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Mine waste classification preceding mining constitutes a proactive solution to classify and segregate mine waste into geo-environmental domains based upon the magnitude of their environmental risks. However, upstream classification requires multi-disciplinary and integrated approaches. This study integrates geological modeling and kinetic modeling to inform upstream mine waste classification based on the pH generated from the main acid-generating and acid-neutralizing reactions once the mine solid waste is stored in oxidizing conditions. Geological models were used to depict the ante-mining spatial distribution of the main reactive minerals: pyrite, albite and calcite. Subsequently, the corresponding block models were created. The dimension of the elementary voxels for each block model was set at 40х40х40 m for this study. The kinetic modeling approach was performed using PHREEQC and VS2DRTI to consider unsaturated conditions. The kinetic modeling simulated a 1D column for each voxel. The column simulates the excavated state of the hosting rock involving kinetic reactions and unsaturated flow under highly oxidizing conditions. Subsequently, the resulting pH for different intervals of time was assigned to its respective voxel. The outcome consists of a spatio-temporal visualization of the pH defining ante-mining geo-environmental domains, thereby providing the opportunity for formulating proactive management measures regarding the hazardous geo-environmental domains., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The increase in the frequency of extreme precipitation events due to climate change, together with the continuous development of cities and surface sealing that hinder water infiltration into the subsoil, is accelerating the search for new facilities to manage stormwater. The Canary Islands (Spain) are taking advantage of the knowledge acquired in the construction of water mines to exploit a novel stormwater management facility, which we have defined as a dry gallery. Dry galleries are constituted by a vertical well connected to a horizontal gallery dug into highly permeable volcanic layers of the vadose zone, from where infiltration takes place. However, the lack of scientific knowledge about these facilities prevents them from being properly dimensioned and managed. In this work, we simulate for the first time the infiltration process and the wetting front propagation from dry galleries based on a 3D unsaturated flow model and provide some recommendations for the installation and sizing of these facilities. The fastest advance of the wetting front takes place during the earliest times of infiltration (<2 h), with plausible propagation velocities and infiltration rates higher than 1000 m∙d -1 and 2 m 3 ∙s -1 . As time progresses, the propagation velocity and infiltration rate decrease as a consequence of the hydraulic gradient attenuation between the gallery and the aquifer. Therefore, stormwater infiltration is a highly transient process in which a sizing underestimation of 100% may be committed if unsaturated conditions or geological configuration are neglected., Competing Interests: Declaration of competing interest Alejandro Garcia Gil reports financial support was provided by Government of Spain. Alejandro Garcia Gil reports financial support was provided by European Union., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Understanding of microplastics transport mechanism is highly important for soil contamination and remediation. The transport behaviors of microplastics in soils are complex and influenced by various factors including soil and particle properties, hydrodynamic conditions, and biota activities. Via a microfluidic experiments we study liquid film entrainment and microplastics transport and retention during two-phase displacement in microchannels with one end connected to the air and the other connected to the liquid with suspended particles. We discover three transport patterns of microplastic particles, ranging from no deposition to particle entrapment and to particle layering within liquid films, depending on the suspension withdrawal rates and the particle volume fraction in the suspension. The general behavior of particle motion is effectively captured by the film thickness evolution which is shown to be dependent on a modified capillary number Ca 0 taking into account the effects of flow velocity, particle volume fraction, and channel shape. We also provide a theoretical prediction of the critical capillary number Ca 0 * for particle entrapment, consistent with the experimental results. In addition, the probability of microplastics being dragged into the trailing liquid film near the gas invading front is found to be proportional to both particle volume fraction and the capillary number. This work elucidates the microplastics transport mechanism during unsaturated flow, and therefore is of theoretical and practical importance to understand the contaminant migration in many natural and engineered systems spanning from groundwater sources to water treatment facilities., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. The authors declare the following financial interests/personal relationships which may be considered as potential competing interests, (Copyright © 2021. Published by Elsevier Ltd.)

Leachate contamination from uncontrolled landfills is a long-lasting environmental hazard that threatens groundwater resources worldwide. We developed a holistic site-characterization approach that incorporates leachate data from the waste body, unsaturated zone, and groundwater with information on landfill geomorphology and climatic conditions. An advanced vadose-zone monitoring system was used to characterize the percolation patterns and chemical properties of the leachates in the waste body and underlying unsaturated zone; a set of observation wells was used to characterize the contaminants' distribution in the groundwater. Multivariate analysis of the chemical composition overcame multiparameter complexity, and pinpointed the dominant factors controlling contaminant migration dynamics. The landfill's mound morphology, constructed with steep slopes, led to runoff generation, limited water infiltration through the waste, and enhanced infiltration of contaminated water at the landfill margins. Aerated conditions in the unsaturated zone under the margins induced leachate degradation and oxidation processes. The chemical composition of leachates under the center of the landfill remained typically anaerobic (high DOC, NH 4 + , Fe 2+ ) despite the low water penetration. The limited water-percolation rates through the waste body and substantial mixing of the leachates with the oxidizing aquifer water led to almost complete degradation of the organic matter and significant nitrogen attenuation in the groundwater. Bromide release from decomposing waste served as an effective tracer for leachate distribution in the subsurface. The holistic approach implemented in this study provides robust and valuable insights into the factors that control landfill contamination potential and can be implemented in other sites with different climatic and geomorphological features., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Fluid flow characteristics are important to assess reservoir performance. Unfortunately, laboratory techniques are inadequate to know these characteristics, which is why numerical methods were developed. Such methods often use computed tomography (CT) scans as input but this technique is plagued by a resolution versus sample size trade-off. Therefore, a super-resolution method using generative adversarial neural networks (GANs) was used to artificially improve the resolution. Firstly, the influence of resolution on pore network properties and single-phase, unsaturated, and two-phase flow was analysed to verify that pores and pore throats become larger on average and surface area decreases with worsening resolution. These observations are reflected in increasingly overestimated single-phase permeability, less moisture uptake at lower capillary pressures, and high residual oil fraction after waterflooding. Therefore, the super-resolution GANs were developed which take low (12 µm) resolution input and increase the resolution to 4 µm, which is compared to the expected high-resolution output. These results better predicted pore network properties and fluid flow properties despite the overestimation of porosity. Relevant small pores and pore surfaces are better resolved thus providing better estimates of unsaturated and two-phase flow which can be heavily influenced by flow along pore boundaries and through smaller pores. This study presents the second case in which GANs were applied to a super-resolution problem on geological materials, but it is the first one to apply it directly on raw CT images and to determine the actual impact of a super-resolution method on fluid predictions.

The weight of Municipal solid waste (MSW) leads to a decrease of void ratio in landfill with depth and the biodegradation of MSW also results in decrease of void ratio with time. The spatial and temporal changes of void ratio of MSW have significant effects on its hydraulic properties and consequently influence the leachate recirculation process. In this paper, an advanced coupled hydro-mechanical-biodegradation (H-M-B) model is proposed to analyze the full coupling process for leachate recirculation taking into account the effect of initial density profile and its change due to biodegradation. A new solver is presented using the finite volume method based on the OpenFOAM platform to implement the coupled H-M-B model. The volume change caused by effective stress, degree of saturation and degradation, and the effect of void ratio change on hydraulic properties, can be taken into account in the coupled H-M-B model. The results calculated by the coupled H-M-B model illustrate the effect of void ratio on hydraulic properties, and the effect of compressibility, initial density and biodegradation on leachate recirculation. This study will contribute to the understanding of the leachate recirculation process and enhance the design of MSW landfills., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Water protection and bioremediation strategies in the vadose zone require understanding the factors controlling bacterial transport for different hydraulic conditions. Breakthrough experiments were made in two different flow conditions: i) an initial bacteria pulse under ponded infiltration into dry sand (-15,000 cm); ii) a second bacteria pulse into the same columns during subsequent infiltration in constant water content and steady-state flow. Escherichia coli (E. coli) and Rhodococcus erythropolis (R. erythropolis) were used to represent hydrophilic and hydrophobic bacteria, respectively. Equilibrium and attachment/detachment models were tested to fit bromide (Br - ) and bacteria transport data using HYDRUS-1D. Derjaguin-Landau-Verwey-Overbeek (DLVO) and extended DVLO (XDLVO) interaction energy profiles were calculated to predict bacteria sorption at particles. Adsorption of bacteria at air-water interfaces was estimated by a hydrophobic force approach. Results suggested greater retention of bacteria in water repellent sand compared with wettable sand. Inverse parameter optimization suggested that physico-chemical attachment of both E. coli and R. erythropolis was thousands of times lower in wettable than repellant sand and straining was 10-fold lower in E. coli for wettable vs repellant sand compared to the exact opposite by orders of magnitude with R. erythropolis. HYDRUS did not provide a clear priority of importance of solid-water or air-water interfaces in bacteria retention. Optimized model parameters did not show a clear relation to the (X)DLVO adsorption energies. This illustrated the ambivalence of (X)DLVO to predict bacterial attachment at solid soil particles of different wetting properties. Simultaneous analysis of mass recovery, numerical modeling, and interaction energy profiles thus suggested irreversible straining due to bacteria sizing as dominant compared to attachment to liquid-solid or liquid-air interfaces. Further studies are needed to distinguish straining mechanisms (i.e. pore structure or film straining) in different hydraulic conditions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The vadose zone typically comprises soil underlain by fractured rock. Often, surface water and groundwater parameters are readily available, but variably saturated flow through soil and rock are oversimplified or estimated as input for hydrological models. In this paper, a series of geotechnical centrifuge experiments are conducted to contribute to the knowledge gaps in: (i) variably saturated flow and dispersion in soil and (ii) variably saturated flow in discrete vertical and horizontal fractures. Findings from the research show that the hydraulic gradient, and not the hydraulic conductivity, is scaled for seepage flow in the geotechnical centrifuge. Furthermore, geotechnical centrifuge modelling has been proven as a viable experimental tool for the modelling of hydrodynamic dispersion as well as the replication of similar flow mechanisms for unsaturated fracture flow, as previously observed in literature. Despite the imminent challenges of modelling variable saturation in the vadose zone, the geotechnical centrifuge offers a powerful experimental tool to physically model and observe variably saturated flow. This can be used to give valuable insight into mechanisms associated with solid-fluid interaction problems under these conditions. Findings from future research can be used to validate current numerical modelling techniques and address the subsequent influence on aquifer recharge and vulnerability, contaminant transport, waste disposal, dam construction, slope stability and seepage into subsurface excavations.

Surfactant miscible-displacement (SMD) column experiments are used to measure air-water interfacial area (A I ) in unsaturated porous media, a property that influences solute transport and phase-partitioning. The conventional SMD experiment results in surface tension gradients that can cause water redistribution and/or net drainage of water from the system ("surfactant-induced flow"), violating theoretical foundations of the method. Nevertheless, the SMD technique is still used, and some suggest that experimental observations of surfactant-induced flow represent an artifact of improper control of boundary conditions. In this work, we used numerical modeling, for which boundary conditions can be perfectly controlled, to evaluate this suggestion. We also examined the magnitude of surfactant-induced flow and its impact on A I measurement during multiple SMD flow scenarios. Simulations of the conventional SMD experiment showed substantial surfactant-induced flow and consequent drainage of water from the column (e.g., from 75% to 55% S W ) and increases in actual A I of up to 43%. Neither horizontal column orientation nor alternative boundary conditions resolved surfactant-induced flow issues. Even for simulated flow scenarios that avoided surfactant-induced drainage of the column, substantial surfactant-induced internal water redistribution occurred and was sufficient to alter surfactant transport, resulting in up to 23% overestimation of A I . Depending on the specific simulated flow scenario and data analysis assumptions used, estimated A I varied by nearly 40% and deviated up to 36% from the system's initial A I . We recommend methods for A I determination that avoid generation of surface-tension gradients and urge caution when relying on absolute A I values measured via SMD., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Colloids are potential vectors of contaminants in the subsurface environment. The knowledge of transport and retention behaviors of colloids is of primary importance for assessment and prediction of subsurface pollution risks. In this study, sand column experiments were conducted to investigate the coupled effects of various interfacial forces on the retention and transport of a hydrophilic silica colloid and a relatively hydrophobic latex colloid. Water column experiments were performed to observe the movement of colloids with air bubbles. Extended DLVO interaction energies and capillary potential energy were calculated to analyze colloid retention at air-water interface (AWI), solid-water interface (SWI), and air-water-solid interface (AWS). Results show that colloid retention decreases due to increase in electrostatic repulsion and Born repulsion as well as decrease in Lewis acid-base attraction and hydrophobic interactions. Water content effect and hydrophobic effect on colloid retention become more predominant in the solution of higher ionic strength. Colloid retention at AWI is minimal (i.e., due to nonexistence of primary and secondary minima) at the ionic strengths <75mM. Capillary potential energy (10 7 -10 8 K B T) of colloids is 4-5 orders of magnitude greater than the extended DLVO interaction energy (~10 3 K B T), suggesting that capillary retention at AWS is the primary mechanism controlling colloid retention in unsaturated porous media. Results from this study show that immobile solid phase (e.g., soil) could be much more important than air phase in determining colloid retention in unsaturated porous media under unfavorable conditions, especially in the solutions of high ionic strengths., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The paper compares the main features of a submerged bed reactor (SuBR) with bubbling and recirculation of gas to those of an unsaturated flow reactor (uSFR) with liquid recirculation. A novel pressurized closed-headspace hydrogenotrophic denitrification system characterized by safe and economic utilization of H2 gas was used for the comparison. Under similar conditions, denitrification rates were lower in the SuBR as a result of a lower effective biofilm surface area and overall gas-liquid mass transfer coefficient kLa. Similar values of effluent DOC were achieved for both reactors, although effluent suspended solids concentration of the SuBR were substantially higher. On the other hand, the required cleaning frequency in the SuBR was 2.5 times lower. Moreover, the SuBR is expected to reduce the recirculation energy consumption by 0.35 kWh/m(3) treated., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Chemical factors and physical constraints lead to coupled effects during particle transport in unsaturated porous media. Studies on unsaturated transport as typical for soils are currently scarce. In unsaturated porous media, particle mobility is determined by the existence of an air-water interface in addition to a solid-water interface. To this end, we measured breakthrough curves and retention profiles of citrate-coated Ag nanoparticles in unsaturated sand at two pH values (5 and 9) and three different flow rates corresponding to different water contents with 1 mM KNO3 as background electrolyte. The classical DLVO theory suggests unfavorable deposition conditions at the air-water and solid-water interfaces. The breakthrough curves indicate modification in curve shapes and retardation of nanoparticles compared to inert solute. Retention profiles show sensitivity to flow rate and pH and this ranged from almost no retention for the highest flow rate at pH=9 to almost complete retention for the lowest flow rate at pH=5. Modeling of the breakthrough curves, thus, required coupling two parallel processes: a kinetically controlled attachment process far from equilibrium, responsible for the shape modification, and an equilibrium sorption, responsible for particle retardation. The non-equilibrium process and equilibrium sorption are suggested to relate to the solid-water and air-water interfaces, respectively. This is supported by the DLVO model extended for hydrophobic interactions which suggests reversible attachment, characterized by a secondary minimum (depth 3-5 kT) and a repulsive barrier at the air-water interface. In contrast, the solid-water interface is characterized by a significant repulsive barrier and the absence of a secondary minimum suggesting kinetically controlled and non-equilibrium interaction. This study provides new insights into particle transport in unsaturated porous media and offers a model concept representing the relevant processes., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Indaziflam is a relatively new herbicide for which sorption-desorption information is lacking, and nothing is available on its metabolites. Information is needed on the multiple soil and pesticide characteristics known to influence these processes. For four soils, the order of sorption was indaziflam (N-[1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: Kf = 5.9, 1/nf = 0.7, Kfoc = 447; sandy loam: Kf = 3.9, 1/nf = 0.9, Kfoc = 276) > triazine indanone metabolite (N-[(1R,2S)-2,3-dihydro-2,6-dimethyl-3-oxo-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: Kf = 2.1, 1/nf = 0.8, Kfoc = 177; sandy loam: Kf = 1.7, 1/nf = 0.9, Kfoc = 118) > fluoroethyldiaminotriazine metabolite (6-[(1R-1-Fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: Kf = 0.3, 1/nf = 0.9, Kfoc = 28; sandy loam: Kf = 0.3, 1/nf = 0.9, Kfoc = 22) = indaziflam carboxylic acid metabolite (2S,3R)-3-[[4-amino-6-[(1R)-1-fluoroethyl]-1,3,5-triazin-2-yl]amino]-2,3-dihydro-2-methyl-1H-indene-5-carboxylic acid) (sandy clay loam: Kf = 0.3, 1/nf = 0.9, Kfoc = 22; sandy loam: Kf = 0.5, 1/nf = 0.8, Kfoc = 32). The metabolites being more polar than the parent compound showed lower sorption. Desorption was hysteretic for indaziflam and triazine indanone metabolite, but not for the other two metabolites. Unsaturated transient flow Kd's were lower than batch Kd's for indaziflam, but similar for fluoroethyldiaminotriazine metabolite. Batch Kd's would overpredict potential offsite transport if desorption hysteresis is not taken into account.