The fractionation of the nitrogen isotopes 14N and 15N in the denitrification process has been studied in laboratory experiments for the step NO2− → N2O. This study has been carried out on natural soils under anaerobic conditions (helium atmosphere). Reduction of N2O is blocked by introduction of a small amount of acetylene in the incubator atmosphere. Variation of experimental conditions of incubation (temperatures, direct or after air-drying incubation of the soil, addition of glucose), greatly modify the reaction rate. 15N is enriched in the substrate during denitrification. The isotopic enrichment factor changes with experimental conditions from about −33 to −11‰. Greatest enrichment is obtained for the lowest reduction rate (low temperature, undried soil). For high rates of denitrification (higher temperature, addition of glucose), the isotopic fractionation decreases. An exponential relation is found between isotopic enrichment, εp/s, and the reaction rate.
We
investigate water infiltration in porous matrices made of bitumen
and salts with different solubilities. Dispersion, inside bitumen,
of either SrSO4 or MgSO4 at 40% mass fraction
was achieved, as a way to model materials used in the context of nuclear
waste conditioning. Pulsed field gradient nuclear magnetic resonance
(PFG-NMR) and environmental scanning electron microscopy (ESEM) measurements
allow us to characterize the evolution of the
porous structure as a consequence of water infiltration (due to a
leaching phenomenon) for durations up to 1.5 year. PFG-NMR enables
performing 1D-imaging of water at different times to monitor its slow
seeping inside the material. Profiles observed at the maximum time
interval (1.5 year) demonstrate that different leaching behaviors
exist depending on whether the salts dispersed inside bitumen are
of the soluble or insoluble type. NMR relaxation and diffusion measurements
were also taken. Remarkably, when performed in combination with 1D-imaging,
such measurements yield information on the surface-to-volume ratio
of the water-filled porous network, at different times, as a function
of depth. In the case of the matrix-containing insoluble salts, relaxation
measurements lead to discrimination between two different water populations
differing by their T
2 or T
1 values. These values are described in the framework
of surface-driven relaxation. A two-step model of leaching is proposed
that globally accounts for the different observations (NMR 1D-imaging,
relaxation/diffusion, as well as ESEM). The present work gives insight
into the leaching behavior of porous bitumen-salt matrices and could
be used as an input for modeling their evolution on longer timescales.
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