Comparison for the simultaneous determination of 237Np and Pu isotopes between TEVA and TK200 resin.

A reliable and stable method was developed to accurately analyze neptunium (237Np) and plutonium isotopes in environmental samples using 242Pu or 236Pu as a tracer. Key parameters, including the valence adjustment conditions and the stabilities of Pu and Np in the different resins, were investigated using TK200 and TEVA resin. It was found that Pu and Np could be efficiently extracted simultaneously using TK200 resin under the optimal loading conditions (6-12 M HNO3) with the addition of 0.01-0.12 M NaNO2 for valence adjustment. These isotopes were subsequently stripped out using a solution containing 0.1 M HCl, 0.05 M HF, and 0.01 M NH2OH·HCl. The separation efficiencies of Pu and Np were >93%, and the chemical yield ratio between Np and Pu was maintained steady at an average of 1.00 ± 0.03 (n > 50) under the optimal conditions. The analytical method was validated by analyzing environmental soil samples spiked with known amounts of 239Pu and 237Np standard solutions or certified reference materials. The measured values of 237Np, 239Pu, and 240Pu obtained by inductively coupled plasma tandem mass spectrometry were consistent with their International Atomic Energy Agency literature values within a 95% confidence interval. These results confirm the reliability and high analytical precision (<6%) of this developed method using Pu as a non-isotopic tracer for monitoring the chemical yield of 237Np. The developed method can also be used for environmental pollutant monitoring and for tracer studies of the 237Np and Pu isotopes.

Simultaneous determination of actinides and 90Sr in large-size soil and sediment samples.

A simultaneous analytical method for sequential separation and determination of actinides and 90Sr in large-size environmental samples has been developed. In this method, successive co-precipitation steps were firstly conducted to remove matrix elements, then sequential column separation method was applied for simultaneous separation and purification of actinides and 90Sr/90Y. By using vacuum box technology, the total analytical time was minimized and batch processing allowed analyzing 12 samples in four days. The activity of 90Sr was obtained immediately by measuring its daughter radionuclide (90Y) with triple-to-double coincidence ratio (TDCR) Cherenkov counting, while the concentrations of Pu isotopes and 241Am could be measured by alpha spectrometry and mass spectrometric techniques. The overall recoveries of Pu, Am, Sr and Y were higher than 70% for the entire procedure, while the recovery ratios of Sr/Y were between 0.95 and 1.04 before chromatographic separation. The developed method was verified using 20 g and 50 g of environmental soil samples spiked with certified reference materials IAEA-384 or IAEA-385 and standard solution of 90Sr/90Y, and good agreement between the expected values and measured results has been achieved.

Effects of sodium salicylate on the determination of Lead-210/Bismuth-210 by Cerenkov counting.

Due to the nature of Cerenkov radiation and instrumental limitations, detection efficiencies of 210Bi by Cerenkov counting are generally quite low (~15%). Sodium salicylate, acting as a wavelength shifter, has been used to improve the detection efficiency of Cerenkov photons. In this study, we found that the addition of sodium salicylate could significantly increase the counting efficiencies of 210Pb/210Bi in aqueous samples. Meanwhile, a sharp increase of the counting efficiency for the alphas from 210Po was also observed with the addition of high concentration of sodium salicylate, implying that scintillation light rather than Cerenkov photons from the alphas has been produced. Detailed studies about the effects of sodium salicylate on the counting of 210Pb, 210Bi and 210Po were conducted. At low concentration (< 0.5 mg g-1) of sodium salicylate, only a small increase in Cerenkov counting efficiency for 210Bi by the wavelength-shifting effect could be observed. Meanwhile, the counting efficiency for 210Bi at high concentration (> 1 mg g-1) of sodium salicylate would significantly increase due to the scintillation effect.

Sequential analyses of actinides in large-size soil and sediment samples with total sample dissolution.

There is a growing demand for the determination of actinides in soil and sediment samples for environmental monitoring and tracing, radiological protection, and nuclear forensic reasons. A total sample dissolution method based on lithium metaborate fusion, followed by sequential column chromatography separation, was developed for simultaneous determination of Pu, Am and Cm isotopes in large-size environmental samples by alpha spectrometry and mass spectrometric techniques. The overall recoveries of both Pu and Am for the entire procedure were higher than 70% for large-size soil samples. The method was validated using 20 g of soil samples spiked with known amounts of 239Pu and 241Am as well as the certified reference materials IAEA-384 (Fangataufa Lagoon sediment) and IAEA-385 (Irish Sea sediment). All the measured results agreed very well with the expected values.

Method of Polonium Source Preparation Using Tellurium Microprecipitation for Alpha Spectrometry.

A thin-layer source for the counting of polonium isotopes by alpha spectrometry can be rapidly prepared using microprecipitation with tellurium. Polonium was first coprecipitated with the reduction of tellurium by stannous chloride, followed by microfiltration onto a membrane filter for counting. This microprecipitation method is faster, cheaper, and more convenient than the traditional spontaneous deposition method, with an excellent Po recovery (>90%) under optimal conditions. The influences of several experimental parameters, including Te(IV) quantity, reaction time, and HCl molarity, were examined to determine the optimal conditions for Te microprecipitation. The decontamination factors of potential interferences from various radionuclides (Ra, Th, U, Pu, Am) for the counting of long-lived polonium isotopes (208Po, 209Po, and 210Po) were also evaluated, and the results confirmed a good selectivity on polonium by this microprecipitation method. Due to its strong resistance to high acidity up to 12 M HCl, the method would be particularly suitable for rapid determination of 210Po in acid leaching solution of solid samples.

Rapid determination of radium-224/226 in seawater sample by alpha spectrometry.

A new radiochemical separation method has been developed for rapid determination of alpha-emitting radium isotopes in seawater samples. This method can be applied for the measurement of 226Ra in seawater samples when 224Ra is used as tracer for chemical recovery correction. Likewise, 226Ra can also be added as tracer for the determination of 224Ra in seawater sample. In the method, radium is first pre-concentrated with hydrous titanium oxide (HTiO) and is purified by combined anion/cation exchange column chromatographic separation. The radium in the eluate is then co-precipitated with HTiO, dissolved in 9 M H2SO4, and followed through a BaSO4 micro-precipitation step to prepare a thin-layer counting source to determine the activities of 224Ra/226Ra by alpha spectrometry. Replicate spike and blank samples were measured to evaluate the performance of the procedure. The minimum detectable activity concentration was determined to be 0.5 mBq·L-1 for 226Ra and 0.4 mBq·L-1 for 224Ra in 1 L of seawater sample with a counting time of 48 h. The method is a promising candidate for rapid measurement for alpha-emitting Ra isotopes in a large population of environment water samples.

Iodine-129 in seawater offshore Fukushima: distribution, inorganic speciation, sources, and budget.

The Fukushima nuclear accident in March 2011 has released a large amount of radioactive pollutants to the environment. Of the pollutants, iodine-129 is a long-lived radionuclide and will remain in the environment for millions of years. This work first report levels and inorganic speciation of (129)I in seawater depth profiles collected offshore Fukushima in June 2011. Significantly elevated (129)I concentrations in surface water were observed with the highest (129)I/(127)I atomic ratio of 2.2 × 10(-9) in the surface seawater 40 km offshore Fukushima. Iodide was found as the dominant species of (129)I, while stable (127)I was mainly in iodate form, reflecting the fact that the major source of (129)I is the direct liquid discharges from the Fukushima NPP. The amount of (129)I directly discharged from the Fukushima Dai-ichi nuclear power plant to the sea was estimated to be 2.35 GBq, and about 1.09 GBq of (129)I released to the atmosphere from the accident was deposited in the sea offshore Fukushima. A total release of 8.06 GBq (or 1.2 kg) of (129)I from the Fukushima accident was estimated. These Fukushima-derived (129)I data provide necessary information for the investigation of water circulation and geochemical cycle of iodine in the northwestern Pacific Ocean in the future.

Speciation analysis of 129I in seawater by carrier-free AgI-AgCl coprecipitation and accelerator mass spectrometric measurement.

A rapid and simple method was developed for speciation analysis of (129)I in seawater by selective coprecipitation of carrier-free iodide and accelerator mass spectrometry (AMS) measurement of (129)I. Iodide was separated from seawater and other species of iodine by coprecipitation of AgI with Ag2SO3, AgCl, and AgBr by addition of only 100 mg/L Ag(+) and 0.3 mmol/L NaHSO3 at pH 4.2-5.5. The separation efficiency of iodide was more than 95%, and crossover between (129)IO3(-) and (129)I(-) fractions is less than 3%. Iodate and total inorganic iodine were converted to iodide by use of NaHSO3 at pH 1-2 and then separated by the same method as for iodide. Ag2SO3 in the coprecipitate was removed by washing with 3 mol/L HNO3 and the excess AgCl and AgBr was removed by use of diluted NH3, and finally a 1-3 mg precipitate was obtained for AMS measurement of (129)I. The recovery of iodine species in the entire procedure is higher than 70%. Six seawater samples collected from the Norwegian Sea were analyzed by this method as well as a conventional anion-exchange chromatographic method; the results from the two methods show no significant difference (p = 0.05). Because only one separation step and fewer chemicals are involved in the procedure, this method is suitable for operation on board sampling vessels, as it avoids the transport of samples to the laboratory and storage for a longer time before analysis, therefore significantly improving the analytical capacity and reliability of speciation analysis of (129)I. This improvement can stimulate oceanographic tracer studies of (129)I.

Speciation and migration of (129)I in soil profiles.

A method has been developed for speciation analysis of ultra low level (129)I in soil using sequential extraction combined with coprecipitation for separation of carrier free iodine and AMS measurement of (129)I. Two loess profiles collected from northwest China were analyzed for species of (129)I and (127)I. Similar partitioning of (129)I and (127)I was observed in the loess profiles, the distribution of iodine isotopes followed an order of organic > leachable > reducible > residue. The (129)I concentrations and (129)I/(127)I ratios decreased exponentially with the depth, and 2 orders of magnitude lower in the deepest layer (60 and 90 cm) compared with the top layer, indicating a significant contribution of anthropogenic input in the upper layer, and high retention of (129)I in soil. The mobility of (129)I in different fractions decreased in an order of leachable > organic > oxides > residue. The results suggest that migration of iodine downwards in the soil profile is a slow process; the oxides and residue are the less mobile fractions of iodine.

Level and source of 129I of environmental samples in Xi'an region, China.

Iodine-129 is widely used as a tracer in various environmental practices such as monitoring of nuclear environmental safety, seawater exchange and transport, geochemical cycle of stable iodine and dating of geological events. The spatial distribution of (129)I concentration varies significantly on global scale because of anthropogenic input from nuclear activities coupled with scarcity of data on environmental (129)I variability in many parts of the world including Asia. Here we report new data on (129)I and (127)I concentrations in soil, vegetation, river water and precipitation collected from Xi'an area, China. The results indicate values for environmental (129)I/(127)I ratios in the investigated area range from 1.1×10(-10) to 43.5×10(-10) with a mean of 20.6×10(-10), which is 1-3 orders of magnitude lower than the ratios observed in Europe, but comparable with those observed in the locations far from direct effect of point release sources and at similar latitude. The main source of (129)I in the investigated area is attributed to the global fallout of both atmospheric nuclear weapons testing and long distance dispersion of fuel reprocessing releases.

Determination of ultralow level 129I/127I in natural samples by separation of microgram carrier free iodine and accelerator mass spectrometry detection.

Separation of carrier free iodine from low iodine level samples and accurate measurement of ultralow level (129)I in micrograms of iodine target are essential but a bottleneck in geological dating of terrestrial system and tracer research using naturally produced (129)I. In this work, we present a carrier free method using coprecipitation of AgI with AgCl for preparing micrograms of iodine target, associated with combustion using a tube furnace for separating iodine from solid samples and anion exchange chromatography for preconcentrating iodine from a large volume of water. An accelerator mass spectrometry was used to measure ultralow level (129)I in micrograms of iodine target. The recovery of iodine in the entire separation procedure is higher than 80% and 65% for solid and water samples, respectively. One microgram iodine in the target (AgI-AgCl) can produce a stable (127)I signal for AMS measurement of (129)I/(127)I, and a detection limit of this method for (129)I is calculated to be 10(5) atoms. This will allow us to accurately determine (129)I in prenuclear geological samples of low iodine concentration with (129)I/(127)I of 10(-12), such as loess, soil, coral, rock, sediment, and groundwater. Some samples with low iodine content have been successfully analyzed, and the lowest value of the (129)I/(127)I ratio of 2 × 10(-11) was observed in 23.5 and 63.5 m loess samples collected in the Loess Plateau, China. The developed method sheds light on a wide application in earth science.