Yihong Xu

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.

Plutonium as a tracer for soil erosion assessment in northeast China

Soil erosion is one of the most serious environmental and agricultural problems faced by human society. Assessing intensity is an important issue for controlling soil erosion and improving eco-environmental quality. The suitability of the application of plutonium (Pu) as a tracer for soil erosion assessment in northeast China was investigated by comparing with that of 137Cs. Here we build on preliminary work, in which we investigated the potential of Pu as a soil erosion tracer by sampling additional reference sites and potential erosive sites, along the Liaodong Bay region in northeast China, for Pu isotopes and 137Cs. 240Pu/239Pu atomic ratios in all samples were approximately 0.18, which indicated that the dominant source of Pu was the global fallout. Pu showed very similar distribution patterns to those of 137Cs at both uncultivated and cultivated sites. 239+240Pu concentrations in all uncultivated soil cores followed an exponential decline with soil depth, whereas at cultivated sites, Pu was homogenously distributed in plow horizons. Factors such as planted crop types, as well as methods and frequencies of irrigation and tillage were suggested to influence the distribution of radionuclides in cultivated land. The baseline inventories of 239+240Pu and 137Cs were 88.4 and 1688 Bq m(-2) respectively. Soil erosion rates estimated by 239+240Pu tracing method were consistent with those obtained by the 137Cs method, confirming that Pu is an effective tracer with a similar tracing behavior to that of 137Cs for soil erosion assessment.

Sequential injection approach for simultaneous determination of ultratrace plutonium and neptunium in urine with accelerator mass spectrometry.

An analytical method was developed for simultaneous determination of ultratrace level plutonium (Pu) and neptunium (Np) using iron hydroxide coprecipitation in combination with automated sequential injection extraction chromatography separation and accelerator mass spectrometry (AMS) measurement. Several experimental parameters affecting the analytical performance were investigated and compared including sample preboiling operation, aging time, amount of coprecipitating reagent, reagent for pH adjustment, sedimentation time, and organic matter decomposition approach. The overall analytical results show that preboiling and aging are important for obtaining high chemical yields for both Pu and Np, which is possibly related to the aggregation and adsorption behavior of organic substances contained in urine. Although the optimal condition for Np and Pu simultaneous determination requires 5-day aging time, an immediate coprecipitation without preboiling and aging could also provide fairly satisfactory chemical yields for both Np and Pu (50-60%) with high sample throughput (4 h/sample). Within the developed method, (242)Pu was exploited as chemical yield tracer for both Pu and Np isotopes. (242)Pu was also used as a spike in the AMS measurement for quantification of (239)Pu and (237)Np concentrations. The results show that, under the optimal experimental condition, the chemical yields of (237)Np and (242)Pu are nearly identical, indicating the high feasibility of (242)Pu as a nonisotopic tracer for (237)Np determination in real urine samples. The analytical method was validated by analysis of a number of urine samples spiked with different levels of (237)Np and (239)Pu. The measured values of (237)Np and (239)Pu by AMS exhibit good agreement (R(2) ≥ 0.955) with the spiked ones confirming the reliability of the proposed method.

Association of Plutonium isotopes with natural soil particles of different size and comparison with 137Cs

Information on how plutonium (Pu) isotopes associate with natural soil particles of different size is very important for the interpretation involved in the application of Pu isotopes as soil erosion tracers. This work investigated the association of Pu isotopes with different particle size fractions of natural soils and compared it with that of 137Cs. Ten bulk soils collected from two different areas were separated into different particle size fractions by a combination of wet sieving and centrifugation techniques and the sub-samples were analyzed for 137Cs, 239Pu and 240Pu. Results showed that the concentrations of both 239+240Pu and 137Cs increase with decreased particle sizes and are closely related to the specific surface areas of soil particles, which demonstrated a similar preferential association of Pu with finer soil particles as 137Cs. The activity ratios of 239+240Pu/137Cs in soil fractions increasing with increased particle size further indicated a less preferential transport of Pu with fine particles compared to 137Cs. These results not only highlight the suitability of Pu isotopes as soil erosion tracers, but also provide useful information for assessing the migration behavior of Pu in contaminated environments.

Comparison of sample preparation methods for reliable plutonium and neptunium urinalysis using automatic extraction chromatography.

This paper describes improvement and comparison of analytical methods for simultaneous determination of trace-level plutonium and neptunium in urine samples by inductively coupled plasma mass spectrometry (ICP-MS). Four sample pre-concentration techniques, including calcium phosphate, iron hydroxide and manganese dioxide co-precipitation and evaporation were compared and the applicability of different techniques was discussed in order to evaluate and establish the optimal method for in vivo radioassay program. The analytical results indicate that the various sample pre-concentration approaches afford dissimilar method performances and care should be taken for specific experimental parameters for improving chemical yields. The best analytical performances in terms of turnaround time (6h) and chemical yields for plutonium (88.7 ± 11.6%) and neptunium (94.2 ± 2.0%) were achieved by manganese dioxide co-precipitation. The need of drying ashing (≥ 7h) for calcium phosphate co-precipitation and long-term aging (5d) for iron hydroxide co-precipitation, respectively, rendered time-consuming analytical protocols. Despite the fact that evaporation is also somewhat time-consuming (1.5d), it endows urinalysis methods with better reliability and repeatability compared with co-precipitation techniques. In view of the applicability of different pre-concentration techniques proposed previously in the literature, the main challenge behind relevant method development is pointed to be the release of plutonium and neptunium associated with organic compounds in real urine assays. In this work, different protocols for decomposing organic matter in urine were investigated, of which potassium persulfate (K2S2O8) treatment provided the highest chemical yield of neptunium in the iron hydroxide co-precipitation step, yet, the occurrence of sulfur compounds in the processed sample deteriorated the analytical performance of the ensuing extraction chromatographic separation with chemical yields of ≤ 50%.

The 137Cs distribution in sediment profiles from the Yangtze River estuary: a comparison of modeling and experimental results

It has been generally accepted when estimating sedimentation rates using the 137Cs dating method that the position of the 137Cs maximum in a sediment profile represents the year 1963. In this paper we validated this approach by developing a model in which the annual 137Cs global fallout flux for the Yangtze River estuary was established on the basis of the Tokyo flux corrected for precipitation rates observed in Shanghai. As the 137Cs maxima in the sediment deposition profiles depend on the sedimentation rates, the sub-sampling intervals were calculated accordingly. Higher measured than the calculated values were found in some cores, what may be due to fluctuating sedimentation rates and an additional deposition of 137Cs from land-based sources. The study provides useful information on the reliability of the measured 137Cs maxima in sediment profiles frequently used for dating of sediments in marine (coastal regions, open seas) as well as in terrestrial (lakes) environments.

Direct measurement of uranium in seawater by inductively coupled plasma mass spectrometry

A simple method for direct measurement of uranium (238U) in seawater using triple quadrupole inductively coupled plasma mass spectrometry (ICP-MS) was established. The method provides a good analytical performance with respect to detection limit, accuracy, precision and sample throughput. During the method development and application, several interesting facts were observed: 1) Comparison results for reference material using different quantitation approaches indicate that isotope dilution (using 233U) is the most reliable to achieve accurate 238U measurement. The results obtained for direct 238U measurement in 50-fold diluted seawater samples (n = 112) also underline the difference between isotope dilution and internal (or external) standardization. 2) Appropriate dilution of seawater is important to minimize the matrix effect on the ICP-MS measurement and 20-50 dilution is recommended for natural seawater samples. 3) The sensitivity of ICP-MS was observed to increase in the beginning of sample measurement, and then decrease with the continuous injection of samples, which is believed as a consequence of matrix effect from the seawater to the ionization efficiency in the plasma. 4) When measuring samples taken from large volume of seawater stored in immovable containers for relatively long period (i.e., several months), the uranium concentration and salinity data showed slightly increasing trends with the increase of water depth in the container. Therefore, cautions need to be paid in sampling representativeness when performing 238U measurement for such long-term stored large volume samples.

Sources of plutonium isotopes and 137 Cs in coastal seawaters of Liaodong Bay and Bohai Strait, China and its environmental implications

In order to investigate the sources of plutonium in seawaters of Liaodong Bay and Bohai Strait, China, surface seawater samples were collected and analyzed for 239+240Pu and 137Cs by radiochemical separation combined with ICP-MS and γ-spectrometry, respectively. A large variation of 239+240Pu activities was observed, ranging from 1.993 to 29.677 mBq/m3 in the Liaodong Bay and from 0.932 to 10.183 mBq/m3 in the Bohai Strait. 137Cs activities showed little variation between the investigated locations, which was attributed to the different behavior characteristics of 239+240Pu and 137Cs in seawaters. The 240Pu/239Pu atom ratios showed a significant variation between the Liaodong Bay (0.185) and Bohai Strait (0.225), indicating that Pu derived from the Pacific Proving Grounds might have been transported to the Bohai Strait but not yet to the Liaodong Bay, which could further provide valuable reference for evaluating the seawater exchange cycle between the Bohai Sea and Yellow Sea.

Sedimentary record of plutonium in the North Yellow Sea and the response to catchment environmental changes of inflow rivers

Plutonium (Pu) isotopes were first determined in surface and core sediment samples collected from the northern North Yellow Sea (NYS) to elucidate their source terms and deposition process as well as the response to catchment environmental changes of inflow rivers. 240Pu/239Pu atom ratios in all sediments showed the typical global fallout value of ∼0.18 without any influences from the nuclear weapons tests conducted recently in the North Korea or early in the Pacific Proving Ground. The large variation of 239+240Pu activities (0.022-0.515 mBq/g) observed in surface sediments should be mainly attributed to the re-suspension and transportation of fine sediments influenced by the Liaonan Costal Current. Based on the two 239+249Pu depth profiles with easily observed onset fallout levels (1952) and global fallout peaks (1963), 239+240Pu served as a valid time mark in the coastal sedimentary system. Riverine input Pu contributed only 15-27% to the total global fallout inventory (92.5-108.8 Bq/m2) in the northern NYS, much lower than that in the Yangtze River estuary (77-80%), indicating a better soil conservation in the northeast China due to higher forest coverage compared to the Yangtze Rivers drainage basin. The increase of riverine input Pu after 1980s reflected the more intense soil erosion degree caused by the land use and cover change due to the increment of human activities in the northeast China at the same period. Our results demonstrated that plutonium is a good indicator for studying sedimentary process and its response to the environment in the coastal area.