Skip to main content
SpringerLink
Log in

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

  • Original Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  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 2007-1407

  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 2008-1139

  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. D3

  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 64:5–57

    CAS  Google Scholar 

  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 44:4782–4788

    Article  CAS  Google Scholar 

  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 13:82–88

    CAS  Google Scholar 

  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 64:59–109

    CAS  Google Scholar 

  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, Atlanta

    Google Scholar 

  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 22:1051–1060

    Article  CAS  Google Scholar 

  10. Sathrugnan K, Hirata S (2004) Determination of inorganic oxyanions of As and Se by HPLC-ICPMS. Talanta 64:237–243

    Article  CAS  Google Scholar 

  11. Neubauer KR, Reuter W, Perrone P, Grosser Z (2004) Simultaneous arsenic and chromium speciation. PerkinElmer, Inc., Application Note 007050_01. Available at http://www.perkinelmer.com/IT/CMSResources/Images/44-74037APP_ArsenicandChromiumSpeciation.pdf. Accessed on 12 May 2011

  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 71:2080–2084

    Article  Google Scholar 

  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 368:214–220

    Article  CAS  Google Scholar 

  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 912:319–327

    Article  CAS  Google Scholar 

  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 779:139–146

    Article  CAS  Google Scholar 

  16. Gómez-Ariza JL, Morales E, Sánchez-Rodas D, Giráldez I (2000) Stability of chemical species in environmental matrices. Trends Anal Chem 19:200–209

    Article  Google Scholar 

  17. Francesconi KA, Kuehnelt D (2004) Determination of arsenic species: a critical review of methods and applications, 2000–2003. Analyst 129:373–395

    Article  CAS  Google Scholar 

  18. Kumar AR, Riyazuddin P (2010) Preservation of inorganic arsenic species in environmental water samples for reliable speciation analyses. Trends Anal Chem 29:1212–1223

    Article  CAS  Google Scholar 

  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 3:371–376

    Article  CAS  Google Scholar 

  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 384:1594–1599

    Article  Google Scholar 

  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 69:430–434

    Article  Google Scholar 

  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 69:1182–1189

    Article  CAS  Google Scholar 

  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 36:2213–2218

    Article  CAS  Google Scholar 

  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 19:995–1009

    Article  CAS  Google Scholar 

  25. Huang JH, Ilgen G (2004) Blank values, adsorption, pre-concentration, and sample preservation for arsenic speciation of environmental water samples. Analytica Chimica Acta 512:1–10

    Article  CAS  Google Scholar 

  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 41:5245–5251

    Article  Google Scholar 

  27. Tolu J, LeHécho I, Bueno M, Thiry Y, Potin-Gautier M (2011) Selenium speciation analysis at trace level in soils. Analytica Chimica Acta 684:126–133

    Article  CAS  Google Scholar 

  28. Cobo MG, Palacios MA, Cámara C (1994) Effect of physicochemical parameters on trace inorganic selenium stability. Analytica Chimica Acta 286:371–379

    Article  CAS  Google Scholar 

  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 545:149–157

    Article  CAS  Google Scholar 

  30. B’Hymer C, Caruso JA (2006) Selenium speciation analysis using inductively coupled plasma-mass spectrometry. J Chromatogr A 1114:1–20

    Article  Google Scholar 

  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 22:931–937

    Article  CAS  Google Scholar 

  32. Palmer CD, Puls RW (1994) Natural attenuation of hexavalent chromium in ground water and soils. US EPA Office of Research and Development, EPA/540/5-94-505

  33. Comber S, Gardner M (2003) Chromium redox speciation in natural waters. J Environ Monit 5:410–413

    Article  CAS  Google Scholar 

  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 72:5047–5054

    Article  CAS  Google Scholar 

  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 York

    Google Scholar 

  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 03-4018

  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, Washington

    Google Scholar 

  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, Washington

    Google Scholar 

  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 18:1386–1390

    Article  Google Scholar 

  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-86/015

  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/S2-87/100

  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. 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, Washington

    Google Scholar 

  44. Mattson SM (1994) Glass fibers in simulated lung fluid: dissolution behavior and analytical requirements. Ann Occup Hyg 38:857–877

    Article  Google Scholar 

  45. Eastes W, Hadley JG (1995) Dissolution of fibers inhaled by rats. Inhalation Toxicol 7:179–196

    Article  CAS  Google Scholar 

  46. Jurinski JB, Rimstidt JD (2001) Biodurability of talc. Am Mineral 86:392–399

    CAS  Google Scholar 

  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 http://fiberscience.owenscorning.com/prokdis/prokdis.html. Accessed 10 May 2011

  48. Gamble JL (1942) Chemical anatomy, physiology, and pathology of extracellular fluid: a lecture syllabus, 6th edn. Harvard University Press, Cambridge, MA

    Google Scholar 

  49. Taggart JE (2002) Analytical methods for chemical analysis of geologic and other materials. US Geological Survey, Open-File Report 02-223

  50. Agency for Toxic Substances and Disease Registry (ATSDR) (2007) Toxicological profile for arsenic. Department of Health and Human Services, Public Health Service, Atlanta

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. US Geological Survey, Denver Federal Center, MS/964, Denver, CO, 80225, USA

    Ruth E. Wolf, Suzette A. Morman, Philip L. Hageman, Todd M. Hoefen & Geoffrey S. Plumlee

Authors
  1. Ruth E. Wolf
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Suzette A. Morman
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Philip L. Hageman
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Todd M. Hoefen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Geoffrey S. Plumlee
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ruth E. Wolf.

Additional information

Published in the special issue Plasma Spectrochemistry with guest editors Juan Castillo and Martín Resano.

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

ESM 1

(PDF 705 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Wolf, R.E., Morman, S.A., Hageman, P.L. et al. Simultaneous speciation of arsenic, selenium, and chromium: species stability, sample preservation, and analysis of ash and soil leachates. Anal Bioanal Chem 401, 2733–2745 (2011). https://doi.org/10.1007/s00216-011-5275-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-011-5275-x

Keywords

Search

Navigation