Plant and Soil

, Volume 361, Issue 1–2, pp 83–95 | Cite as

Ageing of zinc in highly-weathered iron-rich soils

  • Erica Donner
  • Mike J. McLaughlin
  • Mark E. Hodson
  • Diane Heemsbergen
  • Michael St. J. Warne
  • Stephen Nortcliff
  • Kris Broos
Regular Article


Background and aims

The reactivity and bioavailability of soluble metal added to soil decreases with time. This process, called ageing, has mainly been investigated in temperate soils. This paper uses isotopic exchangeability to investigate Zn ageing in a range of highly weathered and/or oxide-rich soils.


Changes in lability of soluble added Zn (450 mg Zn/kg soil) over time was measured in six contrasting soils, with pH adjusted to give ten treatments per soil type ranging from pH 4 to 7.


Decreasing extractability and isotopic exchangeability (lability) over time revealed substantial fixation of added zinc in six highly weathered/variable charge soils. Strong negative relationships between pH and solubility, and pH and lability were observed. In soils with pH > 6.5 a significant proportion of the added metal becomes non-isotopically exchangeable within 15 s of addition. Correlations between Mn solubility and Zn lability throughout the incubation demonstrated the role of redox conditions (and pH) in regulating Zn lability.


Results showed zinc fixation was strongly related to pH and ageing time, and relatively unaffected by soil type and mineralogy. Very rapid reductions in radiolability immediately (<15 s) after spiking suggest that precipitation plays a role in fixation of added soluble zinc at near neutral pH, however spectroscopic studies are needed to confirm this. Radiolability of added zinc was also affected by changing redox conditions during incubation.


Zinc Sorption Ageing E-values Oxisols Tropical soils 



E. Donner would like to thank the Commonwealth Scholarships Commission in the UK for PhD funding, and CSIRO Land and Water (Urrbrae, SA) for hosting the visit during which this work was undertaken. She is also grateful to Ass. Prof. E. Lombi, Dr. F., Zhao, Prof. S. McGrath, and Dr. S. Young for helpful discussions and advice.

Supplementary material

11104_2012_1247_MOESM1_ESM.docx (314 kb)
ESM 1 (DOCX 313 kb)


  1. Almås A, Singh BR (2001) Partitioning and reaction kinetics of Cd-109 and Zn-65 in an alum shale soil as influenced by organic matter at different temperatures. In: Iskandar IK, Kirkham MB (eds) Trace elements in soil: bioavailability, flux and transfer. Lewic Publishers, New York, pp 199–211Google Scholar
  2. Appel C, Ma L (2002) Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils. J Environ Qual 31:581–589PubMedCrossRefGoogle Scholar
  3. Armour JD, Ritchie GSP, Robson AD (1989) Changes with time in the availability of soil applied zinc to navy beans and in the chemical extraction of zinc from soils. Aust J Soil Res 27:699–710CrossRefGoogle Scholar
  4. Backes CA, McLaren RG, Rate AW, Swift RS (1995) Kinetics of cadmium and cobalt desorption from iron and manganese oxides. Soil Sci Soc Am J 58:1615–1623Google Scholar
  5. Bao XM (1997) Ferrous ions and manganous ions. In: Yu TR (ed) Chemistry of variable charge soils. Oxford University Press, New York, pp 473–499Google Scholar
  6. Barrow NJ (1986) Testing a mechanistic model. IV. Describing the effects of pH on zinc retention by soils. J Soil Sci 37:295–302CrossRefGoogle Scholar
  7. Barrow NJ, Brümmer GW, Strauss R (1993) Effects of surface heterogeneity on ion sorption by metal oxides and by soils. Langmuir 9:2606–2611CrossRefGoogle Scholar
  8. Blakemore LC, Searle PL, Daly BK (1987) Methods for chemical analysis of soils. New Zealand Soil Bureau Scientific Report 80. New Zealand Soil Bureau. Department of Scientific and Industrial Research, Lower Hutt, New ZealandGoogle Scholar
  9. Brown AL, Krantz BA, Martin PE (1964) The residual effect of zinc applied to soils. Soil Sci Soc Am Proc 28:236–238CrossRefGoogle Scholar
  10. Bruemmer GW, Gerth J, Tiller KG (1988) Reaction kinetics of the adsorption and desorption of nickel, zinc and cadmium by goethite. I. Adsorption and diffusion of metals. J Soil Sci 39:37–52CrossRefGoogle Scholar
  11. Buekers J, van Laer L, Amery F, van Buggenhout S, Maes A, Smolders E (2007) Role of soil constituents in fixation of soluble Zn, Cu, Ni, and Cd added to soils. Eur J Soil Res 58:1514–1524CrossRefGoogle Scholar
  12. Buekers J, Amery F, Maes A, Smolders E (2008) Long-term reactions of Ni, Zn, and Cd with iron oxyhydroxides depend on crystallinity and structure and on metal concentrations. Eur J Soil Sci 59:706–715CrossRefGoogle Scholar
  13. Collins RN, Merrington G, McLaughlin MJ, Morel J-L (2003) Transformation and fixation of Zn in two polluted soils by changes of pH and organic ligands. Aust J Soil Res 41:905–917CrossRefGoogle Scholar
  14. Crout NMJ, Tye AM, Zhang H, McGrath SP, Young SD (2006) Kinetics of metal fixation in soils: measurement and modelling by isotopic dilution. Environ Toxicol Chem 25:659–663PubMedCrossRefGoogle Scholar
  15. Degryse F, Buekers J, Smolders E (2004) Radio-labile cadmium and zinc in soils as affected by pH and source of contamination. Eur J Soil Sci 55:113–121CrossRefGoogle Scholar
  16. Degryse F, Voegelin A, Jacquat O, Kretzschmar R, Smolders E (2011) Characterization of zinc in contaminated soils: complementary insights from isotopic exchange, batch extractions and XAFS spectroscopy. Eur J Soil Sci 62:318–330. doi: 10.1111/j.1365-2389.2010.01332.x CrossRefGoogle Scholar
  17. Donner E, Broos K, Heemsbergen D, Warne M, St J, McLaughlin MJ, Hodson ME, Nortcliff S (2010) Biological and chemical assessment of zinc ageing in field soils. Environ Pollut 158:339–345PubMedCrossRefGoogle Scholar
  18. Eick MJ, Peak JD, Brady PV, Pesek JD (1999) Kinetics of lead adsorption/desorption on goethite: residence time effect. Soil Sci 164:28–39CrossRefGoogle Scholar
  19. FAO (1988) FAO-Unesco soil map of the world. Revised legend. World Soil Resources Report 60. FAO, RomeGoogle Scholar
  20. Follett RH, Lindsay WL (1971) Changes in DTPA-extractable zinc, iron, manganese, and copper in soils following fertilization. Soil Sci Soc Am Proc 35:600–602CrossRefGoogle Scholar
  21. Gérard E, Echevarria G, Morel C, Sterckeman T, Morel JL (2001) Isotopic exchange kinetics method for assessing cadmium availability in soils. In: Iskandar IK, Kirkham MB (eds) Trace elements in soil: bioavailability, flux and transfer. Lewic Publishers, New York, pp 127–143Google Scholar
  22. Hamon RE, McLaughlin MJ, Cozens G (2002) Mechanisms of attenuation of metal availability in in situ remediation treatments. Environ Sci Technol 36:3991–3996PubMedCrossRefGoogle Scholar
  23. Hettiarachchi GM, Lombi E, McLaughlin MJ, Chittleborough DJ, Johnston C (2010) Chemical behavior of fluid and granular Mn and Zn fertilisers in alkaline soils. Aust J Soil Res 48:238–247CrossRefGoogle Scholar
  24. Holmgren GGS, Meyer MW, Chaney RL, Daniels RB (1993) Cadmium, lead, zinc, copper, and nickel in agricultural soils in the United States of America. J Environ Qual 22:335–348CrossRefGoogle Scholar
  25. Impellitteri CA, Allen HE, Yin Y, You S-J, Saxe JK (2001) Soil properties controlling metal partitioning. In: Selim HM, Sparks D (ed) Heavy metals release in soils. Lewis Publishers, pp 149–165Google Scholar
  26. Isbell RF (1994) Krasnozems—a profile. Aust J Soil Res 31:915–929CrossRefGoogle Scholar
  27. Isbell RF (1996) The Australian soil classification. CSIRO Publishing, CollingwoodGoogle Scholar
  28. Jenkinson DS, Powlson DS (1976) The effects of biocidal treatments on metabolism in soil—V. A method for measuring soil biomass. Soil Biol Biochem 8:209–213CrossRefGoogle Scholar
  29. Latrille C, Denaix L, Lamy I (2003) Interaction of copper and zinc with allophane and organic matter in the B horizon of an Andosol. Eur J Soil Sci 54:357–364CrossRefGoogle Scholar
  30. Lieffering RE, McLay CDA (1995) The effect of hydroxide solutions on dissolution of organic-carbon in some New-Zealand soils. Aust J Soil Res 33:873–881CrossRefGoogle Scholar
  31. Liu ZG, Ding CP, Wu YX, Pan SZ, Xu RK (1997) Oxidation-reduction reactions. In: Yu TR (ed) Chemistry of variable charge soils. Oxford University Press, New York, pp 442–472Google Scholar
  32. Lombi E, Hamon RE, McGrath SP, McLaughlin MJ (2003) Lability of Cd, Cu, and Zn in polluted soils treated with lime, beringite, and red mud and identification of a non-labile colloidal fraction of metals using isotopic techniques. Environ Sci Technol 37:979–984PubMedCrossRefGoogle Scholar
  33. Ma YB, Uren NC (1997) The effects of temperature, time and cycles of drying and rewetting on the extractability of zinc added to a calcareous soil. Geoderma 75:89–97CrossRefGoogle Scholar
  34. Ma YB, Lombi E, Nolan A, McLaughlin MJ (2006a) Short-term natural attenuation of copper in soils: effects of time, temperature and soil characteristics. Environ Toxicol Chem 25:652–658PubMedCrossRefGoogle Scholar
  35. Ma YB, Lombi E, Oliver IW, Nolan AL, McLaughlin MJ (2006b) Long-term aging of copper added to soils. Environ Sci Technol 40:6310–6317PubMedCrossRefGoogle Scholar
  36. McBride MB (1994) Environmental chemistry in soils. Oxford University Press, OxfordGoogle Scholar
  37. McBride MB, Blasiak BB (1979) Zinc and copper solubility as a function of pH in an acid soil. Soil Sci Soc Am J 43:866–870CrossRefGoogle Scholar
  38. McLaughlin MJ (2001) Ageing of metals in soils changes bioavailability. International Council on Metals and the Environment, Fact Sheet on Environmental Risk Assessment, No. 4Google Scholar
  39. Moody PW (1994) Chemical fertility of krasnozems. Aust J Soil Res 32:1015–1041Google Scholar
  40. Naidu R, Syers JK, Tillman RW, Kirkman JH (1990) Effect of liming and added phosphate on charge characteristics of acid soils. J Soil Sci 41:157–164CrossRefGoogle Scholar
  41. Naidu R, Kookana RS, Sumner ME, Harter RD, Tiller KG (1997) Cadmium sorption and transport in variable charge soils: a review. J Environ Qual 26:602–617CrossRefGoogle Scholar
  42. Naidu R, Sumner ME, Harter RD (1998) Sorption of heavy metals in strongly weathered soils: an overview. Environ Geochem Heal 20:5–9CrossRefGoogle Scholar
  43. Nakhone LN, Young SD (1993) The significance of (radio-) labile cadmium pools in soil. Environ Pollut 82:73–77PubMedCrossRefGoogle Scholar
  44. O’Day PA, Parks GA, Brown GE (1994) X-ray absorption spectroscopy of cobalt(II) multinuclear surface complexes and surface precipitates on kaolinite. J Colloid Interface Sci 165:269–289CrossRefGoogle Scholar
  45. Pardo MT (1999) Influence of phosphate on zinc reaction in variable charge soils. Commun Soil Sci Plant Anal 30:725–737CrossRefGoogle Scholar
  46. Pardo MT, Guadalix ME (1996) Zinc sorption–desorption by two andepts: effect of pH and support medium. Eur J Soil Sci 47:257–263CrossRefGoogle Scholar
  47. Parfitt RL (1980) Chemical properties of variable charge soils. In: Theng BKG (ed) Soils with variable charge. New Zealand Society of Soil Science, Palmerston North; Soil Bureau, Department of Scientific and Industrial Research, Lower Hutt, pp 167–194Google Scholar
  48. Qafoku NP, Sumner ME, West LT (2000) Mineralogy and chemistry of some variable charge subsoils. Commun Soil Sci Plant Anal 31:1051–1070CrossRefGoogle Scholar
  49. Rayment GE, Higginson FR (1992) Australian laboratory handbook of soil and water chemical methods. Inkata Press, MelbourneGoogle Scholar
  50. Sauvé S, McBride MB, Hendershot WH (1998) Soil solution speciation of lead (II): effects of organic matter and pH. Soil Sci Soc Am J 62:618–621CrossRefGoogle Scholar
  51. Scheidegger AM, Fendorf M, Sparks DL (1996a) Mechanisms of nickel sorption on pyrophillite: macroscopic and microscopic approaches. Soil Sci Soc Am J 62:618–621Google Scholar
  52. Scheidegger AM, Lamble GM, Sparks DL (1996b) Investigation of Ni adsorption on pyrophillite: an EXAFS study. Environ Sci Technol 30:548–554CrossRefGoogle Scholar
  53. Shuman LM (1975) The effect of soil properties on zinc adsorption by soils. Soil Sci Soc Am Proc 39:454–458CrossRefGoogle Scholar
  54. Soil Survey Staff (1975) Soil taxonomy: a basic system of soil classification for making and interpreting soil surveys. USDA Handbook No. 436. US Government Printing Office, Washington D.C.Google Scholar
  55. Soil Survey Staff (1992) Keys to soil taxonomy (5th ed). SMSS technical monograph No. 19. Pocahontas Press, BlacksburgGoogle Scholar
  56. Sparks DL (1998) Kinetics of soil chemical phenomena: future direction. In: Future prospects for soil chemistry. SSSA Special Publication No. 55, pp 81–103Google Scholar
  57. Sparks DL (2003) Environmental soil chemistry, 2nd edn. Academic, San DiegoGoogle Scholar
  58. Sposito G (1989) The chemistry of soils. Oxford University Press, OxfordGoogle Scholar
  59. Towle SN, Bargar JR, Brown GE, Parks GA, Leckie JO (1997) Surface precipitation of Co(II)(aq) on Al2O3. J Colloid Interface Sci 187:62–82PubMedCrossRefGoogle Scholar
  60. Trivedi P, Axe L (2000) Modeling Cd and Zn sorption to hydrous metal oxides. Environ Sci Technol 34:2215–2223CrossRefGoogle Scholar
  61. Tye AM, Young SD, Crout NMJ, Zhang H, Preston S, Barbosa-Jefferson VL, Davison W, McGrath SP, Paton GI, Kilham K, Resende L (2003) Predicting the activity of Cd2+ and Zn2+ in soil pore water from the radio-labile metal fraction. Geochim Cosmochim Acta 67:375–385CrossRefGoogle Scholar
  62. United States Department of Agriculture (1996) Particle size analysis, particles <2mm (pipet method), air-dry samples (method 3A1). In Soil survey laboratory methods manual. Soil survey investigation report no. 42, pp 31–40Google Scholar
  63. Van Damme A, Degryse F, Smolders E, Sarret G, Dewit J, Swennen R, Manceau A (2010) Zinc speciation in mining and smelter contaminated overbank sediments by EXAFS spectroscopy. Geochim Cosmochim Acta 74:3707–3720CrossRefGoogle Scholar
  64. Van Ranst E, Shamshuddin J, Baert G, Dzwowa PK (1998) Charge characteristics in relation to free iron and organic matter of soils from Bambouto Mountains, Western Cameroon. Eur J Soil Sci 49:243–252CrossRefGoogle Scholar
  65. Zelazny LW, Liming H, Vanwormhoudt AN (1996) Charge analysis of soils and anion exchange. In: Methods of soil analysis. Part 3. Chemical methods—SSSA Book Series No. 5. Soil Science Society of America and American Society of Agronomy, Madison, pp 1231–1253Google Scholar
  66. Zhang XN, Zhou AZ (1997) Surface charge. In: Yu TR (ed) Chemistry of variable charge soils. Oxford University Press, New York, pp 17–63Google Scholar

Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  • Erica Donner
    • 1
    • 2
  • Mike J. McLaughlin
    • 3
    • 4
  • Mark E. Hodson
    • 1
  • Diane Heemsbergen
    • 3
  • Michael St. J. Warne
    • 3
    • 5
  • Stephen Nortcliff
    • 1
  • Kris Broos
    • 3
    • 6
  1. 1.Soil Research CentreThe University of ReadingReadingUK
  2. 2.Centre for Environmental Risk Assessment and RemediationUniversity of South AustraliaMawson LakesAustralia
  3. 3.Centre for Environmental Contaminants Research, CSIRO Land and WaterGlen OsmondAustralia
  4. 4.Soil Science, School of Agriculture Food and Wine, Waite Research InstituteUniversity of AdelaideGlen OsmondAustralia
  5. 5.Department of Environmental Research ManagementCatchment Water Science, Water Quality and Aquatic Ecosystem HealthBrisbaneAustralia
  6. 6.VITO—Flemish Institute for Technological ResearchMolBelgium

Personalised recommendations