Iron Promotes the Retention of Terrigenous Dissolved Organic Matter in Subtidal Permeable Sediments.

Marine permeable sediments are important sites for organic matter turnover in the coastal ocean. However, little is known about their role in trapping dissolved organic matter (DOM). Here, we examined DOM abundance and molecular compositions (9804 formulas identified) in subtidal permeable sediments along a near- to offshore gradient in the German North Sea. With the salinity increasing from 30.1 to 34.6 PSU, the DOM composition in bottom water shifts from relatively higher abundances of aromatic compounds to more highly unsaturated compounds. In the bulk sediment, DOM leached by ultrapure water (UPW) from the solid phase is 54 ± 20 times more abundant than DOM in porewater, with higher H/C ratios and a more terrigenous signature. With 0.5 M HCl, the amount of leached DOM (enriched in aromatic and oxygen-rich compounds) is doubled compared to UPW, mainly due to the dissolution of poorly crystalline Fe phases (e.g., ferrihydrite and Fe monosulfides). This suggests that poorly crystalline Fe phases promote DOM retention in permeable sediments, preferentially terrigenous, and aromatic fractions. Given the intense filtration of seawater through the permeable sediments, we posit that Fe can serve as an important intermediate storage for terrigenous organic matter and potentially accelerate organic matter burial in the coastal ocean.

Mechanisms of cadmium release from manganese-rich sediments driven by exogenous DOM and the role of microorganisms.

Dissolved organic matter (DOM) is a crucial component of natural sediments that alters Cd sequestration. Nevertheless, how different types of DOM fuel Cd mobilization in Mn-rich sediments has not been elucidated. In the present study, four typical DOM, fluvic acid (FA), bovine serum albumin (BSA), sodium alginate (SA), and sodium dodecyl benzene sulfonate (SDBS), were used to amend Cd-contaminated sediment to study their effects on Cd/Mn biotransformation and microbial community response. The results demonstrated that different DOM drive microbial community shifts and enhance microbially mediated Mn oxide (MnO) reduction and Cd release. The amendment of terrestrial- and anthropogenic-derived DOM (FA and SDBS) mainly contributed to enriching Mn-reducing bacteria phylum Proteobacteria, and its abundance increased by 38.16-74.47 % and 56.41-73.98 %, respectively. Meanwhile, microbial-derived DOM (BSA and SA) mainly stimulated the abundances of metal(loid)-resistant bacteria phylum Firmicutes. Accompanied by microbial community structure, diversity, and co-occurrence network shifts, the DOM concentration and oxidation-reduction potential changed, resulting in enhanced Cd mobilization. Importantly, FA stimulated Cd release most remarkably, probably because of the decreased cooperative interactions between bacterial populations, stronger reduction of MnOs, and higher aromaticity and hydrophobicity of the sediment DOM after amendment. This study linked DOM types to functional microbial communities, and explored the potential roles of different DOM types in Cd biotransformation in lake sediments.

Treeline displacement may affect lake dissolved organic matter processing at high latitudes and altitudes.

Climate change induced shifts in treeline position, both towards higher altitudes and latitudes induce changes in soil organic matter. Eventually, soil organic matter is transported to alpine and subarctic lakes with yet unknown consequences for dissolved organic matter (DOM) diversity and processing. Here, we experimentally investigate the consequences of treeline shifts by amending subarctic and temperate alpine lake water with soil-derived DOM from above and below the treeline. We use ultra-high resolution mass spectrometry (FT-ICR MS) to track molecular DOM diversity (i.e., chemodiversity), estimate DOM decay and measure bacterial growth efficiency. In both lakes, soil-derived DOM from below the treeline increases lake DOM chemodiversity mainly through the enrichment with polyphenolic and highly unsaturated compounds. These compositional changes are associated with reductions in bulk and compound-level DOM reactivity and reduced bacterial growth efficiency. Our results suggest that treeline advancement has the potential to enrich a large number of lake ecosystems with less biodegradable DOM, affecting bacterial community function and potentially altering the biogeochemical cycling of carbon in lakes at high latitudes and altitudes.

Characterization of microplastic-derived dissolved organic matter in freshwater: Effects of light irradiation and polymer types.

This study investigated the impacts of light irradiation and polymer types on the leaching behavior of dissolved organic matter (DOM) from microplastics (MPs) in freshwater. Polypropylene had the highest leaching capacity of DOM after photoaging, followed by polystyrene (PS), polyamide (PA) and polyethylene terephthalate (PET). While similarly low levels of DOM were observed in the remaining 5 MP suspensions under UV irradiation and in almost all MP suspensions (except PA) under darkness. These suggest that the photooxidation of some buoyant plastics may influence the carbon cycling of nature waters. Among 9 MP-derived leachates, PET leachates had the highest chromophoric DOM concentration and aromaticity, probably owing to the special benzene rings and carbonyl groups in PET structures and its fast degradation rate. Protein-like substances were the primary fluorescent DOM in MP suspensions (except PS), especially in darkness no other fluorescent substances were found. Considering the bio-labile properties of proteins together, MPs regardless of floating or suspended in an aquatic environment may have prevalent long-term effects on microbial activities. Besides, from monomers to hexamers with newly formed chemical bonds were identified in UV-irradiated MP suspensions. These results will contribute to a deep insight into the potential ecological effects related to MP degradation.

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

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

High arsenic pollution of the eutrophic Lake Taihu and its relationship with iron, manganese, and dissolved organic matter: High-resolution synchronous analysis.

Arsenic (As) is a metalloid that can accumulate in eutrophic lakes and cause adverse health effects to people worldwide. However, the seasonal process and dynamic mechanism for As mobilization in eutrophic lake remains effectively unknown. Here we innovatively used the planar optodes (PO), high-resolution dialysis (HR-Peeper) combined with fluorescence excitation-emission matrix coupled with parallel factor (EEM-PARAFAC) analysis technologies. We synchronously investigate monthly O2, As, iron (Fe), manganese (Mn), and naturally occurring dissolved organic matter (DOM) changes in sediments of Lake Taihu at high resolution in field conditions. We find high As contamination from sediments with 61.88-327.07 µg m-2 d-1 release As fluxes during the algal bloom seasons from May to October 2021. Our results show that an increase in DOM, mainly for humic-like components, resulting in high electron transfer capacity (ETC), promoted the reductive dissolution of Fe and Mn oxides to release As. Partial least square-path modeling (PLS-PM) and random forest modeling analysis identified that Mn oxide reductive dissolution directly accelerated sediments As contamination, which is the crucial factor. Understanding crucial factor controlling As release is especially essential in areas of eutrophic lakes developing effective strategies to manage As-rich eutrophic lake sediments worldwide.

The concentration of dissolved organic matter impacts the neurobehavior in female zebrafish exposed to cyclophosphamide.

Cyclophosphamide (CP) is a broad-spectrum anticancer drug for various cancers and frequently detected in aquatic environments, reaching concentrations up to 22 µg/L. However, there is limited understanding of the toxicities of CP with the presence of dissolved organic matter, a ubiquitous component in aquatic environments, in fish. In this study, we investigated the behaviors, morphological alterations of retina, and related gene transcripts in zebrafish exposed to CP (0 and 50 µg/L) and Humic acid (HA, a main component of DOM) at concentrations of 0, 3, 10, and 30 mg-C/L for 30 days. The results showed that, relative to the zebrafish in CP treatment, HA at 30 mg-C/L increased the locomotion (12.1 % in the light and 7.2 % in the dark) and startle response (9.7 %), while inhibiting the anxiety (12.5 %) and cognition of female zebrafish (24.6 %). The levels of transcripts of neurotransmitter- (tph1b and ache), neuroinflammation-(il-6 and tnfα) and antioxidant-(gpx) related genes in the brain of female adult were also altered by CP with the presence of HA. In addition, HA promoted the transgenerational effects of CP on the neurobehaviors. Therefore, HA can enhance potential neurotoxicity of CP in female fish through alteration neurotransmission related genes. Our findings provide new insights into the toxicity and underlying mechanisms of CP with the presence of dissolved organic matter, thereby contribute to a deeper understanding of the risks posed by CP in aquatic ecosystems.

Spatial variations of DOM in a diverse range of lakes across various frozen ground zones in China: Insights into molecular composition.

Dissolved organic matter (DOM) plays a significant role in aquatic biogeochemical processes and the carbon cycle. As global climate warming continues, it is anticipated that the composition of DOM in lakes will be altered. This could have significant ecological and environmental implications, particularly in frozen ground zones. However, there is limited knowledge regarding the spatial variations and molecular composition of DOM in lakes within various frozen ground zones. In this study, we examined the spatial variations of in-lake DOM both quantitatively, focusing on dissolved organic carbon (DOC), and qualitatively, by evaluating optical properties and conducting molecular characterization using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Lakes in cold regions retained more organic carbon compared to those in warmer regions, the comparison of the mean value of DOC concentration of all sampling sites in the same frozen ground zone showed that the highest mean lake DOC concentration found in the permafrost zone at 21.4 ± 19.3 mg/L. We observed decreasing trends in E2:E3 and MLBL, along with increasing trends in SUVA254 and AImod, along the gradually warming ground. These trends suggest lower molecular weight, reduced aromaticity, and increased molecular lability of in-lake DOM in the permafrost zone compared to other frozen ground zones. Further FT-ICR MS characterization revealed significant molecular-level heterogeneity of DOM, with the lowest abundance of assigned DOM molecular formulas found in lakes within permafrost zones. In all studied zones, the predominant molecular formulas in-lake DOM were compounds consisted by CHO elements, accounting for 40.1 % to 63.1 % of the total. Interestingly, the percentage of CHO exhibited a gradual decline along the warming ground, while there was an increasing trend in nitrogen-containing compounds (CHON%). Meanwhile, a substantial number of polyphenols were identified, likely due to the higher rates of DOM mineralization and the transport of terrestrial DOM derived from vascular plants under the elevated temperature and precipitation conditions in the warming region. In addition, sulfur-containing compounds (CHOS and CHNOS) associated with synthetic surfactants and agal derivatives were consistently detected, and their relative abundances exhibited higher values in seasonal and short-frozen ground zones. This aligns with the increased anthropogenic disturbances to the lake's ecological environment in these two zones. This study reported the first description of in-lake DOM at the molecular level in different frozen ground zones. These findings underline that lakes in the permafrost zone serve as significant hubs for carbon processing. Investigating them may expand our understanding of carbon cycling in inland waters.

Tradeoffs between pH, dissolved organic carbon, and mineral ions regulate cadmium uptake by Solanum hyperaccumulators in calcareous soil.

Soil solution pH and dissolved organic carbon (DOC) influence cadmium (Cd) uptake by hyperaccumulators but their tradeoff in calcareous soils is unclear. This study investigated the mechanisms of Solanum nigrum L. and Solanum alatum Moench in calcareous soil using a combination of concentration gradient experiments (0.6-100 mg Cd kg-1) and soil solution composition analysis. The results showed that the soil solution pH of S. nigrum remained stable despite Cd stress. On average, the soil solution pH of S. alatum was 0.23 units higher than that of S. nigrum, although pH decreased significantly under high Cd stress. In addition, the concentrations of potassium (K) and calcium (Ca) in the soil solution of S. nigrum increased and decreased under low and high levels of Cd stress, respectively. In S. alatum, the K and Ca concentrations in the soil solution generally increased with increasing Cd stress levels. Moreover, the level of DOC in the soil solution of both plants was higher under Cd stress compared to the control, and a gradually increasing trend with Cd stress level was observed in S. alatum. Consequently, the bioconcentration factors of the roots (2.62-19.35) and shoots (1.20-9.59) of both plants were >1, while the translocation factors were <1, showing an obstacle of Solanum hyperaccumulators in transferring Cd into their aboveground parts. Redundancy analysis revealed that the Cd concentration in S. nigrum roots was significantly negatively correlated with the soil solutions of K and Ca. In contrast, Cd concentrations in S. alatum roots and shoots were significantly positively correlated with soil solution DOC, K, and Ca but negatively correlated with pH. Our results suggest that calcareous soil neutralizes the acidity of released protons but does not affect cation exchange, inhibiting DOC in assisting the translocation of Cd within plants.

Labile dissolved organic matter (DOM) and nitrogen inputs modified greenhouse gas dynamics: A source-to-estuary study of the Yangtze River.

Although rivers are increasingly recognized as essential sources of greenhouse gases (GHG) to the atmosphere, few systematic efforts have been made to reveal the drivers of spatiotemporal variations of dissolved GHG (dGHG) in large rivers under increasing anthropogenic stress and intensified hydrological cycling. Here, through a source-to-estuary survey of the Yangtze River in March (spring) and October (autumn) of 2018, we revealed that labile dissolved organic matter (DOM) and nitrogen inputs remarkably modified the spatiotemporal distribution of dGHG. The average partial pressure of CO2 (pCO2), CH4 and N2O concentrations of all sampling sites in the Yangtze River were 1015 ± 225 µatm, and 87.5± 36.5 nmol L-1, and 20.3 ± 6.6 nmol L-1, respectively, significantly lower than the global average. In terms of longitudinal and seasonal variations, higher GHG concentrations were observed in the middle-lower reach in spring. The dominant drivers of spatiotemporal variations in dGHG were labile, protein-like DOM components and nitrogen level. Compared with the historical data of dGHG from published literature, we found a significant increase in N2O concentrations in the Yangtze River during 2004-2018, and the increasing trend was consistent with the rising riverine nitrogen concentrations. Our study emphasized the critical roles of labile DOM and nitrogen inputs in driving the spatial hotspots, seasonal variations and annual trends of dGHG. These findings can contribute to constraining the global GHG budget estimations and controls of GHG emission in large rivers in response to global change.

Carbon Fate, Iron Dissolution, and Molecular Characterization of Dissolved Organic Matter in Thawed Yedoma Permafrost under Varying Redox Conditions.

Permafrost soils store ∼50% of terrestrial C, with Yedoma permafrost containing ∼25% of the total C. Permafrost is undergoing degradation due to thawing, with potentially hazardous effects on landscape stability and water resources. Complicating ongoing efforts to project the ultimate fate of deep permafrost C is the poorly constrained role of the redox environment, Fe-minerals, and its redox-active phases, which may modulate organic C-abundance, composition, and reactivity through complexation and catalytic processes. We characterized C fate, Fe fractions, and dissolved organic matter (DOM) isolates from permafrost-thaw under varying redox conditions. Under anoxic incubation conditions, 33% of the initial C was lost as gaseous species within 21 days, while under oxic conditions, 58% of C was lost. Under anoxic incubation, 42% of the total initial C was preserved in a dissolved fraction. Lignin-like compounds dominated permafrost-thaw, followed by lipid- and protein-like compounds. However, under anoxic incubation conditions, there was accumulation of lipid-like compounds and reduction in the nominal oxidation state of C over time, regardless of the compound classes. DOM dynamics may be affected by microbial activity and abiotic processes mediated by Fe-minerals related to selective DOM fractionation and/or its oxidation. Chemodiversity DOM signatures could serve as valuable proxies to track redox conditions with permafrost-thaw.

Influence of iron (hydr)oxide mineralogy and contents in aquifer sediments on dissolved organic carbon attenuations during aquifer storage and recovery.

Aquifer storage and recovery (ASR) is a promising approach for managing water resources that enhances water quality through biogeochemical reactions occurring within aquifers. Iron (hydr)oxides, which are the predominant metallic oxides in soil, play a crucial role in degrading dissolved organic carbon (DOC), primarily through a process known as dissimilatory iron reduction (DIR). However, the efficiency of this reaction varies depending on the mineralogy and composition of the aquifer, and this understanding is essential for adequate water quality in ASR. The objective of this study is to investigate the impact of iron (hydr)oxide on acetate, as an organic carbon source, attenuation during the ASR. To achieve this, three sets of laboratory sediment columns were prepared, each containing a different type of iron (hydr)oxide minerals: ferrihydrite, goethite, and hematite. Following an acclimation period of 28 days to simulate the microcosm within an aquifer, the columns were continuously supplied with the simulated river water spiked with acetate (DOC 40-60 mg L-1), and the acetate concentration in the effluent was monitored. The result revealed that the column containing ferrihydrite achieved 97% acetate attenuation through DIR with anoxic conditions (DO < 0.1 mg L-1), while the goethite and hematite columns exhibited limited attenuation rates of 40 and 50%, respectively. Furthermore, the efficiency of acetate attenuation in the ferrihydrite columns increased with the content of ferrihydrite but experienced a rapidly declined at higher contents (3-4%), possibly due to the partial conversion of ferrihydrite to goethite as a result of the interaction between ferrihydrite and the Fe(II) produced during DIR. Additionally, an analysis of the microbial community demonstrated that microorganisms known to possess the ability to reduce iron (hydr)oxides under anaerobic conditions were abundant in the ferrihydrite columns.

Dissolved organic matter promoted hydroxyl radical formation and phenanthrene attenuation during oxygenation of iron-pillared montmorillonites.

The oxygenation of Fe(II)-bearing minerals for hydroxyl radicals (HO•) formation and contaminant attenuation receives increasing attentions. However, information on dissolved organic matter (DOM) with different types, concentrations, and molecular weights (MWs) in manipulating HO• formation and contaminant attenuation during mineral oxygenation remain unclear. In this study, four iron-pillared montmorillonites (IPMs) and two DOM samples [e.g., humic acids (HA) and fulvic acids (FA)] were prepared to explore the HO• formation and phenanthrene attenuation during the oxygenation of IPMs in the presence or absence of DOMs. Results showed that iron-pillared and high-temperature calcination procedures extended the interlayer domain of IPMs, which provided favorable conditions for a high HO• production from 1293 to 14537 µmol kg-1. The surface-absorbed/low crystalline Fe(Ⅱ) was the predominant Fe(Ⅱ) fractionations for HO• production, and presence of DOMs significantly enhanced the HO• production and phenanthrene attenuation. Moreover, regardless of the types and concentrations, the low MW (LMW, <1 kDa) fraction within DOM pool contributed highest to HO• production and phenanthrene attenuation, followed by the bulk and high MW (HMW-, 1 kDa∼0.45 µm) fractions, and FA exhibited more efficient effects in promoting HO• production and phenanthrene attenuation than HA. The fluorescent spectral analysis further revealed that phenolic-like fluorophores in LMW-fraction were the main substances responsible for the enhanced HO• production and phenanthrene attenuation. The results deepen our understandings toward the behaviors and fate of aquatic HO• and contaminants, and also provide technical guidance for the remediation of contaminated environments.

Synergetic effect of nitrate on dissolved organic carbon attenuation through dissimilatory iron reduction during aquifer storage and recovery.

Aquifer storage and recovery (ASR) is a promising water management technique in terms of quantity and quality. During ASR, iron (Fe) (hydr)oxides contained in the aquifer play a crucial role as electron acceptors in attenuating dissolved organic carbon (DOC) in recharging water through dissimilatory iron reduction (DIR). Considering the preference of electron acceptors, nitrate (NO3⁻), possibly coexisting with DOC as the prior electron acceptor to Fe (hydr)oxides, might influence DIR by interrupting electron transfer. However, this phenomenon is yet to be clarified. In this study, we systematically investigated the potential effect of NO3⁻ on DOC attenuation during ASR using a series of sediment columns representing typical aquifer conditions. The results suggest that DOC attenuation could be enhanced by the presence of NO3⁻. Specifically, total DOC attenuation was notably higher than that from the stoichiometric calculation simply employing NO3⁻ as the additional electron acceptor to Fe (hydr)oxides, implying a synergetic effect of NO3⁻ in the overall reactions. X-ray photoelectron spectroscopy analyzes revealed that the Fe(II) ions released from DIR transformed the Fe (hydr)oxides into a less bioavailable form, inhibiting further DIR. In the presence of NO3⁻, however, no aqueous Fe(II) was detected, and another form of Fe (hydr)oxide appeared on the sediment surface. This may be attributed to nitrate-dependent Fe(II) oxidation (NDFO), in which Fe(II) is (re)oxidized into Fe (hydr)oxide, which is available for the subsequent DOC attenuation. These mechanisms were supported by the dominance of DIR-relevant bacteria and the growth of NDFO-related bacteria in the presence of NO3⁻.

Urbanization influences dissolved organic matter characteristics but microbes affect greenhouse gas concentrations in lakes.

Recognition and prediction of dissolved organic matter (DOM) properties and greenhouse gas (GHG) emissions is critical to understanding climate change and the fate of carbon in aquatic ecosystems, but related data is challenging to interpret due to covariance in multiple natural and anthropogenic variables with high spatial and temporal heterogeneity. Here, machine learning modeling combined with environmental analysis reveals that urbanization (e.g., population density and artificial surfaces) rather than geography determines DOM composition and properties in lakes. The structure of the bacterial community is the dominant factor determining GHG emissions from lakes. Urbanization increases DOM bioavailability and decreases the DOM degradation index (Ideg), increasing the potential for DOM conversion into inorganic carbon in lakes. The traditional fossil fuel-based path (SSP5) scenario increases carbon emission potential. Land conversion from water bodies into artificial surfaces causes organic carbon burial. It is predicted that increased urbanization will accelerate the carbon cycle in lake ecosystems in the future, which deserves attention in climate models and in the management of global warming.

Dissolved organic matter accelerates microbial degradation of 17 alpha-ethinylestradiol in the presence of iron mineral.

Dissolved organic matter (DOM) and iron minerals widely existing in the natural aquatic environment can mediate the migration and transformation of organic pollutants. However, the mechanism of interaction between DOM and iron minerals in the microbial degradation of pollutants deserves further investigation. In this study, the mechanism of 17 alpha-ethinylestradiol (EE2) biodegradation mediated by humic acid (HA) and three kinds of iron minerals (goethite, magnetite, and pyrite) was investigated. The results found that HA and iron minerals significantly accelerated the biodegradation process of EE2, and the highest degradation efficiency of EE2 (48%) was observed in the HA-mediated microbial system with pyrite under aerobic conditions. Furthermore, it had been demonstrated that hydroxyl radicals (HO•) was the main active substance responsible for the microbial degradation of EE2. HO• is primarily generated through the reaction between hydrogen peroxide secreted by microorganisms and Fe(II), with aerobic conditions being more conducive. The presence of iron minerals and HA could change the microbial communities in the EE2 biodegradation system. These findings provide new information for exploring the migration and transformation of pollutants by microorganisms in iron-rich environments.

Instability in a carbon pool driven by multiple dissolved organic matter sources in a eutrophic lake basin: Potential factors for increased greenhouse gas emissions.

Lakes serve as vital reservoirs of dissolved organic matter (DOM) and play pivotal roles in biogeochemical carbon cycles. However, the sources and compositions of DOM in freshwater lakes and their potential effects on lake sediment carbon pools remain unclear. In this study, seven inflowing rivers in the Lake Taihu basin were selected to explore the potential effects of multi-source DOM inputs on the stability of the lake sediment carbon pool. The results showed the high concentrations of dissolved organic carbon in the Lake Taihu basin, accompanied by a high complexity level. Lignins constituted the majority of DOM compounds, surpassing 40% of the total, while the organic carbon content was predominantly composed of humic acids (1.02-3.01 g kg-1). The high amounts of lignin oxidative cleavage led to CHO being the main molecular structure in the DOM of the seven rivers. The carbon constituents within the sediment carbon reservoir exhibited a positive correlation with dissolved CH4 and CO2, with a notable emphasis on humic acid and dissolved CH4 (R2 = 0.86). The elevated concentration of DOM, coupled with its intricate composition, contributed to the increases in dissolved greenhouse gases (GHGs). Experiments showed that the mixing of multi-source DOM can accelerate the organic carbon mineralization processes. The unit carbon emission efficiency was highest in the mixed group, reaching reached 160.9 µmol∙Cg-1, which also exhibited a significantly different carbon pool. The mixed decomposition of DOM from different sources influenced the roles of the lake carbon pool as source and sink, indicating that the multi-source DOM of this lake basin was a potential driving factor for increased carbon emissions. These findings have improved our understanding of the sources and compositions of DOM in lake basins and revealed their impacts on carbon emissions, thereby providing a theoretical basis for improving assessments of lake carbon emissions.

Organic matter biofiltration performance modeling: Influence of influent water quality, operating conditions, and biomass.

The impact of source water dissolved organic matter (DOM) origin, empty bed contact time (EBCT), temperature, and pretreatment methods on biofiltration performance was evaluated and predictive models based on experimental data were developed. Three DOM source water types, terrestrial, microbial, and treated wastewater (WW) effluent, were utilized. A model was developed to predict biofilter performance for dissolved organic carbon (DOC) removal based on the influent biodegradable DOC (BDOC) fraction, a single active biomass measurement from the top of the filter and the filter EBCT. A biomass distribution model was developed to predict total active biomass throughout the filter based on a single biomass measurement from the top of the filter. The measured BDOC fractions were 21 % for the nonWW impacted source waters, 36 % for the WW effluents and 62 % for the ozonated WW effluents. At an EBCT of 15 min, biofilters removed between 7 and 21 % of the DOC (19 to 50 % for BDOC) depending on the DOM type and use of ozonation. When the EBCT decreased to 5 min DOC removal decreased by 40 % and when increased to 30 min removal increased by 42 %. When the temperature decreased from 22 °C to 6 °C DOC removal was 33 % lower and when increased to 28 °C removal was 42 % higher. ATP values were found to be a function of temperature and DOM origin, as the average ATP values from the WW effluent biofilters were almost double that of the non-WW impacted sources and pre-ozonation of the WW effluent yielded values three times higher. The model was applied to the results of 27 different biofilter runs at three EBCTs yielding one distinct rate constant for the non-WW impacted source waters and one rate constant for the WW effluents. The model was successfully applied to the results of 19 filter runs from the literature and to those from a pilot plant over 6 months of operation.

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.

Mechanistic and Kinetic Consideration of the Photochemically Generated Oxidative Organic Radicals in Dissolved Black Carbon Solutions under Simulated Solar Irradiation.

The photochemically generated oxidative organic radicals (POORs) in dissolved black carbon (DBC) was investigated and compared with that in dissolved organic matter (DOM). POORs generated in DBC solutions exhibited higher one-electron reduction potential values (1.38-1.56 V) than those in DOM solutions (1.22-1.38 V). We found that the photogeneration of POORs from DBC is enhanced with dissolved oxygen (DO) increasing, while the inhibition of POORs is observed in reference to DOM solution. The behavior of the one-electron reducing species (DBC•-/DOM•-) was employed to explain this phenomenon. The experimental results revealed that the DO concentration had a greater effect on DBC•- than on DOM•-. Low DO levels led to a substantial increase in the steady-state concentration of DBC•-, which quenched the POORs via back-electron reactions. Moreover, the contribution of POORs to the degradation of 19 emerging organic contaminants (EOCs) in sunlight-exposed DBC and DOM solutions was estimated. The findings indicate that POORs play an important role in the photodegradation of EOCs previously known to react with triplets, especially in DBC solutions. Compared to DOM solutions, POOR exhibits a lower but considerable contribution to EOC attenuation. This study enhances the understanding of pollutant fate in aquatic environments by highlighting the role of DBC in photochemical pollutant degradation and providing insights into pollutant transformation mechanisms involving POORs.