Korean Journal of Soil Science and Fertilizer (한국토양비료학회지)

Korean Society of Soil Science and Fertilizer (한국토양비료학회)
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Understanding of a Korean Standard for the Analysis of Hexavalent Chromium in Soils and Interpretation of their Results

토양오염공정시험기준 6가크롬 분석의 이해와 결과 해석

  • Kim, Rog-Young (Soil & Fertilizer Management Division, National Academy of Agricultural Science, RDA) ;
  • Jung, Goo-Bok (Climate Change & Agroecology Division, National Academy of Agricultural Science, RDA) ;
  • Sung, Jwa-Kyung (Soil & Fertilizer Management Division, National Academy of Agricultural Science, RDA) ;
  • Lee, Ju-Young (Soil & Fertilizer Management Division, National Academy of Agricultural Science, RDA) ;
  • Jang, Byoung-Choon (Soil & Fertilizer Management Division, National Academy of Agricultural Science, RDA) ;
  • Yun, Hong-Bae (Soil & Fertilizer Management Division, National Academy of Agricultural Science, RDA) ;
  • Lee, Yee-Jin (Soil & Fertilizer Management Division, National Academy of Agricultural Science, RDA) ;
  • Song, You-Seong (Soil & Fertilizer Management Division, National Academy of Agricultural Science, RDA) ;
  • Kim, Won-Il (Chemical Safety Division, National Academy of Agricultural Science, RDA) ;
  • Lee, Jong-Sik (Soil & Fertilizer Management Division, National Academy of Agricultural Science, RDA) ;
  • Ha, Sang-Keun (Soil & Fertilizer Management Division, National Academy of Agricultural Science, RDA)
  • 김록영 (농촌진흥청 국립농업과학원 토양비료관리과) ;
  • 정구복 (농촌진흥청 국립농업과학원 기후변화생태과) ;
  • 성좌경 (농촌진흥청 국립농업과학원 토양비료관리과) ;
  • 이주영 (농촌진흥청 국립농업과학원 토양비료관리과) ;
  • 장병춘 (농촌진흥청 국립농업과학원 토양비료관리과) ;
  • 윤홍배 (농촌진흥청 국립농업과학원 토양비료관리과) ;
  • 이예진 (농촌진흥청 국립농업과학원 토양비료관리과) ;
  • 송요성 (농촌진흥청 국립농업과학원 토양비료관리과) ;
  • 김원일 (농촌진흥청 국립농업과학원 유해화학과) ;
  • 이종식 (농촌진흥청 국립농업과학원 토양비료관리과) ;
  • 하상건 (농촌진흥청 국립농업과학원 토양비료관리과)
  • Received : 2011.09.04
  • Accepted : 2011.10.14
  • Published : 2011.10.31
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Abstract

A new Korean standard for the determination of Cr(VI) in soils has been officially published as ES 07408.1 in 2009. This analytical method is based on the hot alkaline digestion and colorimetric detection prescribed by U.S. EPA method 3060A and 7196A. The hot alkaline digestion accomplished using 0.28 M $Na_2CO_3$ and 0.5 M NaOH solution (pH 13.4) at $90{\sim}95^{\circ}C$ determines total Cr(VI) in soils extracting all forms of Cr(VI), including water-soluble, adsorbed, precipitated, and mineral-bound chromates. This aggressive alkaline digestion, however, proved to be problematic for certain soils which contain large amounts of soluble humic substances or active manganese oxides. Cr(III) could be oxidized to Cr(VI) by manganese oxides during the strong alkaline extraction, resulting in overestimation (positive error) of Cr(VI). In contrast, Cr(VI) reduction by dissolved humic matter or Fe(II) could occur during the neutralization and acidic colorimetric detection procedure, resulting in underestimation (negative error) of Cr(VI). Futhermore, dissolved humic matter hampered the colorimetric detection of Cr(VI) using UV/Vis spectrophotometer due to the strong coloration of the filtrate, resulting in overestimation (positive error) of Cr(VI). Without understanding the mechanisms of Cr(VI) and Cr(III) transformation during the analysis it could be difficult to operate the experiment in laboratory and to evaluate the Cr(VI) results. For this reason, in this paper we described the theoretical principles and limitations of Cr(VI) analysis and provided useful guidelines for laboratory work and Cr(VI) data analysis.

Keywords

References

  1. Australian CSIRO (Center for Environmental Contaminants Research). 2009. M. McLaughlin. Soil Quality Guidelines.
  2. Bartlett, R.J. and J.M. Kimble. 1976. Behavior of chromium in soils: II. Hexavalent forms. J. Environ. Qual. 5(4):383-386.
  3. Brookins, D.G. 1988. Eh-pH diagrams for geochemistry. Springer-Verlag. 176 p.
  4. Canadian CME (Council of Ministers of Environment). 1999. Canadian Soil Quality Guidelines for the Protection of Environmental and Human Health. Chromium. 11 p.
  5. Deltombe, E., N. De Zoubov, and M. Pourbaix. 1966. Chromium. p. 256-271. In Pourbaix, M. (ed.). Atlas of electrochemical equilibria in aqueous solutions. Pergamon Press, Oxford.
  6. DHI Water and Environment (Danish Hydraulic Institute). 2003. Udvaskeligt chrom i jord Bestemt som chrom ekstraheret under basike forhold. Prescription of DHI. Horsholm, Denmark.
  7. DIN 19734 (German Institute for Standardization). 1999. Determination of Chromium(VI) in phosphate buffered solution. Beuth, Berlin (in German).
  8. EN 12506 (European Norm). 2003. Characterization of waste - Analysis of eluates - Determination of pH, As, Ba, Cd, Cl, Co, Cr, Cr(VI), Cu, Mo, Ni, ${NO_{2}}$, Pb, total S, ${SO_{4}^{2-}}$, V, and Zn. European Committee for Standardization (CEN). Brussels.
  9. EN 15192 (European Norm). 2006. Determination of Chromium (VI) in solid material by alkaline digestion and ion chromatography with spectrophotometric detection. European Committee for Standardization (CEN). Brussels.
  10. EN 196-10 (European Norm). 2006. Methods of testing cement - Part 10: Determination of the water soluble chromium (VI) content of cement. European Committee for Standardization (CEN). Brussels.
  11. ES (Korean Standard). 2007. Hexavalent Chromium. Standard for the examination of soil pollution. Ministry of Environment, Republic of Korea (in Korean).
  12. ES 07408.1 (Korean Standard). 2009. Hexavalent Chromium, Cr(VI). Standard for the examination of soil pollution. Ministry of Environment, Republic of Korea (in Korean).
  13. German BMU (German Federal Ministry for the Environment, Nature Conservation and Nuclear Safety). 1999. German Federal Soil Protection and Contaminated Sites Ordinance (BBodSchV). from July 12, 1999 (BGBl. I S. 1554), revised December 23, 2004 (BGBl. I S. 3758). Berlin.
  14. Gomez, V. and M.P. Callao. 2006. Chromium determination and speciation since 2000. Trends Anal. Chem. 25(10):1006-1015. https://doi.org/10.1016/j.trac.2006.06.010
  15. Harzdorf, A.C. 1987. Analytical chemistry of chromium species in the environment, and interpretation of results. Intern. J. Environ. Anal. Chem. 29(4):249-261. https://doi.org/10.1080/03067318708075445
  16. Huo, D., Y. Lu, and H.M. Kingston. 1998. Determination and correction of analytical biases and study on chemical mechanisms in the analysis of Cr(VI) in soil samples using EPA protocols. Environ. Sci. Technol. 32(21):3418-3423. https://doi.org/10.1021/es971029e
  17. Italian Decreto Ministeriale n. 471. 1999. Gazzetta Ufficiale Supplemento Ordinario N. 293 (in Italian).
  18. James, B.R., J.C. Petura, R.J. Vitale, and G.R. Mussoline. 1995. Hexavalent chromium extraction from soils: a comparison of five Methods. Environ. Sci. Technol. 29(9):2377-2381. https://doi.org/10.1021/es00009a033
  19. Japanese MOE (Ministry of Environment). 1994. Environmental quality standards for soil pollution. http://www.env.go.jp/en/water/soil/sp.html
  20. Jung, G.B., S.I. Kwon, M.K. Kim, H. Hwang, S.J. Park, and K.K. Kang. 2011. Comparison of standard analytical methods for heavy metals in soils. Proceedings of Spring Conference of the Korean Society for Soil and fertilizer 2011. p. 316-317.
  21. Kim, R.Y. 2009. Chromium(VI) analysis, chromium(VI) contaminations of soils from North Rhine-Westphalia (Germany), and model experiments for chromium(VI) reduction and chromium(III) oxidation in soils. Ph.D. Thesis. University of Bonn, Bonn, Germany (in German).
  22. Kim, R.Y., G. Welp, and G.W. Bruemmer. 2000. Investigations of Cr(VI) contents in contaminated and noncontaminated soils in NRW. Final report of Institute of Crop Science and Resource Conservation. University of Bonn. On behalf of the State Agency for Nature, Environment and Consumer Protection of North Rhine Westphalia (in German).
  23. Kim, R.Y., G. Welp, I. Mueller, and G.W. Bruemmer. 2002. Cr(VI) in soils: Problems with DIN 19734 as well as Cr(VI) contents and stability in contaminated and noncontaminated soils from North Rhine Westphalia. Altlasten Spektrum, 11(2):59-65 (in German).
  24. Korean MOE (Ministry of Environment, Republic of Korea). 2009. Enforcement Decree of the Soil Environment Conservation Act. 12th. amended. No. 333. 2009.6.25 (in Korean).
  25. Kotas, J. and Z. Stasicka. 2000. Chromium occurrence in the environment and methods of its speciation. Environ. Pollut. 107(3):263-283. https://doi.org/10.1016/S0269-7491(99)00168-2
  26. Makino, T., S. Hasegawa, Y. Sakural, S. Ohno, H. Utagawa, Y. Maejima, and K. Momohara. 2000. Influence of soildrying under field conditions on exchangeable manganese, cobalt, and copper contents. Soil Sci. Plant Nutr. 46(3):581-590. https://doi.org/10.1080/00380768.2000.10409123
  27. Pettine, M. and F.J. Millero. 1990. Chromium speciation in seawater: The probable role of hydrogen peroxide. Limnol. Oceanogr. 35(3):730-736. https://doi.org/10.4319/lo.1990.35.3.0730
  28. Pettine, M. and S. Capri. 2005. Removal of humic matter interference in the determination of Cr(VI) in soil extracts by the diphenylcarbazide method. Anal. Chim. Acta. 540(2):239-246. https://doi.org/10.1016/j.aca.2005.03.041
  29. Pettine, M., L. Campanella, and F.J. Millero. 2002. Reduction of hexavalent chromium by ${H_{2}O_{2}}$ in acidic solutions. Environ. Sci. Technol. 36(5):901-907. https://doi.org/10.1021/es010086b
  30. Ruedel, H., A. Wenzel, and K. Terytze. 2000. Quantification of soluble chromium(VI) in soils and evaluation of ecotoxicological effects. Abstracts of 18th European Conference of the Society for Environmental Geochemistry and Health, 11.-12. September 2000, Glasgow, Scotland.
  31. Swedish EPA (Swedish Environmental Protection Agency). 2002. Development of generic guideline values: model and data used for generic values for contaminated soils in Sweden. Stockholm. 62 p.
  32. Tirez, K., H. Scharf, D. Calzolari, R. Cleven, M. Kisser, and D. Lueck. 2007. Validation of a European standard for the determination of hexavalent chromium in solid material. J. Environ. Monit. 9:749-759. https://doi.org/10.1039/b706724k
  33. Tomoyuki, M., U. Katsuhiro, S. Yasuhiro, and S. Kazuo. 2002. The mechanism of manganese oxide dissolution by soil drying. Symposium no. 28, Paper no. 1292, Presentation Poster. 17th WCSS, 14-21 August 2002, Thailand.
  34. U.S. EPA (United States Environmental Protection Agency). 1992. Method 7196A. Chromium, hexavalent (colorimetric). In Test methods for evaluating solid wastes, physical/chemical methods. SW-846. Revision 1. Office of solid waste and emergency response. Washington, DC. 6 p.
  35. U.S. EPA (United States Environmental Protection Agency). 1996. Method 3060A. Alkaline digestion for hexavalent chromium. In Test methods for evaluating solid wastes. physical/chemical methods. SW-846. Revision 1. Office of solid waste and emergency response. Washington, DC. 15 p.
  36. U.S. EPA (United States Environmental Protection Agency). 1996. Method 7199. Determination of hexavalent chromium in drinking water, groundwater and industrial wastewater effuents by ion chromatography. In Test methods for evaluating solid wastes, physical/chemical methods. SW-846. Update. Office of solid waste and emergency response. Washington, DC. 10 p.
  37. U.S. EPA (United States Environmental Protection Agency). 2007. Method 6800. Elemental and speciated isotope dilution mass spectrometry. Washington, DC. 47 p.
  38. U.S. EPA (United States Environmental Protection Agency). 2011. Regional Screening Levels. http://www.epa.gov/region9/superfund/prg/
  39. Unceta, N., F. Seby, J. Malherbe, and O.F.X. Donard. 2010. Chromium speciation in solid matrices and regulation: a review. Anal. Bioanal. Chem. 397:1097-1111. https://doi.org/10.1007/s00216-009-3417-1
  40. Vitale, R.J., G.R. Mussoline, J.C. Petura, and B.R. James. 1994. Hexavalent chromium extraction from soils: evaluation of an alkaline digestion method. J. Environ. Qual. 23(6):1249-1256.
  41. Vitale, R.J., G.R. Mussoline, J.C. Petura, and B.R. James. 1997. Cr(VI) soil analytical method: a reliable analytical method for extracting and quantifying Cr(VI) in soils. J. Soil Contam. 6(6):581-593. https://doi.org/10.1080/15320389709383591
  42. Welp, G. 1999. Inhibitory effects of the total and watersoluble concentrations of nine different metals on the dehydrogenase activity of a loess soil. Biol. Fertil. Soils. 30:132-139. https://doi.org/10.1007/s003740050599
  43. Welp, G., R.Y. Kim, and G.W. Buemmer. 2001. Background values, mobility, and toxicity of chromium(III) and chromium(VI) in soils. In Ecotoxicological relevance of chromium(III) and chromium(VI) in lime fertilizers, soils, and plants. Series of research group ironworks slag, 9:35-50. Duesseldorf, Germany (in German).

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