{"title":"Source-dependent photoreactivity of dissolved organic matter and its implications for specific disinfection byproduct formation.","authors":"Ruizhe Wang, Yu Luo, Fang Chen, Zhineng Hao, Dong Ren, Junjian Wang","doi":"10.1016/j.watres.2026.126635","DOIUrl":"10.1016/j.watres.2026.126635","url":null,"abstract":"<p><p>Photochemical processing dictates the molecular evolution of dissolved organic matter (DOM) in sunlit waters and its subsequent reactivity during chlorination. However, how source-specific molecular signatures regulate the photochemical transformations of DOM and its associated disinfection by-product (DBP) formation potentials remains poorly understood. Here, DOM samples derived from algae (ADOM), soil (SDOM), litter (LDOM), and wildfire ash (BDOM) were exposed to 28 days of simulated solar irradiation to elucidate source-dependent molecular transformations and their impacts on specific DBP formation. DOM compositional changes were characterized using optical spectroscopy and Fourier transform-ion cyclotron resonance mass spectrometry, and specific DBP formation potentials were assessed via chlorination assays. Distinct molecular signatures differentiated DOM sources, with ADOM enriched in protein- and lipid-like compounds, whereas SDOM, LDOM, and BDOM contained greater proportions of aromatic, lignin-, and tannin-like molecules. Irradiation drove partial convergence of DOM toward a more oxidized state, lower molecular weight, and more aromatic structures via decarboxylation, dealkylation, and deamination. These transformations reduced specific carbonaceous DBP formation (up to 93 %) across most DOM sources, whereas LDOM showed a ∼9 % increase in specific trihalomethane and chloral hydrate formation, likely due to the persistence and transformation of lignin-like precursors. Notably, specific haloacetonitrile formation potentials substantially increased by 99-125 % across all DOM sources, associated with the generation of reactive nitrogenous precursors through photo-oxidation and depolymerization of macromolecules. These findings demonstrate that solar-driven DOM transformation governs distinct carbonaceous and nitrogenous DBP responses, highlighting the need for source-specific molecular insights to predict and manage DBP risks in watersheds.</p>","PeriodicalId":443,"journal":{"name":"Water Research","volume":"306 ","pages":"126635"},"PeriodicalIF":12.8,"publicationDate":"2026-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148704858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Water ResearchPub Date : 2026-10-31DOI: 10.1016/j.watres.2026.127256
Yongding Xue, Jie Liu, Shengqi Li, Bin Ji
{"title":"Adaptive responses and biotransformation of carbamazepine in microalgal-bacterial granular sludge: microbial succession, functional genes, and toxicity redistribution","authors":"Yongding Xue, Jie Liu, Shengqi Li, Bin Ji","doi":"10.1016/j.watres.2026.127256","DOIUrl":"https://doi.org/10.1016/j.watres.2026.127256","url":null,"abstract":"The long-term response and removal mechanisms of microalgal-bacterial granular sludge (MBGS) to persistent pharmaceuticals remain poorly understood. MBGS was exposed to carbamazepine (CBZ) at four concentrations (10 μg L<ce:sup loc=\"post\">-1</ce:sup>, 100 μg L<ce:sup loc=\"post\">-1</ce:sup>, 1 mg L<ce:sup loc=\"post\">-1</ce:sup>, 10 mg L<ce:sup loc=\"post\">-1</ce:sup>) for 35 days. Nutrient removal was maintained or enhanced, whereas chemical oxygen demand removal collapsed at 10 mg L<ce:sup loc=\"post\">-1</ce:sup>. Sludge properties changed non-monotonically without systematic differences from the control. CBZ removal was dose-dependent and shifted from adsorption-dominated on Day 1 to a greater contribution of biodegradation by Day 35, together with a decrease in the protein fraction and the protein-to-polysaccharide ratio of extracellular polymeric substances. Fifteen transformation products were identified, formed through epoxidation, hydroxylation, oxidation, ring opening, and rearrangement; their predicted toxicity was endpoint-dependent, with acridine- and acridone-type products more toxic than CBZ, indicating risk redistribution rather than detoxification. CBZ exposure enriched the filamentous cyanobacterium <ce:italic>Microcoleus</ce:italic> and the heterotrophic genera <ce:italic>Sphingomonas, Thauera</ce:italic>, and <ce:italic>Aquimonas</ce:italic>, and reshaped genes involved in nitrogen metabolism, the tricarboxylic acid cycle, and energy conversion; antibiotic resistance genes, mobile genetic elements, and virulence factor genes also shifted in composition, without consistent dose-dependent enrichment. Overall, CBZ removal involved a concentration-dependent trade-off between transformation and carbon removal; transformation did not necessarily reduce toxicity. These findings emphasize the need to couple treatment performance with transformation-product risk when applying MBGS to pharmaceutical-contaminated wastewater.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"17 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2026-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Water ResearchPub Date : 2026-10-30DOI: 10.1016/j.watres.2026.127240
Tianlie Luo, Yubo Di, Ping Zhang, Xiaojun Chen, Yingying Li, Wenyan Zhao, Dil Khurram, Ruth Antwi-Baah, Guo Liu
{"title":"Molecular Fingerprints of Natural Organic Matter Dictate Eco-Corona Assembly and Stability of Black Phosphorus Nanosheets in Aquatic Environments","authors":"Tianlie Luo, Yubo Di, Ping Zhang, Xiaojun Chen, Yingying Li, Wenyan Zhao, Dil Khurram, Ruth Antwi-Baah, Guo Liu","doi":"10.1016/j.watres.2026.127240","DOIUrl":"https://doi.org/10.1016/j.watres.2026.127240","url":null,"abstract":"Black phosphorus nanosheets (BPNS) show promising results in various environmental applications, yet their fate after release into natural waters is poorly investigated. A critical knowledge gap remains in how the molecular heterogeneity of natural organic matter (NOM) from different sources influences eco-corona formation on BPNS and subsequent colloidal behavior. We systematically investigate this linkage using adsorption kinetics, FT-ICR MS-based molecular fingerprinting, and DFT-assisted charge density difference analysis across five NOM samples (a fulvic acid standard and four environmental isolates). Eco-corona formation on BPNS followed pseudo-second-order kinetics (<ce:italic>R</ce:italic><ce:sup loc=\"post\">2</ce:sup> = 0.998), with protein-like components enhancing initial uptake rates, while lignin-like compounds (56∼67% of assigned formulas) determined the ultimate adsorption capacity. Moreover, FT-ICR MS revealed an increased relative abundance of signals above <ce:italic>m</ce:italic>/<ce:italic>z</ce:italic> 700 in the washed corona extracts compared with the initial NOM samples. In contrast, the relative proportions of carbohydrate-like and lipid-like formulas generally decreased, indicating selective molecular fractionation during eco-corona formation. DFT calculations identified methoxy (-OCH<ce:inf loc=\"post\">3</ce:inf>, -1.359 eV) groups in lignin and carboxyl (-COOH, -1.462 eV) groups in tannin as favorable interaction sites within the examined molecular models, with flat-lying configurations and interfacial charge redistribution visualized by charge density difference (CDD) analysis. Notably, NOM treatments influenced BPNS aggregation and sedimentation behavior, as evidenced by differences in apparent hydrodynamic diameter growth, <ce:italic>C</ce:italic>/<ce:italic>C</ce:italic><ce:inf loc=\"post\">0</ce:inf> ratios, and Zeta potentials over 48 h, suggesting that NOM composition plays an important role in regulating BPNS colloidal stability. These findings establish mechanistic insights linking NOM source composition to adsorption behavior and BPNS stability, highlighting potential implications for the transport and ecological risks of two-dimensional nanomaterials in natural aquatic systems.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"64 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Nitrogen availability modulates soil microbial carbon fixation in wetland through community and metabolic remodelling","authors":"Shouyang Luo, Yanyu Song, Yiting Zhao, Hongli Zhang, Jiusheng Ren, Jitao Zhang, Changchun Song","doi":"10.1016/j.watres.2026.127239","DOIUrl":"https://doi.org/10.1016/j.watres.2026.127239","url":null,"abstract":"Excess agricultural nitrogen (N) from farm drainage and runoff causes wetland water N pollution and destabilizes soil carbon (C) sinks, however, how this N enrichment regulates wetland soil microbial autotrophic C fixation remains unclear. Here, we combined field experiments, <ce:sup loc=\"post\">13</ce:sup>CO<ce:inf loc=\"post\">2</ce:inf> continuous pulse labeling, DNA-stable isotope probing and metagenomics to investigate the dose-dependent effects of N input on soil microbial community assembly, co-occurrence networks, C-fixation pathways, and soil physicochemical properties in Songnen Plain saline-alkali wetlands of China. The results indicate that N input exerts a threshold regulation on microbial C fixation, with distinct depth-dependent responses. Intermediate N input (N2, 10 g N m<ce:sup loc=\"post\">-2</ce:sup> yr<ce:sup loc=\"post\">-1</ce:sup>) alleviates soil microbial N limitation, elevates RubisCO and hydrolase activities, optimizes soil C-N-phosphorus stoichiometry, and promotes the accumulation of mineral-associated organic C. Such intermediate N input remodels microbial community structure, increases microbial diversity and network stability, and enriches key C-fixing taxa including Cyanobacteriota and Alphaproteobacteria, thereby upregulating six core autotrophic C-fixation pathways. In contrast, excessive N (N4, 24 g N m<ce:sup loc=\"post\">-2</ce:sup> yr<ce:sup loc=\"post\">-1</ce:sup>) input induces soil acidification and nutrient imbalance, disrupts microbial network stability, declines functional C-fixing microbiota and suppresses C-fixation gene expression, ultimately reducing soil CO<ce:inf loc=\"post\">2</ce:inf> assimilation and organic C accumulation. Structural equation modelling and random forest analyses further reveal soil microbial biomass N and RubisCO activity are the primary drivers of microbial C fixation, mediated by soil microbial C metabolic pathways and community diversity. This work reveals mechanisms of wetland soil C fixation under agricultural N pollution and informs wetland nutrient management and C-sink conservation.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"18 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Dual Drivers of Groundwater Ammonium Enrichment in Marine Organic-Rich Riparian Zones: Exogenous Nitrate Reduction and Geological Organic Nitrogen Mineralization","authors":"Linna Jia, Jia Xin, Wenlin Ren, Xuewei Li, Shuo Gong, Yiwei Song, Xu Zhang, Jiafeng Yao, Dianjin Xia, Qianyi Zhou","doi":"10.1016/j.watres.2026.127251","DOIUrl":"https://doi.org/10.1016/j.watres.2026.127251","url":null,"abstract":"Marine organic-rich riparian zones are nitrogen cycling hotspots at the land–sea interface; however, the mechanisms driving groundwater ammonium (NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup>-N) enrichment remain elusive. Through an integration of sediment-groundwater chemistry, isotopic tracing, and molecular tools, this study elucidated the spatiotemporal evolution of multi-pathway nitrogen transformations in the Dagu River riparian zone, China. Results indicate that groundwater NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup>-N enrichment is co-driven by exogenous nitrate (NO<ce:inf loc=\"post\">3</ce:inf>⁻-N) reduction and geological organic nitrogen mineralization. Within the NO<ce:inf loc=\"post\">3</ce:inf>⁻-N reduction processes, dissimilatory nitrate reduction to ammonium (DNRA) predominates (84.86% contribution), with potential rates reaching 35 times the sum of denitrification and anaerobic ammonium oxidation (anammox). Seasonally, the dominant NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup>-N production pathway shifts from DNRA in the dry season (78.35%) to mineralization in the wet season (73.01%). Annual estimate of potential nitrogen transformations reveals a pronounced production–consumption asymmetry, where dual production pathways far exceed constrained consumption processes (nitrification, immobilization, and anammox), resulting in a net NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup>-N production potential of 46.22 μmol N kg<ce:sup loc=\"post\">−1</ce:sup> h<ce:sup loc=\"post\">−1</ce:sup>. Spatiotemporally, the activation of the geogenic nitrogen pool during the wet season promoted enhanced metabolic potential in bottom-layer, indicating that deep sedimentary horizons actively participate in nitrogen turnover rather than remaining biogeochemically inert.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"23 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Water ResearchPub Date : 2026-10-28DOI: 10.1016/j.watres.2026.127231
Steven J. Chow, Eva-Maria Braxmaier, Frédéric Haffter, Peter Gläser, Björn Meermann, Juliane Hollender, Christa S. McArdell
{"title":"Uncovering PFAS Emissions in Wastewater Treatment Plants Through Comprehensive Assessment of Targets, Precursors, and Unexplained Organofluorine","authors":"Steven J. Chow, Eva-Maria Braxmaier, Frédéric Haffter, Peter Gläser, Björn Meermann, Juliane Hollender, Christa S. McArdell","doi":"10.1016/j.watres.2026.127231","DOIUrl":"https://doi.org/10.1016/j.watres.2026.127231","url":null,"abstract":"A national sampling campaign across 21 Swiss wastewater treatment plants (WWTPs) assessed the occurrence and fate of per- and polyfluoroalkyl substances (PFASs). A tiered analytical framework combined 66 ultrashort-chain and conventional target analytes, the total oxidizable precursor (TOP) assay, extractable organic fluorine (EOF) analysis, and high-resolution mass spectrometry screening of 6:2 fluorotelomer precursors. Besides trifluoroacetic acid (TFA), zwitterionic 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB; median influent 74.9 ng/L, sludge 47.8 ng/g) dominated PFAS profiles, indicating widespread upstream use. WWTPs receiving high industrial fractions had elevated TFA (up to 1,260 µg/L) and inorganic BF<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">-</ce:sup>. Co-occurrence of bistriflimide (bisFMeSI) and elevated inorganic PF<ce:inf loc=\"post\">6</ce:inf><ce:sup loc=\"post\">-</ce:sup> suggested battery-related inputs at some sites. Conventional biological treatment yielded negligible target removal, whereas addition of powdered activated carbon advanced treatment removed > 50% of 6:2 FTAB and PFOS from WWTP influent to effluent. Effluent concentrations exceeded EU surface water quality standards 2.5- to 330-fold. Median effluent mass loads were ≤ 4.4 µg/day/person for most conventional PFASs. Historical sludge trends (2011-2024) indicate an order-of-magnitude decline in PFOS but increased abundances of fluorotelomer compounds. The TOP assay revealed large untargeted precursor fractions (median 56% influent; 91% sludge) with prominent 6:2 fluorotelomer signatures, partially explained by suspect screening detections of aqueous film-forming foam components (6:2 FTNO, 6:2 FTAA, 6:2 FTSA-HOPrS, and 6:2 FtTAoS). EOF revealed extensive organofluorine mass gaps; targets and oxidizable precursors accounted for < 27% of median EOF in influent and sludge. These findings highlight the need to expand the scope of WWTP monitoring to capture uncharacterized PFAS burdens and manage emerging upstream sources.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"1 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149291074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Water ResearchPub Date : 2026-10-24DOI: 10.1016/j.watres.2026.127211
Peng Qi, Xiaomin Chen, Lan Tang, Haoting Quan, Yongsen Shi, Yanyan Jia, Tianwei Hao, Xingquan Xu, Jiajun Liao, Congrong Ye, Hui Lu
{"title":"Granule size-associated differentiation in photogranular sludge systems: Linking granular properties, microbial ecology, and system function","authors":"Peng Qi, Xiaomin Chen, Lan Tang, Haoting Quan, Yongsen Shi, Yanyan Jia, Tianwei Hao, Xingquan Xu, Jiajun Liao, Congrong Ye, Hui Lu","doi":"10.1016/j.watres.2026.127211","DOIUrl":"https://doi.org/10.1016/j.watres.2026.127211","url":null,"abstract":"Photogranular sludge (PG) systems offer a promising route toward energy-efficient wastewater treatment and resource recovery, yet how granule size is associated with functional differentiation remains poorly understood. Here, mature PGs were separated into three size fractions (<0.5 mm, 0.5–1 mm, and 1–1.5 mm) to characterize size-associated differences in granular properties, microbial ecological organization, and system function. Larger granule-size fractions were characterized by greater physical compaction, with lower pore volume, porosity, and permeability, together with higher surface hydrophobicity and mechanical rigidity. Paradoxically, despite the development of a denser and less permeable structure, larger granules exhibited more integrated microbial networks, stronger phototrophic-heterotrophic associations, and a greater importance of stochastic processes in community assembly. Variation partitioning analysis showed that granule-associated properties jointly accounted for 59.0% of microbial community variation, quantitatively linking granular properties with ecological organization. These ecological shifts coincided with elevated metabolic potential, reflected by higher abundances of key functional genes (<ce:italic>narG, nirS</ce:italic>, and <ce:italic>ppk1</ce:italic>) and enzyme activities. Consequently, the 1–1.5 mm fraction exhibited the highest specific pollutant removal rates, with DOC, TN, and PO<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">3-</ce:sup>-P removal rates increasing by 20.3%, 49.2%, and 32.4%, respectively, compared with the <0.5 mm fraction. Resource recovery also showed pronounced size dependence: small granules maximized alginate-like exopolysaccharide production, medium granules yielded hydrogels with a more compact macroscopic appearance, whereas large granules accumulated the most lipids (39.0% higher than the smallest fraction) and exhibited enhanced lipid biosynthesis potential. Overall, this study establishes a size-associated property-ecology-function framework for PG systems and suggests that managing granule-size distributions may provide a potential operational strategy for simultaneously optimizing wastewater treatment and resource recovery.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"255 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2026-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149290938","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Water ResearchPub Date : 2026-10-24DOI: 10.1016/j.watres.2026.127207
Bing Wen, Shang Gao, Yuanzheng Zhang, Mingyue Gu, Jinzhong Wan, Xiaodong Zhang, Jianbo Huang, Tao Long
{"title":"The Reductive Shield: Elucidating ammonium persistence in industrially contaminated aquifers via isotopic fingerprinting and quantitative redox modeling","authors":"Bing Wen, Shang Gao, Yuanzheng Zhang, Mingyue Gu, Jinzhong Wan, Xiaodong Zhang, Jianbo Huang, Tao Long","doi":"10.1016/j.watres.2026.127207","DOIUrl":"https://doi.org/10.1016/j.watres.2026.127207","url":null,"abstract":"High-concentration ammonium (NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup>) pollution in groundwater associated with industrial agglomerations has become a global environmental challenge due to its complex origins, remediation resistance, and potential ecological health risks. However, the biogeochemical drivers governing its persistence in aquifers remain poorly understood. This study investigates the biogeochemical mechanisms of industrial NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup> pollution in a river terrace aquifer by analyzing 47 groundwater samples from a representative industrial park in Eastern China. By integrating multi-isotope fingerprinting including δ<ce:sup loc=\"post\">15</ce:sup>N-NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup>, δ<ce:sup loc=\"post\">13</ce:sup>C-DOC, δ<ce:sup loc=\"post\">13</ce:sup>C-DIC, δ<ce:sup loc=\"post\">15</ce:sup>N-NO<ce:inf loc=\"post\">3</ce:inf><ce:sup loc=\"post\">-</ce:sup>, and δ<ce:sup loc=\"post\">18</ce:sup>O-NO<ce:inf loc=\"post\">3</ce:inf><ce:sup loc=\"post\">-</ce:sup> with quantitative redox modeling of Total Reductive Capacity and Terminal Electron-Accepting Processes, the primary drivers of NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup> accumulation are identified. Results indicate that the groundwater NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup> accumulation is associated with in-situ mineralization of industrial-derived organic nitrogen (estimated source δ<ce:sup loc=\"post\">15</ce:sup>N ≈ -26.99‰), under a Reductive Shield state characterized by enhanced reductive buffering capacity, Fe-Mn-associated redox buffering, and suppressed ammonium oxidation. While denitrification represents the dominant modeled electron-accepting pathway, Fe-Mn-associated redox processes provide an additional mineral-associated buffering component within the contaminated zones. Together, these processes contribute to limiting ammonium oxidation. Consequently, a masking effect occurs where declining organic carbon levels may coexist with persistent reductive buffering and therefore do not necessarily indicate complete site remediation, thus hiding the persistent NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup> accumulation. Our findings suggest that for high-TRC aquifers, conventional treatment technology such as In-Situ Chemical Oxidation (ISCO) may be constrained by high oxidant demand. Instead, nature-based solutions such as constructed wetlands that provide sustainable aeration and promote NH<ce:inf loc=\"post\">4</ce:inf><ce:sup loc=\"post\">+</ce:sup> oxidation before discharge could be a more effective strategy.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"14 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2026-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149290939","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}