Degradation Of Dissolved Organic Matter Research Articles

Constructing S-scheme Au/g-C3N4/BiVO4 heterojunction with peroxymonosulfate-enhanced photocatalytic activity and mechanism insight

Dissolved organic matter (DOM) in black-odorous water can cause excessive growth of plants and algae, leading to deterioration of water quality. Herein, an S-scheme Au/g-C3N4/BiVO4 heterojunction was constructed using a three-step method for DOM degradation in real black-odorous water in the presence of peroxymonosulfate (PMS). 4Au/g-C3N4/BiVO4/PMS exhibited highly efficient photocatalytic performance, and the DOM removal rate could reach 92.9%, which was 19.1 and 9.9 times higher than that of g-C3N4/PMS and BiVO4/PMS, respectively. The changes of fluorescence components in DOM were detected using synchronous fluorescence spectra and two-dimensional correlated spectroscopy analysis, and the toxicity of catalytically treated black-odorous water was evaluated by growth inhibition of Escherichia coli. A reasonable S-scheme mechanism was suggested by theoretical calculations and photoelectrochemical tests. The S-scheme mechanism and the synergistic effect of photocatalysis and hybrid advanced oxidation process (HAOP) increased the catalytic activity of Au/g-C3N4/BiVO4/PMS.

Photocatalytic peroxydisulfate activation for dissolved organic matter degradation in eutrophic lake water using S-scheme BiVO4/g-C3N4 3D/2D heterojunction under visible light

Large amounts of carbon are stored primarily in dissolved organic matter (DOM), which plays an important indicator of lake eutrophication. However, removing DOM from eutrophic lakes remains a major challenge. Herein, a novel S-scheme flower-like microsphere BiVO4/nanosheet g-C3N4 3D/2D heterojunction was successfully constructed using a two-step method for DOM degradation of real eutrophic lake water in the presence of peroxydisulfate (PDS). 1.0-BiVO4/g-C3N4/PDS exhibited highly efficient photocatalytic performance with an 87.8 % removal rate of DOM for 60 min, which was 5.3 and 8.9 times higher than BiVO4/PDS and g-C3N4/PDS, respectively. Sulfate radical (·SO4−), hydroxyl radical (·OH) and singlet oxygen (1O2) were mainly responsible for DOM degradation in the 1.0-BiVO4/g-C3N4/PDS system, and the transformation pathway of 1O2 was emphatically analyzed. In addition, the changes of fluorescence components in DOM were detected using synchronous fluorescence spectra, second derivative spectra, and two-dimensional correlated spectroscopy analysis. Humic-like fluorescence, fulvic-like fluorescence, and protein-like substances were removed higher than 85.30 %, 73.02 %, and 67.23 % by the 1.0-BiVO4/g-C3N4 catalyst activating the PDS under visible light (VL), respectively. When the toxicity of catalytically treated eutrophic lake water was estimated by growth inhibition of Escherichia coli, the biotoxicity of DOM decreased continuously in the BiVO4/g-C3N4/PDS/VL coupling process. Theoretical calculations and photoelectrochemical tests suggested that the BiVO4/g-C3N4/PDS catalytic activity enhancement was attributed to the S-scheme mechanism and hybrid advanced oxidation process. It is expected that this work can provide new insight into DOM degradation in eutrophic lake water by the heterogeneous photocatalysis combined with the PDS activation system.

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

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

Transformation and degradation processes of dissolved organic matter in shale oil fracturing flowback water: Implications for environmental management

Shale oil extraction yields shale oil fracturing flowback water (SOFFW) rich in recalcitrant soluble organic compounds, the mismanagement of which can cause ecological harm. The current lack of research on dissolved organic matter (DOM) in SOFFW hampers the informed selection and optimization of oxidative methodologies. This study employed diverse characterizations to investigate the degradation and transformation mechanisms of DOM in SOFFW during Fenton oxidation. It identified three primary components in SOFFW, predominantly humic-like substances, the intensity of which was considerably reduced through oxidation. 2D-COS-FTIR analysis revealed that during oxidation, phenolic organic compounds showed preferential reactivity, followed by compounds containing double bonds and, finally, aliphatic compounds. Fenton oxidation effectively degraded highly unsaturated phenolics and polycyclic aromatic hydrocarbons, simultaneously generating an abundance of aliphatic and oxygen-poor unsaturated phenolic compounds. Through carboxylation, demethylation, and hydrogenation reactions, the proportion of large organic molecules (400–700 Da) decreased, leading to the formation of smaller molecules in the 200–400 Da range. Our findings demonstrate that hydroxyl radicals in the Fenton oxidation process react rapidly with electron-rich compounds, such as highly oxygenated unsaturated phenolics, while showing lower reactivity toward aliphatic substances. These findings substantially contribute to the efficient treatment of SOFFW and offer valuable insights for practical applications.

Characterization of dissolved organic matter in rivers impacted by acid mine drainage: Components and complexation with metals

Dissolved organic matter (DOM), a ubiquitous and active ingredient, is extensively involved in the transformation and migration of environmental pollutants in aquatic ecosystems. However, its chemical composition in acid mine drainage (AMD)-impacted rivers remains poorly characterized, hindering our understanding of its role in the biogeochemistry of key elements in contaminated fluvial environments. Here, we investigated the concentration of dissolved organic carbon (DOC) and spectroscopic and molecular characteristics of DOM in a headwater river contaminated with polymetallic mine-derived AMD in southern China. Terrestrial humic-like (C1) and typically groundwater-supplied aromatic protein/tyrosine-like (C2) substances which were partially from AMD, were identified as the predominant fluorescent components in the river water. Notably, tryptophan-like (C3) substances originating from tailings pond spills were only occasionally detected in the river. Although DOM biogeochemical transformations and degradation occurred in the lateral soil-water riparian interface and longitudinal in-stream transport processes, the molecular compositions identified by FT-ICR MS showed a core set of molecular formulae in the lignin/saturated compound/tannin region of the van Krevelen diagram of the water samples across the rivers. The complexation of DOM with typical metals in AMD was investigated using fluorescence quenching experiments. The results showed that the highest binding ability of Fe(III) to C2 followed by C1, with both detected in the experimental water samples. Mg(II) and Ca(II) strengthened the binding of DOM-Fe(III) when the ferric/DOM ratio was low, while Cu(II) weakened the binding of DOM-Fe(III) due to competition. Ca(II) inhibited the binding of Fe(III) to C1 but promoted the binding of the complex to C2 when both Cu(II) and Mg(II) were present. Since DOM-Fe(III) complexation was associated with the cotransport of AMD-derived metals/metalloids in diverse aqueous environments with multiple co-existing ions (typically Ca(II) input for remediation), our study on the composition of DOM and its complexation with metals can contribute to managing and remediating AMD-impacted rivers.

Unraveling sources of cyanate in the marine environment: insights from cyanate distributions and production during the photochemical degradation of dissolved organic matter

Cyanate is a nitrogen and energy source for diverse marine microorganisms, playing important roles in the nitrogen cycle. Despite the extensive research on cyanate utilization, the sources of this nitrogen compound remain largely enigmatic. To unravel the sources of cyanate, distributions and production of cyanate during photochemical degradation of natural dissolved organic matter (DOM) were investigated across various environments, including freshwater, estuarine, coastal areas in Florida, and the continental and slope regions of the North American mid-Atlantic Ocean (NATL). Cyanate production was also examined during the photochemical degradation of exudates from a typical strain of Synechococcus, an important phytoplankton component. To deepen our understanding of the sources and production mechanisms of cyanate, its production was assessed during the photochemical degradation of a natural seawater DOM supplemented with five nitrogen–containing compounds with distinguishing structures and functional groups. Generally, cyanate exhibited higher concentrations in the Florida coastal, estuarine, and freshwater environments than the NATL. However, cyanate distribution did not consistently align with its production rates. Despite significantly low concentrations in the NATL, DOM from this region exhibited cyanate production rates comparable to estuarine and Florida coastal environments. Although relatively high cyanate concentrations were observed in the freshwaters, DOM in this environment exhibited very low cyanate production rates. A highly significant correlation was observed between cyanate and chlorophyll a (Chl a) concentrations in these areas. Moreover, in most estuarine and NATL stations, cyanate concentration and production rate in the Chl a maximum layer were significantly higher than in other layers. Cyanate was produced during the photochemical degradation of the Synechococcus exudates. The cyanate production was significantly enhanced when the natural seawater DOM was supplemented with GlycylGlycine, 4-(methylamino) benzoic acid, 4-[ethyl(methyl)amino] benzaldehyde or methyl 2-aminobenzoate. Our study implies that photochemical degradation of marine DOM, especially phytoplankton-derived DOM, is a substantial source of cyanate in the ocean. Additionally, cyanate may form during the degradation of peptides and small aromatic compounds in DOM, providing novel insights into the nitrogen cycle.

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.

Dynamic distribution and photochemical-microbial coupling degradation of dissolved organic matter in a large river-Influenced Bay

A large river-influenced offshore area is the junction where land and open sea meet, which is important in the biogeochemical processes of dissolved organic matter (DOM). Because hydrodynamic and biogeochemical processes are complex, processes such as the photochemical and microbial degradation of DOM are poorly understood. In this study, to further understand the degradation mechanisms of DOM from different sources, water was sampled from three cruises during autumn 2018 and spring and summer 2019 in Laizhou Bay (LZB), as this bay is greatly influenced by the Yellow River. Field incubation experiments examining the riverine, mixed, and marine DOM photochemical and microbial degradation processes alone or in combination were conducted onboard. Due to the dual influence of the Yellow River input and phytoplankton autogenous production, dissolved organic carbon (DOC) and chromophoric DOM (CDOM) show relatively conservative mixing behaviour with maximum values in summer, and the S275–295 gradually increases from the river to nearshore. In addition, it is indicated that higher primary productivity from large nutrient inputs in areas with moderate salinity during the summer is often accompanied by higher bioavailability DOM based on field investigation results. Various sources of DOM have different sensitivities to photochemical and microbial degradation due to their components and properties. Riverine DOM is susceptible to photochemical degradation, while marine DOM is more susceptible to microbial degradation. Moreover, the low-molecular-weight organic matter produced by photochemical degradation effectively promotes the microbial degradation of DOM from riverine sources, whereas photodegradation from mixed and marine sources do not significantly increase the biodegradation efficiency due to the low content of aromatic substances. Furthermore, photoammonification and bioammonification of autochthonous and allochthonous DOM may be the potential processes driving ammonia regeneration.

Effects of Cu(II)-DOM complexation on DOM degradation: Insights from spectroscopic evidence

The fate of dissolved organic matter (DOM) is primarily governed by its sources, degradation, and transformation processes within the environment. However, the influence of metal-DOM complexation on DOM degradation remains ambiguous. In this study, controlled laboratory experiments were conducted using Cu(II) and natural water from the Duliujian River and the Beidagang Wetland to examine the effects of metal-DOM binding on the degradation pathway of DOM. Our results showed that Cu(II)-DOM complexation affected the distribution of DOM molecular weight with elevated Mw after complexed with Cu(II). Nevertheless, the concentration of DOM decreased over the incubation period due to degradation. In the absence of Cu(II) binding, both wetland and river DOM followed similar degradation pathways, transforming from high to low molecular weight with changes predominantly in the 1–10 kDa size-fraction during DOM degradation. In contrast, in the presence of Cu(II) and thus Cu(II)-DOM binding, the degradation of DOM was enhanced, resulting in higher kinetic rate constants for both wetland and river DOM. The results of differential spectra further confirmed the degradation of DOM with a decrease in bulk spectroscopic properties and an increase in the degree of DOM-Cu(II) complexation. These findings imply a mutually reinforcing relationship between metal-DOM complexation and the degradation of DOM in aquatic environments, providing new insights into the biogeochemical behavior and environmental fate of DOM.

Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets.

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (•O2-) through a one-electron transfer process. 1H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.

Micro-biological degradation and transformation of dissolved organic matter following continuous cropping of tobacco.

In recent years, the problems associated with continuous cropping (CC) that cause soil degradation have become increasingly serious. As a key soil quality property, dissolved organic matter (DOM) affects the circulation of carbon and nutrients and the composition of bacterial communities in soil. However, research on the changes in the molecular composition of DOM after CC is limited. In this study, the soil chemical properties, DOM chemical diversity, bacterial community structure, and their interactions are explored in the soil samples from different CC years (CC1Y, CC3Y, CC5Y, and CC7Y) of tobacco. With increasing CC year of tobacco, most of the soil chemical properties, such as total carbon, total nitrogen and organic matter, decreased significantly, while dissolved organic carbon first decreased and then increased. Likewise, the trends of DOM composition differed with changing duration of CC, such as the tannin compounds decreased from 18.13 to 13.95%, aliphatic/proteins increased from 2.73 to 8.85%. After 7 years of CC, the soil preferentially produced compounds with either high H/C ratios (H/C > 1.5), including carbohydrates, lipids, and aliphatic/proteins, or low O/C ratios (O/C < 0.1), such as unsaturated hydrocarbons. Furthermore, core microorganisms, including Nocardioides, wb1-P19, Aquabacterium, Methylobacter, and Thiobacillus, were identified. Network analysis further indicated that in response to CC, Methylobacter and Thiobacillus were correlated with the microbial degradation and transformation of DOM. These findings will improve our understanding of the interactions between microbial community and DOM in continuous cropping soil.

Molecular insights into the microbial degradation of sediment-derived DOM in a macrophyte-dominated lake under aerobic and hypoxic conditions

The mineralization of dissolved organic matter (DOM) in sediments is an important factor leading to the eutrophication of macrophyte-dominated lakes. However, the changes in the molecular characteristics of sediment-derived DOM during microbial degradation in macrophyte-dominated lakes are not well understood. In this study, the microbial degradation process of sediment-derived DOM in Lake Caohai under aerobic and hypoxic conditions was investigated using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and metagenomics. The results revealed that the microbial degradation of sediment-derived DOM in macrophyte-dominated lakes was more intense under aerobic conditions. The microorganisms mainly metabolized the protein-like substances in the macrophyte-dominated lakes, and the carbohydrate-active enzyme genes and protein/lipid-like degradation genes played key roles in sediment-derived DOM degradation. Organic compounds with high H/C ratios such as lipids, carbohydrates, and protein/lipid-like compounds were preferentially removed by microorganisms during microbial degradation. Meanwhile, there was an increase in the abundance of organic molecular formula with a high aromaticity such as tannins and unsaturated hydrocarbons with low molecular weight and low double bond equivalent. In addition, aerobic/hypoxic environments can alter microbial metabolic pathways of sediment-derived DOM by affecting the relative abundance of microbial communities (e.g., Gemmatimonadetes and Acidobacteria) and functional genes (e.g., ABC.PE.P1 and ABC.PE.P) in macrophyte-dominated lakes. The abundances of lipids, unsaturated hydrocarbons, and protein compounds in aerobic environments decreased by 58 %, 50 %, and 44 %, respectively, compared to in hypoxic environments under microbial degradation. The results of this study deepen our understanding of DOM biodegradation in macrophyte-dominated lakes under different redox environments and provide new insights into nutrients releases from sediment and continuing eutrophication in macrophyte-dominated lakes.

Coastal upwelling systems as dynamic mosaics of bacterioplankton functional specialization

Coastal upwelling areas are extraordinarily productive environments where prokaryotic communities, the principal remineralizers of dissolved organic matter (DOM), rapidly respond to phytoplankton bloom and decay dynamics. Nevertheless, the extent of variability of key microbial functions in such dynamic waters remains largely unconstrained. Our metatranscriptomics analyses of 162 marker genes encoding ecologically relevant prokaryotic functions showed distinct spatial-temporal patterns in the NW Iberian Peninsula upwelling area. Short-term (daily) changes in specific bacterial functions associated with changes in biotic and abiotic factors were superimposed on seasonal variability. Taxonomic and functional specialization of prokaryotic communities, based mostly on different resource acquisition strategies, was observed. Our results uncovered the potential influence of prokaryotic functioning on phytoplankton bloom composition and development (e.g., Cellvibrionales and Flavobacteriales increased relative gene expression related to vitamin B12 and siderophore metabolisms during Chaetoceros and Dinophyceae summer blooms). Notably, bacterial adjustments to C- or N-limitation and DMSP availability during summer phytoplankton blooms and different spatial-temporal patterns of variability in the expression of genes with different phosphate affinity indicated a complex role of resource availability in structuring bacterial communities in this upwelling system. Also, a crucial role of Cellvibrionales in the degradation of DOM (carbohydrate metabolism, TCA cycle, proteorhodopsin, ammonium, and phosphate uptake genes) during the summer phytoplankton bloom was found. Overall, this dataset revealed an intertwined mosaic of microbial interactions and nutrient utilization patterns along a spatial-temporal gradient that needs to be considered if we aim to understand the biogeochemical processes in some of the most productive ecosystems in the world´s oceans.

Universal microbial reworking of dissolved organic matter along environmental gradients.

Soils are losing increasing amounts of carbon annually to freshwaters as dissolved organic matter (DOM), which, if degraded, can offset their carbon sink capacity. However, the processes underlying DOM degradation across environments are poorly understood. Here we show DOM changes similarly along soil-aquatic gradients irrespective of environmental differences. Using ultrahigh-resolution mass spectrometry, we track DOM along soil depths and hillslope positions in forest catchments and relate its composition to soil microbiomes and physico-chemical conditions. Along depths and hillslopes, we find carbohydrate-like and unsaturated hydrocarbon-like compounds increase in abundance-weighted mass, and the expression of genes essential for degrading plant-derived carbohydrates explains >50% of the variation in abundance of these compounds. These results suggest that microbes transform plant-derived compounds, leaving DOM to become increasingly dominated by the same (i.e., universal), difficult-to-degrade compounds as degradation proceeds. By synthesising data from the land-to-ocean continuum, we suggest these processes generalise across ecosystems and spatiotemporal scales. Such general degradation patterns can help predict DOM composition and reactivity along environmental gradients to inform management of soil-to-stream carbon losses.

Divergent Fate and Roles of Dissolved Organic Matter from Spatially Varied Grassland Soils in China During Long-Term Biogeochemical Processes.

Terrestrial dissolved organic matter (DOM) is critical to global carbon and nutrient cycling, climate change, and human health. However, how the spatial and compositional differences of soil DOM affect its dynamics and fate in water during the carbon cycle is largely unclear. Herein, the biodegradation of DOM from 14 spatially distributed grassland soils in China with diverse organic composition was investigated by 165 days of incubation experiments. The results showed that although the high humified fraction (high-HS) regions were featured by high humic-like fractions of 4-25 kDa molecular weight, especially the abundant condensed aromatics and tannins, they unexpectedly displayed greater DOM degradation during 45-165 days. In contrast, the unique proteinaceous and 25-100 kDa fractions enriched in the low humified fraction (low-HS) regions were drastically depleted and improved the decay of bulk DOM but only during 0-45 days. Together, DOM from the high-HS regions would cause lower CO2 outgassing to the atmosphere but higher organic loads for drinking water production in the short term than that from the low-HS regions. However, this would be reversed for the two regions during the long-term transformation processes. These findings highlight the importance of spatial and temporal variability of DOM biogeochemistry to mitigate the negative impacts of grassland soil DOM on climate, waters, and humans.

Deciphering Microbe-Mediated Dissolved Organic Matter Reactome in Wastewater Treatment Plants Using Directed Paired Mass Distance.

Understanding the reaction mechanism of dissolved organic matter (DOM) during wastewater biotreatment is crucial for optimal DOM control. Here, we develop a directed paired mass distance (dPMD) method that constructs a molecular network displaying the reaction pathways of DOM. It couples direction inference and PMD analysis to extract the substrate-product relationships and delta masses of potentially paired reactants directly from sequential mass spectrometry data without formula assignment. Using this method, we analyze the influent and effluent samples from the bioprocesses of 12 wastewater treatment plants (WWTPs) and build a dPMD network to characterize the core reactome of DOM. The network shows that the first step of the transformation triggers reaction cascades that diversify the DOM, but the highly overlapped subsequent reaction pathways result in similar effluent DOM compositions across WWTPs despite varied influents. Mass changes exhibit consistent gain/loss preferences (e.g., +3.995 and -16.031) but different occurrences across WWTPs. Combined with genome-centric metatranscriptomics, we reveal the associations among dPMDs, enzymes, and microbes. Most enzymes are involved in oxygenation, (de)hydrogenation, demethylation, and hydration-related reactions but with different target substrates and expressed by various taxa, as exemplified by Proteobacteria, Actinobacteria, and Nitrospirae. Therefore, a functionally diverse community is pivotal for advanced DOM degradation.

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.

Disentangling Biological Transformations and Photodegradation Processes from Marine Dissolved Organic Matter Composition in the Global Ocean.

Dissolved organic matter (DOM) holds the largest amount of organic carbon in the ocean, with most of it residing in the deep for millennia. Specific mechanisms and environmental conditions responsible for its longevity are still unknown. Microbial transformations and photochemical degradation of DOM in the surface layers are two processes that shape its molecular composition. We used molecular data (via Fourier transform ion cyclotron resonance mass spectrometry) from two laboratory experiments that focused on (1) microbial processing of fresh DOM and (2) photodegradation of deep-sea DOM to derive independent process-related molecular indices for biological formation and transformation (Ibio) and photodegradation (Iphoto). Both indices were applied to a global ocean data set of DOM composition. The distributions of Iphoto and Ibio were consistent with increased photodegradation and biological reworking of DOM in sunlit surface waters, and traces of these surface processes were evident at depth. Increased Ibio values in the deep Southern Ocean and South Atlantic implied export of microbially reworked DOM. Photodegraded DOM (increased Iphoto) in the deep subtropical gyres of Atlantic and Pacific oceans suggested advective transport in warm-core eddies. The simultaneous application of Iphoto and Ibio disentangled and assessed two processes that left unique molecular signatures in the global ocean.

Processes in the Surface Ocean Regulate Dissolved Organic Matter Distributions in the Deep

AbstractMarine dissolved organic matter (DOM) is a major global carbon pool, consisting of thousands of compounds with distinct lifetimes. While marine DOM persists for millennia, its molecular and isotopic composition imply that it is dynamic on shorter timescales. To determine the extent to which DOM deviates from conservative water mass mixing, we conducted a two‐endmember mixing analysis on dissolved organic carbon (DOC) concentration and DOM molecular composition in the Atlantic and Pacific. Endmembers were the deep water masses near their formation sites. For DOM composition, we considered 6118 molecular formulae (MF) identified via Fourier‐transform ion cyclotron resonance mass spectrometry in solid‐phase extracts (SPE) of 837 samples. Bulk DOC and SPE‐DOC concentrations behaved conservatively in both basins and ≥70% of the MF (14–20 μM SPE‐DOC) mixed conservatively. However, a small fraction (10%–20%) of the MF (&lt;3 μM SPE‐DOC) were added or removed during mixing. These MF were more reduced and oxidized, respectively, than the conservative fraction. There were also MF absent from the endmembers; these accounted for ≤1 μM of SPE‐DOC and positively correlated with DOM lability. Based on their distribution across the two basins, we conclude that the conserved MF are formed in the surface subtropical ocean and modified in overturning areas. In the deep ocean, however, these MF are solely controlled by mixing. This finding contrasts with the current paradigm of slow, continuous degradation of recalcitrant DOM in the deep ocean. Our analysis illustrates the importance of the surface ocean in controlling DOM cycling in the deep.

Fluctuating redox conditions accelerate the electron storage and transfer in magnetite and production of dark hydroxyl radicals

Magnetite (Fe3O4), known as a geo-battery that can store and transfer electrons, often co-occurs with sulfide in subsurface environments with fluctuating redox conditions. However, little is known about how fluctuating redox conditions (e.g., sulfidation-oxidation) affect the electron storage and transfer in Fe3O4 that was associated with the production of dark hydroxyl radicals (⋅OH) and the oxidation of dissolved organic matter (DOM). This study revealed that Fe3O4 sulfidated by sulfide (S-Fe3O4) at neutral pH exhibited higher ⋅OH production upon oxygenation than Fe3O4, in which the cumulative ⋅OH concentration increased with increasing initial S/Fe ratio (≤ 0.50), sulfidation duration and number of sulfidation-oxidation cycle. X-ray photoelectron spectroscopy and wet-chemical analyses of Fe and S species of S-Fe3O4 showed that sulfidation enables electron storage in Fe3O4 by increasing both structural and surface Fe(II). Sulfide was converted into S0, acid volatile sulfur (AVS), and chromium-reducible sulfur (CRS) during Fe3O4 sulfidation. S-Fe3O4 with lower AVS/CRS ratio exhibited higher reactivity to produce ⋅OH, indicating the important role of CRS in transferring electrons from Fe(II) to O2. Based on quenching experiments and electron paramagnetic resonance analysis, a one-step two-electron transfer mechanism was proposed for O2 reduction during S-Fe3O4 oxygenation, and surface-bound rather than free ⋅OH were identified as the primary reactive oxygen species. The ⋅OH from S-Fe3O4 oxygenation was shown to be efficient in degradation of DOM. Overall, these results suggested that sulfidation-oxidation can accelerate the electron storage and transfer in Fe3O4 for dark ⋅OH production, having an important impact on the carbon cycling in subsurface environments.