Study of ciprofloxacin removal by biochar obtained from used tea leaves.

In this study, used tea leaves (UTLs) were pyrolyzed to obtain used tea-leaf biochar (UTC), and then the UTC was used as an adsorbent to remove ciprofloxacin (CIP) from aqueous solutions. Batch experiments were conducted to investigate the CIP adsorption performance and mechanism. The results showed that the CIP-adsorbing ability first increased and then declined as the UTC pyrolysis temperature increased. The UTC obtained at 450°C presented excellent CIP-absorbing ability at pH6 and 40°C. The maximum monolayer adsorption capacity was 238.10mg/g based on the Langmuir isotherm model. The pseudo-second-order kinetic equation agreed well with the CIP adsorption process, which was controlled by both external boundary layer diffusion and intra-particle diffusion. The characterization analysis revealed that the OH groups, CC bonds of aromatic rings, CH groups in aromatic rings and phenolic CO bonds play vital roles in the CIP adsorption process, and that the NC, NO, OCO and COH groups of UTC were consumed in large quantities. π-π interactions, hydrogen bonding and electrostatic attraction are inferred as the main adsorption mechanisms. The present work provides not only a feasible and promising approach for UTLs utilization but also a potential adsorbent material for removing high concentrations of CIP from aqueous solutions.

Ecotoxicity of parathion during its dissipation mirrored by soil enzyme activity, microbial biomass and basal respiration.

The application of parathion (PTH) in agriculture can result in its entry into the soil and threaten the soil environment. Monitoring the PTH residues and assessing toxicity on soil health are of paramount importance to the public. Herein, the dissipation of PTH and concomitant influence on microbial activities [FDA hydrolase (FDA‒H), microbial biomass carbon (MBC) and basal respiration (BR)] in coastal solonchaks were investigated. Results showed that the dissipation of PTH in tested soil declined linearly, and the half-lives varied from 5.6 to 56.8 days, depending on pollutant concentrations. The FDA‒H activity and MBC were negatively affected by PTH pollution and exhibited a significantly positive correlation. Two‒way ANOVA analysis demonstrated that microbial activities were affected not only by PTH dose and incubation time but also by their interactions. The integrated biomarker response (IBR/n) index values on day 120 were between 1.02 and 2.89, larger than those on day 1 during PTH dissipation. This implied that the soil quality did not recover though there was no PTH residue in the soil at the end of the experiment. These findings suggested that microbial activities integrated with IBR/n index could elucidate the hazardous impacts of PTH dissipation on biochemical cycling and microorganisms in soil.

Metal-rich hyperaccumulator-derived biochar as an efficient persulfate activator: Role of intrinsic metals (Fe, Mn and Zn) in regulating characteristics, performance and reaction mechanisms.

Biochar has been widely used in advanced oxidation processes (AOPs) for the decomposition of organic contaminants. However, the role of intrinsic metals in hyperaccumulator biomass in the physico-chemical properties and performance of peroxodisulfate (PDS) activation by biochar is still unclear. This work employed hyperaccumulator biomass containing Fe, Mn and Zn, respectively. Result showed that as the pyrolysis temperature of the biochar increased, Fe was gradually reduced to iron oxide and Fe0, and Zn was reduced and volatilized; however, Mn remained in biochar in the form of MnS and CaMnO3 with high valence states. These thermochemical behaviors of intrinsic metals also facilitated graphitized structure growth and pore development (for Zn) and persistent free radicals (PFRs) generation (for Mn and Zn) in biochar, and these processes were crucial for imidacloprid degradation in biochar/PDS systems. Moreover, Fe/Zn@PB9/PDS showed better imidacloprid degradation performance, while Mn species in Mn@PB were catalytically inert. In addition, the radical pathway depending on·SO4- and·OH was the dominant pathway for imidacloprid degradation in the Fe@PB9/PDS systems, while the·O2--mediated 1O2 pathway and 1O2-based nonradical pathway contributed more in the Zn@PB9/PDS systems. These results reveal the role of intrinsic metals in biochar-based catalysts and provide a reference for the preparation of green and efficient hyperaccumulator-derived biochar catalysts for AOPs.

Sulfidated zero valent iron as a persulfate activator for oxidizing organophosphorus pesticides (OPPs) in aqueous solution and aged contaminated soil columns.

Sulfidation treatment is an effective method of improving the catalytic performance of zero-valent iron (ZVI). Here, we prepared sulfidated, micro-sized ZVI (S-mZVI) using ball milling technology to activate persulfate (PS) with the goal of oxidizing organophosphorus pesticides (OPPs) in aqueous solution and aged OPP-contaminated soil columns. Energy dispersive spectroscopy (EDS), X-ray powder diffraction (XRD) and X-ray photoelectron spectrometry (XPS) analyses uncovered the formation of Fe2O3, FeOOH, FeS and FeS2 in the S-mZVI prepared by ball milling with different proportions of elemental S powder to make micro-sized ZVI particles. The presence of sulfur can regulate the morphology of S-mZVI with a dispersed and spherical shape, and it can improve the activation performance of PS. In aqueous solution, 11.2 mg of S-mZVI activated 2.5 mM PS (S-mZVI-PS) with an S/Fe molar ratio of 0.100, and it was the best at activating PS, leading to oxidation-rate constants of 0.030 s-1 for 10 mg/L phorate and 0.026 s-1 for 10 mg/L terbufos, which were much greater than those of the other S-mZVI and mZVI. The results of the soil column experiment showed that the PS, which had a low consumption for the total dosage, achieved higher degradation percentages among the three OPPs in the S-mZVI-PS treatment than those in the mZVI-PS treatment over 120 h, with the best performance achieved by oxidizing 69.7% phorate, 48.0% terbufos and 60.6% aminoparathion. The effluent concentrations of the three OPPs in the S-mZVI-PS treatment were significantly lower than those in the mZVI-PS treatment, while dissolved total iron and Fe(II) displayed the opposite results. These results indicate that S-mZVI prepared by ball milling can effectively activate PS and be applied to remediate OPP-contaminated soil.