Simple fabrication of carboxymethyl cellulose and κ-carrageenan composite aerogel with efficient performance in removal of fluoroquinolone antibiotics from water

Abstract

● A composite aerogel was simply obtained to remove various fluoroquinolones (FQs).

● The structural and textural properties of this composite aerogel are improved.

● Its adsorption capacity was improved at a low content of coexisting Cu²⁺ or Fe³⁺ ion.

● Two substructural analogs of FQs are compared to explore the adsorption mechanisms.

● This aerogel after saturated adsorption can be reused directly for Cu²⁺ adsorption.

3D composite aerogels (CMC-CG) composed of carboxymethyl cellulose and κ-carrageenan were designed and fabricated using the one-pot synthesis technique. The optimized CMC-CG showed a good mechanical property and a high swelling ratio due to its superior textural properties with a proper chemically cross-linked interpenetrating network structure. CMC-CG was utilized for the removal of various fluoroquinolones (FQs) from water and exhibited high adsorption performance because of effective electrostatic attraction and hydrogen bonding interactions. Ciprofloxacin (CIP), a popular FQ, was used as the representative. The optimized CMC-CG had a theoretically maximal CIP uptake of approximately 1.271 mmol/g at the pH of 5.0. The adsorption capacity of CMC-CG was improved in the presence of some cations, Cu²⁺ and Fe³⁺ ions, at a low concentration through the bridging effect but was reduced at a high concentration. The investigation of adsorption mechanisms, based on the adsorption kinetics, isotherms and thermodynamic study, Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy analyses before and after adsorption, and changes in the adsorption performance of CMC-CG toward two molecular probes, further indicated that electrostatic attraction was the dominant interaction rather than hydrogen bonding in this adsorption. CMC-CG after saturated adsorption of CIP could be easily regenerated using a dilute NaCl aqueous solution and reused efficiently. Moreover, the disused aerogel could still be reused as a new adsorbent for effective adsorption of Cu²⁺ ion. Overall, this study suggested the promising applications of this composite aerogel as an eco-friendly, cost-effective, and recyclable adsorbent for the efficient removal of FQs from water.

Graphical abstract

Keywords

Composite aerogel of carboxymethyl cellulose and κ-carrageenan / Fluoroquinolone antibiotics / Adsorption performance / Coexisting substances / Adsorption mechanism / Reusability

References

[1] Al-SakkariE G, AbdeldayemO M, GeninaE E, AminL, BahgatN T, ReneE R, El-SherbinyI M. (2020). New alginate-based interpenetrating polymer networks for water treatment: A response surface methodology based optimization study. International Journal of Biological Macromolecules, 155 : 772– 785

[2] CarabineiroS A C, Thavorn-amornsriT, PereiraM F R, SerpP, FigueiredoJ L. (2012). Comparison between activated carbon, carbon xerogel and carbon nanotubes for the adsorption of the antibiotic ciprofloxacin. Catalysis Today, 186( 1): 29– 34

[3] ChenY, LongY, LiQ, ChenX, XuX. (2019). Synthesis of high-performance sodium carboxymethyl cellulose-based adsorbent for effective removal of methylene blue and Pb(II). International Journal of Biological Macromolecules, 126 : 107– 117

[4] ChenY, WangA, ZhangY, BaoR, TianX, LiJ. (2017). Electro-Fenton degradation of antibiotic ciprofloxacin (CIP): Formation of Fe³⁺-CIP chelate and its effect on catalytic behavior of Fe²⁺/Fe³⁺ and CIP mineralization. Electrochimica Acta, 256 : 185– 195

[5] CuprysA, PulicharlaR, BrarS K, DroguiP, VermaM, SurampalliR Y. (2018). Fluoroquinolones metal complexation and its environmental impacts. Coordination Chemistry Reviews, 376 : 46– 61

[6] DogaruB I, SimionescuB, PopescuM C. (2020). Synthesis and characterization of κ-carrageenan bio-nanocomposite films reinforced with bentonite nanoclay. International Journal of Biological Macromolecules, 154 : 9– 17

[7] DuX, YangW, LiuY, ZhangW, WangZ, NieJ, LiG, LiangH. (2020). Removal of manganese, ferrous and antibiotics from groundwater simultaneously using peroxymonosulfate-assisted in-situ oxidation/coagulation integrated with ceramic membrane process. Separation and Purification Technology, 252 : 117492

[8] DuanW LiM Xiao W WangN NiuB Zhou L ZhengY (2019). Enhanced adsorption of three fluoroquinolone antibiotics using polypyrrole functionalized Calotropis gigantea fiber . Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 574: 178− 187

[9] FanH, MaY, WanJ, WangY, LiZ, ChenY. (2020). Adsorption properties and mechanisms of novel biomaterials from banyan aerial roots via simple modification for ciprofloxacin removal. Science of the Total Environment, 708 : 134630

[10] FreundlichH M F. (1906). Over the adsorption in solution. Journal of Physical Chemistry, 57 : 385– 470

[11] GaoB, ChangQ, CaiJ, XiZ, LiA, YangH. (2021). Removal of fluoroquinolone antibiotics using actinia-shaped lignin-based adsorbents: Role of the length and distribution of branched-chains. Journal of Hazardous Materials, 403 : 123603

[12] GaoB, LiP, YangR, LiA, YangH. (2019). Investigation of multiple adsorption mechanisms for efficient removal of ofloxacin from water using lignin-based adsorbents. Scientific Reports, 9 : 637

[13] GulenB, DemirciviP. (2020). Adsorption properties of flouroquinolone type antibiotic ciprofloxacin into 2:1 dioctahedral clay structure: Box-Behnken experimental design. Journal of Molecular Structure, 1206 : 127659

[14] HoY S, McKayG. (1998). Sorption of dye from aqueous solution by peat. Chemical Engineering Journal, 70( 2): 115– 124

[15] HuangD, WuJ, WangL, LiuX, MengJ, TangX, TangC, XuJ. (2019). Novel insight into adsorption and co-adsorption of heavy metal ions and an organic pollutant by magnetic graphene nanomaterials in water. Chemical Engineering Journal, 358 : 1399– 1409

[16] IgwegbeC A, ObaS N, AniagorC O, AdeniyiA G, IghaloJ O. (2021). Adsorption of ciprofloxacin from water: A comprehensive review. Journal of Industrial and Engineering Chemistry, 93 : 57– 77

[17] KovtunA, CampodoniE, FavarettoL, ZambianchiM, SalatinoA, AmalfitanoS, NavacchiaM L, CasentiniB, PalermoV, SandriM, MelucciM. (2020). Multifunctional graphene oxide/biopolymer composite aerogels for microcontaminants removal from drinking water. Chemosphere, 259 : 127501

[18] KumarM, JaiswalS, SodhiK K, ShreeP, SinghD K, AgrawalP K, ShuklaP. (2019). Antibiotics bioremediation: Perspectives on its ecotoxicity and resistance. Environment International, 124 : 448– 461

[19] LagergrenS. (1989). About the theory of so-called sorption of soluble substances. Kungliga Svenska Vetenskapsakademiens Handlingar, 24 : 1– 39

[20] LangmuirI. (1918). The adsorption of gases on plane surfaces of glass, mica and platinum. Journal of the American Chemical Society, 40( 9): 1361– 1403

[21] LarcipreteR, FabrisS, SunT, LacovigP, BaraldiA, LizzitS. (2011). Dual path mechanism in the thermal reduction of graphene oxide. Journal of the American Chemical Society, 133( 43): 17315– 17321

[22] LiL, ZhaoJ, SunY, YuF, MaJ. (2019). Ionically cross-linked sodium alginate/ĸ-carrageenan double-network gel beads with low-swelling, enhanced mechanical properties, and excellent adsorption performance. Chemical Engineering Journal, 372 : 1091– 1103

[23] LiM F, LiuY G, LiuS B, ShuD, ZengG M, HuX J, TanX F, JiangL H, YanZ L, CaiX X. (2017). Cu(II)-influenced adsorption of ciprofloxacin from aqueous solutions by magnetic graphene oxide/nitrilotriacetic acid nanocomposite: Competition and enhancement mechanisms. Chemical Engineering Journal, 319 : 219– 228

[24] LiN, YangH. (2021). Construction of natural polymeric imprinted materials and their applications in water treatment: A review. Journal of Hazardous Materials, 403 : 123643

[25] LianF, SunB, SongZ, ZhuL, QiX, XingB. (2014). Physicochemical properties of herb-residue biochar and its sorption to ionizable antibiotic sulfamethoxazole. Chemical Engineering Journal, 248 : 128– 134

[26] LiangX C, DuanJ J, XuQ, WeiX Q, LuA, ZhangL N. (2017). Ampholytic microspheres constructed from chitosan and carrageenan in alkali/urea aqueous solution for purification of various wastewater. Chemical Engineering Journal, 317 : 766– 776

[27] LingC, LiuF Q, XuC, ChenT P, LiA M. (2013). An integrative technique based on synergistic coremoval and sequential recovery of copper and tetracycline with dual-functional chelating resin: Roles of amine and carboxyl groups. ACS Applied Materials & Interfaces, 5( 22): 11808– 11817

[28] LiuX, LiuM, ZhangL. (2018). Co-adsorption and sequential adsorption of the co-existence four heavy metal ions and three fluoroquinolones on the functionalized ferromagnetic 3D NiFe₂O₄ porous hollow microsphere. Journal of Colloid and Interface Science, 511 : 135– 144

[29] LuS, LiuW, WangY, ZhangY, LiP, JiangD, FangC, LiY. (2019). An adsorbent based on humic acid and carboxymethyl cellulose for efficient dye removal from aqueous solution. International Journal of Biological Macromolecules, 135 : 790– 797

[30] MaJ, JiangZ, CaoJ, YuF. (2020a). Enhanced adsorption for the removal of antibiotics by carbon nanotubes/graphene oxide/sodium alginate triple-network nanocomposite hydrogels in aqueous solutions. Chemosphere, 242 : 125188

[31] MaJ, XiongY, DaiX, YuF. (2020b). Coadsorption behavior and mechanism of ciprofloxacin and Cu(II) on graphene hydrogel wetted surface. Chemical Engineering Journal, 380 : 122387

[32] MalekiH. (2016). Recent advances in aerogels for environmental remediation applications: A review. Chemical Engineering Journal, 300 : 98– 118

[33] MalekiH, DurãesL, García-GonzálezC A, DelGaudio P, PortugalA, MahmoudiM. (2016). Synthesis and biomedical applications of aerogels: Possibilities and challenges. Advances in Colloid and Interface Science, 236 : 1– 27

[34] MartinsB F, de ToledoP V O, PetriD F S. (2017). Hydroxypropyl methylcellulose based aerogels: Synthesis, characterization and application as adsorbents for wastewater pollutants. Carbohydrate Polymers, 155 : 173– 181

[35] McManusP S, StockwellV O, SundinG W, JonesA L. (2002). Antibiotic use in plant agriculture. Annual Review of Phytopathology, 40( 1): 443– 465

[36] MohammadA KhanM E AbutalebA AliW Tauqeer M YoonT ChoM H (2021). Chapter 8-Aerogel and its composites for sensing, adsorption, and photocatalysis. In: Khan A, Ansari M, Khan A, Asiri A, editors. Advances in Aerogel Composites for Environmental Remediation. Amsterdam: Elsevier, 125– 144

[37] MohapatraM, PadhiT, AnandS, MishraB K. (2012). Ca-Mg-doped surface-modified nano-sized ferrihydrite powder synthesized by surfactant mediation–precipitation technique: A novel super adsorbent for cations. Adsorption Science and Technology, 30( 5): 383– 397

[38] NguyenT T, BuiX T, LuuV P, NguyenP D, GuoW, NgoH H. (2017). Removal of antibiotics in sponge membrane bioreactors treating hospital wastewater: Comparison between hollow fiber and flat sheet membrane systems. Bioresource Technology, 240 : 42– 49

[39] PanJ, LiY, ChenK, ZhangY, ZhangH. (2021). Enhanced physical and antimicrobial properties of alginate/chitosan composite aerogels based on electrostatic interactions and noncovalent crosslinking. Carbohydrate Polymers, 266 : 118102

[40] PeiZ, ShanX Q, KongJ, WenB, OwensG. (2010). Coadsorption of ciprofloxacin and Cu(II) on montmorillonite and kaolinite as affected by solution pH. Environmental Science & Technology, 44( 3): 915– 920

[41] RenJ, LiN, WeiH, LiA, YangH. (2020). Efficient removal of phosphorus from turbid water using chemical sedimentation by FeCl₃ in conjunction with a starch-based flocculant. Water Research, 170 : 115361

[42] SalamaA, ShukryN, El-SakhawyM. (2015). Carboxymethyl cellulose-g-poly(2-(dimethylamino) ethyl methacrylate) hydrogel as adsorbent for dye removal. International Journal of Biological Macromolecules, 73 : 72– 75

[43] SalgueiroA M, Daniel-da-SilvaA L, GirãoA V, PinheiroP C, TrindadeT. (2013). Unusual dye adsorption behavior of κ-carrageenan coated superparamagnetic nanoparticles. Chemical Engineering Journal, 229 : 276– 284

[44] SarmahA K, MeyerM T, BoxallA B. (2006). A global perspective on the use, sales, exposure pathways, occurrence, fate and effects of veterinary antibiotics (VAs) in the environment. Chemosphere, 65( 5): 725– 759

[45] SeyedmohammadiJ, MotavasselM, MaddahiM H, NikmaneshS. (2016). Application of nanochitosan and chitosan particles for adsorption of Zn(II) ions pollutant from aqueous solution to protect environment. Modeling Earth Systems and Environment, 2 : 165

[46] SingerR S, FinchR, WegenerH C, BywaterR, WaltersJ, LipsitchM. (2003). Antibiotic resistance－the interplay between antibiotic use in animals and human beings. Lancet. Infectious Diseases, 3 : 47– 51

[47] SmithM, ScudieroL, EspinalJ, McEwenJ S, Garcia-PerezM. (2016). Improving the deconvolution and interpretation of XPS spectra from chars by ab initio calculations. Carbon, 110 : 155– 171

[48] SunG, LiangT, TanW, WangL. (2018). Rheological behaviors and physical properties of plasticized hydrogel films developed from κ-carrageenan incorporating hydroxypropyl methylcellulose. Food Hydrocolloids, 85 : 61– 68

[49] TangM, JiaR, KanH, LiuZ, YangS, SunL, YangY. (2020). Kinetic, isotherm, and thermodynamic studies of the adsorption of dye from aqueous solution by propylene glycol adipate-modified cellulose aerogel. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 602 : 125009

[50] TeixidóM, PignatelloJ J, BeltránJ L, GranadosM, PecciaJ. (2011). Speciation of the ionizable antibiotic sulfamethazine on black carbon (biochar). Environmental Science & Technology, 45( 23): 10020– 10027

[51] TianY, HeX, ZhouH, TianX, NieY, ZhouZ, YangC, LiY. (2020). Efficient fenton-like degradation of ofloxacin over bimetallic Fe–Cu@Sepiolite composite. Chemosphere, 257 : 127209

[52] ToledoP V O, LimeiraD P C, SiqueiraN C, PetriD F S. (2019). Carboxymethyl cellulose/poly(acrylic acid) interpenetrating polymer network hydrogels as multifunctional adsorbents. Cellulose, 26 : 597– 615

[53] YanH, DaiJ, YangZ, YangH, ChengR. (2011). Enhanced and selective adsorption of copper(II) ions on surface carboxymethylated chitosan hydrogel beads. Chemical Engineering Journal, 174( 2−3): 586– 594

[54] YanH, LiH, YangH, LiA, ChengR. (2013). Removal of various cationic dyes from aqueous solutions using a kind of fully biodegradable magnetic composite microsphere. Chemical Engineering Journal, 223 : 402– 411

[55] YangR, LiD, LiA, YangH. (2018). Adsorption properties and mechanisms of palygorskite for removal of various ionic dyes from water. Applied Clay Science, 151 : 20– 28

[56] YiL, YangJ, FangX, XiaY, ZhaoL, WuH, GuoS. (2020). Facile fabrication of wood-inspired aerogel from chitosan for efficient removal of oil from Water. Journal of Hazardous Materials, 385 : 121507

[57] YinF, LinS, ZhouX, DongH, ZhanY. (2021). Fate of antibiotics during membrane separation followed by physical-chemical treatment processes. Science of the Total Environment, 759 : 143520

[58] YuF, CuiT, YangC, DaiX, MaJ. (2019). κ-Carrageenan/Sodium alginate double-network hydrogel with enhanced mechanical properties, anti-swelling, and adsorption capacity. Chemosphere, 237 : 124417

[59] YuF, LiY, HanS, MaJ. (2016). Adsorptive removal of ciprofloxacin by sodium alginate/graphene oxide composite beads from aqueous solution. Journal of Colloid and Interface Science, 484 : 196– 204

[60] YuY, WuK, XuW, ChenD, FangJ, ZhuX, SunJ, LiangY, HuX, LiR, FangZ. (2021). Adsorption-photocatalysis synergistic removal of contaminants under antibiotic and Cr(VI) coexistence environment using non-metal g-C₃N₄ based nanomaterial obtained by supramolecular self-assembly method. Journal of Hazardous Materials, 404 : 124171

[61] ZengG L, LiuY Y, MaX G, FanY M. (2021). Fabrication of magnetic multi-template molecularly imprinted polymer composite for the selective and efficient removal of tetracyclines from water. Frontiers of Environmental Science & Engineering, 15( 5): 107

[62] ZhangW, DongL, YanH, LiH, KanX, YangH, LiA, ChengR. (2011). Removal of methylene blue from aqueous solutions by straw based adsorbent in a fixed-bed column. Chemical Engineering Journal, 173( 2): 429– 436

[63] ZhangX, ZhouJ, ZhengY, WeiH, SuZ. (2021). Graphene-based hybrid aerogels for energy and environmental applications. Chemical Engineering Journal, 420 : 129700

[64] ZhouQ, OuyangS, AoZ, SunJ, LiuG, HuX. (2019). Integrating biolayer interferometry, atomic force microscopy, and density functional theory calculation studies on the affinity between humic acid fractions and graphene oxide. Environmental Science & Technology, 53( 7): 3773– 3781

[65] ZhuX, LiuY, ZhouC, ZhangS, ChenJ. (2014). Novel and high-performance magnetic carbon composite prepared from waste hydrochar for dye removal. ACS Sustainable Chemistry & Engineering, 2 : 969– 977

RIGHTS & PERMISSIONS

Higher Education Press