A new foam-based method for the (bio)degradation of hydrocarbons in contaminated vadose zone.

An innovative foam-based method for Fenton reagents (FR) and bacteria delivery was assessed for the in situ remediation of a petroleum hydrocarbon-contaminated unsaturated zone. The surfactant foam was first injected, then reagent solutions were delivered and propagated through the network of foam lamellae with a piston-like effect. Bench-scale experiments demonstrated the feasibility of the various treatments with hydrocarbon (HC) removal efficiencies as high as 96 %. Compared to the direct injection of FR solutions, the foam-based method led to larger radii of influence and more isotropic reagents delivery, whereas it did not show any detrimental effect regarding HC oxidation. Despite 25 % of HCs were expelled from the treated zone because of high foam viscosity, average degradation rates were increased by 20 %. At field-scale, foam and reagent solutions injections in soil were tracked both using visual observation and differential electric resistivity tomography. The latter demonstrated the controlled delivery of the reactive solutions using the foam-based method. Even if the foam-based method duration is about 5-times longer than the direct injection of amendment solutions, it provides important benefits, such as the confinement of harmful volatile hydrocarbons during Fenton treatments, the enhanced reagents delivery and the 30 % lower consumption of the latter.

Self-assembly of a diferrous triple-stranded helicate with bis(2,2'-bipyridine) ligands: thermodynamic and kinetic intermediates.

The protonation and iron(II) coordination properties of a bis(2,2'-bipyridine) ligand L were investigated in methanol. The protonated forms showed allosteric effects due to the flexibility of the strand. Speciation studies of the corresponding ferrous complexes were carried out as a function of pH and iron(II) concentrations. A combination of electrospray mass spectroscopy, potentiometry, and spectrophotometry allowed the determination in solution of three ferrous complexes, one mononuclear (L2Fe2+) and two dinuclear (L2Fe2(4+) and L3Fe2(4+)) species. Their structure was deduced from the metal spin state and confirmed by 1H NMR measurements and molecular modeling. The dissociation process of the triple-stranded diferrous helicate L3Fe2(4+) by OH- revealed two rate-limiting steps. The former leads to the formation of a monoferrous triple-stranded compound via a classical mechanism, which involves hydroxy-ferrous complexes. A similar process was observed in the latter step for the release of the ferrous cation from the mononuclear intermediate. Taking into account the structural, thermodynamic, and kinetic features provided by the present study, we could propose a self-assembling mechanism of the triple-stranded diferrous helicate.