Dating of streamwater using tritium in a post nuclear bomb pulse world: continuous variation of mean transit time with streamflow

Tritium measurements of streamwater draining the Toenepi catchment, a small dairy farming area in Waikato, New Zealand, have shown that the mean transit time of the water varies with the flow rate of the stream. Mean transit times through the catchment are 2–5 years during high baseflow conditions in winter, increasing to 30–40 years as baseflow decreases in summer, and then dramatically older water during drought conditions with mean transit time of more than 100 years. Older water is gained in the lower reaches of the stream, compared to younger water in the headwater catchment. The groundwater store supplying baseflow was estimated from the mean transit time and average baseflow to be 15.4 × 10<sup>6</sup> m<sup>3</sup> of water, about 1 m water equivalent over the catchment and 2.3 times total annual streamflow. Nitrate is relatively high at higher flow rates in winter, but is low at times of low flow with old water. This reflects both lower nitrate loading in the catchment several decades ago as compared to current intensive dairy farming, and denitrification processes occurring in the older groundwater. Silica, leached from the aquifer material and accumulating in the water in proportion to contact time, is high at times of low streamflow with old water. There was a good correlation between silica concentration and streamwater age, which potentially allows silica concentrations to be used as a proxy for age when calibrated by tritium measurements. This study shows that tritium dating of stream water is possible with single tritium measurements now that bomb-test tritium has effectively disappeared from hydrological systems in New Zealand, without the need for time-series data

Spectroscopic study of the interaction of U(VI) with transferrin and albumin for speciation of U(VI) under blood serum conditions

International audienceThe quantitative description of the interactions of uranium with blood serum components is of high relevance for a rational design of molecules suitable for in vivo chelation of uranium. We have determined the stability constants for the complexation of U(VI) with human serum transferrin and albumin by time-resolved laser-induced fluorescence spectroscopy and difference ultraviolet spectroscopy. Both proteins interact strongly with U(VI), forming ternary complexes with carbonate acting as a synergistic anion. Together with literature data describing the interaction of U(VI) with low molecular weight inorganic and organic serum components, the speciation of U(VI) in blood serum was calculated. In agreement with published experimental data, the model calculation shows that complexation with proteins and carbonate ion governs U(VI) speciation: 35% of U(VI) is bound to proteins and 65% to carbonate. Among the protein pool, albumin is the main protein interacting with U(VI). In addition, the results show that Ca(II) must be considered in the model as a competitive metal ion with respect to U(VI) for binding to albumin surface sites. Based on these findings several promising molecules for in vivo chelation of U-230 could be identified. (C) 2009 Elsevier Inc. All rights reserved

Investigation of para-sulfonatocalix[n]arenes [n = 6, 8] as potential chelates for 230U

International audienceLiterature reports of the efficacy of para-sulfonatocalix[6]- and calix[8]-arenes as U(VI) complexants indicated that they might be useful for in vivo chelation of the novel therapeutic alhpa-emitter 230U. We have studied the complexation of U(VI) with para-sulfonatocalix[6]arene and para-sulfonatocalix[8]arene by time resolved laser induced fluorescence spectroscopy and using competition methods with Chelex resin and 4-(2-pyridylazo)resorcinol in simplified and in biological media. New thermodynamic parameters describing the stability of U(VI)-para-sulfonatocalix[n]arene [n = 6, 8] complexes were obtained. Although the interactions are strong, the complexes do not exhibit sufficient stability to compete with carbonate ions and serum proteins for complexation of U(VI) under physiological conditions

Dynamics of Capillary Electrochromatography : Experimental Study of Flow and Transport in Particulate Beds

The chromatographic performance with respect to the flow behavior and dispersion in fixed beds of nonporous and macroporous particles (having mean intraparticle pore diameters of 41, 105, and 232 nm) has been studied in capillary HPLC and electrochromatography. The existence of substantial electroosmotic intraparticle pore flow (perfusive electroosmosis) in columns packed with the macroporous particles was found to reduce stagnant mobile mass transfer resistance and decrease the global flow inhomogeneity over the column cross-section, leading to a significant improvement in column efficiency compared to capillary HPLC. The effect of electroosmotic perfusion on axial dispersion was shown to be sensitive to the mobile phase ionic strength and mean intraparticle pore diameter, thus, on an electrical double layer interaction within the particles. Complementary and consistent results were observed for the average electroosmotic flow through packed capillaries. It was found to depend on particle porosity and distinct contributions to the electrical double layer behavior within and between particles. Based on these data an optimum chromatographic performance in view of speed and efficiency can be achieved by straightforward adjustment of the electrolyte concentration and characteristic intraparticle pore size. Copyright © 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim [accessed 2013 November 27th

Dynamics and chemistry of vortex remnants in late Arctic spring 1997 and 2000: Simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS)

High-resolution simulations of the chemical composition of the Arctic stratosphere during late spring 1997 and 2000 were performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS). The simulations were performed for the entire northern hemisphere on two isentropic levels 450 K (~18 km) and 585 K (~24 km).<br> <br> The spatial distribution and the lifetime of the vortex remnants formed after the vortex breakup in May 1997 display different behavior above and below 20 km. Above 20 km, vortex remnants propagate southward (up to 40°N) and are &quot;frozen in'' in the summer circulation without significant mixing. Below 20 km the southward propagation of the remnants is bounded by the subtropical jet. Their lifetime is shorter by a factor of 2 than that above 20 km, owing to significant stirring below this altitude. The behavior of vortex remnants formed in March 2000 is similar but, due to an earlier vortex breakup, dominated during the first 6 weeks after the vortex breakup by westerly winds, even above 20 km.<br> <br> Vortex remnants formed in May 1997 are characterized by large mixing ratios of HCl indicating negligible, halogen-induced ozone loss. In contrast, mid-latitude ozone loss in late boreal spring 2000 is dominated, until mid-April, by halogen-induced ozone destruction within the vortex remnants, and subsequent transport of the ozone-depleted polar air masses (dilution) into the mid-latitudes. By varying the intensity of mixing in CLaMS, the impact of mixing on the formation of ClONO₂ and ozone depletion is investigated. We find that the photochemical decomposition of HNO₃ and not mixing with NO_x-rich mid-latitude air is the main source of NO_x within the vortex remnants in March and April 2000. Ozone depletion in the remnants is driven by ClO_x photolytically formed from ClONO₂. At the end of May 1997, the halogen-induced ozone deficit at 450 K poleward of 30°N amounts to ~12% with ~10% in the polar vortex and ~2% in well-isolated vortex remnants after the vortex breakup

Twentieth Century Black Carbon and Dust Deposition on South Cascade Glacier, Washington State, USA, as Reconstructed From a 158‐m‐Long Ice Core

Light absorbing particles (LAPs) include black carbon (BC) and mineral dust and are of interest due to their positive radiative forcing and contribution to albedo reductions and snow and glacier melt. This study documents historic BC and dust deposition as well as their effect on albedo on South Cascade Glacier (SCG) in Washington State (USA) through the analysis of a 158‐m (139.5‐m water equivalent [w.e.]) ice core extracted in 1994 and spanning the period 1840–1991. Peak BC deposition occurred between 1940 and 1960, when median BC concentrations were 16 times higher than background, likely dominated by domestic coal and forest fire emissions. Post 1960 BC concentrations decrease, followed by an increase from 1977 to 1991 due to melt consolidation and higher emissions. Differences between the SCG record and BC emission inventories, as well as ice core records from other regions, highlight regional differences in the timing of anthropogenic and biomass BC emissions. Dust deposition on SCG is dominated by local sources and is variable throughout the record. Albedo reductions from LAP are dominated by dust deposition, except during high BC deposition events from forest fires and during 1940–1960 when BC and dust similarly contribute to albedo reductions. This study furthers understanding of the factors contributing to historical snowmelt and glacier retreat in the Cascades and demonstrates that ice cores retrieved from temperate glaciers have the potential to provide valuable records of LAP deposition