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The widespread extensive use of synthetic polymers has led to a substantial environmental crisis caused by plastic pollution, with microplastics detected in various environments and posing risks to both human health and ecosystems. The possibility of plastic fragments to be dispersed in the air as particles and inhaled by humans may cause damage to the respiratory and other body systems. Therefore, there is a particular need to study microplastics as air pollutants. In this study, we tested a combination of analytical pyrolysis, gas chromatography-mass spectrometry, and gas and liquid chromatography-mass spectrometry to identify and quantify both microplastics and their additives in airborne particulate matter and settled dust within a workplace environment: a WEEE treatment plant. Using this combined approach, we were able to accurately quantify ten synthetic polymers and eight classes of polymer additives. The identified additives include phthalates, adipates, citrates, sebacates, trimellitates, benzoates, organophosphates, and newly developed brominated flame retardants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Plastic pollution threatens the marine environment, especially due to the adverse effects caused by micro and nano particles interacting with the marine biota. In order to provide reliable data regarding micro and nanoplastic contamination and the related impacts, efficient analytical solutions are needed. We developed a new analysis workflow that uses marine sponges to monitor plastic pollution by characterizing the plastic particles accumulated in their tissue. Specimens of cf. Haliclona (Haplosclerida) were sampled in the Maldivian archipelago. The aim was to optimize the method and to carry out a pilot study of the contamination of the related reef habitat. Particles were isolated, size fractioned, counted and submitted to morphological and chemical characterization. The constituting polymer was identified by infrared microspectroscopy for particles >25 μm, and by pyrolysis coupled with gas chromatography mass spectrometry for those <25 μm. Method recoveries were between 87 and 83% and limits of quantitation (LOQs) were between 6.6 and 30.2 ng/g. Analyses showed that 70% of the sponges presented plastic contamination, with an average of 1.2 particles/g tissue for the 25-150 μm size range, and a total plastic concentration of up to 4.8 μg/g in the 0.2-25 μm size range, with polyolefin being the most represented polymer in both size ranges. Overall, the study demonstrated the reliability of the proposed analytical workflow and of the use of sponges as biosamplers for plastic particles., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Pollution from microplastics (MPs) needs to be evaluated by deploying reliable analytical techniques that provide qualitative and quantitative data on the extent of contamination in the various environmental matrices. Solvent extraction of MPs followed by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) provides data that not only regard the soluble plastics, but also the organic additives contained in MPs and the low-molecular weight degradation products of insoluble plastics. In this study, the potential of microwave-assisted solvent extraction and double-shot Py-GC-MS was investigated in order to obtain quali-quantitative information on polystyrene and on phthalate plasticizers in environmental samples. The method was validated and provided recoveries higher than 96 %, and detection limits lower than 1 ng and 1 μg for phthalates and polystyrene, respectively. We used the method to analyze samples of sand collected from a shoreline in Tuscany (central Italy) and thereby determine the content of phthalates and polystyrene at different depths and distances from the coastline. Qualitative data were also obtained regarding the presence of oxidation products derived from polyethylene and polypropylene. The different contents of plasticizers, plastics, and degradation products in the investigated samples are discussed in relation to how environmental agents affect the leaching and degradation processes of the polymers., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Environmental pollution associated to plastic debris is gaining increasing relevance not only as a threat to ecosystems but also for its possible harmful effects on biota and human health. The release of toxic volatile organic compounds (VOCs) is a potential hazard associated with the environmental weathering of plastic debris. Artificial aging of reference polymers (polystyrene, polypropylene, polyethylene terephthalate, high and low density polyethylene) was performed in a Solar Box at 40 °C and 750 W/m 2 . The volatile degradation products were determined before and after 1, 2, 3 and 4 weeks of aging using a validated analytical procedure combining headspace (HS) with needle trap microextraction (NTME) and gas chromatography/mass spectrometry (GC-MS). A progressive increase in VOCs was observed during artificial photo-degradation, whose chemical profile resulted polymer-dependent and included carbonyls, lactones, esters, acids, alcohols, ethers, aromatics. The amount of extractable fraction in polar solvents generally showed a similar trend. The same analytical procedure was used to determine VOCs released from plastic debris collected at a marine beach. All samples released harmful compounds (e.g. acrolein, benzene, propanal, methyl vinyl ketone, and methyl propenyl ketone), supporting the initial hypothesis that microplastics represent an unrecognized source of environmental pollution., Competing Interests: Declaration of Competing Interest None., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This work presents a method to characterize high molecular esters in beeswax and resinous substances based on the use of microwave-assisted extraction and flow injection analysis-high resolution mass spectrometry that combines the high efficiency of the extraction procedure with the advantages of high resolution mass spectrometry. This approach allows us to identify archaeological beeswax and plant resinous substances by the characterization of the survived intact high molecular weight components. By this way, several raw materials (beeswax, pine resin and pitch, and resin extracted from Euphorbia tirucalli) were studied and used as reference substances. The procedure was then tested on an adhesive dated 44-42 ka BP recovered from Border Cave (KwaZulu-Natal, Africa), allowing us to detect the high molecular weight species even after almost 50,000 years, and then used to chemically investigate unknown archaeological adhesives from Antinoopolis (Egypt), dated to the 4th-5th century AD. The results allowed us to extend our knowledge on the long-term behavior of beeswax and resinous substances., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A fast non-destructive approach based on the use of portable selected ion flow tube-mass spectrometry (SIFT-MS) was used for the first time to characterize organic materials in archaeological artifacts. The high sensitivity, specificity and selectivity SIFT soft chemical ionization mass spectrometry enabled us to investigate the composition of organic residues collected from ancient Egyptian findings in order to demonstrate the robustness of the techniques with different matrices. In addition, we tested SIFT-MS directly on an archaeological Egyptian amphora to prove its suitability as a completely non-invasive technique. Parallel investigations on all the samples were performed by GC/MS analysis to correlate and confirm the data obtained by SIFT-MS. The possibility of using a portable mass spectrometer on an excavation site or in a museum would be a significant step forward in the non-invasive analysis of organic archaeological materials, enabling archeologists and conservators to obtain real-time information on the molecular composition of organic residues., (Copyright © 2019 Elsevier B.V. All rights reserved.)

We propose a new analytical method using reverse phase High performance liquid chromatography (HPLC) coupled through an electrospray source with a tandem quadrupole-time-of-flight (ESI-Q-ToF) mass spectrometric detector for the full characterization and quantitation of the different classes of fatty acids and acylglycerols in lipid samples in a single chromatographic run. In this work, we optimized the derivatization reaction for free fatty acids with 2-hydrazinoquinoline, which is a low-cost approach, using a full factorial design. This reaction does not involve transesterification, thus enabling the free fatty acids to be separated and successfully quantified in the presence of mono-, di- and triacylglycerols without altering the whole glyceride profile. This new analytical method provides a full profile of fatty acids, mono-, di- and triglycerides within a relatively short chromatographic run (less than 40 min), with low operating back-pressure (less than 110 bar). The derivatization of the free fatty acids allows their detection in positive mode, with limits of detection in the range of 0.2-1.9 ng/g, and a dynamic range of two orders of magnitude. The figures of merit of the procedure are competitive with respect to the literature. The method was validated by characterizing two different types of olive oils. Free fatty acid content was quantified, and the results are consistent with literature data. The method was applied to the characterization of cow milk and an infant formula, after the precipitation of proteins and phospholipids, and proved suitable for the detection of short chain fatty acids, free fatty acids and glycerides highlighting differences in the composition of the two milks. The proposed procedure improves the current methods for the analysis of acylglyceride based materials, such as olive oil, and proved promising for the characterization of lipids in complex matrices, such as milk., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this paper we present a new analytical GC/MS method for the analysis of mixtures of free fatty acids and metal soaps in paint samples. This approach is based on the use of two different silylating agents: N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and 1,1,1,3,3,3-hexamethyldisilazane (HMDS). Our experimentation demonstrated that HMDS does not silylate fatty acid carboxylates, so it can be used for the selective derivatization and GC/MS quantitative analysis of free fatty acids. On the other hand BSTFA is able to silylate both free fatty acids and fatty acids carboxylates. The reaction conditions for the derivatization of carboxylates with BSTFA were thus optimized with a full factorial 3 2 experimental design using lead stearate and lead palmitate as model systems. The analytical method was validated following the ICH guidelines. The method allows the qualitative and quantitative analysis of fatty acid carboxylates of sodium, calcium, magnesium, aluminium, manganese, cobalt, copper, zinc, cadmium, and lead and of lead azelate. In order to exploit the performances of the new analytical method, samples collected from two reference paint layers, from a gilded 16th century marble sculpture, and from a paint tube belonging to the atelier of Edvard Munch, used in the last period of his life (1916-1944), were characterized., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Lipid binders have traditionally been determined in paintings by using gas chromatography/mass spectrometry (GC/MS) to identify the characteristic profiles and ratios of fatty acids . However, the presence of mixtures in contemporary and modern oil paints makes the GC/MS determination of fatty acids insufficient to fully characterize the lipid binding media. In this study we prove that triacylglycerol (TAG) profiling by high-performance liquid chromatography with high-resolution tandem mass spectrometry, using ESI in positive and negative ionization modes is highly effective. We exploited this analytical approach to study the curing and degradation processes undergone by six plant oils used in the formulation of media in modern paints, using both natural and artificial ageing experiments. We believe that is the first time that a negative ionization mode has been applied for this purpose and that a survey with HPLC-ESI-Q-ToF has been carried out to study the ageing kinetics of plant oils. TAG profiling enabled us to study the evolution over time of the constituents of modern oils, with respect to curing and ageing. The data analyzed in this study demonstrate that our approach is efficient to study the oxidation of TAGs during ageing. The data also improve current knowledge on the properties of vegetable oils, which could lead to the development of new paint materials and conservation treatments for modern and contemporary works of art., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In the occasion of the celebrations for the 150th anniversary of the founding of Italy (1861-2011), it was decided to analyse the artwork "The Italian Flag" (La Bandiera Italiana) created by the artist Fernando Melani (Pistoia, 1907-1985), one of the precursors of the Poor Art artistic movement in Italy. This project is a follow-up to a previous study which was mainly focused on the pigments and dyes found in his home-studio. The main goal of this paper is to identify a correct diagnostic plan, based on the use of a combination of non-invasive and micro-invasive methodologies, in order to determine the state of preservation and define the best conservation procedures for a contemporary artwork. Visible, infrared and infrared false colour images as well as the Fibre Optic Reflectance Spectroscopy (FORS) technique were applied in situ to analyse The Italian Flag. Laser Induced Breakdown Spectroscopy (LIBS), Fourier Transform Infrared (FT-IR) and micro-Raman spectroscopies, Pyrolysis-Gas Chromatography/Mass Spectroscopy (Py-GC/MS), High Performance Liquid Chromatography with Diode Arrays Detection (HPLC-DAD) and Mass Spectrometric Detection (HPLC-ESI-Q-ToF) were all applied to three small samples detached from the three painted (green-blue, white and red-yellow, respectively) areas of the flag. The combination of the data obtained with all these techniques made possible a comprehensive understanding of both the chemical composition and physical behaviour of the materials used by the artist and supported curators in defining the preventive conservation of this artwork., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Modern oil paints, introduced at the beginning of the 20th century, differ from those classically used in antiquity in their chemical and compositional features. The main ingredients were still traditional drying oils, often used in mixtures with less expensive oils and added with several classes of additives. Consequently, detailed lipid profiling, together with the study of lipid degradation processes, is essential for the knowledge and the conservation of paint materials used in modern and contemporary art. A multi-analytical approach based on mass spectrometry was used for the study of original paint materials from Munch's atelier, owned by the Munch Museum in Oslo. The results obtained in the analysis of paint tubes were compared with those obtained by characterizing a paint sample collected from one of the artist's sketches for the decoration of the Festival Hall of the University of Oslo (1909-1916). Py-GC/MS was used as screening method to evaluate the presence of lipid, proteic or polysaccaridic materials. GC/MS after hydrolysis and derivatization allowed us to determine the fatty acid profile of the paint tubes, and to evaluate the molecular changes associated to curing and ageing. The determination of the fatty acid profile is not conclusive for the characterization of complex mixtures of lipid materials, thus the characterization of the triglyceride profiles was performed using an analytical procedure based on HPLC-ESI-Q-ToF. This paper describes the first application of HPLC-ESI-Q-ToF for the acquisition of the triglyceride profile in a modern paint sample, showing the potentialities of liquid chromatography in the field of lipid characterization in modern paint materials. Moreover, our results highlighted that the application of this approach can contribute to address dating, authenticity and conservation issues relative to modern and contemporary artworks., (Copyright © 2015. Published by Elsevier B.V.)

Alkyd resins have been commonly used as binders in artist paints since the 1940s. The characterization of alkyds in samples from artworks can help to solve attribution and dating issues, investigate decay processes, and contribute to the planning of conservation strategies. Being able to assess the components of industrially formulated paint materials and to differentiate between different trademarks and producers is extremely interesting and requires multi-analytical approaches. In this paper we describe the characterization of commercial alkyd paint materials using a multi-analytical approach based on the integration of three different mass spectrometric techniques: gas chromatography-mass spectrometry (GC/MS), high performance liquid chromatography coupled with electrospray ionization mass spectrometry with a tandem quadrupole-time of flight mass spectrometer (HPLC-ESI-Q-ToF), and flow injection analysis (FIA) in the ESI-Q-ToF mass spectrometer. GC/MS was successful in determining the fatty acid and aromatic fractions of the resins after hydrolysis; HPLC-ESI-Q-ToF analysis enabled us to identify the triglycerides (TAGs) and diglycerides (DAGs) profile of each resin, and FIA analysis was used as a rapid method to evaluate the presence of possible additives such as synthetic polymers., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A new method for the analysis of triglycerides (TAGs) in vegetable oils was developed using a Poroshell 120 EC-C18 column (3.0 mm×50 mm, 2.7 μm) with a high resolution ESI-Q-ToF tandem mass spectrometer as detection system. We used an Agilent Poroshell column, which is characterized by a recently developed stationary phase based on non-porous core particles. The results highlighted the advantages of this column in terms of the dramatic improvement in the number of theoretical plates and in low column backpressure. The developed method enabled us to analyze complex mixtures of more than 40 TAGs within less than 25 min and with a low backpressure (lower than 100 bar), and represents the first application of a core-shell stationary phase in reverse phase HPLC using an ESI-Q-ToF as detection system. The method was optimized on standards of TAGs, validated and applied to several plant oils. By a quantitative point of view, the method showed a very good linearity (r(2)>0.999) in the range 0.1-2.4 μg/g; high intra- and inter-day precision both in terms of retention times (RSD%<0.04%) and peak areas (RSD%<0.3%). Limits of detection and quantitation were lower than 0.03 μg/g and 0.10 μg/g, respectively., (Copyright © 2013 Elsevier B.V. All rights reserved.)