Removal of Polyphenolic Compounds from Olive Mill Wastewater with Sunlight Irradiation Using Nano-Zno–Sio2 Composite

  • Çağlar UlusoyEmail author
  • Delia Teresa Sponza
Conference paper
Part of the Green Energy and Technology book series (GREEN)


Olive mill wastewater (OMW) includes high concentrations of polyphenolic organics. Phenolic compounds in OMW cannot be removed with conventional removal processes. In this study, the polyphenols were removed with nano-ZnO–SiO2 under sunlight. The effects of nano-composite levels, irradiation times, and pH on the phenol removals were investigated. The aim of this study is to photodegrade the total phenol and three polyphenols (gallic acid, para-coumaric acid, t-paracoumaric acid) in the OMW using nano-ZnO–SiO2. The behaviors of elevated nano-ZnO–SiO2 doses (0.5, 1, 3, 5 and 10 g/L), the photodegradation intervals (8, 16, 24 and 36 h) and elevated pHs (4, 7 and 10) during sunlight were researched on the removals of polyphenols in the OMW. The best phenol yield was 73% using 3 g/L nano-ZnO–SiO2 under 24 h sunlight at pH 4. The maximum yields for gallic acid, para-coumaric acid, and t-para-coumaric acid were 90%, 5%, and 5%, respectively.


ZnO–SiO2 Photocatalytic degradation Olive mill wastewater Polyphenols Phenolic compounds 


  1. 1.
    Stasinakis AS, Elia I, Petalas AV, Halvadakis CP (2008) Removal of total phenols from olive-mill wastewater using an agricultural by-product, olive pomace. J Hazard Mater 160:408–413CrossRefGoogle Scholar
  2. 2.
    Jahangiri M, Rahimpour A, Nemati S, Alimohammady M (2014) Recovery of poly-phenols from olive mill wastewater by nanofiltration. Cell Chem Technol 50(9–10):961–966Google Scholar
  3. 3.
    Rosello-Soto E, Koubaa M, Moubarik AP, Lopes R, Saraiva A, Boussetta J, Grimi N, Barba JF (2015) Emerging opportunities for the effective valorization of wastes and by-products generated during olive oil production process: nonconventional methods for the recovery of high-added value compounds. Trends Food Sci Technol 45:296–310CrossRefGoogle Scholar
  4. 4.
    Bertin L, Ferri F, Scoma A, Marchetti L, Fava F (2011) Recovery of high added value natural polyphenols from actual olive mill wastewater through solid phase extraction. Chem Eng J 171:1287–1293CrossRefGoogle Scholar
  5. 5.
    Basta AH, Fierro V, El-Saied H, Celzard A (2009) 2-Steps KOH activation of rice straw: an efficient method for preparing high-performance activated carbons. Bioresour Technol 100:3941–3947CrossRefGoogle Scholar
  6. 6.
    Pagnanelly F, Sara M, Luigi T (2008) New biosorbent materials for heavy metal removal: development guided by active site characterization. Water Res 42:2953–2962CrossRefGoogle Scholar
  7. 7.
    Annab H, Fiol N, Villaescusa I, Essamri A (2019) A proposal for the sustainable treatment and valorisation of olive mill wastes. J Environ Chem Eng 7:102–803CrossRefGoogle Scholar
  8. 8.
    Mostafaa H, Iqdiam BM, Abuagela M, Marshall MR, Pullammanappallil P, Goodrich-Schneiderb R (2018) Treatment of olive mill wastewater using high power ultrasound (HPU) and electro-fenton (EF) method. Chem Eng Process Process Intensif 131:131–136CrossRefGoogle Scholar
  9. 9.
    Deeb AA, Fayyad MK, Alawi MA (2012) Separation of polyphenols from Jordanian olive oil mill wastewater. Hindawi Publishing Corporation Chromatography Research International Volume, Article ID 812127, 8 pGoogle Scholar
  10. 10.
    Mulinnacci N, Romani A, Galardi C, Pinelli P, Giaccherini C, Vincieri FF (2001) Polyphenolic content in olive oil wastewaters and related olive samples. J Agric Food Chem 49:3509–3514Google Scholar
  11. 11.
    Leouıfoudı I, Zyad A, Mouse HA, Amechrouq A, Mbarkı M, Oukerrou MA (2013) Identification and characterisation of phenolic compounds extracted from Moroccan olive mill wastewater. Food Sci Technol Camp 34(2):249–257CrossRefGoogle Scholar
  12. 12.
    Sangeeta M, Renuka L, Karthik KV, Ravishankar R, Anantharaju KS (2017) Synthesis of ZnO, MgO and ZnO/MgO by solution combustion method: characterization and photocatalytic studies. Mater Today: Proc 4(11):11791–11798Google Scholar
  13. 13.
    Lee HB, Yoo YM, Han YH (2006) Characteristic optical properties and synthesis of gold–silica core–shell colloids. Scripta Mater 55:1127–1129CrossRefGoogle Scholar
  14. 14.
    Zhai J, Tao X, Pu Y, Zeng X, Chen J (2010) Core/shell structured ZnO/SiO2 nanoparticles: preparation, characterization and photocatalytic property. Appl Surf Sci 257:393–397CrossRefGoogle Scholar
  15. 15.
    Mohamed RM, Baeissa ES, Mkhalid IA, Al-Rayyani MA (2013) Optimization of preparation conditions of ZnO–SiO2 xerogel by sol–gel technique for photodegradation of methylene blue dye. Appl Nanosci 3:57–63CrossRefGoogle Scholar
  16. 16.
    Ali MA, İsmail AA, Najmy R, Al-Hajry A (2014) Preparation and characterization of ZnO–SiO2 thin films as highly efficient photocatalyst. J Photochem Photobiol A 275:37–46CrossRefGoogle Scholar
  17. 17.
    Areerob Y, Cho JY, Jang WK, Oh WC (2018) Enhanced sonocatalytic degradation of organic dyes from aqueous solutions by novel synthesis of mesoporous Fe3O4-graphene/ZnO@SiO2 nanocomposites. Ultrason Sonochem 41:267–278CrossRefGoogle Scholar
  18. 18.
    Nezamzadeh-Ejhieh A, Bahrami M (2014) Investigation of the photocatalytic activity of supported ZnO–TiO2 on clinoptilolite nano-particles towards photodegradation of wastewater-contained phenol. Desalination Water Treat 55(4):1096–1104CrossRefGoogle Scholar
  19. 19.
    Shah N, Claessyns F, Rimmer S, Arain MB, Rehan T, Wazwaz A, Ahmad MW, Ul-Islam M (2016) Effective role of magnetic core-shell nanocomposites in removing organic and inorganic wastes from water. Recent Pat Nanotechnol 10(3):202–212Google Scholar
  20. 20.
    Rabahi A, Assadi AA, Nasrallah N, Bouzaza A, Maachi R, Wolbert D (2018) Photocatalytic treatment of petroleum industry wastewater using recirculating annular reactor: comparison of experimental and modeling toluene removal. Environ Sci Pollut Res 1–12Google Scholar
  21. 21.
    Tuchmantel W, Kozikowski AP, Romanczyk LJ Jr (1999) Studies inpolyphenolchemistryandbioactivity. 1. Preparation of building blocks from (+) catechin. Procyanidin formation. Synthesis of the cancer cell growth inhibitor, 3-O-galloyl-(2R,3R)-epicatechin-4β,8-[3-O-galloyl-(2R,3R) epicatechin]. J Am Chem Soc 121:12073–12081Google Scholar
  22. 22.
    Flight I, Clifton P (2006) Cereal grains and legumes in the prevention of coronary heart disease and stroke: a review of the literature. Eur J Clin Nutr 60(10):1145–1159Google Scholar
  23. 23.
    Lu Z, Nie G, Belton PS, Tang H, Zhao B (2006) Structure-activity relationship analysis of antioxidant ability and neuroprotective effect of gallic acid derivatives. Neurochem Int 48(4):263–274Google Scholar
  24. 24.
    Tuck KL, Hayball PJ, Stupans I (2002) Structural characterisation of the metabolites of hydroxytyrosol, the principal phenolic component in olive oil, in rats. J Agric Food Chem 50:2404–2409CrossRefGoogle Scholar
  25. 25.
    Visioli F, Poli A, Galli C (2002) Antioxidant and other biological activities of phenols from olives and olive oil. Med Res Rev 22(1):65–75CrossRefGoogle Scholar
  26. 26.
    Bendini A, Cerretani L, Carrasco-Pancorbo A, Gomez-Caravaca AM, Segura Carretero A, Fernandez-Gutierrez A (2007) Phenolic molecules in virgin olive oils: a survey of their sensory properties, health effects, antioxidant activity and analytical methods. An overview of the last decade. Molecules 12:1679–1719CrossRefGoogle Scholar
  27. 27.
    Kiritsakis AK (1998) Flavor components of olive oil—a review. J Am Oil Chem Soc 75:673–681CrossRefGoogle Scholar
  28. 28.
    Medina E, Brenes M, Romero C, García A, De Castro A (2007) Mainantimicrobials compounds in table olives. J Agric Food Chem 55:9817–9823CrossRefGoogle Scholar
  29. 29.
    Servili M, Selvaggini R, Esposto S, Taticchi A, Montedoro G, Morozzi M (2004) Health and sensory properties of virgin olive oil hydrophylic phenols: agronomic and technological aspects of production that affect their occurrence in the oil. J Chromatogr A 1054:113–127CrossRefGoogle Scholar
  30. 30.
    Tura D, Gigliotti C, Pedo S, Failla O, Bassi D, Serraiocco A (2007) Influence of cultivar and site of cultivation on levels of lipophilic and hydrophilic antioxidants in virgin olive oils (Olea europaea L.) and correlations with oxidative stability. Sci Hortic 112:108–119CrossRefGoogle Scholar
  31. 31.
    Vinha A, Ferreres F, Silva B, Valentão P, Gonçalves A, Pereira J, Oliveira M, Sebra R, Andrade P (2005) Phenolic profiles of Portuguese olive fruits (Olea europaea L.): Influences of cultivar and geographical origin. Food Chem 89:561–568CrossRefGoogle Scholar
  32. 32.
    Kalua CM, Allen MS, Bedgood DR, Bishop AG, Prenzler PD (2005) Discrimination of olive oils and fruits into cultivars and maturity stages based on phenolic and volatile compounds. J Agric Food Chem 53:8054–8062CrossRefGoogle Scholar
  33. 33.
    Gomez-Alonso S, Salvador MD, Fregapane G (2002) Phenolic compounds profile of Cornicabra virgin olive oil. J Agric Food Chem 50:6812–6817CrossRefGoogle Scholar
  34. 34.
    Tovar MJ, Motilva MJ, Romero MP (2001) Changes in the phenolic composition of virgin olive oil from young trees (Olea europaea L. cv. Arbequina) grown under linear irrigation strategies. J Agric Food Chem 49:5502–5508CrossRefGoogle Scholar
  35. 35.
    Ranalli A, Contento S, Schiavone C, Simone N (2001) Malaxing temperature affects volatile and phenol composition as well as other analytical features of virgin olive oil. Eur J Lipid Sci Technol 103:228–238CrossRefGoogle Scholar
  36. 36.
    Genick UK, Borgstahl GE, Ng K, Ren Z, Pradervand C, Burke PM, Srajer V, Teng TY, Schildkamp W, McRee DE, Moffat K, Getzoff ED (1997) Structure of a protein photocycle intermediate by millisecond time-resolved crystallography. Science 275(5305):1471–1475CrossRefGoogle Scholar
  37. 37.
    Hoff WD, Düx P, Hård K, Devreese B, Nugteren-Roodzant IM, Crielaard W, Boelens R, Kaptein R, Van Beeumen J, Hellingwerf KJ (1994) Thiol ester-linked p-coumaric acid as a new photoactive prosthetic group in a protein with rhodopsin-like photochemistry. Biochemistry 33(47):13959–13962CrossRefGoogle Scholar
  38. 38.
    Premvardhan LL, Buda F, Van Der Horst MA, Lührs DC, Hellingwerf KJ, Van Grondelle R (2004) Impact of photon absorption on the electronic properties of p-coumaric acid derivatives of the photoactive yellow protein chromophore. J Phys Chem B 108(16):5138–5148CrossRefGoogle Scholar
  39. 39.
    Hellingwerf KJ (2000) Key issues in the photochemistry and signalling-state formation of photosensor proteins. J Photochem Photobiol B Biol 54(2–3):94–102Google Scholar
  40. 40.
    Yamaguchi S, Kamikubo H, Kurihara K, Kuroki R, Niimura N, Shimizu N, Yamazaki Y, Kataoka M (2009) Low-barrier hydrogen bond in photoactive yellow protein. Proc Natl Acad Sci USA 106(2):440–444CrossRefGoogle Scholar
  41. 41.
    Capasso R, Evidente A, Schivo L, Orru G, Marcialis MA, Cristinzio G (1995) Antibacterial polyphenols from olive oil mill waste waters. J Appl Bacteriol 79(4):393–398CrossRefGoogle Scholar
  42. 42.
    Garcia-Castello E, Cassano A, Criscuoli A, Conidi C, Drioli E (2010) Recovery and concentration of polyphenols from olive mill wastewaters by integrated membrane system. Watr Res 44(13):3883–3892CrossRefGoogle Scholar
  43. 43.
    Casa R, D’Annibale A, Pierucetti F (2003) Reduction of the phenolic components in olive-mill wastewater by enzymatic treatment and its impact on durum wheat (Titricum durum Desf.) germinability. Chemosphere 50:959–966CrossRefGoogle Scholar
  44. 44.
    Kashıf N, Ouyang F (2009) Parameters effect on heterogeneous photocatalyse degradation of phenol in aqueous dispersion of TiO2. J Environ Sci 21:527–533CrossRefGoogle Scholar
  45. 45.
    Qamar M, Muneer M, Bahneman D (2006) Heterogeneous photocatalysed degradation of two selected pesticide derivatives, triclopyr and daminozid in aqueous suspensions of titanium dioxide. J Environ Manag 80:99–106CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2020

Authors and Affiliations

  1. 1.Environmental Engineering Department, Engineering FacultyDokuz Eylul UniversityIzmirTurkey

Personalised recommendations