Hydroxyapatite is a readily available, inexpensive, environmentally friendly adsorbent with high adsorption capacity. In this study, a polyaniline-doped nano-hydroxyapatite (PANI@HA) adsorbent was synthesized and employed in a needle trap device for the extraction of polycyclic aromatic hydrocarbons such as naphthalene, fluoranthene, benzo[a]anthracene, phenanthrene, and benzo[a]pyrene for the first time. The synthesized adsorbent was characterized by X-ray diffraction, field emission scanning electron microscopy, and Fourier-transform infrared spectroscopy analysis. Initially, effective variables such as the carryover effect, storage time, accuracy, and precision of the method were examined in the laboratory. The desorption conditions were optimized using the response surface methodology and central composite design methods. From the standpoint of quantitative parameters, the limit of detection and limit of quantitation were determined to be between 0.001 and 0.003 and 0.021 and 0.051 ng mL−1, respectively, which indicates the high sensitivity of the proposed method. Additionally, no significant changes were detected after storage of analytes inside the needle at 4 °C after 60 days. The results of this study also provide a high correlation between the results of sampling with needles containing PANI@HA and with XAD-2 adsorbent tubes (standard NIOSH 5115 method) (R2 = 0.98). Finally, the proposed method was successfully employed in the extraction and determination of polycyclic aromatic hydrocarbons in field (real) samples. In general, it can be concluded that a needle packed with PANI@HA is a reliable and high-performance method for sampling polycyclic aromatic hydrocarbons compared to the NIOSH method.
