Environmental Science and Pollution Research

, Volume 25, Issue 16, pp 15873–15884 | Cite as

The copper complexation ability of a synthetic humic-like acid formed by an abiotic humification process and the effect of experimental factors on its copper complexation ability

  • Ting Yang
  • Mark E. Hodson
Research Article


Humic acids have an important impact on the distribution, toxicity, and bioavailability of hazardous metals in the environment. In this study, a synthetic humic-like acid (SHLA) was prepared by an abiotic humification process using catechol and glycine as humic precursors and a MnO2 catalyst. The effect of physico-chemical conditions (ionic strength from 0.01 to 0.5 M NaNO3, pH from 4 to 8, temperature from 25 to 45 °C, and humic acid concentration from 5 to 100 mg/L) on the complexation ability of SHLA for Cu2+ were investigated. A commercial humic acid (CHA, CAS: 1415-93-6) from Sigma-Aldrich was also studied for comparison. The results showed that for pH 4 to 8, the conditional stability constants (log K) of SHLA and CHA were in the range 5.63–8.62 and 4.87–6.23, respectively, and complexation capacities (CC) were 1.34–2.61 and 1.42–2.31 mmol/g, respectively. The Cu complexation ability of SHLA was higher than that of the CHA due to its higher number of acidic functional groups (SHLA 19.19 mmol/g; CHA 3.87 mmol/g), extent of humification and aromaticity (AL/AR: 0.333 (SHLA); 1.554 (CHA)), and O-alkyl functional groups (SHLA 15.56%; CHA 3.45%). The log K and complexation efficiency (fraction of metal bound to SHLA) of SHLA were higher at higher pH, lower ionic strength, higher temperature, and higher SHLA concentration. Overall, SHLA was a good and promising complexation agent for copper in both soil washing of copper contaminated soil and the treatment of copper-containing wastewater.


Abiotic humification Synthetic humic-like acid Copper Complexation 



We thank the China Scholarship Council and Environment Department, University of York for funding the PhD work. We also appreciate the technical assistance received for FTIR, 13C-NMR (University of York) and for elemental analysis (University of Leeds).

Supplementary material

11356_2018_1836_MOESM1_ESM.docx (259 kb)
ESM 1 (DOCX 259 kb)


  1. Alkorta I, Hernández-Allica J, Becerril JM, Amezaga I, Albizu I, Onaindia M, Garbisu C (2004) Chelate-enhanced phytoremediation of soils polluted with heavy metals. Rev Environ Sci Biotechnol 3:55–70CrossRefGoogle Scholar
  2. Alvarez-Puebla RA, Valenzuela-Calahorro C, Garrido JJ (2004) Cu(II) retention on a humic substance. J Colloid Interface Sci 270:47–55CrossRefGoogle Scholar
  3. Baken S, Degryse F, Verheyen L, Merckx R, Smolders E (2011) Metal complexation properties of freshwater dissolved organic matter are explained by its aromaticity and by anthropogenic ligands. Environ Sci Technol 45:2584–2590CrossRefGoogle Scholar
  4. Baker H, Khalili F (2003) Comparative study of binding strengths and thermodynamic aspects of Cu(II) and Ni(II) with humic acid by Schubert’s ion-exchange method. Anal Chim Acta 497:235–248CrossRefGoogle Scholar
  5. Baker H, Khalili F (2005) A study of complexation thermodynamic of humic acid with cadmium (II) and zinc (II) by Schubert’s ion-exchange method. Anal Chim Acta 542:240–248CrossRefGoogle Scholar
  6. Baumann EW (1974) Investigation of copper(II) chelates of EDTA and DTPA with cupric-selective electrodes. J Radioanal Nucl Chem 36:1827–1832CrossRefGoogle Scholar
  7. Boguta P, D'Orazio V, Sokołowska Z, Senesi N, (2016) Effects of selected chemical and physicochemical properties of humic acids from peat soils on their interaction mechanisms with copper ions at various pHs. J Geochem Explor 168:119–126Google Scholar
  8. Brunetti G, Senesi N, Plaza C (2008) Organic matter humification in olive oil mill wastewater by abiotic catalysis with manganese(IV) oxide. Bioresour Technol 99:8528–8531CrossRefGoogle Scholar
  9. Buffle J, Greter FL, Haerdi W (1977) Measurement of complexation properties of humic and fulvic acids in natural waters with lead and copper ion-selective electrodes. Anal Chem 49:216–222CrossRefGoogle Scholar
  10. Cao J, Lam KC, Dawson RW, Liu WX, Tao S (2004) The effect of pH, ion strength and reactant content on the complexation of Cu2+ by various natural organic ligands from water and soil in Hong Kong. Chemosphere 54:507–514CrossRefGoogle Scholar
  11. Chen Y, Senesi N, Schnitzer M (1977) Information provided on humic substances by E4/E6 ratios1. Soil Sci Soc Am J 41:352–358CrossRefGoogle Scholar
  12. Chen YM, Tsao TM, Liu CC, Huang PM, Wang MK (2010) Polymerization of catechin catalyzed by Mn-, Fe-and Al-oxides. Colloid Surface B 81:217–223CrossRefGoogle Scholar
  13. Chen J, Chen H, Zhang X, Lei K, Kenny JE (2015) Combination of a copper-ion selective electrode and fluorometric titration for the determination of copper (II) ion conditional stability constants of humic substances. Appl Spectrosc 69:1293–1302CrossRefGoogle Scholar
  14. Chin Y, Gschwend PM (1991) The abundance, distribution, and configuration of porewater organic colloids in recent sediments. Geochim Cosmochim Acta 55:1309–1317CrossRefGoogle Scholar
  15. Christl I (2012) Ionic strength-and pH-dependence of calcium binding by terrestrial humic acids. Environ Chem 9:89–96CrossRefGoogle Scholar
  16. Dudare D, Klavins M (2013) Complex-forming properties of peat humic acids from a raised bog profiles. J Geochem Explor 129:18–22CrossRefGoogle Scholar
  17. EPA (2002) National recommended water quality criteria: human health criteria calculation matrix. United States Environmental Protection Agency, EPA-822-R-02-012Google Scholar
  18. EPA (2007) Aquatic life ambient freshwater quality criteria—copper. United States Environmental Protection Agency, EPA-822-R-07-001Google Scholar
  19. Fang K, Yuan D, Zhang L, Feng L, Chen Y, Wang Y (2015) Effect of environmental factors on the complexation of iron and humic acid. J Environ Sci 27:188–196CrossRefGoogle Scholar
  20. Fernández-Gómez MJ, Nogales R, Plante A, Plaza C, Fernández JM (2015) Application of a set of complementary techniques to understand how varying the proportion of two wastes affects humic acids produced by vermicomposting. Waste Manag 35:81–88CrossRefGoogle Scholar
  21. Fu F, Wang Q (2011) Removal of heavy metal ions from wastewaters: a review. J Environ Manag 92:407–418CrossRefGoogle Scholar
  22. Fuentes M, Olaetxea M, Baigorri R, Zamarreño AM, Etienne P, Laîné P, Ourry A, Yvin J, Garcia-Mina JM (2013) Main binding sites involved in Fe (III) and Cu (II) complexation in humic-based structures. J Geochem Explor 129:14–17CrossRefGoogle Scholar
  23. Fukuchi S, Fukushima M, Nishimoto R, Qi G, Sato T (2012) Fe-loaded zeolites as catalysts in the formation of humic substance-like dark-coloured polymers in polycondensation reactions of humic precursors. Clay Miner 47:355–364CrossRefGoogle Scholar
  24. Fukushima M, Miura A, Sasaki M, Izumo K (2009a) Effect of an allophanic soil on humification reactions between catechol and glycine: spectroscopic investigations of reaction products. J Mol Struct 917:142–147CrossRefGoogle Scholar
  25. Fukushima M, Yamamoto K, Ootsuka K, Komai T, Aramaki T, Ueda S, Horiya S (2009b) Effects of the maturity of wood waste compost on the structural features of humic acids. Bioresour Technol 100:791–797CrossRefGoogle Scholar
  26. Fukushima M, Okabe R, Nishimoto R, Fukuchi S, Sato T, Terashima M (2014) Adsorption of pentachlorophenol to a humin-like substance–bentonite complex prepared by polycondensation reactions of humic precursors. Appl Clay Sci 87:136–141CrossRefGoogle Scholar
  27. Garcia-Valls R, Hatton TA (2003) Metal ion complexation with lignin derivatives. Chem Eng J 94:99–105CrossRefGoogle Scholar
  28. Gustafsson JP, Persson I, Oromieh AG, van Schaik JWJ, Sjöstedt C, Kleja DB (2014) Chromium(III) complexation to natural organic matter: mechanisms and modeling. Environ Sci Technol 48:1753–1761CrossRefGoogle Scholar
  29. Hardie AG, Dynes JJ, Kozak LM, Huang PM (2009) The role of glucose in abiotic humification pathways as catalyzed by birnessite. J Mol Catal A Chem 308:114–126CrossRefGoogle Scholar
  30. He E, Lü C, He J, Zhao B, Wang J, Zhang R, Ding T (2016) Binding characteristics of Cu2+ to natural humic acid fractions sequentially extracted from the lake sediments. Environ Sci Pollut Res Int 23:22667–22677CrossRefGoogle Scholar
  31. Hernández D, Plaza C, Senesi N, Polo A (2006) Detection of copper(II) and zinc(II) binding to humic acids from pig slurry and amended soils by fluorescence spectroscopy. Environ Pollut 143:212–220CrossRefGoogle Scholar
  32. Huang PM (1995) The role of short-range ordered mineral colloids in abiotic transformations of organic components in the environment. In: Huang PM, Berthelin J, Bollag J-M, McGill WB, Page AL (eds) Environmental impact of soil component interactions: vol. 1 natural and anthropogenic organics. CRC/Lewis Publishers, Boca Raton, pp 151–167Google Scholar
  33. Huang PM (2000) Abiotic catalysis. In: Sumner ME (ed) Handbook of soil science. CRC Press, Boca Raton, pp B303–B332Google Scholar
  34. Jokic A, Wang MC, Liu C, Frenkel AI, Huang PM (2004) Integration of the polyphenol and Maillard reactions into a unified abiotic pathway for humification in nature: the role of δ-MnO2. Org Geochem 35:747–762CrossRefGoogle Scholar
  35. Kautenburger R, Hein C, Sander JM, Beck HP (2014) Influence of metal loading and humic acid functional groups on the complexation behavior of trivalent lanthanides analyzed by CE-ICP-MS. Anal Chim Acta 816:50–59CrossRefGoogle Scholar
  36. Kim Y, Osako M (2004) Investigation on the humification of municipal solid waste incineration residue and its effect on the leaching behavior of dioxins. Waste Manag 24:815–823CrossRefGoogle Scholar
  37. Lesmana SO, Febriana N, Soetaredjo FE, Sunarso J, Ismadji S (2009) Studies on potential applications of biomass for the separation of heavy metals from water and wastewater. Biochem Eng J 44:19–41CrossRefGoogle Scholar
  38. Li Z, Ma Z, van der Kuijp TJ, Yuan Z, Huang L (2014) A review of soil heavy metal pollution from mines in China: pollution and health risk assessment. Sci Total Environ 468–469:843–853CrossRefGoogle Scholar
  39. Lippold H, Evans NDM, Warwick P, Kupsch H (2007) Competitive effect of iron(III) on metal complexation by humic substances: characterisation of ageing processes. Chemosphere 67:1050–1056CrossRefGoogle Scholar
  40. Liu H, Feng S, Zhang N, Du X, Liu Y (2014) Removal of Cu(II) ions from aqueous solution by activated carbon impregnated with humic acid. Front Envron Sci Eng 8:329–336CrossRefGoogle Scholar
  41. Mahieu N, Olk DC, Randall EW (2000) Accumulation of heterocyclic nitrogen in humified organic matter: a 15N-NMR study of lowland rice soils. Eur J Soil Sci 51:379–389CrossRefGoogle Scholar
  42. Martell AE, Smith RM (1974) Critical stability constants. SpringerGoogle Scholar
  43. Nagasawa K, Wang B, Nishiya K, Ushijima K, Zhu Q, Fukushima M, Ichijo T (2016) Effects of humic acids derived from lignite and cattle manure on antioxidant enzymatic activities of barley root. J Environ Sci Health B 51:81–89CrossRefGoogle Scholar
  44. Nishimoto R, Fukuchi S, Qi G, Fukushima M, Sato T (2013) Effects of surface Fe (III) oxides in a steel slag on the formation of humic-like dark-colored polymers by the polycondensation of humic precursors. Colloid Surface A 418:117–123CrossRefGoogle Scholar
  45. NRM (2017) Potentially toxic elements in agricultural soils. Advice Sheet 18. NRM laboratories, Cawood Scientific. Available on line at 18th Oct 2017
  46. Pandey AK, Pandey SD, Misra V (2000) Stability constants of metal–humic acid complexes and its role in environmental detoxification. Ecotoxicol Environ Saf 47:195–200CrossRefGoogle Scholar
  47. Paradelo M, Pérez-Rodríguez P, Fernández-Calviño D, Arias-Estévez M, López-Periago JE (2012) Coupled transport of humic acids and copper through saturated porous media. Blackwell Publishing Ltd, 708–716Google Scholar
  48. Peng J, Song Y, Yuan P, Cui X, Qiu G (2009) The remediation of heavy metals contaminated sediment. J Hazard Mater 161:633–640CrossRefGoogle Scholar
  49. Perminova IV, Hatfield K (2005) Remediation chemistry of humic substances: theory and implications for technology. Spring, pp. 3–36Google Scholar
  50. Playle RC, Dixon DG, Burnison K (1993) Copper and cadmium binding to fish gills: estimates of metal–gill stability constants and modelling of metal accumulation. Can J Fish Aquat Sci 50:2678–2687CrossRefGoogle Scholar
  51. Plaza C, D'Orazio V, Senesi N (2005a) Copper (II) complexation of humic acids from the first generation of EUROSOILS by total luminescence spectroscopy. Geoderma 125:177–186CrossRefGoogle Scholar
  52. Plaza C, Senesi N, García-Gil JC, Polo A (2005b) Copper(II) complexation by humic and fulvic acids from pig slurry and amended and non-amended soils. Chemosphere 61:711–716CrossRefGoogle Scholar
  53. Qi G, Yue D, Fukushima M, Fukuchi S, Nie Y (2012a) Enhanced humification by carbonated basic oxygen furnace steel slag–I. Characterization of humic-like acids produced from humic precursors. Bioresour Technol 104:497–502CrossRefGoogle Scholar
  54. Qi G, Yue D, Fukushima M, Fukuchi S, Nishimoto R, Nie Y (2012b) Enhanced humification by carbonated basic oxygen furnace steel slag–II. Process characterization and the role of inorganic components in the formation of humic-like substances. Bioresour Technol 114:637–643CrossRefGoogle Scholar
  55. Recatalá L, Sacristán D, Arbelo C, Sánchez J (2012) Can a single and unique cu soil quality standard be valid for different Mediterranean agricultural soils under an accumulator crop? Water Air Soil Pollut 223:1503–1517CrossRefGoogle Scholar
  56. Rodrigues A, Brito A, Janknecht P, Proença MF, Nogueira R (2009) Quantification of humic acids in surface water: effects of divalent cations, pH, and filtration. J Environ Monit 11:377–382CrossRefGoogle Scholar
  57. Ružić I (1982) Theoretical aspects of the direct titration of natural waters and its information yield for trace metal speciation. Anal Chim Acta 140:99–113CrossRefGoogle Scholar
  58. Schnitzer, M., Kahn, S.U., 1972. Humic substances in the environmentGoogle Scholar
  59. Shi W, Shao H, Li H, Shao M, Du S (2009) Progress in the remediation of hazardous heavy metal-polluted soils by natural zeolite. J Hazard Mater 170:1–6CrossRefGoogle Scholar
  60. Sposito G, Weber JH (1986) Sorption of trace metals by humic materials in soils and natural waters. Crit Rev Environ Control 16:193–229CrossRefGoogle Scholar
  61. Stevenson FJ (1994) Humus chemistry: genesis, composition, reactions. John Wiley & SonsGoogle Scholar
  62. Su C (2014) A review on heavy metal contamination in the soil worldwide: situation, impact and remediation techniques. Environ Skeptics Crit 3:24Google Scholar
  63. Swift RS (1996) Organic matter characterization. In: Sparks, D.L. (Ed.), Methods of soil analysis. Part 3. Chemical methods, SSSA book series: 5. WI, USA, 1011–1069Google Scholar
  64. Tang W, Zeng G, Gong J, Liang J, Xu P, Zhang C, Huang B (2014) Impact of humic/fulvic acid on the removal of heavy metals from aqueous solutions using nanomaterials: a review. Sci Total Environ 468–469:1014–1027CrossRefGoogle Scholar
  65. Thermo Scientific Orion (2008) Cupric Ion Selective Electrode User Guide.
  66. Tipping E (2002) Cation binding by humic substances. Cambridge University PressGoogle Scholar
  67. Tu X, Aneksampant A, Kobayashi S, Tanaka A, Nishimoto R, Fukushima M (2017) Advantages and risks of using steel slag in preparing composts from raw organic waste. J Environ Sci Health B 52:30–36CrossRefGoogle Scholar
  68. Vidali R, Remoundaki E, Tsezos M (2011) An experimental and modelling study of Cu2+ binding on humic acids at various solution conditions. Application of the NICA-Donnan model. Water Air Soil Pollut 218:487–497CrossRefGoogle Scholar
  69. Wang MC, Huang PM, (2000) Ring cleavage and oxidative transformation of pyrogallol catalyzed by Mn, Fe, Al, and Si oxides. Soil Sci 165:934–942Google Scholar
  70. Xu J, Tan W, Xiong J, Wang M, Fang L, 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
  71. Yang L, Wei Z, Zhong W, Cui J, Wei W (2016) Modifying hydroxyapatite nanoparticles with humic acid for highly efficient removal of Cu(II) from aqueous solution. Colloid Surf A 490:9–21CrossRefGoogle Scholar
  72. Yuan S, Xi Z, Jiang Y, Wan J, Wu C, Zheng Z, Lu X (2007) Desorption of copper and cadmium from soils enhanced by organic acids. Chemosphere 68:1289–1297CrossRefGoogle Scholar
  73. Zalba P, Amiotti NM, Galantini JA, Pistola S (2016) Soil humic and fulvic acids from different land-use systems evaluated by E4/E6 ratios. Commun Soil Sci Plan 47:1675–1679CrossRefGoogle Scholar
  74. Zhang Y, Yue D, Ma H (2015) Darkening mechanism and kinetics of humification process in catechol-Maillard system. Chemosphere 130:40–45CrossRefGoogle Scholar
  75. Zherebtsov SI, Malyshenko NV, Bryukhovetskaya LV, Lyrshchikov SY, Ismagilov ZR (2015) Sorption of copper cations from aqueous solutions by brown coals and humic acids. Solid Fuel Chem+ 49:294–303CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Environment DepartmentUniversity of YorkYorkUK

Personalised recommendations