Reactive transport modeling of the clogging process at Maqarin natural analogue site

The Maqarin site in Jordan has been investigated for three decades as a natural analogue for the long term changes of materials in contact with hyper-alkaline solutions. Similar processes are expected in radioactive waste disposal sites, where cement based materials are in contact with natural rocks or other e.g. clay based materials. In this context, a numerical reactive transport model was used to study local geochemical alterations and induced porosity changes for the Maqarin marl rock in contact with the hyper-alkaline solution. The geochemical setup for the rock mineralogy and the pore water was calibrated to match measurements from the Maqarin site. The setup includes several clay and zeolite minerals, considers cation exchange processes, and a state-of-the-art model for cement phases. Similar to earlier calculations by Steefel and Lichtner (1998) who used a much simpler geochemical model, the pore clogging occurred after several hundred years at a distance of 5–10 mm from the contact to the hyper-alkaline solution. In our calculations, this was caused by a massive precipitation of ettringite and C–S–H minerals. We performed a sensitivity study by varying the intrinsic diffusion coefficient, the Archie’s law exponential factor, and the mineral surface area available for dissolution and precipitation. We found that the dissolution of clay minerals controls the availability of Al, which is needed for ettringite and C–S–H phase precipitation. Thus, the amount and kinetically controlled dissolution of clay minerals controls the spatial and temporal evolution of porosity changes. The simulations reveal that neither cation exchange processes nor the formation of zeolite minerals strongly influence the geochemical evolution of the system.     

CO2-induced dissolution of low permeability carbonates. Part II: Numerical modeling of experiments

We used the 3D continuum-scale reactive transport models to simulate eight core flood experiments for two different carbonate rocks. In these experiments the core samples were reacted with brines equilibrated with pCO₂ = 3, 2, 1, 0.5 MPa (Smith et al., 2013 [27]). The carbonate rocks were from specific Marly dolostone and Vuggy limestone flow units at the IEAGHG Weyburn-Midale CO₂ Monitoring and Storage Project in south-eastern Saskatchewan, Canada. Initial model porosity, permeability, mineral, and surface area distributions were constructed from micro tomography and microscopy characterization data. We constrained model reaction kinetics and porosity–permeability equations with the experimental data. The experimental data included time-dependent solution chemistry and differential pressure measured across the core, and the initial and final pore space and mineral distribution. Calibration of the model with the experimental data allowed investigation of effects of carbonate reactivity, flow velocity, effective permeability, and time on the development and consequences of stable and unstable dissolution fronts.The continuum scale model captured the evolution of distinct dissolution fronts that developed as a consequence of carbonate mineral dissolution and pore scale transport properties. The results show that initial heterogeneity and porosity contrast control the development of the dissolution fronts in these highly reactive systems. This finding is consistent with linear stability analysis and the known positive feedback between mineral dissolution and fluid flow in carbonate formations. Differences in the carbonate kinetic drivers resulting from the range of pCO₂ used in the experiments and the different proportions of more reactive calcite and less reactive dolomite contributed to the development of new pore space, but not to the type of dissolution fronts observed for the two different rock types. The development of the dissolution front was much more dependent on the physical heterogeneity of the carbonate rock. The observed stable dissolution fronts with small but visible dissolution fingers were a consequence of the clustering of a small percentage of larger pores in an otherwise homogeneous Marly dolostone. The observed wormholes in the heterogeneous Vuggy limestone initiated and developed in areas of greater porosity and permeability contrast, following pre-existing preferential flow paths.Model calibration of core flood experiments is one way to specifically constrain parameter input used for specific sites for larger scale simulations. Calibration of the governing rate equations and constants for Vuggy limestones showed that dissolution rate constants reasonably agree with published values. However the calcite dissolution rate constants fitted to the Marly dolostone experiments are much lower than those suggested by literature. The differences in fitted calcite rate constants between the two rock types reflect uncertainty associated with measured reactive surface area and appropriately scaling heterogeneous distribution of less abundant reactive minerals. Calibration of the power-law based porosity–permeability equations was sensitive to the overall heterogeneity of the cores. Stable dissolution fronts of the more homogeneous Marly dolostone could be fit with the exponent n = 3 consistent with the traditional Kozeny–Carman equation developed for porous sandstones. More impermeable and heterogeneous cores required larger n values (n = 6–8).     

Mixing-induced precipitation and porosity evolution in porous media

The dynamics of porosity evolution are explored during mineral precipitation that is induced by the mixing of two fluids of different compositions. During mineral precipitation in geological formations, the physical parameters that characterize the porous matrix, such as porosity and specific surface area, can change significantly. A series of coupled equations that determine the changes in porosity is outlined and solved for a 2D model domain using a finite element scheme. Using model parameters equivalent to those for calcite precipitation in a saline system, the evolution of porosity is examined for two types of porous media: (1) an initially homogeneous system and (2) a heterogeneous system containing high porosity regions that serve initially as preferential flow paths. In addition, the influence of two different expressions that relate specific surface area to porosity is explored. The simulations in both domains indicated that porosity was reduced primarily in the regions in which significant degrees of mixing occurred. Although an effective barrier was created in these regions, the fluids bypassed the clogged areas allowing precipitation to continue farther “downstream”. Furthermore, mixing-induced precipitation can account for systems in which some high porosity regions are filled while others remain almost unchanged. Thus, mixing-induced precipitation represents a viable mechanism for the infilling of pores in fractured and porous rocks. The simulations also demonstrate that the choice of functional form for specific surface area plays an important role in controlling porosity patterns by influencing both the kinetics of precipitation and the permeability of the porous medium. As specific surface area is currently one of the least constrained parameters in models of porosity evolution, this result highlights the need for future experimental studies in this field of research.     

Modelling Feedback of Chemical Reactions on Flow Fields in Hydrothermal Systems

Coupled reactive transport models of hydrothermal systems provide new insights and deeper understanding of the processes occurring due to fluid flow, heat transfer, solute transport, and chemical reactions. Basic concepts of species transport (diffusion, dispersion, and advection) and chemical precipitation and dissolution reactions are discussed, and five end-member types of reactive transport environments are introduced. One of these reactive transport environments, named ‘reactions within thermal gradients’, is used to demonstrate how free thermal convection can lead to redeposition of minerals and, due to the feedback of reaction on the flow field, a change of the convection pattern. The direct consequence of changing the flow field is a significant variation of the temperature distribution within the modelled area. With the example it is shown how reactive transport simulation can be applied for the detailed study of fossil and recent hydrothermal systems.     

Modeling of non-isothermal multi-component reactive transport in field scale porous media flow systems

A general 2-D finite element multi-component reactive transport code, TRANQUI, was developed, using a sequential iteration approach (SIA). It is well suited to deal with complex real-world thermo-hydro-geochemical problems for single-phase variably water saturated porous media flow systems. The model considers a wide range of hydrological and thermodynamic as well as chemical processes such as aqueous complexation, acid-base, redox, mineral dissolution/precipitation, gas dissolution/ex-solution, ion exchange and adsorption via surface complexation. Under unsaturated conditions only water flow is considered, although gas pressures are allowed to vary in space in a depth-dependent manner specified by the user. In addition to the fully iterative sequential approach (SIA), a sequential non-iterative approach (SNIA), in which transport and chemistry are de-coupled, was implemented and tested. The accuracy and numerical performance of SIA and SNIA have been compared using several test cases. The accuracy of SNIA depends on space and time discretization as well as on the nature of the chemical reactions. The capability of the code to model a real case study in the field is illustrated by its application to the modeling of the hydrochemical evolution of the Llobregat Delta aquitard in northeastern Spain over the last 3500 years during when fresh-water flow from a lower aquifer displaced the native saline aquitard waters. Manzano and Custodio carried out a reactive transport model of this case study by using the PHREEQM code and considering water flow, aqueous complexation, cation exchange and calcite dissolution. Their results compare favorably well with measured porewater chemical data, except for some of the cations. Our code is not only able to reproduce the results of previous numerical models, but leads to computed concentrations which are closer to measured data mainly because our model takes into consideration redox processes in addition to the processes mentioned above. A number of sensitivity runs were performed with TRANQUI in order to analyze the effect of errors and uncertainties on cation selectivities.     

Effects of chemical reactions on density-dependent fluid flow: on the numerical formulation and the development of instabilities

A three-dimensional, reactive numerical flow model is developed that couples chemical reactions with density-dependent mass transport and fluid flow. The model includes equilibrium reactions for the aqueous species, kinetic reactions between the solid and aqueous phases, and full coupling of porosity and permeability changes that result from precipitation and dissolution reactions in porous media. A one-step, global implicit approach is used to solve the coupled flow, transport and reaction equations with a fully implicit upstream-weighted control volume discretization. The Newton–Raphson method is applied to the discretized non-linear equations and a block ILU-preconditioned CGSTAB method is used to solve the resulting Jacobian matrix equations. This approach permits the solution of the complete set of governing equations for both concentration and pressure simultaneously affected by chemical and physical processes. A series of chemical transport simulations are conducted to investigate coupled processes of reactive chemical transport and density-dependent flow and their subsequent impact on the development of preferential flow paths in porous media. The coupled effects of the processes driving flow and the chemical reactions occurring during solute transport is studied using a carbonate system in fully saturated porous media. Results demonstrate that instability development is sensitive to the initial perturbation caused by density differences between the solute plume and the ambient groundwater. If the initial perturbation is large, then it acts as a “trigger” in the flow system that causes instabilities to develop in a planar reaction front. When permeability changes occur due to dissolution reactions occurring in the porous media, a reactive feedback loop is created by calcite dissolution and the mixed convective transport of the system. Although the feedback loop does not have a significant impact on plume shape, complex concentration distributions develop as a result of the instabilities generated in the flow system.     

Evaluation of model complexity and space–time resolution on the prediction of long‐term soil salinity dynamics,western San Joaquin Valley,California

The numerical simulation of long‐term large‐scale (field to regional) variably saturated subsurface flow and transport remains a computational challenge, even with today's computing power. Therefore, it is appropriate to develop and use simplified models that focus on the main processes operating at the pertinent time and space scales, as long as the error introduced by the simpler model is small relative to the uncertainties associated with the spatial and temporal variation of boundary conditions and parameter values. This study investigates the effects of various model simplifications on the prediction of long‐term soil salinity and salt transport in irrigated soils. Average root‐zone salinity and cumulative annual drainage salt load were predicted for a 10‐year period using a one‐dimensional numerical flow and transport model (i.e. UNSATCHEM) that accounts for solute advection, dispersion and diffusion, and complex salt chemistry. The model uses daily values for rainfall, irrigation, and potential evapotranspiration rates. Model simulations consist of benchmark scenarios for different hypothetical cases that include shallow and deep water tables, different leaching fractions and soil gypsum content, and shallow groundwater salinity, with and without soil chemical reactions. These hypothetical benchmark simulations are compared with the results of various model simplifications that considered (i) annual average boundary conditions, (ii) coarser spatial discretization, and (iii) reducing the complexity of the salt‐soil reaction system. Based on the 10‐year simulation results, we conclude that salt transport modelling does not require daily boundary conditions, a fine spatial resolution, or complex salt chemistry. Instead, if the focus is on long‐term salinity, then a simplified modelling approach can be used, using annually averaged boundary conditions, a coarse spatial discretization, and inclusion of soil chemistry that only accounts for cation exchange and gypsum dissolution–precipitation. We also demonstrate that prediction errors due to these model simplifications may be small, when compared with effects of parameter uncertainty on model predictions. The proposed model simplifications lead to larger time steps and reduced computer simulation times by a factor of 1000. Copyright © 2006 John Wiley & Sons, Ltd.     

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

Controls on Ground Water Chemistry in the Central Couloir Sud Rifain,Morocco

Irrigation, urbanization, and drought pose challenges for the sustainable use of ground water in the central Couloir sud rifain, a major agricultural region in north-central Morocco, which includes the cities of Fès and Meknès. The central Couloir is underlain by unconfined and confined carbonate aquifers that have suffered declines in hydraulic head and reductions in spring flow in recent decades. Previous studies have surveyed ground water flow and water quality in wells and springs but have not comprehensively addressed the chemistry of the regional aquifer system. Using graphical techniques and saturation index calculations, we infer that major ion chemistry is controlled (1) in the surficial aquifer by cation exchange, calcite dissolution, mixing with deep ground water, and possibly calcite precipitation and (2) in the confined aquifer and warm springs by calcite dissolution, dolomite dissolution, mixing with water that has dissolved gypsum and halite, and calcite precipitation. Analyses of ²H and ¹⁸O indicate that shallow ground water is affected by evaporation during recharge (either of infiltrating precipitation or return flow), whereas deep ground water is sustained by meteoric recharge with little evaporation. Mechanisms of recharge and hydrochemical evolution are broadly consistent with those delineated for similar regional aquifer systems elsewhere in Morocco and in southern Spain.     

Geochemical evolution of groundwater in hard-rock aquifers of South India using statistical and modelling techniques

ABSTRACT

Multivariate statistical analysis and inverse geochemical modelling techniques were employed to deduce the mechanism of groundwater evolution in the hard-rock terrain of Telangana, South India. Q-mode hierarchical cluster analysis (HCA) and principal component analysis (PCA) were used to extract the hydrogeochemical characteristics and classify the groundwater samples into three principal groups. Use of thermodynamic stability diagrams and inverse geochemical modelling in PHREEQC identified the chemical reactions controlling hydrogeochemistry of each of the groups obtained from statistical analysis. The model output showed that a few phases are governing the water chemistry in this area and the geochemical reactions responsible for evolution of groundwater chemistry along the flow path are (i) dissolution of evaporite minerals (dolomite, halite); (ii) dissolution of primary silicate minerals (albite, anorthite, K-feldspar, biotite); (iii) precipitation of secondary silicate minerals (kaolinite, quartz, gibbsite, Ca-montmorillonite) along with anhydrite and calcite; and (iv) reverse ion exchange processes.     

Experimental simulation of plagioclase diagenesis atP-T conditions of 3.5 km burial depth

Dissolution of plagioclase under the physical conditions at shallow to intermediate burial depths is a prime candidate for secondary porosity generation in feldspathic siliciclastic sediments. The diagenetic behavior of granular aggregates of plagioclase feldspar and quartz has been investigated by experimentation performed in a Bridgeman-type pressure vessel. The experiments, each of two weeks duration, simulated pressure-temperature conditions approximating 3.5 km burial depth. By using a double-acting pore-fluid reservoir, solutions of various chemistries were cycled through samples composed of oligoclase or labradorite feldspar and quartz (90:10 wt% respectively).Scanning electron microscope analysis of the post-experiment samples reveals dissolution features and precipitated products. Dissolution voids of 10 microns occur typically in areas of maximum stress such as crack-tips and grain contacts. Dissolution on a larger scale is exemplified by topographical smoothing of grain su faces. The dissolved species are subsequently reprecipitated as Ca-enriched overgrowths (possibly zeolites) and clays. These precipitates are found individually on the scale of 10 microns and collectively as surface coatings on both feldspar and quartz grains. Atomic absorption spectroscopic analyses of the pore fluid suggest that the fluid chemistry is consistent with the observed experimental precipitates.These experiments show that clay coatings are unnecessary precursors to grain surface dissolution and that the diagenetic precipitation is not mineral selective. Also, the mass transfer of the dissolved species appears to be localized because grains displaying both dissolution and precipitation features are commonplace. Volume changes due to mineral transformation/alteration may increase secondary porosity if the dissolved species produced from dissolution are only partially involved in reprecipitation and the remaining dissolved material is flushed out by the pore fluids. However, if the mass transfer is primarily local then permeability would significantly decrease as precipitates may choke the pore throats.     

MODFLOW/MT3DMS-based reactive multicomponent transport modeling

This paper presents a three-dimensional, MODFLOW/MT3DMS-based reactive multicomponent transport model for saturated porous media. Based on a split-operator technique, the model, referred to as PHT3D, couples the transport simulator MT3DMS and the geochemical modeling code PHREEQC-2. Through the flexible, generic nature of PHREEQC-2, PHT3D can handle a broad range of equilibrium and kinetically controlled reactive processes, including aqueous complexation, mineral precipitation/dissolution, and ion exchange. The diversity of potential applications is demonstrated through simulation of five existing literature benchmarks and a new three-dimensional sample problem. The model might be applied to simulate the geochemical evolution of pristine and contaminated aquifers as well as their cleanup. The latter problem class includes the natural and enhanced attenuation/remediation schemes of a wide range of organic and inorganic contaminants. Processes/reactions not included in the standard PHREEQC-2 database but typical for this type of application (e.g., NAPL dissolution, microbial growth/decay) can be defined and included via the extensible PHREEQC-2 database file.     

The evolution of clay rock/cement interfaces in a cementitious repository for low- and intermediate level radioactive waste

In Switzerland, deep geological storage in clay rich host rocks is the preferred option for low- and intermediate-level radioactive waste. For these waste types cementitious materials are used for tunnel support and backfill, waste containers and waste matrixes. The different geochemical characteristics of clay and cementitious materials may induce mineralogical and pore water changes which might affect the barrier functionality of host rocks and concretes.We present numerical reactive transport calculations that systematically compare the geochemical evolution at cement/clay interfaces for the proposed host rocks in Switzerland for different transport scenarios. We developed a consistent set of thermodynamic data, simultaneously valid for cementitious (concrete) and clay materials. With our setup we successfully reproduced mineralogies, water contents and pore water compositions of the proposed host rocks and of a reference concrete.Our calculations show that the effects of geochemical gradients between concrete and clay materials are very similar for all investigated host rocks. The mineralogical changes at material interfaces are restricted to narrow zones for all host rocks. The extent of strong pH increase in the host rocks is limited, although a slight increase of pH over greater distances seems possible in advective transport scenarios. Our diffusive and partially also the advective calculations show massive porosity changes due to precipitation/dissolution of mineral phases near the interface, in line with many other reported transport calculations on cement/clay interactions. For all investigated transport scenarios the degradation of concrete materials in emplacement caverns due to diffusive and advective transport of clay pore water into the caverns is limited to narrow zones.A specific effort has been made to improve the geochemical setup and the extensive use of solid solution phases demonstrated the successful application of a thermodynamically consistent union of very different materials like hydrated cement and clay phases. A reactive system utilizing a novel solid-solution approach is used, where cation exchange is an intrinsic property of the mineral phase definition. Although such features were not the primary aim of the study, they offer a large potential for studies where ion exchange and changing sorption properties are of interest.     

A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage

CO₂ injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO₂ into the brine. The resulting neutralization will drive further dissolution of both CO₂ and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO₂), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H₂O–CO₂–Na–Cl–CaCO₃ system, so as to model CO₂ injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO₂ plume because the brine below the plume tends to reach high CO₂ concentrations quite rapidly. We conclude that carbonate dissolution needs not to be feared.     

Role of sediment in solute acquisition in the Himalayan glacier meltwater stream,Gangotri glacier,Uttarakhand, India

Low temperature in-stream solute acquisition in a glacial environment with very high suspended sediment is critical for downstream evolution of water chemistry. Present work is carried out on 18 km headwater reach from Gomukh (snout of the Gangotri glacier) to Gangotri along River Bhagirathi, India for understanding the hydrological processes controlling the solute acquisition in the glacial environment. This is the first attempt to conduct dissolution experiments with river bed sediments and meltwater considering different operating variables namely; contact time, seasonality, different sediment particle sizes, different sediment dose, effect of pH, wetting and crushing of bed sediments of the glacial stream. The role of sediment in low temperature solute acquisition process is characterized by sudden release of ions from the sediment in initial few seconds. Equilibrium time was observed to be 600 s (10 min). Further progressive increase in EC was observed from Gomukh to Gangotri, suggesting change in sediment surface characteristics/or source. Higher dissolution was observed from the bed sediments collected in June. It is found that the dissolution increases with increase in sediment doses but decreases with an increase in sediment particle size fraction. Higher solute acquisition was observed from crushed sediment because of an abundance of very fine particles having fresh, aggressive/reactive mineral surfaces which are capable of dissolution. The solute released from wetted sediment is significantly lower than the fresh sediment, which may be attributed to the destruction of microparticles adhering to mineral grains, the removal of fresh reactive surface sites, dissolution of rapidly weathered minerals such as calcite and evolution towards to equilibrium of the solution. Further, higher dissolution was observed with decrease in pH, which may be attributed to the availability of more hydrogen ion concentration of the solution, which favours more solute acquisition from sediment into meltwater.     

PHT3D‐UZF: A Reactive Transport Model for Variably‐Saturated Porous Media

A modified version of the MODFLOW/MT3DMS‐based reactive transport model PHT3D was developed to extend current reactive transport capabilities to the variably‐saturated component of the subsurface system and incorporate diffusive reactive transport of gaseous species. Referred to as PHT3D‐UZF, this code incorporates flux terms calculated by MODFLOW's unsaturated‐zone flow (UZF1) package. A volume‐averaged approach similar to the method used in UZF‐MT3DMS was adopted. The PHREEQC‐based computation of chemical processes within PHT3D‐UZF in combination with the analytical solution method of UZF1 allows for comprehensive reactive transport investigations (i.e., biogeochemical transformations) that jointly involve saturated and unsaturated zone processes. Intended for regional‐scale applications, UZF1 simulates downward‐only flux within the unsaturated zone. The model was tested by comparing simulation results with those of existing numerical models. The comparison was performed for several benchmark problems that cover a range of important hydrological and reactive transport processes. A 2D simulation scenario was defined to illustrate the geochemical evolution following dewatering in a sandy acid sulfate soil environment. Other potential applications include the simulation of biogeochemical processes in variably‐saturated systems that track the transport and fate of agricultural pollutants, nutrients, natural and xenobiotic organic compounds and micropollutants such as pharmaceuticals, as well as the evolution of isotope patterns.     

Advantages of using adaptive remeshing and parallel processing for modelling biodegradation in groundwater

Biodegrading plumes in groundwater are often typified by relatively reactive zones around the fringes and less reactive zones in the core. A high degree of refinement is required at the fringes if a model is to be of use in improving the conceptual understanding of plumes. Two strategies for dealing with the potentially high computational demands are (i) parallel processing, where the workload is shared between multiple processors, and (ii) locally adaptive remeshing, where a refined area of the grid tracks the moving plume fringes through the domain. The partial differential equation toolbox, UG (Unstructured Grids) offers advanced numerical tools including adaptive remeshing, sparse matrix storage schemes, and multigrid solvers. It embraces many of these features within a parallel processing environment. This paper reports on a recent development of UG to simulate field scale reactive biogeochemistry including Monod kinetics, NAPL dissolution, mineral precipitation/dissolution and ion exchange. The non-linear multicomponent reactive transport system is solved with the fully coupled method. Test cases have been used for verification of the new capability. The paper illustrates an application to a 3D field site. It is demonstrated that both adaptive remeshing and parallel processing can improve efficiency and in turn facilitate the incorporation of a more complex set of species and reactions such that understanding of plume processes is enhanced.     

Sampling for isotopic responses in surface waters

This paper considers situations in which stable isotopes may be used as natural tracers of precipitation through to surface waters. Two aspects affecting the applicability of the technique are highlighted: first, the variance through time of isotope concentrations in precipitation, i.e. the isotope input signal, and second, the attenuation or damping of this signal during the transmission of water downwards through the hydrological system. Both factors affect the likelihood of obtaining an isotope response, i.e. a variation of isotope concentrations in a surface water which may be related to variations in the precipitation input. Analysis of precipitation over the Malham area, U.K., reveals large isotopic variations through time. These variations, however, are only poorly correlated with meteorological variables (temperature, precipitation amount, and air mass type). Snowmelt and occluded frontal rainfall are suggested as providing the most reliable ‘spikes’ for an isotopic response at the output in tracing studies. In most hydrological systems, a high degree of signal attenuation is noted. In the Malham area of karst, 57 per cent of the total range of input variation was lost in surface waters, whilst 74 per cent was lost in mobile soil moisture. An isotopic response can only reasonably be expected in a system with rapid throughput, where there is little opportunity for mixing and storage of waters.     

Assessment of radionuclide transport uncertainty in the unsaturated zone of Yucca Mountain

The present study assesses the uncertainty of flow and radionuclide transport in the unsaturated zone at Yucca Mountain using a Monte Carlo method. Matrix permeability, porosity, and sorption coefficient are considered random. Different from previous studies that assume distributions of the parameters, the distributions are determined in this study by applying comprehensive transformations and rigorous statistics to on-site measurements of the parameters. The distribution of permeability is further adjusted based on model calibration results. Correlation between matrix permeability and porosity is incorporated using the Latin Hypercube Sampling method. After conducting 200 Monte Carlo simulations of three-dimensional unsaturated flow and radionuclide transport for conservative and reactive tracers, the mean, variances, and 5th, 50th, and 95th percentiles for quantities of interest (e.g., matrix liquid saturation and water potential) are evaluated. The mean and 50th percentile are used as the mean predictions, and their associated predictive uncertainties are measured by the variances and the 5th and 95th percentiles (also known as uncertainty bounds). The mean predictions of matrix liquid saturation and water potential are in reasonable agreement with corresponding measurements. The uncertainty bounds include a large portion of the measurements, suggesting that the data variability can be partially explained by parameter uncertainty. The study illustrates propagation of predictive uncertainty of percolation flux, increasing downward from repository horizon to water table. Statistics from the breakthrough curves indicate that transport of the reactive tracer is delayed significantly by the sorption process, and prediction on the reactive tracer is of greater uncertainty than on the conservative tracer because randomness in the sorption coefficient increases the prediction uncertainty. Uncertainty in radionuclide transport is related to uncertainty in the percolation flux, suggesting that reducing the former entails reduction in the latter.     

Application of a mixing-ratios based formulation to model mixing-driven dissolution experiments

We address the question of how one can combine theoretical and numerical modeling approaches with limited measurements from laboratory flow cell experiments to realistically quantify salient features of complex mixing-driven multicomponent reactive transport problems in porous media. Flow cells are commonly used to examine processes affecting reactive transport through porous media, under controlled conditions. An advantage of flow cells is their suitability for relatively fast and reliable experiments, although measuring spatial distributions of a state variable within the cell is often difficult. In general, fluid is sampled only at the flow cell outlet, and concentration measurements are usually interpreted in terms of integrated reaction rates. In reactive transport problems, however, the spatial distribution of the reaction rates within the cell might be more important than the bulk integrated value. Recent advances in theoretical and numerical modeling of complex reactive transport problems [De Simoni M, Carrera J, Sanchez-Vila X, Guadagnini A. A procedure for the solution of multicomponent reactive transport problems. Water Resour Res 2005;41:W11410. doi: 10.1029/2005WR004056, De Simoni M, Sanchez-Vila X, Carrera J, Saaltink MW. A mixing ratios-based formulation for multicomponent reactive transport. Water Resour Res 2007;43:W07419. doi: 10.1029/2006WR005256] result in a methodology conducive to a simple exact expression for the space–time distribution of reaction rates in the presence of homogeneous or heterogeneous reactions in chemical equilibrium. The key points of the methodology are that a general reactive transport problem, involving a relatively high number of chemical species, can be formulated in terms of a set of decoupled partial differential equations, and the amount of reactants evolving into products depends on the rate at which solutions mix. The main objective of the current study is to show how this methodology can be used in conjunction with laboratory experiments to properly describe the key processes that occur in a complex, geochemically-active system under chemical equilibrium conditions. We model three CaCO₃ dissolution experiments reported in Singurindy et al. [Singurindy O, Berkowitz B, Lowell RP. Carbonate dissolution and precipitation in coastal environments: Laboratory analysis and theoretical consideration. Water Resour Res 2004;40:W04401. doi: 10.1029/2003WR002651, Singurindy O, Berkowitz B, Lowell RP. Correction to Carbonate dissolution and precipitation in coastal environments: laboratory analysis and theoretical consideration. Water Resour Res 2005;41:W11701. doi: 10.1029/2005WR004433], in which saltwater and freshwater were mixed in different proportions. The integrated reaction rate within the cell estimated from the experiments are modeled independently by means of (a) a state-of-the-art reactive transport code, and (b) the uncoupled methodology of [12, 13], both of which use dispersivity as a single, adjustable parameter. The good agreement between the results from both methodologies demonstrates the feasibility of using simple solutions to design and analyze laboratory experiments involving complex geochemical problems.