Modified biochar activated persulfate for degradation of tetracycline
WANG Shi-sheng1,2, YANG Yu1, SHENG Guang-hong1,2, LIU Yi-yun1,2, LI Shen-bo1
1. School of Energy and Environment, Anhui University of Technology, Ma'anshan 243002, China; 2. Engineering Research Center of Biofilm Water Purification and Utilization Technology of Ministry of Education, Anhui University of Technology, Ma'anshan 243032, China
摘要 Tetracycline hydrochloride (TC) degradation was investigated utilizing hydrogen peroxide modified magnetic biochar (H2O2modified biochar, HMB) as an activator of peroxydisulfate (PDS), with a focus on assessing the impact of initial pH on TC degradation kinetics. The underlying reaction mechanisms and degradation pathways of HMB-activated PDS for TC degradation were elucidated through a series of experimental techniques, including quenching tests, electron paramagnetic resonance (EPR) spectroscopy for identifying active species, X-ray photoelectron spectroscopy (XPS) analysis, density functional theory (DFT) calculations, and liquid-liquid mass spectrometry (LC-MS) detection. Hydrogen peroxide modification significantly enhanced TC removal, achieving a removal rate of 83.9% under the specified conditions of TC concentration (20mg/L), PDS concentration (1mmol/L), and HMB dosage (0.5g/L). This efficacy surpassed that of PDS alone or the unmodified biochar system, albeit exhibiting a decrease in removal efficiency with rising pH levels. Quenching tests and EPR analyses unveiled both radical and non-radical pathways contributing to TC degradation, the active species mainly includes: SO4.-、·OH、O2.-and 1O2. XPS analysis identified carbonyl (C=O) functionalities as the primary active sites responsible for TC degradation within the HMB/PDS system. Complementary DFT calculations were employed to quantitatively assess the contribution of C=O moieties to the HMB/PDS-mediated degradation process. Furthermore, LC-MS analyses coupled with DFT calculations delineated two distinct degradation pathways for TC, involving mechanisms such as deamidation, hydroxylation, demethylation, and dehydration ring opening.
Abstract：Tetracycline hydrochloride (TC) degradation was investigated utilizing hydrogen peroxide modified magnetic biochar (H2O2modified biochar, HMB) as an activator of peroxydisulfate (PDS), with a focus on assessing the impact of initial pH on TC degradation kinetics. The underlying reaction mechanisms and degradation pathways of HMB-activated PDS for TC degradation were elucidated through a series of experimental techniques, including quenching tests, electron paramagnetic resonance (EPR) spectroscopy for identifying active species, X-ray photoelectron spectroscopy (XPS) analysis, density functional theory (DFT) calculations, and liquid-liquid mass spectrometry (LC-MS) detection. Hydrogen peroxide modification significantly enhanced TC removal, achieving a removal rate of 83.9% under the specified conditions of TC concentration (20mg/L), PDS concentration (1mmol/L), and HMB dosage (0.5g/L). This efficacy surpassed that of PDS alone or the unmodified biochar system, albeit exhibiting a decrease in removal efficiency with rising pH levels. Quenching tests and EPR analyses unveiled both radical and non-radical pathways contributing to TC degradation, the active species mainly includes: SO4.-、·OH、O2.-and 1O2. XPS analysis identified carbonyl (C=O) functionalities as the primary active sites responsible for TC degradation within the HMB/PDS system. Complementary DFT calculations were employed to quantitatively assess the contribution of C=O moieties to the HMB/PDS-mediated degradation process. Furthermore, LC-MS analyses coupled with DFT calculations delineated two distinct degradation pathways for TC, involving mechanisms such as deamidation, hydroxylation, demethylation, and dehydration ring opening.
王诗生, 杨玉, 盛广宏, 刘轶鋆, 李申波. 改性生物炭活化过硫酸盐降解盐酸四环素[J]. 中国环境科学, 2024, 44(11): 6122-6131.
WANG Shi-sheng, YANG Yu, SHENG Guang-hong, LIU Yi-yun, LI Shen-bo. Modified biochar activated persulfate for degradation of tetracycline. CHINA ENVIRONMENTAL SCIENCECE, 2024, 44(11): 6122-6131.
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