Changjiang River, the largest one in China, was investigated in detail in this study. Brackish water and seawater samples from the estuary of the Changjiang River were collected during low water season in November, 1998. Boron isotopic compositions were determined by the Cs2BO^＋2-graphite technique with a analytical uncertainty of 0.2‰ for NIST SRM 951 and an average analytical uncertainty of 0.8‰ for the samples. The isotopic compositions of boron, expressed in δ^11B, and boron concentrations in the Changjiang River at Nanjing and seawater from the open marine East Sea, China, are characterized by δ^11B values of -5.4‰ and 40.0‰, as well as 0.0272 and 4.43 mg B/L, respectively. Well-defined correlations between δ^11B values, B concentrations and Cl concentrations are interpreted in terms of binary mixing between fiver input water and East Sea seawater by a process of straightforward dilution. The offsets of δ^11B values are not related to the contents of clastic sediment and to the addition of boron. These relationships favor a conservative behavior of boron at the estuarine of the Changjiang River.  相似文献   

18.
《Chemical Geology》2002,182(2-4):323-334
An optimized procedure for the separation of boron from natural river samples and an improved mass spectrometry determination of boron isotopic ratio are presented. The chemical procedure, based on the use of the boron-specific resin Amberlite IRA 743, is especially efficient in separating boron from natural organic matter-rich samples like river waters.The properties of Amberlite IRA 743 have been investigated. The two factors important in determining the boron affinity for the resin are: the pH value and the ionic strength of the solution from which B is to be extracted. A logarithmic relationship between B partition coefficients and pH values is found. High ionic strength significantly lowers the fixation of B onto the Amberlite resin.The knowledge of the factors controlling the affinity of the resin Amberlite IRA 743 for boron enables us to design a simple and miniaturized chemical separation procedure characterized by (i) three chromatographic steps using, respectively, 50, 10 and 3 μl of resin, (ii) no evaporation step between each column, and (iii) final separation of boron from residual organic matter by sublimation of boric acid at 75 °C.Boron isotopic ratios are measured using an improved cesium metaborate technique, with graphite and mannitol. Adequate loading conditions enable us to obtain typical signal intensities of 5×10−12 A for 250 ng of boron. No in-run isotopic fractionation is observed, the external reproducibility for standards processed through the entire chemical procedure, as well as for samples, corresponds to 0.35‰ (±2σ). According to this precision, a slight, but reproducible isotopic fractionation of 0.4‰ is observed for standards processed through the entire chemical procedure whose origin is discussed, but is still unclear.  相似文献   

19.
The wide boron isotopic variations occurring in natural waters mainly are derived from the 20‰ fractionation between dissolved boric acid and borate anions, associated with the preferential removal from the system of 11B depleted borate ions by adsorption and/or minerals formation. Typical adsorbants of boron dissolved in groundwater are clay minerals of the aquifer matrix. Boron (and strontium) isotopes were used in investigating two alluvial aquifers in Tuscany, where boron concentration is often above 1 mg L− 1 and may attain 8 mg L− 1. The isotopic results indicate that, in the first case (Cecina River basin), the boron contamination is anthropogenic and derives from past discharge into streams of boron-rich industrial wastes. In the second case (Cornia Plain), the dissolved boron is released by boron-rich clayey sediments of the aquifer matrix and has, therefore, a natural origin.  相似文献   

20.
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   

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