The carbonyl functionality of natural organic matter (NOM) is poorly constrained. Here, we treated Suwannee River NOM (SRNOM) with ammonium acetate and sodium cyanoborohydride to convert ketone-containing compounds by reductive amination to their corresponding primary amines. The total dissolved nitrogen content increased by up to 275% after amination. Up to 30% of the molecular formulas of SRNOM contained isomers with ketone functionalities as detected by ultrahigh-resolution mass spectrometry. Most of these isomers contained one or two keto groups. At least 3.5% of the oxygen in SRNOM was bound in ketone moieties. The conversion of reacted compounds increased linearly with O/H values of molecular formulas and was predictable from the elemental composition. The mean conversion rate of reacted compounds nearly followed a log-normal distribution. This distribution and the predictability of the proportion of ketone-containing isomers solely based on the molecular formula indicated a stochastic distribution of ketones across SRNOM compounds. We obtained isotopically labeled amines by using 15N-labeled ammonium acetate, facilitating the identification of reaction products and enabling NMR spectroscopic analysis. 1H,15N HSQC NMR experiments of derivatized samples containing less than 20 μg of nitrogen confirmed the predominant formation of primary amines, as expected from the reaction pathway.

Defoliation by eastern spruce budworm is one of the most important natural disturbances in Canadian boreal and hemi-boreal forests with annual area affected surpassing that of fire and harvest combined, and its impacts are projected to increase in frequency, severity, and range under future climate scenarios. Deciding on an active management strategy to control outbreaks and minimize broader economic, ecological, and social impacts is becoming increasingly important. These strategies differ in the degree to which defoliation is suppressed, but little is known about the downstream consequences of defoliation and, thus, the implications of management. Given the disproportionate role of headwater streams and their microbiomes on net riverine productivity across forested landscapes, we investigated the effects of defoliation by spruce budworm on headwater stream habitat and microbiome structure and function to inform management decisions. We experimentally manipulated a gradient of defoliation among 12 watersheds during a spruce budworm outbreak in the Gaspésie Peninsula, Québec, Canada. From May through October of 2019-2021, stream habitat (flow rates, dissolved organic matter [DOM], water chemistry, and nutrients), algal biomass, and water temperatures were assessed. Bacterial and fungal biofilm communities were examined by incubating six leaf packs for five weeks (mid-August to late September) in one stream reach per watershed. Microbiome community structure was determined using metabarcoding of 16S and ITS rRNA genes, and community functions were examined using extracellular enzyme assays, leaf litter decomposition rates, and taxonomic functional assignments. We found that cumulative defoliation was correlated with increased streamflow rates and temperatures, and more aromatic DOM (measured as specific ultraviolet absorbance at 254 nm), but was not correlated to nutrient concentrations. Cumulative defoliation was also associated with altered microbial community composition, an increase in carbohydrate biosynthesis, and a reduction in aromatic compound degradation, suggesting that microbes are shifting to the preferential use of simple carbohydrates rather than more complex aromatic compounds. These results demonstrate that high levels of defoliation can affect headwater stream microbiomes to the point of altering stream ecosystem productivity and carbon cycling potential, highlighting the importance of incorporating broader ecological processes into spruce budworm management decisions.

Dissolved organic matter (DOM) in riparian sediments plays a vital role in regulating element cycling and pollutant behavior of river ecosystems. Microplastics (MPs) and benthic animals (BAs) have been frequently detected in riparian sediments, influencing the substance transformation in river ecosystems. However, there is still a lack of systematic investigation on the effects of MPs and BAs on sediment DOM. This study investigated the impact of MPs and BAs on the geochemical characteristics of DOM in riparian sediments and their microbial mechanisms. The results showed that MPs and BAs increased sediment DOC concentration by 34.24%∼232.97% and promoted the conversion of macromolecular components to small molecular components, thereby reducing the humification degree of DOM. Mathematical model verified that the changes of keystone microbes composition in sediments were direct factors affecting the characteristics of DOM in riparian sediment. Especially, MPs tolerant microbes, including Planctomicrobium, Rhodobacter, Hirschia and Lautropia, significantly increased DOC concentration and decreased humification degree (P < 0.05). In addition, MPs and BAs could also influence keystone microbes in sediments by altering the structure of microbial network, thereby indirectly affecting DOM characteristics. The study demonstrates the pollution behavior of MPs in river ecosystems and provides a basis for protecting the ecological function of riparian sediments from MPs pollution.

Riparian infiltration zones are crucial for maintaining water quality by reducing the aqueous concentrations of polycyclic aromatic hydrocarbons (PAHs) through adsorption and biodegradation within the aquatic ecosystem. Dissolved organic matter (DOM) are ubiquitous in riparian infiltration zones where they extensively engage in the adsorption and biodegradation of PAHs, thereby influencing PAHs natural attenuation potential within riparian infiltration zones. Few studies have explored the natural attenuation mechanisms of PAHs influenced by DOM in riparian infiltration zones. In this study, the natural attenuation mechanisms of naphthalene (a typical PAHs component), under the influence of DOM, were explored, based on a case riverside source area. Analysis of microbial community structures, and the electron acceptor (e.g., Fe(III), DO/NO3-, SO42-)/electron donor (naphthalene and DOM) concentration changes within the riparian infiltration zone revealed a competitive inhibition relationship between DOM and naphthalene during microbial metabolism. Biodegradation experiments showed that when the concentration of DOM is higher than 4.0 mg·L-1, it inhibits the biodegradation of naphthalene. DOM competitively inhibits the biodegradation of naphthalene through the following mechanisms: (i) triggering microbial antioxidative defense mechanisms, diminishing the available resources for microbial participation in naphthalene degradation; (ii) altering microbial community structure; (iii) modulating microbial EPS composition, reducing the efficiency of microorganisms in utilizing carbon sources; and (iv) inhibiting the expression levels of downstream genes involved in naphthalene degradation. The competitive inhibition constants of DOM with concentrations of 1.0, 2.0, 4.0, 8.0, and 16.0 mg·L-1 on naphthalene biodegradation are -2.0 × 10-3, -5.0 × 10-3,1.0 × 10-3, 4.0 × 10-4, and 1.0 × 10-4, respectively. These findings enhance understanding of PAHs attenuation in riparian infiltration zone, providing a basis for assessing and managing PAHs pollution risks during riparian extraction.

Nutrient pollution has become an important issue to solve in stormwater runoff due to the fast population growth and urbanization that impacts water quality and triggers harmful algal blooms. There is an acute need to link the dissolved organic nitrogen (DON) decomposition with the coupled nitrification and denitrification pathways to realize the pattern shifts in the nitrogen cycle. This paper presented a lab-scale cascade upflow biofiltration system for comparison of nitrate and phosphate removal from stormwater matrices through two specialty adsorbents at three influent conditions. The two specialty adsorbents are denoted as biochar iron and perlite integrated green environmental media (BIPGEM) and zero-valent iron and perlite-based green environmental media (ZIPGEM). An initial condition with stormwater runoff, a second condition with spiked nitrate, and a third condition with spiked nitrate and phosphate were used in this study. To differentiate nitrifier and denitrifier population dynamics associated with the decomposition of DON, integrative analysis of quantitative polymerase chain reaction (qPCR) and 21 tesla Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were performed in association with nitrate removal efficiencies for both media with or without the presence of phosphate. While the qPCR may detect one gene for a single microbe or pathogen and realize the microbial population dynamics in the bioreactors, the 21 T FT-ICR MS can separate and assign elemental compositions to identify organic compounds of DON. Results indicated that ZIPGEM obtained a higher potential for nutrient removal than BIPGEM when the influent was spiked with nitrate and phosphate simultaneously. The sustainable, scalable, and adaptable upflow bioreactors operated in sequence (in a cascade mode) can be expanded flexibly on an as-needed basis to meet the local water quality standards showing process reliability, resilience, and sustainability simultaneously.

Microplastics (MPs) affect the carbon cycle in coastal salt marsh soils. However, studies on their effects on CHCl3 and CHBr3, which are volatile halohydrocarbons that can damage the ozone layer, are lacking. In this study, indoor simulation experiments were conducted to explore the effects of MPs invasion on the source and sink characteristics of soil CHCl3 and CHBr3. The results showed that different concentrations of polyethylene (PE)-MPs promoted CHCl3 and CHBr3 emissions. Emission peaks of the two gases appeared on days 3 and 15 during the culture cycle. CHCl3 and CHBr3 fluxes were mainly affected by soil physicochemical properties and microbial communities. PE-MPs caused changes in soil properties, microorganisms, and related functional genes. Soil total organic carbon, which was significantly and positively correlated with CHCl3. Dissolved organic matter, which was one of the main factors affecting CHBr3, its relative content increased after the addition of PE-MPs. The abundances of Methylocella and Dehalococcoides, which mediate dechlorination reduction, decreased with the addition of PE-MPs. The addition of PE-MPs also significantly varied the abundance of ctrA, which controls dechlorination in soil microorganisms. The gene pceA greatly influenced CHCl3 emissions. In addition, CHBr3 flux was influenced by the interactions between sediment redox and microbial co-metabolic reactions under the control of genes such as TC.FEV.OM and soxB. This study provides theoretical and data support for the source and sink characteristics of volatile halohydrocarbons in coastal salt marshes and highlights the environmental hazards of MPs.

Organic carbon (C) and CO2 pools are closely interactive in aquatic environments. While there are strong indications linking freshwater CO2 to dissolved organic matter (DOM), the specific mechanisms underlying their common pathways remain unclear. Here, we present an extensive investigation from 20 subtropical lakes in China, establishing a comprehensive conceptual framework for identifying CO2 drivers and retrieving CO2 magnitude through co-trajectories of DOM evolution. Based on this framework, we show that lake CO2 during wet period is constrained by a combination of biogeochemical processes, while photo-mineralization of activated aromatic compounds fuels CO2 during dry period. We clearly determine that biological degradation of DOM governs temporal variations in CO2 rather than terrestrial C inputs within the subtropical lakes. Specifically, our results identify a shared route for the uptake of atmospheric polycyclic aromatic compounds and CO2 by lakes. Using machine learning, in-lake CO2 levels are well modelled through DOM signaling regardless of varying CO2 mechanisms. This study unravels the mechanistic underpinnings of causal links between lake CO2 and DOM, with important implications for understanding obscure aquatic CO2 drivers amidst the ongoing impacts of global climate change.

The depth-dependent dynamics of dissolved organic matter (DOM) structure and humification in an artificial lake limits the understanding of lake eutrophication and carbon cycling. Using fluorescence regional integration (FRI) and parallel factor analysis (PARAFAC) models to analyze the 3D fluorescence spectroscopy dataset, we revealed the depth-dependent structure and vertical distribution of DOM in the estuarine and center regions of Lake Hongfeng. The percentage fluorescence response (Pi,n) showed humic acid is an important part of DOM in Lake Hongfeng. Fluorescence results show that the fulvic-like and protein-like materials in HF1-DOM located at the estuarine position showed greater variation in the middle stage, probably due to human influence and sediment suspension. Fluorescence index (PI+II+IV,n/PIII+V,n and FIC4/FIC3) can be used to indicate the degree of humification of DOM in artificial lakes. Results of each index show that the estuary is more affected by human activities, and the humification degree is significantly lower than that of the center of the lake. The evaluation index system of the humification degree of artificial lake established in this study can effectively predict the eutrophication state of the typical area of artificial lake and deeply understand the possible important influence of human activities on the carbon cycle of lake.

The bioavailability and degradation of riverine dissolved organic matter (DOM) play crucial roles in greenhouse gas emissions; however, studies on the kinetic decomposition of fluvial DOM remain scarce. In this study, the decomposition kinetics of dissolved organic carbon (DOC) were characterized using the reactivity continuum model through 28-day bio-incubation experiments with water samples from the Yangtze River. The relationship between DOM composition and decomposition kinetics was analyzed using optical and molecular characterization combined with apparent decay coefficients. Our results revealed that DOM compounds rich in nitrogen and sulfur were predominantly removed, exhibiting a transition from an unsaturated to a saturated state following microbial degradation. These heteroatomic compounds, which constituted 75.61 % of the DOM compounds positively correlated with the decay coefficient k0, underwent preferential degradation in the early stages of bio-incubation due to their higher bioavailability. Additionally, we observed that S-containing fractions with high molecular weight values (MW > 400 Da) may be associated with larger reactivity grades. This study underscored the complex interplay between DOM composition and its kinetic decomposition in river ecosystems, providing further support for the significance of molecular composition in large river DOM as crucial factors affecting decomposition.

During the process of biological treatment, most microorganisms are encapsulated in extracellular polymeric substances (EPS), which protect the cell from adverse environments and aid in microbial attachment. Microorganisms utilize extracellular electron transfer (EET) for energy and information interchange with other cells and the outside environment. Understanding the role of steric EPS in EET is critical for studying microbiology and utilizing microorganisms in biogeochemical processes, pollutant transformation, and bioenergy generation. However, the current study shows that understanding the roles of EPS in the EET processes still needs a great deal of research. In view of recent research, this work aims to systematically summarize the production and functional group composition of microbial EPS. Additionally, EET pathways and the role of EPS in EET processes are detailed. Then factors impacting EET processes in EPS are then discussed, with a focus on the spatial structure and composition of EPS, conductive materials and environmental pollution, including antibiotics, pH and minerals. Finally, strategies to enhance EET, as well as current challenges and future prospects are outlined in detail. This review offers novel insights into the roles of EPS in biological electron transport and the application of microorganisms in pollutant transformation.