Performance and mechanism of carbamazepine removal by FeS-S₂O₈^2– process: experimental investigation and DFT calculations

Abstract

● Synergistic removal of carbamazepine (CBZ) was obtained in the FeS-S₂O₈^2– process.

● SO₄^•− and •OH were identified as the main radicals in the FeS-S₂O₈^2– process.

● Heterogeneous oxidation would be dominant first, followed by homogeneous reaction.

● Degradation pathway of CBZ was well elucidated by experiments and DFT calculations.

As persulfate (S₂O₈^2–) is being increasingly used as an alternative oxidizing agent, developing low-cost and eco-friendly catalysts for efficient S₂O₈^2– activation is potentially useful for the treatment of wastewater containing refractory organic pollutant. In this study, the degradative features and mechanisms of carbamazepine (CBZ) were systematically investigated in a novel FeS- S₂O₈^2– process under near-neutral conditions. The results exhibited that CBZ can be effectively eliminated by the FeS-S₂O₈^2– process and the optimal conditions were: 250 mg/L FeS, 0.5 mmol/L S₂O₈^2–, and pH = 6.0. The existence of Cl⁻ (1 and 50 mmol/L) has little influence on the CBZ elimination, while both HCO₃⁻ and HPO₄²⁻ (1 and 50 mmol/L) significantly suppressed the CBZ removal in the FeS-S₂O₈^2– process. CBZ could be degraded via a radical mechanism in the FeS-S₂O₈^2– process, the working radical species (i.e., SO₄^•− and •OH) were efficiently formed via the promoted decomposition of S₂O₈^2– by the surface Fe²⁺ on the FeS and the dissolved ferrous ions in solution. Based on the identified oxidized products and Fukui index calculations, a possible degradation pathway of CBZ was speculated. More importantly, a two-stage oxidation mechanism of CBZ elimination was speculated in the FeS-S₂O₈^2– process, the activation of S₂O₈^2– by the surface-active Fe^(II) of FeS dominated in the initial 5 min, while homogeneous oxidation reactions played more essential parts than others in the following reaction stage (5–60 min). Overall, this study demonstrated that the FeS-S₂O₈^2– process is capable of removing CBZ from water efficiently.

Graphical abstract

Keywords

FeS / S ₂O ₈ ^2– / Carbamazepine / DFT calculations / Degradation routes

References

[1] Ali J , Wang H , Ifthikar J , Khan A , Wang T , Zhan K , Shahzad A , Chen Z , Chen Z . (2018). Efficient, stable and selective adsorption of heavy metals by thio-functionalized layered double hydroxide in diverse types of water. Chemical Engineering Journal, 332: 387–397

[2] Cai S , Chen B , Qiu X , Li J , Tratnyek P G , He F . (2021). Sulfidation of zero-valent iron by direct reaction with elemental sulfur in water: efficiencies, mechanism, and dechlorination of Trichloroethylene. Environmental Science & Technology, 55(1): 645–654

[3] Cai Y , Fan J , Liu Z . (2022). Enhanced degradation of tetracycline over FeS-based Fenton-like process: autocatalytic decomposition of H₂O₂ and reduction of Fe(III). Journal of Hazardous Materials, 436: 129092

[4] Chen F , Huang G X , Yao F B , Yang Q , Zheng Y M , Zhao Q B , Yu H Q . (2020). Catalytic degradation of ciprofloxacin by a visible-light-assisted peroxymonosulfate activation system: performance and mechanism. Water Research, 173: 115559

[5] Devi P , Das U , Dalai A K . (2016). In-situ chemical oxidation: principle and applications of peroxide and persulfate treatments in wastewater systems. Science of the Total Environment, 571: 643–657

[6] Du J , Guo W , Wang H , Yin R , Zheng H , Feng X , Che D , Ren N . (2018). Hydroxyl radical dominated degradation of aquatic sulfamethoxazole by Fe⁰/bisulfite/O₂: kinetics, mechanisms, and pathways. Water Research, 138: 323–332

[7] Feng M , Qu R , Zhang X , Sun P , Sui Y , Wang L , Wang Z . (2015). Degradation of flumequine in aqueous solution by persulfate activated with common methods and polyhydroquinone-coated magnetite/multi-walled carbon nanotubes catalysts. Water Research, 85: 1–10

[8] Huang S , Xu C , Shao Q , Wang Y , Zhang B , Gao B , Zhou W , Tratnyek P G . (2018). Sulfide-modified zerovalent iron for enhanced antimonite sequestration: characterization, performance, and reaction mechanisms. Chemical Engineering Journal, 338: 539–547

[9] Kim K , Cho E , Thokchom B , Cui M , Jang M , Khim J . (2015). Synergistic sonoelectrochemical removal of substituted phenols: implications of ultrasonic parameters and physicochemical properties. Ultrasonics Sonochemistry, 24: 172–177

[10] Lee J , Von Gunten U , Kim J H . (2020). Persulfate-based advanced oxidation: critical assessment of opportunities and roadblocks. Environmental Science & Technology, 54(6): 3064–3081

[11] Lee Y C, Lo S L, Kuo J, Lin Y L (2012). Persulfate oxidation of perfluorooctanoic acid under the temperatures of 20–40 °C. Chemical Engineering Journal, 198–199: 27–32

[12] Li D , Ali J , Shahzad A , Abdelnasser Gendy E , Nie H , Jiang W , Xiao H , Chen Z , Wang S . (2022a). Persulfate coupled with Cu²⁺/LDH-MoS₄: a novel process for the efficient atrazine abatement, mechanism and degradation pathway. Chemical Engineering Journal, 436: 134933

[13] Li H , Chen J , Hou H , Pan H , Ma X , Yang J , Wang L , Crittenden J C . (2017). Sustained molecular oxygen activation by solid iron doped silicon carbide under microwave irradiation: mechanism and application to norfloxacin degradation. Water Research, 126: 274–284

[14] Li H , Fu Y , Mei C , Wang M . (2022b). Effective degradation of Direct Red 81 using FeS-activated persulfate process. Journal of Environmental Management, 308: 114616

[15] Li J , Wan Y , Li Y , Yao G , Lai B . (2019). Surface Fe(III)/Fe(II) cycle promoted the degradation of atrazine by peroxymonosulfate activation in the presence of hydroxylamine. Applied Catalysis B: Environmental, 256: 117782

[16] Li J , Zhang X , Liu M , Pan B , Zhang W , Shi Z , Guan X . (2018). Enhanced reactivity and electron selectivity of sulfidated zerovalent iron toward chromate under aerobic conditions. Environmental Science & Technology, 52(5): 2988–2997

[17] Li S , Huang T , Du P , Liu W , Hu J . (2020). Photocatalytic transformation fate and toxicity of ciprofloxacin related to dissociation species: experimental and theoretical evidences. Water Research, 185: 116286

[18] Li Y , Yang Y , Lei J , Liu W , Tong M , Liang J . (2021). The degradation pathways of carbamazepine in advanced oxidation process: a mini review coupled with DFT calculation. Science of the Total Environment, 779: 146498

[19] Liang C , Wang Z S , Bruell C J . (2007). Influence of pH on persulfate oxidation of TCE at ambient temperatures. Chemosphere, 66(1): 106–113

[20] Ma L , Liu Y , Yang Q , Jiang L , Li G . (2022). Occurrence and distribution of Pharmaceuticals and Personal Care Products (PPCPs) in wastewater related riverbank groundwater. Science of the Total Environment, 821: 153372

[21] Ma Z , Cao H , Lv F , Yang Y , Chen C , Yang T , Zheng H , Wu D . (2021). Preparation of nZVI embedded modified mesoporous carbon for catalytic persulfate to degradation of reactive black 5. Frontiers of Environmental Science & Engineering, 15(5): 98

[22] Oh S Y, Kang S G, Kim D W, Chiu P C (2011). Degradation of 2,4-dinitrotoluene by persulfate activated with iron sulfides. Chemical Engineering Journal, 172(2–3): 641–646

[23] Pan F , Ji H , Du P , Huang T , Wang C , Liu W . (2021). Insights into catalytic activation of peroxymonosulfate for carbamazepine degradation by MnO₂ nanoparticles in-situ anchored titanate nanotubes: mechanism, ecotoxicity and DFT study. Journal of Hazardous Materials, 402: 123779

[24] Qi C , Liu X , Lin C , Zhang X , Ma J , Tan H , Ye W . (2014). Degradation of sulfamethoxazole by microwave-activated persulfate: kinetics, mechanism and acute toxicity. Chemical Engineering Journal, 249: 6–14

[25] Rodea-Palomares I , Gonzalez-Pleiter M , Gonzalo S , Rosal R , Leganes F , Sabater S , Casellas M , Munoz-Carpena R , Fernandez-Pinas F . (2016). Hidden drivers of low-dose pharmaceutical pollutant mixtures revealed by the novel GSA-QHTS screening method. Science Advances, 2(9): e1601272

[26] Sun B , Guan X , Fang J , Tratnyek P G . (2015). Activation of manganese oxidants with bisulfite for enhanced oxidation of organic contaminants: the involvement of Mn(III). Environmental Science & Technology, 49(20): 12414–12421

[27] Van Den Brandhof E J , Montforts M . (2010). Fish embryo toxicity of carbamazepine, diclofenac and metoprolol. Ecotoxicology and Environmental Safety, 73(8): 1862–1866

[28] Wan M , Shchukarev A , Lohmayer R , Planer-Friedrich B , Peiffer S . (2014). Occurrence of surface polysulfides during the interaction between ferric (hydr)oxides and aqueous sulfide. Environmental Science & Technology, 48(9): 5076–5084

[29] Wang S , Wang J . (2019). Oxidative removal of carbamazepine by peroxymonosulfate (PMS) combined to ionizing radiation: degradation, mineralization and biological toxicity. Science of the Total Environment, 658: 1367–1374

[30] WangXJinYChenWZouRXieJTangYLiXLiL (2021). Electro-catalytic activity of CeO_x modified graphite felt for carbamazepine degradation via E-peroxone process. Frontiers of Environmental Science & Engineering, 15(6); 1–10

[31] Wu R , Wang S . (2021). Integration of microbial reductive dehalogenation with persulfate activation and oxidation (Bio-RD-PAO) for complete attenuation of organohalides. Frontiers of Environmental Science & Engineering, 16(2): 1–22

[32] Xiang W , Chen H , Zhong Z , Zhang C , Lu X , Huang M , Zhou T , Yu P , Zhang B . (2022). Efficient degradation of carbamazepine in a neutral sonochemical FeS/persulfate system based on the enhanced heterogeneous-homogeneous sulfur-iron cycle. Separation and Purification Technology, 282: 120041

[33] Xiang W , Huang M , Wang Y , Wu X , Zhang F , Li D , Zhou T . (2020). New insight in the O₂ activation by nano Fe/Cu bimetals: the synergistic role of Cu⁰ and Fe(II). Chinese Chemical Letters, 31(10): 2831–2834

[34] Yan J , Peng J , Lai L , Ji F , Zhang Y , Lai B , Chen Q , Yao G , Chen X , Song L . (2018). Activation CuFe₂O₄ by hydroxylamine for oxidation of antibiotic sulfamethoxazole. Environmental Science & Technology, 52(24): 14302–14310

[35] Yang S R , He C S , Xie Z H , Li L L , Xiong Z K , Zhang H , Zhou P , Jiang F , Mu Y , Lai B . (2022). Efficient activation of PAA by FeS for fast removal of pharmaceuticals: the dual role of sulfur species in regulating the reactive oxidized species. Water Research, 217: 118402

[36] Zhong Z , Lu X , Yan R , Lin S , Wu X , Huang M , Liu Z , Zhang F , Zhang B , Zhu H . . (2020). Phosphate sequestration by magnetic La-impregnated bentonite granules: a combined experimental and DFT study. Science of the Total Environment, 738: 139636

[37] Zhou C , Zhou P , Sun M , Liu Y , Zhang H , Xiong Z , Liang J , Duan X , Lai B . (2022). Nitrogen-doped carbon nanotubes enhanced Fenton chemistry: role of near-free iron(III) for sustainable iron(III)/iron(II) cycles. Water Research, 210: 117984

[38] Zhou H , Peng J , Li J , You J , Lai L , Liu R , Ao Z , Yao G , Lai B . (2021). Metal-free black-red phosphorus as an efficient heterogeneous reductant to boost Fe³⁺/Fe²⁺ cycle for peroxymonosulfate activation. Water Research, 188: 116529

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