Treatment of emerging pyrrolizidine alkaloids in drinking water by UV/persulfate process: Kinetics, energy efficiency and degradation pathway

[Display omitted] •A total concentration of 41.4 ∼ 342.1 ng/L PAs in treated drinking water was discovered for the first time.•Up to 97 % of heliotrine and N-oxide were degraded by UV/persulfate in 30 min.•Based on steady-state kinetic models, effect of various influence factors were evaluated.•The EE/O calculations suggested UV/PDS was a cost-effective treatment for controlling PA contamination in actual applications.•Degradation pathways of heliotrine and N-oxide oxidated by sulfate radicals were proposed. Pyrrolizidine alkaloids (PAs), recognized as a group of toxic secondary metabolites, have raised growing concerns in recent years due to their potential high toxicity. However, studies on the degradation of PAs in drinking water treatments have yet to be conducted. Herein, the treatment of Heliotrine (HEL) and N-oxide (HELNO), two dominant PAs detected in the treated drinking water, are analyzed for the first time. The UV/peroxydisulfate (UV/PDS) process was demonstrated to be efficient in the degradation of PAs, achieving almost complete removal of HEL and HELNO in 30 min. SO4•− plays a dominant role in the system, with second-order rate constants of 2.3 × 109 M−1 s−1 and 1.0 × 109 M−1 s−1 for HEL and HELNO, respectively. Based on the steady-state kinetic models, the effect of influence factors, including PDS dosage, initial pollutant concentration, pH, dissolved organic matter (DOM), and chloride (Cl−), were evaluated. Acidic conditions were proven to be favorable for PA degradations, primarily contributed to the minimized quenching effect of OH− and phosphate on SO4•−. The inhibitory effect of DOM on radical quenching significantly overweighted the promotion effect of the generated excited triplet DOM (3DOM*), resulting in a diminished degradation efficiency. The pronounced inhibition of Cl− could be attributed to the conversion of SO4•− to OH•, involving the formation of reactive chlorine species. The UV/PDS treatment was suggested economical in the removal of PAs as a post-filtration and before-chlorination treatment through electrical energy per order (EE/O) calculation. Finally, reasonable degradation pathways of HEL and HELNO reacted with SO4•− were proposed, involving the initial one-electron oxidation of HEL/HELNO by SO4•− radical, and further reactions (e.g., hydroxylation, pyrrolidine ring-cleavage and self-coupling) of the formed N-centered cation radicals.