Continuous substoichiometric determination of traces of mercury by radioactive isotope-dilution analysis

The possibility of automating substoichiometric analysis by isotope dilution has been proposed previously. Automation where the analysis is based on solvent extraction has now been carried out experimentally. Preliminary experiments are described by means of which optimum conditions for this type of automated determination can be chosen and its reproducibility and selectivity checked. As an example traces of mercury down to 5 × 10⁻⁶ g are determined and the method is applied to the analysis of low-grade cinnabar ores.     

Determination of iron in silicate rocks by substoichiometric radioisotope dilution analysis

Iron is determined in rocks by an isotope dilution method involving dissolution with hydro fluoric acid, extraction of iron(III) chloride into isopropyl methyl ketone, stripping with dilute nitric acid, and substoichiometric separation of the Fe-EDTA complex on a cation-exchange column. The precision and accuracy are 1.5% relative or better, as indicated by analyses of some U.S. Geological Survey standard rocks.     

A substoichiometric radioisotope dilution study using210Pb

A radioisotope dilution procedure has been developed which permits the determination of lead over a concentration range of 0.1 to 10 ppm. Samples in an ammoniacal cyanide/sulfite medium are labelled with²¹⁰Pb, followed by addition of substoichiometric amount of dithizone. The Pb/HDz/₂ formed is extracted into CH₂Cl₂, and aliquot portions are taken for liquid scintillation counting. Count rate is plotted vs. the reciprocal of the lead concentration, yielding a straight line. An average error of ±3.5% is estimated, based on a linear least squares fit.     

The determination of zinc by substoichiometric isotope dilution

Recently, R??I?KA et al. proposed a determination of zinc in highly pure germanium dioxide by a substoichiometric extraction technique. In the present work, the effects on the substoichiometric extraction of equilibrium time, pH and interfering ions were investigated by radioactive tracer techniques and spectrophotometric measurements. The sensitivity of the procedure is limited by the blanks and the addition of oxalate ions can give rise to inaccurate results. The specific activity of ⁶⁵Zn was also determined by substoichiometric extraction.     

Redox substoichiometric determination of arsenic in biological materials by neutron activation analysis

A redox substoichiometry is proposed for an accurate and precise determination of arsenic. This method is based on the substoichiometric oxidation of trivalent arsenic to pentavalent with potassium bromate or ceric sulfate followed by the separation of these species by thionalide extraction of trivalent arsenic. It was applied to neutron activation analysis of arsenic in the NBS SRM Orchard Leaves and the Shark Powder. The results were obtained with an excellent accuracy and precision.     

Advantages of a two-detector system in automated substoichiometric radioisotope dilution analysis

Automation widens the scope of substoichiometric radioisotope dilution analysis. This is because the very strict requirement of the manual method-chemical separation of exactly equal quantities of the test substance-need no longer be fulfilled: reproducibility of the determination is reached by means of automated operation and activity measurement. The theory given in this paper shows how the choice of suitable chemical reactions is widened and why the reliability and the advantages of isotope dilution analysis are secured by the use of a two-detector system.     

Simultaneous determination of copper,mercury and antimony in biological samples by neutron activation and substoichiometric extraction

A simple and accurate method has been developed for the determination of copper, mercury and antimony by thermal neutron activation analysis involving substoichiometric extraction technique. The results of analysis indicate that copper, mercury and antimony in biological samples can be determined with an accuracy of 5.3%, 5.5% and 6.2%, respectively. Two samples and a standard can be analysed by the proposed method in about 4 hrs. Part of this work was presented at the International Conference on Modern Trends in Activation Analysis, Saclay, Paris, France, October 2–6, 1972.     

Coprecipitation as a means for the determination of zirconium traces by isotope dilution analysis in the presence of substoichiometric amounts of complexones

The possibility of using coprecipitation on Cu(OH)₂·nH₂O and Fe₂O₃·nH₂O precipitates to separate a part of zirconium unreacted with complexone in the presence of a 100-fold amount of impurities has been examined. The reaction between ethylenedia-minetetraacetic acid (EDTA) and zirconium 10⁻³−10⁻⁵ M has been used as substoichiometric reaction. A zirconium determination in the concentration range of 10⁻⁴−10⁻⁶ g/ml in artificial mixtures and steel samples has been developed using the systems of EDTA-Zr−Cu(OH)₂·nH₂O and EDTA−Zr−Fe₂O₃·nH₂O.     

Determination of trace elements and radioactive materials by substoichiometric isotope dilution analysis

Substoichiometric isotope dilution analysis has been applied for the determination of trace elements in liquid samples, of carrier content in radioisotope solution and of concentration of organic reagent. Cu in mineral acids and in ZnSe single crystal was determined by the substoichiometric extraction with dithizone. The values of 1.8 and 0.018 ppm in nitric acid and distilled one and of 1.4 and 0.44 ppm in ZnSe were obtained. Cu and P carrier contents in⁶⁴Cu and³²P solutions were determined by the substoichiometric extractions with dithizone in CCl₄ and with molybdic acid into MIBK in the series of the solutions adding various amounts of Cu or P carrier. An analogous method has been applied for the determination of dithizone and diethyldithiocarbamate solutions. The method was also applied for the determination of⁶⁰Co radioactivity in environmental samples. The analytical result of water samples is described.     

Trace determination of mercury in biological materials by flameless atomic absorption spectrometry

A new rapid wet-ashing procedure for biological material is described. The samples are boiled for 5–10 min in a mixture of nitric and hydrobromic acid under reflux. Mercury is then determined by the flameless cold-vapour, atomic absorption technique and complete release is shown to occur even when the fat present is not fully decomposed. The results are discussed with regard to the normal bromine and iodine content of marine samples. The enhancement obtained with bromine can easily be compensated by digesting the standards. Iodine, however, reduces the peak heights and the content of this element must be judged separately for samples other than fish, which can always be safely analysed without interference.     

Automated wet ashing and multi-metal determination in biological materials by atomic-absorption spectrometry

Ohne Zusammenfassung

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Automated wet ashing and multi-metal determination in biological materials by atomic-absorption spectrometry

     

Determination of lead in biological and environmental samples by203Pb isotope dilution substoichiometric method

A procedure for the determination of lead in various biological and environmental samples by²⁰³Pb radioisotope dilution substoichiometric method is presented. The accuracy of the method by comparison with the literature values of reference materials appears to be good. The standard deviation of the method is less than 10%, and detection limit is about 0.1 g of lead.     

Kinetic micro determination of mercury in natural waters and biological materials

Summary A wet digestion has been developed to prepare water and biological samples for a kinetic determination of mercury using an iodide-catalyzed reaction between cerium(IV) and arsenite(III). A mercury-free control, prepared using ion-exchange with a selective chelating resin, was used by adding mercury standards to make a calibration curve. Both inorganic and organic mercury can be determined by the method described either in water or biological samples containing mercury in the range of 0.05 to 2.0g per ml. The procedure can be used satisfactorily down to the 0.05-ppm level for fresh water and urine with an overall error of less than 5 %. The method can also be employed for the determination of mercury in sea water or blood serum with an error of 10 % or less and gives results which compare favourably with other procedures.

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Zusammenfassung Die nasse Veraschung zur Aufbereitung von Wasserproben und von biologischem Material für die kinetische Quecksilberbestimmung mit Hilfe der jodkatalysierten Cer-Arsenit-Reaktion wurde beschrieben. Durch Ionenaustausch an einem selektiven Harz wurde eine quecksilberfreie Vergleichsprobe hergestellt. Diese diente nach Zusatz bekannter Quecksilbermengen zur Ermittlung einer Eichkurve. Anorganisches und organisch gebundenes Quecksilber kann nach diesem Verfahren in Wasser oder biologischem Material im Bereich zwischen 0,05 und 2,0g/ml bestimmt werden. Für die Größenordnung von 0,05 ppm kann das Verfahren für frisches Wasser und für Harn mit einem durchschnittlichen Fehler unter 5% verwendet werden. Ebenso dient es zur Untersuchung von Meerwasser und Blutserum mit einem Fehler bis zu 10%. Die Ergebnisse stehen mit denen anderer Methoden in gutem Einklang.

     

Simultaneous determination of mercury and selenium in biological materials by radiochemical neutron activation analysis

A simple and sensitive radiochemical neutron activation analysis (RNAA) method has been developed for the simultaneous determination of mercury and selenium in biological materials. The radiochemical procedure is based upon the digestion of irradiated samples with sulphuric and nitric acids followed by subsequent extractions of mercury and selenium into toluene, first of mercury from 7.5 M H₂SO₄-0.01M HBr media and after of selenium from 7M H₂SO₄-1 M HBr media. After washing of the organic phases with similar media, the mercury bromide was back-extracted into 0.034M EDTA in 5% aqueous ammonia and the selenium bromide into 0.14M H₂O₂ in aqueous solution. The¹⁹⁷Hg and the⁷⁵Se were counted on a Ge(Li) detector. The precision and accuracy of the method was checked by analysing NBS Standard Reference Materials: orchard leaves and bovine liver.     

Determination of microamounts strontium by substoichiometric isotope dilution analysis

The isotope dilution with substoichiometric separation for the determination of strontium has been investigated. Strontium can be extracted with a substoichiometric amount of bis-1,2-dicarbollylcobaltate in nitrobenzene in the presence of 15-crown-5. It has been found, that Li⁺, Mg²⁺, Ca²⁺ and Fe³⁺ do not interfere in the strontium determination but the high extraction of K⁺, Na⁺ and NH₄ ⁺ ions results in marked influence.     

Rapid determination of boron traces in silicate materials

Summary This simple method for the determination of boron takes a total time of 20 min. Samples are mixed with CaF₂ suprapur in the ratio 31 and pyrohydrolized in a Leco induction furnace for 15 min under steam of H₂O. The BF₃ liberated is collected in a NaOH-Na₂CO₃ solution (10 g NaOH +1 g Na₂CO₃ per liter). This solution is filled up to 200 ml with twice distilled water; 2 ml of this solution is mixed with conc. sulphuric acid and carminic acid solution and filled up to 50 ml. The absorption is measured by a Zeiss Elko II photometer with filter S 59. Analyses of four internations reference samples show excellent precision with a relative standard deviation of less than 5% (e.g. for a boron content of 2.1 ppm in granite G-2).

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Schnelle Spurenbestimmung von Bor in silicatischem Material

Zusammenfassung Die Borbestimmung mit dieser schnellen und einfachen Methode benötigt ca. 20 min. Die Proben werden mit CaF₂ Suprapur im Verhältnis 31 vermischt und in einem Leco-Induktionsofen 15 min unter Einleitung von Wasserdampf pyrohydrolysiert. Das entstandene BF₃ wird in einer NaOH-Na₂CO₃-Lösung(10 g NaOH+1 gNa₂CO₃pro Liter) aufgefangen. Diese Lösung wird mit zweifach destilliertem Wasser auf 200 ml aufgefüllt; 2 ml dieser Lösung werden mit konz. Schwefelsäure und Carminsäure-Lösung versetzt und auf 50 ml aufgefüllt, bevor ihre Absorption mit einem Zeiss — Elko II — Photometer mit Filter S 59 gemessen wird. Analysen von 4 internationalen Referenzproben zeigen eine hohe Präzision mit einer relativen Standardabweichung von weniger als 5% (z. B. für einen Gehalt von 2,1 ppm Bor im Granit G-2 des USGS).

     

Characterization of neutron transmuted zinc traces in pure copper materials by isotope dilution mass spectrometry

The neutron transmutation doping (NTD) of highly pure copper with zinc was investigated as a promising means of achieving controlled gradation of the zinc content in the range 1-20 microg g(-1). The doping process leads to the enrichment of two stable isotopes 64Zn and 66Zn in a ratio which differs from that of natural isotopic distribution. Mass spectrometric investigations by thermal ionization mass spectrometry (TIMS) were performed to validate the results obtained by gamma spectrometry. The investigations included both determination of the isotopic ratios of the doped zinc isotopes and the analysis of the accumulated zinc contents by isotope dilution (ID) analysis. Thereby a sample-specific correction of the blank could be performed because the isotope 68Zn was not influenced, because of the transmutation process. The results obtained by TIMS prove the strict proportionality of the doped zinc content, in the range 5 to 20 microg g(-1), to the neutron fluence. Comparison with gamma spectrometric results showed a very good agreement within the uncertainties.