Determination of uranium and thorium isotopes in mineral spring waters

Concentrations levels of uranium and thorium isotopes have been analyzed in the m mineral spring waters of a high background region of Brazil: Poços de Caldas and Águas da Prata. The procedure was based on the determination of²³⁸U,²³⁴U,²³²Th,²³⁰Th and²²⁸Th by -spectrometry after separation and purification of the isotopes of interest by using anion-exchange chromatography and preparation of the samples for -measurements by electrodeposition. The concentration varied from <1.1 to 28.4 mBq.l^–1 and from <1.6 to 141 mBq.l^–1 for²³⁸U and²³⁴U, respectively. Thorium isotope measurements varied from <0.2 to 1.8 mBq.l^–1 from <0.3 to 4.9 mBq.l^–1 and from <0.8 to 19.9 mBq.l^–1 for²³²Th,²³⁰Th and²²⁸Th, respectively. Calculations of thorium and uranium isotopic activity ratios were carried out giving values ranging from 1.9 to 7.2, from 1.2 to 3.0 and from 7.7 to 15.3 for²³⁴U/²³⁸U,²³⁰Th/²³²Th and²²⁸Th/²³²Th, respectively. The effective doses due to the intake of²³⁸U and²³⁴U present in these waters are expected to reach values up to 1.4×10^–3 mSv y^–1 and 8.0×10^–3 mSv y^–1, respectively.     

Levels of artificial radionuclides and uranium in rain water collected from Ibaraki (Japan) following the Tomsk-7 accident in Russia

Measurements of some selected radionuclides were carried out in rain waters collected from Ibaraki Prefecture, Japan, following the nuclear accident at Tomsk-7, Russian Federation, in April 1993. The concentrations obtained for artificial radionuclides were⁹⁰Sr1.8 mBq l^–1,¹³⁷Cs0.1 Bq l^–1,¹³¹I0.1 Bq l^–1 and¹²⁹I4 Bq l^–1. Uranium (²³⁸U) concentrations in rainfalls in April 1993 were 6.3–39 ng l^–1. These data were compared to control values obtained previously and there was no appreciable influence on the radioactivity levels in Japan after the Tomsk-7 accident. Since only limited data on the concentrations of¹²⁹I and uranium in rain water are available, these new analytical results contribute to understanding the background levels for these nuclides.     

Simultaneous determination of lead-210, gross beta and gross alpha activities of air filters by pulse shape discrimination liquid scintillation counting

A chemical procedure for transferring deposited solid matter from a cellulose filter into the liquid scintillation cocktail has been described. The influence of chemical and color quenching on alpha and beta detection efficiency, as well as on misclassification of beta and alpha pulses was corrected by an external standard method. Under the chosen pulse shape discrimination level (PSD), the alpha and beta detection efficiencies were above 85% and spillovers of alpha and beta pulses were below 10% and 2% respectively. Determination limits for samples containing up to 200 mg of mineral matter were 0.015 mBq m^–3 for alpha, 0.055 mBq.m^–3 for²¹⁰Pb and 0.055 mBq.m^–3 for beta activity (counting time 12000 s and volume of filtered air 1000 m³). The method has been applied for routine monitoring of²¹⁰Pb as well as for gross alpha and beta activities of longer-living radionuclides (T_1/2.>11 hrs) in suspended air matter.     

An improved method for low-level222Rn determination in environmental waters by liquid scintillation counting with pulse shape analysis

A method in which²²²Rn is extracted from 0.5 1 water samples to 20 ml toluene is described. 10 ml toluene solution with extracted²²²Rn is directly added to a glass scintillation vial containing 10 ml of liquid naphthalene based scintillation cocktail. Apart from diluting by toluene, the final counting solution still has excellent properties in terms of: / separation by pulse shape analysis, detection efficiency and background in the -region. The detection limit of²²²Rn for 0.5 1 water samples was 1.5 mBq l^–1 (for 12,000 s count time). The concentration of²²²Rn in different environmental samples such as rain, tap and mineral waters as well as deep well waters were determined.     

Determination of99Tc in coastal seawater collected in Fukuoka,Japan

Concentrations of⁹⁹Tc were determined by inductively coupled plasma mass spectrometry (ICP-MS) on coastal seawater in the general environment in Japan. Technetium was enriched on iron hydroxide by repetitive co-precipitation method from a large volume of seawater and separated from impurities by solvent extraction and ion-exchange techniques. The concentrations of⁹⁹Tc were 1.0 to 7.4 Bq1^–1, which was one order of magnitude lower than the level reported on seawater from general environment by beta-ray counting. Concentrations of¹³⁷Cs determined on the same seawater were 3.7 and 3.9 mBq1^–1. The activity ratio of⁹⁹Tc/¹³⁷Cs was calculated to be 2.7×10^–4. This ratio was very close to the value expected for fallout from nuclear tests.     

Heliuim-3 mass spectrometry for low-level tritium analysis of environmental samples

Helium-3 (³He) mass spectrometry for the analysis of low-level tritium (³H) concentrations (0.5 to 5 Bq·l^–1) in environmental sample matrices was compared with conventional low-level -decay counting methods. The mass-spectrometry method compared favorably, equalling or surpassing conventional decay-counting methods with respect to most criteria. Additional research and method refinements may make³He mass spectrometry the method of choice for routine, low-level to very-low-level (L<0.5 Bq·l^–1)³H measurements in a wide variety of environmental samples in the future.     

Radiochemical determination of lead-210 in environmental water samples using Cerenkov counting

A relatively simple method has been developed for the determination of²¹⁰Pb via its -emitting daughter,²¹⁰Bi. Lead-210 was separated from interfering elements as lead sulphate. The precipitate was dissolved in an alkaline solution of EDTA and the Cerenkov signal produced by the build-up of²¹⁰Bi was counted 30 days after storage using tritium channel of a liquid scintillation counter. Cerenkov counting efficiency was found to be approximately 20%. A lower limit of detection of 5.1 mBq/1 (based on 3 of the background with 500 minute counting time) was achieved. Chemical recoveries in the range of 70–100% were determined gravimetrically. Interference associated with currently used methods is avoided. Data from from both spiked samples and natural samples are presented.     

Estimation of inorganic phosphate in aqueous solutions of DNA: A modification of the Berenblum-Chain method

Some modifications of the stannous chloride reduction method for the estimation of inorganic phosphate reported by Berenblum-Chain are suggested. By this method, it is possible to measure 25 g l^–1 of phosphorus /P/ as inorganic phosphate in the presence of macromolecules like deoxyribonucleic acid /100 g ml^–1/, as compared to 200 g l^–1 of P by the original method. If a larger sample volume /30 ml/ is used, even 5 g l^–1 of P can be measured.     

Technetium-99 in the Rhône river water

⁹⁹Tc a pure -particle emitter with long half-life (T=2.13×10⁵ y) was measured in Rhône river water and in Mediterranean sea water near the river mouth. The values obtained in the Rhône river allowed us to show the downstream distribution of the effluents from the nuclear fuel reprocessing plant of Marcoule: the⁹⁹Tc activity which is low above the plant, 0.016 mBq 1^–1, is 0.4 mBq 1^–1 at Roquemaure, located 14 km below the plant, and then decreases as a function of distance from the plant.     

Plutonium concentration distribution in bed load sediment samples along the Romanian sector of the Danube river and the Black Sea coast

The concentrations of²³⁸Pu and^{239, 240}Pu were determined in 12 sediment samples collected from the bed of the Romanian Danube river and Black Sea coast during June–September 1994. After the sample material has been properly prepared and²⁴²Pu tracer added, plutonium was separated from americium and curium by anion exchange. After electrodeposition on stainless steel discs the elements were counted with an -spectrometry system with silicon surface-barrier detectors. The^{239, 240}Pu concentrations range between 150 and 800 mBq kg^–1 dry, while the²³⁸Pu concentrations rise up to max 150 mBq kg^–1 dry. Although the chemical yields are rather low (51%) we appreciate the results as valuable since they report for the first time the distribution of the plutonium contamination along the Danube river and the Black Sea coast-Romanian sector.     

Flow injection chemiluminescence determination of l-cysteine in amino acid mixture and human urine with the BrO3 −–quinine system

In this paper, a novel flow injection chemiluminescence (CL) determination of l-cysteine is proposed. The method is based on the CL reaction of l-cysteine and KBrO₃ in acidic medium. The CL intensity was greatly enhanced in the presence of quinine. The CL intensity was linear with l-cysteine concentration in the range of 0.2–80 g L^–1, and the detection limit was 0.1 g L^–1 (3). A complete analysis, including sampling and injecting, could be performed in 1 min, giving a throughput of about 60 h^–1. The relative standard deviation was 1.6% for 0.8 g L^–1 l-cysteine (n=11). The proposed method was satisfactorily applied to the determination of cysteine in an amino acid mixture and human urine. The mechanism of the CL reaction is also discussed.     

Flow injection method for the fluorimetric determination of Zn with 8-(benzenesulphonamido) quinoline

The development of a fluorimetric method for the determination of zinc, based on the fluorescence of the zinc-8-(benzenesulphonamido) quinoline chelate in a micellar medium of sodium dodecylsulfate, is reported. The detection limit is 0.2 g l^–1, the working range is 0.5–700 g l^–1, and the sample throughput is 145 h^–1. The method was evaluated for the determination of zinc in food samples.A batch procedure for the simultaneous determination of zinc and cadmium, based on the synchronous and derivative spectra, is also proposed.     

Application of isotope-dilution laser ablation ICP–MS for direct determination of Pu concentrations in soils at pg g<Superscript>−1</Superscript> levels

The methods available for determination of environmental contamination by plutonium at ultra-trace levels require labor-consuming sample preparation including matrix removal and plutonium extraction in both nuclear spectroscopy and mass spectrometry. In this work, laser-ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) was applied for direct analysis of Pu in soil and sediment samples. Application of a LINA-Spark-Atomizer system (a modified laser ablation system providing high ablation rates) coupled with a sector-field ICP–MS resulted in detection limits as low as 3×10^–13 g g^–1 for Pu isotopes in soil samples containing uranium at a concentration of a few g g^–1. The isotope dilution (ID) technique was used for quantification, which compensated for matrix effects in LA–ICP–MS. Interferences by UH⁺ and PbO₂⁺ ions and by the peak tail of ²³⁸U⁺ ions were reduced or separated by use of dry plasma conditions and a mass resolution of 4000, respectively. No other effects affecting measurement accuracy, except sample inhomogeneity, were revealed. Comparison of results obtained for three contaminated soil samples by use of -spectrometry, ICP–MS with sample decomposition, and LA–ICP–IDMS showed, in general, satisfactory agreement of the different methods. The specific activity of ^239+240Pu (9.8±3.0 mBq g^–1) calculated from LA–ICP–IDMS analysis of SRM NIST 4357 coincided well with the certified value of 10.4±0.2 mBq g^–1. However, the precision of LA–ICP–MS for determination of plutonium in inhomogeneous samples, i.e. if "hot" particles are present, is limited. As far as we are aware this paper reports the lowest detection limits and element concentrations yet measured in direct LA–ICP–MS analysis of environmental samples.Sergei F. Boulyga is on leave from The Radiation Physics and Chemistry Problems Institute, 220109 Sosny, Minsk, Belarus.     

Photometry in a continuous flow system

Summary Sulphate in various environmental samples was determined by measuring the optical absorbance upon reaction with the barium(II) dimethylsulphonazo(III) complex. The measurement took place in a flow-through system. Interferences from phosphate, metal ions and others were eliminated. The results of a turbidimetric measurement, a spectrophotometric measurement with thorin, an automatic titration and the proposed method are compared. The latter allows the determination of sulphate in the range of 1.4–60 mol·l^–1. The standard deviation is 0.3–0.6 mol·l^–1, depending on the type of sample (water) analysed. A determination takes 1.5min.

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Photometric in einem DurchflußsystemBestimmung von Sulphat mit Dimethylsulfonazo(III) in Umweltmaterial mit Hilfe eines Durchflußsystems

Zusammenfassung Sulfat wurde in verschiedenen Umweltproben durch Messung der Extinktion nach Reaktion mit dem Barium(II)-dimethylsulfonazo(III)-komplex im Durchflußsystem bestimmt. Störungen von Phosphat, Metallionen, u.a. wurden beseitigt. Die Ergebnisse einer turbidimetrischen, einer photometrischen, einer automatischen Titration und der vorgeschlagenen Methode werden verglichen. Die Methode ermöglicht die Sulfatbestimmung im Bereich von 1,4–60 mol·l^–1. Die Standardabweichung beträgt 0,3–0,6 mol· l^–1 je nach Typ des Probematerials (Wasser). Eine Bestimmung erfordert 1,5min.

     

Indirect determination of chloride and sulfate ions in alcohol fuel by capillary electrophoresis

A capillary zone electrophoresis method using indirect UV detection for the analysis of chloride and sulfate in alcohol fuel samples was developed. The anions were analyzed in less than 3 min using an electrolyte containing 10 mmol l^–1 chromate and 0.75 mmol l^–1 hexamethonium bromide (HMB) as electroosmotic flow modifier. Coefficients of variation were better than 0.6% for migration time (n=10) and between 2.05 and 2.82% for peak area repeatabilities. Analytical curves of peak area versus concentration in the range of 0.065–0.65 mg kg^–1 for chloride and 0.25–4.0 mg kg^–1 for sulfate were linear with coefficients of correlation higher than 0.9996. The limits of detection for sulfate and chloride were 0.033 and 0.041 mg kg^–1, respectively. Recovery values ranged from 85 to 103%. The method was successfully applied for the quantification of sulfate and chloride in five alcohol fuel samples. The concentration of sulfate varied from 0.45 to 3.12 mg kg^–1. Chloride concentrations were below the methods LOD.     

Measurement of uranium in total diet samples: Daily intake for Japanese

Diet samples were collected by a duplicate portion study of Japanese adults in two districts, a newly-rising town and an established seaside village, of Ishikawa Prefecture, which faces the Sea of Japan. Uranium concentrations in a total of 80 diet samples were determined by -spectrometry after chemical separation. No marked differences between the two districts were found regarding characteristics of food consumption in thirteen categories and in daily intake of²³⁸U per person. The daily intake of²³⁸U per person ranged from 1.1 to 40 mBq with a geometric mean value of 9.6±2.1 mBq. The²³⁴U/²³⁸U activity ratios ranged from 0.7–1.5, with most being from 1.0–1.2. The internal dose estimation system (IDES) was completed with Japanese physical parameters and other parameters of ICRP Publication 30, and then the annaul effective dose equivalent was estimated as 3·10^–7 Sv for²³⁸U in a Japanese adult.     

Determination of131I in milk using heterogeneous liquid scintillation counting

Possibilities of the method based on both the selective separation of radioiodine from milk using anion-exchange resin as well as the¹³¹I counting in heterogeneous mixture of this anex with a liquid scintillator are presented. For samples of 4 dm³ volumes, the separation and counting efficiencies about 78% and 45% are achieved. Under the same experimental conditions the background rate is about 0.25 CPS /15 CPM/ and the LLD corresponds to about 7 mBq.dm^–3 /0.2 pCi. dm^–3/.     

Low level determination of thallium in biological and environmental reference materials by RNAA using several counting methods

A new RNAA procedure was developed capable of low level determination of thallium in biological and environmental samples. After high fluence neutron irradiation in a nuclear reactor, wet ashing of samples and T1(I) separation by solvent extraction with sodium diethyldithiocarbamate at pH 13, several types of counting were employed to compare their detection limits and to utilize the self-validation principle of NAA. The following measurement modes were used: High efficiency counting of -rays of²⁰²T1 and Hg X-rays produced on decay of²⁰⁴T1 using a well-type HPGe detector, combined ^– ray and ^–-counting of²⁰⁴T1 with the aid of a HPGe planar detector, and liquid scintillation counting and counting of Cerenkov radiation of ^–-particles of²⁰⁴T1. The lowest detection limit of 0.034 ng of T1 was achieved on liquid scintillation counting of²⁰⁴T1. The method was applied for the analysis of biological NIST SRMs 1515, 1573a, 1577b and environmental NIST SRM 1633a. Good agreement was found between the thallium certified value in SRM 1633a and values determined in this work by all counting modes. For SRM 1573a, results in agreement were obtained by two counting modes, while counting of Hg X-rays of²⁰⁴T1 was only used for SRMs 1515 and 1577b.     

222RN at Bermuda and Mauna Loa: Local and distant sources

Continuous measurements of atmospheric²²²Rn were made for the past three years by the Environmental Measurements Laboratory (EML) at the Atmosphere/Ocean Chemistry Experiment site located at Tudor Hill, Bermuda and at the National Oceanic and Atmospheric Administration/Climate Monitoring and Diagnostics Laboratory Mauna Loa Observatory. The²²²Rn analyzer is based on the two-filter tube method. At the Bermuda site, monthly median²²²Rn concentration range from 50 to 700 mBq m^–3, and the concentrations vary seasonally, with a maximum in the winter and a minimum in the summer. The concentrations are significantly elevated when local winds traverse the island. At MLO, monthly median²²²Rn concentrations range from 100 mBq m^–3 during the fall months to 400 mBq m^–3 during the spring months. The springtime maximum values correspond to periods of rapid transport in the free troposphere from the Asian continent, corroborated by backward air mass trajectories. The²²²Rn data are also used to help decipher local daily upslope/downslope conditions present at MLO. This study illustrates the value of atmospheric²²²Rn monitoring, when screened through the filter of local meteorology, in studying the transport of continental air to the oceans, as well as the dynamics of local meteorological effects.     

Direct determination of arsenic in sea water by electrothermal atomization atomic absorption spectrometry using D2 and Zeeman background correction

Arsenic in sea water was determined directly by graphite furnace atomic absorption spectrometry (GFAAS) using palladium nitrate as chemical modifier, at an optimum concentration of 15 mg l^–1. Deuterium and Zeeman effect background correction were compared and gave detection limits of 0.6 and 0.8 g l^–1, respectively. Precisions between 8 and 2%, for both correctors, were obtained with an injection volume of 40 l. The accuracy obtained with different reference materials: CRM-403 (1.461 g kg^–1), NASS-4 (1.26 ±0.09 gl^–1) and IAEA/W-4 (24–31 g l^–1) was studied for large injection volumes for both background correction systems. Interferences by chloride, sodium, potassium, calcium and silicon were removed by Zeeman correction, whereas deuterium correction was much less effective and was insufficiently accurate for sea water samples.