Elsa Lacroix

Use of silicate minerals for pH control during reductive dechlorination of chloroethenes in batch cultures of different microbial consortia.

ABSTRACT In chloroethene-contaminated sites undergoing in situ bioremediation, groundwater acidification is a frequent problem in the source zone, and buffering strategies have to be implemented to maintain the pH in the neutral range. An alternative to conventional soluble buffers is silicate mineral particles as a long-term source of alkalinity. In previous studies, the buffering potentials of these minerals have been evaluated based on abiotic dissolution tests and geochemical modeling. In the present study, the buffering potentials of four silicate minerals (andradite, diopside, fayalite, and forsterite) were tested in batch cultures amended with tetrachloroethene (PCE) and inoculated with different organohalide-respiring consortia. Another objective of this study was to determine the influence of pH on the different steps of PCE dechlorination. The consortia showed significant differences in sensitivities toward acidic pH for the different dechlorination steps. Molecular analysis indicated that Dehalococcoides spp. that were present in all consortia were the most pH-sensitive organohalide-respiring guild members compared to Sulfurospirillum spp. and Dehalobacter spp. In batch cultures with silicate mineral particles as pH-buffering agents, all four minerals tested were able to maintain the pH in the appropriate range for reductive dechlorination of chloroethenes. However, complete dechlorination to ethene was observed only with forsterite, diopside, and fayalite. Dissolution of andradite increased the redox potential and did not allow dechlorination. With forsterite, diopside, and fayalite, dechlorination to ethene was observed but at much lower rates for the last two dechlorination steps than with the positive control. This indicated an inhibition effect of silicate minerals and/or their dissolution products on reductive dechlorination of cis-dichloroethene and vinyl chloride. Hence, despite the proven pH-buffering potential of silicate minerals, compatibility with the bacterial community involved in in situ bioremediation has to be carefully evaluated prior to their use for pH control at a specific site.

Evaluation of Silicate Minerals for pH Control During Bioremediation: Application to Chlorinated Solvents

Accurate control of groundwater pH is of critical importance for in situ biological treatment of chlorinated solvents. This study evaluated a novel approach for buffering subsurface pH that relies on the use of silicate minerals as a long-term source of alkalinity. A screening methodology based on thermodynamic considerations and numerical simulations was developed to rank silicate minerals according to their buffering efficiency. A geochemical model including the main microbial processes driving groundwater acidification and silicate mineral dissolution was developed. Kinetic and thermodynamic data for silicate minerals dissolution were compiled. Results indicated that eight minerals (nepheline, fayalite, glaucophane, lizardite, grossular, almandine, cordierite, and andradite) could potentially be used as buffering agents for the case considered. A sensitivity analysis was conducted to identify the dominant model parameters and processes. This showed that accurate characterization of mineral kinetic rate constants and solubility are crucial for reliable prediction of the acid-neutralizing capacity. In addition, the model can be used as a design tool to estimate the amount of mineral (total mass and specific surface area) required in field applications.

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

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.

Use of silicate minerals for long-term pH control during reductive dechlorination of high tetrachloroethene concentrations in continuous flow-through columns

The long-term buffering potential of three silicate minerals (diopside, fayalite and forsterite) present as fine particles in porous quartz sand medium was evaluated in flow-through column experiments over a period of 6.5 months. The columns were operated with PCE concentrations close to saturation and inoculated with the organohalide-respiring consortium SDC-9™, which is able to completely dechlorinate PCE to ethene at high concentrations. In the absence of pH buffering agents, fermentation and organohalide respiration drove the pH close to 6.1, leading to severe inhibition of PCE dechlorination. Forsterite and fayalite were able to maintain the pH close to 7.5 and 6.5, respectively, and to sustain the production of VC and ethene. Diopside gradually lost its buffering capacity during the first 84 days due to the formation of a low reactive leached layer but dechlorination to cis-DCE was still achieved. Among the three minerals tested, forsterite was identified as the best buffering agent. Its presence led to the best PCE removal performance and the highest relative abundance of Dehalococcoides. This study showed that forsterite and fayalite are promising sources of long-term pH buffering for in situ bioremediation of source-zone PCE.