High-Throughput Analysis of Selected Urinary Hydroxy Polycyclic Aromatic Hydrocarbons by an Innovative Automated Solid-Phase Microextraction

Abstract

High-throughput screening of samples is the strategy of choice to detect occupational exposure biomarkers, yet it requires user-friendly apparatus that gives relatively prompt results while ensuring high degrees of selectivity, precision, accuracy and automation, particularly in preparation processes. In the last 10 years, miniaturization has attracted much attention in analytical chemistry and has driven solvent and sample savings and easier automation, the latter thanks to the introduction on the market of three axis autosampler. In light of the above, this contribution describes a novel user-friendly solid-phase microextraction (SPME) off- and on-line platform coupled with gas chromatography triple quadrupole-mass spectrometry to determine urinary 1- and 2-hydroxy-napthalene, 9-hydroxy-phenantrene, 1-hydroxy-pyrene, 3- and 9-hydroxy-benzoantracene and 3-hydroxy-benzo[a]pyrene, metabolites of the related polycyclic aromatic hydrocarbons. In this new procedure chromatography’s sensitivity is combined with the user-friendliness of N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide on-fiber SPME derivatization previous direct immersion sampling, to which is added the quantitative accuracy afforded using specific isotope-labelled internal standards. The detection limits for the seven OH-PAHs were ranged from 0.28 to 1.87 ng/L. Intra-(from 2.5 to 3.0%) and inter-session (from 2.4 to 3.9%) repeatability was also evaluated. This method serves to identify suitable risk-control strategies for occupational hygiene conservation programs

Solid‐phase microextraction for the human biomonitoring of environmental chemicals: Current applications and future perspectives

“…Hence, human biomonitoring of exposure to PAHs is important due to the potential widespread exposure and to their toxicological relevance in humans. Human exposure to PAHs results in the excretion of their respective hydroxylated compounds (OH‐PAHs) in the urine [78,80]. Hence, the direct measure of PAHs (unmetabolized/free form) in the blood/hair or measuring the exposure biomarkers (OH‐PAHs) in the urine can help us understand the actual exposure levels and associated consequent health effects.…”

“…More recent studies were highly focused on measuring metabolites (OH‐PAHs) of PAHs rather than measuring parent PAHs in urine [78,80,84]. Chen and Xu prepared a nanocomposite [using graphene oxide, poly(3,4‐ethylenedioxythiophene), and polypyrrole], which then electrodeposited on the internal surface of a stainless‐steel tube for the online in‐tube SPME [84].…”

“…Dugheri et al. applied an innovative automated SPME (on fiber derivatization and DI sampling) method for the sensitive measurement of seven OH‐PAHs [80]. The commercially available PA fiber (85 μm) with a fast fiber assembly was used for the SPME.…”

Advanced Solid-Phase Microextraction Techniques and Related Automation: A Review of Commercially Available Technologies

“…Between these, HTA has designed the HT2800 T, which is a new-concept two-axis sample preparation system more versatile than the older two-axis. e online autosamplers could be equipped with everything that could be necessary to entirely run SPME techniques, such as tool changer, vortex, centrifugation, balance, trays (allowing different sizes and temperatures), and barcode readers [107]. Frequently, new devices are released on the market to optimize the complete automation of the analytical process.…”

Solid phase microextraction techniques used for gas chromatography: a review

“…The advantages of LVI over other techniques consist in decreased analyte discrimination, better recoveries of thermolabile compounds, and less pronounced adverse effects of non-volatiles present in the sample on the injection process [73]. The most important feature of LVI is that it introduces large volumes of samples (up to hundreds μL) into GC system and thus increase the method's sensitivity [74]. Currently, available LVI methods involve various injection modes, namely: programmed-temperature vaporizing (PTV) solvent split, on-column injection (OCI), direct sample introduction (DSI)/difficult matrix injection (DMI), splitless overflow/concurrent solvent recondensation (CSR), AT-column, through-oven transfer adsorption desorption (TOTAD), and a stomach-shaped insert liner.…”