Formulation and probabilistic assessment of reversible biodegradation pathway of Diclofenac in groundwater

We present a conceptual and mathematical framework leading to the development of a biodegradation model capable to interpret the observed reversibility of the Pharmaceutical Sodium Diclofenac along its biological degradation pathway in groundwater. Diclofenac occurrence in water bodies poses major concerns due to its persistent (and bioactive) nature and its detection in surface waters and aquifer systems. Despite some evidences of its biodegradability at given reducing conditions, Diclofenac attenuation is often interpreted with models which are too streamlined, thus potentially hampering appropriate quantification of its fate. In this context, we propose a modeling framework based on the conceptualization of the molecular mechanisms of Diclofenac biodegradation which we then embed in a stochastic context, thus enabling one to quantify predictive uncertainty. We consider reference environmental conditions (biotic and denitrifying) associated with a set of batch experiments that evidence the occurrence of a reversible biotransformation pathway, a feature that is fully captured by our model. The latter is then calibrated in the context of a Bayesian modeling framework through an Acceptance-Rejection Sampling approach. By doing so, we quantify the uncertainty associated with model parameters and predicted Diclofenac concentrations. We discuss the probabilistic nature of uncertain model parameters and the challenges posed by their calibration with the available data. Our results are consistent with the recalcitrant behavior exhibited by Diclofenac in groundwater and documented through experimental data and support the observation that unbiased estimates of the hazard posed by Diclofenac to water resources should be assessed through a modeling strategy which fully embeds uncertainty quantification.