An optimized procedure for boron separation and mass spectrometry analysis for river samples

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.     

Hydrogen isotopic fractionation of petroleum hydrocarbons during vaporization: implications for assessing artificial and natural remediation of petroleum contamination

Compound-specific H isotope analysis has been used to monitor bioremediation of petroleum hydrocarbons. However, the success of this approach requires a full evaluation of the isotopic effects resulting from evaporation, because light petroleum hydrocarbons undergo both biodegradation and evaporation under natural conditions. The authors determined the H isotope fractionation of common volatile petroleum hydrocarbons, including the C₁₀–C₁₄ n-alkanes, MTBE (tert-butyl methyl ether), and BTEX (benzene, toluene, ethylbenzene, p-xylene and o-xylene) during progressive vaporization under simulated experimental conditions. A decrease in δD values for n-alkanes of up to 33.3‰ and up to 44.5‰ for BTEX compounds when 99% of these substances had evaporated was observed. The results also show that H isotope fractionation increases with n-alkane chain length. Such fractionation patterns are interpreted in terms of competition between the decreased intermolecular binding energy in D-enriched species, and the isotope effect due to the mass difference. In contrast to hydrocarbons, methanol and ethanol show H isotopic enrichment during vaporization, indicating that H-bonding, when present in organic molecules, plays a controlling role on the vapor pressure of different isotope species.     

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。     

直接熔融热电离质谱法测定硼硅玻璃中硼同位素比值

硼硅玻璃是目前压水堆应用最多的可燃毒物材料,产品中硼同位素组成的准确测定对燃耗预估及产品质量判定具有重要意义。文章基于直接熔融热电离质谱法,首先探讨了硅元素对硼酸中硼同位素测量结果的影响,结果表明:Si/B质量比小于9时,硅对NIST 951a硼酸标准物质测量结果无显著干扰,采用直接熔融热电离质谱法测定核电用硼硅玻璃中硼同位素比值具有可行性;随后,详细分析了Na/B摩尔比、甘露醇和石墨加入量3个参数对测试结果的影响,得到的最佳参数为Na/B摩尔比9、加入甘露醇及3μL石墨发射剂;最后,采用优化测试参数,对实际硼硅玻璃样品进行了测试,并以NIST 951a硼酸标准物质为外标对测量结果进行分馏校正,结果发现分馏校正后样品的不确定度来源主要是标准物质。研究成果可满足硼硅玻璃的燃耗预估及产品质量的快速判定需要。     

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。     

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。     

Boron isotopes geochemistry of the Changjiang basin rivers

We report analyses of B isotopic compositions in water and suspended particulate matter collected in the Changjiang and its main tributaries. We showed that four sources control the dissolved boron budget; namely atmospheric deposition, evaporite dissolution, anthropogenic inputs and silicate weathering. The contribution of silicate weathering to the dissolved B load ranges from 40% to 50% for the Changjiang main channel and from 45% to 88% for the main tributaries. The isotopic composition of dissolved boron derived from silicate weathering range from −3‰ up to +9‰ suggesting that isotopic fractionation occurs during silicate weathering. The boron isotopic composition of suspended particulate matter range from −11.4‰ to −6‰. Boron derived from silicate weathering is preferentially carried out by the dissolved load which accounts for 30-96% of the total boron. We show that the isotopic compositions of both the dissolved load and suspended particulate matter are controlled by the competition between boron leaching and boron uptake into secondary phases. The first process is characterized by a loss of boron relative to the bedrock without apparent isotopic fractionation whereas the last one is associated to a large isotopic fractionation which enriches the dissolved boron in heavy isotope.     

硼同位素在矿床学中的应用研究

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。     

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?     

Identification of the origin of salinization in groundwater using multivariate statistical analysis and geochemical modeling: a case study of Kaohsiung,Southwest Taiwan

The study of brine aquifers in southern Taiwan is highly complicated by hybrid geochemical reactions, which obscure important geochemical information. Using multivariate analysis on major and minor ion compositions normalized by Cl⁻ content, chemical constituents were combined into two principal components representing brine mixing and mineral precipitation. Comparing to multivariate analysis on the original data, this procedure reveals more geochemical information. It demonstrates that the brine groundwater of the region is primarily composed of highly evaporated seawater. The evaporation ratio is >70%; a point at which calcite, dolomite and gypsum precipitate. Oxygen and hydrogen isotopic compositions confirm this inference; and further, geochemical modeling quantitatively determined the evaporation ratio to be about 85%. Natural boron contamination is a consequence of brine groundwater. Two evolutionary trends in the plotting of the Cl/B ratio versus Cl⁻ can be identified: (1) Cl/B ratio decreases with boron being released from clay minerals when brine aquifers are flushed with freshwater; and (2) Cl/B ratio increases when seawater of a high Cl/B ratio infiltrates coastal aquifers.     

硼、氯同位素测定方法及地球化学研究进展

近十年来,由于高精度硼、氯同位素测定方法的建立,硼、氯同位素地球化学在研究的深度和广度上都得到了快速发展。硼、氯同位素地球化学的研究已在海洋、盐湖、地下水、蒸发岩、热液矿床、环境等方面开展,并显示出在解决一些地学问题方面所具有的良好前景。该文简要概述了目前国内外硼、氯同位素测定方法和在地球科学的一些领域应用方面取得的成果和进展。     

辽宁砖庙矿区硼矿床硬石膏的发现及成因讨论

在对辽宁砖庙矿区硼矿床的矿物学研究中发现了硬石膏。该矿物产于硼矿体中，与遂安石、菱镁矿、镁橄榄石、袁复礼石、硼铝镁石等共生。通过矿物学研究和稀土元素、硫同位素的分析表明，由于硬石膏是蒸发沉积变质成因的，所以硼矿床也应是蒸发沉积变质成因的     

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。     

Timescales determining the degree of kinetic isotope fractionation by evaporation and condensation

A first order characteristic of the relative abundance of the elements in solar system materials ranging in size from inclusions in primitive meteorites to planetary sized objects such as the Earth and the Moon is that they are very much like that of the Sun for the more refractory elements but systematically depleted to varying degrees in the more volatile elements. This is taken as evidence that evaporation and and/or condensation were important processes in determining the distinctive chemical properties of solar system materials. In some instances there is also isotopic evidence suggesting evaporation in that certain materials are found enriched in the heavy isotopes of their more volatile elements. Here model calculations are used to explore how the relative rates of various key processes determine the relationship between elemental and isotopic fractionation during partial evaporation and partial condensation. The natural measure of time for the systems considered here is the evaporation or condensation timescale defined as the time it would take under the prevailing conditions for evaporation or condensation to completely transfer the element of interest between the two phases of the system. The other timescales considered involve the rate of change of temperature, the rate at which gas is removed from further interaction with the condensed phase, and the rates of diffusion in the condensed and gas phases. The results show that a key determinant of whether or not elemental fractionations have associated isotopic effects is the ratio of the partial pressure of a volatile element (P_i) to its saturation vapor pressure (P_i,sat) over the condensed phase. Systems in which the rate of temperature change or of gas removal are slow compared to the evaporation or condensation timescale will be in the limit P_i ∼ P_i,sat and thus will have little or no isotopic fractionation because at the high temperatures considered here there is negligible equilibrium fractionation of isotopes. If on the other hand the temperature changes are relatively fast, then P_i ≠ P_i,sat and there will be both elemental and isotopic fractionation during partial evaporation or partial condensation. Rapid removal of evolved gas results in P_i ? P_i,sat which will produce isotopically heavy evaporation residues. Diffusion-limited regimes, where transports within a phase are not sufficiently fast to maintain chemical and or isotopic homogeneity, will typically produce less isotopic fractionation than had the phases remained well mixed. The model results are used to suggest a likely explanation for the heavy silicon and magnesium isotopic composition of Type B CAIs (as due to rapid partial melting and subsequent cooling at rates of a few °C per hour), for the uniformity of the potassium isotopic composition of chondrules despite large differences in potassium depletions (as due to volatilization of potassium by reheating in regions of large but variable chondrules per unit volume), and that the remarkable uniformity of the potassium isotopic composition of solar system materials is not a measure of the relative importance of evaporation and condensation but rather due to the solar nebula having evolved sufficiently slowly that materials did not significantly depart from chemical equilibrium.     

Isotopic fractionation of Cu in tektites

Tektites are terrestrial natural glasses of up to a few centimeters in size that were produced during hypervelocity impacts on the Earth’s surface. It is well established that the chemical and isotopic composition of tektites is generally identical to that of the upper terrestrial continental crust. Tektites typically have very low water content, which has generally been explained by volatilization at high temperature; however, the exact mechanism is still debated. Because volatilization can fractionate isotopes, comparing the isotopic composition of volatile elements in tektites with those of their source rocks may help to understand the physical conditions during tektite formation.Interestingly, volatile chalcophile elements (e.g., Cd and Zn) seem to be the only elements for which isotopic fractionation is known so far in tektites. Here, we extend this study to Cu, another volatile chalcophile element. We have measured the Cu isotopic composition for 20 tektite samples from the four known different strewn fields. All of the tektites (except the Muong Nong-types) are enriched in the heavy isotopes of Cu (1.98 < δ⁶⁵Cu < 6.99) in comparison to the terrestrial crust (δ⁶⁵Cu ≈ 0) with no clear distinction between the different groups. The Muong Nong-type tektites and a Libyan Desert Glass sample are not fractionated (δ⁶⁵Cu ≈ 0) in comparison to the terrestrial crust. To refine the Cu isotopic composition of the terrestrial crust, we also present data for three geological reference materials (δ⁶⁵Cu ≈ 0).An increase of δ⁶⁵Cu with decreasing Cu abundance probably reflects that the isotopic fractionation occurred by evaporation during heating. A simple Rayleigh distillation cannot explain the Cu isotopic data and we suggest that the isotopic fractionation is governed by a diffusion-limited regime. Copper is isotopically more fractionated than the more volatile element Zn (δ^66/64Zn up to 2.49‰). This difference of behavior between Cu and Zn is predicted in a diffusion-limited regime, where the magnitude of the isotopic fractionation is regulated by the competition between the evaporative flux and the diffusive flux at the diffusion boundary layer. Due to the difference of ionic charge in silicates (Zn²⁺ vs. Cu⁺), Cu has a diffusion coefficient that is larger than that of Zn by at least two orders of magnitude. Therefore, the larger isotopic fractionation in Cu than in Zn in tektites is due to the significant difference in their respective chemical diffusivity.     

天津蓟县硼矿床锰方硼石矿物的硼同位素研究

天津蓟县硼矿床是世界上唯一的沉积环境特殊的锰方硼石型硼矿床。矿床呈层状产于震旦系碳酸岩泥灰质岩系中 ,矿石呈鲕粒状或球粒状集合体 ,是成因条件极其特殊的矿床类型。含矿岩系为中元古界高于庄组沉积岩系 ,含矿岩性由下而上依次为含锰白云岩、页岩互层→含锰白云岩、泥硅质岩 ,夹锰方硼石矿层→含锰页岩、白云岩→厚层白云岩→薄层白云岩→厚层白云岩 ,锰方硼石矿体在矿层中呈断续相连的团块状或透镜状分布。硼矿物成分简单 ,只有锰方硼石一种矿物 ,锰方硼石矿体呈透镜状断续成层分布 ,东西延长达 30km。东部矿段以锰方硼石为主 ,向西部渐变为菱锰矿。矿石有块状和斑点状。块状矿石全部由球粒状锰方硼石集合体组成 ,w (B2 O3 ) >2 0 % ,最高可达 4 2 %以上。斑点状矿石中锰方硼石集中呈球粒状集合体分布于泥质白云岩中 ,w (B2 O3 ) <7%。首次研究了该硼矿床锰方硼石的硼同位素组成 ,δ11B值为 +6 7‰～ +14 9‰ ,均为正值 ,并且东部大峪矿段的硼同位素值低于西部柏树沟矿段的硼同位素值 ,表明该硼矿床的成矿元素属于海水来源。由于锰方硼石的微量元素组成难以与蒸发岩比较 ,且富含F、Ba、Sn热液富集的元素和Co、Ni、Cr、Ti基性岩浆岩元素以及与Fe、Mn大洋结核有关的元素组分 ,因此锰方硼石应属于     

硼同位素及其地质应用研究

硼的两个稳定同位素（10B 和11B）相对质量差较大,因此,硼同位 素分馏较显著。由于分析测量技术方面的改进和创新, 硼同位素地球化学近年来有了长足 的发展。业已查明,自然界中δ11B值变化为 －37‰～+58‰。其中,较负的 δ11B值见于非海相蒸发硼酸盐矿物和某些电气石,而较正的δ11B值见 于某些盐湖卤水和蒸发海水。现代大洋水的δ11B值十分恒定 (+39,5‰)。原始 地幔的δ11B值估测为－10‰±2‰。陨石的δ11B值很不均一,变化 可达90‰。而月岩的δ11B值变化较小（－6‰～+4‰）。由于硼同位素存在大的 分馏和不同地质体中截然不同的δ11B值,硼同位素地质应用范围十分广泛。目 前,硼同位素在研究星云形成过程和宇宙事件,壳-幔演化和板块俯冲作用过程,判别沉积 环境,研究矿床成因,示踪古海洋和古气候条件,和判断环境污染源区等方面的研究中成效显著。     

Isotopic compositions of oxygen, iron, chromium, and nickel in cosmic spherules: Toward a better comprehension of atmospheric entry heating effects

Large, correlated, mass-dependent enrichments in the heavier isotopes of O, Cr, Fe, and Ni are observed in type-I (metal/metal oxide) cosmic spherules collected from the deep sea. Limited intraparticle variability of oxygen isotope abundances, typically <5‰ in δ¹⁸O, indicates good mixing of the melts and supports the application of the Rayleigh equation for the calculation of fractional evaporative losses during atmospheric entry. Fractional losses for oxygen evaporation from wüstite, assuming a starting isotopic composition equal to that of air (δ¹⁸O = 23.5‰; δ¹⁷O = 11.8‰), are in the range 55%-77%, and are systematically smaller than evaporative losses calculated for Fe (69%-85%), Cr (81%-95%), and especially Ni (45%-99%). However, as δ¹⁸O values increase, fractional losses for oxygen approach those of Fe, Cr, and Ni indicating a shift in the evaporating species from metallic to oxidized forms as the spherules are progressively oxidized during entry heating. The observed unequal fractional losses of O and Fe can be reconciled by allowing for a kinetic isotope mass-dependent fractionation of atmospheric oxygen during the oxidation process and/or that some metallic Fe may have undergone Rayleigh evaporation before oxidation began.In situ measurements of oxygen isotopic abundances were also performed in 14 type-S (silicate) cosmic spherules, 13 from the Antarctic ice and one from the deep sea. Additional bulk Fe and Cr isotopic abundances were determined for two type-S deep-sea spherules. The isotopic fractionation of Cr isotopes suggest appreciable evaporative loss of Cr, perhaps as a sulfide. The oxygen isotopic compositions for the type-S spherules range from δ¹⁸O = −2‰ to + 27‰. The intraspherule isotopic variations are typically small, ∼5% relative, except for the less-heated porphyritic spherules which have preserved large isotopic heterogeneities in at least one case. A plot of δ¹⁷O vs. δ¹⁸O values for these spherules defines a broad parallelogram bounded at higher values of δ¹⁷O by the terrestrial fractionation line, and at lower values of δ¹⁷O by a line parallel to it and anchored near the isotopic composition of δ¹⁸O = −2.5‰ and δ¹⁷O = −5‰. Lack of independent evidence for substantial evaporative losses suggests that much of this variation reflects the starting isotopic composition of the precursor materials, which likely resembled CO, CM, or CI chondrites. However, the enrichments in heavy isotopes indicate that some mixing with atmospheric oxygen was probably involved during atmospheric entry for some of the spherules. Isotopic fractionation due to evaporation of incoming grain is not required to explain most of the oxygen isotopic data for type-S spherules. However spherules with barred olivine textures that are thought to have experienced a more intense heating than the porphyritic ones might have undergone some distillation. Two cosmic spherules, one classified as a radial pyroxene type and the other showing a glassy texture, show unfractionated oxygen isotopic abundances. They are probably chondrule fragments that survived atmospheric entry unmelted.Possible reasons type-I spherules show larger degrees of isotopic fractionation than type-S spherules include: a) the short duration of the heating pulse associated with the high volatile content of the type-S spherule precursors compared to type-I spherules; b) higher evaporation temperatures for at least a refractory portion of the silicates compared to that of iron metal or oxide; c) lower duration of heating of type-S spherules compared to type-I spherules as a consequence of their lower densities.     

Lithium and boron isotopes in illite-smectite: The importance of crystal size

Clay minerals record chemical data about the past, acting like natural computer memory chips. To retrieve the data we must understand how they are stored. To achieve this we have examined the isotopic information revealed by two trace elements, lithium and boron, that are incorporated into the common clay minerals illite-smectite (I-S) during diagenesis. We used hydrothermal experiments at 300°C, 100 MPa, to speed up the reaction of smectite to illite that normally occurs during slow (10-100 Ma) sediment burial. During illitization, Li substitutes into the octahedral sites and B enters the tetrahedral sites of the silicate framework. Both Li and B are also adsorbed in the interlayer of smectite, but Li is preferred over B in the exchange sites. To determine the equilibrium isotope fractionation of the two trace elements it is important to remove these adsorbed interlayer species. By measuring the isotopic composition of Li and B in the silicate framework during reaction, we can address the relative timing of element exchange in the different crystallographic sites. Furthermore, because illitization of smectite is a crystal growth process (not an isomorphous replacement) we have examined the effect of crystal size on the isotope fractionation.The results show that Li and B approach an isotopic steady state when R1 ordering occurs, long before oxygen isotopes equilibrate with the fluid. The isotopic fractionation (α_{mineral-water}) for Li (0.989) is similar to that for B (0.984) at 300°C. However, when separated into <0.2, 0.2-2.0, and >2.0 μm fractions, there are significant differences in measured isotope ratios by as much as 9‰. Crystal growth mechanisms and surface energy effects of nanoscale crystals may explain the observed isotopic differences. The fact that different crystals equilibrate at different rates (based on size) may be applied to natural samples to reveal the changing paleofluid history, provided we understand the conditions of equilibrium. This has very important implications for the interpretation of diagenetic environments, fluid flow, and surficial geochemical cycling.     

Sample preparation for isotopic determination of boron in clay sediments

The procedures of sample preparation for isotopic determination of boron in clay sediments is very cumbersome, by far, there haven’t been relevant reports on that. In order to establish an effective method for sample preparation, a series of experiments were carried out. In this paper, boron in clay sediments was extracted with HCl solution and purified by two-step ion exchange method. Extracted HCl solution should be adjusted to alkalescency before passing through the Amberlite IRA 743 resin column due to the fact that Amberlite IRA 743 resin absorbs boron only from alkalescent solution. However, a mass of hydroxides of Al and Fe will be precipitated when the extracted HCl solution becomes alkalescent. Hydroxides of Al and Fe have a strong adsorption capacity for boron, which can cause boron isotope fractionation. To treat precipitated hydroxides of Al and Fe, four procedures, namely direct ion exchange (DRIE), decationizing ion exchange (DCIE), once sedimentation ion exchange (OSIE) and repeated sedimentation ion exchange (RSIE) were used and assessed. The influences of the four procedures on separation and extraction and isotopic composition of boron in experimental solutions and clay sediments were also discussed. According to the results, the DRIE, DCIE and OSIE are improper. The result of sample determination indicates that when extracting boron via RSIE, with the increase of precipitation times, there’s an obvious decrease in boron content in the precipitated hydroxides while a sharp increase in recovery of boron and it is favorable for weakening the influence of boron isotope fractionation. But the process of RSIE is time consuming and it may introduce boron. It needs further research to establish a more effective sample preparation method for isotopic deter- mination of boron in clay sediments.