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Arsenic (As) is a toxic element, and elevated levels of geogenic As in drinking water pose a threat to the health of several hundred million people worldwide. In this study, we used microfluidics in combination with optical microscopy and X-ray spectroscopy to investigate zerovalent iron (ZVI) corrosion, secondary iron (Fe) phase formation, and As retention processes at the pore scale in ZVI-based water treatment filters. Two 250 μm thick microchannels filled with single ZVI and quartz grain layers were operated intermittently (12 h flow/12 h no-flow) with synthetic groundwater (pH 7.5; 570 μg/L As(III)) over 13 and 49 days. Initially, lepidocrocite (Lp) and carbonate green rust (GRC) were the dominant secondary Fe-phases and underwent cyclic transformation. During no-flow, lepidocrocite partially transformed into GRC and small fractions of magnetite, kinetically limited by Fe(II) diffusion or by decreasing corrosion rates. When flow resumed, GRC rapidly and nearly completely transformed back into lepidocrocite. Longer filter operation combined with a prolonged no-flow period accelerated magnetite formation. Phosphate adsorption onto Fe-phases allowed for downstream calcium carbonate precipitation and, consequently, accelerated anoxic ZVI corrosion. Arsenic was retained on Fe-coated quartz grains and in zones of cyclic Lp-GRC transformation. Our results suggest that intermittent filter operation leads to denser secondary Fe-solids and thereby ensures prolonged filter performance., Environmental Science & Technology, 56 (19), ISSN:0013-936X, ISSN:1520-5851

The functioning of natural and engineered porous media, like soils and filters, depends in many cases on the interplay between biochemical processes and hydrodynamics. In such complex environments, microorganisms often form surface-attached communities known as biofilms. Biofilms can take the shape of clusters, which alter the distribution of fluid flow velocities within the porous medium, subsequently influencing biofilm growth. Despite numerous experimental and numerical efforts, the control of the biofilm clustering process and the resulting heterogeneity in biofilm permeability is not well understood, limiting our predictive abilities for biofilm-porous medium systems. Here, we use a quasi-2D experimental model of a porous medium to characterize biofilm growth dynamics for different pore sizes and flow rates. We present a method to obtain the time-resolved biofilm permeability field from experimental images and use the obtained permeability field to compute the flow field through a numerical model. We observe a biofilm cluster size distribution characterized by a spectrum slope evolving in time between −2 and −1, a fundamental measure that can be used to create spatio-temporal distributions of biofilm clusters for upscaled models. We find a previously undescribed biofilm permeability distribution, which can be used to stochastically generate permeability fields within biofilms. An increase in velocity variance for a decrease in physical heterogeneity shows that the bioclogged porous medium behaves differently than expected from studies on heterogeneity in abiotic porous media. ISSN:0013-936X ISSN:1520-5851

We study the upscaling of pore-scale solute transport in partially saturated porous media at different saturation degrees. The interaction between structural heterogeneity, phases distribution and small-scale flow dynamics induces complex flow patterns and broad probability distributions of flow, which control key aspects of transport, such as residence and arrival times, dispersion, and spatial solute distributions, as well as chemical reactions. A continuous-time random walk (CTRW) framework that integrates the processes of advection, diffusion, and trapping in immobile zones is used to upscale and evaluate the transport of diluted solutes. Results of this model were compared to direct numerical simulations solving the advection-diffusion equation in experimental saturation patterns. The comparison between simulations results, with different Péclet numbers (Pe), and the physics-based upscaled CTRW approach allows for a quantitative analysis of the governing factors of transport in partially saturated porous media. This analysis shows that the fluid phase saturation decreases the advective tortuosity, the media's characteristic length, the fraction of the immobile region, and the mean trapping time. At the same time, for a given saturation degree, the normalized mean trapping time is proportional to the Pe. This suggests that the characteristic trapping length is proportional to the media's characteristic (correlation) length. Moreover, the trapping frequency decreases with increasing Pe., Water Resources Research, 59 (2), ISSN:0043-1397, ISSN:1944-7973

The unsaturated zone, located between the soil surface and the phreatic level, plays an important role in defining the fate of any substance entering the subsoil. In addition to the processes of flow and transport taking place in the liquid phase, surface reactions such as adsorption to the solid phase may occur and increase the residence time of the substance entering the system. In this study, we aim to understand the pore-scale mechanisms that control adsorption in unsaturated systems. We combine 2D pore-scale experimental images with numerical simulations to analyze flow, transport, and adsorption under different liquid saturation degrees. We demonstrate the role of mixing on adsorption at the liquid-solid interfaces by analyzing the deformation in time of a pulse-injected surfactant. We also analyze the impact of the isotherm functional shape and the inclusion of the liquid-gas interfaces as adsorption sites on this surface reaction. The enhancement of mixing as saturation decreases is accompanied by a reduction in the amount of adsorbed mass, located mainly along preferential flow paths, where the solute is primarily transported. For the same isotherm, a nonlinear behavior of adsorption as a function of liquid saturation has been observed. This is explained by the nonlinear variation of the volume fraction of liquid behaving as preferential path or stagnation zone as liquid saturation decreases, despite the linear decrease in the surface area of solids accessible for adsorption., Transport in Porous Media, 146 (1-2), ISSN:0169-3913, ISSN:1573-1634

Drip irrigation is a prescribed strategy to reduce nitrogen leaching- a rather nuanced phenomenon. Sustainable farming strategies need to consider short and long-term rainfall patterns and the timing of fertiliser application.

Bacterial biofilms are found in several environmental and industrial porous media, including soils and filtration membranes. Biofilms grow under certain flow conditions and can clog pores, thereby redirecting the local fluid flow. The ability of biofilms to clog pores, the so-called bioclogging, can have a tremendous effect on the local permeability of the porous medium, creating a pressure buildup in the system, and impacting the mass flow through it. To understand the interplay between biofilm growth and fluid flow under different physical conditions (e.g., at different flow velocities and pore sizes), in the present study, a microfluidic platform is developed to visualize biofilm development using a microscope under externally-imposed, controlled physical conditions. The biofilm-induced pressure buildup in the porous medium can be measured simultaneously using pressure sensors and, later, correlated with the surface coverage of the biofilm. The presented platform provides a baseline for a systematic approach to investigate bioclogging caused by biofilms in porous media under flow conditions and can be adapted to studying environmental isolates or multispecies biofilms.

Bacteria in porous media, such as soils, aquifers, and filters, often form surface-attached communities known as biofilms. Biofilms are affected by fluid flow through the porous medium, for example, for nutrient supply, and they, in turn, affect the flow. A striking example of this interplay is the strong intermittency in flow that can occur when biofilms nearly clog the porous medium. Intermittency manifests itself as the rapid opening and slow closing of individual preferential flow paths (PFPs) through the biofilm–porous medium structure, leading to continual spatiotemporal rearrangement. The drastic changes to the flow and mass transport induced by intermittency can affect the functioning and efficiency of natural and industrial systems. Yet, the mechanistic origin of intermittency remains unexplained. Here, we show that the mechanism driving PFP intermittency is the competition between microbial growth and shear stress. We combined microfluidic experiments quantifying Bacillus subtilis biofilm formation and behavior in synthetic porous media for different pore sizes and flow rates with a mathematical model accounting for flow through the biofilm and biofilm poroelasticity to reveal the underlying mechanisms. We show that the closing of PFPs is driven by microbial growth, controlled by nutrient mass flow. Opposing this, we find that the opening of PFPs is driven by flow-induced shear stress, which increases as a PFP becomes narrower due to microbial growth, causing biofilm compression and rupture. Our results demonstrate that microbial growth and its competition with shear stresses can lead to strong temporal variability in flow and transport conditions in bioclogged porous media.

Biofilms are biological viscoelastic gels composed of bacterial cells embedded in a self-secreted polymeric extracellular matrix (ECM). In environmental settings, such as in the rhizosphere and phyllosphere, biofilm colonization occurs at the solid–air interface. The biofilms’ ability to colonize and expand over these surfaces depends on the formation of osmotic gradients and ECM viscoelastic properties. In this work, we study the influence of biofilm ECM components on its viscoelasticity and expansion, using the model organism Bacillus subtilis and deletion mutants of its three major ECM components, TasA, EPS and BslA. Using a multi-scale approach, we quantified macro-scale viscoelasticity and expansion dynamics. Furthermore, we used a microsphere assay to visualize the micro-scale expansion patterns. We find that the viscoelastic phase angle Φ is likely the best viscoelastic parameter correlating to biofilm expansion dynamics. Moreover, we quantify the sensitivity of the biofilm to changes in substrate water potential as a function of ECM composition. Finally, we find that the deletion of ECM components significantly increases the coherence of micro-scale colony expansion patterns. These results demonstrate the influence of ECM viscoelasticity and substrate water potential on the expansion of biofilm colonies on wet surfaces at the air–solid interface, commonly found in natural environments.

We study pore-scale dynamics of reactive transport in heterogeneous, dual-porosity media, wherein a reactant in the invading fluid interacts chemically with the surface of the permeable grains, lea...

Natural porous systems, like soils and aquifers, are physically and chemically highly heterogeneous. Microorganisms inhabiting these environments are therefore exposed to heterogeneous fluid flow velocities and nutrient landscapes. Bacteria capable of biasing their motion to swim along chemical gradients – known as chemotaxis – profit from their ability to localize and navigate towards nutrient hot spots, such as soil aggregates or plant roots.We propose a novel experimental microfluidic platform to study chemotaxis at the pore-scale, allowing full optical access to the pore space and simultaneously enabling control over the spatio-temporal availability of nutrients. The microfluidic device contains hydrogel features, acting as nutrient hotspots, embedded in a porous medium, made out of transparent polydimethylsiloxane (PDMS) pillars. Nutrients are transported by diffusion from the access channels through the hydrogel into the porous medium, where they are released. The generated nutrient gradients downstream of the hotspots under flow conditions drive the swimming of chemotactic bacteria.This approach enables the study of subsurface processes at the pore-scale under more realistic conditions, and shed new light onto the influence of physical and chemical heterogeneity on bacterial dispersion and residence time in the subsurface.Keywords: porous media, soil, chemotaxis, microfluidics, heterogeneity

There is an expected increase of microplastics (MPs) concentrations in terrestrial ecosystems in the next decades from a variety of sources. Understanding the responses of soil ecosystems to the presence of MPs becomes increasingly important as multiple stressors can act together to negatively impact this environmental compartment, especially in the context of global warming. It has already been shown that MPs (particularly fibers) can influence several parameters of soil structure and function, including aggregate formation, water holding capacity and microbial activity. Furthermore, recent studies suggest that the presence of MPs in soils affects the emissions of the greenhouse gases (GHG) carbon dioxide (CO2) and nitrous oxide (N2O). The mechanisms underpinning the direction and magnitude of MPs effects on GHG emissions from soils are uncertain, mainly due to the lack of knowledge of how the presence of MPs drives changes in soil structure and the subsequent link between soil structure and microbial activity. Here, we hypothesized that the presence of MPs affects soil structure by increasing porosity, leading to higher O2 availability and consequently higher decomposition of soil organic matter (SOM) and lower denitrification activity. In this study, we spiked MPs of different polymers (PET, PLA), morphologies (fragments, fibers) and sizes to a custom built rhizotron (7 x 4 x 1 cm) filled will a clay soil with a MP treatment of 5 w/w%. The soil was initially sterilized, but we added microbial inoculum collected from the same soil and glucose (as a substrate source) in known concentrations to assess soil respiration over time. We determined the spatial distribution of microbial respiration by mapping O2 concentrations using optode imaging, with a resolution of 1 image every 10 minutes over the course of 48 hours. Soil pore size, pore distribution and the pore connectivity network were determined by using X-ray micro-tomography (µCT). GHG emissions were measured by placing replicate set-ups in a Tedlar bag and collecting CO2 and N2O from the headspace in exetainers to be analyzed by gas chromatography. This approach allowed us to collect real-time O2 distribution and compare this to X-ray micro-tomography (µCT) data from the same soil matrix to assess MPs impacts to the soil structure and link it to GHG emissions compared to the control (i.e. no MPs addition). Collectively, in this presentation we will discuss the impacts of MPs addition to soil and on the linkages between soil structure, microbial activity and GHG emissions. This study can serve as a baseline for understanding the important impacts of MPs to soil functioning, which is particularly relevant as plastics are increasingly used directly in agriculture and can have direct releases to the terrestrial ecosystem.

Bacterial biofilms can form in porous media that are of interest in industrial and particularly environmental applications such as in situ groundwater remediation. The presence of biofilms modifies pore-scale and bulk hydrodynamics and consequently solutes transport and reaction kinetics. Porous media consist of highly heterogeneous flow fields and thus biofilm growth is also highly variable resulting in spatially variable biofilm permeabilities. Random processes are often invoked in hydrogeology to model variable quantities. Geo-statistical simulations require numerous realizations of a stochastic process over a grid. Our study leverages highly resolved three-dimensional X-ray computed microtomography images of bacterial biofilms in a tubular reactor to numerically compute pore scale flow and solute transport on a fine grid by considering various realizations of the biofilm permeability field. Using a conservative tracer experiment we first validate our flow and transport model which is then used to understand the impact of a heterogeneous permeability field on fluid-fluid and biologically driven reactions.

The simultaneous presence of liquid and gas in porous media increases flow heterogeneity compared to saturated flows. However, the impact of saturation on flow and transport has so far remained unclear. The presence of gas in the pore space leads to flow reorganization. We develop a theoretical framework that captures the impact of that reorganization on pore-scale fluid velocities. Preferential flow is distributed spatially through a backbone, and flow recirculation occurs in flow dead-ends. We observe, and predict theoretically, that this previously identified flow structure induces a marked change in the scaling of the velocity probability density function compared to the saturated configuration and a sharp transition to strongly anomalous transport. We develop a transport model using the continuous time random walk theory that predicts advective transport dynamics for all saturation degrees. Our results provide a new modeling framework linking phase heterogeneity to flow heterogeneity in unsaturated porous media., Geophysical Research Letters, 49 (3), ISSN:0094-8276, ISSN:1944-8007

Microorganisms capable of biomineralization can catalyze mineral precipitation by modifying local physical and chemical conditions. In porous media, such as soil and rock, these microorganisms live and function in highly heterogeneous physical, chemical and ecological microenvironments, with strong local gradients created by both microbial activity and the pore-scale structure of the subsurface. Here, we focus on extracellular bacterial biomineralization, which is sensitive to external heterogeneity, and review the pore-scale processes controlling microbial biomineralization in natural and engineered porous media. We discuss how individual physical, chemical and ecological factors integrate to affect the spatial and temporal control of biomineralization, and how each of these factors contributes to a quantitative understanding of biomineralization in porous media. We find that an improved understanding of microbial behavior in heterogeneous microenvironments would promote understanding of natural systems and output in diverse technological applications, including improved representation and control of fluid mixing from pore to field scales. We suggest a range of directions by which future work can build from existing tools to advance each of these areas to improve understanding and predictability of biomineralization science and technology., Reviews in Environmental Science and Biotechnology, 21 (1), ISSN:1569-1705, ISSN:1572-9826

The replacement of flood-irrigation systems by drip-irrigation technology has been widely promoted with the aim of a more sustainable use of freshwater resources in irrigated agriculture. However, evidence for an irrigation efficiency paradox emphasizes the need to improve our understanding of the impacts of irrigation transformations on water resources. Here, we developed a distributed hydrological modeling approach to investigate the spatiotemporal effect of flood and drip irrigation on groundwater recharge. The approach recognizes differences in the water balance resulting from the localized application of water in surface drip-irrigated fields and the more extensive application of water in flood irrigation. The approach was applied to the semi-arid Mediterranean region of Valencia (Spain) and calibrated using a multi-objective framework. Multiple process scales were addressed within the framework by considering the annual evaporative index, monthly groundwater level dynamics, and daily soil moisture dynamics. Daily simulations from 1994 to 2015 suggested that, in our hydroclimatic conditions, (a) annual recharge is strongly related to annual rainfall, which had a four times higher impact on recharge than the type of irrigation practice, (b) flood-irrigated recharge tends to exceed drip-irrigated recharge by 10% at annual time scales, (c) however, recharge response to a particular precipitation event is smaller in flood irrigation than in drip irrigation, and (d) 8-18 rainfall events could generate more than half of the annual recharge in drip and flood irrigation, respectively. Our results highlight the importance of understanding the hydrological dynamics under different irrigation practices for supporting irrigation infrastructure policies., Water Resources Research, 57 (8), ISSN:0043-1397, ISSN:1944-7973

We present a set of multiphase flow simulations where supercritical CO$$_2$$ (scCO$$_2$$) displaces water at hydrostatic conditions within three-dimensional discrete fracture networks that represent paths for potential leakage through caprock above CO$$_2$$ storage reservoirs. The simulations are performed to characterize and compare the relative impact of hydraulic and structural heterogeneity in fractured media on the initial movement of scCO$$_2$$ through these caprock formations. In one scenario, intrinsic fracture permeabilities are varied stochastically within a fixed network structure. In another scenario, we generate multiple independent, identically distributed network realizations with varying fracture network densities to explore a wide range of geometric and topological configurations. Analysis of the simulations indicates that network structure, specifically connectivity and the presence of hanging fractures, plays a larger role in controlling the displacement of water by scCO$$_2$$ than variations in local hydraulic properties. We identify active surface area of the network as a single-phase feature that could provide a lower bound on the percentage of the network surface area reached by scCO$$_2$$.

The Mar Menor is the largest lagoon along the Spanish Mediterranean coast. It suffers from eutrophication and algal blooms associated with intensive agricultural activities and urban pressure in the surrounding Campo de Cartagena plain. A balanced discharge of groundwater, carrier of algal nutrients such as nitrate, is essential to ensure the integrity of the coastal lagoon and the availability of groundwater resources inland. We here present a 3D hydrogeological model of the unconfined Quaternary aquifer that discharges into the lagoon. The model couples both surface water balance and groundwater dynamics and has been calibrated to available data in the period 2000-2016. The calibrated model allows understanding of the current state of the aquifer and its link to the lagoon. The potential discharge has been quantified in both space and time and falls between 69.5 and 84.9 hm3/yr during dry and wet periods, respectively (with values of nitrate discharge of 11.4-11.8 Mkg/yr in the absence of aquifer sink terms, e.g., leakage to deeper aquifers and pumping from groundwater wells). The predictive capabilities of the calibrated model can be used to test the impact of different integrated management scenarios on the surface-groundwater dynamics of the catchment. Three plausible management scenarios are proposed that include localized and distributed groundwater pumping (drains and groundwater wells, respectively). Results show the effectiveness of the scenarios in reducing the groundwater and nitrate discharge into the lagoon. The disadvantages of the proposed scenarios, including potential seawater intrusion, need to be balanced with their relative merits for the sustainable development of the region and the survival of the Mar Menor ecosystem. The modelling approach proposed provides a valuable tool for the integrated and holistic management of the Campo de Cartagena-Mar Menor catchment and should be of great interest to similar hydrological systems with high ecological value.

Aquifer natural recharge estimations are a prerequisite for understanding hydrologic systems and sustainable water resources management. As meteorological data series collection is difficult in arid and semiarid areas, satellite products have recently become an alternative for water resources studies. A daily groundwater recharge estimation in the NW part of the Lake Chad Basin, using a soil–plant-atmosphere model (VisualBALAN), from ground- and satellite-based meteorological input dataset for non-irrigated and irrigated land and for the 2005–2014 period is presented. Average annual values were 284 mm and 30°C for precipitation and temperature in ground-based gauge stations. For the satellite-model-based Lake Chad Basin Flood and Drought Monitor System platform (CHADFDM), average annual precipitation and temperature were 417 mm and 29°C, respectively. Uncertainties derived from satellite data measurement could account for the rainfall difference. The estimated mean annual aquifer recharge was always higher from satellite- than ground-based data, with differences up to 46% for dryland and 23% in irrigated areas. Recharge response to rainfall events was very variable and results were very sensitive to: wilting point, field capacity and curve number for runoff estimation. Obtained results provide plausible recharge values beyond the uncertainty related to data input and modelling approach. This work prevents on the important deviations in recharge estimation from weighted-ensemble satellite-based data, informing in decision making to both stakeholders and policy makers., Hydrological Processes, 35 (6), ISSN:0885-6087, ISSN:1099-1085

Coupling of unsaturated flows and surface reactions, including sorption and desorption, takes place in environmental contexts such as soils and the unsaturated zone. Lower sorption coefficients than those observed from batch experiments are found in natural soils. However, a deep understanding of this coupling is missing. To achieve this objective, we designed microfluidics experiments and performed direct numerical simulations based on experimental images at the microscale. We explore the effects of fluid flow dynamics and reaction kinetics on the effective kinetics. We have observed that an increase in the air volume within the porous medium promotes more heterogeneous fluid flow velocities, controlling the mixing of the transported reactant and resulting in a non-monotonic effective kinetic of the surface reaction.

Irrigated agriculture is the major water consumer in the Mediterranean region. Improved irrigation techniques have been widely promoted to reduce water withdrawals and increase resilience to climate change impacts. In this study, we assess the impact of the ongoing transition from flood to drip irrigation on future hydroclimatic regimes in the agricultural areas of Valencia (Spain). The impact assessment is conducted for a control period (1971-2000), a near-term future (2020-2049) and a mid-term future (2045-2074) using a chain of models that includes five GCM-RCM combinations, two emission scenarios (RCP 4.5 and RCP 8.5), two irrigation scenarios (flood and drip irrigation), and twelve parameterizations of the hydrological model Tetis. Results of this modelling chain suggest considerable uncertainties regarding the magnitude and sign of future hydroclimatic changes. Yet, climate change could lead to a statistically significant decrease in future groundwater recharge of up -6.6% in flood irrigation and -9.3% in drip irrigation. Projected changes in actual evapotranspiration are as well statistically significant, but in the order of +1% in flood irrigation and -2.1% in drip irrigation under the assumption of business as usual irrigation schedules. The projected changes and the related uncertainties will pose a challenging context for future water management. However, our findings further indicate that the effect of the choice of irrigation technique may have a greater impact on hydroclimate than climate change alone. Explicitly considering irrigation techniques in climate change impact assessment might therefore be a way towards better informed decision-making.This study has been supported by the IRRIWAM research project funded by the Coop Research Program of the ETH Zurich World Food System Center and the ETH Zurich Foundation, and by the ADAPTAMED (RTI2018-101483-B-I00) and TETISCHANGE (RTI2018-093717-B-I00) research projects funded by the Ministerio de Economia y Competitividad (MINECO) of Spain including EU FEDER funds.

Surfactants, after use, enter the environment through diffuse and point sources such as irrigation with treated and non-treated waste water and urban and industrial wastewater discharges. For the group of non-ionic synthetic surfactant alcohol ethoxylates (AEOs), most of the available information is restricted to the levels and fate in aquatic systems, whereas current knowledge of their behavior in soils is very limited. Here we characterize the behavior of different homologs (C12–C18) and ethoxymers (EO3, EO6, and EO8) of the AEOs through batch experiments and under unsaturated flow conditions during infiltration experiments. Experiments used two different agricultural soils from a region irrigated with reclaimed water (Guadalete River basin, SW Spain). In parallel, water flow and chemical transport were modelled using the HYDRUS-1D software package, calibrated using the infiltration experimental data. Estimates of water flow and reactive transport of all surfactants were in good agreement between infiltration experiments and simulations. The sorption process followed a Freundlich isotherm for most of the target compounds. A systematic comparison between sorption data obtained from batch and infiltration experiments revealed that the sorption coefficient (Kd) was generally lower in infiltration experiments, performed under environmental flow conditions, than in batch experiments in the absence of flow, whereas the exponent (β) did not show significant differences. For the low clay and organic carbon content of the soils used, no clear dependence of Kd on them was observed. Our work thus highlights the need to use reactive transport parameterization inferred under realistic conditions to assess the risk associated with alcohol ethoxylates in subsurface environments., Environmental Pollution, 269, ISSN:0269-7491, ISSN:1878-2450, ISSN:1873-6424

We study mixing-controlled chemical reactions in unsaturated porous media from a pore-scale perspective. The spatial heterogeneity induced by the presence of two immiscible phases, here water and air, in the pore space generates complex flow patterns that dominate reactive mixing across scales. To assess the impact of different macroscopic saturation states (the fraction of pore volume occupied by water) on mixing-controlled chemical reactions, we consider a fast irreversible reaction between two initially segregated dissolved species that mix as one solution displaces the other in the heterogeneous flow field of the water phase. We use the pore-scale geometry and water distributions from the laboratory experiments reported by Jimenez-Martinez et al. (Geophys. Res. Lett. 42: 5316-5324, 2015). We analyze reactive mixing in three complementary ways. Firstly, we post-process experimentally observed spatially distributed concentration data; secondly, we perform numerical simulations of flow and reactive transport in the heterogeneous water phase, and thirdly, we use an upscaled mixing model. The first approach relies on an exact algebraic map between conservative and reactive species for an instantaneous irreversible bimolecular reaction that allows to estimate reactive mixing based on experimental conservative transport data. The second approach is based on reactive random walk particle tracking simulations in the numerically determined flow field in the water phase. The third approach uses a dispersive lamella approach that accounts for the impact of flow heterogeneity on mixing in terms of effective dispersion coefficients, which are estimated from both experimental data and numerical random walk particle tracking simulations. We observe a significant increase in reactive mixing for decreasing saturation, which is caused by the stronger heterogeneity of the water phase and thus of the flow field. This is consistently observed in the experimental data and the direct numerical simulations. The dispersive lamella model, parameterized by the effective interface width, provides robust estimates of the evolution of the product mass obtained from the experimental and numerical data., Transport in Porous Media, 146 (1), ISSN:0169-3913, ISSN:1573-1634

Widespread seafloor methane venting has been reported in many regions of the world oceans in the past decade. Identifying and quantifying where and how much methane is being released into the ocean remains a major challenge and a critical gap in assessing the global carbon budget and predicting future climate [C. Ruppel, J. D. Kessler. Rev. Geophys. 55, 126–168 (2017)]. Methane hydrate ([Formula: see text]) is an ice-like solid that forms from methane–water mixture under elevated-pressure and low-temperature conditions typical of the deep marine settings ([Formula: see text] 600-m depth), often referred to as the hydrate stability zone (HSZ). Wide-ranging field evidence indicates that methane seepage often coexists with hydrate-bearing sediments within the HSZ, suggesting that hydrate formation may play an important role during the gas-migration process. At a depth that is too shallow for hydrate formation, existing theories suggest that gas migration occurs via capillary invasion and/or initiation and propagation of fractures (Fig. 1). Within the HSZ, however, a theoretical mechanism that addresses the way in which hydrate formation participates in the gas-percolation process is missing. Here, we study, experimentally and computationally, the mechanics of gas percolation under hydrate-forming conditions. We uncover a phenomenon—crustal fingering—and demonstrate how it may control methane-gas migration in ocean sediments within the HSZ.

Understanding the interplay between hydrodynamics and biogeochemical processes is of growing importance in environmental applications and studies, especially in the fields of bioremediation and ecology. The majority of the microbial communities living in soil have a surface-attached lifestyle, allowing them to form biofilms. The biofilm growth influences pore geometries by clogging them and thus redirecting the flow, which in return affects biofilm development and local mass transport. After initially clogging single pores, the biofilm structure expands to larger clusters before eventually clogging the porous medium entirely. We study these processes with a soil-born microorganism, Bacillus subtilis, in microfluidic devices mimicking porous media to get a mechanistic understanding of the driving factors of bioclogging of porous media on different scales. Carefully designed porous geometries were used for the experiments to study biofilm growth under different flow conditions. After being seeded with bacteria, devices were exposed to a continuous nutrient flow during several days. Continuously monitoring the pressure evaluation and imaging the biofilm growth using Brightfield microscopy allowed a high temporal resolution of biofilm growth processes. An interplay of hydraulic parameters and geometric features of the porous medium as well as the mass flow rate of nutrients drive the speed of pore clogging. Besides the pore scale clogging, the initiation of biofilm formation as well as the speed of clogging of the entire medium are influenced by the before mentioned parameters. Furthermore, the size and number of the biofilm clusters formed seem to drive the medium scale clogging. This leads to inverting trends concerning the clogging rate in one pore when compared to the porous medium scale for different pore sizes. These results shed light on the pore-scale mechanism as well as driving parameters of biofilm formation and bioclogging and their transferability to the next larger scale, e.g. a porous medium.

We investigate the impact of pore‐scale heterogeneity on reactive mixing using experimental data from inert fluid‐fluid displacement in a quasi 2‐D porous medium. We interpret the invading and defending fluids as the conservative components A+C and B+C of the instantaneous irreversible bimolecular chemical reaction A+B→C and determine the reaction product C. We find strong growth of the reaction rate at short and intermediate times due to deformation of the mixing interface and heterogeneity‐induced increase of the mixing area. This behavior is captured by a dispersive lamella approach that quantifies the mixing dynamics at the interface in terms of temporally evolving effective dispersion coefficients. The latter capture the dominant controls on the evolution of the mixing interface, namely, advective heterogeneity and transverse mixing. Reactive transport formulations based on constant hydrodynamic dispersion coefficients are not able to describe the observed behavior due to the lack of complete mixing on the support scale, which is required for these approaches to hold. These results shed some new light on the origins of heterogeneity‐induced mixing and reaction dynamics in porous media and their systematic upscaling., EC | FP7 | FP7 Ideas: European Research Council (FP7 Ideas). Grant Number: 617511 Ministerio de ciencia, innovación y universidades. Grant Number: RYC-2017-22300 European Research Council (ERC). Grant Number: 617511 Spanish Ministry of Science and Innovation. Grant Number: CEX2018-000794-S Spanish Ministry of Innovation and Universities. Grant Number: RYC-2017-22300

Teaching hydrogeology in the field presents unique cognitive difficulties, including the multidisciplinary and hidden nature of the processes. Lecturers commonly encounter large heterogeneity in student backgrounds, and many students harbor pre-existing mental models of the subsurface that differ from reality. In this study, we assess the influence of a student’s prior knowledge on his/her outcome in an inquiry-based learning strategy designed for a hydrogeology field course. We also assess the effectiveness of this strategy in the students’ conceptual model expression for the field site. Statistical results showed that in general lower scores were obtained in the conceptual model expression than in the inquiry-based learning. However, students with a high prior knowledge showed in average a better performance in the conceptual model expression, although with a larger variability, indicating that the prior knowledge is not a guarantee for an adequate conceptual model conception. In general, a learning bottleneck was identified: going from the split information to the integration of it. In the light of these findings, and in order to improve the student’s ability for conceptual model expression, we recommend the inclusion of specific prior-to-field lessons in the classroom to introduce methodologies for the expression of hydrogeological conceptual models to identify and dispel any prior misconceptions.

Baseflow is fed by groundwater to a large fraction. Estimating water quantity and quality from groundwater stores is essential for water management. However, there are few datasets available that contain detailed water chemistry analysis on high spatial resolution across multiple headwater catchments in (high) Alpine environments. This information is essential to analyze mixing processes on catchment scale from distinct landscape features.We use two data sets: i) water chemistry analysis snapshot sampling campaigns in 7 headwater streams during low‑flow periods across Switzerland, and ii) a detailed chemical screening (every 25 m) in one selected catchment during baseflow, including electric conductivity and temperature. Major ions, stable isotopes, TOC, DOC, trace elements were analyzed for some of the samples (> 80). These data reveal the chemical fingerprint of the contributing groundwater sources. The chemical composition of these contributing sources to baseflow is largely influenced by weathering products depended on lithology and geomorphology. Using maximum likelihood calculations, we define the ion composition and the isotopic signature of the potential major endmembers (up to three), based on the mixed samples along the main stem.The proposed methodology allows to i) reduce uncertainty of the endmembers, and ii) quantify the relative contribution of different lithology and geomorphological features to streamflow and shows iii) which spatial scale of input information is needed to analyze mixing processes from various groundwater sources. Our results show how the contribution of different lithologies, along with topography and geomorphological features, varies spatially throughout Alpine headwater catchments.

Irrigation modernization, here defined as the replacement of traditional flood irrigation systems by pressurized drip-irrigation technology, has been widely promoted with the aim to move towards a more sustainable use of freshwater resources in irrigated agriculture. However, the scale sensitivity of irrigation efficiency challenged the predominantly positive value attributed to irrigation modernization and asked for an integrated evaluation of the technological change at various scales. The aim of this study is therefore to contribute to an improved understanding of the hydrological functioning in a landscape under irrigation modernization. We used local field observations to propose a regional scale modeling approach that allowed to specifically simulate the difference in water balance as a function of irrigation method and crop type. The approach focused on the modification of the spatial input data and had therefore the benefit of being relatively independent of the final choice of the hydrological model. We applied the proposed approach to the semi-arid agricultural area of Valencia (Spain), where regional information about the use of irrigation technologies and irrigation volumes at farm level were available. The distributed hydrological model Tetis was chosen to simulate the daily water balance from 1994 to 2015 for an area of 913 km2 at a spatial resolution of 200 m. Model simulations were based on a random selection of parameter values that were subsequently evaluated in a multi-objective calibration framework. Multiple process scales were addressed within the framework by considering the annual evaporative index, monthly groundwater level dynamics, and daily soil moisture dynamics for evaluation. Simulation results were finally analyzed with a focus on groundwater recharge, which is of particular interest for environmental challenges faced within the study area. Simulation results of groundwater recharge for the entire agricultural area indicated a considerable variability in annual recharge (values from 112 mm up to 337 mm), whereby recharge was strongly controlled by annual rainfall volumes. Annual recharge in flood-irrigated areas tended to exceed annual recharge in drip irrigated-areas except for years with above average rainfall volumes. The observed rainfall dependency could be explained by the fact that recharge in drip-irrigated areas almost exclusively occurred during rainy days, whereby a few heavy rainfall events could produce the majority of annual recharge. Our results indicated interesting differences but also commonalities in groundwater recharge for flood and drip irrigation, and therefore emphasized the importance of explicitly considering irrigation technology when modelling irrigated agricultural areas.

The release of CO2 from the soil into the atmosphere, due to soil respiration, is a major, yet poorly understood flux that regulates the terrestrial carbon balance. In particular, the apparent insensitivity of soil respiration to emerging combined extreme events of heatwave and drought makes terrestrial ecosystems likely to shift from being carbon sinks to sources. Limited understanding of the interactions underlying this response represents one of the key sources of uncertainty in forecasts of atmospheric CO2. Here, we explore plant–microbe–soil interactions under heat and drought using a millifluidic setup that enables direct observations of hydration and oxygen content (the primary factors controlling soil respiration) in the root zone. Our observations reveal movement of water between soil regions via roots (termed root hydraulic redistribution), creating soil respiration hotspots and becoming a carbon source under combined heat and drought.

The dynamics of solute dispersion and mixing in unsaturated flows is analyzed from photo-bleaching experiments in two-dimensional porous micro-models. This technique allows producing pulse line (delta-Dirac) injections of a conservative tracer by bleaching a finite volume of fluorescent without disturbing the flow field. The temporal evolution of the concentration field and the spatial distribution of the air and water phases can be monitored at pore scale. We study the dispersion and mixing of a line of tracer under different water saturations. While dispersion in saturated porous media follows an approximately Fickian scaling, a shift to ballistic scaling is observed as soon as saturation is lowered. Hence, at the time scale of observation, dispersion in our unsaturated flows is dominated by the ballistic separation of tracer blobs within the water phase, between trapped clusters and preferential flow paths. While diffusion plays a minor role in the longitudinal dispersion during the time scale of the experiments, its interplay with fluid deformation is apparent in the dynamics of mixing. The scalar dissipation rates show an initial stretching regime, during which mixing is enhanced by fluid deformation, followed by a dissipation regime, during which diffusion overcomes compression induced by stretching. The transition between these two regimes occurs at the mixing time, when concentration gradients are maximum. We propose a predictive analytical model, based on shear-enhanced diffusion, that captures the dynamics of mixing from basic unsaturated porous media parameters, suggesting that this type of model may be a useful framework at larger scales. This article is protected by copyright. All rights reserved.

Wastewater treatment plants have been identified as important hubs for small particulate plastic, down to the nanometer scale, from urban areas to the environment. The reuse of sludge as fertilizer in agricultural practices can lead to accumulation of plastic in the soil. In this study, nanoplastic particles and microplastic fibers were synthesized with a passive inorganic tracer to aid in faster and more quantitative analysis using inductively coupled plasma mass spectrometry (ICP-MS). Using the anaerobic digestate of a pilot wastewater treatment plant spiked with metal-doped plastic, the excess sludge was dewatered, ensuring realistic associations between sludge and plastic. The resulting sludge cake was affixed atop an unsaturated porous-medium column of glass beads to assess: (i) the release of particulate plastic from the sludge, and (ii) the accumulation and mobility of plastic and organic matter through the column (analogous to a soil). A total of three particulate plastic treatments were assessed, in triplicate, where the plastic and mobile organic fractions were monitored for 14 pore water volumes. Due to size-limited transport, low deattachment from the sludge and reduced mobility through the column were found for microplastic fibers (>95% retention). However, cotransport between the mobile organic fraction and nanoplastic particles was observed, with 50% of both retained in the column. These results contribute to the understanding of the fate of particulate plastics and to assessing the associated environmental risks of particle mobility and percolation, particularly for nanoplastics.

Human endeavours into deep space exploration and the prospects of establishing colonies on nearby planets would invariably involve components of bioregenerative life support for food production, cabin atmosphere renewal, and waste recycling. Growing plants and their microbiomes in porous media under different gravitational fields may present new challenges due to effects of liquid distribution on gaseous exchange with roots and microorganisms. We provide the first direct evidence that capillary driven liquid reconfiguration in porous media under reduced gravity conditions reduces oxygen diffusion pathways and enhances anoxic conditions within bacterial hotspots. Parabolic flight experiments using model porous media inoculated with aerobic and facultative anaerobic bacteria reveal the systematic enhancement of anoxic conditions during the reduced gravity periods in the presence but not in the absence of bacterial activity. The promotion of anoxic conditions under reduced gravity may lead to higher nitrous oxide and methane emissions relative to Earth conditions, on the other hand, anoxic conditions could be beneficial for perchlorate bioremediation of Martian soil. The results highlight changes in soil bacterial microhabitats under reduced gravity and the challenges of managing bioregenerative life support systems in space., Scientific Reports, 10 (1), ISSN:2045-2322

The impact of phases distribution on mixing and reaction is hardly assessable experimentally. We use a multiple point statistical method, which belongs to the family of machine learning algorithms, to generate simulations of phases distributions from data out of laboratory experiments. The simulations honour the saturation of the laboratory experiments, resemble the statistical distributions of several geometric descriptors and respect the physics imposed by capillary forces. The simulated phases distributions are used to compute solute transport. The breakthrough curves reveal that different phases distributions lead to broad ranges of early arrival times and long-term tailings as saturation decreases. For a given saturation, a similar long-term scaling of mixing area, interface length, and corresponding reactivity is observed regardless of phases distribution. However, phases distribution has a clear impact on the final values (before breakthrough) of area of mixing, interface length and mass of reaction product.

Understanding the fundamental mechanisms of fluid flows and reactive transport in natural systems is a major challenge for several fields of Earth sciences (e.g., hydrology, soil science, and volcanology) and geo/environmental engineering (CO2 sequestration, NAPLS contamination, geothermal energy, and oil and gas reservoir exploitation). The hierarchical structures of natural system (e.g., heterogeneity of geological formations) as well as the different behavior of single and multiphase fluids at the pore-scale coupled with the nonlinearity of underlying reactive processes necessitates investigating these aspects at the scale at which they physically occur, the scale of pore and fractures. Recent improvements in pore-scale computational modelling, together with the development of noninvasive microscopic imaging technology and the latest microfluidic technics are allowing the vast field of porous and fractured media research to benefit of major advances due to (1) an improved understanding and description of pore-scale mechanisms and (2) the ability of thinking in terms of coupled processes. The contributions collected in this special issue, although far from constituting a comprehensive picture of the "pore-scale world," however offer a good example of the potentialities of such an approach to investigate a wide range of processes usually observed at macroscale, but whose underlying physical and chemical processes take place at microscale.

Time-lapse electrical resistivity tomography (ERT) is a geophysical method widely used to remotely monitor the migration of electrically-conductive tracers and contaminant plumes in the subsurface. Interpretations of time-lapse ERT inversion results are generally based on the assumption of a homogeneous solute concentration below the resolution limits of the tomogram depicting inferred electrical conductivity variations. We suggest that ignoring small-scale solute concentration variability (i.e., at the sub-resolution scale) is a major reason for the often-observed apparent loss of solute mass in ERT tracer studies. To demonstrate this, we developed a geoelectrical milli-fluidic setup where the bulk electric conductivity of a 2D analogous porous medium, consisting of cylindrical grains positioned randomly inside a Hele–Shaw cell, is monitored continuously in time while saline tracer tests are performed through the medium under fully and partially saturated conditions. High resolution images of the porous medium are recorded with a camera at regular time intervals, and provide both the spatial distribution of the fluid phases (aqueous solution and air), and the saline solute concentration field (where the solute consists of a mixture of salt and fluorescein, the latter being used as a proxy for the salt concentration). Effective bulk electrical conductivities computed numerically from the measured solute concentration field and the spatial distributions of fluid phases agree well with the measured bulk conductivities. We find that the effective bulk electrical conductivity is highly influenced by the connectivity of high electrical conductivity regions. The spatial distribution of air, saline tracer fingering, and mixing phenomena drive temporal changes in the effective bulk electrical conductivity by creating preferential paths or barriers for electrical current at the pore-scale. The resulting heterogeneities in the solute concentrations lead to strong anisotropy of the effective bulk electrical conductivity, especially for partially saturated conditions. We highlight how these phenomena contribute to the typically large apparent mass loss observed when conducting field-scale time-lapse ERT.

Porous media in which different fluid phases coexist are common in nature (e.g., vadose zone and gas-oil reservoirs). In partially saturated porous media, the intricate spatial distributions of the wetting and nonwetting phases causes their flow to be focused onto preferential paths. Using a novel 2-D experimental setup allowing pore-scale measurement of concentration fields in a controlled unsaturated flow, we highlight mechanisms by which mixing of an invading fluid with the resident fluid is significantly enhanced when decreasing saturation. The mean scalar dissipation rate is observed to decrease slowly in time, while under saturated conditions it decays rapidly. This slow decrease is due to sustained longitudinal solute fingering, which causes concentration gradients to remain predominantly transverse to the average flow. Consequently, the effective reactivity is found to be much larger than under saturated conditions. These results provide new insights into the role that multiphase flows play on mixing/reaction in porous media.

Hydraulic fracturing of shale formations in the United States has led to a domestic energy boom. Currently, water is the only fracturing fluid regularly used in commercial shale oil and gas production. Industry and researchers are interested in non-aqueous working fluids due to their potential to increase production, reduce water requirements, and to minimize environmental impacts. Using a combination of new experimental and modeling data at multiple scales, we analyze the benefits and drawbacks of using CO2 as a working fluid for shale gas production. We theorize and outline potential advantages of CO2 including enhanced fracturing and fracture propagation, reduction of flow-blocking mechanisms, increased desorption of methane adsorbed in organic-rich parts of the shale, and a reduction or elimination of the deep re-injection of flow-back water that has been linked to induced seismicity and other environmental concerns. We also examine likely disadvantages including costs and safety issues associated with handling large volumes of supercritical CO2. The advantages could have a significant impact over time leading to substantially increased gas production. In addition, if CO2 proves to be an effective fracturing fluid, then shale gas formations could become a major utilization option for carbon sequestration.

International audience; The simulation of unstable invasion patterns in porous media flow is challenging since small perturbations tend to grow in time, so that slight differences in geometry or initial conditions potentially give rise to significantly different solutions. Here we present a detailed comparison of pore scale simulations and experiments of unstable primary drainage in porous micromodels. The porous medium consists of a Hele-Shaw cell containing cylindrical obstacles. Two experimental flow cells have been constructed by soft lithography, with different degrees of heterogeneity in the grain size distribution. To model two-phase flow at the pore scale, we solve Navier-Stokes equations for mass and momentum conservation in the discretized pore space and employ the Volume of Fluid (VOF) method to track the evolution of the interface. During drainage, if the defending fluid is the most viscous, viscous forces destabilize the interface, giving rise to the formation of preferential flow paths, in the form of a branched fingering structure. We test different numerical models (a 2D vertical integrated model and a full 3D model) and different initial conditions, studying their impact on the simulated spatial distributions of the fluid phases. Although due to the unstable nature of the invasion, small discrepancies between the experimental setup and the numerical model can result in different fluids patterns (see figure), simulations show a satisfactory agreement with the structures observed experimentally. To estimate the ability of the numerical approach to reproduce unstable displacement, we compare several quantities in both the statistical and deterministic sense. We demonstrate the impact of three main sources of uncertainty : i) the uncertainty on the pore space geometry, ii) the interface initialization and ii) three dimensional effects [1]. Simulations in weakly heterogeneous geometries are found to be more challenging because uncertainties on pore neck widths are on the same order of magnitude as the pore to pore variability of those widths.[1] A. Ferrari, J. Jimenez-Martinez ,T. Le Borgne , Y. Méheust, and I. Lunati (2014), Challenges in modeling unstable two-phase flow experiments in porous micromodels, submitted.

Microfluidic investigations of flow and transport in porous and fractured media have the potential to play a significant role in the development of future subsurface energy resource technologies. However, the majority of experimental systems to date are limited in applicability due to operating conditions and/or the use of engineered material micromodels. We have developed a high pressure and temperature microfluidic experimental system that allows for direct observations of flow and transport within geo-material micromodels (e.g. rock, cement) at reservoir conditions. In this manuscript, we describe the experimental system, including our novel micromodel fabrication method that works in both geo- and engineered materials and utilizes 3-D tomography images of real fractures as micromodel templates to better represent the pore space and fracture geometries expected in subsurface formations. We present experimental results that highlight the advantages of using real-rock micromodels and discuss potential areas of research that could benefit from geo-material microfluidic investigations. The experiments include fracture-matrix interaction in which water imbibes into the shale rock matrix from etched fractures, supercritical CO2 (scCO2) displacing brine in idealized and realistic fracture patterns, and three-phase flow involving scCO2-brine-oil.

This paper presents a multicontinuum approach to model fractal temporal scaling of catchment response in hydrological systems. The temporal scaling of discharge is quantified in frequency domain by the transfer function HðxÞ, which is defined as the ratio between the spectra of catchment response and recharge time series. The transfer function may scale with frequency x as HðxÞ x2b. While the classical linear and Dupuit models predict exponents of b52 and b51, observations indicate scalings with noninteger exponents b. Such behaviors have been described by multifractal models, which, however, often lack a relation to the medium characteristics. We revisit and extend the classical linear Dupuit aquifer models and discuss their physical meanings in the light of the resulting aquifer dynamics. On the basis of these classical models, we derive a multicontinuum approach that provides physical recharge models which are able to explain fractal behaviors with exponents 1=2 < b < 2. Furthermore, this approach allows to link the fractal dynamics of the discharge process to the physical aquifer characteristics as reflected in the distribution of storage time scales. We systematically analyze the catchment responses in the proposed multicontinuum models, and identify and quantify the time scales which characterize the dynamics of the catchment response to recharge.

One of the most important issues for water resource management is developing strategies for groundwater modelling that are adaptable to data scarcity. These strategies are particularly important in arid and semi-arid areas where access to data is poor and data collection is difficult, such as the Lake Chad Basin in Africa. In the present study, we establish a numerical groundwater flow model and evaluate the effects of dry and wet periods on groundwater recharge in the Chari–Logone area (96 000 km2) of the Lake Chad Basin. Boundary conditions, flow direction, sources, and sinks for the Chari–Logone local model were obtained by revising and remodelling the Lake Chad Basin regional hydrogeological model (508 400 km2) developed by the BRGM (Bureau de Recherches Geologiques et Minieres) in the 1990s. The simulated aquifer water level showed good agreement with observed levels. Aquifer recharge is primarily determined by river–aquifer interactions and mostly occurs in the southern section of the study area. In wet years, groundwater recharge also occurs in the N'Djamena area. The approach we adopted provided relevant results and was useful as an initial step in more detailed modelling of the area. It also proved to be a useful method for groundwater modelling in large semi-arid and arid regions where available data are scarce. Copyright © 2013 John Wiley & Sons, Ltd.