Aromatic Dissolved Organic Matter Research Articles

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.

Response of a source water quality through a heavy precipitation event: Nutrients, dissolved organic matter and their DBPs formation

To better understand the influence of heavy precipitation event on water supply security, the change of nutrients, dissolved organic matter (DOM) and their corresponding disinfection by-products (DBPs) generation in river were investigated through a heavy precipitation event. The results show that short-term sustained heavy precipitation causes additional load on the river. Significant temporal variations and increases in dissolved oxygen (DO), turbidity, dissolved organic carbon (DOC) and molecular weight of raw water were observed during the heavy precipitation, and dissolved organic nitrogen (DON) showed a remarkably decline with the continuation of precipitation. The molecular weight and aromaticity of DOM increased dramatically with the continuous superposition of precipitation and flow, and the proportion of hydrophobic fraction increased during the study period. Four different fluorescent components were identified, including humic-like (C1, C2 and C3), and protein-like fluorophore C4. Heavy precipitation events affected the mobilization of DOM, while the generation of DBPs increased by 4%–47% during the chlorination, and the elevated river level further increased the DBPs formation. In particular, the HOA fraction was the main contributor of DBPs (up to 70%). The risk of haloacetic acids (HAAs) generation caused by heavy rainfall was concentrated in the river runoff producing and regression periods for both hydrophobic and hydrophilic fractions of DOM. Humification index (HIX) was positively correlated with the yield level of TCM, DCAA, TCAA, and DCAN during chlorination. Chlorination disinfection of raw water during river runoff producing and regression period is likely to increase the haloacetonitriles formation potential (HANsFP), thus posing a vital threat to water supply safety, while chloramination disinfection may significantly relieve the threat. This study provides a theoretical basis for the direct/indirect link between short-term precipitation events and their impact on water quality.

Meta-Analysis of Optical Surrogates for the Characterization of Dissolved Organic Matter.

Optical surrogates, derived from absorbance and fluorescence spectra, are widely used to infer dissolved organic matter (DOM) composition (molecular weight, aromaticity) and genesis (autochthonous vs allochthonous). Despite the broad adoption of optical surrogates, several limitations exist, such as context- and sample-specific factors. These limitations create uncertainty about how compositional interpretations based on optical surrogates are generalized across contexts, specifically if there is duplicative or contradictory information in those interpretations. To explore these limitations, we performed a meta-analysis of optical surrogates for DOM from diverse sources, both from natural systems and after water treatment processes (n = 762). Prior to analysis, data were screened using a newly developed, standardized methodology that applies systematic quality control criteria before reporting surrogates. There was substantial overlap in surrogate values from natural and treated samples, suggesting that the gradients governing the surrogate variability can be generated in both contexts. This overlap provides justification for using optical surrogates originally developed in the context of natural systems to describe DOM changes in engineered systems, although the interpretations may change. Absorbance-based surrogates that describe the amount of spectral tailing (e.g., E2:E3 and S275-295) had a high frequency of strong correlations with one another but not to specific absorbance (SUVA254) or absorbance slope ratio (SR). The fluorescence index (FI) and biological index (β/α) were strongly correlated with one another and to the peak emission wavelength but not to the humification index (HIX). Although SUVA254 and FI have both been correlated to DOM aromaticity in prior research, there was a lack of reciprocity between these optical surrogates across this data set. Additionally, there were patterns of deviations in the wastewater subset, suggesting that effluent organic matter may not follow conventional interpretations, urging caution in the use of optical surrogates to track DOM in water reuse applications. Finally, the meta-analysis highlights that three aspects should be captured when optical spectra are used for DOM interpretation: specific absorbance, absorbance tailing, and the extent of red-shifted fluorescence. We recommend that SUVA254, E2:E3, and FI or β/α be prioritized in future DOM studies to capture these aspects, respectively.

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

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

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.

Seasonal Freezing Drives Spatiotemporal Dynamics of Dissolved Organic Matter (DOM) and Microbial Communities in Reclaimed Water-Recharged River

Although reclaimed water (RW) has become a promising alternative source for alleviating water shortage in arid and semiarid regions, the ecological risks it poses to the receiving water bodies remain largely unknown. Dissolved organic matter (DOM) is crucial for affecting the quality of RW and strongly influences bacterial communities (BCs) in aquatic ecosystems. In this study, we aimed to unravel the role of DOM signatures on the spatiotemporal composition of microbial communities (MCs) in a seasonally ice-sealed urban river that had been chronically replenished by RW. We found that discharging RW resulted in elevated DOM levels in the receiving river. Notably, an increase of 10% in protein-like substances was revealed. The differences between compositional characteristics of DOM and the abundance of riverine BCs between freezing and non-freezing periods were revealed. In the freezing season, humic-like components, aromaticity, and hydrophobicity of DOM were more significant, and bacterial taxa such as Bacteriodetes and Flavobacterium were increased, while Proteobacteria was decreased. Similarly, co-occurrence network analysis revealed an enhanced interplay between DOM and BCs at the same time. However, Klebsiella pneumoniae markedly decreased during the ice-sealed period. These results suggest that variations in DOM characteristics have remarkable impacts on the dynamics of aquatic BCs, which points to the need for a DOM−oriented RW quality monitoring strategy.

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.

Rivers and tidal flats as sources of dissolved organic matter and trace metals in the German Bight (North Sea)

The German Bight in the southern North Sea receives nutrients, dissolved organic matter (DOM), and trace metals from rivers, porewater reflux, and porewater outwelling. We studied the marine, riverine, and porewater sources analyzing molecular transformations of solid-phase extracted (SPE) DOM in the German Bight. We applied a combination of ultrahigh-resolution mass spectrometry (FT-ICR-MS) with quantitative data of dissolved organic sulfur (DOS), dissolved black carbon (DBC), dissolved trace metals (Ba, Co, Gd, Mo, Mn, W), and nutrients (nitrite, nitrate, phosphate, silicate). While aromatic DOM and DBC mainly originated from the rivers, nitrogen-containing, more saturated DOM was enriched offshore suggesting greater contributions of marine (algal) sources. Except for dissolved Mo, rivers were the primary source of trace metals and nutrients. However, tidal flats contributed to dissolved nutrient (e.g., dissolved phosphate), trace metal and DOS inventories of the southern North Sea. The input of DOS from intertidal flats was identified by the molecular index derived from sulfidic porewaters (ISuP), non-conservative behavior of elemental sulfur-to-carbon ratio and sulfur content of molecular formulae (from FT-ICR-MS). Dissolved Mn and Si were removed in the German Bight, likely due to precipitation as Mn(hydr)oxides and biological uptake, respectively. Preliminary estimates suggest that DOS from porewater outwelling is approximately four times higher than DOS discharged by the three main rivers in the region. Our study therefore highlights the need to consider porewater discharge in addition to riverine sources to comprehensively assess elemental budgets within the complex interplay and transformations of DOM, nutrients, and trace metals in coastal ecosystems.

Characterization of microplastic-derived dissolved organic matter in freshwater: Effects of light irradiation and polymer types

This study investigated the impacts of light irradiation and polymer types on the leaching behavior of dissolved organic matter (DOM) from microplastics (MPs) in freshwater. Polypropylene had the highest leaching capacity of DOM after photoaging, followed by polystyrene (PS), polyamide (PA) and polyethylene terephthalate (PET). While similarly low levels of DOM were observed in the remaining 5 MP suspensions under UV irradiation and in almost all MP suspensions (except PA) under darkness. These suggest that the photooxidation of some buoyant plastics may influence the carbon cycling of nature waters. Among 9 MP-derived leachates, PET leachates had the highest chromophoric DOM concentration and aromaticity, probably owing to the special benzene rings and carbonyl groups in PET structures and its fast degradation rate. Protein-like substances were the primary fluorescent DOM in MP suspensions (except PS), especially in darkness no other fluorescent substances were found. Considering the bio-labile properties of proteins together, MPs regardless of floating or suspended in an aquatic environment may have prevalent long-term effects on microbial activities. Besides, from monomers to hexamers with newly formed chemical bonds were identified in UV-irradiated MP suspensions. These results will contribute to a deep insight into the potential ecological effects related to MP degradation.

Interaction of reed litter and biochar presences on performances of constructed wetlands

Constructed wetlands (CWs) are frequently used for effective biological treatment of nitrogen-rich wastewater with external carbon source addition; however, these approaches often neglect the interaction between plant litter and biochar in biochar-amended CW environments. To address this, we conducted a comprehensive study to assess the impacts of single or combined addition of common reed litter and reed biochar (pyrolyzed at 300 and 500 °C) on nitrogen removal, greenhouse gas emission, dissolved organic matter (DOM) dynamics, and microbial activity. The results showed that combined addition of reed litter and biochar to CWs significantly improved nitrate and total nitrogen removal compared with biochar addition alone. Compared to those without reed litter addition, CWs with reed litter addition had more low-molecular-weight and less aromatic DOM and more protein-like fluorescent DOM, which favored the enrichment of bacteria associated with denitrification. The improved nitrogen removal could be attributed to increases in denitrifying microbes and the relative abundance of functional denitrification genes with litter addition. Moreover, the combined addition of reed litter and 300 °C-heated biochar significantly decreased nitrous oxide (30.7 %) and methane (43.9 %) compared to reed litter addition alone, while the combined addition of reed litter and 500 °C-heated biochar did not. This study demonstrated that the presences of reed litter and biochar in CWs could achieve both high microbial nitrogen removal and relatively low greenhouse gas emissions.

New insights into the effect of pyrolysis temperature on the spectroscopy properties of dissolved organic matter in manure-based biochar.

Dissolved organic matter (DOM) derived from biochar takes a crucial role in transport and bioavailability toward contaminants; hence, it is undeniable that a thorough analysis of its properties is important. So far, the effect of pyrolysis temperature on the functional groups, components, and evolutionary sequence of manure-based biochar DOM has not been adequately investigated. Here, DOM was released from two typical livestock manures (cow and pig) at five pyrolysis temperatures (300 ~ 700°C), and it was explored in depth with the aid of moving window 2D correlation spectroscopy (MW-2D-COS) and heterogeneous 2D correlation spectroscopy (hetero-2D-COS). The results demonstrated that the concentration, aromaticity, and hydrophobicity of DOM were greater at high temperatures, and more DOM was liberated from cow manure-based biochar at identical temperature. Protein-like compounds dominated at high temperatures. The pyrolysis temperatures of final configuration transformation points of the fulvic acid-like component and the aromatic ring C=C in DOM were 400°C and 500°C, respectively. Moreover, Fourier transform infrared spectroscopy combined with two-dimensional correlation analysis indicated that the functional group evolution of DOM depends on the pyrolysis temperature and feedstock type. The study provides a new perspective on manure management and environmental applications of biochar.

Non-additive effects on biodegradation of moso bamboo litter- and broadleaf tree litter-leached dissolved organic matter mixtures in a subtropical forest of southern China

Phyllostachys pubescens (moso bamboo) has extensively expanded to subtropical broadleaf forests. However, how moso bamboo expansion influences litter-leached dissolved organic matter (DOM) biodegradation is unclear. In this study, we collected fresh leaf litter of moso bamboo and 10 broadleaf tree species from a subtropical forest in southern China and extracted litter-leached dissolved organic carbon (DOC), dissolved total nitrogen (DTN), and dissolved total phosphorus (DTP). Then, using a 42-day incubation experiment, we measured litter-leached DOM biodegradation of the selected 11 species and assessed the relative mixing effects on biodegradation of bamboo litter- and broadleaf tree litter-leached DOM mixtures with volume mixing ratios of 1:3, 1:1, and 3:1. In the litter leachates, bamboo had lower DOC:DTN ratio, DOC:DTP ratio, and DOM aromaticity (i.e., lower SUVA254 and SUVA350 values) than most broadleaf tree species. Litter-leached DOM biodegradation did not differ among bamboo, Liquidambar formosana, Vernicia fordii, and Cyclobalanopsis glauca, but was greater for bamboo than for the other seven broadleaf tree species. Leaf litter-leached DOM biodegradation correlated negatively with DOC:DTN and DOC:DTP ratios, but exhibited no significant relationship with DOM aromaticity. Regardless of volume mixing ratios, antagonistic effects were observed when bamboo litter-leached DOM was mixed with broadleaf tree litter-leached DOM with comparable biodegradation, whereas synergistic effects occurred when bamboo litter-leached DOM was mixed with broadleaf tree litter-leached DOM with lower biodegradation. The relative mixing effects on DOM biodegradation increased linearly with elevated interspecific difference in litter-leached DOM biodegradation between bamboo and broadleaf tree species across the incubation periods. These findings indicate that moso bamboo expansion will substantially alter litter-leached DOM biodegradation by improving substrate quality and changing species interactions, and the magnitudes of such changing trends are dependent on the native tree litter-leached DOM biodegradation in subtropical broadleaf forests.

Interactions of manganese oxides with natural dissolved organic matter: Implications for soil organic carbon cycling

Metal (oxyhydr)oxides are key factors for the transformation and stabilization of organic carbon (OC) in soil. While sorptive interactions between Al and Fe (oxyhydr)oxides and dissolved organic matter (DOM) are well studied, the role of Mn(IV) oxides (manganates) in DOM sorption, fractionation, and oxidation has not been extensively investigated. Therefore, we examined sorptive interactions between manganates (δ-MnO2, birnessite, cryptomelane; 5 g L−1) and different DOM types (beech litter and Oa/Oe material under pine; ∼100 mg L−1 dissolved organic carbon, DOC) at pH 4 and 7 in different background electrolytes (BGE; no salt, 0.01 M NaCl or CaCl2) for up to 32 h. Changes of DOM solutions and mineral phases were assessed by solid, liquid, and gas analyses, and statistically evaluated for the effects of manganate, DOM type, pH, and BGE on DOC sorption, fractionation, and oxidative transformation. Manganates sorbed 0.2–8.7 mg OC g−1. Per unit mass, δ-MnO2 was least effective in DOC retention due to its high DOC oxidation capacity. Manganates sorbed more DOC at acidic pH and more aromatic pine than more aliphatic beech DOC, with Ca2+ generally facilitating DOC sorption. Up to 56 % of added DOC (average: 25 %) was oxidized to CO2, which is comparable to the extent of DOC respiration by soil microorganisms. DOC oxidation by δ-MnO2 and cryptomelane exceeded that of birnessite, which had the lowest specific surface area of all manganates. However, we found no difference in the efficiency of manganates to oxidize DOC, implying a similar redox activity of phyllo- and tectomanganates. More beech than pine DOM was oxidized to CO2 and an acidic pH facilitated DOC decomposition. While the presence of Na-BGE increased DOC oxidation to CO2 relative to no-salt treatments, Ca-BGE had the opposite effect, as Ca2+ apparently impeded the electron transfer from sorbed OC to structural Mn(III/IV). Contact of DOM with manganates also produced high concentrations of dissolved low-molecular-weight organic acids (mainly formate, acetate, and oxalate), accounting for up to 19 % of the initial DOC concentration. In addition, reduced specific ultraviolet absorbance of DOM solutions at 280 nm indicated preferential sorption of aromatic moieties, especially in Ca-BGE. However, in the absence of Ca2+ and at neutral pH, manganates increased the aromaticity of beech DOM, most likely due to polymerization reactions. No mineral transformations occurred after reaction of manganates with DOM, despite reductive manganate dissolution. Our results imply that soil manganates accumulate more OC in acidic soils and in presence of more aromatic DOM. However, manganates oxidatively destabilize DOC by generating CO2 and low-molecular-weight organic compounds, which is presumably more relevant in acidic soils with low concentrations of polyvalent cations and for more aliphatic DOM. The produced low-molecular-weight organic compounds may promote microbial activity and foster mineral weathering. Our results suggest a pivotal role of manganates in soil OC cycling, including the fate and bioavailability of nutrient elements associated with DOM, and in supporting ligand-promoted mineral weathering and soil formation.

Life after a fiery death: Fire and plant biomass loading affect dissolved organic matter in experimental ponds.

Drier and hotter conditions linked with anthropogenic climate change can increase wildfire frequency and severity, influencing terrestrial and aquatic carbon cycles at broad spatial and temporal scales. The impacts of wildfire are complex and dependent on several factors that may increase terrestrial deposition and the influx of dissolved organic matter (DOM) from plants into nearby aquatic systems, resulting in the darkening of water color. We tested the effects of plant biomass quantity and its interaction with fire (burned vs. unburned plant biomass) on dissolved organic carbon (DOC) concentration and degradation (biological vs. photochemical) and DOM composition in 400 L freshwater ponds using a gradient experimental design. DOC concentration increased nonlinearly with plant biomass loading in both treatments, with overall higher concentrations (>56 mg/L) in the unburned treatment shortly after plant addition. We also observed nonlinear trends in fluorescence and UV-visibleabsorbance spectroscopic indices as a function of fire treatment and plant biomass, such as greater humification and specific UV absorbance at 254 nm (a proxy for aromatic DOM) over time. DOM humification occurred gradually over time with less humification in the burned treatment compared to the unburned treatment. Both burned and unburned biomass released noncolored, low molecular weight carbon compounds that were rapidly consumed by microbes. DOC decomposition exhibited a unimodal relationship with plant biomass, with microbes contributing more to DOC loss than photodegradation at intermediate biomass levels (100-300 g). Our findings demonstrate that the quantity of plant biomass leads to nonlinear responses in the dynamics and composition of DOM in experimental ponds that are altered by fire, indicating how disturbances interactively affect DOM processing and its role in aquatic environments.

New insights into the adsorptive characteristics of trihalomethane precursors from surface water using magnetic powdered activated carbon

Powdered activated carbon (PAC) can effectively eliminate dissolved organic matter (DOM) as a precursor of trihalomethane (THM), but its application has raised concerns regarding its separation and the overelevated formation of brominate THM species in treated water after chlorination. Although magnetic PAC (Mag-PAC) has been proposed as an easily separable adsorbent for water treatment, its removal by Mag-PAC remains unknown. In this study, a novel Mag-PAC adsorbent for removing DOM and controlling THM formation from surface water was fabricated, evaluated using batch experiments, and compared with PAC. Our results found that Mag-PAC blended the advantages of PAC and magnetic particles, having an efficient removal performance toward DOM with an adsorption capacity of 2.84–3.69 mg-C/g and good magnetic separability of 10.15 emu/g. The iron oxide coating on the carbon matrices was predominantly distributed in the presence of crystalline goethite and magnetite structures. Chemisorption was the dominant mechanism of DOM adsorption by Mag-PAC. The sorption rate of DOM was influenced by the impregnation of iron oxide, but such impregnation did not significantly affect the DOM adsorption capacity. Aromatic DOM, humic-acid and fulvic-acid like compounds were efficiently adsorbed by the Mag-PAC. Compared with PAC, Mag-PAC exhibited a higher reduction in lifetime cancer risks from THMs through the ingestion pathway by decreasing the formation potential of trichloromethane and bromodichloromethane, which generated high unit risks among various THM species. These findings highlight the potential of Mag-PAC as an effective sorbent for DOM removal to control the formation of THM in surface water.

Terrestrial dissolved organic matter inputs drive the temporal dynamics of riverine bacterial ecological networks and assembly processes

Rivers receive, transport, and are reactors of terrestrial dissolved organic matter (DOM) and are highly influenced by changes in hydrological conditions and anthropogenic disturbances, but the effect of DOM composition on the dynamics of the bacterial community in rivers is poorly understood. We conducted a seasonal field sampling campaign at two eutrophic river mouth sites to examine how DOM composition influences the temporal dynamics of bacterial community networks, assembly processes, and DOM-bacteria associations. DOM composition and seasonal factors explained 34.7% of the variation in bacterial community composition, and 14.4% was explained purely by DOM composition where specific UV absorbance (SUVA254) as an indicator of aromaticity was the most important predictor. Significant correlations were observed between SUVA254 and the topological features of subnetworks of interspecies and DOM-bacteria associations, indicating that high DOM aromaticity results in more complex and connected networks of bacteria. The bipartite networks between bacterial taxa and DOM molecular formulae (identified by ultrahigh-resolution mass spectrometry) further revealed less specialized bacterial processing of DOM molecular formulae under the conditions of high water level and DOM aromaticity in summer than in winter. A shift in community assembly processes from stronger homogeneous selection in summer to higher stochasticity in winter correlated with changes in DOM composition, and more aromatic DOM was associated with greater similarity in bacterial community composition. Our results highlight the importance of DOM aromaticity as a predictor of the temporal dynamics of riverine bacterial community networks and assembly.

Accumulation of century-old biochar contributes to carbon storage and stabilization in the subsoil

Soil organic carbon (C) is a key component of the global C budget. As soil organic C turnover rates decrease with depth, agricultural practices favoring deep organic C storage will gain importance as long-term climate change mitigation strategies. In addition, amendment of pyrogenic organic matter (biochar) is considered a promising practice for sequestering C in croplands. However, so far the >30 cm depth soil organic C pool, and subsoil biochar dynamics in particular, has been understudied.To address this, we focused on leftovers from pre-industrial charcoal kilns as a proxy to study the accrual of century-old biochar in the subsoil (30–100 cm) in comparison to adjacent control soil. Using thermal and elemental analyses as well as size and density fractionations (i.e., separating particulate and mineral-associated organic matter), we determined the distribution of pyrogenic organic C within the soil profile and investigated its stabilization in depth. We measured the dissolved organic carbon (DOC) concentrations as well as absorbance and fluorescence properties of dissolved organic matter (DOM) at different depths to characterize the effects of century-old biochar accumulation on the current leaching of DOM.Our results showed that the presence of century-old biochar resulted in an increase of 53.8 ± 25.1 t C ha−1 in 0–100 cm, and 12 % of the pyrogenic organic C was stored in 30–60 cm. No difference in C stocks was observed in 60–100 cm between kiln sites and reference soils. Most of the pyrogenic organic C has been translocated as particulate organic matter, either free or occluded, to subsoils. This led to a change in the dominant fraction of organic matter in the E horizon; in reference soils 64.7 % of the total C was associated with mineral phases as opposed to only 42.3 % in soils enriched with biochar. The thermal analysis of the mineral-associated organic matter revealed that pyrogenic organic C was associated with mineral phases. With depth, DOC concentrations decreased and the relative contribution of microbial byproducts to fluorescent DOM increased. The soils enriched with century-old biochar displayed lower DOC concentrations and more aromatic DOM in the Ap horizon, which suggests biochar dissolution is still an on-going process. Our results suggest that the vertical transfers of century-old biochar mainly occurred as particle leaching in macroporosity and bioturbation but continuous dissolution has also contributed in these fine-textured cropland soils. In conclusion, the association of pyrogenic organic C with mineral phases as well as its migration in subsoil horizons promoted its physical disconnection from abiotic and biotic degrading agents, which likely contribute to the long-term stability of biochar.

Difference Analysis of the Composition of Iron (Hydr)Oxides and Dissolved Organic Matter in Pit Mud of Different Pit Ages in Luzhou Laojiao and Its Implications for the Ripening Process of Pit Mud.

Long-term production practice proves that good liquor comes out of the old cellar, and the aged pit mud is very important to the quality of Luzhou-flavor liquor. X-ray diffraction, Fourier transform ion cyclotron resonance mass spectrometry, and infrared spectroscopy were used to investigate the composition characteristics of iron-bearing minerals and dissolved organic matter (DOM) in 2-year, 40-year, and 100-year pit mud and yellow soil (raw materials for making pit mud) of Luzhou Laojiao distillery. The results showed that the contents of total iron and crystalline iron minerals decreased significantly, while the ratio of Fe(II)/Fe(III) and the content of amorphous iron (hydr)oxides increased significantly with increasing cellar age. DOM richness, unsaturation, and aromaticity, as well as lignin/phenolics, polyphenols, and polycyclic aromatics ratios, were enhanced in pit mud. The results of the principal component analysis indicate that changes in the morphology and content of iron-bearing minerals in pit mud were significantly correlated with the changes in DOM molecular components, which is mainly attributed to the different affinities of amorphous iron (hydr)oxides and crystalline iron minerals for the DOM components. The study is important for understanding the evolution pattern of iron-bearing minerals and DOM and their interactions during the aging of pit mud and provides a new way to further understand the influence of aged pit mud on Luzhou-flavor liquor production.

Roles of dissolved organic matter (DOM) in shaping the distribution pattern of heavy metal in the Yangtze River

Dissolved organic matter (DOM) strongly influences the solid-liquid partitioning and migration characteristics of heavy metals, yet little is known about the metal distribution and risk with the participation of DOM in large riverine systems. This study investigated the spatiotemporal distribution of 14 heavy metals and DOM along the entire Yangtze River (over 6000 km), and highlighted the critical roles of DOM in regulating the environmental behaviors of heavy metals. Significant spatial variations of metal contents were observed, with the river source and lower reach remarkably different from the upper-middle reaches. Heavy metals in the Yangtze River were mainly from the natural sources with minor anthropogenic disturbance. We found DOM could promote the conversion of metals from solid to liquid phase and DOM with higher aromaticity showed higher metal affinities. Although low ecological risks were observed in the Yangtze River, potential risks of metal leaching warrant attention, especially for As, Cd and Sb in the middle-lower reaches with higher DOM content and aromaticity. This study established a source-to-sea investigative approach to evaluate the influences of DOM features on metal partitioning, which is crucial for the risk control and sustainable management of large rivers.

Molecular characterization of DOM: A full-scale case study of an advanced DWTP from Jintan, China

Since the variation of dissolved organic matter (DOM) is complicated in the aquatic environment and water treatment processes, adverse effects on human and water quality may be triggered. Nowadays, more drinking water treatment plants (DWTPs) begin using pretreatment and advanced treatment processes for removing refractory DOM to pursue high-quality drinking water, including preozonation, and combined ozonation and biological activated carbon (BAC) treatment. The combination of Fourier transform ion cyclotron resonance mass spectrometer and fluorescence spectroscopy could comprehensively unveil the DOM composition and characteristics in water treatments. This study aims to provide information on the molecular and spectroscopic characteristics of DOM in a DWTP with pretreatments and advanced treatment processes and summarize the removal efficiency of different treatment processes on DOM. Results showed that the removal rate of low-molecular-weight acids (LMW-acids) by BAC was as high as 98 %, reflecting the synergistic effect of ozonation/BAC unit. Pre-ozonation enhanced coagulation process had a good removal effect on CHONS. The diversity of DOM increased and the relative abundance of DOM intensity was reduced in preozonation/coagulation/sedimentation and O3/BAC units. The preozonation-coagulation/sedimentation unit reduced the aromaticity or unsaturation of DOM while the advanced treatment process had a higher removal rate of fluorescent components.