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The application of manganese-oxidizing bacteria (MnOB) to produce manganese oxides (MnOx) has been widely studied, but often overlooking the concurrent formation of MnCO 3 . In this study, we found Ca 2+ plays a crucial role in controlling Mn(II) removal in the bacterium Aurantimonas sp. HBX-1. Under conditions with 6.8 mM Ca 2+ and without adding Ca 2+ , 100 μM Mn(II) was removed by 96.96 % and 38.28 % within 8 days, respectively. X-ray photoelectron spectroscopy (XPS) showed that adding Ca 2+ increased the average oxidation state (AOS) of the solid products from 2.05 to 2.37. X-ray absorption fine structure (XAFS) analysis revealed the product proportions as follows: under Ca 2+ -supplemented condition, the ratio of MnOx (1 < x ≤ 2) to MnCO₃ was 52 % to 28.1 %, while under Ca 2+ -free condition, the ratio shifted to 4.6 % for MnOx (1 < x ≤ 2) and 55.2 % for MnCO₃. Urease activity assay and proteomic analysis confirmed the expression of urease and carbonic anhydrase, leading to the formation of MnCO 3 . Additionally, animal heme peroxidase (AHP) in strain HBX-1 was found to be responsible for Mn(II) oxidation through superoxide production, with Ca 2+ addition promoting its expression level. Given the widespread presence of Ca 2+ in wastewater, its potential impact on the biogeochemical Mn(II) cycle driven by bacteria should be reconsidered., 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.)

Microbial degradation of polyethylene (PE) offers a promising solution to plastic pollution in the marine environment, but research in this field is limited. In this study, we isolated a novel marine strain of Pseudalkalibacillus sp. MQ-1 that can degrade PE. Scanning electron microscopy and water contact angle results showed that MQ-1 could adhere to PE films and render them hydrophilic. Analyses using X-ray diffraction, fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy showed a decrease in relative crystallinity, the appearance of new functional groups and an increase in the oxygen-to‑carbon ratio of the PE films, making them more susceptible to degradation. The results of gel permeation chromatography and liquid chromatography-mass spectrometry indicated the depolymerization of the long PE chains, with the detection of an intermediate, decanediol. Furthermore, genome sequencing was employed to investigate the underlying mechanisms of PE degradation. The results of genome sequencing analysis identified the genes associated with PE degradation, including cytochrome P450, alcohol dehydrogenase, and aldehyde dehydrogenase involved in the oxidative reaction, monooxygenase related to ester bond formation, and esterase associated with ester bond cleavage. In addition, enzymes involved in fatty acid metabolism and intracellular transport have been identified, collectively providing insights into the metabolic pathway of PE degradation., 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.)

Extreme temperature variations are a problem that must be faced in the practical application of microbial fuel cells (MFCs), but MFCs are not extensively described for low and even freezing temperatures. This study assessed the effect of low-temperature shock on the power generation performance and microbial community structure of MFCs. Two scales of MFCs, the small (mL-MFC) and the large (L-MFC), were constructed in the laboratory and their performance was evaluated before and after freezing at -18 °C. The experimental results demonstrate that both MFCs were capable of rapidly restoring their voltage to the previous level after thawing. For the mL-MFC (rGO/Ag), the power density recovered from 194.30 ± 10.84 mW/m 2 to 195.57 ± 4.02 mW/m 2 after thawing. For L-MFC (carbon felt electrodes), the power density increased significantly from the initial 1.79 mW/m 2 to 173.90 mW/m 2 after thawing, but the performance degradation problem after reactor amplification still needs to be solved. The sediment microbial fuel cell (SMFC) was successfully constructed and operated in a natural outdoor environment to maintain high voltage output after the period of frost. Microbial analysis indicated after the frost period, psychrotolerant microorganisms enriched on the anode, such as Flavobacterium and Psychrobacter, while the relative abundance of anaerobic methanogenic bacterium decreased. Overall, freeze-thaw operations had a non-negative impact on the performance of MFCs and provided some references for their practical applications., 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.)

8:2 fluorotelomer sulfonic acid (8:2 FTSA) has been commonly detected in the environment, but its behaviors in plants are not sufficiently known. Here, the regular and multi-omics analyses were used to comprehensively investigate the bioaccumulation, biotransformation, and toxicity of 8:2 FTSA in Arabidopsis thaliana. Our results demonstrated that 8:2 FTSA was taken up by A. thaliana roots and translocated to leaves, stems, flowers, and seeds. 8:2 FTSA could be successfully biotransformed to several intermediates and stable perfluorocarboxylic acids (PFCAs) catalyzed by plant enzymes. The plant revealed significant growth inhibition and oxidative damage under 8:2 FTSA exposure. Metabolomics analysis showed that 8:2 FTSA affected the porphyrin and secondary metabolisms, resulting in the promotion of plant photosynthesis and antioxidant capacity. Transcriptomic analysis indicated that differentially expressed genes (DEGs) were related to transformation and transport processes. Integrative transcriptomic and metabolomic analysis revealed that DEGs and differentially expressed metabolites (DEMs) in plants were predominantly enriched in the carbohydrate metabolism, amino acid metabolism, and lipid metabolism pathways, resulting in greater energy consumption, generation of more nonenzymatic antioxidants, alteration of the cellular membrane composition, and inhibition of plant development. This study provides the first insights into the molecular mechanisms of 8:2 FTSA stress response in plants., 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.)

Biogenic manganese oxides (BioMnO x ) produced by Mn(II)-oxidizing bacteria (MnOB) have garnered considerable attention for their exceptional adsorption and oxidation capabilities. However, previous studies have predominantly focused on the role of BioMnOx, neglecting substantial investigation into MnOB themselves. Meanwhile, whether the xenobiotics could support the growth of MnOB as the sole carbon source remains uncertain. In this study, we isolated a strain termed Pseudomonas sp. AN-1, capable of utilizing phenol as the sole carbon source. The degradation of phenol took precedence over the accumulation of BioMnOx. In the presence of 100 mg L -1 phenol and 100 µM Mn(II), phenol was entirely degraded within 20 h, while Mn(II) was completely oxidized within 30 h. However, at the higher phenol concentration (500 mg L -1 ), phenol degradation reduced to 32% and Mn(II) oxidation did not appear to occur. TOC determination confirmed the ability of strain AN-1 to mineralize phenol. Based on the genomic and proteomics studies, the Mn(II) oxidation and phenol mineralization mechanism of strain AN-1 was further confirmed. Proteome analysis revealed down-regulation of proteins associated with Mn(II) oxidation, including MnxG and McoA, with increasing phenol concentration. Notably, this study observed for the first time that the expression of Mn(II) oxidation proteins is modulated by the concentration of carbon sources. This work provides new insight into the interaction between xenobiotics and MnOB, thus revealing the complexity of biogeochemical cycles of Mn and C., 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.)

Lewis acids of solid catalysts have been featured for a pivotal role in promoting various reactions. Regarding the oxidation protocol to remove formaldehyde, the inherent drawback of the best-studied MnO 2 materials in acidic sites has eventually caused deficiency of active hydroxyls to sustain low-temperature activity. Herein, the cryptomelane-type MnO 2 was targeted and it was tuned via incorporation of Zr metal, exhibiting great advances in not only the complete HCHO-to-CO 2 degradation but also cycling performance. Zr species were existent in doping state in the MnO 2 lattice, rendering lower crystallinity and breaking the regular growth of MnO 2 crystallites, which thereby tripled surface area and created larger volume of smaller mesopores. Meantime, the local electronic properties of Mn atoms were also changed by Zr doping, i.e., more low-valence Mn species were formed due to the electron transfer from Zr to Mn. The results of infrared studies demonstrate the higher possession of Lewis acid sites on ZrMn, and this high degree of electrophilic agents favored the production of hydroxyl species. Furthermore, the reactivity of surface hydroxyls, as investigated by CO temperature programmed reduction and temperature programmed desorption of adsorbed O 2 , was obviously improved as well after Zr modification. It is speculated jointly with the characterizations of the post-reaction catalysts that the accelerated production of active hydroxyls helped rapidly convert formaldehyde into key intermediate-formate, which was then degraded into CO 2 , avoiding the side reaction path with undesired intermediate-hydrocarbonate-over the pristine MnO 2 , where active sites were blocked and formaldehyde oxidation was inhibited. Additionally, Zr decoration could stabilize Lewis acidity to be more resistant to heat degeneration, and this merit brought about advantageous thermal recyclability for cycled application., 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 Inc. All rights reserved.)

Marine microorganisms have been reported to degrade microplastics. However, the degradation mechanisms are still poorly understood. In this study, a bacterium Roseibium aggregatum ZY-1 was isolated from seawater, which can degrade poly(butylene adipate-co-terephthalate) (PBAT). The PBAT-PLA(polylactic acid, PLA) films, before and after degradation, were characterized by scanning electron microscope (SEM) and Fourier transform infrared spectrometer (FTIR), the weight loss rate and water contact angle were measured. The results indicate that ZY-1 colonized on PBAT-PLA film, changed the functional groups and decreased water contact angle of PBAT-PLA film. Moreover, liquid chromatography mass spectrometry (LC-MS) analysis reveales that PBAT was degraded into its oligomers (TB, BTB) and monomers (T, A) during 10 days, and adipic acid (A) could be used as a sole carbon source. The whole genome sequencing analyses illustrate the mechanisms and enzymes such as PETase, carboxylesterases, arylesterase (PpEst) and genes like pobA, pcaBCDFGHIJKT, dcaAEIJK, paaGHJ involved in PBAT degradation. Therefore, the R. aggregatum ZY-1 will be a promising candidate of PBAT degradation., 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.)

N,N-dimethylformamide (DMF) is widely used in various industries, but its direct release into water poses high risks to human beings. Although a lot of DMF-degrading bacteria has been isolated, limited studies focus on the degradation preference among DMF and its analogues. In this study, an efficient DMF mineralization bacterium designated Aminobacter ciceronei DMFA1 was isolated from marine sediment. When exposed to a 0.2% DMF (∼1900 mg/L), strain DMFA1 exhibited a degradation efficiency of 100% within 4 days. The observed growth using formamide as the sole carbon source implied the possible DMF degradation pathway of strain DMFA1. Meanwhile,the strain DMFA1 possesses a broad-spectrum substrate degradation, which could effectively degraded 0.2% N,N-dimethylacetamide (DMAC) and N-methylformamide (NMF). Genomic analysis further confirmed the supposed pathway through annotating the genes encoding N, N-dimethylformamidase (DMFase), formamidase, and formate dehydrogenase. The existence of sole DMFase indicating its substrate specificity controlled the preference of DMAc of strain DMFA1. By integrating multiple sequence alignment, homology modeling and molecular docking, the preference of the DMFase in strain DMFA1 towards DMAc are related to: 1) Mutations in key active site residues; 2) the absence of small subunit; and 3) no energy barrier for substrates entering the active site., 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 Inc. All rights reserved.)

Soil microbes play vital roles in estuarine wetlands. Understanding the soil bacterial community structure and function profiles is essential to reveal the ecological functions of microbes in estuarine wetlands. Herein, soil samples were collected from Liao River estuarine wetland, Northeast China, along the river to the estuarine mouth, and soil bacterial communities were explored. Results showed that soil physiochemical properties, bacterial community structure and functions exhibited distinct variations influenced by geographical location. Bacterial phyla in soils were dominated by Proteobacteria and Bacteroidetes, while Gillisia and Woeseia were the predominant genera. Soil pH, electrical conductivity and nitrogen-related nutrients were the important factors affecting bacterial community structure. Based on PICRUSt prediction, the genes related to metabolism of nitrogen, sulfur and methane showed spatial distribution patterns, and the abundances of most biomarker genes increased as the distance from estuarine mouth extended. These findings could enrich the understanding of soil microbiome in estuarine wetlands., 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.)

Although 6:2 fluorotelomer carboxylic acid (6:2 FTCA), which is one of the most popular substitutes for perfluorooctanoic acid (PFOA), has been widely distributed in environments, little is known about its biotransformation mechanism and phytotoxic effects in plants. Here, we showed that 6:2 FTCA could be taken up by pumpkin (Cucurbita maxima L.) roots from exposure solution and acropetally translocated to shoots. Biotransformation of 6:2 FTCA to different carbon chain perfluorocarboxylic acid (PFCA) metabolites (C2-C7) via α-and β-oxidation in pumpkin was observed, and perfluorohexanoic acid (PFHxA) was the major transformation product. The results of enzyme assays, enzyme inhibition experiments and gene expression analysis indicated that cytochrome P450 (CYP450), glutathione-S-transferase (GST) and ATP-binding cassette (ABC) transporters were involved in the metabolism of 6:2 FTCA in pumpkin. Plant-associated rhizobacteria and endophyte also contributed to 6:2 FTCA degradation through β-oxidation. The chlorophyll (Chl) content and genes involved in photosynthesis were significantly improved by 6:2 FTCA. The reductions of antioxidant and metabolic enzyme activities reflected the antioxidant defense system and detoxification system of pumpkin were both damaged, which were further confirmed by the down-regulating associated genes encoding phenylpropanoid biosynthesis, endoplasmic reticulum-related proteins, ascorbate-glutathione cycle and ABC transporters. This study is helpful to understand the environmental behaviors and toxicological molecular mechanisms of 6:2 FTCA in plants., 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.)

Tellurium (Te) is a rare element within the chalcogen group, and its biogeochemical cycle has been studied extensively. Tellurite (Te(IV)) is the most soluble Te species and is highly toxic to organisms. Chemical or biological Te(IV) reduction to elemental tellurium (Te 0 ) is generally considered an effective detoxification route for Te(IV)-containing wastewater. This study unveils a previously unnoticed Te 0 oxidation process mediated by the manganese-oxidizing bacterium Bacillus sp. FF-1. This bacterium, which exhibits both Mn(II)-oxidizing and Te(IV)-reducing abilities, can produce manganese oxides (BioMnO x ) and Te 0 (BioTe 0 ) when exposed to Mn(II) and Te(IV), respectively. When 5 mM Mn(II) was added after incubating 0.1 mM or 1 mM Te(IV) with strain FF-1 for 16 h, BioTe 0 was certainly re-oxidized to Te(IV) by BioMnOx. Chemogenic and exogenous biogenic Te 0 can also be oxidized by BioMnOx, although at different rates. This study highlights a new transformation process of tellurium species mediated by manganese-oxidizing bacteria, revealing that the environmental fate and ecological risks of Te 0 need to be re-evaluated., 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 Inc.)

Oxide supported noble metals are extensively investigated for ambient formaldehyde oxidation, and the Ag-CoO x complex is one promising combination in terms of cost and activity. Further, we previously observed that cooperating Ag with Li  +  greatly boosted formaldehyde degradation on CoO x . Yet, there is still room for improvement in removal efficiency, mineralization capacity and resistance to severe conditions. These objectives could be realized via strategically formulating the Li + sites of Li-CoO x composite in this sister study. Three samples with Li  +  ---Co 3+ -O 2- connections (L-CO), spinel Li + (LCO-S) and layered Li + (LCO-L) were obtained at low (300 °C), moderate (500 °C) and high (700 °C) temperatures, respectively. The specific Li + positions and componential interaction were demonstrated by Hyperspectral imaging (HSI), XRD, SEM, TEM, HAADF mapping, UV-vis DRS and XPS. Moreover, the effect of reactive oxygen exposure on catalytic oxidation of formaldehyde (330-350 mg/m 3 ) was disclosed through CO-TPR and O 2 -TPD. Compared with the LCO-S and LCO-L, L-CO exhibited dominant formaldehyde degradation due to the larger content of surface oxygen. After Ag decoration, the Li + ---Co 3+ -O 2- connections uniquely caused a strong binding of Ag species with catalyst host, which boosted the amount of reactive oxygen and finally resulted in an even higher elimination of ∼73% (CO 2 yield = ∼21%), 47% higher than that of the L-CO (CO 2 yield = ∼6%). But in contrast, the Ag@LCO-S only achieved ∼53% removal (CO 2 yield = ∼9%) and Ag modification was powerless in altering the inertness of LCO-L, demonstrating that the chemical environment of alkali metal is crucial to effectively tuning the catalyst activity. The advantage of Ag@L-CO in formaldehyde depollution was further reflected from its much better resistance to moisture and aromatic compound omnipresent in indoor air. For the first time, this study extended the understanding of the alkali-metal-promoted formaldehyde oxidation reaction to an in-depth level., 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 Inc. All rights reserved.)

8:2 fluorotelomer carboxylic acid (8:2 FTCA), an important precursor of perfluorocarboxylic acids (PFCAs), is widely detected in environment and biotas. Hydroponic exposures were conducted to investigate the accumulation and metabolism of 8:2 FTCA in wheat (Triticum aestivum L.) and pumpkin (Cucurbita maxima L.). Endophytic and rhizospheric microorganisms co-existing with the plants were isolated to investigate their contributions to degrade 8:2 FTCA. Wheat and pumpkin roots could take up 8:2 FTCA efficiently with the root concentration factor (RCF) as 5.78 and 8.93, respectively. 8:2 FTCA could be biotransformed to 8:2 fluorotelomer unsaturated carboxylic acid (8:2 FTUCA), 7:3 fluorotelomer carboxylic acid (7:3 FTCA), and seven PFCAs with 2-8 carbon chain length in plant roots and shoots. Cytochromes P450 (CYP450) and glutathione-S-transferase (GST) activities in plants were significantly increased, while flavin-dependent monooxygenases (FMOs) activities were not changed, suggesting that CYP 450 and GST were involved in the transformation of 8:2 FTCA in plant tissues. Twelve 8:2 FTCA-degrading endophytic (8 strains) and rhizospheric (4 strains) bacterial strains were isolated from root interior, shoot interior and rhizosphere of plants, respectively. These bacteria were identified as Klebsiella sp. based on the morphology and 16S rDNA sequence, and they could biodegrade 8:2 FTCA to intermediates and stable PFCAs., 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.)

To obtain a versatile formaldehyde oxidation material, simultaneously increasing the oxidative ability, recyclability and deactivation repellence (e.g., enduring the interference from moisture and aromatic compound omnipresent in indoor air) is of great significance. Herein, the above properties of α-MnO 2 were synchronously updated via one step treatment in oxalic acid (H 2 C 2 O 4 ), and an in-depth understanding of the surface properties-performance relationship was provided by systematic characterizations and designed experiments. Compared with the pristine sample, XPS, ESR, O 2 -TPD, CO-TPR and pyridine-IR reveal that H 2 C 2 O 4 created substantial Mn 3+ species on surface, exposing a higher coverage of oxygen vacancies that actively participated in the dissociative activation of gas-phase O 2 into reactive chemically adsorbed oxygen (O C ), and the abundant Lewis acid sites further enabled the effective O 2 activation process. The large amount of oxygen O C promoted the HCHO-to-CO 2 conversion and inhibited the accumulation of formate that required a high temperature of 170 °C to be eliminated, thus conspicuously improving the α-MnO 2 's thermal recovery. The combined H 2 O-TPD, H 2 O-preadsorbed CO-TPR, C 6 H 6 -TPD and C 6 H 6 -preadsorbed CO-TPR investigations shed light on the H 2 C 2 O 4 -induced water and benzene resistance. The notably weakened water and benzene binding strength with the H 2 C 2 O 4 -modified surface together with the unrestrained oxygen O C accounted for the outstanding anti-deactivation performance., 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 © 2022 Elsevier Inc. All rights reserved.)

Single or cooperative incorporation of Ce and Sn elements into α-MnO 2 parent were tried to update the catalytic benzene oxidation performance, and the successive modification via Ce doping and Sn deposition was demonstrated to be a promising methodology to offer high mineralization and avoid moisture-aroused inactivation. Ce doping caused lattice distortion, increased Mn 3+ content to 2.7 times that of the pristine MnO 2 and weakened Mn-O bonds due to electron transfer from Ce 3+ to lattice oxygen, thus facilizing oxygen vacancy formation. Further, Sn deposition on CeMn substrate induced strong metal support interaction (SMSI) due to the core-shell like structure of Sn@CeMn, which promoted the construction of active oxygen vacancies to an even larger extent (1.2 and 2.5 times that of the CeMn and pristine MnO 2 , respectively). The thus-formed larger amount of reactive oxygen species rendered the Sn@CeMn simultaneously with high CO 2 yield and low CO production. Also benefited from the SMSI effect, the Sn@CeMn's ability to continuously activate O 2 and H 2 O into reactive oxygen species (e.g.,·OH radicals) was enhanced, which could offset the negativity caused by water vapor, thereby keeping > 95% removal during 5.5 h water switch on/off investigation at 200 °C. Reaction pathways were uncovered with designed experimentations., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Under the background of indoor air formaldehyde decontamination, a freestanding ultra-light assembly was fabricated via ice-templating approach starting from MnO 2 nanoparticles and environmentally benign agar powder. The 3D composite of agar and MnO 2 (AM-3D) was comparatively studied with powdered counterparts (including pure MnO 2 and mixture of agar and MnO 2 ) and the 3D-structured agar for formaldehyde oxidation, and their physicochemical properties were examined with XRD, ATR, SEM, XPS, isothermal N 2 adsorption, ESR, Raman, CO-TPR and O 2 -TPD. For the single test of formaldehyde oxidation, the AM-3D catalyst exhibited 62.0%-67.0% removal percentage for ~400 mg/m 3 formaldehyde, which did not demonstrate significant advantage over the control samples. However, thanks to the porous 3D agar scaffold with large spatial volume that could promote a rapid gas-phase formaldehyde concentration reduction, and the strong interaction between the dispersed MnO 2 particles and agar substrate that could afford a large amount of reactive oxygen species to further oxidize the adsorbed formaldehyde, the AM-3D composite was a much better HCHO-to-CO 2 converter and possessed much more advantageous stability for repeated cycles of formaldehyde oxidation: even after ten cycles, there was still 41.7% of formaldehyde removed. Furthermore, the viable sunlight irradiation could easily restore the activity of the used AM-3D catalyst back to the level approaching that of the fresh one. Finally, reaction pathways were put forward via the infrared spectroscopic and ion chromatographic investigations on the surface intermediates of the spent materials., 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 © 2022 Elsevier B.V. All rights reserved.)

Endocrine-disrupting chemicals (EDCs) cause serious threats to human health. Five types of MnO 2 were synthesized and characterized. They exhibited different removal performances for three EDCs, i.e., estrone (E1), ethynylestradiol (EE2) and bisphenol A (BPA). Only δ-MnO 2 can completely remove E1 within 120 min at pH 3.0. Free Mn (III) was determined at the beginning of the reaction and participated in the EDCs removal process. Electron spin resonance (ESR) indicated that δ-MnO 2 could produce superoxide anions (·O 2 - ) and singlet oxygen ( 1 O 2 ) in the existence of methanol. The reactive oxygen species (ROS) quenching experiments showed 1 O 2 have certain contribution to the E1 removal by δ-MnO 2 . The source of ROS is mainly the lattice oxygen from δ-MnO 2 , and can be replenished through the layer structure destruction caused by the reaction between Mn(III) and E1. The ROS dependent EDCs removal by δ-MnO 2 leads to a deep understanding on this well-known oxidant., 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 B.V. All rights reserved.)

6:2 fluorotelomer sulfonic acid (6:2 FTSA) is a novel perfluorooctane sulfonate (PFOS) alternative used globally in aqueous film forming foams (AFFFs). Although 6:2 FTSA has been recently detected in the environment, its fate in terrestrial invertebrates remains unclear. The uptake, elimination and biotransformation of 6:2 FTSA in earthworms (Eisenia fetida) were investigated after in vivo and in vitro exposure. 6:2 FTSA could be biodegraded by microorganisms in soil to trifluoroacetic acid (TFA), perfluoropropionic acid (PFPrA), perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA) and perfluorohexanoic acid (PFHxA). The uptake rate constant (k u ) and biota-to-soil accumulation factor (BSAF) of 6:2 FTSA in earthworms were 0.185 g oc /g ww /d and 0.685 g oc /g ww , respectively, indicating high bioaccumulative ability in earthworms. Five terminal perfluorocarboxylic acids (PFCAs) metabolites, including TFA, PFPrA, PFBA, PFPeA and PFHxA were observed in both in vivo and in vitro exposure tests, with TFA as the predominant metabolite. However, no perfluoroheptanoic acid (PFHpA) was observed in the present study. The elimination rate constants (k e ) increased in the order: 6:2 FTSA (0.057/d) < TFA (0.058/d) < PFPrA (0.071/d) < PFBA (0.084/d) < PFHxA (0.182/d) < PFPeA (0.193/d). Biodegradation of 6:2 FTSA in the earthworm homogenates, cytolchrome P450 (CYP450) enzyme solutions and glutathione-s-transferase (GST) enzyme solutions fitted well with the first order kinetics. The biotransformation rate constants (k) were in the following order: homogenates (0.012/h) > CYP450 (0.009/h) > GST (0.007/h), implying that CYP450 and GST were involved in biotransformation of 6:2 FTSA in earthworms. This study provides important theoretical evidence for the fate of 6:2 FTSA in earthworms., Competing Interests: Declaration of competing interest The authors declare that there are no conflicts of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Estrogens distribute widely in the environment as endocrine-disrupting chemicals (EDCs), which have to be monitored to evaluate their environmental impact. Aim to improve the analytical throughput of liquid chromatography-high resolution mass spectrometry (LC-HRMS), a quadruplex stable isotope dansylation method was developed, with which three real samples could be quantitatively analyzed in one injection. As the estrogens were at trace level in complex matrices, magnetic solid-phase extraction (MSPE) was applied to enrich these analytes and remove the interfaces. By integrating MSPE and quadruplex stable isotope dansylation, a solid-phase quadruplex labeling method was developed for the LC-HRMS analysis of estrogen analogues. For the tested seven estrogens, the developed method showed low detection limits (0.1-0.5 ng/L for pond water and 0.01-0.05 μg/kg for poultry manure), good precision (RSD < 5.5%) and accuracy (96.8-108.3%). The method was applied in the determination of estrogens in environmental samples, and the results revealed that all the tested estrogens were present in the estuary water (unquantifiable to 71.2 ng/L) and chicken manure (undetectable to 25.43 μg/kg)., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A simple magnetization method was developed for the preparation of magnetic materials from conventional solid phase packing though coprecipitation and solvothermal approaches. And the prepared magnetic materials were used for magnetic solid phase extraction (MSPE) of biogenic amines (BAs) from beers. Furthermore, to improve the analytical throughput, a solid phase "on-situ" quadraplex isotope dimethyl labeling method was developed for the quantification of BAs by liquid chromatography-high resolution mass spectrometry (LCHRMS). Compared to conventional in-solution labeling, the "on-situ" labeling could simplify the sample preparation procedure and efficiently remove the residuals such as inorganic salts and excessive labeling reagents. The quadraplex labeling, which enabled three real samples and one internal standard sample to be analyzed simultaneously in a single LCHRMS run. For the tested 8 BAs (cadaverine, phenethylamine, spermine, spermidine, tyramine, histamine, putrescine and tryptamine), LODs of 0.02-0.05 μg/L and LOQs of 0.05-0.1 μg/L were achieved at good reproducibility (RSD of 0.5-4.6% and 2.2-7.0% for intra- and inter-day reproducibility, respectively). With this method, six beer samples were analyzed, and these 8 BAs were all detected in the range of low μg/L to 2.9 mg/L, which were lower than maximal residual level (MRL) required in the regulations of China and EU., 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.)

While N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE) is a precursor of perfluorooctane sulfonate (PFOS), its bioaccumulation, transformation and toxicological effects in earthworms (Eisenia fetida) exposed to quartz sands are poorly understood. The present study showed that except for parent EtFOSE, N-ethylperfluorooctane sulfonamide acetate (EtFOSAA), N-ethyl perfluorooctane sulfonamide (EtFOSA), perfluorooctane sulfonamide acetate (FOSAA), perfluorooctane sulfonamide (FOSA) and PFOS were detected in earthworms, with EtFOSAA as the primary biotransformation product. The biota-to-sand accumulation factor (BSAF) and uptake rate coefficient (k u ) of EtFOSE were 5.7 and 0.542/d, respectively. The elimination rate constants (k e ) decreased in the order EtFOSA (0.167/d) ∼ FOSAA (0.147/d) > FOSA (0.119/d) ∼ EtFOSAA (0.117/d) > EtFOSE (0.095/d) > PFOS (0.069/d). No significant effects were observed in malondialdehyde (MDA) contents and acetylcholinesterase (AChE) activities between EtFOSE treatments and controls. EtFOSE could cause significant accumulation of reactive oxygen species (ROS) in earthworms. Peroxidase (POD), superoxide dismutase (SOD) and catalase (CAT) were significantly activated by 41.4-74.3%, 37.2-44.4% and 32.4-52.3% from day 4-10, respectively, while 8-Hydroxy-2-deoxyguanosine (8-OHdG) levels were elevated by 47.7-70.3% from day 8-10, demonstrating that EtFOSE induced oxidative stress and oxidative DNA damage in earthworms. Significant increase of glutathione-S-transferase (GST) with 41.6-62.8% activation (8-10 d) gave indirect evidence on the conjugation of EtFOSE or its corresponding metabolites during phase II of detoxication. This study provides important information on the fate and potential risks of EtFOSE to terrestrial invertebrates., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Perfluorooctane sulfonamide (FOSA) is an important perfluorooctane sulfonate (PFOS) precursor used for commercial applications. In order to investigate the transformation and responses of selected antioxidant and degradation enzymes of FOSA in the plants, in vivo exposure of soybean (Glycine max L. Merrill) and pumpkin (Cucurbita maxima L.) were conducted in the solution-plant microcosms. FOSA was readily taken up by soybean and pumpkin roots and translocated to shoots, and metabolized to PFOS, perfluorohexane sulfonate (PFHxS) and perfluorobutane sulfonate (PFBS). Although morphological and biomass effects were not visible, significant changes in oxidative stress response were observed except for thiobarbituric acid reactive substances (TBARS). Superoxide dismutase (SOD) and peroxidase (POD) activities were significantly increased by 19.2-30.8% and 19.2-20.7% in soybean (8-12 d) respectively, and increased by 39.2-92.8% and 21.1-37.6% in pumpkin (3-12 d) respectively, suggesting an activation of the antioxidant defense system in the plants exposed to FOSA. Glutathione-S-transferase (GST) activities were decreased in soybean (2-12 d) with 9.0-36.1% inhibition and increased in pumpkin (3-12 d) with 22.5-47.3% activation respectively; cytochrome P450 (CYP450) activities were increased markedly in soybean and pumpkin with 13.2-53.6% and 26.7-50.2% activation respectively, giving indirect evidences on the involvement of CYP450 and GST in degradation of FOSA in plants., (Copyright © 2018 Elsevier Inc. All rights reserved.)