Donato Squillaci

Background: In response to the growing demand for the real-time, in-field characterization of odorous anthropogenic emissions, this study develops and uses a MEMS-based micropacked thermal desorption Gas Chromatography system coupled with a PhotoIonization Detector (GC/PID) for Hot Mix Asphalt (HMA) plant emissions. Methods: The innovative portable device, Pyxis GC, enables the high-sensitivity profiling of Volatile Organic Compounds (VOCs), particularly aldehydes and ketones, with sub-ppb detection limits using ambient air as the carrier gas. A comprehensive experimental design optimized the preconcentration parameters, resulting in an efficient, green analytical method evaluated via the Green Analytical Procedure Index (GAPI). Sorbent comparison showed quinoxaline-bridged cavitands outperform the conventional materials. Results and conclusions: The method was successfully deployed on site for source-specific sampling at an HMA plant, generating robust emission fingerprints. To assess environmental impact, a Generalized Additive Model (GAM) was developed, incorporating the process temperature and Sum of Odour Activity Values (SOAV) to predict odour concentrations. The model revealed a significant non-linear influence of temperature on emissions and validated its predictive capability despite the limited sample size. This integrated analytical–statistical approach demonstrates the utility of MEMS technology for real-time air quality assessment and odour dispersion modelling, offering a powerful tool for environmental monitoring and regulatory compliance.

Brominated flame retardants (BFRs), including tetrabromobisphenol A (TBBPA) and dibromoneopentyl glycol (DBNPG), are present in both saturated and unsaturated polyester resins (UPRs). Given their toxicity, it is imperative to assess the content of this group of chemicals to ensure product safety and environmental sustainability, considering the paucity in the literature of analytical methods to evaluate them, particularly in solid matrices as UPRs. This study aimed to develop a fully automated gas chromatographic analysis of these BFRs, utilizing a flame ionization detector (FID), with prior derivatization of TBBPA and DBNPG with acetic anhydride. A chemometric evaluation was conducted for the derivatization step to enhance the yield of the procedure. The optimized method met the desired requirements for specificity, accuracy, and sensitivity, showing limits of detection (LOD) and quantitation (LOQ), respectively, of 1.1 µg/mL and 3.3 µg/mL for DBNPG and 3.6 µg/mL and 10.8 µg/mL for TBBPA. Other conventional detectors, i.e., an Electron Capture Detector (ECD) and a Mass Spectrometer (MS), were tested. The ECD showed a higher sensitivity than the FID and MS; however, its linearity proved to be more limited, making it unsuitable for higher concentration scenarios. The MS detector yielded results comparable with those of the FID, yet the latter is a cheaper and more sensitive alternative.

MonoTrap^TM was introduced in 2009 as a novel miniaturized configuration for sorptive sampling. The method for the characterization of volatile organic compound (VOC) emission profiles from hot mix asphalt (HMA) consisted of a two-step procedure: the analytes, initially adsorbed into the coating in no vacuum- or vacuum-assistance mode, were then analyzed following an automated thermal desorption (TD) step. We took advantage of the theoretical formulation to reach some conclusions on the relationship between the physical characteristics of the monolithic material and uptake rates. A total of 35 odor-active volatile compounds, determined by gas chromatography-mass spectrometry/olfactometry analysis, contributed as key odor compounds for HMA, consisting mainly of aldehydes, alcohols, and ketones. Chemometric analysis revealed that MonoTrap^TM RGC18-TD was the better coating in terms of peak area and equilibrium time. A comparison of performance showed that Vac/no-Vac ratios increased, about an order of magnitude, as the boiling point of target analytes increased. The innovative hybrid adsorbent of silica and graphite carbon monolith technology, having a large surface area bonded with octadecylsilane, showed effective adsorption capability, especially to polar compounds.

An innovative SPME head space GC–MS method, in cooling mode, using a fully automated routine, was developed to detect 2-phenyl-2-propanol, a representative urinary metabolite of cumene. Following an acid hydrolysis and derivatization step with lowered quantities of reagents, acetic anhydride and pyridine, a 30 μm polydimethylsiloxane SPME fiber was used to sample derivatized 2-phenyl-2-propanol, such as benzenemethanol,α,α-dimethyl-acetate, from the headspace. Performances of the method, optimized through experimental design, provide an LOD of 0.034 mg/L and an LOQ 0.10 mg/L, with a short sampling time necessary per sample. The method, developed on standard solutions, will be applied to both occupationally exposed and non-exposed populations.

Healthcare workers handling antineoplastic drugs (ADs) in preparation units run the risk of occupational exposure to contaminated surfaces and associated mutagenic, teratogenic, and oncogenic effects of those drugs. To minimise this risk, automated compounding systems, mainly robots, have been replacing manual preparation of intravenous drugs for the last 20 years now, and their number is on the rise. To evaluate contamination risk and the quality of the working environment for healthcare workers preparing ADs, we applied the Failure Mode Effects and Criticality Analysis (FMECA) method to compare the acceptable risk level (ARL), based on the risk priority number (RPN) calculated from five identified failure modes, with the measured risk level (MRL). The model has shown higher risk of exposure with powdered ADs and containers not protected by external plastic shrink film, but we found no clear difference in contamination risk between manual and automated preparation. This approach could be useful to assess and prevent the risk of occupational exposure for healthcare workers coming from residual cytotoxic contamination both for current handling procedures and the newly designed ones. At the same time, contamination monitoring data can be used to keep track of the quality of working conditions by comparing the observed risk profiles with the proposed ARL. Our study has shown that automated preparation may have an upper hand in terms of safety but still leaves room for improvement, at least in our four hospitals.

Despite the considerable steps taken in the last decade in the context of antineoplastic drug (AD) handling procedures, their mutagenic effect still poses a threat to healthcare personnel actively involved in compounding and administration units. Biological monitoring procedures usually require large volumes of sample and extraction solvents, or do not provide adequate sensitivity. It is here proposed a fast and automated method to evaluate the urinary levels of cyclophosphamide and iphosphamide, composed of a miniaturized solid phase extraction (µSPE) followed by ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis. The extraction procedure, developed through design of experiments (DoE) on the ePrep One Workstation, required a total time of 9.5 min per sample, with recoveries of 77–79% and a solvent consumption lower than 1.5 mL per 1 mL of urine sample. Thanks to the UHPLC-MS/MS method, the limits of quantification (LOQ) obtained were lower than 10 pg/mL. The analytical procedure was successfully applied to 23 urine samples from compounding wards of four Italian hospitals, which resulted in contaminations between 27 and 182 pg/mL.

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.

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.

Antineoplastic drugs are a wide and heterogeneous group of substances that, as universally known, can cause highly severe toxic effects to whoever is exposed. From an occupational safety point of view, surface contaminations inside preparation and administration units are a growing issue and therefore require the development and implementation of sensible and fast monitoring methods. The unlikelihood of a unique all-embracing chromatography, able to correctly retain and separate each analyte led to the need to create an orthogonal normal phase analysis, which might be able to fill the gaps in the more common reversed-phase ones. An existing hydrophilic interaction method has thus been expanded to 6 other drugs and applied to real samples after an evaluation of its performances. The experimental data were then used to evaluate the possibility of estimating reliable relationships between the chromatographic retention and the chemical-structural features of the drugs under analysis.

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.