Core-Shell MnFe Nanocatalyst Derived from Prussian Blue Analogs for Peroxymonosulfate Activation: Nonradical Mechanism and Bimetallic Valence Cycle.

Sulfamethazine (SAT) is widely present in sediment, soil, rivers, and groundwater. Unfortunately, traditional water treatment technologies are inefficient at eliminating SAT from contaminated water. Therefore, developing an effective and ecologically friendly treatment procedure to effectively remove SAT is critical. This has raised concerns about its potential impact on the environment and human health. In this study, metal-organic-inorganic composites consisting of graphene-encapsulated Fe-Mn metal catalyst (Mn3Fe1-NC) were synthesized by calcining MnFe Prussian blue analogs (PBA) under a nitrogen atmosphere. The composites were applied to activate peroxymonosulfate (PMS) and facilitate the degradation of SAT in aquatic environments. The Mn3Fe1-NC, dosed with 5 mg, in combination with PMS, dosed with 1.5 mmol L-1, achieved a 91.8% degradation efficiency of SAT. The transformation of the CN skeleton led to the formation of a carbon shell structure, which consequently reduced metal ion leaching from the material. At various pH levels, the iron and manganese ions were observed to leach out at levels lower than 0.1392 and 0.0580 mg L-1, respectively. In contrast, the Mn3Fe1-NC was found to be minimally impacted by pH levels and coexisting ions present in the aqueous environment. Radical burst experiments and electrochemical analysis tests verified that degradation primarily occurs through the nonradical pathway of electron transfer. The active sites responsible for this process were identified as the Mn (IV) and graphitic-N atoms on the material, which facilitate direct electron transfer. Additionally, the presence of Fe atoms promotes the valence cycling of Mn atoms. This study introduces new insights into the reaction mechanism and the constitutive relationship of catalytic centers in nonradical oxidation reactions.

iRGD-paclitaxel conjugate nanoparticles for targeted paclitaxel delivery.

Paclitaxel (PTX) is a chemotherapeutic agent which shows antitumor activities against a broad spectrum of cancers. Yet, the current formulation of PTX used in clinic may cause a number of adverse reactions, which significantly limit its application. To obtain better clinical use of PTX, we report, for the first time, iRGD-PTX conjugate nanoparticles (NPs) for targeted PTX delivery. iRGD-PTX conjugate was synthesized from thiolated iRGD and 6-maleimidocaproic acid-PTX through Michael addition reaction. iRGD-PTX NPs with hydrodynamic diameter of ~110 nm were self-assembled from iRGD-PTX conjugate in deionized water. The as-prepared iRGD-PTX NPs exhibit good stability in phosphate buffered saline (PBS) buffer and fetal bovine serum containing PBS buffer. iRGD-PTX NPs exhibit sustained drug release behaviors. The in vitro studies show that iRGD-PTX NPs can be internalized by 4T1 cells by integrin αV-mediated endocytosis, resulting in better in vitro antitumor activity as compared to free PTX. The in vivo studies demonstrate that iRGD-PTX NPs exhibit enhanced tumor accumulation. The iRGD-PTX NPs reported here represent a novel PTX nanoplatform to achieve targeted PTX delivery.

Risk-Based Prioritization Method for the Classification of Groundwater Pollution from Hazardous Waste Landfills.

Hazardous waste landfill sites are a significant source of groundwater pollution. To ensure that these landfills with a significantly high risk of groundwater contamination are properly managed, a risk-based ranking method related to groundwater contamination is needed. In this research, a risk-based prioritization method for the classification of groundwater pollution from hazardous waste landfills was established. The method encompasses five phases, including risk pre-screening, indicator selection, characterization, classification and, lastly, validation. In the risk ranking index system employed here, 14 indicators involving hazardous waste landfills and migration in the vadose zone as well as aquifer were selected. The boundary of each indicator was determined by K-means cluster analysis and the weight of each indicator was calculated by principal component analysis. These methods were applied to 37 hazardous waste landfills in China. The result showed that the risk for groundwater contamination from hazardous waste landfills could be ranked into three classes from low to high risk. In all, 62.2 % of the hazardous waste landfill sites were classified in the low and medium risk classes. The process simulation method and standardized anomalies were used to validate the result of risk ranking; the results were consistent with the simulated results related to the characteristics of contamination. The risk ranking method was feasible, valid and can provide reference data related to risk management for groundwater contamination at hazardous waste landfill sites.

Insights into the characteristics of changes in dissolved organic matter fluorescence components on the natural attenuation process of toluene.

Natural attenuation (NA) is of great significance for the remediation of contaminated groundwater, and how to identify NA patterns of toluene in aquifers more quickly and effectively poses an urgent challenge. In this study, the NA of toluene in two typical soils was conducted by means of soil column experiment. Based on column experiments, dissolved organic matter (DOM) was rapidly identified using fluorescence spectroscopy, and the relationship between DOM and the NA of toluene was established through structural equation modeling analysis. The adsorption rates of toluene in clay and sandy soil were 39 % and 26 %, respectively. The adsorption capacity and total NA capacity of silty clay were large. The occurrence of fluorescence peaks of protein-like components and specific products indicated the occurrence of biodegradation. Arenimonas, Acidovorax and Brevundimonas were the main degrading bacteria identified in Column A, while Pseudomonas, Azotobacter and Mycobacterium were the main ones identified in Column B. The pH, ORP, and Fe(II) were the most important factors affecting the composition of microbial communities, which in turn affected the NA of toluene. These results provide a new way to quickly identify NA of toluene.

Co-migration behavior of toluene coupled with trichloroethylene and the response of the pristine groundwater ecosystems - A mesoscale indoor experiment.

Experimental scale and sampling precision are the main factors limiting the accuracy of migration and transformation assessments of complex petroleum-based contaminants in groundwater. In this study, a mesoscale indoor aquifer device with high environmental fidelity and monitoring accuracy was constructed, in which dissolved toluene and trichloroethylene were used as typical contaminants in a 1.5-year contaminant migration experiment. The process was divided into five stages, namely, pristine, injection, accumulation, decrease, and recovery, and characteristics such as differences in contaminant migration, the responsiveness of environmental factors, and changes in microbial communities were investigated. The results demonstrated that the mutual dissolution properties of the contaminants increased the spread of the plume and confirmed that toluene possessed greater mobility and natural attenuation than trichloroethylene. Attenuation of the contaminant plume proceeded through aerobic degradation, nitrate reduction, and sulfate reduction phases, accompanied by negative feedback from characteristic ion concentrations, dissolved oxygen content, the oxidation-reduction potential and microbial community structure of the groundwater. This research evaluated the migration and transformation characteristics of typical petroleum-based pollutants, revealed the response mechanism of the ecosystem to pollutant, provided a theoretical basis for predicting pollutant migration and formulating control strategies.

Efficient utilization of biogenic manganese oxides in bioaugmentation columns for remediation of thallium(I) contaminated groundwater.

Little attention has been paid to the in situ-generated biogenic manganese oxides (BMnOx) for practical implementation in continuous groundwater remediation systems. The enrichment effects of manganese oxidizing bacteria (MOB) in bioaugmentation columns and the in situ-generated BMnOx for continuous thallium(I) (Tl(I)) removal from groundwater were investigated. Results indicated that Pseudomonas Putida MnB1 (strain MnB1) attached on the groundwater sediments (GS) can achieve a maximum of 97.37 % Mn(II) oxidation and generate 29.6 mg/L BMnOx, which was superior than that of traditional quartz sand (QS). The in situ-generated BMnOx in MOB_GS column effectively removed 10-100 µg/L Tl(I) under the interference of high concentrations of Fe(II) and Mn(II) in groundwater. Distinctive microbial enrichment effects occurred in the bioaugmentation columns under the competition of indigenous microbes in groundwater. The release of Mn(II) from the BMnOx inhibited with the decrease in Tl(I) removal efficiency. XAFS analysis revealed Tl(I) was effectively adsorbed by BMnOx and Mn-O octahedra with Tl-O tetrahedral coordination existed in BMnOx. This study provides an in-depth understanding of the in situ-generated BMnOx for the Tl(I) removal and contributes to the application of BMnOx in groundwater remediation.

Natural phosphorus-ferromanganese ore-based composites for the simultaneous remediation of arsenic- and lead-co-contaminated groundwater: synergistic effectiveness, kinetics, and mechanisms.

Natural phosphorus-ferromanganese ore (NPO-NFMO) based composites by mechanical ball milling method, applying for the simultaneous remediation of arsenic (As) and lead (Pb) co-contaminated groundwater. Kinetic behavior adopted pseudo-second-order adsorption mechanism attaining equilibrium in 120 min over a wide pH range (2.0-6.0). NPO-NFMO realized higher adsorption capacity for As(III) (6.8 mg g-1) and Pb(II) (26.5 mg g-1) than those of single NPO (1.7 and 7.8 mg g-1) and NFMO (2.9 and 5.1 mg g-1), indicating that synergistic effects of NPO and NFMO considerably enhanced the adsorption capacity in mixed adsorption system. Fresh and used NPO-NFMO were characterized, and indicated that NPO-NFMO formed stable minerals of PbAs2O6 and PbFe2(AsO4)2(OH)2. The underlying adsorption mechanism indicated that As(III) and Pb(II) removal was involved with multiple mechanisms, including electrostatic adsorption, oxidation, complexation, and coprecipitation. The effects of key reaction parameters including mass ratios of NPO and NFMO, initial metal ion concentration, dosage, solution pH, and co-existing anions in groundwater were systematically investigated. The novel designed NPO-NFMO-based composites can be deemed as a promising amendment for simultaneous immobilization of As(III) and Pb(II) in co-contaminated soil and groundwater.

A novel thermosensitive persulfate controlled-release hydrogel based on agarose/silica composite for sustained nitrobenzene degradation from groundwater.

The increasing risk of organic contamination of groundwater poses a serious threat to the environment and human health, causing an urgent need to develop long-lasting and adaptable remediation materials. Controlled-release materials (CRMs) are capable of encapsulating oxidants to achieve long-lasting release properties in aquifers and considered to be effective strategies in groundwater remediation. In this study, novel hydrogels (ASGs) with thermosensitive properties were prepared based on agarose and silica to achieve controlled persulfate (PS) release. By adjusting the composition ratio, the gelation time and internal pore structure of the hydrogels were regulated for groundwater application, which in turn affected the PS encapsulated amount and release properties. The hydrogels exhibited significant temperature responsiveness, with 6.8 times faster gelation rates and 2.8 times longer controlled release ability at 10 â„ƒ than at 30 â„ƒ. The ASGs were further combined with zero-valent iron to achieve long-lasting degradation of the typical nitrobenzene compound 2,4-dinitrotoluene (2,4-DNT), and the degradation performance was maintained at 50 % within 14 PV, which was significantly improved compared with that of the PS/ZVI system. This study provided new concepts for the design of controlled-release materials and theoretical support for the remediation of organic contamination.

Characteristics of persulfate gel materials in groundwater remediation: Column and tank experiments investigations.

Using persulfate and environment-friendly gel solution as raw materials, persulfate gel sustained-release material (PGSR) and persulfate gelatin gel sustained-release material (G-PGSR) were developed. The main purpose of this study was to evaluate the potential of PGSR and G-PGSR in sustained release, migration and removal performance through column and tank experimental investigations. Results showed that the maximum release rates of PGSR and G-PGSR in water columns were 1.34 and 0.58 mg min-1 and the cumulative release amounts achieved 2950 and 2818 mg within 75 h, representing release efficiencies of 98.3 % and 93.9 %, respectively. In three sand columns, the maximum release rate was 0.32, 0.21, and 0.16 mg min-1 and the cumulative release achieved 473, 426, and 359 mg within 90 h with release efficiencies of 94.7 %, 85.3 %, and 71.7 %, respectively. Release time and rate of PGSR and G-PGSR are constrained by the permeability of porous media. G-PGSR in the sand tank exhibited migration and release characteristic with the slow-release diffusion effect. Lateral diffusion produced higher S2O82- concentration far beyond what was allowed in the tank. The saturated hydraulic conductivity decreased from 4.9 × 10-3, 1.1 × 10-3, and 4.9 × 10-4 cm s-1 to 2.4 × 10-3, 7.4 × 10-4, and 2.1 × 10-4 cm s-1 in columns filled with medium, fine, and silt, respectively. G-PGSR injection did not significantly change the order of magnitude of hydraulic conductivity. 2,4-dinitrotoluene removal performance was affected with the inlet flow rates, which decreased from 92 %, 82 %, and 78 % to 42 %, 28 %, and 8 % during 24 PV at the flow rate of 0.5, 1.5, and 4.5 mL min-1, respectively. Moreover, the removal efficiency was enhanced by G-PGSR with activated carbon as an activator. This study expands our understanding and ability of persulfate gel materials for groundwater remediation and provides a certain research basis for practical applications.

Insights into the synergistic removal mechanisms of thallium(I) by biogenic manganese oxides in a wide pH range.

The behavior and mechanism of thallium (Tl) adsorption by biogenic manganese oxides (BMnOx) are poorly understood. In this study, BMnOx was applied for Tl(I) removal from aqueous solution, and the adsorption interactions were systematically revealed for the first time. BMnOx was successfully prepared with high productivity by effectively oxidizing Mn(II) with a manganese oxide bacterium in an optimal Mn(II) concentration range of 4.0-28 mg/L. Compared with other adsorbents, the prepared BMnOx achieved high Tl(I) adsorption capacity over a wide pH range from 3.0 to 9.0 and high humic acid (HA) concentration (40 mg/L) interference. The experimental results were well depicted by pseudo-second-order kinetics and the Langmuir isotherm model, indicating that chemisorption played the dominant role during the adsorption process. The adsorption mechanisms were verified as synergetic interactions of oxidation-precipitation, electrostatic attraction, ion exchange and surface complexation. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) results suggested that 19.46% of the highly toxic Tl(I) was transformed into the much less toxic product Tl2O3 after adsorption onto BMnOx. This study provides theoretical guidance for high-concentration Tl(I) decontamination from groundwater by biogenic manganese oxides.

Preparation and properties of the persulfate gel materials and application for the remediation of 2,4-dinitrotoluene contaminated groundwater.

This study aims to develop persulfate new gel sustaining-release material (PGSR) and gelatin-gel sustaining-release material (G-PGSR) that can be injected into aquifers and slowly release S2O82- to groundwater. Compatibility and miscibility of colloidal silica gels and gelatin with S2O82- were tested. Morphologies of the as-prepared PGSR and G-PGSR were observed by scanning electron microscope (SEM) and Fourier transform infrared spectrometer (FT-IR). Release characteristics of PGSR containing variable persulfate concentrations (from 1.25 wt% to 5 wt%), silica sol (from 30 wt% to 40 wt%), and gelatin (from 0.5 wt% to 2.0 wt%) were monitored. Viscosities of PGSR solution increased from 5 to 112 cP with increasing silica sol from 30 wt% to 40 wt% during the first 10 min. Viscosities of PGSR solution in 40 wt% silica sol increased to 346 cP within the 30 min and rapidly increased to 8000 cP within the next 30 min followed by the gelation phase. Gelation rates of the PGSR solution increased with increased persulfate concentrations from 1.25 wt% to 5.0 wt%. The maximum release rates achieved at 5 h in G-PGSR were 1.98 mg of S2O82- per min similar to that in PGSR. The release persulfate concentrations in G-PGSR suggested that gelatin and colloidal silica were both compatible and miscible with S2O82-. Meanwhile, the PGSR exhibits a characteristic two-phase increase in viscosity with increased silica sol concentrations, persulfate concentrations, and gelatin concentrations. Compared with the persulfate only system, the degradation efficiency of 2,4-dinitrotoluene (2,4-DNT) was achieved 91.5 % within 3 h, while 78.6 % and 66.9 % degradation efficiency were shown in PGSR and G-PGSR, respectively. The PGSR and G-PGSR both could create persistent oxidation degradation of 2,4-DNT. Results suggested that colloidal silica and gelatin could be used to create PGSR and G-PGSR for persistent oxidation in groundwater remediation.

Experimental Investigation on the Fracture Conductivity Behavior of Quartz Sand and Ceramic Mixed Proppants.

In this paper, a series of fracture conductivity experiments were designed and conducted by an American Petroleum Institute (API) standard fracture conductivity evaluation system. The mixing proportion of quartz sand and ceramic was optimized. By the evaluation of the proppant breakage rate and sphericity analysis of mixed proppant with different sand volume proportions (P S), the proppant mixture conductivity evolution behavior was analyzed. Results of this study showed that the conductivity of mixed proppant was between that of pure ceramic proppant and pure quartz sand proppant under the same conditions. For 20/40 mesh mixed proppant, a small amount of ceramic (25%) in mixed proppant could obtain 1.27-3 times higher conductivity than pure sand, while 40/70 mesh mixed proppant required the addition of 50% or more ceramic. The crushing resistance of mixed proppant determined the decrease of conductivity with the increase of effective closure stresses. A logarithmic empirical model was further derived from the results, which could be used to forecast the performance of fracture conductivity at different effective closure stresses and sand volume proportions.

Comparing the long-term responses of soil microbial structures and diversities to polyethylene microplastics in different aggregate fractions.

Microplastics (MPs) alter soil aggregation stability. However, studies have yet to determine whether these alterations further affect microbial community structures and diversities within different soil aggregates and whether they influence the responses of soil microbial structures and diversities to MPs in different aggregate fractions. In this study, long-term soil incubation experiments and soil fractionation were combined to investigate the effects of polyethylene microplastics (PE-MPs) on soil aggregate properties and microbial communities in soil aggregates with different particle sizes. Results showed that the existence of PE-MPs significantly reduced the physicochemical properties of soil aggregates, inhibited the activities of soil enzymes, and changed the richness and diversity of bacterial and fungal communities. Such variations exerted notable differences in soil aggregate levels. The response sensitivity of bacteria in the silt and clay fraction was higher than that in the macroaggregate fraction, but the response sensitivity of fungi in the macroaggregate fraction was higher than that in the silt and clay fraction. Relationships and path analysis between soil aggregate properties and microbial communities after PE-MPs addition were proposed. PE-MPs affected microbial community structures by directly and indirectly influencing soil microenvironmental conditions. The relative abundances of Acidobacteria, Gemmatimonadetes, Bacteroides, Basidiomycota, Chtridiomyota, and Glomeromycota were significantly correlated with physicochemical properties and soil enzyme activities. Enzyme activities were direct factors influencing soil microbial community structures, and physicochemical properties (i.e., dissolved organic carbon, soil available phosphorus) could indirectly affect these structures by acting on soil enzyme activities. Our findings helped improve our understanding of the responses of soil microbial structures and diversities to MPs through the perspective of different soil aggregates.

Microwave-assisted functionalization of PAN fiber by 2-amino-5-mercapto-1,3,4-thiadiazol with high efficacy for improved and selective removal of Hg2+ from water.

Mercury (Hg2+) contamination in water is associated with potential toxicity to human health and ecosystems. Many research studies have been ongoing to develop new materials for the remediation of Hg2+ pollution in water. In this study, a novel thiol- and amino-containing fibrous adsorbent was prepared by grafting 2-amino-5-mercapto-1,3,4-thiadiazol (AMTD) onto PAN fiber through a microwave-assisted method. The synthesized functional fiber was characterized by FTIR, SEM, and elemental analysis. Adsorption tests depicted that for mercury uptake, PANMW-AMTD fiber exhibited enhanced adsorption capacity compared with other fibrous adsorbents and selective adsorption feature under the interference of other metal ions, including Pb2+, Cu2+, Cd2+, and Zn2+. The influence of pH on the adsorption process was investigated and the effect of temperature revealed that the adsorption sorption process was endothermic and the adsorption performance of PANMW-AMTD was elevated with the increase of temperature. Kinetic studies of PANMW-AMTD fiber followed the pseudo-second-order and the adsorption isotherm of Hg2+ was well fitted by Sips and Langmuir equations, given the maximum adsorption amount of 332.9 mg/g. XPS results suggested that a synergetic coordination effect of sulfur and nitrogen in functional fiber with mercury took responsibility for the adsorption mechanism in the uptake process. In addition, the prepared PANMW-AMTD fiber could easily be regenerated with 0.1 M HCl for five times without significant reduction of mercury removal efficiency. Thus, this study will facilitate the research on novel functional material for the removal of mercury from water.

A comparative study on the treatment of 2,4-dinitrotoluene contaminated groundwater in the combined system: efficiencies, intermediates and mechanisms.

In this study, scrap irons (SI)/granular activated carbons (GAC) micro-electrolysis treatment and persulfate-releasing materials (PRM) treatment were employed to construct the combination reduction and oxidation system to treat 2,4-dinitrotoluene (2,4-DNT) contaminated groundwater. The 2,4-DNT treatment efficiencies in the PRM pre-treatment before SI/GAC micro-electrolysis treatment (FM-1 = PRM + SI/GAC) and SI/GAC micro-electrolysis pre-treatment before the PRM treatment (FM-3 = SI/GAC + PRM) were investigated in two separated columns. As control groups, the separated SI and GAC instead of the SI/GAC mixture were used in another two separated columns (FM-2 = PRM + SI + GAC; FM-4 = SI + GAC + PRM). The highest treatment efficiencies of 2,4-DNT in the FM-1 and FM-3 systems reached 79% and 93% during 5 PV, respectively. We found that the filling position of SI, GAC and PRM significantly affected the variations of pH, oxidation-reduction potential, Fe2+ and S2O82- concentrations in the combined systems. These results indicated that the SI/GAC micro-electrolysis pre-treatment of 2,4-DNT before the PRM treatment (FM-3) is more beneficial. The fifteen main intermediates in the combined system were identified by the detection of liquid chromatograph mass spectrometer. Furthermore, the possible treatment pathways of 2.4-DNT were proposed on the basis of identified intermediates. The treatment mechanisms in the FM-1 and FM-3 systems were proposed with the reduction mechanism in the SI/GAC micro-electrolysis system and the oxidation mechanism in the PRM treatment. Therefore, the combination of the reduction pre-treatment with the SI/GAC micro-electrolysis system and the oxidation post-treatment with persulfate can effectively treat the nitroaromatic compounds contaminated groundwater.

Hydrogeochemical and statistical analysis of high fluoride groundwater in northern China.

Understanding the formation of high fluoride (F-) groundwater in water-scarce northern China is critical for the sustainable development of the region. This study investigates the effects of F- enrichment in groundwater from seven typical regions of northern China, including Datong, Guide, Junggar, Yinchuan, Taiyuan, and Tarim basins and the North China Plain. A literature survey of 534 samples of selected regions showed that 45.13% of groundwater F- exceeded the 1.0 mg/L of Chinese drinking water guideline. Based on the geological background and hydrogeochemical analysis, in Datong and Yinchuan basins and part of the North China Plain, the main types of groundwater are soda water and controlling processes of F- enrichment are salinization, mineral dissolution, and desorption. In Taiyuan and Guide basins with Cl-Na water type, F- enrichment is mainly affected by salinization, cation exchange, and evaporation. The hydrogeochemical characteristics of high F- groundwater in Tarim and Junggar basins reflect the extent of salinization and weathering dissolution of minerals in groundwater. According to PCA, the contribution of salinization and mineral dissolution to F- enrichment is relatively high. Under the alkaline condition, groundwater with high Cl-, HCO3-, and Na+ concentration favors F- enrichment. Based on HCA, index clustering category I explains the influence of pH and buried depth on F- enrichment, and category II explains the effect of different ions. It is concluded that F- enrichment in groundwater is related to hydrogeochemical processes and hydrogeological conditions. The hydrogeochemical and alkaline conditions of groundwater are regulated by mineral dissolution, ion exchange, and evaporation, resulting in different degrees of F- enrichment.

Moisture content-affected electrokinetic remediation of Cr(VI)-contaminated clay by a hydrocalumite barrier.

An electrokinetic-permeable reaction barrier (EK-PRB) system was introduced in this study with hydrocalumite as the barrier material. The combined system effectively remediated the Cr(VI)-contaminated clay after a 72-h treatment, and the Cr(VI) removal efficiency increased with the initial soil moisture content. Further evidence was found that the changing soil pH value and current density were highly associated with the initial moisture content, showing its important roles in the Cr(VI) removal process. Additionally, the total Cr removal efficiency was much lower than that of Cr(VI) owing to the partial conversion of Cr(VI) to Cr(III) in the electrokinetic remediation process. Under high soil moisture conditions (40%), the removal efficiency of Cr(VI) and total Cr was 96.6 and 67.3%, respectively. Further analysis also revealed the new mineral phase, chromate hydrocalumite, for Cr fixation in the hydrocalumite barrier, which was significantly affected by the initial soil moisture content. Our results showed that the EK-PRB system with a hydrocalumite barrier is highly promising with great potential for the effective remediation of Cr(VI)-contaminated clay and engineering implementation.

Nitrogen transport and transformation in the saturated-unsaturated zone under recharge, runoff, and discharge conditions.

Water level (WL) changes are an important factor in the fate and transport of nitrogen in the saturated-unsaturated zone. In this study, the fate of nitrogen was investigated under simulated conditions of replenishment, runoff, and discharge. Three patterns of water level changes of ascent, stability, and descent were simulated under laboratory conditions to study nitrogen transport and transformation. Three columns (I, II, and III) were used to simulate the conditions of replenishment, steady water level, and discharge, respectively. The nitrate-nitrogen (NO3 (-)-N), nitrite-nitrogen (NO2 (-)-N), and ammonia-nitrogen (NH4 (+)-N) concentrations observed at different depths were compared among the three columns at 46.5 and 251.5 h. The results indicated that the NO3 (-)-N concentration decreased with time in both the saturated and unsaturated zones of the three columns (columns I, II, and III). The maximum decreasing concentrations of NO3 (-)-N in the three columns were 14.3, 37.97, and 38.17 mg/L, respectively. However, NH4 (+)-N in the saturated zone increased with time, whereas the NH4 (+)-N concentration decreased in both the saturated and unsaturated zones of other columns. No significant change in NO2 (-)-N concentration was observed in the experiment. These results suggest that water level changes must be considered in the remediation of groundwater nitrate pollution in the field.