Modelling the soil-atmosphere exchange of POPs: Long-term steady state and diurnal fluctuations

Abstract:

Soil-atmosphere exchange is an important transport process influencing environmental fate and transport of many persistent organic pollutants (POPs). This study focuses on modelling the gaseous exchange of a semi-volatile polycyclic aromatic hydrocarbon (phenanthrene) between soil and the atmosphere using the multicomponent reactive transport code MIN3P. MIN3P is typically applied to simulate aqueous and vapor phase subsurface transport and reaction processes. We extended the code to also include an atmospheric boundary layer where eddy diffusion and photodegradation take place. The relevant processes and parameters affecting soil-atmosphere exchange were investigated in several scenarios and at various time scales. We found that phenanthrene is well-mixed in the atmospheric boundary layer under neutral or stable atmospheric conditions due to fast eddy diffusion. Uptake of airborne phenanthrene to soils is limited by the soil properties and initially depends on diffusion in soil gas and sorption to the solids. On the long term seepage water dominates transport into deeper soil layers; biodegradation finally leads to steady-state concentration profiles in the subsurface typically achieved after a few centuries. If concentrations in the atmosphere decrease, e.g. due to environmental legislation, then soils become sources for the POPs for the first two months and function as sinks again for the POPs until new steady state concentrations are reached (after decades to centuries). MIN3P was also used to simulate diurnal soil-atmosphere exchanges of airborne pollutants due to temperature changes and photodegradation, both which cause fluctuations in atmospheric concentrations and therefore affect mass transfer between soil and the atmosphere. The model can further be applied to estimate the environmental fate of other POPs between soil and the atmosphere under different environmental pollution and climate change scenarios.