Aquatic Geochemistry

, Volume 16, Issue 1, pp 85–100 | Cite as

Influence of NOM on the Mobility of Metal(loid)s in Water-Saturated Porous Media

  • George Metreveli
  • Gudrun Abbt-Braun
  • Fritz Hartmann FrimmelEmail author
Original Paper


In this work, the interaction of natural organic matter (NOM) with metal(loid)s (Cu, Pb, Zn, Pt, As) and the role of NOM on the metal(loid) transport in a water-saturated quartz sand column were investigated. For detailed information, size exclusion chromatographic (SEC) measurements and “short pulse” laboratory transport experiments with online metal(loid) and NOM detection were used. The SEC measurements showed the formation of metal–NOM complexes. Cu, Pb, Zn and Pt were predominantly bound to the high molecular mass NOM molecules. The binding capacity of the NOM for metals increased with increasing pH value and in the following order: Zn < Pb < Cu < Pt. No evidence for the formation of As–NOM complexes was found. The transport experiments showed no significant influence of NOM on the mobility of Cu, Pb and Zn. The metal–NOM complexes detected in the SEC experiments were obviously sorbed completely onto the grain surfaces in case of the quartz sand system, or they were dissociated partially during passage through the column. No influence of NOM was observed on the transport of As as well. Inorganic Zn and As species were transported through the column with increasing retardation as the pH value increased. Pt showed a high mobility at a pH of 5, and it decreased at a pH of 7 especially in the presence of NOM. The results support the known fact that a decrease in the pH value results in enhanced transport of inorganic metal(loid) species in water-saturated porous media. On the other hand, the presence of NOM can immobilise the metals through metal–NOM complex formation and the deposition of the complexes onto the stationary phase.


NOM Metal(loid)s SEC Transport experiments Porous media 



The authors thank the German research council (DFG) for financial support within the Graduiertenkolleg 366 and KORESI project (colloidal transport of substances by seepage of rainwater, FR 536/29). Joachim Krenn and Reinhard Sembritzki are gratefully acknowledged for their fine experimental work and ICP-MS measurements.


  1. Abbt-Braun G, Lankes U, Frimmel FH (2004) Structural characterization of aquatic humic substances—the need for a multiple method approach. Aquat Sci 66:151–170CrossRefGoogle Scholar
  2. Bolea E, Gorriz MP, Bouby M, Laborda F, Castillo JR, Geckeis H (2006) Multielement characterization of metal–humic substances complexation by size exclusion chromatography, asymmetrical flow field-flow fractionation, ultrafiltration and inductively coupled plasma-mass spectrometry detection: a comparative approach. J Chromatogr A 1129:236–246CrossRefGoogle Scholar
  3. Christl I, Kretzschmar R (2001) Interaction of copper and fulvic acid at the hematite–water interface. Geochim Cosmochim Acta 65:3435–3442CrossRefGoogle Scholar
  4. Dunnivant FM, Jardine PM, Taylor DL, McCarthy JF (1992a) Transport of naturally occurring dissolved organic carbon in laboratory columns containing aquifer material. Soil Sci Soc Am J 56:437–444Google Scholar
  5. Dunnivant FM, Jardine PM, Taylor DL, McCarthy JF (1992b) Cotransport of cadmium and hexachlorobiphenyl by dissolved organic carbon through columns containing aquifer material. Environ Sci Technol 26:360–368CrossRefGoogle Scholar
  6. Grolimund D, Borkovec M, Barmettler K, Sticher H (1996) Colloid-facilitated transport of strongly sorbing contaminants in natural porous media: a laboratory column study. Environ Sci Technol 30:3118–3123CrossRefGoogle Scholar
  7. Guggenberger G, Glaser B, Zech W (1994) Heavy metal binding by hydrophobic and hydrophilic dissolved organic carbon fractions in a Spodosol A and B horizon. Water Air Soil Pollut 72:111–127CrossRefGoogle Scholar
  8. Her N, Amy G, Foss D, Cho J, Yoon Y, Kosenka P (2002) Optimization of method for detecting and characterizing NOM by HPLC-size exclusion chromatography with UV and on-line DOC detection. Environ Sci Technol 36:1069–1076CrossRefGoogle Scholar
  9. Jardine PM, Weber NL, McCarthy JF (1989) Mechanisms of dissolved organic carbon adsorption on soil. Soil Sci Soc Am J 53:1378–1385CrossRefGoogle Scholar
  10. Jordan RN, Yonge DR, Hathhorn WE (1997) Enhanced mobility of Pb in the presence of dissolved natural organic matter. J Contam Hydrol 29:59–80CrossRefGoogle Scholar
  11. Kalbitz K, Solinger S, Park J-H, Michalzik B, Matzner E (2000) Controls on the dynamics of dissolved organic matter in soils: a review. Soil Sci 165:277–304CrossRefGoogle Scholar
  12. Kretzschmar R, Barmettler K, Grolimund D, Yan Y, Borkovec M, Sticher H (1997) Experimental determination of colloid deposition rates and collision efficiencies in natural porous media. Water Resour Res 33:1129–1137CrossRefGoogle Scholar
  13. Kretzschmar R, Borkovec M, Grolimund D, Elimelech M (1999) Mobile subsurface colloids and their role in contaminant transport. Adv Agron 66:121–193CrossRefGoogle Scholar
  14. Lankes U, Lüdemann H–D, Frimmel FH (2008) Search for basic relations between “molecular size” and “chemical structure” of aquatic natural organic matter—Answers from 13C and 15N CPMAS NMR spectroscopy. Water Res 42:1051–1060CrossRefGoogle Scholar
  15. McCarthy JF, Zachara JM (1989) Subsurface transport of contaminants. Environ Sci Technol 23:496–502Google Scholar
  16. McCarthy JF, Williams TM, Liang L, Jardine PM, Jolley LW, Taylor DL, Palumbo AV, Cooper LW (1993) Mobility of natural organic matter in a sandy aquifer. Environ Sci Technol 27:667–676CrossRefGoogle Scholar
  17. Metreveli G, Frimmel FH (2007) Influence of Na-bentonite colloids on the transport of heavy metals in porous media. In: Frimmel FH, von der Kammer F, Flemming H-C (eds) Colloidal transport in porous media. Springer, Berlin, pp 29–53CrossRefGoogle Scholar
  18. Metreveli G, Kaulisch E-M, Frimmel FH (2005) Coupling of a column system with ICP-MS for the characterisation of colloid-mediated metal(loid) transport in porous media. Acta Hydrochim Hydrobiol 33:337–345CrossRefGoogle Scholar
  19. Nagao S, Matsunaga T, Suzuki Y, Ueno T, Amano H (2003) Characteristics of humic substances in the Kuji River waters as determined by high-performance size exclusion chromatography with fluorescence detection. Water Res 37:4159–4170CrossRefGoogle Scholar
  20. Newton K, Amarasiriwardena D, Xing B (2006) Distribution of soil arsenic species, lead and arsenic bound to humic acid molar mass fractions in a contaminated apple orchard. Environ Pollut 143:197–205CrossRefGoogle Scholar
  21. Oden WI, Amy GL, Conklin M (1993) Subsurface interactions of humic substances with Cu(II) in saturated media. Environ Sci Technol 27:1045–1051CrossRefGoogle Scholar
  22. Robertson AP, Leckie JO (1999) Acid/base, copper binding, and Cu2+/H+ exchange properties of a soil humic acid, an experimental and modeling study. Environ Sci Technol 33:786–795CrossRefGoogle Scholar
  23. Roy SB, Dzombak DA (1997) Chemical factors influencing colloid-facilitated transport of contaminants in porous media. Environ Sci Technol 31:656–664CrossRefGoogle Scholar
  24. Ryan JN, Elimelech M (1996) Colloid mobilization and transport in groundwater. Colloid Surf A 107:1–56CrossRefGoogle Scholar
  25. Sadi BBM, Wrobel K, Wrobel K, Kannamkumarath SS, Castillo JR, Caruso JA (2002) SEC–ICP–MS studies for elements binding to different molecular weight fractions of humic substances in compost extract obtained from urban solid waste. J Environ Monit 4:1010–1016CrossRefGoogle Scholar
  26. Schmitt D, Müller MB, Frimmel FH (2000) Metal distribution in different size fractions of natural organic matter. Acta Hydrochim Hydrobiol 28:400–410CrossRefGoogle Scholar
  27. Schmitt D, Saravia F, Frimmel FH, Schuessler W (2003) NOM-facilitated transport of metal ions in aquifers: importance of complex-dissociation kinetics and colloid formation. Water Res 37:3541–3550CrossRefGoogle Scholar
  28. Schulze D, Krüger A, Segebade C (2000) Stability and mobility of metal–humic complexes isolated from different soils. J Radioanal Nucl Chem 244:51–53CrossRefGoogle Scholar
  29. Shelimov B, Lambert J-F, Che M, Didillon B (1999) Application of NMR to interfacial coordination chemistry: A 195Pt NMR study of the interaction of hexachloroplatinic acid aqueous solutions with alumina. J Am Chem Soc 121:545–556CrossRefGoogle Scholar
  30. Specht CH, Frimmel FH (2000) Specific interactions of organic substances in size-exclusion chromatography. Environ Sci Technol 34:2361–2366CrossRefGoogle Scholar
  31. Specht CH, Kumke MU, Frimmel FH (2000) Characterization of NOM adsorption to clay minerals by size exclusion chromatography. Water Res 34:4063–4069CrossRefGoogle Scholar
  32. Spieker WA, Liu J, Miller JT, Kropf AJ, Regalbuto JR (2002) An EXAFS study of the co-ordination chemistry of hydrogen hexachloroplatinate(IV) 1. Speciation in aqueous solution. Appl Catal A 232:219–235CrossRefGoogle Scholar
  33. Steinborn D, Junicke H (2000) Carbohydrate complexes of platinum-group metals. Chem Rev 100:4283–4317CrossRefGoogle Scholar
  34. Weng L, Fest EPMJ, Fillius J, Temminghoff EJM, Van Riemsdijk WH (2002) Transport of humic and fulvic acids in relation to metal mobility in a copper-contaminated acid sandy soil. Environ Sci Technol 36:1699–1704CrossRefGoogle Scholar
  35. Wood SA (1996) The role of humic substances in the transport and fixation of metals of economic interest (Au, Pt, Pd, U, V). Ore Geol Rev II:1–31CrossRefGoogle Scholar
  36. Zhuang J, Flury M, Jin Y (2003) Colloid-facilitated Cs transport through water-saturated Hanford sediment and Ottawa sand. Environ Sci Technol 37:4905–4911CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2009

Authors and Affiliations

  • George Metreveli
    • 1
  • Gudrun Abbt-Braun
    • 1
  • Fritz Hartmann Frimmel
    • 1
    Email author
  1. 1.Chair of Water Chemistry, Engler-Bunte-InstituteUniversität Karlsruhe (TH)KarlsruheGermany

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