Differential determination of203Hg and14C or35S in double labelled biological samples

The differential determination of²⁰³Hg and¹⁴C or³⁵S in double labelled biological samples is presented. The biological samples were mineralized with 70% HClO₄ and 30% H₂O₂ in minivals MILLI-6. The γ-activity of²⁰³Hg was measured on a well scintillation counter. The total activity, due to²⁰³Hg and¹⁴C or³⁵S, was measured by the liquid scintillation technique after addition of Aquasol into the same vials. The method of external standard channel ratio was used for standardization. Very good recoveries were obtained: 100±0.7% for²⁰³Hg and 94.6–101.0% for¹⁴C and³⁵S. This method could be used for other β, γ and β-active nuclides with similar β-spectra.     

Determination of airborne methyl ethyl ketone peroxide

Summary A new method for the determination of airborne methyl ethyl ketone peroxide (MEKP) is based on the reaction of peroxides with 4-tert-butyl catechol, in which the peroxide radicals oxidize the catechol to the corresponding benzoquinone. The yellow colour generated is measured at 395 nm. Sampling from factory air can be performed by aluminium oxide sampling tubes. Glacial acetic acid is used as a solvent and for the desorption of the peroxide from the aluminium oxide. The detection limit (0.05 mg/m³ for 4 h samples) for the MEKP in air is well below the current hygienic reference value (1.5 mg/m³). The method was used for MEKP determinations during lamination applications in the production of reinforced unsaturated polyester plastics, where the airborne concentrations of the peroxide were well below the current hygienic reference values.     

Determination of radiochemical purity of chlormerodrin-203 by electrophoretic method

An electrophoretic method to control the radiochemical purity of chlormerodrin-203 is described. Optimum conditions for the separation of inorganic and organically bound mercury-203 were determined by investigating its mobility in the concentration range of 1·10⁻⁵–1·10⁻² M NaCl. Maximum separation, of²⁰³Hg and hydroxychlormerodrin was achieved at 0.05M NaCl, at the potential gradient of 8V/cm for 2 hrs.     

Messung von Isotopenverhältnissen des Quecksilbers im Breich Seiner Natürlichen Häufigkeit Durch Photonenaktivierungsanalyse

By irradiation of mercury with 15 MeV bremsstrahlung the radionuclides²⁰³Hg,^199mHg and^197mHg were generated. This method is suitable for determination of the isotopic relations¹⁹⁸Hg/²⁰⁴Hg and²⁰⁰Hg/²⁰⁴Hg. From mercury of natural isotopic content and of mercury enriched in²⁰⁴Hg were prepared samples with defined isotopic relations and these irradiated for two hours at the Mikrotron (23–25 μA) of the Joint Institute of Nuclear Research Dubna. The estimated standard deviation of the measured activation relations is approximately 2% (rel.), those of the mass-spectrometric method approximately 1% (rel.)      

Radiochemical solvent extraction method for the determination of Cd and Hg using thionalide as a single reagent

A radiochemical solvent extraction method has been developed for the simultaneous determination of submicrogram amounts of Cd and Hg using^115mCd and²⁰³Hg tracers respectively and thionalide as a single complexing reagent. Hg was determined by 0.05% thionalide in ethyl methyl ketone (EMK) at pH 8.5, masking Cd with 0.1M KCN. From the aqueous phase Cd was demasked using formal-dehyde-acetic acid, pH adjusted to 9.5 and extracted into 0.05% thionalide in chloroform. The method is simple, fast and yields accurate results.     

Ein Trennverfahren zur Bestimmung von Ag, Cd, Hg und Zn in biologischem Material durch radiochemische Neutronenaktivierungsanalyse

Zusammenfassung Es wurde ein einfaches Trennverfahren für die radiochemische NAA von biologischem Material entwickelt, mit dem aus einem komplexen Nuklidgemisch die Indicator-Radionuklide ^110mAg, ¹⁹⁸Au, ¹¹⁵Cd, ²⁰³Hg und ⁶⁵Zn als eine Gruppe mit Ausbeuten >99% abgetrennt werden können. Besonders geeignet ist dieses Verfahren für die Trennung des ²⁰³Hg von ⁷⁵Se und ⁶⁵Zn von ⁴⁶Sc, die sich bei einer gammaspektrometrischen Messung in der instrumentellen NAA gegenseitig stören. Gleichzeitig können die Nachweisgrenzen für Ag, Au und Cd wesentlich gesteigert werden. Das Verfahren basiert auf dem Aufschluß der bestrahlten Probe in einem Gemisch von HNO₃, HCl und H₂O₂, und auf der Trennung von Ag, Au, Cd, Hg und Zn an Dowex 1X8 aus 1,5 M salzsaurer Probelösung. Die Leistungsfähigkeit dieses Verfahrens wurde an Beispielen der Analyse von Flechten und verschiedenen Pilzarten demonstriert. Bei den verwendeten experimentellen Bedingungen liegen die Nachweisgrenzen in der Größenordnung von 10 ng/g.

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A separation procedure for the determination of Ag, Cd, Hg and Zn in biological material by radiochemical neutron activation analysis

Summary A simple separation procedure for the determination of Ag, Au, Cd, Hg and Zn in biological material by radiochemical neutron activation analysis was developed. It enables the separation of the indicator radionuclides ^110mAg, ¹⁹⁸Au, ¹¹⁵Cd, ²⁰³Hg and ⁶⁵Zn in a group with yields >99% and is well suited for the separation of ²⁰³Hg from ⁷⁵Se and ⁶⁵Zn from ⁴⁶Sc. The separation of these radionuclides is often necessary because of the occurrence of instrumental interferences in the instrumental neutron activation analysis. Simultaneously, the limits of detection for Ag, Au and Cd can significantly be improved. The method is based on the decomposition of the sample in the mixture of HNO₃/HCl/H₂O₂ and on the separation of Ag, Au, Cd, Hg and Zn on Dowex 1X8 from a sample solution being 1.5 M with HCl. The applicability of this method is demonstrated by the analysis of lichens and several kinds of fungi. For the experimental conditions used, the limits of detection are of the order of magnitude of 10 ng/g.

     

Comparative tests on the efficiency of three methods of methylmercury extraction in environmental samples

Mercury is used in gold mining in the Brazilian Amazon and released in significant amounts to the environment as Hg⁰. After its oxidation it may be methylated, mainly in bottom sediments and in the rhizosphere of floating aquatic macrophytes. Methylmercury (MeHg) is highly bioavailable and subject to biomagnification. The objective of this work was to evaluate the efficiency of three methylmercury extraction techniques, applied to replicates of environmental samples (stream sediments from Floresta ­da Tijuca, Rio de Janeiro; and roots of the floating macrophyte Eichhornia crassipes from Lagoinha, Rio de Janeiro) previously incubated with ²⁰³Hg²⁺. Method A is based on acid leaching and extraction of Me²⁰³Hg in toluene. Method B uses alkaline digestion, extraction in dithizone–benzene and separation of organic and inorganic ²⁰³Hg dithizonates by thin‐layer chromatography (TLC). Method C consists in separating the Me²⁰³Hg from the sample matrix by distillation. Total ²⁰³Hg and Me²⁰³Hg were detected by gamma spectrometry or liquid scintillation. For both matrices, Me²⁰³Hg extraction efficiency was better for smaller samples (range: 0.08–0.5 g for sediment, 0.1–0.5 g for E. crassipes roots). For the sediment samples, the three selected methods presented similar Me²⁰³Hg extraction efficiencies: 7–13, 5–14 and 4–17% of total added ²⁰³Hg was found as MeHg for procedures A, B and C, respectively. For E. crassipes roots, on the other hand, a lower extraction efficiency was obtained for the procedure C (11–28% of total ²⁰³Hg present as Me²⁰³Hg) than for methods B (22–36%) and A (20–44%). In all the root samples prepared with procedure B, a strong and durable chemiluminescence effect was observed, which required measuring the final Me²⁰³Hg extracts by gamma spectrometry only. In the specific conditions we used, extraction via distillation required re‐extraction of Me²⁰³Hg in the distillate, due to the presence of traces of inorganic ²⁰³Hg in the latter. Copyright © 1999 John Wiley & Sons, Ltd.     

Quality control of201TlCl solution obtained at IPEN-CNEN/SP

The radiopharmaceutical²⁰¹TlCl(thallium-201 chloride) is used in nuclear medicine for myocardial visualization. The solution of²⁰¹TlCl was prepared using²⁰¹Tl obtained by irradiating a natural mercury target with protons from the CV-28 cyclotron installed at IPEN-CNEN/SP. This solution was subjected to different quality control processes required for its use in medicine. Some of these controls concerned the determination of the radionuclidic impurities:²⁰⁰Tl,²⁰²Tl and²⁰³Hg; the chemical identification of²⁰¹Tl⁺; the hydrazine concentration, mercury contamination and the presence of phosphate. Furthermore. the biological distribution in Wistar rats and tests for sterility, pyrogenicity and toxicity were carried out. It was verified that the solution obtained was in the form of thallous chloride. This radiopharmaceutical gave good heart images in animals but due to the high levels of²⁰⁰Tl and²⁰²Tl its use in humans is not possible unless enriched²⁰²Hg is used as target in the irradiation.     

Determination of plutonium,americium and curium in airborne effluents of nuclear power plants

A radiochemical method has been developed for the determination of²³⁸Pu,^{239, 240}Pu,²⁴¹Am,²⁴²Cm and²⁴⁴Cm in airborne effluents of nuclear power plants. The method involves conversion of transuranium elements to acid-soluble forms, dissolution, purification, electrodeposition and alpha spectrometric determination. Final recovery ranged from 69.0 to 75.4% for plutonium and from 26.8 to 68.3% for americium and curium.     

Relative efficiency calibration of Ge(Li) detector in low energy region

The relative gamma-ray intensities in the energy region between 122 and 411 keV in the decay of¹⁵²Eu were measured by using a Ge(Li) detector. Its efficiency calibration was carried out with the radioactive sources of²⁴¹Am,⁵⁷Co,²⁰³Hg,¹³⁷Cs,¹³³Ba,⁷⁵Se,¹⁶⁹Yb and¹⁹²Ir.     

Measurement techniques for mercury species in ambient air

This review critically evaluates the measurement methodologies most commonly employed for the analysis of the various forms of mercury (Hg) in air. Emphasis is given to the three most common forms of mercury in air [i.e. gaseous elemental mercury (GEM, Hg⁰), reactive gaseous mercury (RGM), and particle-bound mercury (Hg_p)]. Moreover, we also briefly describe methods dealing with gas-phase analysis of organic mercury species (e.g., mostly methyl mercury), as they are also reported to be present in air on rare occasions. To begin with, we describe the approaches to sampling airborne mercury species and associated sample-treatment strategies. We evaluate both conventional and emerging alternative detection techniques for different mercury forms with respect to their applicability in airborne mercury analysis. We also discuss the artifacts and the biases associated with analysis of different mercury species. Finally, the review summarizes current methodological developments for the determination of mercury in air and highlights future prospects for improvements.     

Determination of mercury and methylmercury in hair samples by neutron activation

Mercury and methylmercury in hair samples were determined by neutron activation analysis. Samples were digested in 10M NaOH, and methylmercury was then isolated by solvent extraction with toluene. The isolated methylmercury was then absorbed onto cysteine paper. The dried cysteine paper was activated for six hours in a TRIGA reactor and methylmercury was analysed via 279.2 keV of²⁰³Hg. Methylmercury and total mercury in some standard reference materials were also analysed, and the results were in good agreement with those reported in the literature. Results for hair samples showed that the methylmercury concentration ranged 14–40% of the total mercury. Gas chromatogram showed that methylmercury was only present in the samples analysed. In samples where methylmercury and other organic mercury are presented, the NAA method is good for the determination of the total organic mercury only.     

Comparison of Different Analytical Techniques for the Determination of Organic Mercury

Abstract

Methods for the determination of (1) total organic mercury (Hg) using an extraction +neutron activation analysis, (2) the sum of methyl-Hg+phenyl-Hg using ¹³¹I^?-Cl^? exchange and (3) methyl-Hg using two different Westöö modifications, have been compared. Sample materials were 8 falcon livers, 5 pike livers and 2 pike muscles. Although differences were found between the methods, interaction effects caused by either sample inhomogeneity or bad performance of the analytical methods impeded a clear interpretation of the comparison. Total Hg in the samples was determined by neutron activation analysis (NAA) and atomic absorption spectrometry. The accuracy of the total Hg determination using NAA was verified by the analysis of certified reference material.

In addition to the other organic Hg determinations phenyl-Hg was determined separately in some of the samples by an isotope exchange method using ²⁰³Hg²⁺.

The main conclusion of the study was that there is a demand for reference materials certified for at least total organic Hg and methyl-Hg.     

Untersuchung von systematischen Fehlern bei der Bestimmung von Hg-Gesamtgehalten im Bereich < 10?5% in anorganischen und organischen Matrices mit zwei unabh?ngigen Verbundverfahren

Zusammenfassung Systematische Fehler, die bei der Bestimmung von Hg im ng/g und pg/g-Bereich vor allem bei der Probennahme, Probenvorbereitung und beim Probenaufschluß auftreten, wurden mit ²⁰³Hg Radiotracertechniken und mit zwei für den Spurenbereich entwickelten Verbundverfahren untersucht. Beim emissionsspektrometrischen Verfahren (OES-MIP) wird die Probe im mikrowelleninduzierten Sauerstoff Plasma (MIP) verascht und das Hg nach Abtrennung mit einem Au-Absorber in einem Argon-Plasma angeregt. Das emittierte Hg-Licht wird mit einer Photodiode registriert. Nachweisgrenze: 0,01 ng Hg; Variationskoeffizient: 5% für 1 ng Hg. Beim zweiten Verfahren wird Hg nach dem Probenaufschluß (HClO₃/HNO₃) mit einem mechanisierten Aufschlußsystem nach der Kalt-Dampf-Technik (Ascorbinsäure/SnCl₂ bzw. NaBH₄) freigesetzt, an einem Gold-Absorber gesammelt und anschließend durch flammenlose AAS bei 253,7 nm bestimmt. Nachweisgrenze: 0,5 ng Hg; Variationskoeffizient: 5% für 5 ng Hg.

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Study of systematic errors in the determination of total Hg levels in the range < 10^–5% in inorganic and organic matrices with two reliable spectrometrical determination procedures

Summary In the determination of Hg at ng/g and pg/g levels systematic errors are due to faults in the analytical methods such as intake, preparation and decomposition of a sample. The sources of these errors have been studied both with ²⁰³Hg-radiotracer techniques and two multi-stage procedures developed for the determination of trace levels. The emission spectrometric (OES-MIP) procedure includes incineration of the sample in a microwave induced oxygen plasma (MIP), the isolation and enrichment on a gold absorbent and its excitation in an argon plasma (MIP). The emitted Hg-radiation (253,7 nm) is evaluated photometrically with a semiconductor element. The detection limit of the OES-MIP procedure was found to be 0,01 ng, the coefficient of variation 5% for 1 ng Hg. The second procedure combines a semi-automated wet digestion method (HClO₃/HNO₃) with a reduction-aeration (ascorbic acid/SnCl₂), and the flameless atomic absorption technique (253,7 nm). The detection limit of this procedure was found to be 0,5 ng, the coefficient of variation 5% for 5 ng Hg.

Wir danken der Deutschen Forschungsgemeinschaft Bonn-Bad Godesberg für Personal- und Sachmittel, Herrn Professor Dr. E. Schlichting, Universität Hohenheim für Bodenproben und wertvolle Diskussionen, der Firma Kalle, Wiesbaden, für die Bereitstellung von Kunststoff-Folien sowie Fräulein R. Kolb für ihre Hilfe bei der Durchführung dieser Arbeit.     

Analysis of inorganic mercury species associated with airborne particulate matter/aerosols: method development

This paper describes a method for speciation of Hg associated with airborne particulate matter. This method uses a mini-sampler for sample collection and analysis, thermal desorption for separating Hg species, and inductively coupled plasma mass spectrometry (ICP–MS) for identification and quantification of Hg. Coal fly ash spiked with different Hg compounds (e.g. Hg⁰, HgCl₂, HgO, and HgS) was used for qualitative calibration. A standard reference material with a certified value for Hg concentration was used to evaluate the method. When the temperature of the furnace was programmed at a linear rate of increase of 50° min^–1, different Hg compounds could clearly be separated. Three airborne particulate matter samples were collected in parallel in Toronto, ON, Canada and analyzed using this method. Reproducible results were obtained and Hg⁰, HgCl₂, HgO, and HgS species from these samples were detected.     

Determination of thallium in zinc by proton activation analysis

The determination of thallium in unalloyed zinc by proton activation analysis, based on the ²⁰³Tl (p,3n)²⁰¹Pb reaction, is described. Lead-201 was radiochemically separated from the matrix activities (gallium, copper and zinc) by cation exchange, anodic deposition of lead (IV) oxide and precipitation as lead thionalide. Thallium (III) oxide was used as the standard. The method was applied to the BCR reference materials 321,322,323,324 and 325 Unalloyed Zinc. The detection limit is 17 ng g^?1. The relative standard deviation obtainable is 5-1% in the 1-40 μg g^?1 concentration range.     

Radiometric trace analysis of cobalt with diethyldithiocarbamate-35S,or 203Hg

Two radiometric methods for the determination of submugram amounts of cobalt are described. (A) Cobalt is extracted from an ammoniacal solution with a zinc-diethyldithiocarbamate-³⁵S solution in chloroform. Excess reagent and interfering metals are removed with mercury(II) and cyanide. The ³⁵S in the final organic layer is a measure of the cobalt in this layer. (B) Cobalt is extracted from an ammoniacal solution with a fixed amount of zinc-DDC in chloroform. Excess reagent and complexes of foreign metals are removed by exchange with ²⁰³Hg⁺² and the ²⁰³Hg in the chloroform (compared with a blank) acts as a measure of the cobalt. Method A is applicable to 0.1 μg of cobalt and method B to 0.8 μg. As the efficiency of both processes is variable, isotope dilution with ⁶⁰Co is carried out, A 10-fold excess of foreign metals is permitted in method A and a 4-fold excess in method B ; larger amounts are previously removed, e.g. by extraction with inactive zinc-DDC from sodium hydroxide media.     

A method for assessing and correcting coincidence summing effects for germanium detector efficiency calibrations

The addition of⁵⁴Mn and⁶⁵Zn to a nine-radionuclide standard (containing²⁴¹Am.,¹⁰⁹Cd.⁵⁷Co,¹³⁹Ce,²⁰³Hg.¹¹³Sn,¹³⁷Cs,⁸⁸Y, and⁶⁰Co) provides the capability to determine the extent of coincidence summing for gamma rays from⁸⁸Y and⁶⁰Co. A method for correcting the efficiency points at 1332 keV (⁶⁰Co) and 1836 keV (⁸⁸Y) for coincidence summing is presented.     

Possibilities of ED-XRF with radionuclide sources for analysis of plants

A comparative evaluation of the applicability of different radionuclide sources for the determination of toxic elements in plants by ED-XRF is presented.²³⁸Pu or¹⁰⁹Cd are suggested as most suitable single excitation sources in ED-XRF for monitoring investigations. More elements are determined with a combination of⁵⁵F/¹⁰⁹Cd(²³⁸Pu)/²⁴¹Am. The results obtained by radionuclide ED-XRF analysis of different plants show that the method permits the reliable determination of Br, Ca, Fe, K, Mn, Rb, Sr and Zn in plant bioindicators. For toxic elements like As, Cd, Cu Cr, Hg, Ni, Se and Pb the detection limits of the method are not low enough.     

Effects of polonium-210 on determination of atmospheric gross alpha-radioactivity

Ingrowth and decay of²¹⁰Po on air filters used for gross alpha-determination can lead to errors in estimation of long-lived airborne radioactivity. Interferences are present to some degree in all samples and change with time, making the gross alpha-technique quantitatively invalid. However, since the degree of equilibrium between²¹⁰Po and its parent²¹⁰Pb can be calculated at any time after filter collection, it should be possible to use the gross alpha-method to estimate past atmospheric concentrations of²¹⁰Pb. Measurements on filters after elapsed times of up to 15 years show that such determinations are feasible.