Abstract
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.
Similar content being viewed by others
References
Al-Sakkari E G, Abdeldayem O M, Genina E E, Amin L, Bahgat N T, Rene E R, El-Sherbiny I 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
Carabineiro S A C, Thavorn-amornsri T, Pereira M F R, Serp P, Figueiredo J L (2012). Comparison between activated carbon, carbon xerogel and carbon nanotubes for the adsorption of the antibiotic ciprofloxacin. Catalysis Today, 186(1): 29–34
Chen Y, Long Y, Li Q, Chen X, Xu X (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
Chen Y, Wang A, Zhang Y, Bao R, Tian X, Li J (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
Cuprys A, Pulicharla R, Brar S K, Drogui P, Verma M, Surampalli R Y (2018). Fluoroquinolones metal complexation and its environmental impacts. Coordination Chemistry Reviews, 376: 46–61
Dogaru B I, Simionescu B, Popescu M C (2020). Synthesis and characterization of κ-carrageenan bio-nanocomposite films reinforced with bentonite nanoclay. International Journal of Biological Macromolecules, 154: 9–17
Du X, Yang W, Liu Y, Zhang W, Wang Z, Nie J, Li G, Liang H (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
Duan W, Li M, Xiao W, Wang N, Niu B, Zhou L, Zheng Y (2019). Enhanced adsorption of three fluoroquinolone antibiotics using polypyrrole functionalized Calotropis gigantea fiber. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 574: 178–187
Fan H, Ma Y, Wan J, Wang Y, Li Z, Chen Y (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
Freundlich H M F (1906). Over the adsorption in solution. Journal of Physical Chemistry, 57: 385–470
Gao B, Chang Q, Cai J, Xi Z, Li A, Yang H (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
Gao B, Li P, Yang R, Li A, Yang H (2019). Investigation of multiple adsorption mechanisms for efficient removal of ofloxacin from water using lignin-based adsorbents. Scientific Reports, 9: 637
Gulen B, Demircivi P (2020). Adsorption properties of flouroquinolone type antibiotic ciprofloxacin into 2:1 dioctahedral clay structure: Box-Behnken experimental design. Journal of Molecular Structure, 1206: 127659
Ho Y S, McKay G (1998). Sorption of dye from aqueous solution by peat. Chemical Engineering Journal, 70(2): 115–124
Huang D, Wu J, Wang L, Liu X, Meng J, Tang X, Tang C, Xu J (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
Igwegbe C A, Oba S N, Aniagor C O, Adeniyi A G, Ighalo J O (2021). Adsorption of ciprofloxacin from water: A comprehensive review. Journal of Industrial and Engineering Chemistry, 93: 57–77
Kovtun A, Campodoni E, Favaretto L, Zambianchi M, Salatino A, Amalfitano S, Navacchia M L, Casentini B, Palermo V, Sandri M, Melucci M (2020). Multifunctional graphene oxide/biopolymer composite aerogels for microcontaminants removal from drinking water. Chemosphere, 259: 127501
Kumar M, Jaiswal S, Sodhi K K, Shree P, Singh D K, Agrawal P K, Shukla P (2019). Antibiotics bioremediation: Perspectives on its ecotoxicity and resistance. Environment International, 124: 448–461
Lagergren S (1989). About the theory of so-called sorption of soluble substances. Kungliga Svenska Vetenskapsakademiens Handlingar, 24: 1–39
Langmuir I (1918). The adsorption of gases on plane surfaces of glass, mica and platinum. Journal of the American Chemical Society, 40(9): 1361–1403
Larciprete R, Fabris S, Sun T, Lacovig P, Baraldi A, Lizzit S (2011). Dual path mechanism in the thermal reduction of graphene oxide. Journal of the American Chemical Society, 133(43): 17315–17321
Li L, Zhao J, Sun Y, Yu F, Ma J (2019). Ionically cross-linked sodium alginate/κ-carrageenan double-network gel beads with low-swelling, enhanced mechanical properties, and excellent adsorption performance. Chemical Engineering Journal, 372: 1091–1103
Li M F, Liu Y G, Liu S B, Shu D, Zeng G M, Hu X J, Tan X F, Jiang L H, Yan Z L, Cai X 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
Li N, Yang H (2021). Construction of natural polymeric imprinted materials and their applications in water treatment: A review. Journal of Hazardous Materials, 403: 123643
Lian F, Sun B, Song Z, Zhu L, Qi X, Xing B (2014). Physicochemical properties of herb-residue biochar and its sorption to ionizable antibiotic sulfamethoxazole. Chemical Engineering Journal, 248: 128–134
Liang X C, Duan J J, Xu Q, Wei X Q, Lu A, Zhang L 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
Ling C, Liu F Q, Xu C, Chen T P, Li A 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
Liu X, Liu M, Zhang L (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
Lu S, Liu W, Wang Y, Zhang Y, Li P, Jiang D, Fang C, Li Y (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
Ma J, Jiang Z, Cao J, Yu F (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
Ma J, Xiong Y, Dai X, Yu F (2020b). Coadsorption behavior and mechanism of ciprofloxacin and Cu(II) on graphene hydrogel wetted surface. Chemical Engineering Journal, 380: 122387
Maleki H (2016). Recent advances in aerogels for environmental remediation applications: A review. Chemical Engineering Journal, 300: 98–118
Maleki H, Durães L, García-González C A, Del Gaudio P, Portugal A, Mahmoudi M (2016). Synthesis and biomedical applications of aerogels: Possibilities and challenges. Advances in Colloid and Interface Science, 236: 1–27
Martins B F, de Toledo P V O, Petri D F S (2017). Hydroxypropyl methylcellulose based aerogels: Synthesis, characterization and application as adsorbents for wastewater pollutants. Carbohydrate Polymers, 155: 173–181
McManus P S, Stockwell V O, Sundin G W, Jones A L (2002). Antibiotic use in plant agriculture. Annual Review of Phytopathology, 40(1): 443–465
Mohammad A, Khan M E, Abutaleb A, Ali W, Tauqeer M, Yoon T, Cho M 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
Mohapatra M, Padhi T, Anand S, Mishra B 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
Nguyen T T, Bui X T, Luu V P, Nguyen P D, Guo W, Ngo H 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
Pan J, Li Y, Chen K, Zhang Y, Zhang H (2021). Enhanced physical and antimicrobial properties of alginate/chitosan composite aerogels based on electrostatic interactions and noncovalent crosslinking. Carbohydrate Polymers, 266: 118102
Pei Z, Shan X Q, Kong J, Wen B, Owens G (2010). Coadsorption of ciprofloxacin and Cu(II) on montmorillonite and kaolinite as affected by solution pH. Environmental Science & Technology, 44(3): 915–920
Ren J, Li N, Wei H, Li A, Yang H (2020). Efficient removal of phosphorus from turbid water using chemical sedimentation by FeCl3 in conjunction with a starch-based flocculant. Water Research, 170: 115361
Salama A, Shukry N, El-Sakhawy M (2015). Carboxymethyl cellulose-g-poly(2-(dimethylamino) ethyl methacrylate) hydrogel as adsorbent for dye removal. International Journal of Biological Macromolecules, 73: 72–75
Salgueiro A M, Daniel-da-Silva A L, Girão A V, Pinheiro P C, Trindade T (2013). Unusual dye adsorption behavior of κ-carrageenan coated superparamagnetic nanoparticles. Chemical Engineering Journal, 229: 276–284
Sarmah A K, Meyer M T, Boxall A 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
Seyedmohammadi J, Motavassel M, Maddahi M H, Nikmanesh S (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
Singer R S, Finch R, Wegener H C, Bywater R, Walters J, Lipsitch M (2003). Antibiotic resistance — the interplay between antibiotic use in animals and human beings. Lancet. Infectious Diseases, 3: 47–51
Smith M, Scudiero L, Espinal J, McEwen J S, Garcia-Perez M (2016). Improving the deconvolution and interpretation of XPS spectra from chars by ab initio calculations. Carbon, 110: 155–171
Sun G, Liang T, Tan W, Wang L (2018). Rheological behaviors and physical properties of plasticized hydrogel films developed from κ-carrageenan incorporating hydroxypropyl methylcellulose. Food Hydrocolloids, 85: 61–68
Tang M, Jia R, Kan H, Liu Z, Yang S, Sun L, Yang Y (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
Teixidó M, Pignatello J J, Beltrán J L, Granados M, Peccia J (2011). Speciation of the ionizable antibiotic sulfamethazine on black carbon (biochar). Environmental Science & Technology, 45(23): 10020–10027
Tian Y, He X, Zhou H, Tian X, Nie Y, Zhou Z, Yang C, Li Y (2020). Efficient fenton-like degradation of ofloxacin over bimetallic Fe—Cu@Sepiolite composite. Chemosphere, 257: 127209
Toledo P V O, Limeira D P C, Siqueira N C, Petri D F S (2019). Carboxymethyl cellulose/poly(acrylic acid) interpenetrating polymer network hydrogels as multifunctional adsorbents. Cellulose, 26: 597–615
Yan H, Dai J, Yang Z, Yang H, Cheng R (2011). Enhanced and selective adsorption of copper(II) ions on surface carboxymethylated chitosan hydrogel beads. Chemical Engineering Journal, 174(2–3): 586–594
Yan H, Li H, Yang H, Li A, Cheng R (2013). Removal of various cationic dyes from aqueous solutions using a kind of fully biodegradable magnetic composite microsphere. Chemical Engineering Journal, 223: 402–411
Yang R, Li D, Li A, Yang H (2018). Adsorption properties and mechanisms of palygorskite for removal of various ionic dyes from water. Applied Clay Science, 151: 20–28
Yi L, Yang J, Fang X, Xia Y, Zhao L, Wu H, Guo S (2020). Facile fabrication of wood-inspired aerogel from chitosan for efficient removal of oil from Water. Journal of Hazardous Materials, 385: 121507
Yin F, Lin S, Zhou X, Dong H, Zhan Y (2021). Fate of antibiotics during membrane separation followed by physical-chemical treatment processes. Science of the Total Environment, 759: 143520
Yu F, Cui T, Yang C, Dai X, Ma J (2019). κ-Carrageenan/Sodium alginate double-network hydrogel with enhanced mechanical properties, anti-swelling, and adsorption capacity. Chemosphere, 237: 124417
Yu F, Li Y, Han S, Ma J (2016). Adsorptive removal of ciprofloxacin by sodium alginate/graphene oxide composite beads from aqueous solution. Journal of Colloid and Interface Science, 484: 196–204
Yu Y, Wu K, Xu W, Chen D, Fang J, Zhu X, Sun J, Liang Y, Hu X, Li R, Fang Z (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
Zeng G L, Liu Y Y, Ma X G, Fan Y 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
Zhang W, Dong L, Yan H, Li H, Kan X, Yang H, Li A, Cheng R (2011). Removal of methylene blue from aqueous solutions by straw based adsorbent in a fixed-bed column. Chemical Engineering Journal, 173(2): 429–436
Zhang X, Zhou J, Zheng Y, Wei H, Su Z (2021). Graphene-based hybrid aerogels for energy and environmental applications. Chemical Engineering Journal, 420: 129700
Zhou Q, Ouyang S, Ao Z, Sun J, Liu G, Hu X (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
Zhu X, Liu Y, Zhou C, Zhang S, Chen J (2014). Novel and high-performance magnetic carbon composite prepared from waste hydrochar for dye removal. ACS Sustainable Chemistry & Engineering, 2: 969–977
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Nos. 42061144014 and 51978325).
Author information
Authors and Affiliations
Corresponding author
Additional information
High Lights
• 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.
Supporting Information
Rights and permissions
About this article
Cite this article
Li, N., Gao, B., Yang, R. et al. Simple fabrication of carboxymethyl cellulose and κ-carrageenan composite aerogel with efficient performance in removal of fluoroquinolone antibiotics from water. Front. Environ. Sci. Eng. 16, 133 (2022). https://doi.org/10.1007/s11783-022-1568-x
Received:
Revised:
Published:
DOI: https://doi.org/10.1007/s11783-022-1568-x