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Antibiotic resistance genes (ARGs) as emerging environmental contaminants exacerbate the risk of spreading antibiotic resistance. Natural organic matter (NOM) is ubiquitous in aquatic environments and plays a crucial role in biogeochemical cycles. However, its impact on the dissemination of extracellular antibiotic resistance genes (eARGs) under sunlight exposure remains elusive. This study reveals that environmentally relevant levels of NOM (0.1-20 mg/L) can significantly enhance the natural transformation frequency of the model bacterium Acinetobacter baylyi ADP1 by up to 7.6-fold under simulated sunlight. Similarly, this enhancement was consistently observed in natural water and wastewater systems. Further mechanism analysis revealed that reactive oxygen species (ROS) generated by NOM under sunlight irradiation, primarily singlet oxygen and hydroxyl radicals, play a crucial role in this process. These ROS induce intracellular oxidative stress and elevated cellular membrane permeability, thereby indirectly boosting ATP production and enhancing cell competence of extracellular DNA uptake and integration. Our findings highlight a previously underestimated role of natural factors in the dissemination of eARGs within aquatic ecosystems and deepen our understanding of the complex interplay between NOM, sunlight, and microbes in environmental water bodies. This underscores the importance of developing comprehensive strategies to mitigate the spread of antibiotic resistance in aquatic environments.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Nanomaterials can empower microbial-based chemical production or pollutant removal, e.g., nano zero-valent iron (nZVI) as an electron source to enhance microbial reducing pollutants. Constructing bio-nano interfaces is critical for bio-nano system operation, but low interfacial compatibility due to nanotoxicity challenges the system performance. Inspired by microorganisms' resistance to nanotoxicity by secreting extracellular polymeric substances (EPS), which can act as electron shuttling media, we design a highly compatible bio-nano interface by modifying nZVI with EPS, markedly improving the performance of a bio-nano system consisting of nZVI and bacteria. EPS modification reduced membrane damage and oxidative stress induced by nZVI. Moreover, EPS alleviated nZVI agglomeration and probably reduced bacterial rejection of nZVI by wrapping camouflage, contributing to the bio-nano interface formation, thereby facilitating nZVI to provide electrons for bacterial reducing pollutant via membrane-anchoring cytochrome c. This work provides a strategy for designing a highly biocompatible interface to construct robust and efficient bio-nano systems for environmental implication.

Antibiotic pollution in water environment is an emerging threat to plant health. Developing efficient strategies to reassemble the antibiotic-tolerating endophytes will confer fitness benefits on host plants to alleviate antibiotic stress. Here, introducing environmental microbes was proved as a promising approach to reshape the antibiotic-tolerating plant endophytes under antibiotic stress in aquatic microcosms. The introduction of environmental microbes effectively relieved antibiotic-driven perturbation on plant endophytes, with reduced changes in bacterial diversity and differential bacterial taxa and functional genes. Moreover, introducing environmental microbes facilitated the enrichment of endophytic bacterial genera and functional genes related to drug metabolism, which possessed the potentials to degrade antibiotics. In addition, environmental microbes boosted antibiotic-reshaped endophytes to form more stable bacterial networks for stronger antibiotic tolerance. In consequence, the decreased growth inhibition of antibiotics on host plants and enhanced antibiotic removal from microcosms were achieved by introducing environmental microbes. These findings pursue environmental microbes as practical resources to assist plants in reshaping the stress-alleviating endophytes, potentially improving plant tolerance to water pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Previous studies have highlighted the toxicity of pharmaceuticals and personal care products (PPCPs) in plants, yet understanding their spatial distribution within plant tissues and specific toxic effects remains limited. This study investigates the spatial-specific toxic effects of carbamazepine (CBZ), a prevalent PPCP, in plants. Utilizing desorption electrospray ionization mass spectrometry imaging (DESI-MSI), CBZ and its transformation products were observed predominantly at the leaf edges, with 2.3-fold higher concentrations than inner regions, which was confirmed by LC-MS. Transcriptomic and metabolic analyses revealed significant differences in gene expression and metabolite levels between the inner and outer leaf regions, emphasizing the spatial location's role in CBZ response. Notably, photosynthesis-related genes were markedly downregulated, and photosynthetic efficiency was reduced at leaf edges. Additionally, elevated oxidative stress at leaf edges was indicated by higher antioxidant enzyme activity, cell membrane impairment, and increased free fatty acids. Given the increased oxidative stress at the leaf margins, the study suggests using in situ Raman spectroscopy for early detection of CBZ-induced damage by monitoring reactive oxygen species levels. These findings provide crucial insights into the spatial toxicological mechanisms of CBZ in plants, forming a basis for future spatial toxicology research of PPCPs.

Electroactive bacteria, exemplified by Shewanella oneidensis MR-1, have garnered significant attention due to their unique extracellular electron-transfer (EET) capabilities, which are crucial for energy recovery and pollutant conversion. However, the practical application of MR-1 is constrained by its EET efficiency, a key limiting factor, due to the complexity of research methodologies and the challenges associated with the practical use of gene editing tools. To address this challenge, a novel gene integration system, INTEGRATE, was developed, utilizing CRISPR-mediated transposase technologies for precise genomic insertion within the S. oneidensis MR-1 genome. This system facilitated the insertion of extensive gene segments at different sites of the Shewanella genome with an efficiency approaching 100%. The inserted cargo genes could be kept stable on the genome after continuous cultivation. The enhancement of the organism's EET efficiency was realized through two primary strategies: the integration of the phenazine-1-carboxylic acid synthesis gene cluster to augment EET efficiency and the targeted disruption of the SO3350 gene to promote anodic biofilm development. Collectively, our findings highlight the potential of utilizing the INTEGRATE system for strategic genomic alterations, presenting a synergistic approach to augment the functionality of electroactive bacteria within bioelectrochemical systems.

Wolframite (FeWO 4 ), a typical polyoxometalate, serves as an auspicious candidate for heterogeneous catalysts, courtesy of its high chemical stability and electronic properties. However, the electron-deficient surface-active Fe species in FeWO 4 are insufficient to cleave H 2 O 2 via Fe redox-mediated Fenton-like catalytic reaction. Herein, we doped Sulfur (S) atom into FeWO 4 catalysts to refine the electronic structure of FeWO 4 for H 2 O 2 activation and sulfamethoxazole (SMX) degradation. Furthermore, spin-state reconstruction on S-doped FeWO 4 was found to effectively refine the electronic structure of Fe in the d orbital, thereby enhancing H 2 O 2 activation. S doping also accelerated electron transfer during the conversion of sulfur species, promoting the cycling of Fe(III) to Fe(II). Consequently, S-doped FeWO 4 bolstered the Fenton-like reaction by nearly two orders of magnitude compared to FeWO 4 . Significantly, the developed S-doped FeWO 4 exhibited a remarkable removal efficiency of approximately 100% for SMX within 40 min in real water samples. This underscores its extensive pH adaptability, robust catalytic stability, and leaching resistance. The matrix effects of water constituents on the performance of S-doped FeWO 4 were also investigated, and the results showed that a certain amount of Cl - , SO 4 2- , NO 3 - , HCO 3 - and PO 4 3- exhibited negligible effects on the degradation of SMX. Theoretical calculations corroborate that the distinctive spin-state reconstruction of Fe center in S-doped FeWO 4 is advantageous for H 2 O 2 decomposition. This discovery offers novel mechanistic insight into the enhanced catalytic activity of S doping in Fenton-like reactions and paves the way for expanding the application of FeWO 4 in wastewater treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Nanoagrochemicals present promising solutions for augmenting conventional agriculture, while insufficient utilization of nanobiointerfacial interactions hinders their field application. This work investigates the multiscale physiochemical interactions between nanoagrochemicals and rice ( Oryza sativa L.) leaves and devises a strategy for elevating targeting efficiency of nanoagrochemicals and stress resilience of rice. We identified multiple deposition behaviors of nanoagrochemicals on hierarchically structured leaves and demonstrated the crucial role of leaf microarchitectures. A transition from the Cassie-Baxter to the Wenzel state significantly changed the deposition behavior from superlattice assembly, ring-shaped aggregation to uniform monolayer deposition. By fine-tuning the formulation properties, we achieved a 415.9-fold surge in retention efficiency, and enhanced the sustainability of nanoagrochemicals by minimizing loss during long-term application. This biointerface design significantly relieved the growth inhibition of Cd(II) pollutant on rice plants with a 95.2% increase in biomass after foliar application of SiO 2 nanoagrochemicals. Our research elucidates the intricate interplay between leaf structural attributes, nanobiointerface design, and biological responses of plants, fostering field application of nanoagrochemicals.

Biotic-abiotic hybrid photocatalytic system is an innovative strategy to capture solar energy. Diversifying solar energy conversion products and balancing photoelectron generation and transduction are critical to unravel the potential of hybrid photocatalysis. Here, we harvest solar energy in a dual mode for Cu 2-x Se nanoparticles biomineralization and seawater desalination by integrating the merits of Shewanella oneidensis MR-1 and biogenic nanoparticles. Photoelectrons generated by extracellular Se 0 nanoparticles power Cu 2-x Se synthesis through two pathways that either cross the outer membrane to activate periplasmic Cu(II) reduction or are directly delivered into the extracellular space for Cu(I) evolution. Meanwhile, photoelectrons drive periplasmic Cu(II) reduction by reversing MtrABC complexes in S. oneidensis. Moreover, the unique photothermal feature of the as-prepared Cu 2-x Se nanoparticles, the natural hydrophilicity, and the linking properties of bacterium offer a convenient way to tailor photothermal membranes for solar water production. This study provides a paradigm for balancing the source and sink of photoelectrons and diversifying solar energy conversion products in biotic-abiotic hybrid platforms., (© 2024. The Author(s).)

The prevalence of antibiotic resistance genes (ARGs) in municipal wastewater treatment plants (MWTPs) has emerged as a significant environmental concern. Despite advanced treatment processes, high levels of ARGs persist in the secondary effluent from MWTPs, posing ongoing environmental risks. This study explores the potential of gamma-ray irradiation as a novel approach for sterilizing antibiotic-resistant bacteria (ARB) and reducing ARGs in MWTP secondary effluent. Our findings reveal that gamma-ray irradiation at an absorbed dose of 1.6 kGy effectively deactivates all culturable bacteria, with no subsequent revival observed after exposure to 6.4 kGy and a 96-h incubation in darkness at room temperature. The removal efficiencies for a range of ARGs, including tetO, tetA, bla TEM-1 , sulI, sulII, and tetW, were up to 90.5% with a 25.6 kGy absorbed dose. No resurgence of ARGs was detected after irradiation. Additionally, this study demonstrates a considerable reduction in the abundances of extracellular ARGs, with the transformation efficiencies of extracellular tetracycline and sulfadiazine resistance genes decreasing by 56.3-81.8% after 25.6 kGy irradiation. These results highlight the effectiveness of gamma-ray irradiation as an advanced and promising method for ARB sterilization and ARG reduction in the secondary effluent of MWTPs, offering a potential pathway to mitigate environmental risks associated with antibiotic resistance., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Bacterial nanocellulose (BNC) is an attractive green-synthesized biomaterial for biomedical applications and various other applications. However, effective engineering of BNC production has been limited by our poor knowledge of the related metabolic processes. In contrast to the traditional perception that genome critically determines biosynthesis behaviors, here we discover that the glucose metabolism could also drastically affect the BNC synthesis in Gluconacetobacter hansenii . The transcriptomic profiles of two model BNC-producing strains, G. hansenii ATCC 53582 and ATCC 23769, which have highly similar genomes but drastically different BNC yields, were compared. The results show that their BNC synthesis capacities were highly related to metabolic activities such as ATP synthesis, ion transport protein assembly, and carbohydrate metabolic processes, confirming an important role of metabolism-related transcriptomes in governing the BNC yield. Our findings provide insights into the microbial biosynthesis behaviors from a transcriptome perspective, potentially guiding cellular engineering for biomaterial synthesis.

Iron plaque, as a natural barrier between rice and soil, can reduce the accumulation of pollutants in rice by adsorption, contributing to the safe production of rice in contaminated soil. In this study, we unveiled a new role of iron plaque, i.e., producing hydroxyl radicals (·OH) by activating root-secreted oxygen to degrade pollutants. The ·OH was produced on the iron plaque surface and then diffused to the interfacial layer between the surface and the rhizosphere environment. The iron plaque activated oxygen via a successive three-electron transfer to produce ·OH, involving superoxide and hydrogen peroxide as the intermediates. The structural Fe(II) in iron plaque played a dominant role in activating oxygen rather than the adsorbed Fe(II), since the structural Fe(II) was thermodynamically more favorable for oxygen activation. The oxygen vacancies accompanied by the structural Fe(II) played an important role in oxygen activation to produce ·OH. The interfacial ·OH selectively degraded rhizosphere pollutants that could be adsorbed onto the iron plaque and was less affected by the rhizosphere environments than the free ·OH. This study uncovered the oxidative role of iron plaque mediated by its produced ·OH, reshaping our understanding of the role of iron plaque as a barrier for rice.

The persistence of extracellular antibiotic resistance genes (ARGs) in aquatic environments has attracted increasing attention due to their potential threat to public health and the environment. However, the fate of extracellular ARGs in receiving water remains largely unknown. This study investigated the influence of hematite nanoparticles, a widespread natural mineral, on the photodegradation of extracellular ARGs in river water. Results showed that under exposure to visible light, hematite nanoparticles, at environmental concentrations, resulted in a 3-5 orders of magnitude reduction in extracellular ARGs. This photodegradation of extracellular ARGs is shown to be facet-dependent; the (001) facet of hematite demonstrates a higher removal rate than that of the (100) facet, which is ascribed to its enhanced adsorption capability and higher hydroxyl radical ( • OH) production. Density functional theory (DFT) calculations corroborate this finding, indicating elevated iron density, larger adsorption energy, and lower energy barrier of • OH formation on the (001) facet, providing more active sites and • OH generation for extracellular ARG interaction. Gel electrophoresis and atomic force microscopy analyses further confirm that the (001) facet causes more substantial damage to extracellular ARGs than the (100) facet. These findings pave the way for predicting the photodegradation efficiency of hematite nanoparticles with varied facets, thereby shedding light on the inherent self-purification capacity for extracellular ARGs in both natural and engineered aquatic environments.

Micro(nano)plastics widely detected in aquatic environments have caused serious threat to water quality security. However, as a potential important source of micro(nano)plastics in surface water during the COVID-19 pandemic, the ecological risks of face mask waste to aquatic environments remain poorly understood. Herein, we comprehensively characterized the micro(nano)plastics and organic compounds released from four daily used face masks in aqueous environments and further evaluated their potential impacts on aquatic ecosystem safety by quantitative genotoxicity assay. Results from spectroscopy and high-resolution mass spectrum showed that plastic microfibers/particles (∼11%-83%) and leachable organic compounds (∼15%-87%) were dominantly emitted pollutants, which were significantly higher than nanoplastics (< ∼5%) based on mass of carbon. Additionally, a toxicogenomics approach using green fluorescence protein-fused whole-cell array revealed that membrane stress was the primary response upon the exposure to micro(nano)plastics, whereas the emitted organic chemicals were mainly responsible for DNA damage involving most of the DNA repair pathways (e.g., base/nucleotide excision repair, mismatch repair, double-strand break repair), implying their severe threat to membrane structure and DNA replication of microorganisms. Therefore, the persistent release of discarded face masks derived pollutants might exacerbate water quality and even adversely affect aquatic microbial functions. These findings would contribute to unraveling the potential effects of face mask waste on aquatic ecosystem security and highlight the necessity for more developed management regulations in face mask disposal., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Discarded face masks from the global COVID-19 pandemic have contributed significantly to plastic pollution in surface water, whereas their potential as a reservoir for aquatic pollutants is not well understood. Herein, we conducted a field experiment along a human-impacted urban river, investigating the variations of antibiotic resistance genes (ARGs), pathogens, and water-borne contaminants in commonly-used face masks. Results showed that high-biomass biofilms formed on face masks selectively enriched more ARGs than stone biofilm (0.08-0.22 vs 0.07-0.15 copies/16 S rRNA gene copies) from bulk water, which mainly due to unique microbial communities, enhanced horizontal gene transfer, and selective pressure of accumulated contaminants based on redundancy analysis and variation partitioning analysis. Several human opportunistic pathogens (e.g., Acinetobacter, Escherichia-Shigella, Bacillus, and Klebsiella), which are considered potential ARG carriers, were also greatly concentrated in face-mask biofilms, imposing a potential threat to aquatic ecological environment and human health. Moreover, wastewater treatment plant effluents, as an important source of pollutants to urban rivers, further aggravated the abundances of ARGs and opportunistic pathogens in face-mask biofilms. Our findings demonstrated that discarded face masks provide a hotspot for the proliferation and spread of ARGs and pathogens in urban water, highlighting the urgent requirement for implementing stricter regulations in face mask disposal., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The efficient generation and utilization of ROSs is a key step in determining the achievement of safe drinking water by photocatalytic bacterial inactivation technology. Although graphitic carbon nitride (g-C 3 N 4 ) serves as a green and promising photocatalyst for water disinfection, insufficient bacterial capturing capacity and serious charge recombination of pristine g-C 3 N 4 extremely restrict its bactericidal activity. Herein, we develop a facile thermal exfoliation and thermal polymerization method to prepare the nitrogen-defective ultrathin g-C 3 N 4 nanosheets (DUCN-500). Our results showed that ultrathin nanosheet structure greatly enhanced bacterial capturing capacity of g-C 3 N 4 to increase the utilization efficiency of ROS, which contributed to the performance of DUCN-500 greatly outperforming bulk g-C 3 N 4 . The nitrogen defects increased ROS generation (·O 2 - and H 2 O 2 ) by approximately 4.6 times, which was attributed to negative shift of the conduction band potential and rapid separation of charge carriers. The DUCN-500 could rapidly and completely inactivate Escherichia coli and Bacillus subtilis in real sewage under simulated solar irradiation, accompanied by good anti-interference capability and stability. Additionally, bacterial morphology destruction, the loss of antioxidant enzyme activity and the leakage of protein were proven to be the main mechanisms of photocatalytic sterilization. This study offers new insight into the rational design of efficient g-C 3 N 4 -based photocatalysts for water disinfection., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

Compared to individual UV or chlorine disinfection, the combined UV and chlorine (i.e., UV/chlorine) can substantially promote the degradation of antibiotic resistance genes (ARGs) in the effluent by generating radicals. However, the mechanisms of ARG degradation induced by radicals during UV/chlorine treatment remain largely unknown, limiting further enhancement of ARG degradation by process optimization. Herein, we aimed to uncover the role of different radicals in ARG degradation and the molecular mechanisms of ARG degradation by radicals in UV/chlorine process. The ClO was proven to be responsible for the enhanced ARG degradation during UV/chlorine treatment, while the other radicals (OH, Cl, and Cl 2 - ) played a minor role. This is because ClO possessed both high steady-state concentration and high reactivity toward ARGs (rate constant: 4.29 × 10 10 M -1 s -1 ). The ClO might collaborate with free chlorine to degrade ARG. The ClO degraded ARGs by selectively attacking guanine and thymine but failed to induce strand breakage, while chlorine could break the strand of ARGs. Ultimately, ClO cooperated with chlorine to degrade ARGs quickly by hydroxylation and chlorination of bases and produce many chlorine- and nitrogen-containing products as revealed by high-resolution mass spectrometry. The uncovered degradation mechanisms of ARGs by UV/chlorine provide useful guidelines for process optimization to achieve deep removal of effluent ARGs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Phosphonates, as a kind of important organic phosphorus in wastewater, should be removed in terms of their environmental risks. Unfortunately, traditional biological treatments fail to remove phosphonates effectively due to their biological inertness. The reported advanced oxidation processes (AOPs) usually require pH adjustment or coupling with other technologies to achieve high removal efficiency. Thus, a simple and efficient method for phosphonate removal is urgently needed. Herein, ferrate was found to remove phosphonates effectively in one-step under near-neutral circumstances by coupling oxidation and in-situ coagulation. Nitrilotrimethyl-phosphonic acid (NTMP), a typical phosphonate, could be efficiently oxidized by ferrate to release phosphate. The fraction of phosphate release increased with increasing ferrate dosage and reached 43.1% when 0.15 mM ferrate was added. Fe(VI) was responsible for NTMP oxidation, while Fe(V), Fe(IV) and ⋅OH played a minor role. Ferrate-induced phosphate release facilitated total phosphorus (TP) removal, because the phosphate is more easily removed via ferrate-resultant Fe(III) coagulation than the phosphonates. The coagulation removal of TP could reach up to 90% within 10 min. Furthermore, ferrate exerted high removal efficiencies for other commonly used phosphonates with approximately or up to 90% TP removal. This work provides a one-step efficient method to treat phosphonate-containing wastewaters., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Although surface-enhanced Raman spectroscopy (SERS) offers a promising technology for sensitive detection of environmental pollutants in natural waters, its performance can be greatly affected by the environmental matrix. The lack of identification of the origin and the underlying mechanism of matrix effect hinders the application of SERS in practical environmental analysis. Herein, with silver nanoparticles (AgNPs) as a solution-based SERS substrate, the matrix effect from environmental waters on SERS analysis and the underlying mechanisms were investigated. It was found that natural water matrix could deteriorate SERS performance and cause artefacts in SERS spectra. Among various aqueous components, natural organic matter (NOM), including humic substances and proteins, mainly contributed to the matrix effect on SERS detection, while polysaccharides or inorganic ions had minor influence. The matrix effect from NOM was found to be prevalent for different analytes and SERS substrates. The mechanism of the matrix effect from NOM in the ternary system of analyte, NOM, and nanoparticles was investigated through three mutual interactions. The microheterogeneous repartition of analytes by NOM, other than the formation of NOM-corona or competitive adsorption between NOM and analytes on nanoparticles, was found to play the dominating role in interfering with SERS detection. This work illuminates the origin and underlying mechanisms of the matrix effect, which will promote the practical application of SERS technology in environmental analysis., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Learning and studying the structure-activity relationship in the bio-enzymes is conducive to the design of nanozymes for energy and environmental application. Herein, Fe single-atom nanozymes (Fe-SANs) with Fe-N 5 site, inspired by the structure of cytochromes P450 (CYPs), are developed and characterized. Similar to the CYPs, the hyperoxide can activate the Fe(III) center of Fe-SANs to generate Fe(IV)O intermediately, which can transfer oxygen to the substrate with ultrafast speed. Particularly, using the peroxymonosulfate (PMS)-activated Fe-SANs to oxidize sulfamethoxazole, a typical antibiotic contaminant, as the model hyperoxides activation reaction, the excellent activity within 284 min -1 g -1 (catalyst) mmol -1 (PMS) oxidation rate and 91.6% selectivity to the Fe(IV)O intermediate oxidation are demonstrated. More importantly, instead of promoting PMS adsorption, the axial N ligand modulates the electron structure of FeN 5 SANs for the lower reaction energy barrier and promotes electron transfer to PMS to produce Fe(IV)O intermediate with high selectivity. The highlight of the axial N coordination in the nanozymes in this work provides deep insight to guide the design and development of nanozymes nearly to the bio-enzyme with excellent activity and selectivity., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The transformation of extracellular antibiotic resistance genes (eARGs) is largely influenced by their inevitable photodegradation in environments where they tend to be adsorbed by ubiquitous clay minerals instead of being in a free form. However, the photodegradation behaviors and mechanisms of the adsorbed eARGs may be quite different from those of the free form and still remain unclear. Herein, we found that kaolinite, a common 1:1-type clay, markedly enhanced eARG photodegradation and made eARGs undergo direct photodegradation under UVA. The decrease in the transformation efficiency of eARGs caused by photodegradation was also promoted. Spectroscopy methods combined with density functional theory calculations revealed that the Lewis acid-base interaction between P-O in eARGs and Al-OH on kaolinite delocalized electrons of eARGs, thus resulting in increased photon absorption ability of eARGs. This ultimately led to enhanced photodegradation of kaolinite-adsorbed eARGs. Additionally, divalent Ca 2+ could reduce the Lewis acid-base interaction-mediated adsorption of eARGs by kaolinite, thereby weakening the enhanced photodegradation of eARGs caused by electron delocalization. In contrast, the 2:1-type clay montmorillonite without strong Lewis acid sites was unable to delocalize the electrons to enhance the photodegradation of eARGs. This work allowed us to better evaluate eARGs' fate and risk in real aqueous environments.

The spread of antibiotics and antibiotic resistance genes (ARGs) in environments has posed potential threats to public health. Unfortunately, conventional biological wastewater treatment technologies generally show insufficient removal of antibiotics and ARGs. Bioelectrochemical systems, which can effectively degrade refractory organic pollutants via enhancing microbial metabolisms through electrochemical redox reaction, may provide an alternative for the control of antibiotics and ARGs. Herein, an anaerobic electrochemical membrane bioreactor (AnEMBR) was conducted by combining bioelectrochemical system and anaerobic membrane bioreactor to treat antibiotic-containing wastewater. The AnEMBR at open circuit showed stable CH 4 production and high removal of COD and chlortetracycline (CTC) in treating 2.5-15 mg/L CTC. However, increasing CTC to 45 mg/L completely inhibited the methanogenesis of AnEMBR at open circuit. After applying external voltage in AnEMBR, the performances of AnEMBR were significantly improved (e.g., increased CH 4 production and CTC removal). Moreover, CTC exposure significantly increased the relative abundances of ARGs in sludge, supernatant, and effluent in AnEMBR at open circuit. Applying voltage greatly attenuated the total relative abundances of ARGs in the supernatant and effluent of AnEMBR compared to those at open circuit. This could be attributed to the enrichment of tetracycline degradation gene tetX, which greatly enhanced the removal of CTC by the AnEMBR and thus reduced the selective pressure of CTC on the microorganisms in supernatant and effluent for ARGs proliferation. These results would provide an effective wastewater treatment technology for treating high-level antibiotic-containing wastewater to mitigate the potential risk of ARGs and antibiotics spread in receiving water body., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

A photothermal nanoconfinement reactor (PNCR) system is proposed and demonstrated by using hollow carbon nanospheres (HCNs) to enhance the performance of the chemical reaction. Under light irradiation, the local temperature of the HCN inner void space was much higher than the bulk solution temperature because the confined space concentrates heat and inhibits heat loss. Using the temperature-sensitive model reaction, peroxydisulfate (PDS) activation to oxidize micropollutant, it is shown that the degradation rate of sulfamethoxazole in the PNCR system is 7.1 times of that without nanoconfinement. It is further discovered that the high-quality local heat inside the nanoconfined space shifted the model reaction from an otherwise non-radical pathway to a radical-based pathway. This work provides an interesting strategy to produce a locally high temperature, which has a wide range of applications to energy and environmental fields., (© 2022 Wiley-VCH GmbH.)

The biotic-abiotic photosynthetic system integrating inorganic light absorbers with whole-cell biocatalysts innovates the way for sustainable solar-driven chemical transformation. Fundamentally, the electron transfer at the biotic-abiotic interface, which may induce biological response to photoexcited electron stimuli, plays an essential role in solar energy conversion. Herein, we selected an electro-active bacterium Shewanella oneidensis MR-1 as a model, which constitutes a hybrid photosynthetic system with a self-assembled CdS semiconductor, to demonstrate unique biotic-abiotic interfacial behavior. The photoexcited electrons from CdS nanoparticles can reverse the extracellular electron transfer (EET) chain within S. oneidensis MR-1, realizing the activation of a bacterial catalytic network with light illumination. As compared with bare S. oneidensis MR-1, a significant upregulation of hydrogen yield (711-fold), ATP, and reducing equivalent (NADH/NAD + ) was achieved in the S. oneidensis MR-1-CdS under visible light. This work sheds light on the fundamental mechanism and provides design guidelines for biotic-abiotic photosynthetic systems.

Wastewater treatment plants (WWTPs) are important sources of antibiotic resistance genes (ARGs). Increasing attention has been paid to extracellular ARGs in cell-free form due to their horizontal gene transfer via transformation. However, the fate of the adsorbed form of extracellular ARGs that exist in extracellular polymeric substances (EPS) of activated sludge in WWTP remains largely unknown. Herein, seven EPS-associated ARGs along the anaerobic-anoxic-aerobic (AAO) process were quantified using quantitative polymerase chain reaction. Results show that the absolute abundances of EPS-associated ARGs were 0.69-4.52 logs higher than those of cell-free ARGs. There was no significant difference in the abundances of EPS-associated ARGs along the AAO process. Among these target genes, the abundances of EPS-associated sul genes were higher than those of EPS-associated tet and bla genes. Proteobacteria and Bacteroidetes were identified as the major secretors of EPS-associated ARGs, and they may play an important role in the proliferation of extracellular ARGs. Moreover, the transformation efficiencies of EPS-associated ARGs were 3.55-4.65 logs higher than those of cell-free ARGs, indicating that EPS-associated ARGs have higher environmental risks. These findings have advanced our understanding of EPS-associated ARGs and are useful for the control and risk assessment of ARGs in WWTPs., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Background: Safe and effective vaccines are urgently needed to end the COVID-19 pandemic caused by SARS-CoV-2 infection. We aimed to assess the preliminary safety, tolerability, and immunogenicity of an mRNA vaccine ARCoV, which encodes the SARS-CoV-2 spike protein receptor-binding domain (RBD)., Methods: This single centre, double-blind, randomised, placebo-controlled, dose-escalation, phase 1 trial of ARCoV was conducted at Shulan (Hangzhou) hospital in Hangzhou, Zhejiang province, China. Healthy adults aged 18-59 years negative for SARS-CoV-2 infection were enrolled and randomly assigned using block randomisation to receive an intramuscular injection of vaccine or placebo. Vaccine doses were 5 μg, 10 μg, 15 μg, 20 μg, and 25 μg. The first six participants in each block were sentinels and along with the remaining 18 participants, were randomly assigned to groups (5:1). In block 1 sentinels were given the lowest vaccine dose and after a 4-day observation with confirmed safety analyses, the remaining 18 participants in the same dose group proceeded and sentinels in block 2 were given their first administration on a two-dose schedule, 28 days apart. All participants, investigators, and staff doing laboratory analyses were masked to treatment allocation. Humoral responses were assessed by measuring anti-SARS-CoV-2 RBD IgG using a standardised ELISA and neutralising antibodies using pseudovirus-based and live SARS-CoV-2 neutralisation assays. SARS-CoV-2 RBD-specific T-cell responses, including IFN-γ and IL-2 production, were assessed using an enzyme-linked immunospot (ELISpot) assay. The primary outcome for safety was incidence of adverse events or adverse reactions within 60 min, and at days 7, 14, and 28 after each vaccine dose. The secondary safety outcome was abnormal changes detected by laboratory tests at days 1, 4, 7, and 28 after each vaccine dose. For immunogenicity, the secondary outcome was humoral immune responses: titres of neutralising antibodies to live SARS-CoV-2, neutralising antibodies to pseudovirus, and RBD-specific IgG at baseline and 28 days after first vaccination and at days 7, 15, and 28 after second vaccination. The exploratory outcome was SARS-CoV-2-specific T-cell responses at 7 days after the first vaccination and at days 7 and 15 after the second vaccination. This trial is registered with www.chictr.org.cn (ChiCTR2000039212)., Findings: Between Oct 30 and Dec 2, 2020, 230 individuals were screened and 120 eligible participants were randomly assigned to receive five-dose levels of ARCoV or a placebo (20 per group). All participants received the first vaccination and 118 received the second dose. No serious adverse events were reported within 56 days after vaccination and the majority of adverse events were mild or moderate. Fever was the most common systemic adverse reaction (one [5%] of 20 in the 5 μg group, 13 [65%] of 20 in the 10 μg group, 17 [85%] of 20 in the 15 μg group, 19 [95%] of 20 in the 20 μg group, 16 [100%] of 16 in the 25 μg group; p<0·0001). The incidence of grade 3 systemic adverse events were none (0%) of 20 in the 5 μg group, three (15%) of 20 in the 10 μg group, six (30%) of 20 in the 15 μg group, seven (35%) of 20 in the 20 μg group, five (31%) of 16 in the 25 μg group, and none (0%) of 20 in the placebo group (p=0·0013). As expected, the majority of fever resolved in the first 2 days after vaccination for all groups. The incidence of solicited systemic adverse events was similar after administration of ARCoV as a first or second vaccination. Humoral immune responses including anti-RBD IgG and neutralising antibodies increased significantly 7 days after the second dose and peaked between 14 and 28 days thereafter. Specific T-cell response peaked between 7 and 14 days after full vaccination. 15 μg induced the highest titre of neutralising antibodies, which was about twofold more than the antibody titre of convalescent patients with COVID-19., Interpretation: ARCoV was safe and well tolerated at all five doses. The acceptable safety profile, together with the induction of strong humoral and cellular immune responses, support further clinical testing of ARCoV at a large scale., Funding: National Key Research and Development Project of China, Academy of Medical Sciences China, National Natural Science Foundation China, and Chinese Academy of Medical Sciences., Competing Interests: C-FQ and BY are co-inventors on pending patent applications related to the ARCoV mRNA vaccine. LW is an employee of Suzhou Abogen Biosciences. S-YY and ZH are employees of Walvax. All other authors declare no competing interests., (© 2022 The Author(s). Published by Elsevier Ltd. This is an Open Access article under the CC BY-NC-ND 4.0 license.)

Antibiotic resistance has become a global public health problem. Recently, various environmental pollutants have been reported to induce the proliferation of antibiotic resistance. However, the impact of multiple pollutants (e.g., heavy metals and antibiotics), which more frequently occur in practical environments, is poorly understood. Herein, one widely distributed heavy metal (Ag + ) and one frequently detected antibiotic (tetracycline) were chosen to investigate their coexisting effect on the proliferation of antibiotic resistance in the activated sludge system. Results show that the co-occurrence of Ag + and tetracycline at environmentally relevant concentrations exhibited no distinct inhibition in reactor performances. However, they inhibited the respiratory activity by 42%, destroyed the membrane structure by 218%, and increased membrane permeability by 29% compared with the blank control bioreactor. Moreover, the relative abundances of target antibiotic resistance genes (ARGs) (e.g., tetA, bla TEM-1 , and sulII) in effluent after exposure of coexisting Ag + and tetracycline were increased by 92-1983% compared with those in control reactor, which were 1.1-4.3 folds higher than the sum of the sole ones. These were possibly attributed to the enrichments of antibiotic-resistant bacteria. The results would illumine the coexisting effect of heavy metals and antibiotics on the dissemination of ARGs in activated sludge system., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Hypersaline wastewater is difficult to treat due to the inhibition of salt stress on microbes' viability and metabolic capabilities. Haloarchaea, native microorganisms that thrive in hypersaline habitats, overcome this key obstacle naturally. This review provides a comprehensive overview of the metabolic versatility of Haloarchaea in hypersaline wastewater treatment, including carbon, nitrogen, phosphorus, sulfur, and heavy metal metabolism. It also analyzes factors affecting pollutant removal and addresses metabolic mechanisms. Additionally, haloarchaea microbial characteristics and strategies to cope with salt stress are highlighted. Finally, the biotechnological potential of biomolecules produced from haloarchaea is investigated. To get better insight into the potential of haloarchaea, a deeper investigation of basic metabolism and more in-depth studies of their genomics and applications in actual wastewater are also necessary., Competing Interests: Declaration of interests The authors have no interests to declare., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Nanoparticles contribute to enormous environmental processes, but, due to analytical challenges, the understanding of nanoparticle fate remains elusive in complex environmental matrices. To address the challenge, a core-shell nanoparticle-enhanced Raman spectroscopy (CSNERS) imaging method was developed to selectively track prevalent SiO 2 nanoparticles in an aquatic plant, Lemna minor . By encapsulating gold nanoparticles and Raman reporters inside, the resonance Raman signature was enhanced, thus enabling the sensitive and selective detection of SiO 2 nanoparticles at an environmentally relevant concentration. The panoramic visualization of the translocation pathway of nanoparticles shows an unexpected, fast (in hours) and a preferential accumulation of nanoparticles on the node, leaf edge, root cap, etc., implying the ability of CSNERS to spectroscopically determine nanotoxicity. The core-shell design in CSNERS was capable of multiplex labeling two differently charged nanoparticles and distinguishing their biobehavior simultaneously. Meanwhile, the CSNERS method can be further applied for a variety of nanoparticles, implying its promising applications for nanotoxicity research and biogeochemical study.

Earthworms have shown their effectiveness in reducing the abundances of antibiotic resistance genes (ARGs) from solid waste. However, the mechanisms of the reduced ARGs by earthworm and whether the solid waste would affect the ARGs profile in earthworm gut were poorly understood. Herein, the patterns of ARGs and microbial communities in digested sludge-amended soil and earthworm gut after 80-day cultivation were investigated. Results show that the enrichment of ARGs (e.g., tetA, tetQ, and sulII) in soil caused by digested sludge-amendment was temporary and would recover to their original levels before amendment. In addition, earthworms could contribute to the further reduction of ARG abundances, which was mainly attributed to their gut digestion via shifting the microbial community (e.g., attenuating the anaerobes). However, the amended soil could significantly increase ARGs abundance in the earthworm gut, which may enhance the potential risk of ARGs spread via the food chain. These findings may provide a new sight on the control of ARGs occurrence and dissemination in sludge-amended soil ecosystem with consideration of earthworms., (Copyright © 2021 Elsevier B.V. All rights reserved.)

To date, eutrophication becomes a great concern of vulnerable aquatic systems. Dissolved organic phosphorus (DOP) discharged from wastewater treatment plant (WWTP) holds a large source of phosphorus in receiving water. However, due to the complexity of DOP, their variation and fate in WWTP remain unknown at the molecular level, and are always overlooked. Here, the variation of DOP in a WWTP was uncovered via Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). Results show that 95% of DOP in the influent could be removed by the secondary biological treatment processes. The removed DOP species were mainly lipids with the molecular characteristics of low oxygen content, low unsaturation and low aromaticity. Meanwhile, during biological treatments, some new DOP species, especially lignin/carboxylic rich alicyclic molecules (CRAM) that possessed high oxygen content, high unsaturation and high aromaticity, were produced and released into the secondary effluent. In the subsequent tertiary treatment, coagulation by aluminum salt tended to remove high molecular weight and high oxygen content DOP species in the secondary effluent, which was complementary to the biological treatment. However, the sand filter usually retained microorganisms, which would result in the generation of new DOP species in this process. During the final ultraviolet disinfection process, DOP was effectively mineralized to phosphate, especially the species with high molecular weight and highly unsaturated aromatic DOP species (e.g., lignin/CRAM and tannin), which had higher UV absorbance. The revealed variation of DOP in WWTP is beneficial to optimize the treatment processes to enhance the removal of DOP., (Copyright © 2021. Published by Elsevier Ltd.)

Anaerobic biological treatment technologies are one of the major hotspots of antibiotic resistance genes (ARGs). Previous studies have applied the electrochemical process to improve biogas production, however, it was challenged that high voltages might promote membrane permeability and reactive oxygen species overproduction to promote ARGs proliferation. Herein, the biogas production and ARGs proliferation in an anaerobic electrochemical membrane bioreactor (AnEMBR) were investigated at the gradient voltages of 0-0.9 V. Results show the reactor performances (average CH 4 production and current generation) were distinctly improved with the increase of applied voltage, and reached the optimum at 0.9 V. However, long-term application (>30 day) of 0.9 V deteriorated the reactor performances. Meanwhile, the relative abundances of most target ARGs in the supernatant and effluent of AnEMBR at 0.9 V increased by 0.68-1.55 and 0.42-1.26 logs compared to those before applying voltage, respectively. After disconnecting the circuit, these ARGs abundances all decreased to the original level. Significant correlations between intlI and ARGs (e.g., tetA, tetQ, sulI, and sulII) were observed, indicating horizontal gene transfer may contribute to the increased ARGs. Moreover, the shift of microbial communities caused by the applied voltage enriched potential ARGs-hosts (e.g., Tolumonas), contributing to the proliferation of ARGs., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Ciprofloxacin (CIP), a widely used fluoroquinolone antibiotic, is frequently detected in aqueous environments, and could be assimilated by vegetable plants to possess potential threats to human and animal health through food chains. However, plant uptake of CIP in different chemical speciation has still far from clear now. Thus, the toxicity and uptake of CIP by rice plants were investigated under different solution pH, owing to its contribution to different chemical speciation of CIP. Results display that high pH-driven changes of CIP from cation (CIP + ) to anion (CIP - ) decreased its adsorption and uptake by excised roots and intact plants, respectively. However, CIP concentrations in roots, stems and leaves all exhibited no significant differences with increasing solution pH. Moreover, six intermediates of CIP were detected and two possible transformation pathways were proposed in rice plants, including firstly oxidation and following consecutive cleavage of piperazine ring. After accumulated in plant tissues, CIP significantly inhibited the plant growth, decreased the photosynthetic pigments contents and enhanced the antioxidant enzyme activities in a concentration-dependent manner. Besides, high pH exacerbated the growth inhibition and changed the oxidative damage responses of rice plants to CIP. These findings indicate that the uptake and toxicity of CIP in rice plants were influenced by solution pH-driven changes of its chemical speciation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Antibiotic resistance has been regarded as a global concern and biological wastewater treatment plants (WWTPs) are ideal hotbeds for the emergence and propagation of antibiotic resistance genes (ARGs). Extracellular polymeric substances (EPS), one of the primary components of activated sludge, might affect the distribution of extracellular ARGs in supernatant and EPS matrix, and thus alter their uptake potential by microbial cells. Herein, the presence and significance of EPS-associated ARGs in activated sludge from four WWTPs were assessed. Seven typical ARGs (sulI, sulII, bla TEM-1 , tetA, tetO, tetQ, tetW) and class I integron (intI1) in EPS-associated, cell-free, and intracellular DNA were quantified. Results show that the absolute abundances of EPS-associated, cell-free, and intracellular ARGs were 5.90 × 10 6 -6.45 × 10 9 , 5.53 × 10 4 -4.58 × 10 6 , and 2.68 × 10 8 -1.79 × 10 11 copies/g-volatile suspended solids, respectively. The absolute abundances of EPS-associated ARGs were 0.2-4.6 orders of magnitude higher than those of the corresponding cell-free ARGs. Considering the higher DNA contents in EPS, the transformation abilities of EPS-associated ARGs were 3.3-236.3 folds higher than those of cell-free ARGs. Therefore, EPS-associated ARGs are an important source of extracellular ARGs, and it may play a crucial role in horizontal gene transfer via transformation in WWTPs., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Persulfate-based advanced oxidation technology exhibits great potential for hazardous organic pollutant removal from wastewater. Acceleration of pollutant degradation needs to be elucidated, particularly for heterogeneous catalytic systems. In this study, manganese oxide ordered mesoporous carbon composites (MnO x @OMC) were prepared by nano-casting method and used for persulfate activation to degrade phenol. Kinetics analysis indicate that the rate of phenol degradation using MnO x @OMC composites was improved by 34.9 folds relative to that using a mixture of MnO x and OMC. The phenol toxicity towards Caenorhabditis elegans could be totally reduced within 8 min. The different roles of MnO x and OMC in persulfate activation were confirmed to validate their synergistic effect. MnO x provided major active sites for persulfate activation in accordance with the surface Mn 3+ /Mn 4+ cycle to induce SO 4 •- radicals. The OMC matrix provided the adsorption sites to enrich phenol molecules on the catalytic surface and promote the interfacial electron transfer process for persulfate activation. Moreover, a novel kinetic model with two distinct kinetic stages was established to verify the effects of phenol and persulfate on phenol removal., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Imidazolium based ionic liquids (ILs) have been extensively used in the various industrial fields, however, the dependence of their structure on toxicity and bioavailability by plants is not clear. Thus, in this study, uptake of imidazolium based ILs with different alkyl chain lengths (e.g., [C 2 mim] + and [C 8 mim] + ) by ryegrass and their toxicity to plant growth were investigated. Results show that the two ILs could be removed by ryegrass with high efficiencies, and a higher uptake efficiency and accumulation was observed for [C 2 mim] + with shorter chain length compared with that for [C 8 mim] + . A higher growth inhibition of ryegrass by [C 8 mim] + was observed compared with that by [C 2 mim] + , indicating the long alkyl chain length of ILs had a negative effect on the plant growth. ILs taken up by ryegrass was retained in the roots and their translocation from roots to shoots was restricted. The IL concentration in roots was 0.68 mg/g-fresh weight for [C 2 mim] + and 0.08 mg/g- fresh weight for [C 8 mim] + when the ryegrass was exposed to 10 mg/L ILs. This study proved that plant assimilation of ILs depended on their alky chain lengths, which would be useful for understanding the fate of ILs with various structures in phytoremediation for ILs-contaminated water., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Perfluorooctanoic acid (PFOA), an emerging and persistent pollutant, could cause toxicity effects on aquatic organisms. However, this was generally assessed under high exposure concentrations of PFOA and nutrient-enriched conditions, which was not accordant with the actual environments. Therefore, to comprehensively understand the toxicity effects of PFOA on aquatic organisms, the cellular responses of microalgae, Chlorella pyrenoidosa, to PFOA under different concentrations (≤ 1.0 mg/L) and nutrient conditions were investigated in this study. Results show that PFOA at concentrations less than 1.0 mg/L had no significant effects on algal growth and chlorophyll contents, and no oxidative damages were generated to destroy membrane integrity and morphology. However, N,P-limited and -starved conditions significantly decreased algal growth and chlorophyll contents, and induced oxidative stresses to ruin the structure and function of cell membrane. Moreover, the deficiency of P had more severe negative effect on algae than that of N, and they both influenced the toxicity responses of microalgae to 1.0 mg/L PFOA. The adsorption and uptake percentages of PFOA by algal cells were both less than 10%, and increased adsorption but decreased uptake of PFOA amounts occurred under N,P-limited and -starved conditions. These findings will be useful to understand the toxicity effects of PFOA on microalgae in aquatic environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Extracellular polymeric substances (EPS), one of the main components of activated sludge, could complex with pollutants and thus influence their fate in wastewater treatment system. In this work, the roles of EPS in resisting sulfamethazine (SMZ) shocks were investigated in a continuous flow membrane bioreactor. Results show that SMZ could be intercepted in the EPS of activated sludge during the lag phase of biodegradation. EPS acted as a potential reservoir against SMZ shocks, guaranteeing undetectable SMZ in the effluent. The increased production of EPS in responding to SMZ shocks improved the binding capability of EPS to SMZ. The critical roles of microbial EPS in removing bio-refractory contaminants such as sulfonamides are probably underestimated previously., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Free DNA bases are widely present in the environments, and can be utilized by bacteria for their nucleic acids synthesis or as nutrition sources. In sunlit natural waters, these free bases probably undergo photodegradation which would change the bioavailable bases contents. Though the photodegradation of DNA has been investigated, the photodegradation behaviors of free bases may be quite different from those of DNA-confined bases in consideration of their different chemical environments. Herein, the photodegradation of four free bases (guanine, adenine, thymine and cytosine) was investigated. Results show that direct photodegradation of free bases in phosphate buffer caused by UV was slow. However, the photodegradation of these free bases were greatly enhanced in dissolved organic matter (DOM) solution. In the presence of 10-50 mg/L DOM, the photodegradation rates of free bases were increased by 1.85-14.6 times compared to the controls without DOM. DOM could result in indirect photodegradation by producing hydroxyl radical (•OH) and singlet oxygen ( 1 O 2 ) under irradiation, and this indirect photodegradation enhanced and dominated the free bases photodegradation. The •OH was involved in all four bases photodegradation, while the 1 O 2 only participated in guanine photodegradation. In phosphate buffer, the fastest photodegradation bases were pyrimidine, however, guanine became the fastest photodegradation base in DOM solution due to the selective oxidation of guanine by 1 O 2 . In summary, DOM may be a determinant for free bases photodegradation in natural waters and thereby deeply influence free bases fates in aquatic environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In nature, many microorganisms show resistance to toxic selenite by reducing selenite to non-soluble and low toxic elemental selenium. Extracellular polymeric substances (EPS), a high-molecular-weight biopolymers originated from microbial metabolism, contain many reducing groups and can induce reductive transformation of pollutants. However, the roles of EPS and its redox state in reductive detoxification or reduction removal of selenite, respectively, remain unknown yet. Herein, the reduction of selenite by different sources of EPS was investigated. Selenite was proved to be reduced by EPS and partly transformed to elemental selenium. The formed elemental selenium was mainly selenium nanoparticles confirmed by transmission electron microscopy coupled with energy dispersive spectroscopy. The redox state of EPS governed selenite reduction and elemental selenium formation, and the reduced state of EPS was in favor of selenite reduction. Dissolved oxygen concentration in water regulated EPS redox state and influenced selenite reduction. The thiols, aldehyde and phenolic groups in EPS were responsible for selenite reduction. Under selenite stress, EPS was capable of increasing cell survivability by enhancing microorganisms-mediated selenite reduction. This work revealed the previously undiscovered roles of EPS in selenite reduction and elemental selenium formation in aquatic environments and also suggested a possible crucial role of EPS in selenium biogeochemical cycle., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Ionic liquids, a kind of emerging and persistent organic contaminants, always coexist with heavy metals in aquatic and terrestrial environments. However, the feasibility of phytoremediation to remove ionic liquids and heavy metals co-contaminants is still unclear. Thus, in this study, the hydroponic experiment was conducted to investigate the combined effect of 1-butyl-3-methylimidazolium bromide ([C 4 mim] + Br - ) and cadmium (Cd 2+ ) on growth and physiological indictors of perennial ryegrass, together with their uptake and translocation by plants. Results show that the exposure of ryegrass to [C 4 mim] + and Cd 2+ mixture significantly inhibited the biomass growth and affected the photosynthetic pigments contents in leaves. The increases of lipid peroxidation and catalase, peroxidase activity were also observed under the co-exposure experiments. The mixture toxicity of [C 4 mim] + and Cd 2+ to ryegrass growth showed an additive effect predicted by concentration addition and independent action. [C 4 mim] + uptake and acropetal translocation by ryegrass were significantly inhibited with dosing Cd 2+ . In contrast, [C 4 mim] + had no obvious effect on Cd 2+ uptake by ryegrass, while enhanced Cd 2+ translocation from roots to shoots occurred with increasing [C 4 mim] + dosages. These results indicate that the co-contamination of ionic liquids and heavy metals would affect their fates during phytoremediation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Extracellular DNA (eDNA), which is derived from lysis or secretion of cells, is ubiquitous in various environments and crucial for gene dissemination, bacterial metabolism, biofilm integrity, and aquatic monitoring. However, these processes are largely influenced by damage to eDNA. Photodamage to eDNA, one of the most important types of DNA damage in natural waters, thus far remains unclear. In particular, the roles of the ubiquitous dissolved organic matter (DOM) in this process have yet to be determined. In this study, eDNA photodamage, including both deoxynucleoside damage and strand breaks, proved to be significantly influenced by DOM. DOM competed with eDNA for photons to inhibit the direct photodamage of eDNA. Nevertheless, DOM was photosensitized to produce reactive oxygen species (ROS) (i.e., hydroxyl radicals (·OH) and singlet oxygen ( 1 O 2 )) to enhance the indirect photodamage of eDNA. The ·OH induced damage to four deoxynucleosides and strand breaks, and the 1 O 2 substantially enhanced deoxyguanosine damage. The presence of DOM changed the main photodamage products of deoxynucleosides, additional oxidation products induced by ROS formed besides pyrimidine dimers caused by UV. Results indicate that DOM-mediated indirect photodamage contributed significantly to eDNA photodamage in most water bodies. This study revealed the previously unrecognized crucial role of DOM in the decay of eDNA in waters.

Fish-associated antibiotic resistance genes (ARGs) have attracted increasing attention due to their potential risks to human beings via the food chain. However, data are scarce regarding the antibiotic resistance in fish themselves. Herein, the antibiotic resistance genes (ARGs) were assessed in the gut of four major Chinese freshwater carp (i.e., silver carp, grass carp, bighead carp, and crucian carp) from food retail markets. Results show that the abundances of target ARGs (e.g., tetA, tetO, tetQ, tetW, sulI, sulII, and bla TEM-1 ) and class 1 integrase (intI1) were in the range 9.4 × 10 -6 - 1.6 × 10 -1 and 6.7 × 10 -5 - 5.2 × 10 -2 gene copies per 16S rRNA gene, respectively. The sulI, sulII, and tetQ strongly correlated with silver and mercury resistance genes (e.g., silE and merR). The microbial taxa of fish gut could be partly separated among retail markets based on the PCA analysis. About 15.0% of the OTUs in fish gut were shared and 74.5% of the shared OTUs were identified as Acidobacteria, Bacteroidetes, Chloroflexi, Cyanobacteria, Firmicutes, and Proteobacteria. These phyla may constitute the core microbiota in the guts of the four Chinese freshwater carp. The possible ARG hosts were revealed based on the network analysis, and the presence of pathogen-associated resistant genera in fish gut highlights the need to fully understand their potential human health risks., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

An increasing amount of attention has been given to antimicrobial resistance in the environment because of its substantial threat to human health. The effluent from municipal wastewater treatment plants has been regarded as one of the important sources for the spread of antibiotic resistance genes (ARGs). However, conventional disinfection techniques fail to effectively remove ARGs from effluents. In this work, in situ synthesized hydrated manganese oxide (HMO) coupled with permanganate was applied for the first time in ARG removal from the effluent of wastewater treatment plants. The results show that five ARGs ( sul I, sul II, tet Q, tet O, and tet W) as well as the int I1 and 16S rRNA genes had removal efficiencies of 2.46-4.23 logs, which were significantly higher than those obtained by using these reagents individually. This implied that there was a synergistic effect between permanganate and HMO toward the removal of ARGs. Moreover, the contributions of HMO coagulation and permanganate oxidation to ARG removal were semiquantitatively studied, which demonstrated that destruction of the microbial cells by oxidation and removal of the extracellular ARGs released by coagulation were the two main processes in this system. The results of this study provide an alternative method for ARG removal from the effluent of wastewater treatment plants with high efficiencies to control the spreading of ARGs.

Three-dimensional electrochemical reactor (3DER) is a highly efficient technology for refractory wastewater treatment. Particle electrodes filled between anode and cathode are the core units of 3DER, determining the treatment efficiency of wastewater. However, particle electrodes deactivation due to catalytic sites coverage seriously impedes the continuous operation of 3DER. In this work, granular sludge carbon (GSC) particle electrodes being resistant to deactivation are fabricated by pyrolyzing the mixture of waste sludge, polymethyl methacrylate (PMMA), and copper tailings, whose performances are evaluated by degrading rhodamine B (RhB) wastewater in a continuous-flow 3DER. Results indicate that hierarchical-pore structure comprising macro-, meso-, and micropores is developed in GSC-10-CTs by doping 10 g PMMA and 5 g copper tailings into 100 g waste sludge. PMMA contributes to construct macropores, which is essential for the mass transfer of RhB into GSC particle electrodes of centimeter-size. Copper tailings promote the formation of meso- and micro-pores in GSCs, as well as improving the electrochemical properties. Consequently, GSC-10-CTs packed 3DER exhibits the highest removal efficiency and lowest energy consumption for RhB treatment. In addition, the compressive strength of GSC-10-CTs is enhanced by copper tails, that is crucial to fill into 3DER as particle electrodes. The high-efficient and cost-effective GSC-10-CTs fabricated by waste materials have the potential of substituting commercial granular activated carbon catalysts in the future, consequently promoting the application of 3DER in wastewater treatment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Extracellular antibiotic resistance genes (eARGs) contribute to antibiotic resistance, and as such, they pose a serious threat to human health. eARGs, regarded as an emerging contaminant, have been widely detected in various bodies of water. Degradation greatly weakens their distribution potential and environmental risks. Dissolved organic matter (DOM), mainly consisted of humic substances, carbohydrates, and organic acids, is ubiquitous in diverse waters and significantly affects the degradation of coexisting contaminants. However, the photodegradation of eARGs in natural water, especially regarding the roles of DOM in this process, remains unknown. Herein, we investigated the eARGs photodegradation in waters with and without DOM. Illumination has been found to effectively photodegrade eARGs, and this process was significantly enhanced by DOM. Further experiments revealed that photosensitization of DOM produced hydroxyl radicals ( • OH) to enhance plasmid strand breaks and produced singlet oxygen ( 1 O 2 ) to accelerate the guanine oxidation, which in turn promoted the photodegradation of plasmid-carried eARGs. Transformation assays indicated that eARGs transformation efficiencies were reduced after their photodegradation. The presence of DOM accelerated the decreases of eARGs transformation efficiencies under illumination. DOM concentration and some ions (e.g., NO 3 - , NO 2 - , HCO 3 - , Br - , and Fe 3+ ) affected • OH or 1 O 2 levels, further influencing the photodegradation of eARGs. Overall, eARGs photodegradation in aquatic environments is a crucial process both in the reduction of eARGs concentrations and in transformation efficiencies. This work facilitated us to better understand the fate of eARGs in waters.

The aerobic granular sludge with larger size and more compact spherical structure generally shows excellent performance in antibiotic removal, yet little is known about the long-term effect of environmentally-relevant concentration (μg/L) of antibiotics on the proliferation of antibiotic resistance genes (ARGs) and microbial community in aerobic granules. Herein, a sequencing batch reactor (SBR) was set up with dosing different concentrations (0-500 μg/L) of tetracycline to investigate its influences on microbial communities and ARG levels in aerobic granular sludge. Results show that the bioreactor could effectively remove chemical oxygen demand (COD), nitrogen, and tetracycline during the long-term operation. The quantitative polymerase chain reaction (qPCR) analysis shows that tetracycline at μg/L level could greatly enhance the absolute and relative abundances of tetA, sulII, and bla TEM-1 in the effluent and aerobic granules, indicating tetracycline could serve as a selection pressure on the development of ARGs corresponding to different types of antibiotics in aerobic granules. Pearson's correlation analysis also implies that sulII and bla TEM-1 were correlated strongly with tetA. Moreover, the presence of tetracycline altered the microbial communities and diversity of the effluent and aerobic granules in the bioreactor. These findings would advance our understanding of the proliferation and development of ARGs in aerobic granules under tetracycline pressure and serve as a foundation to guide the application of aerobic granular sludge for treatment of antibiotic-containing wastewater., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Antibiotic resistance genes (ARGs) have been regarded as an emerging pollutant in municipal wastewater treatment plant (WWTP) effluents due to their potential risk to human health and ecological safety when reused for landscape and irrigation. Conventional wastewater treatment processes generally fail to effectively reduce ARGs, especially extracellular ARGs (eARGs), which are persistent in the environment and play an important role in horizontal gene transfer via transformation. Herein, an integrated process of pre-coagulation and microfiltration was developed for removal of ARGs, especially eARGs, from wastewater effluent. Results show that the integrated process could effectively reduce the absolute abundances of total ARGs (tARGs) (>2.9 logs) and eARGs (>5.2 logs) from the effluent. The excellent performance could be mainly attributed to the capture of antibiotic resistant bacteria (ARB) and eARGs by pre-coagulation and co-rejection during subsequent microfiltration. Moreover, the integrated process exhibited a good performance on removing common pollutants (e.g., dissolved organic carbon and phosphate) from the effluent to improve water quality. Besides, the integrated process also greatly reduced membrane fouling compared with microfiltration. These findings suggest that the integrated process of pre-coagulation and microfiltration is a promising advanced wastewater treatment technology for ARGs (especially eARGs) removal from WWTP effluents to ensure water reuse security., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The reductive capacity of microbial extracellular polymeric substances (EPS) plays important roles in environmental processes involved in heavy metal detoxification and organic contaminant degradation. However, the crucial parameter to evaluate the reductive capacity of EPS, electron donating capacity (EDC) lacks a quantitative approach. In this study, a novel mediated electrochemical oxidation (MEO) method was developed to investigate the EDCs of microbial EPS extracted from Shewanella oneidensis MR-1 (S. oneidensis MR-1), Escherichia coli (E. coli) and activated sludge. The results indicate that the MEO approach rapidly and accurately quantifies the EDCs of microbial EPS. S. oneidensis MR-1 EPS possessed the highest EDC value ascribed to their specific redox proteins components. EDCs of S. oneidensis MR-1 EPS were dependent on measurement conditions and increased with growing solution pH and applied potential. EDCs of S. oneidensis MR-1 EPS were depleted gradually during the redox reaction with irreversible oxidation of EPS. The reductive property of microbial EPS was accurately evaluated by quantifying the EDCs of EPS using the MEO approach, as well as their potential in environmental remediation., (Copyright © 2019 Elsevier B.V. All rights reserved.)