Dissolved Organic Matter Extracts 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.

Linkages Between Mineral Element Composition of Soils and Sediments With Hyporheic Zone Dissolved Organic Matter Chemistry Across the Contiguous United States

AbstractThe hyporheic zone is a hotspot for biogeochemical cycling where interactions with mineral metals preserve the release and biodegradation of organic matter (OM). A small fraction of OM can still be exchanged between localized sediments and the overlying water column, and recent evidence suggests there exists a longitudinal structuring in sediment dissolved OM (DOM) chemistry across the continental United States (CONUS). In this study, we tested a hypothesis that water extractable sediment DOM chemistry could be explained by sediment metal contents and integrative watershed scale features at the CONUS scale. Crowdsourced samples were characterized for high resolution mass spectrometry and coupled with sediment metals determined via x‐ray fluorescence as well as with land cover and soil elemental information obtained from national databases. Our results highlight weak relationships between DOM chemistry and elemental composition at the CONUS scale indicating limited transferability of organo‐metal linkages into multi‐scale hydrobiogeochemical models.

Discriminative Behavior of Cyclodextrin Polymers against Dissolved Organic Matter: Role of Cavity Size and Sorbate Properties.

Cyclodextrin polymers (CDPs) are promising next-generation adsorbents in water purification technologies. The selectivity of the polymer derivate cross-linked with tetrafluoroterephthalonitrile (TFN-CDP) for nonionic and cationic micropollutants (MPs) over dissolved organic matter (DOM) renders the adsorbent also attractive for many analytical applications. The molecular drivers of the observed selectivity are, nonetheless, not yet fully understood. To provide new insights into the sorption mechanism, we (i) synthesized TFN-CDPs with different cavity sizes (α-, β-, γ-CDP); (ii) assessed their extraction efficiencies for selected nonionic MPs in competition with different DOM size fractions (<1, 1-3, 3-10, >10 kDa) to test for size-selectivity; and (iii) performed nontargeted, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry analysis on CDP-extracted DOM compounds (<1 kDa) to probe for molecular sorbate properties governing their selective sorption. First, no evidence of size-selectivity was obtained through either the different CD cavity sizes (i) or the two independent approaches (ii) and (iii). Second, we found a dominant impact of sorbate oxygenation and polarity on the extraction of DOM and MPs, respectively, with relatively oxygen-poor/nonpolar molecules favorably retained on all α-, β-, and γ-CDP. Third, our data indicates exclusion of an anionic matrix, such as carboxylic acids, but preferential sorption of cationic nitrogen-bearing DOM, pointing at repulsive and attractive forces with the negatively charged cross-linker as a likely reason. Therefore, we ascribe TFN-CDP's selectivity to nonpolar and electrostatic interactions between MPs/DOM and the polymer building blocks. These molecular insights can further aid in the optimization of efficient and selective sorbent design for environmental and analytical applications.

Bioactivity profile of dissolved organic matter and its relation to molecular composition

Dissolved organic matter (DOM) occupies a huge and uncharted molecular space. Given its properties, DOM can be presented as a promising biotechnological resource. However, research into bioactivities of DOM is still in early stages. In this study, the biotechnological potential of terrestrial and marine DOM, its molecular composition and their relationships are investigated. Samples were screened for their in vitro antibacterial, antifungal, anticancer and antioxidant activities. Antibacterial activity was detected against Staphylococcusaureus in almost all DOM samples, with freshwater DOM showing the lowest IC50 values. Most samples also inhibited Staphylococcusepidermidis, and four DOM extracts showed up to fourfold higher potency than the reference drug. Antifungal activity was limited to only porewater DOM towards human dermatophyte Trichophytonrubrum. No significant in vitro anticancer activity was observed. Low antioxidant potential was exerted. The molecular characterization by FT-ICR MS allowed a broad compositional overview. Three main distinguished groups have been identified by PCoA analyses. Antibacterial activities are related to high aromaticity content and highly-unsaturated molecular formulae (O-poor). Antifungal effect is correlated with highly-unsaturated molecular formulae (O-rich). Antioxidant activity is positively related to the presence of double bonds and polyphenols. This study evidenced for the first time antibacterial and antifungal activity in DOM with potential applications in cosmeceutical, pharmaceutical and aquaculture industry. The lack of cytotoxicity and the almost unlimited presence of this organic material may open new avenues in future marine bioprospecting efforts.Graphical abstract

Molecular composition of dissolved organic matter across diverse ecosystems: Preliminary implications for biogeochemical cycling

Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been widely applied to characterize the molecular composition of dissolved organic matter (DOM) in different ecosystems. Most previous studies have explored the molecular composition of DOM focused on one or a few ecosystems, which prevents us from tracing the molecular composition of DOM from different sources and further exploring its biogeochemical cycling across ecosystems. In this study, a total of 67 DOM samples, including soil, lake, river, ocean, and groundwater, were analyzed by negative-ion electrospray ionization FT-ICR MS. Results show that molecular composition of DOM varies dramatically among diverse ecosystems. Specifically, the forest soil DOM exhibited the strongest terrestrial signature of molecules, while the seawater DOM showed the most abundant of biologically recalcitrant components, for example, the carboxyl-rich alicyclic molecules were abundant in the deep-sea waters. Terrigenous organic matter is gradually degraded during its transport along the river-estuary-ocean continuum. The saline lake DOM showed similar DOM characteristics with marine DOM, and sequestrated abundant recalcitrant DOM. By comparing these DOM extracts, we found that human activities likely lead to an increase in the content of S and N-containing heteroatoms in DOM, this phenomenon was commonly found in the paddy soil, polluted river, eutrophic lake, and acid mine drainage DOM samples. Overall, this study compared molecular composition of DOM extracted from various ecosystems, providing a preliminary comparison on the DOM fingerprint and an angle of view into biogeochemical cycling across different ecosystems. We thus advocate for the development of a comprehensive molecular fingerprint database of DOM using FT-ICR MS across a wider range of ecosystems. This will enable us to better understand the generalizability of the distinct features among ecosystems.

Multiple spectral comparison of dissolved organic matter in the drainage basin of a reservoir in Northeast China: Implication for the interaction among organic matter, iron, and phosphorus

Dissolved organic matter (DOM) plays a major role in ecological systems, affecting the fate and transportation of iron (Fe) and phosphorus (P). To better understand the geochemical cycling of these components, soil and sediment samples were collected around a reservoir downstream of a typical temperate forest in Northeast China. The DOM fractions from these soils, river, and reservoir sediments were extracted and then characterized by spectroscopic techniques. Comparative characterization data showed that the DOM pool of the Xishan Reservoir was partly autochthonous and derived from runoff and deposition of material in terrestrial ecosystems upstream. The upper reaches of the reservoir had significantly lower total Fe (TFe) content in the DOM extracts than those found in the reservoir (p < 0.05). Within the DOM, TFe was correlated with the amino acid tryptophan (p < 0.01). There was also a strong positive correlation between total P (TP) concentrations in DOM and tyrosine (p < 0.01). Organic P (Po) comprised most of the DOM TP, and was related to dissolved organic carbon (DOC) content and the amino acid tyrosine (p < 0.01). The interaction among DOM, Fe, and P appears to be due to complexation with tryptophan (Fe) and tyrosine (P). This suggests that the formation of Fe-DOM-P would be produced more readily than DOM-Fe-P complexes under optimal conditions. The interaction among DOM, Fe, and P can promote the coordinated migration, transformation, and ultimate fate of components that are complex with DOM from riverine and reservoir ecosystems, ultimately leading to accumulation within a reservoir and transport to downstream regions when reservoir dams are released. Reservoir dams can effectively intercept DOM and minerals prevent its flow downstream; however, it is important to understand the co-cycling of DOM, Fe and P within reservoirs, downstream rivers, and ultimately oceans. The involvement of amino acid components of DOM, tyrosine and tryptophan, in DOM complexation is an issue that requires further study.

Developing a Compost Quality Index (CQI) Based on the Electrochemical Quantification of Cd (HA) Reactivity.

The present work demonstrates the use of Cd2+ as a reactivity probe of the fulvic acids (FAs), humic acids (HAs) and dissolved organic matter (DOM) compost extracts. Significant differences were observed between the extracts, with the HA extract showing the highest reactivity. Comparing the different composts, the largest reactivity variation was again observed for HA then FA and finally DOM extracts. The Cd2+ binding extent was used to calculate the quality of composts and compared with a reference of uncomposted organic fertiliser (FLW), leading to the definition of an operational scale of compost quality. The parameter equivalent mass of fertiliser (mEF) was used for this scale sorted the seven composts from 0.353 to 1.09 kg FLW, for compost of sewage sludge (CSS) and vermicompost of domestic waste (CVDW), respectively. The significance of this parameter was verified through a correlation analysis between binding extent and the effect of compost application on lettuce crop growth in a field trial. The results demonstrate the potentiality of FA and HA extracts as markers of compost bioactivity and the use of Cd2+ as a reactivity probe.

Assessment of sample freezing as a preservation technique for analysing the molecular composition of dissolved organic matter in aquatic systems.

Dissolved organic matter (DOM) is widely studied in environmental and biogeochemical sciences, but is susceptible to chemical and biological degradation during sample transport and storage. Samples taken in remote regions, aboard ships, or in large numbers need to be preserved for later analysis without changing DOM composition. Here we compare high-resolution mass spectra of solid phase extractable DOM before and after freezing at -20 °C. We found that freezing increases compositional dissimilarity in DOM by between 0 to 18.2% (median = 2.7% across 7 sites) when comparing replicates that were frozen versus unfrozen, i.e., processed immediately after sampling, as compared with differences between unfrozen replicates. The effects of freezing primarily consisted of a poorer detection limit, but were smaller than other sample preparation and analysis steps, such as solid phase extraction and variable ionisation efficiency. Freezing samples for either 21 or 95 days led to similar and only slight changes in DOM composition, albeit with more variation for the latter. Therefore, we conclude that sample freezing on these time scales should not impede scientific study of aquatic DOM and can be used where it makes logistical sense, such as for large spatial surveys or study of archived samples.

Experimental Insight into the Enigmatic Persistence of Marine Refractory Dissolved Organic Matter.

More than 90% of marine dissolved organic matter (DOM) is biologically recalcitrant. This recalcitrance has been attributed to intrinsically refractory molecules or to low concentrations of molecules, but their relative contributions are a long-standing debate. Characterizing the molecular composition of marine DOM and its bioavailability is critical for understanding this uncertainty. Here, using different sorbents, DOM was solid-phase extracted from coastal, epipelagic, and deep-sea water samples for molecular characterization and was subjected to a 180-day incubation. 1H nuclear magnetic resonance spectroscopy and ultra-high-resolution mass spectrometry (UHRMS) analyses revealed that all of the DOM extracts contained refractory carboxyl-rich alicyclic molecules, accompanied with minor bio-labile components, for example, carbohydrates. Furthermore, dissolved organic carbon concentration analysis showed that a considerable fraction of the extracted DOM (86-95%) amended in the three seawater samples resisted microbial decomposition throughout the 180-day heterotrophic incubation, even when concentrated threefold. UHRMS analysis revealed that DOM composition remained mostly invariant in the 180-day deep-sea incubations. These results underlined that the dilution and intrinsic recalcitrance hypotheses are not mutually exclusive in explaining the recalcitrance of oceanic DOM, and that the intrinsically refractory DOM likely has a relatively high contribution to the solid-phase extractable DOM in the ocean.

Experimental evidence for the impact of phages on mineralization of soil-derived dissolved organic matter under different temperature regimes

Microbial mineralization of dissolved organic matter (DOM) plays an important role in regulating C and nutrient cycling. Viruses are the most abundant biological agents on Earth, but their effect on the density and activity of soil microorganisms and, consequently, on mineralization of DOM under different temperatures remains poorly understood. To assess the impact of viruses on DOM mineralization, we added soil phage concentrate (active vs. inactive phage control) to four DOM extracts containing inoculated microbial communities and incubated them at 18 °C and 23 °C for 32 days. Infection with active phages generally decreased DOM mineralization at day one and showed accelerated DOM mineralization later (especially from day 5 to 15) compared to that with the inactivated phages. Overall, phage infection increased the microbially driven CO2 release. Notably, while higher temperature increased the total CO2 release, the cumulative CO2 release induced by phage infection (difference between active phages and inactivated control) was not affected. However, higher temperatures advanced the response time of the phages but shortening its active period. Our findings suggest that bacterial predation by phages can significantly affect soil DOM mineralization. Therefore, higher temperatures may accelerate host-phage interactions and thus, the duration of C recycling.

Assessment of styrene‐divinylbenzene polymer (PPL) solid‐phase extraction and non‐targeted tandem mass spectrometry for the analysis of xenobiotics in seawater

AbstractAnthropogenic imprints have become a fundamental part of most ecosystems. Our chemical footprint is often detected using targeted approaches, whereas xenobiotics are embedded within the large pool of dissolved metabolites, altered by biotic and abiotic mechanisms. Thus, it is necessary to simultaneously study anthropogenic signals entwined with the variety of organic signatures that exist in aquatic environments. However, methods for non‐targeted analysis of natural metabolites are not always well suited for the analysis of pollutants. Here, we report the reassessment of styrene‐divinylbenzene polymer‐based Priority PolLutant (PPL) solid‐phase extraction (PPL‐SPE), which is typically used to extract marine dissolved organic matter (DOM) for biogeochemical studies, to analyze a set of xenobiotics commonly observed in coastal North Pacific seawater. After PPL extraction and analysis by nontargeted liquid chromatography tandem mass spectrometry (LC–MS/MS), we successfully detected 23 out of 25 selected pharmaceuticals, personal care products, biocides, perfluorocarbons, and polymer additives in a complex marine DOM sample using positive and negative electrospray ionization. We tested two pH conditions to mimic typical marine DOM extraction studies and found mean recovery rates of xenobiotics were approximately 10% higher in seawater pH (pH ~ 8) than in acidified samples (pH ~ 2) for both negative and positive modes, although overall, mean recovery rates were 10% lower in negative mode. Our results indicate that PPL‐SPE in combination with non‐targeted LC–MS/MS is capable of capturing the tested set of xenobiotics, thus allowing the repurposing of biogeochemical sampling strategies as well as existing DOM samples and MS data for the subsequent assessment of anthropogenic impacts in marine environments.

Solid-Phase Extraction of Aquatic Organic Matter: Loading-Dependent Chemical Fractionation and Self-Assembly.

Dissolved organic matter (DOM) is an important component in marine and freshwater environments and plays a fundamental role in global biogeochemical cycles. In the past, optical and molecular-level analytical techniques evolved and improved our mechanistic understanding about DOM fluxes. For most molecular chemical techniques, sample desalting and enrichment is a prerequisite. Solid-phase extraction has been widely applied for concentrating and desalting DOM. The major aim of this study was to constrain the influence of sorbent loading on the composition of DOM extracts. Here, we show that increased loading resulted in reduced extraction efficiencies of dissolved organic carbon (DOC), fluorescence and absorbance, and polar organic substances. Loading-dependent optical and chemical fractionation induced by the altered adsorption characteristics of the sorbent surface (styrene divinylbenzene polymer) and increased multilayer adsorption (DOM self-assembly) can fundamentally affect biogeochemical interpretations, such as the source of organic matter. Online fluorescence monitoring of the permeate flow allowed to empirically model the extraction process and to assess the degree of variability introduced by changing the sorbent loading in the extraction procedure. Our study emphasizes that it is crucial for sample comparison to keep the relative DOC loading (DOCload [wt %]) on the sorbent always similar to avoid chemical fractionation.

Aqueous-phase Oxidation of Dissolved Organic Matter (DOM) from Extracts of Ambient Aerosols

Recently, a large number of laboratory studies have focused on the aqueous-phase photochemistry of single organic compound in atmospheric condensed phases, yet few studies have been conducted on the aqueous-phase photochemical oxidation of real-world complex dissolved organic matter (DOM). Therefore, in this work, we report experimental results for the photochemical oxidation of DOM extracts from ambient fine aerosol samples upon direct photolysis or against OH oxidation, under both simulated sunlight and ultraviolet irradiation conditions. The products at different stages of photolysis were analyzed via UV-vis and spectroscopy and soot-particle aerosol mass spectrometry (SP-AMS) to investigate their optical and chemical characteristics. The results demonstrate the effective degradation of DOM under UV irradiation, and the f44 values of the corresponding products aremuch lower than under sunlight irradiation. A variety of carboxylic acids were generated during liquid-phase photolysis, and oxalic acid was found to be the most abundant. The light absorbance and concentration of HULIS did not change significantly under sunlight illumination; however, under UV and UV+·OH conditions, the concentration of HULIS increased continuously with reaction time. The HULIS concentration at 23 h was approximately four times the initial value, indicating the formation of brown carbon species with carboxyl, hydroxyl, and aromatic and other functional groups. Our results show that the increase in light absorptivity and formation rate of brown carbon from DOM are limited when aqueous-phase oxidation occurs under sunlight illumination. In comparison, DOM can constantly decompose into HULIS or small molecules under ultraviolet light illumination, and the light absorptivity of the remaining organic matter may be relatively high, resulting in final products with a high unit mass absorption efficiency (MAE). We have investigated the aqueous-phase oxidation of actual filter extracts for the first time, and our results provide valuable insights to the formation of air pollution complexes.

Deciphering Dissolved Organic Matter: Ionization, Dopant, and Fragmentation Insights via Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry.

Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) has been increasingly employed to characterize dissolved organic matter (DOM) across a range of aquatic environments highlighting the role of DOM in global carbon cycling. DOM analysis commonly utilizes electrospray ionization (ESI), while some have implemented other techniques, including dopant-assisted atmospheric pressure photoionization (APPI). We compared various extracted DOM compositions analyzed by negative ESI and positive APPI doped with both toluene and tetrahydrofuran (THF), including a fragmentation study of THF-doped riverine DOM using infrared multiple photon dissociation (IRMPD). DOM compositions followed the same trends in ESI and dopant-assisted APPI with the latter presenting saturated, less oxygenated, and more N-containing compounds than ESI. Between the APPI dopants, THF-doping yielded spectra with more aliphatic-like and N-containing compounds than toluene-doping. We further demonstrate how fragmentation of THF-doped DOM in APPI resolved subtle differences between riverine DOM that was absent from ESI. In both ionization methods, we describe a linear relationship between atomic and formulaic N-compositions from a range of DOM extracts. This study highlights that THF-doped APPI is useful for uncovering low-intensity aliphatic and peptide-like components in autochthonous DOM, which could aid environmental assessments of DOM across biolability gradients.

Seasonal changes predominant over manure application in driving dissolved organic matter shifts in agricultural runoff

Non-point source nutrient pollution can cause eutrophication, hypoxic events, and harmful algal blooms in surface waters. Surface water eutrophication is frequently attributed to agricultural runoff, a known source of inorganic and organic nutrients to surface and subsurface waters. Analysis of dissolved organic matter (DOM) using ultrahigh resolution mass spectrometry is an effective tool for characterizing diverse organic nitrogen and phosphorus components of DOM that may be mineralized and/or assimilated and ultimately contribute to eutrophication. An anion exchange resin was applied to extract DOM from surface and subsurface tile runoff from agricultural plots located within the Maumee River watershed (Ohio, USA) that received raw liquid manure, polymer-treated dewatered manure, or no manure (control). DOM extracts were analyzed using Fourier transform ion cyclotron resonance mass spectrometry prior to manure application and during three runoff events after manure application. Organic nitrogen compounds were predominant, making up 38–48% of the total assigned formulas. Principle coordinates analysis indicated clustering predominately by sample month and secondarily by treatment. These findings show that a large amount of variability in DOM in runoff was observed regardless of manure application, indicating the important role played by natural processes in driving transformation of the DOM pool during the growing season. Molecular ions unique to runoff from manure-applied plots were also identified that may be useful in source-tracking of non-point source nutrient pollution in waters draining to Lake Erie.

Optimizing soil dissolved organic matter extraction by grey relational analysis

Dissolved organic matter (DOM) in soil plays an important role in the fate and transport of contaminants. It is typically composed of many compounds, but the effect of different extraction factors on the abundance of different DOM components is unknown. In this study, DOM was extracted from three soils (paddy field, vegetable field and forest soils) with various extraction time, liquid to solid ratios (LSRs), extractant types, and extractant concentrations. The LSR had a significant effect on DOM content, which increased by 0.5–4.0 times among the three soils when LSR increased from 2:1 to 10:1 (P < 0.05). Dissolved organic matter content increased by 4%–53% when extraction time increased from 10 to 300 min (P < 0.05). Extractant concentration had different effects on DOM content depending on the extractant. Higher concentrations of KCl promoted DOM extraction, while higher concentrations of KH2PO4 inhibited DOM extraction. Therefore, grey relational analysis was used to further quantitatively evaluate the effect of extraction time, LSR, and extractant concentration on DOM, using KCl as an extractant. For the paddy field and forest soils, the impact of these three factors on DOM extraction efficiency was in the following order: KCl concentration > LSR > extraction time. However, the effect was different for the vegetable field soil: LSR > extraction time > KCl concentration. Taking all these factors into account, 1.50 mol L−1 KCl and an LSR of 10:1 with a shaking time of 300 min was recommended as the most appropriate method for soil DOM extraction.

Effect of straw-derived dissolved organic matter on the adsorption of sulfamethoxazole to purple paddy soils

The presence of sulfamethoxazole (SMX) in croplands has become an international concern. The environmental behavior and fate of SMX in agricultural soils are not well understood, especially when the adsorption behavior is disturbed by the dissolved organic matter (DOM) released by crop straw. As canola straw is one of the biomasses widely returned to farmlands, we characterized DOM derived from pristine and decomposed canola straw, and explored the effects and mechanisms of the DOMs on regulating SMX adsorption to purple paddy soils. The spectral analysis showed that the molecular weight, aromaticity, and hydrophobicity of canola straw-derived DOM increased as decomposition proceeded. These physicochemical properties collectively determined the effects of the DOM on SMX adsorption. The DOM derived from pristine canola straw increased SMX maximum adsorption capacity of the soils by approximately 2.6 times, but this positive effect gradually decreased to a steady state by day 90 in the straw decomposition period. Nevertheless, the SMX adsorption behavior in the soils was invariably determined by the DOM extracts. These adsorption processes of SMX were well fitted by the double-chamber kinetics model and the Langmuir and Freundlich thermodynamic models. Thermodynamic parameters indicated that SMX adsorption onto the soils was spontaneous and endothermic, and this adsorption characteristics was not significantly (p > 0.05) changed by the DOM extracts. However, the adsorption kinetics were altered by those DOMs, i.e., the fast and slow adsorption processes were both diminished. Correspondingly, co-adsorption and cumulative adsorption were identified as the main mechanisms determining SMX adsorption to the purple paddy soils in the presence of the straw-derived DOMs. These results collectively indicated that the DOMs released by straw in croplands may decrease the ecological risks of organic pollutants by inhibiting their migration processes.

Molecular dynamics of foliar litter and dissolved organic matter during the decomposition process

Decomposing foliar litter organic matter (LOM) in forested watersheds is an essential terrestrial source of dissolved organic matter (DOM) to aquatic ecosystems. To evaluate the relationship of chemical composition between LOM and DOM, we collected freshly fallen leaves of white oak (Quercus alba) and conducted an 80-week field decomposition experiment along a small elevation gradient in a floodplain within the Congaree National Park, South Carolina. Foliar litters were collected for water extraction and instrumental analyses using pyrolysis GC/MS, UV/VIS and fluorescence spectrophotometry. Factor analyses of pyrolysates showed that fresh LOM was mainly composed of lignin compounds (LgC), phenolic compounds (PhC), and carbohydrate (Carb), and the change in composition was relatively small throughout the decomposition process. In contrast, there were two distinct chemical compositions of DOM in early (between 0–8 weeks) and late phases (between 16–80 weeks). The early phase had a higher percentage of PhC, but the late phase contained higher percentages of Carb, unsaturated hydrocarbon (UnSaH), aromatic hydrocarbon (ArH), and nitrogen-containing compounds (Ntg). The fluorescence emission-excitation matrix showed there was an increasing trend in humic and fulvic-like fractions in DOM over time, matching well with increases of UnSaH and ArH fractions from the results of pyrolysis GC/MS. Our study illustrated that the changes of chemical components in LOM and water extractable DOM were not parallel during the decomposition process and the degradation of lignin and phenolic compounds was one of the controlling factors on the production of DOM.

The ultraviolet-visible absorbance and fluorescence characterization of dissolved organic matter derived from the leaf litter of Populus simonii, Artemisia desertorum, Salix cheilophila, and Populus tomentosa.

Dissolved organic matter (DOM) derived from leaf litter plays an important role in maintaining carbon (C) and nitrogen (N) circulation between soils and plants, energy flow, and signaling pathways for plant-microbe interactions of terrestrial ecosystem. In this study, four DOM samples extracted with a 40:1 (v/w) water to sample ratio from the leaf litter of Populus simonii (S1), Artemisia desertorum (S2), Salix cheilophila (S3), and Populus tomentosa (S4) were investigated using the technologies of ultraviolet-visible (UV-Vis) and excitation-emission matrix (EEM) fluorescence spectroscopy. Results showed that the electricity (EC) values of four DOM extracts were significantly different due to the different composition and salt content of each plant. The values of chemical oxygen demand (COD), dissolved organic carbon (DOC), and the sum of values of all peaks' intensities divided by DOC (FI) indicated the higher contents of organic matter in the acid DOM extracts from S1, S2, and S3 (sand-fixing plants) than the neutral DOM extracted from S4. The absorbance shoulder between 250 and 285nm in the UV-Vis spectra and EEM fluorescence spectra of each sample suggested the presence of many different chromophores such as aromatic or phenolic compounds in plant DOM. According to fluorescence regional integration (FRI) and peak picking results, the content of protein-like materials was higher than that of humic-like substances in DOM from S1, S2, and S3 while the opposite phenomena occurred in DOM from S4. Hence, the physicochemical and fluorescence characterization of DOM extracted from the genus Populus of the family Salicaceae S1 and S4 growing under different edaphic and climatic conditions changed much. The findings would be of great significance to understand the origin, composition, dynamics, and biotransformation of DOM in soils formed in different climatic environments.

Measuring the influence of environmental conditions on dissolved organic matter biodegradability and optical properties: a combined field and laboratory study

Fluorescence spectroscopy is a common tool to assess optical dissolved organic matter (DOM) and a number of characteristics, including DOM biodegradability, have been inferred from these analyses. However, recent findings on soil and DOM dynamics emphasize the importance of ecosystem-scale factors, such as physical separation of substrate from soil microbial communities and soil physiochemical cycles driving DOM stability. We apply this principle to soil derived DOM and hypothesize that optical properties can only supply information on biodegradability when evaluated in the larger ecosystem because substrate composition and the activity/abundance of the microbial community ultimately drive DOM degradation. To evaluate biodegradability in this context, we assessed aqueous soil extracts for water extractable organic carbon (WEOC) content, biodegradability, microbial biomass and DOM characteristics using fluorescence spectroscopy across a range of environmental conditions (covariant with season and land use) in northern Vermont, USA. Our results indicate that changes in environmental conditions affect composition, quantity, and biodegradability of DOM. WEOC concentrations were highest in the fall and lowest in the summer, while no significant differences were found between land covers; however, DOM biodegradability was significantly higher in the agricultural site across seasons. Despite a shift in utilized substrate from less aromatic DOM in summer to more aromatic DOM in winter, biodegradability was similar for all seasons. The only exception was cold temperature incubations where microbial activity was depressed, and processing was slowed. These results provide examples on how fluorescence based metrics can be combined with context relevant environmental parameters to evaluate bioavailability in the context of the larger ecosystem.