Nicolas Fatin-Rouge

Size Effects on Diffusion Processes within Agarose Gels

To investigate diffusion processes in agarose gel, nanoparticles with sizes in the range between 1 and 140 nm have been tested by means of fluorescence correlation spectroscopy. Understanding the diffusion properties in agarose gels is interesting, because such gels are good models for microbial biofilms and cells cytoplasm. The fluorescence correlation spectroscopy technique is very useful for such investigations due to its high sensitivity and selectivity, its excellent spatial resolution compared to the pore size of the gel, and its ability to probe a wide range of sizes of diffusing nanoparticles. The largest hydrodynamic radius (R(c)) of trapped particles that displayed local mobility was estimated to be 70 nm for a 1.5% agarose gel. The results showed that diffusion of particles in agarose gel is anomalous, with a diverging fractal dimension of diffusion when the large particles become entrapped in the pores of the gel. The latter situation occurs when the reduced size (R(A)/R(c)) of the diffusing particle, A, is >0.4. Variations of the fractal exponent of diffusion (d(w)) with the reduced particle size were in agreement with three-dimensional Monte Carlo simulations in porous media. Nonetheless, a systematic offset of d(w) was observed in real systems and was attributed to weak nonelastic interactions between the diffusing particles and polymer fibers, which was not considered in the Monte Carlo simulations.

Self-Assembly of Tricuprous Double Helicates: Thermodynamics, Kinetics, and Mechanism

We report in this paper the coordination and kinetic properties of two oligobipyridine strands, which contain three 2,2′-bipyridine subunits separated by oxydimethylene bridges, the 4,4′-bis(CONET2)-substituted L and the 4,4′-bis(CO2Et)-substituted L′. Spectrophotometric measurements allowed the characterization of thermodynamic complexes and kinetic intermediates* which are involved in the self-assembly process of L2Cu3 and L2Cu3 helicates. The reaction presents positive cooperativity for the binding of two 2,2′-bipyridine strands to the cuprous cations. While reactive kinetic intermediates* present distorted coordination geometries around Cu1, the final rearrangement of the tricuprous bistranded helicates allows more closely tetrahedral coordination of each cation and reduces the interactions. Differences in the bulkiness and electronic properties of the L and L′ substituents do not affect significantly the stability of the corresponding helicates, but greatly influence binding rates in the self-assembly process.

PAH contaminated soil remediation by reusing an aqueous solution of cyclodextrins.

We studied the possibility to re-use an aqueous solution of methyl-beta-cyclodextrin (bpmCD) in order to decontaminate a soil polluted by phenanthrene and pyrene. The loss of bpmCD in the soil was insignificant. In order to eliminate polycylic aromatic hydrocarbons (PAHs) from the contaminated aqueous solution, on one hand we tested their photodegradation using TiO(2) suspensions. But it was inefficient, because of the stabilisation of PAHs within the cavity of bpmCD. On the other hand, we removed PAHs by liquid-liquid extraction with colza oil. This allowed the regeneration of cyclodextrins, by concentrating the pollutants in the organic phase with a small loss of carrier. Contaminated soils were almost completely de-polluted after 2d of re-circulation, using a 10mM solution of bpmCD. To reduce the amount of bpmCD loss in the oil phase, we set the fraction of colza oil low, by using a micro-emulsion or by impregnating an organic membrane with the oil. We found this last possibility more interesting.

Surfactant foam technology for in situ removal of heavy chlorinated compounds-DNAPLs

The use of surfactant foam for the remediation of a saturated soil contaminated with a dense non-aqueous phase liquid (DNAPL) was investigated at bench-scale. Despite the presence of the DNAPL, high foam stability was obtained for a mixture of cocamidopropyl betaïne and dodecylsulfate at 0.05%. Foams were assessed in different injection conditions and were compared to commonly used remediation methods. Strong foams improved significantly the DNAPL recovery yield, which amounted up to 98%, owing to the propagation of a flat foam front, with low dissolution (<0.5 g l(-1)) and surfactant consumption (<10 g kg(-1) DNAPL recovered). The effects of important parameters (gas to liquid ratio, injection velocity, gas nature) and methods for foam production on pressure gradient (∇P), remediation efficiency and surfactant consumption were investigated. Even for low injection velocities (4×10(-4) ms(-1)), capillary numbers were high enough (∼8×10(-3)) to push the DNAPL efficiently. DNAPL lowered ∇P for foam propagation because of its destabilising effect. The use of CO2 as gas reduced the ∇Ps for foam propagation by 35%. ∇P were also decreased by 25% for gas to liquid ratios lower than 75%, whereas, DNAPL removal remained high. This technology should lower spreading risks and treatment costs.

Surfactant foam flushing for in situ removal of DNAPLs in shallow soils

An innovative process combining surfactant foam and surfactant flushing (SF) for the remediation of a shallow saturated soil contaminated with a dense non-aqueous phase liquid (DNAPL) residual was investigated at bench-scale. First, foam was formed by injecting DHSS surfactant and nitrogen in alternation in soil (SAG process) at constant pressure. The effect of pressure gradients set point (≤90kPam-1) on DNAPL recovery was investigated. Foam front mobilized DNAPL with a piston-like fast propagation (1.8md-1) despite the low pressure gradients. 34-60% of DNAPL residual was extracted with low surfactant consumption (<0.4kgkg-1 DNAPL removed). Then, a solubilizing agent (Tergitol) was injected into soil, previously treated with foam, to improve the DNAPL removal. It led a removal up to 95% whereas only 2 porous volume (PV) of solubilizing solution were injected. As a comparison, when the solubilizing agent was injected without foam pre-treatment, 40 PV would have been required to lead the removal up to 90%. Considering the overall treatment, the technology we developed requires 10-times less surfactant than the traditional SF technology. This technology is especially suitable for very shallow soils where injection pressure has to be kept at a low level to avoid soil heaving.