Treatment of chlorpyrifos manufacturing wastewater by peroxide promoted-catalytic wet air oxidation, struvite precipitation, and biological aerated biofilter

  • Fu Chen
  • Siyan Zeng
  • Jing MaEmail author
  • Qianlin Zhu
  • Shaoliang Zhang
Research Article


Chlorpyrifos manufacturing wastewater (CMW) is characterized by complex composition, high chemical oxygen demand (COD) concentration, and toxicity. An integrated process comprising of peroxide (H2O2) promoted-catalytic wet air oxidation (PP-CWAO), struvite precipitation, and biological aerated filters (BAF) was constructed to treat CMW at a starting COD of 34000–35000 mg/L, total phosphorus (TP) of 5550–5620 mg/L, and total organophosphorus (TOP) of 4700–4840 mg/L. Firstly, PP-CWAO was used to decompose high concentrations of organic components and convert concentrated and recalcitrant TOP to inorganic phosphate. Copper citrate and ferrous citrate were used as the catalysts of PP-CWAO. Under the optimized conditions, 100% TOP was converted to inorganic phosphate with 95.6% COD removal. Then, the PP-CWAO effluent was subjected to struvite precipitation process for recovering phosphorus. At a molar ratio of Mg2+:NH4+:PO43− = 1.1:1.0:1.0, phosphate removal and recovery reached 97.2%. The effluent of struvite precipitation was further treated by the BAF system. Total removals of 99.0%, 95.2%, 97.3%, 100%, and 98.3% were obtained for COD, total suspended solids, TP, TOP, and chroma, respectively. This hybrid process has proved to be an efficient approach for organophosphate pesticide wastewater treatment and phosphorus reclamation.


Hydrogen peroxide Copper citrate Biomass Organophosphate pesticide Organic phosphorus 


Funding information

This work was financially supported by the Fundamental Research Funds for the Central Universities (2019XKQYMS80).

Compliance with ethical standards

Conflict of interest

The authors declare there are no competing interests.


  1. Anglada Á, Urtiaga A, Ortiz I, Mantzavinos D, Diamadopoulos E (2011) Treatment of municipal landfill leachate by catalytic wet air oxidation: assessment of the role of operating parameters by factorial design. Waste Manag 31:1833–1840CrossRefGoogle Scholar
  2. Bai Y, Sun Q, Sun R, Wen D, Tang X (2011) Bioaugmentation and adsorption treatment of coking wastewater containing pyridine and quinoline using zeolite-biological aerated filters. Environ Sci Technol 45:1940–1948CrossRefGoogle Scholar
  3. Barbosa SG, Peixoto L, Meulman B, Alves MM, Pereira MA (2016) A design of experiments to assess phosphorous removal and crystal properties in struvite precipitation of source separated urine using different Mg sources. Chem Eng J 298:146–153CrossRefGoogle Scholar
  4. Bokare AD, Choi W (2014) Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes. J Hazard Mater 275:121–135CrossRefGoogle Scholar
  5. Catrinescu C, Arsene D, Teodosiu C (2011) Catalytic wet hydrogen peroxide oxidation of para-chlorophenol over Al/Fe pillared clays (AlFePILCs) prepared from different host clays. Appl Catal B 101:451–460CrossRefGoogle Scholar
  6. Chang X, Zeng W, Li N, Li S, Peng Y (2019) Phosphorus recovery from freeze-microwave pretreated sludge supernatant by phosphate sedimentation. Environ Sci Pollut Res. 26:12859–12866. CrossRefGoogle Scholar
  7. Chen F, Luo Z, Liu G, Yang Y, Zhang S, Ma J (2017) Remediation of electronic waste polluted soil using a combination of persulfate oxidation and chemical washing. J Environ Manage 204:170–178CrossRefGoogle Scholar
  8. China EPA (2002) Analysis methods for the examination of water and wastewater, 4th edn. Chinese Environmental Science Press, Beijing (in Chinese)Google Scholar
  9. Cui T, Zhang Y, Han W, Li J, Sun X, Shen J, Wang L (2017) Advanced treatment of triazole fungicides discharged water in pilot scale by integrated system: enhanced electrochemical oxidation, upflow biological aerated filter and electrodialysis. Chem Eng J 315:335–344CrossRefGoogle Scholar
  10. Dheyongera G, Grzebyk K, Rudolf AM, Sadowska ET, Koteja P (2016) The effect of chlorpyrifos on thermogenic capacity of bank voles selected for increased aerobic exercise metabolism. Chemosphere 149:383–390CrossRefGoogle Scholar
  11. Dong Z, Lu M, Huang W, Xu X (2011) Treatment of oilfield wastewater in moving bed biofilm reactors using a novel suspended ceramic biocarrier. J Hazard Mater 196:123–130CrossRefGoogle Scholar
  12. Eisenberg G (1943) Colorimetric determination of hydrogen peroxide. Ind Eng Chem Anal Edit 15:327–328CrossRefGoogle Scholar
  13. Hua L, Ma H, Zhang L (2013) Degradation process analysis of the azo dyes by catalytic wet air oxidation with catalyst CuO/γ-Al2O3. Chemosphere 90:143–149CrossRefGoogle Scholar
  14. Huang K, Xu Y, Wang L, Wu D (2015) Heterogeneous catalytic wet peroxide oxidation of simulated phenol wastewater by copper metal–organic frameworks. RSC Adv 5:32795–32803CrossRefGoogle Scholar
  15. Isgoren M, Gengec E, Veli S (2017) Evaluation of wet air oxidation variables for removal of organophosphorus pesticide malathion using Box-Behnken design. Water Sci Technol 75:619–628CrossRefGoogle Scholar
  16. Kataki S, West H, Clarke M, Baruah DC (2016) Phosphorus recovery as struvite from farm, municipal and industrial waste: feedstock suitability, methods and pre-treatments. Waste Manag 49:437–454CrossRefGoogle Scholar
  17. Kayan B, Gözmen B, Demirel M, Gizir AM (2010) Degradation of acid red 97 dye in aqueous medium using wet oxidation and electro-Fenton techniques. J Hazard Mater 177:95–102CrossRefGoogle Scholar
  18. Levec J, Pintar A (2007) Catalytic wet-air oxidation processes: a review. Catal Today 124:172–184CrossRefGoogle Scholar
  19. Liotta LF (2010) Catalytic oxidation of volatile organic compounds on supported noble metals. Appl Catal B 100:403–412CrossRefGoogle Scholar
  20. Lu M, Zhang Z, Qiao W, Wei X, Guan Y, Ma Q, Guan Y (2010) Remediation of petroleum-contaminated soil after composting by sequential treatment with Fenton-like oxidation and biodegradation. Bioresour Technol 101:2106–2113CrossRefGoogle Scholar
  21. Miklos DB, Remy C, Jekel M, Linden KG, Drewes JE, Huebner U (2018) Evaluation of advanced oxidation processes for water and wastewater treatment–a critical review. Water Res 139:118–131CrossRefGoogle Scholar
  22. Minière M, Boutin O, Soric A (2017) Experimental coupling and modelling of wet air oxidation and packed-bed biofilm reactor as an enhanced phenol removal technology. Environ Sci Pollut Res 24:7693–7704CrossRefGoogle Scholar
  23. Ovejero G, Rodríguez A, Vallet A, Willerich S, García J (2012) Application of Ni supported over mixed Mg–Al oxides to crystal violet wet air oxidation: the role of the reaction conditions and the catalyst. Appl Catal B 111:586–594Google Scholar
  24. Pliego G, Zazo JA, Pariente MI, Rodríguez I, Petre AL, Leton P, García J (2014) Treatment of a wastewater from a pesticide manufacture by combined coagulation and Fenton oxidation. Environ Sci Pollut Res 21:12129–12134CrossRefGoogle Scholar
  25. Qiu G, Song Y, Zeng P, Xiao S, Duan L (2011) Phosphorus recovery from fosfomycin pharmaceutical wastewater by wet air oxidation and phosphate crystallization. Chemosphere 84:241–246CrossRefGoogle Scholar
  26. Quintanilla A, Casas JA, Rodriguez JJ (2010) Hydrogen peroxide-promoted-CWAO of phenol with activated carbon. Appl Catal B 93:339–345CrossRefGoogle Scholar
  27. Rani M, Shanker U (2018) Removal of chlorpyrifos, thiamethoxam, and tebuconazole from water using green synthesized metal hexacyanoferrate nanoparticles. Environ Sci Pollut Res 25:10878–10893CrossRefGoogle Scholar
  28. Samet Y, Agengui L, Abdelhédi R (2010) Electrochemical degradation of chlorpyrifos pesticide in aqueous solutions by anodic oxidation at boron-doped diamond electrodes. Chem Eng J 161:167–172CrossRefGoogle Scholar
  29. Saroha AK (2017) Treatment of industrial organic raffinate containing pyridine and its derivatives by coupling of catalytic wet air oxidation and biological processes. J Clean Prod 162:973–981CrossRefGoogle Scholar
  30. Shih YJ, Abarca RRM, de Luna MDG, Huang YH, Lu MC (2017) Recovery of phosphorus from synthetic wastewaters by struvite crystallization in a fluidized-bed reactor: effects of pH, phosphate concentration and coexisting ions. Chemosphere 173:466–473CrossRefGoogle Scholar
  31. Smith KN, Argyropoulos DS (2002) Quantitative 31P NMR detection of radical species in peroxide bleaching, TAPPI International Pulp Bleaching ConfGoogle Scholar
  32. Wei SP, van Rossum F, van de Pol GJ, Winkler MKH (2018) Recovery of phosphorus and nitrogen from human urine by struvite precipitation, air stripping and acid scrubbing: a pilot study. Chemosphere 212:1030–1037CrossRefGoogle Scholar
  33. Wijeyekoon S, Mino T, Satoh H, Matsuo T (2004) Effects of substrate loading rate on biofilm structure. Water Res 38:2479–2488CrossRefGoogle Scholar
  34. Xu L, Chen M (2018) Development of synthetic route of chlorpyrifos methyl by aqueous phase method. Chem Eng Equip 3:17–20 (in Chinese)Google Scholar
  35. Zeng F, Zhao Q, Jin W, Liu Y, Wang K, Lee DJ (2018) Struvite precipitation from anaerobic sludge supernatant and mixed fresh/stale human urine. Chem Eng J 344:254–261CrossRefGoogle Scholar
  36. Zhang Y, Pagilla K (2010) Treatment of malathion pesticide wastewater with nanofiltration and photo-Fenton oxidation. Desalination 263:36–44CrossRefGoogle Scholar
  37. Zhou S, Xu R, He J, Huang Y, Cai Z, Xu M, Song Z (2018) Preparation of Fe-Cu-kaolinite for catalytic wet peroxide oxidation of 4-chlorophenol. Environ Sci Pollut Res 25:4924–4933CrossRefGoogle Scholar
  38. Zolgharnein J, Shahmoradi A, Ghasemi J (2011) Pesticides removal using conventional and low-cost adsorbents: a review. Clean Soil Air Water 39:1105–1119CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Fu Chen
    • 1
    • 2
  • Siyan Zeng
    • 2
  • Jing Ma
    • 1
    • 3
    Email author
  • Qianlin Zhu
    • 2
  • Shaoliang Zhang
    • 1
  1. 1.Low Carbon Energy InstituteChina University of Mining and TechnologyXuzhouChina
  2. 2.School of Environment Science and Spatial InformaticsChina University of Mining and TechnologyXuzhouChina
  3. 3.Amap, Inra, Cnrs, Ird, CiradUniversity of MontpellierMontpellier Cedex 5France

Personalised recommendations