Hydrogeochemical and hydrodynamic features affecting redox processes in groundwater

This research deals with some hydrogeochemical and hydrodynamic features that affect redox processes in groundwater, presenting three different case studies and methodological approaches. This information is vital when characterizing contaminated sites, planning monitoring, selecting remedial techniques, and assessing health risks. In the San Pedro Sula site case study (Honduras), new insights and an advanced method for the aquifer redox zonation were provided. The Multi-Collocated Factorial Kriging, a multivariate geostatistical technique borrowed from agriculture and soil science, identified simultaneous redox processes, acting at different scales and mainly due to eutrophicated surface-water/groundwater interaction: at short-range, Mn oxihydroxide reductive dissolution and Fe oxi-hydroxide colloidal phase precipitation; at long-range, Fe mobilization. The obtained results are supported by the Principal Component Analysis and hydrogeochemical numerical modeling. The interaction among different contamination events in the VR site allowed to get a deeper insight into the competition for organic substrate among different redox processes. To this purpose, a 1-D Advective-Reactive- Dispersive transport numerical model was implemented, and its results highlighted that the reductive dechlorination is inhibited by the inorganic Terminal Electron Accepting Processes, enriching groundwater in highly toxic by-products of the reductive dechlorination (i.e. Vinyl Chloride). As a matter of fact, the bacteria using inorganic Terminal Electron Acceptors to oxidize the organic substrate are more efficient than the halo-respiring bacteria, that favor reductive dechlorination. The contaminated site of Bussi Officine case study allowed to clarify the hydrodynamic effect on the redox processes and the anoxic condition distribution. The comparison between dissolved chlorinated solvents and the inorganic Terminal Electron Acceptors distribution in the aquifer pointed out that dispersion inhibits all the redox processes because it dilutes the organic substrate concentration in groundwater. On the other hand, the lacustrine deposits rich organic matter (i.e. peat) can be considered as "chemical reactors", that releases by back-diffusion toxic by-product of the reductive dichlorination in groundwater.