Can xenobiotics support the growth of Mn(II)-oxidizing bacteria (MnOB)? A case of phenol-utilizing bacteria Pseudomonas sp. AN-1.

Biogenic manganese oxides (BioMnOx) 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.

Isolation, characteristics, and poly(butylene adipate-co-terephthalate) (PBAT) degradation mechanism of a marine bacteria Roseibium aggregatum ZY-1.

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.

Surficial engineering of active hydroxyls for ambient formaldehyde oxidation via enhanced Lewis acidity over Zr-doped cryptomelane materials.

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 MnO2 materials in acidic sites has eventually caused deficiency of active hydroxyls to sustain low-temperature activity. Herein, the cryptomelane-type MnO2 was targeted and it was tuned via incorporation of Zr metal, exhibiting great advances in not only the complete HCHO-to-CO2 degradation but also cycling performance. Zr species were existent in doping state in the MnO2 lattice, rendering lower crystallinity and breaking the regular growth of MnO2 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 O2, 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 CO2, avoiding the side reaction path with undesired intermediate-hydrocarbonate-over the pristine MnO2, 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.

DMF mineralization and substrate specificity mechanism of Aminobacter ciceronei DMFA1.

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.

Effect of bioturbation of the mitten crab on distribution of tire wear particles and their combined effect on sediment ecosystem.

Tire wear particles (TWPs) are a major source of environmental microplastic pollution which gradually settle and accumulate in sediments after entering the aquatic environment, which can affect the behaviors of benthic organisms. Bioturbation of benthic species could affect the fate, impacts and potential risks of TWPs by altering the properties and structure of sediments. Therefore, in this study, the effect of TWPs on the burrowing activity of Chinese mitten crab (Eriocheir sinensis) was investigated. In addition, the effects of crab bioturbation on the distribution of TWPs and their additives were studied. The combined effects of TWPs and crab bioturbation on the microbial communities in the sediments were also explored. The results of this study showed that both TWPs and the leachate significantly inhibited the burrowing activity of crabs. TWPs in the surface layer of sediments were re-distributed by crab bioturbation and enriched mainly in the sediments near the burrow walls. Meanwhile, the heavy metals (i.e., Zn, Ca, Mg, Ba and Al) used as additives during the tire production in the burrow walls significantly increased as the accumulation of TWPs near burrow walls. In this study, TWP exposure decreased the bacterial diversity and abundance, as well as the functional genes related to carbon and nitrogen cycling process, but crab bioturbation increased them in the sediments of burrow walls by constructing a unique habitat. However, after TWPs entering into burrows, they were significantly decreased in the sediments near the burrow walls like the effects of TWPs, suggesting the negative effects of TWPs could play a dominant role in this combined system. Overall, this study is important for evaluating the distribution and effects of TWP pollution in the sediment ecosystem under biological factors such as bioturbation.

The cryptic step in the biogeochemical tellurium (Te) cycle: Indirect elementary Te oxidation mediated by manganese-oxidizing bacteria Bacillus sp. FF-1.

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 (Te0) is generally considered an effective detoxification route for Te(IV)-containing wastewater. This study unveils a previously unnoticed Te0 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 (BioMnOx) and Te0 (BioTe0) 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, BioTe0 was certainly re-oxidized to Te(IV) by BioMnOx. Chemogenic and exogenous biogenic Te0 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 Te0 need to be re-evaluated.

Competitive Mn(II) removal occurs in Lysinibacillus sp. MHQ-1 through microbially-induced carbonate precipitation (MICP) and indirect Mn(II) oxidation.

Biological Mn(II) removal usually involves adsorption and precipitation of Mn(II) in the form of various minerals. Manganese oxides (MnOx) formation through the activity of Mn(II) oxidation bacteria (MnOB) contributes to the majority of Mn(II) removal. However, whether other bacterial-mediated pathway could couple or competitive with Mn(II) oxidation during Mn(II) removal is scarcely reported. In this study, we reported a competitive Mn(II) removal occurred in nutrient-rich condition during the indirect Mn(II) oxidation of Lysinibacillus sp. MHQ-1, i.e., microbially-induced carbonate precipitation (MICP). In the presence of 1 mM Mn(II), 39.4% of free Mn(II) converted to MnCO3(s) quickly within 100 h, and then 11.6% of initial Mn(II) slowly oxidized to MnOx within 442 h. The urease activity assay and the genome sequencing confirmed the existence of urease and the absence of Mn(II)-oxidizing enzymes in the genome of strain MHQ-1. The urease catalyzed the formation of carbonate ion that reacts with Mn(II) and the formed ammonia raises the pH to initiate indirect Mn(II) oxidation. Genome survey suggests the urease widely exists in various Mn(II)-oxidizing bacteria (MnOB), emphasizing the importance to reconsider the composition, stability and environmental effects of biological Mn(II) removal products in nutrient-rich environment.

Toxic effects of tire wear particles and the leachate on the Chinese mitten crab (Eriocheir sinensis).

Tire wear particles (TWPs) were considered as an important component of microplastic pollution in the aquatic environment. To understand the ecotoxicity of TWPs to crustacean, this study investigated toxic effects of TWPs and the leachate on the mitten crab Eriocheir sinensis and the accumulation of TWPs in the crabs. Although TWPs could be accumulated in various tissues (i.e., liver, gills and gut) of the crabs, exposure to TWPs or the leachate had no lethal effect on the crabs in this study. Lower concentrations of TWPs and the leachate exposure could stimulate the antioxidant defense system of the crabs, while higher concentrations could disrupt the stress defense system. In addition, the energy supply and metabolism of the crabs could also be affected by TWPs or the leachate. The transcriptomic profiles showed that the toxic mechanisms of TWPs and the leachate were not exactly the same. Similar to the results of biochemical analysis, several Gene Ontology (GO) terms and the Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways related to oxidative stress and energy metabolism were significantly regulated by both TWPs and the leachate. However, TWPs could affect the expression of genes enriched in immune-related pathways, while the leachate regulated the enrichment of some other signaling pathways including FoxO signaling pathway, insulin signaling pathway, RIG-I-like receptor signaling pathway, NOD-like receptor signaling pathway, PPAR signaling pathway and neuroactive ligand-receptor interaction. Overall, our study could provide basic biological information for assessing the ecological risk of the TWP pollution in the aquatic environment and was useful to understand the potential toxic mechanisms of the TWPs and the leachate to crustaceans.

Formulating the Li sites of Li-CoOx composites for achieving high-efficiency oxidation removal of formaldehyde over the Ag/Li-CoOx catalyst under ambient conditions.

Oxide supported noble metals are extensively investigated for ambient formaldehyde oxidation, and the Ag-CoOx 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 CoOx. 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-CoOx composite in this sister study. Three samples with Li + ---Co3+-O2- 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/m3) was disclosed through CO-TPR and O2-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+---Co3+-O2- 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% (CO2 yield = âˆ¼21%), 47% higher than that of the L-CO (CO2 yield = âˆ¼6%). But in contrast, the Ag@LCO-S only achieved ∼53% removal (CO2 yield = âˆ¼9%) 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.

Metagenomic insights into the effects of benzyl dodecyl dimethyl ammonium bromide (BDAB) shock on bacteria-driven nitrogen removal in a moving-bed biofilm reactor (MBBR).

The use of disinfectants made from quaternary ammonium compounds (QACs) has greatly increased since the outbreak of SARS-CoV-2. However, the effect of QACs on wastewater treatment performance is still unclear. In this study, a commonly used QAC, i.e., benzyl dodecyl dimethyl ammonium bromide (BDAB), was added to a moving-bed biofilm reactor (MBBR) to investigate BDAB's effect on nutrient removal. When the BDAB concentration was increased to 50 mg L-1, the ammonia removal efficiency (ARE) greatly decreased, as did the nitrate production rate constants (NPR). This inhibition was partly recovered by decreasing the BDAB concentration to 30 mg L-1. Metagenomic sequencing revealed the functional genera present during different stages of the control (Rc) and BDAB-added reactors (Re). The enriched genera (Rudaea, Nitrosospira, Sphingomonas, and Rhodanobacter) in Rc mainly related to the nitrogen metabolism, while the enriched genera in Re was BDAB-concentration dependent. Functional genes analysis suggested that a lack of ammonia oxidase-encoding genes (amoABC) may have caused a decrease in ARE in Re, while the efflux pump-encoding genes emrE, mdfA, and oprM and a gene encoding BAC oxygenase (oxyBAC) were responsible for BDAB resistance. The increase in the total abundance of antibiotic resistance genes (ARGs) in Re revealed a potential risk arising from BDAB. Overall, this study revealed the potential effect and ecological risks of BDAB introduction in WWTPs.

Particulate matter capturing over manganese dioxides with different crystal structures.

Particulate matter (PM) is the main contributor to air pollution, and filtration has been reported to be promising for PM capturing. Considering the complexity of polluted air (volatile organic compounds (VOCs) and ozone are likely concomitant with PM particles) and in view of the versatility of MnO2 for the degradation of VOCs and ozone, the feasibility of MnO2 materials as PM filtering media was investigated in this study, and the effect of crystal structure on PM filtration was clarified. Compared with the layered δ-MnO2, the MnO2 with tunnel structure (including 1 × 2-, 2 × 2- and 3 × 3-MnO2) exhibited greatly enhanced PM removal efficiencies, and particularly, the 3 × 3-MnO2 possessed not only significant activity for adsorbing PM particles but also high utilization efficiency of the active surface. Physicochemical properties of the adsorbents were studied by XRD, ATR, isothermal N2 adsorption, SEM and (HR)TEM. The correlation between pore characteristics and particle elimination activity demonstrates that the most developed mesoporous structure of the 3 × 3-MnO2 sample played an important role in strengthening the PM adsorption capability. Further comparison of the surface properties of the fresh and spent samples reveals that with respective to the occasion of δ-MnO2, the structure of 3 × 3-MnO2 was robust enough to resist collapse after PM capturing and the great accommodation of the inorganic and organic PM substances in the voluminous pores induced strong affinity between PM particles and 3 × 3-MnO2. Thereby, a higher particle filtration ability was retained.

Enhanced oxidative ability, recyclability, water tolerance and aromatic resistance of α-MnO2 catalyst for room-temperature formaldehyde oxidation via simple oxalic acid treatment.

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-MnO2 were synchronously updated via one step treatment in oxalic acid (H2C2O4), 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, O2-TPD, CO-TPR and pyridine-IR reveal that H2C2O4 created substantial Mn3+ species on surface, exposing a higher coverage of oxygen vacancies that actively participated in the dissociative activation of gas-phase O2 into reactive chemically adsorbed oxygen (OC), and the abundant Lewis acid sites further enabled the effective O2 activation process. The large amount of oxygen OC promoted the HCHO-to-CO2 conversion and inhibited the accumulation of formate that required a high temperature of 170 °C to be eliminated, thus conspicuously improving the α-MnO2's thermal recovery. The combined H2O-TPD, H2O-preadsorbed CO-TPR, C6H6-TPD and C6H6-preadsorbed CO-TPR investigations shed light on the H2C2O4-induced water and benzene resistance. The notably weakened water and benzene binding strength with the H2C2O4-modified surface together with the unrestrained oxygen OC accounted for the outstanding anti-deactivation performance.

Leaching of di-2-ethylhexyl phthalate from biodegradable and conventional microplastics and the potential risks.

There has been a growing concern about plastic pollution, both from a health and ecological perspective. One of the major concerns with plastic debris, especially microplastics (MPs) relates to their strong potential for releasing additives and chemicals. Di-2-ethylhexyl phthalate (DEHP) is a common plastic additive widely used as plasticizer in plastic products, and is of global concern due to its widespread contamination in the environment. In this study, two conventional nondegradable plastics (polyethylene (PE) bags and PE mulch) and two biodegradable plastics (poly(butylene adipate co-terephtalate)-starch-based-polylactic acid bags (PBAT/PLA bags) and PLA mulch) were selected to investigate the release of DEHP to seawater. The results showed that leaching potentials of DEHP from different types of MPs varied. Among the four selected MPs, PE mulch had the highest leaching potential (6.88 µg/g), followed by PE bags (4.24 µg/g), PLA mulch (1.10 µg/g) and PBAT/PLA bags (0.89 µg/g). The DEHP leaching kinetic curves of the four MPs were all in line with the pseudo first order model. The potential risk of environmental and human exposure to the leached DEHP was assessed using the average Phthalate Pollution Index (PPI). The calculated PPI indicated low pollution risks of DEHP released by the four MPs in seawater.

Toxicity of tire wear particles and the leachates to microorganisms in marine sediments.

Tire wear particles (TWPs), which are among the microplastic pollutants in the environment, can inevitably accumulate in coastal sediments. The present study comprehensively investigated the effect of pristine TWPs on bacterial community structure in coastal sediments and compared the effect of pristine TWPs and aged TWPs on nine strains of bacteria in sediments. In addition, the effect of the TWP leachate was studied with all the nine bacterial strains and the toxicity-causing substances in the leachate was investigated using Bacillus subtilis. Exposure to TWPs could lead to a shift in bacteria community and affect nitrogen metabolism in marine sediments. Aged TWPs were more toxic than pristine TWPs due to changes in particle surface characteristics. The leachate exhibited greater toxicity than TWPs as well, and Zn was identified to be the major toxicity-causing substance. The overall results of this study are important for understanding the effects of TWPs and the leachates on microorganisms in marine sediments.

Water durability modification of cerium-manganese oxide by tin shell for efficient airborne benzene oxidation.

Single or cooperative incorporation of Ce and Sn elements into α-MnO2 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 Mn3+ content to 2.7 times that of the pristine MnO2 and weakened Mn-O bonds due to electron transfer from Ce3+ 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 MnO2, respectively). The thus-formed larger amount of reactive oxygen species rendered the Sn@CeMn simultaneously with high CO2 yield and low CO production. Also benefited from the SMSI effect, the Sn@CeMn's ability to continuously activate O2 and H2O 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.

Identification and characterization of Fe3O4/peroxodisulfate advanced oxidation products from sulfameter.

Sulfonamides (SAs) are one of the most widely used antibiotics and their residuals in the environment could cause some negative environmental issues. Advanced oxidation such as Fenton-like reaction has been widely applied in the treatment of SAs polluted water. Degradation rates of 95%-99.7% were achieved in this work for the tested 8 SAs, including sulfisomidine, sulfameter (SME), phthalylsulfathiazole, sulfamethoxypyridazine, sulfamonomethoxine, sulfisoxazole, sulfachloropyridazine, and sulfadimethoxine, in the Fe3O4/peroxodisulfate (PDS) oxidation system after the optimization of PDS concentration and pH. Meanwhile, it was found that a lot of unknown oxidation products were formed, which brought up the uncertainty of health risks to the environment, and the identification of these unknown products was critical. Therefore, SME was selected as the model compound, from which the oxidation products were never elucidated, to identify these intermediates/products. With liquid chromatography-high resolution tandem mass spectrometry (LC-HRMS/MS), 10 new products were identified, in which 2-amino-5-methoxypyrimidine (AMP) was confirmed by its standard. The investigation of the oxidation process of SME indicated that most of the products were not stable and the degradation pathways were very complicated as multiple reactions, such as oxidation of the amino group, SO2 extrusion, and potential cross-reaction occurred simultaneously. Though most of the products were not verified due to the lack of standards, our results could be helpful in the evaluation of the treatment performance of SAs containing wastewater.

Micro- and nanoplastics released from biodegradable and conventional plastics during degradation: Formation, aging factors, and toxicity.

The use of biodegradable plastics may solve the pollution caused by conventional plastics in the future. However, microplastics and nanoplastics are produced during the aging process of biodegradable plastics. This work evaluated the formation of secondary microplastics and nanoplastics and the effects of aging factors (UV radiation and mechanical forces) during the degradation processes of various biodegradable plastics (poly(butylene adipate co-terephtalate) (PBAT), poly(butylene succinate) (PBS), and polylactic acid (PLA)) and conventional plastics (polyethylene (PE), polystyrene (PS), and polyvinyl chloride (PVC)). This study also assessed the combined toxicity of secondary microplastics and Triclosan (TCS) on Tigriopus japonicas. The results showed that PLA and PBS could produce many microplastics. Most secondary microplastics were smaller than 50 µm. Primary pellets were more likely to generate microplastics through mechanical degradation than via photooxidation. In contrast, PBAT/PLA and PE bags were more likely to form microplastics through photooxidation than mechanical degradation. The secondary microplastics did not affect the survival of T. japonicas and the toxicity of TCS. This study highlights that risk assessment of biodegradable plastics, especially secondary microplastics, and nanoplastics, should be assessed in future studies.

Ultra-light 3D MnO2-agar network with high and longevous performance for catalytic formaldehyde oxidation.

Under the background of indoor air formaldehyde decontamination, a freestanding ultra-light assembly was fabricated via ice-templating approach starting from MnO2 nanoparticles and environmentally benign agar powder. The 3D composite of agar and MnO2 (AM-3D) was comparatively studied with powdered counterparts (including pure MnO2 and mixture of agar and MnO2) and the 3D-structured agar for formaldehyde oxidation, and their physicochemical properties were examined with XRD, ATR, SEM, XPS, isothermal N2 adsorption, ESR, Raman, CO-TPR and O2-TPD. For the single test of formaldehyde oxidation, the AM-3D catalyst exhibited 62.0%-67.0% removal percentage for ~400 mg/m3 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 MnO2 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-CO2 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.

Acute toxicity of tire wear particles, leachates and toxicity identification evaluation of leachates to the marine copepod, Tigriopus japonicus.

Tire wear particles (TWPs) have been characterized as microplastics in recent years, and many of these TWPs will be eventually deposited in coastal areas, leading to adverse effects to marine organisms. Results of the acute toxicity test in this study showed that the 96-h LC50 values of the particles and leachate were 771.4 mg/L (95% CI = 684.4-869.6 mg/L) and 5.34 g/L (95% CI = 4.75-6.07 g/L), respectively. The chemical constituents of TWP and the leachate are very complex, and little research has been conducted to determine which of these constituents contribute to the toxicity of TWP leachate to marine organisms. Therefore, the composition of the TWP and leachate was analyzed, and a variety of chemicals were identified, including metals (Mn, Zn, etc.) and organic compounds (cyclohexanthiol, 4-ethyl-1,2-dimethylbenzene, benzothiazole, stearic acid, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, etc.). In addition, the marine copepod Tigriopus japonicus was applied as a model species in the toxicity identification evaluation study to characterize, identify and confirm the toxicity-causing substances in the TWP leachate. Zn was identified and confirmed as the main toxicant contributing to the toxicity. Furthermore, Zn concentrations in the leachate over time were investigated. The release of Zn from TWPs to the aquatic environment was slow, and conformed to a parabolic model with a release constant k of 2.06. The organic component, benzothiazole, exhibited an antagonistic effect with zinc in the acute toxicity of the TWP leachate.

Superoxide radical mediated Mn(III) formation is the key process in the activation of peroxymonosulfate (PMS) by Mn-incorporated bacterial-derived biochar.

Biochar was used as a heterogeneous activator for peroxymonosulfate (PMS), and the activation performance strongly depended on the structure, functional groups, and modification of the biochar. In this study, a new type of modified biochar was synthesized by utilizing the Mn(II) adsorption capacity of bacteria. After one-step pyrolysis of Mn(II)-adsorbed bacterial cells at 800 °C, a Mn-incorporated bacterial-derived biochar (Mn-BBC) was successfully produced. It exhibited structural heterogeneity, with MnO located at the surface of the BBC matrix, as shown on the result of SEM and XRD. Compared to BBC, Mn-BBC showed a 10-fold increase (0.0727 min-1 versus 0.0069 min-1) of pollutant removal rate. In addition, it also showed anti-interference capacity against common water matrix (except 10 mM CO32-) and great stability/reusability. Chemical quenching, electron spin resonance, and pyrophosphate trapping indicated an indirect but important role of the superoxide, formed during the self-decomposition of PMS. The MnO on Mn-BBC can be oxidized by superoxide to produce surface Mn(III), which then binds to PMS and forms a surface complex. This complex promotes electron transfer from the pollutant to the Mn-BBC, facilitating the oxidation of the contaminants. Overall, this study confirmed the PMS activation capacity and mechanism of Mn-BBC, which expands the application of BBC-based materials derived from metal-adsorbed microbes.