Anomalous transport of colloids and solutes in a shear zone

Transport experiments with colloids and radionuclides in a shear zone were conducted during the Colloid and Radionuclide Retardation experiment (CRR) at Nagra's Grimsel Test Site. Breakthrough curves of bentonite colloids and uranine, a non-sorbing solute, were measured in an asymmetric dipole flow field. The colloid breakthrough is earlier than that of uranine. Both breakthrough curves show anomalously long late time tails and the slope of the late time tails for the colloids is slightly higher. Anomalous late time tails are commonly associated with matrix diffusion processes; the diffusive interaction of solutes transported in open channels with the adjacent porous rock matrix or zones of stagnant water. The breakthrough curves for different colloid size classes are very similar and show no signs of fractionation due to their (size-dependent) diffusivity. It is proposed that tailing of the colloids is mainly caused by the structure of the flow field and that for the colloid transport, matrix diffusion is of minor importance. This has consequences for the interpretation of the uranine breakthrough. Comparisons of experimental results with numerical studies and with the evaluation of the colloid breakthrough with continuous time random theory imply that the tailing in the conservative solute breakthrough in this shear zone is not only caused by matrix diffusion. Part of the tailing can be attributed to advective transport in fracture networks and advection in low velocity regions. Models based on the advection-dispersion equation and matrix diffusion do not properly describe the temporal and spatial evolution of colloid and solute transport in such systems with a consistent set of parameters.     

Fast method for simulation of radionuclide chain migration in dual porosity fracture rocks

In fractured rocks with a porous rock matrix such as granites, radionuclides will flow with the water in the fracture network. The nuclides will diffuse in and out the rock matrix where they can sorb and be considerably retarded compared to the water velocity. A water parcel entering the network will mix and split at the fracture intersections and parts of the original parcel will traverse a multitude of different fractures. The flowrates, velocities, sizes and apertures of the fractures can vary widely. Normally one must solve the transport equations for every fracture and use the effluent concentration as inlet condition to the next fracture and so on. It is shown that under some weakly simplified conditions it suffices to determine one single parameter group containing information on the flow wetted surface that a water parcel contacts along the entire path. It is also shown how this can be obtained. Then, solving the transport equations only once for time and location along the path gives the concentration and nuclide flux of every nuclide in the chain everywhere along a path. The same solution actually is valid for every path in the network. This dramatically reduces the computation effort. The same approach can be used for models based on streamtubes.     

Dual-domain solute transfer and transport processes: evaluation in batch and transport experiments

Soil macropore networks establish a dual-domain transport scenario in which water and solutes are preferentially channeled through soil macropores while slowly diffusing into and out of the bulk soil matrix. The influence of macropore networks on intra-ped solute diffusion and preferential transport in a soil typical of subsurface-drained croplands in the Midwestern United States was studied in batch- and column-scale experiments. In the batch diffusion studies with soil aggregates, the estimated diffusion radius (length) of the soil aggregates corresponded to the half-spacing of the aggregate fissures, suggesting that the intra-ped fissures reduced the diffusion impedance and preferentially allowed solutes to diffuse into the soil matrix. In the column-scale solute transport experiments, the average diffusion radius (estimated from HYDRUS-2D simulations and a first-order diffusive transfer term) was nearly double that of the batch-scale study. This increase may be attributed to a loss of pore continuity and a compounding of the small diffusion impedance through macropores at the larger scale. The column-scale solute transport experiments also suggest that two preferential networks exist in the soil. At and near soil saturation, a primary network of large macropores (possibly root channels and earthworm burrows) dominate advective transport, causing a high degree of physical and sorption nonequilibrium and simultaneous breakthrough of a nonreactive (bromide) and a reactive (alachlor) solute. As the saturation level decreases, the primary network drains, while transport through smaller macropores (possibly intra-ped features) continues, resulting in a reduced degree of nonequilibrium and separation in the breakthrough curves of bromide and alachlor.     

Fluid flow and solute transport in a network of channels

A new model to describe flow and transort in fractured rocks is proposed. It is based on the concept of a network of channels. The individual channel members are given stochastically selected conductances and volumes. Flow-rate calculations have been performed. For large standard deviations in conductances, channeling becomes pronounced with most of the water flowing in a few paths. The effluent patterns and flow-rate distributions obtained in the simulations have been compared to three field measurements in drifts and tunnels of flow-rate distributions. Standard deviations of channel conductances were between 1.6 and 2.4 in some cases. A particle-following technique was used to simulate solute transport in the network. Non-sorbing as well as sorbing solute transport can be simulated. By using a special technique, solutes that diffuse into the rock matrix can also be simulated.     

Simulation and analysis of solute transport in 2D fracture/pipe networks: the SOLFRAC program

The Time Domain Random Walk (TDRW) method has been recently developed by Delay and Bodin [Delay, F. and Bodin, J., 2001. Time domain random walk method to simulate transport by advection-dispersion and matrix diffusion in fracture networks. Geophys. Res. Lett., 28(21): 4051-4054.] and Bodin et al. [Bodin, J., Porel, G. and Delay, F., 2003c. Simulation of solute transport in discrete fracture networks using the time domain random walk method. Earth Planet. Sci. Lett., 6566: 1-8.] for simulating solute transport in discrete fracture networks. It is assumed that the fracture network can reasonably be represented by a network of interconnected one-dimensional pipes (i.e. flow channels). Processes accounted for are: (1) advection and hydrodynamic dispersion in the channels, (2) matrix diffusion, (3) diffusion into stagnant zones within the fracture planes, (4) sorption reactions onto the fracture walls and in the matrix, (5) linear decay, and (6) mass sharing at fracture intersections. The TDRW method is handy and very efficient in terms of computation costs since it allows for the one-step calculation of the particle residence time in each bond of the network. This method has been programmed in C++, and efforts have been made to develop an efficient and user-friendly software, called SOLFRAC. This program is freely downloadable at the URL (labo.univ-poitiers.fr/hydrasa/intranet/telechargement.htm). It calculates solute transport into 2D pipe networks, while considering different types of injections and different concepts of local dispersion within each flow channel. Post-simulation analyses are also available, such as the mean velocity or the macroscopic dispersion at the scale of the entire network. The program may be used to evaluate how a given transport mechanism influences the macroscopic transport behaviour of fracture networks. It may also be used, as is the case, e.g., with analytical solutions, to interpret laboratory or field tracer test experiments performed in single fractures.     

Numerical modeling of coupled variably saturated fluid flow and reactive transport with fast and slow chemical reactions

The couplings among chemical reaction rates, advective and diffusive transport in fractured media or soils, and changes in hydraulic properties due to precipitation and dissolution within fractures and in rock matrix are important for both nuclear waste disposal and remediation of contaminated sites. This paper describes the development and application of LEHGC2.0, a mechanistically based numerical model for simulation of coupled fluid flow and reactive chemical transport, including both fast and slow reactions in variably saturated media. Theoretical bases and numerical implementations are summarized, and two example problems are demonstrated. The first example deals with the effect of precipitation/dissolution on fluid flow and matrix diffusion in a two-dimensional fractured media. Because of the precipitation and decreased diffusion of solute from the fracture into the matrix, retardation in the fractured medium is not as large as the case wherein interactions between chemical reactions and transport are not considered. The second example focuses on a complicated but realistic advective-dispersive-reactive transport problem. This example exemplifies the need for innovative numerical algorithms to solve problems involving stiff geochemical reactions.     

Contributions of advective and diffusive oxygen transport through multilayer composite caps over mine waste

The relative contributions of four mechanisms of oxygen transport in multilayer composite (MLC) caps placed over oxygen-consuming mine waste were evaluated using numerical and analytical methods. MLC caps are defined here as caps consisting of earthen and geosynthetic (polymeric) components where a composite barrier layer consisting of a geomembrane (1-2 mm thick polymeric sheet) overlying a clay layer is the primary barrier to transport. The transport mechanisms that were considered are gas-phase advective transport, gas-phase diffusive transport, liquid-phase advective transport via infiltrating precipitation and liquid-phase diffusive transport. A numerical model was developed to simulate gas-phase advective-diffusive transport of oxygen through a multilayer cap containing seven layers. This model was also used to simulate oxygen diffusion in the liquid phase. An approximate analytical method was used to compute the advective flux of oxygen in the liquid phase. The numerical model was verified for limiting cases using an analytical solution. Comparisons were also made between model predictions and field data for earthen caps reported by others. Results of the analysis show that the dominant mechanism for oxygen transport through MLC caps is gas-phase diffusion. For the cases that were considered, the gas-phase diffusive flux typically comprises at least 99% of the total oxygen flux. Thus, designers of MLC caps should focus on design elements and features that will limit diffusion of gas-phase oxygen.     

Long-term oxygen depletion from infiltrating groundwaters: model development and application to intra-glaciation and glaciation conditions

Processes that control the redox conditions in deep groundwaters have been studied. The understanding of such processes in a long-term perspective is important for the safety assessment of a deep geological repository for high-level nuclear waste. An oxidising environment at the depth of the repository would increase the solubility and mobility of many radionuclides, and increase the potential risk for radioactive contamination at the ground surface. Proposed repository concepts also include engineered barriers such as copper canisters, the corrosion of which increases considerably in an oxidising environment compared to prevailing reducing conditions. Swedish granitic rocks are typically relatively sparsely fractured and are best treated as a dual-porosity medium with fast flowing channels through fractures in the rock with a surrounding porous matrix, the pores of which are accessible from the fracture by diffusive transport. Highly simplified problems have been explored with the aim to gain understanding of the underlying transport processes, thermodynamics and chemical reaction kinetics. The degree of complexity is increased successively, and mechanisms and processes identified as of key importance are included in a model framework. For highly complex models, analytical expressions are not fully capable of describing the processes involved, and in such cases the solutions are obtained by numerical calculations. Deep in the rock the main source for reducing capacity is identified as reducing minerals. Such minerals are found inside the porous rock matrix and as infill particles or coatings in fractures in the rock. The model formulation also allows for different flow modes such as flow along discrete fractures in sparsely fractured rocks and along flowpaths in a fracture network. The scavenging of oxygen is exemplified for these cases as well as for more comprehensive applications, including glaciation considerations. Results show that chemical reaction kinetics control the scavenging of oxygen during a relatively short time with respect to the lifetime of the repository. For longer times the scavenging of oxygen is controlled by transport processes in the porous rock matrix. The penetration depth of oxygen along the flowpath depends largely on the hydraulic properties, which may vary significantly between different locations and situations. The results indicate that oxygen, in the absence of easily degradable organic matter, may reach long distances along a flow path during the life-time of the repository (hundreds to thousands of metres in a million years depending on e.g. hydraulic properties of the flow path and the availability of reducing capacity). However, large uncertainties regarding key input parameters exist leading to the conclusion that the results from the model must be treated with caution pending more accurate and validated data. Ongoing and planned experiments are expected to reduce these uncertainties, which are required in order to make more reliable predictions for a safety assessment of a nuclear waste repository.     

Interpretation of injection-withdrawal tracer experiments conducted between two wells in a large single fracture

Tracer experiments conducted using a flow field established by injecting water into one borehole and withdrawing water from another are often used to establish connections and investigate dispersion in fractured rock. As a result of uncertainty in the uniqueness of existing models used for interpretation, this method has not been widely used to investigate more general transport processes including matrix diffusion or advective solute exchange between mobile and immobile zones of fluid. To explore the utility of the injection-withdrawal method as a general investigative tool and with the intent to resolve the transport processes in a discrete fracture, two tracer experiments were conducted using the injection-withdrawal configuration. The experiments were conducted in a fracture which has a large aperture (>500 microm) and horizontally pervades a dolostone formation. One experiment was conducted in the direction of the hydraulic gradient and the other in the direction opposite to the natural gradient. Two tracers having significantly different values of the free-water diffusion coefficient were used. To interpret the experiments, a hybrid numerical-analytical model was developed which accounts for the arcuate shape of the flow field, advection-dispersion in the fracture, diffusion into the matrix adjacent to the fracture, and the presence of natural flow in the fracture. The model was verified by comparison to a fully analytical solution and to a well-known finite-element model. Interpretation of the tracer experiments showed that when only one tracer, advection-dispersion, and matrix diffusion are considered, non-unique results were obtained. However, by using multiple tracers and by accounting for the presence of natural flow in the fracture, unique interpretations were obtained in which a single value of matrix porosity was estimated from the results of both experiments. The estimate of porosity agrees well with independent measurements of porosity obtained from core samples. This suggests that: (i) the injection-withdrawal method is a viable tool for the investigation of general transport processes provided all relevant experimental conditions are considered and multiple conservative tracers are used; and (ii) for the conditions of the experiments conducted in this study, the dominant mechanism for exchange of solute between the fracture and surrounding medium is matrix diffusion.     

The effects of matrix diffusion on radionuclide migration in rock column experiments

Rock column experiments were performed to examine the effects of matrix diffusion and hydrodynamic dispersion on the migration of radionuclides at the laboratory scale. Tritiated water and chloride transportation was studied in intact mica gneiss and in altered more porous tonalite columns with narrow flow channels. The column diffusion properties were estimated prior to water flow experiments using the gas diffusion method with helium as the tracer gas. The numerical compartment model for advection and dispersion, with and without matrix diffusion, was used to interpret the tracer transport in the columns. Matrix diffusion behavior was also distinguished from dominating hydrodynamic dispersion in rock column experiments at the slowest water flow rates.     

An interpretation of potential scale dependence of the effective matrix diffusion coefficient

Matrix diffusion is an important process for solute transport in fractured rock, and the matrix diffusion coefficient is a key parameter for describing this process. Previous studies have indicated that the effective matrix diffusion coefficient values, obtained from a large number of field tracer tests, are enhanced in comparison with local values and may increase with test scale. In this study, we have performed numerical experiments to investigate potential mechanisms behind possible scale-dependent behavior. The focus of the experiments is on solute transport in flow paths having geometries consistent with percolation theories and characterized by multiple local flow loops formed mainly by small-scale fractures. The water velocity distribution through a flow path was determined using discrete fracture network flow simulations, and solute transport was calculated using a previously derived impulse-response function and a particle-tracking scheme. Values for effective (or up-scaled) transport parameters were obtained by matching breakthrough curves from numerical experiments with an analytical solution for solute transport along a single fracture. Results indicate that a combination of local flow loops and the associated matrix diffusion process, together with scaling properties in flow path geometry, seems to be an important mechanism causing the observed scale dependence of the effective matrix diffusion coefficient (at a range of scales).     

Influence of hydrological and geochemical processes on the transport of chelated metals and chromate in fractured shale bedrock

Field-scale processes governing the transport of chelated radionuclides in groundwater remain conceptually unclear for highly structured, heterogeneous environments. The objectives of this research were to provide an improved understanding and predictive capability of the hydrological and geochemical mechanisms that control the transport behavior of chelated radionuclides and metals in anoxic subsurface environments that are complicated by fracture flow and matrix diffusion. Our approach involved a long-term, steady-state natural gradient field experiment where nonreactive Br- and reactive 57Co(II)EDTA2- 109CdEDTA2-, and 51Cr(VI) were injected into a fracture zone of a contaminated fractured shale bedrock. The spatial and temporal distribution of the tracer and solutes was monitored for 500 days using an array of groundwater sampling wells instrumented within the fast-flowing fracture regime and a slower flowing matrix regime. The tracers were preferentially transported along strike-parallel fractures coupled with the slow diffusion of significant tracer mass into the bedrock matrix. The chelated radionuclides and metals were significantly retarded by the solid phase with the mechanisms of retardation largely due to redox reactions and sorption coupled with mineral-induced chelate-radionuclide dissociation. The formation of significant Fe(III)EDTA byproduct that accompanied the dissociation of the radionuclide-chelate complexes was believed to be the result of surface interactions with biotite which was the only Fe(III)-bearing mineral phase present in these Fe-reducing environments. These results counter current conceptual models that suggest chelated contaminants move conservatively through Fe-reducing environments since they are devoid of Fe-oxyhydroxides that are known to aggressively compete for chelates in oxic regimes. Modeling results further demonstrated that chelate-radionuclide dissociation reactions were most prevalent along fractures where accelerated weathering processes are expected to expose more primary minerals than the surrounding rock matrix. The findings of this study suggest that physical retardation mechanisms (i.e. diffusion) are dominant within the matrix regime, whereas geochemical retardation mechanisms are dominant within the fracture regime.     

Through-electromigration: a new method of investigating pore connectivity and obtaining formation factors

The retardation of radionuclides and other contaminants in fractured crystalline rock is strongly associated with the diffusive properties of the rock matrix. At present, the scientific community is divided concerning the question of long-range pore connectivity in intrusive igneous rock. This paper presents a fast new method, called the through-electromigration method, of obtaining formation factors and investigating pore connectivity. The method involves the migration of an ionic tracer through a rock sample with an electrical potential gradient as the main driving force. The method is analogous to the through-diffusion method but the experimental time is reduced by orders of magnitude. This enables investigations of pore connectivity, as measurements can be made on longer samples. In a preliminary investigation, the new method is compared to the traditional through-diffusion method as well as to rock resistivity methods. The diffusive properties of nine granitic rock samples from Laxemar in Sweden, ranging from 15 to 121 mm in length, have been investigated and the results are compared.     

Kinematic analysis of solute mass flows in rock fractures with spatially random parameters

Field data of physical properties in heterogeneous crystalline bedrock, like porosity and fracture aperture, is associated with uncertainty that can have a significant impact on the analysis of solute transport in rock fractures. Solutions to the central temporal moments of the residence time probability density function (PDF) are derived in a closed form for a solute Dirac pulse. The solutions are based on a model that takes into account advection along the fracture plane, diffusion into the rock matrix and sorption kinetics in the rock matrix. The most relevant rock properties including fracture aperture and several matrix properties as well as flow velocity are assumed to be spatially random along transport pathways. The mass transport is first solved in a general form along one-dimensional pathways, but the results can be extended to multi-dimensional flows simply by substituting the expected travel time for inert water parcels. Based on data obtained with rock samples taken at Asp? Hard Rock Laboratory in Sweden, the solutions indicate that the heterogeneity of the rock properties contributes to increasing significantly both the variance and the skewness of the residence time probability density function for a pulse travelling in a fracture. The Asp? data suggests that the bias introduced in the variance of the residence time PDF by neglecting the effect of heterogeneity of the rock properties on the radionuclide migration is very large for fractures thinner than a few tenths of a millimetre.     

The effect of a biofilm on solute diffusion in fractured porous media

At sites in fractured rock where contamination has been exposed to the rock matrix for extended periods of time, the amount of contaminant mass residing in the matrix can be considerable. Even though it may be possible to diminish concentrations by the advection of clean water through the fracture features, back diffusion from mass held in the matrix will lead to a continuing source of contamination. In such an event, the development of a biofilm (a thin film of microbial mass) on the wall of the fractures may act to limit or prevent the back diffusion process. The objective of this preliminary study is to explore the influence imparted by the presence of a biofilm on the process of matrix diffusion. The investigation was conducted using radial diffusion cells constructed from rock core in which biofilm growth was stimulated in a central reservoir. Once biofilms were developed, forward diffusion experiments were conducted in which a conservative solute migrated from the central reservoir into the intact rock sample. Diffusion experiments were performed in a total of 11 diffusion cell pairs where biofilm growth was stimulated in one member of the pair and inhibited in the other. The effect of the presence of a biofilm on tracer diffusion was determined by comparison of the diffusion curves produced by each cell pair. A semi-analytical model that accounts for the presence of a biofilm was used to investigate the effect of the biofilm on mass transfer due to changes in the effective porosity, effective diffusion coefficient, and the depth of penetration of the biofilm into the intact rock. The results show that the biofilm acted to plug the rock matrix, rather than forming a discrete layer on the reservoir surface. The reduction in effective porosity due to the biofilm ranged from 6% to 52% with the majority of the samples in the 30% to 50% range. Based on the present results, with more efficient biofilm stimulation, it is reasonable to assume that a more complete plugging of the microcrack porosity might be possible, leaving a much thicker and efficient barrier than could be achieved via a surface biofilm.     

Modelling the migration of contaminants through variably saturated dual-porosity, dual-permeability chalk

In the Hesbaye region in Belgium, tracer tests performed in variably saturated fissured chalk rocks presented very contrasting results in terms of transit times, according to artificially controlled water recharge conditions prevailing during the experiments. Under intense recharge conditions, tracers migrated across the partially or fully saturated fissure network, at high velocity in accordance with the high hydraulic conductivity and low effective porosity (fracture porosity). At the same time, a portion of the tracer was temporarily retarded in the almost immobile water located in the matrix. Under natural infiltration conditions, the fissure network remained inactive. Tracers migrated downward through the matrix, at low velocity in relation with the low hydraulic conductivity and the large porosity of the matrix. Based on these observations, Brouyère et al. (2004a) [Brouyère, S., Dassargues, A., Hallet, V., 2004a. Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation, J. Contam. Hydrol., 72 (1-4), 135-164, doi: 10.1016/j.conhyd.2003.10.009] proposed a conceptual model in order to explain the migration of solutes in variably saturated, dual-porosity, dual-permeability chalk. Here, mathematical and numerical modelling of tracer and contaminant migration in variably saturated fissured chalk is presented, considering the aforementioned conceptual model. A new mathematical formulation is proposed to represent the unsaturated properties of the fissured chalk in a more dynamic and appropriate way. At the same time, the rock water content is partitioned between mobile and immobile water phases, as a function of the water saturation of the chalk rock. The groundwater flow and contaminant transport in the variably saturated chalk is solved using the control volume finite element method. Modelling the field tracer experiments performed in the variably saturated chalk shows the adequacy and usefulness of the new conceptual, mathematical and numerical model.     

Tracer diffusion coefficients in sedimentary rocks: correlation to porosity and hydraulic conductivity

Matrix diffusion is an important transport process in geologic materials of low hydraulic conductivity. For predicting the fate and transport of contaminants, a detailed understanding of the diffusion processes in natural porous media is essential. In this study, diffusive tracer transport (iodide) was investigated in a variety of geologically different limestone and sandstone rocks. Porosity, structural and mineralogical composition, hydraulic conductivity, and other rock properties were determined. The effective diffusion coefficients were measured using the time-lag method. The results of the diffusion experiments indicate that there is a close relationship between total porosity and the effective diffusion coefficient of a rock (analogous to Archie's Law). Consequently, the tortousity factor can be expressed as a function of total porosity. The relationship fits best for thicker samples (> 1.0 cm) with high porosities (> 20%), because of the reduced influence of heterogeneity in larger samples. In general, these correlations appear to be a simple way to determine tortuosity and the effective diffusion coefficient from easy to determine rock porosity values.     

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 technique for estimating one-dimensional diffusion coefficients in low-permeability sedimentary rock using X-ray radiography: comparison with through-diffusion measurements

The measurement of diffusive properties of low-permeability rocks is of interest to the nuclear power industry, which is considering the option of deep geologic repositories for management of radioactive waste. We present a simple, non-destructive, constant source in-diffusion method for estimating one-dimensional pore diffusion coefficients (D(p)) in geologic materials based on X-ray radiography. Changes in X-ray absorption coefficient (Deltamicro) are used to quantify changes in relative concentration (C/C(0)) of an X-ray attenuating iodide tracer as the tracer solution diffuses through the rock pores. Estimated values of D(p) are then obtained by fitting an analytical solution to the measured concentration profiles over time. Measurements on samples before and after saturation with iodide can also be used to determine iodide-accessible porosity (phi(I)). To evaluate the radiography method, results were compared with traditional steady-state through-diffusion measurements on two rock types: shale and limestone. Values of D(p) of (4.8+/-2.5)x10(-11) m(2).s(-1) (mean+/-standard deviation) were measured for samples of Queenston Formation shale and (2.6+/-1.0)x10(-11) m(2).s(-1) for samples of Cobourg Formation limestone using the radiography method. The range of results for each rock type agree well with D(p) values of (4.6+/-2.0)x10(-11) m(2).s(-1) for shale and (3.5+/-1.8)x10(-11) m(2).s(-1) for limestone, calculated from through-diffusion experiments on adjacent rock samples. Low porosity (0.01 to 0.03) and heterogeneous distribution of porosity in the Cobourg Formation may be responsible for the slightly poorer agreement between radiography and through-diffusion results for limestones. Mean values of phi(I) for shales (0.060) and limestones (0.028) were close to mean porosity measurements made on bulk samples by the independent water loss technique (0.062 and 0.020 for shales and limestones, respectively). Radiography measurements offer the advantage of time-saving for diffusion experiments because the experiment does not require steady-state conditions and also allows for visualization of the small-scale heterogeneities in diffusive properties within rocks at the mm to cm scale.