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.     

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.     

Membrane introduction/laser photoionization time-of-flight mass spectrometry

Two-photon resonance enhanced multiphoton ionization (REMPI) has been shown to be a unique ionization method for mass spectrometry, exhibiting both high sensitivity and chemical selectivity. Because REMPI is a gas-phase method, its applications have been limited either to direct analysis of vapor phase samples, or in conjunction with an initial laser desorption or other vaporization step. We describe here for the first time a combination of membrane introduction mass spectrometry (MIMS) and REMPI with time-of-flight mass spectrometry (TOF-MS), which allows for the direct analysis of trace amounts of organic compounds in water samples. The objective of our research was the detection of very low levels of aromatic contaminants, particularly benzene, toluene, and xylene (BTX), in aqueous solutions without interference due to the water. We have measured limits of detection (LOD) for selected aromatics in water below 1 part-per-trillion with an averaging time of less than 10 s using a continuous sample flow.