Contribution Of Dissolved Organic Matter Research Articles

Tracing sources of dissolved organic matter along the terrestrial-aquatic continuum in the Ore Mountains, Germany

There is growing concern about the rising levels of dissolved organic matter (DOM) in surface waters across the Northern hemisphere. However, only limited research has been conducted to unveil its precise origin. Compositional changes along terrestrial-aquatic pathways can help determine the terrestrial sources of DOM in streams. Stream water, soil water and soil horizons were sampled at four sites representing typical settings within a forested catchment in the Ore Mountains (Erzgebirge, Germany) from winter 2020 to spring 2022. The samples were analyzed using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The resulting data were successfully subjected to semi-automatic processing of the molecular composition of DOM, reaching a percentage of identified peaks up to 98 %. Principal component analysis (PCA) and cluster analyses were carried out to identify distinct differences between DOM from the potential sources and in the streams. According to the PCA, organic soil horizons, soil water, and stream water samples could be clearly distinguished. Cluster analysis revealed that soil water DOM at all depths of Peats and deeper horizons of the Peaty Gleysols contributed the most to DOM in the stream section dominated by organic soils. In areas dominated by mineral soils, stream DOM resembled the DOM from the deeper mineral horizons of Cambisols and Podzols. Overall, our results suggested that most of the DOM exported from the catchment was derived from deeper mineral soil horizons, with little contribution of DOM derived from organic soils. Therefore, DOM fingerprint analysis of in-situ soil water proved to be a promising approach for tracing back the main sources of stream water DOM.

Photoreduction of Hg(II) by typical dissolved organic matter in paddy environments

The photochemical behavior of dissolved organic matter (DOM) in surface water and its effect on Hg(II) photoreduction has been extensively studied, but the contribution of DOM in paddy water to Hg(II) photoreduction is largely unknown. Herein, the effect of DOM from biochar (BCDOM), rice straw (RSDOM), and chicken manure (CMDOM) on Hg(II) photoreduction were examined. The comparable reduction efficiency of Hg(II) suggested that DOM-like fraction (62.3–63.7%) contributes more than suspended particulate matter-like fraction (17.7–23.4%) and bacteria-like fraction (13.0–20.0%) in paddy water. Under irradiation, the typical DOM significantly promoted Hg(II) photoreduction, and the reduction efficiency of BCDOM (65.5 ± 2.1%) was higher than that of CMDOM (48.3 ± 2.6%) and RSDOM (32.8 ± 2.4%) in 6 h. The quenching and kinetics experiments showed that superoxide anion (O2•−) was the main reactive species for Hg(II) photoreduction. Fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry revealed that DOM with a higher degree of lignin/carboxy-rich acyclic molecules, condensed aromatics structures, and phenolic compounds could promote the formation of O2•−. These findings highlight the importance of DOM in Hg(II) photoreduction and provide new ideas for regulating Hg cycling and bioavailability in paddy environments.

Dissolved organic matter derived from biodegradable microplastic promotes photo-aging of coexisting microplastics and alters microbial metabolism

Dissolved organic matter (DOM) leaching from biodegradable microplastics (BMPs) and its characteristics and corresponding environmental implication are rarely investigated. In this study, the main component of DOM leachate from the two BMPs (polyadipate/butylene terephthalate (PBAT)/polycaprolactone (PCL)) was verified by using excitation-emission matrix-parallel factor analysis (EEM-PARAFAC). The PBAT-DOM (PBOM) was aromatized and terrestrial. Comparatively, PCL-DOM (PLOM) had low molecular weight. PBOM contained protein-like components while PLOM contained tryptophan and tyrosine components. Interestingly, both PBOM and PLOM could accelerate the decomposition and oxidation of coexisting polystyrene (PS) under light irradiation. Further, the difference in composition and the properties of BMPs-DOM significantly affected its photochemical activity. The high territoriality and protein-like component of PBOM significantly promoted the generation of 1O2 and O2•-, which caused faster disruptions to the backbone of PS. Simultaneously, the microbial community's richness, diversity, and metabolism were obviously improved under the combined pressure of aged PS and BMPs-DOM. This study threw light on the overlooked contribution of DOM derived from BMPs in the aging process of NMPs and their impact on the microbial community and provided a promising strategy for better understanding of combined MPs' fate and environmental risk.

Urban and agricultural land use regulates the molecular composition and bio-lability of fluvial dissolved organic matter in human-impacted southeastern China

AbstractUrbanization and agricultural land use can increase the transport of nutrients to fluvial ecosystems; yet, the overall impact of urban and nonpoint agricultural inputs on the composition, bio-lability, and the fate of fluvial dissolved organic matter (DOM) remains poorly understood. We investigated the optical and molecular composition and bio-lability of DOM in 76 streams and rivers with varying sizes of catchment area (1 ~ 4850 km2) along large gradients of urban and agricultural land use. Optical spectroscopy and Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) were used to determine the chemical composition of DOM, and laboratory bio-incubations were used to assess DOM bio-lability. We found that urban and agricultural land use intensification was associated with the reduced relative contribution of DOM from pristine soils, enriched dissolved organic carbon (DOC), and higher contributions of aliphatic and peptide-like DOM, as well as enrichment of N- and S-containing molecular formulae. Specifically, FT-ICR MS revealed that the relative abundance of CHO-containing formulae decreased while that of CHOS-containing formulae increased with increasing urban land use. DOM bio-availability was higher in rivers draining urbanized and agricultural landscapes and was related to decreased DOM aromaticity and increased proportions of energy-rich aliphatic formulae. Our results suggested that DOM from urbanized and agricultural catchments significantly altered the chemical composition and bio-availability of DOM with potential effects on ecosystem metabolism and the fate of organic carbon in the downstream-linked streams and rivers. Anthropogenic disturbances may thus boost the microbial processing of organic carbon, including uptake, retention, and outgassing in the impacted ecosystems. Graphical Abstract

Characteristics and disinfection by-product formation potential of dissolved organic matter in reservoir water in cold area.

The severe cold in winter with harsh natural conditions in Northeastern China seriously affect the water quality of the reservoir, showing the increased content and more complex types of organic matter, which brings severe challenges to the control of disinfection by-products (DBPs) in drinking water treatment with reservoir water as the water source. In this study, the fractions of dissolved organic matter (DOM) in source water at before ice formation period (P1), ice-age period (P2), and ice begin to melt period (P3) were separated by membrane separation technology. Subsequently, the contributions of DOM fractions with different molecular weights (MW) to DOC, UV254, and SUVA254, and their disinfection by-product formation potential (DBPFP) were evaluated. Although DOM with high MW (5-10kDa) contributed the most to dissolved organic carbon (DOC) and UV254, but the contribution of DOM with low MW (0-1kDa) to DBPs formation could not be ignored, especially during ice-age period. There was no significant difference in the total numbers of DOM formula belonged to low MW fraction at these three periods, mainly including lignin, followed by N-containing saturated compounds and tannins. Additionally, redundancy analysis revealed that DOC and UV254 as the predictors had good correlation with DBPFP, while SUVA254 could not be used as a single indicator to predict the generation potential of DBPs, and could be used as the prediction factors together with AImodwa parameter closely related to DBPFP. The study provided key information for controlling the DBPs formation of DOM in water, especially in the ice-age period, and provided the theoretical basis for water plant production.

Multiple Roles of Dissolved Organic Matter in Advanced Oxidation Processes.

Advanced oxidation processes (AOPs) can degrade a wide range of trace organic contaminants (TrOCs) to improve the quality of potable water or discharged wastewater effluents. Their effectiveness is impacted, however, by the dissolved organic matter (DOM) that is ubiquitous in all water sources. During the application of an AOP, DOM can scavenge radicals and/or block light penetration, therefore impacting their effectiveness toward contaminant transformation. The multiple ways in which different types or sources of DOM can impact oxidative water purification processes are critically reviewed. DOM can inhibit the degradation of TrOCs, but it can also enhance the formation and reactivity of useful radicals for contaminants elimination and alter the transformation pathways of contaminants. An in-depth analysis highlights the inhibitory effect of DOM on the degradation efficiency of TrOCs based on DOM's structure and optical properties and its reactivity toward oxidants as well as the synergistic contribution of DOM to the transformation of TrOCs from the analysis of DOM's redox properties and DOM's transient intermediates. AOPs can alter DOM structure properties as well as and influence types, mechanisms, and extent of oxidation byproducts formation. Research needs are proposed to advance practical understanding of how DOM can be exploited to improve oxidative water purification.

Shifting of dissolved organic matter components and sources in precipitation into an intensified anthropogenic influenced embayment: Interpretation from spectral characteristics and dual stable isotopes

Dissolved organic matter (DOM) is a ubiquitous group of organic compounds in rainwater that contributes to DOM pools and plays a vital role in the marine biogeochemical cycle. Here, we presented the rainwater DOM components and sources attribution (in δ13C-DOMSPE and δ15N-DOMSPE perspective) to an intensified anthropogenic influenced embayment, and discussed the biogeological effects of atmospheric DOM deposition. The results showed an apparent seasonal variation in the DOM concentration dominated by precipitation. Moreover, the excitation-emission matrix spectroscopy coupled a parallel factor analysis (PARAFAC) results revealed that five fluorescent components (C1-C5) of the rainwater DOM. C1 and C5 are protein-like DOM components and derived from biogenic emissions. The fluorescence intensity of C1 and C5 were significantly higher in the wet season, whereas C2 and C3, which are humic-like substances with higher molecular weights and aromatization, were mainly derived from fossil fuel combustion. The δ13C-DOMSPE and δ15N-DOMSPE results indicated that fossil fuel contributed approximately 80% of the DOM in the precipitation in the dry seasons, whereas the marine emission contribution of DOM was higher in the wet seasons due to the influence of air masses originating from the South China Sea. However, the maritime emissions only contributed 4% to the rainwater DOM. The deposition fluxes of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) were 799 mmol·C·m˗2·yr˗1 and 46 mmol·N·m˗2·yr˗1, respectively, and they played a substantial role for the DOM input flux of Daya Bay (28% of DOC and 12% of DON, respectively). Overall, our results suggest that atmospheric wet deposition represents a potentially critical source of organic carbon and nitrogen for coastal waters, particularly in intensified anthropogenically influenced embayments characterized by substantial monsoon shifts between seasons.

Photosensitized Transformation of Peroxymonosulfate in Dissolved Organic Matter Solutions under Simulated Solar Irradiation.

Sulfate radical (SO4•-)-mediated advanced oxidation processes via peroxymonosulfate (PMS) activation have been extensively investigated. However, the phototransformation of PMS in sunlit dissolved organic matter (DOM) solution has not been previously examined. For the first time, the photosensitized transformation of PMS in DOM-enriched solutions under simulated solar irradiation was observed. The generation of reactive species, including 1O2, SO4•-, and •OH, was confirmed by electron paramagnetic resonance and quantified by chemical probes. SO4•- was the primary reactive species generated via the reaction of excited triplet DOM (3DOM*) with PMS. 3DOM* acted as a reactive reductant and was quickly oxidized by PMS, with an estimated reaction rate constant of (4.09 ± 0.21) × 108 M-1 s-1. Compared to 3DOM*, one-electron-reducing DOM (DOM•-) was a minor contributor to the photosensitized transformation of PMS, and the contribution of DOM•- relied on the phenolic constituents. In addition, a series of different types of DOM, including terrestrial DOM, autochthonous DOM, and effluent organic matter and its fractions, were employed to examine the photosensitized transformation kinetics of PMS. Overall, the photosensitized transformation of PMS by irradiated DOM could be a useful and economical approach to generate SO4•- under environmentally relevant conditions.

Activation of peroxydisulfate by ball-milled α-FeOOH/biochar composite for phenol removal: Component contribution and internal mechanisms

Persulfate-based advanced oxidation process is considered as a promising technology for the degradation of phenol, where efficient, cost effective, and green methods with high peroxydisulfate (PS) activation capacity is of increasing demand. In this work, an in-situ liquid phase precipitation combined with ball milling method was applied for the synthesized of α-FeOOH/biochar, as be the PS activator for phenol degradation. Results showed that the ball-milled α-FeOOH and red pine wood biochar prepared at 700 °C (BM-α-FeOOH/PBC700) exhibited the highest catalytic property with PS for phenol oxidation (a phenol removal rate of 100%), compared with the BM-α-FeOOH (16.0%) and BMPBC700 (66.3%). The presence of intermediate products such as hydroquinone and catechol, and total organic carbon (TOC) removal rate (88.9%) proved the oxidation of phenol in the BM-α-FeOOH/PBC700+PS system. The characterization results showed that the functional groups (e.g., CO, C–O, Fe–O, and Si–O), the dissolved organic matter (DOM) in biochar, the loading of Fe element, and higher degree of graphitization and defect structures, contributed to the activation of PS to form free radicals (i.e., SO4·−, ·OH, ·O2−, and hVB+) for phenol oxidation, of which, SO4·− and ·OH account for 72.1% of the phenol removal rate. The specific contribution to the PS activation for phenol oxidation by each part of the materials was calculated based on the “whole to part” experiment. The contribution of DOM, acid-soluble substance, and carbon matrix and basal part in BM-α-FeOOH/PBC700 were 6.0%, 40.9%, and 53.1%, respectively. The reusability experiments of BM-α-FeOOH/PBC700 demonstrated that the composite was relatively stable after four cycles of reuse. Among three co-existing anions (NO3−, Cl−, and HCO3−), HCO3− played the most significant inhibition effects on phenol removal through reducing the phenol removal rate from 89.6% to 77.9%. This work provides guidance for the design of high active and stable carbon materials that activate PS to remove phenol.

Controls on Riverine Dissolved Organic Matter Composition Across an Arctic‐Boreal Latitudinal Gradient

AbstractClimatic changes are transforming northern high‐latitude watersheds as permafrost thaws and vegetation and hydrology shift. These changes have implications for the source and reactivity of riverine dissolved organic matter (DOM), and thus biogeochemical cycling, across northern high‐latitude systems. In this study, we use a latitudinal gradient from the interior to the North Slope of Alaska to evaluate seasonal and landscape drivers of DOM composition in this changing Arctic environment. To assess DOM source and composition, we used absorbance and fluorescence spectroscopy to measure DOM optical properties, lignin biomarker analyses to evaluate vascular plant contribution to the DOM pool, and Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS) to assess DOM compositional changes. We found that seasonal inputs of DOM at elevated discharge during the freshet were typically more aromatic in nature with higher lignin concentrations and carbon‐normalized yields. Landscape characteristics were a major control on dissolved organic carbon (DOC) yields and DOM composition. More northern watersheds, which were steeper, underlain by continuous permafrost, and exhibited a mix of barren and lichen/moss vegetation cover, exported less DOC with relatively more aliphatic DOM compared to more southern basins. Watersheds with deeper active layers exported DOM that was more aromatic with higher polyphenolic and condensed aromatic relative abundances and lignin yields, likely sourced from shallow subsurface flow during high discharge periods. However, contributions from deeper groundwater to streamflow is expected to increase, which would increase interactions of groundwater with mineral soils and decrease aromatic DOM contributions during periods of low discharge.

Investigation into the content and formation of trihalomethanes and molecular change of dissolved organic matter from a typical water plant in south China.

Trihalomethanes (THMs) are a class of disinfection by-products that were proved to have adverse effects to human health. Investigation into its content change and molecular composition variation of its main precursor, which is believed to be dissolved organic matter (DOM) during water purification process, can help understand the formation mechanism of THMs and optimize the processes in drinking water treatment plant (DWTP). This is of great significance to ensure the safety of urban water supply. In this study, detailed changes of THMs' content and formation potential were determined during the water purification process in summer and winter at a typical DWTP in south China. Specific molecular composition changes of DOM were also characterized by ultrahigh-resolution mass spectrometry, to comprehensively study its correlation with the formation of THMs in different water processing units and seasons. The result showed that chlorination will cause drastic changes of water quality and a sharp increase in the concentration of THMs (18.7 times in summer and 13.9 times in winter). Molecular-level characterization of DOM indicates that a range of lignin-like substance with lower O/C (< 0.5) and H/C (< 1.25) vanished and considerable amount of protein-like and tannins-like substance with higher H/C (> 1.25) and O/C (> 0.5) was formed after chlorination. Analysis of Cl-containing products demonstrated that a bulk of CHOCl1 and CHOCl2 compounds with moderate molecular weights were formed in both winter and summer. However, the newly formed CHOCl1 molecules showed a relatively higher mass weight in summer (> 500Da) compared to winter (300-500Da). Seasonal differences also emerged in the result of correlation between the trihalomethanes formation potential and total organic carbon. The correlation coefficient in summer (0.500) was lower than that in winter (0.843). The results suggested that the exhaustive reaction and contribution of DOM to THMs may vary in different seasons.

Spectral Characteristics and Sources of Dissolved Organic Matter from Landscape River During Flood Season in Suzhou Based on EEMs and UV-vis

Based on excitation emission matrix spectroscopy (EEMs) technology combined with the parallel factor analysis (PARAFAC) and UV-vis spectra, the spectral characteristics and sources of dissolved organic matter (DOM) from a landscape river were analyzed during different periods of the flood season in Suzou. Four fluorescent components were identified using the PARAFAC model, including two humus-like components (C1, C4) and two protein-like components (C2, C3), with a significant correlation coefficient (P<0.01) in C2 and C3/C4 and C3 and C4, respectively. During the early flood season, the total fluorescence intensity of the DOM in the river was relatively higher due to the influence of initial rainwater but reduced significantly towards the middle and late flood season. The fluorescence characteristic parameters indicated that the autochthonous contribution of DOM were substantial during the early stages of the flood season. On the contrary, there were increased levels of DOM largely from terrestrial origins during the middle flooding period. During the entire flood season, SUVA254, SUVA260, and E2/E3 exhibited the same trend, that is, decreasing first and then increasing. As a result of the continuous heavy rainfall during the flood season, the nitrogen and phosphorus nutrient content in the channel increased. The algae population did not proliferate in large quantities because of the strong hydrodynamic conditions experienced throughout the flood season. The fluorescence components C2, C3, and C4 exhibited a significant correlation coefficient (P<0.01) with the characteristic parameters (FI, HIX, BIX, and β:α). All the fluorescence components had a high correlation (P<0.05) with DOC. There was a considerable correlation between fluorescence component C1 and Chla. The principal component analysis revealed that the DOM components in the landscape river during different periods of the flood season exhibited notable differences, and the continuous heavy rainfall during the flood season has a substantial influence on the content of C2, C3, and C4 components in the water body.

Hydrologic connectivity determines dissolved organic matter biogeochemistry in northern high‐latitude lakes

AbstractNorthern high‐latitude lakes are undergoing climate‐induced changes including shifts in their hydrologic connectivity with terrestrial ecosystems. How this will impact dissolved organic matter (DOM) biogeochemistry remains uncertain. We examined the drivers of DOM composition for lakes in the Yukon Flats Basin in Alaska, an arid region of low relief that is characteristic of over one‐quarter of circumpolar lake area. Utilizing the vascular plant biomarker lignin, chromophoric dissolved organic matter (CDOM), and ultrahigh‐resolution mass spectrometry, we interpreted DOM compositional changes using lake‐water stable isotope (δ18O‐H2O) composition as a proxy for lake hydrologic connectivity with the landscape. We observed a relative decrease in CDOM in more hydrologically isolated lakes (enriched δ18O‐H2O) without a corresponding decrease in dissolved organic carbon (DOC) concentration. Although DOC and CDOM were weakly correlated, a significant positive relationship between lignin and CDOM (r2 = 0.67) demonstrates that optical parameters are useful for estimating lignin concentration and thus vascular plant contribution to lake DOM. Indicators of allochthonous DOM, including lignin carbon normalized yields, CDOM aromaticity proxies, and relative abundances of polyphenolic and condensed aromatic compound classes, were negatively correlated with δ18O‐H2O (r2 &gt; 0.45), suggesting there is little allochthonous DOM supplied to many of these hydrologically isolated lakes. We conclude that decreased lake hydrologic connectivity, driven by ongoing climate change (i.e., decreased precipitation, warming temperatures), will reduce allochthonous DOM contributions and shift lakes toward lower CDOM systems with ecosystem‐scale ramifications for heat transfer, photochemical reactions, productivity, and ultimately their biogeochemical function.

Spectroscopic and molecular-level characteristics of dissolved organic matter in the Pearl River Estuary, South China

Coastal populations are expanding globally, resulting in great anthropogenic impacts on the organic matter in estuaries and regional carbon cycles. However, the molecular-level characteristics of dissolved organic matter (DOM) within highly disturbed estuaries are still not well understood. Here, water samples collected during two seasons (wet and dry) from the subtropical Pearl River Estuary of China were analyzed using absorption and fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to determine the spatiotemporal variations in the DOM characteristics. In the seaward direction, the abundances of chromophoric and fluorescent DOM decreased by greater percentages than the bulk dissolved organic carbon concentration. The spectroscopy and FT-ICR MS analyses collectively indicated seaward declines in the aromaticity of DOM and terrestrial DOM contributions from natural terrestrial markers and anthropogenic synthetic surfactants. In particular, the S content in DOM was much higher here than in previously reported estuaries, suggesting a strong anthropogenic impact on the estuarine DOM. Greater terrestrial and anthropogenic signatures in DOM were observed in the wet season than in the dry season. Importantly, this study implies that the terrestrial and anthropogenic contributions to DOM were strongly driven by season in the anthropogenically disturbed subtropical estuary.

Absorption and Fluorescence Spectra of Dissolved Organic Matter in Rivers of the Three Gorges Reservoir Area Under the Background of Urbanization

Studying the influences of urbanization on the composition, chemical structure, source and migration of dissolved organic matter (DOM) in rivers is of great significance for aquatic ecosystem protection and biogeochemical carbon (C) cycling. The DOM spectroscopic characteristics of the three typical rivers (Taohuaxi, Nanhe, and Puli) with different urbanization levels in the Three Gorges Reservoir area were investigated using the ultraviolet-visible (UV-Vis) absorption spectrum and three-dimensional fluorescence spectroscopy. The results demonstrated that the higher the degree of urbanization in rivers, the greater the concentrations of DOM and chromophoric dissolved organic matter (CDOM), the lower the humification degree and aromaticity of DOM, the smaller the proportion of hydrophobic components, the higher the relative level of protein-like substance concentration in DOM, and the greater the contribution of DOM from freshly autochthonous origins. The DOM of the three rivers was dominated by fulvic acids (E3/E4>3.5), and CDOM concentration was positively correlated with the concentration of DOM (P<0.01). There were significant positive correlations between the humification degree (SUVA254), aromaticity (SUVA280), and hydrophobic component (SUVA260) (P<0.01). The sources of humic substances in the DOM were mixed by terrestrial input and microbial or algae production (reflected by the fluorescence index averages of 1.7157-1.7571), and mainly from microbial sources.

Colored dissolved organic matter dynamics and anthropogenic influences in a major transboundary river and its coastal wetland.

Most transboundary rivers and their wetlands are subject to considerable anthropogenic pressures associated with multiple and often conflicting uses. In the Eastern Mediterranean such systems are also particularly vulnerable to climate change, posing additional challenges for integrated water resources management. Comprehensive measurements of the optical signature of colored dissolved organic matter (CDOM) were combined with measurements of river discharges and water physicochemical and biogeochemical properties, to assess carbon dynamics, water quality, and anthropogenic influences in a major transboundary system of the Eastern Mediterranean, the Evros (or, Марица or, Meriç) river and its Ramsar protected coastal wetland. Measurements were performed over three years, in seasons characterized by different hydrologic conditions and along transects extending more than 70 km from the freshwater end‐member to two kilometers offshore in the Aegean Sea. Changes in precipitation, anthropogenic dissolved organic matter (DOM) inputs from the polluted Ergene tributary, and the irregular operation of a dam were key factors driving water quality, salinity regimes, and biogeochemical properties in the Evros delta and coastal waters. Marsh outwelling affected coastal carbon quality, but the influence of wetlands was often masked by anthropogenic DOM contributions. A distinctive five‐peak CDOM fluorescence signature was characteristic of upstream anthropogenic inputs and clearly tracked the influence of freshwater discharges on water quality. Monitoring of this CDOM fluorescence footprint could have direct applications to programs focusing on water quality and environmental assessment in this and other transboundary rivers where management of water resources remains largely ineffective.

Distribution of dissolved organic matter in freshwaters using excitation emission fluorescence and Multivariate Curve Resolution

Multivariate Curve Resolution Alternating Least Squares (MCR-ALS) method with the trilinearity constraint is proposed for the analysis of excitation–emission fluorescence data from Dissolved Organic Matter (DOM) in fresh water natural systems, and the results obtained are compared with those obtained with PARAFAC. The effects of different number of components and constraints on the stability of the proposed models are compared. MCR-ALS is shown to be an effective way to characterize and resolve DOM sources in natural fresh water systems from EEM data, with good correlation with experimentally measured DOM concentration values. MATLAB georeferenced mapping is used to illustrate the geographical distribution of resolved DOM contributions. MCR-ALS resolved EEM spectra are used to recognize the corresponding chemical groups assigned to possible DOM sources. Relationships between human activities and the environmental situation of the river system are discussed from these possible DOM sources.

New Insights into the Source of Decadal Increases of Dissolved Organic Matter in Acid-Sensitive Lakes of the Northeastern United States

The last several decades have seen decreases in SO(4)(2-) deposition across the northeastern United States. As a result, SO(4)(2-) concentrations in lakes and streams have also decreased and many surface water bodies have become less acidic. During the same time period, there has been a concurrent increase in dissolved organic carbon (DOC) concentrations in many lakes and streams. We used fluorescence spectroscopy to characterize the dissolved organic matter (DOM) quality of archived samples from nine acid-sensitive lakes in Maine collected between 1993 and 2009, and determined that increased DOM contributions to lakes were primarily derived from litter and soil. All five lakes with increasing DOC trends demonstrated significant decreasing (i.e., more terrestrial) trends in fluorescence index (FI) and significant positive correlations between SO(4)(2-) and FI. This study used the chemical signature of terrestrial DOM to support the hypothesis that increased DOC concentrations in lakes and streams are driven by declining acid deposition and increased solubility of soil organic matter across a large area of the landscape.

Source, biogeochemical cycling, and fluorescence characteristics of dissolved organic matter in an agro‐urban estuary

Seasonal measurements of dissolved organic matter (DOM) fluorescence characteristics were combined with weekly to bi‐weekly measurements of carbon (C), nitrogen (N), and phosphorus (P) (including particulate, dissolved organic and inorganic forms) and chlorophyll to determine how riverine inputs and autochthonous production influence DOM and nutrient dynamics in the Swan‐Canning estuary, Western Australia. Estuarine concentrations of C, N, and P were influenced by multiple factors, including the seasonal riverine flux of DOM, N, and P, the regeneration of mainly inorganic N and P from benthic anoxia, and the delivery of DOM and nutrients from urban drains. Parallel factor analysis of excitation‐emission matrices identified eight fluorescence components that were used to fingerprint three distinct sources of estuarine DOM: (1) riverine DOM derived mainly from vascular plant material, (2) autochthonous DOM recently produced within the estuary (indicated by tryptophan‐like fluorescence), and (3) autochthonous DOM originating from within the lower estuary or coastal marine environment enriched in marine humic‐like and tyrosine‐like fluorescence. Overall, fluorescence DOM characteristics shifted from humic‐like in the upper and mid‐estuary to protein‐like in the lower estuary, which likely reflects the increased contribution of autochthonous relative to terrigenous DOM closer to the estuary mouth. Our findings show that DOM composition varies with season and estuary position as riverine DOM inputs, mainly from terrestrial plant material, are supplemented by autochthonous DOM contributions associated with discrete inputs of inorganic nutrients.

Organic C and N mineralization as affected by dissolved organic matter in paddy soils of subtropical China

In this study, dynamics of dissolved organic matter (DOM) and mineralization of soil organic C and N in subtropical China were investigated. Paddy and upland soils were derived from Tertiary sandstone, Quaternary red clay and river alluvium with low, middle, and high levels of soil fertility. Dissolved organic carbon contents (DOC) varied from 3.8 to 68.7 mg/kg and dissolved organic nitrogen contents (DON) ranged from 2.9 to 18.3 mg/kg, respectively, during the experimental period. Both DOC and DON increased with increasing soil fertility. The content of DOM was characterized by strong seasonal fluctuation in soils, and seasonal patterns showed the maximum value in Nov and the minimum in July. The contribution of DOM to mineralization of C and N was significantly affected by soil types and seasons. DOM removal significantly decreased the cumulative organic C mineralization in soils derived from Tertiary sandstone and River alluvium (by 1.6%–20.3% with an average of 7.1%), while it did not significantly change those in soils derived from Quaternary red clay. Similarly, the cumulative mineralization of N in paddy soils after DOM removal decreased by 6.7%–27.3% over seasons. In this study, DOM played an important role in soil C and N mineralization in subtropical China. It appears that contribution of DOM to minerilization of C and N in paddy soils was possibly related to DOM content and composition.