Nitrogen and boron co-doped lignin biochar for enhancing calcium peroxide activation toward organic micropollutants decontamination in waste activated sludge and related microbial structure dynamics.

This study synthesized dual heteroatom nitrogen and boron-co-doped lignin-based biochar (NB-LGBC) for calcium peroxide (CP) activation to enhance the removal of organic micropollutants (OMPs), namely, 4-nonylphenol (4-NP) from waste activated sludge (WAS). NB-LGBC/CP enhanced 4-NP degradation by arriving at 83 % removal in 12 h. The NB-LGBC/CP system degraded 4-NP via a synergistic interaction (HO•, O2•- radicals, and singlet oxygen) and electron transfer due to the N-B-C bonding configurations. Results of fluorescence excitation-emission matrix (FEEM) analysis revealed significantly increase in biodegradable organics from treated WAS mixture. NB-LGBC/CP treatment enriched alkaliphilic bacterium associated with the predominance of the genus Desulfonatronum within the phylum Proteobacteria in the WAS, which improved the biological treatment capacity of 4-NP. Thus, NB-LGBC in HR-CAOP will be a novel approach for WAS decontamination.

Microbial community structure and potential function associated with poly-3-hydroxybutyrate biopolymer-boosted activation of peroxymonosulfate for waste-activated sludge decontamination.

Excess waste-activated sludge (WAS) is a major biosolid management problem due to its biohazardous and recalcitrant content of phthalate esters (PAEs). This study aimed to assess the combined use of biopolymer, poly-3-hydroxybutyrate and peroxymonosulfate to degrade PAEs and decontaminate WAS. Poly-3-hydroxybutyrate was biosynthesized by Cupriavidus sp. L7L. The combined poly-3-hydroxybutyrate and peroxymonosulfate process removed 86 % of PAEs from WAS in 12 h. The carbonyl groups of poly-3-hydroxybutyrate were conducive to peroxymonosulfate activation leading to PAE degradation followed the radical pathway and surface-mediated electron transfer. Poly-3-hydroxybutyrate and peroxymonosulfate also enriched the PAE-biodegrading microbes in WAS. The microbial population and the functional composition in response to peroxymonosultate treatment was identified, with the genus Sulfurisoma being the most abundant. This synergistic treatment, i.e., advanced oxidation process, was augmented by highly promising microbial polyesters, exhibited important implications for WAS pretreatment toward circular bioeconomy that encompasses carbon-neutral biorefinery and mitigate pollution.

Activation of calcium peroxide by nitrogen and sulfur co-doped metal-free lignin biochar for enhancing the removal of emerging organic contaminants from waste activated sludge.

The accumulation of emerging organic contaminants (EOCs) in waste activated sludge (WAS) is a global concern. In this study, a multi-heteroatom nitrogen and sulfur was successfully embedded into lignin-based biochar (N-S-LGBC) and used it to activate calcium peroxide (CP) for the degradation of 4-nonylphenol (4-NP) in WAS. N-S-LGBC/CP was effective in degrading 85 % of 4-NP within 12 h through the activation of CP owing to hydroxyl radicals and singlet oxygen species generated from the synergism among pyrrolic-N, thiophenic-S, and lattice oxygen, i.e., active sites responsible for 4-NP degradation. These results highlight substrate biodegradability for subsequent bioprocesses that improves WAS treatment in EOC degradation by the N-S-LGBC/CP-mediated process. There was abundance of distinct Aggregatilinea genus within the phylum Chloroflexi during N-S-LGBC/CP treatment, indicating high 4-NP pretreatment efficiency in WAS. This work provides a new understanding of N-S-co-doped carbocatalysts in green and sustainable hydroxyl radical-driven carbon advanced oxidation (HR-CAOP) platforms for WAS remediation.

Suppression of polycyclic aromatic hydrocarbon formation during pyrolytic production of lignin-based biochar via nitrogen and boron co-doping.

Polycyclic aromatic hydrocarbons are toxic byproducts of biochar production. The effects of pyrolysis atmosphere (i.e., N2 and CO2) and temperature (i.e., 300-900 °C) and element doping (i.e., N, B, O, and S) on the production of sixteen high priority polycyclic aromatic hydrocarbons in lignin-based biochar was investigated. N2 atmosphere at 300 °C produced the highest total polycyclic aromatic hydrocarbon content (1698 ± 50 ng/g). Polycyclic aromatic hydrocarbon formation decreased with increase in temperature (31 ± 15 ng/g at 900 °C). CO2 atmosphere significantly decreased yield of polycyclic aromatic hydrocarbons. The effects of heteroatom doping on polycyclic aromatic hydrocarbon formation were investigated for the first time in the pyrolysis synthesis of lignin-based biochar. N-, B-, O, N-B-, and N-S-doping of biochar reduced polycyclic aromatic hydrocarbon formation by 90, 85, 87, 97, and 89%, respectively. Results bring new insights into the role of heteroatom-doping and pyrolysis conditions in controlling polycyclic aromatic hydrocarbon formation in biochars.

Ecological responses of coral reef to polyethylene microplastics in community structure and extracellular polymeric substances.

The relationships and interactions between extracellular polymeric substances (EPS) and microplastics (MPs) in coral reef ecosystems were symmetrically investigated. The current study aims to investigate the responses of scleractinian coral (Goniopora columna) to exposure of model MPs, exemplified by polyethylene (PE), in the size range of 40-48 µm as affected by MPs concentration of MP in the range between 0 and 300 mg L-1 for 14 days. The structure of EPS-associated microbial community was studied using a series of techniques including high-throughput sequencing of 16 S rRNA, transmission electron microscopy (TEM), hydrodynamic diameter, surface charge (via zeta potential), X-ray diffraction (XRD), attenuated total reflectance‒Fourier transform infrared (ATR‒FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and fluorescence excitation-emission matrix (FEEM) spectroscopy. Microbial interactions between PE-MPs and coral caused aggregation and formation of EPS matrix, which resulted in increase and decrease in the relative abundance of Donghicola (Proteobacteria phylum) and Marivita (Proteobacteria phylum) in PE-MP-associated EPS, respectively. Particle size, electrostatic interactions, and complexation with the functional groups of the EPS-based matrix affected the humification index. FEEM spectroscopy analyses suggested the presence of humic- and fulvic-like fluorophores in EPS and dissolved organic matter (DOM) in PE-MP-derived DOM. The findings provided insights into the potential environmental implications of coral-based EPS and co-existing microbial assemblages due to EPS-PE-MP-microbiome interactions throughout the dynamic PE-MP exposure process.

Metal-free catalysis for organic micropollutant degradation in waste activated sludge via poly(3-hydroxybutyrate) biopolymers using Cupriavidus sp. L7L coupled with peroxymonosulfate.

This study employed a novel and environment-friendly biopolymer/oxidant catalytic system, viz., poly(3-hydroxybutyrate)/peroxymonosulfate (PHB/PMS), for pretreating wastewater sludge for the first time. Under optimal conditions, i.e., 3.1 × 10-4 M of PMS and 3.3 g/L of PHB at pH = 6.0, the PAHs in the sludge matrix was decreased by 79 % in 12 h. Increase in salinity (75 % synthetic seawater) achieved 83 % of PAHs degradation. Functional groups (CO) of the biopolymer matrix were active centers for biopolymer-mediated electron transfer that produced reactive oxygen species (SO4-, HO, and 1O2) for adsorption and catalytic oxidation of PAHs in the sludge. Functional metagenomic analysis revealed the main genus, Conexibacter (phylum, Actinobacteria) exhibited PAH-degrading function with high efficiency in the biodegradation of PAHs from sludge pretreated with PHB/PMS. Coupling chemical oxidation and biostimulation using bacterial polymer-based biomaterials is effective and beneficial for pretreating wastewater sludge toward circular bioeconomy.

A poly-(L-serine)/reduced graphene oxide-Nafion supported on glassy carbon (PLS/rGO-Nafion/GCE) electrode for the detection of naproxen in aqueous solutions.

A new electrode was constructed via the anodic electropolymerization of poly-(L-serine) (PLS) on an rGO-Nafion-modified glassy carbon electrode (GCE) for the detection of the emerging organic contaminant naproxen (NPX). The morphology, crystal phase, and surface elements of the electrode were investigated with SEM, TEM, XRD, Raman, ATR-FTIR, zeta potential, C-H-O, and XPS analyses. Results of the surface analysis showed a porous structure resembling graphene sheets inside the Nafion/GCE architecture. Various electrochemical parameters, including scan rate, pH, and NPX concentration, were studied to evaluate the performance of the electrode. The synergistic effect of PLS and rGO-Nafion greatly facilitated the catalytic oxidation of NPX on PLS/rGO-Nafion/GCE. Electrochemical NPX oxidation was a one-electron transfer and adsorption limited process. The optimal working potential was 0.92 V vs. Ag/AgCl. The oxidation current of NPX increased with the increase in the concentration of analyte and scan rate but decreased with pH. The modified electrode exhibited excellent linearity with respect to NPX concentration in the range of 4.3 to 87 µM and limit of detection of 0.23 µM (S/N = 3). The PLS/rGO-Nafion/GCE is a fast, sensitive, reliable, and economical electrode for the detection of NPX in water.

Performance and bacterial community dynamics of lignin-based biochar-coupled calcium peroxide pretreatment of waste-activated sludge for the removal of 4-nonylphenol.

Waste activated sludge contaminated with high levels of 4-nonylphenol (4-NP) is a major environmental concern. We have synthesized lignin-based biochar (LGBC) for use as a carbocatalyst in calcium peroxide (CP)-mediated sewage sludge pretreatment. Treatment of sewage sludge with 3.1 × 10-4 M of CP and 3.0 g L-1 of LGBC removed 76% of 4-NP in 12 h, which were 3.8 and 2.4 times higher than that with the LGBC and CP alone, respectively. There was synergy between reactive oxygen species (HO•, O2•-, and 1O2) and graphitic frameworks of LGBC. Pretreatment using the LGBC/CP system enhanced the release of biodegradable organic xenobiotics from the sludge. LGBC/CP enriched Proteobacteria and Thermostilla bacterial consortium (Planctomycetes) in the sludge and promoted 4-NP biodegradation. This work provides new insights into the chemical and biological mechanisms by which LGBC promotes 4-NP biodegradation in waste activated sludge via hydroxyl radical-driven carbon advanced oxidation pretreatment.

Exposure of Goniopora columna to polyethylene microplastics (PE-MPs): Effects of PE-MP concentration on extracellular polymeric substances and microbial community.

Although the pollution of coral reefs by microplastics (MPs) is an environmental problem of global significance, the effects of MP concentration on scleractinian corals remain largely underexplored. Herein, we exposed a representative scleractinian coral (Goniopora columna) to different concentrations (5-300 mg L-1) of polyethylene microplastics (PE-MPs; 40-48 µm) over seven days and evaluated the changes in microbial community and extracellular polymeric substances (EPS) using fluorescence excitation-emission matrix spectroscopy and amplicon sequence variants (ASV). At a PE-MP concentration of 300 mg L-1, the relative abundance of Bacillus (Firmicutes phylum) and Ruegeria (Proteobacteria phylum) in PE-MP-associated EPS increased and decreased, respectively, while the effects of exposure depended on the particle size of the extracellular polymeric substance (EPS)-based matrix and the humification index. Humic- and fulvic-like substances were identified as critical EPS components produced by microbial activity. The results have shed new insights into short-term responses of G. columna during exposure to different PE-MP concentrations and reveal important coral-MP-microbiome interactions in coral reef ecosystems. Results demonstrated that the coral-MPs interactions should be further evaluated to gain a deeper understanding of the underlying ecotoxicological risks.