Flow and transport in unsaturated fractured rock: effects of multiscale heterogeneity of hydrogeologic properties

The heterogeneity of hydrogeologic properties at different scales may have different effects on flow and transport processes in a subsurface system. A model for the unsaturated zone of Yucca Mountain, Nevada, is developed to represent complex heterogeneity at two different scales: (1) layer scale corresponding to geologic layering and (2) local scale. The layer-scale hydrogeologic properties are obtained using inverse modeling, based on the available measurements collected from the Yucca Mountain site. Calibration results show a significant lateral and vertical variability in matrix and fracture properties. Hydrogeologic property distributions in a two-dimensional, vertical cross-section of the site are generated by combining the average layer-scale matrix and fracture properties with local-scale perturbations generated using a stochastic simulation method. The unsaturated water flow and conservative (nonsorbing) tracer transport through the cross-section are simulated for different sets of matrix and fracture property fields. Comparison of simulation results indicates that the local-scale heterogeneity of matrix and fracture properties has a considerable effect on unsaturated flow processes, leading to fast flow paths in fractures and the matrix. These paths shorten the travel time of a conservative tracer from the source (repository) horizon in the unsaturated zone to the water table for small fractions of total released tracer mass. As a result, the local-scale heterogeneity also has a noticeable effect on global tracer transport processes, characterized by an average breakthrough curve at the water table, especially at the early arrival time of tracer mass. However, the effect is not significant at the later time after 20% tracer mass reaches the water table. The simulation results also verify that matrix diffusion plays an important role in overall solute transport processes in the unsaturated zone at Yucca Mountain.     

Field investigation into unsaturated flow and transport in a fault: model analyses

Results of a fault test performed in the unsaturated zone of Yucca Mountain, Nevada, were analyzed using a three-dimensional numerical model. The fault was explicitly represented as a discrete feature and the surrounding rock was treated as a dual-continuum (fracture-matrix) system. Model calibration against seepage and water-travel-velocity data suggests that lithophysal cavities connected to fractures can considerably enhance the effective fracture porosity and therefore retard water flow in fractures. Comparisons between simulation results and tracer concentration data also indicate that matrix diffusion is an important mechanism for solute transport in unsaturated fractured rock. We found that an increased fault-matrix and fracture-matrix interface areas were needed to match the observed tracer data, which is consistent with previous studies. The study results suggest that the current site-scale model for the unsaturated zone of Yucca Mountain may underestimate radionuclide transport time within the unsaturated zone, because an increased fracture-matrix interface area and the increased effective fracture porosity arising from lithophysal cavities are not considered in the current site-scale model.     

Characterization of flow and transport processes within the unsaturated zone of Yucca Mountain, Nevada, under current and future climates

This paper presents a large-scale modeling study characterizing fluid flow and tracer transport in the unsaturated zone of Yucca Mountain, Nevada, a potential repository site for storing high-level radioactive waste. The study has been conducted using a three-dimensional numerical model, which incorporates a wide variety of field data and takes into account the coupled processes of flow and transport in the highly heterogeneous, unsaturated fractured porous rock. The modeling approach is based on a dual-continuum formulation of coupled multiphase fluid and tracer transport through fractured porous rock. Various scenarios of current and future climate conditions and their effects on the unsaturated zone are evaluated to aid in the assessment of the proposed repository's system performance using different conceptual models. These models are calibrated against field-measured data. Model-predicted flow and transport processes under current and future climates are discussed.     

A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock

The percolation flux in the unsaturated zone (UZ) is an important parameter addressed in site characterization and flow and transport modeling of the potential nuclear-waste repository at Yucca Mountain, NV, USA. The US Geological Survey (USGS) has documented hydrogenic calcite abundances in fractures and lithophysal cavities at Yucca Mountain to provide constraints on percolation fluxes in the UZ. The purpose of this study was to investigate the relationship between percolation flux and measured calcite abundances using reactive transport modeling. Our model considers the following essential factors affecting calcite precipitation: (1) infiltration, (2) the ambient geothermal gradient, (3) gaseous CO(2) diffusive transport and partitioning in liquid and gas phases, (4) fracture-matrix interaction for water flow and chemical constituents, and (5) water-rock interaction. Over a bounding range of 2-20 mm/year infiltration rate, the simulated calcite distributions capture the trend in calcite abundances measured in a deep borehole (WT-24) by the USGS. The calcite is found predominantly in fractures in the welded tuffs, which is also captured by the model simulations. Simulations showed that from about 2 to 6 mm/year, the amount of calcite precipitated in the welded Topopah Spring tuff is sensitive to the infiltration rate. This dependence decreases at higher infiltration rates owing to a modification of the geothermal gradient from the increased percolation flux. The model also confirms the conceptual model for higher percolation fluxes in the fractures compared to the matrix in the welded units, and the significant contribution of Ca from water-rock interaction. This study indicates that reactive transport modeling of calcite deposition can yield important constraints on the unsaturated zone infiltration-percolation flux and provide useful insight into processes such as fracture-matrix interaction as well as conditions and parameters controlling calcite deposition.     

Flow and transport in fractured tuff at Yucca Mountain: numerical experiments on fast preferential flow mechanisms

Recent discovery of bomb-related ³⁶Cl at depth in fractured tuff in the unsaturated zone at the Yucca Mountain candidate high-level waste (HLW) repository site has called into question the usual modeling assumptions based on the equivalent continuum model (ECM). A dual continuum model (DCM) for simulating transient flow and transport at Yucca Mountain is developed. In order to ensure properly converged flow solutions, which are used in the transport simulation, a new flow solution convergence criteria is derived. An extensive series of simulation studies is presented which indicates that rapid movement of solute through the fractures will not occur unless there are intense episodic infiltration events. Movement of solute in the environs of the repository is enhanced if the properties of the tuff layer at the repository horizon are modified from current best-estimate values. Due to a large advective–dispersive coupling between the matrix and fractures, the matrix acts as a major buffer which inhibits rapid transport along the fractures. Consequently, fast movement of solutes through the fractures to the repository depth can only be explained if the matrix–fracture coupling term is significantly reduced from a value that would be calculated on the basis of data currently available.     

Tritium and 36Cl as constraints on fast fracture flow and percolation flux in the unsaturated zone at Yucca Mountain

An analysis of tritium and 36Cl data collected at Yucca Mountain, Nevada suggests that fracture flow may occur at high velocities through the thick unsaturated zone. The mechanisms and extent of this "fast flow" in fractures at Yucca Mountain are investigated with data analysis, mixing models and several one-dimensional modeling scenarios. The model results and data analysis provide evidence substantiating the weeps model [Gauthier, J.H., Wilson, M.L., Lauffer, F.C., 1992. Proceedings of the Third Annual International High-level Radioactive Waste Management Conference, vol. 1, Las Vegas, NV. American Nuclear Society, La Grange Park, IL, pp. 891-989] and suggest that fast flow in fractures with minimal fracture-matrix interaction may comprise a substantial proportion of the total infiltration through Yucca Mountain. Mixing calculations suggest that bomb-pulse tritium measurements, in general, represent the tail end of travel times for thermonuclear-test-era (bomb-pulse) infiltration. The data analysis shows that bomb-pulse tritium and 36Cl measurements are correlated with discrete features such as horizontal fractures and areas where lateral flow may occur. The results presented here imply that fast flow in fractures may be ubiquitous at Yucca Mountain, occurring when transient infiltration (storms) generates flow in the connected fracture network.     

Preliminary 3-D site-scale studies of radioactive colloid transport in the unsaturated zone at Yucca Mountain,Nevada

The U.S. Department of Energy (DOE) is actively investigating the technical feasibility of permanent disposal of high-level nuclear waste in a repository to be situated in the unsaturated zone (UZ) at Yucca Mountain (YM), Nevada. In this study we investigate, by means of numerical simulation, the transport of radioactive colloids under ambient conditions from the potential repository horizon to the water table. The site hydrology and the effects of the spatial distribution of hydraulic and transport properties in the Yucca Mountain subsurface are considered. The study of migration and retardation of colloids accounts for the complex processes in the unsaturated zone of Yucca Mountain, and includes advection, diffusion, hydrodynamic dispersion, kinetic colloid filtration, colloid straining, and radioactive decay. The results of the study indicate that the most important factors affecting colloid transport are the subsurface geology and site hydrology, i.e., the presence of faults (they dominate and control transport), fractures (the main migration pathways), and the relative distribution of zeolitic and vitric tuffs. The transport of colloids is strongly influenced by their size (as it affects diffusion into the matrix, straining at hydrogeologic unit interfaces, and transport velocity) and by the parameters of the kinetic-filtration model used for the simulations. Arrival times at the water table decrease with an increasing colloid size because of smaller diffusion, increased straining, and higher transport velocities. The importance of diffusion as a retardation mechanism increases with a decreasing colloid size, but appears to be minimal in large colloids.     

Field tracer-transport tests in unsaturated fractured tuff.

This paper presents the results of a field investigation in the unsaturated, fractured welded tuff within the Exploratory Studies Facility (ESF) at Yucca Mountain, NV. This investigation included a series of tests during which tracer-laced water was released into a high-permeability zone within a horizontal injection borehole. The tracer concentration was monitored in the seepage collected in an excavated slot about 1.6 m below the borehole. Results showed significant variability in the hydrologic response of fractures and the matrix. Analyses of the breakthrough curves suggest that flow and transport pathways are dynamic, rather than fixed, and related to liquid-release rates. Under high release rates, fractures acted as the predominant flow pathways, with limited fracture-matrix interaction. Under low release rates, fracture flow was comparatively less dominant, with a noticeable contribution from matrix flow. Observations of tracer concentrations rebounding in seepage water, following an interruption of flow, provided evidence of mass exchange between the fast-flowing fractures and slow- or non-flowing regions. The tests also showed the applicability of fluorinated benzoate tracers in situations where multiple tracers of similar physical properties are warranted.     

Tritium and Cl as constraints on fast fracture flow and percolation flux in the unsaturated zone at Yucca Mountain

An analysis of tritium and ³⁶Cl data collected at Yucca Mountain, Nevada suggests that fracture flow may occur at high velocities through the thick unsaturated zone. The mechanisms and extent of this “fast flow” in fractures at Yucca Mountain are investigated with data analysis, mixing models and several one-dimensional modeling scenarios. The model results and data analysis provide evidence substantiating the weeps model [Gauthier, J.H., Wilson, M.L., Lauffer, F.C., 1992. Proceedings of the Third Annual International High-level Radioactive Waste Management Conference, vol. 1, Las Vegas, NV. American Nuclear Society, La Grange Park, IL, pp. 891–989] and suggest that fast flow in fractures with minimal fracture–matrix interaction may comprise a substantial proportion of the total infiltration through Yucca Mountain. Mixing calculations suggest that bomb-pulse tritium measurements, in general, represent the tail end of travel times for thermonuclear-test-era (bomb-pulse) infiltration. The data analysis shows that bomb-pulse tritium and ³⁶Cl measurements are correlated with discrete features such as horizontal fractures and areas where lateral flow may occur. The results presented here imply that fast flow in fractures may be ubiquitous at Yucca Mountain, occurring when transient infiltration (storms) generates flow in the connected fracture network.     

A mountain-scale thermal-hydrologic model for simulating fluid flow and heat transfer in unsaturated fractured rock

A multidimensional, mountain-scale, thermal-hydrologic (TH) numerical model is presented for investigating unsaturated flow behavior in response to decay heat from the proposed radioactive waste repository in the Yucca Mountain unsaturated zone (UZ), The model, consisting of both two-dimensional (2-D) and three-dimensional (3-D) representations of the UZ repository system, is based on the current repository design, drift layout, thermal loading scenario, and estimated current and future climate conditions. This mountain-scale TH model evaluates the coupled TH processes related to mountain-scale UZ flow. It also simulates the impact of radioactive waste heat release on the natural hydrogeological system, including heat-driven processes occurring near and far away from the emplacement tunnels or drifts. The model simulates predict thermally perturbed liquid saturation, gas- and liquid-phase fluxes, and water and rock temperature elevations, as well as the changes in water flux driven by evaporation/condensation processes and drainage between drifts. These simulations provide insights into mountain-scale thermally perturbed flow fields under thermal loading conditions.     

Incorporating layer- and local-scale heterogeneities in numerical simulation of unsaturated flow and tracer transport

This study characterizes layer- and local-scale heterogeneities in hydraulic parameters (i.e., matrix permeability and porosity) and investigates the relative effect of layer- and local-scale heterogeneities on the uncertainty assessment of unsaturated flow and tracer transport in the unsaturated zone of Yucca Mountain, USA. The layer-scale heterogeneity is specific to hydrogeologic layers with layerwise properties, while the local-scale heterogeneity refers to the spatial variation of hydraulic properties within a layer. A Monte Carlo method is used to estimate mean, variance, and 5th, and 95th percentiles for the quantities of interest (e.g., matrix saturation and normalized cumulative mass arrival). Model simulations of unsaturated flow are evaluated by comparing the simulated and observed matrix saturations. Local-scale heterogeneity is examined by comparing the results of this study with those of the previous study that only considers layer-scale heterogeneity. We find that local-scale heterogeneity significantly increases predictive uncertainty in the percolation fluxes and tracer plumes, whereas the mean predictions are only slightly affected by the local-scale heterogeneity. The mean travel time of the conservative and reactive tracers to the water table in the early stage increases significantly due to the local-scale heterogeneity, while the influence of local-scale heterogeneity on travel time gradually decreases over time. Layer-scale heterogeneity is more important than local-scale heterogeneity for simulating overall tracer travel time, suggesting that it would be more cost-effective to reduce the layer-scale parameter uncertainty in order to reduce predictive uncertainty in tracer transport.     

Modeling colloid transport for performance assessment

The natural system is expected to contribute to isolation at the proposed high-level nuclear waste (HLW) geologic repository at Yucca Mountain, NV (YM). In developing performance assessment (PA) computer models to simulate long-term behavior at YM, colloidal transport of radionuclides has been proposed as a critical factor because of the possible reduced interaction with the geologic media. Site-specific information on the chemistry and natural colloid concentration of saturated zone groundwaters in the vicinity of YM is combined with a surface complexation sorption model to evaluate the impact of natural colloids on calculated retardation factors (RF) for several radioelements of concern in PA. Inclusion of colloids into the conceptual model can reduce the calculated effective retardation significantly. Strongly sorbed radionuclides such as americium and thorium are most affected by pseudocolloid formation and transport, with a potential reduction in RF of several orders of magnitude. Radioelements that are less strongly sorbed under YM conditions, such as uranium and neptunium, are not affected significantly by colloid transport, and transport of plutonium in the valence state is only moderately enhanced. Model results showed no increase in the peak mean annual total effective dose equivalent (TEDE) within a compliance period of 10,000 years, although this is strongly dependent on container life in the base case scenario. At longer times, simulated container failures increase and the TEDE from the colloidal models increased by a factor of 60 from the base case. By using mechanistic models and sensitivity analyses to determine what parameters and transport processes affect the TEDE, colloidal transport in future versions of the TPA code can be represented more accurately.     

Commentary: assessment of past infiltration fluxes through Yucca Mountain on the basis of the secondary mineral record-is it a viable methodology?

Two papers recently published in the Journal of Contaminant Hydrology by Marshall et al. [Marshall, B.D., Neymark, L.A., Peterman, Z.E., 2003. Estimation of past seepage volumes from calcite distribution in the Topopah Spring Tuff, Yucca Mountain, Nevada. J. Contam. Hydrol. 62-63, 237-247] and Xu et al. [Xu, T., Sonnenthal, E., Bodvarsson, G., 2003. A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock. J. Contam. Hydrol. 64, 113-127] attempt to assess past volumes of seepage and infiltration fluxes through the vadose zone of Yucca Mountain, Nevada, on the basis of the modeling of the spatial distribution of secondary calcite. In this commentary, we argue that the employed methodology is not viable. In addition, the thermal boundary conditions used in simulations do not correspond to the temperatures of the mineral forming fluids established on the basis of the fluid inclusion studies.     

Investigation of hydrogeologic processes in a dipping layer structure: 2. Transport and biodegradation of organics

Numerical simulation tools have been used to study the dominating processes during transport of aromatic hydrocarbons in the unsaturated soil zone. Simulations were based on field observations at an experimental site located on a glacial delta plain with pronounced layered sedimentary structures. A numerical model for transport in the unsaturated zone, SWMS-3D, has been extended to incorporate coupled multispecies transport, microbial degradation following Monod kinetics and gas diffusive transport of oxygen and hydrocarbons. The flow field parameters were derived from previous work using nonreactive tracers. Breakthrough curves (BTC) from the hydrocarbon field experiment were used to determine sorption parameters and Monod kinetic parameters using a fitting procedure. The numerical simulations revealed that the assumption of homogeneous layers resulted in deviations from the field observations. The deviations were more pronounced with incorporation of reactive transport, compared with earlier work on nonreactive transport. To be able to model reasonable BTC, sorption had to be reduced compared to laboratory experiments. The initial biomass and the maximum utilisation rate could be adjusted to capture both the initial lag phase and the overall degradation rate. Nevertheless, local oxygen limitation is predicted by the model, which was not observed in the field experiment. Incorporation of evaporation and diffusive gas transport of the hydrocarbons did not significantly change the local oxygen demand. The main cause of the observed discrepancies between model and field are attributed to channelling as a result of small-scale heterogeneities such as biopores.     

Migration of a water pulse through fractured porous media

Contaminant transport from waste-disposal sites is strongly affected by the presence of fractures and the degree of fracture matrix interaction. Characterization of potential contaminant plumes at such sites is difficult, both experimentally and numerically. Simulations of water flow through fractured rock were performed to examine the penetration depth of a large pulse of water entering such a system. Construction water traced with lithium bromide was released during the excavation of a tunnel at Yucca Mountain, Nevada, which is located in an unsaturated fractured tuff formation. Modeling of construction-water migration is qualitatively compared with bromide-to-chloride ratio (Br/Cl) data for pore-water salts extracted from drillcores. The influences of local heterogeneities in the fracture network and variations in hydrogeologic parameters were examined by sensitivity analyses and Monte Carlo simulations. The simulation results are qualitatively consistent with the observed Br/Cl signals, although these data may only indicate a minimum penetration depth, and water may have migrated farther through the fracture network.     

Analysis of a mesoscale infiltration and water seepage test in unsaturated fractured rock: Spatial variabilities and discrete fracture patterns

A mesoscale (21 m in flow distance) infiltration and seepage test was recently conducted in a deep, unsaturated fractured rock system at the crossover point of two underground tunnels. Water was released from a 3 mx4 m infiltration plot on the floor of an alcove in the upper tunnel, and seepage was collected from the ceiling of a niche in the lower tunnel. Significant temporal and (particularly) spatial variabilities were observed in both measured infiltration and seepage rates. To analyze the test results, a three-dimensional unsaturated flow model was used. A column-based scheme was developed to capture heterogeneous hydraulic properties reflected by these spatial variabilities observed. Fracture permeability and van Genuchten alpha parameter [van Genuchten, M.T., 1980. A closed-form equation for predicting the hydraulic conductivity of unsaturated soils. Soil Sci. Soc. Am. J. 44, 892-898] were calibrated for each rock column in the upper and lower hydrogeologic units in the test bed. The calibrated fracture properties for the infiltration and seepage zone enabled a good match between simulated and measured (spatially varying) seepage rates. The numerical model was also able to capture the general trend of the highly transient seepage processes through a discrete fracture network. The calibrated properties and measured infiltration/seepage rates were further compared with mapped discrete fracture patterns at the top and bottom boundaries. The measured infiltration rates and calibrated fracture permeability of the upper unit were found to be partially controlled by the fracture patterns on the infiltration plot (as indicated by their positive correlations with fracture density). However, no correlation could be established between measured seepage rates and density of fractures mapped on the niche ceiling. This lack of correlation indicates the complexity of (preferential) unsaturated flow within the discrete fracture network. This also indicates that continuum-based modeling of unsaturated flow in fractured rock at mesoscale or a larger scale is not necessarily conditional explicitly on discrete fracture patterns.     

Axi-symmetric simulation of soil vapor extraction influenced by soil fracturing

Fracturing, either pneumatic or hydraulic, is a method to improve the performance of soil vapor extraction (SVE) in relatively low permeability soils (< 10(-5) cm/s). A two-dimensional model is presented to simulate trichloroethylene (TCE) soil vapor extraction modified by fracturing. Flow and transport is modeled using mobile macropore and micropore networks, which also have been identified in the literature as dual porosity, dual permeability, or heterogeneous flow models. In this model, fluids can flow in both the macropore and micropore networks. This represents a more general model compared to immobile micropore, mobile macropore models presented thus far in the literature for vapor flow and transport in two dimensions. The model considers pressure- and concentration-driven exchange between the macropore and micropore networks, concentration-driven exchange between the gas and sorbed phases within each network, and equilibrium exchange between the gas and water and a sorbed phase within each network. The parameters employed in an example simulation are based on field measurements made at a fractured site. Considered in the simulations were the influence of the volume percentage of fractures, the length of fractures, the relative location of the water table, and the influence of pulsed pumping. For these simulations, internetwork concentration-driven exchange most significantly affected mass removal. The volume percentage of fractures more significantly influence flow and mass removal than the length of fractures. The depth of the water table below the contamination plume only significantly influenced flow and mass removal when the water table was within 60 cm of the bottom of the contaminated soil in the vadose zone for the parameters considered in this study. Pulsed pumping was not found to increase the amount of mass removed in this study.     

Review of unsaturated-zone transport and attenuation of volatile organic compound (VOC) plumes leached from shallow source zones

Reliable prediction of the unsaturated zone transport and attenuation of dissolved-phase VOC (volatile organic compound) plumes leached from shallow source zones is a complex, multi-process, environmental problem. It is an important problem as sources, which include solid-waste landfills, aqueous-phase liquid discharge lagoons and NAPL releases partially penetrating the unsaturated zone, may persist for decades. Natural attenuation processes operating in the unsaturated zone that, uniquely for VOCs includes volatilisation, may, however, serve to protect underlying groundwater and potentially reduce the need for expensive remedial actions. Review of the literature indicates that only a few studies have focused upon the overall leached VOC source and plume scenario as a whole. These are mostly modelling studies that often involve high strength, non-aqueous phase liquid (NAPL) sources for which density-induced and diffusive vapour transport is significant. Occasional dissolved-phase aromatic hydrocarbon controlled infiltration field studies also exist. Despite this lack of focus on the overall problem, a wide range of process-based unsaturated zone - VOC research has been conducted that may be collated to build good conceptual model understanding of the scenario, particularly for the much studied aromatic hydrocarbons and chlorinated aliphatic hydrocarbons (CAHs). In general, the former group is likely to be attenuated in the unsaturated zone due to their ready aerobic biodegradation, albeit with rate variability across the literature, whereas the fate of the latter is far less likely to be dominated by a single mechanism and dependent upon the relative importance of the various attenuation processes within individual site - VOC scenarios. Analytical and numerical modelling tools permit effective process representation of the whole scenario, albeit with potential for inclusion of additional processes - e.g., multi-mechanistic sorption phase partitioning, and provide good opportunity for further sensitivity analysis and development to practitioner use. There remains a significant need to obtain intermediate laboratory-scale and particularly field-scale (actual site and controlled release) datasets that address the scenario as a whole and permit validation of the available models. Integrated assessment of the range of simultaneous processes that combine to influence leached plume generation, transport and attenuation in the unsaturated zone is required. Component process research needs are required across the problem scenario and include: the simultaneous volatilisation and dissolution of source zones; development of appropriate field-scale dispersion estimates for the unsaturated zone; assessment of transient VOC exchanges between aqueous, vapour and sorbed phases and their influence upon plume attenuation; development of improved field methods to recognise and quantify biodegradation of CAHs; establishment of the influence of co-contaminants; and, finally, translation of research findings into more robust practitioner practice.     

Effects of water content on reactive transport of 85Sr in Chernobyl sand columns

It is known that under unsaturated conditions, the transport of solutes can deviate from ideal advective-dispersive behaviour even for macroscopically homogeneous porous materials. Causes may include physical non-equilibrium, sorption kinetics, non-linear sorption, and the irregular distribution of sorption sites. We have performed laboratory experiments designed to identify the processes responsible for the non-ideality of radioactive Sr transport observed under unsaturated flow conditions in an Aeolian sandy deposit from the Chernobyl exclusion zone. Miscible displacement experiments were carried out at various water contents and corresponding flow rates in a laboratory model system. Results of our experiments have shown that breakthrough curves of a conservative tracer exhibit a higher degree of asymmetry when the water content decreases than at saturated water content and same Darcy velocity. It is possible that velocity variations caused by heterogeneities at the macroscopic scale are responsible for this situation. Another explanation is that molecular diffusion drives the solute mass transfer between mobile and immobile water regions, but the surface of contact between these water regions is small. At very low concentrations, representative of a radioactive Sr contamination of the pore water, sorption and physical disequilibrium dominate the radioactive Sr transport under unsaturated flow conditions. A sorption reaction is described by a cation exchange mechanism calibrated under fully saturated conditions. The sorption capacity, as well as the exchange coefficients are not affected by desaturation. The number of accessible exchange sites was calculated on the basis that the solid remained in contact with water and that the fraction of solid phase in contact with mobile water is numerically equal to the proportion of mobile water to total water content. That means that for this type of sandy soil, the nature of mineral phases is the same in advective and non-advective domains. So sorption reaction parameters can be estimated from more easily conducted saturated experiments, but hydrodynamic behaviour must be characterized by conservative tracer experiments under unsaturated flow conditions.     

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.