In aquifer systems, particularly those characterized by homogeneity in the shallow layers, the even distribution of contaminants, such as solutes, solvents, and reductive agents or substrates is frequently impeded. Consequently, this complicates the accurate delineation homogeneity within the groundwater matrix, which is a crucial aspect for the effective subsurface treatment of contaminants. In this study, columnar assays were conducted using acid-activated zero-valent iron [Fe(0), ZVI] emulated in situ remediation across disparate iron-to-sand weight ratios. To decipher the interaction between porosity and solute migration, a mass transfer-centric model was developed to provide quantitative insights during heterogeneous groundwater interventions. The results revealed that nitrate attenuation by Fe(0) rigorously adheres to a first-order kinetic paradigm. The efficiency porosity (n̅) during non-equilibrium (rate-limited) conditions can be calculated under different NO3− concentrations and Fe(0)/sand ratios. This analysis predicts that large porosity and preferential flow will occur in the Fe(0)50/% and Fe(0)25/% columns. The optimal parameters were determined as a mixing ratio of Fe(0)/sand of 0.5/0.5 (volume) and an HRT of 7.3 h when the influent NO3−-N concentration ranged from 20 mg·L−1 to 100 mg·L−1, resulting in enhanced nitrate removal efficiency. A positive correlation was observed between K (a mass-transfer rate coefficient) and Fe(0)/sand ratio. Using a power-law function to fit A [the value of fitting parameter] and the Fe(0)/sand ratio, a positive correlation was calculated that closely resembles the trend observed in lab columns. This model subsequently facilitated the calibration of operational variables, optimizing the in situ amelioration of nitrate-laden groundwater.
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