Journal of Soils and Sediments

, Volume 9, Issue 3, pp 216–228 | Cite as

Characterization of soil heavy metal pools in paddy fields in Taiwan: chemical extraction and solid-solution partitioning

  • Paul F. Römkens
  • Horng-Yuh Guo
  • Chien-Liang Chu
  • Tsang-Sen Liu
  • Chih-Feng Chiang
  • Gerwin F. Koopmans


Background, aim, and scope

Ongoing industrialization has resulted in an accumulation of metals like Cd, Cu, Cr, Ni, Zn, and Pb in paddy fields across Southeast Asia. Risks of metals in soils depend on soil properties and the availability of metals in soil. At present, however, limited information is available on how to measure or predict the directly available fraction of metals in paddy soils. Here, the distribution of Cd, Cu, Cr, Ni, Zn, and Pb in 19 paddy fields among the total, reactive, and directly available pools was measured using recently developed concepts for aerated soils. Solid-solution partitioning models have been derived to predict the directly available metal pool. Such models are proven to be useful for risk assessment and to derive soil quality standards for aerated soils.

Material and methods

Soil samples (0–25 cm) were taken from 19 paddy fields from five different communities in Taiwan in 2005 and 2006. Each field was subdivided into 60 to 108 plots resulting in a database of approximately 3,200 individual soil samples. Total (Aqua Regia (AR)), reactive (0.43 M HNO3, 0.1 M HCl, and 0.05 M EDTA), and directly available metal pools (0.01 M CaCl2) were determined. Solid-solution partitioning models were derived by multiple linear regressions using an extended Freundlich equation using the reactive metal pool, pH, and the cation exchange capacity (CEC). The influence of Zn on metal partitioning and differences between both sampling events (May/November) were evaluated.


Total metals contents range from background levels to levels in excess of current soil quality standards for arable land. Between 3% (Cr) and 30% (Cd) of all samples exceed present soil quality standards based on extraction with AR. Total metal levels decreased with an increasing distance from the irrigation water inlet. The reactive metal pool relative to the total metal content is increased in the order Cr << Ni = Zn < Pb < Cu < Cd and ranged from less than 10% for Cr to more than 70% for Cd. Despite frequent redox cycles, Cd, Pb, and Cu appear to remain rather reactive. The methods to determine the reactive metal pool in soils yield comparable results, although the 0.43 M HNO3 extraction is slightly stronger than HCl and EDTA. The close correlation between these methods suggests that they release similar fractions from soils, probably those reversibly sorbed to soil organic matter (SOM) and clay. The average directly available pool ranged from less than 1% for Cu, Pb, and Cr to 10% for Ni, Zn, and Cd when compared to the reactive metal pool. For Cd, Ni, Zn, and to a lesser extent for Cu and Pb, solid-solution partitioning models were able to explain up to 93% (Cd) of the observed variation in the directly available metal pool. CaCl2 extractable Zn increased the directly available pool for Ni, Cd, and Cu but not that of Pb and Cr. In the polluted soils, the directly available pool was higher in November compared to that in May. Differences in temperature, rainfall, and changes in soil properties such as pH are likely to contribute to the differences observed within the year. The solid-solution partitioning model failed to explain the variation in the directly available Cr pool, probably because Cr is present in precipitates rather than being adsorbed onto SOM and clay. Despite obvious differences in parent material, source of pollution, climate, and land use, solid-solution partitioning of Cd in paddy fields studied here was similar to that in soils from Belgium and the Netherlands.


To assess risks of metals in soils, both analytical procedures as well as models are needed. The three methods tested here to determine the reactive metal pool are highly correlated and either of these can be used. The directly available pool was predicted most accurately by the 0.43 M HNO3 method. The similarity of metal partitioning in paddy soils compared to well-drained soils suggests that changing redox conditions in paddy fields have a limited effect on the geochemical behavior of metals like Cd, Ni, and Zn. Small but significant differences in the directly available metal pool during the year suggest that redox cycles as well as differences in rainfall and temperature affect the size of the directly available metal pool. The large observed spatial heterogeneity of contaminant levels requires ample attention in the setup of soil monitoring programs.


The directly available pool (0.01 M CaCl2) of Cd, Zn, and Ni in paddy fields can be described well by an extended Freundlich model. For Cu and Pb, more information on dissolved organic carbon is needed to obtain a more accurate estimate of the directly available pool.

Recommendations and perspectives

Soil testing protocols and models used in risk assessment consider the availability of pollutants rather than the total metal content. Results from extensive testing indicate that approaches developed for nontropical regions can be applied in paddy fields as well for metals like Cd, Ni, and Zn. This study shows that the chemical behavior under drained conditions in paddy fields is comparable to that observed in soils across the European Union, which allows regions with large scale soil pollution including Taiwan to apply such concepts to derive meaningful experimental protocols and models to assess risks of metals in soils.


Availability Contamination Extraction methods Heavy metals Paddy fields Risk assessment Soil quality standards Solid-solution partitioning models 



The financial support of the Taiwan Environmental Protection Administration (EPA) and Agricultural Research Institute (ARI) is gratefully acknowledged.


  1. Barrett KA, McBride MB (2007) Dissolution of zinc-cadmium sulfide solid solutions in aerated aqueous suspension. Soil Sci Soc Am J 71:322–328CrossRefGoogle Scholar
  2. Bruemmer GW, Gerth J, Tiller KG (1981) Reaction kinetics of the adsorption and desorption of nickel, zinc and cadmium by goethite. I. Adsorption and diffusion of metals. J Soil Sci 39:37–52Google Scholar
  3. Brus D, Li Z, Song J, Koopmans GF, Temminghoff EJM, Yin X, Yao C, Zhang H, Luo YM, Japenga J (2009) Predictions of spatially averaged Cd contents in rice grains and associated health risks in the Fuyang Valley, P.R. China. J Environ Qual 38. doi: 10.2134/jeq2008.0228
  4. Buekers J (2007) Fixation of cadmium, copper, nickel and zinc in soil: kinetics, mechanisms and its effect on metal bioavailability. PhD thesis no. 754, Catholic University Leuven, Leuven, BelgiumGoogle Scholar
  5. Charlatchka R, Cambier P (1999) Influence of reducing conditions on solubility of trace metals in contaminated soils. Water Air Soil Pollut 118:143–167CrossRefGoogle Scholar
  6. Chen ZS (1991) Cd and Pb contamination of soils near plastic stabilizing materials producing plants in Northern Taiwan. Water Air Soil Pollut 57–58:745–754CrossRefGoogle Scholar
  7. Clayton PM, Tiller KG (1979) A chemical method for the determination of heavy metal content of soils in environmental studies. Technical paper no. 41, Division of Soils, CSIRO AustraliaGoogle Scholar
  8. Colombo C, Van Den Berg CMG (1998) Determination of trace metals (Cu, Pb, Zn and Ni) in soil extracts by flow analysis with voltammetric detection. Int J Environ Anal Chem 71:1–17Google Scholar
  9. Contin M, Mondini C, Leita L, De Nobili M (2007) Enhanced soil toxic metal fixation in iron (hydr) oxides by redox cycles. Geoderma 140:164–175CrossRefGoogle Scholar
  10. Daum D, Bogdan K, Schenk MK, Merkel D (2001) Influence of the field water management on accumulation of arsenic and cadmium in paddy rice. In: Horst WJ et al (eds) Plant nutrition—food security and sustainability of agro-ecosystems through basic and applied research. Kluwer, Norwell, pp 290–291Google Scholar
  11. Degryse F, Broos K, Smolders E, Merckx R (2003) Soil solution concentration of Cd and Zn can be predicted with a CaCl2 soil extract. Eur J Soil Sci 54:149–157CrossRefGoogle Scholar
  12. Dudka S, Miller WP (1999) Accumulation of potentially toxic elements in plants and their transfer to human food chain. J Environ Sci Health B 34:681–708CrossRefGoogle Scholar
  13. Elzinga EJ, Sparks DL (1999) Nickel sorption mechanisms in a pyrophyllite–montmorillonite mixture. J Colloid Interf Sci 213:506–512CrossRefGoogle Scholar
  14. EPA (2006) Regulations governing the preliminary assessment of soil and groundwater pollution control sites. Environmental Protection Administration order Huan-Shu-Tu-Tzu no.0950023629, March 29, 2006Google Scholar
  15. Franz E, Römkens PFAM, Van Der Fels-Klerx I (2008) A chain modeling approach to estimate the impact of soil cadmium pollution on human dietary exposure. J Food Prot 71:2504–2513Google Scholar
  16. Fu J, Zhou Q, Liu J, Liu W, Wang T, Zhang Q, Jiang G (2008) High levels of heavy metals in rice (Oryza sativa L.) from a typical E-waste recycling area in southeast China and its potential risk to human health. Chemosphere 71:1269–1275CrossRefGoogle Scholar
  17. He J, Zhu C, Ren Y, Yan Y, Jiang D (2006) Genotypic variation in grain Cd concentration of lowland rice. J Plant Nutr Soil Sci 169:711–716CrossRefGoogle Scholar
  18. Houba VJG, Van Der Lee JJ, Novozamsky I (1997) Soil and plant analysis. Part 1: soil analysis procedures. Wageningen University, WageningenGoogle Scholar
  19. Houba VJG, Temminghoff EJM, Gaikhorst GA, Van Vark W (2000) Soil analysis procedures using 0.01 M calcium chloride as extraction reagent. Commun. Soil Sci. Plant Anal 31:1299–1396CrossRefGoogle Scholar
  20. Hough RL, Tye AM, Crout NMJ, McGrath SP, Zhang H, Young SD (2005) Evaluating a ‘Free Ion Activity Model’ applied to metal uptake by Lolium perenne L. grown in contaminated soils. Plant Soil 270:1–12CrossRefGoogle Scholar
  21. Ingwersen J, Streck T (2006) Modeling the environmental fate of Cd in a large wastewater irrigation area. J Environ Qual 35:1702–1714CrossRefGoogle Scholar
  22. Kashem MA, Singh BR (2004) Transformations in solid phase species of metals as affected by flooding and organic matter. Commun Soil Sci Plant Anal 35:1435–1456CrossRefGoogle Scholar
  23. Kelderman P, Osman AA (2007) Effect of redox potential on heavy metal binding forms in polluted canal sediments in Delft (The Netherlands). Wat Res 41:4251–4261CrossRefGoogle Scholar
  24. Kikuchi T, Okazaki M, Kimura SD, Motobayashi T, Baasansuren J, Hattori T, Abe T (2008) Suppressive effects of magnesium oxide materials on Cd uptake and accumulation into rice grains II: suppression of Cd uptake and accumulation into rice grains due to application of magnesium oxide materials. J Hazard Mat 154:294–299CrossRefGoogle Scholar
  25. Koopmans GF, Römkens PFAM, Fokkema MJ, Song J, Luo YM, Japenga J, Zhao FJ (2008a) Feasibility of phytoextraction to remediate cadmium and zinc contaminated soils. Environ Pollut 156:905–914CrossRefGoogle Scholar
  26. Koopmans GF, Schenkeveld WDC, Song J, Luo YM, Japenga J, Temminghoff EJM (2008b) Influence of EDDS on metal speciation in soil extracts: measurement and mechanistic multicomponent modeling. Environ Sci Technol 42:1123–1130CrossRefGoogle Scholar
  27. Lamothe PJ, Fries TL, Consul JJ (1986) Evaluation of a microwave oven system for the dissolution of geologic samples. Anal Chem 58:1881–1886CrossRefGoogle Scholar
  28. Li P, Wang XX, Zhang TL, Zhou DM, He YQ (2008) Water Air Soil Pollut. doi: 10.1007/s11270-008-9755-3 Google Scholar
  29. Lu LT, Chang IC, Hsiao TY, Yu YH, Ma HW (2007) Identification of pollution source of Cd in soil. Application of material flow analysis and a case study in Taiwan. Environ Sci Pollut Res 14:49–59CrossRefGoogle Scholar
  30. Lofts S, Spurgeon DJ, Svendsen C, Tipping E (2004) Deriving soil critical limits for Cu, Zn, Cd, and Pb: a method based on free ion concentrations. Environ Sci Technol 38:3623–3631CrossRefGoogle Scholar
  31. McBride MB (1994) Environmental chemistry of soils. Oxford University Press, OxfordGoogle Scholar
  32. McBride MB, Barrett KA, Kim B, Hale B (2006) Cd sorption in soils 25 years after amendment with sewage sludge. Soil Sci 171:21–28CrossRefGoogle Scholar
  33. Meers E, Du Laing G, Unamuno V, Ruttens A, Vangronsveld J, Tack FMG, Verloo MG (2007) Comparison of cadmium extractability from soils by commonly used single extraction protocols. Geoderma 141:247–259CrossRefGoogle Scholar
  34. Nelson JL, Boawn LC, Viets FG Jr (1959) A method for assessing Zn status of soils using acid extractable Zn and “titratable alkalinity” values. Soil Sci 88:275–283CrossRefGoogle Scholar
  35. Peijnenburg WJGM, Posthuma L, Zweers PGPC, de Baerselman R, de Groot AC, Van Veen RPM, Jager T (1999) Prediction of metal bioavailability in Dutch field soils for the oligochaete Enchytraeus crypticus. Ecotoxicol Environ Saf 43:170–186CrossRefGoogle Scholar
  36. Peijnenburg WJGM, Zablotskaja M, Vijver MG (2007) Monitoring metals in terrestrial environments within a bioavailability framework and a focus on soil extraction. Ecotoxicol Environ Saf 67:163–179CrossRefGoogle Scholar
  37. Pueyo M, Lopez-Sanchez JF, Rauret G (2004) Assessment of CaCl2, NaNO3, and NH4NO3 extraction procedures for the study of Cd, Cu, Pb and Zn extractability in contaminated soils. Anal Chim Acta 504:217–226CrossRefGoogle Scholar
  38. Qin F, Wen B, Shan X-Q, Xie Y-N, Liu T, Zhang S-Z, Khan SU (2006) Mechanisms of competitive adsorption of Pb, Cu, and Cd on peat. Environ Pollut 144:669–680CrossRefGoogle Scholar
  39. Rattan RK, Datta SP, Chhonkar PK, Suribabu K, Singh AK (2005) Long-term impact of irrigation with sewage effluents on heavy metal content in soils, crops and groundwater—a case study. Agric Ecosyst Environ 109:310–322CrossRefGoogle Scholar
  40. Römkens PFAM, Dolfing J (1998) Effect of Ca on the solubility and molecular size distribution of DOC and Cu binding in soil solution samples. Environ Sci Technol 32:363–369CrossRefGoogle Scholar
  41. Römkens PFAM, Hoenderboom G, Dolfing J (1999) Copper solution geochemistry in arable soils: field observations and model application. J Environ Qual 28:776–783CrossRefGoogle Scholar
  42. Römkens PFAM, Groenenberg JE, Bril J, Vries W (2004) Derivation of partition equations to calculate heavy metal speciation and solubility in soils. Alterra, Wageningen Report no. 305Google Scholar
  43. Saxe JK, Impellitteri CA, Peijnenburg WJGM, Allen HE (2001) Novel model describing trace metal concentrations in the earthworm, Eisenia Andrei. Environ Sci Technol 35:4522–4529CrossRefGoogle Scholar
  44. Schröder TJ, Hiemstra T, Vink JPM, Van Der Zee SEATM (2005) Modeling of the solid-solution partitioning of heavy metals and arsenic in embanked flood plain soils of the rivers Rhine and Meuse. Environ Sci Technol 39:7176–7184CrossRefGoogle Scholar
  45. Simmons RW, Pongsakul P, Saiyasitpanich D, Klinphoklap S (2005) Elevated levels of Cd and Zn in paddy soils and elevated levels of Cd in rice grain downstream of a Zn mineralized area in Thailand: implications for public health. Environ Geochem Health 27:501–511CrossRefGoogle Scholar
  46. Simmons RW, Noble AD, Pongsakul P, Sukreeyapongse O, Chinabut N (2008) Analysis of field-moist Cd contaminated paddy soils during rice grain fill allows reliable prediction of grain Cd levels. Plant Soil 302:125–137CrossRefGoogle Scholar
  47. Singhal JP, Gupta GK (1978) Reactions of zinc with acid and base saturated dickites. Clay Clay Miner 26:365–371CrossRefGoogle Scholar
  48. Tipping E, Rieuwerts J, Pan G, Ashmore MR, Lofts S, Hill MTR, Farago ME, Thornton I (2003) The solid–solution partitioning of heavy metals (Cu, Zn, Cd, Pb) in upland soils of England and Wales. Environ Pollut 125:213–225CrossRefGoogle Scholar
  49. Tipping E, Lawlor AJ, Lofts S, Shotbolt L (2006) Simulating the long-term chemistry of an upland UK catchment: heavy metals. Environ Pollut 141:139–150CrossRefGoogle Scholar
  50. Tiwari RC, Kumar BM (1982) A suitable extractant for assessing plant-available copper in different soils (peaty, red and alluvial). Plant Soil 68:131–134CrossRefGoogle Scholar
  51. Tsukahara T, Ezaki T, Moriguchi J, Furuki K, Shimbo S, Matsuda-Inoguchi N, Ikeda M (2002) Rice as the most influential source of Cd intake among general Japanese population. Sci Total Environ 305:41–51CrossRefGoogle Scholar
  52. USDA (1996) Soil Survey Laboratory Methods Manual. USDA, Washington, D.C. Soil Survey Investigations Report no. 42Google Scholar
  53. US-EPA (2002) Methods for the determination of total organic carbon (TOC) in soils and sediments, NCEA-C-1282 EMASC-001. US-EPA, Las VegasGoogle Scholar
  54. Watanabe T, Zhang ZW, Moon CS, Shimbo S, Nakatsuka H, Matsuda-Inoguchi N, Higashikawa K, Ikeda M (2000) Cadmium exposure of women in general populations in Japan during 1991–1997 compared with 1977–1981. Int. Arch. Occup. Environ. Health 73:26–34CrossRefGoogle Scholar
  55. Weng L, Temminghoff EJM, Van Riemsdijk WH (2001) Contribution of individual sorbents to the control of heavy metal activity in sandy soil. Environ Sci Technol 35:4436–4443CrossRefGoogle Scholar
  56. Xu R (2000) Particle characterization: light scattering methods. Particle Technology Series Vol 13. Kluwer Academic Publishers, DordrechtGoogle Scholar

Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Paul F. Römkens
    • 1
  • Horng-Yuh Guo
    • 2
  • Chien-Liang Chu
    • 2
  • Tsang-Sen Liu
    • 2
  • Chih-Feng Chiang
    • 2
  • Gerwin F. Koopmans
    • 1
  1. 1.Soil Science CenterAlterra–Wageningen URWageningenThe Netherlands
  2. 2.Taiwan Agricultural Research Institute (TARI)WufongROC

Personalised recommendations