Dissolved Organic Matter Inputs Research Articles

Distribution of nutrients and dissolved organic matter in a eutrophic equatorial estuary: the Johor River and the East Johor Strait

Abstract. Estuaries have strong physicochemical gradients that lead to complex variability and often high rates of biogeochemical processes, and they are also often impacted by humans. Yet, our understanding of estuarine biogeochemistry remains skewed towards temperate latitudes. We examined seasonal and spatial variability in dissolved organic matter (DOM) and nutrients along a partly eutrophic, agricultural–urban estuary system in Southeast Asia: the Johor River and the East Johor Strait. Dissolved organic carbon (DOC) and coloured DOM (CDOM) showed non-conservative mixing, indicating significant DOM inputs along the estuary. The CDOM spectral slopes and CDOM : DOC ratios suggest that terrigenous, soil-derived DOM dominates along the Johor River, while phytoplankton production and microbial recycling are important DOM sources in the Johor Strait. CDOM properties were not unambiguous source indicators in the eutrophic Johor Strait, which is likely due to heterotrophic CDOM production. Nitrate concentrations showed conservative mixing, while nitrite concentrations peaked at intermediate salinities of 10–25. Ammonium concentrations decreased with salinity in the Johor River but increased up to 50 µmol L−1 in the Johor Strait, often dominating the dissolved inorganic nitrogen (DIN) pool. Phosphate concentrations were low (<0.5 µmol L−1) throughout the Johor River but increased in the Johor Strait, where DIN : phosphate ratios were typically ≥ 16 : 1. This suggests that the Johor Strait may experience phosphorus limitation and that internal recycling is likely important for maintaining high nutrient concentrations in the Johor Strait. Overall, our results indicate that the Johor River and Johor Strait are clearly not part of the same estuarine mixing continuum and that nutrient recycling processes must be quantified to understand nutrient dynamics in the Johor Strait. Moreover, our results highlight the need for better techniques for DOM source tracing in eutrophic estuaries.

Impact of Hill Fires on Dissolved Organic Matter in Watersheds of Karst Areas Based on Three-Dimensional Fluorescence-Parallel Factor Analysis

Hill fires have the potential to influence dissolved organic matter (DOM) in water bodies, yet fewer studies have investigated the effects of hill fires on DOM within watersheds in karst areas. In this study, we employed the three-dimensional fluorescence-parallel factor analysis (EEM-PARAFAC) method to analyze the DOM fluorescence peaks, component compositions, fluorescence indices, and sources within the water body of the Yuanteng River sub-basin, which was impacted by the hill fire, serving as our primary research focus. The results indicate the presence of three primary fluorescent fractions in the water body of the Yuanteng River: C1, resembling humic acid (fulvic acid); C2, consisting of biopolymers and microbial by-products; and C3, containing proteins such as tyrosine and tryptophan. The Yuanteng River exhibited elevated levels of humus-like substances, diminished concentrations of protein-like substances, and demonstrated higher biogenic, freshness, and humification indices compared to unaffected water samples, reflecting the impact of the hill fire. Elevated levels of exogenous humic acid-like inputs into the waters of the Yuanteng River, along with exogenous inputs of DOM, were primarily influenced by stable, high-molecular-weight organic matter. Additionally, agricultural effluent, domestic sewage, and anthropogenic activities contributed to these inputs to a lesser degree. The impacts of endogenous inputs are mainly related to the restoration of ecosystems. The occurrence of hill fires has significantly influenced the composition of dissolved organic matter in the waters of the Yuanteng River. A comprehensive analysis of the impacts of hill fires on dissolved organic matter in water bodies can serve as a valuable reference for characterizing DOM in the water bodies of the Yuanteng River. Furthermore, it can inform strategies for environmental protection, facilitate the traceability of pollutants in water bodies, and contribute to environmental and ecological restoration efforts following hill fires in the region.

Humic-like components in dissolved organic matter inhibit cadmium sequestration by sediment

China's lakes are plagued by cadmium (Cd) pollution. Dissolved organic matter (DOM) significantly regulates Cd(II) transport properties at the sediment-water interface. Understanding the effects of different DOM components on the transportation properties of Cd(II) at the sediment-water interface is essential. In this study, typical DOM from different sources was selected to study Cd(II) mobility at the sediment-water interface. Results showed that terrestrial-derived DOM (fulvic acids, FA) and autochthonous-derived DOM (α-amylase, B1) inhibit Cd(II) sequestration by sediments (42.5% and 5.8%, respectively), while anthropogenic-derived DOM (sodium dodecyl benzene sulfonate, SDBS) increased the Cd(II) adsorption capacity by sediments by 2.8%. Fluorescence quenching coupling with parallel factor analysis (EEM-PARAFAC) was used to characterize different DOM components. The results showed that FA contains three kinds of components (C1, C3: protein-like components, C2: humic-like components); SDBS contains two kinds of components (C1, C2: protein-like components); B1 contains three kinds of components (C1, C2: protein-like components, C3: humic-like components).Three complex reaction models were used to characterize the ability of Cd(II) complex with DOM, and it was found that the humic-like component could hardly be complex with Cd(II). Accordingly, humic-like components compete for Cd(II) adsorption sites on the sediment surface and inhibit Cd(II) adsorption from sediments. Fourier transform infrared spectroscopy (FTIR) of the sediment surface before and after Cd(II) addition was analyzed and proved the competitive adsorption theory. This study provides a better understanding of the Cd(II) mobilization behavior at the sediment-water interface and indicates that the input of humic-like DOM will increase the bioavailability of Cd.

Anthropogenic dissolved organic matter accumulation fuels greenhouse gas diffusive emissions in urban lakes along trophic state levels

Lakes are an important reservoir of dissolved organic matter (DOM) and also emit large amounts of greenhouse gases (GHGs), such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). Yet, the linkages between quantity and quality of DOM and GHGs emissions are still not well understood. Hence, we investigated how DOM optical properties mediated dissolved GHGs levels and diffusive fluxes along a trophic state level in subtropical urban lakes, China. Our study showed that anthropogenic protein-like DOM (tryptophan- and tyrosine-like components) dominated the DOM pools, comprising 62% of total fluorescence DOM (FDOM). Partial least squares path modeling (PLS-PM) showed that the direct contribution of relative abundance of DOM to CO2 and CH4 diffusion in the highly-eutrophic state was higher than in the mesotrophic and lightly/moderately-eutrophic states. In particular, protein-like DOM primarily accounted for CO2 variations (44%-49%), while humic- and protein-like DOM contributed comparably to CH4 variations (38%-40% vs. 36%-40%). Furthermore, in the lightly/moderately- and highly-eutrophic states, nutrients contributed to DOM, CO2 and CH4 in both direct and indirect ways, while phytoplankton (chlorophyll a, Chl-a) negatively and directly affected carbon emissions. However, only nitrogen content directly contributed to N2O production and diffusion in the mesotrophic and lightly/moderately-eutrophic states. We concluded that protein-like DOM enrichment had the potential to trigger CO2 and CH4 diffusion and this process was largely mediated by nutrient levels. N2O diffusion was found to be mainly influenced by nitrogen loadings and forms. Our findings highlight the urgency for effective strategies to reduce anthropogenic DOM inputs and control nutrient levels to reduce GHGs diffusion in highly human-impacted aquatic systems.

Effect of DOM derived from composting on the changes of Pb bioactivity in black soil

Exogenous dissolved organic matter (DOM) plays an important role in the migration and transformation of heavy metals in soil. This study investigated the effect of composting-DOM with different maturity on changes of Pb bioactivity in soil, and evaluated the soil environmental factors driving these changes. The results showed that the activating ability of DOM to Pb in chernozem and dark brown soil increased by 4.11%−22.42% and 13.22%−30.15%, respectively. And the order followed: fresh manure (FDOM) > immature compost (IDOM) > mature compost (MDOM). The pH and dissolved organic carbon (DOC) were the main factors driving the changes in diethylenetriaminepentaacetic acid extraction (DTPA) -Pb in chernozem and dark brown soil, respectively. In chernozem, the input of MDOM can reduce the proportion of easily mobile fractions of Pb. While, DOM promotes the transformation of Pb from organic bound and residual fractions to exchangeable and carbonate bound fractions under other conditions. Moreover, the input of DOM can also drive the transformation of Pb species by regulating soil pH, electrical conductivity (EC), organic matter (SOM), DOC, and enzyme activity.

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

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

Terrestrial dissolved organic matter inputs accompanied by dissolved oxygen depletion and declining pH exacerbate CO2 emissions from a major Chinese reservoir

Terrestrial inputs and subsequent degradation of dissolved organic matter (DOM) in lake ecosystems can result in rapid depletion of dissolved oxygen (DO). Inputs of terrestrial DOM including organic acids can also lead to decreases in pH. However, to date, few studies have investigated the linkages between terrestrial DOM inputs, DO and pH levels in the water column, and carbon dioxide (CO2) emissions from lake ecosystems. Based on monthly field sampling campaigns across 100 sites in Lake Qiandao, a major man-made drinking water reservoir in China, from May 2020 to April 2021, we estimated an annual CO2 efflux (FCO2) of 37.2 ± 29.0 gC m−2 yr−1, corresponding to 0.02 ± 0.02 TgC yr−1 from this lake. FCO2 increased significantly with decreasing DO, chlorophyll-a (Chl-a) and δ2H-H2O, while FCO2 increased with increasing specific UV absorbance (SUVA254) and a terrestrial humic-like component (C2). We found that DO concentration and pH declined with increasing terrestrial DOM inputs, i.e. increased SUVA254 and terrestrial humic-like C2 levels. Vertical profile sampling revealed that the partial pressure of CO2 (pCO2) increased with increasing terrestrial DOM fluorescence (FDOM), while DO, pH, and δ13C-CO2 declined with increasing terrestrial FDOM. These results highlight the importance of terrestrial DOM inputs in altering physico-chemical environments and fueling CO2 emissions from this lake and potentially other aquatic ecosystems.

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

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

Dissolved organic matter movements from forests influence downstream soil CO2 flux during thawing

Soil CO2 flux is critical for atmospheric carbon emissions and is highly influenced by soil respiration. Dissolved organic matter (DOM) from upland forests can transport to downstream wetlands and then influence soil respiration during thawing. Current studies have mainly focused on a uniform forest or wetland, whereas the soil CO2 flux changing characteristics affected by watershed DOM movements within the forest wetland catchment during thawing are rarely understood. In this study, the in situ measurement, field sampling, and multiple analysis methods were adopted. First, the soil CO2 flux and soil respiration rates were acquired by eddy covariance tower and portable greenhouse analyzer, respectively. The higher soil CO2 flux occurred during thawing might be partly attributed to the bursts of stored CO2. Then, the relationship between dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) concentrations in water samples, and soil CO2 flux was analyzed by linear regression analysis. DOM from forests can be transported to downstream wetlands via surface runoff, and then promotes soil CO2 flux during thawing. Finally, the soil microbial abundances near the in situ measured sites of forests and wetlands were also compared with the corresponding soil respiration rates. LMWs contains in DOM inputs may influence soil respiration rates by altering soil microbial abundance. Overall, watershed DOM movement from forests can influence downstream soil CO2 flux during thawing in which microbes might exert effects via altering soil respiration rates.

Spatial variation of dissolved organic matter in the Tuojiang River Basin in Chengdu, China: insights based on EEMs-PARAFAC analysis.

Three-dimensional excitation-emission matrix fluorescence spectroscopy coupled with parallel factor analysis was adopted to investigate the characteristics of dissolved organic matter (DOM) components in water samples collected from the Tuojiang River Basin in Chengdu, including its main stream and tributaries. Four DOM components that matched with three fluorescence peaks were identified in the whole river basin and tributaries; while three components corresponding to four fluorescence peaks were identified in the main stream. In all cases, humic-like components accounted for high proportions of the DOM. Correlation analysis revealed the same sources for four components in the whole river basin and its tributaries, whereas two components had different sources in the main stream. Ultraviolet absorbance parameters (SUVA254, SR) and fluorescence parameters (BIX, HIX, FI, β:α) indicated the dominant autochthonous sources of DOM in the whole river basin. Higher terrestrial inputs of DOM were observed in the tributaries than in the main stream. In the areas influenced by human activities (6#, 17#, 18#), the sources of DOM showed strong terrestrial characteristics and high degrees of humification and aromatization, as well as serious pollution. The results of this study have potentially far-reaching implications for environmental water management in the area.

Phosphorus availability and fractions responses to chemodiversity of exogenous dissolved organic matter in lime concretion black soil

AbstractThe chemodiversity of exogenous dissolved organic matter (DOM) is significantly increased during the composting process, yet its influence on soil phosphorus (P) transformation is uncertain. A 60‐day incubation experiment was conducted to assess the availability and fractions of P in lime concretion black soil in response to exogenous DOM input, with three treatments: control (CK), soil with DOM from 30 days decomposed straw (DOM1) and soil with DOM from 90 days decomposed straw (DOM2). The results demonstrated that the addition of DOM caused an increase in the content of available P in the soil, particularly the addition of DOM1 with more protein‐like substances and a lower degree of humification. Compared to the control, DOM1 and DOM2 treatments showed an increase in available P content of 17.3%–54.3% and 0.6%–18.2%, respectively. However, the response of the soil's physicochemical and biological properties varied considerably. DOM1 treatment caused a marked decrease in soil pH compared to DOM2 treatment, which then led to the release of Ca2+ and Mg2+ and improved the solubility of inactive P. Moreover, DOM1 treatment was found to significantly raise the content of microbial biomass P (MBP), particularly at 60 days. The Mantel test and random forest analysis revealed that the strongest correlation was between MBP and available P. Furthermore, DOM1 treatment had a stimulating effect on the growth of phosphate‐solubilizing microorganisms, including Arthrobacter, Penicillium and Mortierella. This investigation could provide insights into how the chemodiversity of exogenous DOM affects the activation of legacy‐P in soil, thus enhancing the soil P supply capacity in agricultural systems.

Contrasting dissolved organic matter biodegradation and bacterial cytometric features in oligotrophic and ultraoligotrophic Patagonian lakes

Abstract Biodegradation process of dissolved organic matter (DOM) could be affected by its concentration and quality. Two biodegradation experiments were conducted in two contrasting seasons in two oligotrophic and one ultraoligotrophic temperate lakes, which comprise a natural gradient of dissolved organic carbon (DOC) concentration and quality (including lakes of < 83.33 μM). We examined associations between biodegradation and bacterial cytometric descriptors (i.e. abundance, DNA relative content, etc.) and with different DOM characteristics. The biolabile DOC (BDOC) was higher in shallow oligotrophic lakes, which displayed higher DOC concentration than the deep ultraoligotrophic one. The BDOC was mainly relatable not only to DOC concentration but also with DOM quality [fluorescent terrestrial-humic component normalized by DOC (C2:DOC), lignin content (a*350) and biological index]. We found a positive association between biodegradation process and high nucleic acid–content bacterial group. The bacterioplankton cytometric features were shaped by DOM concentration and quality along the biodegradation process. We concluded that in oligotrophic lakes, DOC concentration was the main driver of BDOC, whereas in ultraoligotrophic lakes, DOM quality played a more central role. This study contributes to better understand the biodegradation process in pristine low-DOC lakes with natural variation in allochthonous DOM inputs and with implications in the biogeochemical cycles.

Potential impacts of climate and anthropogenic-induced changes on DOM dynamics among the major Chinese rivers

Dissolved organic matter (DOM) is closely linked to human activities in drainage basins and plays a crucial role in maintaining ecosystem functioning and reflecting environmental quality. However, the impacts of climate and anthropogenic-induced changes on DOM in riverine systems under increasingly warming conditions still need to be better understood, particularly at large regional scales. To address this knowledge gap, we analyzed a dataset containing 386 published measurements for nine major Chinese river systems, examining dissolved organic carbon (DOC) concentrations and optical properties of chromophoric DOM (CDOM) under diverse environmental conditions, including mean air temperature, precipitation, surface solar radiation, population density, and land use. Our findings indicate that riverine DOC concentrations are significantly higher in northern China (at ∼46.8%) than in the south. This disparity is primarily due to the high input of soil erosion-induced DOM from drying-affected lands (57.0%), farmland (49.1%), and forests in the north. The high temperate and strong hydrological conditions would lead to DOM degradation easily in the riverine system in the south of China. Our study highlights that various climatic and anthropogenic factors, such as agriculture, vegetation coverage, soil erosion, surface solar radiation, and precipitation, individually or in combination, can affect DOM dynamics in river systems. Therefore, considering alterations in DOM dynamics resulting from climate and environmental changes is crucial for carbon-neutral policies and sustainable river ecosystem assessments.

Hydrochemical characteristics of groundwater in a plain river network region: Establishing linkages between source and water quality variables

The chemical characteristics of groundwater can indicate water quality condition and provide useful information for pollution source identification. This study aimed to understand the effects of dissolved organic matter (DOM) on ionic composition of groundwater and identify the main ions and sources of pollution. The Lake Taihu is a typical eutrophic lake in China. In this study, the hydrochemical composition of groundwater in the surrounding aquifer of Lake Taihu Basin was analyzed. The results showed that the values of water quality index (WQI) range from 13.29 to 56.26 (good water quality). The dominant hydrochemical type of groundwater was Ca–Mg–HCO3 type, and the rock dominance was the major mechanism controlling the groundwater chemistry. With an increasing concentration in dissolved organic carbon (DOC), the Na+, Mg2+, and HCO3– concentrations all showed a sharp increase followed by a slow increase, while the NO3– concentration showed an opposite trend, indicating the DOM can affect the ions composition. In addition, K+ was positively correlated with NO3–, As, and Cd. Hence, DOM input may directly or indirectly change the hydrochemistry of groundwater. Besides, the NO3– concentration in groundwater was much higher than that in Lake Taihu, indicating that the NO3– in groundwater mainly came from surface soil leaching. The anthropogenic sources are probably the main sources of different ions, including K+, NO3–, As, and Cd. This study can help to better understand the effects of lake eutrophication on groundwater and its pathways.

Effects of warming on quantity and structure of litter-derived dissolved organic matter in subtropical natural Castanopsis kawakamii forests.

Litter-derived dissolved organic matter (DOM) is an important source of soil DOM, and the response of which to climate warming may change forest soil carbon and nitrogen dynamics, such as soil carbon and nitrogen mineralization. In this study, we conducted a field manipulative warming experiment in natural Castanopsis kawakamii forests. Combined with litter leaching solution collected in the field and ultraviolet-visible and three-dimensional fluorescence spectroscopy analyses, we explored the effects of warming on the content and structure of litter-derived DOM in subtropical evergreen broad-leaved forests. The results showed that litter-derived dissolved organic carbon and nitrogen content exhibited monthly dynamics, with the peak (in April) and the mean monthly content being 1.02 and 0.15 g·m-2, respectively. Litter-derived DOM had higher fluorescence index and lower biological index, indicating the microbial-origin of DOM from litter. The litter DOM mainly included humic-like fractions and tryptophan-like substances. Warming did not affect the content, aromaticity, hydrophobicity, molecular weight, fluorescence index, biological index and humification index of DOM, suggesting neutral effect of warming on the quantity and structure of litter DOM. Warming also did not affect the relative contribution of main components in DOM, indicating that the temperature variation exerted no effects on microbial degradation. In summary, warming did not change the quantity and quality of litter-derived DOM in subtropical evergreen broadleaved forests, indicating warming had little effect on litter-derived DOM input to soil.

Probing Molecular-Level Dynamic Interactions of Dissolved Organic Matter with Iron Oxyhydroxide via a Coupled Microfluidic Reactor and an Online High-Resolution Mass Spectrometry System.

The interactions between dissolved organic matter (DOM) and iron (Fe) oxyhydroxide are crucial in regulating the biogeochemical cycling of nutrients and elements, including the preservation of carbon in soils. The mechanisms of DOM molecular assembly on mineral surfaces have been extensively studied at the mesoscale with equilibrium experiments, yet the molecular-level evolution of the DOM-mineral interface under dynamic interaction conditions is not fully understood. Here, we designed a microfluidic reactor coupled with an online solid phase extraction (SPE)-LC-QTOF MS system to continually monitor the changes in DOM composition during flowing contact with Fe oxyhydroxide at circumneutral pH, which simulates soil minerals interacting with constant DOM input. Time-series UV-visible absorption spectra and mass spectrometry data showed that after aromatic DOM moieties were first preferentially sequestered by the pristine Fe oxyhydroxide surface, the adsorption of nonaromatic DOM molecules with greater hydrophobicity, lower acidity, and lower molecular weights (<400) from new DOM solutions was favored. This is accompanied by a transition from mineral surface chemistry-dominated adsorption to organic-organic interaction-dominated adsorption. These findings provide direct molecular-level evidence to the zonal model of DOM assembly on mineral surfaces by taking the dynamics of interfacial interactions into consideration. This study also shows that coupled microfluidics and online high-resolution mass spectrometry (HRMS) system is a promising experimental platform for probing microscale environmental carbon dynamics by integrating in situ reactions, sample pretreatment, and automatic analysis.

Response of zooplankton to inputs of terrestrial dissolved organic matter: Food quality constraints induced by microbes

AbstractTerrestrial inputs of dissolved organic matter (DOM) stimulate microbial growth by supplying organic carbon and DOM‐associated nutrients, and thus increase food availability for zooplankton. Terrestrial inputs of DOM might decrease the content of eicosapentaenoic acid (EPA) in particular organic matter (POM) due to an increase in biomass of EPA‐poor microbes, for example, heterotrophic bacteria and autotrophic cyanobacteria, thereby reducing food quality and filter‐feeding zooplankton's biomass. We performed a 26‐d mesocosm experiment where terrestrial DOM was manipulated by adding (treatments) and kept without adding (controls) 13C‐labeled maize leachate to evaluate the effect of food quality changes induced by terrestrial DOM inputs on zooplankton. DOM addition treatments had significantly higher concentrations of POM and Chlorophyll a relative to controls, but significant lower EPA content of POM, responding to increased biomass of bacteria and chlorophytes. Biomass and EPA content of filter‐feeding cladoceran Chydorus sphaericus was significantly reduced by terrestrial DOM addition. Stable isotope analyses showed 13C enrichments in bacteria and cryptophytes in the treatment of 13C‐labeled maize leachate, indicating a growth stimulation of heterotrophic microbes by organic carbon addition. Although the 13C enrichment in Chydorus evidenced the extensive use of terrestrial DOM by this cladoceran, positive relationships between Chydorus biomass and EPA content of POM suggest that terrestrial DOM inputs increase food quality constrains on filter‐feeding zooplankton. Our study suggests that the response of filter‐feeding zooplankton to inputs of terrestrial DOM depends on how the terrestrial inputs change the microbial communities and thus the food quality in the receiving aquatic ecosystems.

Seasonal and diel modulation of DOM in a mangrove-dominated estuary.

Rivers and estuaries are the main links between continents and oceans. The Paraíba do Sul River is among the most important rivers of the southeastern Brazilian region, carrying an average of 0.08 Tg of dissolved organic matter (DOM) to the ocean but has been facing significant changes in river discharge. In this study, we aimed to provide insights into the sources and transformations of chromophoric dissolved organic matter (CDOM) and fluorescent dissolved organic matter (FDOM) sources across a salinity gradient under changing river discharge scenarios. Three spatial surveys were performed covering the entire salinity gradient of the main estuarine channel and surrounding mangrove waters under contrasting river discharge (178 to 1240 m3 s-1), and diel sampling was conducted in the mangrove tidal creek. The characterization of DOM through the parallel factor analysis (PARAFAC) model identified six components across the river-ocean gradient and mangrove creek: terrestrial origin (C1 - fulvic acid and C2 and C3 - humic-like), protein-like (C4), tryptophan-like (C5), and tyrosine-like (C6). Our results showed a shift in DOM composition and contribution along the salinity gradient, from terrestrial (C3) to autochthonous (C5 and C6) signatures. The October-17 dry campaign was characterized by a higher proportion of microbial protein-like component C4 and a lower contribution of humic-like components compared to February-17 and March-18 across the salinity gradient with an increase in the mixing zone. The DOM compositions of the February 17 dry and March 18 wet campaigns were similar. Additionally, the March-18 wet campaign, marked by the highest river discharge, showed higher inputs of terrestrial DOM (C1-C3 components) compared to February-17 in the estuary, which allowed DOM to be transported rather than transformed. The mangrove diel study showed that tidal fluctuations are also an important driver of carbon input to the mangrove creek with a possible impact on DOM composition in estuarine waters.

Organic matter cycling in a model restored wetland receiving complex effluent

Wetlands have been used to treat anthropogenic effluents for decades due to their intense biogeochemical processes that transform and uptake nutrients, organic matter, and toxins. Despite these known functions, we lack generalizable knowledge of effluent-derived dissolved organic matter (DOM) cycling in wetlands. Here, we quantify the cycling of DOM in one of Canada’s more economically important wetland complexes (Frank Lake, Alberta), restored to hydrologic permanence in the 1980s using urban and agro-industrial effluents. Optical analyses and PARAFAC (parallel factor analysis) modelling showed a clear compositional change from more bioavailable and protein-like DOM at effluent input sites to more aromatic and humic-like at the wetland outflow, likely due to DOM processing and inputs from marsh plants and wetland soils. Microbial incubations showed that effluent DOM was rapidly consumed, with the half-life of DOM increasing from as low as 35 days for effluent, to 462 days at the outflow, as a function of compositional shifts toward aromatic, humic-like material. Long-term averaged dissolved organic carbon (DOC) export was low compared to many wetlands (10.3 ± 2.0 g C m−2 yr−1). Consistent with predictions based on water residence time, our mass balance showed Frank Lake was a net source of DOM across all measured years, but shifted from a source to sink among wet and drought years that respectively shortened or lengthened the water residence and DOM processing times. Overall, Frank Lake processes and transforms effluent DOM, despite being a longer-term net source of DOM to downstream environments.

Innovative approach to reveal source contribution of dissolved organic matter in a complex river watershed using end-member mixing analysis based on spectroscopic proxies and multi-isotopes

Dissolved organic matter (DOM) in river watersheds dynamically changes based on its source during a monsoon period with storm event. However, the variations in DOM in urban and rural river watersheds that are dominated by point and non-point sources have not been adequately explored to date. We developed an innovative approach to reveal DOM sources in complex river watershed systems during pre-monsoon, monsoon, and post-monsoon periods using end-member mixing analysis (EMMA) by combining multi-isotope values (δ13C-DOC, δ15N-NO3 and δ18O-NO3) and spectroscopic indices (fluorescence index [FI], biological index [BIX], humification index [HIX], and specific UV absorbance [SUVA]). Several potential end-members of DOM sources were collected from watersheds, including top-soils, groundwater, plant group (fallen leaves, riparian plants, suspended algae), and different effluents (cattle and pig livestock, agricultural land, urban, industry facility, swine treatment facility and wastewater treatment facility). Concentrations of dissolved organic carbon, dissolved organic nitrogen, NO3-N, and NH4-N increased during the monsoon period with an increase in the input of anthropogenic DOM, which have higher HIX values owing to the flushing effect. The results of EMMA indicate that soil and agricultural effluents accounted for a substantial contribution of anthropogenic DOM at varying rates based on seasons. We also found that results of EMMA based on combining spectroscopic indices and δ13C-DOC isotope values were more accurate in tracing DOM sources with respect to land-use characteristics compared to applying only spectroscopic indices. The positive relationship between FI, BIX and δ15N-NO3 were revealed that nitrate would be decomposed from DOM affected by intensive agricultural activities. In addition, consistent with the EMMA results, the molecular composition of the DOM was clearly evidenced by a large number of CHON formulas, accounting for over 50% of the total characterized compounds, including pesticides and pharmaceuticals used in agriculture farmland and livestock. Our results clearly demonstrated that EMMA based on combing multi-stable isotopes and spectroscopic indices could be trace the DOM source, which is important for understanding changes in the DOM quality, and application of nitrate isotopes and molecular analysis supports in-depth interpretation. This study provides easy and intuitive techniques for the estimation of the relative impacts of DOM sources in complex river watersheds, which can be verified in various ways rather than relying on a single technique approach.