Surface volatilization modeling of (semi-)volatile hydrophobic organic compounds: The role of reference compounds

Volatilization of hazardous hydrophobic organic compounds is often observed in many water, wastewater and soil treatment (bio)processes. Several models have been developed to quantify and predict gas-liquid pollutant transfer, being the proportionality coefficient model (PCM) one of the most commonly used, particularly in wastewater treatment. The PCM is based on the use of oxygen as a reference compound, which has a low resistance to the transfer in the gas phase. However, this resistance might be important for (semi-)volatile organic compounds - or (semi-)VOCs, which may render the use of the PCM model inaccurate. This study proposes an experimental methodology and a modeling approach for the use of the two-reference compound model (2RCM) that considers both the liquid-side and the gas-side resistances, by using water and oxygen as references. Results showed that the 2RCM predicts more accurately the overall mass transfer coefficients than the PCM for a VOC and two semi-VOCs tested in this study. In addition, the 2RCM was found to be a more robust method to estimate mass transfer coefficient of any compound and its use can be extrapolated to all substances. Finally, the relevance and limitations of both models was established.