Migration characteristics study of iodine in crushed Beishan granite column under dynamic flow condition

Journal of Radioanalytical and Nuclear Chemistry - The migration of iodine on Beishan granite was studied by the dynamic column method using an UV detector. Migration parameters, such as...     

Sorption of iodine on Beishan granite: effect of speciation and humic acid

Sorption of iodine on Beishan granite was studied by batch method. Great difference exists in the sorption behaviors of I^? and IO₃^?. Under acidic condition, the sorption of IO₃^? improves dramatically, and IO₃^? could partly convert to I^?. However, the sorption of I^? is close to zero at all studied pH. Humic acid can slight improve the sorption of IO₃^?, but greatly improve the sorption of I^? in acidic condition. The postulated sorption mechanisms of IO₃^? are electrical interaction and followed by reduction.     

Eu(III)在北山花岗岩上的吸附作用

用电位滴定法研究了甘肃北山花岗岩(BS03,600m)的酸、碱性质,用批式法研究了Eu(III)在该花岗岩上的吸附行为.实验结果表明:在离子强度I=0.1M的NaCl溶液中,北山花岗岩的pHPZNPC为9.4,当I增大至0.4M时,pHPZNPC为9.0.不同离子强度下花岗岩的电位滴定曲线与类似条件下蒙脱石的相仿.Eu(III)在北山花岗岩上的吸附分配比(Kd)随pH、离子强度和Eu(III)浓度的变化而变化.在低pH范围,Eu(III)的Kd值随离子强度的增大显著减小,而在高pH值范围,离子强度对Kd的影响甚微.用模型定量解释了Eu(III)在北山花岗岩上的吸附随pH、离子强度和Eu(III)浓度而变化的实验数据,该模型包含Eu3+与花岗岩发生的阳离子交换反应以及Eu(III)与花岗岩表面羟基发生两个内层表面配合反应(inner-sphere surface complexation reactions).用所建模型对离子强度为0.1M时Eu(III)在北山花岗岩上的吸附行为作了预测,并与文献报道的类似条件下Am(III)在北山花岗岩上的吸附实验数据作了比较.     

Micro determination of iodine by a catalytic method

Summary A procedure is described for the determination of quantities of iodide of the order of 0,05 to 3 in 1 ml. solution or in a suitable amount of solid sample (sodium chloride). The method is based upon the strong catalytic effect of iodide upon the reaction between ceric sulfate and an excess of arsenious acid in dilute sulfuric acid (1,5–2N). The effect of temperature and foreign substances has been investigated and procedures have been given which are applicable in the presence of salts affecting the rate of the catalyzed reaction. By refinement of the experimental technique it should be possible to determine quantities of iodine much smaller than 0,05.

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Zusammenfassung Es wird ein Verfahren für die quantitative Bestimmung von Jodid in Mengen von 0,05–3 in einer Lösung von 1 ccm oder in einer entsprechenden Menge fester Substanz (NaCl) beschrieben. Die Methode beruht auf einem stark katalysierenden Einfluß des Jod-Ions auf die Reaktion zwischen Cerisulfat und überschüssiger arseniger Säure in verd. Schwefelsäure. Der Einfluß von Temperatur und Fremdsubstanzen ist untersucht und Verfahren sind ausgearbeitet worden, die bei Anwesenheit von Salzen, die den Ablauf der katalysierten Reaktion beeinträchtigen, anwendbar sind. Durch Verbesserung der experimentellen Technik sollte es möglich sein, Mengen von Jod, die viel kleiner als 0,05 sind, nachzuweisen.

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Résumé Un procédé est décrit concernant la détermination des quantités de iodure de l'ordre 0,05 à 3 dans une solution de 1 ml ou dans une quantité appropriée d'un corps solide (chlorure de sodium). Cette méthode se base sur l'effet puissant catalytique du iodure sur la réaction entre le cérisulfate et un excès d'acide arsénieux dans l'acide sulfurique dilué (1,5–2n). L'effet de la température et des substances hétérogènes est recherché, et on indique des procédés lesquels peuvent être appliqués s'il y a des sels exerçant une influence sur le dosage de la réaction catalysée. Grâce à l'amélioration de la technique expérimentale, il sera possible de déterminer des quantités de iodure même plus petites que 0,05.

     

Determination of iodine value fatty acids by a flow-injection method

An automated method for determining the iodine value for various industrial fatty acids is described. The method is based on flow-injection techniques and the chemistry is a modified version of the standard Wij's solution method. The system is fully computerized with an AIM-65 microcomputer. Two detection system, u.v.-visible absorbance and potentiometric sensing, are compared. Results comparable to the conventional method are obtained. Continuous-run sample throughput rates of 12 h^?1 are eralistic.     

Determination of iodine in organic iodine compounds by the non-equilibrium isotopic exchange method

A new type of the isotope exchange method of analysis is proposed. The method can be applied to the exchange system in which the rate of the exchange reaction is rather slow but measurable, before the exchange equilibrium is attained. The validity of the principle of the method is verified experimentally with several exchange systems of RyI+KI^*⇌RyI^*+KI (RyI stands for alkyl, alkylene or benzyl iodide) type. The iodine content of the organic iodine compounds can be determined with an error of ±4%.     

The influence of pH on diffusion of 75Se(IV) in Beishan granite

The through-diffusion method and batch sorption experiments were used to explore the influence of pH on the diffusion behavior of ⁷⁵Se(IV) in matrix Beishan granite (BsG). In the pH range of 2.0–8.5, the D_e values of ⁷⁵Se(IV) in BsG decreased first and then increased with pH increasing, while the changing trend of K_d was nearly opposite. It was speculated that the influence of pH on the diffusion of ⁷⁵Se(IV) in BsG was due to the joint effects of different species distribution of Se, change in surface charge of BsG and change in ionic strength at various pH values.

     

Evaluation of sorption and diffusion behavior of selenium in crushed granite by through-diffusion column tests

Distribution coefficients (K _d), apparent diffusion coefficients (D _a) and retardation factor (Rf) in this work obtained by batch and through-diffusion experiments have been performed, respectively. The accumulative concentration method developed by Crank (The mathematics of diffusion, 12) was applied to realize apparent and effective diffusion coefficient (D _a and D _e) of Se. Besides, a non-reactive radionuclide, HTO, was initially conducted in through-diffusion experiment for assessing the ability of radionuclide retardation. The distribution coefficients (K _d) obtained by batch tests in 14 days under aerobic and anaerobic systems were 6.98 ± 0.35 and 5.21 ± 0.25 mL/g. Moreover, Rf^cal and K _d ^cal of Se obtained from accumulative concentration’s method in through-diffusion test showed an obvious discrepancy with the increase of length/diameter (L/D) ratio. However, it presented an agreement of Rf^H/Se and K _d ^H/Se in a various L/D ratio by comparison of apparent diffusion coefficient’s (D _a) between HTO and Se. It appears that the Rf^H/Se and K _d ^H/Se obtained from the through-diffusion experiments are lower than those derived from the batch experiments. Therefore, it demonstrates that reliable Rf and K _d of Se by through-diffusion experiments could be achieved at a non-reactive radiotracer (HTO) prior to tests and will be more confident in long-term performance assessment of disposal repository.     

A study of the iodinated resin column for the determination of iodine in biological fluids by radiochemical neutron activation analysis

The iodinated resin technique for separation of¹²⁸I directly from neutron irradiated biological fluids is attractive due to its rapidity, simplicity and high degree of radiochemical purity; however, some doubts exist about the yields of iodine which can be recovered, particularly from organically bound iodine. In the present study, chemical yields on the resin column were studied for irradiated urine, serum and milk by standard additions of iodide and thyroxine. It was found that yields are not quantitative but lie in the range 80–95%, depending on the matrix, with a variability of up to 6% standard deviation. In addition it was shown that no significant adsorption of iodine occurs on polythene ampoules from irradiated biological fluids of natural pH. Some comparative experiments between the resin technique and the oxygen flask ignition method on fluids before or after drying, respectively, showed satisfactory agreement. It is concluded that the iodinated resin technique is suitable for routine analyses or large scale screening programs.Presented in part at SAC 83, Edinburgh, July 1983.     

Depth-induced deviation of column bioleaching for uranium embedded in granite porphyry by defined mixed acidophilic bacteria

Journal of Radioanalytical and Nuclear Chemistry - The bioleaching performance in column reactors from a refractory uranium ore by Acidithiobacillus ferrooxidans (A. ferrooxidans),...     

Determination of iodine in common salt by an automatic reaction-rate method

An automatic reaction-rate method is described for the ultramicro determination of iodine in common salt. The method utilizes the acceleration of the reaction between ceric sulfate and arsenious acid by iodine. The time required for the reaction to consume a fixed amount of ceric ions is measured automatically and related directly to the iodine concentration. Measurements btained in salt samples containing 3 to 7500 μg of iodine per 100g were precise to within 2% or 0.3 μg of iodine, whichever is larger. Measurement times varied from a few sec to about 2min.     

Separation of iodine produced from fission with a porous metal silver column in99Mo production

In Argentina, at the Ezeiza Atomic Center,¹³¹I is produced by wet distillation of natural tellurium dioxide irradiated with thermal neutrons in a pool-type reactor. In order to recover the¹³¹I present in the production process of fission⁹⁹Mo obtained by irradiation of UAL_x/Al targets (with 90% enriched uranium) a separation method was developed. Iodine isotopes can be separated from a sodium hydroxide solution containing fission products using a column filled with alternate beds of glass microspheres and porous metal silver. Tests with tracers were performed in radiochemical laboratory. Following this results, a series of tests with higher activities (3 TBq of⁹⁹Mo and 0.7 TBq of¹³¹I) were carried out in hot cells. Molybdenum passes through the silver column, while¹³¹I retention was 92–97% in tracer test and 90% in optimised hot cell tests. This result depends on several facts that are discussed. An initial separation of iodine isotopes diminishes radiation damage on ion-exchange resin used in the subsequent molybdenum purification, improving its retention and elution yield.     

Utilization of a mixed-bed column for the removal of iodine from radioactive process waste solutions

A boron carbide capsule was previously designed and tested by Pacific Northwest National Laboratory (PNNL) and Washington State University (WSU) for spectral-tailoring in mixed spectrum reactors. The presented work used this B₄C capsule to create a fission product sample from the irradiation of highly enriched uranium (HEU) with a fast fission neutron spectrum. An HEU foil was irradiated inside of the capsule in WSU’s 1 MW TRIGA reactor at full power for 200 min to produce 5.8 × 10¹³ fissions. After 3 days of cooling, the sample was shipped to PNNL for radiochemical separations and analysis by gamma and beta spectroscopy. Fission yields for products were calculated from the radiometric measurements and compared to measurements from thermal neutron induced fission (analyzed in parallel with the non-thermal sample at PNNL) and published evaluated fast-pooled and thermal nuclear data. Reactor dosimetry measurements were also completed to fully characterize the neutron spectrum and total fluence of the irradiation.     

Development of a definitive method for iodine speciation in aquatic systems

Summary A definitive method of isotope dilution mass spectrometry (IDMS) was developed to determine four different iodine species in aquatic systems (iodide, iodate and two organoiodine compounds: one of the organic species is chromatographically elutable from a column filled with an anion exchanger resin, the other one is not). The iodine species were analysed after the isotope dilution step with an enriched ¹²⁹I spike and after their chromatographic separation. The total iodine concentration was measured after decomposition of organic compounds in the aquatic system by UV irradiation. Different types of natural water samples (river water, water of a pond, moorland lake water) were analysed and important water parameters like pH-value, redox potential, oxygen content and dissolved organic carbon were measured for each of these samples. The total iodine concentration in the different samples differed only slightly in the range of 2–7 g/l. In most of the moorland lake water samples only the two organoiodine species could be detected. In these samples the concentration of iodide and iodate was less than the detection limit of 0.5 g/l and 0.1 g/l, respectively. On the other hand, all four iodine species could be determined in most of the river water samples. Positive correlations were found for the oxygen content of the water samples and the iodate concentration as well as for the redox potential and the anionic organoiodine compound.In memoriam of Dr. I. Linus Barnes who died in January, 1990. Dr. Barnes was senior scientist at the National Institute of Standard and Technology in Gaithersburg, USA. He made numerous outstanding contributions to the field of mass spectrometry and IDMS     

Scale-up of “myxalin” purification by a pseudoaffinity method using a radial flow column

Summary Myxalin is a newly defined bacterial anticoagulant. It has been previously purified on Histidyl-Sepharose, on a small scale. We describe a scale-up of this procedure using a radial flow column (Sepragen^?). This design permits the use of the same soft gel matrix with 15-fold increase in flow rate compared to the linear system and a simple extrapolation of the operating conditions when optimized on a smaller scale gave no decrease in resolution. There are moreover, better activity yields and very interesting economic advantages.     

Simultaneous determination of hydrogen as its iodine equivalent and of nitrogen by a volumetric method

Summary The method developed for simultaneous determination of hydrogen (by means of an equivalent amount of iodine) and of nitrogen by a volumetric method, is based on a flash combustion technique in a stream of CO₂ (100 ml/min) with controlled addition of O₂ (20%). Hydrogen is determined by conversion of water into hydrogen chloride on anhydrous magnesium chloride heated at 600–650° C, and reaction of the hydrogen chloride with Ag₂OI₂ at 220° C to yield iodine, which is collected on silver and weighed. The precision of the determination of hydrogen is excellent, the standard deviation being 0.008–0.017% abs., about a tenth of that obtained by the classical methods. The error in the determination of hydrogen was ±0.006% abs.

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Gleichzeitige Bestimmung von Wasserstoff als dessen Jodäquivalent und von Stickstoff auf volumetrischem Wege

Zusammenfassung Die entwickelte Methode zur gleichzeitigen Bestimmung von Wasserstoff in Form seines Jodäquivalents und von Stickstoff auf gasvolumetrischem Wege beruht auf der Entflammungsmineralisation im CO₂-Strom (100 cm³/min) mit kontrolliertem Zusatz von O₂ (20%). Der Gasstrom wird zusätzlich über P₂O₅ getrocknet. Die dem Wasserstoff äquivalente Jodmenge wird an metallischem Silber gebunden und gravimetrisch bestimmt, wobei Wasser bei 600–650° C mit Magnesiumchlorid in Chlorwasserstoff übergeführt wird, der nachfolgend bei 220° C mit Ag₂Oj₂ zu Jod umgesetzt wird. Für Verbindungen, die neben C, H, N und O auch Br, Cl, P und S enthalten, werden Wasserstoffresultate mit hoher Präzision erzielt:s _H beträgt 0,008 bis 0,017% absolut und ist etwa 10mal kleiner als bei den üblichen, klassischen Methoden. Die Genauigkeit der Wasserstoffbestimmung entspricht einem mittleren Fehler=±0,006% absolut. Die Resultate für den Wasserstoff und Stickstoff verlangen eine Blindwertkorrektur.

     

马一嘉,罗冰虹,谭凯馨

硫在作物生长过程中必不可少的营养元素之一,主要参与作物生理代谢及生长发育。因此,土壤中硫的含量一直是人们关注的热点,快速准确的检测方法也成为人们研究土壤中硫的关键。在高温燃烧碘量法测定土壤硫含量中,碘酸钾溶液滴定亚硫酸时,对于低含量样品,滴定终点的判断较为困难。通过大量的试验,采用硫代硫酸钠滴定吸收器中反应后剩余的碘酸钾溶液,滴定终点由蓝色消失为无色。终点便于肉眼的观察,提高了分析结果的准确性和再现性;采用EXCEL中的LINEST函数回归标准物质滴定校准工作曲线,方法简便快速。通过国家一级标准物质的分析验证,方法准确度高、精密度好,适用于大批量土壤样品中低含量硫的测定。     

Validation of a column liquid chromatographic method for phytate

A column liquid chromatographic method that uses a spectrophotometric detector for the analysis of phytate and other inositol phosphates in foodstuffs and seeds is described. It has been tested thoroughly and sent to 6 other laboratories where there was an interest in such an analytical method and the equipment was available for performing it. These samples were blinded to the individual collaborators. Also sent was a standard wheat bran sample available from the American Association of Cereal Chemists with a standard phytate value reported as 3.2%. The postcolumn sulfosalicylic acid reaction was developed in the 1950s as an analytical method for ferric ion. All reagents are aqueous solutions and the specific pH values of each are important. The column separation is at pH 4, which dissociates all phosphate analogs. The ferric sulfosalicylate is at pH 1.8. The postcolumn reaction is then at pH 2.0-2.3. At this pH, the sulfosalicylate complexes one ferric ion and will yield it to a stronger complexing agent such as a phosphate ester. At higher pH values, sulfosalicylate complexes 2 ferric ions and will yield neither to these anions. The method sensitivity is 8-12 nmoles/injection.