Reactive transport of micropollutants in laboratory aquifers undergoing transient exposure periods.

Groundwater quality is of increasing concern due to the ubiquitous occurrence of micropollutant mixtures. Stream-groundwater interactions near agricultural and urban areas represent an important entry pathway of micropollutants into shallow aquifers. Here, we evaluated the biotransformation of a micropollutant mixture (i.e., caffeine, metformin, atrazine, terbutryn, S-metolachlor and metalaxyl) during lateral stream water flow to adjacent groundwater. We used an integrative approach combining concentrations and transformation products (TPs) of the micropollutants, compound-specific isotope analysis (δ13C and δ15N), sequencing of 16S rRNA gene amplicons and reactive transport modeling. Duplicate laboratory aquifers (160 cm × 80 cm × 7 cm) were fed with stream water and subjected over 140 d to three successive periods of micropollutant exposures as pulse-like (6000 µg L-1) and constant (600 µg L-1) injections under steady-state conditions. Atrazine, terbutryn, S-metolachlor and metalaxyl persisted in both aquifers during all periods (<10 % attenuation). Metformin attenuation (up to 14 %) was only observed from 90 d onwards, suggesting enhanced degradation over time. In contrast, caffeine dissipated during all injection periods (>90 %), agreeing with fast degradation rates (t1/2 < 3 d) in parallel microcosm experiments and detection of TPs (theobromine and xanthine). Significant stable carbon isotope fractionation (Δδ13C ≥ 6.6 ‰) was observed for caffeine in both aquifers, whereas no enrichment in 15N occurred. A concentration dependence of caffeine biotransformation in the aquifers was further suggested by model simulations following Michaelis-Menten kinetics. Changes in bacterial community composition reflected long-term bacterial adaptation to micropollutant exposures. Altogether, the use of an integrative approach can help to understand the interplay of subsurface hydrochemistry, bacterial adaptations and micropollutants biotransformation during stream-groundwater interactions.

Pore scale modelling of DNAPL migration in a water-saturated porous medium.

A numerical simulator based on the discrete network model approach has been developed to simulate drainage processes in a water-saturated porous medium. To verify the predictive potential of the approach to simulate the unstable migration of a dense nonaqueous phase liquid (DNAPL) at the pore scale, the numerical model was applied to laboratory experiments conducted on a sand-filled column. The parameters relative to pore body size and pore throat size used in the construction of the equivalent network were derived from discrete grain-size distribution of the real porous medium. The observed water retention curve (WRC) was first simulated by desaturation of the network model. The good agreement of the modelled WRC with the experimental one highlights that the applied approach reproduces the main characteristics of the real pore space. The numerical model was then applied to rate controlled experiments performed on a homogenous sand-filled column to study the gravity-driven fingering phenomenon of immiscible two-phase flow of water and a DNAPL. The numerical results match within 10% based on the standard deviation with the experiments. They correctly reproduce the effect of several system parameters, such as flow mode (upward flow and downward flow) and the flow rate, on the stability of the water/DNAPL front in a saturated porous medium.