Urinary polycyclic aromatic hydrocarbons and monohydroxy metabolites as biomarkers of exposure in coke oven workers.
OBJECTIVE
To assess exposure to polycyclic aromatic hydrocarbons (PAHs) using 13 unmetabolised PAHs (U-PAHs) and 12 monohydroxy metabolites (OHPAHs) in urine, and to compare the utility of these biomarkers.


METHODS
55 male Polish coke oven workers collected urine spot samples after a workshift. U-PAHs (naphthalene, acenaphtylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[a]pyrene) were determined by automatic solid phase micro-extraction followed by gas chromatography/mass spectrometry (GC/MS). OHPAHs (1- and 2-hydroxynaphthalene, 2- and 9-hydroxyfluorene, 4-, 9-, 3-, 1- and 2-hydroxyphenanthrene, 1-hydroxypyrene, 6-hydroxychrysene, 3-hydroxybenzo[a]pyrene) were determined, after liquid/liquid extraction and derivatisation, by GC/MS.


RESULTS
U-PAHs from naphthalene to chrysene were found in 100% of samples, and heavier U-PAHs in 7-22% of samples. OHPAHs up to 1-hydroxypyrene were found in 100% of samples, while 6-hydroxychrysene and 3-hydroxybenzo[a]pyrene were always below the quantification limit. Median naphthalene, phenanthrene, pyrene, chrysene and benzo[a]anthracene levels were 0.806, 0.721, 0.020, 0.032 and 0.035 microg/l, while hydroxynaphthalenes, hydroxyphenanthrenes and 1-hydroxypyrene levels were 81.1, 18.9 and 15.4 microg/l. For each chemical, the ratio between U-PAH and the corresponding OHPAH ranged from 1:26 to 1:1000. Significant correlations between logged values of U-PAHs and OHPAHs, between U-PAHs, and between OHPAHs were found, with Pearson's r ranging from 0.27 to 0.97.


CONCLUSIONS
Current analytical techniques allow specific and simultaneous measurement of several urinary determinants of PAHs in humans. The results of these measurements support the use of U-PAHs as biomarkers of exposure and suggest the spectrum of chemicals to be investigated, including carcinogenic chrysene and benzo[a]anthracene, should be widened.
Rossella
F
F
Department of Occupational and Environmental Medicine, University of Milan and Fondazione IRCCS Ospedale Maggiore Policlinico, Mangiagalli e Regina Elena, Via S Barnaba, 8 - 20122 Milan, Italy.
Campo
L
L
Pavanello
S
S
Kapka
L
L
Siwinska
E
E
Fustinoni
S
S
D000328:Adult; D015415:Biomarkers / Q000652:urine; D003077:Coke; D003367:Cotinine / Q000652:urine; D003404:Creatinine / Q000652:urine; D006801:Humans; D008297:Male; D016273:Occupational Exposure / Q000032:analysis*; D011044:Poland; D011084:Polycyclic Aromatic Hydrocarbons / Q000652:urine*; D011110:Polymorphism, Genetic; D012907:Smoking / Q000652:urine
D015415:Biomarkers; D003077:Coke; D011084:Polycyclic Aromatic Hydrocarbons; D003404:Creatinine; D003367:Cotinine