Hidden Role of Organic Matter in the Immobilization and Transformation of Iodine on Fe-OM Associations.

The biogeochemical processes of iodine are typically coupled with organic matter (OM) and the dynamic transformation of iron (Fe) minerals in aquifer systems, which are further regulated by the association of OM with Fe minerals. However, the roles of OM in the mobility of iodine on Fe-OM associations remain poorly understood. Based on batch adsorption experiments and subsequent solid-phase characterization, we delved into the immobilization and transformation of iodate and iodide on Fe-OM associations with different C/Fe ratios under anaerobic conditions. The results indicated that the Fe-OM associations with a higher C/Fe ratio (=1) exhibited greater capacity for immobilizing iodine (∼60-80% for iodate), which was attributed to the higher affinity of iodine to OM and the significantly decreased extent of Fe(II)-catalyzed transformation caused by associated OM. The organic compounds abundant in oxygen with high unsaturation were more preferentially associated with ferrihydrite than those with poor oxygen and low unsaturation; thus, the associated OM was capable of binding with 28.1-45.4% of reactive iodine. At comparable C/Fe ratios, the mobilization of iodine and aromatic organic compounds was more susceptible in the adsorption complexes compared to the coprecipitates. These new findings contribute to a deeper understanding of iodine cycling that is controlled by Fe-OM associations in anaerobic environments.

Geogenic Phosphorus Enrichment in Groundwater due to Anaerobic Methane Oxidation-Coupled Fe(III) Oxide Reduction.

Accumulation of geogenic phosphorus (P) in groundwater is an emerging environmental concern, which is closely linked to coupled processes involving FeOOH and organic matter under methanogenic conditions. However, it remains unclear how P enrichment is associated with methane cycling, particularly the anaerobic methane oxidation (AMO). This study conducted a comprehensive investigation of carbon isotopes in dissolved inorganic carbon (DIC), CO2, and CH4, alongside Fe isotopes, microbial communities, and functions in quaternary aquifers of the central Yangtze River plain. The study found that P concentrations tended to increase with Fe(II) concentrations, δ56Fe, and δ13C-DIC, suggesting P accumulation due to the reductive dissolution of FeOOH under methanogenic conditions. The positive correlations of pmoA gene abundance versus δ13C-CH4 and Fe concentrations versus δ13C-CH4, and the prevalent presence of Candidatus_Methanoperedens, jointly demonstrated the potential significance of Fe(III)-mediated AMO process (Fe-AMO) alongside traditional methanogenesis. The increase of P concentration with δ13C-CH4 value, pmoA gene abundance, and Fe concentration suggested that the Fe-AMO process facilitated P enrichment in groundwater. Redundancy analysis confirmed this assertion, identifying P concentration as the primary determinant and the cooperative influence of Fe-AMO microorganisms such as Candidatus_Methanoperedens and Geobacter on P enrichment. Our work provided new insights into P dynamics in subsurface environments.

Enrichment of Geogenic Organoiodine Compounds in Alluvial-Lacustrine Aquifers: Molecular Constraints by Organic Matter.

Organoiodine compounds (OICs) are the dominant iodine species in groundwater systems. However, molecular mechanisms underlying the geochemical formation of geogenic OICs-contaminated groundwater remain unclear. Based upon multitarget field monitoring in combination with ultrahigh-resolution molecular characterization of organic components for alluvial-lacustrine aquifers, we identified a total of 939 OICs in groundwater under reducing and circumneutral pH conditions. In comparison to those in water-soluble organic matter (WSOM) in sediments, the OICs in dissolved organic matter (DOM) in groundwater typically contain fewer polycyclic aromatics and polyphenol compounds but more highly unsaturated compounds. Consequently, there were two major sources of geogenic OICs in groundwater: the migration of the OICs from aquifer sediments and abiotic reduction of iodate coupled with DOM iodination under reducing conditions. DOM iodination occurs primarily through the incorporation of reactive iodine that is generated by iodate reduction into highly unsaturated compounds, preferably containing hydrophilic functional groups as binding sites. It leads to elevation of the concentration of the OICs up to 183 µg/L in groundwater. This research provides new insights into the constraints of DOM molecular composition on the mobilization and enrichment of OICs in alluvial-lacustrine aquifers and thus improves our understanding of the genesis of geogenic iodine-contaminated groundwater systems.

Determination of high-risk factors and related spatially influencing variables of heavy metals in groundwater.

Identifying high-risk factors (heavy metals (HMs) and pollution sources) by coupling receptor models and health risk assessment model (HRA) is a novel approach within the field of risk assessment. However, this coupled model ignores the contribution of spatial differentiation to high-risk factors, resulting in the assessment being subjective. Taking Dongting Plain (DTP) as an example, a coupling framework by jointly using the positive matrix factorization model (PMF), HRA, Monte Carlo simulation, and geo-detector was developed, aiming to identify high-risk factors in groundwater, and further explore key environmental variables influencing the spatial heterogeneity of high-risk factors. The results showed that at least 82.86 % of non-carcinogenic risks and 97.41 % of carcinogenic risks were unacceptable for people of all ages, especially infants and children. According to the relationships among HMs, pollution sources, and health risks, As and natural sources were defined as high-risk HMs and sources, respectively. The interactions among Holocene thickness, oxidation-reduction potential, and dissolved organic carbon emerged as the primary drivers of spatial variability in high-risk factors, with their combined explanatory power reaching up to 74%. This proposed framework provides a scientific reference for future studies and a practical reference for environmental authorities in developing effective pollution management measures.

Coupled Processes Involving Organic Matter and Fe Oxyhydroxides Control Geogenic Phosphorus Enrichment in Groundwater Systems: New Evidence from FT-ICR-MS and XANES.

The enrichment of geogenic phosphorus (P) in groundwater systems threatens environmental and public health worldwide. Two significant factors affecting geogenic P enrichment include organic matter (OM) and Fe (oxyhydr)oxide (FeOOH). However, due to variable reactivities of OM and FeOOH, variable strategies of their coupled influence controlling P enrichment in groundwater systems remain elusive. This research reveals that when the depositional environment is enriched in more labile aliphatic OM, its fermentation is coupled with the reductive dissolution of both amorphous and crystalline FeOOHs. When the depositional environment is enriched in more recalcitrant aromatic OM, it largely relies on crystalline FeOOH acting concurrently as electron acceptors while serving as "conduits" to help itself stimulate degradation and methanogenesis. The main source of geogenic P enriched by these two different coupled processes is different: the former is P-containing OM, which mainly contained unsaturated aliphatic compounds and highly unsaturated-low O compounds, and the latter is P associated with crystalline FeOOH. In addition, geological setting affects the deposition rate of sediments, which can alter OM degradation/preservation, and subsequently affects geochemical conditions of geogenic P occurrence. These findings provide new evidence and perspectives for understanding the hydro(bio)geochemical processes controlling geogenic P enrichment in alluvial-lacustrine aquifer systems.

Paleo-Geomorphology Determines Spatial Variability of Geogenic Ammonium Concentration in Quaternary Aquifers.

Naturally occurring (i.e., geogenic) ammonium in groundwater has been widely detected globally, but the major controls on its regional distribution have been poorly characterized. Here, we identified the dominant role of paleo-geomorphology driven by paleo-climate in controlling the spatial variability of geogenic ammonium in groundwater using random forest algorithm and revealed the underlying mechanisms based on borehole sediment analysis of data obtained from the Dongting Lake Plain of the central Yangtze River basins in China. In the paleo-channel (PC) area, the aquifer depth-matched sediments were deposited during the last deglaciation when warm climate resulted in rapid filling into incised valleys, and terrestrial organic matter (OM) mainly as lignin experienced less degradation prior to sedimentation and had lower humification, higher N abundance, and nominal oxidation state of carbon (NOSC). In the paleo-interfluve (PI) area, the depth-matched sediments were deposited during the last glaciation, followed by intensive erosion in the surface during the last glacial maximum, and terrestrial OM mainly as lignin had been partly degraded into aliphatics prior to sedimentation and had higher humification, lower N abundance, and NOSC. As a result, under the present anaerobic conditions, less-humic and N-rich OM with more oxidized C tends to be more intensively mineralized into ammonium in the PC area than those in the PI area. These findings highlight the importance of paleo-geomorphology with paleo-climate in controlling the enrichment of geogenic ammonium in groundwater, which has a universal significance for understanding the genesis and distribution of high N loads in the aquatic environment worldwide.

Groundwater Quality and Health: Making the Invisible Visible.

Linking groundwater quality to health will make the invisible groundwater visible, but there are knowledge gaps to understand the linkage which requires cross-disciplinary convergent research. The substances in groundwater that are critical to health can be classified into five types according to the sources and characteristics: geogenic substances, biogenic elements, anthropogenic contaminants, emerging contaminants, and pathogens. The most intriguing questions are related to quantitative assessment of human health and ecological risks of exposure to the critical substances via natural or induced artificial groundwater discharge: What is the list of critical substances released from discharging groundwater, and what are the pathways of the receptors' exposure to the critical substances? How to quantify the flux of critical substances during groundwater discharge? What procedures can we follow to assess human health and ecological risks of groundwater discharge? Answering these questions is fundamental for humans to deal with the challenges of water security and health risks related to groundwater quality. This perspective provides recent progresses, knowledge gaps, and future trends in understanding the linkage between groundwater quality and health.

Novel Insights into Dissolved Organic Matter Processing Pathways in a Coastal Confined Aquifer System with the Highest Known Concentration of Geogenic Ammonium.

High levels of geogenic ammonium in groundwater is a highly neglected nitrogen pool in coastal aquatic systems. Although organic matter (OM) mineralization is known to significantly influence geogenic ammonium enrichment, the detailed mechanism underlying ammonium enrichment based on dissolved organic matter (DOM) characterization in coastal aquifer systems remains unclear. In this study, we characterized the optical and molecular signatures of DOM coupled with hydrogeochemistry and multiple isotopes (H/O/C/N) to elucidate in detail the mechanisms underlying the anomalously high ammonium in the coastal confined aquifer system of the Pearl River Delta, which exhibits the highest reported geogenic ammonium concentration in groundwater on the Earth. We identified three DOM fluorescent components, a marine humic-like component (C1) and two other humic-like components (C2 and C3). The autochthonous OM was first processed to the C1 component, which was further transformed to C2 and C3 components. In terms of molecular classes, the processing pathway from bacterial- or algal-derived OM to aliphatic compounds and highly unsaturated-low O compounds was identified, and highly unsaturated-low O compounds were accumulated as the main products. Compounds containing two or three N atoms were processed, and compounds with one N atom gradually accumulated, which was further degraded into CHO compounds. The ammonium (up to 179 mg/L as N) was gradually enriched due to the decomposition of CHO+3N to CHO+2N, CHO+1N, and CHO compounds. Owing to the longer residence time and less frequent fresh water flushing, the produced ammonium was retained in the aquifer as a "long-term result". The contrasting DOM characteristics, together with the differing depositional and hydrogeological conditions, give rise to the higher levels of geogenic ammonium in coastal confined aquifer systems compared with inland alluvial-lacustrine confined aquifer systems. To our knowledge, this is the first study to characterize DOM and its relationship with geogenic ammonium in coastal aquifer systems.

Dissolved organic matter characterization in high and low ammonium groundwater of Dongting Plain, central China.

High levels of ammonium in groundwater is a potential threat to drinking water security and ecological status. The role of dissolved organic matter (DOM) in mobilization of natural ammonium in groundwater is crucial but the intrinsic link between them has still been poorly understood. This study used high-pressure size exclusion chromatography (HPSEC) and fluorescence excitataion-emission-matrix spectra (EEMs) with parallel factor analysis (PARAFAC) to elucidate the influence of DOM characteristics in groundwater systems having contrastive ammonium levels in Dongting Plain, central Yangtze River. The results indicate that NH4+-N concentration in groundwater of western plain (0-16.75 mg/L) are much higher compared with southern plain (0-1.5 mg/L). The groundwater in western plain is in a more reductive environment and characterized by larger molecular weight (MW) of DOM and lower polydispersity (ρ), whereas DOM with relatively small molecular weight and high polydispersity is detected in the south with a more oxidative condition. The groundwater in western plain is characterized by lower fluorescence index (f450/500) and biological index (BIX), and dominated by the high molecular weight terrestrial humic-like component and larger amounts of microbial humic-like components. Protein-like is the main component in groundwater of southern plain with higher f450/500 and BIX. The ammonium concentration in groundwater correlates well with molecular weight and increases significantly with the content of high molecular weight terrestrial humic-like component, indicating that mobilization of ammonium is more closely associated with the terrestrial organic matter of high molecular weight. This study further enriches the theory on mobilization of ammonium in Quaternary alluvial-lacustrine aquifer systems and provides theoretical basis for the local water supply security.

Distribution, origin and speciation of soil selenium in the black soil region of Northeast China.

Selenium (Se) is an essential trace element within human beings that hold with crucial biological functions. Investigating the complex origin of soil Se is of great importance to scientifically approach the land use of Se-rich land use, and the respective promotion of regional economic development. In this study, 160 soil samples from 10 profiles in farmland and woodland were collected in Hailun city, which is a typical black soil region in Northeast China, in order to characterize the distribution and speciation of Se in the black soil, and to identify the origin of soil Se. The total selenium content in the soil ranges from 0.045 to 0.444 µg g-1, with an average selenium content in black soil (0.318 µg g-1) of three times greater than that found in the yellow-brown soil (0.114 µg g-1). The land-use type has a significant influence on the distribution of selenium in the black soil. Moreover, Se and heavy metals have a significant (positive or negative) correlation, in which TOC plays an important role. The black soil presents a consistent REE distribution pattern with underlying yellow-brown soil indicating black soil originates from yellow-brown soil. REE geostatistical analysis suggests that the soil Se partly originates from shale weathering and enriches in black soil. Moreover, elemental geochemical analysis and XRD results show that the paleoclimate change from humid and warm to dry and cold is favorable for organic matter accumulation, resulting in less leaching and enhanced adsorption of selenium into the black soil.

Contribution of groundwater discharge and associated contaminants input to Dongting Lake, Central China, using multiple tracers (222Rn, 18O, Cl-).

Lacustrine groundwater discharge (LGD) can play an important role in water and contaminant mass balance of lakes. Dongting Lake is the second largest fresh lake in China which is connected to Yangtze River and has quite prominent ecological status and function within Yangtze River basin. However, the effect of groundwater discharge on the balance of water and contaminant in Dongting Lake has long been overlooked. This study estimated the groundwater discharge and associated contaminants input into Dongting Lake during the dry season using multiple tracers (222Rn, 18O, Cl-). After sensitivity analysis of different models, it is found that the result of 222Rn mass balance model is the most reliable. Based on the 222Rn mass balance model, the groundwater discharge rate is estimated to be 73.94 mm/d and the contribution of LGD to water balance is 10.94%. As the main nutrient components, NH3-N, P and Si from groundwater input account for 23.65%, 5.12% and 30.15%  % of the total input, respectively. As the main heavy metal components, Fe, Mn and As from groundwater input all account for more than 50% of the total input. Although the LGD rate is relatively small, the contaminant input from LGD is significant enough, which may be a potential threat to the ecological stability of Dongting Lake. In this study, the mass balance models of multiple tracers were integrated to understand the role of groundwater in maintaining the water balance and pollution status of Dongting Lake, which has certain reference significance for the LGD study in plain lakes or reservoirs with complex water systems in humid regions.

Enrichment of Geogenic Ammonium in Quaternary Alluvial-Lacustrine Aquifer Systems: Evidence from Carbon Isotopes and DOM Characteristics.

Geogenic ammonium in groundwater owing to mineralization of natural organic matter (NOM) has been reported in different geologic settings, but detailed mechanisms responsible for high ammonium concentration levels are poorly understood. To this end, we chose Quaternary high ammonium aquifer systems in central Yangtze River basins and used carbon isotopes in both dissolved organic carbon and inorganic carbon together with characterization of dissolved organic matter (DOM) and groundwater chemistry to reveal mechanisms related to the genesis of ammonium. The results indicate that high levels of geogenic ammonium (up to 33.50 mg/L as N) occur due to long-term water-rock interactions in a relatively sluggish hydrogeological environment with abundant organic matter that is rich in both C and N. The stable carbon isotope data suggest that ammonium in the groundwater is released from intensive degradation of organic matter with higher contents of ammonium associated with methanogenesis. The optical signatures of DOM indicate ammonium in the groundwater is mostly associated with terrestrial humic-like components rather than protein-like components. Molecular characterization of DOM by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) shows that, compared to low ammonium groundwater, high ammonium groundwater has larger mass weights, greater abundance of CHO+N compounds, higher percentages of lignin- and condensed-hydrocarbon-like components, lower H/C ratios, higher nominal oxidation state of carbon (NOSC) values and more double bonds, rings, and aromatic structures. Strong degradation of NOM and preferential utilization of energetically more favorable, terrestrial humic-like components (lignin-like as the main class) with high NOSC values facilitates the formation of high ammonium groundwater. To the best of our knowledge, this is the first effort to use carbon isotopes and DOM characteristics to identify enrichment mechanisms for geogenic ammonium in alluvial-lacustrine aquifer systems.

Iron isotope evidence for arsenic mobilization in shallow multi-level alluvial aquifers of Jianghan Plain, central China.

Intake of groundwater with arsenic (As) concentrations exceeding the World Health Organization standard of 10 µg L-1 adversely impacts over 100 million people worldwide. Geogenic As contaminated groundwater within central Yangtze River Basin has recently been reported, but the variations within different depths of aquifers are not commonly observed and the processes controlling As variations have yet to be resolved. Here we report the significant As variations within two different depths (10 m and 25 m) of shallow multi-level alluvial aquifers at Jianghan Plain, a floodplain in the central Yangtze River Basin, which is also a recently discovered geogenic As affected area with cases of waterborne arsenicosis. The multi-year monitoring of aquifer chemistry results show that the As concentrations increase with the Fe(II) concentrations when As contents are relatively lower (<200 µg L-1) in upper phreatic aquitard (at 10 m depth), while decrease with Fe(II) concentrations when As contents are much greater in lower confined aquifer (at 25 m depth), and the highest is up to 1070 µg L-1. Iron isotope analysis were conducive to characterize Fe cycling in the aquifers and thus illustrate geochemical processes controlling As mobilization of shallow groundwaters. Results showed that groundwater is generally enriched in isotopically light Fe with δ56Fe values between - 1.60‰ and + 0.06‰ (median - 0.55‰). In the upper phreatic aquitard, microbial reductive dissolution of As-associated Fe(III) oxides, hydroxides and oxyhydroxides is the major process controlling As concentrations lower than 200 µg L-1. The reduction process could lead to the increasing As concentrations with the gradually increasing δ56Fe values, and a positive correlation between Fe and Î´56Fe, and between dissolved As and δ56Fe values is observed, respectively. In strongly reducing conditions as the lower confined aquifer, jointly microbial reduction of sulfate promotes the As mobilization through HS- abiotic reduction of Fe(III) minerals, resulting in As concentrations greater than 200 µg L-1. These findings could provide new insights for differentiating the major factors controlling As mobilization at different depths of aquifers, and provide better water managements for similar geogenic As-affected shallow alluvial aquifers.

Occurrence and risk assessment of antibiotics in surface water and groundwater from different depths of aquifers: A case study at Jianghan Plain, central China.

The occurrence of 14 antibiotics (fluoroquinolones, tetracyclines, macrolides and sulfonamides) in groundwater and surface water at Jianghan Plain was investigated during three seasons. The total concentrations of target compounds in the water samples were higher in spring than those in summer and winter. Erythromycin was the predominant antibiotic in surface water samples with an average value of 1.60µg/L, 0.772µg/L and 0.546µg/L respectively in spring, summer and winter. In groundwater samples, fluoroquinolones and tetracyclines accounted for the dominant proportion of total antibiotic residues. The vertical distributions of total antibiotics in groundwater samples from three different depths boreholes (10m, 25m, and 50m) exhibited irregular fluctuations. Consistently decreasing of antibiotic residues with increasing of depth was observed in four (G01, G02, G03 and G05) groundwater sampling sites over three seasons. However, at the sampling sites G07 and G08, the pronounced high concentrations of total antibiotic residues were detected in water samples from 50m deep boreholes instead of those at upper aquifer in winter sampling campaign, with the total concentrations of 0.201µg/L and 0.100µg/L respectively. The environmental risks posed by the 14 antibiotics were assessed by using the methods of risk quotient and mixture risk quotient for algae, daphnids and fish in surface water and groundwater. The results suggested that algae might be the aquatic organism most sensitive to the antibiotics, with the highest risk levels posed by erythromycin in surface water and by ciprofloxacin in groundwater among the 14 antibiotics. In addition, the comparison between detected antibiotics in groundwater samples and the reported effective concentrations of antibiotics on denitrification by denitrifying bacteria, indicating this biogeochemical process driven by microorganisms won't be inhibitory influenced by the antibiotic residues in groundwater.

Source-oriented health risk assessment of groundwater nitrate by using EMMTE coupled with HHRA model.

Conventional concentration-oriented approaches for nitrate risk diagnosis only provide overall risk levels without identifying risk values of individual sources or sources accountable for potential health risks. Therefore, a hybrid model combining the end-member mixing model tool on Excel™ (EMMTE) with human health risk assessment (HHRA) was developed to assess the source-oriented health risks for groundwater nitrate, particularly in the Poyang Lake Plain (PLP) region. The results indicated that the EMMTE and the Bayesian stable isotope mixing model (MixSIAR) exhibited remarkable consistency in source apportionment of groundwater nitrate. The source contribution of groundwater nitrate in PLP was related to land use types, hydrogeological conditions, and soil properties. Notably, manure and sewage sources, contributing up to 53.4 %, represented the largest nitrate pollution sources, with a significant contribution of soil nitrogen and nitrogen fertilizers. The non-carcinogenic risk for four potential sources was below the acceptable threshold of 1. Given the factors including rainfall dilution and economic development, attention should be directed towards mitigating the health risks posed by manure and sewage. This study can verify the efficacy of EMMTE in source apportionment and offer valuable insights for decision-makers to regulate the largest sources of nitrate contamination and enhance groundwater management efficiency.

Characteristics of dissolved organic matter contribute to Geogenic ammonium enrichment in coastal versus alluvial-lacustrine aquifers.

Elevated concentration levels of geogenic ammonium in groundwater arise from the mineralization of nitrogen-containing natural organic matter in various geological settings worldwide, especially in alluvial-lacustrine and coastal environments. However, the difference in enrichment mechanisms of geogenic ammonium between these two types of aquifers remains poorly understood. To address this knowledge gap, we investigated two representative aquifer systems in central Yangtze (Dongting Lake Plain, DTP) and southern China (Pearl River Delta, PRD) with contrasting geogenic ammonium contents. The use of optical and molecular characterization of DOM combined with hydrochemistry and stable carbon isotopes has revealed differences in DOM between the two types of aquifer systems and revealed contrasting controls of DOM on ammonium enrichment. The results indicated higher humification and degradation of DOM in DTP groundwater, characterized by abundant highly unsaturated compounds. The degradation of DOM and nitrogen-containing DOM was dominated by highly unsaturated compounds and CHO+N molecular formulas in highly unsaturated compounds, respectively. In contrast, the DOM in PRD groundwater was more biogenic, less degraded, and contained more aliphatic compounds in addition to highly unsaturated compounds. The degradation of DOM and nitrogen-containing DOM was dominated by aliphatic compounds and polyphenols and CHO+N molecular formulas in highly unsaturated compounds and polyphenols, respectively. As DOM degraded, the ammonium production efficiency of DOM decreased, contributing to lower ammonium concentrations in DTP groundwater. In addition, the CHO+N(SP) molecular formulas were mainly of microbial-derived and gradually accumulated with DOM degradation. In this study, we conducted the first comprehensive investigation into the patterns of groundwater ammonium enrichment based on DOM differences in various geological settings.

Identification of methane cycling pathways in Quaternary alluvial-lacustrine aquifers using multiple isotope and microbial indicators.

Groundwater rich in dissolved methane is often overlooked in the global or regional carbon cycle. Considering the knowledge gap in understanding the biogeochemical behavior of methane in shallow aquifers, particularly those in humid alluvial-lacustrine plains with high organic carbon content, we investigated methane sources and cycling pathways in groundwater systems at the central Yangtze River basins. Composition of multiple stable isotopes (2H/18O in water, 13C in dissolved inorganic carbon, 13C/2H in methane, and 13C in carbon dioxide) was combined with the characteristics of microbes and dissolved organic matter (DOM) in the study. The results revealed significant concentrations of biogenic methane reaching up to 13.05 mg/L in anaerobic groundwater environments with abundant organic matter. Different pathways for methane cycling (methanogenic CO2-reduction and acetate-fermentation, and methane oxidation) were identified. CO2-reduction dominated acetate-fermentation in the two methanogenic pathways primarily associated with humic DOM, while methane oxidation was more closely associated with microbially derived DOM. The abundance of obligate CO2-reduction microorganisms (Methanobacterium and Methanoregula) was higher in samples with substantial CO2-reduction, as indicated by isotopic composition. The obligate acetate-fermentation microorganism (Methanosaeta) was more abundant in samples exhibiting evident acetate-fermentation. Additionally, a high abundance of Candidatus Methanoperedens was identified in samples with apparent methane oxidation. Comparing our findings with those in other areas, we found that various factors, such as groundwater temperature, DOM abundance and types, and hydrogeological conditions, may lead to differences in groundwater methane cycling. This study offered a new perspective and understanding of methane cycling in worldwide shallow alluvial-lacustrine aquifer systems without geothermal disturbance.

Deciphering the spatial heterogeneity of groundwater arsenic in Quaternary aquifers of the Central Yangtze River Basin.

Significant spatial variability of groundwater arsenic (As) concentrations in South/Southeast Asia is closely associated with sedimentogenesis and biogeochemical cycling processes. However, the role of fine-scale differences in biogeochemical processes under similar sedimentological environments in controlling the spatial heterogeneity of groundwater As concentrations is poorly understood. Within the central Yangtze Basin, dissolved organic matter (DOM) and microbial functional communities in the groundwater and solid-phase As-Fe speciation in Jianghan Plain (JHP) and Jiangbei Plain (JBP) were compared to reveal mechanisms related to the spatial heterogeneity of groundwater As concentration. The optical signatures of DOM showed that low molecular terrestrial fulvic-like with highly humified was predominant in the groundwater of JHP, while terrestrial humic-like and microbial humic-like with high molecular weight were predominant in the groundwater of JBP. The inorganic carbon isotope, microbial functional communities, and solid-phase As-Fe speciation suggest that the primary process controlling As accumulation in JHP groundwater system is the degradation of highly humified OM by methanogens, which drive the reductive dissolution of amorphous iron oxides. While in JBP groundwater systems, anaerobic methane-oxidizing microorganisms (AOM) coupled with fermentative bacteria, iron reduction bacteria (IRB), and sulfate reduction bacteria (SRB) utilize low molecular weight DOM degradation to drive biotic/abiotic reduction of Fe oxides, further facilitating the formation of carbonate associated Fe and crystalline Fe oxides, resulting in As release into groundwater. Different biogeochemical cycling processes determine the evolution of As-enriched aquifer systems, and the coupling of multiple processes involving organic matter transformation­iron cycling­sulfur cycling-methane cycling leads to heterogeneity in the spatial distribution of As concentrations in groundwater. These findings provide new perspectives to decipher the spatial variability of As concentrations in groundwater.

Unravelling the impacts of soluble Mn(III)-NOM on arsenic immobilization by ferrihydrite or goethite under aquifer conditions.

The environmental fate of arsenic (As) relies substantially on its speciation, which occurs frequently coupled to the redox transformation of manganese. While trivalent manganese (Mn(III)), which is known for its high reactivity, is believed to play a role in As mobilization by iron (oxyhydr)oxides in dynamic aquifers, the exact roles and underlying mechanisms are still poorly understood. Using increasingly complex batch experiments that mimick As-affected aquifer conditions in combination with time-resolved characterization, we demonstrate that Mn(III)-NOM complexes play a crucial role in the manganese-mediated immobilization of As(III) by ferrihydrite and goethite. Under anaerobic condition, Mn(III)-fulvic acid (FA) rapidly oxidized 31.8% of aqueous As(III) and bound both As(III) and As(V). Furthermore, Mn(III)-FA exerted significantly different effects on the adsorption of As by ferrihydrite and goethite. Mn(III)-FA increased the adsorption of As by 6-16% due to the higher affinity of oxidation-produced As(V) for ferrihydrite under circumneutral conditions. In contrast, As adsorption by crystalline goethite was eventually inhibited due to the competitive effect of Mn(III)-FA. To summarize, our results reveal that Mn(III)-NOM complexes play dual roles in As retention by iron oxides, depending on the their crystallization. This highlights the importance of Mn(III) for the fate of As particularly in redox fluctuating groundwater environments.

Effects of reservoir construction on optical and molecular characteristics of dissolved organic matter in a typical P-contaminated river.

The source and composition characteristics of dissolved organic matter (DOM) are crucial to identify and evaluate the sources of pollution in the watershed. The construction of reservoirs changes the hydrological condition and pollutant fate of the river. However, the effects of reservoirs' construction on DOM in the watershed and the underlying mechanisms are still unclear. This study aims to examine and compare the characteristics of DOM in reservoirs and streams in the Huangbai River, a typical reservoir-affected and P-contaminated river within the Yangtze River catchment. The results showed that DOM in reservoirs was characterized by more contribution from autochthonous source, under the influence of reservoirs' construction; while, DOM in rivers was mainly originated from terrestrial input. Reservoirs had more lipid-like and protein-like compounds, while rivers contained more oxy-aromatic-like compounds. The percentage of CHOP molecules in reservoirs was significantly higher than that in rivers. The underlying mechanism is that more suitable conditions were created for plankton to grow after constructing reservoirs, which converted inorganic orthophosphate into organic phosphorus, and over time, organic phosphorus was gradually enriched in reservoirs, which exacerbated the risk of eutrophication in the reservoir water body. This study can provide theoretical support for monitoring and evaluation of water quality in reservoir-affected rivers.