Activation of iron oxide minerals in an aquifer by humic acid to promote adsorption of organic molecules.

In aquifers, the sequestration and transformation of organic carbon are closely associated with soil iron oxides and can facilitate the release of iron ions from iron oxide minerals. There is a strong interaction between dissolved organic matter (DOM) and iron oxide minerals in aquifers, but the extent to which iron is activated by DOM exposure to active iron minerals in natural aquifers, the microscopic distribution of minerals on the surface, and the mechanisms involved in DOM molecular transformation are currently unclear. This study investigated the nonbiological reduction transformation and coupled adsorption of iron oxide minerals in aquifers containing DOM from both macro- and micro perspectives. The results of macroscopic dynamics experiments indicate that DOM can mediate soluble iron release during the reduction of iron oxide minerals, that pH strongly affects DOM removal, and that DOM is more efficiently degraded at low rather than high pH values, suggesting that a low pH is conducive to DOM adsorption and oxidation. Spherical aberration-corrected scanning transmission electron microscopy (SACTS) indicates that the reacted mineral surfaces are covered with large amounts of carbon and that dynamic agglomeration of iron, carbon, and oxygen occurs. At the nanoscale, three forms of DOM are found in the mineral surface agglomerates (on the surfaces, inside the surface agglomerates, and in the polymer pores). The microscopic organic carbon and iron mineral reaction patterns can form through oxidation reactions and selective adsorption effects. Fourier transform ion cyclotron resonance mass spectra indicate that both synergistic and antagonistic reactions occur between DOM and the minerals, that the release of iron is accompanied by DOM decomposition and humification, that large oxygen- and carbon-containing molecules are broken down into smaller oxygen- and carbon-containing compounds and that more molecules are produced through oxidation under acidic rather than alkaline conditions. These molecules provide adsorption sites for sediment, meaning that more iron can be released. Microscopic evidence for the release of iron was acquired. These results improve the understanding of the geochemical processes affecting iron in groundwater, the nonbiological transformation mechanisms that occur at the interfaces between natural iron minerals and organic matter, groundwater pollution control, and the environmental behavior of pollutants.

Influence of DOM and microbes on Fe biogeochemistry at a riverbank filtration site.

Riverbank filtration (RBF) constitutes an important part of the water cycle, which involves active natural filtration leading to pollution of river water being intercepted and retained. The RBF has the function of water purification, but retention of exogenous pollutants in the RBF system complicates biogeochemical processes due to the presence of primary active components. In this study, we verified the essential role of microbial mediation during the interactions between primary Fe minerals in the RBF system and dissolved organic matter (DOM) in river water based on lab-scale experiments. The results demonstrated that DOM from infiltration of river water increased the amount of iron (Fe) released from the sediment in RBF, leading to an increase in Fe concentration in groundwater by higher than one order of magnitude. In particular, the existence of Fe bacteria even made this effect more thorough and more complex. Abiotic reduction was shown to play a more significant role in increasing Fe release than microbe-mediated reduction. Increasing the amount of Fe released could change the distribution of Fe minerals at the sediment surface, thereby affecting the structure of the microbial community in the RBF system and decreasing the DOM concentration in the groundwater. Moreover, As and Mn were found to behave in a similar manner as Fe due to their close biochemical properties when interacting with primary minerals in sediment. This study not only provides mechanistic insight into the higher Fe concentrations encountered in the groundwater of nearby rivers but also has important practical implications for developing nature-based technologies for water pollution control and environmental remediation.

Coupling flow and electric fields to simulate migration and remediation of uranium in groundwater remediated by electroosmosis and a permeable reactive bio-barrier.

Combined remediation technologies are increasingly being considered to uranium contaminated groundwater, such as the joint utilize of permeable reactive bio-barrier (Bio-PRB) and electrokinetic remediation (EKR). While the assessment of uranium plume evolution in the combined remediation system (CRS) have often been impeded by insufficient understanding of multi-physical field superposition. Therefore, advanced knowledge in multi-physical field coupling in groundwater flow will be crucial to the practical application of these techniques. A two-dimensional multi-physical field coupling model was constructed for predicting the uranium degradation in CRS. The study demonstrates that the coupling model is able to predict the uranium plume evolution and rapidly evaluate the performance of CRS components. The results show that field electric direction and flow field strength are the key factors that affect the retardation and remediation performance of CRS. The reverse electric field direction significantly affected the contact reaction time of uranium in the system. The uranium residence time in the reverse electric field was 3.8 d, which was significantly greater than the original electric field (2.0 d). Depending on the voltage, the reverse electric field direction was 16%-36% more efficient than the original direction. The strength of the flow field was about two orders of magnitude higher than that of the electric field, so the groundwater flow rate dominated remediation efficiency. Reducing the flow rate by 1/2 could improve the performance of the system by approximately 66%. In addition, the coupling model can be utilized to design standard CRS for real site of uranium contaminated groundwater. To meet the optimal performance, the direction of the electric field should be set opposite to the flow field. This work has successfully used a coupling model to predict uranium contaminant-plume evolution in CRS and estimate the performance of each component.

Thyroid Hormone Disruption by Organophosphate Esters Is Mediated by Nuclear/Membrane Thyroid Hormone Receptors: In Vitro, In Vivo, and In Silico Studies.

Earlier mechanistic studies of many prohibited flame retardants (FRs) highlighted their thyroid hormone-disrupting activity through nuclear thyroid hormone receptors (nTRs), whereas some alternative FRs such as organophosphate esters (OPEs) exerted weak nTR-disrupting effects. However, an increasing number of studies have revealed that OPEs also exert thyroid hormone-disrupting effects, and the underlying mechanism is unclear. Herein, the thyroid hormone-disrupting effects and mechanisms of 8 typical OPEs were investigated using integrated in vitro, in vivo, and in silico assays. All tested chemicals competitively bound to the membrane thyroid hormone receptor (mTR) [the 20% relative inhibitory concentration (RIC20): (3.5 ± 0.2) × 101 to (4.9 ± 1.0) × 107 nM], and Cl-OPEs and alkyl-OPEs had lower RIC20 values. In contrast, only 4 OPEs showed nTR antagonistic activities at higher concentrations [≥ (4.8 ± 0.8) × 103 nM]. Cl-OPEs and alkyl-OPEs preferentially interacted with mTR. Molecular docking illustrated that OPEs docked into mTRs, consistent with the competitive binding assay. In vivo analyses of zebrafish embryonic development confirmed that tris(1,3-dichloro-2-propyl) phosphate induced inappropriate expression of proteins, and these protein interactions might be associated with mTR according to the quantitative proteomic analysis. Based on the results, mTR might play a critical role in mediating the thyroid hormone-disrupting effects of OPEs.

Valuation of ecosystem damage induced by soil-groundwater pollution in an arid climate area: Framework, method and case study.

Groundwater is an important source of water, even the only source in some arid areas. However, climate changing and ecosystem damage induced by pollution aggravate water resource crisis. The "polluter pays" principle is deeply rooted in efforts to manage the polluted sites, particularly in the soil-groundwater environment. Unfortunately, there is no ecosystem damage compensation mechanism generally accepted by all stakeholders. In this study, we establish an assessment framework and valuation methods for ecosystem damage induced by soil-groundwater pollution in an arid climate area based on a "pollution source → target (soil-groundwater) → receptor (humans, animals, and plants) → damages → stakeholders (human society and ecosystem)" model that is usually applied in groundwater risk assessment research. Five economic loss are included in the valuation methods: (1) human health loss, (2) emergency disposal cost, (3) direct economic loss, (4) ecological restoration cost, and (5) ecosystem services loss. We apply the framework to a case study in an arid climate area, northwest China and calculate the total economic loss from ecosystem damage in the case study at 12.6 million yuan. The largest proportion of the total loss was the ecological restoration cost (85.6%), followed by the emergency disposal cost (11.2%), and finally ecosystem services loss (3.2%). Valuation of ecosystem damage from environmental pollution is essentially a socioeconomic issue. This study supplies a new framework and methods for valuing ecosystem damage induced by pollution, and offers suggestions for environmental management to reduce the damage caused by soil-groundwater pollution to health and ecosystems.

Spatiotemporal distribution and risk assessment of organophosphorus pesticides in surface water and groundwater on the North China Plain, China.

90 groundwater samples and 14 surface water samples were collected in wet season (summer) and dry season (winter) in the North China Plain (NCP), and analyzed for 11 organophosphorus pesticides (OPPs). The results showed that the main types of OPPs in surface water and groundwater were dimethoate, dichlorvos, methyl-parathion, malathion in both summer and winter. The OPP concentrations in groundwater and surface water were higher in summer than in winter. In the vertical direction, the distribution characteristics of different four types of groundwater sampling points are different. In the horizontal direction: farmland adjacent to a river (FAR) > central farmland (CF) > nonfarm area adjacent to a river (NFAR) > central nonfarm area (CNF). The OPPs concentrations in surface water adjacent to farmland were higher than that in surface water adjacent to nonfarm area. The main factors influencing the distribution of OPPs in the groundwater and surface water were the interaction process between them, the groundwater flow field and the OPPs used in agricultural activities. The ecological risk of OPPs to surface water was greater in summer than in winter. Water Flea was at medium risk, and malathion had the greatest influence on Water Flea in both summer and winter. The non-carcinogenic and carcinogenic risks of the four main OPPs in surface water were higher than in groundwater, and were higher in summer than in winter, but they would not lead to adverse health effects on local residents.

Microbial response to biogeochemical profile in a perpendicular riverbank filtration site.

Due to extensive water exchanges and abundant active biochemical compositions, active and complex hydrogeochemical processes often exist in riverbank filtration (RBF). The distribution of microbes is considered to be profoundly affected by these processes and is considered to impact the hydrogeochemical processes and the migration and transformation of water pollutants in turn and then impact the water quality. The distribution of microbes and their response to the physiochemical properties along a vertical RBF profile perpendicular to the Songhua River in Northeast China was explored by using 16 S rRNA and redundancy analysis (RDA). The results showed that various microbes were found in the vertical riparian filter (RBF) curve, including Actinobacteria, Proteobacteria, Acidobacteria, Chloroflexi, and Firmicutes. With increasing depth (vertical) and distance from the river (lateral), the microbial community and diversity in the RBF sediment profile decreased. Nitrospirota, Pseudomonas, Gammaproteobacteria, Ochrobactrum, Acinetobacter and Desulfobacterota of the RBF core taxa were also significantly correlated with the biotransformation behavior of typical groundwater pollutants (ammonia, Fe, Mn and S). The amount of As in the RBF is too low to sustain microbial survival. Some microbes in RBF can also degrade natural organic pollutants. This study not only revealed the spatial distribution of geological microbes under the impact of hydrological processes but also lays a foundation for the further study of the hydrobiogeochemical processes of active biochemical compositions in groundwater and water quality evolution, which is of positive significance to ensure the quality safety of the drinking water supplied by RBFs.

Construction, application and validation of a new algorithm for determining light nonaqueous-phase liquid fluxes in unsaturated zones.

An analytical algorithm coupling free-phase migration, precipitation, and natural attenuation through volatilization and biodegradation (FPVB) was developed to calculate the flux of light nonaqueous-phase liquid (LNAPL) leaking from unsaturated zone to groundwater. Sandbox and soil column experiments were performed to identify the LNAPL migration characteristics and states to provide data to establish and verify FPVB algorithm. For free-phase migration, the Kinematic Oily Pollutant Transport (KOPT) model was used to determine LNAPL movement velocity and leakage time. The correlations of water saturation, residual LNAPL saturation and the cumulative dissolution ratio of residual LNAPL were described using an empirical formula for the precipitation leaching process. Equations for diesel volatilization kinetics and first order degradation were used to describe the natural attenuation processes. Coupling the algorithms for the different stages gave the final FPVB algorithm. The FPVB algorithm was used to describe the pollution situation at a real site, and the results were consistent with the actual situation. The FPVB algorithm could be used to quickly assess the scale and degree of pollution with little information on the parameters for the actual LNAPL leakage event.

Spatiotemporal evolution of groundwater nitrate nitrogen levels and potential human health risks in the Songnen Plain, Northeast China.

As one of the most widespread pollutants worldwide, nitrogen has long been a concern in the environment, including groundwater. However, due to the limitations of investigations and study progress, there is still a poor understanding of groundwater nitrogen pollution and its potential effects on human health in many areas, particularly in developing countries. The spatiotemporal evolution of groundwater nitrate nitrogen levels and potential human health risks in the Songnen Plain, Northeast China were comprehensively studied based on both our own test data and available published data that were collected by us over a study period from 1995 to 2015. Groundwater nitrate nitrogen concentrations exhibited significant temporal and spatial differences: there was an increasing trend with time; and the distribution of high concentration areas expanded from the central and western areas to the east with time. The similar pattern existed in the potential health risks posed to the residents considering the two exposure pathways including drinking water and dermal contact. The effects of groundwater nitrate nitrogen on human health depend on the nitrate concentration but there were also age differences, namely, in the order of infants > children > adult females ≈ adult males, according to the hazard quotient (HQ) used in the human health risk assessment (HHRA) model. The spatiotemporal evolution of groundwater nitrate nitrogen levels and potential human health risks indicate that the issue of nitrogen pollution in groundwater in the study area is worsening and needs further attention. The drivers that increased nitrate nitrogen concentrations in the groundwater of the study area were the increased fertilizer use due to the increased cultivated land area and implementation of a land fertility policy by the local government. It should be acknowledged that the results have uncertainties that not only come from the layout of sampling points and selection of spatial interpolation methods but also come from the parameter settings in the assessment model and assumptions of drinking water scenarios. However, the conclusions still have important reference value for groundwater pollution control and management and human health risk supervision and early warning.

Influence of surface-water irrigation on the distribution of organophosphorus pesticides in soil-water systems, Jianghan Plain, central China.

Surface-water irrigation is one of the most important irrigation methods in areas with abundant surface water. Although this method of irrigation is both economical and convenient, many contaminants are also introduced into the soil-water systems such as organophosphorus pesticides (OPPs). To study the influence of surface-water irrigation on the distribution of OPPs in soil-water systems, 42 water samples (38 groundwater and four surface water) and 85 soil samples (78 profile soil samples and seven topsoil samples) were taken from Shahu in the Jianghan Plain, China. Shahu is a typical Chinese surface-water irrigation district. During sampling, three types of areas were considered: surface-water irrigated areas, groundwater-irrigated areas away from rivers, and non-irrigated areas adjacent to rivers. The results showed that the concentrations of OPPs in the groundwater and soil in the surface-water irrigated farmland were higher than those in groundwater-irrigated farmland. The groundwater flow field and surface-water irrigation were responsible for the OPPs. Thus, it is clear that the surface-water irrigation had a strong influence on the distribution of OPPs in soil-water systems. Principal component analysis for OPPs content in groundwater showed that the key influencing factors on the distribution of OPPs in groundwater were the groundwater flow field and current pesticide use.

Quality change mechanism and drinking safety of repeatedly-boiled water and prolonged-boil water: a comparative study.

Quality, safety and potability of repeatedly-boiled water (RBW) and prolonged-boil water (PBW) lead to concern and even misgivings in the public from time to time, especially in China, and other societies have a habit of drinking boiled water, with improvements of living standards and owing to increasing concerns for human health. This phenomenon is mainly attributed to the fact that the conclusions drawn from existing scientific experiments could not respond well to the concerns. In order to make up for this deficiency, tap water was selected to carry out RBW and PBW experiments independently. The quality changes of RBW and PBW show very similar trends that are not as great as might be imagined, and both are impacted by the tap water quality and the physiochemical effects. The dominating physiochemical effects are the water evaporation and the resulting concentration of unreactive components (most dissolved components), which can be easily explained by the existing evaporation-concentration theory. The results show that tap water will be still safe and potable after being frequently boiled or after having undergone prolonged boiling, as long as it satisfies the sanitary standards of drinking water prior to heating. Therefore, there is no need to worry about drinking RBW or PBW in daily life.

Life Cycle Energy Analysis of Reclaimed Water Reuse Projects in Beijing.

To illustrate the benefits of water reuse project, the process-based life cycle analysis (LCA) could be combined with input-output LCA to evaluate the water reuse project. Energy is the only evaluation parameter used in this study. Life cycle assessment of all energy inputs (LCEA) is completed mainly by the life cycle inventory (LCI), taking into account the full life cycle including the construction, the operation, and the demolition phase of the project. Assessment of benefit from water reuse during the life cycle should focus on wastewater discharge reduction and water-saving benefits. The results of LCEA of Beijing water reuse project built in 2014 in a comprehensive way shows that the benefits obtained from the reclaimed water reuse far exceed the life cycle energy consumption. In this paper, the authors apply the LCEA model to estimate the benefits of reclaimed water reuse projects quantitatively.

Application of the Risk-Based Early Warning Method in a Fracture-Karst Water Source, North China.

The paper proposes a risk-based early warning considering characteristics of fracture-karst aquifer in North China and applied it in a super-large fracture-karst water source. Groundwater vulnerability, types of land use, water abundance, transmissivity and spatial temporal variation of groundwater quality were chosen as indexes of the method. Weights of factors were obtained by using AHP method based on relative importance of factors, maps of factors were zoned by GIS, early warning map was conducted based on extension theory with the help of GIS, ENVI+IDL. The early warning map fused five factors very well, serious and tremendous warning areas are mainly located in northwest and east with high or relatively high transmissivity and groundwater pollutant loading, and obviously deteriorated or deteriorated trend of petroleum. The early warning map warns people where more attention should be paid, and the paper guides decision making to take appropriate protection actions in different warning levels areas.

Groundwater nitrate pollution and human health risk assessment by using HHRA model in an agricultural area, NE China.

In order to learn the pollution circumstance of groundwater nitrate detailedly in Songnen Plain of Northeast China and estimate its potential risk to human health of local residents, a total of 389 groundwater samples were collected in 2014 and studied from residential areas and public water supply wells in 11 cities and counties in southeastern of Songnen Plain. The analysis results showed that the spatial distributions of main chemical components in groundwater had great variations with statistical concentrations in the order of TDS> HCO3> Ca> NO3> Cl> Na> SO4> Mg> K> NH4> NO2. As for NO3, it ranged from less than 0.02mg/L to 497mg/L with an average value of 39.46mg/L indicating an obviously anthropogenic pollution. Even more than 32% of the samples exceeded the Grade III threshold (20mg/L of N) according to China's standard. The results obtained from principal component analysis showed that high NO3 concentration could be attributed to human activities, especially the excessive use of chemical fertilizers in agriculture. Further, a human health risk assessment (HHRA) model derived from the US Environmental Protection Agency (USEPA) was applied to estimate the potential health risk of groundwater nitrate considering both drinking water and dermal contact pathways. The results indicated that potential health risks of adult males and females within about 60% of the area were at the acceptable level, while those within about 40% were beyond the acceptable level. The area at the acceptable level for children covered 49% of the total area while the same value for infants was 37%. The NO3 concentration in southeast and northeast of the study area was the highest so that residents in these regions were at the highest health risk. In conclusion, risk levels for different crowds in the study area varied obviously, generally in the order of infants> children> adult females> adult males, and the potential health risks of residents, especially minors and rural residents, should cause enough attention both from the society and the academic community.

Measurement of NAPL-water interfacial areas and mass transfer rates in two-dimensional flow cell.

The nonaqueous-phase liquid (NAPL)-water interfacial area and the mass transfer rate across the NAPL and water interface are often key factors in in situ groundwater pollution treatment. In this study, the NAPL-water interfacial area and residual NAPL saturation were measured using interfacial and partitioning tracer tests in a two-dimensional flow cell. The results were compared with previous column and field experiment results. In addition, the mass transfer rates at various NAPL-water interfacial areas were investigated. Fe2+-activated persulfate was used for in situ chemical oxidation remediation to remove NAPL gradually. The results showed that the reduction of NAPL-water interfacial areas as well as NAPL saturation by chemical oxidation caused a linear decrease in the interphase mass transfer rates (R2 = 0.97), revealing the relationship between mass transfer rates and interfacial areas in a two-dimensional system. The NAPL oxidation rates decreased with the reduction of interfacial areas, owing to the control of NAPL mass transfer into the aqueous phase.

The spatial and seasonal variability of the groundwater chemistry and quality in the exploited aquifer in the Daxing District, Beijing, China.

The aquifer in the Beijing Plain is intensively used as a primary source to meet the growing needs of the various sectors (drinking, agricultural, and industrial purposes). The analysis of groundwater chemical characteristics provides much important information useful in water resources management. To characterize the groundwater chemistry, reveal its spatial and seasonal variability, and determine its quality suitability for domestic and agricultural uses, a total of 200 groundwater samples were collected in June and October 2012 from 100 exploited wells in Daxing District, Beijing, China. All of the indices (39 items) listed in the Quality Standard for Groundwater of China (QSGC) as well as eight additional common parameters were tested and analyzed for all samples, based on which research target was achieved. The seasonal effect on the groundwater chemistry and quality was very slight, whereas the spatial changes were very obvious. The aquifer is mainly dominated by HCO3-Ca·Mg-type water. Of the 39 quality indices listed in QSGC, 28 indices of all of the samples for the 2 months can be classified into the excellent level, whereas the remaining 11 indices can be classified into different levels with the total hardness, NO3, NO2, and Fe being the worst, mainly distributed in the residential and industrial land. According to the general quality index, the groundwater can be classified from good to a relatively poor level, mainly from southeast to northwest. Furthermore, the relatively poor-level area in the northwest expands to the southeast more than in the past years, to which people should pay attention because this reverse spatial distribution relative to the natural law indicates an obvious, anthropogenic impact on the groundwater. In addition, the groundwater in this area is generally very suitable for irrigation year-round. Nevertheless, we recommend performing agricultural water-saving measures for the sustainable development of water and urbanization, groundwater recovery, and ecological safety.

Flood irrigation increases the release of phosphorus from aquifer sediments into groundwater.

Nonpoint source pollution caused by agricultural activities has long attracted widespread attention from people in society and academia. Many studies have found that human activities not only convey exogenous pollutants into aquifers but also affect the mobilization and transport of geogenic pollutants in aquifers. Geogenic groundwater with high phosphorus concentrations has been found, but it is unclear whether the changes in hydrogeochemical conditions caused by flood irrigation in paddy fields affect the fate of phosphorus. We investigated the temporal and spatial distribution characteristics of phosphorus in groundwater under the influence of flood irrigation through laboratory experiments, proved its impact on phosphorus in groundwater, and explored the mechanisms influencing P concentrations. The results show that flood irrigation can increase the release of phosphorus in the aquifer media and greatly increase the phosphorus concentration in the groundwater of the study area, which has a negative impact on groundwater quality. The main mechanism of increase in phosphorus concentration in groundwater involves an increase in the reducibility of the aquifer via flood irrigation; as a result, iron oxides are reductively dissolved and iron-bound phosphorus is released into the groundwater. Changes in pH also result in the dissolution of calcium phosphate minerals and the release calcium-bound phosphorus. This study not only advances the theory of multielement-coupled hydrogeochemistry but also provides a reference for agricultural planning and groundwater pollution prevention and control in rice-growing areas.

Spatial heterogeneity: Necessary and feasible for revealing soil trace elements pollution, sources, risks, and their links.

The source diversity and health risk of trace elements (TEs) in soil make it necessary to reveal the relationship between pollution, source, and risk. However, neglect of spatial heterogeneity restricts the reliability of existing identification methods. In this study, spatial heterogeneity is proposed as a necessary and feasible factor for accurately dissecting the pollution-source-risk link of soil TEs. A comprehensive framework is developed by integrating positive matrix factorization, Geodetector, and risk evaluation tools, and successfully applied in a mining-intensive city in northern China. Overall, the TEs are derived from natural background (28.5 %), atmospheric deposition (25.6 %), coal mining (21.8 %), and metal industry (24.1 %). The formation mechanism of heterogeneity for high-variance TEs (Se, Hg, Cd) is first systematically deciphered by revealing the heterogeneous source-sink relationship. Specifically, Se is dominated (76.5 %) by heterogeneous coal mining (q=0.187), Hg is determined (92.6 %) by the heterogeneity of metal mining (q=0.183) and smelting (q=0.363), and Cd is caused (50.9 %) by heterogeneous atmospheric deposition (q>0.254) co-influenced by the terrains and soil properties. Highly heterogeneous sources are also noteworthy for their potential to pose extreme risks (THI=1.122) in local areas. This study highlights the necessity of integrating spatial heterogeneity in pollution and risk assessment of soil TEs.

Driving mechanism of different nutrient conditions on microbial mediated nitrate reduction in magnetite-present river infiltration zone.

Significant research is focused on the ability of riparian zones to reduce groundwater nitrate contamination. Owing to the extremely high redox activity of nitrate, naturally existing electron donors, such as organic matter and iron minerals, are crucial in facilitating nitrate reduction in the riparian zone. Here, we examined the coexistence of magnetite, an iron mineral, and nitrate, a frequently observed coexisting system in sediments, to investigate nitrate reduction features at various C/N ratios and evaluate the response of microbial communities to these settings. Additionally, we aimed to use this information as a foundation for examining the effect of nutritional conditions on the nitrate reduction process in magnetite-present environments. These results emphasise the significance of organic matter in enabling dissimilatory nitrate reduction to ammonium (DNRA) and enhancing the connection between nitrate reduction and iron in sedimentary environments. In the later phases of nitrate reduction, nitrogen fixation was the prevailing process in low-carbon environments, whereas high-carbon environments tended to facilitate the breakdown of organic nitrogen. High-throughput sequencing analysis revealed a robust association between C/N ratios and alterations in microbial community composition, providing insights into notable modifications in essential functioning microorganisms. The nitrogen-fixing bacterium Ralstonia is more abundant in ecosystems with scarce organic matter. In contrast, in settings rich in organic matter, microorganisms, such as Acinetobacter and Clostridia, which may produce ammonia, play crucial roles. Moreover, the population of iron bacteria grows in such an environment. Hence, this study proposes that C/N ratios can influence Fe(II)/Fe(III) conversions and simultaneously affect the process of nitrate reduction by shaping the composition of specific microbial communities.

DOM accumulation in the hyporheic zone promotes geogenic Fe mobility: A laboratory column study.

Hyporheic zone (HZ) systems have a natural purification capacity, and they are commonly used to provide high quality drinking water. However, the presence of organic contaminants in HZ systems in anaerobic environments causes the aquifer sediments to release metals (e.g., Fe) at levels above drinking water standards, which affects the quality of groundwater. In this study, the effects of typical organic pollutants (dissolved organic matter (DOM)) on Fe release from anaerobic HZ sediments were investigated. Ultraviolet fluorescence spectroscopy, three-dimensional excitation-emission matrix fluorescence spectroscopy, excitation-emission matrix spectroscopy coupled with parallel factor analysis and Illumina MiSeq high-throughput sequencing were used to determine the effects of the system conditions on Fe release from HZ sediments. Compared with the control conditions (low traffic and low DOM as a baseline), the Fe release capacity was enhanced by 26.7 % and 64.4 % at low flow rate (85.8 m/d) and high organic matter concentration (1200 mg/L), which was consistent with the residence-time effect. The transport of heavy metals under different system conditions varied with the influent organic composition. The influent organic matter composition and fluorescence parameters (the humification index, biological index and fluorescence index) were closely related to the release of the Fe effluent, while these factors had less influence on Mn and As. From 16S rRNA analysis of the aquifer media at different depths at the end of the experiment, under low flow rate and high influent concentration conditions, reduction of Fe minerals by Proteobacteria, Actinobacteriota, Bacillus, and Acidobacteria promoted the release of Fe. These functional microbes play an active role in the Fe biogeochemical cycle in addition to reducing Fe minerals to promote Fe release. In summary, this study reveals the effects of the flow rate and influent DOM concentration on the release and biogeochemistry of Fe in the HZ. The results presented herein will contribute to a better understanding of the release and transport of common groundwater contaminants in the HZ and other groundwater recharge environments.