Riverine Dissolved Organic Matter Research Articles

Photochemical fate of β-blocker pindolol in riverine and its downstream coastal waters

Pindolol (PIN) is a commonly used β-blocker drug and has been frequently detected in various natural waters. Comprehensive understanding of its environmental photochemical transformation is necessary to assess its environmental risk. In this study, the photodegradation kinetics and mechanisms of PIN in both freshwater and coastal water were investigated for the first time. The photodegradation experiments were carried out by steady-state photochemical experiment under simulated sunlight irradiation. The results showed that the photodegradation rate of PIN in the freshwater of the Pearl River estuary was significantly faster than that in its downstream coastal water. In river water, PIN can undergo both direct photolysis and indirect photolysis induced by riverine dissolved organic matter (DOM) mainly through excited triplet-state of DOM and singlet oxygen, while direct photolysis dominated its degradation in coastal water. The promotion effect was found to be much greater for Suwannee River Natural Organic Matter (SRNOM) than that of the sampled riverine DOM, due to its high steady-state concentrations of reactive species. Interestingly, coastal DOM in northern and southern China were found to have similar promotion effects on PIN photodegradation for the first time, but both less than that of riverine DOM. A total of seven degradation products of PIN resulting from hydroxylation, hydrogen abstraction and cleavage of ether bond were identified. Biological toxicity of one products were found to be higher than that of PIN. These results are of significance for knowing the persistence and ecological risk of PIN in natural waters.

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.

Peatlands Versus Permafrost: Landscape Features as Drivers of Dissolved Organic Matter Composition in West Siberian Rivers

AbstractWest Siberia contains some of the largest soil carbon stores on Earth owing to vast areas of peatlands and permafrost, with the region warming far faster than the global average. Organic matter transported in fluvial systems is likely to undergo distinct compositional changes as peatlands and permafrost warm. However, the influence of peatlands and permafrost on future dissolved organic matter (DOM) composition is not well characterized. To better understand how these environmental drivers may impact DOM composition in warming Arctic rivers, we used ultrahigh resolution Fourier‐transform ion cyclotron resonance mass spectrometry to analyze riverine DOM composition across a latitudinal gradient of West Siberia spanning both permafrost‐influenced and permafrost‐free watersheds and varying proportions of peatland cover. We find that peatland cover explains much of the variance in DOM composition in permafrost‐free watersheds in West Siberia, but this effect is suppressed in permafrost‐influenced watersheds. DOM from warm permafrost‐free watersheds was more heterogenous, higher molecular weight, and relatively nitrogen enriched in comparison to DOM from cold permafrost‐influenced watersheds, which were relatively enriched in energy‐rich peptide‐like and aliphatic compounds. Therefore, we predict that as these watersheds warm, West Siberian rivers will export more heterogeneous DOM with higher average molecular weight than at present. Such compositional shifts have been linked to different fates of DOM in downstream ecosystems. For example, a shift toward higher molecular weight, less energy‐rich DOM may lead to a change in the fate of this material, making it more susceptible to photochemical degradation processes, particularly in the receiving Arctic Ocean.

Linking the source, molecular composition, and reactivity of dissolved organic matter in major rivers across the pearl river delta

Dissolved organic matter (DOM) constitutes a substantial portion of the global carbon cycle and serves as the largest reservoir of reactive carbon on Earth. Studying DOM's sources, molecular compositions, and reactivity is central to understanding the fate and environmental effects of organic carbon, yet, links between DOM composition and reactivity remain to be established. In this study, stable carbon isotopic composition and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) were combined with degradation experiments to comprehensively study DOM's properties in the major rivers across the Pearl River Delta (PRD) in South China. The increasing δ13C-DOC along the Pearl River at the PRD suggests that terrestrial DOM from upstream was gradually diluted by local processes. Although affected by different interaction patterns of multiple sources, a major component of DOM, enriched in CHO and lignins, is molecularly indistinguishable in different rivers (molecular Bray-Curtis dissimilarity of 15%–31%). The photo-degradation removed 34% (PDOC%) of initial DOM within 14 days, twice that by biodegradation (BDOC%). In contrast to earlier research, the distinctive integration of molecular characterization with DOM degradation kinetics indicates that both regional (common shared molecules) and local (partial shared and unique molecules) derived DOM play a collective role in governing the bio-degradation kinetics of DOM, while the photo-degradation kinetics of DOM are barely correlated to molecular composition. The thorough investigation of DOM molecular composition and its correlation with bulk DOM properties in the PRD region, though requiring further investigation into its mechanisms, offers valuable insights into the role of riverine DOM in coastal hypoxia and the global carbon cycle.

Deciphering riverine dissolved organic matter biodegradation: Evidence from three-dimensional fluorescence

Biological degradation contributes significantly to aquatic dissolved organic matter (DOM) turnover. Yet to date, the specific biological pathways involved in DOM degradation are still obscure. Here, we show how DOM changes in response to 28-d incubation in a karst river, via the combined fluorescent excitation-emission matrix (EEM) with parallel factor analysis (PARAFAC) and peak picking. Tyrosine-, tryptophan- and UV humic-like components were identified as the primary DOM in original waters. Notable decreases of protein-like components were observed after 15 ℃ incubation, suggesting preferential consumption of biogenic DOM. Elevated temperature (30 ℃), however, caused significant decreases in visible humic-like and terrestrial fulvic-like components, but an increase in UV humic-like components in comparison to 15 ℃ incubation (p < 0.05). Humification index (HIX) decreased dramatically after 15 ℃ incubation, indicating that biological processes regulated river DOM properties. Our results highlight the significant biogenic signals in karst rivers, and evidence that fluorescence measurement can decipher riverine DOM biodegradation as a useful approach.

Exploring the Complexities of Dissolved Organic Matter Photochemistry from the Molecular Level by Using Machine Learning Approaches.

Dissolved organic matter (DOM) sustains a substantial part of the organic matter transported seaward, where photochemical reactions significantly affect its transformation and fate. The irradiation experiments can provide valuable information on the photochemical reactivity (photolabile, photoresistant, and photoproduct) of molecules. However, the inconsistency of the fate of irradiated molecules among different experiments curtailed our understanding of the roles the photochemical reactions have played, which cannot be properly addressed by traditional approaches. Here, we conducted irradiation experiments for samples from two large estuaries in China. Molecules that occurred in irradiation experiments were characterized by the Fourier transform ion cyclotron resonance mass spectrometry and assigned probabilistic labels to define their photochemical reactivity. These molecules with probabilistic labels were used to construct a learning database for establishing a suitable machine learning (ML) model. We further applied our well-trained ML model to "un-matched" (i.e., not detected in our irradiation experiments) molecules from five estuaries worldwide, to predict their photochemical reactivity. Results showed that numerous molecules with strong photolability can be captured solely by the ML model. Moreover, comparing DOM photochemical reactivity in five estuaries revealed that the riverine DOM chemistry largely determines their subsequent photochemical transformation. We offer an expandable and renewable approach based on ML to compatibly integrate existing irradiation experiments and shed insight into DOM transformation and degradation processes.

High Voltage: The Molecular Properties of Redox-Active Dissolved Organic Matter in Northern High-Latitude Lakes.

Redox-active functional groups in dissolved organic matter (DOM) are crucial for microbial electron transfer and methane emissions. However, the extent of aquatic DOM redox properties across northern high-latitude lakes and their relationships with DOM composition have not been thoroughly described. We quantified electron donating capacity (EDC) and electron accepting capacity (EAC) in lake DOM from Canada to Alaska and assessed their relationships with parameters from absorbance, fluorescence, and ultrahigh resolution mass spectrometry (FT-ICR MS) analyses. EDC and EAC are strongly tied to aromaticity and negatively related to aliphaticity and protein-like content. Redox-active formulae spanned a range of aromaticity, including highly unsaturated phenolic formulae, and correlated negatively with many aliphatic N and S-containing formulae. This distribution illustrates the compositional diversity of redox-sensitive functional groups and their sensitivity to ecosystem properties such as local hydrology and residence time. Finally, we developed a reducing index (RI) to predict EDC in aquatic DOM from FT-ICR MS spectra and assessed its robustness using riverine DOM. As the hydrology of the northern high-latitudes continues to change, we expect differences in the quantity and partitioning of EDC and EAC within these lakes, which have implications for local water quality and methane emissions.

Spatiotemporal response of dissolved organic matter diversity to natural and anthropogenic forces along the whole mainstream of the Yangtze River

The Yangtze River, the largest river in Asia, plays a crucial role in linking continental and oceanic ecosystems. However, the impact of natural and anthropogenic disturbances on composition and transformation of dissolved organic matter (DOM) during long-distance transport and seasonal cycle is not fully understood. By using a combination of elemental, isotopic and optical techniques, as well as Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), we investigated DOM abundance and composition along the whole mainstream at highly spatial resolution in the dry and early wet seasons. Our findings showed that the concentration and flux of dissolved organic carbon (DOC) in the Yangtze River was much lower compared with other worldwide larger rivers. The distribution of δ13CDOC and higher abundance of humic-like fluorescent component and highly unsaturated and phenolics (HUPs) compound reflected a prominent contribution of allochthonous DOM. Further optical and molecular analysis revealed humic-like fluorescent components were coupled with CHO molecules and HUPs compound with higher aromatic, unsaturated, molecular weight and stable characteristics between upstream and midstream reaches. With increasing agricultural and urban land downstream, there were more heteroatomic formulae and labile aliphatic and protein-like compounds which were derived from human activities and in situ primary production. Meanwhile, DOM gradually accumulates with slow water flow and additional autochthonous organics. Weaker solar radiation and water dilution during the dry/cold season favours highly aromatic, unsaturated and oxygenated DOM compositions. Conversely, higher discharge during the wet/warm season diluted the terrestrial DOM, but warm temperatures could promote phytoplankton growth that releases labile aliphatic and protein-like DOM. Besides, chemical sulfurization, hydrogenation and oxygenation were found during molecular cycling processes. Our research emphasizes the active response of riverine DOM to natural and anthropogenic controls, and provides a valuable preliminary background to better understand the biogeochemical cycling of DOM in a larger river.

Separately tracking the sources of hydrophobic and hydrophilic dissolved organic matter during a storm event in an agricultural watershed

The hydrophobicity of dissolved organic matter (DOM) affects various aspects of its environmental impacts in terms of water quality, sorption behaviors, interactions with other pollutants, and water treatment efficiency. In this study, source tracking of river DOM was conducted separately for hydrophobic acid (HoA-DOM) and hydrophilic (Hi-DOM) fractions using end-member mixing analysis (EMMA) in an agricultural watershed during a storm event. EMMA with optical indices of bulk DOM revealed larger contributions of soil (24 %), compost (28 %), and wastewater effluent (23 %) to riverine DOM under high versus low flow conditions. Molecular level analysis of bulk DOM revealed more dynamic features, showing an abundance of CHO and CHOS formulae in riverine DOM under high- and low flow conditions. CHO formulae originated from soil (78 %) and leaves (75 %) and contributed to the increasing CHO abundance during the storm event, whereas CHOS formulae likely originated from compost (48 %) and wastewater effluent (41 %). The characterization of bulk DOM at the molecular level demonstrated that soil and leaves are the dominant contributors for the high-flow samples. However, in contrast to the results of bulk DOM analysis, EMMA with HoA-DOM and Hi-DOM revealed major contributions from manure (37 %) and leaf DOM (48 %) during storm events, respectively. The results of this study highlight the importance of individual source tracking of HoA-DOM and Hi-DOM for the proper evaluation of the ultimate roles of DOM in affecting river water quality and for a better understanding of DOM dynamics and transformation in natural and engineered systems.

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

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

Interactions between dissolved organic matter and the microbial community are modified by microplastics and heat waves

Dissolved organic matter (DOM) exists widely in natural waters and plays an important role in river carbon cycles and greenhouse gas emissions through microbial interactions. However, information on DOM–microbe associations in response to environmental stress is limited. River environments are the main carriers of microplastic (MP) pollution, and global heat waves (HWs) are threatening river ecology. Here, through MP exposure and HW simulation experiments, we found that DOM molecular weight and aromaticity were closely related to initial microbial communities. Moreover, MP-derived DOM regulated microbial community abundance and diversity, influenced microorganism succession trajectories as deterministic factors, and competed with riverine DOM for microbial utilization. SimulatedHWs enhanced the MP-derived DOM competitive advantage and drove the microbial community to adopt a K-strategy for effective recalcitrant carbon utilization. Relative to single environmental stressor exposure, combined MP pollution and HWs led to a more unstable microbial network. This study addresses how MPs and HWs drive DOM–microbe interactions in rivers, contributes to an in-depth understanding of the fate of river DOM and microbial community succession processes, and narrows the knowledge gap in understanding carbon sinks in aquatic ecosystems influenced by human activities and climate change.

Seasonal Variations of Dissolved Organic Matter in Urban Rivers of Northern China

Dissolved organic matter (DOM) is ubiquitously present in aquatic environments, playing an important role in the global carbon cycle and water quality. It is necessary to reveal the potential sources and explore spatiotemporal variation of DOM in rivers, especially in urban zones impacted by human activities. It was designed to aim to explore spatiotemporal variations of DOM in urban rivers and ascertain the influencing factors. In this study, dissolved organic carbon (DOC) concentrations, UV-Vis absorption spectroscopy, and 3D fluorescence spectroscopy combined with parallel factor analysis were utilized to characterize DOM composition in urban rivers (the Jiyun, Chaobai, and Yongding rivers) in Tianjin city, northern China. The results showed that DOC (1.28 to 25.85 mg·L−1), generally, was at its highest level in spring, followed by summer, and lowest in autumn and winter, and that the absorption parameters E250:365 (condensation degree/molecular weight, 7.88), SUVA254 (aromaticity, 3.88 L mg C−1 m−1), a355 (content of chromophores, 4.34 m−1), a260 (hydrophobicity, 22.02 m−1), and SR (molecular weight, 1.08) of CDOM (chromophoric DOM) suggested that DOM is mainly composed of low-molecular-weight fulvic acid and protein-like moieties, and had the capability of participating in pollutant migrations and transformations. The results demonstrated significant seasonal differences. Generally, high DOC content was detected in rivers in urban suburbs, due to anthropogenic inputs. Three fluorescence components were identified, and the fluorescence intensity of the protein class reached the highest value, 294.47 QSU, in summer. Different types of land use have different effects on the compositions of riverine DOM; more protein-like DOM was found in sections of urban rivers. The correlation between DOC concentration and the CDOM absorption coefficient was found to be unstable due to deleterious input from industrial and agricultural wastewater and from domestic sewage from human activities. HIX and BIX elucidated that the source of CDOM in three river watersheds was influenced by both terrestrial and autochthonous sources, and the latter prevailed over the former. Geospatial data analysis indicated that CDOM in autumn was sourced from plant detritus degradation from forest land or from the urban green belt; construction land had a great influence on DOC and CDOM in riparian buffer areas. It was revealed that DOM in the watershed is highly impacted by nature and human activities through land use, soil erosion, and surface runoff/underground percolation transport; domestic sewage discharge constituted the primary source and was the greatest determiner among the impacts.

Origin, composition, and accumulation of dissolved organic matter in a hypersaline lake of the Qinghai-Tibet Plateau

Inland saline lakes are widely distributed and commonly exist in arid and semi-arid regions. Dissolved organic matter (DOM) in saline lakes plays an important role in the global carbon cycle and is a key regulator of saline lake ecosystem functions through biotic and abiotic processes. However, the origin, composition, and cycling of DOM in saline lakes, especially hypersaline lakes, remain largely unknown. In this study, two lake brine DOM samples and three input river DOM samples from a hypersaline lake, Da Qaidam Lake (DQL) in the Qaidam Basin of the Qinghai-Tibet Plateau (QTP), were isolated and analyzed using a multi-analytical approach. The results indicated that, although terrestrial in origin, the DOM composition and features of DQL were dominated by indigenous in-lake processes owing to the very long water residence time of the lake brine. Lake DOM contained more aliphatic compounds but fewer aromatic compounds than DOM from the rivers. Lake DOM also exhibited more chemodiversity and contained highly saturated and oxidized components that were incorporated with heteroatoms. Despite the limited contributions from riverine DOM, some special features of lake DOM, such as the high content of sulfur-bearing components, may be partly related to the long-term accumulation of hotspring riverine input. Flocculation, photodegradation, microbial degradation, evapo-concentration, and primary production processes were considered synergistic factors in the persistence and features of the hypersaline lake DOM. The results of this study can further our knowledge of the transformation and long-term turnover of DOM in hypersaline lakes and how DOM chemodiversity changes across wide aquatic ecosystems.

Response of dissolved organic matter chemistry to flood control of a large river reservoir during an extreme storm event

With the frequent occurrence of extreme floods under global climate change-induced storm events, reservoir operation has been highlighted for river flood control, complicating the transport and transformation of riverine dissolved organic matter (DOM), one of the largest reactive carbon pools on earth. In particular, the response of riverine DOM chemistry to reservoir flood control during extreme storm events is still unclear. To fill this knowledge gap, the mechanism of DOM variation in Yangtze River with the world's largest Three Gorges Reservoir (TGR) operation during an extreme storm event was explored. Optical and molecular properties of DOM varied significantly from upstream to downstream in non-TGR area, while no significant variation in DOM chemistry was observed in TGR area. The results uncovered a short time transformation of DOM from non-TGR area to TGR area, demonstrating that although storm event induced chemodiversity bloom of riverine DOM, flood control of TGR “re-constrained” DOM to more similar chemistry mainly under the influence of turbidity involved DOM transformation (e.g., adsorption/desorption and flocculation). Furthermore, combined with the hydrological information, we found that although TGR temporarily blocked dissolved organic carbon (DOC) flow during the flood event, the abundance of biologically recalcitrant DOC increased in TGR, which would contribute to its further transportation to downstream watershed. This study emphasizes the impact of TGR on extreme storm event-induced DOM dynamics, which also hints a better understanding of the crucial role of anthropogenic activity in affecting carbon cycling under extreme climate change.

Temperature effects on microbial dissolved organic matter metabolisms: Linking size fractions, fluorescent compositions, and functional groups

This study elucidated the compositional and structural variations of size fractions of microbially-induced dissolved organic matter (DOM) caused by short-term temperature changes (5 to 35 °C), taking riverine DOM as an example. A simple and efficient method combining fractionation-[parallel factor analysis and two-dimensional Fourier-transform infrared correlation spectroscopy (PARAFAC-2D FTIR COS)]-correlation was introduced to link fluorescent DOM components and their structures in terms of surface functional groups. Results indicated that the higher temperature stimulated the decomposition of aromatics (sizes decreased from 10 kDa-0.22 μm to <10 kDa) and the transformation of proteins to humics (with sizes <0.22 μm); while both the higher and lower temperatures inhibited the utilization of larger-sized DOM (>0.22 μm, especially the non-fluorescence part) and synthesis of larger-sized microbial-derived proteins and humics (>0.22 μm), which may result in more smaller-sized (<10 kDa) and refractory aromatics transported from rivers to oceans in the warming future. However, the structure-determined DOM behaviors could be less affected by temperature since the fluorescent proteins and humics revealed similar functional group compositions, such as carboxyl, hydroxyl, carbonyl/aldehyde, carboxylic anhydride, and carboxamide groups. These findings have strong implications for DOM biogeochemistry in future temperature-shock scenarios. The proposed method will support in-depth analyses of structure-regulated processes from a mechanistic perspective.

Spatiotemporal Variation of Riverine Dissolved Organic Matter Degradation Based on EEMs-PARAFAC: A Case Study of Shili River in Jiujiang, Jiangxi Province, China, as a Typical Demonstration City of the Yangtze River protection Strategy

This study investigated the spatio-temporal distribution of dissolved organic matter (DOM) composition and its sources before and after degradation in the Shili River watershed in Jiujiang (China). Spatio-temporal variation of riverine DOM water samples before and after five days of degradation in a simulated channel was characterized by spectral feature analysis using three-dimensional excitation-emission matrix fluorescence spectroscopy coupled with parallel factor analysis. Across all water samples (#1,#2 and #3) before and after degradation, a total of four fluorescent components in DOM were identified: C1, C2, C3, and C4. The aromaticity index (SUVA254) was negatively correlated with the C2 and C3 components and biological index (BIX) and freshness index (β:α), but it had little correlation with the humification index (HIX). The greater the aromaticity of DOM in water, the lower the proportion of recently produced DOM and its biological activity. The C3 component had a strong positive correlation with BIX, β:α, and C2. The results suggested that C2 and C3 were derived from the same substances. According to the fluorescence parameters, DOM was dominated by autochthonous contributions. The fluorescence intensity of DOM increased gradually along the direction of water flow. The increase of water temperature in spring and autumn enhanced the endogenous level of DOM. The levels and fluctuations of BIX and β:α in different seasons and different sampling points were basically consistent. DOC concentration does not fully represent the localized nature of the DOM. The analysis of some fluorescence parameters and light absorption parameters showed that the DOM source was more internal than terrestrial. This study reveals the composition, source and temporal and spatial characteristics of DOM in the Shili River Basin, which has theoretical guiding significance for water environment management.

Variation in riverine dissolved organic matter (DOM) optical quality during snowmelt- and rainfall-driven events in a forested wetland watershed

The spring snowmelt period is an important time for organic matter mobilization and export in peatland and wetland dominated systems. The hydrologic flowpaths that transport melting snow and soil water to surface waters can vary over relatively short time periods (several days to weeks) depending on the timing and rate of melt and the occurrence of freeze–thaw cycles and rain-on-snow events. Dynamic flowpaths can alter dissolved organic carbon (DOC) concentrations and dissolved organic matter (DOM) optical properties in surface waters due to differential melt and mobilization of snow, ice, and soil waters. In 2018 and 2020, we measured the DOC concentration and DOM optical properties in a woody wetland-dominated watershed in northern Minnesota during spring snowmelt (2018 & 2020) and early growing season (2018 only) events. We examined patterns in riverine DOC, DOM, and hydrochemical tracers across event hydrographs to infer changes in hydrologic connectivity across this seasonal transition. Measurements of riverine DOM optical properties, calcium concentration, and water isotopic composition indicated that DOM shifted from a primarily groundwater source and more fresh character during the dormant season to a more shallow wetland soil source and recalcitrant character during the early growing season. Seasonal variations in DOM optical properties and highly complex hysteresis patterns of DOM indices (e.g., Fluorescence Index, Humification Index, β/α, E250:E365, and the fluorescence peak ratio T:C) during individual events may reflect spatial heterogeneity in soil thawing throughout the watershed and temporal variations in water table elevation, affecting flowpath depths and connectivity to DOM pools within the soil profile. This study provides an important seasonal and event-scale baseline against which to evaluate potential changes in riverine DOM quantity and quality associated with predicted changes in climate and snow cover in organic matter-rich ecosystems.

Seasonally variable interactions between dissolved organic matter and mineral particles in an agricultural river

Streams and rivers form an important link in the global carbon cycle by transporting and transforming large amounts of carbon imported from terrestrial ecosystems to the oceans. Since streams in agricultural areas often experience increased concentrations of suspended mineral particles from soil erosion, they are important sites where dissolved organic carbon (DOC) may be adsorbed to particles and retained in the sediment. As the extent of adsorption varies with the molecular composition of dissolved organic matter (DOM), which is seasonally variable, we expect also the fraction of organic material that adsorbs to mineral particles to fluctuate over time. We sampled the agriculturally impacted River Fyrisån (Sweden) monthly during 1 year, and measured DOC concentration and DOM composition based on several optical properties. At each sampling occasion, we estimated the potential for adsorption by exposing the samples to a reference clay. The potential for adsorption was greatest when riverine DOM had the most terrestrial character, as this fraction of the DOM pool was selectively adsorbed to clay surfaces. The extent of adsorption was negatively related to the concentration of base cations, most notably calcium. We suggest that the observed relationships between the potential for adsorption, DOM composition and base cations are linked by discharge. A bioavailability test at one sampling occasion suggested that DOM remaining after exposure to clay particles was more biodegradable. This implies that adsorption may alter the degradation potential of DOM remaining in solution, which could have far reaching effects on the fate of organic carbon.

Insights into the role of the microbial community lifestyle strategies in variations of the dissolved organic matter molecular composition along an effluent-dominated river

Urbanization has dramatically changed the quality and quantity of dissolved organic matter (DOM) fluxes in rivers, thereby affecting the diversity and lifestyle strategies of microbial communities. However, relationships between DOM molecular composition and microbial lifestyle strategies in effluent-dominated rivers are poorly understood. Herein, we investigated the variations in DOM structure and composition of an effluent-dominated river and further revealed how these changes alter the abundance and lifestyle strategies of microbial communities. Results demonstrated that macromolecular (MW > 35 kDa) humic-like substances constituted the major components of effluent-dominated riverine DOM. Also, due to the degradation of humic-like substances, the accumulation of protein-like substances was observed from upstream to downstream areas, corresponding to an apparent decrease in overall aromaticity. The abundance of bacterial, Actinobacteria, and eukaryotic was higher in the upstream and midstream areas but relatively lower in the downstream area. The response of bacterial and Actinobacteria communities to the changes in DOM composition was more prominent as compared to that of eukaryotic. Based on multivariate statistical analysis, the decrease in aromatic components (MW > 35 kDa) was mainly attributed to the degradation of Proteobacteria and Actinobacteria (K-strategists), resulting in a decrease in their relative abundance along the river course. Proteins and polysaccharides (15 kDa < MW < 35 kDa, MW < 6 kDa) were more easily utilized by Firmicutes and Bacteroidetes (r-strategists), leading to an increase in their relative abundance. With the decrease of macromolecular humic-like substances and the increase of protein-like substances, river microbial communities shifted from K-strategists to r-strategists. This work unveils the evolution of DOM in an effluent-dominated river and the influence of the degradation of macromolecular humic-like substances on r/K-strategists.

The Contribution of Endmembers to Mixtures of Leaf Leachates and Riverine DOM can be Determined by Measuring Their Size and Fluorescence Properties

The molecular mass distribution (MMD) and fluorescence properties of dissolved organic matter (DOM) are important characteristics for tracing and predicting its pathways, processes, and fate in aquatic systems. For the first time, asymmetrical flow field-flow fractionation (AF4) with coupled absorbance and fluorescence detectors was used to determine the contribution of endmembers to three mixtures of leaf leachate and riverine DOM in various proportions. Parallel factor analysis (PARAFAC) and fractogram deconvolution were used to decompose and distinguish the size distributions and fluorescence excitation-emission matrices (EEMs) of mixture constituents. It was determined that: 1) Both size and optical properties were conservative tracers in mixtures; 2) Fractogram deconvolution was extremely helpful for discriminating endmember size properties; 3) The contributions of endmembers to overall DOC concentration were accurately estimated using both the proportion of a humic-like PARAFAC component (0.93 &amp;lt; R2 &amp;lt; 1.00), and the ratios of deconvoluted peaks (0.88 &amp;lt; R2 &amp;lt; 0.98). The fluorescence at the peak maximum of the MMD was lacking in protein-/polyphenol-like and microbial humic-like fluorescence compared to the whole sample (−11 ± 9 and −10 ± 7%, respectively); however, the contribution of endmembers to the MMD (A254) were also effectively predicted using both the proportion of a microbial humic-like PARAFAC component (0.91 &amp;lt; R2 &amp;lt; 0.98) and the ratio of deconvoluted peaks (0.94 &amp;lt; R2 &amp;lt; 0.98).