Reactive transport modelling of push-pull tests: A versatile approach to quantify aquifer reactivity

Push-pull tests (PPTs) were evaluated with 1-D radially axisymmetric multi-component geochemical reactive transport modelling (RTM) to assess aquifer reactivity controlling groundwater quality. Nutrient fate and redox processes were investigated in an Aquifer Storage and Recovery (ASR) system, in which oxic tile drainage water (TDW; nitrate similar to 14 mg/L; phosphate similar to 17 mg/L) was stored in an anoxic aquifer for later re-use as irrigation water. During the PPTs, the ASR system did not operate. PPTs were performed in two monitoring wells (MW2, MW3), with 1 m well screens in contrasting geochemical formations at different depths. In these wells, 300 L TDW was injected, and consecutively 720 L was abstracted within 12 days, during which water quality changes were studied. The RTM simulated cation exchange, precipitation of Hydrous Ferric Oxides, Iron (III)-phosphate and Calcium-phosphate minerals, and surface complexation as equilibrium processes. Oxidation of Pyrite, soil organic matter, and dissolved ferrous iron were simulated with kinetic rate expressions. Oxygen (within 2 days) and nitrate (within 4-7 days) were fully reduced during the PPTs. The main reductants were ferrous iron (Monitoring Well (MW) 2: 2%, MW3: 13%), soil organic matter (MW2: 93%, MW3: 6%), and Pyrite (MW2: 5%, MW3: 81%). The intra aquifer differences in dominant reduction pathways are remarkable as higher reduction rates coincided with lower contents of soil organic matter and Pyrite, respectively. Phosphate was mostly re abstracted (MW2: 73%, MW3: 64%) and partially immobilized due to precipitation of Iron-hydroxyphosphates (MW2: 4.6%, MW3: 35%), Hydroxyapatite (MW2: 23%, MW3: 0%), and to a lesser extent by surface complexation on various minerals (MW2-3: <1%). The PPT-RTM approach enables a better understanding of reaction networks controlling water quality changes, and the reaction kinetics. PPT-RTM is a promising tool in exploratory studies or regular monitoring of water quality aspects of subsurface water technologies.