Rapid determination of 99Tc in environmental samples by high resolution ICP-MS coupled with on-line flow injection system

High resolution inductively coupled plasma mass spectrometry coupled with an on-line flow injection system (FI-HR-ICP-MS) was applied to determine the ultra-trace level ⁹⁹Tc in soil. The flow injection system (PrepLab) was composed of two TEVA-Spec^Òresins, reduced remarkably the sample amounts and the analysis time, compared to the conventional analytical methods. In the flow injection system, Mo and Ru were sufficiently eliminated by using the flow injection system, with the decontamination factors of 1.6^.10⁴ and 9.9^.10⁵, respectively. With the present method, it was possible to determine ultra-low level of ⁹⁹Tc in 3-6 g soil at 3–5 hours of analysis time per sample. The relative standard deviation for each sample was less than 4%. The detection limits for ⁹⁹Tc was 85 fg^.ml^–1 (0.05 mBq^.ml^–1), which was calculated from the three times standard deviation of the count rate of the blank.     

Determination and lebels of99Tc in environmental and biological samples

In this paper, the physical and chemical methods used in our laboratory for the measurement of⁹⁹Tc in natural samples are reviewed. Levels of⁹⁹Tc in rainwater, algae, and freshwater samples are given. In addition, and estimation of the radiological impact of⁹⁹Tc to the population, derived from our earliear atmospheric⁹⁹Tc measurements, is presented. For rainwater, levels of¹³⁷Cs are also given for comparison.Work partially supported by the contract PB86-0207 of the Spanish CICYT.     

Determination of99Tc in rain and dry fallout by ICP-MS

Due to the difficulty of⁹⁹Tc analysis, data are insufficient for discussing its behavior in the environment. In this study, we focused on the determination of⁹⁹Tc in rain and dry fallout samples. The samples were collected monthly at Nakaminato, Japan, from June 1993. They were concentrated by heating on a hot plate without any loss of Tc. The solution was filtrated and then a liquid-liquid extraction (LLX) with trioctylamine (TOA), which works as a liquid anion exchanger, was carried out. Technetium was extracted from 5% HNO₃ solution into the organic phase with a high extractability. After being back-extracted from TOA/xylene into 1M K₂CO₃, LLX with cyclohexanone was used to remove ruthenium, which has a stable isotope of mass 99. Technetium was back-extracted into deionized water, and the solution was measured by inductively coupled plasma mass spectrometry (ICP-MS). The average recovery under the experimental conditions was 67% and the instrumental detection limit was 0.04 ppt (0.03 mBq/mL).     

Determination of <Superscript>99</Superscript>Tc in environmental samples and depleted uranium penetrators using ICP-MS

A new method was developed for the determination of ⁹⁹technetium (Tc) by ICP-MS. We report, for the first time, an activity of ⁹⁹Tc for the reference material IAEA-315. For the IAEA-375, IAEA-373 and IAEA-381, our results confirmed the values already reported in the literature. The developed method was used for analysing sediments from the Yenisei river (collected downstream of a nuclear fuel reprocessing plant) and for characterizing corrosion products of depleted uranium penetrators that were fired during the Balkan conflict.     

Comparison of a radiation counting method and ICP-MS for the determination of99Tc in environmental samples

Results of⁹⁹Tc measurements between radiation and non-radiation counting methods were compared using four radiation sources for which⁹⁹Tc has been previously determined with a gas-flow proportional counter or a GM counter. Each⁹⁹Tc source consisted of a stainless steel planchet bound by mylar films. Seaweeds collected from the Irish Sea were analyzed and⁹⁹Tc was electroplated on the planchet. The⁹⁹Tc in each sample was separated and measured again by inductively coupled plasma mass spectrometry (ICP-MS). Tc was continuously removed from each sample with 2M HNO₃ and 2M NaOH. After the solution containing Tc was adjusted to 0.1M HNO₃, Tc was extracted on a novel extraction chromatographic resin to separate it from Ru. The total recoveries for Tc on the planchet samples were almost the same with an average of 91%. The results of⁹⁹Tc measurements by both radiation and non-radiation counting methods agreed well with each other.     

Determination of 99Tc in environmental samples by anion exchange and liquid-liquid extraction at controlled valency

A method for collecting ⁹⁹Tc from 200-2-400 1 of sea water by anion exchange has been developed. Further decontamination of ^103.106Ru was achieved by repeated evaporation of RuO₄ from 0.05 M sulphuric acid at 100° C, followed by extraction of TcO^-₄ into 5% triisooctylamine-xylene at controlled valency. ^110mAg was precipitated as AgCl. An average overall radiochemical yield of 70% was found for Tc. Decontamination factors were between 3 10⁵ and 2 10⁷ for Ru and 2 10⁵ for Ag. A method for determining ⁹⁹Tc in seaweed by wet ashing and simple extraction into 5% triisooctylamine-xylene is also presented.     

Comparison of two ICP-MS set-ups for measuring 99Tc in large volume water samples

Large volume fjord and seawater samples have been radiochemically prepared for ICP-MS analysis in order to test the robustness of the procedure and to carry out a comparison of two ICP-MS set-ups. A sector field instrument (MicroMass PT2) coupled with an ultrasonic nebuliser and a quadrupole ICP-MS (Perkin-Elmer Elan 6000) coupled with an electrothermal vaporisation (ETV) unit were used. The results showed that the radiochemical procedure was robust, removing Ru and Mo to acceptable levels, and that the two set-ups gave results that were in agreement. The correlation coefficient between the sets of 11 results was 1.0 +/- 0.05. The importance of establishing the matrix effect when using an ETV is discussed.     

Determination of plutonium in environmental samples with quadrupole ICP-MS

A method for rapid determination of plutonium isotopes in environmental samples with ultrasonic nebulisation and quadrupole ICP-MS detection was established. Techniques for sample dissolution, pre-concentration and chemical separation were evaluated and the optimal scheme outlined. Comparisons with α-spectrometry and high resolution ICP-MS confirmed the suitability of the method when applied to different environmental matrices within the global fallout concentration range in the northern hemisphere as well as more contaminated sites. Operational detection limits were 0.5–1.5 fg/l for fresh waters and 0.03–0.1 ng/kg for lake sediments and saline marsh sediments.     

Methodological studies of the determination of 99Tc in matrix-rich environmental samples

A few experiments testing technetium behavior at different conditions for complex matrixes (soils, sediments) were performed. It was confirmed that the incineration of samples soaked with ammonia can be done without technetium losses. Next, for the precipitation of iron(III) hydroxide at different pH levels, the degree of co-precipitation of technetium was studied. It can be helpful during purification of very matrix-rich and massive samples. Finally the technetium and rhenium fractionation during separation of technetium from the environmental samples was studied. This test clearly showed limitations for using Re as yield tracer during ⁹⁹Tc analyses in case of mineral matrixes.     

Determination of nitrated-polyaromatic hydrocarbons (nitro-PAHs) in environmental samples by high resolution chromatographic techniques

An analytical procedure is described for the fractionation of organic compounds present in environmental samples and the determination of nitro polyaromatic hydrocarbons (nitro-PAHs). Both low and high resolution liquid chromatography are employed for the prefractionation of the soluble organic fraction (SOF) extracted from particulate matter or gaseous pollutants collected on adsorption traps. High resolution gas chromatography is used to analyze four fractions containing alkanes, PAHs, nitro-PAHs, and other polar PAHs. Nitrogen-containing species are separated by GC and detected specifically using an alkali flame (NPD) detector. Flame ionization (FID) detection, GC-MS of positive ions, and negative ion chemical ionization MS of the whole fraction is used for the identification and quantitation of the various components. The composition of SOF extracted from particulate matter emitted from diesel exhausts is elucidated and a large number of nitro-PAHs identified by the combination of the various techniques.     

Analysis of99Tc atmospheric samples

The analysis of⁹⁹Tc was carried out in filter, peat and rainwater samples. A solvent extraction technique was used to separate Tc from them, where tributylphosphate was the extracting agent. Radiochemical yield was obtained by using^99mTc as an internal tracer. A typical value of 60% was found for it. However, problems encountered in its determination are discussed in the text. Additionally, rainwater samples were analyzed for¹³⁷Cs. This was adsorbed in ammonium phosphomolibdate. Radiochemical yield was obtained by using¹³⁴Cs as an internal tracer.Work partially supported under Contract CAICYT No. 2849/83.     

Determination of technetium-99 in environmental samples: A review

Due to the lack of a stable technetium isotope, and the high mobility and long half-life, ⁹⁹Tc is considered to be one of the most important radionuclides in safety assessment of environmental radioactivity as well as nuclear waste management. ⁹⁹Tc is also an important tracer for oceanographic research due to the high technetium solubility in seawater as TcO₄⁻. A number of analytical methods, using chemical separation combined with radiometric and mass spectrometric measurement techniques, have been developed over the past decades for determination of ⁹⁹Tc in different environmental samples. This article summarizes and compares recently reported chemical separation procedures and measurement methods for determination of ⁹⁹Tc. Due to the extremely low concentration of ⁹⁹Tc in environmental samples, the sample preparation, pre-concentration, chemical separation and purification for removal of the interferences for detection of ⁹⁹Tc are the most important issues governing the accurate determination of ⁹⁹Tc. These aspects are discussed in detail in this article. Meanwhile, the different measurement techniques for ⁹⁹Tc are also compared with respect to advantages and drawbacks. Novel automated analytical methods for rapid determination of ⁹⁹Tc using solid extraction or ion exchange chromatography for separation of ⁹⁹Tc, employing flow injection or sequential injection approaches are also discussed.     

Determination of technetium-99 in environmental samples by solvent extraction at controlled valence

Distribution coefficients of technetium and ruthenium are determined under different conditions with CCl₄, cyclohexanone, and 5% tri-isooctylamine (TIOA)/xylene. A method for analyzing⁹⁹Tc in environmental samples has been developed by solvent extraction in which the valences of technetium and ruthenium are controlled with H₂O₂ and NaClO. Technetium and ruthenium which are oxidized to TcO ₄ ^– and RuO ₄ ^– by NaClO are separated by extraction with CCl₄ at pH 4. The RuO ₄ ^– is reduced to low valence and technetium is kept in the TcO ₄ ^– state with H₂O₂. Technetium, ruthenium, and other nuclides are subsequently separated by solvent extraction with cyclohexanone and 5% TIOA/xylene. The decontamination of the procedure is 1.35·10⁵ for¹⁰³Ru and 1.66·10⁵ for^110mAg. The chemical yield of technetium-99 is 55%.On leave from Institute of Atomic Energy, Beijing, China     

Determination of 99Tc in bentonite clay samples using inductively coupled plasma mass spectrometry

A method was developed for the determination of ⁹⁹Tc at low concentrations in clay samples. The chemical treatment of the samples prior to chemical separation and analysis comprised leaching with sulphuric acid/ sodium bromate. After leaching, pertechnetate was extracted with Alamine-336/chloroform and then back-extracted into nitric acid. Detection was carried out using inductively coupled plasma mass spectrometry, ICP-MS. The instrumental detection limit was 0.45 pg/mL, which corresponds to 0.28 mBq/mL. With the use of a desolvating nebuliser, the detection limit was lowered by about a factor of five. The results were compared with a method using radiometric detection. Received: 16 April 1998 / Revised: 12 June 1998 / Accepted: 16 June 1998     

Determination of 99Tc in bentonite clay samples using inductively coupled plasma mass spectrometry

A method was developed for the determination of ⁹⁹Tc at low concentrations in clay samples. The chemical treatment of the samples prior to chemical separation and analysis comprised leaching with sulphuric acid/ sodium bromate. After leaching, pertechnetate was extracted with Alamine-336/chloroform and then back-extracted into nitric acid. Detection was carried out using inductively coupled plasma mass spectrometry, ICP-MS. The instrumental detection limit was 0.45 pg/mL, which corresponds to 0.28 mBq/mL. With the use of a desolvating nebuliser, the detection limit was lowered by about a factor of five. The results were compared with a method using radiometric detection.     

Determination of traces of 237Np in environmental samples by ICP-MS after separation using TOA extraction chromatography

A simple, rapid, cost-efficient, and robust method for separation of 237Np with an extraction chromatographic column (TOA: tri-n-octylamine on Teflon powder) is outlined in detail and further improved for direct ICP-MS analysis. The column efficiently retained 237Np in 2 mol L(-1) HNO3 medium and all of the 237Np was easily eluted with 0.02 mol L(-1) oxalic acid in 0.16 mol L(-1) HNO3 at 95 degrees C. The separated solutions were free from most matrix elements and were aspirated into the ICP-MS directly. The decontamination factor for 238U is more than 10(4). The instrumental detection limit for 237Np was 0.46 pg mL(-1), which corresponds to 1.2 x 10(-5) Bq mL(-1). The method is more rapid than traditional radiometric techniques. It is also considered to be more suitable for environmental monitoring than existing methods based on TOA.     

Determination of technetium-99 and neptunium-237 in environmental samples by inductively coupled plasma mass spectrometry

New analytical techniques using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) were applied to the determination of technetium-99 (Tc-99) and neptunium-237 (Np-237) in environmental samples. The determination of Tc-99 consists of a cyclohexanone solvent extraction method to eliminate the interference isobar (Ru-99). An anion exchange with acetic acid media and a TTA-xylene solvent extraction were used for the determination of Np-237. Technetium-95m and Np-239 were used as chemical recovery tracers in these methods. The concentrations of Tc-99 and Np-237 in the typical surface soil samples in Japan ranged form 8.1×10² to 1.8×10^–1 Bq/kg-dry, from 3.3×10^–3 to 8.0×10^–3 Bq/kg-dry, respectively.     

Determination of stable lead isotope ratios in environmental samples: Combination of microwave digestion and ICP-MS

Microwave digestion was applied as pretreatment of environmental samples for the determination of lead isotope ratios by ICP-MS. Microwave digestion decomposed the samples easily and rapidly without lead contamination. The lead isotope ratios could be measured directly by ICP-MS without tedious lead purification, because the influence of the matrix elements on measurements of lead isotope ratios is small enough to be ignored.