Modeling of enhanced in situ biodenitrification at different scales: Integration of microbiological, hydrogeochemical, and isotope biogeochemical processes

Abstract

In this thesis, an integrated reactive transport model has been developed that takes into account microbiology, geochemistry, and isotope geochemistry. The first section of the thesis (Chapter 2) addresses the development of a biogeochemical model with isotope geochemistry. The goal of this chapter is the setup of the conceptual relationships among microbiology, geochemistry, and isotope geochemistry (δ15N-NO3-, δ18O-NO3-, δ13C-DIC, and all geochemistry of δ13C) during Enhanced in situ Biodenitrification. Thus, one of the most complete biogeochemical models in the literature of EIB has been developed. The model was validated with a batch-scale biodenitrification experiment using groundwater and sediment from a Roda de Ter (Osona, Spain) site and two different external organic carbon sources, i.e., ethanol and glucose. In both cases, the model fit notably well with the experimental data. Moreover, the developed model also incorporated the nitrite accumulation observed in the glucose experiment. Consideration of the water-rock interaction in the model determined that if ethanol is used as an organic carbon source, carbonate mineral precipitation is induced, whereas if glucose is used, carbonate mineral dissolution is observed. Moreover, nitrate isotope incorporation facilitated the determination of the extent of denitrification at the field scale. Finally, the incorporation of a carbon isotope flow in the model was another tool used to verify the full consistence of the model due to the central role of inorganic carbon in biodenitrification and water-rock interactions. Moreover, modeling of carbon isotope flow showed that both ethanol and glucose were inversely fractionated. After the conceptual model was carried out, it was applied to an Enhanced in situ Biodenitrification application in fractured media (also Roda de Ter (Spain)). The main goal of this chapter is to incorporate the groundwater flow equations into a previously develop biogeochemical model and to validate it in media with a complex hydrogeology. It was observed that certain batch parameters can be used directly in the field (maximum consumption rate of electron donor (kmax) and stoichiometric relationships) and that the other parameters (saturation constants (Ks) and decay (b)) should be adapted, but the modifications involved less than one order of magnitude. Moreover, the induced calcite precipitation caused a change of porosity of less than 3%. As a secondary goal, the use of the Rayleigh equation to determine the extent of EIB was also verified from a practical perspective. The model demonstrated that the Rayleigh equation underestimated the percentage of degradation by approximately 60-80% and increasingly at the fringes of the plume. Chapter 4 focuses on a model that reproduces the system under different injection conditions and with the presence of important biofilm growth. This chapter evaluates how different feeding strategies modify the hydraulic properties of the media. It was observed that a weekly feeding strategy did not modify the hydraulic properties of the media, whereas daily feeding significantly modified the dispersivity. These changes in dispersivity implied an increase in heterogeneity and a consequent change in the conceptual model of flow transport along the column from normal to non-Fickian. This transition was well characterized using a single-rate mass transfer model. Moreover, the long-term model demonstrated that use of a feeding strategy with less carbon than predicted by stoichiometry implied a reduction of biomass without a reduction in nitrate degradation rates (because of the presence of an important biomass population). Overall, the elaboration of this thesis has contributed to the knowledge of all processes involved in Enhanced in situ Biodenitrification and their quantification using numerical models. The developed model will allow improvement in the design, planning, monitoring and optimization of this technology at the field scale.

Date of Award	1 Oct 2014
Original language	English
Supervisor	Albert Folch Sancho (Director) & Boris M. van Breukelen (Director)