Simultaneous speciation of arsenic, selenium, and chromium: species stability, sample preservation, and analysis of ash and soil leachates

  • Ruth E. WolfEmail author
  • Suzette A. Morman
  • Philip L. Hageman
  • Todd M. Hoefen
  • Geoffrey S. Plumlee
Original Paper


An analytical method using high-performance liquid chromatography separation with inductively coupled plasma mass spectrometry (ICP-MS) detection previously developed for the determination of Cr(III) and Cr(VI) has been adapted to allow the determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) under the same chromatographic conditions. Using this method, all six inorganic species can be determined in less than 3 min. A dynamic reaction cell (DRC)–ICP-MS system was used to detect the species eluted from the chromatographic column in order to reduce interferences. A variety of reaction cell gases and conditions may be utilized with the DRC–ICP-MS, and final selection of conditions is determined by data quality objectives. Results indicated all starting standards, reagents, and sample vials should be thoroughly tested for contamination. Tests on species stability indicated that refrigeration at 10 °C was preferential to freezing for most species, particularly when all species were present, and that sample solutions and extracts should be analyzed as soon as possible to eliminate species instability and interconversion effects. A variety of environmental and geological samples, including waters and deionized water [leachates] and simulated biological leachates from soils and wildfire ashes have been analyzed using this method. Analytical spikes performed on each sample were used to evaluate data quality. Speciation analyses were conducted on deionized water leachates and simulated lung fluid leachates of ash and soils impacted by wildfires. These results show that, for leachates containing high levels of total Cr, the majority of the chromium was present in the hexavalent Cr(VI) form. In general, total and hexavalent chromium levels for samples taken from burned residential areas were higher than those obtained from non-residential forested areas. Arsenic, when found, was generally in the more oxidized As(V) form. Selenium (IV) and (VI) were present, but typically at low levels.


Speciation HPLC-ICP-MS Arsenic Selenium Chromium Hexavalent chromium 

Supplementary material

216_2011_5275_MOESM1_ESM.pdf (706 kb)
ESM 1 (PDF 705 kb)


  1. 1.
    Plumlee GS, Martin DA, Hoefen T, Kokaly R, Hageman P, Eckberg A, Meeker GP, Adams M, Anthony M, Lamothe PJ (2007) Preliminary analytical results for ash and burned soils from the October 2007 southern California wildfires. US Geological Survey Open-File Report 2007-1407Google Scholar
  2. 2.
    Hageman PL, Plumlee GS, Martin DA, Hoefen TM, Meeker GP, Adams M, Lamothe PJ, Anthony MW (2008) Leachate geochemical results for ash and burned soil samples from the October 2007 southern California wildfires. US Geological Survey Open-File Report 2008-1139Google Scholar
  3. 3.
    Hageman PL (2007) U.S. Geological Survey field leach test for assessing water reactivity and leaching potential of mine wastes, soils, and other geologic and environmental materials. US Geological Survey Techniques and Methods, book 5, chap. D3Google Scholar
  4. 4.
    Plumlee GS, Morman SA, Ziegler TL (2006) The toxicological geochemistry of earth materials: an overview of processes and the interdisciplinary methods used to understand them. Mineralogical Soc Am: Rev Mineral Geochem, Med Mineral Geochem 64:5–57Google Scholar
  5. 5.
    Gray JE, Plumlee GS, Morman SA, Higueras PL, Crock JG, Lowers HA, Witten ML (2010) In vitro studies evaluating leaching of mercury from mine waste calcine using simulated human body fluids. Environ Sci Technol 44:4782–4788CrossRefGoogle Scholar
  6. 6.
    Gammelgaard B, Jensen K, Steffansen B (1999) In vitro metabolism and permeation studies in rat jejunum: organic chromium compared to inorganic chromium. J Trace Elements Med Biol 13:82–88Google Scholar
  7. 7.
    Reeder RJ, Schoonen MAA, Lanzirotti A (2006) Metal speciation and its role in bioaccessibility and bioavailability. Mineralogical Soc Am: Rev Mineral Geochem, Med Mineral Geochem 64:59–109Google Scholar
  8. 8.
    Agency for Toxic Substances and Disease Registry (ATSDR) (2008) Toxicological profile for chromium (draft for public comment). US Department of Health and Human Services, Public Health Service, AtlantaGoogle Scholar
  9. 9.
    Wolf RE, Morrison JM, Goldhaber MB (2007) Simultaneous determination of Cr(III) and Cr(VI) using reversed-phased ion-pairing liquid chromatography with dynamic reaction cell inductively coupled plasma mass spectrometry. J Anal At Spectrom 22:1051–1060CrossRefGoogle Scholar
  10. 10.
    Sathrugnan K, Hirata S (2004) Determination of inorganic oxyanions of As and Se by HPLC-ICPMS. Talanta 64:237–243CrossRefGoogle Scholar
  11. 11.
    Neubauer KR, Reuter W, Perrone P, Grosser Z (2004) Simultaneous arsenic and chromium speciation. PerkinElmer, Inc., Application Note 007050_01. Available at Accessed on 12 May 2011
  12. 12.
    Darrouzès J, Bueno M, Lespès G, Holeman M, Potin-Gautier M (2006) Optimisation of ICPMS collision/reaction cell conditions for the simultaneous removal of argon based interferences of arsenic and selenium in water samples. Talanta 71:2080–2084CrossRefGoogle Scholar
  13. 13.
    Lindemann T, Prange A, Dannecker W, Neidhart B (2000) Stability studies of arsenic, selenium, antimony, and tellurium species in water, urine, fish and soil extracts using HPLC/ICP-MS. Fresenius J Anal Chem 368:214–220CrossRefGoogle Scholar
  14. 14.
    Roig-Navarro AF, Martinez-Bravo Y, López FJ, Hernández F (2001) Simultaneous determination of arsenic species and chromium (VI) by high-performance liquid chromatography–inductively coupled plasma-mass spectrometry. J Chromatogr A 912:319–327CrossRefGoogle Scholar
  15. 15.
    Pantsar-Kallio M, Manninen PKG (1997) Simultaneous determination of toxic arsenic and chromium species in water samples by ion chromatography-inductively coupled plasma mass spectrometry. J Chromatogr A 779:139–146CrossRefGoogle Scholar
  16. 16.
    Gómez-Ariza JL, Morales E, Sánchez-Rodas D, Giráldez I (2000) Stability of chemical species in environmental matrices. Trends Anal Chem 19:200–209CrossRefGoogle Scholar
  17. 17.
    Francesconi KA, Kuehnelt D (2004) Determination of arsenic species: a critical review of methods and applications, 2000–2003. Analyst 129:373–395CrossRefGoogle Scholar
  18. 18.
    Kumar AR, Riyazuddin P (2010) Preservation of inorganic arsenic species in environmental water samples for reliable speciation analyses. Trends Anal Chem 29:1212–1223CrossRefGoogle Scholar
  19. 19.
    Gallagher PA, Schwegel CA, Wei X, Creed JT (2001) Speciation and preservation of inorganic arsenic in drinking water sources using EDTA with IC separation and ICP-MS detection. J Environ Monit 3:371–376CrossRefGoogle Scholar
  20. 20.
    Sánchez-Rodas D, Oliveira V, Sarmiento AM, Gómez-Ariza JL, Nieto JM (2006) Preservation procedures for arsenic speciation in a stream affected by acid mine drainage in southwestern Spain. Anal Bioanal Chem 384:1594–1599CrossRefGoogle Scholar
  21. 21.
    Daus B, Weiss H, Mattusch J, Wennrich R (2005) Preservation of arsenic species in water samples using phosphoric acid—limitations and long-term stability. Talanta 69:430–434CrossRefGoogle Scholar
  22. 22.
    Oliveira V, Sarmiento AM, Gómez-Ariza JL, Nieto JM, Sánchez-Rodas D (2006) New preservation method for inorganic arsenic speciation in acid mine drainage samples. Talanta 69:1182–1189CrossRefGoogle Scholar
  23. 23.
    Bednar AJ, Garbarino JR, Ranville JF, Wildeman TR (2002) Preserving the distribution of inorganic arsenic species in groundwater and acid mine drainage samples. Environ Sci Technol 36:2213–2218CrossRefGoogle Scholar
  24. 24.
    McCleskey RB, Nordstrom DK, Maest AS (2004) Preservation of water samples for arsenic (III/V) determinations: an evaluation of the literature and new analytical results. Appl Geochem 19:995–1009CrossRefGoogle Scholar
  25. 25.
    Huang JH, Ilgen G (2004) Blank values, adsorption, pre-concentration, and sample preservation for arsenic speciation of environmental water samples. Analytica Chimica Acta 512:1–10CrossRefGoogle Scholar
  26. 26.
    Planer-Freidrich B, London J, McCleskey RB, Nordstrom DK, Wallschläger D (2007) Thioarsenates in geothermal waters of Yellowstone National Park: determination, preservation, and geochemical importance. Environ Sci Technol 41:5245–5251CrossRefGoogle Scholar
  27. 27.
    Tolu J, LeHécho I, Bueno M, Thiry Y, Potin-Gautier M (2011) Selenium speciation analysis at trace level in soils. Analytica Chimica Acta 684:126–133CrossRefGoogle Scholar
  28. 28.
    Cobo MG, Palacios MA, Cámara C (1994) Effect of physicochemical parameters on trace inorganic selenium stability. Analytica Chimica Acta 286:371–379CrossRefGoogle Scholar
  29. 29.
    Chen YW, Zhou XL, Tong J, Truong Y, Belzile N (2005) Photochemical behavior of inorganic and organic selenium compounds in various aqueous solutions. Analytica Chimica Acta 545:149–157CrossRefGoogle Scholar
  30. 30.
    B’Hymer C, Caruso JA (2006) Selenium speciation analysis using inductively coupled plasma-mass spectrometry. J Chromatogr A 1114:1–20CrossRefGoogle Scholar
  31. 31.
    Pan F, Tyson JF, Uden PC (2007) Simultaneous speciation of arsenic and selenium in human urine by high-performance liquid chromatography inductively coupled plasma mass spectrometry. J Anal At Spectrom 22:931–937CrossRefGoogle Scholar
  32. 32.
    Palmer CD, Puls RW (1994) Natural attenuation of hexavalent chromium in ground water and soils. US EPA Office of Research and Development, EPA/540/5-94-505Google Scholar
  33. 33.
    Comber S, Gardner M (2003) Chromium redox speciation in natural waters. J Environ Monit 5:410–413CrossRefGoogle Scholar
  34. 34.
    Huo D, Kingston HMS (2000) Correction of species transformations in the analysis of Cr(VI) in solid environmental samples using speciation isotope dilution mass spectrometry. Anal Chem 72:5047–5054CrossRefGoogle Scholar
  35. 35.
    Metze D, Jakubowski N, Klockow D (2005) Speciation of chromium. In: Cornelis R (ed) Handbook of elemental speciation II: species in the environment, food, medicine and occupational health. Wiley, New YorkGoogle Scholar
  36. 36.
    Ball JW, McCleskey RB (2003) A new cation-exchange method for accurate field speciation of hexavalent chromium. US Geological Survey, Water-Resources Investigations Report 03-4018Google Scholar
  37. 37.
    SW-846 EPA Method 7199 (1996) Determination of hexavalent chromium in drinking water, groundwater, and industrial wastewater effluents by ion chromatography. In: SW-846 (ed) Test methods for evaluating solid waste, physical/chemical methods. US Environmental Protection Agency, WashingtonGoogle Scholar
  38. 38.
    SW-846 EPA Method 7196A (1992) Chromium, hexavalent (colorimetric). In: SW-846 (ed) Test methods for evaluating solid waste, physical/chemical methods. US Environmental Protection Agency, WashingtonGoogle Scholar
  39. 39.
    Séby F, Charles S, Gagean M, Garraud H, Donard OFX (2003) Chromium speciation by hyphenation of high-performance liquid chromatography to inductively coupled plasma-mass spectrometry—study of the influence of interfering ions. J Anal At Spectrom 18:1386–1390CrossRefGoogle Scholar
  40. 40.
    Ulmer NS (1986) Effect of chlorine on chromium speciation in tap water. US Environmental Protection Agency, Water Engineering Research Laboratory, Cincinnati, Ohio, EPA/600/M-86/015Google Scholar
  41. 41.
    Clifford D, Chau JM (1988) The fate of chromium(III) in chlorinated water. US Environmental Protection Agency, Water Engineering Research Laboratory, Cincinnati, Ohio, EPA/600/S2-87/100Google Scholar
  42. 42.
    Linsinger TPJ, Auclair G, Raffaelli B, Lamberty A, Gawlik BM (2011) Conclusions from 13 years of stability testing of CRMs for determination of metal species. Trends in Analytical Chemistry. doi: 10.1016/j.trac.2011.01.015
  43. 43.
    SW-846 EPA Method 6020A (2007) Inductively coupled plasma mass spectrometry. In: SW-846 (ed) Test methods for evaluating solid waste, physical/chemical methods. US Environmental Protection Agency, WashingtonGoogle Scholar
  44. 44.
    Mattson SM (1994) Glass fibers in simulated lung fluid: dissolution behavior and analytical requirements. Ann Occup Hyg 38:857–877CrossRefGoogle Scholar
  45. 45.
    Eastes W, Hadley JG (1995) Dissolution of fibers inhaled by rats. Inhalation Toxicol 7:179–196CrossRefGoogle Scholar
  46. 46.
    Jurinski JB, Rimstidt JD (2001) Biodurability of talc. Am Mineral 86:392–399Google Scholar
  47. 47.
    Bauer J, Mattson SM, Eastes W (1997) In-vitro acellular method for determining fiber durability in simulated lung fluid. Owens Corning, Corning, NY. Available at Accessed 10 May 2011
  48. 48.
    Gamble JL (1942) Chemical anatomy, physiology, and pathology of extracellular fluid: a lecture syllabus, 6th edn. Harvard University Press, Cambridge, MAGoogle Scholar
  49. 49.
    Taggart JE (2002) Analytical methods for chemical analysis of geologic and other materials. US Geological Survey, Open-File Report 02-223Google Scholar
  50. 50.
    Agency for Toxic Substances and Disease Registry (ATSDR) (2007) Toxicological profile for arsenic. Department of Health and Human Services, Public Health Service, AtlantaGoogle Scholar

Copyright information

© Springer-Verlag (outside the USA) 2011

Authors and Affiliations

  • Ruth E. Wolf
    • 1
    Email author
  • Suzette A. Morman
    • 1
  • Philip L. Hageman
    • 1
  • Todd M. Hoefen
    • 1
  • Geoffrey S. Plumlee
    • 1
  1. 1.US Geological SurveyDenver Federal CenterDenverUSA

Personalised recommendations