Application of displacement extraction chromatography in activation analysis

A method based on exchange reactions of metals with coordination compounds and termed displacement extraction chromatography is proposed. The method consists essentially in the successive displacement of elements with lower extraction constants, present in the form of coordination compounds in the organic phase on the column, by substoichiometric amounts of elements with higher extraction constants, admitted to the column in aqueous solution. The method was used to determine various contaminations in yttrium, molybdenum, zirconium, niobium and beryllium by activation analysis.     

Nuclear activation methods for the characterization of fossil fuels

A review is presented on the use of neutron activation analysis (NAA) for the analyses of coal, oil shale, tar sands and petroleum. Fast NAA has been widely used for the determination of oxygen, and to a limited extent, of other elements such as nitrogen and silicon. Reactor NAA followed by instrumental counting, and in specific cases, after radiochemical separations is discussed. Thermal and epithermal neutrons are both used. Limited use of the²⁵²Cf source has been made in fuel analysis. A complementary technique to NAA is the photon-activation analysis with linear accelerator. It can determine over thirty elements, many of them not possible to do by NAA. Round-robin analyses of standard coal, fly ash, or oil shale samples indicate nuclear activation methods are comparable in accuracy and precision to X-ray fluorescence or atomic spectrometric methods for most elements.     

Multielement neutron activation analysis of biological materials using chemical group separation and Ge(Li) gamma spectrometry

Neutron activation analysis (NAA) for the determination of some trace elements in biological materials is described. The method presented permits the simple and rapid determination of Se, Ag, Au, Sb, Pt (via¹⁹⁹Au), Hg, Co, Ni (via⁵⁸Co), Fe, Zn, Mo, Sn, Cr, Cd, Cu and As after radiochemical separation from Na, K, Cs, Rb and partially Br. For this purpose, postirradiation separation by extraction with mercury or zinc amalgam was used. Separation of gold by extraction with ethyl acetate or by precipitation with dimethylglyoxime was applied for the determination of gold and platinum in biological materials.     

Anwendung der Substöchiometrischen Verdrängung in Ionen-Assoziations-Systemen Für die Aktivierungsanalyse

The possibility of substoichiometric displacement in ion association systems of metal halogenide anions (chlorides and iodides) and extraction reagent cations is demonstrated. Tetrephenylarsonium halogenide, ternary amines and quaternary ammonium halogenides were used as extraction reagents. The method was applied to the determination of several impurities in aluminium by activation analysis.     

Determination of cadmium by differentialn pulse anodic-stripping voltammetry after salting-out extraction into acetonitrile

A selective and specific method is presented for anodic-stripping voltammetric determination of cadmium after extraction with 0.1Mtetrabutylammonium iodide solution in acetonitrile from aqueous ammonium sulphate solutions. The detection limit of this method is 0.2 ng ml (in the acetonitrile extract). Interference from matrices or large amounts of elements reduced at more positive potentials can be eliminated by prior extraction. The method has been applied to trace analysis for cadmium in zinc, lead and indium metals, and some inorganic salts.     

On the distribution of trace elements in human skeletons

Instrumental neutron activation analysis and flameless atomic absorption spectrometry have been used to study the occurence and distribution with a maximum of 25 elements in multiple sites of a skeleton and in the iliac crest of 69 ancient human skeletons. To study the distribution of trace elements between the different bone fractions the material of each sampling site was chemically treated to separate the collagen and the mineral from one another. Losses or contamination during the extraction procedure have been controled in detail by balance calculations. The elements can be subdivided into several groups due to the balance calculation and their association with the mineral. The analysis of the skeleton showed that the trace elements are distributed in varying degrees within a bone and throughout the skeleton their variation seems to be related to functional and structural conditions of the sampling site. The element content was observed to be higher at epiphyseal areas of long bones than in the shaft and higher in trabecular than in cortical bones. It was found that the element content of a single bone sample depends largely on the mass ratio spongiosa/compacta at the sampling site. By investigating an ancient population group, information about the “natural levels” and biological variation of trace elements was obtained. The results for F, Pb, Sr, and Zn in particular suggest that these elements could be useful in the study of health problems in man which involves the bone tissue.     

Utilizing Distinct Neutron Spectra and a System of Equations to Differentiate Competing Reactions in Activation Analysis

In activation analysis, the continuous neutron spectrum produced in a nuclear reactor can be both beneficial and detrimental. A continuous spectrum allows for activation of particular elements by using any number of neutron energies. However, upper threshold energies exist for most elements where reactions other than an (n, ) absorption will occur. In this situation, two different parent nuclides can be activated to the same product, which creates a problem in performing a quantitative analysis of one or the other nuclide. A methodology is presented where a system of equations is used to solve for the quantities of both nuclides by using different irradiation ports, and using specific neutron filters to "customize" the neutron flux.     

Use of tetracycline as complexing agent in radiochemical separations

The use of the antibiotic agent tetracycline for analytical purposes in solvent extraction procedures is presented. Individual extraction curves for the lanthanides, zinc, scandium, uranium, thorium, neptunium and protactinium were obtained. Separation of those elements one from another, and of uranium from selenium, bromine, antimony, barium, tantalum and tungsten was carried out. In all cases benzyl alcohol was the diluent used to dissolve tetracycline hydrochloride. Sodium chloride was used as supporting electrolyte for the lanthanide separations and sodium perchlorate for the other elements mentioned. Stability or formation constants for the lanthanide complexes as well as for thorium complex with tetracycline were determined by using the methods of average number of ligands, the limiting value (for thorium), the two parameters and the weighted least squares. For the lanthanides, the stability constants of the complexes Ln(TC)₃ go from 9.35±0.22 for lanthanum up to 10.84±0.11 for lutetium. For the Th(TC)₄ complex the formation constant is equal to 24.6±0.3. Radioisotopes of the respective elements were used for the determinations. When more than one radioelement was present in an experiment, a multichannel analyser coupled to Ge(Li) or NaI(Tl) detectors was used for counting the activities. When only one radioisotope was used, counting of the radioisotopes was made with a single-channel analyser (integral mode counting) coupled to a NaI(Tl) detector. Uranium was determined by activation analysis (epithermal neutrons). Radioisotopes of the elements were obtained by irradiation in the IPEN swimming-pool reactor. The natural radioisotope^{2 3 4}Th was used as label in the thorium experiments. In some separation procedures such as in the case of the pair uranium-neptunium, and of the pair scandium-zinc, the separation was obtained by properly adjusting the pH value of the aqueous phases, before the extraction operation. In other cases, addition of masking agents to the extraction system was required in order to perform the separation between the elements under study. In this way ethylenediaminetetraacetic acid (EDTA) was used as masking agent for scandium and the lanthanides in order to allow separation of uranium from those elements. Diethylenetriaminepentaacetic acid (DTPA) was used as masking agent for thorium in order to extract uranium into the organic phase. Separations of protactinium from thorium, and of uranium from protactinium and thorium, were accomplished by using sodium fluoride as masking agent for protactinium and DPTA as masking agent for thorium and protactinium at the same time. In the case of the separation of the lanthanides one from another it is necessary to resort to a multi-stage extraction procedure since the stability constants for those elements are too close.     

Photon and proton activation analysis of iron and steel standards using the internal standard method coupled with the standard addition method

The internal standard method coupled with the standard addition method has been applied to photon activation analysis and proton activation analysis of minor elements and trace impurities in various types of iron and steel samples issued by the Iron and Steel Institute of Japan (ISIJ). Samples and standard addition samples were once dissolved to mix homogeneously, an internal standard and elements to be determined and solidified as a silica-gel to make a similar matrix composition and geometry. Cerium and yttrium were used as an internal standard in photon and proton activation, respectively. In photon activation, 20 MeV electron beam was used for bremsstrahlung irradiation to reduce matrix activity and nuclear interference reactions, and the results were compared with those of 30 MeV irradiation. In proton activation, iron was removed by the MIBK extraction method after dissolving samples to reduce the radioactivity of⁵⁶Co from iron via⁵⁶Fe(p,n)⁵⁶Co reaction. The results of proton and photon activation analysis were in good agreement with the standard values of ISIJ.     

Neutron activation analysis of pure uranium: Preconcentration of impurity elements

We have developed a radiochemical neutron activation analysis technique (RNAA) of pure uranium with using extraction chromatographic separation of ²³⁹Np from impurity elements in TBP-6M HNO₃ media. The estimation of influence of fission products of ²³⁵U on the results by radiochemical neutron activation analysis has been carried out. For it we have performed NAA with preconcentration of impurity elements. Experiments show that in this case the apparent concentration of Y, Zr, Mo, Cs, La, Ce, Pr, Nd exceeds the true concentration by 2500–3000 times. Therefore, determination of these elements is not possible by RNAA. This technique allowed to use the determination of 26 impurity elements with detection limit 10⁻⁵–10⁻⁹% by mass. This developed technique may be used for the determination of impurities in uranium and its compounds.     

Neutron activation analysis of trace elements in sea water samples (author's transl)

Analytical values of trace elements in sea water samples have been fluctuated according to the sampling locations, the analytical procedures and so on. It is very important in marine chemistry to elucidate the cause of such concentration variations. This report is the analytical results of the samples obtained in the Pacific Ocean, the Indian Ocean and the Sea of Japan, by means of neutron activation analysis. As the preconcentration, APDC-chelate extraction and freeze-drying were adopted. The specimens obtained by this extraction from 500 or 800 ml samples were irradiated by KUR reactor for 1 min, 1 hr to 10 hrs and the gamma-ray spectrometry with a Ge(Li) detector was used for the determination of V, Mn, Cu, Zn, U, Fe, Co, Ni, Ag, Sb and Au. By about 80 hrs irradiation of the specimens obtained by freeze-drying from 20 ml samples and their gamma-ray spectrometry, Sc, Cr, Fe, Co, Zn, Rb, Sr, Ag, Sb and Cs were determined. The former procedure gives concentrations of elements in species reactable with APDC, but the latter method shows entire concentrations of the elements in the sea water samples. Some considerations on the analytical values and the comparisons of the both methods are described.     

Determination of trace elements by neutron activation analysis using dinonylnaphthalene sulfonic acid as a preconcentrating agent

Dinonylnaphthalene sulfonic acid (HD) has been used as a preconcentrating agent to enrich trace metal ions and to separate the interfering elements such as Na, K, Cl and Br which normally exist in the natural aqueous systems. Experiments were performed by extracting the ions in the aqueous medium with HD in n-hexane and subsequently back-extracted into a minimal volume of acid solution. Factors influencing the extraction efficiency of the ions of interest were investigated. The preconcentration technique developed in this study was applied to the determination of trace elements in biological and natural water samples by neutron activation analysis.     

Wirkungsbezogene Analytik: Zielgerichteter Stoffnachweis im Wasser

A new concept is introduced for water analysis, based on a tight hyphenation of chemical analysis and biotests. Biomolecular recognition elements such as proteins and nucleic acids integrated in specific reaction chains are used for binding and selective enrichment of (unknown) bio‐effective substances in water samples. After extraction or elution of the ligands or as an entire ligand‐target molecule‐complex the ligands were subsequently identified by high‐resolution, trace analysis instruments such as mass spectrometry. The so‐called bioresponse‐linked instrumental analysis combines the detection of potential biological effects with the exact identification of the causing agents. This methodolical strategy will help to optimize interpretations and to minimize costs in water analysis.     

Activation analysis of high-purity silicon

The triple comparator method is used for the analysis of impurities of high purity silicon by neutron activation. The ratios of the specific photopeak activities of the isotopes investigated to the specific photopeak activities of the gold, indium and cobalt comparators were determined. The triple comparator method avoids some tedious problems in the multi-element activation analysis and it is very well suited for the determination of ‘non-expected’ elements. Research associate of the N. F. W. O.     

A highly selective diethyldithiocarbamate extraction system in activation analysis of copper,indium, manganese and zinc

A versatile separation system based on the extraction of dithiocarbamates and applicable to the determination of copper, managanese, zinc and indium in a wide selection of materials by activation analysis is described. After the dissolution of the sample and a few simple operations which eliminate specific interferences, depending upon the material (e. g. sodium and gold in the NBS Standard Reference Glasses), carbamates are extracted under specific conditions by addition of appropriate complexing agents and selective stripping. Extreme separation factors permit interference-free counting using a sodium iodide detector. For example, indium is separated from a hundred thousand fold excess of manganese in the determination of the two elements in Orchard Leaves. Results are also presented for all four elements in Bowen's Kale, NBS Bovine Liver, and for Cu, In and Mn in the 0.02 ppm and 1 ppm SRM glasses.     

Sample treatment in chromatography-based speciation of organometallic pollutants.

Speciation analysis is nowadays performed routinely in many laboratories to control the quality of the environment, food and health. Chemical speciation analyses generally include the study of different oxidation state of elements or individual organometallic compounds. The determination of the different chemical forms of elements is still an analytical challenge, since they are often unstable and concentrations in different matrices of interest are in the microg l(-1) or even in the ng l(-1) range (e.g., estuarine waters) or ng g(-1) in sediments and biological tissues. For this reason, sensitive and selective analytical atomic techniques are being used as available detectors for speciation, generally coupled with chromatography for the time-resolved introduction of analytes into the atomic spectrometer. The complexity of these instrumental couplings has a straightforward consequence on the duration of the analysis, but sample preparation to separate and transfer the chemical species present in the sample into a solution to be accepted readily by a chromatographic column is the more critical step of total analysis, and demands considerable operator skills and time cost. Traditionally, liquid-liquid extraction has been employed for sample treatment with serious disadvantages, such as consumption, disposal and long-term exposure to organic solvent. In addition, they are usually cumbersome and time-consuming. Therefore, the introduction of new reagents such as sodium tetraethylborate for the simultaneous derivatization of several elements has been proposed. Other possibilities are based in the implementation of techniques for efficient and accelerated isolation of species from the sample matrix. This is the case for microwave-assisted extraction, solid-phase extraction and microextraction, supercritical fluid extraction or pressurized liquid extraction, which offer new possibilities in species treatment, and the advantages of a drastic reduction of the extraction time and the embodiment into on-line flow analysis systems. This new generation of treatment techniques constitutes a good choice as fast extraction methods for feasible species-selective analysis of organometallic compounds under the picogram level, that can be used for national regulatory agencies, governmental and industrial quality control laboratories, and consequently, for manufacturers of analytical instrumentation.     

Solvent extraction of Au(III) for preparation of a carrier-free multitracer and an Au tracer from an Au target

Separation of Au(III) and various carrier-free radionuclides by solvent extraction was investigated using an Au target irradiated by an energetic heavy-ion beam. Percentage extraction of Au(III) and coextraction of the radionuclides were determined with varying parameters such as kinds of solvent, molarity of HCl or pH, and Au concentration. Under the conditions where Au(III) was effectively extracted, namely extraction with ethyl acetate or isobutyl methyl ketone from 3 mol·dm^–3 HCl, carrier-free radionuclides of many elements were found to be more or less coextracted. Coextraction of radionuclides of some elements was found to increase with an increase in the concentration of Au(III). This finding is ascribed to the formation of strong association of the complex of these elements with chloroauric acid. In order to avoid serious loss of these elements by the extraction, lowering of the Au(III) concentration or the use of a masking agent such as sodium citrate is necessary. Gold(III) was shown to be effectively back extracted with a 0.1 mol·dm^–3 aqueous solution of 2-amino-2-hydroxymethyl-1,3-propanediol. Thus, a radiochemical procedure has been established for preparing a carrier-free multitracer and an Au tracer with carrier form from an Au target irradiated with a heavy-ion beam. Both tracers are now used individually for chemical and biological experiments.     

Microviscosity of ions and salting-out in the extraction of rare-earth and transplutonium elements

A chemical procedure has been developed for the separation of U, Th, Fe, Sc, Na, Ta and Mo, which interfere in neutron activation analysis of the lanthanide elements in rocks. This methods in based on the extraction of interferents, before irradiation of the samples, using a solution of tetracycline in benzyl alcohol. The lanthanide elements remain in the aqueous phase and are coprecipitated with calcium oxlate or ferric hydroxide for irradiation and subsequent determination by gamma-ray spectrometry. Conditions for the separation of these interferences are examined determining the extraction curves. The chemical separation procedure was applied in the analysis of lanthanides in geological materials and the results showing the accuracy and the reproducibility of the method are presented. The sensitivity for all the lanthanides was determined.     

Operationally defined extraction procedures for soil and sediment analysis: II. Certified reference materials

Single or sequential extraction procedures are often used for soil and sediment studies to determine forms or phases of elements (e.g. `bioavailable' forms of elements). The significance of the analytical results is highly dependent on the extraction procedures used, owing to the `operationally defined' character of these schemes which requires the adoption of standardized protocols. The first part of the present review discusses the aspects of standardization of leaching and extraction schemes as applied to environmental analysis. This second part focuses on the validation aspects of such procedures and describes the preparation and certification of soil and sediment reference materials certified for their extractable trace element contents, following standardized single and sequential extraction procedures.     

Mercury and trace element fractionation in Almaden soils by application of different sequential extraction procedures

A comparative evaluation of the mercury distribution in a soil sample from Almaden (Spain) has been performed by applying three different sequential extraction procedures, namely, modified BCR (three steps in sequence), Di Giulio–Ryan (four steps in sequence), and a specific SEP developed at CIEMAT (six steps in sequence). There were important differences in the mercury extraction results obtained by the three procedures according to the reagents applied and the sequence of their application. These findings highlight the difficulty of setting a universal SEP to obtain information on metal fractions of different mobility for any soil sample, as well as the requirement for knowledge about the mineralogical and chemical characteristics of the samples. The specific six-step CIEMAT sequential extraction procedure was applied to a soil profile (Ap, Ah, Bt1, and Bt2 horizons). The distribution of mercury and major, minor, and trace elements in the different fractions were determined. The results indicate that mercury is mainly released with 6 M HCl. The strong association of mercury with crystalline iron oxyhydroxides, present in all the horizons of the profile, and/or the solubility of some mercury compounds in such acid can explain this fact. Minor mercury is found in the fraction assigned to oxidizable matter and in the final insoluble residue (cinnabar).