Enhanced degradation of organic contaminants by zero-valent iron/sulfite process under simulated sunlight irradiation

Abstract

Degradation of propranolol (PrP) by a combined zero-valent iron and sulfite system under simulated sunlight irradiation (ZVI/sulfite/photo) was investigated. Simulated sunlight irradiation enhanced the degradation of PrP by accelerating the decomposition of ferric sulfite complex as a result to producing sulfite radical (SO3•−). As bubbles would block the transport of photons in the reaction solution, mechanical aeration rather than purging air was suggested to sustain the essential dissolved oxygen. The degradation of PrP increased with the elevation of initial ZVI concentration from 0.05 to 0.5 mM, but decreased a little with further increasing ZVI concentration to 1.0 mM. The degradation of PrP raised from 68.5% to 98.7% while sulfite dose increased from 0.1 to 2.0 mM. High removal efficiencies were always achieved when the initial PrP concentration ranged from 10 to 40 μM. As HSO3− which can efficiently complex Fe(II) and transfer Fe(III) to Fe(II) is the dominant species of sulfite at pH 4.0–6.0, the highest removal of PrP was achieved at pH 4.0–6.0. The presence of bicarbonate and humic acid significantly retarded the removal of PrP, while chloride ions could promote the removal of PrP to some extent. SO4•−, HO• and SO5•− were suggested to account for PrP removal, while SO4•− was evidenced to be the dominant radicals. Good reuse of ZVI in the system was also achieved as the removal of PrP kept higher than 80% after repeatedly used for 5 times. Possible degradation pathways of PrP in the ZVI/sulfite/photo system were accordingly proposed based on LC-MS and density functional theory calculation. The removal of amitriptyline, nitrobenzene, imipramine and methylparaben in the ZVI/sulfite/photo system was also evaluated. As a reducing agent, sulfite is expected to consume the possible formed bromine-containing intermediates as a result to inhibiting the formation of bromate, which is better than the activated persulfate system.