Journal of Soils and Sediments

, Volume 11, Issue 8, pp 1334–1344 | Cite as

The influence of temperature, pH/molarity and extractant on the removal of arsenic, chromium and zinc from contaminated soil

  • Lea Rastas Amofah
  • Christian Maurice
  • Jurate Kumpiene
  • Prosun Bhattacharya



Normal soil washing leave high residual pollutant content in soil. The remediation could be improved by targeting the extraction to coarser fractions. Further, a low/high extraction pH and higher temperature enhance the pollutant removal, but these measures are costly. In this study, the utility of NaOH, oxalate–citrate (OC) and dithionite–citrate–oxalate (DCO) solutions for extracting of arsenic, chromium and zinc from contaminated soil were assessed and compared. In addition the effects of NaOH concentration and temperature on NaOH extractions, and those of temperature and pH on OC and DCO extractions, were evaluated.

Materials and methods

A two-level, full-factorial design with a centre point was implemented. Two factors, concentration and temperature,were evaluated in NaOH extractions, and pH and temperature for OC and DCO solutions. In all cases, the extraction temperature was 20°C, 30°C and 40°C. The studied NaOH concentrations were 0.05, 0.075 and 0.1 M. The pH in OC solutions was 3, 5 and 7, and in DCO solutions, 4.7, 6.3 and 6.7. Water-washed and medium coarse soil fraction of arsenic, chromium and zinc contaminated soil was agitated for 15 min with the extraction solution.

Results and discussion

In NaOH extractions, the temperature and (less strongly) NaOH concentration significantly affected As and Cr mobilisation, but only the latter affected Zn mobilisation. Both pH and temperature significantly (and similarly) influenced As and Cr mobilisation in OC extractions, while only the pH influenced Zn mobilisation. In contrast, the extraction temperature (but not pH) influenced As, Cr and Zn mobilisation in DCO extractions.


For all extractants, mobilisation was most efficient at elevated temperature (40°C). None of the extractants reduced the soil’s As content to below the Swedish EPA’s guideline value. Use of DCO is not recommended because dithionite has a short lifetime and residual arsenic contents in DCO-extracted soil are relatively high. Instead, sequential extraction with NaOH followed by OC solutions (affording significant reductions in As, Cr and Zn levels in the soil with short extraction times) at 40°C is recommended.


Extraction Factorial design Mobilisation Polluted soil Soil washing Water-washed soil 



The Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning (ID 2006-25-6874-34), the European Union Structural Funds, the Northern Sweden Soil Remediation Centre, EDF Objective 2, Contract MCN IO No 43173 and The J Gust Richert Memorial Fund are acknowledged for the financial support of this study.

Supplementary material

11368_2011_411_Fig3_ESM.jpg (109 kb)
Fig. 1

VMINTEQ simulation result for extraction using 0.1 M NaOH solution at 40°C—saturation indices for minerals. Red text indicates oversaturation of mineral species, blue text undersaturation and green text equilibrium (JPEG 109 kb)

11368_2011_411_MOESM1_ESM.tif (209 kb)
High-resolution image file (TIFF 209 kb)
11368_2011_411_Fig4_ESM.jpg (109 kb)
Fig. 2

VMINTEQ simulation result for extraction using dithionite–citrate–oxalate solution at pH 6.3 and 30°C—saturation indices for minerals. Red text indicates oversaturation of mineral species, blue text undersaturation and green text equilibrium (JPEG 109 kb)

11368_2011_411_MOESM2_ESM.tif (207 kb)
High-resolution image file (TIFF 206 kb)


  1. Alam M, Tokunaga S (2006) Chemical extraction of arsenic from contaminated soil. J Environ Sci Health A Tox Hazard Subst Environ Eng 41:631–7643CrossRefGoogle Scholar
  2. Alam MGM, Tokunaga S, Maekawa T (2001) Extraction of arsenic in a synthetic arsenic-contaminated soil using phosphate. Chemosphere 43:1035–1041CrossRefGoogle Scholar
  3. Andersson A, Nilsson Å, Håkansson L (1991) Metal concentration of the mor layer. Report 3990:85, Swedish Environmental Protection AgencyGoogle Scholar
  4. Arwidsson Z, Johansson E, von Kronhelm T, Allard B, van Hees P (2010) Remediation of metal contaminated soil by organic metabolites from fungi I—production of organic acids. Water Air Soil Pollut 205:215–226CrossRefGoogle Scholar
  5. Berggren Kleja D, Elert M, Gustafsson JP, Jarvis N, Norrström A-C (2006) Mobility of metals in soil. Report 5536, Swedish Environmental Protection Agency. Stockholm, SwedenGoogle Scholar
  6. Bhattacharya P, Mukherjee AB, Jacks G, Nordqvist S (2002) Metal contamination at a wood preservation site: characterisation and experimental studies on remediation. Sci Total Environ 290:165–180CrossRefGoogle Scholar
  7. Cornell R, Schwertmann U (2003) The iron oxides: structure, properties, reactions, occurrences and uses. Wiley, Weinheim, pp 664Google Scholar
  8. Dermont G, Bergeron M, Mercier G, Richer-Laflèche M (2008) Soil washing for metal removal: a review of physical/chemical technologies and field applications. J Hazard Mater 152:1–31CrossRefGoogle Scholar
  9. Devaney AM, Guess RG (1982) Sodium thiosulphate in hydrosulphite bleaching. Pulp Paper Can 83:TR60–64Google Scholar
  10. El-Khosht Salama N (2001) Utilization of surfactants or organic acids with/without chelating agents for the removal of arsenic from contaminated soil. Doctoral Thesis, Oklahoma States UniversityGoogle Scholar
  11. Swedish Environmental Protection Agency (Swedish EPA) (2009) Generic guideline values for contaminated soils—model description and guidance. Report 5976, Swedish Environmental Protection Agency, StockholmGoogle Scholar
  12. Fendorf SE (1995) Surface reactions of chromium in soils and waters. Geoderma 67:55–71CrossRefGoogle Scholar
  13. Furrer G, Stumm W (1986) The coordination chemistry of weathering: I. Dissolution kinetics of δ-Al2O3 and BeO. Geochim Cosmochim Acta 50:1847–1860CrossRefGoogle Scholar
  14. Gerlach RW, Nocerino JM (2003) Guidance for obtaining representative laboratory analytical subsamples from particulate laboratory samples. EPA/600/R-03/027.134, United States Environmental Protection AgencyGoogle Scholar
  15. Girouard E, Zagury GJ (2009) Arsenic bioaccessibility in CCA-contaminated soils: influence of soil properties, arsenic fractionation, and particle-size fraction. Sci Total Environ 407:2576–2585CrossRefGoogle Scholar
  16. Gräfe M, Sparks DL (2005) Kinetics of zinc and arsenate co-sorption at the goethite–water interface. Geochim Cosmochim Acta 69:4573–4595CrossRefGoogle Scholar
  17. Grafe M, Eick MJ, Grossl PR, Saunders AM (2002) Adsorption of arsenate and arsenite on ferrihydrite in the presence and absence of dissolved organic carbon. J Environ Qual 31:1115–1123CrossRefGoogle Scholar
  18. Gräfe M, Tappero RV, Marcus MA, Sparks DL (2008) Arsenic speciation in multiple metal environments II. Micro-spectroscopic investigation of a CCA contaminated soil. J Colloid Interface Sci 321:1–20CrossRefGoogle Scholar
  19. Gustafsson JP (2007) Visual MINTEQ version 2.53. Accessed 20 Aug 2007
  20. Hopp L, Nico PS, Marcus MA, Peiffer S (2008) Arsenic and chromium partitioning in a podzolic soil contaminated by chromated copper arsenate. Environ Sci Technol 42:6481–6486CrossRefGoogle Scholar
  21. Jang Y, Townsend T, Ward M, Bitton G (2002) Leaching of arsenic, chromium, and copper in a contaminated soil at a wood preserving site. Bull Environ Contam Toxicol 69:808–816CrossRefGoogle Scholar
  22. Jang M, Hwang JS, Choi SI, Park JK (2005) Remediation of arsenic-contaminated soils and washing effluents. Chemosphere 60:344–354CrossRefGoogle Scholar
  23. Jang M, Hwang JS, Choi SI (2007) Sequantial soil washing techniques using hydrochloric acid and sodium hydroxide for remediating arsenic-contaminated soils in abandoned iron-ore mines. Chemosphere 66:8–17CrossRefGoogle Scholar
  24. Ko I, Chang Y-Y, Lee C-H, Kim K-W (2005) Assessment of pilot-scale acid washing of soil contaminated with As, Zn and Ni using the BCR three-step sequential extraction. J Hazard Mater 127:1–13CrossRefGoogle Scholar
  25. Kuhlman M, Greenfield T (1999) Simplified soil washing processes for a variety of soils. J Hazard Mater 66:31–45CrossRefGoogle Scholar
  26. Kumpiene J, Ragnvaldsson D, Lövgren L, Tesfalidet S, Gustavsson B, Lättström A, Leffler P, Maurice C (2009) Impact of water saturation level on arsenic and metal mobility in the Fe-amended soil. Chemosphere 74:206–215CrossRefGoogle Scholar
  27. Lee M, Sung Paik I, Do W, Kim I, Lee Y, Lee S (2007) Soil washing of As-contaminated stream sediments in the vicinity of an abandoned mine in Korea. Environ Geochem Health 29:319–329CrossRefGoogle Scholar
  28. Legiec IA, Griffin LP, Walling PD Jr, Breske TC, Angelo MS, Isaacson RS, Lanza MB (1997) DuPont soil washing technology program and treatment of arsenic contaminated soils. Environ Prog 16:29–34CrossRefGoogle Scholar
  29. Lidelöw S, Ragnvaldsson D, Leffler P, Tesfalidet S, Maurice C (2007) Field trials to assess the use of iron-bearing industrial by-products for stabilisation of chromated copper arsenate-contaminated soil. Sci Total Environ 387:68–78CrossRefGoogle Scholar
  30. Livesey NT, Huang PM (1981) Adsorption of arsenate by soils and its relation to selected chemical properties and anions. Soil Sci 131:88–94CrossRefGoogle Scholar
  31. Manning BA, Goldberg S (1997) Arsenic(III) and arsenic(V) adsorption on three California soils. Soil Sci 162:886–895CrossRefGoogle Scholar
  32. Masscheleyn PH, Delaune RD, Patrick WH Jr (1991) Effect of redox potential and pH on arsenic speciation and solubility in a contaminated soil. Environ Sci Technol 25:1414–1419CrossRefGoogle Scholar
  33. McBride MB (1994) Environmental chemistry of soils. Oxford University Press, New YorkGoogle Scholar
  34. Mohapatra D, Singh P, Zhang W, Pullammanappallil P (2005) The effect of citrate, oxalate, acetate, silicate and phosphate on stability of synthetic arsenic-loaded ferrihydrite and Al-hydrite. J Hazard Mater B124:95–100CrossRefGoogle Scholar
  35. Mulligan CN, Yong RN, Gibbs BF (2001) Remediation technologies for metal-contaminated soils and groundwater: an evaluation. Eng Geol 60:193–207CrossRefGoogle Scholar
  36. Nordberg D, Stenberg J (2005) Remediation of wood impregnation sites. Master’s thesis, Luleå University of TechnologyGoogle Scholar
  37. Rastas Amofah L, Maurice C, Bhattacharya P (2008) Extraction of arsenic from soils contaminated with wood preservation chemicals. Soil Sediment Contam 19:142–159Google Scholar
  38. Reichle RA, McCurdy KG, Hepler LG (1975) Zinc hydroxide: solubility product and hydroxy-complex stability constants from 12.5–75°C. Can J Chem 53:3841–3845CrossRefGoogle Scholar
  39. Rueda EH, Ballesteros MC, Grassi RL, Blesa MA (1992) Dithionite as a dissolving reagent for goethite in the presence of EDTA and citrate. Application to soil analysis. Clays Clay Miner 40:575–585CrossRefGoogle Scholar
  40. Sadiq M (1997) Arsenic chemistry in soils: an overview of thermodynamic predictions and field observations. Water Air Soil Pollut 93:117–136Google Scholar
  41. Shi R, Jia Y, Wang C, Yao S (2008) Mechanism of arsenate mobilisation from goethite by aliphatic carboxylic acid. J Hazard Mater 163:1129–1133CrossRefGoogle Scholar
  42. Skogsjö E (2010) Status report of remediation in the country 2009. Swedish Environmental Protection Agency, StockholmGoogle Scholar
  43. Solo-Gabriele H, Khan B, Townsend T, Song J-K, Jambeck J, Dubey B, Yang Y-C, Cai Y (2003) Arsenic and chromium speciation of leachates from CCA-treated wood, Florida Center, GainesvilleGoogle Scholar
  44. Song J, Townsend T, Solo-Gabriele H, Jang Y-C (2006) Hexavalent chromium reduction in soils contaminated with chromated copper arsenate preservative. Soil Sediment Contam 15:387–399CrossRefGoogle Scholar
  45. Swedish Standards Institute (SIS) (1981) Determination of dry matter and ignition residue in water, sludge and sediment. SS 028113, SIS, StockholmGoogle Scholar
  46. Swedish Standards Institute (SIS) (1992) Geotechnical tests—particle size distribution—sedimentation, hydrometer methods. SS 027124, SIS, StockholmGoogle Scholar
  47. Thomas GW (1996) Soil pH and soil acidity. In: Sparks DL (eds) Methods of soil analysis. Part 3. Chemical methods. SSSA Book series No. 5. SSSA, Madison, pp 475–490Google Scholar
  48. Tsang S, Phu F, Baum MM, Poskrebyshev GA (2007) Determination of phosphate/arsenate by a modified molybdenum blur method and reduction of arsenate by S2O42−. Talanta 71:1560–1568CrossRefGoogle Scholar
  49. United States Environmental Protection Agency (1997) Engineering bulletin: technology alternatives for the remediation of soils contaminated with As, Cd, Cr, Hg, and Pb. EPA/540/S-97/500, U.S. Environmental Protection Agency, Office of Emergency and Remedial Response, and Research and Development. Cincinnati, U.S.Google Scholar
  50. Van Benschoten JE, Reed BE, Matsumoto MR, McGarvey PJ (1994) Metal removal by soil washing for an iron oxide coated sandy soil. Water Environ Res 66:168–174Google Scholar
  51. Xu H, Allard B, Grimvall A (1988) Influence of pH and organic substance on the adsorption of As(V) on geologic materials. Water Air Soil Pollut 40:293–305Google Scholar
  52. Zhang Y, Kallay N, Matijevic E (1985) Interaction of metal hydrous oxides with chelating agents. 7. Hematite-oxalic acid and citric acid systems. Langmuir 1:201–206CrossRefGoogle Scholar
  53. Zinder B, Furrer G, Stumm W (1986) The coordination chemistry of weathering: II. Dissolution of Fe(III) oxides. Geochim Cosmochim Acta 50:1861–1869CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Lea Rastas Amofah
    • 1
  • Christian Maurice
    • 1
  • Jurate Kumpiene
    • 1
  • Prosun Bhattacharya
    • 2
  1. 1.Department of Civil, Environmental and Natural Resources EngineeringLuleå University of TechnologyLuleåSweden
  2. 2.Department of Land and Water Resources EngineeringRoyal Institute of Technology (KTH)StockholmSweden

Personalised recommendations