Identification and characterization of 1-hydroxypyrene contents in urine as a marker of exposure to pah in workers of electrolysis workshops at aluminum production

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S.F. Shayakhmetov, A.N. Alekseenko, A.V. Merinov, O.M. Zhurba


East-Siberian Institute of Medical and Ecological Research, 3 12A mikrorayon, Angarsk, 665826, Russian Federation


Potential harmful effects produced by highly toxic aromatic hydrocarbons (PAH) on health of workers employed at aluminum production make it necessary to identify biomarkers of exposure to the toxicants and to assess health risks.

Our research goal was to identify and assess contents of 1-hydroxypytene (1-ОНРyr) as a biomarker of exposure to PAH. The chemical was identified in urine of workers from electrolysis workshops where either conventional or updated aluminum production technologies were employed. We comparatively examined contents of the marker metabolite 1-ОНРyr in urine of 142 workers with basic occupations employed at electrolysis workshops with different aluminum production technologies (the test group) and 14 people who were included in the reference group. The chemical was identified with the authors’ high-sensitivity gas chromatography-mass spectrometry method for 1-OHPyr identification in urine with the lower limit of detection being equal to 0.1 µg/l and total error not exceeding 15 %.

The research results revealed high 1-ОНРyr contents in urine of workers employed at electrolysis workshops. These contents were by 2–30 times higher than the permissible value of the biological exposure index (BEI) and were associated with exposure to PAH components, an aluminum production technology applied in a given workshop and a worker’s occupation. The highest PAH burdens as per 1-ОНРyr contents in urine and associated health risks were determined for workers who handled anodes of electrolyzers and crane operators in workshops that employed a conventional technology with self-baking anodes. The lowest ones were established for electrolysis operators and anode frame operators in workshops that employed an updated technology with prebake anodes. It is noteworthy that 1-ОНРyr contents were by 2.7–4.7 times higher than permissible BEI value in urine of EOT (bridge) crane operators since these cranes were located in the upper zone of the analyzed electrolysis workshops.

Our research results allow us to recommend the inclusion of biological monitoring of 1-OHPyr contents in urine of workers employed at electrolysis workshops of aluminum productions into periodical medical examinations. This is necessary for developing activities aimed at primary and secondary prevention of occupational and work-related diseases.

aluminum production, polycyclic aromatic hydrocarbons, biomarker of exposure, 1-hydroxypyrene, workers, gas chromatography-mass spectrometry, biological monitoring, biological media
Shayakhmetov S.F., Alekseenko A.N., Merinov A.V., Zhurba O.M. Identification and characterization of 1-hydroxypyrene contents in urine as a marker of exposure to pah in workers of electrolysis workshops at aluminum production. Health Risk Anal-ysis, 2022, no. 3, pp. 90–97. DOI: 10.21668/health.risk/2022.3.08.eng
  1. IARC Working Group on the Evaluation of Carcinogenic Risks to Humans. Some non-heterocyclic polycyclic aromatic hydrocarbons and some related exposures. IARC Monogr. Eval. Carcinog. Risks Hum., Lyon, 2010, vol. 92, 853 p.
  2. Ifegwu O.C., Anyakora C. Polycyclic aromatic hydrocarbons: Part I. Exposure. Advances in Clinical Chemistry, 2015, vol. 72, pp. 277–304. DOI: 10.1016/bs.acc.2015.08.001
  3. Yang L., Zhang H., Zhang X., Xing W., Wang Y., Bai P., Zhang L., Hayakawa K. [et al.]. Exposure to atmospheric particulate matter-bound polycyclic aromatic hydrocarbons and their health effects: a review. Int. J. Environ. Res. Public Health, 2021, vol. 18, no. 4, pp. 2177. DOI: 10.3390/ijerph18042177
  4. Abdel-Shafy H.I., Mansour M.S.M. A review on polycyclic aromatic hydrocarbons: Source, environmental impact, effect on human health and remediation. Egyptian journal of petroleum, 2016, vol. 25, no. 1, pp. 107–123. DOI: 10.1016/j.ejpe.2015.03.011
  5. Plotnikova O.A., Melnikov G.V., Tikhomirova E.I. Polycyclic aromatic hydrocarbons: characteristics, sources, stand-ardization, spectroscopic determination methods (review). Teoreticheskaya i prikladnaya ekologiya, 2021, no. 4, pp. 12–19. DOI: 10.25750/1995-4301-2021-4-012-019 (in Russian).
  6. Taranina O.A., Burkat V.S. Control methods of tarry substances (fume of coal-tar pitch) into the atmosphere as part of industrial environmental control at aluminum smelters of the Russian Federation. Ekologicheskie sistemy i pribory, 2017, no. 6, pp. 3–7 (in Russian).
  7. Kurteeva L.I., Morozov S.V., Anshits A.G. The sources of carcinogenic PAH emission in aluminium production using Soderberg cells. Advances in the Geological Storage of Carbon Dioxide. Nato Science Series: IV: Earth and Environmental Sciences, 2006, vol. 65, pp. 57–65. DOI: 10.1007/1-4020-4471-2_06
  8. Meditsina truda pri elektroliticheskom poluchenii alyuminiya [Occupational medicine for electrolytic aluminum pro-duction]. In: O.F. Roslyi, E.I. Likhacheva eds. Ekaterinburg, Ekaterinburgskii meditsinskii nauchnyi tsentr profilaktiki i okhrany zdorov'ya rabochikh prompredpriyatii Publ., 2011, 160 p. (in Russian).
  9. Zaitseva N.V., Zemlyanova M.A., Chashchin V.P., Gudkov A.B. Scientifiic principles of use of biomarkers in medico-ecological studies (review). Ekologiya cheloveka, 2019, no. 9, pp. 4–14. DOI: 10.33396/1728-0869-2019-9-4-14 (in Russian).
  10. Shilov V.V., Markova O.L., Kuznetsov A.V. Biomonitoring of influence of harmful chemicals on the basis of the modern biomarkers. Literature review. Gigiena i sanitariya, 2019, vol. 98, no. 6, pp. 591–596. DOI: 10.18821/0016-9900-2019-98-6-591-596 (in Russian).
  11. Ny E.T., Heederik D., Kromhout H., Jongeneelen F. The relationship between polycyclic aromatic hydrocarbons in air and in urine of workers in a Söderberg potroom. Am. Ind. Hyg. Assoc. J., 1993, vol. 54, no. 6, pp. 277–284. DOI: 10.1080/15298669391354685
  12. Jongeneelen F.J. Benchmark guideline for urinary 1-hydroxypyrene as biomarker of occupational exposure to polycyclic aromatic hydrocarbons. The Annals of Occupational Hygiene, 2001, vol. 45, no. 1, pp. 3–13. DOI: 10.1093/annhyg/45.1.3
  13. Zhang Y., Ding J., Shen G., Zhong J., Wang C., Wei S., Chen C., Chen Y. [et al.]. Dietary and inhalation exposure to polycyclic aromatic hydrocarbons and urinary excretion of monohydroxy metabolites – A controlled case study in Beijing, China. Environ. Pollut., 2014, vol. 184, pp. 515–522. DOI: 10.1016/j.envpol.2013.10.005
  14. Yamano Y., Hara K., Ichiba M., Hanaoka T., Pan G., Nakadate T. Urinary 1-hydroxypyrene as a comprehensive car-cinogenic biomarker of exposure to polycyclic aromatic hydrocarbons: a cross-sectional study of coke oven workers in China. Int. Arch. Occup. Environ. Health, 2014, vol. 87, no. 7, pp. 705–713. DOI: 10.1007/s00420-013-0913-6
  15. Käfferlein H.U., Marczynski B., Simon P., Angerer J., Rihs H.-P., Wilhelm M., Straif K., Pesch B., Brüning T. Internal exposure to carcinogenic polycyclic aromatic hydrocarbons and DNA damage: A null result in brief. Arch. Toxicol., 2021, vol. 86, no. 8, pp. 1317–1321. DOI: 10.1007/s00204-012-0882-7
  16. Levin J.O., Rhén M., Sikström E. Occupational PAH exposure: urinary 1-hydroxypyrene levels of coke oven workers, aluminium smelter pot-room workers, road pavers, and occupationally non-exposed persons in Sweden. Science of the Total Environment, 1995, vol. 163, no. 1–3, pp. 169–177. DOI: 10.1016/0048-9697(95)04488-M
  17. Barbeau D., Persoons R., Marques M., Hervé C., Laffitte-Rigaud G., Maitre A. Relevance of urinary 3-hyd-roxybenzo(a)pyrene and 1-hydroxypyrene to assess exposure to carcinogenic polycyclic aromatic hydrocarbon mixtures in met-allurgy workers. Ann. Occup. Hyg., 2014, vol. 58, no. 5, pp. 579–590. DOI: 10.1093/annhyg/meu004
  18. 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. Journal of chromatography B, 2008, vol. 875, no. 2, pp. 531–540. DOI: 10.1016/j.jchromb.2008.10.017
  19. Shin H.-S., Lim H.-H. Simultaneous determination of 2-naphthol and 1-hydroxy pyrene in urine by gas chromatogra-phy-mass spectrometry. Journal of chromatography B, 2011, vol. 879, no. 7–8, pp. 489–494. DOI: 10.1016/j.jchromb.2011.01.009
  20. Alekseenko A.N., Zhurba O.M., Merinov A.V., Shayakhmetov S.F. Determination of 1-hydroxypyrene as a biomarker for the effects of polycyclic aromatic hydrocarbons in urine by chromatography–mass spectrometry. Journal of analytical chemistry, 2020, vol. 75, no. 1, pp. 84–89. DOI: 10.1134/S1061934820010025
  21. Shayakhmetov S.F., Meshchakova N.M., Lisetskaya L.G., Merinov A.V., Zhurba O.M., Alekseyenko A.N., Rukav-ishnikov V.S. Hygienic aspects of working conditions in the modern production of aluminum. Gigiena i sanitariya, 2018, vol. 97, no. 10, pp. 899–904. DOI: 10.18821/0016-9900-2018-97-10-899-904 (in Russian).
  22. Rosly O.F., Gurvich V.B., Plotko E.G., Kuzmin S.V., Fedoruk A.A., Roslaya N.A., Yarushin S.V., Kuzmin D.V. Emerging issues concerning hygiene in the Russian aluminum industry. Meditsina truda i promyshlennaya ekologiya, 2012, no. 11, pp. 8–12 (in Russian).
  23. Klöslová Z., Drímal M., Balog K., Koppová K., Dubajová J. The relations between polycyclic aromatic hydrocarbons exposure and 1-OHP levels as a biomarker of the exposure. Cent. Eur. J. Public Health, 2016, vol. 24, no. 4, pp. 302–307. DOI: 10.21101/cejph.a4179
  24. Alekseenko A.N., Zhurba O.M., Merinov A.V., Shayakhmetov S.F. Optimization of conditions for the sample preparation using mathematical planning for determination of 1-hydroxypyrene in urine using method of gas chromatography-mass spectrometry. Gigiena i sanitariya, 2020, vol. 99, no. 10, pp. 1153–1158. DOI: 10.47470/0016-9900-2020-99-10-1153-1158 (in Russian).
  25. Buchet J.P., Gennart J.P., Mercado-Calderon F., Delavignette J.P., Cupers L., Lauwerys R. Evaluation of exposure to polycyclic aromatic hydrocarbons in a coke production and a graphite electrode manufacturing plant: assessment of urinary excre-tion of
    1-hydroxypyrene as a biological indicator of exposure. Br. J. Ind. Med., 1992, vol. 49, no. 11, pp. 761–768. DOI: 10.1136/oem.49.11.761
  26. Tuček M., Bencko V., Volný J., Petanová J. A contribution to the health risk assessment of exposure to exhaust gases in custom officers at border crossing. Ceske Pracovni Lekarstvi, 2006, vol. 7, no. 2, pp. 76–83.
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