Determination of extremely low (236)U/(238)U isotope ratios in environmental samples by sector-field inductively coupled plasma mass spectrometry using high-efficiency sample introduction

A method by inductively coupled plasma mass spectrometry (ICP-MS) was developed which allows the measurement of (236)U at concentration ranges down to 3 x 10(-14)g g(-1) and extremely low (236)U/(238)U isotope ratios in soil samples of 10(-7). By using the high-efficiency solution introduction system APEX in connection with a sector-field ICP-MS a sensitivity of more than 5,000 counts fg(-1) uranium was achieved. The use of an aerosol desolvating unit reduced the formation rate of uranium hydride ions UH(+)/U(+) down to a level of 10(-6). An abundance sensitivity of 3 x 10(-7) was observed for (236)U/(238)U isotope ratio measurements at mass resolution 4000. The detection limit for (236)U and the lowest detectable (236)U/(238)U isotope ratio were improved by more than two orders of magnitude compared with corresponding values by alpha spectrometry. Determination of uranium in soil samples collected in the vicinity of Chernobyl nuclear power plant (NPP) resulted in that the (236)U/(238)U isotope ratio is a much more sensitive and accurate marker for environmental contamination by spent uranium in comparison to the (235)U/(238)U isotope ratio. The ICP-MS technique allowed for the first time detection of irradiated uranium in soil samples even at distances more than 200 km to the north of Chernobyl NPP (Mogilev region). The concentration of (236)U in the upper 0-10 cm soil layers varied from 2 x 10(-9)g g(-1) within radioactive spots close to the Chernobyl NPP to 3 x 10(-13)g g(-1) on a sampling site located by >200 km from Chernobyl.     

Resolving Chernobyl vs. global fallout contributions in soils from Poland using Plutonium atom ratios measured by inductively coupled plasma mass spectrometry

Plutonium in Polish forest soils and the Bór za Lasem peat bog is resolved between Chernobyl and global fallout contributions via inductively coupled plasma mass spectrometric measurements of 240Pu/230Pu and 241Pu/239Pu atom ratios in previously prepared NdF3 alpha spectrometric sources. Compared to global fallout, Chernobyl Pu exhibits higher abundances of 240Pu and 241Pu. The ratios 240Pu/230Pu and 241Pu/239Pu co-vary and range from 0.186 to 0.348 and 0.0029 to 0.0412, respectively, in forest soils (241Pu/239Pu = 0.2407 x [240Pu/239Pu] - 0.0413; r2 = 0.9924). Two-component mixing models are developed to apportion 239+240Pu and 241Pu activities; various estimates of the percentage of Chernobyl-derived 239+240Pu activity in forest soils range from < 10% to > 90% for the sample set. The 240Pu/230Pu - 241Pu/239Pu atom ratio mixing line extrapolates to estimate 241Pu/239Pu and the 241Pu/239+240Pu activity ratio for the Chernobyl source term (0.123 +/- 0.0007; 83 +/- 5; 1 May 1986). Sample 241Pu activities, calculated using existing alpha spectrometric 239+240Pu activities, and the 240Pu/230Pu and 241Pu/239Pu atom ratios, agree relatively well with previous liquid scintillation spectrometry measurements. Chernobyl Pu is most evident in locations from northeastern Poland. The 241Pu activities and/or the 241Pu/239Pu atom ratios are more sensitive than 240Pu/239Pu or 238Pu/239+240Pu activity ratios at detecting small Chernobyl 239+240Pu inputs, found in southern Poland. The mass spectrometric data show that the 241Pu activity is 40-62% Chernobyl-derived in southern Poland, and 58-96% Chernobyl in northeastern Poland. The Bór za Lasem peat bog (49.42 degrees N, 19.75 degrees E), located in the Orawsko-Nowotarska valley of southern Poland, consists of global fallout Pu.     

Selection of a suitable mobile phase for the speciation of four arsenic compounds in drinking water samples using ion-exchange chromatography coupled to inductively coupled plasma mass spectrometry

The performance of two mobile phase buffers, phosphate and TRIS, were compared for the speciation of four arsenic species: arsenate (As(V)), arsenite (As(III)), mono methylarsonic acid (MMA), and dimethyl arsinic acid (DMA) in drinking water, using ion-exchange chromatography inductivelycoupled plasma mass spectrometry (IEC-ICP-MS). The mobile phase containing TRIS acetate buffer ("TRIS") demonstrated superior perfomance in baseline separation of all four arsenic species and the internal standard. It is also applicable to high-throughput sample analysis as it minimized the frequency required to clean the sampling interface due to salt build-up when compared to the phosphate mobile phase. The method was evaluated for its precision, accuracy, linearity and detection limits. The method was successfully applied for the analysis of drinking water samples.     

Anthropogenic 236U at Rocky Flats,Ashtabula river harbor,and Mersey estuary: three case studies by sector inductively coupled plasma mass spectrometry

236U (t(1/2)=2.3 x 10(7) y) is formed as a result of thermal neutron capture by (235)U. In naturally occurring U ores, where a high neutron flux is present from spontaneous fission of (238)U, (236)U/(238)U atom ratios are approximately 10(-4) ppm. In the natural Earth's crust, unaffected by nuclear fallout, these ratios are expected to be on the order of 10(-8) ppm. Reactor-irradiated U, however, exhibits high (236)U/(238)U atom ratios approaching 10(4) ppm. As a result, the presence of very small quantities of reactor-irradiated U will significantly enhance the "background" (236)U/(238)U atom ratio. When sufficiently elevated (236)U/(238)U ratios are present, the determination of (236)U/(238)U by rapid inductively coupled plasma mass spectrometric (ICPMS) methods is attractive. We have used sector ICPMS at medium resolving power (R=3440) to measure (236)U/(238)U atom ratios with a determination limit of 0.2 ppm. The limiting factors in the measurement are the (235)U(1)H(+) isobar and background signal at m/z 236 arising from the (238)U(+) peak tail. Based upon the analysis of replicates and considerations of possible systematic errors, uncertainties of +/-5% are found for (236)U/(238)U atom ratios of 1-100 ppm. This procedure has been demonstrated in studies of anthropogenic (236)U in the environment at three locations: (a) offsite soils from the vicinity of the Rocky Flats Environmental Technology site (Golden, Colorado, USA); (b) sediments from the Ashtabula River (Ohio, USA); and (c) sediments from the Mersey estuary (Liverpool, UK). In each of these three locations, definite plumes of elevated (236)U/(238)U are identified and characterized. Maximum (236)U/(238)U atom ratios observed in RFETS-vicinity soils, the Ashtabula River, and the Mersey Estuary are 2.8, 140, and 4.4 ppm, respectively.     

Separation and measurement of thorium, plutonium, americium, uranium and strontium in environmental matrices

A technique for the isolation of thorium (Th), plutonium (Pu), americium (Am), uranium (U) and strontium (Sr) isotopes from various environmental matrices has been adapted from a previously published method specific to water samples (Maxwell, 2006). Separation and isolation of the various elemental fractions from a single sub-sample is possible, thereby eliminating the need for multiple analyses.The technique involves sample dissolution, concentration via calcium phosphate co-precipitation, rapid column extraction using TEVA™, TRU™ and Sr-Spec™ resin cartridges, alpha spectrometry for Th, Pu, U and Am and Cerenkov counting for Sr.Various standard reference materials were analysed and chemical yields are in the range of 70-80% for Th, Am, U and Sr and 50-60% for Pu. Sample sizes of up to 10 L for water, 5 g for dry soil and sediment and 10 g for dry vegetation and seaweed can be processed using this technique.