Reactive Transport Modeling for Exploring the Potential of Water Quality Sensors to Estimate Hydrocarbon Levels in Groundwater

Petroleum products have contaminated groundwater with harmful organic compounds, such as benzene, toluene, ethylbenzene, and xylenes (BTEX). Collecting and analyzing polluted groundwater samples is expensive and undertaken infrequently. However, quick remedial action in case of unexpected events requires continuous monitoring. In‐situ water quality sensors (pH, EC, DO, ORP) may show correlations with the components of dissolved petroleum hydrocarbon (PHC) such as aromatics and non‐volatile mobile fractions. Correlations are prerequisite to ultimately develop real‐time prediction models. Since suitable field data sets are limited, we simulated the fate of hydrocarbons in groundwater under various realistic conditions using a reactive transport model as novel approach to explore when, where, and why correlations occur. A stationary oil source zone continuously dissolved at the top of a heterogeneous and shallow sandy aquifer over a two‐dimensional cross‐section. Our model considered transient conditions (fluctuating water table) and spatially uniform hydrogeochemical composition. We observed a strong correlation between PHCs and water quality sensors (rolling Spearman's correlation > |0.8|) at varying periods. These correlations are strongly affected by the location of observation wells, the aquifer's hydraulic conductivity, and the availability of calcite and oxide minerals, and other electron acceptors. DO and ORP are significant for the early detection of hydrocarbon contamination, whereas pH and EC are important features for the long‐term monitoring of hydrocarbons. Our findings lay the foundation for the subsequent development of a data analysis model to detect and estimate in real time PHC levels in groundwater using in‐situ water quality sensors. Plain Language Summary Groundwater contamination by petroleum products, including benzene, toluene, ethylbenzene, and xylenes (BTEX), is a serious environmental concern. However, the collection and analysis of polluted groundwater samples are expensive and infrequently conducted. In the event of unexpected contamination, quick remedial action is crucial, which requires continuous monitoring of groundwater quality. We investigated whether in‐situ water quality sensors like pH, electrical conductivity (EC), dissolved oxygen (DO), and oxidation‐reduction potential (ORP) can predict the concentration of dissolved petroleum hydrocarbons (PHC) in groundwater. Understanding the correlations between these sensors and