Environmental Science and Pollution Research

, Volume 24, Issue 19, pp 15995–16006 | Cite as

Sorption mechanism of enrofloxacin on humic acids extracted from Brazilian soils

  • Mónica J. Martínez-Mejía
  • Isabela Sato
  • Susanne RathEmail author
Research Article


Veterinary antimicrobials are emerging environmental contaminants of concern. In this study, the sorption of enrofloxacin (ENR) onto humic acids (HAs) extracted from three Brazilian soils was evaluated. HAs were characterized by elemental analysis and solid 13C nuclear magnetic resonance spectroscopy. The sorption of ENR onto HAs was at least 20-fold higher than onto the soils from which they were separated. Ionic and cation bridging are the primary interactions involved. The interactions driven by cation exchange are predominant on HAs, which appear to have abundant carboxylic groups and a relatively high proportion of H-bond donor moieties with carbohydrate-like structures. Interactions explained by cation bridging and/or surface complexation on HAs are facilitated by moieties containing conjugated ligands, significant content of oxygen-containing functional groups, such as phenolic-OH or lignin-like structures. HAs containing electron-donating phenolic moieties and carboxylic acid ligand groups exhibit a sorption mechanism that is primarily driven by strong metal binding, favoring the formation of ternary complexes between functional groups of the organic matter and drugs.


Humic acids from Brazilian soils Fluoroquinolone sorption on humic acids Veterinary drugs Sorption mechanism Ionic and cation bridging 



The authors gratefully acknowledge financial support from FAPESP (Proc. 2012/01767-0, 2013/09543-7). The authors thank CNPq for the research grants awarded to Mónica J. Martínez-Mejía (CNPq 159676/2013-9).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11356_2017_9210_MOESM1_ESM.docx (104 kb)
ESM 1 (DOCX 104 kb).


  1. Abdala DB, da Silva IR, Vergutz L, Sparks DL (2015) Long-term manure application effects on phosphorus speciation, kinetics and distribution in highly weathered agricultural soils. Chemosphere 119:504–514CrossRefGoogle Scholar
  2. Al-Faiyz YSS (2017) CPMAS 13C NMR characterization of humic acids from composted agricultural Saudi waste. Arab J Chem 10:S839–S853Google Scholar
  3. Anđelković T, Perović J, Purenović M, Anđelković D (2004) Destabilization and aggregation of aqueous humic acids solution by metal ions. Facta Universitatis Series: Physics, Chemistry and Technology 3, 6Google Scholar
  4. Aristilde L, Sposito G (2010) Binding of ciprofloxacin by humic substances: a molecular dynamics study. Environ Toxicol Chem 29:90–98CrossRefGoogle Scholar
  5. Baidoo E, Ephraim JH, Darko G, Akoto O (2014) Potentiometric studies of the acid–base properties of tropical humic acids. Geoderma 217–218:18–25CrossRefGoogle Scholar
  6. Buol SW, Southard RJ, Graham RC, McDaniel PA (2011) U.S. soil taxonomy, soil genesis and classification, 6th edn. Wiley-Blackwell, Oxford, UK, pp 207–232Google Scholar
  7. Canellas LP, Berner PG, da Silva SG, e Silva MB, Santos GA (2000) Frações da matéria orgânica em seis solos de uma toposseqüência no Estado do Rio de Janeiro. Pesq Agrop Brasileira 35:133–143CrossRefGoogle Scholar
  8. Carrasquillo AJ, Bruland GL, MacKay AA, Vasudevan D (2008) Sorption of ciprofloxacin and oxytetracycline zwitterions to soils and soil minerals: influence of compound structure. Environmental Science & Technology 42:7634–7642CrossRefGoogle Scholar
  9. Chen H, Ma LQ, Gao B, Gu C (2013) Effects of Cu and Ca cations and Fe/Al coating on ciprofloxacin sorption onto sand media. J Hazard Mater 252–253:375–381CrossRefGoogle Scholar
  10. Dionisio AC, Rath S (2016) Abamectin in soils: analytical methods, kinetics, sorption and dissipation. Chemosphere 151:17–29CrossRefGoogle Scholar
  11. Dobbss LB, Rumjaneck VM, Baldotto MA, Velloso ACX, Canellas LP (2009) Caracterização química e espectroscópica de ácidos húmicos e fúlvicos isolados da camada superficial de latossolos brasileiros. Rev Bras Cienc Solo 33:51–63CrossRefGoogle Scholar
  12. Doretto KM, Peruchi LM, Rath S (2014) Sorption and desorption of sulfadimethoxine, sulfaquinoxaline and sulfamethazine antimicrobials in Brazilian soils. Sci Total Environ 476–477:406–414CrossRefGoogle Scholar
  13. Empresa Brasileira de Pesquisa Agropecuária - EMBRAPA. Centro Nacional de Pesquisa do Solo (2013) Sistema brasileiro de classificação de solos, 3rd edn. Embrapa Solos, Brasilia DFGoogle Scholar
  14. International Humic Substances Society, IHSS (2017) Publishing PhysicsWeb. Accessed 15 May 2017
  15. Kotzerke A, Sharma S, Schauss K, Heuer H, Thiele-Bruhn S, Smalla K, Wilke B-M, Schloter M (2008) Alterations in soil microbial activity and N-transformation processes due to sulfadiazine loads in pig-manure. Environ Pollut 153:315–322CrossRefGoogle Scholar
  16. Leal RMP, Figueira RF, Tornisielo VL, Regitano JB (2012) Occurrence and sorption of fluoroquinolones in poultry litters and soils from São Paulo State, Brazil. Sci Total Environ 432:344–349CrossRefGoogle Scholar
  17. Leal RMP, Allenoi LRF, Tornisielo VL, Regitano JB (2013) Sorption of fluoroquinolones and sulfonamides in 13 Brazilian soils. Chemosphere 92:979–985CrossRefGoogle Scholar
  18. Liang C, Dang Z, Xiao B, Huang W, Liu C (2006) Equilibrium sorption of phenanthrene by soil humic acids. Chemosphere 63:1961–1968CrossRefGoogle Scholar
  19. Limousin G, Gaudet JP, Charlet L, Szenknect S, Barthès V, Krimissa M (2007) Sorption isotherms: a review on physical bases, modeling and measurement. Appl Geochem 22:249–275CrossRefGoogle Scholar
  20. Lin JS, Pan HY, Liu SM, Lai HT (2010) Effects of light and microbial activity on the degradation of two fluoroquinolone antibiotics in pond water and sediment. J Environ Sci Heal B 45:456–465CrossRefGoogle Scholar
  21. Liu ZG, Sun PZ, Pavlostathis SG, Zhou XF, Zhang YL (2013) Adsorption, inhibition, and biotransformation of ciprofloxacin under aerobic conditions. Bioresour Technol 144:644–651CrossRefGoogle Scholar
  22. MacKay AA, Seremet DE (2008) Probe compounds to quantify cation exchange and complexation interactions of ciprofloxacin with soils. Environmental Science & Technology 42:8270–8276CrossRefGoogle Scholar
  23. Manzatto CV, Freitas Jr ED, Peres JRR (2002) Uso agrícola dos solos brasileiros. Rio de Janeiro: Embrapa SolosGoogle Scholar
  24. Nascimento PC, Lani JL, Mendonça ES, Zoffoli HJO, Peixoto HTM (2010) Teores e características da matéria orgânica de solos hidromórficos do Espírito Santo. Revista Brasileira de Ciência do Solo 34:339–348CrossRefGoogle Scholar
  25. Nowara A, Burhenne J, Spiteller M (1997) Binding of fluoroquinolone carboxylic acid derivatives to clay minerals. J Agr Food Chem 45:1459–1463CrossRefGoogle Scholar
  26. OECD (2000) Organization for economic co-operation and development, test guideline 106Google Scholar
  27. 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. Environ Sci Technol 44:915–920CrossRefGoogle Scholar
  28. Peruchi LM, Fostier AH, Rath S (2015) Sorption of norfloxacin in soils: analytical method, kinetics and Freundlich isotherms. Chemosphere 119:310–317CrossRefGoogle Scholar
  29. Pils JRV, Laird DA (2007) Sorption of tetracycline and chlortetracycline on K- and Ca-saturated soil clays, humic substances, and clay−humic complexes. Environ Sci Technol 41:1928–1933CrossRefGoogle Scholar
  30. Ritchie JD, Perdue EM (2003) Proton-binding study of standard and reference fulvic acids, humic acids, and natural organic matter. Geochim Cosmochim Acta 67:85–96CrossRefGoogle Scholar
  31. Ross DL, Riley CM (1993) Physicochemical properties of the fluoroquinolone antimicrobials V. Effect of fluoroquinolone structure and pH on the complexation of various fluoroquinolones with magnesium and calcium ions. Int J Pharm 93:121–129CrossRefGoogle Scholar
  32. Shigaki F, Sharpley A, Prochnow LI (2006) Animal-based agriculture, phosphorus management and water quality in Brazil: options for the future. Sci Agr 63:194–209CrossRefGoogle Scholar
  33. ŠMejkalová D, Spaccini R, Piccolo A (2008) Multivariate analysis of CPMAS 13C-NMR spectra of soils and humic matter as a tool to evaluate organic carbon quality in natural systems. Eur J Soil Sci 59:496–504CrossRefGoogle Scholar
  34. Stevenson FJ (1994) Humus chemistry: genesis, composition. Wiley, ReactionsGoogle Scholar
  35. Tan Y, Guo Y, Gu X, Gu C (2015) Effects of metal cations and fulvic acid on the adsorption of ciprofloxacin onto goethite. Environ Sci Pollut Res 22:609–617CrossRefGoogle Scholar
  36. Teixidó M, Medeiros J, Beltrán J, Prat MD, Granados M (2014) Sorption of enrofloxacin and ciprofloxacin in agricultural soils: effect of organic matter. Adsorpt Sci Technol 32:153–163CrossRefGoogle Scholar
  37. Tolls J (2001) Sorption of veterinary pharmaceuticals in soils: a review. Environ Sci Technol 35:3397–3406CrossRefGoogle Scholar
  38. Uivarosi V (2013) Metal complexes of quinolone antibiotics and their applications: an update. Molecules 18:11153CrossRefGoogle Scholar
  39. Vasudevan D, Bruland GL, Torrance BS, Upchurch VG, MacKay AA (2009) pH-dependent ciprofloxacin sorption to soils: interaction mechanisms and soil factors influencing sorption. Geoderma 151:68–76CrossRefGoogle Scholar
  40. Wu QF, Li ZH, Hong HL, Li RB, Jiang WT (2013) Desorption of ciprofloxacin from clay mineral surfaces. Water Res 47:259–268CrossRefGoogle Scholar
  41. Zech W, Senesi N, Guggenberger G, Kaiser K, Lehmann J, Miano TM, Miltner A, Schroth G (1997) Factors controlling humification and mineralization of soil organic matter in the tropics. Geoderma 79:117–161CrossRefGoogle Scholar
  42. Zhang J, Li Z, Ge G, Sun W, Liang Y, Wu L (2009) Impacts of soil organic matter, pH and exogenous copper on sorption behavior of norfloxacin in three soils. J Environ Sci 21:632–640CrossRefGoogle Scholar
  43. Zhang Q, Zhao L, Dong YH, Huang GY (2012) Sorption of norfloxacin onto humic acid extracted from weathered coal. J Environ Manag 102:165–172CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  1. 1.Institute of ChemistryUniversity of Campinas – UNICAMPCampinasBrazil

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