Column Experiments Research Articles

Evaluating the behavior and environmental risks of carbamazepine and its metabolites in soil aquifer treatment: Insights from deconjugation dynamics and toxicity assessment

The presence of pharmaceuticals in the environment has been a growing concern. Recent studies highlight the ecological risks of pharmaceuticals, but most risk assessments focus on the parent drug, neglecting metabolites. This study examines the behavior and environmental risks of carbamazepine (CBZ) and its metabolites in soil aquifer treatment (SAT) for wastewater reclamation. Findings indicate that CBZ metabolites' total concentration exceeds that of CBZ. Notably, carbamazepine-N-glucuronide (CBZ-N-Glu) concentration decreased from 48.12 ng/L to undetectable levels during SAT, while CBZ concentration increased from 64.87 to 95 ng/L, suggesting possible deconjugation of CBZ-N-Glu. Batch and column experiments confirmed the hypothesis, showing a gradual disappearance of CBZ-Glu and a corresponding rise in CBZ concentration when CBZ-N-Glu was spiked into a recirculated SAT system. Quantitative structure-activity relationships (QSAR) analysis revealed that CBZ exhibits higher acute and chronic toxicity, with metabolites showing varying levels of developmental toxicity. The study also evaluates the persistence, mobility, and toxicity (PMT) characteristics of CBZ and its metabolites, highlighting CBZ-N-Glu's particularly adverse PMT characteristics compared to CBZ. In summary, the residual pharmaceuticals in the reclaimed water process should be evaluated systematically, considering both the parent compounds and their metabolites.

Cu (II) adsorption in rice husk for water treatment: Batch and fixed column experiments

Cu (II) is a heavy metal found in water bodies and harmful to the environment and human health. Thus, this study evaluated Cu (II) adsorption in rice husk using batch and fixed bed tests, employing synthetic solutions and real water samples to simulate contaminated water treatment. Batch tests were performed using rice husk and synthetic Cu (II) solutions with concentrations varying from 1 to 128 mgL−1. The isothermal behavior of the adsorption process was evaluated using Langmuir and Freundlich nonlinear models, whereas mechanisms and adsorption rates were assessed using pseudo-first and pseudo-second order kinetic models. The fixed bed column was mounted on a 5-cm thick rice husk adsorbent bed and synthetic and real solutions were employed (concentration: 8 mg L−1; flux: 13 mL min−1). The equilibrium was reached after 20 min, with the best adjustment to the pseudo-second order model. The experimental data were better adjusted to the Langmuir model (estimated qmax: 7.19 mgg−1). The adsorption column exhibited adsorption capacities of 1.28 and 1.12 mgg−1 and saturation percentages of 83 % and 79 % for synthetic and real solutions, respectively, and were adjusted to Thomas model. The results indicate that rice husk can be an effective alternative for Cu (II) removal in contaminated water.

Experimental and numerical study of cadmium fate and transport mechanisms during artificial recharge in agricultural regions

Agricultural Managed Aquifer Recharge (AgMAR) uses agricultural lands and floodwater to enhance groundwater recharge, but its effectiveness can be hindered by heavy metals like cadmium (Cd), which pose risks to groundwater quality. Cd is particularly concerning due to its high mobility and persistence in the environment. This study investigates Cd's fate and transport in agricultural regions during MAR, focusing on sandy loam soils through batch and column experiments. Equilibrium and kinetic batch studies were conducted under varying Cd concentrations and exposure times to quantify the adsorption capacity and rate. HYDRUS-2D was used to simulate Cd's transport in soil under various ponding depths and Cd concentrations. Results showed a maximum Cd adsorption capacity of 439.58 mg/kg, with the Freundlich isotherm providing a better fit (R2 = 0.98) and indicating heterogeneous adsorption sites (n = 0.389). The kinetic experiment indicated chemisorption as the predominant mechanism, with an equilibrium adsorption capacity of 236.49 mg/kg. The pseudo-second-order kinetic model (rate constant 0.0016 h⁻1, R2 = 0.99) suggested that adsorption kinetics are influenced by Cd concentration and available adsorption sites. The column experimental findings supported by HYDRUS-2D modeling successfully explained the fate and transport of Cd within the soil columns. The model fitted parameter values for Freundlich adsorption isotherm coefficient (KF), linearity factor (Nu), and kinetic rate coefficient are (α) 47.37 L/kg, 0.00389 cm³/ppm and 0.0029 min⁻1, respectively. Modeling scenarios further elucidated the transport dynamics of Cd under simulated AgMAR conditions. Modeling scenarios indicated that with constant ponding of 5 cm over a year, Cd at 20 and 40 ppb concentrations in floodwater could potentially migrate below root zone systems. This study highlights the critical role of understanding Cd fate and transport in optimizing AgMAR systems and reducing Cd pollution risks, providing valuable insights for developing effective monitoring and management strategies.

Photoaged tire wear particles hinder the transport of Pb(II) in urban soils under acid rain: Experimental and numerical investigations

Rapid urbanization brought lots of serious environmental contamination, including the accumulation of heavy metals, acid rain, and the emission of tire wear particles (TWPs), with detrimental effects for terrestrial ecosystems. Nevertheless, how naturally aged TWPs affect the mobilization of heavy metals in soils under acid rain is still unclear. Here, we investigate the adsorption and transport mechanisms of Pb(II) co-existing with acid rainwater in soil-TWP mixtures via batch experiments, column experiments and modeling. Results showed that photoaged TWP significantly prolonged the Pb(II) adsorption equilibrium time (1 to 16 h) and enhanced the Pb(II) adsorption capacity of soils. Soil column profiles confirmed that TWP effectively boosted the initial accumulation of lead in the topsoil and thus impeded the downward transport of lead. The retardation factor (R) estimated by the linear two-site sorption model (TSM) fitting the Pb(II) breakthrough curves gradually increased from 1.098 to 16.38 in soils with TWP (0–10 %). Comparative results of linear or nonlinear TSM suggested nonlinear sorption replacing linear sorption as the main Pb(II) sorption mechanism under 1 % and 10 % TWP. This research provides significant insights into the implications of TWP on the Pb(II) retention behaviors and highlights the severer potential remobilization risks of Pb(II) in urban soils under different acid rain environments.

Transport and retention mechanisms of highly suspended biochar in aquifer media

Biochar-based in-situ reaction zones are promising methods for groundwater remediation. However, the transport and retention of biochar in aquifer media remain unclear. Herein, biochar with high suspensibility was developed through nitrogen doping. A linear regression was used to analyze the relationship between particle size, concentration, time, and suspension rate. Seepage column experiments were conducted to investigate the transport and retention mechanisms of biochar in the aquifer medium. The ratio of biochar particle size (dp) to medium particle size (Dp) affected the permeability coefficient. At a 3.0 g/L injected concentration, hydraulic conductivity decreased within 3.3 × 10−3 ≤ dp/Dp ≤ 8.4 × 10−3. Within 9.7 × 10−3 ≤ dp/Dp ≤ 1.9 × 10−2, hydraulic conductivity first increased and then decreased. Within 2.5 × 10−2 ≤ dp/Dp ≤ 5.7 × 10−2, hydraulic conductivity slightly increased and then stabilized. This study confirms that nitrogen-doped biochar is an excellent remediation material for in-situ reaction zone.

Efficient arsenic removal from water using iron-impregnated low-temperature biochar derived from henequen fibers: performance, mechanism, and LCA analysis

The present study aims to investigate the low-energy consumption and high-efficiency removal of arsenic from aqueous solutions. The designed adsorbent Fe/TBC was synthesized by impregnating iron on torrefaction henequen fibers. Isothermal adsorption experiments indicated maximum adsorption capacities of 7.30 mg/g and 8.98 mg/g for arsenic(V) at 25.0 °C and 40.0 °C, respectively. The interference testing showed that elevated levels of pH, HCO3− concentration, and humic acid content in the solution could inhibit the adsorption of arsenic by Fe/TBC. Characterization of the adsorbent before and after adsorption using FTIR and SEM–EDS techniques confirmed arsenic adsorption mechanisms, including pore filling, electrostatic interaction, surface complexation, and H-bond adhesion. Column experiments were conducted to treat arsenic-spiked water and natural groundwater, with effective treatment volumes of 550 mL and 8792 mL, respectively. Lastly, the life cycle assessment (LCA) using OpenLCA 2.0.3 software was performed to treat 1 m3 of natural groundwater as the functional unit. The results indicated relatively significant environmental impacts during the Fe/TBC synthesis stage. The global warming potential resulting from the entire life cycle process was determined to be 0.8 kg CO2-eq. The results from batch and column experiments, regeneration studies, and LCA analysis indicate that Fe/TBC could be a promising adsorbent for arsenic(V).

Eco-friendly and cost-effective synthesis of hierarchical porous HKUST-1 from thin waste electric cables for enhanced cationic dye removal

HKUST-1, as a type of metal-organic framework (MOF), has attracted significant interest for various applications. However, its use for adsorption applications is hindered by its microporous structure, which negatively impacts the diffusion and mass transfer of large particles (> 2 nm). Concurrently, waste electric cables from discarded vehicles and electronic equipment pose significant environmental challenges. To address these issues, we developed a novel recycling method using copper hydroxide recovered from waste-thin electric cables as the metal source for synthesizing hierarchical porous HKUST-1 (W) using a green approach at a low temperature. The resulting HKUST-1 (W) exhibited interesting properties compared to the typical HKUST-1 (C) synthesized from commercial precursors, showing a microporous-mesoporous structure with enhanced molecular mass transport, while HKUST-1 (C) exhibited only micropores. Moreover, the waste-derived HKUST-1 (W) formed interconnected small particles with enhanced methylene blue (MB) removal properties compared to HKUST-1 (C), mainly due to its hierarchical porous structure facilitating easy mass transfer of MB. To evaluate the industrial potential of our adsorbent, we conducted a fixed-bed adsorption column (FBAC) experiment, which showed that HKUST-1 (W) achieved a high removal efficiency of 99 %, confirming its effectiveness as a dye adsorbent in both batch experiments and a FBAC. This approach opens new perspectives in applying upcycled waste-based materials in synthesizing hierarchical porous MOFs.

Characteristics of hollow micron zero valent iron and its transport properties in groundwater: Effect of key engineering parameters and retention mechanism

In this study, a hollow micron zero-valent iron (H-mZVI) was synthesized, and its transport and retention property in saturated porous media was determined via a series of column experiments. Furthermore, the maximum migration distance (Lmax) and sedimentation rate coefficient (Kdep) models of H-mZVI in saturated porous media were established using statistical methods. The results revealed a distinct hollow structure in H-mZVI, with a density of 1.03±0.03 g/cm3, significantly lower than solid micron zero-valent iron (4.57±0.15 g/cm3). FTIR and XRD analyses indicated no formation of new functional groups on H-mZVI's surface, with iron being the main component. The column experiment demonstrated that the Lmax of H-mZVI in saturated porous media was 4.15 times that of solid micron zero-valent iron (mZVI) under the same conditions. The prediction model of Lmax aligned with the linear model, where Lmax correlated positively with particle size, injection velocity, and H-mZVI concentration, but inversely with ionic strength. Medium particle size and injection velocity were the main engineering parameters to control H-mZVI. The prediction model of Kdep accorded with the quadratic model, and an interaction was observed between medium particle size and injection velocity, which jointly affected the deposition rate of H-mZVI. Moreover, the single particle capture coefficient (η0) was hereby calculated and analyzed using the T-E theory. Interception primarily governed the precipitation of H-mZVI in saturated porous media, with gravity sedimentation contributing minimally to η0.

Responses of Methane Emission and Bacterial Community to Fertilizer Reduction Plus Organic Materials over the Course of an 85-Day Leaching Experiment

Methane produced from paddy fields has a negative impact on global climate change. However, the role of soil bacterial community composition in mediating methane (CH4) emission from waterlogged paddy soil using the column experiment is poorly known. In the present study, various fertilization treatments were adopted to investigate the effects of fertilizer reduction combined with organic materials (CK: control; CF: conventional fertilization; RF: 20% fertilizer reduction; RFWS: RF plus wheat straw amendment; RFRS: RF plus rapeseed shell amendment; RFAS: RF plus astragalus smicus amendment) on CH4 emission and soil bacterial community during an 85-day leaching experiment. We hypothesized that the fertilizer reduction plus the organic materials could enrich the bacterial communities and increase CH4 emission. The average CH4 flux varied from 0.03 μg m−2 h−1 to 76.19 μg m−2 h−1 among all treatments in the nine sampling times, which may account for the experimental conditions such as air temperature, moisture, and anthropogenic factors. In addition, high-throughput sequencing was utilized to investigate the alteration of the soil bacterial community structure. It was revealed that the diversity and composition of the bacterial community in the topsoil amended with organic materials underwent significant shifts after the 85-day leaching experiment. Proteobacteria was identified as the dominant phylum of the soil bacteria, with an average proportion of 35.2%. For Firmicutes, the proportion of RFRS (11%) was higher than that in the CK (8%), RF (8%), RFWS (7%), RFAS (6%), and CF (5%) treatments. Additionally, Gammaproteobacteria and Alphaproteobateria were supposed to be the major class bacterial communities, with average proportions of 12.8% and 12.2%, respectively. For the RFWS treatment, the contribution of Alphaproteobateria was the highest among all the bacterial relative abundance. According to the correlation heatmap analysis, the top ten bacterial communities were positively related to soil microbial biomass carbon (MBC) and ammonia nitrogen (NH4+-N) (p < 0.01). The findings also indicated that the RFRS treatment was the favorable management to alleviate CH4 emission during an 85-day leaching experiment or possibly in paddy production. Collectively, these results predict that the impacts of different treatments on CH4 production are strongly driven by soil microbial communities and soil properties, with soil bacteria being more prone to the crop residue degradation stage and more sensitive to soil properties. The discoveries presented in this study will be useful for assessing the efficacy and mechanisms of organic material amendments on CH4 emissions in paddy soil.

Humic acid enhances the co-transport of colloids and phosphorus in saturated porous media

Phosphorus (P) has been widely recognized as a substance that is difficult to transport due to its tendency to become easily fixed in the soil. However, many reports demonstrate that groundwater P pollution is rising in humus-rich areas. Research is urgently needed to confirm (or reject) the hypothesis that increased P pollution is related to humus, as there is currently limited quantitative research on this topic. In this study, we conducted a series of batch equilibrium adsorption-desorption experiments and column experiments to quantify the effects of montmorillonite colloids (MCs) and humic acids (HCs, the main components of humus) on the P transport behavior. The results indicate that P's adsorption and desorption behavior on MCs can be well simulated using the Langmuir and Temkin models (R2 > 0.91). Compared to the non-HC treatments, HCs significantly increased MCs' P adsorption and desorption capacity 5.18 and 7.21 times, respectively. Moreover, HCs facilitated the transport ability of the MC-P mixture through the saturated quartz sand column. In a 0.1 M NaCl solution, the MC-P mixture is nearly completely adsorbed on the surface of quartz sand, with a penetration rate of only 0.5%. In contrast, the HC-MC-P mixture can evidently penetrate further at a rate of 26.1%. The transport parameters fitted using HYDRUS-1D further indicated that the presence of humic acids significantly decreased the deposition coefficients of colloids, thereby enhancing the co-transport of colloids and P through the quartz sand porous medium. The potential mechanism of P pollution in humus-rich areas is likely enhanced by the formation of an HC-colloid-P mixture, which greatly increases the adsorption amount of P on colloids and enhances the electrostatic and spatial repulsion between colloids as well as between colloids and quartz sand. It reduces the aggregation and adsorption of colloids, ultimately transferring P into groundwater through colloid-facilitated co-transport. The findings of this study clarified the relationship between the transport of P, colloids, and HCs, which provides a theoretical basis for explaining the P pollution mechanism in humus-rich areas.

Cadmium sequestration with MgCuAl-layered double hydroxide@montmorillonite nanocomposite in batch and circulated fluidized bed column experiments

In this study, montmorillonite cationic clay coated with MgCuAl-Layered double hydroxide nanoparticles was investigated for its capacity to adsorb cadmium ion (Cd2+) from aqueous solutions. Montmorillonite, MgCuAl−LDH, and a novel MgCuAl-Layered double hydroxide@montmorillonite nanocomposite (MCA−LDH@MMt) were characterized using various mechanisms including BET surface areas, XRD, TEM, FTIR, and SEM/EDS analysis. The adsorption behaviour of MCA−LDH@MMt towards Cd2+ ion was studied using batch and continuous flow systems. pH, contact time, initial Cd2+concentration, MCA−LDH@MMt dose and particle size, agitation speed, and temperature were examined in the batch system. The higher removal efficiency of Cd2+was reported at pH 5 at 70 mg/l initial concentration and 0.2 g/100 ml best adsorbent dose with 150 rpm. The adsorption of Cd2+ on MCA−LDH@MMt followed Langmuir model and yielded a maximum adsorption capacity of 129.82 mg/g. While the pseudo-second-order model better simulates the cadmium kinetics data, and adsorption rate parameters values showing that the adsorption process was chemisorption and the rate-determining step of controlling cadmium adsorption onto MCA−LDH@MMt not intra-particle diffusion. A three-phase, commonly known as gas-liquid-solid circulated fluidized bed column was used to continuously eliminate Cd2+. Four influencing parameters were studied: liquid and air flow rate, bed height, and initial Cd2+concentration. The adsorption efficiency of Cd2+in a continuous system increased when the liquid flow rate decreased and the bed height increased. The time required for MCA−LDH@MMt to reach saturation increases as the bed height and the air flow rate increase. Column data were described using Bohart-Adams, Thomas, and Yoon and Nelson models of adsorption for given experimental conditions. The Bohart-Adams could represent the initial regime of the breakthrough curves, while the Thomas model was better at describing the whole curve of metal ion adsorption for a given experimental condition.

Sediment size effects on non-Darcy flow: insights from Izbash equation and Forchheimer inertial coefficient analysis

The transition from Darcy to non-Darcy flow regimes was investigated using column experiments. This revealed key relationships between sediment characteristics and critical thresholds for the onset of the non-Darcy flow regime, as well as inertial flow parameters. An exponential dependence of the critical Reynolds number (Rec) on hydraulic conductivity (K) and a linear dependence on sediment size (d50) was found. The analysis revealed a potentially universal relationship between the critical hydraulic gradient (Ic) and K, with a power-law exponent of –3/2, consistent with previous investigations. Additionally, Ic was found to be inversely proportional to the power law of the square root of d50. Novel relationships are derived for estimating the Izbash equation inertial exponent (n) and the Forchheimer inertial coefficient (β\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\beta$$\\end{document}) based on sediment characteristics. The exponent (n) was found to decrease with d50 and increase with K, following power-law relationships. A new equation is proposed, capable of predicting β\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\beta$$\\end{document} with slightly improved accuracy, outperforming numerous and previously proposed empirical equations. Additionally, these data validate the works of Ergun and Irmay as an alternative for β\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\beta$$\\end{document} estimation using porosity and sediment size. As the attainment of statistical significance in multiparameter curve fitting can be trivial, it has led to the proliferation of empirical equations for estimating β. This study highlights the limitations of existing empirical methods in determining β and emphasizes the necessity for a universal approach to predict this critical parameter, which will facilitate broader adoption of the Forchheimer equation.

Understanding the transitional phase of nitrate removal in three different specialty adsorbents for stormwater treatment

Excess nitrogen input from nonpoint sources driven by hydrologic and anthropogenic disturbances has become a significant ecological challenge in receiving water bodies. Moreover, nitrate removal by cost-effective filtration media has still not performed up to expectation because of the knowledge gap in the transitional phase from physicochemical to microbiological processes. This study developed three cost-effective, sustainable, and adaptable green sorption media (GSM), namely CPS (clay–perlite with sand sorption media), ZIPGEM (zero-valent iron and perlite green environmental media), and BIPGEM (biochar, zero-valent iron, and perlite-based green environmental media), made of readily available and recyclable materials, to compare nitrate removal methods for stormwater treatment and elucidate the transitional phase. The primary adsorption mechanism was chemisorption, and subsequent biofilm growth sustained removal efficiency for a long-lasting period. Adsorption kinetics, adsorption equilibrium, material characterization, and fixed-bed column experiments with a 2-stage cultivation approach were undertaken to characterize the transitional phase in these GSM, based on breakthrough curves, maximum adsorption capacity, and microbial population dynamics for nitrification and denitrification. As shown in the column study, BIPGEM had the highest adsorption capacity (7.637 mg∙g−1), followed by ZIPGEM (2.16 mg∙g−1), and CPS (0.1798mg∙g−1). The biochar in BIPGEM provides a better cultivation environment for nitrifying and denitrifying bacteria, contributing sufficient electron donors. Biofilm production and maturation enabled the BIPGEM to maintain 30 % nitrate removal in a steady state even after 2000 h of operation in the first stage. When the biofilm reached maturation, BIPGEM’s nitrate removal percentage was up to 70 % via denitrification in the second stage.

Sorption experiments as efficient as possible: Mini-column experiments (MCE) using HPLC-ICP-MS coupling with a new data analysis approach to determine sorption parameters

To quantify retention and sorption parameters, diffusion-, batch- or column experiments are common practice. However, these are either not close to nature, extremely time-consuming or material intensive. A promising approach to eliminate these problems is the performance of mini-column experiments (MCE). Due to dynamic retention and realistic solid–liquid ratios, these are close to nature and resource-efficient. The aim of this work is to perform highly controllable MCE using a HPLC (high-performance liquid chromatography) system and HPLC-ICP-MS (inductively coupled plasma mass spectrometry) coupling. With this approach, ultra-fast sorption experiments are possible only using 100–150 mg adsorbent and 160 mL eluent. That means, sorption experiments are even more time- and cost-efficient and also more controllable than with conventional methods. The presented method is based on a newly developed MCE-HPLC-ICP-MS coupling, which was applied to investigate the sorption of Eu(III) on kaolinite and sand in 10 mM NaCl. With that it was possible to carry out dynamic sorption experiments in just 5–15 h and thus determine e.g. maximum loading capacity (qmax) in a very short amount of time. Furthermore, a quantification method for eluates of high ionic strength is presented. Here, the sorption of Cs(I) on calcium silicate hydrate (C-S-H) phases in 10 mM and 100 mM NaCl was investigated. For validation, the sorption distribution ratios (Rd) obtained were compared with those from batch experiments. These agreed very well with each other and with those from the literature. Overall, with MCE more sorption parameters can be determined much faster, more accurately and more efficient than with the conventional methods.

Degradation of Oxytetracycline in Saturated Porous Media by In Situ Chemical Oxidation Using Oxygen-Doped Graphitic Carbon Nitride and Peroxymonosulfate: Laboratory-Scale Column Experiments

Oxytetracycline (OTC) is frequently detected in groundwater and soil, posing substantial risks to the subsurface environment via persistence, phytotoxicity, changing bacterial communities, and antibiotic resistance. In situ chemical oxidation (ISCO) is one of the best alternatives for removing OTC from groundwater. However, its feasibility has rarely been investigated using columns for which optimal conditions can be obtained for practical applications. Thus, a system consisting of oxygen-doped graphitic carbon nitride (OgCN) and peroxymonosulfate (PMS) (OgCN/PMS) was tested for OTC removal using continuous-flow experiments with columns packed with sand and glass beads (GBs). The sand column exhibited better adsorption and degradation of OTC than the GB column in pulse injection experiments, regardless of whether OgCN was packed. Additional experiments were performed using a column saturated with the OTC solution and another filled with deionized water to simulate ISCO, using GB as the medium, to evaluate the net OTC removal by catalytic oxidation, excluding adsorption. Performance improved with increased OgCN packing, PMS dosage, retention time, and pH. Anions slightly affected the performance due to scavenging and propagation of radicals. These findings indicate the high potential of OgCN/PMS for ISCO and the usefulness of column experiments in field applications.

Impact of Water Saturation on the Fate and Mobility of Antibiotics in Reactive Porous Geomedia.

Understanding contaminant transport through unsaturated porous media is a considerable challenge, given the complex interplay of nonlinear physical and biogeochemical processes driven by variations in water saturation. In this study, we tackled this challenge through a series of column experiments involving fine (100-300 μm) and coarse (1.0-1.4 mm) sand particles coated with birnessite (MnO2) under variable saturation degrees. Dynamic flow experiments in sand columns revealed that desaturation altered the ability of MnO2 in removing tetracycline (TTC), a redox-active antibiotic, yet the effect depends on the sand type and then on the saturation degree. Moderate saturation degrees in fine-grained sand columns promoted fractional and preferential water flow which favored a more acidic pH and increased dissolved oxygen levels. These conditions enhanced TTC removal, despite the reduced physical accessibility of reactive phases. In contrast, lower saturation degrees in coarse-grained sand columns induced stronger flow heterogeneity with a very small fraction of the water content participating in flow. The mobility behavior of all the columns was predicted using transport models that consider TTC adsorption and transformation, as well as dual porosity under variable water saturation degrees. This research offers valuable insights into predicting the fate and transport of redox-active contaminants in unsaturated soils and subsurface environments.

High adsorption capacities for dyes by a pH-responsive sodium alginate/sodium lignosulfonate/carboxylated chitosan/polyethyleneimine adsorbent

Dyes are indispensable for the rapid development of society, but untreated dye wastewater can threaten human health. In this study, an adsorbent (SA/SL/CCS/PEI@MNPs) was synthesized by one-pot method using magnetic nanoparticles (MNPs), sodium alginate (SA), sodium lignosulfonate (SL), carboxylated chitosan (CCS) and polyethyleneimine (PEI). The adsorbent was mesoporous micrometer-sized particles with pore size of 34.92 nm, which was favorable for dynamic column experiments. SA/SL/CCS/PEI@MNPs possessed pH-responsive performance. Under acidic condition, the maximum adsorption capacities for anionic dyes (tartrazine, reactive black-5, indigo carmine) reached >550 mg/g. Under alkaline condition, those for cationic dyes (methylene blue, methyl violet, neutral red) exceeded 1900 mg/g. The function of the various modifiers was investigated. The results indicated that the incorporation of SL, CCS and PEI was able to provide plenty of sulfonate, carboxylate and amino/imine reactive groups so that adsorption capacities of dyes were improved. The adsorption mechanism was explored by FTIR and XPS. At the same time, the adsorption mechanism was more deeply analyzed using molecular dynamics simulations and radial distribution function. It was demonstrated that the dyes adsorption on the SA/SL/CCS/PEI@MNPs was mainly due to electrostatic attraction and π-π interaction. In addition, the adsorbent had good reusability, and the removal still reached over 90 % after five cycles. In conclusion, the adsorbent displayed a broad prospect for the adsorption of organic dyes.

Fate and transport of fragmented and spherical microplastics in saturated gravel and quartz sand.

Microplastics in urban runoff undergo rapid fragmentation and accumulate in the soil, potentially endangering shallow groundwater. To improve the understanding of microplastic transport in groundwater, column experiments were performed to compare the transport behavior of fragmented microplastics (FMPs ∼1-µm diameter) and spherical microplastics (SMPs ∼1-, 10-, and 20-µm diameter) in natural gravel (medium and fine) and quartz sand (coarse and medium). Polystyrene microspheres were physically abraded with glass beads to mimic the rapid fragmentation process. The experiments were conducted at a constant flow rate of 1.50 m day-1 by injecting two pore volumes of SMPs and FMPs. Key findings indicate that SMPs showed higher breakthrough, compared to FMPs in natural gravel, possibly due to size exclusion of the larger SMPs. Interestingly, FMPs exhibited higher breakthrough in quartz sand, likely due to tumbling and their tendency to align with flow paths, while both sizes (larger and smaller relative to FMPs) of SMPs exhibited higher removal in quartz sand. Therefore, an effect due to shape and size was observed.

Application of machine learning approaches to predict ammonium nitrogen transport in different soil types and evaluate the contribution of control factors

The loss of nitrogen in soil damages the environment. Clarifying the mechanism of ammonium nitrogen (NH4+-N) transport in soil and increasing the fixation of NH4+-N after N application are effective methods for improving N use efficiency. However, the main factors are not easily identified because of the complicated transport and retardation factors in different soils. This study employed machine learning (ML) to identify the main influencing factors that contribute to the retardation factor (Rf) of NH4+-N in soil. First, NH4+-N transport in the soil was investigated using column experiments and a transport model. The Rf (1.29 – 17.42) was calculated and used as a proxy for the efficacy of NH4+-N transport. Second, the physicochemical parameters of the soil were determined and screened using lasso and ridge regressions as inputs for the ML model. Third, six machine learning models were evaluated: Adaptive Boosting, Extreme Gradient Boosting (XGB), Random Forest, Gradient Boosting Regression, Multilayer Perceptron, and Support Vector Regression. The optimal ML model of the XGB model with a low mean absolute error (0.81), mean squared error (0.50), and high test r2 (0.97) was obtained by random sampling and five-fold cross-validation. Finally, SHapely Additive exPlanations, entropy-based feature importance, and permutation characteristic importance were used for global interpretation. The cation exchange capacity (CEC), total organic carbon (TOC), and Kaolin had the greatest effects on NH4+-N transport in the soil. The accumulated local effect offered a fundamental insight: When CEC > 6 cmol+ kg−1, and TOC > 40 g kg−1, the maximum resistance to NH4+-N transport within the soil was observed. This study provides a novel approach for predicting the impact of the soil environment on NH4+-N transport and guiding the establishment of an early-warning system of nutrient loss.

Impact of diatomit on the transport behavior of unmodified and carboxyl-modified nanoplastics in saturated porous media

Due to the extensive use of plastic products and unreasonable disposal, nanoplastics contamination has become one of the important environmental problems that mankind must face. The composition and structure of porous media can determine the complexity and diversity of the transport behavior of nanoplastics. In this study, the influence of diatomite (DIA) on the nanoplastics transport in porous media is investigated by column experiments combined with XDLVO interaction energy and transport model. Results suggest that the recovery rates of unmodified polystyrene nanoparticles (PSNPs) and carboxyl-modified polystyrene nanoparticles (PSNPs-COOH) in the porous media containing DIA decreases compared with that in the pure quartz sand (QS), and the BTCs showed a “blocking” pattern. The presence of DIA inhibits the transport of both PSNPs and PSNPs-COOH, but the inhibition is not significant. This may be because the presence of DIA provides more favorable deposition sites for PSNPs and PSNPs-COOH to some extent. However, since DIA itself carries a certain negative charge, this can only play a role in compressing the double electric layer for PSNPs and PSNPs-COOH with the same negative charge, and cannot destabilize them. The migration capacity of PSNPs and PSNPs-COOH is strongest in the DIA-QS porous media at pH = 7, and is weak at pH = 9 and pH = 5. The inhibition of migration at pH = 9 can be attributed to the dissolution of the DIA surface under alkaline conditions and the formation of pore and defect structures, which provide more deposition sites for PSNPs and PSNPs-COOH. The presence of humic acid (HA) leads to an increase in the mobility of PSNPs and PSNPs-COOH, and the mobility is enhanced with HA concentration. The mobility of PSNPs and PSNPs-COOH in DIA-QS decreases with ionic valence and ionic strength, and PSNPs-COOH is more significantly inhibited compared to PSNPs.