Malaysian Journal of Analytical Sciences Vol 20 No 2 (2016): 205 - 223

 

 

 

CHROMATOGRAPHIC DETERMINATION OF TOLUENE AND ITS METABOLITES IN URINE FOR TOLUENE EXPOSURE – A REVIEW

 

(Penentuan Kromatografi Toluena dan Metaboliknya di dalam Urin bagi Pendedahan Toluena – Satu Ulasan)

 

Mohamad Raizul Zinalibdin1, 2, Abdul Rahim Yacob1, Mohd Marsin Sanagi1, 3*

 

1Department of Chemistry, Faculty of Science,

Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia

2Department of Chemistry,

Johor Branch, Jalan Abdul Samad, 80100 Johor Bahru, Johor, Malaysia

3Centre for Sustainable Nanomaterials,

Ibnu Sina Institute for Scientific and Industrial Research,

Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia

 

*Corresponding author: marsin@kimia.fs.utm.my

 

 

Received: 1 November 2015; Accepted: 10 March 2016

 

 

Abstract

The determinations of toluene and their metabolites in biological samples such as urine and blood allow the estimation of the degree of exposure to this chemical. Chromatographic methods and preliminary methods are now universally employed for this purpose. Preliminary color test methods are well established for qualitative determination of toluene and its metabolites. Mobile test kits using color test methods are a vast tool for screening urine samples but chromatographic methods are still needed for confirmation and quantitative analysis. Gas chromatography (GC) methods are well-adapted for the determination of toluene metabolite in urine, but these methods often require several pretreatment steps. Meanwhile, high performance liquid chromatography (HPLC) is becoming a powerful tool for the accurate and easy determination of toluene metabolites considering its decisive advantages for routine monitoring. Furthermore, recent development in HPLC could widen the usefulness of this method to solve the most complex analytical problems that could be encountered during the measurement.

 

Keywords: toluene, toluene metabolites, preliminary test, gas chromatography, high performance liquid chromatography

 

Abstrak

Penentuan toluena dan metabolitnya dalam sampel biologi seperti urin dan darah membolehkan anggaran tahap pendedahan terhadap bahan kimia ini. Kaedah kromatografi dan kaedah awalan merupakan kaedah yang sering digunakan untuk tujuan ini pada masa kini. Kaedah awalan menggunakan ujian warna telah dibangunkan untuk penentuan kualitatif toluena dan metabolit. Kit ujian mudah alih menggunakan ujian warna meluas digunakan bagi pemeriksaan sampel urin tetapi kaedah kromatografi masih diperlukan untuk pengesahan analisis kuantitatif. Kaedah kromatografi gas adalah kaedah yang kerap digunakan bagi menentukan metabolit toluena dalam urin namun kaedah ini sering memerlukan beberapa langkah rawatan awal. Sementara itu, kromatografi cecair berprestasi tinggi (HPLC) menjadi alat yang berkuasa untuk penentuan tepat dan mudah metabolit toluena memandangkan kelebihannya yang jelas untuk pemantauan rutin. Tambahan pula, perkembangan terkini dalam HPLC boleh memperluaskan kegunaan kaedah ini bagi menyelesaikan masalah analisis rumit yang boleh dihadapi semasa pengukuran.

 

Kata kunci: toluena, metabolit toluena, ujian awalan, kromatografi gas, kromatografi cecair berprestasi tinggi

 

References

1.       Basselt, R. C. (2002). Disposition of toxic drugs and chemical in man, 6th Edition, .Biomedical Publication, Foster  City pp. 5 – 1200.

2.       Coopmana, V. A., Cordonniera, J. A. and de Meyere, C. A. (2005). Fatal workplace accident involving ethyl acetate: a distribution study. Forensic Science International, 154: 92 – 95.

3.       Wille, S. M. R. and Lambert, W. E. E. (2004). Volatile substance abuse-post mortem diagnosis. Forensic Science International, 142: 135 –156.

4.       Esmail, A., Pottier, L. and Wright, S. (1993). Deaths from volatile substances abuse in those under 18 years: results from a national epidemiological study. Archives Disorder Children, 69: 256 – 360.

5.       Ukai, H., Inui, S., Takada, S., Dendo, J., Ogawa, J., Isobe, K., Ashida, T., Tamura, M., Tabuki, K. and Ikeda, M. (1997). Types of organic solvents used in small to medium scale industries in Japan: A nationwide field survey. International Archives Occupational Environmental Health, 70: 385 – 592.

6.       Yasugi, T., Kawai, T., Endo, G., Monna, T., Odachi, T., Yamaoka, K., Hariguchi, S. and Ikeda, M. (1998). Types of organic solvents used in workplaces and work environment conditions with special references to reproducibility of work environment classification. Industrial Health, 36: 223 – 233.

7.       Moon, C-S., Lee, J-T., Chun, J-H. and Ikeda, M. (2001). Use of solvents in industries in Korea; experience in Sinpyeong-Jangrim indusrial complex. International Archives Occupational Environmental Health, 74: 148 –152.

8.       Watson, J. M. (1982). Solvent abuse: presentation and clinical diagnosis. Human Toxicology, 1: 249 – 256.

9.       Lof, A., Hansen, S. H., Naslund P., Steiner, E., Wallen, M. and Hjelm, E.W. (1990). Relationship between uptake and elimination of toluene and debrisquine hydroxylation polymorphism. Clinical Pharmacology and Therapeutics, 47: 412 – 417. 

10.    Ogata, M., Sugiyama, K. and Moriyasu, H. (1962). Studies on poisoning IV. Toluene concentration in air and urinary hippuric acid measured by paper chromatography and mass screening examination method. Acta Medica Okayama, 16: 283 – 292.

11.    Yacob, A. R. and Zinalibdin, M. R. (2013). Detection of hippuric acid: A glue solvent metabolite using a mobile test kit.  Arabian Journal of Chemistry, 6: 115 – 120.

12.    Yacob, A. R. and Said, N. (2014). Ortho-Cresol as Indicator for Toluene Exposure among Workers. 2014 4th International Conference on Environment Science and Engineering, IACSIT Press, Singapore, 68: 14 –18.

13.    Inoue, O., Seiji, K., Suzuki, T., Watanabe, T., Natkasuka, H., Satao, H. and Ikeda, M. (1991). Simultaneous determination of hippuric acid,o-, m -, and p -methylhippuric acid, phenylglyoxylic acid, and mandelic acid by HPLC . Bulletin Environmental Contamination. Toxicology, 47: 204 – 210.

14.    Yang, Y. D. (1998). Simultaneous determination of creatine, uric acid, creatinine and hippuric acid in urine by high performance liquid chromatography. Biomedical Chromatography, 12 (2): 47 – 49.

15.    Poggi, G., Giusiani, M., Palagi, U., Paggiaro, P. L., Loi, A. M., Dazzi, F. and Baschieri, L. (1982). High-performance liquid chromatography for the quantitative determination of the urinary metabolites of toluene, xylene, and styrene. International Archives of Occupational and Environmental Health, 50(1): 25 – 31.

16.    Ogii K. (1988). Determination of Hippuric Acid in Cadaveric Urine and Urinary Stain by High Performance Liquid Chromatography. Journal Tokyo Woman Medicine Collection, 58: 627 – 636.

17.    Fujii T., Kawabe S., Horike T., Taguchi T. amd Ogata M. (1999). Simultaneous Determination of the Urinary Metabolites of Toluene, Xylene and Styrene using High Performance Capillary Electrophoresis: Comparison with High Performance Liquid Chromatography. Journal Chromatography B. 41: 730 –740.

18.    Lee, C. E., Lee, J., Lee, J., Eom, H.Y., Kim, M. K., Suh, J. H., Yeom, H., Kim, U., Youm, J. R. and Han, S. B. (2009). Rapid HPLC Method for the Simultaneous Determination of Eight Urinary metabolites of toluene, xylene and styrene. Bulletin Korean Chemical Society, 30(9): 2021 – 2026.

19.    Inoue, O., Kanno, E., Yusa, T., Kakizaki, M., Ukai, H., Okamoto, S., Higashikawa, K. and Ikeda, M. (2002). Urinary benzylmercapturic acid as a marker of occupational exposure to toluene. International Archives Occupational Environmental Health, 75: 341 – 347.

20.    Inoue, O., Kanno, E., Kasia, K., Ukai, H., Okamoto, S. and Ikeda, M. (2004). Benzylmercapturic acid is superior to hippuric acid and o-cresol as a urinary marker of occupational exposure to toluene. Toxicology Letter, 147: 177 –186.

21.    Serap, A. A., Pembe, O., Yusuf, K.., Huseyin. K. and Suheyla, E. (2001). Medicolegal Aspects of Blood-Urine Toluene and Urinary Ortho-Cresol concentration in Toluene Exposure. Turkish Journal Medical Science, 31: 415 – 419.

22.    Monteiro, C., Franco, J. M., Proença, P., Castañera, A., Claro, A., Vieira, D. N. and Corte-Real, F. (2014). Qualitative and quantitative analysis of a group of volatile organic compounds in biological samples by HS-GC/FID: application in practical cases. Forensic Science International, 243: 137 –143.

23.    De Carvalho, D., Lanchote, V. L., Bonato, P. S., Queiroz, R. H. C., Santos, A. C. and Dreossi S. A. C. (1991). A new derivatization procedure for the analysis of hippuric acid and m-methyl-hippuric acid by gas chromatography. International Archive Environmental Health, 63: 33 – 37.

24.    Pacenti, M., Dugheri, S., Villanelli, F., Bartolucci, G., Calamai, L., Boccalon, P., Arcangeli, G., Vecchione, F., Alessi, P., Kikic, I. and Cupelli, V. (2008). Determination of organic acids in urine by solid-phase microextraction and gas chromatography-ion trap tandem mass spectrometry previous ‘in sample’ derivatization with trimethyloxonium tetrafluoroborate. Biomedical Chromatography, 22: 1155 – 1163.

25.    Kongtip, P., Vararussami, J. and Pruktharathikul, V. (2001). Modified method for determination of hippuric acid and methylhippuric acid in urine by gas chromatography. Journal of Chromatography B: Biomedical Sciences and Applications, 751(1): 199 – 203.

26.    De Paiva, M. J. N., Martins, I. and de Siqueira, M. E. P. B. (2007). Analysis of o-cresol in urine by solid phase microextraction capillary gas chromatography. Journal Brazillian Chemical Society, 18 (5): 1034 –1039.

27.    Truchon, G., Tardif, R. and Brodeur, J. (1996). Gas chromatographic Determination of urinary o-cresol for the monitoring of toluene exposure. Journal of Analytical Toxicology, 20: 309 – 312.

28.    Ikeda, M. (1996). Selected solvents.4.6 Toluene. In: Mikheev MI (ed) Biological monitoring of chemical exposure in workplace. World Health Organization, Geneva, (1) 4: 205 – 217.

29.    Ikeda, M. and Ohtsuji, M. (1969). Significance of urinary hippuric acid determination as an index of toluene exposure. British Journal Industrial Medicine, 26: 244 – 246.

30.    Lauwerys, R. (1983). Toluene In: Alessio L, Berlin A, Roi R, Boni M (eds) Human biological monitoring of industrial chemicals, Joint Research Centre Ispra Establishment CEC 1: 159 – 175.

31.    Siqueira, M. E. and Paiva, M. J. (2002). Hippuric acid in urine: references values. Revision Saude Publica, 36: 723 – 727.

32.    Sugita, M., Aikawa, H., Suzuki, K., Yamasaki, T., Minowa, H., Etoh, R. and Kasuga, H. (1988). Urinary hippuric acid excretion in everyday life. Tokai Journal Exposure Clinical Medical, 13: 185 – 190.

33.    Villanueva, M. B., Jonai, H., Kanno, S. and Takeuchi, Y. (1994). Dietary sources and background levels of hippuric acid in urine; comparison of Philiphine and Japanese levels. Industrial Health, 32: 339 – 346.

34.    Michitsuji, H., Ohara, A., Yamaguchi, K. and Fujiki, Y. (1987). Effect of intake of refreshments in excretion of hippuric acid in urine. Matsushita Medical Journal, 26: 105 – 116.

35.    Kawai, T., Yamauchi, T., Miyama, Y., Sakurai, H., Ukai, H., Takada, S., Ohashi, F. and Ikeda, M. (2007). Benzyl alcohol as a marker of occupational exposure to toluene. Industrial Health, 95: 143 – 150.

36.    Hasegawa, K., Shiojima, S., Koizumi, A. and Ikeda M. (1983). Hippuric acid and o-cresol in the urine of workers exposed to toluene. International Archive Occupational Environmental Health, 52: 197 – 208.

37.    Nise, G. (1992). Urinary excretion of o-cresol and hippuric acid after toluene exposure in rotogravure printing. International Archives Occupational Environmental Health, 63: 377 – 381.

38.    Maestri, L., Ghittori, S. and Imbriabu, M. (1997). Determination of specific mercapturic acids as an index of exposure to environmental benzene, toluene and styrene. Industrial Health, 35: 489 – 502.

39.    Angerer, J., Schildbach, M. and Kramer, A. (1998). S-p-toluylmercapturic acid in the urine of workers exposed to toluene; a new biomarker for toluene exposure. Archives Toxicology, 72: 119 – 123.

40.    Inoue, O., Seiji, K. and Watanabe T. (1993). Effect of smoking and drinking on excretion of hippuric acid among toluene exposed workers. International Archives Occupational Environmental Health, 64: 425 – 430.

41.    Kawai, T., Mizunuma, K., Okada, Y., Horiguchi, S. and Ikeda, M. (1996). Toluene itself as the best urinary marker of toluene exposure. International Archives Occupational Environmental Health, 68: 289 – 297.

42.    Lovreglio, P., Barbieri A., Carrieri, M., Sabatini, L., Fracasso, M.E., Doria, D., Drago, I., Basso, A., D’Errico, M. N., Bartolucci, G.. B., Violante, F. S. and Soleo, L. (2010). Validity of new biomarkers of internal dose for use in the biological monitoring of occupational and environmental exposure to low concentrations of benzene and toluene. International Archives Occupational Environmental Health, 83: 341 – 356.

43.    Park S. W., Kim N. Y., Yang Y. G, Seo B. and Paeng K. .J. (1998). Toluene Distribution of Glue Sniffers Biological Fluid Samples in Korea. Journal of Forensic Science, 43: 888 – 890.

44.    Anderson C. E. and Loomis G.. A. (2003). Recognition and Prevention of Inhalant Abuse. American Academy Family Physician, 68: 869 – 874.

45.    Ameno K., Fuke C., Ameno S., Kirui T., Sogo K. and Ijiri I. (1989). A Fatal Case of Oral Ingestion of Toluene. Journal Forensic Science International, 41: 255 – 260.

46.    Yamazaki K., Tanaka E. and Misawa S. (1992). Urinary ortho-cresol Concentrations as an Indicator of Toluene Inhalation in Glue Sniffer. Journal Forensic Science, 32: 215 – 223.

47.    Zuppi C., Rossetti D. V., Vitali A., Vincenzoni F., Giardina B., Castagnola M. and Messana I. (2003). Determination of Urinary Hippuric Acid by Micellar Electrokinetic Capillary Chromatography. Journal Chromatography B, 793: 223 – 228.

48.    Amorim L. C. A. and Alvarez-Leite E. M. (1997). Determination of o-cresol by Gas Chromatography and Comparison with Hippuric Acid Levels in Urine Sample of Individuals Exposed to Toluene. Journal Toxicology Environmental Health, 30: 101 – 107.

49.    World Health Organisation (WHO) (2000). Air quality guidelines for Europe. WHO Regional Publications, European Series, No. 91. 2nd edition. WHO Regional Office for Europe. Copenhagen.

50.    Croes K., McCarthy P. T. and Flanagan R. J. (1994). Simple and Rapid HPLC of Quinine, Hydroxychloroquine, Chloroquine and Desethylchloroquine in Serum, whole Blood and Filter Paper Adsorbed Dry Blood. Journal Analaytical Toxicology, 18: 255 – 260.

51.    Flanagan R. J., Braithwaite R. A., Brown S. S., Widdop B. and de Wolff F. A. (1995). Basic Analytical Toxicology. World Health Organization, Geneva.

52.    Gaffney, G.. W., Schreier, K., Diferrante, N. and Altman, K. I. (1954). The quantitative determination of hippuric acid. Journal Biology Chemical, 206: 695 – 698.

53.    Umberger, C. J. and Fiorese, F. F. (1963). Colorimetric method of hippuric acid. Clinical Chemistry, 9: 191 – 196.

54.    Tomokuni, K. and Ogata, M. (1972). Direct colorometric determination of hippuric acid in urine. Clinical Chemistry, 18(4): 349 – 351.

55.    Yoshida, M., Akane, A., Mitani, T. and Watabiki, T. (2005). Simple colorimetric semi quantitation method of hippuric acid in urine for demonstration of toluene abuse. Journal of Legal Medicine, 7(3): 198 – 200.

56.    Matsui, H., Kasao, M. and Imamura, S. (1978). High-performance liquid chromatographic determination of hippuric acid in human urine. Journal of Chromatography, 145(2): 231 – 236.

57.    Bevine, H., Olsson, U., Hemgard, A., Kristensson, J., Palmborg, J. and Sollenberg J. (1990). High Performance Liquid Chromatographic Analysis of Hippuric Acid in Human Blood Plasma. Journal of Chromatography, 532: 45 – 53.

58.    Kubota, K., Horai, Y., Kushida, K. and Ishizaki, T. (1988). Determination of benzoic acid and hippuric acid in human plasma and urine by high-performance liquid chromatography. Journal of Chromatography, 425(1): 67 – 75.

59.    Ogata, M. and Taguchi, T. (1987). Quantitation of urinary metabolites of toluene, xylene, styrene, ethylbenzene, benzene and phenol by automated high performance liquid chromatography. International Archives of Occupational and Environmental Health, 59(3): 263 – 272.

60.    Daneshfar, A., Toulabi, P. and Sahrai R. (2010). Determination of hippuric acid in biological fluids using single drop liquid-liquid-liquid microextraction. The Royal Society of Chemistry, 2: 564 – 569. 

61.    Moein, M. M., El-Beqqali, A., Javanbakht, M., Karimi, M., Akbari-adergani, B. and Abdel-Rehim, M. (2014). On-line detection of hippuric acid by microextraction with a molecularly imprinted polysulfone membrane sorbent and liquid chromatography-tandem mass spectromethy. Journal of Chromatography A, 1372: 55 – 62.

62.    Buchet, J. P. and Lauwerys, R. R. (1973). Measurement of urinary hippuric and m-methylhippuric acids by gas chromatography. British Journal of Industrial Medicine, 30(2): 125 – 128.

63.    Kira, S. (1977). Measurement by gas chromatography of urinary hippuric acid and methylhippuric acid as indices of toluene and xylene exposure. British Journal of Industrial Medical, 34: 305 – 309.

64.    Veuleman, H., Van Vlem, E., Janssens, H. and Masschelein, R. (1979). Exposure to toluene and urinary hippuric acid excretion in a group of heliorotagravure printing workers. International Archives Occupational Environmental Health, 44: 99 – 107.

65.    Van Roosmalen, P. B. and Drummond, I. (1978). Simultaneous determination by gas chromatography of the major metabolites in urine of toluene, xylenes and styrene. British Journal Industrial Medical, 35: 56 – 60.

66.    Campbell, L., Wilson, H. K., Samuel, A. M. and Gompertz, D. (1988). Interactions of m-xylene and aspirin metabolism in man. British Journal Industrial Medical, 30: 125 – 128.

67.    Sanagi, M. M., Salleh, S., Wan Ibrahim, W. A. and Abu Naim, A. (2011). Determination of organophosphorus pesticides using molecularly imprinted polymer solid phase extraction. Malaysian Journal of Analytical Sciences, 15(2): 175 – 183.  

68.    Ahmadi, F., Asgharloo, H., Sadeghi, S., Gharehbagh-Aghababa, V. and Adibi, M. (2009). Post-derivatization procedure for determination of hippuric acid after extraction by an automated micro solid phase extraction system and monitoring by gas chromatography. Journal of Chromatography B, 877: 2945 – 2951.

69.    Ogata, M., and Taguchi, T. (1986). Quantitative analysis of urinary glycine conjugates by high performance liquid chromatography: excretion of hippuric acid and methylhippuric acids in the urine of subjects exposed to vapors of toluene and xylenes. International Archives of Occupational and Environmental Health, 58(2): 121–129.

70.    Ogata, M., and Taguchi, T. (1987). Quantitation of urinary metabolites of toluene, xylene, styrene, ethylbenzene, benzene and phenol by automated high performance liquid chromatography. International Archives of Occupational and Environmental Health, 59(3): 263 –272.

71.    Yacob, A. R. and Zinalibdin M. R. (2010). High Performance Liquid Chromatography Determination of urinary hippuric acid and benzoic acid as indices for glue sniffer urine. World Academy of Science and Technology, 38: 973 – 978.

72.    Ohashi, Y., Mamiya, T., Mitani, K., Wang, B., Takigawa, T., Kira, S. and Kataoka, H. (2006). Simultaneous determination of urinary hippuric acid, o-, m- and p- methylhippuric acids, mandelic acid and phenylglyoxylic acid for biomonitoring of volatile organic compounds by gas chromatography-mass spectrometry. Analytica Chimica Acta, 566: 167 – 171.

 

 




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