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Analytical and Bioanalytical Chemistry

, Volume 411, Issue 7, pp 1397–1407 | Cite as

Urinary hydroxypyrene determination for biomonitoring of firefighters deployed at the Fort McMurray wildfire: an inter-laboratory method comparison

  • Biban Gill
  • Alicia Mell
  • Meera Shanmuganathan
  • Karl Jobst
  • Xu Zhang
  • David Kinniburgh
  • Nicola Cherry
  • Philip Britz-McKibbinEmail author
Research Paper

Abstract

Urinary 1-hydroxypyrene (OH-Pyr) is widely used for biomonitoring human exposures to polycyclic aromatic hydrocarbons (PAHs) from air pollution and tobacco smoke. However, there have been few rigorous validation studies reported to ensure reliable OH-Pyr determination for occupational health and risk assessment. Herein, we report an inter-laboratory method comparison for urinary OH-Pyr when using gas chromatography-high-resolution mass spectrometry (GC-HRMS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) on urine specimens collected from firefighters (n = 42) deployed at the 2016 Fort McMurray wildfire. Overall, there was good mutual agreement in urinary OH-Pyr quantification following enzyme deconjugation with an average bias of 39% with no significant deviation from linearity (slope = 1.36; p > 0.05), whereas technical precision (< 12%) and average recovery (> 85%) were acceptable when using a stable-isotope internal standard. Faster analysis times (4 min) were achieved by LC-MS/MS without chemical derivatization, whereas lower detection limits (0.64 ng/L, S/N = 3) was realized with solid-phase extraction prior to GC-HRMS. A median creatinine normalized OH-Pyr concentration of 128 ng/g was measured for firefighters that were below the recommended biological exposure index due to delays between early stages of emergency firefighting and urine sample collection. Similar outcomes were also measured for 3-hydroxyphenanthrene and 9-hydroxyfluorene that were positively correlated with urinary OH-Pyr (p < 0.05), implying similar uptake, distribution, and liver biotransformation processes. Optimal specimen collection strategies post-deployment together with standardized protocols for OH-PAH analysis are critical to accurately evaluate smoke exposure in firefighters, including experimental conditions to ensure quantitative enzyme hydrolysis of urine samples.

Graphical abstract

Keywords

PAHs Firefighters Risk assessment Smoke exposure Urinary biomarkers Fort McMurray 

Notes

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Ethical approval

Ethics approval was obtained by the Health Ethics Review Board at the University of Alberta prior to sample collection (#Pro000625284).

Informed consent

Informed consent was obtained from all participants included in the study.

Supplementary material

216_2018_1569_MOESM1_ESM.pdf (439 kb)
ESM 1 (PDF 438 kb)

References

  1. 1.
    Cherry N, Haynes W. Effects of the Fort McMurray wildfires on the health of evacuated workers: follow-up of 2 cohorts. CMAJ Open. 2017;5:E638–45.CrossRefPubMedPubMedCentralGoogle Scholar
  2. 2.
    Landis MS, Edgerton ES, White EM, Wentworth GR, Sullivan AP, Dillner AM. The impact of the 2016 Fort McMurray Horse River Wildfire on ambient air pollution levels in the Athabasca Oil Sands Region, Alberta, Canada. Sci Total Environ. 2018;618:1665–76.CrossRefPubMedGoogle Scholar
  3. 3.
    Cherry N, Akililu Y-A, Beach J, Britz-McKibbin P, Elbourne R, Galarneau J-M, et al. Urinary 1-hydroxypyrene and skin contamination in firefighters deployed to the Fort McMurray fire. Ann Work Expo Health. 2019;  https://doi.org/10.1093/annweh/wxz006.
  4. 4.
    Polycyclic Aromatic Hydrocarbons (PAHs): BEI(R), 7th Edition Documentation, American Conference of Governmental Industrial Hygienists (ACGIH), Cinanatti, OH, USA, 2017;1–25.Google Scholar
  5. 5.
    Fernando S, Shaw L, Shaw D, Gallea M, Vandenenden L, House R, et al. Evaluation of firefighter exposure to wood smoke during training exercises at burn houses. Environ Sci Technol. 2016;50:1536–43.CrossRefPubMedGoogle Scholar
  6. 6.
    Navarro KM, Cisneros R, Noth EM, Balmes JR, Hammond SK. Occupational exposure to polycyclic aromatic hydrocarbon of wildland firefighters at prescribed and wildland fires. Environ Sci Technol. 2017;51:6461–9.CrossRefPubMedGoogle Scholar
  7. 7.
    Keir JLA, Akhtar US, Matschke DMJ, Kirkham TL, Chan HM, Ayotte P, et al. Elevated exposures to polycyclic aromatic hydrocarbons and other organic mutagens in Ottawa firefighters participating in emergency, On-Shift Fire Suppression. Environ Sci Technol. 2017;51:12745–55.CrossRefPubMedGoogle Scholar
  8. 8.
    Reports C. Fatalities among volunteer and career firefighters--United States, 1994-2004. MMWR Morb Mortal Wkly Rep. 2006;55:453–5.Google Scholar
  9. 9.
    Guidotti TI. Evaluating causality for occupational cancers: the example of firefighters. Occup Med (Chic Ill). 2007;57:466–71.CrossRefGoogle Scholar
  10. 10.
    Strickland P, Kang D. Urinary 1-hydroxypyrene and other PAH metabolites as biomarkers of exposure to environmental PAH in air particulate matter. Toxicol Lett. 1999;108:191–9.CrossRefPubMedGoogle Scholar
  11. 11.
    Shimada T, Guengerich FP. Inhibition of human cytochrome P450 1A1-, 1A2-, and 1B1-mediated activation of procarcinogens to genotoxic metabolites by polycyclic aromatic hydrocarbons. Chem Res Toxicol. 2006;19:288–94.CrossRefPubMedGoogle Scholar
  12. 12.
    Jongeneelen FJ, Anzion RBM, Scheepers PTJ, Bos RP, Henderson PT, Nijenhuis EH, et al. 1-hydroxypyrene in urine as a biological indicator of exposure to polycyclic aromatic hydrocarbons in several work environments. Ann Occup Hyg. 1988;32:35–43.PubMedGoogle Scholar
  13. 13.
    Li Z, Sandau CD, Romanoff LC, Caudill SP, Sjodin A, Needham LL, et al. Concentration and profile of 22 urinary polycyclic aromatic hydrocarbon metabolites in the US population. Environ Res. 2008;107:320–31.CrossRefPubMedGoogle Scholar
  14. 14.
    Hansen ÅM, Mathiesen L, Pedersen M, Knudsen LE. Urinary 1-hydroxypyrene (1-HP) in environmental and occupational studies-A review. Int J Hyg Environ Health. 2008;211:471–503.Google Scholar
  15. 15.
    Lu PL, Chen ML, Mao IF. Urinary 1-hydroxypyrene levels in workers exposed to coke oven emissions at various locations in a coke oven plant. Arch Environ Health. 2002;57:255–61.CrossRefPubMedGoogle Scholar
  16. 16.
    Bouchard M, Viau C. Urinary excretion kinetics of pyrene and benzo(a) pyrene metabolites following intravenous administration of the parent compounds or the metabolites. Toxicol Appl Pharmacol. 1996;139:301–9.CrossRefPubMedGoogle Scholar
  17. 17.
    Chang CM, Edwards SH, Arab A, Del Valle-Pinero AY, Yang L, Hatsukami DK. Biomarkers of tobacco exposure: summary of an FDA-sponsored public workshop. Cancer Epidemiol Biomark Prev. 2017;26:291–302.CrossRefGoogle Scholar
  18. 18.
    Nolte CG, Schauer JJ, Cass GR, Simoneit BR. Highly polar organic compounds present in wood smoke and in the ambient atmosphere. Environ Sci Technol. 2001;35:1912–9.CrossRefPubMedGoogle Scholar
  19. 19.
    Li Z, Trinidad D, Pittman EN, Riley EA, Sjodin A, Dills RL, et al. Urinary polycyclic aromatic hydrocarbon metabolites as biomarkers to woodsmoke exposure-results from a controlled exposure study. J Expo Sci Environ Epidemiol. 2016;26:241–8.CrossRefPubMedGoogle Scholar
  20. 20.
    Fagundes RB, Abnet CC, Strickland PT, Kamangar F, Roth MJ, Taylor PR, et al. Higher urine 1-hydroxy pyrene glucuronide (1-OHPG) is associated with tobacco smoke exposure and drinking maté in healthy subjects from Rio Grande do Sul, Brazil. BMC Cancer. 2006;6:139–46.CrossRefPubMedPubMedCentralGoogle Scholar
  21. 21.
    Jongeneelen FJ, Anzion RBM, Henderson PT. Determination of hydroxylated metabolites of polycyclic aromatic hydrocarbons in urine. J Chromatogr B Biomed Sci Appl Elsevier. 1987;413:227–32.CrossRefGoogle Scholar
  22. 22.
    Strickland PT, Kang D, Bowman ED, Fitzwilliam A, Downing TE, Rothman N, et al. Identification of 1-hydroxypyrene glucuronide as a major pyrene metabolite in human urine by synchronous fluorescence spectroscopy and gas chromatography-mass spectrometry. Carcinogenesis. 1994;15:483–7.CrossRefPubMedGoogle Scholar
  23. 23.
    Campo L, Fustinoni S, Buratti M, Cirla PE, Martinotti I, Foà V. Unmetabolized polycyclic aromatic hydrocarbons in urine as biomarkers of low exposure in asphalt workers. J Occup Environ Hyg. 2007;4:100–10.CrossRefGoogle Scholar
  24. 24.
    Ramsauer B, Sterz K, Hagedorn H-W, Engl J, Scherer G, McEwan M, et al. A liquid chromatography/tandem mass spectrometry (LC-MS/MS) method for the determination of phenolic polycyclic aromatic hydrocarbons (OH-PAH) in urine of non-smokers and smokers. Anal Bioanal Chem. 2011;399:877–89.CrossRefPubMedGoogle Scholar
  25. 25.
    Raponi F, Bauleo L, Ancona C, Forastiere F, Paci E, Pigini D, et al. Quantification of 1-hydroxypyrene, 1- and 2-hydroxynaphthalene, 3-hydroxybenzo [a] pyrene and 6-hydroxynitropyrene by HPLC-MS/MS in human urine as exposure biomarkers for environmental and occupational surveys. Biomarkers Taylor & Francis. 2017;22:575–83.Google Scholar
  26. 26.
    Campo L, Rossella F, Fustinoni S. Development of a gas chromatography/mass spectrometry method to quantify several urinary monohydroxy metabolites of polycyclic aromatic hydrocarbons in occupationally exposed subjects. J Chromatogr B Anal Technol Biomed Life Sci. 2008;875:531–40.CrossRefGoogle Scholar
  27. 27.
    Rossella F, Campo L, Pavanello S, Kapka L, Siwinska E, Fustinoni S. Urinary polycyclic aromatic hydrocarbons and monohydroxy metabolites as biomarkers of exposure in coke oven workers. Occup Environ Med. 2009;66:509–16.CrossRefPubMedGoogle Scholar
  28. 28.
    Poster DL, Schantz MM, Sander LC, Wise SA. Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples: a critical review of gas chromatographic (GC) methods. Anal Bioanal Chem. 2006;386:859–81.CrossRefPubMedGoogle Scholar
  29. 29.
    Rylance J, Gordon SB, Naeher LP, Patel A, Balmes JR, Adetona O, et al. Household air pollution: a call for studies into biomarkers of exposure and predictors of respiratory disease. AJP Lung Cell Mol Physiol. 2013;304:L571–8.CrossRefGoogle Scholar
  30. 30.
    Chong J, Soufan O, Li C, Caraus I, Li S, Bourque G, et al. MetaboAnalyst 4.0: towards more transparent and integrative metabolomics analysis. Nucleic Acids Res. 2018;46:W486–94.CrossRefPubMedPubMedCentralGoogle Scholar
  31. 31.
    Jongeneelen FJ. Benchmark guideline for urinary 1-hydroxypyrene as biomarker of occupational exposure to polycyclic aromatic hydrocarbons. Ann Occup Hyg. 2001;45:3–13.CrossRefPubMedGoogle Scholar
  32. 32.
    Jain RB. Trends and concentrations of selected polycyclic aromatic hydrocarbons in general US population: Data from NHANES 2003-2008. Cogent Environ Sci. 2015;1:1031508.CrossRefGoogle Scholar
  33. 33.
    Ciarrocca M, Rosati MV, Tomei F, Capozzella A, Andreozzi G, Tomei G, et al. Is urinary 1-hydroxypyrene a valid biomarker for exposure to air pollution in outdoor workers? A meta-analysis. J Expo Sci Environ Epidemiol. 2014;24:17–26.CrossRefPubMedGoogle Scholar
  34. 34.
    Li Z, Romanoff L, Bartell S, Pittman EN, Trinidad DA, McClean M, et al. Excretion profiles and half-lives of ten urinary polycyclic aromatic hydrocarbon metabolites after dietary exposure. Chem Res Toxicol. 2012;25:1452–61.CrossRefPubMedPubMedCentralGoogle Scholar
  35. 35.
    Bristow T, Harrison M, Sims M. The application of gas chromatography/atmospheric pressure chemical ionisation time-of-flight mass spectrometry to impurity identification in pharmaceutical development. Rapid Commun Mass Spectrom. 2010;24:1673–81.CrossRefPubMedGoogle Scholar
  36. 36.
    Wang S, Cyronak M, Yang E. Does a stable isotopically labeled internal standard always correct analyte response?: a matrix effect study on a LC/MS/MS method for the determination of carvedilol enantiomers in human plasma. J Pharm Biomed Anal. 2007;43:701–7.CrossRefPubMedGoogle Scholar
  37. 37.
    Li Z, Romanoff LC, Trinidad DA, Hussain N, Jones RS, Porter EN, et al. Measurement of urinary monohydroxy polycyclic aromatic hydrocarbons using automated liquid-liquid extraction and gas chromatography/isotope dilution high-resolution mass spectrometry. Anal Chem. 2006;78:5744–51.CrossRefPubMedGoogle Scholar
  38. 38.
    Xu X, Zhang J, Zhang L, Liu W, Weisel CP. Selective detection of monohydroxy metabolites of polycyclic aromatic hydrocarbons in urine using liquid chromatography/triple quadrupole tandem mass spectrometry. Rapid Commun Mass Spectrom Wiley. 2004;18:2299–308.CrossRefGoogle Scholar
  39. 39.
    Jacob P, Wilson M, Benowitz NL. Determination of phenolic metabolites of polycyclic aromatic hydrocarbons in human urine as their pentafluorobenzyl ether derivatives using liquid chromatography-tandem mass spectrometry. Anal Chem. 2007;79:587–98.CrossRefPubMedGoogle Scholar
  40. 40.
    Macedo A, Macri J, Hudecki P, Saoi M, McQueen MJ, Britz-McKibbin P. Validation of a capillary electrophoresis assay for monitoring iodine nutrition in populations for prevention of iodine deficiency: an interlaboratory method comparison. J Appl Lab Med. 2017;3:649–60.CrossRefGoogle Scholar
  41. 41.
    Alhamdow A, Lindh C, Albin M, Gustavsson P, Tinnerberg H, Broberg K. Early markers of cardiovascular disease are associated with occupational exposure to polycyclic aromatic hydrocarbons. Sci Rep. 2017;7:9426–37.CrossRefPubMedPubMedCentralGoogle Scholar
  42. 42.
    Strickland P, Kang D, Sithisarankul P. Polycyclic aromatic hydrocarbon metabolites in urine as biomarkers of exposure and effect. Environ Health Perspect. 1996;104:927–32.PubMedPubMedCentralGoogle Scholar
  43. 43.
    Morgan MS. The biological exposure indices: a key component in protecting workers from toxic chemicals. Environ Health Perspect. 1997;105:105–15.PubMedPubMedCentralGoogle Scholar
  44. 44.
    Mastrianni KR, Andrew Lee L, Brewer WE, Dongari N, Barna M, Morgan SL. Variations in enzymatic hydrolysis efficiencies for amitriptyline and cyclobenzaprine in urine. J Anal Toxicol. 2016;40:732–7.PubMedGoogle Scholar
  45. 45.
    Dwivedi P, Zhou X, Powell TG, Calafat AM, Ye X. Impact of enzymatic hydrolysis on the quantification of total urinary concentrations of chemical biomarkers. Chemosphere. 2018;199:256–62.CrossRefPubMedPubMedCentralGoogle Scholar
  46. 46.
    Alshaarawy O, Elbaz HA, Andrew ME. The association of urinary polycyclic aromatic hydrocarbon biomarkers and cardiovascular disease in the US population. Environ Int. 2016;89:174–8.CrossRefPubMedGoogle Scholar
  47. 47.
    Cakmak S, Hebbern C, Cakmak JD, Dales RE. The influence of polycyclic aromatic hydrocarbons on lung function in a representative sample of the Canadian population. Environ Pollut. 2017;228:1–7.CrossRefPubMedGoogle Scholar
  48. 48.
    Barr DB, Wang RY, Needham LL. Biologic monitoring of exposure to environmental chemicals throughout the life stages: requirements and issues for consideration for the National Children’s study. Environ Health Perspect. 2005;113:1083–91.CrossRefPubMedPubMedCentralGoogle Scholar
  49. 49.
    Heudorf U, Angerer J. Urinary monohydroxylated phenanthrenes and hydroxypyrene - the effects of smoking habits and changes induced by smoking on monooxygenase-mediated metabolism. Int Arch Occup Environ Health. 2001;74:177–83.CrossRefPubMedGoogle Scholar
  50. 50.
    Li Z, Romanoff LC, Lewin MD, Porter EN, Trinidad DA, Needham LL, et al. Variability of urinary concentrations of polycyclic aromatic hydrocarbon metabolite in general population and comparison of spot, first-morning, and 24-h void sampling. J Expo Sci Environ Epidemiol. 2010;20:526–35.CrossRefPubMedGoogle Scholar
  51. 51.
    Jongeneelen FJ, Van Leeuwen FE, Oosterink S, Anzion RBM. Ambient and biological monitoring of cokeoven workers : determinants of the internal dose of polycyclic aromatic hydrocarbons. Br J Ind Med. 1990;47:454–61.PubMedPubMedCentralGoogle Scholar
  52. 52.
    Adetona O, Simpson CD, Li Z, Sjodin A, Calafat AM, Naeher LP. Hydroxylated polycyclic aromatic hydrocarbons as biomarkers of exposure to wood smoke in wildland firefighters. J Expo Sci Environ Epidemiol. 2017;27:78–83.CrossRefPubMedGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Biban Gill
    • 1
  • Alicia Mell
    • 1
    • 2
  • Meera Shanmuganathan
    • 1
  • Karl Jobst
    • 2
  • Xu Zhang
    • 3
  • David Kinniburgh
    • 3
  • Nicola Cherry
    • 4
  • Philip Britz-McKibbin
    • 1
    Email author
  1. 1.Department of Chemistry and Chemical BiologyMcMaster UniversityHamiltonCanada
  2. 2.Laboratory Branch, Ontario Ministry of the EnvironmentConservation and ParksTorontoCanada
  3. 3.Alberta Centre for ToxicologyUniversity of CalgaryCalgaryCanada
  4. 4.Division of Preventative MedicineUniversity of AlbertaEdmontonCanada

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