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Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH ARTICLE

Swelling and aggregation of Leonardite upon pH change and PbII binding: an AFM study

Federico dos Reis Copello A , Leonardo Lizarraga B , Silvia Orsetti C and Fernando V. Molina A D
+ Author Affiliations
- Author Affiliations

A INQUIMAE, Instituto de Química Física de Materiales, Ambiente y Energía, and Departamento de Química Inorgánica, Analítica y Química Física, FCEN, UBA, Buenos Aires C1428EGA, Argentina.

B CIBION, Centro de Investigaciones en Bionanociencias, CONICET, Consejo Nacional de Investigaciones Científicas y Técnicas ‘Elizabeth Jares Erijman’, Buenos Aires C1425FQD, Argentina.

C Institut für Geowissenschaften, Zentrum für angewandte Geowissenschaften, Eberhard-Karls Universität Tübingen, Tübingen 72074, Germany.

D Corresponding author. Email: fmolina@qi.fcen.uba.ar

Environmental Chemistry 15(3) 162-170 https://doi.org/10.1071/EN17224
Submitted: 5 December 2017  Accepted: 23 February 2018   Published: 25 June 2018

Environmental context. Natural organic materials, such as humic substances, play key roles in the binding and environmental fate of metals. We study the interaction of protons and metal ions with humic acids, and show changes to the mechanical properties of the particles and their capability to fix metal pollutants. The results will help refine current models of metal behaviour in the environment.

Abstract. The swelling and aggregation of Leonardite humic acid, due to acid–base and PbII binding interactions, was studied through atomic force microscopy (AFM) tapping mode measurements and correlated with potentiometric experiments. These experiments allowed determination of parameters for the non-ideal competitive adsorption (NICA)-elastic polyelectrolyte network (EPN) model, which predicts size and electrostatic potential changes. AFM observations showed growth of agglomerates at low pH values. Height distribution analysis allowed discrimination of single particles from agglomerates. The size of individual particles increased slightly with pH increase. Agglomeration was evaluated through the dispersity, which increased at pH < 5, concomitant with a decrease of the electrostatic repulsion and an increase of protonated carboxylic groups, thus the agglomeration is attributed to both factors. In the presence of PbII, agglomeration is observed to rise strongly with the increase in metal concentration, which is attributed to bridging of humic particles by PbII ions. The AFM ex situ results suggest consistency between NICA-EPN predictions and experimental behaviour.

Additional keywords: environmental colloids, metals, soil chemistry.


References

Baigorri R, Fuentes M, González-Gaitano G, García-Mina JM (2007). Analysis of molecular aggregation in humic substances in solution. Colloids and Surfaces A: Physicochemical and Engineering Aspects 302, 301–306.
Analysis of molecular aggregation in humic substances in solutionCrossref | GoogleScholarGoogle Scholar |

Baldssock JA, Nelson PN (1999). Soil organic matter. In ‘Handbook of soil science’. (Ed. ML Sumner) pp. B75–B84. (CRC: Boca Raton, FL)

Balnois E, Wilkinson KJ (2002). Sample preparation techniques for the observation of environmental biopolymers by atomic force microscopy. Colloids and Surfaces A: Physicochemical and Engineering Aspects 207, 229–242.
Sample preparation techniques for the observation of environmental biopolymers by atomic force microscopyCrossref | GoogleScholarGoogle Scholar |

Balnois E, Wilkinson KJ, Lead JR, Buffle J (1999). Atomic force microscopy of humic substances: effects of pH and ionic strength. Environmental Science & Technology 33, 3911–3917.
Atomic force microscopy of humic substances: effects of pH and ionic strengthCrossref | GoogleScholarGoogle Scholar |

Benedetti MF, Milne CJ, Kinniburgh DG, Van Riemsdijk WH, Koopal LK (1995). Metal ion binding to humic substances: application of the non-ideal competitive adsorption model. Environmental Science & Technology 29, 446–457.
Metal ion binding to humic substances: application of the non-ideal competitive adsorption modelCrossref | GoogleScholarGoogle Scholar |

Buffle J, Altmann RS, Filella M, Tessier A (1990). Complexation by natural heterogeneous compounds: site occupation distribution functions, a normalized description of metal complexation. Geochimica et Cosmochimica Acta 54, 1535–1553.
Complexation by natural heterogeneous compounds: site occupation distribution functions, a normalized description of metal complexationCrossref | GoogleScholarGoogle Scholar |

Chen C, Wang X, Jiang H, Hu W (2007). Direct observation of macromolecular structures of humic acid by AFM and SEM. Colloids and Surfaces A: Physicochemical and Engineering Aspects 302, 121–125.
Direct observation of macromolecular structures of humic acid by AFM and SEMCrossref | GoogleScholarGoogle Scholar |

Chilom G, Rice JA (2009). Structural organization of humic acid in the solid state. Langmuir 25, 9012–9015.
Structural organization of humic acid in the solid stateCrossref | GoogleScholarGoogle Scholar |

da Costa Saab S, Carvalho ER, Bernardes Filho R, de Moura MR, Martin-Neto L, Mattoso LHC (2010). pH effect in aquatic fulvic acid from a Brazilian river. Journal of the Brazilian Chemical Society 21, 1490–1496.
pH effect in aquatic fulvic acid from a Brazilian riverCrossref | GoogleScholarGoogle Scholar |

David C, Mongin S, Rey-Castro C, Galceran J, Companys E, Garcés JL, Salvador J, Puy J, Cecilia J, Lodeiro P, Mas F (2010). Competition effects in cation binding to humic acid: conditional affinity spectra for fixed total metal concentration conditions. Geochimica et Cosmochimica Acta 74, 5216–5227.
Competition effects in cation binding to humic acid: conditional affinity spectra for fixed total metal concentration conditionsCrossref | GoogleScholarGoogle Scholar |

Duval JFL, Wilkinson KJ, Van Leeuwen HP, Buffle J (2005). Humic substances are soft and permeable: evidence from their electrophoretic mobilities. Environmental Science & Technology 39, 6435–6445.
Humic substances are soft and permeable: evidence from their electrophoretic mobilitiesCrossref | GoogleScholarGoogle Scholar |

García R, Pérez R (2002). Dynamic atomic force microscopy methods. Surface Science Reports 47, 197–301.
Dynamic atomic force microscopy methodsCrossref | GoogleScholarGoogle Scholar |

Goldberg S (2005). Equations and models describing adsorption processes in soils. In ‘Chemical processes in soils’. (Eds MA Tabatabai, DL Sparks) pp. 489–518. (Soil Science Society of America: Madison, WI)

Gorham JM, Wnuk JD, Shin M, Fairbrother H (2007). Adsorption of natural organic matter onto carbonaceous surfaces: atomic force microscopy study. Environmental Science & Technology 41, 1238–1244.
Adsorption of natural organic matter onto carbonaceous surfaces: atomic force microscopy studyCrossref | GoogleScholarGoogle Scholar |

Guo J, Ma J (2006). AFM study on the sorbed NOM and its fractions isolated from River Songhua. Water Research 40, 1975–1984.
AFM study on the sorbed NOM and its fractions isolated from River SonghuaCrossref | GoogleScholarGoogle Scholar |

Gustafsson JP, Pechova P, Berggren D (2003). Modeling metal binding to soils: the role of natural organic matter. Environmental Science & Technology 37, 2767–2774.
Modeling metal binding to soils: the role of natural organic matterCrossref | GoogleScholarGoogle Scholar |

Israelachvili JN (2010). ‘Intermolecular and surface forces, 3rd edn.’ (Academic Press: Amsterdam)

Kinniburgh DG, Milne CJ, Benedetti MF, Pinheiro JP, Filius J, Koopal LK, Van Riemsdijk WH (1996). Metal ion binding by humic acid: application of the NICA-Donnan model. Environmental Science & Technology 30, 1687–1698.
Metal ion binding by humic acid: application of the NICA-Donnan modelCrossref | GoogleScholarGoogle Scholar |

Kinniburgh DG, Van Riemsdijk WH, Koopal LK, Borkovec M, Benedetti MF, Avena MJ (1999). Ion binding to natural organic matter: competition, heterogeneity, stoichiometry and thermodynamic consistency. Colloids and Surfaces A: Physicochemical and Engineering Aspects 151, 147–166.
Ion binding to natural organic matter: competition, heterogeneity, stoichiometry and thermodynamic consistencyCrossref | GoogleScholarGoogle Scholar |

Lenoir T, Matynia A, Manceau A (2010). Convergence-optimized procedure for applying the NICA–Donnan model to potentiometric titrations of humic substances. Environmental Science & Technology 44, 6221–6227.
Convergence-optimized procedure for applying the NICA–Donnan model to potentiometric titrations of humic substancesCrossref | GoogleScholarGoogle Scholar |

Liu C, Frenkel AI, Vairavamurthy A, Huang PM (2001). Sorption of cadmium on humic acid: mechanistic and kinetic studies with atomic force microscopy and X-ray absorption fine structure spectroscopy. Canadian Journal of Soil Science 81, 337–348.
Sorption of cadmium on humic acid: mechanistic and kinetic studies with atomic force microscopy and X-ray absorption fine structure spectroscopyCrossref | GoogleScholarGoogle Scholar |

Matynia A, Lenoir T, Causse B, Spadini L, Jacquet T, Manceau A (2010). Semi-empirical proton binding constants for natural organic matter. Geochimica et Cosmochimica Acta 74, 1836–1851.
Semi-empirical proton binding constants for natural organic matterCrossref | GoogleScholarGoogle Scholar |

Milne CJ, Kinniburgh DG, De Wit JCM, Van Riemsdijk WH, Koopal LK (1995). Analysis of proton binding by a peat humic acid using a simple electrostatic model. Geochimica et Cosmochimica Acta 59, 1101–1112.
Analysis of proton binding by a peat humic acid using a simple electrostatic modelCrossref | GoogleScholarGoogle Scholar |

Milne CJ, Kinniburgh DG, Tipping E (2001). Generic NICA–Donnan model parameters for proton binding by humic substances. Environmental Science & Technology 35, 2049–2059.
Generic NICA–Donnan model parameters for proton binding by humic substancesCrossref | GoogleScholarGoogle Scholar |

Milne CJ, Kinniburgh DG, van Riemsdijk WH, Tipping E (2003). Generic NICA–Donnan model parameters for metal-ion binding by humic substances. Environmental Science & Technology 37, 958–971.
Generic NICA–Donnan model parameters for metal-ion binding by humic substancesCrossref | GoogleScholarGoogle Scholar |

Molina FV (2013). ‘Soil colloids: properties and ion binding.’ (CRC Press: Boca Raton, FL).

Montenegro AC, Orsetti S, Molina FV (2014). Modelling proton and metal binding to humic substances with the NICA-EPN model. Environmental Chemistry 11, 318–332.
Modelling proton and metal binding to humic substances with the NICA-EPN modelCrossref | GoogleScholarGoogle Scholar |

Orsetti S, Andrade EM, Molina FV (2010). Modeling ion binding to humic substances: elastic polyelectrolyte network model. Langmuir 26, 3134–3144.
Modeling ion binding to humic substances: elastic polyelectrolyte network modelCrossref | GoogleScholarGoogle Scholar |

Orsetti S, Marco-Brown JL, Andrade EM, Molina FV (2013). Pb(II) binding to humic substances: an equilibrium and spectroscopic study. Environmental Science & Technology 47, 8325–8333.
Pb(II) binding to humic substances: an equilibrium and spectroscopic studyCrossref | GoogleScholarGoogle Scholar |

Plaschke M, Rothe J, Schäfer T, Denecke MA, Dardenne K, Pompe S, Heise K-H (2002). Combined AFM and STXM in situ study of the influence of Eu(III) on the agglomeration of humic acid. Colloids and Surfaces A: Physicochemical and Engineering Aspects 197, 245–256.
Combined AFM and STXM in situ study of the influence of Eu(III) on the agglomeration of humic acidCrossref | GoogleScholarGoogle Scholar |

Puy J, Galceran J, Huidobro C, Companys E, Samper N, Garcés JL, Mas F (2008). Conditional affinity spectra of Pb2+-humic acid complexation from data obtained with AGNES. Environmental Science & Technology 42, 9289–9295.
Conditional affinity spectra of Pb2+-humic acid complexation from data obtained with AGNESCrossref | GoogleScholarGoogle Scholar |

Puy J, Huidobro C, David C, Rey-Castro C, Salvador J, Companys E, Garcés JL, Galceran J, Cecília J, Mas F (2009). Conditional affinity spectra underlying NICA isotherm. Colloids and Surfaces A: Physicochemical and Engineering Aspects 347, 156–166.
Conditional affinity spectra underlying NICA isothermCrossref | GoogleScholarGoogle Scholar |

Ritchie JD, Perdue EM (2003). Proton-binding study of standard and reference fulvic acids, humic acids, and natural organic matter. Geochimica et Cosmochimica Acta 67, 85–96.
Proton-binding study of standard and reference fulvic acids, humic acids, and natural organic matterCrossref | GoogleScholarGoogle Scholar |

Senesi N, Loffredo E (1998). The chemistry of soil organic matter. In ‘Soil physical chemistry’. (Ed. DL Sparks) pp. 239–370. (CRC Press: Boca Raton, FL)

Simpson AJ, Kingery WL, Hayes MH, Spraul M, Humpfer E, Dvortsak P, Kerssebaum R, Godejohann M, Hofmann M (2002). Molecular structures and associations of humic substances in the terrestrial environment. Naturwissenschaften 89, 84–88.
Molecular structures and associations of humic substances in the terrestrial environmentCrossref | GoogleScholarGoogle Scholar |

Sutton R, Sposito G (2005). Molecular structure in soil humic substances: the new view. Environmental Science & Technology 39, 9009–9015.
Molecular structure in soil humic substances: the new viewCrossref | GoogleScholarGoogle Scholar |

Tipping E (1998). Humic ion-binding model VI: an improved description of the interactions of protons and metal ions with humic substances. Aquatic Geochemistry 4, 3–47.
Humic ion-binding model VI: an improved description of the interactions of protons and metal ions with humic substancesCrossref | GoogleScholarGoogle Scholar |

Wershaw RL (2004). Evaluation of conceptual models of natural organic matter (humus) from a consideration of the chemical and biochemical processes of humification (Scientific Investigations Report No. 2004-5121). USGS, Denver, CO.

Zhong Q, Inniss D, Kjoller K, Elings VB (1993). Fractured polymer/silica fiber surface studied by tapping mode atomic force microscopy. Surface Science Letters 290, L688–L692.
Fractured polymer/silica fiber surface studied by tapping mode atomic force microscopyCrossref | GoogleScholarGoogle Scholar |