Revisiting gas-chromatography/mass-spectrometry molar response factors for quantitative analysis (FID or TIC) of glycosidic linkages in polysaccharides produced by oral bacterial biofilms.

Methylation analysis was performed on methylated alditol acetate standards and Streptococcus mutans extracellular polymeric substances (EPS) produced from wild-type and Gtf knockout strains (∆GtfB, ∆GtfB, and ∆GtfD). The methylated alditol acetate standards were representative of glycosidic linkages found in S. mutans EPS and were used to calibrate the GC-MS system for an FID detector and MS (TIC) and produce molar response factor, a necessary step in quantitative analysis. FID response factors were consistent with literature values (Sweet et al., 1975) and found to be the superior option for quantitative results, although the TIC response factors now give researchers without access to an FID detector a needed option for molar response factor correction. The GC-MS analysis is then used to deliver the ratio of the linkage types within a biofilm.

Sustained oxidation of Tea-Fe(III)/H2O2 simultaneously achieves sludge reduction and carbamazepine removal: The crucial role of EPS regulation.

Establishing an economic and sustained Fenton oxidation system to enhance sludge dewaterability and carbamazepine (CBZ) removal rate is a crucial path to simultaneously achieve sludge reduction and harmless. Leveraging the principles akin to "tea making", we harnessed tea waste to continually release tea polyphenols (TP), thus effectively maintaining high level of oxidation efficiency through the sustained Fenton reaction. The results illustrated that the incorporation of tea waste yielded more favorable outcomes in terms of water content reduction and CBZ removal compared to direct TP addition within the Fe(III)/hydrogen peroxide (H2O2) system. Concomitantly, this process mainly generated hydroxyl radical (•OH) via three oxidation pathways, effectively altering the properties of extracellular polymeric substances (EPS) and promoting the degradation of CBZ from the sludge mixture. The interval addition of Fe(III) and H2O2 heightened extracellular oxidation efficacy, promoting the desorption and removal of CBZ. The degradation of EPS prompted the transformation of bound water to free water, while the formation of larger channels drove the discharge of water. This work achieved the concept of treating waste with waste through using tea waste to treat sludge, meanwhile, can provide ideas for subsequent sludge harmless disposal.

Identification of extracellular polymeric substances layer barrier in chloroquine phosphate-disturbed anammox consortia and mechanism dissection on cytotoxic behavior by computational chemistry.

The over-dosing use of chloroquine phosphate (CQ) poses severe threats to human beings and ecosystem due to the high persistence and biotoxicity. The discharge of CQ into wastewater would affect the biomass activity and process stability during the biological processes, e.g., anammox. However, the response mechanism of anammox consortia to CQ remain unknown. In this study, the accurate role of extracellular polymeric substances barrier in attenuating the negative effects of CQ, and the mechanism on cytotoxic behavior were dissected by molecular spectroscopy and computational chemistry. Low concentrations (≤6.0 mg/L) of CQ hardly affected the nitrogen removal performance due to the adaptive evolution of EPS barrier and anammox bacteria. Compact protein of EPS barrier can bind more CQ (0.24 mg) by hydrogen bond and van der Waals force, among which O-H and amide II region respond CQ binding preferentially. Importantly, EPS contributes to the microbiota reshape with selectively enriching Candidatus_Kuenenia for self-protection. Furthermore, the macroscopical cytotoxic behavior was dissected at a molecular level by CQ fate/distribution and computational chemistry, suggesting that the toxicity was ascribed to attack of CQ on functional proteins of anammox bacteria with atom N17 (f-=0.1209) and C2 (f+=0.1034) as the most active electrophilic and nucleophilic sites. This work would shed the light on the fate and risk of non-antibiotics in anammox process.

Synergetic conditioning via oxalic acid enhanced Fe2+/CaO2 and skeleton construct to achieve deep dewatering of sewage sludge.

Extracellular polymeric substance (EPS) with highly hydrophilic groups and sludge with high compressibility are determined sludge dewaterability. Herein, Fe2+ catalyzed calcium peroxide (CaO2) assisted by oxalic acid (OA) Fenton-like process combined with coal slime was applied to improve sludge dewaterability. Results demonstrated that the sludge treated by 0.45/1/1.1-OA/Fe2+/CaO2 mM/g DS, the water content (WC), specific resistance to filtration and capillary suction time dropped to 53.01%, 24.3 s and 1.2 × 1012 m/kg, respectively. Under coal slime ratio as 0.6, WC and compressibility were further reduced to 42.72% and 0.66, respectively. The hydroxyl radicals generated by OA/Fe2+/CaO2 under near-neutral pH layer by layer collapsed EPS, resulting in the degradation and migration of inner releasing components and the exposure of inner sludge flocs skeleton. The hydrophilic tryptophan-like protein of TB-EPS were degraded into aromatic protein of S-EPS and exposed inner hydrophobic sites. The protein secondary structures were transformed by destroying hydrophilic functional groups, which were attributed to the reducing α-helix ratio and reconstructing ß-sheet. Moreover, coal slime as the skeleton builder lowered compressibility and formed more macropores to increase the filterability of pre-oxidized sludge for the higher intensity of rigid substances. This study deepened the understanding of OA enhanced Fenton-like system effects on sludge dewaterability and proposed a cost-effective and synergistic waste treatment strategy in sludge dewatering.

Sewer sediment adhesion degeneration and gelatinous biopolymer deconstruction by structural cation chelation and alkaline macromolecule hydrolysis for improving hydraulic erosion.

Sediment siltation has been regarded as the serious challenge in sewer system, which dominantly root in the gelatinous extracellular polymeric substance (EPS) structure and cohesive ability. Considering the crucial roles of divalent cation bridging and macromolecular biopolymer winding in sediment EPS formation and adhesive behavior, an innovative combination strategy of sodium pyrophosphate (SP)-mediated divalent cation chelation and alkaline biopolymer hydrolysis was developed to degenerate sediment adhesion. At the SP dosage of 0.25 g/g TS and the alkaline pH 12, the SP + pH 12 treatment triggered structural transformation of aromatic proteins (α-helix to ß-turn) and functional group shifts of macromolecular biopolymers. In this case, the deconstruction and outward dissolution of gelatinous biopolymers were achievable, including proteins (tyrosine-like proteins, tryptophan-like proteins), humic acids, fulvic acids, polysaccharides and various soluble microbial products. These were identified as the major driving forces for sediment EPS matrix disintegration and bio-aggregation deflocculation. The extraction EPS content was obviously increased by 18.88 mg COD/g TS. The sediment adhesion was sensitive to EPS matrix damage and gelatinous biopolymer deconstruction, leading to considerable average adhesion degeneration to 0.98 nN with reduction rate of 78.32%. As such, the sediments could be disrupted into dispersive fragments with increased surface electronegativity and electric repulsion (up to -45.6 mV), thereby the sediment resistance to hydraulic erosion was impaired, providing feasibility for in-situ sediment floating and removal by gravity sewage flow in sewer.

Understanding microplastic aging driven by photosensitization of algal extracellular polymeric substances.

The aging of microplastics (MPs) is extremely influenced by photochemically-produced reactive intermediates (PPRIs), which are mediated by natural photosensitive substances. Algal extracellular polymeric substances (EPS) can produce PPRIs when exposed to sunlight. Nonetheless, the specific role of EPS in the aging process of MPs remains unclear. This work systematically explored the aging process of polystyrene (PS) MPs in the EPS secreted by Chlorella vulgaris under simulated sunlight irradiation. The results revealed that the existence of EPS accelerated the degradation of PS MPs into particles with sizes less than 1 µm, while also facilitating the formation of hydroxy groups on the surface. The release rate of dissolved organic matter (DOM) from PS MPs was elevated from 0.120 mg·L-1·day-1 to 0.577 mg·L-1·day-1. The primary factor contributing to the elevated levels of DOM was humic acid-like compounds generated through the breakdown of PS. EPS accelerated the aging process of PS MPs by primarily mediating the formation of triplet excited states (3EPS*), singlet oxygen (1O2), and superoxide radicals (O2∙-), resulting in indirect degradation. 3EPS* was found to have the most substantial impact. This study makes a significant contribution to advance understanding of the environmental fate of MPs in aquatic environments impacted by algal blooms.

Biochar inoculated with Rhodococcus biphenylivorans altered microecological regulation by promoting quorum sensing and electron transfer: Up-regulation of related genes and enhancement of phenol and ammonia degradation.

Bioaugmentation is an efficient method for improving the efficiency of coking wastewater removal. Nevertheless, how different immobilization approaches affect the efficiency of bioaugmentation remains unclear, as does the corresponding mechanism. With the assistance of immobilized bioaugmentation strain Rhodococcus biphenylivorans B403, the removal of synthetic coking wastewater was investigated (drying agent, alginate agent, and absorption agent). The reactor containing the absorption agent exhibited the highest average removal efficiency of phenol (99.74 %), chemical oxygen demand (93.09 %), and NH4+-N (98.18 %). Compared to other agents, the covered extracellular polymeric substance on the absorption agent surface enhanced electron transfer and quorum sensing, and the promoted quorum sensing benefited the activated sludge stability and microbial regulation. The phytotoxicity test revealed that the wastewater's toxicity was greatly decreased in the reactor with the absorption agent, especially under high phenol concentrations. These findings showed that the absorption agent was the most suitable for wastewater treatment bioaugmentation.

Spectra metrology for interaction of heavy metals with extracellular polymeric substances (EPS) of Pseudomonas aeruginosa OMCS-1 reveals static quenching and complexation dynamics of EPS with heavy metals.

The adsorption behavior and interaction mechanisms of extracellular polymeric substances (EPS) of Pseudomonas aeruginosa OMCS-1 towards chromium (Cr), lead (Pb), and cadmium (Cd) were investigated. EPS-covered (EPS-C) cells exhibited significantly higher (p < 0.0001; two-way ANOVA) removal of Cr (85.58 ± 0.39%), Pb (81.98 ± 1.02%), and Cd (73.88 ± 1%) than EPS-removed (EPS-R) cells. Interactions between EPS-heavy metals were spontaneous (ΔG<0). EPS-Cr(VI) and EPS-Pb(II) binding were exothermic (ΔH<0), while EPS-Cd(II) binding was endothermic (ΔH>0) process. EPS bonded to Pb(II) via inner-sphere complexation by displacement of surrounding water molecules, while EPS-Cr(VI) and EPS-Cd(II) binding occurred through outer-sphere complexation via electrostatic interactions. Increased zeta potential of Cr (29.75%), Pb (41.46%), and Cd (46.83%) treated EPS and unchanged crystallinity (CIXRD=0.13), inferred EPS-metal binding via both electrostatic interactions and complexation mechanism. EPS-metal interaction was predominantly promoted through hydroxyl, amide, carboxyl, and phosphate groups. Metal adsorption deviated EPS protein secondary structures. Strong static quenching mechanism between tryptophan protein-like substances in EPS and heavy metals was evidenced. EPS sequestered heavy metals via complexation with C-O, C-OH, CO/O-C-O, and NH/NH2 groups and ion exchange with -COOH group. This study unveils the fate of Cr, Pb, and Cd on EPS surface and provides insight into the interactions among EPS and metal ions for metal sequestration.

Photochemical behaviors of sludge extracellular polymeric substances from bio-treated effluents towards antibiotic degradation: Distinguish the main photosensitive active component and its environmental implication.

Activated sludge extracellular polymeric substances (ASEPSs) comprise most dissolved organic matters (DOMs) in the tail water. However, the understanding of the link between the photolysis of antibiotic and the photo-reactivity/photo-persistence of ASEPS components is limited. This study first investigated the photochemical behaviors of ASEPS's components (humic acids (HA), hydrophobic substances (HOS) and hydrophilic substances (HIS)) separated from municipal sludge's EPS (M-EPS) and nitrification sludge's EPS (N-EPS) in the photolysis of sulfadiazine (SDZ). The results showed that 60% of SDZ was removed by the M-EPS, but the effect in the separated components was weakened, and only 24% - 39% was degraded. However, 58% of SDZ was cleaned by HOS in N-EPS, which was 23% higher than full N-EPS. M-EPS components had lower steady-state concentrations of triplet intermediates (3EPS*), hydroxyl radicals (·OH) and singlet oxygen (1O2) than M-EPS, but N-EPS components had the highest concentrations (5.96 ×10-15, 8.44 ×10-18, 4.56 ×10-13 M, respectively). The changes of CO, C-O and O-CO groups in HA and HOS potentially correspond to reactive specie's generation. These groups change little in HIS, which may make it have radiation resistance. HCO-3 and NO-3 decreased the indirect photolysis of SDZ, and its by-product N-(2-Pyrimidinyl)1,4-benzenediamine presents high environmental risk.

Migration and morphological transformation patterns of heavy metals on sludge cells and extracellular polymeric substances (EPS) under the influence of different treatments.

The impediment of sludge resource utilization stems from the presence of heavy metals within the sludge matrix. To optimize heavy metal removal techniques from undried sludge, it is essential to study the distribution of heavy metals in the sludge flocs structure and the changes in morphology in the sludge cells after different treatments. In this study, the sludge was subjected to chemical treatments using citric acid (CA), EDTA, and saponin, as well as electrokinetic treatment at 2 V/cm. The distribution and migration of Cu, Ni, and Zn in sludge flocs after various treatment methods were analyzed. The heavy metals were found to migrate from intracellular to extracellular polymeric substances (EPS) without causing extensive sludge cell lysis. They gradually diffused outward with the dispersion of the EPS layer. The migration efficiency of the three heavy metals in the sludge flocs was Zn, Ni, and Cu. This was mainly related to the initial distribution and morphology of the heavy metals. Under the influence of chemicals and an electric field, the acid-soluble and reducible heavy metals in the cells partially migrated to the EPS, while the stable heavy metals transformed into an unstable state. Furthermore, the order of chemical reagents in terms of their effect on the migration efficiency of heavy metals was CA > EDTA > Saponin, owing to the varying binding strengths of heavy metals and their impact on the degree of loosening of the EPS. Especially after CA treatment a greater proportion of Cu, Ni, and Zn were transferred from the cells to the EPS. The acidification effect near the anode during electrokinetic treatment intensifies the migration of heavy metals. This study provides basic research for subsequent engineering optimization aimed at removing heavy metals from sludge.

Impact of changes in biofilm composition response following chlorine and chloramine disinfection on nitrogenous disinfection byproduct formation and toxicity risk in drinking water distribution systems.

In practical drinking water treatment, chlorine and chloramine disinfection exhibit different mechanisms that affect biofilm growth. This study focused on the influence of biofilm composition changes, especially extracellular polymeric substance (EPS) fractions, on the potential formation and toxicity of nitrogenous disinfection by-products (N-DBP). Significant differences in microbial diversity and community structure were observed between the chlorine and chloramine treatments. Notably, the biofilms from the chloramine-treated group had higher microbial dominance and greater accumulation of organic precursors, as evidenced by the semi-quantitative confocal laser-scanning microscopy assay of more concentrated microbial aggregates and polysaccharide proteins in the samples. Additionally, the chloramine-treated group compared with chlorine had a higher EPS matrix content, with a 13.5 % increase in protein. Furthermore, the protein distribution within the biofilm differed; in the chlorine group, proteins were concentrated in the central region, whereas in the chloramine group, proteins were primarily located at the water-biofilm interface. Notably, functional prediction analyses of protein fractions in biofilms revealed specific functional regulation patterns and increased metabolism-related abundance of proteins in the chlorine-treated group. This increase was particularly pronounced for proteins such as dehydrogenases, reductases, transcription factors, and acyl-CoA dehydrogenases. By combining the Fukui function and density functional calculations to further analyse the effect of biofilm component changes on N-DBP production under chlorine/chloramine and by assessing the toxicity risk potential of N-DBP, it was determined that chloramine disinfection is detrimental to biofilm control and the accumulation of protein precursors has a higher formation potential of N-DBPs and toxicity risk, increasing the health risk of drinking water.

Effects of microbubble pretreatment on physiochemical and microbial properties of excess activated sludge.

Fast increased amount of excess activated sludge (EAS) from wastewater treatment plants has aroused universal concerns on its environmental risks and demands for appropriate treatments, while effective treatment is dependent upon proper pretreatment. In this study, air-supplied microbubbles (air-MBs) with generated size of 25.18 to 28.25 µm were used for EAS pretreatment. Different durations (30, 60, 90, and 120 s) yielded sludge with varied physiochemical conditions, and 60 s decreased sludge oxidation status and significantly increased adenosine triphosphate (ATP) content. Soluble, loosely-bound, and tightly-bound extracellular polymeric substances (SEPS, LB-EPS, and TB-EPS) were extracted from the sludge through a stepwise approach and examined through three-dimensional excitation-emission matrix (3D-EEM) and quantitative analysis. The results showed that 60- and 120-s treatments generated stronger fluorescence intensities on dissolved organic matters (DOMs) of protein-like and fulvic acid in LB-EPS and TB-EPS, which indicated the decrease of counterparts in EAS, and therefore facilitated sludge dewaterability and reduction. The dominant microbial communities in EAS, including Proteobacteria, Bacteroidota, Chloroflexi, and Actinobacteriota, were not significantly affected by MB pretreatment. The results collectively revealed the effects of MB pretreatment on EAS and indicated that MBs could be an effective pretreatment technique for EAS treatment process.

Influences of extracellular polymeric substances (EPS) recovered from waste sludge on the ability of Jiaozhou Bay to self-remediate of diesel-polluted seawater.

The introduction of EPS recovered from waste sludge may have an impact on the process of microbial remediation of oil-contaminated seawater. This study investigated the effect of EPS on the self-remediation capacity of diesel-polluted seawater in Jiaozhou Bay. Hydrocarbon attenuation and microbial activity were monitored in seawater collected from five islands after diesel and N, P addition, with and without EPS, incubated under aerobic conditions. Compared to seawater without EPS, degradation of TPH (total petroleum hydrocarbon) doubled and improved degradation of non-volatile (C16-C24) hydrocarbons to some extent in EPS-added seawater. The introduction of EPS led to changes in microbiota richness and diversity, significantly stimulating the growth of Proteobacteria and Firmicutes phyla or Bacillus and Pseudomonas genera. RT-qPCR analysis indicated EPS caused higher increases in cytochrome P450 gene copies than alkB. Prediction of alkane decay genes from 16S rRNA sequencing data revealed that EPS addition obviously promoted genes related to ethanol dehydrogenation function in the microbial community. Additionally, EPS enhanced the enzymatic activities of alkane hydroxylase, ethanol dehydrogenase, phosphatase and lipase, but increased protease and catalase inconspicuously. The above outlook that environmental sustainability of EPS from waste sludge for diesel-contaminated seawater remediation may provide new perspectives for oil spill bioremediation.

Enhanced granulation of activated sludge in an airlift reactor for organic carbon removal and ammonia retention from industrial fermentation wastewater: A comparative study.

Ammonia retention and recovery from high-nitrogenous wastewater are new concepts being used for nitrogen management. A microaerophilic activated sludge system was developed to convert organic nitrogen into ammonia and retain it for its recovery; however, the settleability of activated sludge remains a challenge. Therefore, this study proposed an aerobic granular sludge system as a potential solution. Two types of sequencing batch reactors-airlift and upflow reactors-were operated to investigate the feasibility of fast granule formation, the performance of organic carbon removal and ammonia retention, and the dynamics of microbial community composition. The operation fed with industrial fermentation wastewater demonstrated that the airlift reactor ensured a more rapid granule formation than the upflow reactor because of the high shear force, and it maintained a superior ammonia retention stability of approximately 85 %. Throughout the operational period, changes in hydraulic retention time (HRT), settling time, and exchange ratio altered the granular particle sizes and microbial community compositions. Rhodocyclaceae were replaced with Comamonadaceae, Methylophilaceae, Xanthomonadaceae, and Chitinophagaceae as core taxa instrumental in granulation, likely because of their extracellular polymeric substance secretion. As the granulation process progressed, a significant decrease in the relative abundances of nitrifying bacteria-Nitrospiraceae and Nitrosomonadaceae-was observed. The reduction of settling time and HRT enhanced granulation and inhibited the activity of nitrifying bacteria. The success in granulation for ammonia conversion and retention in this study accelerates the paradigm shift from ammonia removal to ammonia recovery from industrial fermentation wastewater.

Adaptation strategies and functional transitions of microbial community in pyrene-contaminated soils promoted by lead with Pseudomonas veronii and its extracellular polymeric substances.

Pyrene was designated as a remediation target in this study, and low contamination of lead (Pb) was set to induce heavy metal stress. Pseudomonas veronii and its extracellular polymeric substances (EPSs) were chosen for biofortification, with the aim of elucidating the structural, metabolic, and functional responses of soil microbial communities. Community analysis of soil microorganisms using high-throughput sequencing showed that the co-addition of P. veronii and EPSs resulted in an increase in relative abundance of phyla associated with pyrene degradation, and formed a symbiotic system dominated by Firmicutes and Proteobacteria, which involved in pyrene metabolism. Co-occurrence network analysis revealed that the module containing P. veronii was the only one exhibiting a positive correlation between bacterial abundance and pyrene removal, indicating the potential of bioaugmentation in enriching functional taxa. Biofortification also enhanced the abundance of functional gene linked to EPS production (biofilm formation-Pseudomonas aeruginosa) and pyrene degradation. Furthermore, 17 potential functional bacteria were screened out using random forest algorithm. Lead contamination further promoted the growth of Proteobacteria, intensified cooperative associations among bacteria, and increased the abundance of bacteria with positive correlation with pyrene degradation. The results offer novel perspectives on alterations in microbial communities resulting from the synergistic impact of heavy metal stress and biofortification.

Formation of extracellular polymeric substances corona on TiO2 nanoparticles: Roles of crystalline phase and exposed facets.

Nanoparticles (NPs) in the environment can interact with macromolecules in the surrounding environment to form eco-corona on their surfaces, which in turn affects the environmental fate and toxicity of nanoparticles. Wastewater treatment plants containing large amounts of microbial extracellular polymeric substances (EPS) are an important source of NPs into the environment, where the formation of EPS coronas on NPs is critical. However, it remains unclear how the crystalline phase and exposed facets, which are intrinsic properties of NPs, affect the formation of EPS coronas on NPs. This study investigated the formation of EPS corona on three TiO2 NPs (representing the most widely used engineered NPs) with different crystalline phases and exposed facets. The protein type and abundance in EPS coronas on TiO2 NPs varied depending on the crystalline phase and exposed facets. Anatase with {101} facets and {001} facets preferred to adsorb proteins with lower molecular weights and higher H-bonding relevant amino acids, respectively, while EPS corona on rutile with {110} facets had proteins with higher hydrophobicity. In addition, the selective adsorption of proteins was primarily determined by steric hindrance, hydrogen bonding, and hydrophobic interaction between TiO2 NPs and proteins, which were affected by changes in aggregation state, surface hydroxyl density, and hydrophobicity of TiO2 NPs induced by crystalline phase and exposed facets. Moreover, crystalline phase and exposed facets-induced EPS corona changes altered the aggregation state and oxidation potential of TiO2-EPS corona complexes. These findings emphasize the important role of crystalline phase and exposed facets in the environmental behavior of nanoparticles and may provide insights into the safe design of nanoparticles.

The role of extracellular polymeric substances (EPS) in chemical-degradation of persistent organic pollutants in soil: A review.

Persistent organic pollutants (POPs) in soil show high environmental risk due to their high toxicity and low biodegradability. Studies have demonstrated the degradation function of microbial extracellular polymeric substances (EPS) on POPs in various matrices. However, the degradation mechanisms and the factors that influence the process in soil have not been clearly illustrated. In this review, the characteristics of EPS were introduced and the possible mechanisms of EPS on degradation of organic pollutants (e.g., external electron transfer, photodegradation, and enzyme catalysis) were comprehensively discussed. In addition, the environmental conditions (e.g., UV, nutrients, and redox potential) that could influence the production and degradation-related active components of EPS were addressed. Moreover, the current approaches on the application of EPS in biotechnology were summarized. Further, the future perspectives of enhancement on degradation of POPs by regulating EPS were discussed. Overall, this review could provide a new thought on remediation of POPs by widely-existing EPS in soil with low-cost and minimized eco-disturbance.

Extracellular polymeric substances altered the physicochemical properties of molybdenum disulfide nanomaterials to mitigate its toxicity to Chlorella vulgaris.

Although the toxic effects of two-dimensional nanomaterials (2D-NMs) have been widely reported, the influence of extracellular polymeric substances (EPS) on the environmental fate and risk of 2D-NMs in aquatic environments is largely unknown, and the processes and mechanisms involved remain to be revealed. Herein, we investigated the impact of EPS secreted by microalgae (Chlorella vulgaris (C. vulgaris)) on the environmental transformation and risk of molybdenum disulfide (MoS2). We found that the attachment of EPS increased the thickness of MoS2 (from 2 nm to 5 nm), changed it from a monolayer sheet to a fuzzy multilayer structure, and promoted the formation of defects on MoS2. The blue-shift of the peak associated with the plasmon resonances in the 1 T phase and the generation of electron-hole pairs suggested that EPS altered the surface electronic structure of MoS2. EPS interacted mainly with the S atoms on the 1 T phase, and the attachment of EPS promoted the oxidation of MoS2. The reduction in hydrodynamic diameter (Dh) and the decrease in zeta potential indicated that EPS inhibited the agglomeration behavior of MoS2 and enhanced its dispersion and stability in aqueous media. Notably, EPS reduced the generation of free radicals (superoxide anion (•O2-), singlet oxygen (1O2), and hydroxyl radicals (•OH-)). Furthermore, EPS mitigated the toxicity of MoS2 to C. vulgaris, such as attenuated reduction in biomass and chlorophyll content. Compared to pristine MoS2, MoS2 + BG11 + EPS exhibited weaker oxidative stress, membrane damage and lipid peroxidation. The adsorption of EPS on MoS2 surface reduced the attachment sites of MoS2, making MoS2 less likely to be enriched on the cell surface. The findings have significant contribution for understanding the interactions between EPS and MoS2 in aquatic ecosystems, providing scientific guidance for risk assessment of 2D-NMs.

Iron-Nitrogen Amendment Reduced Perfluoroalkyl Acids' Phyto-Uptake in the Wheat-Soil Ecosystem: Contributions of Dissolved Organic Matters in Soil Solution and Root Extracellular Polymeric Substances.

Understanding the mechanisms underlying perfluoroalkyl acids (PFAAs) translocation, distribution, and accumulation in wheat-soil ecosystems is essential for agricultural soil pollution control and crop ecological risk assessment. This study systematically investigated the translocation of 13 PFAAs under different iron and nitrogen fertilization conditions in a wheat-soil ecosystem. Short-chain PFAAs including PFBA, PFPeA, PFHxA, and PFBS mostly accumulated in soil solution (10.43-55.33%) and soluble extracellular polymeric substances (S-EPS) (11.39-14.77%) by the adsorption to amino- (-NH2) and hydroxyl (-OH) groups in dissolved organic matter (DOM). Other PFAAs with longer carbon chain lengths were mostly distributed on the soil particle surface by hydrophobic actions (74.63-94.24%). Iron-nitrogen amendments triggered (p < 0.05) soil iron-nitrogen cycling, rhizospheric reactive oxygen species fluctuations, and the concentration increases of -NH2 and -OH in the DOM structure. Thus, the accumulation capacity of PFAAs in soil solution and root EPS was increased. In sum, PFAAs' translocation from soil particles to wheat root was synergistically reduced by iron and nitrogen fertilization through increased adsorption of soil particles (p < 0.05) and the retention of soil solution and root EPSs. This study highlights the potential of iron-nitrogen amendments in decreasing the crop ecological risks to PFAAs' pollution.

Impacts of extracellular polymeric substances on the behaviors of micro/nanoplastics in the water environment.

Increasing pollution of microplastics (MPs) and nanoplastics (NPs) has caused widespread concern worldwide. Extracellular polymeric substances (EPS) are natural organic polymers mainly produced by microorganisms, the major components of which are polysaccharides and proteins. This review focuses on the interactions that occur between EPS and MPs/NPs in the water environment and evaluates the effects of these interactions on the behaviors of MPs/NPs. EPS-driven formation of eco-corona, biofilm, and "marine snow" can incorporate MPs and NPs into sinking aggregates, resulting in the export of MPs/NPs from the upper water column. EPS coating greatly enhances the adsorption of metals and organic pollutants by MPs due to the larger specific surface area and the abundance of functional groups such as carboxyl, hydroxyl and amide groups. EPS can weaken the physical properties of MPs. Through the synergistic action of different extracellular enzymes, MPs may be decomposed into oligomers and monomers that can enter microbial cells for further mineralization. This review contributes to a comprehensive understanding of the dynamics of MPs and NPs in the water environment and the associated ecological risks.