Synthesis of trans-dihydronaphthalene-diol and evaluation of their use as standards for PAH metabolite analysis in fish bile by GC-MS

Abstract

Phenols and trans-1,2-dihydro-1,2-diols are metabolites commonly formed in vivo in fish upon exposure to polycyclic aromatic hydrocarbons (PAHs). These metabolites are excreted via the bile and gas chromatography-mass spectrometry (GC-MS) analysis of bile is becoming more frequently used for evaluating PAH exposure levels in fish. Current protocols focus on the detection and quantification of phenols formed during in vivo oxidation of PAHs, leaving out analyses and quantification of other oxidation products such as trans-1,2-dihydro-1,2-diols, potentially underestimating exposure levels. Herein, four trans-1,2-dihydro-1,2-diols, namely trans-1,2-dihydronaphthalene-1,2-diol, trans-6-methyl-1,2-dihydronaphthalene-1,2-diol, trans-5,7-dimethyl-1,2-dihydronaphthalene-1,2-diol, and trans-4,6,7-trimethyl-1,2-dihydronaphthalene-1,2-diol, were successfully prepared and used as standards in the GC-MS analysis, aiming to further develop this qualitative and quantitative analytical method for the determination of PAH exposures. This study shows that the currently used GC-MS analysis, including sample workup, is not suitable for determining the quantity of the corresponding diols derived from naphthalene and methylated naphthalenes. Alternative approaches are needed to provide a correct estimate of PAH exposure levels.