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We reviewed the toxicokinetics of styrene to introduce reliable surrogates for the biological monitoring of styrene workers. We have also discussed the extraction techniques and analytical methods of styrene and its metabolites. Sample preparation is the main bottleneck of the analytical techniques for styrene and its metabolites. Although some microextraction methods have been developed to overcome such disadvantages, some still have limitations such as long extraction time, fiber swelling and breakage, and the cost and the limited lifetime of the fiber. Among all, microextraction by packed sorbents, coupled with HPLC with ultraviolet detection (MEPS‐HPLC‐UV), can be the method of choice for determining styrene metabolites. Few studies investigated unchanged styrene in breath samples. Chemical determination of styrene in exhaled breath provides new insights into organ toxicity in workers with inhalation exposures and can be considered a fascinating tool in risk assessment strategies. Taking blood samples is invasive and less accepted by workers. In contrast, breath analysis is the most attractive method for workers because breath samples are easy to collect and non‐invasive, and sample collection does not require the transfer of workers to health facilities. Therefore, developing selective and sensitive methods for determining styrene in breath samples is recommended for future studies. [ABSTRACT FROM AUTHOR]

Mandelic acid (MA) is a major metabolite of ethylbenzene and styrene. For the first time, a selective, fast, and easy-to-use procedure was developed for the determination of MA in urine samples. The new procedure is based on MIMEPS, the combination of a molecularly imprinted polymer (MIP) and microextraction by packed sorbent (MEPS). High-performance liquid chromatography with ultraviolet detection (HPLC-UV) was used for the separation and determination of MA. The bulk polymerization method was used to synthesize the MIP, and the MIP and non-imprinted polymer (NIP) were characterized by Fourier transform infrared spectroscopy. The selectivity of the MIP was investigated in the presence of interferents. In addition, we investigated the various parameters that affect the performance of the MEPS, including the pH of the sample, the number of extraction cycles, sample volume, and the types and volumes of the washing and elution solvents. A six-point calibration curve was obtained in the range of 0.2-20 µg/mL ( R = 0.9994). The extraction recovery was more than 88.8%. The limit of detection and the limit of quantitation were 0.06 and 0.2 µg/mL, respectively. The intra- and inter-day precisions were in the range of 3.6-4.7% and 3.8-5.1%, respectively. The accuracy was −8.4 to −11.1%. The optimized procedure was selective, sensitive, and rapid, and it was both user friendly and environmentally friendly. The sample preparation process took only about 5 min, so the MIMEPS-HPLC-UV procedure is recommended as an alternative for the biomonitoring of workers exposed to ethylbenzene and/or styrene. [ABSTRACT FROM AUTHOR]