Control of groundwater pH during bioremediation: Improvement and validation of a geochemical model to assess the buffering potential of ground silicate minerals

• Silicate minerals can be used as pH control agent for in situ bioremediation of PCE.
• Abiotic batch experiments showed that five silicate minerals can neutralize acidity.
• A geochemical model for assessing pH buffering capacity of silicates was validated.
• The model was revised and improved by including secondary precipitation.

Accurate control of groundwater pH is of critical importance for in situ biological treatment of chlorinated solvents. The use of ground silicate minerals mixed with groundwater is an appealing buffering strategy as silicate minerals may act as long-term sources of alkalinity. In a previous study, we developed a geochemical model for evaluation of the pH buffering capacity of such minerals. The model included the main microbial processes driving groundwater acidification as well as mineral dissolution. In the present study, abiotic mineral dissolution experiments were conducted with five silicate minerals (andradite, diopside, fayalite, forsterite, nepheline). The goal of the study was to validate the model and to test the buffering capacity of the candidate minerals identified previously. These five minerals increased the pH from acidic to neutral and slightly basic values. The model was revised and improved to represent better the experimental observations. In particular, the experiments revealed the importance of secondary mineral precipitation on the buffering potential of silicates, a process not included in the original formulation. The main secondary phases likely to precipitate were identified through model calibration, as well as the degree of saturation at which they formed. The predictions of the revised geochemical model were in good agreement with the observations, with a correlation coefficient higher than 0.9 in most cases. This study confirmed the potential of silicates to act as pH control agents and showed the reliability of the geochemical model, which can be used as a design tool for field applications.