The solid‐phase microextraction (SPME), invented by Pawliszyn in 1989, today has a renewed and growing use and interest in the scientific community with fourteen techniques currently available on the market. The miniaturization of traditional sample preparation devices fulfills the new request of an environmental friendly analytical chemistry. The recent upswing of these solid‐phase microextraction technologies has brought new availability and range of robotic automation. The microextraction solutions propose today on the market can cover a wide variety of analytical fields and applications. This review reports on the state‐of‐the‐art innovative solid‐phase microextraction techniques, especially those used for chromatographic separation and mass‐spectrometric detection, given the recent improvements in availability and range of automation techniques. The progressively implemented solid‐phase microextraction techniques and related automated commercially available devices are classified and described to offer a valuable tool to summarize their potential combinations to face all the laboratories requirements in terms of analytical applications, robustness, sensitivity, and throughput.

High-throughput screening of samples is the strategy of choice to detect occupational exposure biomarkers, yet it requires a user-friendly apparatus that gives relatively prompt results while ensuring high degrees of selectivity, precision, accuracy and automation, particularly in the preparation process. Miniaturization has attracted much attention in analytical chemistry and has driven solvent and sample savings as easier automation, the latter thanks to the introduction on the market of the 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 and triple quadrupole-mass spectrometry to determine urinary metabolites of polycyclic aromatic hydrocarbons 1- and 2-hydroxy-naphthalene, 9-hydroxy-phenanthrene, 1-hydroxy-pyrene, 3- and 9-hydroxy-benzoantracene, and 3-hydroxy-benzo[a]pyrene. In this new procedure, chromatography’s sensitivity is combined with the user-friendliness of N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide on-fiber SPME derivatization using direct immersion sampling; moreover, specific isotope-labelled internal standards provide quantitative accuracy. The detection limits for the seven OH-PAHs ranged from 0.25 to 4.52 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.

Metal-additive manufacturing (AM), particularly the powder-bed fusion (PBF) technique, is undergoing a transition from the short-run production of components to higher-volume manufacturing. The industry’s increased production efficiency is paired with a growing awareness of the risks related to the inhalation of very fine metal powders during PBF and AM processes, and there is a pressing need for a ready-to-use approach to assess the risks and the occupational exposure to these very final metal powders. This article presents a study conducted in an AM facility, which was conducted with the aim to propose a solution to monitor incidental airborne particle emissions during metal AM by setting up an analytical network for a tailored approach to risk assessment. Quantitative data about the respirable and inhalable particle and metal content were obtained by gravimetric and ICP-MS analyses. In addition, the concentrations of airborne particles (10–300 nm) were investigated using a direct reading instrument. A qualitative approach for risk assessment was fulfilled using control banding Nanotool v2.0. The results show that the operations in the AM facility are in line with exposure limit levels for both micron-sized and nano-sized particles. The particulate observed in the working area contains metals, such as chromium, cobalt, and nickel; thus, biological monitoring is recommended. To manage the risk level observed for all of the tasks during the AM process, containment and the supervision of an occupational safety expert are recommended to manage the risk. This study represents a useful tool that can be used to carry out a static evaluation of the risk and exposure to potentially harmful very fine metal powders in AM; however, due to the continuous innovations in this field, a dynamic approach could represent an interesting future perspective for occupational safety.

Carbonyl compounds (CCs) are products present both as vapors and as condensed species adsorbed on the carbonaceous particle matter dispersed in the air of urban areas, due to vehicular traffic and human activities. Chronic exposure to CCs is a potential health risk given the toxicity of these chemicals. The present study reports on the measurement of the concentrations of 14 CCs in air as vapors and 2.5 µm fraction PM by the ENVINT GAS08/16 gas/aerosol sampler, a serial sampler that uses annular denuder, as sampling device. The 14 CCs were derivatized during sampling prior to gas-chromatographic separation and multiple detection by mass spectrometry, nitrogen-phosphorus thermionic, electron capture detection. Outdoor air multiple samples were collected in four locations in the urban area of Florence. The results evidenced that formaldehyde, acetaldehyde, and acetone were the more abundant CCs in the studied areas. The data collected was discussed considering the particle to vapor ratio of each CC found. The CCs pollution picture obtained was tentatively related to the nature and intensity of the traffic transiting by the sampling sites. This approach allowed to determine 14 CCs in both concentrated and diluted samples and is proposed as a tool for investigating outdoor and indoor pollution.

Formaldehyde (FA) is a toxic compound and a human carcinogen. Regulating FA-releasing substances in commercial goods is a growing and interesting topic: worldwide production sectors, like food industries, textiles, wood manufacture, and cosmetics, are involved. Thus, there is a need for sensitive, economical, and specific FA monitoring tools. Solid-phase microextraction (SPME), with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) on-sample derivatization and gas chromatography, is proposed for FA monitoring of real-life samples. This study reports the use of polydimethylsiloxane (PDMS) as a sorbent phase combined with innovative commercial methods, such as multiple SPME (MSPME) and cooling-assisted SPME, for FA determination. Critical steps, such as extraction and sampling, were evaluated in method development. The derivatization was performed at 60 °C for 30 min, followed by 15 min sampling at 10 °C, in three cycles (SPME Arrow) or six cycles (SPME). The sensitivity was satisfactory for the method’s purposes (LOD-LOQ at 11-36 ng L⁻¹, and 8-26 ng L⁻¹, for SPME and SPME Arrow, respectively). The method’s linearity ranges from the lower LOQ at trace level (ng L⁻¹) to the upper LOQ at 40 mg L⁻¹. The precision range was 5.7–10.2% and 4.8–9.6% and the accuracy was 97.4% and 96.3% for SPME and SPME Arrow, respectively. The cooling MSPME set-up applied to real commercial goods provided results of quality comparable to previously published data.

Airborne benzene in workplaces has progressively decreased due to preventive actions and the redesigning of facility processes. Professionals who assess occupational exposure should select techniques to detect benzene levels comparable to ambient air exposure. Thus, sensitive biomarkers are needed to discriminate the effects of confounding factors, such as smoking or sorbic acid (SA). In order to identify sensitive biomarkers and to study their correlation with confounding factors, 23 oil refinery workers were enrolled in the study; their airborne benzene exposures and biomarkers were monitored. Urinary benzene (U-B), t,t-muconic acid (t,t-MA), and S-phenylmercapturic acid (SPMA) were quantified. Urinary cotinine (U-C) and t,t-sorbic acid (t,t-SA) were evaluated to flag smoking and SA intake, respectively. The benzene measured in personal inhalation sampling ranged from 0.6 to 83.5 (median 1.7) µg/m³. The concentration range of the biomarkers, U-B, t,t-MA, and SPMA, were 18–4893 ng/m³, <10–79.4 µg/g creatinine, and <0.5–3.96 µg/g creatinine, respectively. Pearson tests were carried out; the best correlations were between airborne benzene and U-B (µg/L r = 0.820, p < 0.001) and between benzene and SPMA (g/L r = 0.812, p < 0.001), followed by benzene and t,t-MA (mg/L r = 0.465, p = 0.039). From our study, U-B and SPMA result to be the most reliable biomarkers to assess the internal number of low doses of benzene exposure, thanks to their specificity and sensitivity.