Degradation and chlorination mechanism of fumaric acid based on SO₄^•-: an experimental and theoretical study

It is well known that chloride ions could affect the oxidation kinetics and mechanism of contaminant based on SO₄^•- in the wastewater. Here, the degradation of an organic acid, fumaric acid (FA), was investigated in the presence of chloride (0-300 mM) by the Fe(II)/peroxymonosulfate (Fe(II)/PMS) system. A negative impact of chloride was observed on the rates of FA degradation. The degree of inhibitory effect was higher in Fe(II)/PMS addition order. Some chlorinated byproducts were identified during the FA oxidation process in the presence of Cl^- by the ultraperformance liquid chromatography and quadrupole-time of flight mass spectrometer (UPLC-QTOF-MS). With the increasing content of Cl^-, an accumulation of adsorbable organic halogen (AOX), an increase in acute toxicity, and an inhibition of mineralization were observed. According to the results of kinetic modeling, the production and transformation of oxidative species were dependent on Cl^- dosage and reaction time. SO₄^•- was supposed to be the main radical for FA degradation with Cl^- concentration below 5 mM, whereas Cl₂^•- was primarily responsible for the depletion of FA at [Cl^-] > 5 mM. A possible degradation pathway of FA was discussed. This study reveals the potential environmental risk of organic acid and is necessary to explore useful strategies for ameliorating the treatment of chloride-rich wastewater.