Origin Of Dissolved Organic Matter Research Articles

The use of the self-organizing map (SOM) methodology to study the dissolved organic matter (DOM) in different water body types.

This study investigated the characteristics of dissolved organic matter (DOM) in two distinct water bodies, through the utilization of three-dimensional fluorescence spectroscopy coupled with self-organizing map (SOM) methodology. Specifically, this analysis concentrated on neurons 3, 14, and 17 within the SOM model, identifying notable differences in the DOM compositions of a coal subsidence water body (TX) and the MaChang Reservoir (MC). The humic substance content of DOM TX exceeded that of MC. The origin of DOM in TX was primarily linked to agricultural inputs and rainfall runoff, whereas the DOM in MC was associated with human activities, displaying distinctive autochthonous features and heightened biological activity. Principal component analysis revealed that humic substances dominated the DOM in TX, while the natural DOM in MC was primarily autochthonous. Furthermore, a multiple linear regression model (MLR) determined that external pollution was responsible for 99.11% of variation in the humification index (HIX) of water bodies.

Biogeochemistry of dissolved organic matter and inorganic solutes in soil profiles of tropical pasturelands

Tropical soils play a critical role in the global biogeochemical cycles and are essential for maintaining the Earth's carbon balance. Understanding the dynamics of dissolved organic matter (DOM) is paramount due to its implications for ecosystem functioning and nutrient cycling. This study comprehensively evaluated the origin, distribution, and composition of DOM and inorganic solutes in Brazilian tropical agricultural soils. Multiple analytical techniques were utilized to assess DOM from soil profiles (0–100 cm depth) across a spectrum of land uses, including a native Atlantic Forest, a degraded pasture, as well as intensive grazing, extensive grazing, and silvopastoral systems. Inorganic elements were quantified to assess the coupling between the organic and inorganic biogeochemical cycles. The dominance of C4 carbon in topsoil layers suggested substantial contributions of organic matter from grasses to the soil organic matter pool. However, with increased depth, C3 carbon inputs became more prominent, indicating the influence of forest vegetation that existed prior to the implementation of agricultural managements. DOM concentrations decreased with soil depth due to reduced carbon inputs, sorption to minerals, or oxidation. DOM composition did not show significant changes among different land use and managements. Lignin was identified as the primary contributor to oxidized DOM with increasing soil depth. The composition of DOM exhibited a shift from more aromatic and higher molecular weight compounds in topsoil layers to smaller, more aliphatic compounds in subsoil layers. Our key findings revealed that aliphatic compounds, particularly fatty acids, tend to accumulate in deeper soil layers. This phenomenon was consistent in pastures dominated by grasses but not in soils near treed vegetation. Overseeding (from C3 plants) did not significantly impact DOM compositions, emphasizing the persistence of C4 plants in these systems. The presence of inorganic elements in soil water extracts showed minimal impact on DOM dynamics, suggesting decoupled organic and inorganic biogeochemical cycles in tropical pasturelands.

Organic matter biofiltration performance modeling: Influence of influent water quality, operating conditions, and biomass

The impact of source water dissolved organic matter (DOM) origin, empty bed contact time (EBCT), temperature, and pretreatment methods on biofiltration performance was evaluated and predictive models based on experimental data were developed. Three DOM source water types, terrestrial, microbial, and treated wastewater (WW) effluent, were utilized. A model was developed to predict biofilter performance for dissolved organic carbon (DOC) removal based on the influent biodegradable DOC (BDOC) fraction, a single active biomass measurement from the top of the filter and the filter EBCT. A biomass distribution model was developed to predict total active biomass throughout the filter based on a single biomass measurement from the top of the filter. The measured BDOC fractions were 21 % for the nonWW impacted source waters, 36 % for the WW effluents and 62 % for the ozonated WW effluents. At an EBCT of 15 min, biofilters removed between 7 and 21 % of the DOC (19 to 50 % for BDOC) depending on the DOM type and use of ozonation. When the EBCT decreased to 5 min DOC removal decreased by 40 % and when increased to 30 min removal increased by 42 %. When the temperature decreased from 22 °C to 6 °C DOC removal was 33 % lower and when increased to 28 °C removal was 42 % higher. ATP values were found to be a function of temperature and DOM origin, as the average ATP values from the WW effluent biofilters were almost double that of the non-WW impacted sources and pre-ozonation of the WW effluent yielded values three times higher. The model was applied to the results of 27 different biofilter runs at three EBCTs yielding one distinct rate constant for the non-WW impacted source waters and one rate constant for the WW effluents. The model was successfully applied to the results of 19 filter runs from the literature and to those from a pilot plant over 6 months of operation.

Linkages between fluorescent dissolved organic matter and lignin phenols in the Canada Basin, Arctic Ocean

Lignin is one of the more refractory components of dissolved organic matter (DOM) and its concentration and composition are used to trace terrigenous DOM in the ocean. In this study, lignin oxidation products (LOP), and chromophoric and fluorescent DOM were measured in Polar Mixed Layer (PML), Atlantic water (AW), and Canada Basin Deep Water (CBDW) layers in the Canada Basin to elucidate the composition and source of terrestrial DOM. Significant differences in total lignin phenol concentration (Σ11) and cinnamyl to vanillyl ratio (C/V) measured with CuO oxidation in PML, AW, and CBDW samples were found. The fluorescence intensities of humic-like C1 were correlated with Σ11 in PML, congruent with the humic-like terrestrial origin. However, no significant correlation was found when all layers are considered (p > 0.05), suggesting a change in the molecular composition of C1. The protein-like C3 and C5 intensities were strongly correlated with Σ11 (rs = 0.55–0.64) corroborating that lignins can contribute to the protein-like fluorescence in the water column. The principal component analysis (PCA) confirmed the origin and composition of DOM vary between the different water masses, especially in terms of C/V, DOC, and fluorescent components. Significant relationships between humic-like fluorescence intensities and C/V reveal the significant contribution of woody sources to humic material in the Canada Basin. Elevated S/V and humic-like C6 levels were associated with a cold eddy DOM sample but further studies are required to validate the use of these DOM characteristics to trace deep eddy.

Response of dissolved organic matter characteristics to nitrogen addition in a boreal peatland of Northeast China

Boreal peatlands, a crucial stock of dissolved organic matter (DOM), are susceptible to increased reactive nitrogen (N) inputs. However, the response of DOM characteristics to elevated N availability in these ecosystems is still obscure. Here, we investigated the seasonal variability of DOM quantity and characteristics in surface water and soil pore water after 5-year multi-level N addition (0, 3, 6, and 12 g N m−2 year−1) in a permafrost peatland of Northeast China. In this study, we used the excitation-emission matrix fluorescent spectroscopy combined with fluorescence regional integration, parallel factor analysis, and fluorescence parameters to decipher the effects of N addition on DOM composition, origin, and fate. Irrespective of N addition level, increased N availability reduced dissolved organic carbon concentrations in surface water and soil pore water. However, DOM characteristics are more responsive to N addition in soil pore water than in surface water. Nitrogen addition did not affect DOM composition in surface water, but altered the proportions of tyrosine-, tryptophan-, fulvic acid-, and humic-like DOM in soil pore water. Moreover, the changing trends of DOM composition were diverse during the growing season. In addition, compositional transformations of DOM did not change its biogenic signals, freshness, and humification in both surface water and soil pore water across the growing season. Our results suggest that increased N availability reduces DOM quantity and alters DOM chemical composition, which will improve our understanding of soil organic matter dynamics in boreal peatlands.

Source characterization of dissolved organic matter in the eastern Beagle Channel from a spring situation

Dissolved organic matter (DOM) was analyzed by its optical and fluorescent properties in order to study its distribution, source and transformation in relation to microbial abundances, chlorophyll and physicochemical gradients along a transect in the eastern Beagle Channel (BC) during austral spring 2019. Moreover, DOM evolution was followed during three tidal cycles in two fixed stations (F1, F2) separated by the Mackinlay Strait, a hydrographic frontier between water masses under stronger continental influence (inner sector) and that of less modified Sub-Antarctic waters (outer sector). The fluorescence signals of protein- and humic-like compounds were used as a proxy for labile and non-labile material, respectively, while the concentration of nano-, pico- and virioplankton populations, chlorophyll-a (Chl-a) and dissolved organic carbon (DOC) were used as a proxy for biological activity. Moreover, several spectroscopic indices, such as the indicator of microbially produced DOM (BIX), the Freshness index (FIX), an indicator of molecular weight, the Slope Ratio (SR) and an indicator of chromophoric DOM (CDOM), were used to trace the quality and origin of DOM. Chl-a concentration was generally low in the sampling area (< 1 μg L−1) but increased towards the end of the campaign and especially during the visit of F1 along with the concentration of picoeukaryotes and the protein-like fluorophores evidencing the onset of a bloom event. Protein-like fluorophores peaked in the euphotic zone of the inner sector of the BC while humic-like material of terrestrial origin was homogeneously distributed throughout the water column and showed a decreasing gradient towards the outer sector and Atlantic waters. Furthermore, the inner sector was characterized by higher amounts of CDOM, high molecular weight material and more recalcitrant DOM. Accumulation of autochthonous humic-like material in bottom waters of the inner sector along with enhanced values of FIX and BIX preceded by colored organic material suggest an efficient functioning of the microbial carbon pump fueled by terrestrial DOM sources in these waters.

A Tropical Cocktail of Organic Matter Sources: Variability in Supraglacial and Glacier Outflow Dissolved Organic Matter Composition and Age Across the Ecuadorian Andes

AbstractThe biogeochemistry of rapidly retreating Andean glaciers is poorly understood, and Ecuadorian glacier dissolved organic matter (DOM) composition is unknown. This study examined molecular composition and carbon isotopes of DOM from supraglacial and outflow streams (n = 5 and 14, respectively) across five ice capped volcanoes in Ecuador. Compositional metrics were paired with streamwater isotope analyses (δ18O) to assess if outflow DOM composition was associated with regional precipitation gradients and thus an atmospheric origin of glacier DOM. Ecuadorian glacier outflows exported ancient, biolabile dissolved organic carbon (DOC), and DOM contained a high relative abundance (RA) of aliphatic and peptide‐like compounds (≥27%RA). Outflows were consistently more depleted in Δ14C‐DOC (i.e., older) compared to supraglacial streams (mean −195.2 and −61.3‰ respectively), perhaps due to integration of spatially heterogenous and variably aged DOM pools across the supraglacial environment, or incorporation of aged subglacial OM as runoff was routed to the outflow. Across Ecuador, Δ14C‐DOC enrichment was associated with decreased aromaticity of DOM, due to increased contributions of organic matter (OM) from microbial processes or atmospheric deposition of recently fixed and subsequently degraded OM (e.g., biomass burning byproducts). There was a regional gradient between glacier outflow DOM composition and streamwater δ18O, suggesting covariation between regional precipitation gradients and the DOM exported from glacier outflows. Ultimately, this highlights that atmospheric deposition may exert a control on glacier outflow DOM composition, suggesting regional air circulation patterns and precipitation sources in part determine the origins and quality of OM exported from glacier environments.

Interactions between particulate organic matter and dissolved organic matter in a weak dynamic bay revealed by stable isotopes and optical properties

Few studies have incorporated the tools of stable isotopes and optical properties to study the biogeochemical process of organic matter (OM), including particulate organic matter (POM) and dissolved organic matter (DOM), which prevents our comprehension of the interactions between POM and DOM in the marine environment. In this study, the origin, distribution, and fate of POM and DOM in Tieshangang Bay, a weak dynamic bay were investigated by measuring δ13C and δ15N of POM, dissolved organic carbon (DOC), and absorption and fluorescence of DOM (CDOM and FDOM). In the upper bay, POM source was mainly originated from terrestrial discharge, whereas the high fluorescence index (FI) indicated that external aquatic organism activity dominated DOM sources. In contrast, in the outer bay, the slightly increased δ13C and enriched δ15N of POM and enhanced fluorescence intensities of protein-like DOM components indicated the considerable contributions of the in situ biological activities to OM. A net addition of DOC and optical components of DOM occurred in both the upper and outer bays. The decomposition of terrestrial POM was responsible for the addition of DOM due to the weak dynamics in the upper bay, whereas the enhanced primary production and the strong decomposition of freshly produced POM jointly contributed to the addition of DOM in the outer bay. Our study suggests that hydrodynamics regulate the biogeochemistry and interactions of POM and DOM in the weak dynamic bay.

DOM influences Hg methylation in paddy soils across a Hg contamination gradient

Rice paddies provide optimum conditions for Hg methylation, and paddy soil is a hot spot for Hg methylation and the predominant source of methylmercury (MeHg) accumulated in rice grains. The role of dissolved organic matter (DOM) in controlling Hg bioavailability and methylation in rice paddy systems remains unclear. Paddy soils from eight various cultivation sites in China were chosen to investigate the variations in soil DOM and the influence of DOM concentration and optical characteristics on Hg methylation in rice paddy systems. In the present study, 151 rhizosphere soil samples were collected, and UV–Vis absorption and fluorescent spectroscopy were used to identify the optical properties of DOM. The relationship between MeHg and DOM's optical property indices revealed the production of MeHg consumes lower molecular weight DOM. Moreover, the correlation between DOM concentration and its optical characteristics highlighted the significant role of humic components on MeHg variability in paddy soil. Variation and correlation results demonstrated the allochthonous origin of DOM in the Hg-contaminated soil, with a higher molecular weight and humic character of DOM, as well as the dominant role of autochthonous DOM in promoting Hg methylation in uncontaminated soil. The current study indicated that soil organic matter and its dissolved fractions tend to limit Hg bioavailability and subsequently diminish MeHg production in contaminated paddy soils. Furthermore, the leading roles of allochthonous DOM in protecting MeHg from degradation and autochthonous DOM signatures in enhancing MeHg production in paddy soils. Overall, these findings provide insight into the correlative distributions of DOM and Hg along a Hg concentration gradient in paddy soil, thereby highlighting their potential role in controlling Hg bioavailability and regulating Hg methylation in the soil ecosystems.

Size exclusion chromatography and stable carbon isotopes reveal the limitations of solid phase extraction with PPL to capture autochthonous DOM production

The study of the elemental and carbon isotopic composition of dissolved organic matter (DOM) is of great interest in deciphering the origin and transformations of organic matter in estuarine and coastal environments. Styrene-divinylbenzene copolymer (PPL) sorbent is currently the most commonly used material for the isolation of DOM from environmental samples. It is notably used for the development of molecular formula-based indices used to study DOM reactivity. However, any extraction procedure (including with PPL) will fractionate the DOM. If this fractionation is not well constrained it can lead to biased interpretations of the biogeochemical processes affecting DOM. In this work we investigate the fractionation effects of the PPL sorbent on the size class distribution of DOM and the carbon isotopic composition of the PPL retentate. The use of size exclusion chromatography, that does not require a pre-concentration step, allows a precise study of the fractionation of DOM (including aromaticity) by the PPL resin. Extractions performed on two types of humic substances dissolved in artificial seawater, using the PPL resin, showed high extraction yield (> 85%) and the stable isotopic carbon composition (δ13C) of these compounds was successfully recovered. These results indicate that salinity is not a parameter affecting extraction yield on PPL sorbent. For a hydrophilic compound (atropine) the extraction efficiency was low (33%) and δ13C signature was underestimated. Size exclusion chromatography measurements, in samples collected along a salinity gradient, demonstrate that the PPL sorbent strongly fractionates DOM. Although the DOM size class distributions in freshwaters and marine waters were initially different, their retentates were marked by similar size class distributions. This work demonstrates that PPL resin captures DOM compounds with less nitrogenous content and it seems to have a lower affinity for aromatic compounds of marine origin than of terrigenous origin. The study of DOM distribution in a macro-tidal estuary demonstrated the limitations of PPL resin extraction in capturing an internal N-rich DOM production event at the time of sampling. Futhermore, the isotopic composition of the PPL resin retentate appears to depend on the extraction efficiency of the more hydrophobic compounds which changed along the salinity gradient. This study recommends careful interpretations of data that only rely on PPL extractions, particularly for works tracking the origin of DOM in estuaries and comparing DOM composition across ocean biogeochemical domains.

Phytoplankton assemblage shifts with dissolved organic matter properties: A functional perspective for sentinel lakes

Abstract Climate change is altering both dissolved organic matter (DOM) properties and phytoplankton dynamics in lakes. High‐altitude lakes are good sentinels of global change. However, their value as sentinels depends on how well we understand their functioning. This study analysed physical, chemical and biological data during three pre‐defined periods running from complete ice‐cover right to the end of the ice‐free season, in a high‐altitude oligotrophic lake. A functional approach was used to assess how relationships between DOM and the planktonic community vary over time. Phytoplankton functional change was found to occur with shifts in DOM. During the ice‐influenced period, from February to the end of the thaw, the phytoplankton community was dominated by small autotrophs and mixotrophic flagellates and DOM from sediment and terrestrial origin dominated the DOM pool of the lake. Phytoplankton diversity and richness increased during the post‐snowmelt overturn period, when terrestrial DOM dominated the DOM pool. Finally, large siliceous autotrophs, competitive under low nitrogen concentrations and high temperature, dominated almost exclusively during the late summer period (LSP). Increased phytoplankton biomass meant that phytoplankton‐derived DOM was dominant during the LSP. These phenological changes in the phytoplankton community resulted in functional shifts at the base of the food web. Based on the relationships between the variables in the study, it can be deduced that the nature of the relationship between phytoplankton and bacteria progressively shifted from strong top‐down control exerted by phytoplankton over bacteria towards predominantly bottom‐up control at the end of the ice‐free season. Synthesis. Using a field survey starting from complete ice‐cover and lasting right to the end of the ice‐free season in a sentinel lake, we show seasonal shifts in the link between DOM properties and plankton community traits. Differences in environmental conditions and DOM origin explained variation in phytoplankton community structure and function, pointing to seasonal shifts in microbial food web interactions. Our research suggests that, under climate change, the balance between mixotrophy and autotrophy and the control exerted by phytoplankton over bacterioplankton will change in oligotrophic high‐altitude lakes with large, vegetated catchments.

Dissolved organic matter concentration and composition discontinuity at the peat–pool interface in a boreal peatland

Abstract. Pools are common features of peatlands and can represent from 5 % to 50 % of the peatland ecosystem's surface area. Pools play an important role in the peatland carbon cycle by releasing carbon dioxide and methane to the atmosphere. However, the origin of this carbon is not well constrained. A hypothesis is that the majority of the carbon emitted from pools predominantly originates from mineralized allochthonous (i.e., plant-derived) dissolved organic matter (DOM) from peat rather than in situ primary production. To test this hypothesis, this study examined the origin, composition, and degradability of DOM in peat porewater and pools of an ombrotrophic boreal peatland in northeastern Quebec (Canada) for 2 years over the growing season. The temporal evolution of dissolved organic carbon (DOC) concentration, the optical properties, molecular composition (THM-GC-MS), stable isotopic signature (δ13C-DOC), and degradability of DOM were determined. This study demonstrates that DOM, in both peat porewater and pools, presents a diverse composition and constitutes highly dynamic components of peatland ecosystems. The molecular and isotopic analyses showed that DOM in pools was derived from plants. However, DOM compositions in the two environments were markedly different. Peat porewater DOM was more aromatic, with a higher molecular weight and DOC : DON (dissolved organic nitrogen) ratio compared to pools. The temporal dynamics of DOC concentration and DOM composition also differed. In peat porewater, the DOC concentration followed a strong seasonal increase, starting from 9 mg L−1 and reaching a plateau above 20 mg L−1 in summer and autumn. This was explained by seasonal peatland vegetation productivity, which is greater than microbial DOM degradation. In pools, DOC concentration also increased but remained 2 times lower than in the peat porewaters at the end of the growing season (∼ 10 mg L−1). Those differences might be explained by a combination of physical, chemical, and biological factors. The limited hydraulic conductivity in deeper peat horizons and associated DOM residence time might have favored both DOM microbial transformation within the peat and the interaction of DOM aromatic compounds with the peat matrix, explaining part of the shift of DOM compositions between peat porewater and pools. This study did not report any photolability of DOM and only limited microbial degradability. Thus, it is likely that the DOM might have been microbially transformed at the interface between peat and pools. The combination of DOM quantitative and qualitative analyses presented in this study demonstrates that most of the carbon present within and released from the pools originates from peat vegetation. These results demonstrate that pools represent a key component of the peatland ecosystem ecological and biogeochemical functioning.

Impacts of spectral characteristics of dissolved organic matter on methylmercury contents in peatlands, Northeast China.

Dissolved organic matter (DOM) plays an important role in promoting or suppressing methylmercury (MeHg) production in wetlands. However, the effects of DOM spectral characteristics on MeHg levels remain poorly understood in boreal peatlands in Northeast China, where is undergoing remarkable climate warming. In the present work, soil samples were collected from 22 peatlands in the Greater Khingan Mountains (GKM) to test the hypothesis that DOM spectral properties control MeHg levels. DOM was characterized by UV-Vis absorption and fluorescence spectroscopy; the three-dimensional fluorescence excitation-emission matrix (EEM) was used to unveil the origin of DOM. The average total mercury (THg) and MeHg contents were 112.76µg/kg and 12.43µg/kg across all peatlands, respectively. There was a significantly positive correlation between MeHg and the longitudespanning the range from 120 to 123°E (p < 0.05). Proportions of MeHg to THg (%MeHg), 12.3% on average, were positively correlated with DOM humification degree at p < 0.05 level. Protein-like components of DOM (P-like) were negatively related to %MeHg. DOM had positive effects on THg, and P-like components, HIX and BIX can negatively affect THg as well as MeHg. Our findings demonstrate that the spectral characteristics of DOM in soil are crucial to the content of methyl mercury in the GKM soil.

Interference of dissolved organic matter and its constituents on the accurate determination of hydrogen peroxide in water

Hydrogen peroxide (H2O2) is ubiquitous in natural waters, and plays an important role in both biological and chemical processes. This study investigated the influence of dissolved organic matter (DOM) and its substituents on the accurate measurement of H2O2 by peroxidase-mediated depletion of scopoletin fluorescence method which is one of the most widely used methods for the determination of low concentration H2O2 in water. Six DOM and its 24 substituents interfered the determination of H2O2 at environmentally relevant concentration of 200 nM with different levels except 2,6-dimethoxy-1,4-benzoquinone and benzoic acid, which may be associated with origin and types of DOM, and numbers and position of active functional groups in DOM constituents. Each substance concentration and the corresponding decreasing ratio to the measured H2O2 concentration was fitted well to the linear model (R2 > 0.9), and the obtained interfering ratios (k, (mgC L−1)−1), expressing the degree of DOM or its substituents per unit concentration to the measurement of H2O2, were approximate for DOM, but the order of magnitude of k values of DOM constituents took on a large span from 10–3 to 10–7. When DOM levels exceed 0.1 mgC L−1 or its substituent concentration is at nM level (low to 20 nM), the H2O2 content will be underestimated substantially. A quantitative structure–activity relationship model with remarkable stability and strong predictability for the k of DOM substituents to H2O2 measurement was established, and the k was related to the electron transfer capacity, hydrophobicity and stability of these compounds.

Relationships between the Physicochemical Properties of Dissolved Organic Matter and Its Reaction with Sodium Borohydride.

The reaction of dissolved organic matter (DOM) with sodium borohydride has been used to understand the geographic origin of DOM and investigate the photophysical model underlying DOM's optical properties. However, the physicochemical properties of DOM (e.g., molecular size and charge) that influence the kinetics and ultimate reducibility of DOM by borohydride remain poorly characterized. Herein, we studied the kinetics of DOM-borohydride reactions by recording absorbance and fluorescence spectra at a high temporal frequency (every ∼10 min for 24 h) for a diverse set of DOM isolates of aquatic and soil origin. The reducibility of DOM by sodium borohydride (as judged by relative removal of initial absorbance) varied appreciably among the DOM samples studied, with soil humic substances being less reducible than aquatic humic substances and natural organic matter. While statistically significant correlations were found between the reducibility of DOM and descriptors of molecular size, these descriptors were not able to differentiate the reducibility of soil versus aquatic DOM isolates that had similar bulk properties. Thus, it appears that the extent of absorbance removal by borohydride is largely driven by the origin of the humic substance isolate (aquatic vs soil) instead of molecular size or charge. Borohydride reduction resulted in increased fluorescence emission across UV and visible excitation wavelengths. However, the enhanced emission at visible excitation decreased over a time period of hours to days, suggesting that reduction of an important subset of DOM chromophores is reversible. This reversibility in fluorescence emission is consistent with the small role of quinones in the absorbance of DOM but suggests a more important role for quinone-containing charge-transfer contacts in the fluorescence of DOM, particularly at visible excitation wavelengths.

Insight into interactions of heavy metals with livestock manure compost-derived dissolved organic matter using EEM-PARAFAC and 2D-FTIR-COS analyses

Dissolved organic matter (DOM), as the most active ingredient in compost, directly determines the speciation and environmental behavior of HMs. Here, the binding properties of DOM derived from chicken-manure compost (CHM), cow-manure compost (COM) and pig-manure compost (PIM) with HMs were explored by analyses of Fluorescence excitation-emission matrix parallel factor (EEM-PARAFAC) and two-dimensional correlation Fourier transform infrared spectroscopy (2D-FTIR-COS). Results showed that the binding characteristics vary with origin of DOM and type of HMs. The fulvic-like component dominated the transformation of HMs speciation, and CHM-DOM had higher affinity with HMs and greater risk causing pollution due to its higher aromaticity, molecular weight and distribution of fluorescent components. Moreover, Cu(II) can efficiently bind to DOM with the stability constants (log kM) ranging from 4.53 to 5.38, followed by Pb(II) (3.34–3.57), whereas Cd(II) can hardly bind to DOM. The amide and polysaccharide were the predominant sites for HMs binding in CHM-DOM, and polysaccharide and phenolic in COM-DOM, while phenolic and amide in PIM-DOM, respectively. Although the proportion of protein-like components and non-fluorescent polysaccharides in DOM were low, their role in HMs binding should not be ignored. In brief, the environmental risk caused by livestock manure compost may originate from interactions between DOM and HMs.

Linkages between greenhouse gases (CO2, CH4, and N2O) and dissolved organic matter composition in a shallow estuary

Estuarine systems receive large amounts of organic matter that enhance the production of greenhouse gases (GHGs), such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). Despite considerable research on GHGs and dissolved organic matter (DOM) distribution in estuaries, little is known about the linkage between these gases and DOM composition. Here we evaluated the relationship between three GHGs (CO2, CH4, and N2O) and DOM composition, determined through optical properties, in Guadalete estuary (Bay of Cadiz, Spain). The partial pressure of CO2, and CH4 and N2O concentrations ranged between 332.8 and 6807.1 μatm, 19.9–6440.1 nM, and 6.8–283.9 nM, respectively. Thus, the Guadalete estuary was a source of CO2, CH4 and N2O to the atmosphere. We validated three PARAFAC components related to humic-like fluorescence from terrestrial, microbial and effluent sources, and one with protein-like material. Humic-like components accounted for 86% ± 6% of the total FDOM pool, indicating a predominantly allochthonous DOM origin. The three GHGs were significantly linked to DOC concentration and DOM composition, exhibiting different patterns in these linkages. Terrestrial and microbial humic-like substances with increasing aromaticity might enhance pCO2 in Guadalete estuary. Dissolved CH4 concentrations showed the strongest relationship with DOM composition, indicating that humic and protein-like material are linked with their distribution. In contrast, dissolved N2O was only related with the protein-like fraction and with humic-like material derived from anthropogenic activities (sewage and agriculture). Our results further indicate that a possible coupling between benthic fluxes of GHGs and DOM might be occurring in this shallow estuary. We conclude that it is important to account for DOM composition when studying GHGs distribution in estuarine systems to understand their roles and potential responses associated with climate change.

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

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

Spectroscopic indices trace spatiotemporal variability of dissolved organic matter in a river system with Karst characteristic

River acts as a continuum of dissolved organic matter (DOM) transport and transformation. However, underlying controls of fluvial DOM spatiotemporal variability has yet to be revealed. Here, we explored the DOM component, molecular weight and source in the Longchuan River, a headwater tributary of the Yangtze with Karst characteristic. Concentrated rainfall, severe soil erosion and in-situ metabolism primarily controlled DOM component and molecular weight in the Karst river, resulting in accumulation of recalcitrant (high molecular weight) DOMs from tributaries to the main stem in the post-wet period. We found a robust relationship between DOM absorption coefficients (a280 and a350) and dissolved organic carbon (DOC) concentrations from a multiple linear regression model: [DOC] = 0.098a285 + 0.591a350 + 1.337 (R2 = 0.83, p < 0.001). High fluorescence index (FI) values (>1.9) indicated a dominant origin of autochthonous DOM. Biological index (BIX) values exhibited an increasing trend along the flow direction, suggesting a large amount of recently produced DOM from phytoplankton downstream. Our findings demonstrated that both allochthonous and autochthonous inputs regulated DOM dynamics in a river continuum with Karst characteristic, highlighting spatiotemporal variability of DOM response to River Continuum Concept (RCC).

Factors controlling the distributions of dissolved organic matter in the East China Sea during summer

To determine the distribution of dissolved organic matter (DOM) in the East China Sea (ECS) during the summer, we measured the dissolved organic carbon (DOC) and nitrogen (DON), fluorescent dissolved organic matter (FDOM), and chlorophyll a (Chl. a) in the upper 100-m layer of this region during July and September 2015. The DOC (r2 = 0.72 and 0.78 in July and September, respectively) and DON (r2 = 0.43 and 0.33) were significantly correlated with salinity, suggesting that the river is the primary origin of DOM. However, we found that at a DOC “pulse” under a salinity ranging from 24 to 35, the extrapolating DOC values (304 ± 11 μM) were twice higher than those with a salinity of close to 0, as found in a previous study. The excess DOC concentration seemed to be attributed to the microbial metabolism during transport from the estuary based on the good relationships between DOC and marine humic-like FDOM (r2 = 0.42 and 0.47), as well as the fluorescence, humification, and biological indexes, but showed no correlation with Chl. a. Thus, the results of our study indicate that microbial activities can be a significant factor controlling the distribution of DOM in the ECS during summer.