Chemical aging of biochar-zero-valent iron composites in groundwater: Impact on Cd(II) and Cr(VI) co-removal.

Biochar (BC), zero-valent iron (ZVI), and their composites are promising materials for use in permeable reactive barriers, although further research is needed to understand how their properties change during long-term aging in groundwater. In this study, BC, ZVI and their composites (4BC-1ZVI) were subjected to the chemical aging tests in five media (deionized water, NaCl, NaHCO3, CaCl2 and a mixture of CaCl2 and NaHCO3 solutions) for 20 days. After treatment, the microscopic analysis and performance tests for the co-removal of Cd(II) and Cr(VI) were carried out. The results indicated that the removal of Cd(II) by aged 4BC-1ZVI followed a pseudo-second-order model, whereas the removal of Cr(VI) was better fitted with a pseudo-first order model. The aging mechanism of 4BC-1ZVI was primarily governed by iron corrosion/passivation, the reduction of soluble components, and the formation of carbonate minerals. Less Fe3O4/ γ-Fe2O3 was formed during aging in deionized water, NaCl and CaCl2 solutions. The corrosion products, Fe3O4/ γ-Fe2O3, FeCO3 and α/γ-FeOOH, were observed after aging in NaHCO3 and a mixture of NaHCO3 and CaCl2 solutions. The decrease in the soluble components of biochar led to a decrease in cation exchange, while carbonate minerals contributed to Cd(II) precipitation. This work provides insights into the aging processes of BC-ZVI composites for long-term groundwater remediation applications.

Biocathode-anode cascade system in PRB: Efficient degradation of p-chloronitrobenzene in groundwater.

The consistent presence of p-chloronitrobenzene (p-CNB) in groundwater has raised concerns regarding its potential harm. In this study, we developed a biocathode-anode cascade system in a permeable reactive barrier (BACP), integrating biological electrochemical system (BES) with permeable reactive barrier (PRB), to address the degradation of p-CNB in the groundwater. BACP efficiently accelerated the formation of biofilms on both the anode and cathode using the polar periodical reversal method, proving more conducive to biofilm development. Notably, BACP demonstrated a remarkable p-CNB removal efficiency of 94.76 % and a dechlorination efficiency of 64.22 % under a voltage of 0.5 V, surpassing the results achieved through traditional electrochemical and biological treatment processes. Cyclic voltammetric results highlighted the primary contributing factor as the synergistic effect between the bioanode and biocathode. It is speculated that this system primarily relies on bioelectrocatalytic reduction as the predominant process for p-CNB removal, followed by subsequent dechlorination. Furthermore, electrochemical and microbiological tests demonstrated that BACP exhibited optimal electron transfer efficiency and selective microbial enrichment ability under a voltage of 0.3-0.5 V. Additionally, we investigated the operational strategy for initiating BACP in engineering applications. The results showed that directly introducing BACP technology effectively enhanced microbial film formation and pollutant removal performance.

Purification of acidic wastewater containing Cd(II) using a red mud-loess mixture: Column test, breakthrough curve, and speciation of Cd.

In this study, the safety of a red mud-loess mixture (RM-L) for the remediation of groundwater polluted by acid mine drainage (AMD) containing Cd(II) in mining areas was systematically analyzed and clarified. The effects of the initial concentration, flow rate, and packing height on the breakthrough performance and longevity of RM-L as a permeable reactive barrier (PRB) packing material were explored by column tests. The results show that the breakthrough time, saturation time, and adsorption capacity of Cd(II) in RM-L increased with decreasing initial concentration and flow rate, as well as increasing packing height. Moreover, RM-L had a long-term effective acid buffering capacity for acidic wastewater containing Cd(II). An increase in the packing height led to a longer longevity of the PRB than the theoretical value. In addition, the speciation of Cd on RM-L was dominated by carbonate form and iron-manganese oxide form. The surface of the RM-L particles evolved from a dense lamellar structure to small globular clusters after purifying the acidic wastewater containing Cd(II), due to the corrosion of H+ and the reoccupation and coverage by increasingly enriched adsorbates and precipitates of heavy metal ions.

Hotspots of Dissolved Arsenic Generated from Buried Silt Layers along Fluctuating Rivers.

Previous studies along the banks of the tidal Meghna River of the Ganges-Brahmaputra-Meghna Delta demonstrated the active sequestration of dissolved arsenic (As) on newly formed iron oxide minerals (Fe(III)-oxides) within riverbank sands. The sand with high solid-phase As (>500 mg/kg) was located within the intertidal zone where robust mixing occurs with oxygen-rich river water. Here we present new evidence that upwelling groundwater through a buried silt layer generates the dissolved products of reductive dissolution of Fe(III)-oxides, including As, while mobilization of DOC by upwelling groundwater prevents their reconstitution in the intertidal zone by lowering the redox state. A three end-member conservative mixing model demonstrated mixing between riverbank groundwater above the silt layer, upwelling groundwater through the silt layer, and river water. An electrochemical mass balance model confirmed that Fe(III)-oxides were the primary electron acceptor driving the oxidation of DOC sourced from sediment organic carbon in the silt. Thus, the presence of an intercalating silt layer in the riverbanks of tidal rivers can represent a biogeochemical hotspot of As release while preventing its retention in the hyporheic zone.

Improving landfill liner performance with bentonite-slag blend permeated with ammonia for a Municipal solid waste landfill.

Leachate emanating from landfills contains ammonia which may cause serious health effects on living things. An effectively designed clay barrier should not allow the contaminant to infiltrate the soil and groundwater systems. The utilization of certain industrial by-products in engineered landfill barriers, not only reduces the need for conventional liner materials but also helps in sustainable waste management. This study investigated the hydraulic conductivity, unconfined compressive strength, compaction, and adsorption characteristics of lithomargic clay blended with an optimum percentage of bentonite (10%) and granulated blast furnace slag (15%) permeated with ammonia. The results revealed that increasing the content of granulated blast furnace slag decreased the maximum dry density while increasing the optimum moisture content. In comparison to lithomargic clay, the hydraulic conductivity of the amended soil liner permeated with ammonia decreased from a value of 3 × 10-8 m/s to 5 × 10-10 m/s. The unconfined compressive strength of the amended soil specimens showed an increasing trend with curing times (i.e., 0, 14, 28, and 56 days). The batch adsorption results revealed that Freundlich and Langmuir's isotherm fits the equilibrium adsorption data and the adsorption of ammonia on clay liner follows non-linear behaviour. Overall, the experimental results implied that lithomargic clay blended with 10% bentonite and 15% granulated blast furnace slag can be used as an impermeable soil reactive barrier in engineered landfills.

Analytical model for the mitigation of VOC vapor with horizontal permeable reactive barrier in the contaminated site considering non-uniform source.

Volatile organic compounds (VOCs) contamination at the groundwater may cause vapor intrusion and pose significant threats to human health. As a novel low-carbon mitigation technology, a horizontal permeable reactive barrier (HPRB) is proposed to remove the VOC vapor in the vadose zone and mitigate the vapor intrusion risk. To estimate the performance of HPRB in the contaminated site with a non-uniform source, a transient two-dimensional analytical model is developed in this study to simulate the VOC vapor migration and oxidation processes in the layered soil. The analytical model is verified against the experimental results and numerical simulation first and the parameter study is then conducted. The HPRB has good performance for the contaminated sites involving factors including deep source and local soil with low effective diffusivity. To consider the vertical heterogeneity of the local soil, the traditional equivalent homogeneity method has limitations in considering the horizontal migration of VOC vapor and is not suitable for the two-dimensional model. On the contrary, the artificial layered method based on the proposed analytical model has better accuracy and is recommended to be adopted in practice. Leading to the exponential decrease in the VOC vapor concentration at the ground surface, increasing the thickness of HPRB is an effective measure to enhance the performance of HPRB. The fitting exponential function can be applied to determine the minimum design value of the thickness of HPRB in practice.

Design of a two functional permeable reactive barrier for synergistic enzymatic and microbial bioremediation of phenol-contaminated waters: laboratory column evaluation : Enzymatic and microbial bioremediation of phenol in a bilayer permeable reactive barrier.

The present study aimed to develop a system using a combination of enzymatic and microbial degradation techniques for removing phenol from contaminated water. In our prior research, the HRP enzyme extracted from horseradish roots was utilized within a core-shell microcapsule to reduce phenolic shock, serving as a monolayer column. To complete the phenol removal process, a second column containing degrading microorganisms was added to the last column in this research. Phenol-degrading bacteria were isolated from different microbial sources on a phenolic base medium. Additionally, encapsulated calcium peroxide nanoparticles were used to provide dissolved oxygen for the microbial population. Results showed that the both isolated strains, WC1 and CC1, were able to completely remove phenol from the contaminated influent water the range within 5 to 7 days, respectively. Molecular identification showed 99.8% similarity for WC1 isolate to Stenotrophomonas rizophila strain e-p10 and 99.9% similarity for CC1 isolate to Bacillus cereus strain IAM 12,605. The results also indicated that columns using activated sludge as a microbial source had the highest removal rate, with the microbial biofilm completely removing 100% of the 100 mg/L phenol concentration in contaminated influent water after 40 days. Finally, the concurrent use of core-shell microcapsules containing enzymes and capsules containing Stenotrophomonas sp. WC1 strain in two continuous column reactors was able to completely remove phenol from polluted water with a concentration of 500 mg/L for a period of 20 days. The results suggest that a combination of enzymatic and microbial degrading systems can be used as a new system to remove phenol from polluted streams with higher concentrations of phenol by eliminating the shock of phenol on the microbial population.

Struvite and ethylenediaminedisuccinic acid (EDDS) enhance electrokinetic-biological permeable reactive barrier removal of copper and lead from contaminated loess.

Removal of heavy metals using the electrokinetic (EK) remediation technology is restricted by soils containing a fraction of clay particles above 12%. Furthermore, it is also affected by hydroxide precipitation (focusing phenomenon) close to the cathode. A modified EK reactor containing a permeable reactive barrier (PRB) was proposed herein where the enzyme-induced carbonate precipitation (EICP) treatment was incorporated into the PRB. Despite that, NH4+-N pollution induced by the urea hydrolysis resulting from the EICP treatment causes serious threats to surrounding environments and human health. There were four types of tests applied to the present work, including CP, TS1, TS2, and TS3 tests. CP test neglected the bio-PRB, while TS1 test considered the bio-PRB. TS2 test based on TS1 test tackled NH4+-N pollution using the struvite precipitation technology. TS3 test based on TS2 test applied EDDS to enhance the removal of Cu and Pb. In CP test, the removal efficiency applied to Cu and Pb removals was as low as approximately 10%, presumably due to the focusing phenomenon. The removal efficiency was elevated to approximately 24% when the bio-PRB and the electrolyte reservoir were involved in TS1 test. TS2 test indicated that the rate of struvite precipitation was 40 times faster than the ureolysis rate, meaning that the struvite precipitate had sequestered NH4+ before it started threatening surrounding environments. The chelation between Cu2+ and EDDS took place when EDDS played a part in TS3 test. It made Cu2+ negatively surface charged by transforming Cu2+ into EDDSCu2-. The chelation caused those left in S4 and S4 to migrate toward the bio-PRB, whereas it also caused those left in S1 and S2 to migrate toward the anode. Due to this reason, the fraction of Cu2+ removed by the bio-PRB and the electrolyte reservoir is raised to 32% and 26% respectively, and the fraction of remaining Cu was reduced to 41%. Also, the removal efficiency applied to Pb removal was raised to 50%. Results demonstrate the potential of struvite and EDDS-assisted EK-PRB technology as a cleanup method for Cu- and Pb-contaminated loess.

Cr(VI) Reduction and Sequestration by FeS Nanoparticles Formed in situ as Aquifer Material Coating to Create a Regenerable Reactive Zone.

Remediation of large and dilute plumes of groundwater contaminated by oxidized pollutants such as chromate is a common and difficult challenge. Herein, we show that in situ formation of FeS nanoparticles (using dissolved Fe(II), S(-II), and natural organic matter as a nucleating template) results in uniform coating of aquifer material to create a regenerable reactive zone that mitigates Cr(VI) migration. Flow-through columns packed with quartz sand are amended first with an Fe2+ solution and then with a HS- solution to form a nano-FeS coating on the sand, which does not hinder permeability. This nano-FeS coating effectively reduces and immobilizes Cr(VI), forming Fe(III)-Cr(III) coprecipitates with negligible detachment from the sand grains. Preconditioning the sand with humic or fulvic acid (used as model natural organic matter (NOM)) further enhances Cr(VI) sequestration, as NOM provides additional binding sites of Fe2+ and mediates both nucleation and growth of FeS nanoparticles, as verified with spectroscopic and microscopic evidence. Reactivity can be easily replenished by repeating the procedures used to form the reactive coating. These findings demonstrate that such enhancement of attenuation capacity can be an effective option to mitigate Cr(VI) plume migration and exposure, particularly when tackling contaminant rebound post source remediation.

A field study of a novel permeable-reactive-biobarrier to remediate chlorinated hydrocarbons contaminated groundwater.

Chlorinated hydrocarbons (CHs) pose significant health risks due to their suspected carcinogenicity, necessitating urgent remediation efforts. While the combination of zero-valent iron (Fe0) and microbial action shows promise in mitigating CH contamination, field studies on this approach are scarce. We devised a novel three-layer permeable reactive barrier (PRB) material incorporating Fe0 and coconut shell biochar, effectively implemented at a typical CH-contaminated site. Field monitoring data revealed conducive conditions for reductive dechlorination of CHs, characterized by low oxygen levels and a relatively neutral pH in the groundwater. The engineered PRB material consistently released organic carbon and iron, fostering the proliferation of CH-dechlorinating bacteria. Over a 250-day operational period, the pilot-scale PRB demonstrated remarkable efficacy in CH removal, achieving removal efficiencies ranging from 21.9% to 99.6% for various CH compounds. Initially, CHs were predominantly eliminated through adsorption and iron-mediated reductive dechlorination. However, microbial reductive dechlorination emerged as the predominant mechanism for sustained and long-term CHs removal. These findings underscore the economic viability and effectiveness of our approach in treating CH-contaminated groundwater, offering promising prospects for broader application in environmental remediation efforts.

A framework for estimating soil water characteristic curve and hydraulic conductivity function of permeable reactive media.

The unsaturated behavior of permeable reactive barriers (PRB) is a critical component in predicting the removal efficiency through the adsorption of contaminants. This study investigates the framework to estimate the soil water characteristic curve (SWCC) and hydraulic conductivity function (HCF) for iron oxide-coated sand (IOCS) and zeolite, which are common materials used in PRBs. A multistep outflow (MSO) experiment was performed and the results of the MSO experiment were used to optimize associated parameters in Kosugi's SWCC and HCF. In addition, three scenarios of optimization analysis were investigated to evaluate the best-fitting model for estimating SWCC and HCF. The low root mean square error (RMSE) of fitted parameters indicates the Kosugi model well described the observed suction profiles in MSO experiments. In addition, the lowest RMSE and coefficient of variation suggested the inclusion of the additional parameter ß provided the best estimation of the three materials (clean sand, IOCS, and zeolite). The physically reasonable estimation of SWCC and HCF of the three materials from the optimized parameters suggests the proposed framework is a reasonable model for the unsaturated behavior of PRBs.

Machine learning vs. statistical model for prediction modeling and experimental validation: Application in groundwater permeable reactive barrier width design.

Permeable reactive barrier (PRB) is an effective in-situ technology for groundwater remediation. The important factors in PRB design are the width and reactive material. In this study, the beaded coal mine drainage sludge (BCMDS) was employed as the filling material to adsorb arsenic pollutants in groundwater, aiming to design the width of PRB. The design methods involving traditional continue column experiments and empirical formulas, as well as machine learning (ML) predictions and statistical methods, which are compared with each other. Traditional methods are determined based on breakthrough curves under several conditions. ML method has advantages in predicting the width of mass transfer zone (WMTZ), which simultaneously consider the characteristics of material, pollutant, and environmental conditions, with data collected from articles. After data preprocessing and model optimizing, selected the XGBoost algorithm based on the high accuracy, which shows good prediction for WMTZ (R2 = 0.97, RMSE = 0.15). The experimentally derived WMTZ values were also used to validate the predictions, demonstrating the ML low error rate of 7.04 % and the feasibility. Subsequent statistical analysis of multiple linear regression (MLR) showed the error rate of 39.43 %, interpret superiority of ML due to the complexity of influencing factors and the insufficient precision of math regression. Compared to traditional width design methods, ML can improve design efficiency and save experimental time and manpower. Further expansion of the dataset and optimization of algorithms could enhance the accuracy of ML, overcoming existing limitations and gaining broader applications.

Assessment of rapid initiators and long-lasting nutrients for developing biological permeable reactive barriers to treat mine-contaminated groundwater.

The formation of mine-contaminated groundwater as a result of acidic mine drainage from the oxidation of sulfur-containing minerals entering the groundwater. Biological permeable reactive barrier (Bio-PRB) technology is excellent for the remediation of mine-contaminated groundwater. Usually, the organic substrates utilized in Bio-PRB are a combination of rapid initiators, which are readily bioavailable, and long-lasting nutrients, which are more difficult to degrade. Herein, we investigated the effectiveness of three rapid initiators and three long-lasting nutrients to remove sulfate from simulated mine-contaminated groundwater via simulated column experiments. The rapid initiators comprised crude glycerol, sodium acetate, and industrial syrup (IS), and the long-lasting nutrients included biodiesel emulsified oil, soybean oil emulsified oil, and high-carbon alcohol emulsified oil (HO). Microorganisms were stimulated using IS to create a sulfate reduction system owing to its high total organic carbon content (24.30 g L-1), achieving optimal sulfate removal rate (1.69 mmol dm-3 d-1). The fastest (2.93 mmol dm-3 d-1) and highest (88%) sulfate removal rates were achieved using HO, which is probably associated with the ability of HO to provide the most suitable C/N ratio (111.75) and induce the growth of sulfate-reducing bacteria (SRB) for substrate degradation. Conversely, a high concentration of sulfate reduction products inhibited SRB growth in the HO column. The addition of organic materials promoted SRB growth and various organic substrate-degrading bacteria. Furthermore, the competitive growth of methanogens (86.6%) may be responsible for the decrease in the relative abundance of SRB during the later stages of the experiment in the HO column.

Monitoring of copper adsorption on biochar using spectral induced polarization method.

Copper contaminant generated from mining and industrial smelting poses potential risks to human health. Biochar, as a low-energy and cost-effective biomaterial, holds value in Cu remediation. Spectral Induced Polarization (SIP) technique is employed in this study to monitor the Cu remediation processes of by biochar in column experiments. Cation exchange at low Cu2+ concentrations and surface complexation at high Cu2+ concentrations are identified as the major mechanisms for copper retention on biochar. The normalized chargeability (mn) from SIP signals linearly decreased (R2 = 0.776) with copper retention under 60 mg/L Cu influent; while mn linearly increases (R2 = 0.907, 0.852) under high 300 and 700 mg/L Cu influents. The characteristic polarizing unit sizes (primarily the pores adsorbing Cu2+) calculated from Schwartz equation match well with experimental results by mercury intrusion porosimetry (MIP). It is revealed that Cu2+ was driven to small pores (∼3 µm) given high concentration gradient (influent Cu2+ concentration of 700 mg/L). Comparing to activated carbon, biochar is identified as an ideal adsorbent for Cu remediation, given its high adsorption capacity, cost-effectiveness, carbon-sink ability, and high sensitivity to SIP responses - the latter facilitates its performance assessment.

A review of passive acid mine drainage treatment by PRB and LPB: From design, testing, to construction.

An extensive volume of acid mine drainage (AMD) generated throughout the mining process has been widely regarded as one of the most catastrophic environmental problems. Surface water and groundwater impacted by pollution exhibit extreme low pH values and elevated sulfate and metal/metalloid concentrations, posing a serious threat to the production efficiency of enterprises, domestic water safety, and the ecological health of the basin. Over the recent years, a plethora of techniques has been developed to address the issue of AMD, encompassing nanofiltration membranes, lime neutralization, and carrier-microencapsulation. Nonetheless, these approaches often come with substantial financial implications and exhibit restricted long-term sustainability. Among the array of choices, the permeable reactive barrier (PRB) system emerges as a noteworthy passive remediation method for AMD. Distinguished by its modest construction expenses and enduring stability, this approach proves particularly well-suited for addressing the environmental challenges posed by abandoned mines. This study undertook a comprehensive evaluation of the PRB systems utilized in the remediation of AMD. Furthermore, it introduced the concept of low permeability barrier, derived from the realm of site-contaminated groundwater management. The strategies pertaining to the selection of materials, the physicochemical aspects influencing long-term efficacy, the intricacies of design and construction, as well as the challenges and prospects inherent in barrier technology, are elaborated upon in this discourse.

High-purity monoclinic pyrrhotite derived from natural pyrite with excellent removal performance for Cr (VI) and its mechanism.

Pyrrhotite, especially the monoclinic type, is a promising material for removing Cr (VI) from wastewater and groundwater due to its high reactivity. However, the purity of the preparation monoclinic pyrrhotite from heated natural pyrite is not high enough, and the role of possible sulfur vacancies in pyrrhotite's crystal structure has been largely ignored in the removal mechanism of Cr (VI). In this work, we characterized the phase composition changes of annealed pyrite in inert gas and prepared high-purity (~ 96%) monoclinic pyrrhotite at the optimal condition. We found that it could remove 18.6 mg/g of Cr (VI) by redox reaction, which is the best value reported of natural pyrite-derived materials so far. As the reactive media material of simulated permeable reactive barrier, the service life of the high-purity monoclinic pyrrhotite column is 297 PV, which is much longer than that of the pyrite column (50 PV). A new founding is that S2- and S vacancy play the essential role during the redox reaction of pyrrhotite and Cr (VI). Monoclinic pyrrhotite had more S vacancy than hexagonal pyrrhotite and pyrite, which explained its superior Cr (VI) removal performance.

Utilizing machine learning for reactive material selection and width design in permeable reactive barrier (PRB).

Permeable reactive barrier (PRB) is an important groundwater treatment technology. However, selecting the optimal reactive material and estimating the width remain critical and challenging problems in PRB design. Machine learning (ML) has advantages in predicting evolution and tracing contaminants in temporal and spatial distribution. In this study, ML was developed to design PRB, and its feasibility was validated through experiments and a case study. ML algorithm showed a good prediction about the Freundlich equilibrium parameter (R2 0.94 for KF, R2 0.96 for n). After SHapley Additive exPlanation (SHAP) analysis, redefining the range of the significant impact factors (initial concentration and pH) can further improve the prediction accuracy (R2 0.99 for KF, R2 0.99 for n). To mitigate model bias and ensure comprehensiveness, evaluation index with expert opinions was used to determine the optimal material from candidate materials. Meanwhile, the ML algorithm was also applied to predict the width of the mass transport zone in the adsorption column. This procedure showed excellent accuracy with R2 and root-mean-square-error (RMSE) of 0.98 and 1.2, respectively. Compared with the traditional width design methodology, ML can enhance design efficiency and save experiment time. The novel approach is based on traditional design principles, and the limitations and challenges are highlighted. After further expanding the data set and optimizing the algorithm, the accuracy of ML can make up for the existing limitations and obtain wider applications.

Decoding the divalent cation effect on sulfidation of zero-valent iron: Phase evolution and FeSx assembly.

The decontamination ability of sulfidated zero-valent iron (S-ZVI) can be enhanced by the effective assembly of iron sulfides (FeSx) on neglected heterogeneous surfaces by liquid-phase precipitation. However, S-ZVI preparation with the usual pickling is detrimental to orderly interfacial assembly and leads to an imbalance between electron transfer optimization and electron storage. In this work, S-ZVI was prepared in solutions containing trace divalent cation, and it removed Cr(VI) up to 323.25 times higher than ZVI. This result is achieved by surface sites protonation of divalent cations regulating the phase evolution on the ZVI surface and inducing FeSx chemical assembly. Regulation of divalent cation and S(-II) content further promotes FeSx targeted assembly and reduces electron storage consumption as much as possible. The barrier for FeSx assembly is found to lie at the ZVI interface rather than in the deposition between FeSx. Chemical assembly at heterogeneous interfaces is a prerequisite for the ordered assembly of FeSx. In addition, S-ZVI prepared in simulated groundwater showed extensive preparation pH and universality for remediation scenarios. These findings provide new insights into the development of in-situ sulfidation mechanisms with particular implications for S-ZVI applied to soil and groundwater remediation by the regulation of heterogeneous interfacial assembly.

Coupling of polyhydroxybutyrate and zero-valent iron for enhanced treatment of nitrate pollution within the Permeable Reactive Barrier and its downgradient aquifer.

Permeable Reactive Barriers (PRBs) have been utilized for mitigating nitrate pollution in groundwater systems through the use of solid carbon and iron fillers that release diverse nutrients to enhance denitrification efficiency. We conduct laboratory column tests to evaluate the effectiveness of PRBs in remediating nitrate pollution both within the PRB and in the downgradient aquifer. We use an iron-carbon hydrogel (ICH) as PRB filler, which has different weight ratios of polyhydroxybutyrate (PHB) and microscale zero-valent iron (mZVI). Results reveal that denitrification in the downgradient aquifer accounts for at least 19.5 % to 32.5 % of the total nitrate removal. In the ICH, a higher ratio of PHB to mZVI leads to higher contribution of the downgradient aquifer to nitrate removal, while a lower ratio results in smaller contribution. Microbial community analysis further reveals that heterotrophic and mixotrophic bacteria dominate in the downgradient aquifer of the PRB, and their relative abundance increases with a higher ratio of PHB to mZVI in the ICH. Within the PRB, autotrophic and iron-reducing bacteria are more prevalent, and their abundance increases as the ratio of PHB to mZVI in the ICH decreases. These findings emphasize the downgradient aquifer's substantial role in nitrate removal, particularly driven by dissolved organic carbon provided by PHB. This research holds significant implications for nutrient waste management, including the prevention of secondary pollution, and the development of cost-effective PRBs.

Monitoring the remediation of groundwater polluted by MSW landfill leachates by activated carbon and zeolite with spectral induced polarization technique.

The municipal solid waste (MSW) landfill in Hangzhou, China utilized zeolite and activated carbon (AC) as permeable reactive barrier (PRB) fill materials to remediate groundwater contaminated with MSW leachates containing ammonium, chemical oxygen demand (COD), and heavy metals. The spectral induced polarization (SIP) technique was chosen for monitoring the PRB because of its sensitivity to pore fluid chemistry and mineral-fluid interface composition. During the experiment, authentic groundwater collected from the landfill site was used to permeate two columns filled with zeolite and AC, and the SIP responses were measured at the inlet and outlet over a frequency range of 0.01-1000 Hz. The results showed that zeolite had a higher adsorption capacity for COD (7.08 mg/g) and ammonium (9.15 mg/g) compared to AC (COD: 2.75 mg/g, ammonium: 1.68 mg/g). Cation exchange was found to be the mechanism of ammonium adsorption for both zeolite and AC, while FTIR results indicated that π-complexation, π-π interaction, and electrostatic attraction were the main mechanisms of COD adsorption. The Cole-Cole model was used to fit the SIP responses and determine the relaxation time (τ) and normalized chargeability (mn). The calculated characteristic diameters of zeolite and AC based on the Schwarz equation and relaxation time (τ) matched the pore sizes observed from SEM and MIP, providing valuable information on contaminant distribution. The mn of zeolite was positively linear with adsorbed ammonium (R2 = 0.9074) and COD (R2 = 0.8877), while the mn of AC was negatively linear with adsorbed ammonium (R2 = 0.8192) and COD (R2 = 0.7916), suggesting that mn could serve as a surrogate for contaminant saturation. The laboratory-based real-time non-invasive SIP results showed good performance in monitoring saturation and provide a strong foundation for future field PRB monitoring.