Development of new PDMS in tube extraction microdevice for enhanced monitoring of polycyclic aromatic hydrocarbons and their derivatives in water

Abstract

Contamination by polycyclic aromatic hydrocarbons (PAHs) is an urgent environmental concern, given its atmospheric dispersion and deposition in water bodies and soils. These compounds and their nitrated and oxygenated derivatives, which can exhibit high toxicities, are prioritized in environmental analysis contexts. Amid the demand for precise analytical techniques, comprehensive two-dimensional chromatography coupled with mass spectrometry (GCxGC/Q-TOFMS) has emerged as a promising tool, especially in the face of challenges like co-elution. This study introduces an innovation in the pre-concentration and detection of PAHs using an extraction fiber based on polydimethylsiloxane (PDMS), offering greater robustness and versatility. The proposed technique, termed in-tube extraction, was developed and optimized to effectively retain PAHs and their derivatives in aqueous media, followed by GCxGC/Q-TOFMS determination. Fiber characterization, using techniques such as TG, DTG, FTIR, and SEM, confirmed the hydrophobic compounds retention properties of the PDMS. The determination method was validated, pointing to a significant advancement in the detection and analysis of PAHs in the environment, and proved effective even for traces of these compounds. The results showed that the detection limits (LOD) and quantification limits (LOQ) ranged from 0.07 ng L−1 to 1.50 ng L−1 and 0.33 ng L−1 to 6.65 ng L−1, respectively; recovery ranged between 72 % and 117 %; and the precision intraday and interday ranged from 1 % to 20 %. The fibers were calibrated in the laboratory, with exposure times for analysis in the equilibrium region ranging from 3 to 10 days. The partition coefficients between PDMS and water were also evaluated, showing logarithm values ranging from 2.78 to 5.98. The fibers were applied to the analysis of real water samples, demonstrating high capacity. Additionally, given the growing demand for sustainable methods, the approach presented here incorporates green chemistry principles, providing an efficient and eco-friendly solution to the current chemical analysis scenario.