Removal of nitrate and pesticides from groundwater by nano zero-valent iron injection pulses under biostimulation and bioaugmentation scenarios in continuous-flow packed soil columns

This study evaluates the NO3- removal from groundwater through Heterotrophic Denitrification (HDN) (promoted by the addition of acetate and/or an inoculum rich in denitrifiers) and Abiotic Chemical Nitrate Reduction (ACNR) (promoted by pulse injection of zerovalent iron nanoparticles (nZVI)). HDN and ACNR were applied, separately or combined, in packed soil column experiments to complement the scarce research on pulse-injected nZVI in continuous-flow systems mimicking a Well-based Denitrification Barrier. Together with NO3-, the removal of two common pesticides (dieldrin and lindane) was evaluated. Results showed that total NO3- removal (>97%) could be achieved by either bioestimulation with acetate (converting NO3- to N2(g) via HDN) or by injecting nZVI (removing NO3- via ACNR). In the presence of nZVI, NO3- was partially converted to N2(g) and to a lower extent NO2-, with unreacted NO3- being likely adsorbed onto Fe-(oxy)hydroxides. Combination of both HDN and ACNR resulted in even a higher NO3- removal (>99%). Interestingly, nZVI did not seem to pose any toxic effect on denitrifiers. These results showed that both processes can be alterned or combined to take advantage of the benefits of each individual process while overcoming their disadvantages if applied alone. With regard to the target pesticides, the removal was high for dieldrin (>93%) and moderate for lindane (38%), and it was not due to biodegradation but to adsorption onto soil. When nZVI was applied, the removal increased (generally >91%) due to chemical degradation by nZVI and/or adsorption onto formed Fe-(oxy)hydroxides.