Massimo Rolle

Enhancement of dilution and transverse reactive mixing in porous media: experiments and model-based interpretation.

Transport and natural attenuation of contaminant plumes in groundwater are often controlled by transverse dispersion. The extent of mixing between dissolved reaction partners at the fringe of a plume determines its length and depends strongly on the groundwater flow field. Transient flow conditions as well as the focusing of the flow in high-permeability zones may enhance transverse mixing of dissolved species and, therefore, create favorable conditions for the natural attenuation of contaminant plumes. The aim of the present study is to experimentally test the influence of these processes on solute mixing and to directly compare the results with those under analogous homogeneous and steady-state conditions. We have performed conservative and reactive tracer experiments in a quasi two-dimensional tank filled with glass beads of different sizes. The experiments have been carried out in both homogeneous and heterogeneous porous media under steady-state and transient (i.e. oscillating) flow fields. We used fluorescein as conservative tracer; whereas an alkaline solution (NaOH) was injected into ambient acidic water (HCl) in the reactive experiments. A pH indicator was added to the reacting solutions in order to visualize the emerging plume. We simulated the laboratory experiments with a numerical model and compared the outcomes of the model with the measured concentrations at the outlet of the tank and with the observed tracer plumes. Spatial moments, a newly defined flux-related dilution index, the product mass fluxes and the reaction enhancement factors were calculated to quantify the differences in mixing and reaction extent under various experimental conditions. The results show that flow focusing in heterogeneous porous media significantly enhances transverse mixing and mixing-controlled reactions, whereas temporally changing flow fields appear to be of minor importance.

Enhanced biodegradation by hydraulic heterogeneities in petroleum hydrocarbon plumes

In case of dissolved electron donors and acceptors, natural attenuation of organic contaminant plumes in aquifers is governed by hydrodynamic mixing and microbial activity. Main objectives of this work were (i) to determine whether aerobic and anaerobic biodegradation in porous sediments is controlled by transverse dispersion, (ii) to elucidate the effect of sediment heterogeneity on mixing and biodegradation, and (iii) to search for degradation-limiting factors. Comparative experiments were conducted in two-dimensional sediment microcosms. Aerobic toluene and later ethylbenzene degradation by Pseudomonas putida strain F1 was initially followed in a plume developing from oxic to anoxic conditions and later under steady-state mixing-controlled conditions. Competitive anaerobic degradation was then initiated by introduction of the denitrifying strain Aromatoleum aromaticum EbN1. In homogeneous sand, aerobic toluene degradation was clearly controlled by dispersive mixing. Similarly, under denitrifying conditions, microbial activity was located at the plumes fringes. Sediment heterogeneity caused flow focusing and improved the mixing of reactants. Independent from the electron accepting process, net biodegradation was always higher in the heterogeneous setting with a calculated efficiency plus of 23-100% as compared to the homogeneous setup. Flow and reactive transport model simulations were performed in order to interpret and evaluate the experimental results.

Biogeochemical and isotopic gradients in a BTEX/PAH contaminant plume: model-based interpretation of a high-resolution field data set.

A high spatial resolution data set documenting carbon and sulfur isotope fractionation at a tar oil-contaminated, sulfate-reducing field site was analyzed with a reactive transport model. Within a comprehensive numerical model, the study links the distinctive observed isotope depth profiles with the degradation of various monoaromatic and polycyclic aromatic hydrocarbon compounds (BTEX/PAHs) under sulfate-reducing conditions. In the numerical model, microbial dynamics were simulated explicitly and isotope fractionation was directly linked to the differential microbial uptake of lighter and heavier carbon isotopes during microbial growth. Measured depth profiles from a multilevel sampling well with high spatial resolution served as key constraints for the parametrization of the model simulations. The results of the numerical simulations illustrate particularly well the evolution of the isotope signature of toluene, which is the most rapidly degrading compound and the most important reductant at the site. The resulting depth profiles at the observation well show distinct differences between the small isotopic enrichment in the contaminant plume core and the much stronger enrichment of up to 3.3 per thousand at the plume fringes.

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.

On the importance of diffusion and compound-specific mixing for groundwater transport: an investigation from pore to field scale.

Mixing processes significantly affect and limit contaminant transport and transformation rates in the subsurface. The correct quantification of mixing in groundwater systems must account for diffusion, local-scale dispersion and the flow variability in heterogeneous flow fields (e.g., flow-focusing in high-conductivity and de-focusing in low-conductivity zones). Recent results of multitracer laboratory experiments revealed the significant effect of compound-specific diffusive properties on the physical displacement of dissolved species across a representative range of groundwater flow velocities. The goal of this study is to investigate the role of diffusion and compound-specific mixing for solute transport across a range of scales including: (i) pore-scale (~10⁻² m), (ii) laboratory bench-scale (~10⁰ m) and (iii) field-scale (~10² m). We investigate both conservative and mixing-controlled reactive transport using pore-scale modeling, flow-through laboratory experiments and simulations, and field-scale numerical modeling of complex heterogeneous hydraulic conductivity fields with statistical properties similar to the ones reported for the extensively investigated Borden aquifer (Ontario, Canada) and Columbus aquifer (Mississippi, USA, also known as MADE site). We consider different steady-state and transient transport scenarios. For the conservative cases we use as a metric of mixing the exponential of the Shannon entropy to quantify solute dilution either in a given volume (dilution index) or in a given solute flux (flux-related dilution index). The decrease in the mass and the mass-flux of the contaminant plumes is evaluated to quantify reactive mixing. The results show that diffusive processes, occurring at the small-scale of a pore channel, strongly affect conservative and reactive solute transport at larger macroscopic scales. The outcomes of our study illustrate the need to consider and properly account for compound-specific diffusion and mixing limitations in order to accurately describe and predict conservative and reactive transport in porous media.

Stochastic evaluation of mixing-controlled steady-state plume lengths in two-dimensional heterogeneous domains

We study plumes originating from continuous sources that require a dissolved reaction partner for their degradation. The length of such plumes is typically controlled by transverse mixing. While analytical expressions have been derived for homogeneous flow fields, incomplete characterization of the hydraulic conductivity field causes uncertainty in predicting plume lengths in heterogeneous domains. In this context, we analyze the effects of three sources of uncertainty: (i) The uncertainty of the effective mixing rate along the plume fringes due to spatially varying flow focusing, (ii) the uncertainty of the volumetric discharge through (and thus total mass flux leaving) the source area, and (iii) different parameterizations of the Darcy-scale transverse dispersion coefficient. The first two are directly related to heterogeneity of hydraulic conductivity. In this paper, we derive semi-analytical expressions for the probability distribution of plume lengths at different levels of complexity. The results are compared to numerical Monte Carlo simulations. Uncertainties in mixing and in the source strength result in a statistical distribution of possible plume lengths. For unconditional random hydraulic conductivity fields, plume lengths may vary by more than one order of magnitude even for moderate degrees of heterogeneity. Our results show that the uncertainty of volumetric flux through the source is the most relevant contribution to the variance of the plume length. The choice of different parameterizations for the local dispersion coefficient leads to differences in the mean estimated plume length.

Numerical simulation of isotope fractionation in steady-state bioreactive transport controlled by transverse mixing

Compound-specific stable isotope analysis (CSIA) has increasingly been used as a tool to assess intrinsic biodegradation at contaminated field sites. Typically, the Rayleigh equation is used to estimate the extent of biodegradation from measured isotope ratios of the contaminant. However, if the rate-limiting step in overall degradation is not the microbial reaction itself, the Rayleigh equation may no more be applicable. In this study we simulate biodegradation of continuously emitted petroleum hydrocarbons in groundwater systems. These contaminants are effectively degraded at the plume fringe where transverse dispersion makes them mix with dissolved electron acceptors present in the ambient groundwater. We simulate reactive transport to study the coupled effects of transverse mixing and biodegradation on the spatial patterns of carbon isotope signatures and their interpretation based on depth-integrated sampling which represents the most common setup in the assessment of contaminated sites. We present scenarios mimicking a hydraulically uniform laboratory experiment and a field-scale application considering heterogeneous conductivity fields. We compare cases in which isotopologue-specific transverse dispersion is considered to those where this additional fractionation process is neglected. We show that these effects cause significant shifts in the isotopic signals and may lead to overestimation of biodegradation. Moreover, our results provide evidence that the rate-limiting effect of transverse mixing on the overall degradation spatially varies along the length of a steady-state contaminant plume. The control of biodegradation by transverse dispersion and the fractionating effect of dispersion modulate the fractionation caused by the microbial reaction alone. As a consequence, significantly nonlinear isotopic patterns are observed in a Rayleigh plot. Simulations in heterogeneous flow domains show that these effects persist at larger field scales and are sensitive to the degree of mixing enhancement, determined by the heterogeneity of the hydraulic conductivity fields, and to the groundwater flow velocity.

Experimental investigation of compound-specific dilution of solute plumes in saturated porous media: 2-D vs. 3-D flow-through systems

Dilution of solute plumes in groundwater strongly depends on transverse mixing. Thus, the correct parameterization of transverse dispersion is of critical importance for the quantitative description of solute transport. In this study we perform flow-through laboratory experiments to investigate the influence of transport dimensionality on transverse mixing. We present a high-resolution experimental setup to study solute dilution and transverse dispersion in three-dimensional porous media. We conduct multi-tracer experiments in the new 3-D setup and compare the results with the outcomes of analogous tracer experiments performed in a quasi 2-D system. We work under steady-state flow and transport conditions and consider a range of velocities relevant for groundwater flow (0.5-8 m/day). Transverse dispersion coefficients are determined from high-resolution concentration profiles at the outlet of the flow-through chambers (7×7 ports in the 3-D setup and 7 ports in the quasi 2-D system), considering conservative tracers with significantly different aqueous diffusion coefficients, namely fluorescein and dissolved oxygen. To quantify dilution in the 2-D and 3-D systems, we experimentally determine the flux-related dilution index using the flow rates and the concentrations measured at the inlet and outlet ports, and we propose semi-analytical expressions to predict its evolution with travel distance in uniform groundwater flow. The experimental results in the quasi 2-D and 3-D flow-through systems are consistent and show a compound-specific behavior of the transverse dispersion coefficient and its non-linear dependence on the seepage velocity in both setups. The degree of dilution and the compound-specific effects of transverse dispersion are considerably more pronounced in 3-D than in quasi 2-D transport systems.

Helical flow in three‐dimensional nonstationary anisotropic heterogeneous porous media

Characterizing the topology of three-dimensional steady-state flow fields is useful to describe the physical processes controlling the deformation of solute plumes and, consequently, obtain helpful information on mixing processes without solving the transport equation. In this work, we study the topology of flow in three-dimensional nonstationary anisotropic heterogeneous porous media. In particular, we apply a topological metric, i.e., the helicity density, and two complementary kinematic descriptors of mixing, i.e., stretching and folding, to investigate: (i) the flow field resulting from applying a uniform-in-the-average hydraulic gradient within a fully resolved heterogeneous three-dimensional porous medium with a nonstationary anisotropic covariance function of the locally isotropic hydraulic log conductivity; (ii) the flow field obtained by averaging a set of Monte Carlo realizations of the former field; (iii) the flow field obtained considering the blockwise uniform anisotropic effective conductivity tensor computed for the fully resolved case. While in the fully resolved case, the local helicity density is zero as a consequence of the local isotropy of hydraulic conductivity, it differs from zero in the other two cases. We show, therefore, that this topological metric is scale dependent and should be computed at the appropriate scale to be informative about the leading patterns of plume deformation. Indeed, streamlines are helical in all three cases at scales larger than the characteristic scale of spatial variability. We apply stretching and folding metrics to investigate the scales at which plume deformation is more influenced by helical motion than by the effect of small-scale spatial heterogeneity in the hydraulic-conductivity field. Under steady-state flow conditions, stretching, which quantifies the increasing length of an interface, dominates at short distances from a given starting plane, while folding, which describes how this interface is bent to fill a finite volume of space, dominates further downstream and can be correlated with the appearance of large-scale secondary motion. We conclude that three-dimensional flows in porous media may show a complex topology whose analysis is relevant for the description of plume deformation. These results have important implications for the understanding of mixing processes, as shown in detail in the companion paper focusing on solute transport.

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.