Dissolved Organic Matter Compounds Research Articles

Unraveling the role of anthropogenic and hydrologic drivers with respect to the optical and molecular properties of dissolved organic matter and organic phosphorus in a P-contaminated river

Anthropogenic and hydrological drivers are key factors influencing the fate of dissolved organic matter (DOM) and dissolved organic phosphorus (DOP) in river runoff. However, how anthropogenic disturbances and hydrological conditions jointly affect the composition and characteristics of DOM and DOP in river runoff remains unclear. This study used fluorescence spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry, and the stable water isotopes to interpret the chemical composition and properties of DOM and DOP as well as their linkages to anthropogenic disturbances and hydrological conditions in a typical P-contaminated tributary to the central Yangtze River. The results show in the wet season, the average abundance of humic-like components in DOM exceeded 60 %, while the average abundance of tryptophan-like components in DOM exceeded 50 % in the dry season. During the dry season, hydrological conditions had a greater impact on highly unsaturated DOM compounds compared to anthropogenic disturbances because a decrease in precipitation reduced the transport of terrestrial DOM into aquatic systems and increased water retention time in the river, promoting the production of unsaturated compounds from photochemistry. The effects of the two factors were similar in the wet season because active agricultural activities and intense precipitation jointly facilitated the entry of exogenous humics into the runoff, leading to the similar relative abundance of highly unsaturated DOM compounds associated with both factors. Anthropogenic disturbances had a greater impact on aliphatic DOM and DOP than hydrological conditions, which was associated with intense human activities in the watershed, such as phosphate mining, agricultural cultivation, and domestic sewage discharge. This study provides new knowledge about the composition, properties and underlying mechanisms of DOM and DOP in the P-contaminated watershed runoff.

Molecular composition limits the reaction kinetics of riverine dissolved organic matter decomposition

The bioavailability and degradation of riverine dissolved organic matter (DOM) play crucial roles in greenhouse gas emissions; however, studies on the kinetic decomposition of fluvial DOM remain scarce. In this study, the decomposition kinetics of dissolved organic carbon (DOC) were characterized using the reactivity continuum model through 28-day bio-incubation experiments with water samples from the Yangtze River. The relationship between DOM composition and decomposition kinetics was analyzed using optical and molecular characterization combined with apparent decay coefficients. Our results revealed that DOM compounds rich in nitrogen and sulfur were predominantly removed, exhibiting a transition from an unsaturated to a saturated state following microbial degradation. These heteroatomic compounds, which constituted 75.61 % of the DOM compounds positively correlated with the decay coefficient k0, underwent preferential degradation in the early stages of bio-incubation due to their higher bioavailability. Additionally, we observed that S-containing fractions with high molecular weight values (MW > 400 Da) may be associated with larger reactivity grades. This study underscored the complex interplay between DOM composition and its kinetic decomposition in river ecosystems, providing further support for the significance of molecular composition in large river DOM as crucial factors affecting decomposition.

Microbial stratification and DOM removal in drinking water biofilters: Implications for enhanced performance

Biofiltration is a low-cost, low-energy technology that employs a biologically activated bed of porous medium to reduce the biodegradable fraction of the dissolved organic matter (DOM) pool in source water, resulting in the production of drinking water. Microbial communities at different bed depths within the biofilter play crucial roles in the degradation and removal of dissolved organic carbon (DOC), ultimately impacting its performance. However, the relationships between the composition of microbial communities inhabiting different biofilter depths and their utilisation of various DOC fractions remain poorly understood. To address this knowledge gap, we conducted an experimental study where microbial communities from the upper (i.e., top 10 cm) and lower (i.e., bottom 10 cm) sections of a 30-cm long laboratory-scale biofilter were recovered. These communities were then individually incubated for 10 days using the same source water as the biofilter influent. Our study revealed that the bottom microbial community exhibited lower diversity yet had a co-occurrence network with a higher degree of interconnections among its members compared to the top microbial community. Moreover, we established a direct correlation between the composition and network structure of the microbial communities and their ability to utilise various DOM compounds within a DOM pool. Interestingly, although the bottom microbial community had only 20 % of the total cell abundance compared to the top community at the beginning of the incubation, it utilised and hence removed approximately 60 % more total DOC from the DOM pool than the top community. While both communities rapidly utilised labile carbon fractions, such as low-molecular-weight neutrals, the utilisation of more refractory carbon fractions, like high-molecular-weight humic substances with an average molecular weight of more than ca. 1451 g/mol, was exclusive to the bottom microbial community. By employing techniques that capture microbial diversity (i.e., flow cytometry and 16S rRNA amplicon sequencing) and considering the complexities of DOM (i.e., LCOCD), our study provides novel insights into how microbial community structure could influence the microbial-mediated processes of engineering significance in drinking water production. Finally, our findings could offer the opportunity to improve biofilter performances via engineering interventions that shape the compositions of biofilter microbial communities and enhance their utilisation and removal of DOM, most notably the more classically humified and refractory DOM compound groups.

Combination Mechanism of Soil Dissolved Organic Matter and Cu2+ in Vegetable Fields, Forests and Dry Farmland in Lujiang County

Dissolved organic matter (DOM) serves as a critical link in the migration and transformation of heavy metals at the soil–solid interface, influencing the migration behaviour and transformation processes of Cu2+ in soil. There have been studies on the combination mechanisms between DOM and Cu2+ in paddy soils. However, the adsorption/complexation and redox processes between DOM and Cu2+ in other agricultural soil types (such as dry farmland and vegetable fields) are unclear. In order to reveal the combination process of DOM with Cu in different agricultural soil types and the dynamic changes in chemical behaviour that occur, this study analysed the variability of DOM components and structure in three soils using three-dimensional fluorescence spectroscopy and X-ray photoelectron spectroscopy. In addition, the priority order of different DOM compounds in combination with Cu and the change process in relation to the Cu valence state in the soil of Lujiang County, Anhui Province, was revealed based on laboratory experiments. The results showed that the composition of soil DOM was mainly composed of humic-like and fulvic-like substances with a clear terrestrial origin and that the organic matter showed a high degree of decomposition characteristics. The results indicated that the composition of soil DOM is mainly composed of humic and fulvic acid-like substances, and they have obvious characteristics of terrestrial origin. In addition, the soil organic matter showed high decomposition characteristics. The complex stability constants (lgKM) of humic acid-like substances with Cu2+ follow the order of forest land (lgKM = 5.21), vegetable land (lgKM = 4.90), and dry farmland (lgKM = 4.88). The lgKM of fulvic acid-like substances with Cu2+ is in the order of dry farmland (lgKM = 4.51) and vegetable land (lgKM = 4.39). Humic acid-like substances in soil DOM combine preferentially with Cu2+, showing a stronger chelating affinity than fulvic acid-like substances. Cu2+ complexes mainly include hydroxyl, phenolic hydroxyl and amino functional groups are included in soil DOM, accompanied by redox reactions. In comparison to dry farmland, the soil DOM in forest and vegetable fields undergoes more intense redox reactions simultaneously with the chelation of Cu2+. Therefore, the application of organic fertilisers to vegetable and forest soils may lead to uncertainties concerning the fate of heavy metals with variable chemical valence. These results contribute to a deeper understanding of the interaction mechanisms between DOM and Cu2+ in agricultural soils.

Dearomatization drives complexity generation in freshwater organic matter

Dissolved organic matter (DOM) is one of the most complex, dynamic and abundant sources of organic carbon, but its chemical reactivity remains uncertain1–3. Greater insights into DOM structural features could facilitate understanding its synthesis, turnover and processing in the global carbon cycle4,5. Here we use complementary multiplicity-edited 13C nuclear magnetic resonance (NMR) spectra to quantify key substructures assembling the carbon skeletons of DOM from four main Amazon rivers and two mid-size Swedish boreal lakes. We find that one type of reaction mechanism, oxidative dearomatization (ODA), widely used in organic synthetic chemistry to create natural product scaffolds6–10, is probably a key driver for generating structural diversity during processing of DOM that are rich in suitable polyphenolic precursor molecules. Our data suggest a high abundance of tetrahedral quaternary carbons bound to one oxygen and three carbon atoms (OCqC3 units). These units are rare in common biomolecules but could be readily produced by ODA of lignin-derived and tannin-derived polyphenols. Tautomerization of (poly)phenols by ODA creates non-planar cyclohexadienones, which are subject to immediate and parallel cycloadditions. This combination leads to a proliferation of structural diversity of DOM compounds from early stages of DOM processing, with an increase in oxygenated aliphatic structures. Overall, we propose that ODA is a key reaction mechanism for complexity acceleration in the processing of DOM molecules, creation of new oxygenated aliphatic molecules and that it could be prevalent in nature.

Comparison on molecular transformation of dissolved organic matter during Fenton and activated carbon adsorption processes for chemical cleaning wastewater treatment

This study employed Fenton oxidation and powdered activated carbon (PAC) adsorption processes for the removal of recalcitrant dissolved organic matter (DOM) in chemical cleaning wastewater (CCW) to meet discharge standards. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to identify resistant compounds and investigate the transformation characteristics of DOM. CCW mainly contained surfactant exhibiting heteroatom-rich characteristics, and both processes exhibited effective DOM removal but distinct selectivity towards different subclasses of formulas. PAC adsorption significantly decreased the number of DOM compounds and more effective in aromatic compounds than Fenton oxidation. The aliphatic compounds (AImod ≤ 0.5, 1.5 ≤ H/C ≤ 2.0) predominantly with saturated and reduced states were resistant to PAC adsorption, and particularly a specific CHONSP formula was the predominant contributor to residual DOM in the effluent. In contrast, Fenton oxidation degraded most substances in the CCW except for a few saturated and reduced compounds primarily consisting of CHO, resulting in an increase in DOM number. Two unsaturated subclasses, carboxylic-rich alicyclic molecules/lignin-like structures (primarily CHON) and carbohydrates (primarily CHONP and CHONSP), were prominently produced after Fenton oxidation. The major mechanisms governing Fenton oxidation of surfactant in CCW primarily involved dealkylation (25.2 %), oxygen addition (21.2 %), and decarboxylation (19.8 %). Given the unique removal preferences and resistance observed in Fenton and PAC processes, a combination approach could be explored in the future to achieve advanced overall performance.

Unraveling sources of cyanate in the marine environment: insights from cyanate distributions and production during the photochemical degradation of dissolved organic matter

Cyanate is a nitrogen and energy source for diverse marine microorganisms, playing important roles in the nitrogen cycle. Despite the extensive research on cyanate utilization, the sources of this nitrogen compound remain largely enigmatic. To unravel the sources of cyanate, distributions and production of cyanate during photochemical degradation of natural dissolved organic matter (DOM) were investigated across various environments, including freshwater, estuarine, coastal areas in Florida, and the continental and slope regions of the North American mid-Atlantic Ocean (NATL). Cyanate production was also examined during the photochemical degradation of exudates from a typical strain of Synechococcus, an important phytoplankton component. To deepen our understanding of the sources and production mechanisms of cyanate, its production was assessed during the photochemical degradation of a natural seawater DOM supplemented with five nitrogen–containing compounds with distinguishing structures and functional groups. Generally, cyanate exhibited higher concentrations in the Florida coastal, estuarine, and freshwater environments than the NATL. However, cyanate distribution did not consistently align with its production rates. Despite significantly low concentrations in the NATL, DOM from this region exhibited cyanate production rates comparable to estuarine and Florida coastal environments. Although relatively high cyanate concentrations were observed in the freshwaters, DOM in this environment exhibited very low cyanate production rates. A highly significant correlation was observed between cyanate and chlorophyll a (Chl a) concentrations in these areas. Moreover, in most estuarine and NATL stations, cyanate concentration and production rate in the Chl a maximum layer were significantly higher than in other layers. Cyanate was produced during the photochemical degradation of the Synechococcus exudates. The cyanate production was significantly enhanced when the natural seawater DOM was supplemented with GlycylGlycine, 4-(methylamino) benzoic acid, 4-[ethyl(methyl)amino] benzaldehyde or methyl 2-aminobenzoate. Our study implies that photochemical degradation of marine DOM, especially phytoplankton-derived DOM, is a substantial source of cyanate in the ocean. Additionally, cyanate may form during the degradation of peptides and small aromatic compounds in DOM, providing novel insights into the nitrogen cycle.

Chemodiversity of Dissolved Soil Organic Matter from Amazon Rainforest as Influenced by Deforestation.

Many biogeochemical processes are modulated by dissolved organic matter (DOM), but the drivers influencing the chemodiversity of DOM compounds in Amazonian soils are poorly understood. It has also been theorized whether deforestation controls the decline of DOM. In this study, we collected soil samples from thirty sites across different regions of Brazil's Legal Amazon, and we investigated the trade-offs among soil physical-chemical properties and DOM chemodiversity. We employed optical spectroscopy, Fourier transform ion cyclotron resonance, and multivariate analysis. Our results indicated that, despite variations in land use and soil physical-chemical properties, factors such as the deforested site, geometric mean diameter, weighted average diameter, and soil organic carbon were the main influencers of DOM chemodiversity variation. These findings highlight the importance of considering DOM chemodiversity as closely related to land use and its potential use in developing deforestation models for predicting soil quality decline in Brazil's Legal Amazon.

Biochar mediates nitrogen investment strategy involved in Chinese fir growth as revealed by molecular information on soil dissolved organic matter

Soil dissolved organic matter (DOM) is the most reactive pool of soil organic matter. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is a powerful tool for obtaining molecular-level DOM information. The ongoing atmospheric nitrogen (N) deposition could cause some negative effects on tropical and subtropical forest ecosystems, and biochar is considered to be an effective soil ameliorator. However, few studies have evaluated the effects of biochar and N deposition, either separately or in combination, on the molecular composition of soil DOM. In this study, we conducted a pot experiment using Chinese fir seedlings amended with biochar (0, 12, and 36 t biochar ha−1, prepared from corn stover at 450 °C) and inorganic N (NH4NO3: 0, 40, and 80 kg N ha−1 y-1) in a full factorial design (four replications per treatment) and characterized soil DOM using FT-ICR-MS. A total of 6084 types of formulas were identified in this study. All 36 samples had 2109 types of formulas in common, which had much lower N/C and P/C ratios than the bulk DOM samples. Permutation-based multivariate analysis of variance revealed that both N addition and biochar application had a significant impact on DOM chemodiversity. N addition increased the relative abundance of lignins and lipids, which may be a way for Chinese fir to acclimate to an acidic environment by expanding roots and fixing N. Biochar amendment increased the relative abundance of carbohydrates and tannins in soil DOM at each N application level. Soil pH is a key soil variable controlling DOM composition, and an increase in pH after biochar amendment contributed greatly to the occurrence of DOM compounds with an O/C > 0.5, which are easily degradable. In particular, lignins associated with low N/C were more abundant at higher pH. Biochar application also improved the efficiency of roots in acquiring nutrients, reduced the relative biomass of roots, and decreased the relative content of lignins or lipids, which primarily originated from the roots. In summary, biochar amendment effectively alleviated the negative effects of N addition by investing more N into the production of easily degradable DOM compounds and stimulating the biogeochemical cycle of N.

Probing the optical and molecular properties of sedimentary dissolved organic matter in the laminated diatom mats from the southern Mariana Trench

Laminated diatom mats (LDMs) deposition, formed by the aggregation of giant diatoms (e.g., Ethmodiscus rex), are recognized as a crucial driver of the global carbon and silicon cycles due to their substantial contribution to the flux of organic carbon and biogenic silica. The biogenic silica-rich sediment is one of the typical sediment types in the deep-sea setting of the tropical Pacific Ocean. Here, we analyzed the concentrations of pore-water dissolved organic carbon (DOC) and phosphate (PO43−), the optical properties, and molecular compositions of dissolved organic matter (DOM) in the two LDMs cores and one non-LDMs core retrieved from the southern Mariana Trench. Our results showed that the LDMs sediments with higher total organic carbon (TOC) contents have lower concentrations of DOC and chromophoric dissolved organic matter (CDOM), compared to the non-LDMs core. Meanwhile, the LDMs samples exhibited lower relative intensity of fluorescent proteins-like, molecular lability boundary (MLBL%) and higher values for humification index (HIX) and aromaticity modification (AImod) compared to the non-LDM core, indicating a higher level of stability and recalcitrance of DOM likely resulting from microbial degradation of relatively labile DOM compounds. Furthermore, the LDMs samples were characterized by a high abundance of CHO-containing DOM components and a low abundance of nitrogen- and sulfur-containing components, potentially linked to microbial degradation of hydrocarbon compounds that were enriched in the LDMs sediments. Additionally, the unique formulas in the LDMs samples demonstrated higher degree of recalcitrance suggested by higher aromaticity and fraction of CRAM, which may be attributed to microbial transformation of DOM. These findings add to our limited knowledge of the optical properties and molecular composition of DOM in the deep-sea opal-rich sediments, and have implications for understanding DOM cycling in the deep oceans.

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.

Organic amendment application affects the release behaviour, bioavailability, and speciation of heavy metals in zinc smelting slag: Insight into dissolved organic matter

Organic amendments are commonly used in assisted phytostabilization of mine wastes by improving their physicochemical and biological properties. These amendments are susceptible to leaching and degradation, resulting in the generation of dissolved organic matter (DOM), which significantly influences the geochemical behaviour of heavy metals (HMs). However, the geochemical behaviour of HMs in metal smelting slag driven by organic amendment-derived DOM remains unclear. In this study, we investigated the impact of cow manure-derived DOM on the release behaviour, bioavailability, and speciation of HMs (Cu, Pb, Zn, and Cd) in zinc smelting slag using a multidisciplinary approach. The results showed that DOM enhanced the weathering of the slag, with a minimal impact on the slag’s mineral phases, except for causing gypsum dissolution. The DOM addition resulted in a slight increase in HM release from the slag during the initial inoculation period, followed by a reduction in HM release during the later period. Furthermore, the DOM addition increased the diversity and relative abundance of the bacterial community. This, in turn, led to a decrease in the dissolved organic carbon (DOC) content and enhanced the transformation of labile DOM compounds into recalcitrant compounds. The variation in HM release during various inoculation periods can be attributed to the bacterial decomposition and transformation of DOM, which further enhanced the transformation of HM fractions. Specifically, during the later period, DOM promoted the conversion of a portion of the reducible and oxidizable fractions of Cu, Pb, and Zn into the acid-soluble and residual fractions. Moreover, it partially transformed the reducible, oxidizable, and residual fractions of Cd into the acid-soluble fraction. Overall, this study provides new insights into the geochemical behaviour of HMs in slag governed by the coupling effect of DOM and the bacterial community. These findings have implications for the use of organic amendments in assisted phytostabilization of metal smelting slag. Environmental implicationMetal smelting slag is hazardous due to its high levels of HMs, and its improper disposal has serious consequences for the ecosystem. Organic amendments are employed in assisted phytostabilization of the slag site by improving its microecological properties. However, the impact of organic amendment-derived DOM on HM migration and transformation in slag remains unclear. This study indicated that the coupling effects of DOM and microbes governed the geochemical behaviour of HMs in slag. These findings provide new insights into how organic amendments impact the geochemical behaviour of HMs in slag, contributing to the development of phytostabilization technology.

Instability in a carbon pool driven by multiple dissolved organic matter sources in a eutrophic lake basin: Potential factors for increased greenhouse gas emissions

Lakes serve as vital reservoirs of dissolved organic matter (DOM) and play pivotal roles in biogeochemical carbon cycles. However, the sources and compositions of DOM in freshwater lakes and their potential effects on lake sediment carbon pools remain unclear. In this study, seven inflowing rivers in the Lake Taihu basin were selected to explore the potential effects of multi-source DOM inputs on the stability of the lake sediment carbon pool. The results showed the high concentrations of dissolved organic carbon in the Lake Taihu basin, accompanied by a high complexity level. Lignins constituted the majority of DOM compounds, surpassing 40% of the total, while the organic carbon content was predominantly composed of humic acids (1.02–3.01 g kg−1). The high amounts of lignin oxidative cleavage led to CHO being the main molecular structure in the DOM of the seven rivers. The carbon constituents within the sediment carbon reservoir exhibited a positive correlation with dissolved CH4 and CO2, with a notable emphasis on humic acid and dissolved CH4 (R2 = 0.86). The elevated concentration of DOM, coupled with its intricate composition, contributed to the increases in dissolved greenhouse gases (GHGs). Experiments showed that the mixing of multi-source DOM can accelerate the organic carbon mineralization processes. The unit carbon emission efficiency was highest in the mixed group, reaching reached 160.9 μmol∙Cg−1, which also exhibited a significantly different carbon pool. The mixed decomposition of DOM from different sources influenced the roles of the lake carbon pool as source and sink, indicating that the multi-source DOM of this lake basin was a potential driving factor for increased carbon emissions. These findings have improved our understanding of the sources and compositions of DOM in lake basins and revealed their impacts on carbon emissions, thereby providing a theoretical basis for improving assessments of lake carbon emissions.

Selectivity of β-Cyclodextrin Polymer toward Aquatic Contaminants: Insights from Ultrahigh-Resolution Mass Spectrometry of Dissolved Organic Matter.

Selectivity in solid-phase extraction (SPE) materials has become increasingly important for analyte enrichment in sensitive analytical workflows to alleviate detrimental matrix effects. Molecular-level investigation of matrix constituents, which are preferentially extracted or excluded, can provide the analytical chemist with valuable information to learn about their control on sorbent selectivity. In this work, we employ nontargeted Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) to elucidate the molecular chemodiversity of freshwater-derived dissolved organic matter (DOM) extracted by the selective model sorbent β-cyclodextrin polymer (β-CDP) in comparison to conventional, universal SPE sorbents (i.e., Oasis HLB, Supel-Select HLB, and LiChrolut EN). Statistical analysis of MS data corroborated the highly selective nature of β-CDP by revealing the extracted DOM spectra that are most dissimilar to original compositions. We found that its selectivity was characterized by pronounced discrimination against highly oxygenated and unsaturated DOM compounds, which were associated with the classes of lignin-like, tannin-like, and carboxylic-rich alicyclic molecules. In contrast, conventional sorbents excluded less highly oxygenated compounds and showed a more universal extraction behavior for a wide range of DOM compositional space. We lay these findings in a larger context that aids the analyst in obtaining an a priori estimate of sorbent selectivity toward any target analyte of interest serving thereby an optimization of sample preparation. This study highlights the great value of nontargeted ultrahigh-resolution MS for better understanding of targeted analytics and provides new insights into the selective sorption behavior of novel sorbents.

Unveiling the molecular responses of dissolved organic matter in landfill leachate to activated carbon adsorption

Powdered activated carbon (PAC) is an effective method for removing dissolved organic matter (DOM) in membrane bioreactor effluent of landfill leachate (MBR effluent). Among commercially available PACs, wood-based PAC (WoAC) and coal-based PAC (CoAC) are two most common ones. However, the interactions between two PACs and DOM in MBR effluent at the molecular level as well as the effect of PACs properties on the adsorption of DOM compounds are not fully understood. To address the gap, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), three-dimensional fluorescence excitation-emission matrix (EEM) spectroscopy and other spectroscopic techniques were employed to study the change of DOM in MBR effluent when adsorbed by WoAC and CoAC. The results showed that CoAC had a better removal performance of DOM (89.2% for UV254 and 78.4% for DOC) than WoAC (80.9% for UV254 and 70.8% for DOC), which was likely due to the Fe component in CoAC playing an important role in the DOM adsorption process. Both WoAC and CoAC exhibited preferential adsorption for compounds with high unsaturation or poor oxygen. Moreover, the Fe component in CoAC may bind with some functional groups (e.g., carboxyl groups) in unsaturated compounds, which may enhance the adsorption of unsaturated compounds. These findings deepen our understanding of PAC-DOM interactions at the molecular level and provide guidance for designing cost-effective PACs for landfill leachate treatment.

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.

Soil microbial community, dissolved organic matter and nutrient cycling interactions change along an elevation gradient in subtropical China

To identify possible dominating processes involved in soil microbial community assembly, dissolved organic matter (DOM) and multi-nutrient cycling (MNC) interactions and contribute to understanding of climate change effects on these important cycles, we investigated the interaction of soil chemistry, DOM components and microbial communities in five vegetation zones - ranging from evergreen broad-leaved forest to alpine meadow - along an elevation gradient of 290–1960 m in the Wuyi Mountains, Fujian Province, China. Soil DOM composition and microbial community assembly were characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and Illumina MiSeq high-throughput sequencing, respectively. Sloan's neutral model and the modified stochasticity ratio were used to infer community assembly processes. Key microbial drivers of the soil MNC index were identified from partial least squares path models. Our results showed that soil DOM composition is closely related to the vegetation types along an elevation gradient, the structure and composition of the microbial community, and soil nutrient status. Overall, values of the double bond equivalent (DBE), modified aromaticity index (AImod) increased, and H/C ratio and molecular lability boundary (MLBL) percentage decreased with elevation. Lignins/CRAM-like structures compounds dominated soil DOM in each vegetation type and its relative abundance decreased with elevation. Aliphatic/protein and lipids components also decreased, but the relative abundance of aromatic structures and tannin increased with elevation. The alpha diversity index of soil bacteria gradually decreased with elevation, with deterministic processes dominating the microbial community assembly in the highest elevation zone. Bacterial communities were conducive to the decomposition of labile degradable DOM compounds (H/C ≥ 1.5) at low elevation. In the cooler and wetter conditions at higher-elevation sites the relative abundance of potentially resistant soil DOM components (H/C < 1.5) gradually increased. Microbial community diversity and composition were important predictors of potential soil nutrient cycling. Although higher elevation sites have higher nutrient cycling potential, soil DOM was assessed to be a more stable carbon store, with apparent lower lability and bioavailability than at lower elevation sites. Overall, this study increases understanding of the potential linkage between soil microbial community, multiple nutrient cycling and DOM fate in subtropical mountain ecosystems that can help predict the effect of climate change on soil carbon sequestration and thus inform ecosystem management.

Molecular characterization of dissolved organic matter in urban stormwater pond and municipal wastewater discharges transformed by the Florida red tide dinoflagellate Karenia brevis

Karenia brevis blooms occur almost annually in southwest Florida, imposing significant ecological and human health impacts. Currently, 13 nutrient sources have been identified supporting blooms, including nearshore anthropogenic inputs such as stormwater and wastewater outflows. A 21-day bioassay was performed, where K. brevis cultures were inoculated with water sourced from three stormwater ponds along an age gradient (14, 18, and 34 yrs.) and one municipal wastewater effluent sample, with the aim of identifying biomolecular classes and transformations of dissolved organic matter (DOM) compounds used by K. brevis. All sample types supported K. brevis growth and showed compositional changes in their respective DOM pools. Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) catalogued the molecular composition of DOM and identified specific compound classes that were biodegraded. Results showed that K. brevis utilized species across a wide range of compositions that correspond to amino sugars, humic, and lignin-like biomolecular classes. The municipal wastewater and the youngest stormwater pond (SWP 14) effluent contained the largest pools of labile DOM compounds which were bioavailable to K. brevis, which indicates younger stormwater pond effluents may be as ecologically important as wastewater effluents to blooms. Conversely, generation of DOM compounds of greater complexity and a wide range of aromaticity was observed with the older (SWP 18 and SWP 34) stormwater pond treatments. These data confirm the potential for stormwater ponds and/or wastewater to contribute nutrients which can potentially support K. brevis blooms, revealing the need for improved nutrient retention strategies to protect coastal waters from the potential ill effects of urban effluent.

Analyzing the Pollution Sources and Mechanisms of Urban Rivers Based on Identifying the Molecular Signature of Dissolved Organic Matter

Dissolved organic matter (DOM) is an essential component of river pollutants. Under the new situation of black water treatment in urban areas of China, in view of the widespread problem of unclear sources of multiple pollutants, further analysis of DOM components in urban rivers from the molecular level is a key link to deeply explore the sources, causes, and mechanism of river pollution so as to achieve efficient management. In this study, the urban rivers in the central city were selected as the research object, and a total of five rivers were selected that were seriously affected by the discharge sewage of four combined and separated sewer systems, respectively. Using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), this study identified the molecular formulae and analyzed the elemental composition and compound groups of DOM in water and sediment samples at each site in dry and wet weather. The results showed that:①although CHO molecules and lignins were the main compounds in the urban river DOM, the high proportion of lipids, proteins, and heteroatomic compounds (especially CHOS molecules) revealed the anthropogenic pollution in rivers, which also led to the increase in DOC, TN, and NH+4-N. ②Surfactants such as C17H28O3S and C18H30O3S were ubiquitous in all urban rivers, which could be used as markers of domestic wastewater pollution. ③In wet weather, the rainfall inputs, storm runoffs, and hydraulic disturbance jointly led to the increase in the proportion of CHO molecules and lignin compounds; the decrease in proteins and lipids; the rise of DOC, TN, and NH+4-N concentrations in river water; and the decrease in DOC, TN, and NH+4-N concentrations and proteins and lipids in river sediments. ④The abundance of multi-heteroatomic compounds and condensed aromatics in the combined sewer system was higher than that in the separated sewer system, which may have been more severely polluted by domestic wastewater and storm runoff, especially kitchen wastewater. This study provides new insight for clarifying the critical causes of pollution in the new stage and provides an essential basis for further precision prevention and control of water pollution.

Transformation of dissolved organic matter and related arsenic mobility at a surface water-groundwater interface in the Hetao Basin, China

Porewater arsenic mobility above the groundwater table has been recognized as a potential cause of arsenic-rich groundwater, but the processing pathways of dissolved organic matter (DOM) in that hyporheic zone and their effect on porewater arsenic release remain poorly understood. To address these issues, two porewater profiles were sampled in a surface water-groundwater interaction zone from the Hetao Basin, China, to monitor the porewater geochemistry and DOM molecular characteristics. The results show that the porewater arsenic, Fe(II), and DOC concentrations were all significantly higher than those of the intruding pond water, and were located above the conservative mixing model lines. This indicates a net release of these solutes from the sediment. By comparing the porewater with pond water DOM, we found that the carboxyl-rich alicyclic molecules (CRAM) were selectively preserved, carbohydrates and aliphatics/proteins were preferentially consumed, and low O/C-ratio compounds with high bioproduction index (I_bioprod) and terrestrial index (I_terr) were produced. The transformation of CHO to CHOS compounds also represented a pathway of recalcitrant DOM production. The produced recalcitrant organic compounds mostly contributed to the elevated porewater DOC concentrations, but their contribution decreased along the filtration path. The consumption of labile DOM compounds would be responsible for Fe(III) hydroxide reduction and arsenic release. The generated recalcitrant DOM may also be a driver of porewater arsenic mobility by acting as electron shuttles. This study highlights the importance of the hyporheic zone in shaping shallow groundwater DOM composition and the potential contribution to arsenic enrichment.