In-situ activation of biomimetic single-site bioorthogonal nanozyme for tumor-specific combination therapy.

Copper-catalyzed click chemistry offers creative strategies for activation of therapeutics without disrupting biological processes. Despite tremendous efforts, current copper catalysts face fundamental challenges in achieving high efficiency, atom economy, and tissue-specific selectivity. Herein, we develop a facile "mix-and-match synthetic strategy" to fabricate a biomimetic single-site copper-bipyridine-based cerium metal-organic framework (Cu/Ce-MOF@M) for efficient and tumor cell-specific bioorthogonal catalysis. This elegant methodology achieves isolated single-Cu-site within the MOF architecture, resulting in exceptionally high catalytic performance. Cu/Ce-MOF@M favors a 32.1-fold higher catalytic activity than the widely used MOF-supported copper nanoparticles at single-particle level, as first evidenced by single-molecule fluorescence microscopy. Furthermore, with cancer cell-membrane camouflage, Cu/Ce-MOF@M demonstrates preferential tropism for its parent cells. Simultaneously, the single-site CuII species within Cu/Ce-MOF@M are reduced by upregulated glutathione in cancerous cells to CuI for catalyzing the click reaction, enabling homotypic cancer cell-activated in situ drug synthesis. Additionally, Cu/Ce-MOF@M exhibits oxidase and peroxidase mimicking activities, further enhancing catalytic cancer therapy. This study guides the reasonable design of highly active heterogeneous transition-metal catalysts for targeted bioorthogonal reactions.

Pathways of inhibition of filamentous sludge bulking by slowly biodegradable organic compounds.

The organic compound composition of wastewater, serves as a crucial indicator for the operational performance of activated sludge processes and has a major influence on the development of filamentous bulking in activated sludge. This study focused on the impact of typical soluble and slowly-biodegradable organic compounds, investigating the pathways through which these substrates affect the occurrence of filamentous bulking in systems operated under both high- and low-oxygen conditions. Results showed that slowly-biodegradable organic compounds lead to a concentrated distribution of microorganisms within flocs, with inward growth of filamentous bacteria. Both Tween-80 and granular starch treated systems exhibited a significant increase in protein content. The glucose system, utilizing soluble substrates, exhibited a markedly higher total polysaccharide content. Microbial communities in the Tween-80 and granular starch treated systems were characterized by a higher abundance of bacteria known to enhance sludge flocculation and settling, such as Competibacter, Xanthomonadaceae and Zoogloea. These findings are of high significance for controlling the operational performance and stability of activated sludge systems, deepening our understanding and providing a novel perspective for the improvement of wastewater treatment processes.

Enhanced VOC emission with increased temperature contributes to the shift of O3-precursors relationship and optimal control strategy.

Assessing the impact of anthropogenic volatile organic compounds (VOCs) on ozone (O3) formation is vital for the management of emission reduction and pollution control. Continuous measurement of O3 and the major precursors was conducted in a typical light industrial city in the YRD region from 1 May to 25 July in 2021. Alkanes were the most abundant VOC group, contributing to 55.0% of TVOCs concentration (56.43 ± 21.10 ppb). OVOCs, aromatics, halides, alkenes, and alkynes contributed 18.7%, 9.6%, 9.3%, 5.2% and 1.9%, respectively. The observational site shifted from a typical VOC control regime to a mixed regime from May to July, which can be explained by the significant increase of ROx production, resulting in the transition of environment from NOx saturation to radical saturation with respect to O3 production. The optimal O3 control strategy should be dynamically changed depending on the transition of control regime. Under NOx saturation condition, minimizing the proportion of NOx in reduction could lead to better achievement of O3 alleviation. Under mixed control regime, the cut percentage gets the top priority for the effectiveness of O3 control. Five VOCs sources were identified: temperature dependent source (28.1%), vehicular exhausts (19.9%), petrochemical industries (7.2%), solvent & gasoline usage (32.3%) and manufacturing industries (12.6%). The increase of temperature and radiation would enhance the evaporation related VOC emissions, resulting in the increase of VOC concentration and the change of ROx circulation. Our results highlight determination of the optimal control strategies for O3 pollution in a typical YRD industrial city.

A screening model for predicting the potential of soil colloids-enhanced leaching of hydrophobic organic contaminants to groundwater at contaminated sites.

Modeling the fate and transport of organic pollutants at contaminated sites is critical for risk assessment and management practices, such as establishing realistic cleanup standards or remediation endpoints. Against the conventional wisdom that highly hydrophobic persistent organic pollutants (POPs) (e.g., polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons) in surface soils are essentially immobile, mounting evidence has demonstrated the potential of these contaminants leaching into the groundwater, due to enhanced transport by soil colloids. Here, we develop a Colloids-Enhanced Transport (CET) model, which can be used as a simple screening tool to predict the leaching potential of POPs into groundwater, as mediated by soil colloids. The CET model incorporates several processes, including the release of POPs-bearing colloids into the porewater, the vertical transport of colloids and associated POPs in the vadose zone, the mixing of POPs-containing soil leachate with groundwater, and the migration of POPs-bearing colloids in saturated zone. Thus, using parameters that can be easily obtained (e.g., annual rainfall, soil type, and common hydrogeological properties of the subsurface porous media), the CET model can estimate the concentrations of POPs in the saturated zone from the observed POPs concentrations in surface or shallow subsurface zones. The CET model can also be used to derive soil quality standards or cleanup endpoints by back-calculating soil concentrations based on groundwater protection limits.

Preferential association of PBDEs and PAHs with mineral particles vs. dissolved organic carbon: Implications for groundwater contamination at e-waste sites.

Polybrominated biphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) are commonly detected contaminants at e-waste recycling sites. Against the conventional wisdom that PBDEs and PAHs are highly immobile and persist primarily in shallow surface soils, increasing evidence shows that these compounds can leach into the groundwater. Herein, we compare the leachabilities of PBDEs vs. PAHs from contaminated soils collected at an e-waste recycling site in Tianjin, China. Considerable amounts of BDE-209 (0.3-2 ng/L) and phenanthrene (42-106 ng/L), the most abundant PBDE and PAH at the site, are detected in the effluents of columns packed with contaminated soils, with the specific concentrations varying with hydrodynamic and solution chemistry conditions. Interestingly, the leaching potential of BDE-209 appears to be closely related to the release of colloidal mineral particles, whereas the leachability of phenanthrene correlates well with the concentration of dissolved organic carbon in the effluent, but showing essentially no correlation with the concentration of mineral particles. The surprisingly different trends of the leachability observed between BDE-209 and phenanthrene is counterintuitive, as PBDEs and PAHs often co-exist at e-waste recycling sites (particularly at the sites wherein incineration is being practiced) and share many similarities in terms of physicochemical properties. One possible explanation is that due to its extremely low solubility, BDE-209 predominantly exists in free-phase (i.e., as solid (nano)particles), whereas the more soluble phenanthrene is mainly sorbed to soil organic matter. Findings in this study underscore the need to better understand the mobility of highly hydrophobic organic contaminants at contaminated sites for improved risk management.

Seasonal changes of chemodiversity along with microbial succession in a municipal wastewater treatment plant.

The relationship between chemodiversity and microbial succession in wastewater treatment plants (WWTPs) is highly intricate and bidirectional. The specific contribution of the microbial community to changes in the composition of dissolved organic matter (DOM) within different biological treatment units remains unclear, as does the reciprocal influence of DOM composition on microbial succession. In this study, spectroscopy ((Excitation-emission matrix) EEM-PARAFAC, Ultraviolet (UV)-spectrum, Fourier transform infrared spectrometer (FT-IR)), Liquid chromatograph mass spectrometer (LC‒MS) and Fourier transform ion cyclotron resonance (FT-ICR) MS along with high-throughput sequencing technology were used to explore the relationship between chemodiversity and microbial succession in WWTPs concerning seasonal changes. The results showed that WWTPs with anaerobic/anoxic/oxic (A2O) processes can metabolize and transform most of the wastewater DOM, and the anaerobic unit has the highest removal rate for fluorescence DOM (FDOM, 14.07%-64.43%); the anaerobic unit increased aliphatic/proteins and lignin-like molecules but decreased relative intensity, while the anoxic unit removed unsaturated hydrocarbons, aromatic structures, and lignin-like substances. The impact of seasonal changes on the composition and removal of FDOM and DOM in wastewater treatment is significant, and the variations that occur during different seasons affect microbial activity, as well as the production, degradation, and transformation of organic compounds throughout the wastewater treatment process. Network analysis shows that Parcubacteria_genera_incertae_sedis plays a crucial role in DOM chemodiversity, highlighting the crucial contribution of microbial communities to both the structure and operation of the entire DOM network. The results in this study could provide some theoretical and practical basis for guiding the process optimization of WWTPs.

Role of urea in the retention of DON in soil by clay minerals: Analysis based upon molecular weight.

As a widely used fertilizer, urea significantly promotes the leaching of dissolved organic nitrogen (DON) in soils and aggravates nitrogen contamination in groundwater. Clay minerals are considered the most important factor in retaining DON. However, the effect of urea on the retention of DON with different molecular weights by clay minerals is unknown. In this study, the retention of both low-molecular weight DON (LMWD) and high-molecular weight DON (HMWD) by clay minerals in the presence of urea was investigated. For this purpose, batch adsorption and soil column leaching experiments, characterization analysis (Fourier transform infrared spectroscopy X-ray diffraction, and X-ray photoelectron spectroscopy), and molecular dynamics simulations were carried out. Urea had a positive effect on the adsorption of LMWD, whereas a competitive effect existed for the adsorption of HMWD. The dominant interactions among DON, urea, and clay minerals included H-bonding, ligand exchange, and cation exchange. The urea was preferentially adsorbed on clay minerals and formed a complex, which provided more adsorption sites to LMWD and only a few to HMWD. The presence of urea increased the retention of LMWD and decreased the retention of HMWD in clay minerals. The retention capacity of LMWD increased by 6.9%-12.8%, while that of HMWD decreased by 6.7%-53.1%. These findings suggest that LMWD tended to be trapped in soils, while HMWD was prone to be leached into groundwater, which can be used to evaluate the leaching of DON from soil to groundwater.

Alcohol regulated phase change absorbent for efficient carbon dioxide capture: Mechanism and energy consumption.

Phase change absorbents based on amine chemical absorption for CO2 capture exhibit energy-saving potential, but generally suffer from difficulties in CO2 regeneration. Alcohol, characterized as a protic reagent with a low dielectric constant, can provide free protons to the rich phase of the absorbent, thereby facilitating CO2 regeneration. In this investigation, N-aminoethylpiperazine (AEP)/sulfolane/H2O was employed as the liquid-liquid phase change absorbent, with alcohol serving as the regulator. First, appropriate ion pair models were constructed to simulate the solvent effect of the CO2 products in different alcohol solutions. The results demonstrated that these ion pair products reached the maximum solvation-free energy (ΔEsolvation) in the rich phase containing ethanol (EtOH). Desorption experiment results validated that the inclusion of EtOH led to a maximum regeneration rate of 0.00763 mol/min, thus confirming EtOH's suitability as the preferred regulator. Quantum chemical calculations and 13C NMR characterization were performed, revealing that the addition of EtOH resulted in the partial conversion of AEP-carbamate (AEPCOO-) into a new product known as ethyl carbonate (C2H5OCOO-), which enhanced the regeneration reactivity. In addition, the decomposition paths of different CO2 products were simulated visually, and every reaction's activation energy (ΔEact) was calculated. Remarkably, the ΔEact for the decomposition of C2H5OCOO- (9.465 kJ/mol) was lower than that of the AEPCOO- (26.163 kJ/mol), implying that CO2 was more likely to be released. Finally, the regeneration energy consumption of the alcohol-regulated absorbent was estimated to be only 1.92 GJ/ton CO2, which had excellent energy-saving potential.

Effects of isoprene on the ozonolysis of Δ3-carene and ß-caryophyllene: Mechanisms of secondary organic aerosol formation and cross-dimerization.

Elucidating the mutual effects between the different volatile organic compounds (VOCs) is crucial for comprehending the formation mechanism of atmospheric secondary organic aerosols (SOA). Here, the mixed VOCs experiments of isoprene and Δ3-carene/ß-caryophyllene were carried out in the presence of O3 using an indoor smog chamber. The suppression effect of isoprene was recognized by the scanning mobility particle sizer spectrometer, online vacuum ultraviolet free electron laser (VUV-FEL) photoionization aerosol mass spectrometry, and quantum chemical calculations. The results indicate that the suppression effect of isoprene on the ozonolysis of Δ3-carene and ß-caryophyllene shows fluctuating and monotonous trends, respectively. The carbon content of the precursor could be the main factor for regulating the strength of the suppression effect. Plausible structures and formation mechanisms of several new products generated from the single VOC precursor and VOC-cross-reaction are proposed, which enrich the category of VOC oxidation products. Meanwhile, a new dimerization mechanism of the RO2 + R'O2 reaction is suggested, which offers an intriguing perspective on the gas phase formation process of particle phase accretion products. The present findings provide valuable insights into clarifying the pivotal roles played by isoprene in the interplay between different VOCs and understanding of SOA formation mechanisms of VOC mixtures, especially nearby the emission origins.

In situ growth of iron incorporated Ni3S2 nanosheet on nickel foam in mediating electron transfer to peroxymonosulfate for pollutant abatement.

Catalytic oxidation of organic pollutants is a well-known and effective technique for pollutant abatement. Unfortunately, this method is significantly hindered in practical applications by the low efficiency and difficult recovery of the catalysts in a powdery form. Herein, a three-dimensional (3D) framework of Fe-incorporated Ni3S2 nanosheets in-situ grown on Ni foam (Fe-Ni3S2@NF) was fabricated by a facile two-step hydrothermal process and applied to trigger peroxymonosulfate (PMS) oxidation of organic compounds in water. A homogeneous growth environment enabled the uniform and scalable growth of Fe-Ni3S2 nanosheets on the Ni foam. Fe-Ni3S2@NF possessed outstanding activity and durability in activating PMS, as it effectively facilitated electron transfer from organic pollutants to PMS. Fe-Ni3S2@NF initially supplied electrons to PMS, causing the catalyst to undergo oxidation, and subsequently accepted electrons from organic compounds, returning to its initial state. The introduction of Fe into the Ni3S2 lattice enhanced electrical conductivity, promoting mediated electron transfer between PMS and organic compounds. The 3D conductive Ni foam provided an ideal platform for the nucleation and growth of Fe-Ni3S2, accelerating pollutant abatement due to its porous structure and high conductivity. Furthermore, its monolithic nature simplified the catalyst recycling process. A continuous flow packed-bed reactor by encapsulating Fe-Ni3S2@NF catalyst achieved complete pollutant abatement with continuous operation for 240 h, highlighting its immense potential for practical environmental remediation. This study presents a facile synthesis method for creating a novel type of monolithic catalyst with high activity and durability for decontamination through Fenton-like processes.

Humic-like components in dissolved organic matter inhibit cadmium sequestration by sediment.

China's lakes are plagued by cadmium (Cd) pollution. Dissolved organic matter (DOM) significantly regulates Cd(II) transport properties at the sediment-water interface. Understanding the effects of different DOM components on the transportation properties of Cd(II) at the sediment-water interface is essential. In this study, typical DOM from different sources was selected to study Cd(II) mobility at the sediment-water interface. Results showed that terrestrial-derived DOM (fulvic acids, FA) and autochthonous-derived DOM (α-amylase, B1) inhibit Cd(II) sequestration by sediments (42.5% and 5.8%, respectively), while anthropogenic-derived DOM (sodium dodecyl benzene sulfonate, SDBS) increased the Cd(II) adsorption capacity by sediments by 2.8%. Fluorescence quenching coupling with parallel factor analysis (EEM-PARAFAC) was used to characterize different DOM components. The results showed that FA contains three kinds of components (C1, C3: protein-like components, C2: humic-like components); SDBS contains two kinds of components (C1, C2: protein-like components); B1 contains three kinds of components (C1, C2: protein-like components, C3: humic-like components).Three complex reaction models were used to characterize the ability of Cd(II) complex with DOM, and it was found that the humic-like component could hardly be complex with Cd(II). Accordingly, humic-like components compete for Cd(II) adsorption sites on the sediment surface and inhibit Cd(II) adsorption from sediments. Fourier transform infrared spectroscopy (FTIR) of the sediment surface before and after Cd(II) addition was analyzed and proved the competitive adsorption theory. This study provides a better understanding of the Cd(II) mobilization behavior at the sediment-water interface and indicates that the input of humic-like DOM will increase the bioavailability of Cd.

Characterization and function of particulate organic matter: Evidence from lakes undergoing ecological restoration.

Particulate organic matter (POM) plays a crucial role in the organic composition of lakes; however, its characteristics remain poorly understood. This study aimed to characterize the structure and composition of POM in Lake Baiyangdian using many kinds of techniques and investigate the effects of different extracted forms of POM on water quality. The suspended particulate matter in the lake had complex compositions, with its components primarily derived from aquatic plants and their detritus. The organic matter content of the suspended particulate matter was relatively high (organic carbon content 27.29-145.94 g/kg) for the sum of three extractable states (water-extracted organic matter [WEOM], humic acid, and fulvic acid) and one stable bound state (humin). Spatial distribution analysis revealed that the POM content in the water increased from west to east, which was consistent with the water flow pattern influenced by the Baiyangdian water diversion project. Fluorescence spectroscopy analysis of the WEOM showed three prominent peaks with excitation/emission wavelengths similar to those of dissolved organic matter peaks. These peaks were potentially initial products of POM conversion into dissolved organic matter. Furthermore, the intensity of the WEOM fluorescence peak (total fluorescence peak intensity) was negatively correlated with the inorganic nitrogen concentration in water (p < 0.01), while the intensity of the HA fluorescence peak showed a positive correlation with the inorganic nitrogen concentration (p < 0.01). This suggested that exogenous organic matter inputs led to the diffusion of alkaline dissolved nitrogen from sediment into water, while degradation processes of aquatic plant debris contributed to the decrease in inorganic nitrogen concentrations in the water column. These findings enhance our understanding of POM characteristics in shallow lakes and the role of POM in shallow lake ecosystems.

Plant-substrate biochar properties critical for mediating reductive debromination of 1,2-dibromoethane.

Dibromoethane is a widespread, persistent organic pollutant. Biochars are known mediators of reductive dehalogenation by layered FeII-FeIII hydroxides (green rust), which can reduce 1,2-dibromoethane to innocuous bromide and ethylene. However, the critical characteristics that determine mediator functionality are lesser known. Fifteen biochar substrates were pyrolyzed at 600 °C and 800 °C, characterized by elemental analysis, X-ray photo spectrometry C and N surface speciation, X-ray powder diffraction, specific surface area analysis, and tested for mediation of reductive debromination of 1,2-dibromoethane by a green rust reductant under anoxic conditions. A statistical analysis was performed to determine the biochar properties, critical for debromination kinetics and total debromination extent. It was shown that selected plant based biochars can mediate debromination of 1,2-dibromoethane, that the highest first order rate constant was 0.082/hr, and the highest debromination extent was 27% in reactivity experiments with 0.1 µmol (20 µmol/L) 1,2-dibromoethane, ≈ 22 mmol/L FeIIGR, and 0.12 g/L soybean meal biochar (7 days). Contents of Ni, Zn, N, and P, and the relative contribution of quinone surface functional groups were significantly (p < 0.05) positively correlated with 1,2-dibromoethane debromination, while adsorption, specific surface area, and the relative contribution of pyridinic N oxide surface groups were significantly negatively correlated with debromination.

Bioaccessibility and health risk assessment of hydrophobic organic pollutants in soils from four typical industrial contaminated sites in China.

There have been reports of potential health risks for people from hydrophobic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated hydrocarbons (PCHs), and organophosphate flame retardants (OPFRs). When a contaminated site is used for residential housing or public utility and recreation areas, the soil-bound organic pollutants might pose a threat to human health. In this study, we investigated the contamination profiles and potential risks to human health of 15 PAHs, 6 PCHs, and 12 OPFRs in soils from four contaminated sites in China. We used an in vitro method to determine the oral bioaccessibility of soil pollutants. Total PAHs were found at concentrations ranging from 26.4 ng/g to 987 ng/g. PCHs (0.27‒14.3 ng/g) and OPFRs (6.30‒310 ng/g) were detected, but at low levels compared to earlier reports. The levels of PAHs, PCHs, and OPFRs released from contaminated soils into simulated gastrointestinal fluids ranged from 1.74% to 91.0%, 2.51% to 39.6%, and 1.37% to 96.9%, respectively. Based on both spiked and unspiked samples, we found that the oral bioaccessibility of pollutants was correlated with their logKow and molecular weight, and the total organic carbon content and pH of soils. PAHs in 13 out of 38 contaminated soil samples posed potential high risks to children. When considering oral bioaccessibility, nine soils still posed potential risks, while the risks in the remaining soils became negligible. The contribution of this paper is that it corrects the health risk of soil-bound organic pollutants by detecting bioaccessibility in actual soils from different contaminated sites.

A review of functions and mechanisms of clay soil conditioners and catalysts in thermal remediation compared to emerging photo-thermal catalysis.

High temperatures and providing sufficient time for the thermal desorption of persistent organic pollutants (POPs) from contaminated clay soils can lead to intensive energy consumption. Therefore, this article provides a critical review of the potential additives which can improve soil texture and increase the volatility of POPs, and then discusses their enhanced mechanisms for contributing to a green economy. Ca-based additives have been used to reduce plasticity of bentonite clay, absorb water and replenish system heat. In contrast, non-Ca-based additives have been used to decrease the plasticity of kaolin clay. The soil structure and soil plasticity can be changed through cation exchange and flocculation processes. The transition metal oxides and alkali metal oxides can be applied to catalyze and oxidize polycyclic aromatic hydrocarbons, petroleum and emerging contaminants. In this system, reactive oxygen species (•O2- and •OH) are generated from thermal excitation without strong chemical oxidants. Moreover, multiple active ingredients in recycled solid wastes can be controlled to reduce soil plasticity and enhance thermal catalysis. Alternatively, the alkali, nano zero-valent iron and nano-TiN can catalyze hydrodechlorination of POPs under reductive conditions. Especially, photo and photo-thermal catalysis are discussed to accelerate replacement of fossil fuels by renewable energy in thermal remediation.

Effects of salinity and betaine addition on anaerobic granular sludge properties and microbial community succession patterns in organic saline wastewater.

In this study, the effects of different salinity gradients and addition of compatible solutes on anaerobic treated effluent water qualities, sludge characteristics and microbial communities were investigated. The increase in salinity resulted in a decrease in particle size of the granular sludge, which was concentrated in the range of 0.5-1.0 mm. The content of EPS (extracellular polymeric substances) in the granular sludge gradually increased with increasing salinity and the addition of betaine (a typical compatible solute). Meanwhile, the microbial community structure was significantly affected by salinity, with high salinity reducing the diversity of bacteria. At higher salinity, Patescibacteria and Proteobacteria gradually became the dominant phylum, with relative abundance increasing to 13.53% and 12.16% at 20 g/L salinity. Desulfobacterota and its subordinate Desulfovibrio, which secrete EPS in large quantities, dominated significantly after betaine addition.Their relative abundance reached 13.65% and 7.86% at phylum level and genus level. The effect of these changes on the treated effluent was shown as the average chemical oxygen demand (COD) removal rate decreased from 82.10% to 79.71%, 78.01%, 68.51% and 64.55% when the salinity gradually increased from 2 g/L to 6, 10, 16 and 20 g/L. At the salinity of 20 g/L, average COD removal increased to 71.65% by the addition of 2 mmol/L betaine. The gradient elevated salinity and the exogenous addition of betaine played an important role in achieving stability of the anaerobic system in a highly saline environment, which provided a feasible strategy for anaerobic treatment of organic saline wastewater.

Exploring the diversity of dissolved organic matter (DOM) properties and sources in different functional areas of a typical macrophyte - derived lake combined with optical spectroscopy and FT-ICR MS analysis.

Lake Baiyangdian is one of China's largest macrophyte - derived lakes, facing severe challenges related to water quality maintenance and eutrophication prevention. Dissolved organic matter (DOM) was a huge carbon pool and its abundance, property, and transformation played important roles in the biogeochemical cycle and energy flow in lake ecosystems. In this study, Lake Baiyangdian was divided into four distinct areas: Unartificial Area (UA), Village Area (VA), Tourism Area (TA), and Breeding Area (BA). We examined the diversity of DOM properties and sources across these functional areas. Our findings reveal that DOM in this lake is predominantly composed of protein - like substances, as determined by excitation - emission matrix and parallel factor analysis (EEM - PARAFAC). Notably, the exogenous tyrosine-like component C1 showed a stronger presence in VA and BA compared to UA and TA. Ultrahigh - resolution mass spectrometry (FT - ICR MS) unveiled a similar DOM molecular composition pattern across different functional areas due to the high relative abundances of lignan compounds, suggesting that macrophytes significantly influence the material structure of DOM. DOM properties exhibited specific associations with water quality indicators in various functional areas, as indicated by the Mantel test. The connections between DOM properties and NO3N and NH3N were more pronounced in VA and BA than in UA and TA. Our results underscore the viability of using DOM as an indicator for more precise and scientific water quality management.

Relative humidity-dependent evolution of molecular composition of α-pinene secondary organic aerosol upon heterogeneous oxidation by hydroxyl radicals.

Heterogeneous oxidation by gas-phase oxidants is an important chemical transformation pathway of secondary organic aerosol (SOA) and plays an important role in controlling the abundance, properties, as well as climate and health impacts of aerosols. However, our knowledge on this heterogeneous chemistry remains inadequate. In this study, the heterogeneous oxidation of α-pinene ozonolysis SOA by hydroxyl (OH) radicals was investigated under both low and high relative humidity (RH) conditions, with an emphasis on the evolution of molecular composition of SOA and its RH dependence. It is found that the heterogeneous oxidation of SOA at an OH exposure level equivalent to 12 hr of atmospheric aging leads to particle mass loss of 60% at 25% RH and 95% at 90% RH. The heterogeneous oxidation strongly changes the molecular composition of SOA. The dimer-to-monomer signal ratios increase dramatically with rising OH exposure, in particular under high RH conditions, suggesting that aerosol water stimulates the reaction of monomers with OH radicals more than that of dimers. In addition, the typical SOA tracer compounds such as pinic acid, pinonic acid, hydroxy pinonic acid and dimer esters (e.g., C17H26O8 and C19H28O7) have lifetimes of several hours against heterogeneous OH oxidation under typical atmospheric conditions, which highlights the need for the consideration of their heterogeneous loss in the estimation of monoterpene SOA concentrations using tracer-based methods. Our study sheds lights on the heterogeneous oxidation chemistry of monoterpene SOA and would help to understand their evolution and impacts in the atmosphere.

A new insight into the straw decomposition associated with minerals: Promoting straw humification and Cd immobilization.

Organic matter (OM) derived from the decomposition of crop residues plays a key role as a sorbent for cadmium (Cd) immobilization. Few studies have explored the straw decomposition processes with the presence of minerals, and the effect of newly generated organo-mineral complexes on heavy metal adsorption. In this study, we investigated the variations in structure and composition during the rice straw decomposition with or without minerals (goethite and kaolinite), as well as the adsorption behavior and mechanisms by which straw decomposition affects Cd immobilization. The degree of humification of extracted straw organic matter was assessed using excitation-emission matrix (EEM) fluorescence and Ultraviolet-visible spectroscopy (UV-vis), while employing FTIR spectroscopy and XPS to characterize the adsorption mechanisms. The spectra analysis revealed the enrichment of highly aromatic and hydrophobic components, indicating that the degree of straw decomposition and humification were further intensified during incubation. Additionally, the existence of goethite (SG) accelerated the humification of OM. Sorption experiments revealed that the straw humification increased Cd adsorption capacity. Notably, SG exhibited significantly higher adsorption performance compared to the organic matter without minerals (RS) and the existence of kaolinite (SK). Further analysis using FT-IR spectroscopy and XPS verified that the primary mechanisms involved in Cd immobilization were complexion with -OH and -COOH, as well as the formation of Cd-π binds with aromatic C=C on the surface of solid OMs. These findings will facilitate understanding the interactions of the rice straw decomposing with soil minerals and its remediation effect on Cd-contaminated farmland.

Dissolved organic matter characteristics linked to bacterial community succession and nitrogen removal performance in woodchip bioreactors.

Woodchip bioreactors are an eco-friendly technology for removing nitrogen (N) pollution. However, there needs to be more clarity regarding the dissolved organic matter (DOM) characteristics and bacterial community succession mechanisms and their association with the N removal performance of bioreactors. The laboratory woodchip bioreactors were continuously operated for 360 days under three influent N level treatments, and the results showed that the average removal rate of TN was 45.80 g N/(m3·day) when the influent N level was 100 mg N/L, which was better than 10 mg N/L and 50 mg N/L. Dynamic succession of bacterial communities in response to influent N levels and DOM characteristics was an important driver of TN removal rates. Medium to high N levels enriched a copiotroph bacterial module (Module 1) detected by network analysis, including Phenylobacterium, Xanthobacteraceae, Burkholderiaceae, Pseudomonas, and Magnetospirillaceae, carrying N-cycle related genes for denitrification and ammonia assimilation by the rapid consumption of DOM. Such a process can increase carbon limitation to stimulate local organic carbon decomposition to enrich oligotrophs with fewer N-cycle potentials (Module 2). Together, this study reveals that the compositional change of DOM and bacterial community succession are closely related to N removal performance, providing an ecological basis for developing techniques for N-rich effluent treatment.