High-precision measurement of U-Pu-Np-Am concentrations and isotope ratios in environmental reference materials by mass spectrometry.

We report results of precise and sensitive mass spectrometric measurements of uranium, plutonium, neptunium, and americium concentrations and isotope ratios in a variety of environmental reference materials. Most of our work has been done on NIST SRM 4350b, River Sediment, but we also present results for NIST SRM 4354, Lake Sediment; NIST SRMs 4355 and 4355a, Peruvian Soil; NIST SRM 4357, Ocean Sediment; NIST SRM 1648a, Urban Particulate Material; NIST SRM 1649b, Urban Dust; IAEA CRM 385, Ocean Sediment; USGS BCR-2, Columbia River Basalt; and USGS BHVO-2, Hawaiian Volcanic Observatory Basalt. These materials reflect a wide range in long-lived actinide concentrations (e.g. 1E4 to 1E10 atoms 239Pu/g) and isotope ratios. Measurements were performed in a clean laboratory by isotope dilution, multi-collector thermal ionization and multi-collector inductively coupled plasma mass spectrometry. In general, our results are in agreement with, but lower the uncertainty of, literature or certificate values for these reference materials. Our uranium results for the basalts also confirm previously reported high-precision mass spectrometric results from our laboratory. In many cases our measurements of U-Pu-Np-Am nuclides appear to be novel. Extensive results for NIST SRM 4350b, River Sediment, indicate that this material is heterogeneous for Pu-Np-Am concentrations and isotope ratios at a sample size of 5 g or lower. Pu-Np isotope ratios and a241Pu-241Am model age of 1954 reflect a mix of plutonium production operations at the nearby Hanford, Washington site, and global atmospheric fallout from nuclear weapons testing. Results for the oceanic sediment materials (NIST SRM 4357 and IAEA 385) collected near Sellafield, U.K. vary but are also indicative of local anthropogenic sources of varying Pu isotopic composition and a mean 241Pu-241Am model age of 1964. Large environmental fractionation between Pu and Np is observed for the ocean, river, and lake sediment reference materials. Novel measurements for the two air particulate SRMs indicate high U, Pu and Np concentrations for these collections in 1976-1977 with an anomalous regional fallout Pu isotopic signature. Results for BHVO-2 and other Hawaiian basalts indicate that those which erupted before or during the period of abundant atmospheric nuclear weapons testing (1950-1970) contain significant levels of Pu (on the order of 1E7 atoms 239Pu/g) with a global fallout Pu isotopic composition, compared to more recent eruptions which incorporated less Pu. Hence, Hawaiian basalts may provide an integrated temporal record of anthropogenic actinide fallout deposition from the atmosphere since eruption.

Dietary vitamin E reaches the mitochondria in the flight muscle of zebra finches but only if they exercise.

Whether dietary antioxidants are effective for alleviating oxidative costs associated with energy-demanding life events first requires they are successfully absorbed in the digestive tract and transported to sites associated with reactive species production (e.g. the mitochondria). Flying birds are under high energy and oxidative demands, and although birds commonly ingest dietary antioxidants in the wild, the bioavailability of these consumed antioxidants is poorly understood. We show for the first time that an ingested lipophilic antioxidant, α-tocopherol, reached the mitochondria in the flight muscles of a songbird but only if they regularly exercise (60 min of perch-to-perch flights two times in a day or 8.5 km day-1). Deuterated α-tocopherol was found in the blood of exercise-trained zebra finches within 6.5 hrs and in isolated mitochondria from pectoral muscle within 22.5 hrs, but never reached the mitochondria in caged sedentary control birds. This rapid pace (within a day) and extent of metabolic routing of a dietary antioxidant to muscle mitochondria means that daily consumption of such dietary sources can help to pay the inevitable oxidative costs of flight muscle metabolism, but only when combined with regular exercise.

Uranium-series constraints on radionuclide transport and groundwater flow at the Nopal I uranium deposit, Sierra Pena Blanca, Mexico.

Uranium-series data for groundwater samples from the Nopal I uranium ore deposit were obtained to place constraints on radionuclide transport and hydrologic processes for a nuclear waste repository located in fractured, unsaturated volcanic tuff. Decreasing uranium concentrations for wells drilled in 2003 are consistent with a simple physical mixing model that indicates that groundwater velocities are low ( approximately 10 m/y). Uranium isotopic constraints, well productivities, and radon systematics also suggest limited groundwater mixing and slow flow in the saturated zone. Uranium isotopic systematics for seepage water collected in the mine adit show a spatial dependence which is consistent with longer water-rock interaction times and higher uranium dissolution inputs at the front adit where the deposit is located. Uranium-series disequilibria measurements for mostly unsaturated zone samples indicate that (230)Th/(238)U activity ratios range from 0.005 to 0.48 and (226)Ra/(238)U activity ratios range from 0.006 to 113. (239)Pu/(238)U mass ratios for the saturated zone are <2 x 10(-14), and Pu mobility in the saturated zone is >1000 times lower than the U mobility. Saturated zone mobility decreases in the order (238)U approximately (226)Ra > (230)Th approximately (239)Pu. Radium and thorium appear to have higher mobility in the unsaturated zone based on U-series data from fractures and seepage water near the deposit.