Stability Of Dissolved Organic Matter Research Articles

Synergetic Effect of Digestate Dissolved Organic Matter and Phosphogypsum Properties on Heavy Metals Immobilization in Soils

The main idea was to justify the natural, technological, and ecological aspects of digestate-based composite for heavy metals (HMs) binding in soil due to organic matter content and mineral additives’ biosorption properties. The study aimed to determine the potential of a composite made from digestate and phosphogypsum for remediation of HMs polluted soils and the role of dissolved organic matter (DOM) in binding HMs. Methods used included a literature review to identify the mechanisms for HM binding to digestate DOM, a laboratory setup for producing a digestate-based composite with digestate (from manure or sewage sludge) mixed with phosphogypsum, and an analysis of digestate fluorescence properties. Results show that a composite based on digestate from manure as feedstock had a higher fluorescence complexity index than a composite with sewage sludge digestate (2.2 and 1.71, respectively). However, the DOM stability in the sewage sludge digestate composite was higher than reported in the literature, probably due to the mineral composition of phosphogypsum, which resulted in a high HMs sorption capacity and its positive effect on soil microbial activity. Based on the theoretical substantiation of DOM content and its binding properties, manure was the most effective feedstock type out of the two tested if digestate was used for HM remediation. Using a digestate-based composite with phosphogypsum can potentially reduce the ecological risk levels imposed by HM-contaminated soils from considerably too low.

Bacterial community regulation of soil organic matter molecular structure in heavy metal-rich mangrove sediments

Heavy metals (HMs) profoundly impact soil carbon storage potential primarily through soil carbon structure. The association between HM content and soil carbon structure in mangrove sediments remains unclear, likely due to the involvement of microorganisms. In this study, surface sediments in the Futian National Mangrove Nature Reserve were sampled to investigate the chemical structure of soil organic carbon (SOC), the molecular composition of dissolved organic matter (DOM), and potential interactions with microorganisms. HMs, except for Ni, were positively correlated with soil carbon. HMs significantly reduced the alkyl C/O-alkyl C ratio, aromaticity index, and aromatic C values, but increased the labile carboxy/amide C and carbonyl C ratio in SOC. HMs also increased DOM stability, as reflected by the reduced abundance of labile DOM (lipids and proteins) and increased proportion of stable DOM (tannins and condensed aromatics). Bacteria increased the decomposition of labile DOM components (unsaturated hydrocarbons) and the accumulation of stable DOM components (lignins) under HM enrichment. In addition, the association between the bacterial groups and DOM molecules was more robust than that with fungal groups, indicating bacteria had a more significant impact on DOM molecular composition. These findings help in understanding the molecular mechanisms of soil carbon storage in HM-rich mangroves.

Dissolved organic matter defines microbial communities during initial soil formation after deglaciation

Ecosystem succession and pedogenesis reshuffle the composition and turnover of dissolved organic matter (DOM) and its interactions with soil microbiome. The changes of these connections are especially intensive during initial pedogenesis, e.g. in young post-glacial areas. The temporal succession and vertical development of DOM effects on microbial community structure remains elusive. Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS), high-throughput sequencing, and molecular ecological networks, we characterized the molecular diversity of water-extractable DOM and identified its links to microbial communities in soil profiles along deglaciation chronosequence (12, 30, 40, 52, 80, and 120 years) in the southeastern Tibetan Plateau. Low-molecular-weight compound content decreased, whereas the mid- and high-molecular-weight compounds increased with succession age and soil depth. This was confirmed by the increase in double bond equivalents and averaged oxygen-to‑carbon ratios (O/C), and decrease in hydrogen-to‑carbon ratios (H/C), which reflect DOM accumulation and stabilization. Microbial community succession shifted towards the dominance of oligotrophic Acidobacteria and saprophytic Mortierellomycota, reflecting the increase of stable DOM components (H/C < 1.5 and wider O/C). Less DOM-bacterial positive networks during the succession reduced specialization of labile DOM production (such as lipid- and protein-like compounds), whereas more DOM-fungal negative networks increased specialization of stable DOM decomposition (such as tannin- and condensed aromatic-like compounds). Consequently, DOM stability is not intrinsic during initial pedogenesis: stable DOM compounds remain after fast bacterial utilization of labile DOM compounds, whereas fungi decompose slowly the remaining DOM pools.

Hydrological management constraints on the chemistry of dissolved organic matter in the Three Gorges Reservoir

Reservoirs are well known as a far-reaching human modification on the functions of natural river networks. However, changes in the chemistry and reactivity of dissolved organic matter (DOM) responding to hydrological management for water retention structures, and its influence on the river carbon cycle, remain poorly understood. Here we show that hydrological management does shape the molecular composition of DOM in the world's largest Three Gorges Reservoir, as revealed by optical spectroscopy and ultrahigh-resolution mass spectrometry. Relatively higher terrestrial input, molecular complexity, isomeric complexity, and environmental stability of DOM were observed during the storage period, whereas the inverse occurred during the drainage period. The results demonstrate that the hydrodynamic processes, which are mainly controlled by water intrusion from mainstream to tributaries, are likely the underlying mechanism controlling DOM chemistry. Integrated with observations from worldwide river reservoirs, the DOM degradation experiments suggest that reservoir hydrological management would enhance DOM mineralization, thereby increase CO2 emission and change the river carbon cycle.

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.

Impact of UV radiation on DOM transformation on molecular level using FT-ICR-MS and PARAFAC.

Dissolved organic matter (DOM) is an omnipresent constituent of natural water bodies. Reuse and transformation of DOM compounds in the water column is driven by physicochemical and biological processes leading to the production of refractory DOM. Typically, breakdown of DOM chemical compounds into smaller or more condensed fragments is triggered by ultraviolet (UV) radiation. Here, we present a study on the photodegradation of DOM produced during an incubation experiment with a natural microbial community. At the end of the first incubation without UV irradiation, the samples from 3 mesocosms were filtered to remove microbes and particles and continuously exposed to UV radiation (280-365nm). We investigated DOM in depth via monitoring of dissolved organic carbon (DOC) concentrations, DOM molecular characterization by Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and excitation emission matrix spectroscopy (EEMS). Analysis of variance indicated no significant differences in the DOC concentration between treatments. Main peaks in the fluorescent DOM (FDOM) were photo-bleached by UV radiation, and an increase in the fluorescent intensity of selected peaks was observed on irradiated samples toward the end of the experiment. Parallel factor analysis (PARAFAC) indicated the presence of three main components in all treatments: C1 (Marine humic M), C2 (Bacterial produced humic C), C3 (Tyrosine), and an additional component in the dark incubation of mesocosm 3, C4 (Tryptophan). Despite an intensive filtration protocol through 0.7, 0.2 and 0.1μm filters, low bacterial abundances were determined (<2.5×10-3 cells mL-1). We observed a direct correlation between structural indices and the intensity of PARAFAC components. Average double bond equivalent and aromaticity were strongly positively correlated with PARAFAC components C1 and C2 for one or more mesocosm. Moreover, FT-ICR-MS showed that under the tested conditions, the refractory character of the DOM assessed as the similarity to a deep ocean DOM reference did not increase on molecular level. Thus, mechanisms other than photochemical transformations of relatively recent DOM are likely necessary to facilitate long-term stability of DOM in the oceans.

Transformation and degradation mechanism of landfill leachates in a combined process of SAARB and ozonation

Dissolved organic matter (DOM) in mature landfill leachate is significantly different from that in young landfill leachate; the composition of DOM greatly influences both biological treatment and advanced treatment processes. In the present study, the transformation and degradation mechanisms of landfill leachates in a combined semi-aerobic aged refuse biofilter (SAARB) and ozonation process was investigated using organic removal analysis, molecular weight distribution (MWD), 3D-EEM-PARAFAC analysis, UV–Vis spectroscopy, and linear regression. Results revealed that the DOM in mature landfill leachate contained a greater amount of aromatic substances and had higher molecular weight than DOM in young landfill leachate. After the SAARB process, humus contained in the SAARB was discharged with effluent from both mature and young landfill leachate. Due to the differences in composition and structure of organic matter, the COD removal efficiency (17.89%) of SAARB effluent from treating mature landfill leachate (mature SAARB effluent) was much lower than that (45.91%) of SAARB effluent from treating young landfill leachate (young SAARB effluent) under the same operational parameters of the ozonation process. As indicated by PARAFAC analysis, better chemical stability of DOM in mature SAARB effluent resulted in inferior ozone treatment efficiency. Furthermore, the hydrophobicity and the concentration of benzene ring compounds in the mature and young SAARB effluent were reduced significantly by the ozonation process. Therefore, great improvements in the biodegradability of SAARB effluents were achieved in the ozonation process. Overall, the results of this study provide suggestions and guidance for practical applications of these technologies.

Inoculation with Compost-Born Thermophilic Complex Microbial Consortium Induced Organic Matters Degradation While Reduced Nitrogen Loss During Co-Composting of Dairy Manure and Sugarcane Leaves

This investigation was carried out on the effects of compost-born thermophilic complex microbial consortium (TCMC) composed of Ureibacillus suwonensis (TB42), Geobacillus thermodenitrificans (TB62) and Bacillus licheniformis (TA65) on co-composting of dairy manure and sugarcane leaves. The study assessed the TCMC influence on physicochemical parameters and dissolved organic matter (DOM) properties. Compared to the control (CP), the inoculated pile (CPT) showed a longer thermophilic phase, a faster organic matter degradation, a better Kjeldahl nitrogen preservation as well as a greater aromaticity and stability of DOM. Consequently, the inoculation with TCMC agent was effective in reducing the loss of nitrogen and accelerating maturity of compost.

Antecedent soil moisture prior to freezing can affect quantity, composition and stability of soil dissolved organic matter during thaw

There are large amounts of dissolved organic matter (DOM) released into the soil during spring thaw, but its bioavailability and components are still unknown. The quantity, composition and stability of DOM in water extracts of forest soils during thaw were studied after two-month freezing with 9 levels of soil moisture ranging from 10% to 90% water-filled pore space (WFPS), by measuring soil carbon dioxide (CO2) flux, biodegradable dissolved organic carbon (BDOC) and nitrogen (BDON), ultraviolet absorbance and parallel factor analysis of fluorescence excitation-emission matrices. Concentrations of BDOC, BDON, DOC and DON were lowest around 30% WFPS and relatively higher and lower soil moisture both increased DOM and BDOM concentrations in thawing soil. With increasing WFPS, the dominant component of soil DOM changed from humic acid-like substances to fulvic acid-like substances and the biological origin of DOM increased gradually. The protein-like component accounted for 8–20% of soil DOM and was affected by vegetation type and WFPS singly and interactively. The results implied that forest soils with more than 50% WFPS before winter freezing could release large amounts of fulvic acid-like DOM, which would be easily biodegraded and emitted as CO2 or run off with ground water during spring snow thaw.

Water Dynamics and Its Role in Structural Hysteresis of Dissolved Organic Matter.

Knowledge of structural dynamics of dissolved organic matter (DOM) is of paramount importance for understanding DOM stability and role in the fate of solubilized organic and inorganic compounds (e.g., nutrients and pollutants), either in soils or aquatic systems. In this study, fast field cycling (FFC) (1)H NMR relaxometry was applied to elucidate structural dynamics of terrestrial DOM, represented by two structurally contrasting DOM models such as Suwanee River (SRFA) and Pahokee peat (PPFA) fulvic acids purchased by the International Humic Substance Society. Measurement of NMR relaxation rate of water protons in heating-cooling cycles revealed structural hysteresis in both fulvic acids. In particular, structural hysteresis was related to the delay in re-establishing water network around fulvic molecules as a result of temperature fluctuations. The experiments revealed that the structural temperature dependency and hysteresis were more pronounced in SRFA than in PPFA. This was attributed to the larger content of hydrogel-like structure in SRFA stabilized, at a larger extent, by H-bonds between carboxylic and phenolic groups. Moreover, results supported the view that terrestrial DOM consist of a hydrophobic rigid core surrounded by progressively assembling amphiphilic and polar molecules, which form an elastic structure that can mediate reactivity of the whole DOM.

Diel cycles in the fluorescence of dissolved organic matter in dystrophic Wisconsin seepage lakes: Implications for carbon turnover

We monitored the dynamics of chromophoric dissolved organic matter (CDOM) fluorescence in two Wisconsin bog lakes over timescales ranging from hours to months. Peatland-derived dissolved organic matter (DOM) was the major solute in both bog lakes, and diel cycles were dominant features of the CDOM fluorescence time series. Two distinct diel cycles that differed in amplitude and timing were observed: one in oxic epilimnia and a second in anoxic, hypolimnetic waters. These cycles were not attributable to instrumental artifacts (i.e., daily oscillations of temperature, ambient light, or battery voltage), hydrologic forcing, or the effects of inner filtering, pH, or redox conditions. High light extinction coefficients, especially in the ultraviolet region (∼ 10 m−1 to 30 m−1), suggest that DOM photolysis was negligible at the depths of the CDOM fluorescence probes in these dark-water lakes (dissolved carbon concentration: 10 mg C L−1 to 20 mg C L−1). The diel cycles were apparently governed primarily by biological activities that mediate DOM production (release) and destruction (uptake). Rates of carbon turnover derived from properties of the epilimnetic CDOM fluorescence cycle (0.28 mg C L−1 d−1) were similar to rates of net ecosystem production based on daily CO2 dynamics (0.32 mg C L−1 d−1). It appears that a small, secondary pool of labile organic carbon turns over at relatively high rates in these bog lakes, consistent with the two-compartment view of DOM stability.

Contribution of dissolved organic matter to carbon storage in forest mineral soils

AbstractDissolved organic matter (DOM) is often considered the most labile portion of organic matter in soil and to be negligible with respect to the accumulation of soil C. In this short review, we present recent evidence that this view is invalid. The stability of DOM from forest floor horizons, peats, and topsoils against microbial degradation increases with advanced decomposition of the parent organic matter (OM). Aromatic compounds, deriving from lignin, likely are the most stable components of DOM while plant‐derived carbohydrates seem easily degradable. Carbohydrates and N‐rich compounds of microbial origin produced during the degradation of DOM can be relatively stable. Such components contribute much to DOM in the mineral subsoil. Sorption of DOM to soil minerals and (co‐)precipitation with Al (and probably also with Fe), especially of the inherently stable aromatic moieties, result in distinct stabilization. In laboratory incubation experiments, the mean residence time of DOM from the Oa horizon of a Haplic Podzol increased from &lt;30 y in solution to &gt;90 y after sorption to a subsoil. We combined DOM fluxes and mineralization rate constants for DOM sorbed to minerals and a subsoil horizon, and (co‐)precipitated with Al to estimate the potential contribution of DOM to total C in the mineral soil of a Haplic Podzol in Germany. The contribution of roots to DOM was not considered because of lack of data. The DOM‐derived soil C ranges from 20 to 55 Mg ha–1 in the mineral soil, which represents 19%–50% of the total soil C. The variation of the estimate reflects the variation in mineralization rate constants obtained for sorbed and (co‐)precipitated DOM. Nevertheless, the estimates indicate that DOM contributes significantly to the accumulation of stable OM in soil. A more precise estimation of DOM‐derived C in soils requires mineralization rate constants for DOM sorbed to all relevant minerals or (co‐)precipitated with Fe. Additionally, we need information on the contribution of sorption to distinct minerals as well as of (co‐)precipitation with Al and Fe to DOM retention.

A critical review of three methods used for the measurement of mercury (Hg 2+)-dissolved organic matter stability constants

Three experimental techniques – ion exchange, liquid–liquid extraction with competitive ligand exchange, and solid-phase extraction with competitive ligand exchange (CLE–SPE) – were evaluated as methods for determining conditional stability constants ( K) for the binding of mercury (Hg 2+) to dissolved organic matter (DOM). To determine the utility of a given method to measure stability constants at environmentally relevant experimental conditions, experimental results should meet three criteria: (1) the data must be experimentally valid, in that they were acquired under conditions that meet all the requirements of the experimental method, (2) the Hg:DOM ratio should be determined and it should fall within levels that are consistent with environmental conditions, and (3) the stability constants must fall within the detection window of the method. The ion exchange method was found to be limited by its detection window, which constrains the method to stability constants with log K values less than about 14. The liquid–liquid extraction method was found to be complicated by the ability of Hg–DOM complexes to partition into the organic phase. The CLE–SPE method was found to be the most suitable of these methods for the measurement of Hg–DOM stability constants. Stability constants for DOM isolates measured using the CLE–SPE method at environmentally relevant Hg:DOM ratios were log K = 25–30 (M −1). These values are consistent with the strong Hg 2+ binding expected for reduced S-containing binding sites.

Dissolved organic matter originating from the riparian shrub Salix gracilistyla

To estimate the importance of leaching of dissolved organic matter (DOM) as a pathway through which organic matter is supplied to stream ecosystems, we examined the amount of leachate over time and chemical properties of DOM leached from leaves in different conditions. The samples used were green leaves, yellow senescent leaves, and leaf litter of Salix gracilistyla Miq., which is the dominant riparian plant species in the middle reaches of rivers in western Japan. We analyzed dissolved organic carbon (DOC), total sugar, and polyphenol in the leachate of leaf samples collected from a fluvial bar in the middle reaches of the Ohtagawa River in Hiroshima Prefecture, Japan. Considerable leaching of DOC from senescent leaves [37.3 mg g−1 dry weight (dw) leaf] and leaf litter (8.1 mg g−1 dw leaf) occurred within 24 h after immersion. In contrast, DOC leached from green leaves was negligible until 1 week after leaf immersion. Carbon loss of leaves by leaching within 24 h after leaf immersion was estimated to be less than 8%, suggesting that leaching of DOC from S. gracilistyla leaves is a minor pathway through which organic matter is supplied to stream ecosystems. DOM leached from the leaves included sugar and polyphenol, which were among the major chemical forms of DOM leached from the leaves (based on the molecular mass). In a laboratory experiment in which the difference in the stability of DOM between the chemical forms was examined, sugar decomposed more rapidly than polyphenol.

Fractional precipitation of humic acid from colored natural waters

Humic acid (HA) is usually defined in the soil and aquatic sciences as that fraction of base-soluble soil organic matter or dissolved organic matter (DOM) which is insoluble in acid. Stepwise titration of bulk DOM from four samples of bog pore water and stream water were undertaken to study the fractional precipitation of HA. Three independent methods: DOC analysis, absorbance measurements at 330 nm, and densitometry of photographic negatives of filters, were used to quantify the precipitation of HA. Half of the HA which would be precipitable at pH 2.0 can be precipitated at pH values from 3.4 to 4.6. These preliminary results have implications for the stability of DOM in waters that experience pH decreases, and for the capacity of DOM to complex metals.