Fate Of Dissolved Organic Matter Research Articles

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.

Insight into the dynamics of dissolved organic matter components under latitude change perturbation

Dissolved organic matter (DOM) which can help the transportation of nutrients and pollutants plays essential role in the aquatic ecosystems. However, the dynamics of individual DOM component under the change of latitude have not been elucidated to date. The composition and dynamics of DOM were assessed in this study. Two individual parallel factor analysis (PARAFAC) components were found in each sampling site in Heilongjiang. To further characterize the inner change of the identified PARAFAC components, two-latitude correlation spectroscopy (2DCOS) technique was applied to the excitation loadings data. Interestingly, not all the fluorophore in a PARAFAC component change in the same direction as the overall change of a component. From upstream to downstream, the peak A1 in PARAFAC component C1 showed a downward trend, but peak A2 presented an upward trend. In PARAFAC component C2, the peak T2 and peak T3 showed an inverse changing trend under latitude perturbation. Furthermore, basic nutrients parameters in Heilongjiang were also characterized in each sampling sites. The relationships between DOM and nutrients showed that component C1 made a significant contribution to chemical oxygen demand (COD) and biochemical oxygen demand (BOD5). The evolutions of DOM peak A1 and peak A2 were accompanied by the changing of Total phosphorus (TP). The findings in this study could make a contribution to explore the fate of DOM in high humic-like substance containing river.

Unraveling heterogeneity of dissolved organic matter in highly connected natural water bodies at molecular level

The exploring of molecular-level heterogeneity of dissolved organic matter (DOM) in highly connected water bodies is of great importance for pollution tracing and lake management, and provides new perspectives on the transformations and fate of DOM in aquatic systems. However, the inherent homogeneity of DOM in connected water bodies poses challenges for its heterogeneity analysis. In this work, an innovative method combining fluorescence spectroscopy, high-resolution mass spectrometry (HRMS), and cluster analysis was developed to reveal the heterogeneity of DOM in highly connected water bodies at the molecular level. We detected 4538 molecules across 36 sampling sites in Chaohu Lake using HRMS. Cluster analysis based on excitation-emission matrix (EEM) data effectively divided the sampling sites into four clusters, representing the water bodies from West Chaohu Lake, East Chaohu Lake, agricultural land, and urban areas. Analysis of DOM in the western and eastern parts of the lake revealed that aerobic degradation led to a decrease in CHOS and aliphatic compounds, alongside an increase in CHO and highly unsaturated and phenolic compounds. Furthermore, we unveiled the characteristics and sources of heterogeneity in DOM from agricultural land and urban areas. Our method accurately captured the heterogeneous distribution of DOM in the lake and revealed the heterogeneous composition of DOM at molecular level. This work underscores the importance of integrating complementary spectroscopic analyses with HRMS in DOM research with similar compositions.

Seasonal changes of dissolved organic matter chemistry and its linkage with greenhouse gas emissions in saltmarsh surface water and porewater interactions

Dissolved organic matter (DOM) is one of the largest reactive reservoirs of carbon on earth. Saltmarshes play an essential role in shaping the fate of DOM and greenhouse gas (GHG) production in surface water and groundwater interactions in coastal areas. However, the coupling mechanism between DOM and GHG production is poorly understood. In this study, DOM in both surface water and porewater were analyzed by 3D excitation-emission-matrix spectroscopy under different seasonal and tidal conditions in a saltmarsh. Protein-like DOM was likely to produce CH4, while humic-like DOM tended to produce CO2. CH4 concentration was highly enriched in porewater because increasing fresh groundwater flow introduced small-sized protein-like DOM. Based on the mass balance model, >98.5% of CH4 was oxidated to CO2 in sediment-water interface. The degradation of sediment-derived DOC (especially humic-like DOM) contributes ∼80% of the total amount of CO2 in surface water. Both hydrodynamics and chemical reactions are suggested to influence greenhouse gas (GHG) emissions. Hydrodynamics (e.g., tidal pumping) are controlling factors in short timescales (hourly/weekly) while chemical reactions become crucial in influencing DOM chemistry and related degradation rate on seasonal scales. These findings emphasize the importance of the coupling mechanism at different time scales between DOM characteristics and GHG emissions in saltmarshes.

Molecular insight into DOM fate using EEM-PARAFAC and FT-ICR MS and concomitant heavy metal behaviors in biologically treated landfill leachate during coagulation: Al speciation dependence

Various combined processes with pre-coagulation have been developed for biologically treated landfill leachate, but the microscopic-level processes occurring during coagulation remain largely unknown. Herein, dissolved organic matter (DOM) fate using fluorescence excitation emission matrix spectroscopy combined with parallel factor analysis and electrospray ionization coupled Fourier transform-ion cyclotron resonance mass spectrometry and concomitant heavy metal (HM) behaviors were explored at the molecular level. In addition, AlCl3 and two polyaluminum chloride (PACl) species (dominated by [AlO4Al12(OH)24(H2O)12]7+ and [(AlO4)2Al28(OH)56(H2O)26]18+, respectively) were used. The results show that all coagulants are efficient at removing DOM. PACl was found to be advantageous over AlCl3 in overcoming pH fluctuation, which is ascribed to the different dominant mechanisms, namely, entrapment and sweep flocculation for AlCl3 and charge neutralization for PACl. Consequently, PACl was more effective at removing humic substances, usually high-molecular-weight, oxygen-rich and unsaturated, than protein substances. For HM removal, PACl was likewise better and more stable, where As, Cu, Ni, Co and Hg were removed predominantly via adsorption, and Cr, Zn, Pb, Cd and Mn were removed via coprecipitation. Correlation analysis showed that humic substances tended to complex with HMs and be removed synergistically due to the ubiquitous occurrences of aromatic structures and oxygen-containing functional groups.

Soil microbial community, dissolved organic matter and nutrient cycling interactions change along an elevation gradient in subtropical China

To identify possible dominating processes involved in soil microbial community assembly, dissolved organic matter (DOM) and multi-nutrient cycling (MNC) interactions and contribute to understanding of climate change effects on these important cycles, we investigated the interaction of soil chemistry, DOM components and microbial communities in five vegetation zones - ranging from evergreen broad-leaved forest to alpine meadow - along an elevation gradient of 290–1960 m in the Wuyi Mountains, Fujian Province, China. Soil DOM composition and microbial community assembly were characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and Illumina MiSeq high-throughput sequencing, respectively. Sloan's neutral model and the modified stochasticity ratio were used to infer community assembly processes. Key microbial drivers of the soil MNC index were identified from partial least squares path models. Our results showed that soil DOM composition is closely related to the vegetation types along an elevation gradient, the structure and composition of the microbial community, and soil nutrient status. Overall, values of the double bond equivalent (DBE), modified aromaticity index (AImod) increased, and H/C ratio and molecular lability boundary (MLBL) percentage decreased with elevation. Lignins/CRAM-like structures compounds dominated soil DOM in each vegetation type and its relative abundance decreased with elevation. Aliphatic/protein and lipids components also decreased, but the relative abundance of aromatic structures and tannin increased with elevation. The alpha diversity index of soil bacteria gradually decreased with elevation, with deterministic processes dominating the microbial community assembly in the highest elevation zone. Bacterial communities were conducive to the decomposition of labile degradable DOM compounds (H/C ≥ 1.5) at low elevation. In the cooler and wetter conditions at higher-elevation sites the relative abundance of potentially resistant soil DOM components (H/C < 1.5) gradually increased. Microbial community diversity and composition were important predictors of potential soil nutrient cycling. Although higher elevation sites have higher nutrient cycling potential, soil DOM was assessed to be a more stable carbon store, with apparent lower lability and bioavailability than at lower elevation sites. Overall, this study increases understanding of the potential linkage between soil microbial community, multiple nutrient cycling and DOM fate in subtropical mountain ecosystems that can help predict the effect of climate change on soil carbon sequestration and thus inform ecosystem management.

Molecular insights into the impacts of acid mine drainage on dissolved organic matter dynamics in pit lakes

Pit lakes are artificial hydrological features created by mining operations that typically suffer from acid mine drainage (AMD), which not only endangers water quality but also exacerbates carbon loss. However, the impacts of AMD on the fate and role of dissolved organic matter (DOM) in pit lakes remain unclear. This study employed negative electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with biogeochemical analysis to examine DOM molecular variations and environmental controls across the AMD-induced acidic and metalliferous gradients in five pit lakes. The results demonstrated distinct DOM pools in pit lakes characterized by the prevalence of smaller aliphatic compounds compared to other waterbodies. AMD-induced geochemical gradients promoted DOM heterogeneity among pit lakes, with acidic pit lakes containing more lipid-like compounds. Acidity and metals enhanced DOM photodegradation, reducing the content, chemo-diversity and aromaticity. Organic sulfur was detected in high abundance, potentially from sulfate photo-esterification and mineral flotation agent. Furthermore, microbial involvements in carbon cycling were revealed by DOM-microbe correlation network, but microbial contributions to the DOM pools decreased under acidic and metal stresses. These findings highlight abnormal carbon dynamics caused by AMD pollution and integrate DOM fate into pit lake biogeochemistry, thereby contributing to management and remediation.

Unveiling the roles of dissolved organic matters derived from different biochar in biochar/persulfate system: Mechanism and toxicity

Biochar has been frequently used as a persulfate (PS) activator due to its attractive properties, but dissolved organic matter (DOM) derived from the non‑carbonized part of biochar has received less attention, not to mention its specific role and impact in biochar/PS systems. In this study, wheat straw, municipal sludge, and swine bone were selected as the representative feed stocks of biochar. Subsequently, these three types of biochar were adopted to explore the roles of DOM in biochar/PS systems. Although the composition and amount of DOM derived from different biochar were discrepant, they exhibited similar effect in biochar/PS systems. To be specific, the pore-clogging effect of DOM on biochar suppressed the adsorption capacity and catalytic performance of the three biochar. Furthermore, the removal of DOM decreased the environmental risk of these biochar/PS systems and enhanced the stability of the involved biochar. With respect to the variation in degradation mechanism, the removal of DOM increased the proportion of electron transfer pathway in unison, but the diminution in the roles of O2•¯ and 1O2 was more remarkable in bone-derived-biochar/PS systems. Additionally, the toxicity test illustrated that the leakage and accumulation of DOM were toxic to Chlorella sp., and the DOM from sludge-derived-biochar presented the highest toxicity. Overall, this study analyzes the roles of DOM derived from different biochar in biochar/PS systems and evaluates their environmental risk, which contributes to a comprehensive understanding of the fate of DOM derived from biochar.

Composition of dissolved organic matter (DOM) in wastewater treatment plants influent affects the efficiency of carbon and nitrogen removal

Wastewater treatment plants (WWTPs) play a critical role in receiving, removing, and discharging dissolved organic matter (DOM) in aquatic systems. To date, understanding the composition and fate of DOM in different WWTPs with various environmental and socioeconomic conditions is limited. This study analyzed DOM components in the influent and effluent samples from 49 WWTPs in China using EEM-PARAFAC and ESI-FT-ICR-MS methods. The influencing factors of DOM components in the influent were also analyzed. Geographic location and GDP showed significant (p < 0.05) correlations with DOM components in the influent. The removal efficiency of DOM in WWTPs was closely related to the DOM compositions, where carbohydrates, lipids, and protein-like components (removal efficiencies > 75 %) were more readily decomposed than the humic-like components, lignin, and tannin. The relative fraction of humic-like compound C3 in the influent was correlated negatively with total nitrogen (TN) and chemical oxygen demand (COD) removal in WWTPs (p < 0.05). Besides, the relative fraction of DOM containing the element sulfur also showed significant negative correlations with the humification of DOM (p < 0.05). The results from EEM-PARAFAC and ESI-FT-ICR-MS methods showed no obvious correlation for the DOM characterizations except for humic-like fluorescent fraction C3 and lignin, while significant positive correlations (p < 0.05) between the aromatic index (AI_mod) from the ESI-FT-ICR-MS analysis and the humification index (HIX) from spectrofluorimetry. This supports the use of these spectral indexes as simple surrogates to represent part chemical compositions in further research.

Dissolved organic matter tracers reveal contrasting characteristics in the concentrated flow zone and matrix-with-fractures zone of a sulfate-contaminated karst aquifer in South China

Dissolved organic matter (DOM) is of great importance in biogeochemical processes, such as sulfate reduction, in groundwater. H2S is generated from microbial-mediated sulfate reduction fueled by DOM and erodes carbonate. However, understanding the transformation and fate of DOM in sulfated-contaminated karst aquifers is still poor. Here, fluorescence spectroscopy was used to characterize the DOM pool in the sulfate-contaminated (from human activities) karst aquifer of the Zengpiyan Site, South China, by investigating the groundwater flow system. A comparison of fluorescence DOM (FDOM) characteristics between the concentrated flow zone (CFZ) composed of highly permeable small conduits and fracture networks and the matrix-with-fractures zone (MFZ) made of low permeable fractures and matrix rock aquifers was done. The relative groundwater residence times for all sample sites were estimated using γCa/γMg, which are consistent with those of the groundwater tracer test. The FDOM in groundwater in the CFZ was composed mainly of terrestrial-derived fulvic acid (FA)- and humic acid (HA)-like components, with relatively small contributions of microbially derived tryptophan (TPH)-like components. Compared with CFZ groundwater, the MFZ groundwater showed a longer residence time and reducing conditions, more bioavailable DOM, dominant TPH-like components with relatively small contributions of FA-like components, and fewer humus and hydrophobic structures. Hydrogeological conditions indirectly altered DOM composition by altering the biotic and abiotic activity conditions. The coexistence of relatively strong reducibility conditions and the higher proportion of bioavailable DOM in the MFZ would promote sulfate reduction to H2S gas, possibly amplifying carbonate dissolution, leading to the erosion of cultural relics. It is hoped that this study will contribute to knowledge on DOM behavior in karst aquifers and provide a scientific basis for cave site protection.

Contrasting the physical and chemical characteristics of dissolved organic matter between glacier and glacial runoff from a mountain glacier on the Tibetan Plateau

Accelerated melting of mountain glaciers due to global warming has a significant impact on downstream biogeochemical evolution because a large amount of labile dissolved organic matter (DOM) is released. However, the DOM evolution processes from glacier to downstream are not well understood. To investigate these processes, samples from the glacial surface and terminating runoff of a mountain glacier on the Tibetan Plateau were collected simultaneously throughout the melting season. The samples were analyzed to determine the dissolved organic carbon (DOC) contents and chemical compositions by means of a combination of fluorescence excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results indicate that the DOC concentrations were higher in the snow samples than in the glacial runoff samples, although a significantly higher concentration of inorganic ions was found in the glacial runoff samples, suggesting the dominant source of DOM in the glacial runoff was the glacier. The EEM-PARAFAC revealed four fluorescent components in both the snow and glacial runoff samples. However, significantly different ratios between the four components of these two categories of samples suggested chemical, physical and/or biological evolution of DOM during transport. Molecular chemical composition analyses by FT-ICR MS revealed that the DOM composition varied dramatically between the glacier and the glacial runoff. More than 50 % of the molecules were transformed from aliphatic and peptide-like compounds in the snow samples into highly unsaturated and phenolic-like compounds in the glacial runoff samples. The potential chemical transformation of DOM was likely related to biological and/or photolytic evolution during transport. Our results suggest that chemical evolution of glacial DOM could occur during the downstream transport, which is expected to be useful for further research exploring the fate of DOM and carbon cycling from the cryospheric environment and evaluating the biogeochemical effects.

Linkages Between Optical and Molecular Signatures of Dissolved Organic Matter Along the Yangtze River Estuary-to-East China Sea Continuum

Changes in the molecular composition of dissolved organic matter (DOM) and its light-absorbing component (CDOM) along the river–coastal ocean continuum are crucial for better understanding the source and fate of DOM in coastal oceans. Both optical (absorbance and fluorescence) techniques and ultrahigh-resolution mass spectrometry have been widely used to trace DOM cycling. However, to the best of our knowledge, the linkage between these two techniques is rarely investigated along the river–coastal ocean continuum. In this regard, bulk characterization, optical techniques, and ultrahigh-resolution mass spectrometry [Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS)] were applied to determine the DOM chemistry along a spatial transect from the Yangtze River Estuary (YRE) to the East China Sea. The results showed that DOM in the YRE was mainly controlled by the mixing of freshwater and seawater. Besides terrestrial input, multiple sources (tributary input from the Huangpu River, wastewater input, and sediment resuspension and subsequent release at the turbidity maximum zone) have been identified. In addition, the linkages between CDOM and thousands of formulas were developed based on Spearman’s rank correlations between optical parameters and FT-ICR MS peaks. The linkages showed that the molecular groups associated with the optical parameters generally agreed with conventional biogeochemical interpretations. Nevertheless, each technique has its unique advantage and weakness in interpreting DOM composition. Therefore, the combination of the untargeted FT-ICR MS approach and optical techniques could be valuable for studying the DOM sources and transformation in large river estuarine systems.

Photodegradation, bacterial metabolism, and photosynthesis drive the dissolved organic matter cycle in the Heilongjiang River

Dissolved organic matter (DOM) plays a vital role in the biogeochemistry of aquatic ecosystems. However, the mechanisms of DOM cycling in the water column during different seasons have not been fully elucidated to date. The differences in DOM degradation in summer, autumn, and winter water columns were evaluated in this study. The results showed that bacteria played an essential role in the degradation of DOM in the summer water column. Photochemical degradation was the primary degradation pathway of DOM in the autumn and winter water columns. Notably, while DOM is degraded, photosynthetic bacteria produce organic matter through photosynthesis to replenish the water column. EEM-PARAFAC analysis indicated more tryptophan component C1 in summer, but the contents of humic substance component C2 and terrestrial substance C3 were higher in autumn and winter. In summer, more tryptophan-like components were consumed by bacteria, and Cyanobacteria produced more organic matter through photosynthesis to replenish the water column. Moreover, a similar bacterial community structure and a more active tryptophan biosynthesis pathway were found in autumn and winter. Random forest models identified representative bacteria involved in the DOM transformation process in different seasons. The above findings may be helpful to explore the degradation characteristics of DOM in different seasons and predict the fate of DOM in the water column in the future.

Heterogeneous viral contribution to dissolved organic matter processing in a long-term macrocosm experiment.

Viruses saturate environments throughout the world and play key roles in microbial food webs, yet how viral activities affect dissolved organic matter (DOM) processing in natural environments remains elusive. We established a large-scale long-term macrocosm experiment to explore viral dynamics and their potential impacts on microbial mortality and DOM quantity and quality in starved and stratified ecosystems. High viral infection dynamics and the virus-induced cell lysis (6.23-64.68% d-1) was found in the starved seawater macrocosm, which contributed to a significant transformation of microbial biomass into DOM (0.72-5.32μgL-1d-1). In the stratified macrocosm, a substantial amount of viral lysate DOM (2.43-17.87μgL-1d-1) was released into the upper riverine water, and viral lysis and DOM release (0.35-5.75μgL-1d-1) were reduced in the mixed water layer between riverine water and seawater. Viral lysis was stimulated at the bottom of stratified macrocosm, potentially fueled by the sinking of particulate organic carbon. Significant positive and negative associations between lytic viral production and different fluorescent DOM components were found in the starved and stratified macrocosm, indicating the potentially complex viral impacts on the production and utilization of DOM. Results also revealed the significant viral contribution to pools of both relatively higher molecular weight labile DOM and lower molecular weight recalcitrant DOM. Our study suggests that viruses have heterogeneous impact on the cycling and fate of DOM in aquatic environments.

Fate of dissolved organic matter substructure in a full-scale wastewater treatment plant by using size exclusion chromatography multi-excitation-emission matrix analysis

Dissolved organic matter (DOM) in wastewater treatment plant (WWTP) effluent threats aquatic environment and challenges engineered aquatic systems. In order to predict its environmental risk and guide the selection of suitable strategy and technology, understanding the removal efficiency and the fate of DOM along the treatment is helpful. Herein, to qualitatively and quantitatively estimate the composition of DOM in a full-scale WWTP in northern China, a combined approach of chromatography and spectroscopy was employed, and the contribution of size-dependent substructure to the global feature of DOM was discussed simultaneously. The results suggest that the WWTP could remove the free proteins of low molecular size by physical treatment with removal ratios of 46.4% and 41.0% for tyrosine and tryptophan, respectively, whereas humic-like and humic-protein complex accumulate in the effluent of treatment with a ratio of 40.6%. Biotreatment is of importance for changing the proportion of different types of DOM, especially for anaerobic tank and the anoxic tank, which results in the increase of humification. Size exclusive chromatography (SEC) coupled with multi emission maps identifies six DOM substructures. Two protein-like DOM were removed by the WWTP, except the composition with the molecular weight ranging from 0.75 to 0.25 kDa, whereas humic-like DOM with whole size range accumulated to varying extent. The standard deviation analysis states that the structure variation of bulk DOM in the WWTP is primarily contributed by the decrease of small-sized proteins and the increase of humic-like DOM. This study presents insight into the fate and behavior of DOM components during the full-scale WWTP treatment and provides guidelines for altering DOM-treating technologies. Besides, innovative strategies suggest using DOM as a resource based on the critical review of previous research.

Gradients of Anthropogenic Nutrient Enrichment Alter N Composition and DOM Stoichiometry in Freshwater Ecosystems

AbstractA comprehensive cross‐biome assessment of major nitrogen (N) species that includes dissolved organic N (DON) is central to understanding interactions between inorganic nutrients and organic matter in running waters. Here, we synthesize stream water N chemistry across biomes and find that the composition of the dissolved N pool shifts from highly heterogeneous to primarily comprised of inorganic N, in tandem with dissolved organic matter (DOM) becoming more N‐rich, in response to nutrient enrichment from human disturbances. We identify two critical thresholds of total dissolved N (TDN) concentrations where the proportions of organic and inorganic N shift. With low TDN concentrations (0–1.3 mg/L N), the dominant form of N is highly variable, and DON ranges from 0% to 100% of TDN. At TDN concentrations above 2.8 mg/L, inorganic N dominates the N pool and DON rarely exceeds 25% of TDN. This transition to inorganic N dominance coincides with a shift in the stoichiometry of the DOM pool, where DOM becomes progressively enriched in N and DON concentrations are less tightly associated with concentrations of dissolved organic carbon (DOC). This shift in DOM stoichiometry (defined as DOC:DON ratios) suggests that fundamental changes in the biogeochemical cycles of C and N in freshwater ecosystems are occurring across the globe as human activity alters inorganic N and DOM sources and availability. Alterations to DOM stoichiometry are likely to have important implications for both the fate of DOM and its role as a source of N as it is transported downstream to the coastal ocean.

The fate of dissolved organic matter along the mangrove creek-to-estuary continuum

Dissolved organic matter (DOM) can be transported from mangrove wetlands to the ocean, as a key link in the global carbon cycle. The continuum between mangrove creeks and the ocean is a prime location for facilitating reactions between DOM and sunlight or microbes. Yet, little is known about the sources, transformation, and fate of DOM in the transport continuum at the critical land-to-sea zone. Here, water samples were collected in the estuary of southeastern China along mangrove creeks. We found that DOC concentrations ranged from 6.65 to 110.48 mg/L along the creek-to-estuary continuum. The high accumulation of DOC can be due to the high residence time of seawater and more sensitivity to environmental disturbance. 1.75 times higher DOC concentrations were showed in the lower area than the upper area of the transporting continuum. DOM materials in mangrove creeks were characterized by mostly labile, highly degradable proteins. Terrestrial index (TI) and marine-derived index (MI) were respectively used to described allochthonous and autochthonous characteristics of DOM. The DOM showed a high TI and low MI in the upper area and low TI and high MI in the lower area of outputting continuum. DOM quality along the mangrove to estuary continuum corresponded with environmental heterogeneity. Biodegradation and photo-biodegradation experiments were conducted on DOM samples over 20-days. A rapid 40–65% decrease was observed in DOC concentration in response to biodegradation. About 45% decrease of DOC concentration in photodegradation, afterward less loss in photo-biodegradation than was examined with biodegradation alone. Chromophoric dissolved organic matter (CDOM) concentrations of the continuum were in fluctuating changes during biodegradation. CDOM was preferentially removed 60–90% then increased significantly in photo-biodegradation. Photo-mediated protein-like substances were demonstrated in strong reactions during biodegradation. Compared to biodegradation alone, DOM quality can be distinctly altered during photo-biodegradation. This study demonstrates that DOM quality was gradually homogenized due to interaction with sunlight and microbes during transport from the mangrove creek to the ocean.

Synchronous Biodegradability and Production of Dissolved Organic Matter in Two Streams of Varying Land Use.

In aquatic ecosystems, dissolved organic matter (DOM) composition is driven by land use, microbial activity, and seasonal variation in hydrology and water temperature, and, in turn, its microbial bioavailability is expected to vary due to differences in its composition. It is commonly assumed that DOM of terrestrial origin is resistant to microbial activity because it is composed of more complex aromatic compounds. However, the effect of DOM sources on the microbial reworking and degradation of the DOM pool remains debated. We performed laboratory incubation experiments to examine how temporal changes in DOM composition influence its microbial biodegradability in two contrasting streams (agricultural and forested) in southern Ontario, Canada. Despite a more allochthonous-like DOM signature in the forest stream and a more autochthonous-like DOM signature in the agriculture stream, we found that biodegradation and production of DOC were the same in both streams and synchronous throughout the sampling period. However, the initial DOM composition impacted how the DOM pool changed upon degradation. During the incubations, both autochthonous-like and allochthonous-like fractions of the DOM pool increased. We also found that a greater change in DOM composition during the incubations induced higher degradation of carbon. Finally, temporal variation in DOC biodegradation and production over time or across streams was not related to DOM composition, although there was a significant relationship between BDOC and nutrient concentrations in the agriculture stream. This observation potentially challenges the notion that DOM origin predicts its bioavailability and suggests that broad environmental factors shape DOC consumption and production in aquatic ecosystems. More research is needed to better understand the drivers of microbial biodegradability in streams, as this ultimately determines the fate of DOM in aquatic ecosystems.

Adsorption and molecular weight fractionation of dissolved organic matters with different origins on colloidal surface

Dissolved organic matter (DOM) adsorption on colloid surface occurred ubiquitously in aquatic ecosystems, while variations in molecular weight (MW) distribution during adsorption remained poorly understood. In this study, the adsorption and MW fractionation of aquatic DOMs with different origins (e.g., macrophyte- and algae-derived, MDOM and ADOM, respectively) on colloid surface were examined using total organic carbon, absorption and fluorescence spectroscopy, and flow field flow fractionation (FlFFF) analysis. Both the total organic carbon and spectroscopic results showed the predominant adsorption of DOMs within the first 45 min, which behaved not synchronously with MW fractionation. Quantitative FlFFF analysis further indicated that the organic ligands with different MWs exhibited different adsorption affinities on colloid surface. It was found that 5–15 kDa and 50 kDã0.45 μm were preferential adsorption fraction for humic- and protein-like MDOM, respectively, while 0.3–2 kDa and 0.3–50 kDa were preferential adsorption fraction for humic- and protein-like ADOM, respectively. Therefore, the MW fractionation of DOMs upon adsorption was highly dependent on DOM origins as well as specific components. Results obtained herein can enlarge our insights into adsorption and the resultant behavior and fate of DOMs that were highly related with the MW fractionation in aquatic environments.

The composition difference of macrophyte litter-derived dissolved organic matter by photodegradation and biodegradation: Role of reactive oxygen species on refractory component.

The overgrowth of macrophytes has become serious due to increasing eutrophication in shallow lakes. The primary degradation processes of macrophytes litter, including photodegradation and biodegradation, induce considerable patchiness in the concentration and bioavailability of dissolved organic matter (DOM). In this study we investigated the composition evolution of DOM derived from emergent aquatic plant litter, Phragmites australis, in microbial degradation, photodegradation, and the combination of bio- and photo-degradation. Results revealed that the effects of photo- and biodegradation on the composition difference of macrophyte litter-derived DOM during short- and long-term degradation phase were different. Although large changes in DOM were observed after five days of incubation, the abundance and chemical composition were similar in the three treatments. However, more concentration of DOM was produced by combined photo- and biodegradation at the long-term degradation phase, and the composition of DOM showed less lignin-like formulae, as well as less condensed aromatic and aromatic compounds when compared to sole treatments. More reactive oxygen species (ROS) were found under the combined treatments, thus the contents of refractory components (condensed aromatic- and aromatic compound groups) were reduced. This study provide deeper insight into the fate of DOM and relevant biogeochemical processes in eutrophic lakes.