有孔虫中硼的分离及其正热电离质谱法测定

针对大洋钻探计划(0DP)钻孔中有孔虫数量少、硼含量低的特点，改进了硼特效树脂和阴、阳混合离子交换树脂相结合进行分离硼的方法，成功地实现了硼的分离，并且首次采用正热电离质语法测定了有孔虫中硼同位素的比值。由于硼的分离过程不产生同位素分馏，测定结果令人满意。     

The determination of plutonium by mass spectrometry using a [242]-plutonium tracer

An isotopic dilution method is described for the determination ot plutonium in samples of irradiated uranium using a ²⁴²Pu tracer. An aliquot of tracer is added to the sample and the mixture treated to ensure isotopic exchange; plutonium is then separated by an ion exchange procedure and an isotopic analysis made using an M.S.5. mass spectrometer. The precision (3 σ) for an aliquot containing 0.1 μg plutonium is 0.6%. A possible application of the method would be its use for control analyses of the feed solution in a chemical plant processing natural uranium fuel elements as, for example, the Windscale primary separation plant.     

Separation of magnesium isotopes by NTOE bonded merrifield peptide resin

Separation of magnesium isotopes was investigated by chemical ion exchange with synthesyzed 1,12-diaza-3,4:9,10-dibenzo-5,8-dioxacyclo pentadecane(NTOE) bonded merrifield peptide resin using elution chromatographic technique. The capacity of novel diazacrown ion exchanger was 0.29 meq/g dry resin. The heavier isotopes of magnesium were concentrated in the solution phase, while the lighter isotopes were enriched in the resin phase. The glass ion exchange column used in our experiment was 32 cm long with inner diameter of 0.2 cm, and 0.5M NH₄Cl solution was used as an eluent. The single stage separation factor was determined according to the method of GLUECKAUF from the elution curve and isotopic assays. The separation factors of ²⁴Mg²⁺–²⁵Mg²⁺, ²⁴Mg²⁺–²⁶Mg²⁺, and ²⁵Mg²⁺–₂₆Mg²⁺ were 1.063, 1.080, and 1.021, respectively.     

Determination of traces of bismuth by isotopic exchange reaction in the organic phase

A new radioanalytical method has been developed based on homogeneous isotopic exchange in the organic phase. The theory of the method is presented and discussed. This method has been applied for the simple, selective and rapid determination of bismuth based on the isotopic exchange between bismuth diethyldithiocarbamate and bismuth iodide complex labelled with²¹⁰Bi. As little as 0.01 μg of the metal can be determined.     

Separation of lithium isotopes by NDOE bonded Merrifield peptide resin

The novel NDOE (1,12,15-triaza-3,4:9,10-dibenzo-5,8-dioxacycloheptadecane) ion exchange resin was prepared. The ion exchange capacity of NDOE azacrown ion exchanger was 0.2 meq/g dry resin. A study on the separation of lithium isotopes was carried out with NDOE novel azacrown ion exchange resin. The lighter isotope,⁶Li concentrated in the solution phase, while the heavier isotope,⁷Li is enriched in the resin phase. By column chromatography (0.1 cm I.D.×32 cm height) using 2.0M NH₄Cl as an eluent, a separation factor,a=1.0201 was obtained.     

Fractionation of nitrogen stable isotopes by ion exchange chromatography

The ion exchange chromatography displacement technique was used for the enrichment of ¹⁵N. The runs were conducted in laboratory and bench scales using two systems of columns filled with Wofatit KPS ion exchange resin (medium porosity type). Ammonia NH₄ ⁺/NH₃ aq. was chosen as the isotopic exchange system. The ammonium bands formed in the columns were eluted by means of sodium hydroxide solution. Hydrodynamic patterns in the column beds was evaluated in terms of dimensionless Reynolds number. The results show that separation process can be performed in the turbulent or laminar flow regime.     

Separation of magnesium isotopes by a 2'-aminomethyl-18-crown-6 bonded Merrifield peptide resin

Separation of magnesium isotopes was investigated by chemical ion exchangewith synthesized 2'-aminomethyl-18-crown-6 (AM18C6) bonded Merrifieldpeptide resin using an elution chromatographic technique. The capacity ofthe novel crown ion exchanger was found to be 2.3 meq/g dry resin. The heavierisotopes of magnesium were enriched in the solution phase, while the lighterisotopes were enriched in the resin phase. The single stage separation factorwas determined according to the method of GLUECKAUF from the elution curveand isotopic assays. The separation factors of ²⁴Mg–²⁵ Mg, ²⁵ Mg–²⁶ Mg, and ²⁴ Mg–²⁶ Mg isotope pair fractionations were 1.012, 1.005, and 1.022, respectively.     

Chromatographic separation of neodymium isotopes by using chemical exchange process

The neodymium isotope effects were investigated in Nd–malate ligand exchange system using the highly porous cation exchange resin SQS-6. The temperature of the chromatographic columns was kept constant at 50 °C by temperature controlled water passed through the columns jackets. The separation coefficient of neodymium isotopes, ?’s, was calculated from the isotopic ratios precisely measured by means of an ICP mass spectrometer equipped with nine collectors as ion detectors. The separation coefficient, ? × 10⁵, were calculated and found to be 1.4, 4.8, 5.4, 10.6, 16.8 and 20.2 for ¹⁴³Nd, ¹⁴⁴Nd, ¹⁴⁵Nd, ¹⁴⁶Nd, ¹⁴⁸Nd and ¹⁵⁰Nd, respectively.     

Enrichment of Magnesium Isotopes by 2′-Aminomethyl-15-Crown-5 Bonded Merrifield Peptide Resin

Magnesium isotope enrichment was investigated by chemical ion exchange with a synthesized 2-aminomethyl-15-crown-5 bonded Merrifield peptide resin using elution chromatography. The capacity of the novel crown ion exchanger was found to be 2.25 meq/g dry resin. The heavier isotopes of magnesium were enriched in the solution phase, while the lighter isotopes were enriched in the resin phase. The separation factor was determined according to the method of GLUECKAUF from the elution curve and isotopic assays. The separation factors of ²⁴Mg²⁺–²⁵Mg²⁺, ²⁴Mg²⁺–²⁶Mg²⁺, and ²⁵Mg²⁺–²⁶Mg²⁺ isotope pair fractionations were 1.00095, 1.00857, and 1.00014, respectively.     

Isotopic exchange of gaseous ammonia 14NH3 and 15NH3 in sulfonated macroreticular ion exchangers

Adsorption and ¹⁵NH₃ isotopic exchange was performed on dry macroreticular polystyrene ion exchanges crosslinked with varying amounts of divinylbenzene and partially neutralized by ¹⁴NH₃. Data on pressure changes and mass spectrometric analyses of isotopic composition of the gaseous phase were used to calculate equilibrium distribution of ¹⁴NH₃ and ¹⁵NH₃ under various dislocation conditions. It was established that along with the exchange of ¹⁴NH₃ to a gaseous phase, ¹⁵NH₃ penetrates to the mass of ion exchanger. This is evidently due to the migration of ammonia among functional groups. It was found that by thermal desorption under reduced pressure ammonia is released only from functional groups located on the surface of ion exchanger.     

Separation of lithium isotopes by N4S2 azacrown ion exchanger

The novel N₄S₂ azacrown ion exchange resin was prepared. The ion exchange capacity of N₄S₂ ion exchanger was 0.34 meq/g dry resin. A study on the separation of lithium isotopes was carried out with N₄S₂ azacrown ion exchange resin. The lighter isotope,⁶Li is concentrated in the resin phase, while the heavier isotope,⁷Li is enriched in the solution phase. With column chromatography [0.1 cm (I.D.)×32 cm (height)] using 2.0M NH₄Cl as an eluent, separation factor, a=1.034 was obtained.     

Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography

A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg²⁺, Ca²⁺, and Sr²⁺ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV‐absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg²⁺, Ca²⁺, and Sr²⁺ were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg²⁺, Ca²⁺, and Sr²⁺ within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S /N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded.     

Adsorption and isotope effects by ion exchange with 1-aza-12-crown-4 bonded Merrifield peptide resin

Magnesium isotope effects were investigated by chemical ion exchange with synthesized 1-aza-12-crown-4 bonded Merrifield peptide resin using elution chromatography. The capacity of azacrown ion exchanger was 0.89 meq/g dry resin. The heavier isotopes of magnesium were enriched in the resin phase, while the lighter isotopes were enriched in the solution phase. The hydration effect is less than the complexation and isotope mass effects. The single stage separation factor was determined according to the method of Glueckauf from the elution curve and isotopic assays. The separation factors of 24Mg(2+)-25Mg(2+), 24Mg(2+)-26Mg(2+), and 25Mg(2+)-26Mg(2+) were 1.012, 1.023, and 1.011, respectively.     

Separation and preconcentration of131I− and131IO 3 − in a liquid-liquid system

The application of isotope exchange in a liquid-liquid system for the separation and preconcentration of¹³¹I^– and¹³¹IO^3/– from water is described. For this purpose a solution of elemental iodine in tri-n-butyl phosphate diluted with toluene was used. The influence of various factors on the separation efficiency of¹³¹I was investigated. These are: time of the exchange, concentration of a carrier in the aqueous phase, concentration of I₂ in the organic phase, volume ratio of the phases, pH, foreign ions, storage of the organic phase, etc. The method is quite rapid and the selective preconcentration of these chemical forms of radioiodine from water can be accomplished even in the presence of the most important fission products. This method makes also possible to separate these chemical forms from each other under controlled pH conditions. The activity of the separated radioiodine can be measured advantageously, e.g., by homogeneous liquid scintillation counting after decolourization of the organic phase.     

Sequential determination of Am, Cm, Pu, Np and U by extraction chromatography

Environmental contamination by artificial radionuclides and the evaluation of their sources require precise isotopic analysis and accurate determination of actinide elements above all plutonium and americium. These can be achieved by alpha spectrometry or by inductively coupled plasma mass spectrometry (ICP-MS) after chemical separation. In the present work, a simple, rapid method has been developed for the sequential separation of actinide elements from aqueous solutions and their determination by alpha spectrometry. Extraction chromatography was applied to the separation of ²⁴¹Am, ²⁴⁴Cm, ^{239 + 240,238}Pu, ²³⁷Np and ^238,235,234U using microporous polyethylene supporting tri-n-octylamine as the stationary phase and hydrochloric acid with and without reducing agents as the mobile phase. Actinide in 9 M HCl solution is introduced into the anion exchange column; Pu (IV), Np (IV) and U(VI) are retained on the column while Am (III) and Cm passed through. Pu is eluted first, reductively, after which, Np and then U are eluted. The method can be applied to all aqueous solutions which do not contain strong complexing or precipitation agents for the elements considered.     

Rapid sample digestion by fusion and chemical separation of Hf for isotopic analysis by MC-ICPMS

A new method for rapid sample digestion and efficient chemical separation of Hf and REE from rock samples for precise isotopic analysis is presented. Samples are digested by fusion in the presence of a lithium borate flux at 1100 °C and dissolved whilst molten in dilute nitric or hydrochloric acid. Prior to chemical separation using ion exchange techniques, Li and B from the flux material and Si from the sample are separated from the remaining major elements, REE and high field strength elements (HFSE) in the sample by Fe-hydroxide co-precipitation. The chemical separation of Hf is a two-stage procedure designed to first remove the remaining matrix elements (e.g. Fe, Ba) in the sample using standard cation exchange techniques, followed by separation of Hf from the REE and HFSE on TEVA extraction chromatographic resin. Hf yields are >90% and total procedural blanks are ca. 50 pg. Hf isotope ratios of a synthetic standard solution and replicate digestions of international rock standards BHVO-1 and BCR-1 measured on multi-collector inductively coupled plasma mass spectrometer (MC-ICPMS) reproduce similarly to ≤50 ppm (2 S.D.). The following elemental ratios are routinely obtained for elements, which interfere isobarically or may affect the ionisation and/or fractionation behaviour of Hf during analysis: ¹⁷⁶Yb/¹⁷⁶Hf<0.0001; ¹⁷⁶Lu/¹⁷⁶Hf<0.00001; Ti/Hf<0.05. This technique also provides a means of separating Nd from the REE fraction for isotopic analysis and, potentially, may be adapted for measurement of Lu/Hf ratios by isotope dilution techniques.     

The kinetics and mechanism of bromide ion isotope exchange reaction in strongly basic anion-exchange resin duolite A-162 determined by the radioactive tracer technique

In the present investigation, ⁸²Br radioactive isotope was used as a tracer to study the kinetics and mechanism of exchange reaction between an ion exchange resin and an external bromide ion solution. In an attempt to study the reversible bromide ion isotopic exchange reaction kinetics, it was expected that whether the initial step was the exchange of radioactive bromide ions from the solution into the ion exchange resin (forward reaction) or from the ion exchange resin into the solution (reverse reaction), two ion isotopic exchange reactions should occur simultaneously, which was further confirmed by the experimental specific reaction rates of 0.130 and 0.131 min⁻¹, respectively. The results can be used to standardize process parameters so as to optimize the utilization of ion exchange resins in various industrial applications. The text was submitted by the authors in English.     

Separation of lithium isotopes by elution chromatography with an AB18C6 bonded Merrifield peptide resin

Cation exchange chromatographic separation of lithium isotopes was carried out with an 4'-aminobenzo-18-crown-6(AB18C6) bonded Merrifield peptide resin. This resin has a capacity of 2.25 meq/g dry resin. Upon column elution chromatography, a single stage separation factor of 1.0095, was obtained by the Glueckauf theory from the elution curve and isotopic assays. The heavier isotope, ⁷Li, was concentrated in the resin phase, while the lighter one, ⁶Li, concentrated in the solution phase.     

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...     

Radiohochspannungsionophoretische Untersuchungen der Isotopenaustauschreaktionen zwischen Polythionaten,Thiosulfat und Sulfit

The isotopic exchange of³⁵S between thiosulfate/sulfite and tetrathionate/thiosulfate is examined. The kinetic data are determined. In both cases the reactions are of second order. As the isotopic exchange between tetrathionate/thiosulfate is very fast, these reaction components are used in high dilution. Furthermore, the extent of exchange during the separation is determined.