Estimation of the Maximum Consumption of Permanganate by Aquifer Solids Using a Modified Chemical Oxygen Demand Test

Knowledge of the consumption of permanganate by naturally occurring reduced species associated with aquifer materials is required for site screening and design purposes to support permanganate in situ chemical oxidation (ISCO) applications. It has been established that this consumption is not a singled-valued quantity, but rather is kinetically controlled. Current methods to determine this permanganate natural oxidant demand (NOD) involve the use of well-mixed batch tests, which are time consuming and subject to test variables (e.g., concentration, mass of oxidant to solid ratio, reaction duration, and mixing conditions) that significantly affect the results. In this paper, we propose a modified chemical oxygen demand (COD) test using permanganate, which can be used to determine the maximum permanganate NOD of an aquifer material. As an initial point of comparison, we tested aquifer materials collected from eight potential ISCO sites using this modified or permanganate COD method, the traditional dichromate COD method, and a method based on well-mixed batch reactors. The results from this comparison indicated that there was no statistically significant difference (α = 5%) between the results of the permanganate COD test and the maximum NOD from the well-mixed batch reactors, while on average the dichromate COD test overestimated the maximum NOD by 100%. The permanganate COD test results were highly correlated to the batch-test maximum NOD data (r = 0.996), and to the total organic carbon and amorphous Fe content of the aquifer materials (r = 0.91). A limited sensitivity investigation of this proposed permanganate COD test revealed that the suspected formation of manganese oxides, a reaction byproduct, may lead to increased experimental variability. However, in spite of this concern we recommend that this proposed permanganate COD method is a quick and economical approach for estimating the maximum permanganate NOD for aquifer materials to support permanganate ISCO site screening and initial design purposes.