Environmental Science and Pollution Research

, Volume 26, Issue 11, pp 10685–10694 | Cite as

Sorption of copper and norfloxacin onto humic acid: effects of pH, ionic strength, and foreign ions

  • Ling ZhaoEmail author
  • Juan Liu
  • Hui Wang
  • Yuan-hua Dong
Research Article


Copper (Cu) and norfloxacin (Nor) are frequently used as feed additives for animal growth promotion, which results in a great probability of Cu2+ and Nor coexisting in animal excretion and in soils. Sorption of Cu2+ and Nor on soil organic matter (SOM) can markedly affect their environmental fate. Thus, humic acid (HA), a major fraction of SOM, was chosen to investigate the cosorption behaviors of Cu2+ and Nor on HA under different solution chemistry conditions (pHs, ionic strengths, and foreign ions). The addition of Nor decreased the maximum adsorption capacity (Qm) of Cu2+ and an increasing effect was observed with increasing Nor concentration. Meanwhile, the addition of Cu2+ also markedly inhibited the sorption of Nor on HA. The Qm of Cu2+ increased with increasing pH from 3.0 to 5.0 whether Nor was present or not, but more addition of Nor led to less increment in Qm of Cu2+ at the same pH. The Qm of Nor was observed at pH 4.0 without Cu2+, but that was found at pH 5.0 and 3.0 with the addition of 20 and 100 mg L−1 Cu2+, respectively. The sorption of Cu2+ on HA decreased with increasing ionic strength and followed an order of NaH2PO4 > Na2SO4 ≈ NaNO3 at pH 5.0 whether Nor was present or not. Additionally, the higher valence cation had a stronger inhibition effect on Cu2+ sorption. The competition between Cu2+ and Nor for sorption on HA under the same conditions indicated that the coexistence of Cu2+ and Nor may enhance the feasibility of their mobility and environmental risk.


Copper Norfloxacin Humic acid Cosorption pH Ionic strength 


Funding information

This study received financial support from the National Natural Science Foundation of China (41571308 and 41371319).

Supplementary material

11356_2019_4515_MOESM1_ESM.docx (1006 kb)
ESM 1 (DOCX 1005 kb)


  1. Andrade LR, Farina M, Filho AMG (2004) Effects of copper on Enteromorpha flexuosa (Chlorophyta) in vitro. Ecotox Environ Safe 58:117–125CrossRefGoogle Scholar
  2. Berendsen BJA, Wegh RS, Memelink J, Zuidema T, Stolker AAM (2015) The analysis of animal faeces as a tool to monitor antibiotic usage. Talanta 132:258–268CrossRefGoogle Scholar
  3. Biglke M, Weyer S, Wilcke W (2010) Copper isotope fractionation during complexation with insolubilized humic acid. Environ Sci Technol 44:5496–5502CrossRefGoogle Scholar
  4. Bui TX, Choi H (2010) Influence of ionic strength, anions, cations, and natural organic matter on the adsorption of pharmaceuticals to silica. Chemosphere 80:681–686CrossRefGoogle Scholar
  5. Chen YS, Zhang HB, Luo YM, Song J (2012) Occurrence and assessment of veterinary antibiotics in swine manures: a case study in East China. Chin Sci Bull 57(6):606–614CrossRefGoogle Scholar
  6. Cheng D, Liao P, Yuan SH (2016) Effects of ionic strength and cationic type on humic acid facilitated transport of tetracycline in porous media. Chem Eng J 284:389–394CrossRefGoogle Scholar
  7. El-Eswed B, Khalili F (2006) Adsorption of Cu(II) and Ni(II) on solid humic acid from the Azraq area, Jordan. J Colloid Interface Sci 299:497–503CrossRefGoogle Scholar
  8. Engebretson RR, von Wandruszka R (1998) Kinetic aspects of cation-enhanced aggregation in aqueous humic acids. Environ Sci Technol 32:488–493CrossRefGoogle Scholar
  9. Golet EM, Alder AC, Giger W (2002) Environmental exposure and risk assessment of fluoroquinolone antibacterial agents in wastewater and river water of the Gatt Valley watershed, Switzerland. Environ Sci Technol 36:3645–3651CrossRefGoogle Scholar
  10. Goyne KW, Chorover J, Kubicki JD, Zimmerman AR, Brantley SL (2005) Sorption of the antibiotic ofloxacin to mesoporous and nonporous alumina and silica. J Colloid Interface Sci 283:160–170CrossRefGoogle Scholar
  11. Gu XY, Tan YY, Tong F, Gu C (2015) Surface complexation modeling of coadsorption of antibiotic ciprofloxacin and Cu(II) and onto goethite surfaces. Chem Eng J 269:113–120CrossRefGoogle Scholar
  12. Han LF, Gao B, Lu J, Zhou Y, Xu DY, Gao L, Sun K (2017) Pollution characteristics and source identification of trace metals in riparian soils of Miyun Reservoir, China. Ecotoxicol Environ Saf 144:321–329Google Scholar
  13. Hari AC, Paruchuri RA, Sabatini DA, Kibbey TCG (2005) Effects of pH and cationic and nonionic surfactants on the adsorption of pharmaceuticals to a natural aquifer material. Environ Sci Technol 39:2592–2598CrossRefGoogle Scholar
  14. Iskrenova-Tchoukova E, Kalinichev AG, Kirkpatrick RJ (2010) Metal cation complexation with natural organic matter in aqueous solutions: molecular dynamics simulations and potentials of mean force. Langmuir 26(20):15909–15919CrossRefGoogle Scholar
  15. Ji X, Shen Q, Liu F, Ma J, Xu G, Wang Y, Wu M (2012) Antibiotic resistance gene abundances associated with antibiotics and heavy metals in animal manures and agricultural soils adjacent to feedlots in Shanghai, China. J Hazard Mater 235:178–185CrossRefGoogle Scholar
  16. Kahle MK, Stamm C (2007) Sorption of the veterinary antimicrobial sulfathiazole to organic materials of different origin. Environ Sci Technol 41:132–138CrossRefGoogle Scholar
  17. Kaštelan-Macan M, Petrovic M (1995) Competitive sorption of phosphate and marine humic substances on suspended particulate matter. Water Sci Technol 32(9–10):349–355CrossRefGoogle Scholar
  18. Kohanski MA, Dwyer DJ, Collins JJ (2010) How antibiotics kill bacteria: from targets to networks. Nat Rev Microbiol 8:423–435CrossRefGoogle Scholar
  19. Komy ZR, Shaker AM, Heggy SEM, El-Sayed MEA (2014) Kinetic study for copper adsorption onto soil minerals in the absence and presence of humic acid. Chemosphere 99:117–124CrossRefGoogle Scholar
  20. Negreanu Y, Pasternak Z, Jurkevitch E, Cytryn E (2012) Impact of treated wastewater irrigation on antibiotic resistance in agricultural soils. Environ Sci Technol 46:4800–4808CrossRefGoogle Scholar
  21. OECD (2000) Adsorption–desorption using a batch equilibrium method, technical guideline 106, OECD guidelines for testing of chemicals. OECD Publications, ParisGoogle Scholar
  22. Ogiyama S, Sakamoto K, Suzuki H, Ushio S, Anzai T, Inubushi K (2005) Accumulation of zinc and copper in an arable field after animal manure application. Soil Sci Plant Nutr 51:801–808CrossRefGoogle Scholar
  23. Pan M, Chu LM (2017) Occurrence of antibiotics and antibiotic resistance genes in soils from wastewater irrigation areas in the Pearl River Delta region, southern China. Sci Total Environ 624:145–152Google Scholar
  24. Pei ZG, Shan XQ, Kong JJ, 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
  25. Pei ZG, Shan XQ, Zhang SZ, Kong JJ, Wen B, Zhang J, Zheng LR, Xie YN, Janssens K (2011) Insight to ternary complexes of co-adsorption of norfloxacin and Cu(II) onto montmorillonite at different pH using EXAFS. J Hazard Mater 186:842–848CrossRefGoogle Scholar
  26. Pils JV, Laird DA (2007) Sorption of tetracycline and chlortetracycline on K- and Ca-saturated soil clays, humic substances, and clay-humic complexes. Environ Sci Technol 41:1928–1933Google Scholar
  27. Prado AGS, Torres JD, Martins PC, Pertusatti J, Bolzon LB, Faria EA (2006) Studies on copper(II)- and zinc(II)-mixed ligand complexes of humic acid. J Hazard Mater 136:585–588CrossRefGoogle Scholar
  28. Qi YB, Zhu J, Fu QL, Hu HQ, Huang QY (2017) Sorption of Cu by humic acid from the decomposition of rice straw in the absence and presence of clay minerals. J Environ Manag 200:304–311CrossRefGoogle Scholar
  29. Qian MR, Wu HZ, Wang JM, Zhang H, Zhang ZL, Zhang YZ, Lin H, Ma JW (2016) Occurrence of trace elements and antibiotics in manure-based fertilizers from the Zhejiang Province of China. Sci Total Environ 559:174–181CrossRefGoogle Scholar
  30. Sheals J, Granström M, Sjöberg S, Persson P (2003) Coadsorption of Cu(II) and glyphosate at the water-goethite (α-FeOOH) interface: molecular structures from FTIR and EXAFS measurements. J Colloid Interface Sci 262:38–47CrossRefGoogle Scholar
  31. Simpson MJ, Chefetz B, Hatcher PG (2003) Phenanthrene sorption to structurally modified humic acids. J Environ Qual 32:1750–1758CrossRefGoogle Scholar
  32. Soler-Rovira P, Madejón E, Madejón P, Plaza C (2010) In situ remediation of metal-contaminated soils with organic amendments: role of humic acids in copper bioavailability. Chemosphere 79:844–849CrossRefGoogle Scholar
  33. Vignoli Muniz GS, Llontop Incio J, Alves OC, Krambrock K, Teixeira LR, Louro SRW (2018) Fluorescence and electron paramagnetic resonance studies of norfloxacin and N-donor mixed-ligand ternary copper(II) complexes: stability and interaction with SDS micelles. Spectrochim Acta A Mol Biomol Spectrosc 189:133–138CrossRefGoogle Scholar
  34. Wallis SC, Gahan LR, Charles BG, Hambley TW, Duckworth PA (1996) Copper(II) complexes of the fluoroquinolone antimicrobial ciprofloxacin, synthesis, X-ray structural characterization, and potentiometric study. J Inorg Biochem 62:1–16CrossRefGoogle Scholar
  35. Wang MC, Chen CY, Chang JH (2004) Significance of different characteristics of humic acids from lake sediment and uncultivated mountain soil. J Chin Inst Environ Eng 14:207–216Google Scholar
  36. Wang YJ, Jin DA, Sun RJ, Zhu HW, Zhou DM (2008) Adsorption and cosorption of tetracycline and copper(II) on montmorillonite as affected by solution pH. Environ Sci Technol 42:3254–3259CrossRefGoogle Scholar
  37. Wang LF, Wang LL, Ye XD, Le WW, Ren XM, Sheng GP, Yu HQ, Wang XK (2013) Coagulation kinetics of humic aggregates in mono- and di-valent electrolyte solutions. Environ Sci Technol 47:5042–5049CrossRefGoogle Scholar
  38. Wang H, Chu Y, Fang C (2017) Occurrence of veterinary antibiotics in swine manure from large-scale feedlots in Zhejiang province, China. Bull Environ Contam Toxicol 98(4):472–477CrossRefGoogle Scholar
  39. Weber WJ Jr, McGinley PM, Katz LE (1992) A distributed reactivity model for sorption by soils and sediments. 1. Conceptual basis and equilibrium assessments. Environ Sci Technol 26:1955–1962CrossRefGoogle Scholar
  40. Xu QG, Zhang MK (2017) Source identification and exchangeability of heavy metals accumulated in vegetable soils in the coastal plain of eastern Zhejiang province, China. Ecotoxicol Environ Saf 142:410–416CrossRefGoogle Scholar
  41. Xu JL, Tan WF, Xiong J, Wang MX, Fang LC, Koopal LK (2016) Copper binding to soil fulvic and humic acids: NICA-Donnan modeling and conditional affinity spectra. J Colloid Interface Sci 473:141–151CrossRefGoogle Scholar
  42. Yang K, Miao GF, Wu WH, Lin DH, Pan B, Wu FC, Xing BS (2015) Sorption of Cu2+ on humic acids sequentially extracted from a sediment. Chemosphere 138:657–663CrossRefGoogle Scholar
  43. Zhang J, Dai JL, Wang RQ, Li FS, Wang WX (2009) Adsorption and desorption of divalent mercury (Hg2+) on humic acids and fulvic acids extracted from typical soils in China. Colloids Surf A Physicochem Eng Asp 335:194–201CrossRefGoogle Scholar
  44. 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
  45. Zhang JH, Lu MY, Wan J, Sun YH, Lan HX, Deng XY (2018) Effects of pH, dissolved humic acid and Cu2+ on the adsorption of norfloxacin on montmorillonite-biochar composite derived from wheat straw. Biochem Eng J 130:104–112CrossRefGoogle Scholar
  46. Zhao L, Dong YH, Wang H (2010) Residues of veterinary antibiotics in manures from feedlot livestock in eight provinces of China. Sci Total Environ 408:1069–1075CrossRefGoogle Scholar
  47. Zhu D, Herbert BE, Schlautman MA (2003) Sorption of pyridine to suspended soil particles studied by deuterium nuclear magnetic resonance. Soil Sci Soc Am J 67:1370–1377CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Ling Zhao
    • 1
    • 2
    Email author
  • Juan Liu
    • 1
    • 2
  • Hui Wang
    • 1
    • 2
  • Yuan-hua Dong
    • 1
    • 2
  1. 1.Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil ScienceChinese Academy of SciencesNanjingPeople’s Republic of China
  2. 2.University of Chinese Academy of SciencesBeijingChina

Personalised recommendations