Dissolved Organic Matter Concentration Research Articles

Post column infusion of an internal standard into LC-FT-ICR MS enables semi-quantitative comparison of dissolved organic matter in original samples.

Ultrahigh resolution mass spectrometry hyphenated with liquid chromatography (LC) is an emerging tool to explore the isomeric composition of dissolved organic matter (DOM). However, matrix effects limit the potential for semi-quantitative comparison of DOM molecule abundances across samples. We introduce a post-column infused internal standard (PCI-IS) for reversed-phase LC-FT-ICR MS measurements of DOM and systematically evaluate matrix effects, detector linearity and the precision of mass peak intensities. Matrix effects for model compounds spiked into freshwater DOM samples ranging from a headwater stream to a major river were reduced by 5-10% for PCI-IS corrected mass peak intensities as compared to raw (i.e., untransformed) intensities. A linear regression of PCI-IS corrected DOM mass peak intensities across a typical DOM concentration range (2-15 mg dissolved organic carbon L-1) in original, non-extracted freshwater samples demonstrates excellent linearity of the detector response (r2 > 0.9 for 98% of detected molecular formulas across retention times). Importantly, PCI-IS could compensate for 80% of matrix effects across an environmental gradient of DOM composition from groundwater to surface water. This enabled studying the ionization efficiency of DOM isomers and linking the observed differences to the biogeochemical sources. With PCI-IS original, non-extracted DOM samples can be analysed by LC-FT-ICR MS without carbon load adjustment, and mass peak intensities can be reliably used to semi-quantitatively compare isomer abundances between compositionally similar DOM samples.

Dissolved organic matter quality in thermokarst lake water and sediments across a permafrost gradient, Western Siberia

Thermokarst (thaw) lakes of permafrost peatlands are among the most important sentinels of climate change and sizable contributors of greenhouse gas emissions (GHG) in high latitudes. These lakes are humic, often acidic and exhibit fast growing/drainage depending on the local environmental and permafrost thaw. In contrast to good knowledge of the thermokarst lake water hydrochemistry and GHG fluxes, the sediments pore waters remain virtually unknown, despite the fact that these are hot spots of biogeochemical processes including GHG generation. Towards better understating of dissolved organic matter (DOM) quality at the lake water – sediment interface and in the sediments pore waters, here we studied concentration and optical (UV, visual) properties of DOM of 11 thermokarst lakes located in four permafrost zones of Western Siberia Lowland. We found systematic evaluation of DOM concentration, SUVA and various optical parameters along the vertical profile of lake sediments. The lake size and hence, the stage of lake development, had generally weak control on DOM quality.The permafrost zone exhibited clear impact on DOM porewater concentration, optical characteristics, aromaticity and weight average molecular weight (WAMW). The lowest quality of DOM, reflected in highest SUVA and WAMW, corresponding to the dominance of terrestrial sources, was observed at the southern boundary of the permafrost, in the sporadic/discontinuous zone. This suggests active mobilization of organic matter leachates from the interstitial peat and soil porewaters to the lake, presumably via subsurface or suprapermafrost influx. Applying a substitute space for time scenario for future evolution of OM characteristics in thermokarst lake sediments of Western Siberia, we foresee a decrease of DOM quality, molecular weight and potential bioavailability in lakes of continuous permafrost zone, and an increase in these parameters in the sporadic/discontinuous permafrost zone.

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.

Effect of removing bacteria and dissolved organic matter on DMS production in Nannochloropsis oceanica concentrates

The aim of this study was to determine the influence of bacteria and organic matter on the occurrence of dimethyl sulfide (DMS) over the shelf life of Nannochloropsis oceanica concentrates. Two concentrates were compared: Control treatment, composed of biomass collected by centrifugation and diluted to a cell density of 5 × 109 cells·mL−1, and a washed concentrate treatment, where the biomass underwent successive centrifugations to remove dissolved organic matter (DOM) and bacteria before being diluted to a cell density of 5 × 109 cells·mL−1. Both concentrates were stored at two temperatures: 23 °C for 10 days and 4 °C for 85 days. Cellular viability, bacterial density, DOM, and DMS concentration were assessed. The washing process was responsible for removing approximately 84 % of the bacterial load from the concentrates. This significant reduction played a crucial role in decreasing the concentrations of DOM and DMS over the storage period. Furthermore, the process did not impair the cellular viability of microalgae. The findings underscore the importance of carefully managing bacterial and organic components in microalgal concentrates, especially when considering the preservation of freshness and cellular viability, which are key factors in applications such as larviculture.

Salt pollution reduces turbidity, dissolved organic matter, and cyanobacteria in experimental vernal pool communities

Anthropogenic activities such as the over-application of road deicers are causing an increase in the concentration of salts in historically fresh waters. Experimental and field investigations demonstrate that freshwater salinization disrupts ecosystem functions and services, causing the death of freshwater organisms and changes to nutrient conditions. Wetland habitats are one system negatively affected by salt pollution, including ephemeral wetlands (vernal pools) that fill with salt-polluted water after snowmelt. In urbanized areas, the degradation of these ecosystems could result in irreversible ecological damage including reduced water quality and a reduction in biodiversity. To investigate the effects of freshwater salinization on vernal pool communities, we exposed soils from vernal pools to water containing no salt (control), or four concentrations of three salts standardized by chloride concentration (50 mg Cl− L−1, 100 mg Cl− L−1, 200 mg Cl− L−1, and 400 mg Cl− L−1; magnesium chloride, calcium chloride, and sodium chloride). The results of this experiment suggest that emerging zooplankton communities in vernal pools are sensitive to low concentrations of salt pollution, and that alternative salts such as magnesium chloride and calcium chloride are more toxic than sodium chloride. We did not find positive or negative changes in the abundance of eukaryotic phytoplankton but did find negative effects of salt on cyanobacteria abundance, possibly due to corresponding reductions in turbidity which might be needed as a fixation site for cyanobacteria to form heterocysts. Finally, we found that salt pollution likely caused flocculation of Dissolved Organic Matter (DOM), resulting in reduced concentrations of DOM which could alter the buffering capacity of freshwater systems, light attenuation, and the populations of planktonic heterotrophs.

Disinfection by-product formation potential in response to variability in dissolved organic matter and nutrient inputs: Insights from a mesocosm study

Changes in rainfall patterns driven by climate change affect the transport of dissolved organic matter (DOM) and nutrients through runoff to freshwater systems. This presents challenges for drinking water providers. DOM, which is a heterogeneous mix of organic molecules, serves as a critical precursor for disinfection by-products (DBPs) which are associated with adverse health effects. Predicting DBP formation is complex due to changes in DOM concentration and composition in source waters, intensified by altered rainfall frequency and intensity. We employed a novel mesocosm approach to investigate the response of DBP precursors to variability in DOM composition and inorganic nutrients, such as nitrogen and phosphorus, export to lakes. Three distinct pulse event scenarios, mimicking extreme, intermittent, and continuous runoff were studied. Simultaneous experiments were conducted at two boreal lakes with distinct DOM composition, as reflected in their color (brown and clear lakes), and bromide content, using standardized methods. Results showed primarily site-specific changes in DBP precursors, some heavily influenced by runoff variability. Intermittent and daily pulse events in the clear-water mesocosms exhibited higher haloacetonitriles (HANs) formation potential linked to freshly produced protein-like DOM enhanced by light availability. In contrast, trihalomethanes (THMs), associated with humic-like DOM, showed no significant differences between pulse events in the brown-water mesocosms. Elevated bromide concentration in the clear mesocosms critically influenced THMs speciation and concentrations. These findings contribute to understanding how changing precipitation patterns impact the dynamics of DBP formation, thereby offering insights for monitoring the mobilization and alterations of DBP precursors within catchment areas and lake ecosystems.

The binding effects and mechanisms of dissolved organic matter (DOM) on the fate of mercury in sludge anaerobic digestion combined with thermal hydrolysis

Dissolved organic matter (DOM) plays an important role in regulating the fate of mercury (Hg), e.g., mobility, bioavailability, and toxicity. Clarifying the role of DOM in binding Hg in the treatment processes of sewage sludge is important for relieving Hg contamination risks in land applications. However, the impacts of DOM on Hg binding in sewage sludge are still unclear. In this study, we investigated the evolution of Hg and its speciation in full-scale sludge anaerobic digestion (AD) with thermal hydrolysis. The role of DOM in binding Hg(II) was further analyzed. The results showed that AD with thermal hydrolysis led to an increase in the Hg content in the sludge (from 3.72 ± 0.47 mg/kg to 10.75 ± 0.16 mg/kg) but a decrease in Hg mobility (the mercury sulfide fraction increased from 60.56% to 79.78%). Further adsorption experiments revealed that at equivalent DOM concentrations, DOM with a low molecular weight (MW<1 kDa) in activated sludge, DOM with a medium molecular weight (1 kDa<MW<5 kDa) in thermally hydrolyzed sludge, and DOM with a high molecular weight (MW> 5kDa) in both anaerobically digested sludge and conditioned sludge showed high adsorption capacities of Hg(II), with 1372.54, 535.28, 942.09 and 801.51 mg Hg/g DOM, respectively. Parallel factor analysis (PARAFAC) and fluorescence quotient (FQ) results showed that tryptophan-like and tyrosine-like substances had high binding affinities for Hg(II). Furthermore, X-ray photoelectron spectroscopy (XPS) indicated that the reduced organic sulfur contained in the DOM was potentially chemisorbed with Hg through the bonding of Hg-S and Hg-O. These results indicated that DOM may play special roles in regulating Hg speciation. The association between DOM and Hg(II), such as the significant positive correlation (p<0.05) between the dissolution rate of Hg(II) and release of tryptophan-like substances during thermal hydrolysis, suggested the potential way for removing Hg from sludge.

Linking Dissolved Organic Matter Composition to Landscape Properties in Wetlands Across the United States of America

AbstractWetlands are integral to the global carbon cycle, serving as both a source and a sink for organic carbon. Their potential for carbon storage will likely change in the coming decades in response to higher temperatures and variable precipitation patterns. We characterized the dissolved organic carbon (DOC) and dissolved organic matter (DOM) composition from 12 different wetland sites across the USA spanning gradients in climate, landcover, sampling depth, and hydroperiod for comparison to DOM in other inland waters. Using absorption spectroscopy, parallel factor analysis modeling, and ultra‐high resolution mass spectroscopy, we identified differences in DOM sourcing and processing by geographic site. Wetland DOM composition was driven primarily by differences in landcover where forested sites contained greater aromatic and oxygenated DOM content compared to grassland/herbaceous sites which were more aliphatic and enriched in N and S molecular formulae. Furthermore, surface and porewater DOM was also influenced by properties such as soil type, organic matter content, and precipitation. Surface water DOM was relatively enriched in oxygenated higher molecular weight formulae representing HUPHigh O/C compounds than porewaters, whose DOM composition suggests abiotic sulfurization from dissolved inorganic sulfide. Finally, we identified a group of persistent molecular formulae (3,489) present across all sites and sampling depths (i.e., the signature of wetland DOM) that are likely important for riverine‐to‐coastal DOM transport. As anthropogenic disturbances continue to impact temperate wetlands, this study highlights drivers of DOM composition fundamental for understanding how wetland organic carbon will change, and thus its role in biogeochemical cycling.

The suspension stability of nanoplastics in aquatic environments revealed using meta-analysis and machine learning

Nanoplastics (NPs) aggregation determines their bioavailability and risks in natural aquatic environments, which is driven by multiple environmental and polymer factors. The back propagation artificial neural network (BP-ANN) model in machine learning (R2 = 0.814) can fit the complex NPs aggregation, and the feature importance was in the order of surface charge of NPs > dissolved organic matter (DOM) > functional group of NPs > ionic strength and pH > concentration of NPs. Meta-analysis results specified low surface charge (0 ≤ |ζ| < 10 mV) of NPs, low concentration (< 1 mg/L) and low molecular weight (< 10 kg/mol) of DOM, NPs with amino groups, high ionic strength (IS > 700 mM) and acidic solution, and high concentration (≥ 20 mg/L) of NPs with smaller size (< 100 nm) contribute to NPs aggregation, which is consistent with the prediction in machine learning. Feature interaction synergistically (e.g., DOM and pH) or antagonistically (e.g., DOM and cation potential) changed NPs aggregation. Therefore, NPs were predicted to aggregate in the dry period and estuary of Poyang Lake. Research on aggregation of NPs with different particle size,shapes, and functional groups, heteroaggregation of NPs with coexisting particles and aging effects should be strengthened in the future. This study supports better assessments of the NPs fate and risks in environments.

Combined effects of pH and dissolved organic matter on the availability of pharmaceuticals and personal care products in aqueous environment

The interaction between pharmaceuticals and personal care products (PPCPs) with dissolved organic matter (DOM) can alter their bioavailability and toxicity. Nevertheless, little is known about how pH and DOM work together to affect the availability of PPCPs. This study investigated the impact of pH and DOM on the availability of seven PPCPs, namely Carbamazepine, Estrone, Bisphenol A, Testosterone Propionate, Triclocarban, 4-tert-Octylphenol and 4-n-Nonylphenol, using negligible depletion solid-phase microextraction (nd-SPME). The uptake kinetics of PPCPs by the nd-SPME fibers increased proportionally with DOM concentrations, likely due to enhanced diffusive conductivity in the unstirred water layer. At neutral pH, the partitioning coefficients of PPCPs for Humic Acid (log KDOC 3.87–5.25) were marginally higher than those for Fulvic Acid (log KDOC 3.64–5.11). Also, the log KDOC values correlated linearly with the log DOW (pH 7.0) values of PPCPs, indicating a predominant role for hydrophobic interactions in the binding of DOM and PPCPs. Additionally, specific interactions like hydrogen bonding, π-π, and electrostatic interactions occur for certain compounds, influenced by the polarity and spatial conformation of the compounds. For these ionizable PPCPs, the log DDOC values exhibit a strong dependence on pH due to the dual influence of pH on both DOM and PPCPs. The log DDOC values rose from pH 1.0 to 3.0, peaked at pH 5.0 to 9.0, and then (sharply) declined from 11.0 to 13.0. The reasons are that in strong acidic circumstances, the coiled and compressed shape of DOM inhibits the hydrophobic interaction, whereas in strong alkaline conditions, significant electrostatic repulsion reduces the sorption. This study reveals that the effects of DOM on the bioavailability of PPCPs are dependent on both pH and the specific compound involved.

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.

Concentration and compositional controls on degradation of permafrost‐derived dissolved organic matter on the Qinghai–Tibetan Plateau

AbstractUnderstanding the fate of permafrost‐derived dissolved organic matter (DOM) is critical for unraveling its role in carbon cycling. However, it remains unclear whether the high lability of permafrost‐derived DOM can be attributed to intrinsic chemical properties or elevated carbon concentrations. We investigated the dynamics of permafrost DOM from the Qinghai–Tibetan Plateau using both biodegradation and photodegradation experiments. Biodegradation and photodegradation of permafrost‐derived DOM exhibited distinct qualitative preferences for specific chemical groups (i.e., peptide‐like and aromatics, respectively). Notably, reducing the initial concentration of dissolved organic carbon (DOC) by half and a quarter resulted in shifts in biodegradable DOC content from 11.2% to 11.5% and 8.5%, respectively, accompanied by a corresponding decrease in the biodegradation rate from 0.11 to 0.06 and 0.03. This insight highlights the importance of recognizing the interplay between DOM quality and concentration and bears broader significance for our understanding of the fate of permafrost‐derived DOM in natural ecosystems.

Differences in dissolved organic matter and analysis of influencing factors between plantations pure and mixed forest soils in the loess plateau

The dissolved organic matter (DOM) in forest ecosystems significantly impacts soil carbon cycling due to its active turnover characteristics. However, whether different plantation forest soil profiles exhibit distinct DOM characteristics remains unclear. Hence, utilizing fluorescence spectroscopy and the parallel factor analysis (PARAFAC) method, a 1-meter soil profile analysis was carried out on three distinct artificial forests (Pinus tabuliformis (PT), Quercus crispula (QC), and a mixed forest of PT and QC (MF)), concurrently assessing the impact of soil chemical properties and enzyme activity on dissolved organic matter (DOM). The findings indicated that the mean concentration of dissolved organic carbon (DOC) was greatest in the MF and lowest in PT, exhibiting considerable variation with soil depth, suggesting that mixed tree species may promote the discharge of organic matter. The fluorescence spectra revealed two distinct peaks: humic-like fluorescence peaks (Peaks A and C) and a protein-like fluorescence peak (Peak T), with the most intense fluorescence observed in MF soil. As the soil depth increased, the fluorescence intensity of Peaks A and C steadily declined, while the intensity of Peak T rose. Four DOM components were identified in three types of plantations forests: surface soil was dominated by humic acid-like fluorescent components (C1 and C2), while the deep soil was primarily characterized by protein-like fluorescence components (C3 and C4). Different soil profile fluorescence parameter indices indicated that the source of DOM in the surface soil (i.e., 0–20 cm) was mainly allochthonous inputs, whereas, in the deep soil (i.e., 60–100 cm), it was mainly autochthonous, such as microbial activity. The findings from the partial least squares path modeling (PLS-PM) revealed that TP, aP, NH4+-N, and the combined impact of soil enzymes were influential in shaping the diversity of DOM attributes. Put differently, alterations in DOM concentration were concomitantly influenced by forest classification, soil characteristics, and depth. It has been demonstrated that, in contrast to monoculture forests, the establishment of mixed forest models has been more advantageous in enhancing the soil dissolved organic matter (DOM). These discoveries offer innovative perspectives on the dynamic characteristics of DOM in soil profiles and its influencing factors under different plantations forest planting patterns.

Storm-driven hydrological, seasonal, and land use/land cover impact on dissolved organic matter dynamics in a mid-Atlantic, USA coastal plain river system characterized by 21 T FT-ICR mass spectrometry

Introduction: Dissolved organic matter (DOM) as primary and secondary energy sources can be transported via rivers to estuaries and impact coastal biogeochemical cycles. Storm-induced high discharge events can alter the dominant river flow paths and enhance leaching of shallow organic-rich soil layers, leading to elevated terrestrial DOM export. Land use/land cover (LULC) and associated anthropogenic interventions (including artificial reservoirs and agricultural irrigation) can control sources and transformation processes of exported DOM along with hydrologic factors. The relative significance of LULC, hydrological factors, and temperature variations with seasons will differ depending on geographical locations and complicate their incorporation in biogeochemical models of DOM dynamics. This study investigates the role of LULC, seasonality, and storm events on DOM concentrations and molecular composition in the Murderkill River system.Method: Surface water samples were collected seasonally and before/after storm events from 6 sites representing forested, agricultural, and developed LULC units. The DOM was characterized via parallel factor analysis of excitation-emission matrix data and electrospray ionization 21 T Fourier-transform ion cyclotron resonance mass spectrometry to determine potential DOM sources and enable the development of a conceptual model for DOM dynamics in rivers impacted by anthropogenic reservoirs.Result and Discussion: Our results suggest that storm-induced shallow and overland flow paths can increase surface-vegetation/plant-litter derived DOM based on atomic ratios associated with specific biogenic precursors (i.e., lignin, tannins, and/or oxygenated aromatic DOM), particularly in winter when autochthonous production was suppressed due to reduced temperatures. We further demonstrate that the damming effects of artificial reservoirs enhance the role of seasonal patterns of autochthonous production, disrupting storm-shunt process and stimulating significantly more bio-produced DOM export during spring and summer (i.e., tryptophan/tyrosine-like. N- and S- containing, phytoplankton-derived compounds). Collectively, these results demonstrate how artificial reservoirs alter the characteristics of DOM exported from rivers with implications for understanding carbon export and fate at river-estuary interfaces.

Optical characteristics of dissolved organic matter in relation to phytoplankton in Lake Erhai, China

Dissolved organic matter (DOM), as the primary form of organic carbon in lakes, is crucial for the lake carbon cycling. As an important component of lake ecosystems, phytoplankton plays a crucial role in carbon fixation. However, we are not yet clear about the contribution of phytoplankton composition to DOM. To clarify this issue, we conducted we conducted continuous monitoring for 6 months in Lake Erhai, a plateau lake in China. Through quantitative detection of phytoplankton and spectral characteristic analysis, four fluorescence components were identified: tryptophan-like (C1), tyrosine-like (C2), fulvic-like (C3), and humic-like (C4). The Fluorescence Index (FI) ranged from 1.70 to 2.54, and the Biogenic Index (BIX) was above 0.8, indicating the DOM in Lake Erhai’s overlying water was predominantly autochthonous. Cyanophyta prevailed in September and November, while Chlorophyta dominated in other months. Phytoplankton diversity was significantly related to DOM concentration that may be related to the difference in the DOM contribution of different phytoplankton. The effect of phytoplankton biomass on C3 and C4 was prominent. Whereas, phytoplankton did not stimulate C1 and C2 significantly, indicating that protein-like may originate from terrestrial input and microbial activity. The composition of phytoplankton significantly affects the DOM composition in Lake Erhai. Therefore, the autochthonous DOM production by phytoplankton warrants further consideration in plateau lake systems.

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.

Mechanisms of cadmium release from manganese-rich sediments driven by exogenous DOM and the role of microorganisms

Dissolved organic matter (DOM) is a crucial component of natural sediments that alters Cd sequestration. Nevertheless, how different types of DOM fuel Cd mobilization in Mn-rich sediments has not been elucidated. In the present study, four typical DOM, fluvic acid (FA), bovine serum albumin (BSA), sodium alginate (SA), and sodium dodecyl benzene sulfonate (SDBS), were used to amend Cd-contaminated sediment to study their effects on Cd/Mn biotransformation and microbial community response. The results demonstrated that different DOM drive microbial community shifts and enhance microbially mediated Mn oxide (MnO) reduction and Cd release. The amendment of terrestrial- and anthropogenic-derived DOM (FA and SDBS) mainly contributed to enriching Mn-reducing bacteria phylum Proteobacteria, and its abundance increased by 38.16–74.47 % and 56.41–73.98 %, respectively. Meanwhile, microbial-derived DOM (BSA and SA) mainly stimulated the abundances of metal(loid)-resistant bacteria phylum Firmicutes. Accompanied by microbial community structure, diversity, and co-occurrence network shifts, the DOM concentration and oxidation-reduction potential changed, resulting in enhanced Cd mobilization. Importantly, FA stimulated Cd release most remarkably, probably because of the decreased cooperative interactions between bacterial populations, stronger reduction of MnOs, and higher aromaticity and hydrophobicity of the sediment DOM after amendment. This study linked DOM types to functional microbial communities, and explored the potential roles of different DOM types in Cd biotransformation in lake sediments.

Spectroscopic studies of the role of dissolved organic matter in acenaphthene photodegradation in liquid water and ice

The effect of concentration and origin of dissolved organic matter (DOM) on acenaphthene (Ace) photodegradation in liquid water and ice was investigated, and the components in DOM which were involved in Ace photodegradation were identified. The DOM samples included Suwannee River fulvic acid (SRFA), Elliott soil humic acid (ESHA), and an effluent organic matter (EfOM) sample. Due to the production of hydroxyl radical (•OH) and triplet excited-state DOM (3DOM*) which react with Ace, DOM had promotion effects on Ace photodegradation. However, the promotion effects of DOM were prevailed over by their suppressing effect of DOM including screening light effect, intermediates reducing effect and RS quenching effect, and thus, the photodegradation rates of Ace decreased in the presence of the three DOM with concentrations of 0.5–7.5 mg C/L in liquid water and ice. ESHA had higher light absorption and thus had higher screening light effect on Ace photodegradation in liquid water than SRFA and EfOM. At each DOM concentration, ESHA exhibited higher promotion effect on Ace photodegradation than SRFA and EfOM, in liquid water and ice. The binding of Ace with DOM was indicated by decreases in fluorescence intensity of Ace when coexisted with DOM. However, the binding of Ace to DOM played an unimportant role in suppressing Ace photodegradation. The photodegradation behavior of fluorophores in Ace with DOM present in ice was not similar to that in liquid water. C–O, C═O, carboxyl groups O–H and aliphatic C–H functional groups in DOM were involved in the interaction of DOM with Ace. The presence of Ace seemed to have no influence on the photodegradation behavior of functional groups in DOM.

Co-influence of biochar-supported effective microorganisms and seasonal changes on dissolved organic matter and microbial activity in eutrophic lake

DOM (dissolved organic matter) play a crucial role in lakes' geochemical and carbon cycles. Eutrophication evolution would influence nutrient status of waters and investigating the DOM variation helps a better understanding of bioremediation on environmental behavior of DOM in eutrophic lakes. In our study, the contents, compositions and characteristics of systematic DOM&SOM (sediment organic matter) were greatly influenced by seasonal changes. But the effective bioremediations obviously reduced the DOM concentration and thus mitigated the eutrophication outbreak risks in water bodies due to the increased MBC (microbial biomass carbon), microbial activity and metabolism. In early summer, the overall DOM in each treatment were readily low levels and derived from both autochthonous and exogenous origins, dominated by fulvic acid-like. In midsummer, the DOM contents and characteristics in each treatment increased significantly as phytoplankton activity improved, and the majority of DOM were humic acid-like and mainly of biological origin. The greatest differences of enzymes, MBC, microbial metabolism and DOM&SOM removal among different treatments were observed in summer months. In autumn, the systematic DOM&SOM slightly reduced due to the deceased microbial activity, in which the microbial humic acids were main component and derived from endogenous sources. Additionally, the gradually decreased SOM with cultivated time in each treatment was a result of microbiological conversion of SOM into DOM. For various treatments, BE, BE.A, BE.C and BE.E increased the MBC, enzymatic and microbial activities due to the application of biochar-supported EMs. Among these, BE and BE.A, especially BE.A with oxygen supplement, achieved the most desirable effect on reducing systematic DOM&SOM levels and increasing enzymatic and microbial activities. The group of EM also reduced the levels of DOM&SOM as improved degradation of EMs for DOM. However, BC, BE.C and BE.E finally did not achieved the desirable effect on reducing DOM&SOM due to the suppression of microbial activities, respectively, from high dose of biochar, weakening of dominant species and additional introduction of EMs in low liveness.

Photochemical processes transform dissolved organic matter differently depending on its initial composition

Dissolved organic matter (DOM) is one of the most important fluxes in the global carbon cycle but its response to light exposure remains unclear at a molecular-level. The chemical response of DOM to light should vary with its molecular composition and environmental conditions while some basic hypotheses are still unclear, such as the balance between photobleaching and photo-humification and the question of oxidative properties. Here we exposed aquatic DOM from diverse freshwaters impacted by different levels of anthropogenic activity and algal exudates to environmentally-realistic light conditions. We found that photobleaching occurred in DOM with relatively high initial humic content producing low H/C molecules, whereas DOM with low initial humic content was humified. DOM pools with relatively high initial saturation and low aromaticity were prone to transform towards more unsaturated molecular formulae and high H/C molecules with a distinct decrease of bioavailability. Photo-transformation was mainly influenced by reactive intermediates, with reactive oxygen species (ROS) playing a dominant role in humification when the initial humus content of DOM was high. In contrast, for algal DOM with high protein content, it was likely that the autoxidation of excited state DOM was more important than indirect oxidation involving ROS. Our results reveal how photo-transformation patterns depend on the initial composition of DOM and provide new insights into the role of photochemical processes in biogeochemical cycling of DOM.