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Removal of Phosphate from Aqueous Solution Using Alginate/Iron (III)

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Removal of Phosphate from Aqueous Solution Using Alginate/Iron (III) Water Air Soil Pollut (2016) 227: 427 DOI 10.1007/s11270-016-3128-0 Removal of Phosphate from Aqueous Solution Using Alginate/ Iron (III) Chloride Capsules: a Laboratory Study Hanna Siwek & Artur Bartkowiak & Małgorzata Włodarczyk & Katarzyna Sobecka Received: 14 April 2016 /Accepted: 18 October 2016 /Published online: 31 October 2016 # The Author(s) 2016. This article is published with open access at Springerlink.com Abstract Binding phosphate at participation of algi- equation show that by using several times smaller nate/FeCl3 capsules was studied with laboratory exper- amounts of iron, it is possible to remove similar or iments. The hydrogel microcapsules were obtained with bigger amounts of phosphorus than with other adsor- the dropping-in method, by gelation of sodium alginate bents containing iron. The alginate/FeCl3 adsorbent water solution by iron (III) chloride solution. Phosphate removes phosphate in a wide pH spectrum—from 4 to adsorption characteristics were studied in a static batch 10. Results suggest that the proposed adsorbent has system with respect to changes in contact time, initial potential in remediation of contaminated waters by phosphates concentration, pH of solution, and tempera- phosphate. ture. After 24 h of the tests, average 87.5% of phosphate ions were removed from the natural water solutions; Keywords Alginate . Iron (III) chloride . Phosphorus after 48 h, an equilibrium was reached. The adsorption removal . Surface water. Adsorption data were well fit by the Freundlich isotherm model. Parameter k of the isotherms amounted from 43.4 to 104.7, whereas parameter n amounted from 0.362 to 1 Introduction 0.476. The course of processes of phosphate adsorption and iron desorption to aquatic phase, as well as changes The research works on reasons and rate of eutrophica- in pH, suggests that phosphate adsorption is a major tion of surface waters and contents and transformations mechanism of phosphate removal, whereas simulta- of biogenic elements in the natural aquatic environ- neously, but at a much lower degree, a process of ment, which had been conducted for dozens of years, precipitation of phosphate by iron (III) ions released showed that, in the majority of cases, availability of from the capsules to the solution takes its place. phosphorus is a crucial factor controlling development Parameters calculated in the Freundlich isotherm of planktonic microorganisms (Forsberg and Ryding 1980;White1989; Correll 1996; Abell et al. 2010). : H. Siwek (*) M. Włodarczyk Shortage of phosphorus in the environment leads to a Department of General and Ecological Chemistry, West substantial reduction of productivity of water reser- Pomeranian University of Technology, Szczecin, ul. J. Słowackiego 17, 71-434 Szczecin, Poland voirs, while a surplus generally impedes the process e-mail: [email protected] of their eutrophication. Influence of phosphorus on : trophic conditions in waters depends not only on its A. Bartkowiak K. Sobecka quantity but also on phosphoric compounds manage- Center of Bioimmobilisation and Innovative Packaging Materials, Faculty of Food Sciences and Fisheries, West Pomeranian ment in the entire aquatic ecosystem. Therefore, University of Technology, Szczecin, ul. K. Janickiego 35, renaturisation and reclamation of eutrophiced water 71-270 Szczecin, Poland reservoirs is based, first of all, on reduction of 427 Page 2 of 10 Water Air Soil Pollut (2016) 227: 427 allochtonous and autochtonous deposits of phospho- aquatic environments. Generally, biosorbents are cation rus. Both in the process of wastewater treatment and exchangers binding in their structures metals, whereas inactivation of bioavailable forms of phosphorus in adsorption of assimilable forms of biogenic elements water reservoirs, generally, chemical methods are in requires their chemical modification. Scientific research use. If phosphorus compounds occur in colloidal ar- has proven that building iron in structures of biosorbents rangements, they are removed in volumetric coagula- improves qualities of sorptive phosphate in water solu- tion process with clear phases of destabilization and tions significantly (Unnithan et al. 2002; Eberhardt et al. flocculation. If phosphorus occurs as a true solution, a 2006;EberhardtandMin2008). A considerable rise in process of chemical precipitation takes place. For this adsorption of phosphate was observed after iron (III) purpose, the substances containing the multivalent hy- ions (Fe (III))-treated; refined aspen wood fiber droxides and salts of aluminum (Tandyrak et al. 2001; (Eberhardt et al. 2006;EberhardtandMin2008), coir Hullebusch et al. 2002), calcium (Dittrichm and path (Krishnan and Haridas 2008), eggshell waste Koschel 2002), and iron (Perkins and Underwood (Mezenner and Bensmaili 2009 ), and Staphylococcus 2001; Deppe and Benndorf 2002) are primarily used. xylosus biomass (Aryal and Liakopoulou-Kyriakides Apart from many advantages, such as high efficiency 2011). and a significant improvement on all stages of waste- Substances of a similar ability to bind iron cations water treatment, chemical precipitation has some dis- include alginate salts, which, when mixed with additives advantages too. For instance, it changes pH of condi- such as polyurethane (Sone et al. 2009), phosphorylated tioned water and does not provide a possibility to chitin (Jayakumar et al. 2009), or ferromagnetic citrate, regenerate most of the coagulant effectively, due to form adsorbents of high adsorption capacity to metals which they are recommended rather for single appli- such as nickel (Ngomsik et al. 2009; Jayakumar et al. cations (Genz et al. 2004). Because the coagulation 2009), zinc, copper (Jayakumar et al. 2009), and lead and precipitation processes in the natural waters are (Sone et al. 2009). Alginate acid is a natural biopolymer accompanied by co-precipitation and adsorption pro- (anionic polysaccharide) extracted from algae. Alginate cesses of different forms of phosphorus (Xiong and is nontoxic, non-immunogenic, and biodegradable and Peng 2011), a variety of adsorbents are added to water, when connected with multivalent metals, e.g., calcium, for instance, iron oxide in order to increase their rate forms structures of large specific areas (Bartkowiak and and to decrease the desorption of phosphorus com- Hunkeler 1999; Hill and Khan 2008). The sorption pounds from the bottom sediments (Geelhoed et al. properties of natural polysaccharide in the form of hy- 1997; Zeng and Li 2004; Chitrakar et al. 2006). Other drogel capsules, for instance, calcium alginate have widely promoted adsorbents are lanthanum-modified been confirmed, among others in the research bentonite (Haghseresht et al. 2009), natural zeolite concerning the purification of water from radionuclides (Tian et al. 2009; Dionisiou et al. 2013;Mengetal. (Mimura et al. 2001) and heavy metals (Nayak and 2013), mesoporus silicate material (Zhang et al. 2011), Lahiri 2006; Hui et al. 2015). composite adsorbents containing two (or more) differ- Perfect adsorptive qualities of alginate in the form ent metal oxides (Long et al. 2011;Lietal.2014), and of small hydrogel capsules have been confirmed poly (vinyl alcohol) hydrogel beads with aluminum through researches concerning purifying water from (Hui et al. 2014). Tian et al. (2009) recommended heavy metals with radioactive characteristics (Mimura adsorption as one of the most effective removal pro- et al. 2001). One may assume that adsorbents obtain- cesses for the low concentration of phosphorus. ed on the basis of alginate, having immobilized in it Modern technologies for removal of phosphorus salts of multivalent metals, which are used in con- should be based on such materials which do not pose a ventional methods of water treatment, might finally toxicological threat to the environment, can be recov- feature a strong affinity to phosphate. The purpose of ered and reused, as well as facilitate separation of the this paper was to examine kinetics of bonds of phos- deposited phosphorus and its reuse as, e.g., fertilizer (de- phate at participation of the alginate/Fe (III) hydrogel Basahan and Bashan 2004;Tianetal.2009). One of the capsules. Within the framework of conducted tests, it possible solutions could be application of biosorbents or is planned to determine adsorption isotherms and adsorbents obtained from biomass, which are more and check the impact of pH and temperature on this more frequently in use for removing impurities from process. Water Air Soil Pollut (2016) 227: 427 Page 3 of 10 427 2MaterialsandMethods Table 1 Selected indicators of quality of the tested water Water pH N_NH4 N_NO2 N_NO3 P_PO4 2.1 Preparation of Alginate/Fe (III) Hydrogel Capsules (mg L−1) (mg L−1) (mg L−1) (mg L−1) To receive the hydrogel capsules, an injection method W1 7.61 0.58 0.004 0.17 0.02 with creation of a hydrogel polyelectrolyte complex— W2 7.93 0.72 0.001 0.21 0.09 gelation of droplets of aquatic solution of polysaccha- ride with gelating salt. The polysaccharide, which was used for that purpose, was sodium alginate (Keltone HV, alginate/Fe (III) were put into 50-mL Erlenmeyer flasks. ISP-Germany), while the role of the gelating salt was Each portion of the capsules contained 2 mg of Fe. For played by iron (III) chloride (FeCl3 6H2O) each water, eight measurement series, repeated three (EUROCHEM BGD, Tarnów, Poland) in the form of times, were prepared. Changes in phosphate concentra- 0.155 M solution. The sodium alginate solution (1.5%) tion, pH, and a general content of iron in aquatic
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