Reactive Transport Research Articles

The 34S/32S homogeneity of Chemical Vapor Transport (CVT) Reaction-synthesized pyrites

Abstract The Chemical Vapor Transport (CVT) Reaction is an important and efficient method of synthesizing pyrite crystals. CVT-grown pyrites have been comprehensively investigated for physical properties and elemental chemical compositions. However, the isotopic compositions have not been investigated. In this study, four series of pyrite crystals (PY3, PY4, PY5, and PY6) were synthesized using the CVT method, with PY5 undoped and the others doped with nickel. The synthesized crystals were characterized qualitatively with confocal laser Raman microspectroscopy and quantitatively by EMPA, LA-ICP-MS, SIMS, and IRMS. The synthetic products are irregular polycrystalline aggregates or cubic and octahedral monocrystals, with characteristic Raman bands at ~344 cm–1, ~380 cm–1/377 cm–1, ~427 cm–1/430 cm–1, and S/Fe weight and atomic ratios of 1.15–1.17 and 2.01–2.04, respectively, indicative of pyrite. The pyrites contain traces of inevitable impurities such as Si and Br. The nickel contents of Ni-doped pyrites are heterogeneous, 39–27 300 ppm for PY3, 24–21 700 ppm for PY4, and 57–2610 ppm for PY6. By comparison, the δ34S values obtained by SIMS are relatively homogeneous (PY3 = 17.3 ± 0.9‰, PY4 = 17.7 ± 0.8‰, PY5 = 17.9 ± 0.8‰, PY6 = 17.7 ± 0.6‰, ±2SD), and are consistent with IRMS δ34S values (17.8 ± 0.2‰ for PY3, 18.3 ± 0.9‰ for PY4, 18.2 ± 0.3‰ for PY5, 18.1 ± 0.1‰ for PY6, ±2SD). The homogeneity of 34S/32S suggests that CVT has the potential to synthesize reference materials for the determination of sulfur isotopic composition of pyrite using in situ techniques. Additionally, we also investigated the matrix effects of nickel in pyrite on the measurement of 34S/32S by SIMS, and a preliminary equation of Δ34S (‰) = –0.59 × Ni (wt%)0.27 (R2 = 0.3), where Δ34S is the discrepancy between in situ and bulk δ34S values, was derived for calibration.

Illuminating the “Invisible”: Substantial Deep Respiration and Lateral Export of Dissolved Carbon From Beneath Soil

AbstractDissolved organic and inorganic carbon (DOC and DIC) influence water quality, ecosystem health, and carbon cycling. Dissolved carbon species are produced by biogeochemical reactions and laterally exported to streams via distinct shallow and deep subsurface flow paths. These processes are arduous to measure and challenge the quantification of global carbon cycles. Here we ask: when, where, and how much is dissolved carbon produced in and laterally exported from the subsurface to streams? We used a catchment‐scale reactive transport model, BioRT‐HBV, with hydrometeorology and stream carbon data to illuminate the “invisible” subsurface processes at Sleepers River, a carbonate‐based catchment in Vermont, United States. Results depict a conceptual model where DOC is produced mostly in shallow soils (3.7 ± 0.6 g/m2/yr) and in summer at peak root and microbial respiration. DOC is flushed from soils to the stream (1.0 ± 0.2 g/m2/yr) especially during snowmelt and storms. A large fraction of DOC (2.5 ± 0.2 g/m2/yr) percolates to the deeper subsurface, fueling deep respiration to generate DIC. DIC is exported predominantly from the deeper subsurface (7.1 ± 0.4 g/m2/yr, compared to 1.3 ± 0.3 g/m2/yr from shallow soils). Deep respiration reduces DOC and increases DIC concentrations at depth, leading to commonly observed DOC flushing (increasing concentrations with discharge) and DIC dilution patterns (decreasing concentrations with discharge). Surprisingly, respiration processes generate more DIC than weathering in this carbonate‐based catchment. These findings underscore the importance of vertical connectivity between the shallow and deep subsurface, highlighting the overlooked role of deep carbon processing and export.

Does water transparency control the banding in shallow water iron formations?

Abstract Iron formations (IFs) are marine chemical sediments that are conined to the Precambrian rock record and provide unique insights into the co-evolution of the atmosphere-hydrosphere and biosphere through almost three billion years of Earth’s history. IFs commonly appear throughout the Archaean until the Palaeoproterozoic ca. 1.8 billion years ago and re-appear during the “Snowball Earth” epoch in the Neoproterozoic. The formation and deposition mechanism(s) of IFs are, however, still incompletely understood, hindering unique interpretations of palaeoenvironments. Many IFs are banded iron formations (BIFs) with layer thickness of alternating Fe- and Si-rich layers ranging over several orders of magnitude from the nanometre to the metre scale. A second textural type, so called granular iron formations (GIFs) that form above storm wave base become widespread in the Palaeoproterozoic. Understanding the fundamental mechanisms that are responsible for the textural types and the periodicity of banding in BIFs is crucial to link these features to the environmental and geochemical evolution of the Earth. We here provide a conceptual model that highlights the role of changing light conditions and water transparency for Iron Formation (IF) precipitation. We show that the model is particularly feasible for IFs deposited in shallow waters but may also be applicable for some IFs deposited in deeper water settings. The model builds on other primary Banded Iron Formation (BIF) precipitation models postulating that Fe(III)-(oxyhydr)oxide production can be dominated by anoxygenic photoautotrophic Fe2+-oxidising bacteria. These so called photoferrotrophs are adapted to very low light levels corresponding to about 1% of the light level required by oxygen-producing phototrophs allowing them to thrive deep down in the water column. The depth of Fe(III)-(oxyhydr)oxide production is mainly controlled by water turbidity which controls how deep photosynthetically available radiation (PAR) penetrates the water column. Eutrophic conditions result in relatively shallow Fe(III)-(oxyhydr)oxide production depth due to turbidity either induced by the biomass itself and/or by particles that are actively or passively produced by microorganisms (e.g., Fe(III) and Mn(IV)-(oxyhydr)oxides, sulphides), triggering the formation of Fe-rich bands. During oligotrophic stages, Fe(III)-(oxyhydr)oxides are only produced relatively deep down in the water column, so that only silica-rich bands form in the Fe(III)-(oxyhydr)oxide free upper water column. Reactive transport modelling adopted from Ozaki et al., (2019) shows that besides upwelling and nutrient supply, alternating Fe(III) production depth is mainly associated with changing light conditions as a result of water transparency. Periodicities reflected by alternating Fe- and Si-rich bands in IFs in our model can thus be associated with: (1) nutrient supply patterns; (2) additional sources of turbidity in the water column such as Fe(III) and Mn(IV) oxide particles, sulphides, and wind-blown silicate particles; or (3) formation and clearing of organic haze in the atmosphere. One or all of these reasons for low light conditions seem to become more important in the Palaeoproterozoic (<2.4 Ga) and could be partly responsible for the more widespread occurrences of shallow marine granular IFs relative to former epochs, which is often assigned to the gradual oxidation of the ocean. Our model shows that variable water transparency should be considered as additional factor for IF deposition especially for shallow marine settings. This model also reasonably explains the prominent layering in BIFs as syn-depositional feature.

Pore‐Scale Modeling of Reactive Transport with Coupled Mineral Dissolution and Precipitation

AbstractWe present a new pore‐scale model for multicomponent advective‐diffusive transport with coupled mineral dissolution and precipitation. Both dissolution and precipitation are captured simultaneously by introducing a phase transformation vector field representing the direction and magnitude of the overall phase change. An effective viscosity model is adopted in simulating fluid flow during mineral dissolution‐precipitation that can accurately capture the velocity field without introducing any empirical parameters. The proposed approach is validated against analytical solutions and interface tracking simulations in simplified structures. After validation, the proposed approach is employed in modeling realistic rocks where mineral dissolution and precipitation are dominant at different locations. We have identified three regimes for mineral dissolution‐precipitation coupling: (a) compact dissolution‐precipitation where dissolution is dominant near the inlet and precipitation is dominant near the outlet, (b) wormhole dissolution with clustered precipitation where dissolution generates wormholes in the main flow paths and precipitation clogs the secondary flow paths, and (c) dissolution dominant where all solid grains are gradually dissolved. In the three regimes, the proposed approach provides reliable porosity‐permeability relationships that cannot be described well by traditional macroscale models. We find that the permeability can increase while the overall porosity decreases when the main flow paths are expanded by dissolution and adjacent pore spaces are clogged by precipitation.

Chemical Transport Reactions and Simulation of the Behavior of Various Ceramics in the T-11M Tokamak with Experimental Confirmation on Electrical Porcelain

Chemical Transport Reactions and Simulation of the Behavior of Various Ceramics in the T-11M Tokamak with Experimental Confirmation on Electrical Porcelain

Impact of thermodynamics and kinetics on the carbon capture performance of the amine-based CO2 capture system

Solvent-based CO2 capture is a commonly employed post-combustion technique in processes involving absorber-stripper columns. This study focused on computer simulations with equilibrium- and rate-based modeling of CO2 capture using the amine solvents 2-amino-2-methyl-1-propanol (AMP), diethanolamine (DEA), and methyl diethanolamine (MDEA) and thermodynamic methods involving electrolyte NRTL models. The objective of this study was to understand the impacts of rate-based modeling, the type of amine, and thermodynamic methods on carbon capture. Within this study, the amine-based CO2 capture process from coal-power plant flue gas was studied using Aspen Plus modeling. Simulations were also conducted to determine the impact of thermodynamics and kinetics on the CO2 capture performance of the system. The results were analyzed on the basis of captured CO2 according to the solvents and models. The equilibrium approach was mostly invalid because of the oversimplified ideal stage assumptions through the column. The lowest carbon capture capacity was obtained with MDEA, while DEA yielded the best results. A sensitivity analysis with rate-based modeling showed the significant impact of the inlet CO2 composition. The amine-based CO2 capture process simulation included solution chemistry, electrolyte thermodynamics, rigorous transport property modeling, reaction kinetics, and rate-based multistage simulation, which could be applicable to different solvent systems.

Two Film Approach to Continuum Scale Mixing and Dispersion with Equilibrium Bimolecular Reaction

Reliable reactive transport models require careful separation of mixing and dispersion processes. Here we treat displacing and displaced fluids as two separate fluid phases and invoke Whitman’s classical two-film theory to model mass transfer between the two phases. We use experimental data from Gramling’s bimolecular reaction experiment to assess model performance. Gramling’s original model involved just three coupled PDEs. In this context, our new formulation leads to a set of seven coupled PDEs but only requires the specification of two extra parameters, associated with the mass transfer coefficient and its dependence on time. The two film mass transfer model provides a simple and theoretically based method for separating mixing from dispersion in Eulerian continuum-scale methods. The advantage of this approach over existing methods is that it enables the simulation of equilibrium chemical reactions without having to invoke unrealistically small reaction rate coefficients. The comparison with Gramling’s experimental data confirms that our proposed method is suitable for simulating realistic and complicated bimolecular reaction behaviour. However, further work is needed to explore alternative methods for avoiding the need of a time-dependent mass transfer rate coefficient.

Stochastic 1-D reactive transport simulations to assess silica and carbonate phases during the CO2 reinjection process in metasediments

Stochastic 1-D reactive transport simulations to assess silica and carbonate phases during the CO2 reinjection process in metasediments

Heat and Mass Transfer Model for a Counter-Flow Moving Packed-Bed Oxidation Reactor/Heat Exchanger

Abstract Particle-based thermochemical energy storage (TCES) through metal oxide redox cycling is advantageous compared to traditional sensible and latent heat storage (SHS and LHS) due to its higher operating temperature and energy density, and the capability for long-duration storage. However, overall system performance also depends on the efficiency of the particle-to-working fluid heat exchangers (HXs). Moving packed-bed particle-to-supercritical CO2 (sCO2) HXs have been extensively studied in SHS systems. Integrating the oxidation reactor (OR) for discharging with a particle-to-sCO2 HX is a natural choice, for which detailed analysis is needed for OR/HX design and operation. In this work, a 2D continuum heat and mass transfer model coupling transport phenomena and reaction kinetics is developed for a shell-and-plate moving-bed OR/HX. For the baseline design, the model predicted ∼75% particle bed extent of oxidation at the channel exit, yielding a total heat transfer rate of 16.71 kW for 1.0 m2 heat transfer area per channel, while the same design with inert particles (SHS only) gives only 4.62 kW. A parametric study was also conducted to evaluate the effects of particle, air, and sCO2 flowrates, channel height and width, and average particle diameters. It is found that the respective heat transfer rate and sCO2 outlet temperature can approach ∼25 kW and >1000 °C for optimized designs for the OR/HX. The present model will be valuable for further OR/HX design, scale-up, and optimization of operating conditions.

Comprehensive analysis on the combined effects of reaction kinetics and heat transfer on biomass pyrolysis

The current study links the heat transport phenomena and reaction kinetics when the pyrolysis was occurring of sugarcane bagasse (SCB) biomass. A thermogravimetric analyzer was used to conduct a kinetic research on the pyrolysis of biomass in a nitrogen atmosphere, covering a heating rate range of 10–40 °C/min. The thermogravimetric studies (TGA) allowed for the differentiation of three stages associated with the breakdown of hemicellulose, cellulose, and lignin. Using three first-order processes and the Arrhenius theory, the activation energy and pre-exponential factor were determined.Three important components of biomass—lignin, hemicellulose, and cellulose—were assumed to respond independently and in parallel in the kinetics model. Additionally, the transport characteristics of each component were assessed using their respective kinetic values and other thermo-physical characteristics. The regulating mechanism was then anticipated by the heat transfer map for three elements with different particle sizes. The transfer qualities were mainly influenced by particle size, at a crucial dimension dictating the shift in the system for several parts.

Tellurium Transport and Enrichment in Volcanogenic Massive Sulfide Deposits: Numerical Simulations of Vent Fluids and Comparison to Modern Sea-Floor Sulfides

Abstract Volcanogenic massive sulfide deposits may represent a significant future source of Te, which is a critical element important for the green energy transition. Tellurium is enriched in these settings by up to 10,000 times over its crustal abundance, indicating that fluids in sea-floor hydrothermal systems may transport and precipitate Te. The major element composition of these hydrothermal fluids is controlled by fluid-rock interaction and is well documented based on experimental, modeling, and natural studies; however, controls on Te mobility are still unknown. To better understand Te enrichment in this deposit type, numerical simulations of the mafic-hosted Vienna Woods and the felsic-hosted Fenway sea-floor vents in the Manus basin were performed to predict Te mobility in modern sea-floor hydrothermal vent fluids and Te deposition during sulfide formation. These simulations demonstrate that the mobility of Te in sea-floor hydrothermal systems is primarily controlled by fluid redox and temperature. Tellurium mobility is low in reduced hydrothermal fluids, whereas mobility of this metal is high at oxidized conditions at temperatures above 250°C. Numerical simulations of the reduced vent fluids of the mafic-hosted Vienna Woods site at the back-arc spreading center in the Manus basin yielded Te concentrations as low as 0.2 ppt. In contrast, the more oxidized model fluids of the felsic-hosted Fenway site located on Pual Ridge in the eastern Manus basin contain 50 ppt Te. The models suggest that Te enrichment in these systems reflects rock-buffer control on oxygen fugacity, rather than an enriched source of Te. In fact, the mafic volcanic rocks probably contain more Te than felsic volcanic rocks. The association of elevated Te contents in the felsic-hosted Fenway system likely reflects magmatic volatile input resulting in lower pH and higher Eh of the fluids. More generally, analysis of sulfide samples collected from modern sea-floor vent sites confirms that redox buffering by the host rocks is a first-order control on Te mobility in hydrothermal fluids. The Te content of sulfides from sea-floor hydrothermal vents hosted by basalt-dominated host rocks is generally lower than those of sulfides from vents located in felsic volcanic successions. Literature review suggests that this relationship also holds true for volcanogenic massive sulfides hosted in ancient volcanic successions. Results from reactive transport simulations further suggest that Te deposition during sulfide formation is primarily temperature controlled. Modeling shows that tellurium minerals are coprecipitated with other sulfides at high temperatures (275°–350°C), whereas Te deposition is distinctly lower at intermediate (150°–275°C) and low temperatures (100°–150°C). These predictions agree with geochemical analyses of sea-floor sulfides as Te broadly correlates positively with Cu and Au enrichment in felsic-hosted systems. The findings of this study provide an important baseline for future studies on the behavior of Te in hydrothermal systems and the processes controlling enrichment of this critical mineral in polymetallic sulfide ores.

Numerical Simulation of Chemical Reactions’ Influence on Convective Heat Transfer in Hydrothermal Circulation Reaction Zones

Chemical reactions, mineral diffusion, and deposition are pivotal in understanding the mechanisms of mineral deposition and the formation of seafloor sulfides in the hydrothermal circulation process. To understand the formation process of anhydrite in submarine hydrothermal systems, a computational model that combined component transport and chemical reactions was established and simulated using the mass transport model. The deposition rate of calcium sulfate was defined, and the effects of factors such as porosity, ion concentration, and inflow velocity on the temperature field in the reaction zone were thoroughly investigated. The distribution of temperature, porosity, and velocity during the reaction process was obtained, allowing for the identification of the chemical reaction patterns of certain ions in the early stages of hydrothermal activity. The simulation revealed the occurrence of biochemical reactions between two types of ions, leading to their deposition on the solid framework of a porous medium. With the increase in inflow velocity and solute concentration, the average porosities of the porous medium decreased by 0.495% and 0.468%, respectively, which consequently altered the structure of the rock. Such findings contribute to the inference of formation and extinction mechanisms of seafloor crusts and hydrothermal chimneys.

Reactive direct simulation Monte Carlo modeling of gas reactive transport in three dimensional porous fibrous media across rarefied to continuum regimes

Gas flow in complex porous media can vary across rarefied to continuum regimes depending on the characteristic size of porous media. To study the gas reactive transport process in three dimensional porous fibrous media across rarefied to continuum regimes, a comprehensive reactive direct simulation Monte Carlo model coupling with heat conduction and radiation model as well as reaction process is proposed. The results calculated by the proposed model are verified to fit well with those obtained using analytical model and experimental data. The “inlet” effect promoting the skeleton temperature is found. There are existing competitions between the heat conduction, reaction rate and convection, radiation process. The temperature of porous fibrous media skeleton increases with the catalyst coverage, and decreases with increase of Knudsen number. When the proportion of hydrogen increases, the increase in the temperature of the porous fibrous media skeleton is initially rapid and then gradual. These studies help to deeply understand the chemical reaction mechanism in porous media across rarefied to continuum regimes.

Molecular Dynamics Simulation of Complex Reactivity with the Rapid Approach for Proton Transport and Other Reactions (RAPTOR) Software Package.

Simulating chemically reactive phenomena such as proton transport on nanosecond to microsecond and beyond time scales is a challenging task. Ab initio methods are unable to currently access these time scales routinely, and traditional molecular dynamics methods feature fixed bonding arrangements that cannot account for changes in the system's bonding topology. The Multiscale Reactive Molecular Dynamics (MS-RMD) method, as implemented in the Rapid Approach for Proton Transport and Other Reactions (RAPTOR) software package for the LAMMPS molecular dynamics code, offers a method to routinely sample longer time scale reactive simulation data with statistical precision. RAPTOR may also be interfaced with enhanced sampling methods to drive simulations toward the analysis of reactive rare events, and a number of collective variables (CVs) have been developed to facilitate this. Key advances to this methodology, including GPU acceleration efforts and novel CVs to model water wire formation are reviewed, along with recent applications of the method which demonstrate its versatility and robustness.

Multiscale study of reactive transport and multiphase heat transfer processes in catalyst layers of proton exchange membrane fuel cells

Improving the performance of proton exchange membrane fuel cells (PEMFCs) requires deep understanding of the reactive transport processes inside the catalyst layers (CLs). In this study, a particle-overlapping model is developed for accurately describing the hierarchical structures and oxygen reactive transport processes in CLs. The analytical solutions derived from this model indicate that carbon particle overlap increases ionomer thickness, reduces specific surface areas of ionomer and carbon, and further intensifies the local oxygen transport resistance (Rother). The relationship between Rother and roughness factor predicted by the model in the range of 800-1600 s m-1 agrees well with the experiments. Then, a multiscale model is developed by coupling the particle-overlapping model with cell-scale models, which is validated by comparing with the polarization curves and local current density distribution obtained in experiments. The relative error of local current density distribution is below 15% in the ohmic polarization region. Finally, the multiscale model is employed to explore effects of CL structural parameters including Pt loading, I/C, ionomer coverage and carbon particle radius on the cell performance as well as the phase-change-induced (PCI) flow and capillary-driven (CD) flow in CL. The result demonstrates that the CL structural parameters have significant effects on the cell performance as well as the PCI and CD flows. Optimizing the CL structure can increase the current density and further enhance the heat-pipe effect within the CL, leading to overall higher PCI and CD rates. The maximum increase of PCI and CD rates can exceed 145%. Besides, the enhanced heat-pipe effect causes the reverse flow regions of PCI and CD near the CL/PEM interface, which can occupy about 30% of the CL. The multiscale model significantly contributes to a deep understanding of reactive transport and multiphase heat transfer processes inside PEMFCs.

Understanding the first activation step of electrochemical CO2 reduction over Ag and Ni-N-C active sites

Understanding the first elementary step of CO2 activation over electrode surfaces is a prerequisite for its following precise valorization process. Even for CO2-to-CO conversion, the simplest 2e− reduction reaction, the identity of its rate-limiting step (RLS) and the dependence of its reaction kinetics remain controversial. Herein, we comparatively evaluate the electrocatalytic kinetics of CO2 reduction over Ni-N-C single atom catalyst, polycrystalline and oxide-derived Ag nanocatalysts at well-defined reactant mass transport conditions using a membrane electrode assembly electrolyzer. We find the reaction kinetics for CO evolution is independent of CO2 partial pressure on Ni-N-C but be dependent on polycrystalline Ag, whereas this dependency is weakened on oxide-derived Ag with more under-coordinated surface sites exposed. The first principles calculations reveal the initial electron transfer to CO2 is the RLS for both oxide-derived and polycrystalline-Ag, while the subsequent proton transfer to CO2− is the RLS for Ni-N-C. Our findings indicate that the distinct electrostatic interactions between active sites and the adsorbed CO2 primarily contribute to these differences.

Attaining Substantially Enhanced Oxygen Evolution Reaction Rates on Ni Foam Catalysts in a Gas Diffusion Electrode Setup

Water electrolysis plays a central role in the transition to a fossil‐free society, but there are significant challenges to overcome in order to increase its availability on a large scale. Alkaline water electrolysis is a mature and scalable technology, although it has several disadvantages compared to electrolyzers working in acidic environments. In particular, the use of highly alkaline aqueous electrolytes can lead to corrosion, and the achieved current densities are relatively low. This study addresses the latter limitation by introducing a gas diffusion electrode (GDE) setup as a novel development tool that bridges the gap between research and practical applications in commercial devices such as fuel cells and electrolyzers. A high surface area Ni foam catalyst that can sustain exceptional oxygen evolution reaction (OER) current densities of up to 4 A cm−2 in a quasi‐steady‐state within our GDE setup operating in an alkaline environment is presented. The high performance of this Ni‐based benchmark catalyst is attributed to its deposition onto a mesh‐like porous transport layer (PTL) via hydrogen‐templated electrodeposition. This forms a porous foam‐like structure that augments the mass transport of the gaseous reactants at the GDE.

Design Strategies for Anti‐Freeze Electrolytes in Aqueous Energy Storage Devices at Low Temperatures

AbstractWith the continuous development of electrochemical energy storage technology, especially in the current pursuit of environmental sustainability and safety, aqueous energy storage devices, due to their high safety, environmental friendliness, and cost‐effectiveness, are becoming an important direction of development in the field of energy storage. Diverse application scenarios require that energy storage systems be capable of continuous power supply under low temperature conditions. However, conventional aqueous electrolytes freeze at extremely low temperatures, causing limited ion transport and slow reaction kinetics, degrading the performance of the energy storage system. The design of low‐temperature anti‐freeze aqueous electrolytes has become an effective way to address this issue. In this review, the deep connection between hydrogen bonds (HBs) interactions in aqueous electrolytes and the liquid‐to‐solid conversion process, and the fundamental principles of the anti‐freeze mechanism is first explored. Subsequently, a systematic categorization and discussion of the design strategies for low‐temperature anti‐freeze aqueous electrolytes are conducted. Finally, potential directions are proposed. This review aims to provide comprehensive scientific guidance and technical reference for the development of anti‐freeze aqueous electrolytes with excellent low‐temperature performance, thereby promoting the application and innovation of aqueous energy storage devices in low‐temperature environments.

Upscaling the reaction rates in porous media from pore- to Darcy-scale

Modeling and prediction of reactive transport in porous media are challenging due to the complexity of the characterization of reactions across spatial and time scales. The application of reaction rates obtained from batch experiments to porous media is not valid because it disregards the influences of flow pathways, distribution of residence time, transport limitations within the porous media, as well as neglecting the impact of surface mineralogy heterogeneity. In this study, we presented how the pore-scale modeling can help to improve the Darcy-scale simulations. First, the reactive transport was simulated in a pore-network model and was validated against the experiments. Then, the pore-network results were averaged to obtain the effective reaction rates as a function of pore velocity, the inlet concentration, and the resident concentration. The upscaled function was incorporated into the Darcy-scale model and showed a significant improvement in predicting the concentration profiles. Notably, the use of batch reaction rates in the Darcy model (ADRE-batch) led to significant underestimation, up to 93%, of the required pore volume injection for complete contaminant removal from the simulation domain.

A quantitative description of barite thermodynamics, nucleation and growth for reactive transport modelling

The regression of available thermodynamic data in the BaSO4–NaCl–H2O system yielded Pitzer ion interaction parameters that accurately describe the activities of aqueous species and mineral solubilities in this system. This thermodynamics description is compared with published Pitzer parameter sets, and combined with a model for the kinetics of barite nucleation and growth, based on classical nucleation theory. Both the thermodynamic and nucleation/growth models have been incorporated into the PHREEQC computer code to facilitate calculation of the extent and consequences of barite formation in natural and engineered systems. Results of geochemical modelling calculations agree adequately with the amount of barite scale thicknesses derived from calliper measurements from an oil well if the effective surface free energy of barite nuclei is assumed to be ∼50 mJ m−2. Better results, however, are achieved using a temperature dependent effective surface free energy. In contrast, calculations performed by ignoring the effects of barite nucleation lead to a substantial overestimation of the amount of scale formed in our modelled systems. The success of our mineral nucleation and growth model to describe scaling in our modelled system suggests this description of precipitation rates can be applied to many other mineral-aqueous fluid systems, in particular where supersaturation is slight and the solids forming have substantial surface free energy.