Jixin Qiao

Determination of plutonium isotopes in waters and environmental solids: A review.

A number of analytical methods have been developed in the past few years for environmental monitoring of plutonium (Pu) isotopes around nuclear facilities within protocols for emergency preparedness as well as for risk assessment of contaminated areas resulting from nuclear weapon tests, nuclear accidents, and the discharge of nuclear waste. This article summarizes and critically compares recently reported methods for determination of Pu isotopes in waters and environmental solid substrates, in which sample pre-treatment is imperative for separation of the target species from matrix ingredients and/or potentially interfering nuclides prior to detection by radiometric or mass spectrometric techniques. Also discussed, via representative examples, is the automation of the entire analytical protocol by on-line extraction chromatography and ion exchange chromatography using flow injection (FI) or sequential injection (SI) approaches.

Rapid Determination of Plutonium Isotopes in Environmental Samples Using Sequential Injection Extraction Chromatography and Detection by Inductively Coupled Plasma Mass Spectrometry

This article presents an automated method for the rapid determination of 239Pu and 240Pu in various environmental samples. The analytical method involves the in-line separation of Pu isotopes using extraction chromatography (TEVA) implemented in a sequential injection (SI) network followed by detection of isolated analytes with inductively coupled plasma mass spectrometry (ICP-MS). The method has been devised for the determination of Pu isotopes at environmentally relevant concentrations, whereby it has been successfully applied to the analyses of large volumes/amounts of samples, for example, 100-200 g of soil and sediment, 20 g of seaweed, and 200 L of seawater following analyte preconcentration. The investigation of the separation capability of the assembled SI system revealed that up to 200 g of soil or sediment can be treated using a column containing about 0.70 g of TEVA resin. The analytical results of Pu isotopes in the reference materials showed good agreement with the certified or reference values at the 0.05 significance level. Chemical yields of Pu ranged from 80 to 105%, and the decontamination factors for uranium, thorium, mercury and lead were all above 10(4). The duration of the in-line extraction chromatographic run was <1.5 h, and the proposed setup was able to handle up to 20 samples (14 mL each) in a fully automated mode using a single chromatographic column. The SI manifold is thus suitable for rapid and automated determination of Pu isotopes in environmental risk assessment and emergency preparedness scenarios.

Determination of plutonium isotopes (238Pu, 239Pu, 240Pu, 241Pu) in environmental samples using radiochemical separation combined with radiometric and mass spectrometric measurements.

This paper reports an analytical method for the determination of plutonium isotopes ((238)Pu, (239)Pu, (240)Pu, (241)Pu) in environmental samples using anion exchange chromatography in combination with extraction chromatography for chemical separation of Pu. Both radiometric methods (liquid scintillation counting and alpha spectrometry) and inductively coupled plasma mass spectrometry (ICP-MS) were applied for the measurement of plutonium isotopes. The decontamination factors for uranium were significantly improved up to 7.5 × 10(5) for 20 g soil compared to the level reported in the literature, this is critical for the measurement of plutonium isotopes using mass spectrometric technique. Although the chemical yield of Pu in the entire procedure is about 55%, the analytical results of IAEA soil 6 and IAEA-367 in this work are in a good agreement with the values reported in the literature or reference values, revealing that the developed method for plutonium determination in environmental samples is reliable. The measurement results of (239+240)Pu by alpha spectrometry agreed very well with the sum of (239)Pu and (240)Pu measured by ICP-MS. ICP-MS can not only measure (239)Pu and (240)Pu separately but also (241)Pu. However, it is impossible to measure (238)Pu using ICP-MS in environmental samples even a decontamination factor as high as 10(6) for uranium was obtained by chemical separation.

Plutonium in Soils from Northeast China and Its Potential Application for Evaluation of Soil Erosion

Surface and soil core samples from northeast China were analyzed for Pu isotopes. The measured 240Pu/239Pu atomic ratios and 239 + 240Pu/137Cs activity ratios revealed that the global fallout is the dominant source of Pu and 137Cs at these sites. Migration behavior of Pu varying with land type and human activities resulted in different distribution of Pu in surface soils. A sub-surface maximum followed by exponential decline of 239 + 240Pu concentrations was observed in an undisturbed soil core, with a total 239 + 240Pu inventory of 86.9 Bq/m2 and more than 85% accumulated in 0 ~ 20 cm layers. While only half inventory of Pu was obtained in another soil core and no sub-surface maximum value occurred. Erosion of topsoil in the site should be the most possible reason for the significantly lower Pu inventory, which is also supported by the reported 137Cs profiles. These results demonstrated that Pu could be applied as an ideal substitute of 137Cs for soil erosion study in the future.

High-Throughput Sequential Injection Method for Simultaneous Determination of Plutonium and Neptunium in Environmental Solids Using Macroporous Anion-Exchange Chromatography, Followed by Inductively Coupled Plasma Mass Spectrometric Detection

This paper reports an automated analytical method for rapid and simultaneous determination of plutonium and neptunium in soil, sediment, and seaweed, with detection via inductively coupled plasma mass spectrometry (ICP-MS). A chromatographic column packed with a macroporous anion exchanger (AG MP-1 M) was incorporated in a sequential injection (SI) system for the efficient retrieval of plutonium, along with neptunium, from matrix elements and potential interfering nuclides. The sorption and elution behavior of plutonium and neptunium onto AG MP-1 M resin was compared with a commonly utilized AG 1-gel-type anion exchanger. Experimental results reveal that the pore structure of the anion exchanger plays a pivotal role in ensuring similar separation behavior of plutonium and neptunium along the separation protocol. It is proven that plutonium-242 ((242)Pu) performs well as a tracer for monitoring the chemical yield of neptunium when using AG MP-1 M resin, whereby the difficulties in obtaining a reliable and practicable isotopic neptunium tracer are overcome. An important asset of the SI setup is the feasibility of processing up to 100 g of solid substrates using a small-sized (ca. 2 mL) column with chemical yields of neptunium and plutonium being ≥79%. Analytical results of three certified/standard reference materials and two solid samples from intercomparison exercises are in good agreement with the reference values at the 0.05 significance level. The overall on-column separation can be completed within 3.5 h for 10 g of soil samples. Most importantly, the anion-exchange mini-column suffices to be reused up to 10-fold with satisfactory chemical yields (>70%), as demanded in environmental monitoring and emergency scenarios, making the proposed automated assembly well-suited for unattended and high-throughput analysis.

Sequential injection method for rapid and simultaneous determination of 236U, 237Np, and Pu isotopes in seawater.

An automated analytical method implemented in a novel dual-column tandem sequential injection (SI) system was developed for simultaneous determination of (236)U, (237)Np, (239)Pu, and (240)Pu in seawater samples. A combination of TEVA and UTEVA extraction chromatography was exploited to separate and purify target analytes, whereupon plutonium and neptunium were simultaneously isolated and purified on TEVA, while uranium was collected on UTEVA. The separation behavior of U, Np, and Pu on TEVA-UTEVA columns was investigated in detail in order to achieve high chemical yields and complete purification for the radionuclides of interest. (242)Pu was used as a chemical yield tracer for both plutonium and neptunium. (238)U was quantified in the sample before the separation for deducing the (236)U concentration from the measured (236)U/(238)U atomic ratio in the separated uranium target using accelerator mass spectrometry. Plutonium isotopes and (237)Np were measured using inductively coupled plasma mass spectrometry after separation. The analytical results indicate that the developed method is robust and efficient, providing satisfactory chemical yields (70-100%) of target analytes and relatively short analytical time (8 h/sample).

Speciation analysis of 129I, 137Cs, 232Th, 238U, 239Pu and 240Pu in environmental soil and sediment

The environmental mobility and bioavailability of radionuclides are related to their physicochemical forms, namely species. We here present a speciation analysis of important radionuclides including (129)I (also (127)I), (137)Cs, (232)Th, (238)U and plutonium isotopes ((239)Pu and (240)Pu) in soil (IAEA-375) and sediment (NIST-4354) standard reference materials and two fresh sediment samples from Øvre Heimdalsvatnet Lake, Norway. A modified sequential extraction protocol was used for the speciation analysis of these samples to obtain fractionation information of target radionuclides. Analytical results reveal that the partitioning behaviour, and thus the potential mobility and bioavailability, are exclusively featured for the individual radionuclide. Iodine is relatively mobile and readily binds to organic matter, while plutonium is mainly bound to both organic matter and nitric acid leachable fractions. Thorium is predominated in nitric acid leachable fraction and caesium is primarily observed in nitric acid and aqua regia leachable fractions and residue. Our analytical results reveal that around 50% of uranium might still remain in the residue which could not be extracted with aggressive acid, namely, aqua regia.

Bead injection extraction chromatography using high-capacity lab-on-valve as a front end to inductively coupled plasma mass spectrometry for urine radiobioassay.

A novel bead injection (BI) extraction chromatographic microflow system exploiting a high-capacity lab-on-valve (LOV) platform coupled with inductively coupled plasma mass spectrometric detection is developed for rapid and automated determination of plutonium in human urine. A column attached to the LOV processing unit is loaded online with a metered amount of disposable extraction chromatographic resin (up to 330 mg of TEVA (abbreviation for tetravalent actinides)) through programmable beads transport. Selective capture and purification of plutonium onto the resin beads is then performed by pressure driven flow after preliminary sample pretreatment. The analytical results demonstrate the large capacity of bead surfaces for uptake of Pu within the tailor-made LOV platform that fosters processing of large-sized biological samples, e.g., 1 L of human urine, along with good reproducibility for automatic column renewal (0.319 ± 0.004 g, n = 5). The chemical yields of plutonium were averagely better than 90% under the optimal experimental conditions, and the entire analytical procedure could be accomplished within a short time frame (<3 h) as compared to manual counterparts (1-2 days). Therefore, the developed system is well suited for expedient analysis of low-level plutonium in urine of exposed individuals as required in emergency situations.

Rapid Determination of Technetium-99 in Large Volume Seawater Samples Using Sequential Injection Extraction Chromatographic Separation and ICP-MS Measurement

An automated method was developed for rapid determination of (99)Tc in large volume seawater samples. The analytical procedure involves preconcentration of technetium with coprecipitation, online separation using extraction chromatography (two TEVA columns) implemented in a sequential injection setup, and measurement of (99)Tc by inductively coupled plasma mass spectrometry (ICP-MS). Chromatographic behaviors of technetium, molybdenum, and ruthenium were investigated, and the mechanism of adsorption and elution of TcO(4)(-) on a TEVA column using HNO(3) was explored. The results show that not only NO(3)(-) but also acidity (or concentration of H(+)) of the loading or eluting solution affect the adsorption and desorption of TcO(4)(-) on TEVA resin. Decontamination factors of more than 1 × 10(6) for ruthenium and 5 × 10(5) for molybdenum are achieved. Chemical yields of technetium in the overall procedure range from 60% to 75% depending on the sample volumes, and a detection limit of 7.5 mBq/m(3) (or 11.5 pg/m(3)) for 200 L of seawater was obtained. Compared with the conventional analytical procedure, the developed method significantly reduces analytical time. A batch of samples (n > 4) can be analyzed within 24 h. The method has been successfully applied for rapid and automated determination of low level (99)Tc in large volume seawater samples. The analytical results of seawater samples collected in Denmark show a good agreement with the values obtained using the conventional method.

Reliable determination of 237Np in environmental solid samples using 242Pu as a potential tracer

This paper reports an analytical method for rapid determination of neptunium ((237)Np) in environmental solid samples exploiting automated sequential injection (SI)-based anion exchange separation. Pivotal issues on analytical method performance were investigated including sorption behavior of (237)Np onto various AG 1-type anion exchangers; suitability of (242)Pu as a tracer for (237)Np determination in environmental solid samples; and long-term chemical stability of tetravalent Np. Experimental results revealed that the degree of resin cross-linking has a significant influence on the separation efficiency in terms of chemical yields of (237)Np and removal of interfering nuclides. Although ca. 30% of sorbed Np onto AG 1- × 4 was stripped out during HCl rinsing step for the removal of Th, chemical yield ratios of (237)Np to (242)Pu were proven steady with an average value of 0.67 ± 0.04 (n=15) under selected experimental conditions. Disulfite-8M HNO(3) was selected as a redox pair for valence adjustment to Np(IV) and the tetravalent Np in the sample solution was demonstrated to be stabilized for up to 5 days under 3°C. The analytical results for reference materials showed a good agreement with the expected values, thereby demonstrating the usefulness of (242)Pu as a non-isotopic tracer for (237)Np chemical yield monitoring. The on-column separation procedure fosters rapid analysis as required in emergency situations since each individual sample can be handled within 2.5h, and leads to a significant decrease in labor intensity compared to conventional batch-wise protocols.