In this study, an electrochemical/peroxymonosulfate/Fe(III) (EC/PMS/Fe(III)) system was established for efficient degradation of four naphthenic acids (NAs) compounds including cyclohexanecarboxylic (CHA), heptanoic (HPA), benzoic (BA) and 2-methylhexanoic acids (2-MHA). The introduction of electric field enhances the redox cycle of Fe(III)/Fe(II) to activate PMS for degredation of NAs. Complete degradation of NAs compounds (5 mg/L) has been achieved within 30 min in the EC/PMS/Fe(III) system. The results of electron paramagnetic resonance (EPR) analysis, scavenging experiment, and chemical probe experiments indicated hydroxyl radical ( • OH), sulfate radical (SO 4 •− ) and singlet oxygen ( 1 O 2 ) are primary reactive oxygen species (ROS) in the EC/PMS/Fe(III) system. NAs compounds with different structures exhibit inconsistent degradation efficiency in current system ( k CHA > k BA > k HPA > k 2-MHA ), depending on the selectivity of the different ROS and stability of respective intermediate organic radicals. Besides, multiple degradation pathways of CHA, mainly including hydroxylation and carbonylation , were proposed by combining the results of mass spectrometry analysis with the calculated Fukui index based on density functional theory (DFT) calculation. In addition, the EC/PMS/Fe(III) system exhibited robust performance with the addition of co-existing ions. This work provides a novel strategy for efficient degradation of NAs for future remediation of petroleum wastewater.
This work investigated the activation of peroxymonosulfate by electrochemical (EC) system assisted with Fe(III)-nitrilotriacetic acid (NTA) complex for degradation of persistent naphthenic acids (NAs) under neutral initial pH conditions. As NAs are a complicated mixture, 1-adamantanecarboxylic acid (ACA) was selected as the model NA compound for degradation experiment. The addition of NTA is to chelate with Fe(III), gaining stability under neutral pH condition to facilitate the circulation of Fe(II)/Fe(III) by the electrochemical process to activate PMS. The EC/Fe(III)-NTA/PMS system was explored with applicable pH range of 3–9 and an optimized molar ratio 1: 2 for Fe: NTA. Results of quenching and chemical probe experiment together with results of electron paramagnetic resonance (EPR) analysis revealed the main reactive species of the system, including • OH, SO 4 •− , 1 O 2 and possibly Fe(IV). With the addition of NTA, the yields of • OH, SO 4 •− , 1 O 2 were enhanced. Results of mass spectrometry analysis and DFT calculations indicated the formation of 9 degradation byproducts of ACA via three primary degradation pathways such as hydroxyl substitution, carbonyl substitution, and decarboxylation . Furthermore, the EC/Fe(III)-NTA/PMS system could achieve excellent removal efficiency of ACA with different anions such as Cl - , HCO 3 - , NO 3 - and H 2 PO 4 - in the background. The practical applicability of the system was also verified with the high removal of commercial NAs mixture standard. Overall results have indicated the EC/Fe(III)-NTA/PMS system could be utilized for efficient reclamation of authentic oil and gas industrial wastewater under natural pH conditions.
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