Effect of oxalate and pH on photodegradation of pentachlorophenol in heterogeneous irradiated maghemite System

Abstract Photochemical degradation in the system of iron oxides and oxalic acid (OX) is the important reaction for detoxification of organic pollutants in natural environments, including surface soils, surface water, and even aerosols, and it was more effective at low pH according to previous studies. However, in this study, the photodegradation of pentachlorophenol (PCP) proceeded rapidly at different pH conditions in the system with maghemite and OX under UV light illumination. It was observed that the removal of PCP was 77.7% ± 0.90%, 79.9% ± 0.80% and 74.3% ± 1.50% at initial pH of 3.5, 5.0 and 7.0, respectively. To explore the degradation mechanism, the interaction of OX and maghemite were systematically studied as a function of pH. The presence of OX of 1.2 mM effectively decreased the iso-electric point (iep) of the maghemite from 5.6 to 1.8. The maximum adsorption amount of maghemite adsorbing OX increased with increasing pH value from 208 mmol kg −1 at pH = 3.5 to 293 mmol kg −1 at pH = 9.0. However, PCP (0.0375 mM) inhibited the adsorption of oxalic acid at pH = 3.5 and pH = 5.0 but promoted it at pH = 7.0 and pH = 9.0. When the initial content of OX was 1.2 mM, the highly active compounds of Fe(C 2 O 4 ) 3 3− as Fe(III) and Fe(C 2 O 4 ) 2 2− as Fe(II) were the dominant species at different pH. The formation of H 2 O 2 also relied on the value of pH and the concentration range of H 2 O 2 during PCP degradation was 0–1.67 mg L −1 , 0–1.16 mg L −1 and 0–0.16 mg L −1 at initial pH of 3.5, 5.0 and 7.0, respectively. The low pH conditions favored the iron cycling, the H 2 O 2 generation and the broken of aromatic ring of PCP, so as to enhance the degradation rates of PCP. At the high pH conditions, due to the slowdown of the iron cycling and the decreased amount of H 2 O 2 formation, the direct photolysis was responsible for the enhanced degradation of PCP. The foundation of high photochemical efficiencies of OX and maghemite for PCP degradation at large-scale pH conditions improves the photochemical mechanisms of OX-iron oxide system and is of important for understanding the transformation of organic pollutants in light environments.