Combined effects of aquifer heterogeneity and subsurface dam on nitrate contamination in coastal aquifers.

Subsurface dams are effective for seawater intrusion mitigation, yet they can cause upstream nitrate accumulation. This research examines the interplay between subsurface dam construction and aquifer layering on nitrate pollution in coastal settings, employing numerical models to simulate density-driven flow and reactive transport. The study reveals that while subsurface dams are adept at curbing seawater intrusion, they inadvertently broaden the nitrate accumulation zone, especially when a low-K layer is present. Heterogeneous aquifers see more pronounced nitrate accumulation from subsurface dams. This effect is pronounced as it influences dissolved organic carbon dynamics, with a notable retreat inland correlating with the expansion of the nitrate pollution plume. A critical finding is that controlling seawater intrusion via dam height adjustment within the Effective Damming Region effectively reduces nitrate levels and bolsters freshwater output. However, exceeding the critical threshold-where the dam surpasses the low-K layer's bottom-results in a substantial shift in nitrate concentration, underscoring the need for precise dam height calibration to avoid aggravating nitrate pollution. This study's innovative contribution lies in its quantification of the nuanced effects of subsurface dams in stratified aquifers, providing an empirical basis for dam design that considers the layered complexities of coastal aquifers. The insights offer a valuable framework for managing nitrate contamination, thus informing sustainable coastal groundwater management and protection strategies.

Hydrodynamic behavior of freshwater-saltwater mixing zone in the context of subsurface physical barriers.

The seawater intrusion (SWI) process lasts for decades in real world, thus the research on dynamic process of SWI is essential. The freshwater-saltwater mixing zone plays a crucial role in governing the groundwater movement and the solute transport in coastal aquifers. To date, there has been a lack of research on the hydrodynamic behavior of the mixing zone in the presence of subsurface physical barriers. In this work, we employed laboratory experiments and numerical simulations to investigate the dynamics of the mixing zone, comparing scenarios with and without subsurface physical barriers. The findings indicate that the construction of a subsurface physical barrier will not immediately slow down the seawater intrusion velocity and change the salinity distribution of mixing zone. The block effect of subsurface physical barriers with different heights or bottom opening sizes became apparent only when the wedge toe approached the physical barriers. The widening effect of increasing longitudinal dispersivity on the mixing zone width was more pronounced during the dynamic process compared to the steady state. Furthermore, the widening effect of increasing longitudinal dispersivity on the mixing zone was more significant compared to transverse dispersivity in both the SWI and subsurface dam scenarios throughout the intrusion process. However, in the cutoff wall scenarios, the widening effect of increasing transverse dispersivity became more obvious during the later intrusion period. Our conclusions provide a reference for the groundwater management in coastal aquifers. According to the current seawater intrusion situation, the local water bureau can predict the seawater intrusion velocity and the temporal changes of mixing zone after the construction of physical barriers.

A critical review of the central role of microbial regulation in the nitrogen biogeochemical process: New insights for controlling groundwater nitrogen contamination.

With the increase of nitrogen (N) input in vadose zones-groundwater systems, N contamination in groundwater has become a global environmental and geological issue that has a profound impact on the ecological environment and human health. N migration in the vadose zone is the most significant means of contaminating the groundwater aquifer. However, the current research on the control of groundwater N contamination focuses solely on the content change of certain indicators and is unable to comprehend the cause and subsequent development of groundwater N contamination. These factors pose significant environmental management challenges in areas where groundwater is contaminated with nitrate. In recent years, research on the migration and transformation behavior of various N forms in vadose zones-groundwater systems has yielded some breakthroughs but also encountered some roadblocks. The biogeochemical behavior of nitrogen consists of a series of intricate chain reaction cycles (called N-cycle). The crucial role of microorganisms in the N biogeochemical process has attracted the interest of soil carbon- and N-cycle researchers and become a hot topic of study. Nonetheless, the role of microbial regulation in groundwater systems has been largely neglected and needs to be summarized immediately. Consequently, this review summarizes recent advancements, mechanisms, and challenges, and proposes a dynamic perspective on microbial regulation. On the basis of these findings, we propose a dynamic and comprehensive groundwater N system centered on microbial regulation. In addition, we critically summarized the migration and transformation behavior of the most recent N indicators, the impact of global environmental change on each N component, and the non-negligible effects of these factors on the control of groundwater N contamination. Future research must focus on the migration and transformation behavior of nitrogen in the deep vadose zone, based on the dynamic regulation of microorganisms, and complete the missing pieces of the developed N-cycle index system. These are essential for providing scientific guidance for global N management and effectively mitigating N contamination in groundwater.

APCS-MLR model: A convenient and fast method for quantitative identification of nitrate pollution sources in groundwater.

Nitrate (NO3-) contamination in groundwater has diverse sources and complicated transformation processes. To effectively control NO3- pollution in groundwater systems, quantitative and accurate identification of NO3- sources is critical. In this work, we applied hydrochemical characteristics and isotope analysis to determine NO3- source apportionment. For the first time, the NO3- source contributions were calculated using hydrochemical indicators combined with multivariate statistical model (PCA-APCS-MLR). The results interpret that chemical fertilizers (58.11%) and natural sources (22.69%) were the primary NO3- sources in the vegetable cultivation area (VCA) which were rather close to the estimation by Bayesian isotope mixing model (SIAR). In particular, the contributions of chemical fertilizers in the VCA differed by only 3.79% between the two methods. Compared with previous approaches e.g. SIAR, the key advantage of the proposed PCA-APCS-MLR model is that it only requires the hydrochemical indicators which can be easily measured. A series of complicated experiments including measurement of isotope data of NO3- in groundwater, monitoring of in-situ pollution source information and calculation of isotopic enrichment factor can be simply avoided. The PCA-APCS-MLR model offers a much more convenient and faster method to determine the contribution rates of NO3- pollution sources in groundwater.

Determination of the nitrogen isotope enrichment factor associated with ammonification and nitrification in unsaturated soil at different temperatures.

For nitrogen (N) migration and transformation from unsaturated soil to groundwater, the N stable isotope (δ15N) was modified due to the isotope fractionation effect. To quantitatively evaluate the N cycle in groundwater systems, the determination of isotope fractionation is decisive. In this research, for the first time, incubation experiments were conducted to quantitatively investigate the N isotope enrichment factor (ϵp/s) associated with ammonification in unsaturated soil. Under weak isotopic fractionation, the Rayleigh function cannot be directly applied during ammonification. Thus, we proposed a different method calculating the ϵp/s values during ammonification, which were -0.03‰ for 15 °C and -2.34‰ for 30 °C. Moreover, for the first time, experimental equipment is presented to explore the isotopic fractionation effects under the co-occurrence of nitrification and volatilization. The results indicated that the isotope effect of volatilization during nitrification can be ignored in this study, and the ϵp/s values during nitrification were -10.59 and -6.81‰ at 15 and 30 °C, respectively. This work provides a novel arrangement determining the crucial parameters for identifying nitrate pollution sources in groundwater systems.

Assessment of the hydrodynamics role for groundwater quality using an integration of GIS, water quality index and multivariate statistical techniques.

To explore the impact of groundwater hydrodynamics on water quality, a cost-effective geospatial model was developed using geographic information system (GIS) technology and the Dupuit assumption. Meanwhile, the groundwater quality in the Dagu River Basin was evaluated based on the water quality index (WQI) and multivariate statistical analyses. In April (dry season) and September (rainy season) 2017, the groundwater level was automatically monitored from 115 wells, and the water quality including 21 hydrochemical parameters was sampled from 37 wells. Results reveal that the WQI values varied from 35.01 to 64.74, with mean values of 51.89 and 47.87 in the rainy and dry seasons. Approximately 80% of the samples exhibited moderate water quality, with no significant difference between the rainy and dry seasons. Nitrate pollution and the integrated water quality in the central and northern regions were generally worse than that in the southern region. The Darcy velocity in the central and northern regions was relatively high with a maximum rate of 0.56 m/d, compared with the southern region. This correlation illustrates the effect of groundwater hydrodynamics on quality. The sowing of greater chemical fertilizers combined with faster groundwater movement is likely responsible for the large-scale nitrate pollution in the central and northern regions. Results also proved the accuracy of the geospatial model with a valid uncertainty. The geospatial model provides a valuable alternative for the spatial analysis of the effect of groundwater hydrodynamics on water quality.

Effects of carbon availability in a woody carbon source on its nitrate removal behavior in solid-phase denitrification.

Woody biomass is the most common natural carbon source applied in solid-phase denitrification (SPD). However, its denitrification ability is low in the SPD process due to its poor carbon availability. In this study, sawdust samples were pretreated to various degrees, and then filled into SPD bioreactors to reveal the relationship between carbon availability and denitrification behaviors. The behaviors include the denitrification process, internal effects of major factors (carbon availability, pH and temperature), and the presence of bacterial communities. Results shown that the long-term denitrification rate of pretreated sawdust was increased by 4.5-4.8 times over that of untreated sawdust (29.3 mg N L-1 sawdust d-1). However, despite improving the pretreatment degree of the sawdust in the bioreactor, the long-term denitrification rate shown no further increase. The denitrification rate was most influenced by the temperature, followed by the pH, and then the sawdust pretreatment degree. The denitrification rate increased with decreasing pH and rising temperature of the pretreated sawdust. The removed nitrate was rarely converted into nitrite or nitrous oxide, but ammonium was produced at high pH and temperature for the pretreated sawdust. The adverse effects of ammonium and dissolved organic carbon (DOC) reduced when the pH of the pretreated sawdust was lowered to 6.5. Hydrolytic and denitrifying bacteria formed the main SPD bioreactor bacteria, whose abundances increased with increasing sawdust pretreatment degree. The results were beneficial to reduce the hydrolytic retention time and adverse products for the SPD system using woody carbon source.

An index system constructed for ecological stress assessment of the coastal zone: A case study of Shandong, China.

Coastal zones, which have high ecological value and environmental function and play a key role in human development, face intense ecological stress from human activities. This study constructed an assessment index system for coastal zones and proposed a coastal ecological stress index (CESI) model. This method was then applied to the Shandong coastal zone. The results showed an increase in ecological stress from 2001 to 2016 and implied a further growth trend. The stress caused by terrigenous pollution was the most prominent, with the ecological stress index showing significant spatial difference. Qingdao exerted the highest ecological stress on the population and economy, while Yantai showed the highest stress on the coastal index. The CESI model effectively reflects the temporal and spatial characteristics of the coastal ecological stress and provides a theoretical basis for the management of different regions.

Effects of alkali-treated agricultural residues on nitrate removal and N2O reduction of denitrification in unsaturated soil.

Lignocellulosic agricultural residues were utilized as denitrification carbon substrates to improve the purification capacity of unsaturated soil and alleviate nitrate pollution of groundwater. In this study, corncob and wheat straw were treated by calcium hydroxide to improve biodegradability and enhance denitrification potential. Calcium hydroxide treatment decreased the contents of lignin (i.e., from 16.7 wt% to 15.2 wt% in corncob and from 21.9 wt% to 20.6 wt% in wheat straw), increased potential biodegradable carbon by 4.4-5.3 times, reached complete nitrate removal 7-14 days earlier and decreased N2O/(N2O+N2) ratios by 85-99%. The results provide an insight into the application of alkali-treated agricultural residues as denitrification carbon sources to alleviate nitrate transport to groundwater and reduce potential greenhouse effect.

Effective control of modified palygorskite to NH4+-N release from sediment.

Sediment capping is an in situ treatment technology that can effectively restrain nutrient and pollutant release from the sediment in lakes and reservoirs. Research on sediment capping has focused on the search for effective, non-polluting and affordable capping materials. The efficiency and mechanism of sediment capping with modified palygorskite in preventing sediment ammonia nitrogen (NH4+-N) release to surface water were investigated through a series of batch and sediment capping experiments. Purified palygorskite and different types of modified palygorskite (i.e. heated, acid-modified and NaCI-modified palygorskite) were used in this investigation. Factors affecting control efficiency, including the temperature, thickness and grain size of the capping layer, were also analysed. The batch tests showed that the adsorption of NH4+-N on modified palygorskite achieved an equilibration in the initial 45 min, and the adsorption isotherm followed the Freundlich equation. Sediment capping experiments showed that compared with non-capped condition, covering the sediment with modified palygorskite and sand both inhibited NH4+-N release to the overlying water. Given its excellent chemical stability and strong adsorption, heated palygorskite, which has a NH4+-N release inhibition ratio of 41.3%, is a more effective sediment capping material compared with sand. The controlling effectiveness of the modified palygorskite increases with thicker capping layer, lower temperature and smaller grain size of the capping material.

Revisiting the Application of Machine Learning Approaches in Predicting Aqueous Solubility.

The solubility of chemical substances in water is a critical parameter in pharmaceutical development, environmental chemistry, agrochemistry, and other fields; however, accurately predicting it remains a challenge. This study aims to evaluate and compare the effectiveness of some of the most popular machine learning modeling methods and molecular featurization techniques in predicting aqueous solubility. Although these methods were not implemented in a competitive environment, some of their performance surpassed previous benchmarks, offering gradual but significant improvements. Our results show that methods based on graph convolution and graph attention mechanisms demonstrated exceptional predictive abilities with high-quality data sets, albeit with a sensitivity to data noise and errors. In contrast, models leveraging molecular descriptors not only provided better interpretability but also showed more resilience when dealing with inherent noise and errors in data. Our analysis of over 4000 molecular descriptors used in various models identified that approximately 800 of these descriptors make a significant contribution to solubility prediction. These insights offer guidance and direction for future developments in solubility prediction.

Nitrate and nitrite reduction by adsorbed Fe(II) generated from ligand-promoted dissolution of biogenic iron minerals in groundwater.

Chemical denitrification by redox-active Fe(II) species is pivotal in the coupled iron and nitrogen cycles. The reductive dissolution of ferric minerals by ligand can generate Fe(II)-ligand complexes, but their reducing capability for electrophilic pollutants like nitrate and nitrite remains uncertain. Here, biogenic secondary iron minerals (SIM) after dissimilatory iron reduction were reductively dissolved by oxalate and the siderophore desferrioxamine B, and subsequently the partially-dissolved SIM (SIMD) effectively removed NO2- from groundwater via reduction, while exhibiting much lower reactivity towards NO3-. The dissolution and removal processes were well-fitted with the Kabai model and the pseudo-second-order adsorption model, respectively. The equilibrium NO2- removal capacity (qe) of SIMD reached 0.146-0.223 mmol/g, accompanied with the rate constants as 0.433-0.810 g/(mmol·h). The emission of N2O and NO verified the occurrence of chemical denitrification during NO2- removal by SIMD. From the perspective of Fe(II) reactivity, SIMD exhibited higher densities of surface Fe(II) and more negative Eh values than SIM, and these two indicators showed linear correlations with the removal rates. Combined with microscopic, electrochemical and spectral analysis, our results indicated the redox reaction of adsorbed Fe(II)-complexes with NO2- on SIMD surface. The concurrent substance biochar was also considered, as it indirectly influenced dissolution and pollutant removal by shifting the iron mineral phase in SIM from magnetite to goethite. These findings highlight the significant role of reductive dissolution of iron mineral in N transformation, expand the electron pool available to support chemical denitrification, and have implications for Fe and N cycling coupling with pollutant reduction.

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.

Multiomics profiling of the therapeutic effect of Dan-deng-tong-nao capsule on cerebral ischemia-reperfusion injury.

BACKGROUND: Stroke is a complex physiological process associated with intestinal flora dysbiosis and metabolic disorders. Dan-deng-tong-nao capsule (DDTN) is a traditional Chinese medicine used clinically to treat cerebral ischemia-reperfusion injury (CIRI) for many years. However, little is known about the effects of DDTN in the treatment of CIRI from the perspective of gut microbiota and metabolites. PURPOSE: This study aimed to investigate the regulatory roles of DDTN in endogenous metabolism and gut microbiota in CIRI rats, thus providing a basis for clinical rational drug use and discovering natural products with potential physiological activities in DDTN for the treatment of CIRI. METHODS: The chemical composition of DDTN in vitro and in vivo was investigated using ultra-high performance liquid chromatography-high resolution mass spectrometry (UHPLCHRMS), followed by target prediction using reverse molecular docking. Secondly, a biological evaluation of DDTN ameliorating neural damage in CIRI was performed at the whole animal level. Then, an integrated omics approach based on UHPLCHRMS and 16S rRNA sequencing was proposed to reveal the anti-CIRI effect and possible mechanism of DDTN. Finally, exploring the intrinsic link between changes in metabolite profiles, changes in the intestinal flora, and targets of components to reveal DDTN for the treatment of CIRI. RESULTS: A total of 112 chemical components of DDTN were identified in vitro and 10 absorbed constituents in vivo. The efficacy of DDTN in the treatment of CIRI was confirmed by alleviating cerebral infarction and neurological deficits. After the DDTN intervention, 21 and 26 metabolites were significantly altered in plasma and fecal, respectively. Based on the fecal microbiome, a total of 36 genera were enriched among the different groups. Finally, the results of the network integration analysis showed that the 10 potential active ingredients of DDTN could mediate the differential expression of 24 metabolites and 6 gut microbes by targeting 25 target proteins. CONCLUSION: This study was the first to outline the landscapes of metabolites as well as gut microbiota regulated by DDTN in CIRI rats using multi-omics data, and comprehensively revealed the systematic relationships among ingredients, targets, metabolites, and gut microbiota, thus providing new perspectives on the mechanism of DDTN in the treatment of CIRI.

Matrix-assisted laser desorption/ionization mass spectrometry for the rapid and high throughput analysis of betaine and trigonelline in Lycium chinense Mill. and trigonelline in coffee.

A rapid, simple, effective, and green method for the determination of betaine and trigonelline from Lycium chinense Mill. (LCM) and the quantification of the trigonelline in coffee was proposed and validated by matrix-assisted laser desorption ionization time-of-flight mass spectrometric (MALDI-TOF MS) detection. Due to without chromatographic separation, the method greatly shortened the detection time. The detection of betaine and trigonelline concentration showed good linearity in the range of 1-100 µg/mL and 0.01-100 µg/mL, with correlation coefficients r2 = 0.9962 and 0.9946, respectively. The good reproducibility and reliability of the method were demonstrated by excellent intraday and interday precisions with RSD <8.3%, and the recovery of betaine and trigonelline ranged from 92.2% to 116.0%. Analysis of LCM and coffee extracts (raw, light-roasted, and dark-roasted coffee beans) gave results in agreement with the literature. The method appeared as a fast and reliable alternative method for routine Lycium chinense and coffee analysis.

Unraveling spatial metabolome of the aerial and underground parts of Scutellaria baicalensis by matrix-assisted laser desorption/ionization mass spectrometry imaging.

BACKGROUND: Scutellaria baicalensis Georgi, a traditional Chinese medicine, is clinically applied mainly as the dried root of Scutellaria baicalensis, and the aerial parts of Scutellaria baicalensis, its stems and leaves, are often consumed as "Scutellaria baicalensis tea" to clear heat, dry dampness, reduce fire and detoxify, while few comparative analyses of the spatial metabolome of the aerial and underground parts of Scutellaria baicalensis have been carried out in current research. METHODS: In this work, Matrix-assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) was used to visualize the spatial imaging of the root, stem, and leaf of Scutellaria baicalensis at a high resolution of 10 µm, respectively, investigating the spatial distribution of the different secondary metabolites in the aerial and underground parts of Scutellaria baicalensis. RESULTS: In the present results, various metabolites, such as flavonoid glycosides, flavonoid metabolites, and phenolic acids, were systematically characterized in Scutellaria baicalensis root, stem, and leaf. Nine glycosides, 18 flavonoids, one organic acid, and four other metabolites in Scutellaria baicalensis root; nine glycosides, nine flavonoids, one organic acid in Scutellaria baicalensis stem; and seven flavonoids and seven glycosides in Scutellaria baicalensis leaf were visualized by MALDI-MSI. In the underground part of Scutellaria baicalensis, baicalein, wogonin, baicalin, wogonoside, and chrysin were widely distributed, while there was less spatial location in the aerial parts. Moreover, scutellarein, carthamidin/isocarthamidin, scutellarin, carthamidin/isocarthamidin-7-O-glucuronide had a high distribution in the aerial parts of Scutellaria baicalensis. In addition, the biosynthetic pathways involved in the biosynthesis of significant flavonoid metabolites in aerial and underground parts of Scutellaria baicalensis were successfully localized and visualized. CONCLUSIONS: MALDI-MSI offers a favorable approach for investigating the spatial distribution and effective utilization of metabolites of Scutellaria baicalensis. The detailed spatial chemical information can not only improve our understanding of the biosynthesis pathways of flavonoid metabolites, but more importantly, suggest that we need to fully exert the overall medicinal value of Scutellaria baicalensis, strengthening the reuse and development of the resources of Scutellaria baicalensis aboveground parts.

Influence of pH on bioclogging in porous media during managed aquifer recharge (MAR): Effectiveness and mechanism.

To investigate the effect of pH on bioclogging process during managed aquifer recharge, three laboratory-scale column experiments were conducted and the relative hydraulic conductivity, bacterial cell number and the concentrations of polysaccharide, protein and EPS were measured under pH 5, 7, and 9, respectively. High-throughput sequencing was also used to determine the characteristics of bacterial community under different pH conditions. The development of bioclogging was rather different for the case of pH 5. 7, and 9; i.e., the growth process and number of bacteria differed with pH. The shortest growth period and lowest number of bacteria were observed at pH 5. In addition, the difference in bacterial EPS concentration was mainly associated with the polysaccharides. The variation in pH led to different bacterial community composition and diversity. The acid-resistant Elizabethkingia and Bacillus were abundant at pH 5, while Chryseobacterium and Klebsiella had relatively high abundances at pH 7. In contrast, the basophilic Exiguobacterium accounted for >80% of the total bacterial abundance at pH 9. This work is of great significance to explore bioclogging mechanism during MAR process, and provides insights and guidances for field-based managed aquifer recharge.

Causal interpretation for groundwater exploitation strategy in a coastal aquifer.

Machine learning models (ML), as a collection of nonparametric or semiparametric estimation methods, can successfully encode the distribution of the problems into its trainable parameters based on observation data. However, the distributions of hydrological variables may change suddenly under complex environmental conditions, leading to biased estimates when using ML models. This work is the first attempt to solve this issue using structural causal models (SCM). Specifically, two SCM were constructed based on hydrological conditions and monitoring data. Then the Propensity Score estimator and the Double Machine Learning estimator were employed to estimate the causal effects of four treatments on the mean Cl- concentration (MCL) in the coastal aquifer. The results showed that pumping groundwater from area A1 or increasing the river level directly leads to a decrease in MCL, while pumping area A3 directly leads to an increase in MCL. Moreover, MCL can be effectively controlled by cooperative-treatment strategies. Finally, two practical exploitation strategies are derived. In the planting month, it should increase groundwater pumping from area A1, limit groundwater pumping from A2, and prohibit groundwater pumping from A3. For the normal month, it is proposed to increase the height of the rubber dam to raise the river level and reduce groundwater pumping from A1 and A2.

Repulsion driven by groundwater level difference around cutoff walls on seawater intrusion in unconfined aquifers.

Cutoff walls have been widely used to prevent seawater intrusion (SWI) in coastal regions. Previous studies generally concluded that the ability of cutoff walls to prevent seawater intrusion depends on the higher flow velocity at the wall opening, which we have shown is not the most critical mechanism. In this work, we implemented numerical simulations to explore the driving force of cutoff walls on the repulsion of SWI in both homogeneous and stratified unconfined aquifers. The results delineated that the inland groundwater level was raised by cutoff walls, which generated a significant groundwater level difference beside two sides of the wall and thus provided a large hydraulic gradient to repel SWI. We further concluded that by increasing inland freshwater influx, the construction of cutoff wall could result in a high inland freshwater hydraulic head and fast freshwater velocity. The high inland freshwater hydraulic head posed a large hydraulic pressure to push the saltwater wedge seawards. Meanwhile, the fast freshwater flow could rapidly carry the salt from the mixing zone to the ocean and induce a narrow mixing zone. This conclusion explained the reason that the cutoff wall can improve the efficiency of SWI prevention through recharging freshwater upstream. With a defined freshwater influx, the mixing zone width and saltwater pollution area mitigated with the increase of the ratio between high and low hydraulic conductivity values (KH/KL) of the two layers. This was because the increase of KH/KL caused a higher freshwater hydraulic head, a faster freshwater velocity in the high-permeability layer, and the prominent change of flow direction at the interface between the two layers. According to the above findings, we deduced that any way to increase the inland hydraulic head upstream of the wall would improve the efficiency of cutoff walls, such as the freshwater recharge, the air injection, and the subsurface dam.

Dynamic influence of land reclamation on the nitrate contamination and saltwater redistribution.

Previous research concerning the effect of land reclamation on seawater intrusion mostly focused on the modification of the saltwater wedge and the dynamics of freshwater-saltwater interface after land reclamation, utilizing both analytical and numerical models. So far, the impact of land reclamation on the recharging and accumulation of land-based pollutants such as nitrate has been disregarded. In this work, we are the first to examine the impact of land reclamation on the discharge of nitrate together with the movement of saltwater. The influence of reclamation area and filled soil permeability on nitrate pollution and saltwater redistribution is revealed using a series of field-scale simulations based on numerical models including density flow combined with reactive transport. It was discovered that land reclamation might, on the one hand, result in a substantial redistribution based on the initial saltwater-freshwater interface and, on the other hand, significantly modify the nitrate discharge. This in total would drastically alter the distribution of nitrate in the subsurface. The reclamation area and the permeability of the reclamation material are the two elements that determine the amount of variance. For the cases with hydraulic conductivities increasing from 5 to 50 m/d, the salt mass reduction rate showed a trend of first increased (84.78 %-95.58 %) and then slowly decreased (95.58 %-74.01 %). Meanwhile, the nitrate reduction rate decreased from 80.08 % to 12.93 %, when hydraulic conductivities increased from 5 to 50 m/d. It was also found that coastal nitrate accumulation was always intensified with the enlargement of the reclamation area. Finally, we are able to assist engineers in optimizing their land reclamation strategies by taking into account both the degree of saltwater intrusion and nitrate enrichment.