Dissolved Organic Matter Components Research Articles

Urban and agricultural influences on the coastal dissolved organic matter pool in the Algoa Bay estuaries

While anthropogenic pollution is a major threat to aquatic ecosystem health, our knowledge of the presence of xenobiotics in coastal Dissolved Organic Matter (DOM) is still relatively poor. This is especially true for water bodies in the Global South with limited information gained mostly from targeted studies that rely on comparison with authentic standards. In recent years, non-targeted tandem mass spectrometry has emerged as a powerful tool to collectively detect and identify pollutants and biogenic DOM components in the environment, but this approach has yet to be widely utilized for monitoring ecologically important aquatic systems. In this study we compared the DOM composition of Algoa Bay, Eastern Cape, South Africa, and its two estuaries. The Swartkops Estuary is highly urbanized and severely impacted by anthropogenic pollution, while the Sundays Estuary is impacted by commercial agriculture in its catchment. We employed solid-phase extraction followed by liquid chromatography tandem mass spectrometry to annotate more than 200 pharmaceuticals, pesticides, urban xenobiotics, and natural products based on spectral matching. The identification with authentic standards confirmed the presence of methamphetamine, carbamazepine, sulfamethoxazole, N-acetylsulfamethoxazole, imazapyr, caffeine and hexa(methoxymethyl)melamine, and allowed semi-quantitative estimations for annotated xenobiotics. The Swartkops Estuary DOM composition was strongly impacted by features annotated as urban pollutants including pharmaceuticals such as melamines and antiretrovirals. By contrast, the Sundays Estuary exhibited significant enrichment of molecules annotated as agrochemicals widely used in the citrus farming industry, with predicted concentrations for some of them exceeding predicted no-effect concentrations. This study provides new insight into anthropogenic impact on the Algoa Bay system and demonstrates the utility of non-targeted tandem mass spectrometry as a sensitive tool for assessing the health of ecologically important coastal ecosystems and will serve as a valuable foundation for strategizing long-term monitoring efforts.

Structure and composition of dissolved organic matters in sludge by ultrasonic treatment

The leaching of dissolved organic matter (DOM) from the sludge into the liquid phase is induced by ultrasound. However, there is limited investigation into the structure and molecular composition of sludge DOM in this process. The molecular structure and composition of sludge DOM in ultrasonic treatment were comprehensively elucidated in this study. The sludge dissolved organic carbon (DOC) and three-dimensional fluorescence spectroscopy (3D-EEM) image had most significant change at 15-min ultrasonic time and 1.2 W/mL ultrasonic density, respectively. Gas Chromatography-Mass Spectrometry (GC-MS) analysis indicated that ultrasonic treatment of sludge reduced the macromolecules to small molecules in DOM. Then, electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) analysis revealed that lignin, tannins, and carbohydrates were the main components of sludge DOMs after ultrasound treatment. analysis revealed that lignin, tannins, and carbohydrates were the main components of sludge DOMs after ultrasound treatment. Furthermore, through the Van Krevelen analysis, the major components were CHO (48.50%) and CHOS (23.20%) in the DOM of ultrasonicated sludge. This research provides the basis for the practical application of ultrasonic treatment of sludge and provides basic information for DOM components.

Development of dissolved organic matter-based indicators to understand the degradation of organic contaminants in reverse osmosis concentrate from potable reuse systems

Reverse osmosis (RO)-based treatment of municipal wastewater effluent allows for potable reuse, but this process generates reverse osmosis concentrate (ROC) that needs further treatment before disposal. This study investigated the application of UV-based advanced oxidation processes (AOPs) to degrade nine contaminants of emerging concern (CECs) from real ROC waste streams, using UV-only and UV-AOPs with hydrogen peroxide, free chlorine, and persulfate. Dissolved organic matter (DOM) in ROC was characterized using fluorescence excitation emission matrix data and analyzed by a four-component parallel factor (PARAFAC) analysis model. UV-only treatment showed considerable removal of CECs that displayed high values of quantum yields and molar absorption coefficients. UV-AOP treatment of ROC exhibited heavy scavenging of reactive species during CEC degradation. A probe-based approach established that hydroxyl radical was the dominant reactive species in all UV-AOPs. A kinetic analysis of PARAFAC components of DOM showed that the visible humic-like and protein-like components exhibited the higher reaction kinetics compared to UV humic-like and nutrient-like components. The strong linear correlation of protein-like component and seven of the nine CECs across multiple AOPs indicated that they have similar reactivity, enabling the establishment of chemical-reactivity based surrogates for prediction CEC fate in ROC wastes.

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

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

Production and prediction of hydroxyl radicals in distinct redox-fluctuation zones of the Yellow River Estuary

Hydroxyl radicals (·OH) produced in subsurface sediments play an important role in biogeochemical cycles. One of the major sources of·OH in sediments is associated with reduced compounds (e.g., iron and organic matter) oxygenation. Moreover, the properties of iron forms and dissolved organic matter (DOM) components varied significantly across redox-fluctuation zones of estuaries. However, the influence of these variations on mechanisms of·OH production in estuaries remains unexplored. Herein, sediments from riparian zones, wetlands, and rice fields in the Yellow River Estuary were collected to systematically explore the diverse mechanisms of·OH generation. Rhythmic continuous·OH production (82–730 μmol/kg) occurred throughout the estuary, demonstrating notable spatial heterogeneity. The amorphous iron form and humic-like DOM components were the key contributors to·OH accumulation in estuary wetlands and freshwater restoration wetlands, respectively. The crystalline iron form and protein-like DOM components influenced the capabilities of iron reduction and continuous·OH production. Moreover, the orthogonal partial least squares models outperformed various multivariate models in screening crucial factors and predicting the spatiotemporal production of·OH. This study provides novel insights into varied mechanisms of·OH generation within distinct redox-fluctuation zones in estuaries and further elucidates elemental behavior and contaminant fate in estuarine environments. Environmental implicationGiven that estuaries serve as sinks for anthropogenic pollutants, various organic pollutants (e.g., emerging contaminants such as antibiotics) have been widely detected in estuarine environments. The production of·OH in sediments has been proven to affect the fate of contaminants. Therefore, the varied mechanisms of·OH in estuarine environments, dominated by diverse iron forms and DOM components, were explored in this study. MLR and OPLS models exhibited good performance in screening crucial factors and predicting·OH production. Our work highlights that in estuarine subsurface environments, the presence of·OH potentially leads to a natural degradation of pollutants.

Unraveling the photochemical behavior of dissolved organic matter derived from hydrothermal carbonization process water: Insights from molecular transformation and photoactive species

Hydrothermal carbonization process water (HTPW) has been utilized as a substitute for chemical fertilizers in agricultural applications. However, the input of HTPW into paddy water, particularly the significant proportion of dissolved organic matter (DOM) in HTPW (DOM-HTPW), directly engages in photochemical transformations, a phenomenon often overlooked. This study observed a consistent decrease in humification (SUVA280, 7.7–53.9%) and aromaticity (SUVA254, 6.1–40.0%) of DOM-HTPW after irradiation. The primary active photobleaching components of DOM-HTPW varied depending on the feedstock, such as protein for chicken manure DOM-HTPW and lignin for rice straw DOM-HTPW. The photochemical activity of DOM-HTPW was augmented by its lower molecular weight and higher hydrophilic composition, particularly evident in chicken manure DOM-HTPW, which exhibited higher generation rates for 1O2 (35.1–37.1%), 3DOM* (32.8–43.9%), and O2•− (28.6–48.8%) as measured by molecular probes. DOM-HTPW effectively facilitated the phototransformation of tetracycline, with the contribution of O2•− being more significant than 3DOM* and 1O2. These findings shed new light on the understanding the photochemical processes of DOM-HTPW as exogenous DOM and the interconnected fate of contaminants in aquatic environments.

Reduced sulfur compounds and carboxylic acid groups in dissolved PFRs of iron-biochar enhance Cr(VI) reduction in anaerobic conditions

In addition to the adsorption and immobilization capacities of iron-modified biochars, these materials produce persistent free radicals (PFRs) that can carry out metal [i.e., Cr(VI)] redox transformations, but the primary forms and active species of PFRs involved are not well understood. Here, we investigated the key species of PFRs of α-Fe2O3-modified biochar (MBC) and their influence on Cr(VI) reduction under anaerobic conditions simulating paddy soil environments. MBC produced bulk phenoxyl PFRs that promoted Cr(VI) reduction due to the catalytic effect of the transition metal Fe. In addition, MBC was more efficient in reducing Cr(VI) under anaerobic conditions than under aerobic conditions due to the more active and accessible dissolved PFRs present in the dissolved organic matter (DOM). The electron transfer capacity of DOM was demonstrated by excitation-emission matrix (EEM) spectrophotometry combined with parallel factor analysis, which showed that the protein-like and humic-like components of DOM were involved in Cr(VI) reduction. Furthermore, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) analysis indicated that reduced-S compounds (O/S < 4) and carboxylic acid (–COO) groups in the unsaturated aliphatic and lignin-like compounds are potentially the main active species accelerating Cr(VI) reduction under anaerobic conditions. Our results provide new insights into the role of dissolved PFRs from iron-modified biochar in promoting Cr(VI) reduction under anaerobic conditions such as flooded soils.Graphical

Labile dissolved organic matter (DOM) and nitrogen inputs modified greenhouse gas dynamics: A source-to-estuary study of the Yangtze River

Although rivers are increasingly recognized as essential sources of greenhouse gases (GHG) to the atmosphere, few systematic efforts have been made to reveal the drivers of spatiotemporal variations of dissolved GHG (dGHG) in large rivers under increasing anthropogenic stress and intensified hydrological cycling. Here, through a source-to-estuary survey of the Yangtze River in March (spring) and October (autumn) of 2018, we revealed that labile dissolved organic matter (DOM) and nitrogen inputs remarkably modified the spatiotemporal distribution of dGHG. The average partial pressure of CO2 (pCO2), CH4 and N2O concentrations of all sampling sites in the Yangtze River were 1015 ± 225 μatm, and 87.5± 36.5 nmol L−1, and 20.3 ± 6.6 nmol L−1, respectively, significantly lower than the global average. In terms of longitudinal and seasonal variations, higher GHG concentrations were observed in the middle-lower reach in spring. The dominant drivers of spatiotemporal variations in dGHG were labile, protein-like DOM components and nitrogen level. Compared with the historical data of dGHG from published literature, we found a significant increase in N2O concentrations in the Yangtze River during 2004–2018, and the increasing trend was consistent with the rising riverine nitrogen concentrations. Our study emphasized the critical roles of labile DOM and nitrogen inputs in driving the spatial hotspots, seasonal variations and annual trends of dGHG. These findings can contribute to constraining the global GHG budget estimations and controls of GHG emission in large rivers in response to global change.

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.

Spatial distribution characteristics and interaction effects of DOM and microbial communities in kelp cultivation areas

The influence of macroalgae cultivation on aquaculture carbon sinks is significant, with microbial carbon (C) pumps contributing to a stable inert dissolved carbon pool in this context. Concurrently, dissolved organic matter (DOM) exchange at the marine sediment-water interface profoundly affects global ecosystem element cycling. However, the interactions between DOM and bacterial communities at the sediment-water interface in kelp cultivation areas, especially regarding microbial function prediction, have not been fully explored. This study analyzed the DOM characteristics, environmental factors, and bacterial community structure in the Tahewan kelp——Saccharina japonica cultivated area and compared them with those in non-cultivated areas. The results indicated significantly higher dissolved organic carbon (DOC) concentrations in the kelp culture area, particularly in surface seawater and overlying water. The dominant bacterial phyla in both regions included Pseudomonadota, Actinomycetota, and Bacteroidota in both regions, while Desulfobacterota was more prevalent in the sediment environment of the cultivated region. Parallel factor analysis (EEM-PARAFAC) was used to identify DOM components, among which component C2 (a microbial humic-like substance DOM) was highly resistant to microbial degradation. We infer that C2 has similar properties to recalcitrant dissolved organic matter (RDOM). Analysis of the predicted functional genes based on 16S rRNA gene data showed that methanol oxidation, methylotrophy, and methanotrophy were significant in the bottom seawater of the cultivation area. The carbon (C), nitrogen (N), and sulfur (S) cycle functional genes in the sediment environment of the kelp cultivation area were more active than those in other areas, especially in which sulfate reduction and denitrification were the two main processes. Furthermore, a DOM priming effect was identified in the cultivated sediment environment, where kelp-released labile dissolved organic matter (LDOM) stimulates rapid degradation of the original RDOM, potentially enhancing C sequestration.

The bacterial influencing mechanisms of salinity fluctuations in a brackish-water lake on the dissolved organic matter characteristics of pore water

The dissolved organic matter (DOM) components in lake water have been widely studied; however, few previous studies have considered the growth of Phragmites australis in brackish lakes. It has not been well understood how salinity variations influence the DOM compositions in pore water and its bacterial mechanisms in lakes with Phragmites australis. This experiment included three salinity groups (1,200 mg/L, 3,600 mg/L, and 6,000 mg/L) to study the interactions between bacteria and DOM in pore water under a salinity gradient. The results showed that the maximum fluorescence intensity (Fmax) of DOM measured by excitation-emission fluorescence spectroscopy decreased with increasing salinity. Higher salinity reduced the Fmax of protein-like substances and resulted in DOM becoming more aromatic. Salinity affected DOM composition due to the responses of functional bacterial communities. Thiobacillus was salt-tolerant and dominated in the sediments, and its relative abundance was negatively correlated with the Fmax of protein-like components. The relative abundance of Flavobacterium showed a positive correlation with salinity and a negative correlation with the Fmax of the fulvic acid-like component. Pseudomonas, Brevundimonas, and Polaromonas were negatively correlated with salinity and the Fmax of the fulvic acid-like component, while being positively correlated with the Fmax of tyrosine-like and aromatic protein substances. Higher salinity inhibited the metabolism gene modules of tryptophan and tyrosine. The results of this study may offer a novel perspective on comprehending the biochemical cycling of fluorescent DOM, encompassing tryptophan-like, tyrosine-like, and fulvic acid-like components in brackish lakes with fluctuating salinity.

Methods for molecular characterization of dissolved organic matter in the alpine water environment: an overview

The alpine area has become a sensitive indicator and amplifier of global climate change and human activities because of its unique geographical and climatic conditions. Being an essential part of biochemical cycling, dissolved organic matter (DOM) could effectively help understand the process, structure, and function of alpine aquatic ecosystems. Due to the low content and sampling difficulties, the analysis of DOM in alpine water demands high sensitivity with low sample volume, which has not been comprehensively reviewed. This review summarizes the DOM sampling, pretreatment, and analysis methods involving the characterization of concentration, spectroscopy, and molecular structure. Overall, conventional parameters are the basis of advanced characterization methods. Spectroscopic tests can reveal the optical properties of DOM in response to lights from ultraviolet to infrared wavelengths, to distinguish the chemical composition. Molecular structure characterizations can provide microscopic information such as functional groups, element ratios, and molecular weights. The combination of multiple methods can depict DOM composition from multiple perspectives. In sum, optimized sampling and pretreatment, high-sensitivity molecular characterization, and method integration are crucial for effectively analyzing DOM components in alpine waters. These perspectives help to standardize the DOM characterization process and to understand the correlation between DOM composition and its properties, as well as the migration and transformation of DOM.

Coagulation pretreatment coupled with indigenous microalgal-bacterial consortium system for on-site treatment of rural black wastewater

Improper treatment of rural black wastewater (RBW) presents substantial challenges, including the wastage of resource, environmental contamination, and economic consequences. This study proposed an integrated process for RBW treatment, consisting of coagulation/flocculation (C/F) pretreatment and subsequent inoculation of indigenous microalgal-bacterial consortium (IMBC) for nitrogen recovery, namely C/F-IMBC process. Specifically, the optimal C/F conditions (polyaluminium chloride of 4 g/l, polyacrylamide of 50 mg/l, and pH of 6) were determined through a series of single-factor experiments, considering CN, turbidity, and dissolved organic matter (DOM) removal, economic cost, and potential influence on the water environment. Compared to the sole IMBC system for RBW treatment, the proposed C/F-IMBC process exhibited a remarkable 1.23-fold increase in microalgal growth and a substantial 17.6–22.6 % boost in nitrogen recovery. The altered RBW characteristic induced by C/F pretreatment was supposed to be responsible for the improved system performance. In particular, the abundance of DOM was decreased and its composition was simplified after C/F pretreatment, based on the analysis for excitation-emission matrices with parallel factor and gas chromatography–mass spectrometry, thus eliminating the potential impacts of toxic DOM components (e.g., Bis(2-ethylhexyl) phthalate) on IMBC activity. It should also be noted that C/F pretreatment modified microbial community structure as well, thereby regulating the expression of nitrogen-related genes and enhancing the system nitrogen recovery capacity. For instance, the functional Cyanobacteria responsible for nutrient recovery was enriched by 1.95-fold and genes involved in the assimilatory nitrate reduction to ammonia pathway were increased by 1.52-fold. These fundamental findings are expected to offer insights into the improvement of DOM removal and nitrogen recovery for IMBC-based wastewater treatment system, and provide valuable guidance for the development of sustainable on-site RBW treatment technologies.

Insights into priming effects of dissolved organic matter degradation in urban lakes with different trophic states

Priming effect (PE) is recognized as an important potential mechanism for dissolved organic matter (DOM) degradation in aquatic ecosystems. However, the priming effects (PEs) of various priming substances on the degradation of DOM pools in urban lakes along diverse trophic states remain unknown. To address this knowledge gap, the PEs and drivers of glucose and plant leachate of lake water with three trophic states were investigated. We reveal differences in the bioavailability of DOM in lake water, glucose, and plant leachate. The PE of the same priming substance was significantly higher in highly-eutrophic lake water than in mesotrophic lake. The priming intensity induced by glucose was significantly higher when compared to plant leachate. Regarding the addition of glucose, humic-like components (C1 and C3) showed slight PE, while the tyrosine-like component C2 showed negative PE. However, the positive PEs were observed on three components after adding plant leachate. The driver of PE by glucose shifted from nutrients to DOM components with increasing trophic levels. The PEs induced by plant leachate were affected by nutrients, chlorophyll-a (Chl-a), water chemistry, and DOM components in lightly/moderately-eutrophic lake water. This study revealed the intensities, directions, and drivers of PEs, providing essential insights into uncovering the DOM biogeochemical process in urban lakes.

Molecular insights into the bonding mechanisms between selenium and dissolved organic matter

Natural organic matter (NOM) plays a critical role in the mobilization and bioavailability of metals and metalloids in the aquatic environment. Selenium (Se), an environmental contaminant of aquatic systems, has drawn increasing attention over the years. While Se is a vital micronutrient to human beings, animals and plants, excess Se intake may pose serious long-term risks. However, the interaction between Se and dissolved organic matter (DOM) remains relatively unexplored, especially the reaction mechanisms and interactions of specific NOM components of certain molecular weight and the corresponding functional group change. Herein, we report an investigation on the interactions between Se and DOM by focusing on the mass distribution profile change of operationally defined molecular weight fractions of humic acid (HA) and fulvic acid (FA). The results showed that across all molecular weights studied, HA fractions were more prone to enhanced aggregation upon introduction of Se into the system. For FA, the presence of Se species results in aggregation, dissociation, and redox reactions with the first two being the major mechanisms. Total organic carbon analysis (TOC), UV–vis spectroscopy (UV–vis), and Orbitrap MS data showed that [10, 30] kDa MW fraction had the largest aromatic decrease (CRAM-like, lignin-like and tannin-like) upon addition of SeO2 via dissociation as the dominant mechanism. Fourier transform infrared spectroscopy (FT-IR) revealed that Se based bridging or chelation of functional groups from individual DOM components through hydrogen bonding in the form of SeO⋯H and possibly Se⋯H and/or attractive electrostatic interactions lead to aggregated DOM1⋯Se⋯DOM2. It was concluded from two-dimensional correlation analyses of excitation emission matrix (EEM) and FT-IR that the preferred Se-binding follows lipid ➔ peptide ➔ tannin ➔ aromatic functionalities. These results provide new understanding of Se interactions with various NOM components in aquatic environments and provide insight for Se assessing health risk and/or treatment of Se contaminated water.

Differential response of Hg-methylating and MeHg-demethylating microbiomes to dissolved organic matter components in eutrophic lake water

Methylmercury (MeHg) production in aquatic ecosystems is a global concern because of its neurotoxic effect. Dissolved organic matter (DOM) plays a crucial role in biogeochemical cycling of Hg. However, owing to its complex composition, the effects of DOM on net MeHg production have not been fully understood. Here, the Hg isotope tracer technique combined with different DOM treatments was employed to explore the influences of DOM with divergent compositions on Hg methylation/demethylation and its microbial mechanisms in eutrophic lake waters. Our results showed that algae-derived DOM treatments enhanced MeHg concentrations by 1.42−1.53 times compared with terrestrial-derived DOM. Algae-derived DOM had largely increased the methylation rate constants by approximately 1−2 orders of magnitude compared to terrestrial-derived DOM, but its effects on demethylation rate constants were less pronounced, resulting in the enhancement of net MeHg formation. The abundance of hgcA and merB genes suggested that Hg-methylating and MeHg-demethylating microbiomes responded differently to DOM treatments. Specific DOM components (e.g., aromatic proteins and soluble microbial byproducts) were positively correlated with both methylation rate constants and the abundance of Hg-methylating microbiomes. Our results highlight that the DOM composition influences the Hg methylation and MeHg demethylation differently and should be incorporated into future Hg risk assessments in aquatic ecosystems.

In the presence of the other: How glyphosate and peptide molecules alter the dynamics of sorption on goethite

The interactions with soil mineral surfaces are among the factors that determine the mobility and bioavailability of organic contaminants and of nutrients present in dissolved organic matter (DOM) in soil and aquatic environments. While most studies focus on high molar mass organic matter fractions (e.g., humic and fulvic acids), very few studies investigate the impact of DOM constituents in competitive sorption. Here we assess the sorption behavior of a heavily used herbicide (i.e., glyphosate) and a component of DOM (i.e., a peptide) at the water/goethite interface, inclusive of potential glyphosate-peptide interactions. We used in-situ ATR-FTIR (attenuated total reflectance Fourier-transform infrared) spectroscopy to study sorption kinetics and mechanisms of interaction as well as conformational changes to the secondary structure of the peptide. NMR (nuclear magnetic resonance) spectroscopy was used to assess the level of interaction between glyphosate and the peptide and changes to the peptide' secondary structure in solution. For the first time, we illustrate competition for sorption sites results in co-sorption of glyphosate and peptide molecules that affects the extent, kinetics, and mechanism of interaction of each with the surface. In the presence of the peptide, the formation of outer-sphere glyphosate-goethite complexes is favored albeit inner-sphere glyphosate-goethite bonds (i.e., POFe) are still formed. The presence of glyphosate induces secondary structural shifts of the sorbed peptide that maximizes the formation of H-bonds with the goethite surface. However, glyphosate and the peptide do not seem to interact with one another in solution nor at the goethite surface upon sorption. The results of this work highlight potential consequences of competition for sorption sites, for example the transport of organic contaminants and nutrient-rich (i.e., nitrogen) DOM components in relevant environmental systems. Predicting the rate and extent with which organic pollutants are removed from solution by a given solid is also one of the most critical factors for the design of effective sorption systems in engineering applications.

Removal of particulate matter and dissolved organic matter from sedimentation sludge water during pre-sedimentation process: Performances and mechanisms

Sedimentation sludge water (SSW), a prominent constituent of wastewater from drinking water treatment plants, has received limited attention in terms of its treatment and utilization likely due to the perceived difficulties associated with managing SSW sludge. This study comprehensively evaluated the water quality of SSW by comparing it to a well-documented wastewater (filter backwash water (FBW)). Furthermore, it investigated the pollutant variations in the SSW during pre-sedimentation process, probed the underlying reaction mechanism, and explored the feasibility of employing a pilot-scale coagulation-sedimentation process for SSW treatment. The levels of most water quality parameters were generally comparable between SSW and FBW. During the pre-sedimentation of SSW, significant removal of turbidity, bacterial counts, and dissolved organic matter (DOM) was observed. The characterization of DOM components, molecular weight distributions, and optical properties revealed that the macromolecular proteinaceous biopolymers and humic acids were preferentially removed. The characterization of particulates indicated that high surface energy, zeta potential, and bridging/adsorption/sedimentation/coagulation capacities in aluminum residuals of SSW, underscoring its potential as a coagulant and promoting the generation and sedimentation of inorganic-organic complexes. The coagulation-sedimentation process could effectively remove pollutants from low-turbidity SSW ([turbidity]0 < 15 NTU). These findings provide valuable insights into the water quality dynamics of SSW during the pre-sedimentation process, facilitating the development of SSW quality management and enhancing its reuse rate.

Inhibition mechanisms of biochar-derived dissolved organic matter to triclosan photodegradation: A remarkable role of aliphatics

Endocrine disrupting chemicals like triclosan (TCS) have been thought to be an emergent environmental pollutant. The ubiquitous dissolved organic matter (DOM) is able to interrelate with TCS and hamper its phototransformation. However, how the components in DOM can inhibit the photodegradation of DOM/TCS complex is largely unknown. Herein, we discovered that TCS photodegradation with biochar-derived DOM (BDOM) was interfered by both binding affinity and reactive oxygen species (ROS) productivity. BDOM can not only stimulate TCS photodegradation by producing ROS, but also inhibit the removal of TCS through the interactions between BDOMs and TCS. The quantification of BDOM's impact on TCS photodegradation revealed that BDOM hampered TCS removal with the proportion of −7.95 to −11.24% at pH 8.5, but strengthened it to 13.20% at pH 7.0. Binding process was more easily to inhibit TCS photodegradation in molecular form, while anionic TCS photodegradation was dominated by ROS productivity. Different inhibition mechanisms were involved in TCS photodegradation depending on the components of BDOMs. The hydroxyls and aromatic carbonyls might have hindered the attack of ROS on the phenolic hydroxyl of TCS via hydrogen bond interaction or π-π electron donor-acceptor interaction. Through hydrophobic interaction, the mobile aliphatics could greatly shield TCS to prevent ROS attack by wrapping or twining TCS, playing a significant role in inhibiting TCS removal. Results from this present study can afford a new viewpoint in elucidating the function of BDOMs in the phototransformation of organics and decrease the spread of antibiotic resistance genes.

Insight into the dynamics of dissolved organic matter components under latitude change perturbation

Dissolved organic matter (DOM) which can help the transportation of nutrients and pollutants plays essential role in the aquatic ecosystems. However, the dynamics of individual DOM component under the change of latitude have not been elucidated to date. The composition and dynamics of DOM were assessed in this study. Two individual parallel factor analysis (PARAFAC) components were found in each sampling site in Heilongjiang. To further characterize the inner change of the identified PARAFAC components, two-latitude correlation spectroscopy (2DCOS) technique was applied to the excitation loadings data. Interestingly, not all the fluorophore in a PARAFAC component change in the same direction as the overall change of a component. From upstream to downstream, the peak A1 in PARAFAC component C1 showed a downward trend, but peak A2 presented an upward trend. In PARAFAC component C2, the peak T2 and peak T3 showed an inverse changing trend under latitude perturbation. Furthermore, basic nutrients parameters in Heilongjiang were also characterized in each sampling sites. The relationships between DOM and nutrients showed that component C1 made a significant contribution to chemical oxygen demand (COD) and biochemical oxygen demand (BOD5). The evolutions of DOM peak A1 and peak A2 were accompanied by the changing of Total phosphorus (TP). The findings in this study could make a contribution to explore the fate of DOM in high humic-like substance containing river.