Unveiling the effect of different dissolved organic matter (DOM) on catalytic dechlorination of nFe/Ni particles: Corrosion and passivation effect.

Dissolved organic matter (DOM), which is ubiquitously distributed in groundwater, has a crucial role in the fate and reactivity of iron materials. However, there is a lack of direct evidence on how different DOMs interact with nFe/Ni in promoting or inhibiting the dechlorination efficiency of chlorinated aromatic contaminants. By comparing humic acid (HA), fulvic acid (FA), and biochar-derived dissolved organic matter (BDOM) at different pyrolysis temperatures, we first demonstrated that the dechlorination effect of nFe/Ni on 2,4-dichlorophenol (2,4-DCP) depended on the nature of DOMs and their adsorption on nFe/Ni. HA showed an enhancing effect on the dechlorination of 2,4-DCP by nFe/Ni, while the inhibition effect of other DOMs resulted in the following dechlorination order: BDOM300 ≈FA>BDOM700 ≈BDOM500. The C2 component with higher aromaticity and molecular weight promoted the corrosion of nFe/Ni and the production of reactive hydrogen atoms (H*). The effects of different DOMs on nFe/Ni include that (1) HA accelerates the corrosion and H* production of nFe/Ni, (2) FA and BDOM300 enhance the corrosion but inhibit H* production, and (3) Both nFe/Ni corrosion and H* formation are suppressed by BDOM500/BDOM700. Therefore, this study will provide a reference for understanding the nature of DOM-nFe/Ni interaction and improving the catalytic activity of nFe/Ni when different DOMs coexist in practical applications.

Preferential role of distinct phytochemicals in biosynthesis and antibacterial activity of silver nanoparticles.

Biosynthesis of silver nanoparticles (AgNPs) by plant extracts and its antibacterial utilization has attracted great attention due to the spontaneous reducing and capping capacities of phytochemicals. However, the preferential role and mechanisms of the functional phytochemicals from different plants on AgNPs synthesis, and its catalytic and antibacterial performance remain largely unknown. This study used three widespread arbor species, including Eriobotrya japonica (EJ), Cupressus funebris (CF) and Populus (PL), as the precursors and their leaf extracts as reducing and stabilizing agents for the biosynthesis of AgNPs. A total of 18 phytochemicals in leaf extracts were identified by ultra-high liquid-phase mass spectrometer. For EJ extracts, most kinds of flavonoids participated in the generation of AgNPs by a reduced content of 5∼10%, while for CF extracts, about 15∼40% of the polyphenols were consumed to reduce Ag+ to Ag0. Notably, the more stable and homogeneous spherical AgNPs with smaller size (≈38 nm) and high catalytic capacity on Methylene blue were obtained from EJ extracts rather than CF extracts, and no AgNPs were synthesized from PL extracts, indicating that flavonoids are superior than polyphenols to act as reducer and stabilizer in AgNPs biosynthesis. The antibacterial activities against Gram-positive (Staphylococcus aureus and Bacillus mycoides) and Gram-negative bacteria (Pseudomonas putida and Escherichia coli) were higher in EJ-AgNPs than that in CF-AgNPs, which confirmed the synergistic antibacterial effects of flavonoids combined with AgNPs in EJ-AgNPs. This study provides a significant reference on the biosynthesis of AgNPs with efficient antibacterial utilization underlying effect of abundant flavonoids in plant extracts.

Impact of different zero valent iron-based particles on anaerobic microbial dechlorination of 2,4-dichlorophenol: Comparison of dechlorination performance and the underlying mechanism.

The integration of iron-based materials and anaerobic microbial consortia has been extensively studied owing to its potential to enhance pollutant degradation. However, few studies have compared how different iron materials enhance the dechlorination of chlorophenols in coupled microbial systems. This study systematically compared the combined performances of microbial community (MC) and iron materials (Fe0/FeS2 +MC, S-nZVI+MC, n-ZVI+MC, and nFe/Ni+MC) for the dechlorination of 2,4-dichlorophenol (DCP) as one representative of chlorophenols. DCP dechlorination rate was significantly higher in Fe0/FeS2 +MC and S-nZVI+MC (1.92 and 1.67 times, with no significant difference between two groups) than in nZVI+MC and nFe/Ni+MC (1.29 and 1.25 times, with no significant difference between two groups). Fe0/FeS2 had better performance for the reductive dechlorination process as compared with other three iron-based materials via the consumption of any trace amount of oxygen in anoxic condition and accelerated electron transfer. On the other hand, nFe/Ni could induce different dechlorinating bacteria as compared to other iron materials. The enhanced microbial dechlorination was mainly due to some putative dechlorinating bacteria (Pseudomonas, Azotobacter, Propionibacterium), and due to improved electron transfer of sulfidated iron particles. Therefore, Fe0/FeS2 as a biocompatible as well as low-cost sulfidated material can be a good alternative for possible engineering applications in groundwater remediation.

Ball-milled PET plastic char as an electron shuttle accelerated anaerobic degradation of 2,4,6-trichlorophenol in water environment.

1The combination of carbonaceous materials and microbial degradation is an attractive measure in improving the removal efficiency of organic pollutants in water environment. In this study, the anaerobic dechlorination in a coupled system of ball-milled plastic chars (BMPCs) and the microbial consortium were investigated. The anaerobic microorganism cultured from raw sludge (CAM) contributed to the dechlorination of the 2,4,6-trichlorophenol (2,4,6-TCP) into 4-chlorophenol (4-CP) as the final product via ortho-dechlorination in all testing groups. The dechlorination rate was accelerated in different BMBC plus CAM groups than that in only CAM group (0.048 d-1), of which, it was greater in BMPC-500 plus CAM group (0.375 d-1) than that in BMPC-700 plus CAM group (0.171 d-1). The electron exchange capacity (EEC) of BMPCs decreased with the increase of pyrolysis temperature (0.053 mmol e-/g for BMPC-500 and 0.037 mmol e-/g for BMPC-700), which directly affected anaerobic dechlorination. Direct interspecies electron transfer (DIET) of BMPCs also boosted the biogas yield by 1.5 times compared to that without BMPCs. Microbial community analysis illustrated that BMPCs helped to enrich the putative dechlorinating bacteria. The abundance of Clostridium_aenus_stricto_12, as a dominant dechlorinator, significantly increased from 0.02 % to 11.3 % (without BMPCs), 39.76 % (BMPC-500) and 9.3 % (BMPC-700), and followed by， Prevotella and Megaspheara, which was reported to take part in anaerobic dechlorination and digestion as H2 producers, also increased in the presence of BMPC. This study contributes to the realization of 2,4,6-TCP in-situ reduction technology and provides a scientific reference for anaerobic dechlorination by cultured anaerobes combined with BMPCs.

Enhanced removal of aged and differently functionalized polystyrene nanoplastics using ball-milled magnetic pinewood biochars.

In this study, simple and environmentally friendly magnetic biochars were successfully prepared by ball-milling biochar with Fe3O4 nanoparticles to remove NPs from water. The magnetic biochars synthesized at various pyrolysis temperatures of 300 °C (MBC300), 500 °C (MBC500), and 700 °C (MBC700) were used to eliminate the unmodified (PS), aged under UV radiation (UVPS), amine-modified (PS-NH2) and carboxylate-modified (PS-COOH) polystyrene NPs of 100 nm in size. Results showed that the removal efficiency of MBC300, MBC500, and MBC700 for PS were 43.67, 82.73 and 57.02%, which were 3.01, 5.76, and 3.10 times greater than that of corresponding pristine biochars at the same temperatures, respectively, and the strongest removal efficiency of MBC500 was 95.2% since it has the largest specific surface area and abundant oxygen-containing functional groups. The surface properties of the NPs affected their removal, and the PS-NH2 had the highest removal rate using magnetic biochars. Compared to pristine biochars, the magnetic biochars displayed faster adsorption kinetics. The Langmuir maximum adsorption capacity of magnetic biochars for NPs were 107.7181-229.5772 mg/g, much greater than those of the pristine biochars (55.4602-80.3096 mg/g). Mechanism analysis revealed that the hydrophobicity, electrostatic attraction, H-bonding formation and π-π conjunction between the NPs and MBCs contributed to the adsorption process. This work highlights the promising potential of ball milling to be used as a simple technique for the preparation of magnetic biochar to remove NPs, especially NPs with various surface groups.

Characteristics of ball-milled PET plastic char for the adsorption of different types of aromatic organic pollutants.

Ball-milled plastic char (BMPC) was manufactured by ball-milling of native plastic char (PC) that was synthesized via slow pyrolysis of polyethylene terephthalate (PET) water bottle waste, and its adsorption characteristics of aqueous phenanthrene (PHE), phenol, and 2,4,6-trichlorophenol (2,4,6-TCP) and its possible mechanisms were investigated. With the increase of PC pyrolysis temperature, the specific surface area of BMPC increased obviously, forming larger functional groups compared to PC. Boehm titration showed that total acidic groups of BMPC decreased significantly with the increase of pyrolysis temperature. The sorption kinetics of three adsorbates was adequately simulated by pseudo-second-order model (R2 > 0.99). Langmuir model fitted well the adsorption isotherms of PHE and phenol, while Freundlich model simulated the adsorption isotherm of 2,4,6-TCP better. The adsorption amount of PHE, phenol, and 2,4,6-TCP increased significantly as the pyrolysis temperature increased. The maximum BMPC adsorption capacity reached 21.9 mg·g-1 (for PHE), 106 mg·g-1 (for phenol), and 303 mg·g-1 (for 2,4,6-TCP) at 25 °C in aqueous solution. FTIR analysis suggested that surface sorption-based π-π interaction was a dominant mechanism of PHE adsorption; meanwhile, H-bonding between O-containing groups on BMPC and hydroxyl groups of adsorbates was responsible for phenol and 2,4,6-TCP removal. This paper shows that BMPC can be used as adsorbent for treating aromatic compounds in aqueous environment and has an economic worth of application.

Enhanced microbial reduction of aqueous hexavalent chromium by Shewanella oneidensis MR-1 with biochar as electron shuttle.

Biochar, carbonaceous material produced from biomass pyrolysis, has been demonstrated to have electron transfer property (associated with redox active groups and multi condensed aromatic moiety), and to be also involved in biogeochemical redox reactions. In this study, the enhanced removal of Cr(VI) by Shewanella oneidensis MR-1(MR-1) in the presence of biochars with different pyrolysis temperatures (300 to 800 °C) was investigated to understand how biochar interacts with Cr(VI) reducing bacteria under anaerobic condition. The promotion effects of biochar (as high as 1.07~1.47 fold) were discovered in this process, of which the synergistic effect of BMBC700(ball milled biochar) and BMBC800 with MR-1 was noticeable, in contrast, the synergistic effect of BMBCs (300-600 °C) with MR-1 was not recognized. The more enhanced removal effect was observed with the increase of BMBC dosage for BMBC700+MR-1 group. The conductivity and conjugated O-containing functional groups of BMBC700 particles themselves has been proposed to become a dominant factor for the synergistic action with this strain. And, the smallest negative Zeta potential of BMBC700 and BMBC800 is thought to favor decreasing the distance from microbe than other BMBCs. The results are expected to provide some technical considerations and scientific insight for the optimization of bioreduction by useful microbes combining with biochar composites to be newly developed.

Study on synthesis and application of tetrabasic lead sulfate as the positive active material additive for lead-acid batteries.

Tetrabasic lead sulfate (4BS) was used as a positive active material additive for lead-acid batteries, which affirmatively affected the performance of the battery. Herein, tetrabasic lead sulfate was synthesized from scrap lead paste that was formed through the production process of the lead-acid batteries. This solves the disposing problem of the scrap lead paste that is challenging in the production of the lead-acid batteries. Scrap lead paste was first pre-treated and the 4BS with high purity and crystalline was synthesized by sintering at the temperature of 450°C and hold time of 7 h. As demonstrated by X-ray diffraction and scanning electron microscopy test and Material Studio software calculation, the purity of synthesized 4BS is higher than 98 wt%, small particles have pillar forms and are evenly distributed. Moreover, the synthesized 4BS of 1 wt% was added to the positive lead paste and then valve-regulated lead-acid battery was made after the pasting, curing and formation processes. The effectiveness of the lead-acid batteries after adding 4BS as crystal seeds was evaluated, and the 100% charge-discharge cycle life of the new battery (523 times) was about 1.4 times higher than that of general lead-acid batteries (365 times).

The synthesis of a Bi2MoO6/Bi4V2O11 heterojunction photocatalyst with enhanced visible-light-driven photocatalytic activity.

A novel Bi2MoO6/Bi4V2O11 heterostructured photocatalyst was successfully fabricated using a facile one-pot solvothermal method. This heterojunction consists of homogeneous dispersed Bi4V2O11 nanocrystals anchored on the surface of Bi2MoO6 nanoflakes, endowing the heterojunction with nanosized interfacial contact. Based on the favorable interfacial contact, the band alignment at the heterojunction effectively facilitated photo-generated carrier transfer, which was verified by photoelectrochemical and photoluminescence measurements. Thereby, in contrast with pristine Bi2MoO6 and Bi4V2O11, the as-synthesized heterojunction with nanoscale contact exhibited significantly enhanced photocatalytic activity towards the degradation of MB and the reduction of Cr(vi). In addition, the as-fabricated Bi2MoO6/Bi4V2O11 heterojunction exhibited good cycling stability for MB degradation after 4 cycles. Finally, a plausible photocatalytic mechanism for MB degradation over the Bi2MoO6/Bi4V2O11 heterojunction was discussed in detail. This work not only reports a highly efficient photocatalyst but also sheds light on the design and optimization of a heterojunction.