Natural Dissolved Organic Matter Research Articles

Molecular fractionation mediates genotoxicity evolution of hydrochar-derived dissolved organic matter at the iron oxyhydroxides-water interface

Adsorption fractionation of dissolved organic matter (DOM) induced by soil minerals is a common geochemical process, which has been widely documented on natural DOM. Hydrochar is a promising functional material in soil remediation but can continuously release abundant endogenic DOM with potential biotoxicity. However, adsorption fractionation at molecular level and its influence on toxicity evolution of hydrochar-derived DOM (HDOM) at genetic level at the soil-water interface remain poorly understood. Herein, we investigated the molecular fractionation of HDOM on three typical soil iron minerals (i.e., ferrihydrite, goethite, and hematite). Results from ultrahigh-resolution mass spectrum showed that HDOM molecules with high molecular weight and high contents of unsaturated oxidized or aromatic structures (e.g., unsaturated phenolic compounds, polyphenols, and organic acids) were preferentially absorbed by iron oxyhydroxides, while aliphatic molecules and poorly oxygenated compounds (e.g., hydrocarbon, phenols, and alcohols) were retained in aqueous phase. Furthermore, we quantitatively evaluated their genotoxicity variation using a toxicogenomics assay using green fluorescence protein-fused whole-cell array, and results showed that oxidative, protein, membrane, and DNA stresses were primary responses upon exposure to original HDOM. Interface fractionation induced by iron oxyhydroxides significantly reduced genotoxicity of HDOM, especially for oxidative, membrane and DNA stresses. Overall, the selective absorption of HDOM molecules by iron oxyhydroxides shifted its biotoxicity, which might change the ecological effects of hydrochar amendment, e.g., microbial community structure, environmental pollutant transformation, and even the ecological function of terrestrial and aquatic ecosystems. These findings would contribute to unraveling the environmental geochemistry process of HDOM in the natural soil-water interface and provide a new insight into the biotoxicity of hydrochar usage to terrestrial and aquatic environments.

The use of the self-organizing map (SOM) methodology to study the dissolved organic matter (DOM) in different water body types.

This study investigated the characteristics of dissolved organic matter (DOM) in two distinct water bodies, through the utilization of three-dimensional fluorescence spectroscopy coupled with self-organizing map (SOM) methodology. Specifically, this analysis concentrated on neurons 3, 14, and 17 within the SOM model, identifying notable differences in the DOM compositions of a coal subsidence water body (TX) and the MaChang Reservoir (MC). The humic substance content of DOM TX exceeded that of MC. The origin of DOM in TX was primarily linked to agricultural inputs and rainfall runoff, whereas the DOM in MC was associated with human activities, displaying distinctive autochthonous features and heightened biological activity. Principal component analysis revealed that humic substances dominated the DOM in TX, while the natural DOM in MC was primarily autochthonous. Furthermore, a multiple linear regression model (MLR) determined that external pollution was responsible for 99.11% of variation in the humification index (HIX) of water bodies.

Molecular weight-dependent differences in spectral properties and metal-binding behaviors of dissolved organic matter from different lakes

Dissolved organic matter (DOM) plays an important role in governing metal speciation and migration in aquatic systems. In this study, various DOM samples were collected from Lakes Erhai, Kokonor, and Chaka, and size-fractionated into high molecular weight (HMW, 1 kDa–0.7 μm) and low molecular weight (LMW, <1 kDa) fractions for measurements of dissolved organic carbon (DOC), spectral properties, and metal binding behaviors. Our results demonstrated that samples from Lake Chaka exhibited the highest DOC concentration and fluorescence indices but the lowest percentage of carbohydrates. Regardless of sampling locations, the HMW-DOM fractions contained higher abundances of aromatic DOM, carbohydrates and protein-like substances, but lower abundance of fulvic acid-like substances compared to those in the LMW fractions. Metal titration experiments coupled with the excitation-emission matrix (EEM)-parallel factor (PARAFAC) modeling revealed that the quenching of the PARAFAC-derived fluorescent components was more pronounced in the presence of Cu(II) compared to Pb(II). Humic-like components emerged as a superior model, exhibiting higher binding affinities for Cu(II) than protein-like substances, while the opposite trend was observed for Pb(II). In samples obtained from Lakes Erhai and Kokonor, the condition stability constants (Log KM) for the binding of both Cu(II) and Pb(II) with the HMW-DOM fraction were higher than those with the LMW-DOM fraction. Conversely, a contrasting trend was observed for Lake Chaka. This study highlighted the heterogeneity in spectral properties and metal-binding behaviors of natural DOMs, contributing to an improved understanding of the molecular interactions between DOM components and metal ions and their environmental fate in aquatic ecosystems.

Factors Governing Site and Charge Density of Dissolved Natural Organic Matter

Rising organic charge in northern freshwaters is attributed to increasing levels of dissolved natural organic matter (DNOM) and changes in water chemistry. Organic charge concentration may be determined through charge balance calculations (Org.−) or modelled (OAN−) using the Oliver and Hruška conceptual models, which are based on the density of weak acid functional sites (SD) present in DNOM. The charge density (CD) is governed by SD as well as protonation and complexation reactions on the functional groups. These models use SD as a key parameter to empirically fit the model to Org.−. Utilizing extensive water chemistry datasets, this study shows that spatial and temporal differences in SD and CD are influenced by variations in the humic-to-fulvic ratio of DNOM, organic aluminum (Al) complexation, and the mole fraction of CD to SD, which is governed by acidity. The median SD values obtained for 44 long-term monitored acid-sensitive lakes were 11.1 and 13.9 µEq/mg C for the Oliver and Hruška models, respectively. Over 34 years of monitoring, the CD increased by 70%, likely due to rising pH and declining Al complexation with DNOM. Present-day median SD values for the Oliver and Hruška models in 16 low-order streams are 13.8 and 15.8 µEq/mg C, respectively, and 10.8 and 12.5 µEq/mg C, respectively, in 10 high-order rivers.

Predicting the dissolved natural organic matter (DNOM) concentration and the specific ultraviolet absorption (sUVa) index in a browning central European stream

Over the past four decades, an increase in Dissolved Natural Organic Matter (DNOM) and colour, commonly referred to as browning, has been noted in numerous watercourses in the northern hemisphere. Understanding the fluctuations in DNOM quality is a prerequisite for gaining insights into the biogeochemical processes governing DNOM fluxes. Such knowledge is also pivotal for water treatment plants to effectively tailor their strategies for removing DNOM from raw water. The specific ultraviolet absorbance (sUVa) index has been a widely applied measurement for assessing DNOM quality. The sUVa index is the UV absorbance (OD254) of water normalized for DNOM concentration. We have used a long-term dataset spanning from 2007 to 2022, taken from the Malše River in South Bohemia, to model DNOM and the sUVa index. We have applied regression models with a process-oriented perspective and have also considered the influence of climate change. Both DNOM and the sUVa index is positively related to temperature, runoff and pH, and negatively related to ionic strength over the studied period. Two distinct model approaches were employed, both explaining about 40% of the variation in sUVa over the studied period. Based on a moderate IPCC monthly climate scenario, simulations indicate that both DNOM and the sUVa index averages remain fairly stable, with a slight increase in winter season minima projected towards the year 2099. A slight decline in summer season maxima is simulated for DNOM, while the sUVa summer maximum remain stable. These findings suggest a robust resilience in both DNOM and the sUVa index against anticipated changes in temperature and runoff for the Malše River in South Bohemia.

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.

Coupling between Increased Amounts of Microplastics and Dissolved Organic Compounds in Water

Microplastic (MP) pollution is a rapidly spreading global problem, threatening the use and sustainability of freshwater resources. MPs in water can act as both a source and sink of dissolved organic compounds. This review summarizes the current knowledge of interactions between MPs and dissolved organic compounds, including the adsorption and release of dissolved organic compounds by MPs and the impacts of MPs on the source and sink of natural dissolved organic matter (DOM) in aquatic ecosystems. The key mechanisms for the adsorption of dissolved organic compounds on MPs are hydrophobic interactions, van der Waals forces, and π–π interactions. Particle size, morphological characteristics, density, and environmental factors (pH, ionic strength, and UV radiation) have a great influence on the adsorption of dissolved organic compounds on MPs. Although research on the interactions between dissolved organic compounds and MPs has progressed rapidly, to date, research on the impacts of increasing amounts of MPs on natural DOM cycles (production, transformation, and fate) in aquatic ecosystems has been very limited. Knowledge gaps and future research directions are outlined at the end of this review.

Natural and anthropogenic dissolved organic matter in landfill leachate: Composition, transformation, and their coexistence characteristics

A large number of natural and anthropogenic wastes were landfilled, and dissolved organic matter (DOM) were formed during landfill. However, the composition, transformation, and coexistence characteristics of natural and anthropogenic DOM in leachate remain unclear. Fourier transform ion cyclotron resonance mass spectrometry, size exclusion chromatography, gas chromatography coupled with mass spectrometry, and three-dimensional excitation-emission matrix spectrum were employed to clarify comprehensively the abovementioned question. The results showed that natural DOM in young leachate constituted mainly straight-chain organic acids, protein substances, and building blocks of humic substances (BB). Straight-chain organic acids vanished in old leachates, and the concentration of protein substances and BB decreased from 44% to 26% and from 47% to 12%, respectively, while CHON and CHONS were degraded to CHO and CHOS during the process. As to anthropogenic DOM, its types and relative content in leachate increased during landfill, and aromatic acids, terpenes, halogenated organics, indoles, and phenols became the main organic components in old leachate. Compared to natural DOM, anthropogenic DOM was degraded slowly and accumulated in leachate, and some of the natural DOM facilitated the dechlorination of dichlorinated organic compounds. This study demonstrates that landfill led to an increase in humic substances and halogenated organic compounds in old leachate, which was intensified with concentrated leachate recirculation.

Adsorption and thermal stability of dissolved organic matter on Ca- and Mg-exchanged montmorillonite: Implications for persistence in soils and sediments

Dissolved organic matter (DOM) represents a vital and highly dynamic component of organic matter in the environment. Despite its significance, there is still limited knowledge regarding how different base cations and chemical conditions influence the preservation of complex natural DOM through adsorption. This study aimed to investigate the adsorption of natural DOM onto montmorillonite (Mt) by systematically exploring the effects of exchanging cations (Ca2+ and Mg2+), pH levels (4 and 7), and DOM molecular weight (< 10, 10–100, and > 100 kDa) on the mechanisms and thermal stability of adsorbed DOM. To this end, we conducted a series of adsorption experiments, complemented by spectroscopic and thermal analyses. Our results revealed that lower pH and higher DOM molecular weight enhanced adsorption, with affinity for carbohydrate-like compounds. Notably, changes in d001 spacing and peak broadening indicated intercalation of DOM into the interlayer space of Mt, which was positively correlated with the amount of DOM adsorbed. Conversely, increased adsorption was found to negatively correlate with thermal stability. This was attributed to the prevalence of weaker DOM-DOM interactions occurring at higher DOM weight and lower pH, owing to reduced repulsion among protonated organic molecules, in contrast to stronger electrostatic interactions near the Mt surface that appeared to dominate at lower DOM weight and higher pH conditions. Intriguingly, no clear preference for DOM adsorption on Ca- or Mg-exchanged Mt was observed, suggesting similar efficiencies of these cations in stabilizing DOM through cation-bridging. Our findings provide significant insights into the mechanisms involved in mineral-organic associations and have implications for understanding the persistence of DOM in soils and sediments.

Quantifying Stochastic Processes in Shaping Dissolved Organic Matter Pool with High-Resolution Mass Spectrometry.

Natural dissolved organic matter (DOM) represents a ubiquitous molecular mixture, progressively characterized by spatiotemporal resolution. However, an inadequate comprehension of DOM molecular dynamics, especially the stochastic processes involved, hinders carbon cycling predictions. This study employs ecological principles to introduce a neutral theory to elucidate the fundamental processes involving molecular generation, degradation, and migration. A neutral model is thus formulated to assess the probability distribution of DOM molecules, whose frequencies and abundances follow a β-distribution relationship. The neutral model is subsequently validated with high-resolution mass spectrometry (HRMS) data from various waterbodies, including lakes, rivers, and seas. The model fitting highlights the prevalence of molecular neutral distribution and quantifies the stochasticity within DOM molecular dynamics. Furthermore, the model identifies deviations of HRMS observations from neutral expectations in photochemical and microbial experiments, revealing nonrandom molecular transformations. The ecological null model further validates the neutral modeling results, demonstrating that photodegradation reduces molecular stochastic dynamics at the surface of an acidic pit lake, while random distribution intensifies at the river surface compared with the porewater. Taken together, the DOM molecular neutral model emphasizes the significance of stochastic processes in shaping a natural DOM pool, offering a potential theoretical framework for DOM molecular dynamics in aquatic and other ecosystems.

Browning of Scottish surface water sources exposed to climate change

Levels of dissolved natural organic matter (DNOM) are increasing in our boreal watercourses. This is manifested by an apparent increase in its yellow to brown colour of the water, i.e., browning. Sound predictions of future changes in colour of our freshwaters is a prerequisite for predicting effects on aquatic fauna and a sustainable operation of drinking water facilities using surface waters as raw water sources. A model for the effect of climate on colour (mg Pt L-1) has been developed for two surface raw water sources in Scotland, i.e., at Bracadale and Port Charlotte. Both sites are situated far out on the Scottish west coast, without major impact of acid rain, with limited amounts of frost, and with limited recent land-use changes. The model was fitted to 15 years long data-series on colour measurements, provided by Scottish Water, at the two sites. Meteorological data were provided by UK Met. The models perform well for both sites in simulating the variation in monthly measured colour, explaining 89 and 90% of the variation at Bracadale and Port Charlotte, respectively. These well fitted models were used to predict future changes in colour due to changes in temperature and precipitation based on median climate data from a high emission climate RCP8.5 scenario from the HadCM3 climate model (UKCP18). The model predicted an increase in monthly average colour during growing season at both sites from about 150 mg Pt L-1 to about 200 mg Pt L-1 in 2050–2079. Temperature is found to be the most important positively driver for colour development at both sites.

Potential bioavailability of representative pyrogenic organic matter compounds in comparison to natural dissolved organic matter pools

Abstract. Pyrogenic organic matter (PyOM) from wildfires impacts river corridors globally and is widely regarded as resistant to biological degradation. Though recent work suggests PyOM may be more bioavailable than historically perceived, estimating bioavailability across its chemical spectrum remains elusive. To address this knowledge gap, we assessed potential bioavailability of representative PyOM compounds relative to ubiquitous dissolved organic matter (DOM) with a substrate-explicit model. The range of potential bioavailability of PyOM was greater than natural DOM; however, the predicted thermodynamics, metabolic rates, and carbon use efficiencies (CUEs) overlapped significantly between all OM pools. Compound type (e.g., natural versus PyOM) had approximately 6-fold less impact on predicted respiration rates than simulated carbon and oxygen limitations. Within PyOM, the metabolism of specific chemistries differed strongly between unlimited and oxygen-limited conditions – degradations of anhydrosugars, phenols, and polycyclic aromatic hydrocarbons (PAHs) were more favorable under oxygen limitation than other molecules. Notably, amino sugar-like, protein-like, and lignin-like PyOM had lower carbon use efficiencies relative to natural DOM of the same classes, indicating potential impacts in process-based model representations. Overall, our work illustrates how similar PyOM bioavailability may be to that of natural DOM in the river corridor, furthering our understanding of how PyOM may influence riverine biogeochemical cycling.

Soil organic matter facilitates the transport of microplastic by reducing surface hydrophobicity

Groundwater contamination by microplastic (MP) causes increasing concern about the critical factors that determine MP transport mechanisms in the vadose zone. Strong water repellency of native microplastic surfaces and respective attractive hydrophobic interactions with components of the soil matrix limits its mobility. However, adsorption of dissolved organic matter (DOM) onto microplastic surfaces can potentially make them more hydrophilic, enhancing their mobility. Consequently, the main objective of this study was to systematically determine the effects of DOM on both the surface properties and the mobility of polystyrene microplastic (PSP), and to use the extended DLVO theory (XDLVO) to predict PSP transport behavior with natural DOM for the first time. Breakthrough experiments were conducted in columns filled with quartz sand, through which PSP (1 µm) were percolated at either 0 or 5 mg/L dissolved organic carbon (DOC) derived from beech (Fagus sylvatica) litter at ionic strengths ranging from 0.5 to 2.5 mM CaCl2, since the cation background also affects wettability and mobility. Using sessile drop contact angle and zeta potential measurements, XDLVO interaction energy components including Lewis acid-base energies were approximated. Breakthrough curve analysis confirmed that DOM coming from natural sources strongly enhanced the mobility of PSP in the quartz sand matrix, in particular at higher ionic strength. At 2.5 mM CaCl2, the presence of DOM increased PSP breakthrough from 1 % to 60 %. Consequently, in the absence of DOM, laser microscope images showed much more pronounced formation of microplastic clusters on quartz grain surfaces than at co-percolation of PSP with DOM. This behavior could be clearly predicted with the XLDVO approach, which suggests at 0 mg/L DOC a deep primary energy minimum between individual PSP and between PSP and quartz surfaces. In contrast, repulsive hydrophilic interactions between the surfaces were predicted at 5 mg/L DOC. We conclude that even low concentrations of DOM, as usually found in subsoil, can significantly enhance the mobility of microplastic in soils via rendering the surfaces more hydrophilic. This implies potentially serious repercussions for the spread of this contaminant in the environment.

Electrochemically activated peroxymonosulfate (PMS) pretreatment for fouling remediation during membrane distillation of surface water: Role of PMS concentration and dosing mode

Membrane distillation (MD) provides a potential method to supply large volumes of good quality potable water from surface water resources, avoiding the risk of long-term water shortages. However, the high abundance of dissolved natural organic matter (DOM) in surface water induces severe membrane fouling, which reduces productivity and increases energy consumption. Therefore, for the first time, electrochemically activated peroxymonosulfate (PMS) treatment was applied prior to the direct contact (DC)-MD process with the aim of reducing the deposition of organics and inorganics on the membrane and reducing membrane fouling. Results showed that supplying PMS continuously at a rate of 0.10 mM/min, eliminated 30.4% of dissolved organic carbon (DOC). Furthermore, fluorescence parallel factor (PARAFAC) analysis showed that >60% of two fluorescent substances were removed after 60 min of the electrochemically activated PMS pretreatment at a current density of 5 mA/cm2. Electrochemical activation of PMS generated •OH directly, facilitating the removal and degradation of DOM. In terms of the DCMD performance, almost no normalized flux decline was observed for the DCMS process after 0.01 mM/min pre-oxidation, while 44.8% flux decay occurred in the standalone DCMD treating raw surface water. Compared with continuous dosing, the use of a one-time dosing mode achieved a better outcome, as more small organic molecules generated in continuous dosing mode are not conducive to membrane fouling control. Therefore, electrochemically activated PMS could be an effective tool to mitigate membrane fouling in MD processes, although the characteristics of membrane and feed should be considered.

Improved Predictions of Dissolved Organic Carbon–Water Partitioning and Unveiling the Chemodiversity of Dissolved Organic Matter

Dissolved organic matter (DOM) is a complex mixture of organic compounds with chemical heterogeneity in natural soils, sediments, and waters. Predicting the dissolved organic carbon (DOC)–water partition coefficients (KDOC) of organic pollutants to DOMs from various sources is important for assessing their fate and bioavailability. However, the accuracy of the recently developed polyparameter linear free energy relationship (pp-LFER) KDOC models is generally restricted by the small data set, inclusion of experimental data from unreliable measurement methods, or undefined selection standards. The aim of this study was to establish pp-LFER models for predicting the KDOC of nonionic organic chemicals to a variety of sources of DOMs and to get an understanding of DOM chemodiversity. A reliable and expanded experimental KDOC data set was compiled. Improved pp-LFER models were developed and assessed for All DOM (DOM from all sources), Aldrich humic acid (HA), Roth HA, soil porewater DOM, sediment porewater DOM, natural aquatic DOM, natural terrestrial DOM, natural DOM, and commercial DOM. The models developed in this study were reasonably robust and accurate with a root mean square error (RMSE) of 0.538 for the All DOM model and RMSE from 0.196 to 0.860 for the specific DOMs. Also, the models generally performed better than previously published ones. Moreover, the system parameters of the models well described the chemical variabilities between soil porewater DOM and sediment porewater DOM, between natural aquatic DOM and natural terrestrial DOM, and between natural DOM and commercial DOM regarding polarizability, dipolarity, H-bond-accepting and -donating ability, and cavity formation energy. This study provides effective tools to assess the tendencies of organic chemicals to DOMs and improves our understanding of the chemical heterogeneity of DOMs from different sources.

Molecular-level insights into the heterogeneous variations and dynamic formation mechanism of leached dissolved organic matter during the photoaging of polystyrene microplastics

Microplastics (MPs) and their derivatives have received worldwide attention owing to their adverse effects on ecosystems. However, molecular diversity and dynamic formation of dissolved organic matter (DOM) during the photoaging of MPs remain unclear. Herein, we explored a molecular‒level formation mechanism for polystyrene MP (MPPS)‒derived DOM (PSDOM) during the photoaging of MPs to explain the evolution, heterogeneity, and sequential response of molecules to irradiation. Two‒dimensional correlation spectroscopy was applied to correlate the variations of PSDOM molecules detected by Fourier transform–ion cyclotron resonance mass spectrometry with those of MPPS functional groups detected by Fourier transform infrared spectroscopy. Irradiation‒induced PSDOM contained the most highly unsaturated structures with oxygen, but showed fewer aromatic structures than natural aquatic DOM. Photochemical transformations occurred between saturated‒reduced and oxidized molecules during PSDOM leaching, with the low‒oxidized and high‒oxidized molecules undergoing considerable changes in the normal carbon oxidation state and molecular number, respectively. The primary sequential response of PSDOM molecules to increasing irradiation time [low‒oxidized/high‒weight (450<m/z<800) → high‒oxidized → saturated/low‒weight molecules (m/z<450)] corresponded to the response of MPPS functional groups (aromatic C‒H → carbonyl → aromatic ring, CH2 bend → C‒H groups), demonstrating well synergistic relationships between them. These novel findings will contribute to the understanding of underappreciated behaviors or risks of MPDOM in aquatic ecosystems.

The enhance mechanism of DOM on tetracyclines degradation by electrochemical technology: A improvement of treatment processes

Tetracyclines (TC) is a typical broad-spectrum antimicrobial agent, and excessive use of TC can lead to a large accumulation of residual tetracycline in water. DOM is organic substances that can pass through the 0.45 μm filter. While dissolved organic matter (DOM) is one of the most significant substances in water, which has an important effect on water treatment. In this study, ultraviolet and visible spectrophotometry (UV–Vis) is applied to explore DOM to the effect of the electrochemical degradation. Three-dimension excitation emission matrix fluorescence spectroscopy (3D-EEM) is used to identify the component variation of DOM after the electrochemical oxidation (EO). Liquid chromatograph mass spectrometer (LC-MS) is used to confirm the degradation pathway of TC whether spontaneous or electrochemical oxidation. High performance liquid chromatography (HPLC) suggests the ROS production by DOM in the electrochemical oxidation under different conditions. Results show that DOM can promote the degradation of TC in the electrochemical oxidation. Tailwater DOM containssubstances can produce persistent free radicals, which can promote the degradation under light and dark conditions, natural source DOM can produce more free radicals under light. Therefore, TC wastewater should be added tailwater to promote the degradation of TC before the further water treatment. Otherwise, TC can be degraded to differentpathways (light, electricity, and degrade spontaneously). This study provides a significant idea for practical water treatment of tetracyclines, and promotes the practical application of electrochemical technology.

Unraveling the role of natural and pyrogenic dissolved organic matter in photodegradation of biodegradable microplastics in freshwater

Biodegradable plastic is often perceived as a possible solution for microplastic (MP) pollution. Photodegradation is an important transformation pathway of biodegradable MPs in aquatic environments. However, the influence mechanisms of dissolved organic matter (DOM) from different sources on photodegradation of biodegradable MPs are poorly understood. This study explored the role of naturally and pyrogenically sourced DOM in the photodegradation of polylactic acid (PLA) MPs. The aromatics of natural DOM (NDOM) were higher than those of biochar-sourced DOM (BDOM) and showed a stronger improvement in PLA-MPs degradation, as evidenced by particle size reduction, crystallinity increase and polymerization decrease, breakage of surface morphology, and increase in oxygen-containing functional groups on MPs’ surface (O/C increase: 65.1% for NDOM; 34.9% for BDOM). Reactive oxygen species analysis showed that the excited triplet states of DOM (3DOM*) generated by NDOM produced more •OH and 1O2 than that of BDOM, accelerating PLA-MPs photodegradation. Such photodegradation processes were further enhanced through the sorption of DOM by PLA-MPs, in which non-aromatic components were preferentially sorbed, causing the enrichment of aromatics in the solution, leading to more 3DOM* formation. This study improves the understanding of the migration and transformation of biodegradable MPs with the presence of DOM.Graphical

The bio- and thermal lability of dissolved organic matter as revealed by high-resolution mass spectrometry and thermal chemical analyses

It is critical to understand the chemical structures and lability of dissolved organic matter (DOM) in aquatic environments, as DOM represents one of the largest reduced carbon pools on earth. To achieve a comprehensive view of its composition and reactivity, DOM from both riverine and coastal waters were concurrently extracted via both ultrafiltration and modified styrene divinyl benzene polymer (PPL) based solid-phase-extraction (SPE), and further compared through multi-dimensional angles, including elemental analysis, total hydrolyzable amino acid composition, high-resolution liquid chromatography mass spectrometry (under both electrospray ionization modes), and thermochemical analysis. With a very low percentage (< 5%) of shared molecules, ultrafiltered-DOM (UDOM) and SPE-extracted DOM (SPEDOM) showed distinct differences in their bio- and thermal labilities. SPEDOM not only contained more “degraded” biomarkers, such as glycine, β-alanine, and γ-aminobutyric acid, but was also dominated by a higher abundance of more bio-recalcitrant lignin-like structures. Furthermore, thermogravimetric analysis revealed a higher activation energy of SPEDOM (138.8 ± 0.5 kJ·mol−1) than that of UDOM (125.4 ± 2.8 kJ·mol−1), suggesting that SPEDOM is more thermally recalcitrant than UDOM. Consistently, thermal slicing ramped pyrolysis showed a lower percentage of recalcitrant pyrolyzates (e.g., aromatic and phenol structures), but a higher contribution of labile compound classes (e.g., aliphatic structures) in UDOM, as well as a higher diversity of pyrolyzates from UDOM than SPEDOM. Taken together, our results demonstrated a highly heterogeneous nature in DOM composition and distinctly different bio- and thermal labilities between UDOM and SPEDOM, indicating that characterization of different fractions of DOM is needed for a comprehensive evaluation of natural DOM.

Characterization of dissolved black carbon and its binding behaviors to ceftazidime and diclofenac pharmaceuticals: Employing the molecular weight fractionation

As the ubiquitous component of the aquatic environment, dissolved organic matter (DOM) readily bind with residual pharmaceutical contaminants (PCs) and influence their environmental behaviors. However, the binding mechanisms between dissolved black carbon (DBC), a vital part of the natural DOM pool, and PCs were poorly researched. In this study, the bulk DBC was divided into four fractions in molecular weight (MW) via an ultrafiltration system, and the properties of DBC and their binding interaction with two kinds of typical PCs (ceftazidime (CAZ) and diclofenac (DCF)) were explored concretely. The results showed that low MW component was the main contributor to bulk DBC, and the aromaticity increased with the increase of MW. The categories of chemical structures and fluorescent substances in different MW DBC were similar. Multispectral techniques showed that the oxygen-enriched compounds in DBC had the higher affinity to CAZ/DCF. The –NH–, –COOH, –NH2 groups in CAZ molecules appeared to form the hydrogen bond with DBC. Fluorescence quenching experiments were analyzed, and the binding mechanisms were specifically expounded from the thermodynamic perspective. The fluorophore of fulvic acid-like compounds (FA) were quenched by both static and dynamic quenching mechanisms, while only static quenching occurred for humic acid-like compounds (HA). For bulk DBC, the hydrogen bond and van der Waals force were the major forces in the HA-CAZ system, while the hydrophobic force made the primary contribution to the HA-DCF system, which might be ascribed to the higher hydrophobic nature of DCF. Notably, with the increase of HA MW, the main binding mode of HA-CAZ/DCF changed from hydrophobic force to hydrogen bond and van der Waals force gradually, which also directly proved that various noncovalent interactions co-driven the binding processes. Our findings are beneficial to better assess the fate of DBC and PCs and the corresponding complexes in the aquatic environment.