Prediction of Base-Catalyzed Hydrolysis Kinetics of Polychlorinated Dibenzo-p-Dioxins by Density Functional Theory Calculations.
Environ Sci Technol
; 58(12): 5483-5490, 2024 Mar 26.
Article
in En
| MEDLINE
| ID: mdl-38484382
ABSTRACT
Polychlorinated dibenzo-p-dioxins (PCDDs), comprising 75 congeners, have gained considerable attention from the general public and the scientific community owing to their high toxic potential. The base-catalyzed hydrolysis of PCDDs is crucial for the assessment of their environmental persistence. Nonetheless, owing to the substantial number of congeners and low hydrolysis rates of PCDDs, conducting hydrolysis experiments proves to be exceedingly time-consuming and financially burdensome. Herein, density functional theory and transition state theory were employed to predict the base-catalyzed hydrolysis of PCDDs in aquatic environments. Findings reveal that PCDDs undergo base-catalyzed hydrolysis in aquatic environments with two competing pathways prevailing dioxin ring-opening and reduced reactivity in the hydrolytic dechlorination pathway. The resultant minor products include hydroxylated PCDDs, which exhibit thermodynamic stability surpassing that of the principal product, chlorinated hydroxydiphenyl ethers. The half-lives (ranging from 17.10 to 1.33 × 1010 h at pH = 8) associated with the base-catalyzed hydrolysis of PCDDs dissolved in water were shorter compared to those within the water-sediment environmental system. This observation implies that hydroxide ions can protect aquatic environments from PCDD contamination. Notably, this study represents the first attempt to predict the base-catalyzed hydrolysis of PCDDs by using quantum chemical methods.
Key words
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Polychlorinated Biphenyls
/
Dioxins
/
Polychlorinated Dibenzodioxins
Language:
En
Journal:
Environ Sci Technol
Year:
2024
Document type:
Article
Affiliation country:
China