Reactive Transport Processes Research Articles

Antibiotics, antibiotic resistance and associated risk in natural springs from an agroecosystem environment.

This study investigates the occurrence, transport, and risks associated to antibiotic residues, antibiotic resistance genes (ARGs) and antibiotic resistant Escherichia coli (AR-E. coli) in eleven natural springs in an agroecosystem environment with intense livestock production, where groundwater nitrate concentration usually sets above 50 mg L-1. Out of 23 multiple-class antibiotics monitored, tetracycline and sulfonamide residues were the most ubiquitous, and they were detected at concentrations ranging from ng L-1 to μg L-1. Five ARGs were monitored, conferring resistance to the antibiotic classes of major use in livestock production. Thus, genes conferring resistance to sulfonamides (sul1 and sul2) and tetracyclines (tetW) as well as a gene proxy for anthropogenic pollution (intI1) were present in most springs. sul1 was the most abundant, with absolute concentrations ranging from 4 × 102 to 5.6 × 106 gene copies L-1 water. AR-E. coli showing resistance to sulfonamides and tetracyclines was also detected, with a prevalence up to approximately 40 % in some sites but with poor correlations with the concentration of antibiotic residues and ARGs. The occurrence of antibiotics, ARGs and AR-E. coli was characterized by large seasonal variations which were mostly associated to both hydrological factors and reactive transport processes. Finally, a risk assessment approach pointed out towards low risk for both the groundwater environment and human health, when spring water is used for direct human consumption, associated with the occurrence of antibiotics, ARGs and AR-E. coli. However, long-term effects cannot be neglected, and proper actions must be taken to preserve groundwater quality.

Two-Dimensional Continuous Model in Bimolecular Reactive Transport

In this work, a continuum 2D model is proposed to study the interaction at the interface of reactive transport processes in porous media. The analysis of the segregation produced by poor reactant homogenization at the poral scale is addressed by a parametric heuristic model that considers the relative gradient of the reacting species involved in the process. The micro inhomogeneities are incorporated by means of longitudinal and transversal mechanical dispersion coefficients. A two-dimensional continuous model for the bimolecular reactive transport is considered where modelling parameters are estimated numerically from experimental data. A competitive effect between segregation and dispersion is observed that is analyzed by means of numerical experiments. The two-dimensional model reproduces properly both the total mass of the product as well as its increase with the velocity of flow and the inhomogeneity of the advanced front. The methodology used is simple and fast, and the numerical results presented here indicate its effectiveness.

A microfluidic chip for geoelectrical monitoring of critical zone processes.

We miniaturize geoelectrical acquisition using advanced microfabrication technologies to investigate coupled processes in the critical zone. We focus on the development of the complex electrical conductivity acquisition with the spectral induced polarization (SIP) method on a microfluidic chip equipped with electrodes. SIP is an innovative detection method that has the potential to monitor biogeochemical processes. However, due to the lack of microscale visualization of the processes, the interpretation of the SIP response remains under debate. This approach at the micrometer scale allows working in well-controlled conditions, with real-time monitoring by high-speed and high-resolution microscopy. It enables direct observation of microscopic reactive transport processes in the critical zone. We monitor the dissolution of pure calcite, a common geochemical reaction studied as an analog of the water-mineral interactions. We highlight the strong correlation between SIP response and dissolution through image processing. These results demonstrate that the proposed technological advancement will provide a further understanding of the critical zone processes through SIP observation.

Pore-scale investigation on mineral dissolution and evolution in hydrological properties of complex porous media with binary minerals

A pore-scale numerical model for reactive transport process based on lattice Boltzmann method is adopted to simulate the mineral dissolution in complex porous media with binary minerals. The effect of binary mineral, solute concentration and dissolution rate on hydrological properties evolution of complex porous media is investigated. Simulation results show that binary minerals could inhibit the mineral dissolution and further alter the temporal evolution trend of related hydrological properties compared to monomineralic porous media. Changes in pore structure of complex porous media could be divided into three stages: slow increase, significant increase and slightly-stable increase stage in succession. A simple model is barely suitable for characterizing the porosity-permeability evolution of the complex porous media. Temporal evolution in reactive specific surface during mineral dissolution could be characterized by the fractal model. Although solute concentration could change the mineral dissolution process, it has no effect on the evolution relationship of hydrological properties between permeability, reactive specific surface and porosity. Mineral dissolution rate would alter the above-mentioned relationships by changing the reactive transport regime.

Pore-scale study of three-phase reactive transport processes in porous media

Coupled three-phase flow and reactive transport processes are widely encountered in many scientific and engineering problems. In the present study, a pore-scale model based on the lattice Boltzmann method is developed to simulate coupled three-phase flow and reactive transport processes. The model is validated by contact angle test of droplets on a curved surface and confined reactive mass transport in a three-phase system. The pore-scale model validated is then employed to study the three-phase reactive transport in channels and porous media. The evolution of the three-phase distribution, the concentration field, and the contact line length are discussed in detail. For a two-channel structure, the result shows that as the viscosity ratio increases, the phase with higher viscosity is more difficult to be displaced. Moreover, as the surface tension force between two certain phases increases, the third phase tends to form a film between the two phases, thus suppressing the reactive transport between the two phases. Finally, pore-scale simulation results of three-phase flow in a two-dimensional porous medium show that as viscosity of the phase to be displaced increases, the recovery rate of the displaced phase decreases, and the displacing phase tends to follow the mechanism of viscous fingering. Finally, while the viscosity of the displaced phase can be reduced due to the existence of the species, the recovery rate does not necessarily increase and sometimes even reduces due to the combined bypass and lubrication effects.

Pore-scale study of mineral dissolution in heterogeneous structures and deep learning prediction of permeability

Reactive transport processes in porous media with dissolution of solid structures are widely encountered in scientific and engineering problems. In the present work, the reactive transport processes in heterogeneous porous structures generated by Monte Carlo stochastic movement are simulated by using the lattice Boltzmann method. Six dissolution patterns are identified under different Peclet and Damkohler numbers, including uniform pattern, hybrid pattern, compact pattern, conical pattern, dominant pattern, and ramified pattern. Particularly, when Peclet and Damkohler numbers are larger than 1, the increase in the heterogeneity rises the chance of preferential channel flow in the porous medium and thus intensifies the wormhole phenomena, leading to higher permeability. The pore-scale results also show that compared with the specific surface area, the permeability is more sensitive to the alteration of the structural heterogeneity, and it is challenging to propose a general formula between permeability and porosity under different reactive transport conditions and structural heterogeneity. Thus, deep neural network is employed to predict the permeability–porosity relationship. The average value of mean absolute percentage error of prediction of 12 additional permeability–porosity curves is 6.89%, indicating the promising potential of using deep learning for predicting the complicated variations of permeability in heterogeneous porous media with dissolution of solid structures.

Reactive Transport Modeling with a Coupled OpenFOAM®-PHREEQC Platform

Reactive transport modeling has established itself as a key player to analyze sophisticated hydro-geochemical interactions that occur over spatiotemporal scales on par with subsurface applications. In this paper, we benchmarked a new reactive transport package—porousMedia4Foam at the continuum scale considering complex and well-established cases available in the reactive transport modeling community. porousMedia4Foam was born by the successful coupling of two open-source packages—OpenFOAM® and PHREEQC. The flow governing equations, transport of species and the evolution of porous media properties are handled by OpenFOAM®, whereas the geochemistry is exclusively handled by PHREEQC. We further demonstrated the capability of using porousMedia4Foam to investigate reactive transport processes considering unstructured meshes. As porousMedia4Foam is an open-source package with included benefits to account for reactive transport processes occurring at various scales—pore, hybrid, and Darcy scales, we believe that porousMedia4Foam opens a new dimension to analyze reactive transport physics for various intriguing subsurface applications.

Pore-Scale Heterogeneities Improve the Degradation of a Self-Inhibiting Substrate: Insights from Reactive Transport Modeling

In situ bioremediation is a common remediation strategy for many groundwater contaminants. It was traditionally believed that (in the absence of mixing-limitations) a better in situ bioremediation is obtained in a more homogeneous medium where the even distribution of both substrate and bacteria facilitates the access of a larger portion of the bacterial community to a higher amount of substrate. Such conclusions were driven with the typical assumption of disregarding substrate inhibitory effects on the metabolic activity of enzymes at high concentration levels. To investigate the influence of pore matrix heterogeneities on substrate inhibition, we use a numerical approach to solve reactive transport processes in the presence of pore-scale heterogeneities. To this end, a rigorous reactive pore network model is developed and used to model the reactive transport of a self-inhibiting substrate under both transient and steady-state conditions through media with various, spatially correlated, pore-size distributions. For the first time, we explore on the basis of a pore-scale model approach the link between pore-size heterogeneities and substrate inhibition. Our results show that for a self-inhibiting substrate, (1) pore-scale heterogeneities can consistently promote degradation rates at toxic levels, (2) the effect reverses when the concentrations fall to levels essential for microbial growth, and (3) an engineered combination of homogeneous and heterogeneous media can increase the overall efficiency of bioremediation.

Analytical solutions for reactive shear dispersion with boundary adsorption and desorption

Surface reactions such as the adsorption and desorption at boundaries are very common for solute dispersion in many applications of chemistry, biology, hydraulics, etc. To study how reversible adsorption affects the transient dispersion, Zhang, Hesse & Wang (J. Fluid Mech., vol. 828, 2017, pp. 733–752) have investigated the temporal evolution of moments using the Laplace transform method. Owing to difficulties introduced by the adsorption–desorption boundary condition, great challenges arise from the inverse Laplace transform: dealing with the singularities by the residue theorem can tremendously increase complexities. This work provides a much simpler analytical method to derive solutions in a more compact form that is valid for the entire range of the reactive transport process. Such a progress demonstrates that the classic framework of separation of variables can be extended and applied to this more general adsorption–desorption condition, based on which higher-order statistics including skewness and kurtosis can be explicitly explored in practice. Also extended is Gill's generalised dispersion model for solute concentration distributions, which can now address the entire transient dispersion characteristics, instead of just applied for the long-time asymptotic reactive process as done previously. Regarding the most classic Taylor dispersion problem, we investigate the influence of the reversible adsorption–desorption on the solute cloud in a tube flow. Not only the transient dispersion characteristics of transverse-average concentration distribution but also those of the bulk, surface and total-average distributions are discussed. We further investigate the influence of initial conditions on the non-uniformity of the transient dispersion over the cross-section.

A pore-scale study for reactive transport processes in double-layer gradient electrode as negative side of a deep eutectic solvent electrolyte-based vanadium-iron redox flow battery

Porous electrodes are critical component of redox flow batteries (RFBs), that decide the fluid, species/charge transport and electrochemical reaction properties during the operation of RFBs. It is a potential way to elevate the performance of RFBs by applying the porous electrodes with gradient pore structures. However, it is still lack of a suitable numerical model to understand the reactive transport processes in the heterogeneous pore structures, thus to design and develop the optimal RFB electrodes. Using a lattice Boltzmann model, this work studies the pore-scale reactive transfer behaviors in a double-layer gradient electrode assembling as the negative side of deep eutectic solvents electrolyte-based vanadium-iron RFB, that consists of a graphite felt near the current collector side and a carbon paper near the membrane side. The numerical results reveal the galvanostatic discharging performance of double-layer electrode under the different electrolyte feeding modes and flow rates. Comparing with full flow-through feeding mode, the interdigitated flow feeding mode would give rise to serious inhomogeneity of electrolyte flowing at the low flow rate condition, thereby resulting in the sluggish convective mass transfer performance near the membrane side. Moreover, the total power loss of double-layer electrode is higher than that of the mono-layer carbon paper electrode within the low flow rate range. Conversely, the double-layer electrode with interdigitated flow mode can achieve the lowest total power loss than mono-layer electrodes at the high inlet flow rate. This work provides a new pathway to investigate the RFB power performance effected by the gradient porous structures of electrodes.

Thermochemical energy conversion behaviour in the corrugated heat storage unit with porous metal support

Because of the low charging temperature, salt hydrate-based adsorption thermochemical energy storage (TCES) is currently a significant technology that promises long-term energy storage. A corrugated-shaped heat storage unit (HSU) in which embedding porous metal bracket is proposed in this work to enhance heat transfer between the thermochemical material (TCM) wrapped inside and the heat fluid transfer (HTF) in the external corrugated channel. The thermo-chemical conversion behaviours, including reactive transport processes during dehydration (charging) and hydration (discharging), as well as the influence of parameters, are comprehensively investigated. The numerical results indicate that increasing the HTF temperature facilitates the charging process while the discharging can be promoted by decreasing reaction bed temperature. The time required to complete charging and discharging for the reference cases is 2990 s and 5700 s. For both charging and discharging powers of reactive bed, the values dramatically surge in a short time and then gradually decrease, with the maximum powers of 2638 W and 1866 W, respectively. Boosting evaporation temperature (water vapour pressure) accelerates hydration while the effect of condensation temperature on dehydration is insignificant. The reaction period can be further shortened by heightening the thermal conductivity of TCM, and the porosity also has a distinct influence on the reaction. Compared to the storage unit of a straight external channel without a metal bracket inside, this heat storage module saves 34% and 23% in charging and discharging times. The results of this work provide insights into the prediction and improvement of thermochemical conversion behaviours.

A Multicomponent Reactive Transport Model for Integrated Surface‐Subsurface Hydrology Problems

AbstractDespite the widespread use of integrated hydrology models in a variety of applications, consideration of multicomponent reactive transport is still not common. The implementation of these processes requires coupling transport at the surface‐subsurface interface and efficient solution of the non‐linear geochemical model that is consistent with the integrated hydrology solution. The Advanced Terrestrial Simulator provides a flexible multiphysics framework that facilitated this process. In this work, the integrated reactive transport process kernel (PK) was weakly coupled to the integrated hydrology PK. In turn, integrated transport and reactions were coupled using an operator splitting approach. This splitting enabled an explicit solution of the integrated transport problem, including a novel algorithm to calculate exchange fluxes across the surface‐subsurface interface and a point‐by‐point solution of the geochemical problem. Geochemical capabilities were added using well‐established external codes, but rather than using a custom interface to each, a generic interface was used that clearly specifies the variables and operations used by the chemistry PK. The implementation is demonstrated with two example simulations: transport of a tracer in a soil column as it saturates over time and water ponds on the surface and reactive transport in a hillslope driven by successive wet‐dry cycles that result in infiltration, runoff and exfiltration processes.

Pore-Scale Mechanisms of Solid Phase Emergence During DNAPL Remediation by Chemical Oxidation.

In situ chemical oxidation (ISCO) has proven successful in the remediation of aquifers contaminated with dense nonaqueous phase liquids (DNAPLs). However, the treatment efficiency can often be hampered by the formation of solids or gas, reducing the contact between remediation agents and residual DNAPLs. To further improve the efficiency of ISCO, fundamental knowledge is needed about the complex multiphase flow and reactive transport processes as new solid and fluid phases emerge at the microscale. Here, via microfluidic experiments, we study the pore-scale dynamics of trichloroethylene degradation by permanganate. We visualize how the remediation evolves under the influence of solid phase emergence and explore the roles of injection rate, oxidant concentration, and stabilization supplement. Combining image processing, pressure analysis, and stoichiometry calculations, we provide comprehensive descriptions of the oxidant concentration-dependent growth patterns of the solid phase and their impact on the remediation efficiency. We further corroborate the stabilization mechanism provided by phosphate supplement, which is effective in inhibiting solid phase generation and thus highly beneficial for the oxidation remediation. This work elucidates the pore-scale mechanisms during remediation of chlorinated solvents with a particular context in the solid phase production and the associated effects, which is of general significance to understanding various processes in natural and engineered systems involving solid phase emergence or aggregation phenomena, such as groundwater and soil remediation.

Pore-scale study of effects of relative humidity on reactive transport processes in catalyst layers in PEMFC

High surface area carbon (HSC) particles can be adopted to increase the specific surface area of catalyst layer (CL) in proton exchange membrane fuel cells. Relative humidity (RH) has a significant effect on the Pt activity inside HSC particles, and the underlying mechanisms need to be further investigated. In this study, a pore-scale model considering the effects of RH on the reactive transport processes inside the CLs is developed. Two kinds of liquid water distributions affected by the RH, including capillary condensation in pores and ultra-thin liquid film on Pt surface, are considered. The liquid water distribution, Pt activity and local oxygen transport resistance (Rlocal) under different RH are studied in detail. It is found that as RH increases from 0.3 to 1.0, the condensed water in micropores of HSC particles increases, resulting in an increase in reactive surface area by about 43 %. Combined effect of the RH, Pt loading, I/C ratio and different kinds of carbon particles is investigated. It is found that due to the lack of sufficient reaction sites, compared with that under a high Pt loading, Rlocal under a low Pt loading is more sensitive to the RH. Besides, since the Pt activity inside HSC particles depends on the condensed water, the Rlocal of HSC particles is more sensitive to the RH than solid carbon particles. Finally, the Rlocal at low ionomer content is more sensitive to RH due to low ionomer coverage on Pt particles. The present study provides a pore-scale model for investigating the coupled effects of RH and CL porous structures on local transport processes, and can facilitate the optimization of CL nanoscale structures for better cell performance.

Global random walk solvers for reactive transport and biodegradation processes in heterogeneous porous media

Flow and multicomponent reactive transport in saturated/unsaturated porous media are modeled by ensembles of computational particles moving on regular lattices according to specific random walk rules. The occupation number of the lattice sites is updated with a global random walk (GRW) procedure which spreads the particles from a lattice site with computational costs comparable to those for a single random walk step in sequential procedures. To cope with the nonlinearity and the degeneracy of the Richards equation the GRW flow solver uses linearization techniques similar to the L-scheme developed in finite element/volume approaches. Numerical schemes for reactive transport, coupled with the flow solver via numerical solutions for saturation and water flux, are implemented in splitting procedures. Diffusion–advection steps are solved by GRW algorithms using either biased or unbiased random walk probabilities. Since the number of particles in GRW simulations can be as large as the number of molecules involved in chemical reactions, one avoids the cumbersome problem of rescaling particle densities to approximate concentrations. Reaction steps are therefore formulated in terms of concentrations, as in deterministic approaches. The numerical convergence of the new schemes is demonstrated by comparisons with manufactured analytical solutions. Coupled flow and reactive transport problems of contaminant biodegradation described by the Monod model are further solved and the influence of flow nonlinearity/degeneracy and of the spatial heterogeneity of the medium is investigated numerically.

Three-dimensional lattice Boltzmann simulation of reactive transport and ion adsorption processes in battery electrodes of cation intercalation desalination cells

Cation intercalation desalination (CID) has gained great popularity in the field of water desalination because of its excellent desalination performance. Due to lack of understanding of the relationship between electrode microstructures and reactive adsorption processes in CIDs, the further development of high-performance CID electrodes has been hindered. To this end, the influences of electrode microstructures on the desalination performance of CID cells were investigated from the pore-scale level in this work. The three-dimensional microstructures of porous electrodes are first reconstructed by an improved random generation method. Based on the reconstructed porous electrodes, the flow, mass transfer and intercalation reaction processes under the constant current are simulated using the lattice Boltzmann method. The effects of applied current density, porosity and size of active particles on the change of liquid-phase sodium concentration and Na-intercalated degree in the solid phase are evaluated. The simulation results show that increasing the current density can accelerate the ion intercalation and desalination rates. During the desalination, the ion concentration is unevenly distributed in the pores of porous electrodes, and the intercalation degrees are different along the electrode thickness direction and in the particle radial direction. The increase of porosity can alleviate the concentration polarization of liquid-phase sodium ion and reduce the difference of particle intercalation degree between the front- and back-sides of the electrode. In addition, the increase of porosity can accelerate the desalination process, but cannot improve the total salt removal. Reducing particle size can shorten the time for particles to reach the sodium-rich state, but it can aggravate the polarization of sodium ion concentration in the liquid phase at both ends of the electrode. This work reveals the ion intercalation behavior in the CID and its relationship with the electrode microstructures, and may provide useful information for the design and research of CID.

Pore-scale simulation of two-phase flow and oxygen reactive transport in gas diffusion layer of proton exchange membrane fuel cells: Effects of nonuniform wettability and porosity

Enhancing oxygen transport and reducing water flooding in the gas diffusion layer (GDL) of proton exchange membrane fuel cells are important for improving cell performance. In this study, a pore-scale model based on the lattice Boltzmann method is proposed, which considers two-phase flow, oxygen diffusion and electrochemical reaction in the GDL. The invasion speed of the water into the GDL is determined by the water generation rate and correspondingly the oxygen consumption rate. The model is then adopted to study effects of wettability and porosity distribution on the liquid water saturation, oxygen concentration and current density. The results demonstrate that while reducing the total saturation in the GDL is important, decreasing the local saturation near the microporous layer (MPL)/GDL interface is also crucial for enhancing cell performance. It is found that GDL with locally enhanced hydrophobicity at the MPL/GDL interface or gradually increased porosity from the GDL bottom to the GDL top can improve cell performance. Particularly, by delicately designing the GDL porosity, the current density can be considerably increased by 201%. The developed pore-scale model provides a useful tool for understanding the underlying multiphase reactive transport processes in GDL and designing the microscopic structures of GDL.

Chemical and Reactive Transport Processes Associated with Hydraulic Fracturing of Unconventional Oil/Gas Shales.

Hydraulic fracturing of unconventional oil/gas shales has changed the energy landscape of the U.S. Recovery of hydrocarbons from tight, hydraulically fractured shales is a highly inefficient process, with estimated recoveries of <25% for natural gas and <5% for oil. This review focuses on the complex chemical interactions of additives in hydraulic fracturing fluid (HFF) with minerals and organic matter in oil/gas shales. These interactions are intended to increase hydrocarbon recovery by increasing porosities and permeabilities of tight shales. However, fluid-shale interactions result in the dissolution of shale minerals and the release and transport of chemical components. They also result in mineral precipitation in the shale matrix, which can reduce permeability, porosity, and hydrocarbon recovery. Competition between mineral dissolution and mineral precipitation processes influences the amounts of oil and gas recovered. We review the temporal/spatial origins and distribution of unconventional oil/gas shales from mudstones and shales, followed by discussion of their global and U.S. distributions and compositional differences from different U.S. sedimentary basins. We discuss the major types of chemical additives in HFF with their intended purposes, including drilling muds. Fracture distribution, porosity, permeability, and the identity and molecular-level speciation of minerals and organic matter in oil/gas shales throughout the hydraulic fracturing process are discussed. Also discussed are analysis methods used in characterizing oil/gas shales before and after hydraulic fracturing, including permeametry and porosimetry measurements, X-ray diffraction/Rietveld refinement, X-ray computed tomography, scanning/transmission electron microscopy, and laboratory- and synchrotron-based imaging/spectroscopic methods. Reactive transport and spatial scaling are discussed in some detail in order to relate fundamental molecular-scale processes to fluid transport. Our review concludes with a discussion of potential environmental impacts of hydraulic fracturing and important knowledge gaps that must be bridged to achieve improved mechanistic understanding of fluid transport in oil/gas shales.

Emergent Behavior at the Calcite–Water Interface during Reactive Transport in a Simple Microfluidic Channel

Geochemical reactive transport processes in natural mineral–fluid systems may produce a wide array of emergent phenomena that are difficult to predict from basic principles and to reproduce in model systems. Here, we present experimental results obtained from a simple microfluidic system with which we explored the consequences of reacting the calcite (104) cleavage surface with an acidic Pb-bearing solution (pH = 3.5, [Pb]total = 5 mM) as a function of flow rate. This system is relevant to passive remediation systems for Pb-rich acid mine drainage. We observed periodic banding in the amounts of Pb sorption at flow velocities ≥926 μm s–1, where the band spacing was spatially correlated with the amount of calcite dissolution and the development of micropyramidal topography on the calcite (104) surface. The equivalent coverage of Pb deposited in these Pb-rich bands was at least several monolayers per unit cell, yet there was no evidence for precipitation of any secondary Pb phase implying incorporation of Pb within the near-surface calcite lattice. We also observed spatial variations in nucleation and growth of euhedral secondary Pb-carbonate minerals hydrocerusite and cerussite at flow rates ≤278 μm s–1. These findings demonstrate potential for exploiting the rich phenomenology afforded by the interplay among transport phenomena and chemical kinetics in experimental systems designed to yield deeper insights into geochemical self-organization.

Multi-scale random walk models for reactive transport processes in fracture-matrix systems

Random walk methods are particularly well suited for modeling (anomalous) transport processes in complex systems, from heterogeneous porous domains to fractured rocks. Taking full advantage of their multi-scale attributes, these methods can be integrated into multi-scale modeling strategies where they are used for (i) performing small-scale simulations with a high level of description of the heterogeneities, (ii) defining statistical functions that describe these heterogeneities at a larger scale, and (iii) providing upscaled descriptions of the processes while taking into account the impact of the small-scale heterogeneities. In this work, we define such a strategy considering (i) structural heterogeneities with heterogeneous porosity fields incorporated into fracture-matrix systems and (ii) the reactivity of the system with chemical reactions that are not restricted to linear first-order reactions as it is the case in existing upscaled formulations. To this end, we develop two new modeling methods: the Reactive-Time Domain Random Walk (R-TDRW) and Upscaled Reactive TDRW (UR-TDRW) approaches at small and large scale, respectively. The numerical methods and multi-scale strategy are presented with a general formulation and applied to single-species transport and reaction in fracture-matrix systems. We analyze the impact of different levels of structural heterogeneities, and the impact of the reactivity, on the breakthrough curves computed at both scales and on the statistical functions that are used in the multi-scale strategy. This strategy is validated by demonstrating the good agreement between the results obtained at different scales, showing promising applications for future work in large-scale fracture networks.