Henry's law constants of volatile organic compounds between 0 and 95 °C - Data compilation and complementation in context of urban temperature increases of the subsurface.

In urban areas with frequently occurring contamination by volatile organic hydrocarbons (VOC) possible uncontrolled contaminant mobilization e.g. by volatilization is feared in case of subsurface temperature increases induced by high temperature underground thermal energy storage (HT-UTES) or due to urban heat islands (UHI). However, volatilization of VOC is the main process utilized by thermal remediation approaches, wherefore a combination of contaminant remediation with UTES is increasingly discussed. To predict VOC volatilization under changing temperature conditions, which is substantially characterized by Henry's law constants (H), temperature dependency of H must be known substance-specifically in the total concerned temperature range. To provide an overview of available H and to evaluate their quality, published data of 41 pollutants were compiled, revealing the need for further measurements above 40 °C for at least 24 compounds (as e.g. TCE/PCE, BTEX). Additionally, the temperature dependence of H was calculated based on the compiled data using an established temperature regression function. Furthermore, H was complementarily measured for 10 relevant VOCs between 10 and 90 °C using the EPICS-method (Equilibrium Partitioning In Closed Systems). The measurements quantified the expected strong increase in H with rising temperature while providing high data quality (R = 0.84-0.99, mostly low standard deviations), thus improving the general data availability of H for VOCs and extending the scope of the regression function. The newly measured data and enhanced evaluation of compiled data contribute to a more reliable assessment of the pollutant behaviour in terms of volatilization at elevated temperatures caused e.g. by UTES or UHI.