Mechanism of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide degradation in UV light-emitting diodes lamp driven sodium sulfite activation process

Process Safety and Environmental Protection(2022)

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摘要
DOPO (9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is emerging organic phosphorus flame retardant, which has gained greatly attention because of its adverse health effects on aquatic organisms. In this study, UV light-emitting diodes lamp driven sodium sulfite activation (UV254/Sulfite) process was employed as an advanced reduction process to remove DOPO, and its mechanisms were revealed. The pseudo first order rate constant of DOPO (kobs-DOPO) in UV254/Sulfite process initially decreased from 6.95 × 10−5 s−1 to 5.11 × 10−5 s−1, and subsequently increased to 1.61 × 10−4 s−1 as the sulfite concentration increased from 0 to 10 mM, indicating that the negative effect of HSO3- on DOPO degradation was the dominate factor in UV254/Sulfite process at low sulfite concentration (< 2 mM), while the yields of hydrated electron (eaq-) increased as the sulfite concentration gradually reaching to a high value (10 mM), resulting in enhancing DOPO degradation significantly. In addition, the coexisted water matrix in deionized water and natural surface water weakened DOPO degradation in UV254/Sulfite process, and this inhibition strengthened as the concentrations of water matrix raised. The DOPO degradation pathway indicated that eaq- attacked phosphaphenanthrene structure of DOPO and contributed to its detoxification which was confirmed by Quantitative Structure-Activity Relationship (QSAR) assessment.
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关键词
DOPO degradation,Hydrated electron,UV254/Sulfite,Advanced reduction process (ARP),Products toxicity
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