Amount Of Dissolved Organic Matter Research Articles

The loss of dissolved organic matter from biological soil crust at various successional stages under rainfall of different intensities: Insights into the changes of molecular components at different rainfall stages

Biological soil crusts (BSCs) are typical covers in arid and semiarid regions. The dissolved organic matter (DOM) of BSCs can be transported to various aquatic ecosystems by rainfall-runoff processes. However, the spatiotemporal variation in quality and quantity of DOM in runoff remains unclear. Herein, four kinds of runoff plots covered by four successional stages of BSCs were set up on slopes, including bare runoff plot (BR), cyanobacteria crust covered runoff plot (CR), mixed crust covered runoff plot (MIR), and moss crust covered runoff plot (MOR). The quantity and quality of DOM in runoff during rainfall was investigated based on the stimulated rainfall experiments combined with optical spectroscopy and ultra-high resolution mass spectrometry analyses. The results showed that the DOM concentrations (i.e., 0.30 to 45.25 mg L−1) in runoff followed the pattern of MOR>MIR>CR>BR, and they were exponentially decreased with rainfall duration. The DOM loss rate of BR (8.26 to 11.64 %) was significantly greater than those of CR, MIR, and MOR (0.84 to 3.22 %). Highly unsaturated compounds (HUCs), unsaturated aliphatic compounds (UACs), saturated compounds (SCs), and peptide-like compounds (PLCs) were the dominated compounds of the water extractable DOM from the original soils. Thereinto, PLCs and UACs were more easily leached into runoff during rainfall. The relatively intensity of HUCs in runoff generally decreased with rainfall duration, while the relatively intensities of UACs, PLCs, and SCs slightly increased with rainfall duration. These findings suggested that the DOM loss rate was effectively decreased with the successional of BSCs during rainfall; meanwhile, some labile compounds (e.g., PLCs and UACs) were transported into various aquatic ecosystems by rainfall-runoff processes.

Optical properties and molecular compositions of dissolved organic matter in multiple runoff components during rainfalls on the karst hillslope

Understanding the chemical composition, origin, and molecular structure of dissolved organic matter (DOM) in multi-interface runoff is essential for comprehending the fate of laterally transported DOM in complex soil-epikarst systems of karst hillslopes. Limited information, however, is available for the optical properties and molecular compositions of the transported OM in multiple runoff components on the karst hillslope in relation to land-uses and soil thicknesses. In this study, we conducted a study to observe the changes in the quantity and quality of DOM in multiple interface flow (surface, subsurface, and epikarst) during natural rainfall events in 2022 in karst hillslopes that are covered by different land uses (cropland and shrubland) and soil thicknesses (with mean depths of 66.0 cm for deeper soil and 35.4 cm for shallower soil) in the karst region of southwest China. chemcial compositions of runoff DOM were determined by optical analysis and microbial compositions in runoff were inferred with high-throughput sequencing. The results showed that the soil-epikarst structure was controlling the runoff DOM quantity and quality during rainfall events. A decrease in the aromaticity, humification, unsaturation, and oxidation degree and an increase in carbohydrate, aminosugars, protein, and lipid compounds were found from surface to epikarst flow, indicating that plant-and soil-derived carbon decreased, while the microbially-derived carbon increased. The results were further comfirmed by the higher bacterial richness and diversity, along with fungal diversity in the epikarst flow compared to other runoff components. The bio-labile protein materials (C2) were the most important component of runoff DOM output in karst hillslopes. In surface and subsurface flow, rainfall amount, runoff rate, and discharge significantly affected the DOM concentration and quality during rainfalls, indicating that the dynamics of DOM in runoff from karst hillslopes were predominantly influenced by hydrological processes. Furthermore, the runoff DOM quality in cropland was dominated by lower unsaturation and oxidation degrees and higher protein component, compared to those in shrubland. The compositions of DOM in runoff from hillslope plots with thicker soils were primarily characterized by microbially-derived materials. Our findings were conducive to understanding the mechanism governing the migration of DOM quality and quantity in discharge during multi-interface hydrological processes on karst hillslopes.

Quantity and quality characteristics of DOM loss in sloping cropland under natural rainfall in Southwestern China

Rainfall events lead to dissolved organic matter (DOM) loss in sloping cropland, resulting in a high risk of soil carbon emissions and water pollution. However, limited studies have concentrated on the quality of DOM during different loss pathways in sloping cropland. In this study, the characteristics of DOM loss were explored during different loss pathways (surface runoff, interflow (0–20 cm), interflow (20–40 cm), and sediment) under different slope gradients (10° and 15°), based on natural rainfall. The results showed that surface runoff was the primary carrier of DOM in the sloping cropland, occupying 33 %-43 % of the total loss flux. The slope gradient significantly increased the DOM loss flux of surface runoff and sediment (p < 0.05). Parallel factor analysis (PARAFAC) analyses indicated that four fluorescent components of DOM were detected in both the runoff and sediment. The humic-like components (C1 and C2) accounted for higher than 70 % of the DOM in surface runoff. The protein-like components (C3 and C4) tended to dominate the DOM in the sediment and accounted for 63.02 %-66.93 %. An increased slope gradient exacerbated hydrophobic carbon loss in runoff. The hydrophobicity and aromaticity of DOM in sediment were higher than those in surface runoff. The molecular weight and bioavailability of DOM in sediment were lower than those in surface runoff. The range of humification index (HIX) was 0.63–0.70, indicating a low degree of DOM humification in sloping cropland. Our study clarified the differences between DOM quantity and quality during different loss pathways, which can provide a theoretical foundation for the effective prevention and control of DOM loss and the sustainable agricultural development of sloping cropland.

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.

Dynamic Changes of Dissolved Organic Matter Derived from Algal Decomposition and the Environmental Effects in Eutrophic Lakes

The global occurrences of lake eutrophication have led to algal bloom and the subsequent algal decomposition, releasing high amounts of algae-derived dissolved organic matter (DOM) into the lake water. Algae-derived DOM could regulate the quantity and composition of DOM in lake water and further impact the biogeochemical cycles of multiple elements. In this study, the dynamic changes in the quantity and quality of DOM during algal decomposition under different eutrophic scenarios (e.g., from oligotrophication to severe eutrophication) were monitored, and the corresponding environmental effects (e.g., microbial responses and greenhouse gas emissions) caused by algal decomposition were further explored. The results showed that algal decomposition significantly increased the DOM levels, bioavailability, and intensities of fluorescent components in the water. The total DOM levels gradually decreased, whereas the average molecular weight increased along the decomposition process. Furthermore, unsaturated hydrocarbon and aliphatic compounds were preferentially utilized by microorganisms during algal decomposition, and some refractory molecules (e.g., lignin, condensed hydrocarbons, and tannin with high O/C values) were synchronously generated, as evidenced by the results from ultra-high-resolution mass spectrometry. The dominant bacterial species during algal decomposition shifted from Proteobacteria (46%) to Bacteroidetes (42%). In addition, algae addition resulted in 1.2-5 times the emissions of CO2 and CH4 from water, and the emission rates could be well predicted by the optical index of a254 in water. This study provides comprehensive perspectives for understanding the environmental behaviors of aquatic DOM and further paves the ways for the mitigation of lake eutrophication.

Unveiling temporal variation in dissolved organic matter (DOM) by high-frequency spectroscopic measurements in a shallow eutrophic lake

Dissolved organic matter (DOM) plays an important role in biogeochemistry of lake ecosystems. Studies measuring DOM at short intervals in lakes are still rare, thus its short-term dynamics are largely unknown. We investigated DOM temporal variation in large and shallow eutrophic Lake Võrtsjärv (Estonia) during one growing season (May–September 2016) using field-deployable spectrometer In Situ Spectral Analyzer (GO Systemelektronik GmbH) to measure absorbance spectra (wavelength range 200–708 nm) at a 2-hour interval coupled with monthly discrete water sampling. Collected spectra were analyzed together with some in-lake variables, lake metabolic rates, and meteorological and hydrological data using Boosted Regression Tree (BRT) and Random Forest (RF) models. Different spectral parameters were used to assess total and allochthonous DOM quantity, and relative share of autochthonous DOM. All parameters, i.e., DOM quantity and quality, varied on a large scale. For example, dissolved organic carbon (DOC) concentrations ranged from 12.0 to 17.3 mg L-1. High levels of DOM were mainly of allochthonous origin; strong relationship with inflow indicated the same. Relative share of autochthonous DOM increased with rising air temperature as primary production rose in warm water; however, we did not find any direct relationships with gross primary production. RF and BRT models explained up to 38% and 63% of DOM temporal variability, respectively. Our results showed that monthly water samples did not capture large variation in DOM. Therefore, high-frequency measurements using in situ spectrometer improve temporal representativeness of DOM monitoring in lakes compared to traditional sampling methods.

Hydrological alteration drives chemistry of dissolved organic matter in the largest freshwater lake of China (Poyang Lake)

As the largest reactive organic carbon pool, dissolved organic matter (DOM) plays an important role in various biogeochemical processes in lake ecosystems. Recently, climate change-induced extreme events (e.g., floods and droughts) have significantly modified the hydrological patterns of lakes worldwide, and regulated the quality and quantity of DOM. However, the responses of DOM chemistry to hydrological alteration in lakes remain poorly understood. Here we investigated the influences of hydrological alteration on sources, composition, and characteristics of DOM in Poyang Lake, the largest freshwater lake in China, using a combination of bulk chemical, optical and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) techniques. Results show various sources of DOM (autochthonous, allochthonous, and anthropogenic inputs) and significant variations in DOM chemistry across four hydrological periods (the retreating, dry, rising, and flooding periods) in Poyang Lake. During the retreating, rising, and flooding periods, DOM was characterized by higher aromaticity, humification degree, and recalcitrance, and exhibited pronounced allochthonous signatures. In contrast, DOM contained more S-containing molecules and aliphatic compounds during the dry period, displaying relatively stronger autochthonous features. Terrestrial inputs and the lignin-CHOS formation process are likely the primary underlying mechanisms shaping the differences in DOM chemistry in Poyang Lake. Our research demonstrates the significant impacts of hydrological alteration on DOM dynamics, and provides an improved understanding of DOM biogeochemical cycles and carbon cycling in large aquatic systems under global climate change.

Contrasting optical properties of dissolved organic matter between oceanic regions near the Getz and Dotson ice shelves in the Amundsen Sea, West Antarctica

The Amundsen Sea, located in West Antarctica, is experiencing rapid melting due to the intrusion of Circumpolar Deep Water, which is causing ice sheet thinning and basal melting. The resulting changes can affect the biogeochemical cycle of dissolved organic matter (DOM) by supplying iron from sea ice and/or glacier, thereby influencing primary production and ocean circulation. Therefore, it is crucial to understand the dynamics of the DOM in this region. In this study, our primary focus was to examine the optical properties of DOM in the oceanic regions adjacent to the West Getz Ice Shelf (WGIS) and the Dotson Ice Shelf (DIS). Significant differences in DOM optical properties, including the chromophoric DOM (CDOM) absorption coefficient at 350 nm (a350), spectral slope coefficient (S275–295), and specific UV absorbance at 254 nm (SUVA254), were observed between the WGIS and DIS regions (t-test, p < 0.05). Notably, the WGIS regions exhibited high a350 values. Additionally, the S275–295 and SUVA254 values, which serve as indices of molecular weight, indicated that the DOM pool in the WGIS regions was dominated by high molecular weight compounds with a substantial proportion of aromatic compounds. In contrast, the low values of a350 and SUVA254 along with the high S275–295 values in the DIS region suggested the dominance of low molecular weight CDOM associated with compounds of lower aromaticity. Furthermore, significant negative correlations were found between biomass of Phaeocystis antarctica (P. antarctica) and phosphate (PO4) in the WGIS regions (r2 = 0.82, p < 0.01 for WGIS 1 and r2 = 0.73, p < 0.01 for WGIS 2). However, no significant relationship was observed in the DIS region. These findings suggest that the high value and molecular weight of a350, extending from the surface layer to the deep layer, in the WGIS regions were associated with autochthonous sources, primarily driven by the colony-forming bloom of P. antarctica. These findings demonstrate that the quantity and quality of DOM in the Amundsen Sea are strongly affected by bloom conditions. The results emphasize that a combination of physical and biological processes interacts in complex ways to determine the characteristics of DOM in the Amundsen Sea.

MIEX resin and enhanced coagulation treatment of high-bromide natural water: Chlorine reactivity and DBP precursors removal

Both organic and inorganic constituents play a major role in the formation and speciation of disinfection by-products (DBPs) under chlorination. In this study, the removal of organic and inorganic precursors to DBPs by ion exchange and coagulation was examined, and the relationships between characteristics of dissolved organic matter (DOM), chlorine reactivity, and the formation of DBPs in high-bromide natural water were investigated. Formation potential tests were conducted for trihalomethanes (THMs) and haloacetronitriles (HANs) before and after the different treatments (coagulation, magnetic ion exchange (MIEX) resin, and combined MIEX/coagulation). At a low resin dose, MIEX was more effective than coagulation for DOM removal. The advantages of the MIEX resin were more prominent at a high resin dose because substantial amounts of DOM and bromide were simultaneously removed. The maximum bromide uptake on the MIEX resin was 0.02 mg-Br/mL. A 4-component PARAFAC model was developed using a dataset of 148 fluorescence excitation-emission matrices (EEMs) generated from pre-chlorinated and post-chlorinated samples. The maximum fluorescence intensities of humic-like components were found to be strongly correlated to THMs formation (R2 = 0.79–0.89). The MIEX treatment substantially lowered the formation of THMs (19–51%) and HANs (70–95%) due to its ability to remove humic-like DOM and bromide. The fluorescence loss for humic-like DOM was found to increase over a chlorination time of 3 days, suggesting that these compounds had stronger reactivity to chlorine compared to protein-like DOM. The chlorine reactivity of protein-like DOM increased after treatments as the residual chlorine was able to react with the less reactive fractions of DOM after chlorine-reactive compounds were removed.

Adsorption and thermal stability of dissolved organic matter on Ca- and Mg-exchanged montmorillonite: Implications for persistence in soils and sediments

Dissolved organic matter (DOM) represents a vital and highly dynamic component of organic matter in the environment. Despite its significance, there is still limited knowledge regarding how different base cations and chemical conditions influence the preservation of complex natural DOM through adsorption. This study aimed to investigate the adsorption of natural DOM onto montmorillonite (Mt) by systematically exploring the effects of exchanging cations (Ca2+ and Mg2+), pH levels (4 and 7), and DOM molecular weight (< 10, 10–100, and > 100 kDa) on the mechanisms and thermal stability of adsorbed DOM. To this end, we conducted a series of adsorption experiments, complemented by spectroscopic and thermal analyses. Our results revealed that lower pH and higher DOM molecular weight enhanced adsorption, with affinity for carbohydrate-like compounds. Notably, changes in d001 spacing and peak broadening indicated intercalation of DOM into the interlayer space of Mt, which was positively correlated with the amount of DOM adsorbed. Conversely, increased adsorption was found to negatively correlate with thermal stability. This was attributed to the prevalence of weaker DOM-DOM interactions occurring at higher DOM weight and lower pH, owing to reduced repulsion among protonated organic molecules, in contrast to stronger electrostatic interactions near the Mt surface that appeared to dominate at lower DOM weight and higher pH conditions. Intriguingly, no clear preference for DOM adsorption on Ca- or Mg-exchanged Mt was observed, suggesting similar efficiencies of these cations in stabilizing DOM through cation-bridging. Our findings provide significant insights into the mechanisms involved in mineral-organic associations and have implications for understanding the persistence of DOM in soils and sediments.

Dissolved organic matter and nutrient processing in organic-rich subterranean estuaries: Implications for future land use and climate scenarios

The subterranean estuary (STE) is a recognized reactive biogeochemical zone at the groundwater–seawater interface in coastal regions. However, few studies have explored dissolved organic matter (DOM) and nutrient processes in buried organic-rich STEs (with up to 20 % of organic matter content), despite their potential contributions to coastal water hypoxia and greenhouse gas emissions. This study conducted controlled laboratory experiments to investigate the physicochemical controls on DOM and nutrient processing in organic-rich STEs, considering variations in groundwater nitrate (NO3–) concentrations, salt concentration, seawater ions, and incubation times. Results showed elevated levels of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) in pore water, primarily from particulate organic matter (POM) degradation that originated from decayed vascular plants. POM-to-DOM degradations further resulted in the accumulation of ammonium (NH4+) and highly unsaturated compounds in all treatments. The addition of high-ionic-strength treatments (e.g., seawater and sodium chloride [NaCl] solution) reduced DOC solubility and selectively removed dissolved aromatic compounds in porewater. The cation-rich seawater shifted the porewater NH4+ generation pathway from predominantly biological (re)mineralization in freshwater to abiotic (desorption via ion exchange) pathways in the saline water setup. Orthophosphate (PO43−) dynamics were likely to be influenced by the iron-rich sediment surface in both freshwater and saline water scenarios. Our experiments further indicated that the long-term incubation enriched DOM concentration with a high degradation state. This work demonstrated that organic-rich STEs are significant sources of less labile DOM and NH4+ to coastal waters. In the context of global climate change, our results illustrate the sensitivity of DOM and nutrient biogeochemical cycling in STEs to salinization and altered residence time, consequently affecting the quantity and quality of DOM and nutrients transported to coastal waters.

Fluorescence spectroscopic characterization of dissolved organic matter in the wastewater treatment plant and hybrid constructed wetlands coupling system in winter: A case study in eastern China

Dissolved organic matter (DOM) in municipal wastewater can have a detrimental effect on aquatic ecosystems, as DOM can participate in the global carbon cycle and change the transport of other pollutants. The characteristics of DOM can also affect the utilization efficiency of dissolved organic carbon by microorganisms in water. In this study, variations in DOM quantity and quality in a full-scale wastewater treatment plant (WWTP) coupled with a hybrid constructed wetland (CW) system during cold periods were characterized by using excitation-emission matrix spectroscopy combined with parallel factor analysis (EEM-PARAFAC). The results showed that the DOM concentration significantly decreased after exiting the WWTP, while a slight increase was found in the CW. The coupled system could significantly eliminate influent DOM with a removal efficiency of 92.1%. The CW system could still remove DOM even in winter. Five fluorescent components, including three humic-like components, one protein-like component and one tyrosine-like component, were identified. Although the biological treatment process in the WWTP contributed a large number of protein-like substances, the optical indices showed that the bioavailability of wastewater was gradually reduced, indicating that DOM was selectively removed by the integrated system. Moreover, there were significant correlations between water quality parameters and DOM indices. This study could contribute to a better understanding of the elimination process of dissolved organic carbon in coupled systems of WWTPs and CWs and offer novel ideas for organic carbon resource recovery and water quality monitoring in watershed environments.

Removing DOM from chloride modified hydrochar could improve Cu2+ adsorption capacity from aqueous solution

The behavior and composition of hydrochar-based dissolved organic matter (DOM) would affect the efficiency of copper (Cu) removal from wastewater through adsorption. In this study, the reed was hydrolyzed in the presence of feedwater with and without ZnCl2, FeCl3, and SnCl4 to produce pristine hydrochars (PHCs), which were named H2O-HC, ZnCl2-HC, FeCl3-HC, and SnCl4-HC. After removal of DOM, washed hydrochars (WHCs) were obtained, labelled as W–H2O-HC, W-ZnCl2-HC, W-FeCl3-HC, and W-SnCl4-HC. The release dynamics of DOM from PHCs were analyzed, and the adsorption behaviors of Cu2+ on both PHCs and WHCs were investigated. The results showed that chloride-modifications were beneficial for the porosity, specific surface area (SSA), and functional groups of WHCs. Meanwhile, the quantity of hydrochar-based DOM was significantly affected by chloride-modifications. In particular, the relative contents of Ar–P and Fa-L in the DOM released from hydrochars varied with time and modification. Furthermore, the Qe of Cu2+ adsorption on WHCs followed the order of W-SnCl4-HC > W-FeCl3-HC > W-ZnCl2-HC > W–H2O-HC at 15 °C. Compared to PHCs, the adsorption capacity of Cu2+ on WHCs was improved by 7.15–119.77% at the temperature of 35 °C. Simultaneously, the adsorption capacity of Cu2+ in WHCs showed a significant correlation with the SSA via physical adsorption (P < 0.05). Moreover, XPS analysis revealed that Cu2+ adsorption also occurred via complexation and chelation through newly formed Cu–O group between W-SnCl4-HC and Cu2+. Notably, the increase of Cu2+ adsorption in WHCs was significantly correlated with the release of Fa-L and Ar–P from PHCs (P < 0.05). This study found that the content and composition of hydrochar-based DOM could be a major driving factor for Cu2+ adsorption.

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.

Lignin phenol quantification from machine learning‐assisted decomposition of liquid chromatography‐absorbance spectroscopy data

AbstractAnalysis of lignin in seawater is essential to understanding the fate of terrestrial dissolved organic matter (DOM) in the ocean and its role in the carbon cycle. Lignin is typically quantified by gas or liquid chromatography, coupled with mass spectrometry (GC‐MS or LC‐MS). MS instrumentation can be relatively expensive to purchase and maintain. Here we present an improved approach for quantification of lignin phenols using LC and absorbance detection. The approach applies a modified version of parallel factor analysis (PARAFAC2) to 2nd derivative absorbance chromatograms. It is capable of isolating individual elution profiles of analytes despite co‐elution and overall improves sensitivity and specificity, compared to manual integration methods. For most lignin phenols, detection limits below 5 nmol L−1 were achieved, which is comparable to MS detection. The reproducibility across all laboratory stages for our reference material showed a relative standard deviation between 1.47% and 16.84% for all 11 lignin phenols. Changing the amount of DOM in the reaction vessel for the oxidation (dissolved organic carbon between 22 and 367 mmol L−1), did not significantly affect the final lignin phenol composition. The new method was applied to seawater samples from the Kattegat and Davis Strait. The total concentration of dissolved lignin phenols measured in the two areas was between 4.3–10.1 and 2.1–3.2 nmol L−1, respectively, which is within the range found by other studies. Comparison with a different oxidation approach and detection method (GC‐MS) gave similar results and underline the potential of LC and absorbance detection for analysis of dissolved lignin with our proposed method.

Effects of incorporating Mn into goethite on adsorption of dissolved organic matter and potentially toxic elements in soil: Isotherms, kinetics, and mechanisms

Goethite is ubiquitous in the environment and plays key role in preserving dissolved organic matter (DOM) and deactivating potentially toxic elements (PTEs) by adsorbing DOM and PTEs. Various non-Fe metals are usually incorporated into natural goethite, substituting Fe in the goethite structure, which dramatically influence the physico-chemical properties and adsorption behavior of the goethite. In the present study, adsorption of DOM and Pb(II) on Mn-substituted goethite samples was investigated. The results displayed that the specific surface area (SSA) of mineral samples increased by 67.6% as the incorporation of Mn for Fe, from 25.71 m2 g−1 for pure goethite to 43.09 m2 g−1for Mn-goethite. Besides, the Mn substitution caused more hydroxyl groups and relatively fewer positive charges on mineral surface, and Mn in the Mn-goethite samples was predominantly present as Mn(III). The amount of DOM adsorbed to per unit mass of goethite was increased as Mn content increased, which was attributed to Mn incorporation increasing the SSA of mineral samples. However, the SSA-normalized absorption capacity for goethite to DOM was decreased by Mn because Mn substitution decreased the number of positive charges of mineral samples, which weakened the electrostatic attraction between DOM and the minerals. The amount of Pb(II) adsorbed to per unit mass of goethite was increased by Mn substitution, and the amount of Pb(II) adsorbed to per unit SSA of goethite increased as the amount of Mn substitution increased, indicating that the increased capacity for adsorbing Pb was not only caused by the SSA increasing but also by there were more surface hydroxyl groups on the Mn-goethite than pure goethite and Pb(II) preferentially adsorbed to Mn sites on the Mn-goethite. The present study results showed that Mn-goethite could be used to sequester DOM and remediate soil contaminated with PTEs because Mn-goethite has a high adsorption capacity and is environmentally benign.

How does anthropogenic activity influence the spatial distribution of dissolved organic matter in rivers of a typical basin located in the Loess Plateau, China

River ecosystems interact strongly with adjacent terrestrial environments and receive dissolved organic matter (DOM) from a variety of sources, all of which are vulnerable to human activities and natural processes. However, it is unclear how and to what extent human and natural factors drive DOM quantity and quality changes in river ecosystems. Here, three fluorescence components were identified via optical techniques, including two humic-like substances and one protein-like component. The protein-like DOM was mainly accumulated in anthropogenically impacted regions, while humic-like components exhibit the opposite trend. Furthermore, the driving mechanisms of both natural and anthropogenic factors on the variations in DOM composition were investigated using partial least squares structural equation modelling (PLS-SEM). Human activities, especially agriculture, positively influence the protein-like DOM directly by enhancing anthropogenic discharge with protein signals and also indirectly by affecting water quality. Water quality directly influences the DOM composition by stimulating in-situ production through a high nutrient load from anthropogenic discharge and inhibiting the microbial humification processes of DOM due to higher salinity levels. The microbial humification processes can also be restricted directly by a shorter water residence time during the DOM transport processes. Furthermore, protein-like DOM was more sensitive to direct anthropogenic discharge than indirect in-situ production (0.34 vs. 0.25), especially from non-point source input (39.1%), implying that agricultural industry optimization may be an efficient way to improve water quality and reduce protein-like DOM accumulation.

Dissolved Organic Matter as Affected by Forms and Doses of Nitrogen Applied to Soils of Temperate Deciduous Forests in China

Dissolved organic matter (DOM) is an important component in the biogeochemical cycles of elements like nitrogen (N) and carbon. The aim of this study was to elucidate the effect of long-term inorganic N addition on the quantity and quality of DOM in forest soils. A field study was conducted on three forms of inorganic N, namely (NH4)2SO4, NH4NO3, and NaNO3, applied at low (50 kg N ha−1) or high (150 kg N ha−1) annual doses from 2011 to 2019. The total dose was split into eight equal monthly doses applied during the growing season (from March to October). Both the form and the dose increased the content of dissolved organic carbon (DOC) in soil, the strongest effect being that of NaNO3. However, the higher dose had a weaker effect because of N enrichment. UV-visible (UV-vis) and excitation-emission matrix (EEM) spectroscopy showed that the addition of N made DOM more aromatic and increased the degree of humification. EEM-parallel factor analysis (PARAFAC) modelling suggested that DOM in the forest soils mainly contained a fulvic-like constituent (C1), humic-like substances (C2), and aromatic protein-like components (C3). The addition did not change the position of the DOM fluorophore in the soil but affected the proportions of the three PARAFAC-derived components (increasing those of C1 and C2 but decreasing that of C3), indicating that long-term addition of N may amplify the decrease in protein-like constituents of surface soil. Hence, N addition increased the complexity of the DOM structure.

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.

Removal of dissolved organic matter from the woodchip bioreactor start-up by foam fractionation.

Denitrifying woodchip bioreactors are passive, low-tech systems primarily designed to remove nitrate from shallow ground waters as well as point source discharges. Despite their capacity to achieve constant nitrate removal over several years, natural aquatic environments may be affected by the leaching of dissolved organic matter (DOM) from fresh woodchips during start-up. Simple on-site measures might reduce the woodchip leachate during start-up and thus add to the overall environmental sustainability of woodchip bioreactor installations. The aim of the study was to investigate whether foam fractionators could provide an effective solution. Water was flowed through fresh laboratory-scale woodchip bioreactors and recirculated through foam fractionators for 11 days. The bioreactors removed nitrate but increased phosphate and ammonia, which were not effectively removed via foam fractionation. However, foam fractionation did remove 37.8 ± 4.7% of the dissolved chemical oxygen demand (CODdiss) leached during the first 11 days of operation. Fluorescence spectroscopy revealed that the DOM composition differed between the foam and water, where the foam fraction contained higher amounts of DOM associated with the highest bioavailability and hence the greatest potential environmental impact. Optimised foam fractionators could therefore help to reduce the environmental impact of DOM leachate from woodchip bioreactors during start-up.