Reactive Transport Research Articles

Quantifying remediation of chlorinated volatile compounds by sulfidated nano zerovalent iron treatment using numerical modeling and CSIA

Sulfidated nanoscale zerovalent iron (S-nZVI) has demonstrated promising reactivity and longevity for remediating chlorinated volatile compounds (cVOC) contaminants in laboratory tests. However, its effectiveness in field applications remains inadequately evaluated. This study provides the first quantitative evaluation of the long-term effectiveness of carboxymethyl cellulose-stabilized S-nZVI (CMC-S-nZVI) at a cVOC-contaminated field site. A reactive transport model-based numerical approach delineates the change in cVOC concentrations and carbon isotope values (i.e., δ13C from compound-specific stable isotope analysis (CSIA)) caused by dissolution of dense non-aqueous phase liquid, sorption, and pathway-specific degradation and production, respectively. This delineation reveals quantitative insights into remediation effectiveness typically difficult to obtain, including extent of degradation, contributions of different degradation pathways, and degradation rate coefficients. Significantly, even a year after CMC-S-nZVI application, degradation remains an important process effectively removing various cVOC contaminants (i.e., chlorinated ethenes, 1,2-dichloroethanes, and chlorinated methanes) at an extent varying from 5 %-62 %. Although the impacts of CMC-S-nZVI abundance on degradation vary for different cVOC and for different sampling locations at the site, for the primary site contaminants of tetrachloroethene and trichloroethene, their predominance of dichloroelimination pathway (≥ 88 %), high degradation rate coefficient (0.4–1.7 d-1), and occurrence at locations with relatively high CMC-S-nZVI abundance strongly indicate the effectiveness of abiotic remediation. These quantitative assessments support that CMC-S-nZVI supports sustainable ZVI-based remediation. Further, the novel numerical approach presented in this study provides a powerful tool for quantitative cVOC remediation assessments at complex field sites where multiple processes co-occur to control both concentration and CSIA data.

Epigenetic control of metabolic identity across cell types.

Constraint-based network modelling is a powerful tool for analysing cellular metabolism at genomic scale. Here, we conducted an integrative analysis of metabolic networks reconstructed from RNA-seq data with paired epigenomic data from the EpiATLAS resource of the International Human Epigenome Consortium (IHEC). Applying a state-of-the-art contextualisation algorithm, we reconstructed metabolic networks across 1,555 samples corresponding to 58 tissues and cell types. Analysis of these networks revealed the distribution of metabolic functionalities across human cell types and provides a compendium of human metabolic activity. This integrative approach allowed us to define, across tissues and cell types, i) reactions that fulfil the basic metabolic processes (core metabolism), and ii) cell type-specific functions (unique metabolism), that shape the metabolic identity of a cell or a tissue. Integration with EpiATLAS-derived cell type-specific gene-level chromatin states and enhancer-gene interactions identified enhancers, transcription factors, and key nodes controlling core and unique metabolism. Transport and first reactions of pathways were enriched for high expression, active chromatin state, and Polycomb-mediated repression in cell types where pathways are inactive, suggesting that key nodes are targets of repression. This integrative analysis forms the basis for identifying regulation points that control metabolic identity in human cells.

Anoxic corrosion of carbon steel in high pH cementitious media and high temperature conditions: New insights on the formation of (Fe,Al)Si-hydrogarnet corrosion product

The corrosion of carbon steel in alkaline anaerobic conditions and high temperature (80°C) was studied through mock-up tests representative of imperfect contact between steel and cementitious material. The evolution of the whole system, including cement mineralogy, reservoir solution chemistry, corrosion product and rate, was followed over one year. SEM-EDX and XRD analyses indicated that the corrosion product layer was mostly constituted of (Fe,Al)Si-Hydrogarnet ((Fe,Al)Si-HG) and that its densification progressively inhibited corrosion. Thermodynamic and reactive transport modelling helped to better constrain the chemical and temperature conditions of (Fe,Al)Si-HG formation.

Multicomponent and Surface Charge Effects on PFOS Sorption and Transport in Goethite-Coated Porous Media under Variable Hydrochemical Conditions.

Perfluorooctanesulfonate (PFOS), a toxic anionic perfluorinated surfactant, exhibits variable electrostatic adsorption mechanisms on charge-regulated minerals depending on solution hydrochemistry. This work explores the interplay of multicomponent interactions and surface charge effects on PFOS adsorption to goethite surfaces under flow-through conditions. We conducted a series of column experiments in saturated goethite-coated porous media subjected to dynamic hydrochemical conditions triggered by step changes in the electrolyte concentration of the injected solutions. Measurements of pH and PFOS breakthrough curves at the outlet allowed tracking the propagation of multicomponent reactive fronts. We performed process-based reactive transport simulations incorporating a mechanistic network of surface complexation reactions to quantitatively interpret the geochemical processes. The experimental and modeling outcomes reveal that the coupled spatio-temporal evolution of pH and electrolyte fronts, driven by the electrostatic properties of the mineral, exerts a key control on PFOS mobility by determining its adsorption and speciation reactions on goethite surfaces. These results illuminate the important influence of multicomponent transport processes and surface charge effects on PFOS mobility, emphasizing the need for mechanistic adsorption models in reactive transport simulations of ionizable PFAS compounds to determine their environmental fate and to perform accurate risk assessment.

Impact of ionic strength on goethite colloids co-transported with arsenite (As3+) through a saturated sand column under anoxic condition: Experiment and mathematical modeling

The knowledge about co-transport of goethite and As3+ to investigate the effect of goethite colloids on As3+ transport under various degrees of seawater intrusion, particular extremely conditions, in groundwater environment is still limited. The main objective is to investigate the influence of seawater intrusion on the sorption, migration, and reaction of As3+and goethite colloids into sand aquifer media under anoxic conditions by using the bench-scale and reactive geochemical modeling. The research consisted of two parts as follows: 1) column transport experiments consisting of 8 columns, which were packed by using synthesis groundwater at IS of 0.5, 50, 200, and 400 mM referring to the saline of seawater system in the study area, and 2) reactive transport modeling, the mathematical model (HYDRUS-1D) was applied to describe the co-transport of As3+ and goethite. Finally, to explain the interaction of goethite and As3+, the Derjaguin-Landau-Verwey-Overbeek (DLVO) calculation was considered to support the experimental results and HYDRUS-1D model. The results of column experiments showed goethite colloids can significantly inhibit the mobility of As3+ under high IS conditions (>200 mM). The Rf of As3+ bound to goethite grows to higher sizes (47.5 and 65.0 μm for 200 and 400 mM, respectively) of goethite colloid, inhibiting As3+ migration through the sand columns. In contrast, based on Rf value, goethite colloids transport As3+ more rapidly than a solution with a lower IS (0.5 and 50 mM). The knowledge gained from this study would help to better understand the mechanisms of As3+ contamination in urbanized coastal groundwater aquifers and to assess the transport of As3+ in groundwater, which is useful for groundwater management, including the optimum pumping rate and long-term monitoring of groundwater quality.

Modelling the Fate of Linear Alkylbenzene Sulfonate in Agricultural Soil Columns during Inflow of Surfactant Pulses from Domestic Wastewaters

Linear alkylbenzene sulfonate (LAS), a widely used anionic surfactant, is present in wastewater and can be discharged, causing environmental damage. When biodegradation is negligible, adsorption and desorption reactions play an important role, depending on the media characteristics (organic matter and clays) and hydrodynamic parameters. Previously published laboratory column data are modelled with PHREEQC (version 2.18) in three scenarios of LAS input: spill (LAS pulse), continuous discharge (LAS adsorption step) and remediation (LAS desorption step). The distribution coefficients (0.1–4.9 × 10−3 L/g) in the sand columns are lower than those determined in this paper from batch tests and in columns of 25% and 50% agricultural soil mixtures (1–70 × 10−3 L/g). Considering the Freundlich constant parameters from the modelling, the results are similar to the distribution coefficients, but the linear isotherms are more consistent throughout. The mass transfer coefficient from the sand columns is lower than the agricultural soil columns (20–40 h−1), indicating longer elution times for the heavier homologues and a higher percentage of agricultural soil. For lighter homologues, fast migration could cause contamination of aquifers. The great persistence of LAS in the environment necessitates the development of mitigation strategies using reactive transport models, which predict longer times for the remediation of LAS homologues.

Photosynthetic performance of the red algae Gracilariopsis lemaneiformis under high seawater pH: Excess reactive oxygen production due to carbon limitation.

The red algae Gracilariopsis lemaneiformis is extensively cultivated at high densities, leading to significant increases in regional seawater pH due to its photosynthetic removal of inorganic carbon. We conducted a study on G. lemaneiformis cultured under various pH conditions (normal pH, pH 9.3, and pH 9.6) and light levels (dark and 100 μmol photons m-2 s-1) to investigate how high pH seawater environments affect the metabolic processes of G. lemaneiformis. The high pH did not directly damage the photosynthetic light reactions or the Calvin cycle. Instead, the observed reduction in photosynthetic rates was primarily due to CO2 limitation. However, under illuminated conditions, a high pH environment leads to a decrease in electron transport efficiency (ETo/RC) and reaction center density (RC/CSo), while simultaneously increasing the levels of hydrogen peroxide (H2O2), malondialdehyde (MDA), and the activity of antioxidant enzymes. Under illuminated conditions, the limitation of inhibit the photosynthetic electron transport process, leading to energy imbalance and excessive production of reactive oxygen species, which in turn resulted in lipid peroxidation of the cell membrane. This might be one of the inducing factors responsible for the bleaching in sea-farmed G. lemaneiformis plants.

Influence of structural properties and connectivity of initial fracture network on incipient karst genesis

A karst system is generally difficult to characterize especially regarding its conduits pattern and morphology. Even though speleology allows to map the geometry of cave systems, a large part of karst conduit networks remains unreachable underground. In this study, we use a reactive transport model that simulates dissolution processes in fracture networks to investigate the effect of discrete fracture network (DFN) properties (i.e., anisotropy, connectivity, fracture intersection types) on incipient karst conduit geometry under different boundary conditions (constant hydraulic head versus constant flow rate conditions, directional versus concentrated recharge conditions). We focused on single fracture (with/without cementation) and ladder like fracture networks which are common on limestone. Results show that fracture network properties, play a major role in the final geometry and topology of the incipient karst conduit patterns. Also, the presence of cement on a single fracture favors tortuous and curvilinear wormholes, while the anisotropy of the fracture network favors the formation of anisotropic incipient karst geometries. Finally, the type of hydraulic BC remains a major factor that governs dissolution processes and thus incipient karst conduit geometry.

Computational microfluidics of reactive transport processes with solid dissolution and self-induced multiphase flow

There are still many unclear mechanisms in the multiphase reactive flow with solid dissolution processes. In this study, the reactive transport processes coupled with solid dissolution and self-induced multiphase flow in three-dimensional (3D) structures with increasing complexity is studied by developing a 3D computational microfluidic method, which considers multiphase flow, interfacial mass transport, heterogeneous chemical reactions, and solid structure evolution. Solid dissolution diagram in a simple channel in the framework of multiphase flow is proposed, with six coupled multiphase flow and solid dissolution patterns identified and the transition between different patterns discussed. Then, multiphase reactive flow in a porous chip is further studied, and the interesting 3D phenomena are discovered, including enhanced solid dissolution in the middle and enriched bubble generation at the corner along the thickness direction. Considering the importance of reactive surface area, correlations of reactive surface area-porosity-saturation with different dissolution patterns are proposed based on the pore-scale results. Finally, the computational microfluidic model is extended to investigate the multiphase reactive flow in a 3D digital core. Different dissolution patterns are recognized using the local porosity evolution character, and the corresponding pore size distribution and bubble characteristics are deciphered. These findings advance understanding of multiphase reactive transport processes and contribute to improve continuum-scale reactive transport modeling.

A coupled three-dimensional wormhole modeling in heterogenous carbonate lithology in limited-entry and openhole completions

Wormhole propagation in carbonate formation is a well-researched area with several proposed empirical, analytical, and numerical models to predict the process efficiency. The most reliable and up-to-date model is the two-scale continuum (TSC) model, based on numerical simulation of reactive transport in a porous medium. The model has been utilized in two and occasionally in three-dimensional space but has yet to consider the lithology impact in three-dimensional space (3D). This study demonstrated the impact of lithology considering both openhole and limited-entry completion in 3D space. Moreover, the model considered the acid temperature impact on acidizing efficiency. Results showed that limited entry results in a longer wormhole at the expense of its coverage along the wellbore. Similarly, the higher the number of perforations, the lower the wormhole radius but the higher the coverage. Increasing acid temperature results in better dolomite and lower limestone acid stimulation efficiency. In mixed mineralogy, the positive impact of temperature appears at 50 °C and higher. Wormholes propagate in the limestone sections in layered formation with openhole completion, leaving the dolomite under-stimulated, even at high acid temperatures. Limited entry completion in dolomite layers did not prevent the acid from traveling to the limestone layers but provided limited stimulation in the dolomite section. This is the first study to utilize the TSC model to predict the acid stimulation outcomes at field conditions in 3D space.

Anchoring Multi‐Coordinated Bismuth Metal Atom Sites on Honeycomb‐Like Carbon Rods Achieving Advanced Potassium Storage

AbstractCarbonaceous materials are recognized for their high conductivity and adaptable structures, making them potential candidates for potassium‐ion batteries (PIBs). Yet, their application has been restricted due to challenges like limited potassium storage and slow kinetics. Addressing these issues, this study presents a novel method by anchoring nitrogen‐oxygen‐coordinated bismuth metal atom sites onto honeycomb‐like carbon rods, termed Bi‐N4‐O2@HCR. This aims to enhance PIB performance by exploiting carbonaceous materials' strengths and mitigating their limitations. Through comprehensive experiments and theoretical simulations, it is found that Bi‐N4‐O2 sites enrich potassium storage and facilitate potassium ion migration, thus improving transport efficiency and reaction kinetics. The resulting anode showcased rapid and durable potassium storage, with a remarkable capacity of 190.7 mAh g−1 at 30 A g−1 and maintaining 192.2 mAh g−1 over 4200 cycles at 5 A g−1, outperforming many existing carbon anodes. Additionally, in full cell tests, it exhibited excellent rate performance and ultra‐long cycle life, sustaining up to 8000 cycles with a stable capacity of 88.9 mAh g−1 at 5 A g−1. This research underscores the significance of incorporating unique metal sites on carbon substrates to advance battery technology.

Implementation of temporal moments to elucidate the reactive transport of metformin and erythromycin in the saturated porous media.

This study investigates the fate and transport dynamics of metformin (MTN) and erythromycin (ETM), both classified as pharmaceutical and personal care products (PPCPs), in a saturated sandy soil column using temporal moment analysis (TMA). The key flow and transport parameters, including Darcy velocity, longitudinal dispersivity, adsorption, and degradation coefficients, were analyzed. The results reveal that MTN, a highly mobile contaminant, is eliminatedfrom the column in approximately 40days, while ETM shows significant adsorption due to its hydrophobic and adsorptive nature. Darcy velocity significantly affects PPCP transport; a one-order magnitude change alters contaminant mass recovery at the column outlet by 88% for MTN and 39-fold for ETM. Longitudinal dispersivity has minimal impacton the transport of PPCPs. However adsorption primarily governs the fateofPPCPs with high adsorption coefficients (Kd), and degradation rates control the fateoflow-sorbing PPCPs. A one-order magnitude change in Kd results in a 55% change in the zeroth temporal moment (ZTM) of MTN and a 30-fold change in the case of ETM. Additionally, a one-order magnitude change in the degradation coefficient leads to a 60% variation in MTN's ZTM and a 5% variation in ETM's ZTM. Thus, TMA is a valuable tool for understanding PPCP dynamics in subsurface environments, providing critical insights for managing their increasing concentrations.

Unlocking the decomposition limitations of the Li2C2O4 for highly efficient cathode preliathiations

The development of high-energy-density Li-ion batteries is hindered by the irreversible capacity loss during the initial charge-discharge process. Therefore, pre-lithiation technology has emerged in the past few decades as a powerful method to supplement the undesired lithium loss, thereby maximizing the energy utilization of LIBs and extending their cycle life. Lithium oxalate (Li2C2O4), with a high lithium content and excellent air stability, has been considered one of the most promising materials for lithium compensation. However, the sluggish electrochemical decomposition kinetics of the material severely hinders its further commercial application. Here, we introduce a recrystallization strategy combined with atomic Ni catalysts to modulate the mass transport and decomposition reaction kinetics. The decomposition potential of Li2C2O4 is significantly decreased from ∼4.90V to ∼4.30V with a high compatibility with the current battery systems. In compared to the bare NCM//Li cell, the Ni/N-rGO and Li2C2O4 composite (Ni-LCO) modified cell releases an extra capacity of ∼11.7 ​%. Moreover, this ratio can be magnified in the NCM//SiOx full cell, resulting in a 30.4 ​% higher reversible capacity. Overall, this work brings the catalytic paradigm into the pre-lithiation technology, which opens another window for the development of high-energy-density battery systems.

Recent Advances in Geochemical and Mineralogical Studies on CO2–Brine–Rock Interaction for CO2 Sequestration: Laboratory and Simulation Studies

The urgent need to find mitigating pathways for limiting world CO2 emissions to net zero by 2050 has led to intense research on CO2 sequestration in deep saline reservoirs. This paper reviews key advancements in lab- and simulation-scale research on petrophysical, geochemical, and mineralogical changes during CO2–brine–rock interactions performed in the last 25 years. It delves into CO2 MPD (mineralization, precipitation, and dissolution) and explores alterations in petrophysical properties during core flooding and in static batch reactors. These properties include changes in wettability, CO2 and brine interfacial tension, diffusion, dispersion, CO2 storage capacity, and CO2 leakage in caprock and sedimentary rocks under reservoir conditions. The injection of supercritical CO2 into deep saline aquifers can lead to unforeseen geochemical and mineralogical changes, possibly jeopardizing the CCS (carbon capture and storage) process. There is a general lack of understanding of the reservoir’s interaction with the CO2 phase at the pore/grain scale. This research addresses the gap in predicting the long-term changes of the CO2–brine–rock interaction using various geochemical reactive transport simulators. Péclet and Damköhler numbers can contribute to a better understanding of geochemical interactions and reactive transport processes. Additionally, the dielectric constant requires further investigation, particularly for pre- and post-CO2–brine–rock interactions. For comprehensive modeling of CO2 storage over various timescales, the geochemical modeling software called the Geochemist’s Workbench was found to outperform others. Wettability alteration is another crucial aspect affecting CO2–brine–rock interactions under varying temperature, pressure, and salinity conditions, which is essential for ensuring long-term CO2 storage security and monitoring. Moreover, dual-energy CT scanning can provide deeper insights into geochemical interactions and their complexities.

Elucidating the Transport of Electrons and Molecules in a Solid Electrolyte Interphase Close to Battery Operation Potentials Using a Four-Electrode-Based Generator-Collector Setup.

In lithium-ion batteries, the solid electrolyte interphase (SEI) passivates the anode against reductive decomposition of the electrolyte but allows for electron transfer reactions between anode and redox shuttle molecules, which are added to the electrolyte as an internal overcharge protection. In order to elucidate the origin of these poorly understood passivation properties of the SEI with regard to different molecules, we used a four-electrode-based generator-collector setup to distinguish between electrolyte reduction current and the redox molecule (ferrocenium ion Fc+) reduction current at an SEI-covered glassy carbon electrode. The experiments were carried out in situ during potentiostatic SEI formation close to battery operation potentials. The measured generator and collector currents were used to calculate passivation factors of the SEI with regard to electrolyte reduction and with regard to Fc+ reduction. These passivation factors show huge differences in their absolute values and in their temporal evolution. By making simple assumptions about molecule transport, electron transport, and charge transfer reaction rates in the SEI, distinct passivation mechanisms are identified, strong indication is found for a transition during SEI growth from redox molecule reduction at the electrode | SEI interface to reduction at the SEI | electrolyte interface, and good estimates for the transport coefficients of both electrons and redox molecules are derived. The approach presented here is applicable to any type of electrochemical interphase and should thus also be of interest for interphase characterization in the fields of electrocatalysis and corrosion.

Fluid inertia controls mineral precipitation and clogging in pore to network-scale flows

Mineral precipitation caused by fluid mixing presents complex control and predictability challenges in a variety of natural and engineering processes, including carbon mineralization, geothermal energy, and microfluidics. Precipitation dynamics, particularly under the influence of fluid flow, remain poorly understood. Combining microfluidic experiments and three-dimensional reactive transport simulations, we demonstrate that fluid inertia controls mineral precipitation and clogging at flow intersections, even in laminar flows. We observe distinct precipitation regimes as a function of Reynolds number (Re). At low Reynolds numbers (Re < 10), precipitates form a thin, dense layer along the mixing interface, which shuts precipitation off, while at high Reynolds numbers (Re > 50), strong three-dimensional flows significantly enhance precipitation over the entire intersection, resulting in rapid clogging. When injection rates from two inlets are uneven, flow symmetry-breaking leads to unexpected flow bifurcation phenomena, which result in enhanced concurrent precipitation in both downstream channels. Finally, we extend our findings to rough channel networks and demonstrate that the identified inertial effects on precipitation at the intersection scale are also present and even more dramatic at the network scale. This study sheds light on the fundamental mechanisms underlying mixing-induced mineral precipitation and provides a framework for designing and optimizing processes involving mineral precipitation.

HTO and selenate diffusion through compacted Na-, Na–Ca-, and Ca-montmorillonite

Radionuclide transport in smectite clay barrier systems used for nuclear waste disposal is controlled by diffusion, with adsorption significantly retarding transport rates. While a relatively minor component of spent nuclear fuel, 79Se is a major driver of the safety case for spent fuel disposal due to its long half-life (3.3 × 105 yr) and its low adsorption to clay (KD < 10 L/kg), thus a thorough understanding of Se diffusion through clay is critical for understanding the long-term safety of spent fuel disposal systems. Through-diffusion experiments with tritiated water (HTO, conservative tracer) and Se(VI) were conducted with a well-characterized, purified montmorillonite source clay (SWy-2) under a constant ionic strength (0.1 M) and three different electrolyte compositions: Na+, Ca2+, and a Na + -Ca2+ mixture at pH 6.5 in order to probe the effects of electrolyte composition and interlayer cation composition on clay microstructure, Se(VI) aqueous speciation, and ultimately diffusion. The results were modeled using a reactive transport modeling approach to determine values of porosity (ε), De (effective diffusion coefficient), and KD (distribution coefficient for adsorption). HTO diffusive flux was higher in Ca-montmorillonite (De = 1.68 × 10−10 m2 s−1) compared to Na-montmorillonite (De = 7.83 × 10−11 m2 s−1). This increase in flux is likely due to a greater degree of clay layer stacking in the presence of Ca2+ compared to Na+, which leads to larger inter-particle pores. Overall, the Se(VI) flux was much lower than the HTO flux due to anion exclusion, with Se(VI) flux following the order Ca (De = 1.03 × 10−11 m2 s−1) > Na–Ca (De = 2.12 × 10−12 m2 s−1) > Na (De = 1.28 × 10−12 m2 s−1). These differences in Se(VI) flux are due to a combination of factors, including (1) larger accessible porosity in Ca-montmorillonite due to clay layer stacking and smaller electrostatic effects compared to Na-montmorillonite, (2) larger accessible porosity for neutral-charge CaSeO4 species which makes up 32% of aqueous Se(VI) in the pure Ca system, and (3) possibly higher Se(VI) adsorption for Ca-montmorillonite. Through a combination of experimental and modeling work, this study highlights the compounding effects that electrolyte and counterion compositions can have on radionuclide transport through clay. Diffusion models that neglect these effects are not transferable from laboratory experimental conditions to in situ repository conditions.

A scale-bridging model for proton exchange membrane fuel cells: Understanding interactions among multi-physics transports, electrochemical reactions and heterogeneous aging

The lifetime issues caused by catalyst degradation is one of the most critical challenges for the commercial application of proton exchange membrane fuel cells. However, the understanding concerning the interactions among transport, reaction, and catalyst degradation is inadequate for further durability enhancement. Herein, a scale-bridging model that couples a cell-scaled model to reveal the reactive transport process and a catalyst-scaled model to unveil Pt degradation is proposed to capture the degradation characteristics. It is found that the heterogeneous aging is observed in both the through-plane and channel-rib directions due to the enhanced mass loss near the membrane and the water accumulation under the rib, resulting in the mitigation of the core reaction region away from the membrane, thereby causing an increase in ohmic loss after cycles. More importantly, the local oxygen transport resistance increases with degradation, leading to a remarkable cell performance loss under high current density. Additionally, the influences of cell voltage load and inlet humidity on Pt degradation are also investigated. And the proposed gradient catalyst layer shows a significant mitigating effect on Pt degradation. This work reveals the degradation-performance interactions, which is conducive to design the high-performance fuel cell to prolong lifetime.

SUPHRE: A Reactive Transport Model With Unsaturated and Density‐Dependent Flow

AbstractAlthough unsaturated and density‐dependent flow affect solute fate in groundwater, they are rarely both included in reactive transport models. Using the operator‐splitting method, a new reactive transport model (SUPHRE) was developed by combining a variable‐saturation and variable‐density multiple‐component solute transport model (SUTRA‐MS) with a geochemical reaction module (PhreeqcRM). In contrast to existing reactive transport models, SUPHRE accounts for both unsaturated and density‐dependent flow. Model setup for SUPHRE is convenient, as only one setup file is required in addition to the usual input files of SUTRA‐MS and PhreeqcRM. By further implementing a time‐variant boundary condition into SUTRA‐MS, SUPHRE can simulate multi‐component reactive transport in tidally influenced coastal unconfined aquifers where unsaturated and density‐dependent flow prevail. Two examples were used to validate the new reactive transport model, including single‐species decay and sorption within a one‐dimensional soil column and a four‐species decay chain in a two‐dimensional aquifer. Following validation, SUPHRE was adopted to reveal unsaturated flow effects on oxygen consumption and nitrate reduction in tidally influenced coastal unconfined aquifers. Whether for simulating oxygen consumption or nitrate reduction, there were visible deviations between numerical results without and with unsaturated flow, highlighting that unsaturated flow can affect reactive solute transport and transformation.

Structure-activity relationship between pore morphology and thermochemical energy storage properties based on MgCO3/MgO

Thermochemical energy storage (TCES) is a pivotal technology for addressing the space-time mismatches in energy supply and demand. MgCO3/MgO carrier offers the advantages of high energy density, seasonal storage capability, and abundant nontoxic reserves. However, it is encumbered by poor exothermic activity and kinetic irreversibility. In this study, innovative preparation approaches for MgCO3/MgO have been developed, involving the regulation of physical morphology, so as to reveal the structure-activity relationship between pore morphology and TCES properties. The results indicate that SD-cotton-MgO (MgO prepared by structure-directing agent, cotton) could carbonate up to 76.98 %, facilitated by its mesopores that aid in the transport of reactants. SGSC-MgO (MgO prepared by sol-gel self-combustion method) exhibits the fastest reaction rate at the initial stage, with a rate of 593.1 μmol/min/g adsorbent because distributed macropores expose the other nanopores. As for SD-CPM-MgO (MgO prepared by structure-directing agent, carboniferous polysaccharide microsphere), owning to long pore distance of micropores hindering CO2 diffusion, its kinetics gradually decreases as the CPM size decreases. Porous media with mixed aperture could exhibit strong kinetic performance. Furthermore, the heat storage density and maximum power of SD-cotton-MgO increase as the endothermic temperature rises, achieving a peak energy density of 1385.7 kJ/kg MgCO3 at 400 °C. Still, its heat release density increases and then decreases with exothermic temperature, reaching 1964.3 kJ/kg MgO at 320 °C. Finally, the cycle stability is contingent on the activation of the chemical modification for the first heat release and antidegradation of the physical structure for subsequent cycles. SD-cotton-MgO doped with Na0.5K0.5NO3 maintains at 50 % after 30 cycles, exhibiting no collapse or agglomeration due to its robust porous structure with strong thermal stability and permeability.