Low-toxicity and efficient removal of emerging contaminants in marine aquaculture wastewater by hydrodynamic cavitation/calcium peroxide Fenton-like system

Abstract

Mariculture wastewater often contains emerging contaminants and elevated chloride concentrations, posing significant treatment challenges. This study developed and assessed a novel process that integrates hydrodynamic cavitation with calcium peroxide for the removal of the antibiotic tetracycline. The hydrodynamic cavitation/calcium peroxide system exhibited superior tetracycline degradation across a wider pH range compared to the homogeneous Fenton-like system, achieving over 92% removal at pH 3 with a synergistic coefficient of 9.40, while maintaining 61% efficiency under neutral conditions. Additionally, it achieved a chemical oxygen demand removal rate of 50.73% from actual mariculture wastewater, surpassing the performance of the homogeneous Fenton-like system. This approach also significantly reduced the formation of toxic disinfection by-products. The concentrations of trihalomethanes (0.29 μg/L), dichloroacetic acid (1.38 μg/L), and trichloroacetic acid (0.41 μg/L) were lower than those produced by the homogeneous Fenton-like system, resulting in an effluent with a markedly reduced toxicity-weighted concentration. Liquid chromatography-mass spectrometry analysis did not identify any stable large-molecule chlorine-containing intermediate products. Coupled with experiments on the hydrodynamic cavitation degradation of dichloroacetic acid, these findings suggest that the extreme conditions generated by hydrodynamic cavitation can effectively disrupt the C–Cl bond, thereby preventing the accumulation of chlorine-containing by-products. This study establishes the hydrodynamic cavitation/calcium peroxide system as an efficient and environmentally safe technology for the treatment of antibiotic-contaminated high-salinity wastewater.

Graphical abstract

Keywords

Hydrodynamic cavitation / Calcium peroxide / Mariculture wastewater / Disinfection by-products / Advanced oxidation processes / Fenton-like

Highlight

	● HC/CaO2 system achieved efficient TC removal over a wide pH range.
	● Outperforms the Fe2+/CaO2 homogeneous Fenton-like system.
	● The system significantly reduced toxic DBPs formation and effluent toxicity.
	● Reveals unique low-DBPs mechanism of HC/CaO2 in high-saline mariculture wastewater.
	● Effective COD removal in real mariculture wastewater met discharge standards.

References

[1] Ahmad F , Zhu D C , Sun J Z . (2021). Environmental fate of tetracycline antibiotics: degradation pathway mechanisms, challenges, and perspectives. Environmental Sciences Europe, 33(1): 64

[2] Ali M , Tariq M , Sun Y , Huang J Y , Gu X G , Ullah S , Nawaz M A , Zhou Z Y , Shan A L , Danish M . et al. (2021). Unveiling the catalytic ability of carbonaceous materials in Fenton-like reaction by controlled-release CaO₂ nanoparticles for trichloroethylene degradation. Journal of Hazardous Materials, 416: 125935

[3] Andia J P M , Cayte A E T , Rodriguez J M I , Belón L L , Málaga M A C , Teixeira L A C . (2021). Combined treatment based on synergism between hydrodynamic cavitation and H₂O₂ for degradation of cyanide in effluents. Minerals Engineering, 171: 107119

[4] Cai J H , Li Y H , Liu Y Q , Wang B L , Li M B . (2025). Ionic strength-driven cavitation nucleation: from energy deposition-based to tension-based cavitation. International Journal of Multiphase Flow, 191: 105306

[5] Ding W , Hong F , Ying D W , Huang Y P , Khan S N , Jia J P . (2024). A comprehensive study on the effects of annular protrusion for cavitation intensification in Venturi tubes. Chemical Engineering Journal, 498: 155306

[6] Gągol M , Przyjazny A , Boczkaj G . (2018). Wastewater treatment by means of advanced oxidation processes based on cavitation–a review. Chemical Engineering Journal, 338: 599–627

[7] Gao Y W , Li M B , Sun C , Zhang X H . (2022). Microbubble-enhanced water activation by cold plasma. Chemical Engineering Journal, 446: 137318

[8] He X H , Kai T , Ding P . (2021). Heterojunction photocatalysts for degradation of the tetracycline antibiotic: a review. Environ-mental Chemistry Letters, 19(6): 4563–4601

[9] Hu B , Wu C D , Zhang Z L , Wang L . (2014). Sonophotocatalytic degradation of trichloroacetic acid in aqueous solution. Ceramics International, 40(5): 7015–7021

[10] Hu Q , Zhang J H , Pan Y D , Ding K , Xu C Y , Hou J Y , Liu W X , Thanachayanont C , Lampang T N , Chen M L . et al. (2025). Oxygen-containing functional groups of biochars enhancing the oxygen release of CaO₂ and the generation of free radicals. Process Safety and Environmental Protection, 198: 107126

[11] Huang C H , Tang Z R , Xi B D , Tan W B , Guo W , Wu W X , Ma C Y . (2021). Environmental effects and risk control of antibiotic resistance genes in the organic solid waste aerobic composting system: a review. Frontiers of Environmental Science & Engineering, 15(6): 127

[12] Huang C Q , Wang Z Z , Cheng S J , Liu Y P , Deng B L , Xu S Y , Yu L , Yu Y . (2024). Challenges and strategies of chlorine inhibition in anode systems for seawater electrolysis. Science China Chemistry, 67(10): 3198–3208

[13] Iskander S M , Zeng T , Smiley E , Bolyard S C , Novak J T , He Z . (2020). Formation of disinfection byproducts during Fenton’s oxidation of chloride-rich landfill leachate. Journal of Hazardous Materials, 382: 121213

[14] Li S , Wu Y N , Zheng H S , Li H B , Zheng Y J , Nan J , Ma J , Nagarajan D , Chang J S . (2023). Antibiotics degradation by advanced oxidation process (AOPs): recent advances in ecotoxicity and antibiotic-resistance genes induction of degradation products. Chemosphere, 311: 136977

[15] Lu J , Zhang C , Wu J . (2022). Removal of steroid hormones from mariculture system using seaweed Caulerpa lentillifera. Frontiers of Environmental Science & Engineering, 16(2): 15

[16] Meng L , Dong J Y , Chen J , Lu J H , Ji Y F . (2023). Degradation of tetracyclines by peracetic acid and UV/peracetic acid: reactive species and theoretical computations. Chemosphere, 320: 137969

[17] Mutke X A M , Swiderski P , Drees F , Akin O , Lutze H V , Schmidt T C . (2024). Efficiency of ozonation and sulfate radical-AOP for removal of pharmaceuticals, corrosion inhibitors, X-ray contrast media and perfluorinated compounds from reverse osmosis concentrates. Water Research, 255: 121346

[18] Nie G , Hu K S , Ren W , Zhou P , Duan X G , Xiao L , Wang S B . (2021). Mechanical agitation accelerated ultrasonication for wastewater treatment: sustainable production of hydroxyl radicals. Water Research, 198: 117124

[19] Niemczewski B . (2011). Maximisation of cavitation intensity in ultrasonic cleaning in aqueous solutions through selection of salt solution. Transactions of the IMF, 89(2): 104–108

[20] Qu G J , Jia P , Zhang T , Tang S , Pervez M N , Pang Y X , Li B , Cao C J , Zhao Y P . (2023). Synergistic activation of peroxymonosulfate by intrinsic defect and graphitic N of N,P co-doped carbon microspheres for BPA degradation. Chemical Engineering Journal, 475: 145888

[21] Sun Y C , Wang C , May A L , Chen G , Yin Y C , Xie Y C , Lato A M , Im J , Löffler F E . (2023). Mn(III)-mediated bisphenol a degradation: mechanisms and products. Water Research, 235: 119787

[22] Troia A , Ripa D M , Lago S , Spagnolo R . (2004). Evidence for liquid phase reactions during single bubble acoustic cavitation. Ultrasonics Sonochemistry, 11(5): 317–321

[23] Wang J , Wang Z J , Vieira C L Z , Wolfson J M , Pingtian G , Huang S D . (2019). Review on the treatment of organic pollutants in water by ultrasonic technology. Ultrasonics Sonochemistry, 55: 273–278

[24] Wang M L , Cheng J H , Xu W W , Zhu D D , Zhang W Y , Wen Y J , Guan W B , Jia J P , Lu Z Y . (2025). Self-cleaning electrode for stable synthesis of alkaline-earth metal peroxides. Nature Nanotechnology, 20(1): 67–74

[25] Weng M T , Cai M Q , Xie Z Q , Dong C Y , Zhang Y , Song Z J , Shi Y J , Jin M C , Wang Q , Wei Z S . (2022). Hydrodynamic cavitation-enhanced heterogeneous activation of persulfate for tetracycline degradation: synergistic effects, degradation mechanism and pathways. Chemical Engineering Journal, 431: 134238

[26] Yin S N , Chen X F , Li R Z , Sun L L , Yao C Y , Li Z . (2024). Wearable, biocompatible, and dual-emission ocular multisensor patch for continuous profiling of fluoroquinolone antibiotics in tears. ACS Nano, 18(28): 18522–18533

[27] Zhao K , Padervand M , Ren H T , Jia T T , Guo Q Q , Yang L P , Wang C Y . (2024). Enhancing tetracycline removal efficiency through ozone micro–nano bubbles: environmental implication and degradation pathway. ACS ES&T Engineering, 4(8): 1860–1870

RIGHTS & PERMISSIONS

Higher Education Press 2026