Efficient phosphate recovery and water disinfection are critical for addressing environmental sustainability challenges. However, conventional nanomaterials have exhibited unsatisfactory performance and limited controllability, complicating their application in wastewater treatment. Here, we propose urchin-like La/Cu-Fe3O4 nanocapsules (NCs) featuring perpendicular La/Cu nanosheets surrounding an Fe3O4 nanosphere core. These NCs were synthesized using high-density adsorption and a controlled crystallization strategy, yielding a hydrotalcite-like structure that enhances phosphate adsorption and disinfection through osmotic pressure-mediated mechanisms. The La/Cu-Fe3O4 NCs exhibited an exceptional phosphate adsorption capacity of up to 1085.56 mg PO43− g–1, with rapid adsorption kinetics achieving equilibrium within 5 min. Coexisting ions facilitated the penetration of phosphate ions into the NCs, promoting stable binding with La and achieving 100

The vadose zone acts as a natural buffer that prevents contaminants such as arsenic (As) from contaminating groundwater resources. Despite its capability to retain As, our previous studies revealed that a substantial amount of As could be remobilized from soil under repeated wet-dry conditions. Overlooking this might underestimate the potential risk of groundwater contamination. This study quantified the remobilization of As in the vadose zone and developed a prediction model based on soil properties. 22 unsaturated soil columns were used to simulate vadose zones with varying soil properties. Repeated wet-dry cycles were conducted upon the As-retaining soil columns. Consequently, 13.9-150.6 mg/kg of As was remobilized from the columns, which corresponds to 37.0-74.6 % of initially retained As. From the experimental results, a machine learning model using a random forest algorithm was established to predict the potential for As remobilization based on readily accessible soil properties, including organic matter (OM) content, iron (Fe) content, uniformity coefficient, D30, and bulk density. Shapley additive explanation analyses revealed the interrelated effects of multiple soil properties. D30, which is inter-related with Fe content, exhibited the highest contribution to As remobilization, followed by OM content, which was partially mediated by bulk density.

Arsenic (As) pollution in soil from various anthropogenic sources potentially threatens groundwater by migrating downward through a vadose zone. As goes through complex biogeochemical reactions such as sorption, desorption, and/or redox transformation, which affects its retention in this zone. A retardation factor is a critical solute-transport parameter to quantitatively assess the retention of As in this zone, and eventually to predict the potential risk of groundwater contamination. Despite its importance, however, there is still limited information to quantify the retardation factor in a vadose zone, compared to in the saturated condition. This study aimed to assess the retardation factor of As using twenty-two unsaturated soil columns coupled with the non-equilibrium solute-transport modeling. We employed a multiple linear regression approach to develop a prediction model for the retardation factor based on the soil properties. Soil columns with 3-cm inner diameter and 45-cm height were packed with six different field soils at various bulk densities. Distilled water was infiltrated into each column at a constant flowrate, until a steady-state unsaturated condition was achieved. The distilled water was replaced with a solution containing As and a conservative tracer (chloride, Cl), to obtain their breakthrough curves. The retardation factor of As was determined by inversely fitting the breakthrough data of As and Cl with Mobile-Immobile model integrated in HYDRUS 1-D software. The derived retardation factors of As in the mobile and immobile zones ranged 1.58–6.93 and 1.44–25.48, respectively. These showed high degree of dependence on soil properties. In the mobile water zone, iron content and organic matter content emerged as the two most influential properties affecting As transport, impeding As mobility. Conversely, in the immobile water zone, coefficient of uniformity and bulk density were identified as the most influential factors, enhancing As retention. Based on the results, empirical equations were derived to predict the retardation factors of As in a vadose zone based on the aforementioned soil properties.

We examined oil-water displacement under constant pressure difference conditions, simulating natural aquifer environments using microfluidic chips with different wettability and pore geometries. The results showed lower oil retention in hydrophobic chips than hydrophilic ones, contrary to previous microfluidic chip experiments conducted under constant flow rate conditions. This is because hydrophobic surfaces reduce capillary pressure drop but increase viscous pressure drop for compensation, leading to higher flow rate and displacement. Additionally, complex pore geometries in hydrophilic chips cause oil clusters to break into smaller blobs, reducing retention and enhancing the relative permeability of water. These findings suggest that relying solely on hydrophobicity may be ineffective in retaining oil in porous materials under constant pressure difference conditions, highlighting the need for more careful consideration in groundwater remediation design.

Despite the role of the vadose zone protecting groundwater from contamination, the non-stationarity in this zone makes it difficult to predict the behavior of petroleum hydrocarbons (PH) therein. In laboratory soil columns with sandy and sandy loam soils, we simulated a vadose zone subjected to repeated groundwater-level fluctuation (GLF) to evaluate the behavior of PH under hydrodynamic conditions. The GLF vertically redistributed the PH, the extent of which was pronounced in the sandy soil with a high initial concentration due to the enhanced transport of the immiscible PH through the larger pores. The frequency of GLF did not show a substantial effect on the extent of PH redistribution but largely affected their attenuation. The greater GLF hindered PH volatilization by maintaining a high degree of water saturation, while the subsequent development of a local anaerobic regime inhibited biodegradation, which was more apparent in the sandy loam. Finally, a specific potential risk index was introduced to quantitatively compare the potential risk of PH contamination in different vadose zones exposed to GLF. Overall, the sandy soil contaminated with the higher total PH (TPH) concentration showed markedly higher potential risk indices (i.e., 18.4-29.0%), while the ones comprised of the sandy loam showed 0.6-4.9%, which increased under the greater number of GLF cycles.

Aquifer storage and recovery (ASR) is a promising water management technique in terms of quantity and quality. During ASR, iron (Fe) (hydr)oxides contained in the aquifer play a crucial role as electron acceptors in attenuating dissolved organic carbon (DOC) in recharging water through dissimilatory iron reduction (DIR). Considering the preference of electron acceptors, nitrate (NO3-), possibly coexisting with DOC as the prior electron acceptor to Fe (hydr)oxides, might influence DIR by interrupting electron transfer. However, this phenomenon is yet to be clarified. In this study, we systematically investigated the potential effect of NO3- on DOC attenuation during ASR using a series of sediment columns representing typical aquifer conditions. The results suggest that DOC attenuation could be enhanced by the presence of NO3-. Specifically, total DOC attenuation was notably higher than that from the stoichiometric calculation simply employing NO3- as the additional electron acceptor to Fe (hydr)oxides, implying a synergetic effect of NO3- in the overall reactions. Xray photoelectron spectroscopy analyzes revealed that the Fe(II) ions released from DIR transformed the Fe (hydr)oxides into a less bioavailable form, inhibiting further DIR. In the presence of NO3-, however, no aqueous Fe(II) was detected, and another form of Fe (hydr)oxide appeared on the sediment surface. This may be attributed to nitrate-dependent Fe(II) oxidation (NDFO), in which Fe(II) is (re)oxidized into Fe (hydr)oxide, which is available for the subsequent DOC attenuation. These mechanisms were supported by the dominance of DIR-relevant bacteria and the growth of NDFO-related bacteria in the presence of NO3-.

Water and wastewater treatment plants (WWTPs) receive various types of microplastics (MPs), with fibers and fragments being dominant shapes. Here we investigated the removal behavior and transformation of MPs (polypropylene and polyethylene terephthalate fibers and fragments) in simulated water and wastewater treatment units, including activated sludge process, coagulation, sand filtration, and advanced oxidation/disinfection. Sand filtration demonstrated the highest average efficiency in removing MPs (98 %), followed by activated sludge process (61 %) and coagulation (55 %), which was associated with their physicochemical properties (shape, size, density, surface functional groups, etc). In activated sludge process and coagulation, the polymer type had a greater impact on the removal of MPs than the particle shape, while in sand filtration, the particle shape played a more important role. When subjected to the long-term operation and backwashing of sand filters, approximately 15 % of the initially filtered fragments broke through the sand media, with nearly no fibers escaping. UV-based advanced oxidation and chlorination induced the leaching of dissolved organic matters with different molecular characteristics from fragment MPs, resulting in varying levels of cytotoxicity and bacterial toxicity. Our study provides important information for predicting the fate of MPs and mitigating their impacts in WWTPs.

Aquifer storage and recovery (ASR) is a promising approach for managing water resources that enhances water quality through biogeochemical reactions occurring within aquifers. Iron (hydr)oxides, which are the predominant metallic oxides in soil, play a crucial role in degrading dissolved organic carbon (DOC), primarily through a process known as dissimilatory iron reduction (DIR). However, the efficiency of this reaction varies depending on the mineralogy and composition of the aquifer, and this understanding is essential for adequate water quality in ASR. The objective of this study is to investigate the impact of iron (hydr)oxide on acetate, as an organic carbon source, attenuation during the ASR. To achieve this, three sets of laboratory sediment columns were prepared, each containing a different type of iron (hydr)oxide minerals: ferrihydrite, goethite, and hematite. Following an acclimation period of 28 days to simulate the microcosm within an aquifer, the columns were continuously supplied with the simulated river water spiked with acetate (DOC 40–60 mg L−1), and the acetate concentration in the effluent was monitored. The result revealed that the column containing ferrihydrite achieved 97% acetate attenuation through DIR with anoxic conditions (DO < 0.1 mg L−1), while the goethite and hematite columns exhibited limited attenuation rates of 40 and 50%, respectively. Furthermore, the efficiency of acetate attenuation in the ferrihydrite columns increased with the content of ferrihydrite but experienced a rapidly declined at higher contents (3–4%), possibly due to the partial conversion of ferrihydrite to goethite as a result of the interaction between ferrihydrite and the Fe(II) produced during DIR. Additionally, an analysis of the microbial community demonstrated that microorganisms known to possess the ability to reduce iron (hydr)oxides under anaerobic conditions were abundant in the ferrihydrite columns.

Soil microbiome is responsible for crucial biochemical reactions by interacting with organic compounds in the injection wells in aquifer storage and recovery (ASR) processes. This study investigated seasonal variations in organic compounds and microbial communities in a simulated ASR system. For this purpose, eleven pilot-scale soil columns were operated in ASR mode over 13 months. River water was intermittently fed into the simulated ASR system after sedimentation pretreatment. As a result, the sand ratios in soil texture were slightly increased from 93.2-93.4 % to 96.6-98.1 % while the total organic carbon content in the soil was accumulated and maintained at < 0.2 % during the ASR operation. During the sedimentation process, 9-31 % of dissolved organic carbon (DOC) was removed in the water, while during the storage in the soil column, the DOC in water was fluctuated. However, the DOC concentration (less than 4 mg/L) in the effluent was stably maintained until the end of operational periods. High-throughput sequencing results showed that the predominant phylum was Proteobacteria. Interestingly, at the species level, the microbial community structure clearly shifted with elapsed time and column location; various organic degrading soil microbiome having different physiological characteristics (e.g., oxygen, substrate, and temperature) became predominant. Outcomes of this study suggest that soil microbiome can facilitate the establishment of stable ASR processes for river water treatment by contributing to bioattenuation.

The vadose zone acts as a natural buffer against groundwater contamination, and thus, its attenuation capacity (AC) directly affects groundwater vulnerability to pollutants. A regression model from the previous study predicting the overall AC of soils against diesel was further expanded to the GIS-based overlay-index model. Among the six physicochemical parameters used in the regression model, saturation degree (SD) is notably susceptible to climatological and meteorological events. To accommodate the lack of soil SD historical data, a series of infiltration simulations were separately conducted using Phydrus code with moving boundary conditions (i.e., rainfall records). The temporal variation of SD and the resulting AC under transient conditions are captured by building a space–time cube using a temporal raster across the study area within the designated time frame (1997–2022). The emerging hot spot analysis (EHSA) tool, based on the Getis–Ord Gi* and Mann–Kendall statistics, is applied to further identify any existing pattern associated with both SD and AC in both space and time simultaneously. Under stationary conditions, AC decreases along depth and is relatively lower near water bodies. Similarly, AC cold spot trends also show up near water bodies under transient conditions. The result captures not only the trends across time but also shows the exact location where the changes happen. The proposed framework provides an efficient tool to look for locations that have a persistently low or a gradually decreasing ability to attenuate diesel over time, indicating the need for stricter management regulations from a long-term perspective.

Evaluating and predicting the natural attenuation capacity (AC) of a vadose zone is essential for determining groundwater vulnerability to contamination from upper sources. However, it remains unclear how the physicochemical properties of vadose zone soils affect AC owing to their complexity and spatial heterogeneity. In this study, we developed a regression model for estimating the AC of a vadose zone against diesel using datasets from different soils with a wide range of physicochemical properties. Among the 17 properties, six (i.e., organic matter (OM), total phosphorous (TP), coefficient of uniformity, particle size (D30), van Genuchten’s n, saturation degree (SD)) were selected as primary regressors. The results indicate that biogeochemical factors, including OM and TP, have decisive effects on the AC. Finally, the regression model was expanded to a GIS-based spatial model and applied to Namyangju, Korea using the index-overlay method. The produced AC map showed a nonmonotonic decrease along the depth, and the areas closer to the water bodies generally represented low AC values, most likely due to the lower OM, TP, and higher SD. This study provides an empirical basis for future research initiatives for spatial and temporal AC dynamics, which complements conventional intrinsic groundwater vulnerability models such as DRASTIC.

In natural environments, the fate and migratory behavior of metalloid contaminants such as antimony (Sb) significantly depend on the interfacial reactivity of mineral surfaces. Although boehmite (gamma-AlOOH) is widely observed in (sub)surface environments, its underlying interaction mechanism with Sb oxyanions at the molecular scale remains unclear. Considering Sb-contaminated environmental conditions in this study, we prepared boehmite under weakly acidic conditions for use in the systematic investigation of interfacial interactions with Sb (III) and Sb(V). The as -synthesized boehmite showed a nanorod morphology and comprised four crystal facets in the following order: 48.4% (010), 27.1% (101), 15.0% (001), and 9.5% (100). The combined results of spectroscopic analyses and theoretical calculations revealed that Sb(III) formed hydrogen bonding outer-sphere complexation on the (100), (010), and (001) facets and that Sb(V) preferred to form bidentate inner-sphere complexation via mononuclear edge-sharing configuration on the (100), (001), and (101) facets and binuclear corner-sharing configuration on the (010) facet. These findings indicate that the facet-mediated thermodynamic stability of the surface complexation determines the interaction affinity toward the Sb species. This work is the first to document the contribution of boehmite to (sub)surface media, improving the ability to forecast the fate and behavior of Sb oxyanions at mineral-water interfaces.

The anomalous (i.e., non-Fickian) transport characteristics (e.g., early arrival/long tailing and other non-Gaussian plume properties) make it challenging to apply classical transport theories to the transport and retention of microplastics in soil due to their heterogeneity. This overview attempts 1) to delineate the previous studies on the transport of colloids and MPs, which used the recently developed analytical devices (e.g., microfluidics and micro-CT) and process-based (e.g., lattice Boltzmann method (LBM) and pore network modeling (PNM)) or data-driven models (e.g., machine learning (ML) techniques) and 2) to provide future directions for bridging the pore- and continuum-scale properties. Although the LBM and PNM offer significant advantages in depicting particle transport at the pore scale, their employment at larger scales is hindered by computational demands. Nonetheless, applying these methods to generate datasets for ML techniques is anticipated to provide a robust tool for an accurate and rapid continuum-scale microplastics transport model.

The fate and transport of microplastics (MPs) during deep bed filtration were investigated using combined laboratory experiments and numerical modeling. A series of column experiments were conducted within the designated ranges of six operating parameters (i.e., size of the MP and collector, seepage velocity, porosity, temperature, and ionic strength). A variance-based sensitivity analysis, the Fourier amplitude sensitivity test, was conducted to determine the priority in affecting both the attachment coefficient at the pore scale, and the subsequent stabilized height of the breakthrough curve at the continuum scale, which follows non-monotonic trends with singularity in the size of MP (i.e., 1 µm). Finally, Damkohler numbers were introduced to analyze the dominant mechanisms (e.g., attachment, detachment, or straining) in the coupled hydro-chemical process. The robustness of conceptual frameworks bridges the gap between pore-scale interactions and the explicit MPs removal in the continuum scale, which could support decision-making in determining the priority of parameters to retain MPs during deep bed filtration.

The nonstationary nature of water and oxygen content in the vadose zone determines various biogeochemical reactions regarding arsenic (As) therein, which affects the groundwater vulnerability to As contamination at a site. In the present study, we evaluated the effect of soil organic matter (OM) on the behavior of As using specifically designed soil columns that simulated the vadose zone. Three wet-dry cycles were applied to each of the four columns with different OM contents and bulk densities. OM was found to exhibit variable effects, either inhibiting or accelerating the mobilization of As, depending on bulk density. At a moderate bulk density (< 1.27 g/cm3), OM slightly lowered the pH of pore water, which enhanced the sorption of As onto the iron (Fe) oxides, promoting the retention of As in soil. In the soil column with a relatively higher bulk density (1.36 g/cm3), however, the dissimilatory reduction of iron oxides was triggered by rich OM under oxygen-limited conditions. X-ray absorption spectroscopy analysis revealed that alternate wetting and drying transformed the Fe oxides in the soil by reductive dissolution and subsequent re-precipitation. Consequently, As was not stably retained in the soil, and its mobilization downwards was further accelerated.

The migration of petroleum hydrocarbons in vadose zone involves complex coupled processes such as downward displacement and natural attenuation. Despite its significance in determining groundwater vulnerability to petroleum contamination and optimizing the remedial strategy, it has not been comprehensively studied in terms of overall processes under field-relevant conditions. In this study, a series of unsaturated soil column experiments were conducted by simulating subsurface diesel contamination within a vadose zone using different soil textures at different soil bulk densities and initial diesel concentrations, while partly exposing them to simulated precipitation. The results showed that the soil column with less fine fraction was favorable for the downward migration of diesel but unfavorable for its natural degradation. However, precipitation complicated the relative conductivities of multiple fluids (water, air, and diesel) through the pore network, therby decreasing diesel migration and degradation. For example, the downward migration of diesel in the SL column decreased by 8.4% under precipitation, while the overall attenuation rate dropped to almost 0.24% of its original state. Lowering bulk density (from 1.5 to 1.23 g/cm3), however, could enhance the attenuation rate presumably due to the secured void space for the incoming fluids. A high initial concentration of diesel (2%; w/w) inhibited its natural attenuation, while its influence on its vertical propagation after the precipitation was not significant. The present findings provide a mechanistic basis for approximating the behavior of petroleum hydrocarbons in a random vadose zone.

Despite its environmental significance, little is known about denitrification in vadose zones owing to the complexity of such environments. Here, we investigated denitrification in unsaturated soils with different pore distributions. To this end, we performed batch-type denitrification experiments and analyzed microbial community shifts before and after possible reactions with nitrates to clarify the relevant denitrifying mechanism in the microcosms. For quantitative comparison, pore distribution in the test soil samples was characterized based on the uniformity coefficient (Cu) and water saturation degree (SD). Micro-CT analysis of the soil pore distribution confirmed that the proportion of bigger-sized pores increased with decreasing Cu. However, oxygen diffusion into the system was controlled by SD rather than Cu. Within a certain SD range (51-67%), the pore condition changed abruptly from an oxic to an anoxic state. Consequently, denitrification occurred even under unsaturated soil conditions when the SD increased beyond 51-67%. High throughput sequencing revealed that the same microbial species were potentially responsible for denitrification under both partially (SD 67%), and fully saturated (SD of 100%) conditions, implying that the mechanism of denitrification in a vadose zone, if it exists, might be possibly similar under varying conditions.

Aquifer storage and recovery (ASR) is an important water resources management technique that involves the injection of a large volume of water underground. For the successful implementation of an ASR project, a target aquifer should have a sufficient injection capacity, which is the maximum volume of water that can be safely injected. In nature, no aquitard is perfectly impermeable, and inter-aquifer leakage may have a major impact on injection capacity. Despite the importance of determining the injection capacity for ASR planning, there is no quantitative methodology that estimates the injection capacity of leaky aquifers. In this study, we first develop a solution for injection capacity with inter-aquifer leakage based on the Hantush - Jacob solution, and conduct a comprehensive sensitivity analysis to elucidate the influence of inter-aquifer leakage on injection capacity. From the sensitivity analysis, we show that inter-aquifer leakage can impact injection capacity by more than one order of magnitude, depending on the hydrogeological and operational parameters. We then develop a practical mapping methodology that estimates the injection capacity of leaky aquifers. We demonstrate the proposed methodology by applying it to a potential ASR site in Minnesota, USA, where ASR is considered as a solution to alleviate groundwater contamination by PFAS chemicals. The case study results reveal significant spatial variability in injection capacity over the study area and show an average increase in the injection capacity of about 26% compared to that in the nonleaky scenario. We also analyze the uncertainty in the estimated injection capacity due to the variability of aquitard properties and show that the variability of aquitard vertical hydraulic conductivity leads to a larger uncertainty in the estimated injection capacity than does the variability of aquitard thickness. This study elucidates the effects of inter-aquifer leakage on injection capacity and provides a practical methodology for injection capacity mapping.

Identifying the cause of inconsistent landfarming efficacy is critical to designing optimal remedial strategies for petroleum-contaminated sites. We assessed contaminated soils collected from two former military bases in South Korea to better understand the role and influence of different factors. Landfarming remediation was simulated in the laboratory by applying comparable practices (such as tillage and bioaugmentation) and the relevant mechanism was examined. We then systematically examined potential factors affecting petroleum-removal efficacy, including the content of fine soil particles, the initial concentration and composition of petroleum contaminants, and the degree of soil-contaminant interaction. The distribution range of total petroleum hydrocarbons (TPHs) and the size of unresolved complex mixture (UCM) found in gas chromatography data showed that petroleum composed of TPHs with lower carbon numbers and having smaller size of UCM could be treated more effectively by landfarming. Incorporating the evaluation of the distribution range and UCM properties of petroleum, rather than simply considering its total concentration, is a more accurate and efficient method for determining the site-specific suitability of landfarming as a remedial option, as well as for assessing the necessity of supplementary processes.

Study Region. Two areas in Minnesota, USA: Buffalo aquifer in Clay County and Jordan aquifer in Olmsted County. There are concerns about the long-term sustainability of groundwater resources in the two aquifers. Study Focus. Aquifer storage and recovery is an important tool for water resources management in various geographic and socio-economic contexts. However, practical guidelines regarding the assessment of injection capacity remain limited. In this study, we present a quantitative methodology which is based on the Theis solution. The methodology allows an efficient estimation of well-based injection capacity and generation of an aquifer-scale injection capacity map. We present a detailed workflow for applying the methodology and demonstrate its application to the two study areas. The tool developed in this study can be easily applied to other areas. New Hydrological Insights for the Region. The two study areas show significant spatial variability in injection capacity. In the Buffalo aquifer, the variability is mainly controlled by transmissivity, whereas in the Jordan aquifer, it is mainly controlled by maximum allowable hydraulic head change. Assuming an injection duration of one month and considering the 90-percentile value of the injection capacity at each site, we found that two and four wells are required to inject the volume of water equivalent to one month of domestic water requirements for the cities of Moorhead and Rochester, respectively.