Competitive adsorption of ofloxacin enantiomers to goethite: experiments and modelling
Xiaopeng Qin
A B E , Xiaofei Zhong B C , Ping Du A B , Juan Chen A B , Junfeng Jia A B , Ying He A B , Fei Liu C E and Liping Weng D
+ Author Affiliations
- Author Affiliations
A Department of Technology Assessment, Technical Centre for Soil, Agricultural and Rural Ecology and Environment, Ministry of Ecology and Environment, Beijing 100012, China.
B State Key Laboratory of Environmental Criteria and Risk Assessment, Institute of Soil and Solid, Chinese Research Academy of Environmental Sciences, Beijing 100012, China.
C Key Laboratory of Groundwater Circulation and Environmental Evolution, Ministry of Education, School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083, China.
D Department of Soil Quality, Wageningen University PO Box 47, 6700 AA, Wageningen, The Netherlands.
E Corresponding authors. Email: qinxp@craes.org.cn; feiliu@cugb.edu.cn
Environmental Chemistry 18(1) 38-44 https://doi.org/10.1071/EN20123
Submitted: 24 August 2020 Accepted: 17 December 2020 Published: 8 January 2021
Environmental context. The concentration, types and distribution of antibiotics in soils can have environmental effects and can be modelled using laboratory systems. Adsorption of ofloxacin (OFL) and levofloxacin (LEV) enantiomers to goethite can probe this behaviour and each binds differently to the solid phase. The different behaviour of LEV and OFL in relation to solid-solution partitioning will affect their environmental fate.
Abstract. The adsorption of ofloxacin enantiomers, namely levofloxacin (LEV) and ofloxacin (OFL), to goethite was investigated using batch experiments. Structural information of aqueous and adsorbed LEV or OFL was obtained with ultraviolet–visible (UV-Vis), three-dimensional excitation–emission matrix (EEM) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopic methods. The results indicated that LEV molecules formed a bridging bidentate complex (≡(FeO)2–LEV) with the surface of goethite, and OFL formed a monodentate complex (≡FeO–OFL). The adsorption of OFL to goethite was stronger than that of LEV, owing to differences in their physicochemical properties and bonding modes. The adsorption of LEV and OFL to goethite in single systems was well simulated using the charge distribution multi-site complexation (CD-MUSIC) model, but their adsorption in the LEV–OFL–goethite systems was overestimated at pH ~5.2 and high concentrations of LEV–OFL mixture (19.59 μM), in which the predicted amounts of adsorbed LEV and OFL were higher (20.0, 30.8 %) than the experimental results. Compared with the unprotonated LEV or OFL, the protonated (>99.9 %) ones were mainly adsorbed to the surface of goethite, and the single species may be used during their following modelling.
Keywords: adsorption, CD-MUSIC model, chiral, competition, enantiomer, goethite, levofloxacin, ofloxacin.
References
Antelo J, Avena M, Fiol S, López R, Arce F (2005). Effects of pH and ionic strength on the adsorption of phosphate and arsenate at the goethite–water interface. Journal of Colloid and Interface Science 285, 476–486.| Effects of pH and ionic strength on the adsorption of phosphate and arsenate at the goethite–water interfaceCrossref | GoogleScholarGoogle Scholar | 15837462PubMed |
Buerge IJ, Bächli A, Kasteel R, Portmann R, López-Cabeza R, Schwab LF, Poiger T (2019). Behavior of the chiral herbicide imazamox in soils: pH-dependent, enantioselective degradation, formation and degradation of several chiral metabolites. Environmental Science & Technology 53, 5725–5732.
| Behavior of the chiral herbicide imazamox in soils: pH-dependent, enantioselective degradation, formation and degradation of several chiral metabolitesCrossref | GoogleScholarGoogle Scholar |
Celis R, Gámiz B, Facenda G, Hermosín MC (2015). Enantioselective sorption of the chiral fungicide metalaxyl on soil from non-racemic aqueous solutions: environmental implications. Journal of Hazardous Materials 300, 581–589.
| Enantioselective sorption of the chiral fungicide metalaxyl on soil from non-racemic aqueous solutions: environmental implicationsCrossref | GoogleScholarGoogle Scholar | 26259163PubMed |
Chen L, Lang H, Liu F, Jin S, Yan T (2018). Presence of antibiotics in shallow groundwater in the northern and south-western regions of China. Ground Water 56, 451–457.
| Presence of antibiotics in shallow groundwater in the northern and south-western regions of ChinaCrossref | GoogleScholarGoogle Scholar | 28940442PubMed |
Córdova-Kreylos AL, Scow KM (2007). Effects of ciprofloxacin on salt marsh sediment microbial communities. The ISME Journal 1, 585–595.
| Effects of ciprofloxacin on salt marsh sediment microbial communitiesCrossref | GoogleScholarGoogle Scholar | 18043666PubMed |
Gámiz B, Hermosín MC, Celis R (2016). Sorption, persistence and leaching of abscisic acid in agricultural soils: an enantiomer-selective study. Geoderma 269, 112–118.
| Sorption, persistence and leaching of abscisic acid in agricultural soils: an enantiomer-selective studyCrossref | GoogleScholarGoogle Scholar |
Ghosh S, Badruddoza AZM, Uddin MS, Hidajat K (2011). Adsorption of chiral aromatic amino acids onto carboxymethyl-b-cyclodextrin bonded Fe3O4/SiO2 core–shell nanoparticles. Journal of Colloid and Interface Science 354, 483–492.
| Adsorption of chiral aromatic amino acids onto carboxymethyl-b-cyclodextrin bonded Fe3O4/SiO2 core–shell nanoparticlesCrossref | GoogleScholarGoogle Scholar | 21167497PubMed |
Golet EM, Alder AC, Hartmann A, Ternes TA, Giger W (2001). Trace determination of fluoroquinolone antibacterial agents in urban wastewater by solid-phase extraction and liquid chromatography with fluorescence detection. Analytical Chemistry 73, 3632–3638.
| Trace determination of fluoroquinolone antibacterial agents in urban wastewater by solid-phase extraction and liquid chromatography with fluorescence detectionCrossref | GoogleScholarGoogle Scholar | 11510827PubMed |
Goyne KW, Chorover J, Kubicki JD, Zimmerman AR, Brantley SL (2005). Sorption of the antibiotic ofloxacin to mesoporous and non-porous alumina and silica. Journal of Colloid and Interface Science 283, 160–170.
| Sorption of the antibiotic ofloxacin to mesoporous and non-porous alumina and silicaCrossref | GoogleScholarGoogle Scholar | 15694437PubMed |
Hiemstra T, Van Riemsdijk WH (1996). A surface structural approach to ion adsorption: the charge distribution (CD) model. Journal of Colloid and Interface Science 179, 488–508.
| A surface structural approach to ion adsorption: the charge distribution (CD) modelCrossref | GoogleScholarGoogle Scholar |
Hiemstra T, De Wit JCM, Van Riemsdijk WH (1989). Multisite proton adsorption modeling at the solid/solution interface of (hydr)oxides: a new approach: II. Application to various important (hydr)oxides. Journal of Colloid and Interface Science 133, 105–117.
| Multisite proton adsorption modeling at the solid/solution interface of (hydr)oxides: a new approach: II. Application to various important (hydr)oxidesCrossref | GoogleScholarGoogle Scholar |
Hiemstra T, Antelo J, Rahnemaie R, Van Riemsdijk WH (2010). Nanoparticles in natural systems I: The effective surface area of the natural oxide fraction in field samples. Geochimica et Cosmochimica Acta 74, 41–58.
| Nanoparticles in natural systems I: The effective surface area of the natural oxide fraction in field samplesCrossref | GoogleScholarGoogle Scholar |
Keizer MG, Van Riemsdijk WH (1998). ECOSAT: equilibrium calculation of speciation and transport. Technical report of the Soil Quality Department. (Wageningen University: Wageningen).
Kubicki JD, Paul KW, Kabalan L, Zhu Q, Mrozik MK, Aryanpour M, Pierre-Louis AM, Strongin DR (2012). ATR-FTIR and density functional theory study of the structures, energetics, and vibrational spectra of phosphate adsorbed onto goethite. Langmuir 28, 14573–14587.
| ATR-FTIR and density functional theory study of the structures, energetics, and vibrational spectra of phosphate adsorbed onto goethiteCrossref | GoogleScholarGoogle Scholar | 22985265PubMed |
Le-Deygen IM, Skuredina AA, Uporov IV, Kudryashova EV (2017). Thermodynamics and molecular insight in guest–host complexes of fluoroquinolones with β-cyclodextrin derivatives, as revealed by ATR-FTIR spectroscopy and molecular modeling experiments. Analytical and Bioanalytical Chemistry 409, 6451–6462.
| Thermodynamics and molecular insight in guest–host complexes of fluoroquinolones with β-cyclodextrin derivatives, as revealed by ATR-FTIR spectroscopy and molecular modeling experimentsCrossref | GoogleScholarGoogle Scholar | 28852813PubMed |
Liu W, Gan J, Schlenk D, Jury WA (2005). Enantioselectivity in environmental safety of current chiral insecticides. Proceedings of the National Academy of Sciences of the United States of America 102, 701–706.
| Enantioselectivity in environmental safety of current chiral insecticidesCrossref | GoogleScholarGoogle Scholar | 15632216PubMed |
Maia AS, Tiritan ME, Castro P (2018). Enantioselective degradation of ofloxacin and levofloxacin by the bacterial strains Labrys portucalensis F11 and Rhodococcus sp. FP1. Ecotoxicology and Environmental Safety 155, 144–151.
| Enantioselective degradation of ofloxacin and levofloxacin by the bacterial strains Labrys portucalensis F11 and Rhodococcus sp. FP1Crossref | GoogleScholarGoogle Scholar | 29510309PubMed |
Matallo M, Romero E, Sánchez-Rasero F, Peña A, Dios G (1998). Adsorption of mecoprop and dichlorprop on calcareous and organic matter-amended soils: comparative adsorption of racemic and pure enantiomeric forms. Journal of Environmental Science and Health. Part B, Pesticides, Food Contaminants, and Agricultural Wastes 33, 51–66.
| Adsorption of mecoprop and dichlorprop on calcareous and organic matter-amended soils: comparative adsorption of racemic and pure enantiomeric formsCrossref | GoogleScholarGoogle Scholar |
Paul T, Machesky ML, Strathmann TJ (2012). Surface complexation of the zwitterionic fluoroquinolone antibiotic ofloxacin to nano-anatase TiO2 photocatalyst surfaces. Environmental Science & Technology 46, 11896–11904.
| Surface complexation of the zwitterionic fluoroquinolone antibiotic ofloxacin to nano-anatase TiO2 photocatalyst surfacesCrossref | GoogleScholarGoogle Scholar |
Paul T, Liu J, Machesky ML, Strathmann TJ (2014). Adsorption of zwitterionic fluoroquinolone antibacterials to goethite: a charge distribution-multisite complexation model. Journal of Colloid and Interface Science 428, 63–72.
| Adsorption of zwitterionic fluoroquinolone antibacterials to goethite: a charge distribution-multisite complexation modelCrossref | GoogleScholarGoogle Scholar | 24910036PubMed |
Qin X, Liu F, Wang G, Weng L, Li L (2014a). Adsorption of levofloxacin onto goethite: effects of pH, calcium and phosphate. Colloids and Surfaces. B, Biointerfaces 116, 591–596.
| Adsorption of levofloxacin onto goethite: effects of pH, calcium and phosphateCrossref | GoogleScholarGoogle Scholar | 24269055PubMed |
Qin X, Liu F, Wang G, Li L, Wang Y, Weng L (2014b). Modeling of levofloxacin adsorption to goethite and the competition with phosphate. Chemosphere 111, 283–290.
| Modeling of levofloxacin adsorption to goethite and the competition with phosphateCrossref | GoogleScholarGoogle Scholar | 24997930PubMed |
Qin X, Du P, Chen J, Liu F, Wang G, Weng L (2018). Effects of natural organic matter with different properties on levofloxacin adsorption to goethite: experiments and modeling. Chemical Engineering Journal 345, 425–431.
| Effects of natural organic matter with different properties on levofloxacin adsorption to goethite: experiments and modelingCrossref | GoogleScholarGoogle Scholar |
Ross DL, Riley CM (1990). Aqueous solubilities of some variously substituted quinolone antimicrobials. International Journal of Pharmaceutics 63, 237–250.
| Aqueous solubilities of some variously substituted quinolone antimicrobialsCrossref | GoogleScholarGoogle Scholar |
Sanganyado E, Fu Q, Gan J (2016). Enantiomeric selectivity in adsorption of chiral β-blockers on sludge. Environmental Pollution 214, 787–794.
| Enantiomeric selectivity in adsorption of chiral β-blockers on sludgeCrossref | GoogleScholarGoogle Scholar | 27155096PubMed |
Sanganyado E, Lu Z, Fu Q, Schlenk D, Gan J (2017). Chiral pharmaceuticals: a review on their environmental occurrence and fate processes. Water Research 124, 527–542.
| Chiral pharmaceuticals: a review on their environmental occurrence and fate processesCrossref | GoogleScholarGoogle Scholar | 28806704PubMed |
Shao B, Sun X, Zhang J, Hu J, Dong H, Yang Y (2008). Determination of ofloxacin enantiomers in sewage using two-step solid-phase extraction and liquid chromatography with fluorescence detection. Journal of Chromatography. A 1182, 77–84.
| Determination of ofloxacin enantiomers in sewage using two-step solid-phase extraction and liquid chromatography with fluorescence detectionCrossref | GoogleScholarGoogle Scholar | 18221747PubMed |
Sousa I, Claro V, Pereira JL, Amaral A, Cunha-Silva L, Castro B, Feio M, Pereira E, Gameiro P (2012). Synthesis, characterization and antibacterial studies of a copper(ii) levofloxacin ternary complex. Journal of Inorganic Biochemistry 110, 64–71.
| Synthesis, characterization and antibacterial studies of a copper(ii) levofloxacin ternary complexCrossref | GoogleScholarGoogle Scholar | 22469700PubMed |
Tackett JE (1989). FT-IR characterization of metal acetates in aqueous solution. Applied Spectroscopy 43, 483–489.
| FT-IR characterization of metal acetates in aqueous solutionCrossref | GoogleScholarGoogle Scholar |
Tanaka M, Kurata T, Fujisawa C, Ohshima Y, Aoki H, Okazaki O, Hakusui H (1993). Mechanistic study of inhibition of levofloxacin absorption by aluminum hydroxide. Antimicrobial Agents and Chemotherapy 37, 2173–2178.
| Mechanistic study of inhibition of levofloxacin absorption by aluminum hydroxideCrossref | GoogleScholarGoogle Scholar | 8257141PubMed |
Trivedi P, Vasudevan D (2007). Spectroscopic investigation of ciprofloxacin speciation at the goethite–water interface. Environmental Science & Technology 41, 3153–3158.
| Spectroscopic investigation of ciprofloxacin speciation at the goethite–water interfaceCrossref | GoogleScholarGoogle Scholar |
Urbaniak B, Kokot ZJ (2009). Analysis of the factors that significantly influence the stability of fluoroquinolone–metal complexes. Analytica Chimica Acta 647, 54–59.
| Analysis of the factors that significantly influence the stability of fluoroquinolone–metal complexesCrossref | GoogleScholarGoogle Scholar | 19576385PubMed |
Weng L, Van Riemsdijk WH, Hiemstra T (2008). Humic nanoparticles at the oxide–water interface: interactions with phosphate ion adsorption. Environmental Science & Technology 42, 8747–8752.
| Humic nanoparticles at the oxide–water interface: interactions with phosphate ion adsorptionCrossref | GoogleScholarGoogle Scholar |
Yan B, Niu CH (2017). Modeling and site energy distribution analysis of levofloxacin sorption by biosorbents. Chemical Engineering Journal 307, 631–642.
| Modeling and site energy distribution analysis of levofloxacin sorption by biosorbentsCrossref | GoogleScholarGoogle Scholar |
Yan H, Row KH (2007). Rapid chiral separation and impurity determination of levofloxacin by ligand-exchange chromatography. Analytica Chimica Acta 584, 160–165.
| Rapid chiral separation and impurity determination of levofloxacin by ligand-exchange chromatographyCrossref | GoogleScholarGoogle Scholar | 17386599PubMed |
Zeng S, Zhong J, Hu J, Pan L, Li Y (1999). High-performance liquid chromatography separation and quantitation of ofloxacin enantiomers in rat microsomes. Journal of Chromatography. B, Biomedical Sciences and Applications 728, 151–155.
| High-performance liquid chromatography separation and quantitation of ofloxacin enantiomers in rat microsomesCrossref | GoogleScholarGoogle Scholar | 10379667PubMed |
Zhao Y, Liu F, Qin X (2017). Adsorption of diclofenac onto goethite: adsorption kinetics and effects of pH. Chemosphere 180, 373–378.
| Adsorption of diclofenac onto goethite: adsorption kinetics and effects of pHCrossref | GoogleScholarGoogle Scholar | 28415038PubMed |
Zhao X, Hu Z, Yang X, Cai X, Wang Z, Xie X (2019). Non-covalent interactions between fluoroquinolone antibiotics with dissolved organic matter: a 1H NMR binding site study and multispectroscopic methods. Environmental Pollution 248, 815–822.
| Non-covalent interactions between fluoroquinolone antibiotics with dissolved organic matter: a 1H NMR binding site study and multispectroscopic methodsCrossref | GoogleScholarGoogle Scholar | 30852295PubMed |
Zhou Z, Zhang Z, Feng L, Zhang J, Li Y, Lu T, Qian H (2020). Adverse effects of levofloxacin and oxytetracycline on aquatic microbial communities. The Science of the Total Environment 734, 139499
| Adverse effects of levofloxacin and oxytetracycline on aquatic microbial communitiesCrossref | GoogleScholarGoogle Scholar | 32464375PubMed |
