Groundwater Dissolved Organic Matter Research Articles

Spectral and Molecular Insights into the Characteristics of Dissolved Organic Matter in Nitrate-Contaminated Groundwater

The characteristics of dissolved organic matter (DOM) serves as indicators of nitrate pollution in groundwater. However, the specific DOM components associated with nitrate in groundwater systems remain unclear. In this study, dual isotopes of nitrate, three-dimensional Excitation emission matrices (EEMs) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was utilized to uncover the sources of nitrate and their associations with DOM characteristics. The predominant nitrate in the targeted aquifer was derived from soil organic nitrogen (mean 46.0%) and manure &sewage (mean 34.3%). The DOM in nitrate-contaminated groundwater (nitrate-nitrogen > 20mg/L) exhibited evident exogenous characteristics, with a bioavailable content 2.58 times greater than that of uncontaminated groundwater. Regarding the molecular characteristics, DOM molecules characterized by CHO + 3N, featuring lower molecular weights and H/C ratios, indicated potential for mineralization, while CHONS formulas indicated the exogenous features, providing the potential for accurate traceability. These findings provide insights at the molecular level into the characterization of DOM in nitrate-contaminated groundwater and offer scientific guidance for decision-making regarding the remediation of groundwater nitrate pollution.

Ammonium enrichment, nitrate attenuation and nitrous oxide production along groundwater flow paths: Carbon isotopic and DOM optical evidence

Dissolved organic matter (DOM) plays a crucial role in the biogeochemical processing of reactive nitrogen in groundwater systems. However, the impacts of DOM on release of geogenic ammonium and transport and transformation of reactive nitrogen including nitrate attenuation under dynamics in groundwater level characteristic for floodplain environments remain unclear. In this study, we have identified the influence of riparian water level fluctuations on changes in the redox conditions, groundwater geochemical composition including the DOM mobilization in the piedmont recharge and the discharge area along groundwater flow paths. We have also evaluated the pivotal roles of DOM degradation in transport and transformation of nitrogen species including geogenic ammonium enrichment, nitrate attenuation, and dissolved nitrous oxide (N2O) production combining the stable carbon isotopic signatures and the optical characteristics of DOM. Along groundwater flow paths, the seasonal amplitudes of surface water levels were higher in the piedmont recharge area than those in the plain discharge area, and four DOM fluorescent components were identified through the parallel factor analysis (PARAFAC), with two terrestrial humic-like components (C1 and C2) in the piedmont recharge area, and two microbial humic-like components (C3 and C4) in the plain transition-discharge area. A positive correlation between stable dissolved inorganic carbon isotopic signatures (δ13C-DIC) and ammonium-nitrogen concentrations indicated that microbial degradation processes of DOM concomitantly promote the release of geogenic ammonium into groundwater. Ammonium enrichment and nitrate attenuation trend in groundwater was noted as one moved from the recharge area to the discharge area. Evidently, a clear correlation emerged where elevated dissolved N2O concentrations were linked to diminished ammonium-nitrogen levels and elevated nitrate-nitrogen levels. Additionally, groundwater exhibited higher dissolved N2O levels in the piedmont recharge area compared to the plain discharge area. These findings revealed that the impacts of groundwater DOM degradation on nitrate attenuation and dissolved N2O production in similar geogenic ammonium-affected Quaternary alluvial aquifers along groundwater flow paths, and established the theoretical basis for ensuring the security of local groundwater supply.

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.

Molecule-based quantification of dissolved organic matter sources in high-arsenic groundwater

Compositions of dissolved organic matter (DOM) in high-arsenic groundwater are usually sourced from the recharged groundwater DOM and the in-situ mobilized organic matter (OM) from aquifer sediments. However, relative importance of the two sources in DOM remains unclear. To quantify sources of DOM, Fourier transform ion cyclotron resonance mass spectrometry was used to analyze molecular characteristics of groundwater DOM and water-soluble organic matter (WSOM) in sediments along an inferred groundwater flow path in the Hetao Basin, China. Results showed that dissolved arsenic concentrations gradually increased from 1.92 to 402 μg/L along the flow path, being mainly due to the DOM degradation-triggered Fe(III) oxide reduction. The DOM molecules being unique to the background groundwater represented the in-situ mobilized OM, which showed the similar abundance to the DOM molecules being common to its depth-matched WSOM. An increasing trend of the relative abundance of the in-situ mobilized OM to the total DOM molecules along the flow path was recognized (from 0 % to 44.5 %). This suggests that the relative contribution of the in-situ mobilized OM to the groundwater DOM increased along with dissolved arsenic concentration. Furthermore, the biodegradable pool among the in-situ mobilized OM was significantly positively correlated with dissolved arsenic, indicating that this in-situ mobilized OM exhibited a dominant role in groundwater arsenic enrichment. The study provides novel insights into contribution of the in-situ mobilized OM to DOM and arsenic mobility in groundwater systems.

Short-term photodegradation of autochthonous and allochthonous dissolved organic matter in Lake Taihu, China.

Photochemistry is one of the key processes that shape the quality of dissolved organic matter (DOM) in aquatic systems, yet the photoreactivity of DOM from different sources remains largely unclear. In this study, DOM from 10 typical autochthonous and allochthonous sources in Lake Taihu basin were exposed to simulated sunlight, and quantitative and compositional changes of the DOM were explored by measuring its UV-Visable absorption and fluorescence spectroscopy. Photochemical release of nutrients was also explored during the incubations. Results showed that, although DOM from most sources experienced photobleaching effects with decreased absorption coefficients at254 nm (a(254)) and fluorescencecomponent intensities after light exposure, photochemical alterations of DOM linked to their original composition. Macrophyte-derived (Potamogeton malaianus) DOM, with the largest molecular size, showed increased a(254), humic- andprotein-like fluorescence component(C1 and C2)abundances, and inorganic nutrient concentrations relative to dark controls, indicating photo-release of labile components. However, DOM with relatively higher aromaticity, e.g., fromagricultural water and the lake, showed photobleaching effects and increased humification degree, probably due to the loss of aromatic components. Allochthonous anthropogenic DOM, e.g., from sewage, showed stronger photo-ammonification, likely relating to the fresh labile N-containing compositions. The form of inorganicnutrient releases during theDOM photolysis also varied with the original DOM sources. Macrophyte-derived DOM incubations showed larger photo-releases of NO3- and PO43-, while NO2- dominated inorganicnutrient releases during groundwater DOM lightincubations. Thus, this study concludes that the photoreactivity of DOM closely relates to its original composition and sources.

Arsenic-dissolved organic matter complexation in water soluble extracts from lignite

Arsenic in groundwater is a global threat to public health. Recently, As mobility has been tied to the concentration and chemical characteristics of dissolved organic matter (DOM) through formation of As-DOM complexes. To date, there has been a wide range of DOM types studied to understand As-DOM interactions, but most of these have focused on surface water derived materials and not groundwater DOM. We address this gap in knowledge by simulating groundwater DOM using water extractable organic matter (WEOM) from two lignite deposits and treating the extracts with increasing concentrations of As. As-DOM complexes were measured using size-exclusion chromatography coupled to multiple detectors including an inductively coupled plasma mass spectrometer (ICPMS) for As detection as well as fluorescence and variable wave detectors for organic matter detection. First, we found two different size fractions of As-DOM, one of ∼1 kDa and another of ∼15 kDa, depending on the DOM types. The smaller As-DOM complex (∼1 kDa) was approximately 10 times more abundant than the larger complex (∼15 kDa). Second, we found that the lignite derived DOMs showed higher conditional distribution coefficients than did the surface water reference material (Suwanee River Natural Organic Matter, SRNOM). Finally, the data showed good fit (R2 > 0.92) to one-site ligand binding models, and the lignite derived DOMs showed higher maximum sorbate concentrations (Bmax) compared to SRNOM. Together, this study shows that As-DOM complexation is an important control on As speciation, even in groundwater systems.

Spatial and seasonal controls on dissolved organic matter composition in shallow aquifers under the rapidly developing city of Patna, India

The distribution and composition of dissolved organic matter (DOM) affects numerous (bio)geochemical processes in environmental matrices including groundwater. This study reports the spatial and seasonal controls on the distribution of groundwater DOM under the rapidly developing city of Patna, Bihar (India). Major DOM constituents were determined from river and groundwater samples taken in both pre- and post-monsoon seasons in 2019, using excitation-emission matrix (EEM) fluorescence spectroscopy. We compared aqueous fluorescent DOM (fDOM) composition to satellite-derived land use data across the field area, testing the hypothesis that the composition of groundwater DOM, and particularly the components associated with surface-derived ingress, may be controlled, in part, by land use. In the pre-monsoon season, the prominence of tryptophan-like components likely generated from recent biological activity overwhelmed the humic-like and tyrosine-like fluorescence signals. Evidence from fluorescence data suggest groundwater in the post-monsoon season is composed of predominantly i) plant-derived matter and ii) anthropogenically influenced DOM (e.g. tryptophan-like components). Organic tracers, as well as Eh and Cl−, suggest monsoonal events mobilise surface-derived material from the unsaturated zone, causing dissolved organic carbon (DOC) of more microbial nature to infiltrate to >100 m depth. A correlation between higher protein:humic-like fluorescence and lower vegetation index (NDVI), determined from satellite-based land use data, in the post-monsoon season, indicates the ingression of wastewater-derived OM in groundwater under the urban area. Attenuated protein:humic-like fluorescence in groundwater close to the river points towards the mixing of groundwater and river water. This ingress of surface-derived OM is plausibly exacerbated by intensive groundwater pumping under these areas. Our approach to link the composition of aqueous organics with land use could easily be adapted for similar hydrogeochemical settings to determine the factors controlling groundwater DOM composition in various contexts.

Transformation of dissolved organic matter and related arsenic mobility at a surface water-groundwater interface in the Hetao Basin, China

Porewater arsenic mobility above the groundwater table has been recognized as a potential cause of arsenic-rich groundwater, but the processing pathways of dissolved organic matter (DOM) in that hyporheic zone and their effect on porewater arsenic release remain poorly understood. To address these issues, two porewater profiles were sampled in a surface water-groundwater interaction zone from the Hetao Basin, China, to monitor the porewater geochemistry and DOM molecular characteristics. The results show that the porewater arsenic, Fe(II), and DOC concentrations were all significantly higher than those of the intruding pond water, and were located above the conservative mixing model lines. This indicates a net release of these solutes from the sediment. By comparing the porewater with pond water DOM, we found that the carboxyl-rich alicyclic molecules (CRAM) were selectively preserved, carbohydrates and aliphatics/proteins were preferentially consumed, and low O/C-ratio compounds with high bioproduction index (I_bioprod) and terrestrial index (I_terr) were produced. The transformation of CHO to CHOS compounds also represented a pathway of recalcitrant DOM production. The produced recalcitrant organic compounds mostly contributed to the elevated porewater DOC concentrations, but their contribution decreased along the filtration path. The consumption of labile DOM compounds would be responsible for Fe(III) hydroxide reduction and arsenic release. The generated recalcitrant DOM may also be a driver of porewater arsenic mobility by acting as electron shuttles. This study highlights the importance of the hyporheic zone in shaping shallow groundwater DOM composition and the potential contribution to arsenic enrichment.

Phosphorus in shallow and deep groundwater: Importance of P/Fe ratio in Fe(III) oxides in aquifer sediments

The causes of the differential enrichment of dissolved phosphorus (P) in the shallow and deep aquifers remain elusive. In this study, groundwater and aquifer sediments were sampled from the Songnen Basin to explore the behaviour and mobilization mechanism of P in a shallow sandy aquifer and a deep sand-gravel aquifer by means of hydrogeochemical analyses and characterizations of dissolved organic matter (DOM) and sedimentary Fe minerals. The results showed that both aquifers were enriched in dissolved P, being mainly related to the organic matter degradation and Fe(III) oxides reduction. Comparatively, total dissolved phosphorus concentrations in shallow groundwater were significantly higher than those in the deep one (p < 0.01), owing to the stronger extent of reductive dissolution of Fe(III) oxides with higher P/Fe molar ratio in the shallow aquifer. Moreover, groundwater DOM with more humic substances in the shallow aquifer promoted the P mobilization via electron shuttling and/or competitive adsorption. In the deep aquifer, reductive dissolution of Fe(III) oxides with high P content resulted in the enrichment of groundwater P. In the two aquifers, immobilization of P via Fe(II) mineral precipitation played a minor role in the fate of groundwater P. This study underlines that geogenic enrichment of P in groundwater can occur in the sand-gravel aquifers with high contents of P and Fe(III) oxides under reducing conditions, and highlights that P/Fe molar ratio in Fe(III) oxides is the most important factor controlling dissolved P in groundwater systems.

Complementary Elucidation of the Molecular Characteristics of Groundwater Dissolved Organic Matter Using Ultrahigh-Resolution Mass Spectrometry Coupled with Negative- and Positive-Ion Electrospray Ionization.

The formula assignment of the Fourier transform ion cyclotron resonance mass spectrometry coupled with positive-ion electrospray ionization [ESI(+)-FT-ICR MS] is challenging because of the extensive occurrence of adducts. However, there is a paucity of automated formula assignment methods for ESI(+)-FT-ICR MS spectra. The novel automated formula assignment algorithm for ESI(+)-FT-ICR MS spectra developed herein has been applied to elucidate the composition of dissolved organic matter (DOM) in groundwater during air-induced ferrous [Fe(II)] oxidation. The ESI(+)-FT-ICR MS spectra of groundwater DOM were profoundly impacted by [M + Na]+ adducts and, to a lesser extent, [M + K]+ adducts. Oxygen-poor and N-containing compounds were frequently detected when the FT-ICR MS was operated in the ESI(+) mode, while the components with higher carbon oxidation states were preferentially ionized in the negative-ion electrospray ionization [ESI(-)] mode. Values for the difference between double-bond equivalents and the number of oxygen atoms from -13 to 13 are proposed for the formula assignment of the ESI(+)-FT-ICR MS spectra of aquatic DOM. Furthermore, for the first time, the Fe(II)-mediated formation of highly toxic organic iodine species was reported in groundwater rich in Fe(II), iodide, and DOM. The results of this study not only shed light on the further algorithm development for comprehensive characterization of DOM by ESI(-)-FT-ICR MS and ESI(+)-FT-ICR MS but also highlight the importance of appropriate treatment of specific groundwater prior to use.

Dissolved Organic Matter Sources in High Arsenic Groundwater From a Sand‐Gravel Confined Aquifer

AbstractSources of dissolved organic matter (DOM) triggering arsenic enrichment in deep confined groundwater is a highly debated issue. Along these lines, the spectroscopic and molecular characteristics of DOM were monitored in both shallow unconfined and deep confined groundwater from the Songnen Basin, China. Results demonstrated that deep groundwater with higher dissolved arsenic concentrations was characterized by more abundant labile organic compounds than shallow groundwater. The three‐end‐member mixing model estimated that shallow groundwater had more fraction of surface water, while deep groundwater was primarily recharged by lateral groundwater flow. Groundwater DOM sources were estimated from the fluorescence index (FI) values, which suggests that shallow groundwater DOM was primarily sourced from surface water with stronger terrestrial signatures. However, deep groundwater DOM was mainly sourced from in situ sedimentary organic matter release or by‐products from microbial activity with stronger microbial signatures. Higher values of degradation index (I_deg) indicate that deep groundwater DOM had undergone greater degradation extents than the shallow one. The microbial DOM degradation in anoxic environments mainly occurred via a pathway where more saturated and low‐molecular‐mass compounds were preferentially degraded to produce more mid‐molecular‐mass compounds with unsaturated, aromatic, and microbial signatures. This explained the significant positive correlations between groundwater arsenic concentrations and FI and I_deg values. A stronger DOM degradation state in deep groundwater was conducive to more arsenic enrichment than that in the shallow one. This work successfully identified distinct sources of shallow and deep groundwater DOM, and proposed a paradigm of DOM processing pathways during arsenic enrichment under anoxic environments.

Groundwater Plays an Important Role in Controlling Riverine Dissolved Organic Matter in a Cold Alpine Catchment, the Qinghai–Tibet Plateau

AbstractIn cold alpine areas, the hydrological control on dissolved organic matter (DOM) export in relation to permafrost distribution remains uncertain on a catchment scale. To address this, the seasonal variations in DOM chemical features of groundwater and stream water were examined from 2013 to 2019 in a representative catchment on the northeastern Qinghai–Tibet Plateau, which is covered by both permafrost (at elevations higher than 3,500 m a.s.l.) and seasonally frozen areas. The results show that the highest dissolved organic carbon (DOC) concentration occurred during the thawing period (April–May), while the highest DOC flux occurred during the thawed period (June–early October). In the permafrost area, the freeze–thaw process significantly influenced the groundwater flow paths and DOM. During the thawing period, with shallow groundwater flow path through the organic soil layer, the stream water DOM recharged by suprapermafrost groundwater was characterized by high aromaticity and high DOC concentrations. During the thawed period, the deepening groundwater flow path through the mineral layer and dilution by overland flow, resulted in low DOC concentrations and DOM with lower aromaticity in stream water. When groundwater flowed from the permafrost area into the porous aquifers in the seasonally frozen area, the groundwater flow path also affected DOM dynamics. The stream water at the catchment outlet, which received groundwater discharge from the porous aquifer, showed a lower peak DOC concentration, a higher proportion of protein‐like DOM, and a higher contribution of cold season DOC flux to annual DOC flux when compared to the water flowing out from the permafrost area. Our work highlights the role of the thick, porous aquifer in the seasonally frozen area in regulating DOM export. The results suggest that the cold alpine area may exhibit a stronger positive feedback to climate warming than that in Arctic areas.

Novel insights into source apportionment of dissolved organic matter in aquifer affected by anthropogenic groundwater recharge: Applicability of end-member mixing analysis based optical indices

The composition and main sources of dissolved organic matter (DOM) in groundwater may change significantly under long-term anthropogenic groundwater recharge (AGR); however, the impact of AGR on quantitative sources of groundwater DOM has seldom been reported. This study evaluated the applicability of optical indices combined with mixing stable isotope analysis in R (MixSIAR) in end-member mixing analysis (EMMA) of groundwater DOM. Fluorescent indices, including C1%, C2%, and C3%, were more sensitive to AGR than other absorbance indices, as indicated by the significant difference between the dominant area of artificial groundwater recharged by surface water and the dominant area of natural groundwater recharged by atmospheric precipitation (NGRP). BIX-C1% was selected as the optimal dual index after the screening protocol of groundwater DOM for EMMA. Our results showed that DOM in the aquifer was mainly subject to autochthonous DOM and the contribution of background groundwater to AGRSW and NGRP groundwater accounted for 36.15% ± 32.41% and 55.46% ± 37.17% (p < 0.05), respectively. Therefore, AGR significantly changed the native DOM in the groundwater. In allochthonous sources of DOM, sewage and surface water contributed 29.54% ± 24.87% and 21.32% ± 28.08%, and 24.79% ± 15.56% and 15.21% ± 14.20% to AGRSW and NGRP groundwater, respectively. The contribution of surface water to AGRSW groundwater was significantly higher than that to NGRP groundwater (p < 0.05), indicating that AGR introduced significantly more DOM from surface water to groundwater. This study provides novel insights into the quantitative source apportionment of DOM in groundwater under long-term AGR, which will facilitate the environmental risk assessment of present AGR measures and the sustainable management of clean water.

Fluorescence characteristics and source analysis of DOM in groundwater during the wet season in the CKDu zone of North Central Province, Sri Lanka

The dissolved organic matter (DOM) should be purified for safe drinking water due to disinfection by-products (DBPs) produced by disinfectants reaction with DOM. Current research on groundwater in the chronic kidney disease with unknown etiology (CKDu) zone of the North Central Province (NCP) in Sri Lanka has focused mainly on aquatic chemistry, with limited attention paid to the spatial distribution, compositional sources and factors of DOM. Therefore, the structure, composition, source and spatial distribution of the DOM of two kinds of groundwater samples collected from dug well and tube well in the NCP during the wet season were determined, compared and analyzed by analytical tools such as parallel factor analysis (PARAFAC). Results show that the average concentrations of TOC in these two groundwater samples are generally higher than 5.0 mg/L, and the concentration of TOC in the groundwater of the shallow weathered aquifer is higher than that of the deep hard rock aquifer, while its distribution of the two aquifers are on contrary. The DOM in the dug well has three types and four components, including humus-like component C1 (33.36%) and C2 (38.60%), protein-like component C3 (13.09%) and heterogeneous organic component C4 (14.95%). In the tube well, two types and two components of the DOM are determined, including humus-like component CⅠ (69.80%) widely existing in natural water and soluble microbial by-product CⅡ (30.20%) produced by microbial community activities. In the dug well, DOM is mainly exogenous input, the higher ion concentration in water affected the fluorescence intensity of humus and protein components. And in the tube well, DOM has obvious endogenous characteristics, and higher pH value may inhibit the production of protein like fluorescent substances to a certain extent.

Sources, spectral characteristics, and fluxes of dissolved organic matter in coastal groundwater and river water in western Guangdong, China

Groundwater discharge and river runoff are two important ways for allochthonous dissolved organic matter (DOM) to enter the ocean, but they vary spatially. Currently, the source, composition, and efflux of groundwater and riverine dissolved organic matter to the tropical northern South China Sea remain poorly understood, preventing an accurate estimate of coastal carbon budgets. In July 2021, nine groundwater and six river water samples were collected along the coast of western Guangdong and were characterized using dissolved organic carbon (DOC) analysis, UV-visible, and fluorescence spectroscopy techniques. Atypical absorption spectra were strongly observed in groundwaters, which were mainly attributed to the high-level nitrates. An exponential-Gaussian equation showed that the average contribution of nitrate to total groundwater absorbances was up to 36% at ∼ 300 nm. Groundwater showed lower levels of DOC, colored dissolved organic matter (CDOM), and fluorescent dissolved organic matter (FDOM) as compared to river water, whereas the humic-like components dominated both groundwater and river water FDOM pools. Higher values of spectral slope S350–400, fluorescence index, biological index, and the ratio of two humic-like fluorescence jointly reveal that groundwater DOM mainly originated from microbial activities, whereas the river water DOM had considerable contribution from terrestrial soil. High precipitation, natural or agricultural land types, and a lack of seawater intrusion are expected to cause low levels of groundwater DOM in western Guangdong. Among 52 rivers from across the globe, high watershed productivity and precipitation may lead to high–moderate DOM levels in river water in western Guangdong. The DOM fluxes via fresh groundwater discharge in western Guangdong are comparable in magnitude to those by river runoff, accounting for 16%–18% of the Pearl River DOM fluxes. Based on the slopes of linear correlations between CDOM and DOC obtained in groundwater samples and 52 rivers, as well as the data on water fluxes and DOC levels, the global CDOM fluxes via groundwater discharge and river runoff are estimated to be 3.5–12.2 × 1012 m2 yr−1 and 4.3 ± 0.3 × 1014 m2 yr−1, respectively, highlighting the importance of considering groundwater discharge and river runoff in coastal carbon budgets.

Biodegradation of dissolved organic matter and sedimentary organic matter in high arsenic groundwater system: Evidence from lipid biomarkers and compound-specific carbon isotopes

Organic matter plays important roles in arsenic mobility. Whether sedimentary or dissolved organic matter is the predominant electron donors is still on debate. To fill this gap, both sediments and groundwater were collected from the Hetao Basin, a typical arid-semiarid area hosting high arsenic groundwater, to characterize diagnostic biomarkers and compound-specific carbon isotopes of lipids in dissolved organic matter (DOM) and its depth-matched sedimentary organic matter (SOM). Results showed that SOM in both clay and sand layers were mainly sourced from terrestrial higher plants, but sand SOM had additional sources from microbial and petroleum OM. Compound-specific carbon isotope compositions of DOM and SOM showed that δ13C of low molecular weight (LMW) n-alkanes (δ13CL) were more positive than those of high molecular weight (HMW) n-alkanes (δ13CH). The δ13CH in groundwater (δ13CH-DOM) and sediments (δ13CH-SOM) fall in the range of C3 plants, indicating that DOM and SOM had similar origins. More positive δ13CL than δ13CH suggests preferential degradation of LMW compounds in both sediments and groundwater. In comparison with SOM, more microbial-derived OM was observed in groundwater DOM, especially in high‑arsenic groundwater. High arsenic groundwater was accompanied by the low ratio of n-alkanes to hopanes in depth-matched SOM, and the great difference between δ13CL and δ13CH and low terrestrial/microbial ratios (TAR) in groundwater DOM. This indicates that SOM and DOM should be utilized by indigenous bacteria to fuel the reductive dissolution of Fe oxides for arsenic release into groundwater. Furthermore, more abundant LMW compounds and weaker odd-to-even predominance in DOM than those in SOM support that DOM encountered stronger biodegradation. This study highlights that preferential biodegradation of DOM (especially LMW components and petroleum sourced OM) would provide electrons for the reductive dissolution of arsenic-bearing Fe/Mn oxides and thus induce arsenic enrichment in groundwater.

Response of bacterial communities and function to dissolved organic matters in groundwater contaminated by landfill leachate.

The migration and transformation of dissolved organic matter (DOM) caused by landfill leachate leakage affected the phylogenetic development of bacterial communities in groundwater around the landfill. Previous studies mainly focused on the hydrochemical properties of DOM in groundwater contaminated by landfill leachate and the relationships between groundwater quality parameters and bacterial communities. However, the changes in DOM components and bacterial communities caused by landfill leachate leakage and their correlations remained unclear. In this work, we analyzed the evolution characteristics of DOM and identified the bacterial communities and their corresponding functions in groundwater around the landfill. The results showed that DOM content in groundwater increased after the diffusion of landfill leachate to groundwater. Significant differences in characteristics between DOM components were presented at different locations in the landfill leachate plume due to the physical dilution and bacterial degradation of DOM. One of the obvious manifestations was the tendency of humic acid-like substances to accumulate at downstream points. Samples from the contaminated aquifer had higher diversity and abundance of bacterial communities than those in the uncontaminated aquifer. Anaerobic or facultative anaerobic bacteria played predominant roles in contaminated groundwater, due to the input of organic matter, nitrate, and ammonia nitrogen. Redundancy analysis indicated that the content of fulvic acid-like DOM had a conspicuous impact on the composition of bacterial communities in the polluted groundwater. Vogesella were the dominant bacteria at the genus level in groundwater around the landfill. Furthermore, Vogesella were significant for microbial utilization and played an important role in the production of fulvic acid-like DOM. These results indicated that landfill leachate pollution posed a potential threat to the structure and function of bacterial communities in groundwater, and provided a basis for exploring the interaction between DOM composition and bacterial communities in groundwater plume contaminated by landfill leachate.

Large-scale study on groundwater dissolved organic matter reveals a strong heterogeneity and a complex microbial footprint

Dissolved organic matter (DOM) in terrestrial groundwater is generally low in concentration compared to inland surface waters. However, the overall amount of groundwater DOM is huge, as there is 100 times more fresh groundwater than fresh surface water. To date, research on groundwater DOM has merely focused on specific threats to humans such as e.g. DOM and heavy metal complexations and DOM from hydrocarbon contamination. A comprehensive, large-scale study of groundwater is still missing. Here, we examine DOM properties in a large-scale approach with regards to surface characteristics such as land use and altitude, aquifer characteristics as well as microbial features. We analyzed 1600 water samples from 100 groundwater bodies all over Austria with regards to their DOM quantity, quality and bacterial abundance (BA). DOM quality was evaluated with self-organizing maps on fluorescence excitation-emission-matrices (EEMs) combined with Ward clustering and subsequent parallel factor analysis to describe DOM properties of each cluster. We evaluated how these clusters differed among each other, based on DOC and nitrate concentrations, BA and selected environmental characteristics. Our results show that fluorescence components in groundwater resemble components found in other groundwater studies, in studies from forest streams, the dark ocean, agricultural catchments and wastewater treatment plants. The latter fluorescence components were associated with a cluster that is characterized by agricultural and urban land use, as well as by high nitrate concentrations. Clusters with an increased abundance of high-molecular weight and humic components, commonly associated with vascular plant and soil origin, correlated with a higher bacterial abundance. This observation provides evidence that elevated numbers of suspended bacteria mainly originate from the surface. Our study shows that DOM fluorescence can be a fast monitoring tool to identify aquifers under anthropogenic stress and delineate sensitive recharge areas with high surface-groundwater interaction.

Quantification of groundwater versus fish-farm sources of nutrients in the coastal water off Jeju Island, Korea, using fluorescent dissolved organic matter as a tracer

The concentrations of nutrients and dissolved organic matter (DOM) in the coastal waters off Jeju Island, Korea, are known to be influenced mainly by submarine groundwater discharge (SGD) and fish-farm effluents, in addition to the background open-ocean seawater from the Tsushima Current. However, the differentiation of the effect of fish-farm effluents from SGD is very challenging since most of the farms in this island utilize groundwater as a rearing water. Thus, in this study, we measured the concentrations of nutrients and fluorescent DOM (FDOM) in seawater, fresh groundwater (FGW), and farm water in two coastal areas off Jeju Island, in May and August 2021, in order to determine the effect of SGD versus fish-farm effluents. The results showed that humic-like FDOM (FDOMH) and NH4+ concentrations were greatly enriched owing to organic matter decomposition in the farm waters. We used FDOMH, as a tracer for the farm effluent. The end-member mixing model for FDOMH and salinity showed that FGW contributed about 73% of NO3− (avg. 17 ± 20 μM), whereas the farm effluent contributed about 95% of NH4+ (avg. 5.6 ± 4.1 μM) and 71% of FDOMH (avg. 0.86 ± 0.49 R.U.) in the coastal waters. Thus, our result shows that fish-farm effluents can be an important source of anthropogenic DOM and nutrients in coastal waters, where farms are being operated intensively.

A new conceptual framework for the transformation of groundwater dissolved organic matter

Groundwater comprises 95% of the liquid fresh water on Earth and contains a diverse mix of dissolved organic matter (DOM) molecules which play a significant role in the global carbon cycle. Currently, the storage times and degradation pathways of groundwater DOM are unclear, preventing an accurate estimate of groundwater carbon sources and sinks for global carbon budgets. Here we reveal the transformations of DOM in aging groundwater using ultra-high resolution mass spectrometry combined with radiocarbon dating. Long-term anoxia and a lack of photodegradation leads to the removal of oxidised DOM and a build-up of both reduced photodegradable formulae and aerobically biolabile formulae with a strong microbial signal. This contrasts with the degradation pathway of DOM in oxic marine, river, and lake systems. Our findings suggest that processes such as groundwater extraction and subterranean groundwater discharge to oceans could result in up to 13 Tg of highly photolabile and aerobically biolabile groundwater dissolved organic carbon released to surface environments per year, where it can be rapidly degraded. These findings highlight the importance of considering groundwater DOM in global carbon budgets.