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.