珊瑚中硼的分离及其同位素组成的测定

介绍了用硼特效树脂和阴、阳混合离子交换树脂相结合进行珊瑚中硼的分离和纯化方法，满足了正热电离质谱法测定硼同位素的要求，并且对几个珊瑚样品进行了硼的分离和硼同位素组成的测定，结果满意，为研究珊瑚中的硼同位素示踪古海洋环境变化提供了可能。     

硼硅酸盐矿物硼的化学分离纯化与同位素测定方法

采用碱熔法分解电气石样品,研究了3种不同纯化分离方法对硼回收和同位素测定的影响。实验表明:电气石中富含的Fe³⁺和Al³⁺对甲亚胺-H酸分光光度法测定硼含量有较大干扰,并在硼特效树脂交换分离中形成氢氧化物沉淀,阻塞交换柱;同时吸附溶液中硼元素造成回收率降低。本实验依次采用阴/阳离子混合树脂,硼特效树脂和阴/阳离子混合树脂三步离子交换进行电气石样品的纯化分离方法,实现了复杂基体中硼的完全回收（回收率99%）。在TIMS（Triton TI）采用H3和H4法拉第杯,并通过优化Zoom Optics参数（Focus Quad:15;Dispersion Quad:-85）实现静态双接收硼同位素组成测定。本方法对NIST SRM 951标准样品测定结果为¹¹B/¹⁰B=4.05044±0.00012（2σ,n=8,1μg B）,测定内外精度优于传统的动态峰跳扫。NIST SRM951测定结果为-0.3‰,表明预处理过程中无硼同位素分馏效应。天然样品硼同位素组成分别采用静态多接收PTIMS-Cs₂BO₂⁺法和MC-ICP-MS测定,数据点基本分布在1:1线上,说明MC-ICP-MS测定结果与PTIMS方法结果相一致。     

低硼富含有机质的河/雨水正热电离硼同位素的测定

对低硼富含有机质的河/雨水样品硼的分离方法及硼同位素组成的测定进行了研究.采用硼特效树脂富集河/雨水样品,结合微升华技术去除有机质;采用正热离子质谱法进行硼同位素组成的测定.全流程回收率在97.50%～101.17%之间,测试数据和多接受电感耦合等离子体质谱比较接近,测试精度小于0.05‰.经本方法处理后的样品能满足同...     

三步离子交换方法用于粘土沉积物酸溶相中硼同位素测定

在采用酸溶法进行粘土沉积物中硼同位素组成测定时,大量存在的Al、Fe、稀土等元素在较高pH溶液中会形成能强烈吸附硼的氢氧化物沉淀,对硼的提取和硼同位素的测定产生较大影响.有效去除这些干扰元素一直是测定粘土沉积物酸溶相中硼同位素组成的瓶颈.本实验采用三步离子交换法萃取和纯化粘土沉积物中的硼,以AG 50W×8阳离子树脂柱去除所有能生成水不溶性氢氧化物的Al、Fe、稀土等元素,再采用Amberlite IRA 743硼特效树脂柱提取硼,最后采用Ion-exchangerⅡ与AG 50W×8组成的阴阳离子混合树脂柱进一步纯化硼提取液.结果表明,采用以上三步离子交换法提取粘土沉积物中硼的回收率高于90％,未观察到明显的硼同位素分馏,可满足粘土沉积物酸溶相中硼同位素组成高精度测定的需要.     

盐湖卤水硼同位素测定中硼的二次离子交换分离

根据盐湖卤水水化学特点,介绍了一种用阳、阴离子交换树脂,动态和静态交换相结合,对盐湖卤水中的硼进行分离纯化的简易方法。用该方法从盐湖卤水中分离出来的硼足以满足同位素质谱分析的需要,分离过程不产生同位素分馏,获得了理想的实验结果。     

正热电离静态多接收偏硼酸铯离子测定硼同位素

利用表面热电离质谱仪(Triton TI)的"Zoom Quad"功能,采用静态多接收偏硼酸钯离子(Cs2BO+2)测定标准样品NIST 951 H3BO3和珊瑚与有孔虫样品的硼同位素,研究了涂样量对硼同位素组成测定的影响,探讨静态多接收与传统的动态峰跳扫方法相比,在测定精度、准确度、样品量以及测试时间上的优势.实验结果表明,在测试精度和准确度相同的情况下,静态双接收所需样品量可以低至0.1 μg,且测试时间可缩短一半.对0.1 μg NIST 951 H3BO3静态双接收测定的硼同位素比值11B/10B = 4.05159±0.00023(2σm, n=10),与世界主要实验室的测试值相符.最后对0.1 μg珊瑚和有孔虫样品进行了测定,也取得了较好的结果.     

微色谱柱分离/ICP-AES测定环境样品中的痕量硼

本文采用色谱系统对水样品（温泉水、卤水）中的硼进行分离富集，探讨了影响其分离富集的条件。实验表明，在pH＝8条件下，硼可被树脂完全吸附，用3mL 1mol/L硫酸可以从吸附术上完全解吸硼，浓缩物用ICP－AES进行测定，所建立的方法简便、准确，适合于含盐量高及其它水样品中微量硼的测定。     

(硬)石膏矿物中硼的提取分离及硼同位素测定

(硬)石膏作为海湖水蒸发过程中常见的硫酸盐矿物,能很好反映原始母液的组成及相关水文地质信息。硼属于易溶元素,常赋存于各种蒸发岩矿物中,目前硼同位素在矿床学,地球化学,古环境等地球科学中已得到广泛应用。由于(硬)石膏硼含量较低且难溶于水和盐酸,所以其硼含量及硼同位素组成特征研究较少。本研究通过物相转化与树脂交换法提取纯化(硬)石膏中的硼:首先使用碳酸氢铵与石膏混合,将微溶硫酸钙转化为难溶碳酸钙,随后使用盐酸溶解,一次转化率为85%,两次转化与分解可以保证石膏的完全溶解;之后经过硼特效树脂(Amberlite IRA 743)完成硼富集及阴阳离子混合树脂(Ion ExchangeⅡ和Dowex50W×8)对硼的纯化;最终通过He改进的正热电离质谱法测定硼同位素。测得试剂石膏中的硼含量为(3.501±0.128)μg/g(n=12,RSD=3.6%),平均加标回收率为100.5%;同时加标试剂石膏的δ~(11)B值为17.98‰±0.21‰(n=3,RSD=1.2%),说明整个流程的重复性良好,可以满足(硬)石膏中硼含量及其硼同位素组成的准确测定。     

负热电离质谱测定硼同位素的涂样试剂比较

目前人们并未注意到利用负热电离质谱方法测定硼同位素所采用涂样试剂中BO^-的同质异位素CNO^-离子的存在和影响。对硼同位素测定采用的不同涂样试剂进行比较，结果发现在去硼海水和硝酸盐溶液中存在BO2^-的同质异位素CNO^-离子，干扰离子不仅来自有机物，而且可能来自硝酸根。在硼同位素测定中，检查空白中的43峰和43／42比值是必要的。实验表明MgCl2 NaOH混合溶液是负热电离质谱测定硼同位素的较为理想的涂样试剂。     

电感耦合等离子体质谱法测定硼同位素丰度

以硼同位素标准物质NIST SRM 951配制标准溶液,在优化的仪器操作条件下对电感耦合等离子体质谱(ICP-MS)测定的硼同位素质量进行校正,求出校正因子,确定了样品的线性浓度范围,选定样品浓度为1.1 mg/L。在同样的仪器条件下首先测定了硼标准物质的硼同位素丰度比,测量误差为0.2%,然后测定了硼同位素浓缩过程中硼样品的硼同位素丰度比,测定结果的相对标准偏差为1.1%。此外考察了仪器的稳定性。实验结果表明本方法“记忆效应”小,结果可靠,测量精度高。     

Boron Separation by the Two—step Ion—Exchange for the Isotopic Measurement of Boron

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Ion Exchange Extraction of Boron from Aqueous Fluids by Amberlite IRA 743 Resin

The ion exchange characteristics d Amherlite IRA 743 resin for extracting boron from aqueous fluids have been investigated in detail. The results show that AmherHte IRA 743 resin, a boron specific ion exchange resin, can quantitatively extract boron as the B (OH)4- spedes from weakly basle solution. Some exchangeable anions such as CI- and SO4^2- are present, resulting in an increase in pH value of the loeded solution within the nan, and the boron in natural aqueous fluids with low nH is also extracted by Amberlite IRA 743 resin. However, the voiume of loaded solution must be restricted. The maximum voiume of loaded solution giving quantitative extraction of boron decreases for sample soh.,tiom of lower pH value. Warm HCI solution is more effective than room temperature HCI solution for eluting boron from Amberllte IRA 743 resin.     

Resin selection and single-step production and recovery of lactic acid from pretreated wood

Four ion-exchange resins (Amberlite IRA 900, IRA 400, IRA 96, and IRA 67) were employed for lactic acid recovery from simultaneous saccharification and fermentation (SSF) media. The best resins (Amberlite IRA 900 and IRA 400) were assayed for capacity, regenerant consumption, percentage of lactic acid recovery, and product concentration. Almost quantitative lactic acid recoveries at constant capacities were achieved in four sequential loading/regeneration cycles. A strong-base resin (Amberlite IRA 400) was selected for intermittent lactic acid separation in a typical SSF process, in which pretreated wood was saccharified by cellulases in the presence of Lactobacillus delbrueckii. The dynamics of lactic acid generation and lactic acid recovery were established.     

Synthesis, characterization and application of a novel sorbent, glucamine-modified MCM-41, for the removal/preconcentration of boron from waters

A novel sorbent was prepared by the functionalization of an inorganic support material, MCM-41, with N-methylglucamine for the uptake of boron from aqueous solutions prior to its determination by inductively coupled plasma optical emission spectrometry (ICP-OES). Characterization of the newly synthesized material was performed using BET, XRD, TEM, SEM and DRIFTS techniques, in addition to its C and N elemental content. Sorption behavior of the novel sorbent for boron was also investigated and found to obey Freundlich and Dubinin-Radushkevich (D-R) isotherm models. The maximum amount of B (as H₃BO₃) that can be sorbed by the sorbent was calculated from the D-R isotherm and was found to be 0.8 mmol B g⁻¹ of sorbent. The applicability of the new sorbent for the removal/preconcentration of boron from aqueous samples was examined by batch method. It was found that the sorbent can take up 85% of boron in 5 min whereas quantitative sorption is obtained in 30 min. Any pH greater than 6 can be used for sorption. Desorption from the sorbent was carried out using 1.0 M HNO₃. The sorption efficiency of the new sorbent was also compared to that of Amberlite IRA 743, a commercial resin with N-methylglucamine functional groups. Within the experimental conditions employed, the new sorbent was found to have higher sorption efficiency than the commercial resin. For method validation, spike recovery tests were performed at various concentration levels in different water types and were found to be between 83-95 and 75-92% for ultra pure water and geothermal water, respectively.     

Selectivity study of strongly acidic cation exchange resin Amberlite IR-120

The thermodynamic measurements was carried out to study the selectivity of cation exchange resin Amberlite IR-120 in protonated form with respect to Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ ions in solution. The equilibrium constant K was calculated using the activity coefficients of ions in solution as well as in the resin. The K values calculated for the reacting systems increase with temperature that suggests the endothermic exchange reactions with estimated enthalpy values of 38.8, 20.6, 8.45, and 7.24 kJ mol⁻¹, respectively. On the basis of calculated parameters, the selectivity of ion exchange resin with respect to various bivalent ions in the solution was predicted. The method used in our experimental work provides a basis for characterization of ion exchange resins, which can be promising materials for efficient separation of ions from industrial waste effluents.     

Exchange studies of 5-sulphosalicylic acid in amberlite IRA 401 Cl anion exchange resin

Exchange studies of 5-sulphosalicylic acid in Amberlite IRA 401 Cl anion exchange resin have been carried out at 25°C in a stirred vessel. The exchange rates have been interpreted on the basis of a simple diffusion model.     

Synthesis of new chiral ionic liquids from α-hydroxycarboxylic acids

New functionalized optically active N-methylimidazolium ionic liquids with an asymmetric center at the β-position to the imdazole ring were synthesized as bromide salts from optically active α-hydroxycarboxylic acids. The bromide anions were exchanged by carboxylate anions with Amberlite IRA 400 ionic exchange resin.     

Protonation and ion exchange equilibria of weak base anion-exchange resins

Protonation and ion exchange equilibria of weak base anion-exchange resins, in which tertiary amine moieties were introduced as a functional group, were investigated by applying NMR spectroscopy to species adsorbed into the resins. ³¹P NMR signals of the phosphinate ion in the resin phases shifted to a lower field due to the influence of protonation of the tertiary amine groups of the resins in the pH range of 4-10. Protonation constants of the tertiary amine groups in styrene-divinylbenzene (DVB)-based resins were estimated to be K_H = 10^6.4 for Amberlite IRA96 and 10^6.5 for DIAION WA30 by the ³¹P NMR method using the phosphinate ion as a probe species. In addition to the low field shift caused by the protonation of the tertiary amine moieties, another low field shift was observed for the phosphinate ion in acrylic acid-DVB-based resins at a rather high pH. This shift should be due to an unexpected deprotonation in the acrylic resin: a tautomerism accompanying the proton release from the amide form to the imide one in the functional group, thus, the resin could exhibit a cation exchange property at the high pH. Protonation constants of the tertiary amine moieties in the acrylic resins were estimated to be 10^8.8 for DIAION WA10, 10^9.0 for Amberlite IRA67 and 10^9.3 for Bio-Rad AG 4-X4 on the basis of the Henderson-Hasselbalch equation using the resin phase pH estimated by the ¹³³Cs and ¹H NMR signal intensities.     

Ion Exchange Separation of Platinum and Palladium by Nucleophilic Displacement With Thiocyanate or Thiourea1,2

The separation of platinum and palladium, by adsorption onto weak base anion exchange resins, Amberlite XE 299, or ionex (derived from Amberlite XE-305) from 1M hydrochloric acid, followed by ligand substitution with sulfur nucleophiles is described.

In the thiourea system, cationic thiourea complexes are produced, which cannot be readsorbed into the resin. In the thiocyanate system the formation of Pd(SCN)₄ ^2- is favored in both solution and polymer phases. The Pd(SCN)₄ ^2-. readsorption into the anion exchange resin is the basis for the separation of platinum from palladium.