Christina M. Haberer

A high-resolution non-invasive approach to quantify oxygen transport across the capillary fringe and within the underlying groundwater.

Oxygen transport across the capillary fringe is relevant for many biogeochemical processes. We present a non-invasive technique, based on optode technology, to measure high-resolution concentration profiles of oxygen across the unsaturated/saturated interface. By conducting a series of quasi two-dimensional flow-through laboratory experiments, we show that vertical hydrodynamic dispersion in the water-saturated part of the capillary fringe is the process limiting the mass transfer of oxygen. A number of experimental conditions were tested in order to investigate the influence of grain size and horizontal flow velocity on transverse vertical dispersion in the capillary fringe. In the same setup, analogous experiments were simultaneously carried out in the fully water-saturated zone, therefore allowing a direct comparison with oxygen transfer across the capillary fringe. The outcomes of the experiments under various conditions show that oxygen transport in the two zones of interest (i.e., the unsaturated/saturated interface and the saturated zone) is characterized by very similar transverse dispersion coefficients. An influence of the capillary fringe morphology on oxygen transport has not been observed. These results may be explained by the narrow grain size distribution used in the experiments, leading to a steep decline in water saturation at the unsaturated/saturated interface and to the absence of trapped gas in this transition zone. We also modeled flow (applying the van Genuchten and the Brooks-Corey relationships) and two-dimensional transport across the capillary fringe, obtaining simulated profiles of equivalent aqueous oxygen concentration that were in good agreement with the observations.

Impact of Heterogeneity on Oxygen Transfer in a Fluctuating Capillary Fringe

We performed quasi-two-dimensional flow through laboratory experiments to study the effect of a coarse-material inclusion, located in the proximity of the water table, on flow and oxygen transfer in the capillary fringe. The experiments investigate different phases of mass transfer from the unsaturated zone to anoxic groundwater under both steady-state and transient flow conditions, the latter obtained by fluctuating the water table. Monitoring of flow and transport in the different experimental phases was performed by visual inspection of the complex flow field using a dye tracer solution, measurement of oxygen profiles across the capillary fringe, and determination of oxygen fluxes in the effluent of the flow-through chamber. Our results show significant effects of the coarse-material inclusion on oxygen transfer during the different phases of the experiments. At steady state, the oxygen flux across the unsaturated/saturated interface was considerably enhanced due to flow focusing in the fully water-saturated coarse-material inclusion. During drainage, a zone of higher water saturation formed in the fine material overlying the coarse lens. The entrapped oxygen-rich aqueous phase contributed to the total amount of oxygen supplied to the system when the water table was raised back to its initial level. In case of imbibition, pronounced air entrapment occurred in the coarse lens, causing oxygen to partition between the aqueous and gaseous phases. The oxygen mass supplied to the anoxic groundwater following the imbibition event was found to be remarkably higher (approximately seven times) in the heterogeneous system compared with a similar experiment performed in a homogeneous porous medium.

Experimental Sensitivity Analysis of Oxygen Transfer in the Capillary Fringe

Oxygen transfer in the capillary fringe (CF) is of primary importance for a wide variety of biogeochemical processes occurring in shallow groundwater systems. In case of a fluctuating groundwater table two distinct mechanisms of oxygen transfer within the capillary zone can be identified: vertical predominantly diffusive mass flux of oxygen, and mass transfer between entrapped gas and groundwater. In this study, we perform a systematic experimental sensitivity analysis in order to assess the influence of different parameters on oxygen transfer from entrapped air within the CF to underlying anoxic groundwater. We carry out quasi two-dimensional flow-through experiments focusing on the transient phase following imbibition to investigate the influence of the horizontal flow velocity, the average grain diameter of the porous medium, as well as the magnitude and the speed of the water table rise. We present a numerical flow and transport model that quantitatively represents the main mechanisms governing oxygen transfer. Assuming local equilibrium between the aqueous and the gaseous phase, the partitioning process from entrapped air can be satisfactorily simulated. The different experiments are monitored by measuring vertical oxygen concentration profiles at high spatial resolution with a noninvasive optode technique as well as by determining oxygen fluxes at the outlet of the flow-through chamber. The results show that all parameters investigated have a significant effect and determine different amounts of oxygen transferred to the oxygen-depleted groundwater. Particularly relevant are the magnitude of the water table rise and the grain size of the porous medium.

Modeling long-term uptake and re-volatilization of semi-volatile organic compounds (SVOCs) across the soil-atmosphere interface.

Soil-atmosphere exchange is important for the environmental fate and atmospheric transport of many semi-volatile organic compounds (SVOCs). This study focuses on modeling the vapor phase exchange of semi-volatile hydrophobic organic pollutants between soil and the atmosphere using the multicomponent reactive transport code MIN3P. MIN3P is typically applied to simulate aqueous and vapor phase transport and reaction processes in the subsurface. We extended the code to also include an atmospheric boundary layer where eddy diffusion takes place. The relevant processes and parameters affecting soil-atmosphere exchange were investigated in several 1-D model scenarios and at various time scales (from years to centuries). Phenanthrene was chosen as a model compound, but results apply for other hydrophobic organic compounds as well. Gaseous phenanthrene was assumed to be constantly supplied to the system during a pollution period and a subsequent regulation period (with a 50% decline in the emission rate). Our results indicate that long-term soil-atmosphere exchange of phenanthrene is controlled by the soil compartment - re-volatilization thus depends on soil properties. A sensitivity analysis showed that accumulation and transport in soils in the short term is dominated by diffusion, whereas in the long term groundwater recharge and biodegradation become relevant. As expected, sorption causes retardation and slows down transport and biodegradation. If atmospheric concentration is reduced (e.g. after environmental regulations), re-volatilization from soil to the atmosphere occurs only for a relatively short time period. Therefore, the model results demonstrate that soils generally are sinks for atmospheric pollutants. The atmospheric boundary layer is only relevant for time scales of less than one month. The extended MIN3P code can also be applied to simulate fluctuating concentrations in the atmosphere, for instance due to temperature changes in the topsoil.

Modeling short-term concentration fluctuations of semi-volatile pollutants in the soil-plant-atmosphere system.

Temperature changes can drive cycling of semi-volatile pollutants between different environmental compartments (e.g. atmosphere, soil, plants). To evaluate the impact of daily temperature changes on atmospheric concentration fluctuations we employed a physically based model coupling soil, plants and the atmosphere, which accounts for heat transport, effective gas diffusion, sorption and biodegradation in the soil as well as eddy diffusion and photochemical oxidation in the atmospheric boundary layer of varying heights. The model results suggest that temperature-driven re-volatilization and uptake in soils cannot fully explain significant diurnal concentration fluctuations of atmospheric pollutants as for example observed for polychlorinated biphenyls (PCBs). This holds even for relatively low water contents (high gas diffusivity) and high sorption capacity of the topsoil (high organic carbon content and high pollutant concentration in the topsoil). Observed concentration fluctuations, however, can be easily matched if a rapidly-exchanging environmental compartment, such as a plant layer, is introduced. At elevated temperatures, plants release organic pollutants, which are rapidly distributed in the atmosphere by eddy diffusion. For photosensitive compounds, e.g. some polycyclic aromatic hydrocarbons (PAHs), decreasing atmospheric concentrations would be expected during daytime for the bare soil scenario. This decline is buffered by a plant layer, which acts as a ground-level reservoir. The modeling results emphasize the importance of a rapidly-exchanging compartment above ground to explain short-term atmospheric concentration fluctuations.