SpringerLink
Log in

Determination of seven arsenic compounds in urine by HPLC-ICP-DRC-MS: a CDC population biomonitoring method

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

Abstract

A robust analytical method has been developed and validated by use of high-performance liquid chromatography inductively coupled plasma mass spectrometry with Dynamic Reaction Cell™ (DRC) technology that separates seven arsenic (As) species in human urine: arsenobetaine (AB), arsenocholine, trimethylarsine oxide (TMAO), arsenate (As(V)), arsenite (As(III)), monomethylarsonate, and dimethylarsinate. A polymeric anion-exchange (Hamilton PRP® X-100) column was used for separation of the species that were detected at m/z 75 by ICP-DRC-MS (PerkinElmer™ SCIEX® ELAN DRCII™) using 10% hydrogen–90% argon as the DRC gas. The internal standard (As) is added postcolumn via an external injector with a sample loop. All analyte peaks were baseline-separated except AB and TMAO. Analytical method limits of detection for the various species ranged from 0.4 to 1.7 μg L−1 as elemental As. As(III) conversion to As(V) was avoided by adjusting the urine sample to <pH 6. Analyses of the National Institute of Standards and Technology standard reference material (SRM) 2670 and 2670a elevated and National Institute for Environmental Studies certified reference material (CRM) no. 18 for arsenic species yielded results within the certified SRM–CRM limits for As species; likewise, the sum of all species compared favorably to SRM 2670 and 2670a target values for total As. This As speciation method is now being used in a production mode for the analysis of a US population survey, the National Health and Nutrition Examination Survey, as well as for other biomonitoring studies of As exposure. This method meets our requirement for sample throughput of 2,000–3,000 sample analyses per year.

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (Germany)

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. World Health Organization (2001) UN synthesis report on arsenic in drinking water. WHO, Geneva, Switzerland. http://www.who.int/water_sanitation_health/dwq/arsenic3/en/. Accessed June 18, 2008

  2. Nordstrom DK (2002) Science 296:2143–2145

    Article  CAS  Google Scholar 

  3. Welch AH, Westjohn DB, Helsel DR, Wanty RB (2000) Ground Water 38:589

    Article  CAS  Google Scholar 

  4. Centeno JA, Tseng CH, Van der Voet GB, Finkelman RB (2007) Ambio 36:78–81

    Article  CAS  Google Scholar 

  5. Agency for Toxic Substances and Disease Registry (2007) Toxicological profile for arsenic—update, Public Health Service

  6. Wasson SJ, Linak WP, Gullett BK, King CJ, Touati A, Huggins FE, Chen Y, Shah N, Huffman GP (2005) Environ Sci Technol 39:8865–76

    Article  CAS  Google Scholar 

  7. Agency for Toxic Substances and Disease Registry (2005). US DHHS: Atlanta, GA, 2005, http://www.atsdr.cdc.gov/cercla/05list.html. Accessed Dec 14, 2007

  8. Environmental Protection Agency (2001). In: 40 CFR Parts 9, 141 and 142, USEPA (ed) Federal Register 66:6976–7066

  9. Fowler BA, Chou C-HSJ, Jones RL, Chen C-J (2007) Chapter 19: arsenic. In: Nordberg GF, Fowler BA, Nordberg M, Friberg LT (eds) Handbook on the toxicology of metals. 3rd edn. Academic, Burlington

    Google Scholar 

  10. Smith AH, Hopenhaynrich C, Bates MN, Goeden HM, Hertzpicciotto I, Duggan HM, Wood R, Kosnett MJ, Smith MT (1992) Environ Health Perspect 97:259–267

    Article  CAS  Google Scholar 

  11. Ahsan H, Perrin M, Rahman A, Parvez F, Stute M, Zheng Y, Milton AH, Brandt-Rauf P, van Geen A, Graziano J (2000) J Occup Environ Med 42:1195–1201

    Article  CAS  Google Scholar 

  12. Anawar HM, Akai J, Mostofa KM, Safiullah S, Tareq SM (2002) Environ Int 27:597–604

    Article  CAS  Google Scholar 

  13. Centeno JA, Mullick FG, Martinez L, Page NP, Gibb H, Longfellow D, Thompson C, Ladich ER (2002) Environ Health Perspect 110:883–886

    CAS  Google Scholar 

  14. Tchounwou PB, Patlolla AK, Centeno JA (2003) Toxicol Pathol 31:575–588

    CAS  Google Scholar 

  15. Bates MN, Rey OA, Biggs ML, Hopenhayn C, Moore LE, Kalman D, Steinmaus C, Smith AH (2004) Am J Epidemiol 159:381–389

    Article  Google Scholar 

  16. Hopenhayn-Rich C, Biggs ML, Kalman DA, Moore LE, Smith AH (1996) Environ Health Perspect 104:1200–1207

    Article  CAS  Google Scholar 

  17. Aposhian HV (1997) Annu Rev Pharmacol Toxicol 37:397–419

    Article  CAS  Google Scholar 

  18. Goering PL, Aposhian HV, Mass MJ, Cebrian M, Beck BD, Waalkes MP (1999) Toxicol Sci 49:5–14

    Article  CAS  Google Scholar 

  19. Suzuki KT, Tomita T, Ogra Y, Ohmichi M (2001) Chem Res Toxicol 14:1604–1611

    Article  CAS  Google Scholar 

  20. Steinmaus C, Bates MN, Yuan Y, Kalman D, Atallah R, Rey OA, Biggs ML, Hopenhayn C, Moore LE, Hoang BK, Smith AH (2006) J Occup Environ Med 48:478–488

    Article  CAS  Google Scholar 

  21. Arbouine MW, Wilson HK (1992) J Trace Elem Electrolytes Health Dis 6:153–160

    CAS  Google Scholar 

  22. Buchet JP, Pauwels J, Lauwerys R (1994) Environ Res 66:44–51

    Article  CAS  Google Scholar 

  23. Heinrich-Ramm R, Mindt-Prufert S, Szadkowski D (2002) J Chromatogr B Analyt Technol Biomed Life Sci 778:263–73

    Article  CAS  Google Scholar 

  24. World Health Organization (2001) Arsenic and arsenic compounds, 2nd edn. World Health Organization, Geneva

    Google Scholar 

  25. Brima EI, Haris PI, Jenkins RO, Polya DA, Gault AG, Harrington CF (2006) Toxicol Appl Pharmacol 216:122–130

    Article  CAS  Google Scholar 

  26. Apostoli P, Cornelis R, Duffus J, Hoet P, Lison D (2006) Environmental health criteria 234, World Health Organization, Geneva, Switzerland

  27. Le XC, Cullen WR, Reimer KJ (1994) ClinChem 40:617–624

    CAS  Google Scholar 

  28. B’Hymer C, Caruso JA (2004) J Chromatogr A 1045:1–13

    Article  CAS  Google Scholar 

  29. Francesconi KA, Kuehnelt D (2004) Analyst 129:373–95

    Article  CAS  Google Scholar 

  30. Lai VWM, Sun Y, Ting E, Cullen WR, Reimer KJ (2004) Toxicol Appl Pharmacol 198:297–306

    Article  CAS  Google Scholar 

  31. Ali I, Jain CK (2004) Int J Environ Anal Chem 84:947–964

    Article  CAS  Google Scholar 

  32. Brima EI, Jenkins RO, Haris PI (2006) Spectrosc Int J 20:125–151

    CAS  Google Scholar 

  33. Lindberg A-L, Goessler W, Grander M, Nermell B, Vahter M (2007) Toxicol Lett 168:310–318

    Article  CAS  Google Scholar 

  34. Pearson GF, Greenway GM, Brima EI, Haris PI (2007) J Anal At Spectrom 22:361–369

    Article  CAS  Google Scholar 

  35. Le XC, Lu X, Ma M, Cullen WR, Aposhian HV, Zheng B (2000) Anal Chem 72:5172–5177

    Article  CAS  Google Scholar 

  36. Suzuki KT, Mandal BK, Ogra Y (2002) Talanta 58:111–119

    Article  CAS  Google Scholar 

  37. Pan FM, Tyson JF, Uden PC (2007) Int J Environ Anal Chem 22:931–937

    CAS  Google Scholar 

  38. Zheng J, Kosmus W, Pichler-Semmelrock F, Kock M (1999) J Trace Elem Med Biol 13:150–156

    CAS  Google Scholar 

  39. Brisbin JA, B’Hymer C, Caruso JA (2002) Talanta 58:133–145

    Article  CAS  Google Scholar 

  40. Iserte LO, Roig-Navarro AF, Hernandez F (2004) Analytica Chimica Acta 527:97–104

    Article  CAS  Google Scholar 

  41. Milstein LS, Essader A, Pellizzari ED, Fernando RA, Raymer JH, Levine KE, Akinbo O (2003) Environ Health Perspect 111:293–296

    CAS  Google Scholar 

  42. Wei HY, Brockhoff-Schwegel CA, Creed JT (2001) J Anal At Spectrom 16:12–19

    Article  CAS  Google Scholar 

  43. Todorov TI, Ejnik JW, Mullick FG, Centeno JA (2005) Microchimica Acta 151:263–268

    Article  CAS  Google Scholar 

  44. Centers for Disease Control and Prevention (CDC). US Department of Health and Human Services, Hyattsville, http://www.cdc.gov/nchs/nhanes.htm. Accessed April 16, 2008

  45. Tanner S, Baranov VI, Vollkopf U (2000) J Anal At Spectrom 15:1261–1269

    Article  CAS  Google Scholar 

  46. Caldwell KL, Jones RL, Verdon CP, Jarrett JM, Caudill SP, Osterloh JD (2008) J Expo Sci Environ Epidemiol. doi.10.1038/jes.2008.32

  47. Tan SH, Horlick G (1986) Appl Spectrosc 40:445–460

    Article  CAS  Google Scholar 

  48. Jarrett JM, Jones RL, Caldwell KL, Verdon CP (2007) Atomic Spectrosc 28:113–122

    CAS  Google Scholar 

  49. Yoshinaga J, Chatterjee A, Shibata Y, Morita M, Edmonds JS (2000) Clin Chem 46:1781–1786

    CAS  Google Scholar 

  50. Sloth JJ, Larsen EH, Julshamn K (2004) J Anal At Spectrom 19:973–978

    Article  CAS  Google Scholar 

  51. Wrobel K, Wrobel K, Parker B, Kannamkumarath SS, Caruso JA (2002) Talanta 58:899–907

    Article  CAS  Google Scholar 

  52. Rubin CS, Holmes AK, Belson MG, Jones RL, Flanders WD, Kieszak SM, Osterloh J, Luber GE, Blount BC, Barr DB, Steinberg KK, Satten GA, McGeehin MA, Todd RL (2007) Environ Health Perspect 115:151–157

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We thank Cynthia Ward, Christopher Freedman, and Jeffery Jarrett for their invaluable contributions.

Disclaimer

The findings and conclusions in this report are those of the authors and do not necessarily represent the views of the Centers for Disease Control and Prevention or the US Public Health Service.

Author information

Authors and Affiliations

  1. Inorganic and Radiation Analytical Toxicology Branch, Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, 4770 Buford Highway, N.E., Mail Stop F-50, Atlanta, GA, 30341, USA

    Carl P. Verdon, Kathleen L. Caldwell & Robert L. Jones

  2. Battelle Memorial Institute, Atlanta, GA, 30341, USA

    Mark R. Fresquez

Authors
  1. Carl P. Verdon
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kathleen L. Caldwell
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mark R. Fresquez
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Robert L. Jones
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Carl P. Verdon.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Verdon, C.P., Caldwell, K.L., Fresquez, M.R. et al. Determination of seven arsenic compounds in urine by HPLC-ICP-DRC-MS: a CDC population biomonitoring method. Anal Bioanal Chem 393, 939–947 (2009). https://doi.org/10.1007/s00216-008-2537-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-008-2537-3

Keywords

Search

Navigation