Managed aquifer recharge (MAR) enhances freshwater security and augments local groundwater supplies. However, geochemical and hydrological shifts during MAR can release toxic, geogenic contaminants from sediments to groundwater, threatening the viability of MAR as a water management strategy. Using reactive transport modeling coupled with aquifer analyses and measured water chemistry, we investigate the causal mechanisms of arsenic release during MAR via injection in the Orange County Groundwater Basin. Here, injection water is oxygenated, highly purified recycled water produced by advanced water treatment. Injection occurs via a well screened at several depth intervals ranging from 160-365 m, allowing recharge into multiple confined horizons (zones) of the aquifer system. However, these zones are characterized by varying degrees of prior oxidation due to historic, long-term infiltration from the overlying aquifer. The resulting sediment geochemical heterogeneity provides a critical control on the release (or retention) of arsenic. In zones with prior oxidation, As mobilization occurs via arsenate desorption from Fe-(hydr)oxides, primarily associated with shifts in pH; within zones that remain reduced prior to injection, As release is attributed to the oxidative dissolution of As-bearing pyrite. We find that As release can be attributed to various geochemical mechanisms within a single injection well owing to geochemical heterogeneity across the aquifer system.