Journal of Soils and Sediments

, Volume 17, Issue 2, pp 352–363 | Cite as

Phosphate-induced aggregation kinetics of hematite and goethite nanoparticles

  • Chen-Yang Xu
  • Ren-Kou Xu
  • Jiu-Yu Li
  • Kai-Ying Deng
Soils, Sec 2 • Global Change, Environ Risk Assess, Sustainable Land Use • Research Article



The purpose of the present study is to examine the effect of phosphate on the aggregation kinetics of hematite and goethite nanoparticles.

Materials and methods

The dynamic light scattering method was used to study the aggregation kinetics of hematite and goethite nanoparticles.

Results and discussion

Specific adsorption of phosphates could promote aggregation through charge neutralization at low P concentrations, stabilize the nanoparticle suspensions at medium P concentrations, and induce aggregation through charge screening by accompanying cations at high P concentrations. Two critical coagulation concentration (CCC) values were obtained in each system. In NaH2PO4, the goethite CCC at low phosphate concentrations was smaller than hematite and vice versa at high phosphate concentrations. Stronger phosphate adsorption by goethite rapidly changed the zeta potential from positive to negative at low phosphate concentrations, and the zeta potential became more negative at high phosphate concentrations. The clusters of hematite nanoparticles induced by phosphate adsorption had an open and looser structure. Solution pH and the phosphate adsorption mechanisms in NaH2PO4, KH2PO4, and Na3PO4 solutions affected zeta potential values and controlled the stability of hematite suspensions during aggregation. High pH and preference for non-protonated inner-sphere complexes in Na3PO4 solution decreased the zeta potential of positively charged hematite and promoted aggregation. Activation energies followed the order NaH2PO4 > KH2PO4 > Na3PO4 at low P concentrations. K+ was more effective than Na+ in promoting hematite aggregation due to the non-classical polarization of cations.


Phosphate can enhance or inhibit the aggregation of hematite and goethite nanoparticles in suspensions by changing surface charge due to specific adsorption onto the particles. The phosphate-induced aggregation of the nanoparticles mainly depended on the initial concentration of phosphate.


Activation energy Aggregation kinetics Goethite Hematite Phosphate speciation Total average aggregation rate 



This study was supported by the National Natural Science Foundation of China (41271010 and 41230855), the State Key Development Program for Basic Research of China (2015CB158200), and the Youth Innovation Promotion Association, CAS.

Supplementary material

11368_2016_1550_MOESM1_ESM.docx (317 kb)
ESM 1 (DOCX 317 kb)


  1. Anderson MA, Tejedor-Tejedor MI, Stanforth RR (1985) Influence of aggregation on the uptake kinetics of phosphate by goethite. Environ Sci Technol 19:632–637CrossRefGoogle Scholar
  2. Arai Y, Sparks DL (2007) Phosphate reaction dynamics in soils and soil components: a multiscale approach. Adv Agron 94:135–179CrossRefGoogle Scholar
  3. Arai Y, Livi K, Sparks DL (2005) Phosphate reactivity in long-term poultry litter-amended southern Delaware sandy soils. Soil Sci Soc Am J 69:616–629CrossRefGoogle Scholar
  4. Atkinson R, Posner A, Quirk JP (1967) Adsorption of potential-determining ions at the ferric oxide-aqueous electrolyte interface. J Phys Chem 71:550–558CrossRefGoogle Scholar
  5. Borda T, Celi L, Zavattaro L, Sacco D, Barberis E (2011) Effect of agronomic management on risk of suspended solids and phosphorus losses from soil to waters. J Soil Sediment 11:440–451CrossRefGoogle Scholar
  6. Breeuwsma A, Lyklema J (1973) Physical and chemical adsorption of ions in the electrical double layer on hematite (α-Fe2O3). J Colloid Interf Sci 43:437–448CrossRefGoogle Scholar
  7. Chen KL, Elimelech M (2006) Aggregation and deposition kinetics of fullerene (C60) nanoparticles. Langmuir 22:10994–11001CrossRefGoogle Scholar
  8. Chen KL, Elimelech M (2009) Relating colloidal stability of fullerene (C60) nanoparticles to nanoparticles charge and electrokinetic properties. Environ Sci Technol 43:7270–7276CrossRefGoogle Scholar
  9. Chen KL, Mylon SE, Elimelech M (2006) Aggregation kinetics of alginate-coated hematite nanoparticles in monovalent and divalent electrolytes. Environ Sci Technol 40:1516–1523CrossRefGoogle Scholar
  10. Cheng H, Wu C, Winnik MA (2004) Kinetics of reversible aggregation of soft polymeric particles in dilute dispersion. Macromolecules 37:5127–5129CrossRefGoogle Scholar
  11. Chorover J, Zhang J, Amistadi MK, Buffle J (1997) Comparison of hematite coagulation by charge screening and phosphate adsorption: differences in aggregate structure. Clay Clay Miner 45:690–708CrossRefGoogle Scholar
  12. Cordell D, Drangert J-O, White S (2009) The story of phosphorus: global food security and food for thought. Global Environ Chang 19:292–305CrossRefGoogle Scholar
  13. Duman O, Tunç S (2009) Electrokinetic and rheological properties of Na-bentonite in some electrolyte solutions. Micropor Mesopor Mat 117:331–338CrossRefGoogle Scholar
  14. Elser J, Bennett E (2011) Phosphorus cycle: a broken biogeochemical cycle. Nature 478:29–31CrossRefGoogle Scholar
  15. Elzinga EJ, Kretzschmar R (2013) In situ ATR-FTIR spectroscopic analysis of the co-adsorption of orthophosphate and Cd(II) onto hematite. Geochim Cosmochim Acta 17:53–64CrossRefGoogle Scholar
  16. Elzinga EJ, Sparks DL (2007) Phosphate adsorption onto hematite: an in situ ATR-FTIR investigation of the effects of pH and loading level on the mode of phosphate surface complication. J Colloid Interf Sci 308:53–70CrossRefGoogle Scholar
  17. Gao Y, Mucci A (2001) Acid base reactions, phosphate and arsenate complication, and their competitive adsorption at the surface of goethite in 0.7 M NaCl solution. Geochim Cosmochim Acta 65:2361–2378CrossRefGoogle Scholar
  18. Gilbert N (2009) Environment: the disappearing nutrient. Nature 461:716–718CrossRefGoogle Scholar
  19. Hackley VA, Anderson MA (1989) Effects of short-range forces on the long-range structure of hydrous iron oxide aggregates. Langmuir 5:191–198CrossRefGoogle Scholar
  20. He YT, Wan J, Tokunaga T (2008) Kinetic stability of hematite nanoparticles: the effect of particle sizes. J Nanopart Res 10:321–332CrossRefGoogle Scholar
  21. Huang X (2004) Intersection of isotherms for phosphate adsorption on hematite. J Colloid Interf Sci 271:296–307CrossRefGoogle Scholar
  22. Huisman NLH, Karthikeyan KG, Lamba J, Thompson AM, Peaslee G (2013) Quantification of seasonal sediment and phosphorus transport dynamics in an agricultural watershed using radiometric fingerprinting techniques. J Soil Sediment 13:1724–1734CrossRefGoogle Scholar
  23. Jia M, Li H, Zhu H, Tian R, Gao X (2013) An approach for the critical coagulation concentration estimation of polydisperse colloidal suspensions of soil and humus. J Soil Sediment 13:325–335CrossRefGoogle Scholar
  24. Ju-Nam Y, Lead JR (2008) Manufactured nanoparticles: an overview of their chemistry, interactions and potential environmental implications. Sci Total Environ 400:396–414CrossRefGoogle Scholar
  25. Kloster N, Brigante M, Zanini G, Avena M (2013) Aggregation kinetics of humic acids in the presence of calcium ions. Colloid Surface A 427:76–82CrossRefGoogle Scholar
  26. Kunz W (2010) Specific ion effects in colloidal and biological systems. Curr Opin Colloid In 15:34–39CrossRefGoogle Scholar
  27. Kunz W, Henle J, Ninham BW (2004) ‘Zur Lehre von der Wirkung der Salze’ (about the science of the effect of salts): Franz Hofmeister’s historical papers. Curr Opin Colloid In 9:19–37CrossRefGoogle Scholar
  28. Kuo S, Lotse GE (1973) Kinetics of phosphate adsorption and desorption by hematite and gibbsite. Soil Sci 116:400–406CrossRefGoogle Scholar
  29. Li Q, Tang Y, He X, Li H (2015) Approach to theoretical estimation of the activation energy of particle aggregation taking ionic nonclassic polarization into account. AIP Adv 5Google Scholar
  30. Liang L, Morgan JJ (1990) Chemical aspects of iron oxide coagulation in water: laboratory studies and implications for natural systems. Aquat Sci 52:32–55CrossRefGoogle Scholar
  31. Lichtenbelt JWT, Ras HJMC, Wiersema PH (1974) Turbidity of coagulating lyophobic sols. J Colloid Interf Sci 46:522–527CrossRefGoogle Scholar
  32. Lin MY, Lindsay HM, Weitz DA, Ball RC, Klein R, et al. (1989) Universality in colloid aggregation. Nature 339:360–362CrossRefGoogle Scholar
  33. Liu X, Li H, Du W, Tian R, Li R, et al. (2013) Hofmeister effects on cation exchange equilibrium: quantification of ion exchange selectivity. J Phys Chem C 117:6245–6251CrossRefGoogle Scholar
  34. Luengo C, Brigante M, Antelo J, Avena M (2006) Kinetics of phosphate adsorption on goethite: comparing batch adsorption and ATR-IR measurements. J Colloid Interf Sci 300:511–518CrossRefGoogle Scholar
  35. Mylon SE, Chen KL, Elimelech M (2004) Influence of natural organic matter and ionic composition on the kinetics and structure of hematite colloid aggregation: implications to iron depletion in estuaries. Langmuir 20:9000–9006CrossRefGoogle Scholar
  36. Schwertmann U, Cornell RM (2000) Iron oxides in the laboratory: preparation and characterization, 2nd edn. Weinheim, VCHCrossRefGoogle Scholar
  37. Sei J, Jumas J, Olivier-Fourcade J, Quiquampoix H, Staunton S (2002) Role of iron oxides in the phosphate adsorption properties of kaolinites from the Ivory Coast. Clay Clay Miner 50:217–222CrossRefGoogle Scholar
  38. Sen TK, Khilar KC (2006) Review on subsurface colloids and colloid-associated contaminant transport in saturated porous media. Adv Colloid Interfac 119:71–96CrossRefGoogle Scholar
  39. Shigaki F, Sharpley A, Prochnow LI (2007) Rainfall intensity and phosphorus source effects on phosphorus transport in surface runoff from soil trays. Sci Total Environ 373:334–343CrossRefGoogle Scholar
  40. Tejedor-Tejedor MI, Anderson MA (1990) Protonation of phosphate on the surface of goethite as studied by CIR-FTIR and electrophoretic mobility. Langmuir 6:602–611CrossRefGoogle Scholar
  41. Tian R, Li H, Zhu H, Liu X, Gao X (2013) Ca2+ and Cu2+ induced aggregation of variably charged soil particles: a comparative study. Soil Sci Soc Am J 77:774–781CrossRefGoogle Scholar
  42. Tian R, Yang G, Li H, Gao X, Liu X, et al. (2014) Activation energies of colloidal particle aggregation: towards a quantitative characterization of specific ion effects. Phys Chem Chem Phys 16:8828–8836CrossRefGoogle Scholar
  43. Tian R, Yang G, Zhu C, Liu X, Li H (2015) Specific anion effects for aggregation of colloidal minerals: a joint experimental and theoretical study. J Phys Chem C 119:4856–4864CrossRefGoogle Scholar
  44. Tobias DJ, Hemminger JC (2008) Getting specific about specific ion effects. Science 319:1197–1198CrossRefGoogle Scholar
  45. Wang L-F, Wang L-L, Ye X-D, Li W-W, Ren X-M, et al. (2013a) Coagulation kinetics of humic aggregates in mono-and di-valent electrolyte solutions. Environ Sci Technol 47:5042–5049CrossRefGoogle Scholar
  46. Wang X, Liu F, Tan W, Li W, Feng X, et al. (2013b) Characteristics of phosphate adsorption-desorption onto ferrihydrite: comparison with well-crystalline Fe (hydr) oxides. Soil Sci 178:1–11CrossRefGoogle Scholar
  47. Xu C-Y, Deng K-Y, Li J-Y, Xu R-K (2015) Impact of environmental conditions on aggregation kinetics of hematite and goethite nanoparticles. J Nanopart Res 17:1–13CrossRefGoogle Scholar
  48. Yang J-L, Zhang G-L, Shi X-Z, Wang H-J, Cao Z-H, et al. (2009) Dynamic changes of nitrogen and phosphorus losses in ephemeral runoff processes by typical storm events in Sichuan Basin, Southwest China. Soil Till Res 105:292–299CrossRefGoogle Scholar
  49. Zhang MK, He ZL, Calvert DV, Stoffella PJ (2003) Colloidal iron oxide transport in sandy soil induced by excessive phosphorus application. Soil Sci 168:617–626CrossRefGoogle Scholar
  50. Zhu X, Chen H, Li W, He Y, Brookes P, et al. (2014) Aggregation kinetics of natural soil nanoparticles in different electrolytes. Eur J Soil Sci 65:206–217CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.State Key Laboratory of Soil and Sustainable Agriculture, Institute of Soil ScienceChinese Academy of SciencesNanjingChina
  2. 2.University of Chinese Academy of SciencesBeijingChina

Personalised recommendations