Register      Login
Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH ARTICLE

Optimisation of orthophosphate and turbidity removal using an amphoteric chitosan-based flocculant–ferric chloride coagulant system

Henry K. Agbovi A and Lee D. Wilson https://orcid.org/0000-0002-0688-3102 A B
+ Author Affiliations
- Author Affiliations

A University of Saskatchewan, Department of Chemistry, 110 Science Place, Thorvaldson Building (Room 165), Saskatoon, Saskatchewan, Canada S7N 5C9.

B Corresponding author. Email: lee.wilson@usask.ca

Environmental Chemistry 16(8) 599-612 https://doi.org/10.1071/EN19100
Submitted: 2 April 2019  Accepted: 24 June 2019   Published: 26 July 2019

Environmental context. The fate and build-up of phosphate nutrients in aquatic environments is an urgent environmental problem affecting global water security. This study, guided by a statistical design method, optimises the flocculation properties of a biopolymer for removing orthophosphate from water. This improved technology has potential widespread applications for removal of orthophosphate from water and wastewater treatment systems.

Abstract. A coagulation-flocculation process was employed to remove turbidity (Ti) and orthophosphate (Pi) in aqueous media using a ferric chloride (FeCl3) and a grafted carboxymethyl chitosan (CMC) flocculant system. The amphoteric CMC-CTA flocculant was synthesised by grafting 3-chloro-2-hydroxypropyl trimethylammonium chloride (CTA) onto the biopolymer backbone of CMC. Here, CMC-CTA denotes the covalent grafting of CTA onto CMC. Optimisation of the variables for Pi and Ti removal was conducted using a jar test system based on the experimental design obtained from the response surface methodology (RSM). The Box–Behnken design was used to evaluate the individual and interactive effects of four independent variables: CMC-CTA dosage, FeCl3 dosage, pH and settling time. The RSM analysis showed that the experimental data followed a quadratic polynomial model with the following optimal conditions: [CMC-CTA] = 3.0 mg L−1, [FeCl3] = 10.0 mg L−1, pH 6.8 and settling time = 35 min. Optimum conditions led to a Pi removal of 96.4 % and turbidity removal of 96.7 % based on the RSM optimisation, in good agreement with experimental results with an initial concentration of 30.0 mg Pi L−1. The coagulation-flocculation process is characterised by a combination of electrostatic charge neutralisation, polymer bridging and a polymer adsorption mechanism.

Additional keywords: Box–Behnken design, coagulation, flocculation, quaternised carboxymethyl chitosan, response surface methodology.


References

Agbovi HK, Wilson LD (2017). Flocculation Optimization of Orthophosphate with FeCl3 and Alginate Using the Box-Behnken Response Surface Methodology. Industrial & Engineering Chemistry Research 56, 3145–3155.
Flocculation Optimization of Orthophosphate with FeCl3 and Alginate Using the Box-Behnken Response Surface MethodologyCrossref | GoogleScholarGoogle Scholar |

Agbovi HK, Wilson LD (2018). Design of amphoteric chitosan flocculants for phosphate and turbidity removal in wastewater. Carbohydrate Polymers 189, 360–370.
Design of amphoteric chitosan flocculants for phosphate and turbidity removal in wastewaterCrossref | GoogleScholarGoogle Scholar | 29580420PubMed |

Agbovi HK, Wilson LD, Tabil LG (2017). Biopolymer Flocculants and Oat Hull Biomass To Aid the Removal of Orthophosphate in Wastewater Treatment. Industrial & Engineering Chemistry Research 56, 37–46.
Biopolymer Flocculants and Oat Hull Biomass To Aid the Removal of Orthophosphate in Wastewater TreatmentCrossref | GoogleScholarGoogle Scholar |

Ali SA, Singh RP (2009). Synthesis and Characterization of a Modified Chitosan. Macromolecular Symposia 277, 1–7.
Synthesis and Characterization of a Modified ChitosanCrossref | GoogleScholarGoogle Scholar |

Apau J, Agbovi HK, Wemegah DD (2013). Assessment of the Water Quality of Boreholes in the Aburi Municipality of Eastern Region of Ghana. Journal of Science and Technology 33, 89–97.
Assessment of the Water Quality of Boreholes in the Aburi Municipality of Eastern Region of GhanaCrossref | GoogleScholarGoogle Scholar |

Attour A, Touati M, Tlili M, Ben Amor M, Lapicque F, Leclerc J (2014). Influence of operating parameters on phosphate removal from water by electrocoagulation using aluminum electrodes. Separation and Purification Technology 123, 124–129.
Influence of operating parameters on phosphate removal from water by electrocoagulation using aluminum electrodesCrossref | GoogleScholarGoogle Scholar |

Benyoucef S, Amrani M (2011). Adsorption of phosphate ions onto low cost Aleppo pine adsorbent. Desalination 275, 231–236.
Adsorption of phosphate ions onto low cost Aleppo pine adsorbentCrossref | GoogleScholarGoogle Scholar |

Bhatia S, Othman Z, Ahmad AL (2007). Coagulation-flocculation process for POME treatment using Moringa oleifera seeds extract: Optimization studies. Chemical Engineering Journal 133, 205–212.
Coagulation-flocculation process for POME treatment using Moringa oleifera seeds extract: Optimization studiesCrossref | GoogleScholarGoogle Scholar |

Bidgoli H, Zamani A, Taherzadeh MJ (2010). Effect of carboxymethylation conditions on the water-binding capacity of chitosan-based superabsorbents. Carbohydrate Research 345, 2683–2689.
Effect of carboxymethylation conditions on the water-binding capacity of chitosan-based superabsorbentsCrossref | GoogleScholarGoogle Scholar | 20971451PubMed |

Bolto B, Gregory J (2007). Organic polyelectrolytes in water treatment. Water Research 41, 2301–2324.
Organic polyelectrolytes in water treatmentCrossref | GoogleScholarGoogle Scholar | 17462699PubMed |

Bratby J (2006). ‘Coagulation and flocculation in water and wastewater treatment, 2nd edn.’ (IWA Publishing: London)

Bratskaya SY, Pestov AV, Yatluk YG, Avramenko VA (2009). Heavy metals removal by flocculation/precipitation using N-(2-carboxyethyl) chitosans. Colloids and Surfaces. A, Physicochemical and Engineering Aspects 339, 140–144.
Heavy metals removal by flocculation/precipitation using N-(2-carboxyethyl) chitosansCrossref | GoogleScholarGoogle Scholar |

Cai Z, Song Z, Shang S, Yang C (2007). Study on the flocculating properties of quaternized carboxymethyl chitosan. Polymer Bulletin 59, 655–665.
Study on the flocculating properties of quaternized carboxymethyl chitosanCrossref | GoogleScholarGoogle Scholar |

Dawood AS, Li Y (2014). Wastewater flocculation using a new hybrid copolymer: Modeling and optimization by response surface methodology. Polish Journal of Environmental Studies 23, 43–50.

de Abreu FR, Campana-Filho SP (2009). Characteristics and properties of carboxymethylchitosan. Carbohydrate Polymers 75, 214–221.
Characteristics and properties of carboxymethylchitosanCrossref | GoogleScholarGoogle Scholar |

Dey KP, Mishra S, Sen G (2017). Synthesis and characterization of polymethylmethacrylate grafted barley for treatment of industrial and municipal wastewater. Journal of Water Process Engineering 18, 113–125.
Synthesis and characterization of polymethylmethacrylate grafted barley for treatment of industrial and municipal wastewaterCrossref | GoogleScholarGoogle Scholar |

Dunets CS, Zheng Y (2015). Combined Precipitation / Flocculation Method for Nutrient Recovery from Greenhouse Wastewater. HortScience 50, 921–926.
Combined Precipitation / Flocculation Method for Nutrient Recovery from Greenhouse WastewaterCrossref | GoogleScholarGoogle Scholar |

Filipkowska U, Jóźwiak T, Szymczyk P (2014). Application of Cross-Linked Chitosan for Phosphate Removal From Aqueous Solutions. Progress on Chemistry and Application of Chitin and Its Derivatives 19, 5–14.
Application of Cross-Linked Chitosan for Phosphate Removal From Aqueous SolutionsCrossref | GoogleScholarGoogle Scholar |

Gautam RK, Banerjee S, Gautam PK, Chattopadhyaya MC (2014). Remediation Technologies for Phosphate Removal From Wastewater: An Overview. Advances in Environmental Research 36, 1–23.

Ge HC, Luo DK (2005). Preparation of carboxymethyl chitosan in aqueous solution under microwave irradiation. Carbohydrate Research 340, 1351–1356.
Preparation of carboxymethyl chitosan in aqueous solution under microwave irradiationCrossref | GoogleScholarGoogle Scholar | 15854605PubMed |

Ghafari S, Aziz HA, Isa MH, Zinatizadeh AA (2009). Application of response surface methodology (RSM) to optimize coagulation-flocculation treatment of leachate using poly-aluminum chloride (PAC) and alum. Journal of Hazardous Materials 163, 650–656.
Application of response surface methodology (RSM) to optimize coagulation-flocculation treatment of leachate using poly-aluminum chloride (PAC) and alumCrossref | GoogleScholarGoogle Scholar | 18771848PubMed |

Golder AK, Samanta AN, Ray S (2006). Removal of phosphate from aqueous solutions using calcined metal hydroxides sludge waste generated from electrocoagulation. Separation and Purification Technology 52, 102–109.
Removal of phosphate from aqueous solutions using calcined metal hydroxides sludge waste generated from electrocoagulationCrossref | GoogleScholarGoogle Scholar |

Gregory J (1973). Rates of flocculation of latex particles by cationic polymers. Journal of Colloid and Interface Science 42, 448–456.
Rates of flocculation of latex particles by cationic polymersCrossref | GoogleScholarGoogle Scholar |

Holme HK, Foros H, Pettersen H, Dornish M, Smidsrùd O (2001). Thermal depolymerization of chitosan chloride. Carbohydrate Polymers 46, 287–294.
Thermal depolymerization of chitosan chlorideCrossref | GoogleScholarGoogle Scholar |

Hoogeveen NG, Cohen Stuart MA, Fleer GJ (1996). Can charged (block co)polymers act as stabilisers and flocculants of oxides?. Colloids and Surfaces. A, Physicochemical and Engineering Aspects 117, 77–88.
Can charged (block co)polymers act as stabilisers and flocculants of oxides?Crossref | GoogleScholarGoogle Scholar |

Hudson JJ, Taylor WD, Schindler DW (2000). Phosphate concentrations in lakes. Nature 406, 54–56.
Phosphate concentrations in lakesCrossref | GoogleScholarGoogle Scholar | 10894537PubMed |

Inan H, Alaydın E (2014). Phosphate and nitrogen removal by iron produced in electrocoagulation reactor. Desalination and Water Treatment 52, 1396–1403.
Phosphate and nitrogen removal by iron produced in electrocoagulation reactorCrossref | GoogleScholarGoogle Scholar |

Kasper DR (1971). Theoretical and experimental investigations of the flocculation of charged particles in aqueous solutions by polyelectrolytes of opposite charge. PhD dissertation, California Institute of Technology.

Kleimann J, Gehin-Delval C, Auweter H, Borkovec M (2005). Super-stoichiometric charge neutralization in particle-polyelectrolyte systems. Langmuir 21, 3688–3698.
Super-stoichiometric charge neutralization in particle-polyelectrolyte systemsCrossref | GoogleScholarGoogle Scholar | 15807622PubMed |

Kumar SS, Bishnoi NR (2017). Coagulation of landfill leachate by FeCl3: process optimization using Box–Behnken design (RSM). Applied Water Science 7, 1943–1953.
Coagulation of landfill leachate by FeCl3: process optimization using Box–Behnken design (RSM)Crossref | GoogleScholarGoogle Scholar |

Lee JD, Lee SH, Jo MH, Park PK, Lee CH, Kwak JW (2000). Effect of coagulation conditions on membrane filtration characteristics in coagulation - Microfiltration process for water treatment. Environmental Science & Technology 34, 3780–3788.
Effect of coagulation conditions on membrane filtration characteristics in coagulation - Microfiltration process for water treatmentCrossref | GoogleScholarGoogle Scholar |

Lee CS, Robinson J, Chong MF (2014). A review on application of flocculants in wastewater treatment. Process Safety and Environmental Protection 92, 489–508.
A review on application of flocculants in wastewater treatmentCrossref | GoogleScholarGoogle Scholar |

Li Y, Liu Z, Zhao H, Xu Y, Cui F (2007). Statistical optimization of xylanase production from new isolated Penicillium oxalicum ZH-30 in submerged fermentation. Biochemical Engineering Journal 34, 82–86.
Statistical optimization of xylanase production from new isolated Penicillium oxalicum ZH-30 in submerged fermentationCrossref | GoogleScholarGoogle Scholar |

Li S, Zhou P, Yao P, Wei Y, Zhang Y, Yue W (2010). Preparation of O-Carboxymethyl-N-Trimethyl Chitosan Chloride and Flocculation of the Wastewater in Sugar Refinery. Journal of Applied Polymer Science 116, 2742–2748.
Preparation of O-Carboxymethyl-N-Trimethyl Chitosan Chloride and Flocculation of the Wastewater in Sugar RefineryCrossref | GoogleScholarGoogle Scholar |

Li N, Hu Y, Lu Y-Z, Zeng RJ, Sheng G-P (2016). Multiple response optimization of the coagulation process for upgrading the quality of effluent from municipal wastewater treatment plant. Scientific Reports 6, 26115
Multiple response optimization of the coagulation process for upgrading the quality of effluent from municipal wastewater treatment plantCrossref | GoogleScholarGoogle Scholar | 27189652PubMed |

Mahaninia MH, Wilson LD (2016). Cross-linked chitosan beads for phosphate removal from aqueous solution. Journal of Applied Polymer Science 133, 42949
Cross-linked chitosan beads for phosphate removal from aqueous solutionCrossref | GoogleScholarGoogle Scholar |

Mohammed SAM, Shanshool HA (2009). Phosphorus Removal from Water and Waste Water by Chemical Precipitation Using Alum and Calcium Chloride. Iraqi Journal of Chemical and Petroleum Engineering 10, 35–42.

Montgomery DC (2013). ‘Design and analysis of experiments, 8th edn.’ (Wiley: Hoboken, NJ)

Murthy MSRC, Swaminathan T, Rakshit SK, Kosugi Y (2000). Statistical optimization of lipase catalyzed hydrolysis of methyloleate by response surface methodology. Bioprocess Engineering 22, 35–39.
Statistical optimization of lipase catalyzed hydrolysis of methyloleate by response surface methodologyCrossref | GoogleScholarGoogle Scholar |

Napper DH (1983). ‘Polymeric stabilization of colloidal dispersions.’ (Academic Press Inc.: New York, NY)

Palamakula A, Nutan MTH, Khan MA (2004). Response surface methodology for optimization and characterization of limonene-based coenzyme Q10 self-nanoemulsified capsule dosage form. AAPS PharmSciTech 5, 114–121.
Response surface methodology for optimization and characterization of limonene-based coenzyme Q10 self-nanoemulsified capsule dosage formCrossref | GoogleScholarGoogle Scholar |

Peleka EN, Mavros PP, Zamboulis D, Matis Ka (2006). Removal of phosphates from water by a hybrid flotation-membrane filtration cell. Desalination 198, 198–207.
Removal of phosphates from water by a hybrid flotation-membrane filtration cellCrossref | GoogleScholarGoogle Scholar |

Razali MAA, Ahmad Z, Ahmad MSB, Ariffin A (2011). Treatment of pulp and paper mill wastewater with various molecular weight of polyDADMAC induced flocculation. Chemical Engineering Journal 166, 529–535.
Treatment of pulp and paper mill wastewater with various molecular weight of polyDADMAC induced flocculationCrossref | GoogleScholarGoogle Scholar |

Rojas-Reyna R, Schwarz S, Heinrich G, Petzold G, Schutze S, Bohrisch J (2010). Flocculation efficiency of modified water soluble chitosan versus commonly used commercial polyelectrolytes. Carbohydrate Polymers 81, 317–322.
Flocculation efficiency of modified water soluble chitosan versus commonly used commercial polyelectrolytesCrossref | GoogleScholarGoogle Scholar |

Sathasivan A (2010). Water and wastewater treatment technologies – biological phosphorus removal processes for wastewater treatment. Encyclopedia of Life Support Systems, 1–16. Available at http://www.eolss.net/Sample-Chapters/C07/E6-144-10.pdf [verified 9 July 2019]

Sher F, Malik A, Liu H (2013). Industrial polymer effluent treatment by chemical coagulation and flocculation. Journal of Environmental Chemical Engineering 1, 684–689.
Industrial polymer effluent treatment by chemical coagulation and flocculationCrossref | GoogleScholarGoogle Scholar |

Singh A, Srivastava A, Tripathi A, Dutt NN (2016). Optimization of Brilliant Green Dye Removal Efficiency by Electrocoagulation Using Response Surface Methodology. World Journal of Environmental Engineering 4, 23–29.
Optimization of Brilliant Green Dye Removal Efficiency by Electrocoagulation Using Response Surface MethodologyCrossref | GoogleScholarGoogle Scholar |

Sø HU, Postma D, Jakobsen R, Larsen F (2011). Sorption of phosphate onto calcite; results from batch experiments and surface complexation modeling. Geochimica et Cosmochimica Acta 75, 2911–2923.
Sorption of phosphate onto calcite; results from batch experiments and surface complexation modelingCrossref | GoogleScholarGoogle Scholar |

Tanada S, Kabayama M, Kawasaki N, Sakiyama T, Nakamura T, Araki M, Tamura T (2003). Removal of phosphate by aluminum oxide hydroxide. Journal of Colloid and Interface Science 257, 135–140.
Removal of phosphate by aluminum oxide hydroxideCrossref | GoogleScholarGoogle Scholar | 16256465PubMed |

Trinh TK, Kang L-S (2010). Application of Response Surface Method as an Experimental Design to Optimize Coagulation Tests. Environmental Engineering Research 15, 63–70.
Application of Response Surface Method as an Experimental Design to Optimize Coagulation TestsCrossref | GoogleScholarGoogle Scholar |

Trinh TK, Kang LS (2011). Response surface methodological approach to optimize the coagulation-flocculation process in drinking water treatment. Chemical Engineering Research & Design 89, 1126–1135.
Response surface methodological approach to optimize the coagulation-flocculation process in drinking water treatmentCrossref | GoogleScholarGoogle Scholar |

Usharani K, Lakshmanaperumalsamy P (2016). Box-Behnken experimental design mediated optimization of aqueous methylparathion biodegradation by Pseudomonas aeruginosa MPD strain. Journal of Microbiology, Biotechnology and Food Sciences 05, 534–547.
Box-Behnken experimental design mediated optimization of aqueous methylparathion biodegradation by Pseudomonas aeruginosa MPD strainCrossref | GoogleScholarGoogle Scholar |

Usharani K, Muthukumar M (2013). Optimization of aqueous methylparathion biodegradation by Fusarium sp in batch scale process using response surface methodology. International Journal of Environmental Science and Technology 10, 591–606.
Optimization of aqueous methylparathion biodegradation by Fusarium sp in batch scale process using response surface methodologyCrossref | GoogleScholarGoogle Scholar |

Vasudevan S, Lakshmi J, Jayaraj J, Sozhan G (2009). Remediation of phosphate-contaminated water by electrocoagulation with aluminium, aluminium alloy and mild steel anodes. Journal of Hazardous Materials 164, 1480–1486.
Remediation of phosphate-contaminated water by electrocoagulation with aluminium, aluminium alloy and mild steel anodesCrossref | GoogleScholarGoogle Scholar | 18977084PubMed |

Wang J, Chen Y, Yuan S, Sheng G, Yu H (2009). Synthesis and characterization of a novel cationic chitosan-based flocculant with a high water-solubility for pulp mill wastewater treatment. Water Research 43, 5267–5275.
Synthesis and characterization of a novel cationic chitosan-based flocculant with a high water-solubility for pulp mill wastewater treatmentCrossref | GoogleScholarGoogle Scholar | 19765791PubMed |

Yan LG, Xu YY, Yu HQ, Xin XD, Wei Q, Du B (2010). Adsorption of phosphate from aqueous solution by hydroxy-aluminum, hydroxy-iron and hydroxy-iron-aluminum pillared bentonites. Journal of Hazardous Materials 179, 244–250.
Adsorption of phosphate from aqueous solution by hydroxy-aluminum, hydroxy-iron and hydroxy-iron-aluminum pillared bentonitesCrossref | GoogleScholarGoogle Scholar | 20334967PubMed |

Yang Z, Shang Y, Lu Y, Chen Y, Huang X, Chen A, Jiang Y, Gu W, Qian X, Yang H, Cheng R (2011). Flocculation properties of biodegradable amphoteric chitosan-based flocculants. Chemical Engineering Journal 172, 287–295.
Flocculation properties of biodegradable amphoteric chitosan-based flocculantsCrossref | GoogleScholarGoogle Scholar |

Yang Z, Shang Y, Huang X, Chen Y, Lu Y, Chen A, Jiang Y, Gu W, Qian X, Yang H, Cheng R (2012). Cationic content effects of biodegradable amphoteric chitosan-based flocculants on the flocculation properties. Journal of Environmental Sciences 24, 1378–1385.
Cationic content effects of biodegradable amphoteric chitosan-based flocculants on the flocculation propertiesCrossref | GoogleScholarGoogle Scholar |

Yeoman S, Stephenson T, Lester JN, Perry R (1988). The removal of phosphorus during wastewater treatment: a review. Environmental Pollution 49, 183–233.
The removal of phosphorus during wastewater treatment: a reviewCrossref | GoogleScholarGoogle Scholar | 15092663PubMed |

Yetilmezsoy K, Demirel S, Vanderbei RJ (2009). Response surface modeling of Pb(II) removal from aqueous solution by Pistacia vera L.: Box-Behnken experimental design. Journal of Hazardous Materials 171, 551–562.
Response surface modeling of Pb(II) removal from aqueous solution by Pistacia vera L.: Box-Behnken experimental designCrossref | GoogleScholarGoogle Scholar | 19577844PubMed |

Yuan B, Shang Y, Lu Y, Qin Z, Jiang Y, Chen A, Qian X, Wang G, Yang H, Cheng R (2010). The flocculating properties of chitosan-graft-polyacrylamide flocculants (I) – effect of the grafting ratio. Journal of Applied Polymer Science 117, 1876–1882.
The flocculating properties of chitosan-graft-polyacrylamide flocculants (I) – effect of the grafting ratioCrossref | GoogleScholarGoogle Scholar |

Zemmouri H, Drouiche M, Sayeh A, Lounici H, Mameri N (2013). Chitosan Application for Treatment of Beni-Amrane’s Water Dam. Energy Procedia 36, 558–564.
Chitosan Application for Treatment of Beni-Amrane’s Water DamCrossref | GoogleScholarGoogle Scholar |

Zhang W, Shang Y, Yuan B, Jiang Y, Lu Y, Qin Z, Chen A, Qian X, Yang H, Cheng R (2010). The flocculating properties of chitosan-graft-polyacrylamide flocculants (II) – test in pilot scale. Journal of Applied Polymer Science 117, 2016–2024.
The flocculating properties of chitosan-graft-polyacrylamide flocculants (II) – test in pilot scaleCrossref | GoogleScholarGoogle Scholar |