Optimization of a miniaturized solid-phase microextraction method followed by gas chromatography mass spectrometry for the determination of twenty four volatile and semivolatile compounds in honey from Galicia (NW Spain) and foreign countries

An analytical miniaturized methodology based on solid-phase-microextraction (mini_SPME) followed by gas chromatography coupled to mass spectrometry (GC-MS) has been developed for the identification of volatile and semivolatile compounds in honey samples. The main influential experimental parameters, such as the type of fibre coating, extraction temperature, solvent addition, extraction mode, ionic strength, and sample dilution were optimized. A design of experiments (DOE) was conducted including twenty-four target compounds. The final extraction conditions comprised the use of 200 mg of honey mixed with 200 μL of water (100%, w/v), employing a DVB/CAR/PDMS fibre in the headspace mode at 100 °C for 30 min. The mini_SPME-GC-MS method was successfully validated in terms of linearity, repeatability, reproducibility and accuracy. Finally, it was applied to a broad range of varieties of real honey samples from Galicia (NW Spain), as well as some foreign honeys, demonstrating suitabilityThis research was supported by GO project FEADER 2018/054B. The authors belong to the National Network for the Innovation in miniaturized sample preparation techniques, RED2018-102522-T (Ministry of Science, Innovation and Universities, Spain), to the Galician Competitive Research Groups IN607B 2019/13 and ED431 2020/06 and to the CRETUS Strategic Partnership ED431 2018/01 (Xunta de Galicia)S

Evaluating the presence and contents of phytochemicals in honey samples: phenolic compounds as indicators to identify their botanical origin

Honey is a natural product well known for its beneficial properties. It contains phytochemicals, a wide class of nutraceuticals found in plants, including compounds with highly demonstrated antimicrobial and antioxidant capacities as phenolic compounds and flavonoids. The main goal of this work is the development of a miniaturized and environmentally friendly methodology to obtain the phenolic profile of Galician honeys (Northwest Spain) from different varieties such as honeydew, chestnut, eucalyptus, heather, blackberry and multi-floral. The total phenolic content (TPC) and antioxidant activity (AA) were also evaluated. As regards sample preparation, miniaturized vortex (VE) and ultrasound assisted extraction (UAE) employing aqueous-based solvents were performed. Individual quantification of 41 target phenolic compounds was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Results revealed the presence of 25 phenolic compounds in the 91 analyzed samples, reaching concentrations up to 252 µg g−1. Statistical tools such as analysis of variance (ANOVA) and principal component analysis (PCA) were employed to obtain models that allowed classifying the different honeys according to their botanical origin. Obtained results, based on TPC, AA and ∑phenolic compounds showed that significant differences appeared depending on the honey variety, being several of the identified phenol compounds being responsible of the main differentiationThis research was funded by project GO FEADER 2018/054B (Xunta de Galicia). The authors belong to the National Network for the Innovation in miniaturized sample preparation techniques, RED2018-102522-T (Ministry of Science, Innovation and Universities, Spain), and to the Galician Competitive Research Groups IN607B 2019/13 and ED431 2020/06 (Xunta de Galicia). This study is based upon work from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society. All these programmes are co-funded by FEDER (EU)S

Assessment of the bioaccessibility of PAHs and other hazardous compounds present in recycled tire rubber employed in synthetic football fields

Recycled tire crumb rubber (RTCR) surfaces contain harmful and carcinogenic substances, which can be ingested by the users of these facilities, mainly athletes and children. In this work, the potential in-vitro oral bioaccessibility of eighteen polycyclic aromatic hydrocarbons (PAHs) from RTCR employed as infill in synthetic football fields was studied in human synthetic body fluids (saliva, gastric, duodenal and bile), prepared according the Unified Bioaccessibility Method. Solid-phase extraction (SPE) using commercial sorbents and a new green material based on cork (cork industry by-product) were used to isolate the bioaccessible PAHs before gas chromatography-tandem mass spectrometry analysis. The method was optimized and validated attending the analytical figures of merit. The feasibility of cork biosorbent for the extraction of the compounds was demonstrated, as well as the suitability of the UBM method to perform the digestion with good precision. The application to real samples collected from football fields demonstrated the presence of 17 of the 18 target PAHs in the biofluids. Most volatile PAHs such as NAP, ACY, ACE, FLU, PHN and ANC, achieved the highest bioaccessibility percentage levels. The carcinogenic B[a]P was detected in 75 % of the samples at concentrations up to 2.5 ng g−1 (bioaccessible fraction). Children exposure assessment was carried out to identify potential risk. Other hazardous and environmentally problematic compounds such as N-(1,3-Dimethylbutyl)-N′-phenyl-p-phenylenediamine-quinone (6PPD-quinone), recently related with the dead of coho salmon, and hexamethoxymethylmelamine (HMMM), among others, were also detected. This is the first study in which the bioaccesibility from real crumb rubber samples of 15 out of the 16 PAHs considered as priority pollutants by the United States Environmental Protection Agency (EPA) and the presence of 6PPD-quinone and HMMM in the bioaccessible fractions is reportedThis research was supported by projects RETOS PID2019-104336RB-I00, UNST10-1E-491 and RED2018-102522-T (Ministry of Science and Innovation, Spain), and ED431 2020/06 and IN607B 2022/15 (Xunta de Galicia). This study is based upon work from the Sample Preparation Study Group and Network and upon work from the IUPAC project No. 2021-015-2-500. All these programs are co-funded by FEDER (EU)S

Global evaluation of the chemical hazard of recycled tire crumb rubber employed on worldwide synthetic turf football pitches

Social and environmental concern about the use of crumb rubber from end-of-life car tires in the construction of different sport and recreational facilities is increasing due to the presence of hazardous compounds. The aim of this research was the assessment of 42 organic chemicals, including polycyclic aromatic hydrocarbons (PAHs), phthalates, adipates, antioxidants and vulcanisation agents in a large number of infill samples (91) from synthetic turf football pitches of diverse characteristics and geographical origin. Samples were taken worldwide, in 17 countries on 4 continents, to show the global dimension of this problem. Ultrasound assisted extraction was employed to extract the target compounds, followed by gas chromatography coupled to tandem-mass spectrometry (UAE-GC–MS/MS). Seventy-eight crumb rubber samples as well as thirteen samples of alternatives materials, such as cork granulates, thermoplastic elastomers and coconut fibre, were analyzed. The results highlight the presence of all target PAH in most rubber samples at concentrations up to μg g−1, including the eight ECHA (European Chemicals Agency) PAHs considered as carcinogenic, and anthracene (ANC), pyrene (PYR) and benzo[ghi]perylene (B[ghi]P), catalogued as substances of very high concern (SVHC). Endocrine disruptors such as some plasticizers (mainly phthalates), and other compounds like benzothiazole (BTZ) and 2-mercaptobenzothiazole (MBTZ) were found reaching the mg g−1 level. This confirms the presence of the hazardous substances in the recycled crumb rubber samples collected all around the world. Three crumb rubber samples exceeded the limit of 20 μg g−1 for the sum of the eight ECHA PAHs. Regarding the chemical composition of other infill alternatives, cork appears to be adequate, while the thermoplastic elastomers contained high levels of some plasticizers. In addition, the plastic infill as well as the crumb rubber both are microplastics. Microplastics are considered contaminants of emerging concern since they do not biodegrade and remain in the environment for a long timeThis research was supported by projects RETOS PID2019-104336RB-I00 (Ministry of Science and Innovation, Spain) and UNST10-1E-491 (Infrastructure Program, Ministry of Science and Innovation, Spain). The authors belong to RED2018-102522-T (Ministry of Science, Innovation and Universities, Spain) and to the Galician Competitive Research Groups IN607B 2019/13 and ED431 2020/06 (Xunta de Galicia). This study is based upon work from COST Action CA16215 and from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society. All these programs are co-funded by FEDER (EU). This work was also financially supported by: (i) Base Funding UIDB/00511 2020 of the Laboratory for Process Engineering, Environment, Biotechnology and Energy (LEPABE), by national funds through the FCT/ MCTES (PIDDAC); (ii) Project SAFEGOAL (Ref. PTDC/EQU-EQU/28101/2017; POCI-01-0145-FEDER-028101), funded by FEDER funds through COMPETE2020 – Programa Operacional Competitividade e Internacionalização (POCI) and by national funds (PIDDAC) through FCT/ MCTES. N.R. thanks the Portuguese Foundation for Science and Technology (FCT) for the financial support of his work contract through the Scientific Employment Stimulus - Institutional Call - [CEECINST/00049/2018]S

Sonochemical degradation of triclosan in water and wastewater

The sonochemical degradation of 5 μg l−1 triclosan, a priority micro-pollutant, in various environmental samples (seawater, urban runoff and influent domestic wastewater) as well as in model solutions (pure and saline water) was investigated. Experiments were conducted with a horn-type sonicator operating at 80 kHz frequency and a nominal applied power of 135 W, while solid-phase microextraction coupled with gas chromatography–electron capture detector (SPME/GC–ECD) was employed to monitor triclosan degradation. The latter followed pseudo-first order kinetics with the rate constant being (min−1): 0.2284 for seawater > 0.1051 for 3.5% NaCl in deionised water > 0.0597 for centrifuged urban runoff ∼ 0.0523 for untreated urban runoff > 0.0272 for deionised water > 0.0063 for wastewater influent. SPME/GC–ECD and SPME coupled with gas chromatography–mass spectrometry (SPME/GC–MS) were also used to check for the formation of chlorinated and other toxic by-products; at the conditions in question, the presence of such compounds was not confirmedL.S.-P. and R.B. acknowledge the regional government Junta de Galicia for their doctoral and travel grantsS

Combined (d)SPE-QuEChERS Extraction of Mycotoxins in Mixed Feed Rations and Analysis by High Performance Liquid Chromatography-High-Resolution Mass Spectrometry

The objective of this work was the development of a methodology capable of simultaneously determine 26 mycotoxins in mixed feed rations collected in 20 dairy farms. A sample preparation methodology based on a combination of (d)SPE and QuEChERS extractions was used. Liquid chromatography-high resolution mass spectrometry was employed for both identification and quantification purposes. To this respect, a powerful workflow based on data-independent acquisition, consisting of fragmenting all precursor ions entering the mass spectrometer in narrow m/z isolation windows (SWATH), was implemented. SWATH data file then contains all the information that would be acquired in a multitude of different experimental approaches in a single all-encompassing dataset. Analytical method performance was evaluated in terms of linearity, repeatability and matrix effect. Relative recoveries were also measured, giving values above 80% for most compounds. Matrix-matched calibration was carried out and enabled reaching the low ng mL−1 level for many mycotoxins. The observed matrix effect, in most cases suppressive, reached even values higher than 60%. The repeatability was also adequate, showing a relative standard deviation lower than 10%. All unified samples analyzed showed co-occurrence of two or more mycotoxins, recurrently zearalenone, fumonisin B1, and β-zearalenol, with an occurrence frequency ranging from 60% to 90%This work was supported by the CONECTA-PEME GALAC project IN852A 2016/103. This work was also supported by the project IGDC13-1E-2026 (Infrastructure Program, MINECO, Spain). The authors belong to the Galician Competitive Research Groups GPC 2017/04 and GPC IN607B 2019/13, and to the CRETUS Strategic Partnership (ED431E 2018/01). All these programs are co-funded by FEDER (UE)S

Complementarity of two approaches based on the use of high-resolution mass spectrometry for the determination of multi-class antibiotics in water. Photodegradation studies and non-target screenings

The development of analytical methodologies to monitor different antibiotic families in water and the implementation of alternatives for their efficient elimination are a great challenge. The aim of this research was to develop a method based on solid-phase extraction followed by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry to analyse multi-class antibiotics, including macrolides, cephalosporins, fluoroquinolones, sulfonamides and diaminopyrimidines, in waters. Several parameters affecting the extraction such as the sample pH, type of sorbent and cartridge, elution volume and breakthrough volume were optimized. The method was validated in real samples, and matrix effect was assessed, demonstrating that the use of isotopically labelled surrogate compounds was mandatory to avoid standard addition calibration for each individual samples. Urban and hospital wastewater samples, as well as natural waters, were analysed, confirming the presence of 12 of the 14 target compounds at concentrations up to 3.5 µg L−1. Non-target analysis based on data-independent workflow was also performed, enabling the identification of 94 pollutants. Preliminary photodegradation experiments were also assessed, revealing the total removal of many target compounds after the first 5–10 min of UVC irradiation. In addition, 20 by-products formed after photolysis could be identified using a non-target approachOpen Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This research was supported by projects EQC2018-005011-P (Ministry of Science, Innovation and Universities, Spain) and IGDC-1E-2026 (Infrastructure Program, MINECO, Spain). The authors belong to the National Network for the Innovation in miniaturized sample preparation techniques, RED2018-102522-T (Ministry of Science, Innovation and Universities, Spain) and to the Galician Competitive Research Groups IN607B 2019/13 and ED431 2020/06 (Xunta de Galicia). This study is based upon work from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society. All these programmes are co-funded by FEDER (EU)S

Miniaturized matrix solid-phase dispersion for the analysis of ultraviolet filters and other cosmetic ingredients in personal care products

A method based on micro-matrix solid-phase dispersion (μ-MSPD) followed by gas-chromatography tandem mass spectrometry (GC–MS/MS) was developed to analyze UV filters in personal care products. It is the first time that MSPD is employed to extract UV filters from cosmetics samples. This technique provides efficient and low-cost extractions, and allows performing extraction and clean-up in one step, which is one of their main advantages. The amount of sample employed was only 0.1 g and the extraction procedure was performed preparing the sample-sorbent column in a glass Pasteur pipette instead of the classic plastic columns in order to avoid plastizicer contamination. Factors affecting the process such as type of sorbent, and amount and type of elution solvent were studied by a factorial design. The method was validated and extended to other families of cosmetic ingredients such as fragrance allergens, preservatives, plasticizers and synthetic musks, including a total of 78 target analytes. Recovery studies in real sample at several concentration levels were also performed. Finally, the green extraction methodology was applied to the analysis of real cosmetic samples of different natureThis research was supported by the project UNST10-1E-491 (Ministry of Science and Innovation, Spain). The authors belong to the Galician Competitive Research Group GPC2017/04 and to the CRETUS Strategic Partnership (ED431 2018/01). All these programs are co-funded by FEDER (EU)S

Development of a solid phase microextraction gas chromatography tandem mass spectrometry methodology for the analysis of sixty personal care products in hydroalcoholic gels ˗ hand sanitizers ˗ in the context of COVID-19 pandemic

Because of the coronavirus pandemic, hydroalcoholic gels have become essential products to prevent the spread of COVID-19. This research aims to develop a simple, fast and sustainable microextraction methodology followed by gas chromatography tandem mass spectrometry (GC-MS/MS) to analyze simultaneously 60 personal care products (PCPs) including fragrances allergens, synthetic musks, preservatives and plasticizers in hand sanitizers. Micro-matrix-solid-phase dispersion (μMSPD) and solid-phase microextraction (SPME) were compared with the aim of obtaining high sensitivity and sample throughput. SPME demonstrated higher efficiency being selected as sample treatment. Different dilutions of the sample in ultrapure water were assessed to achieve high sensitivity but, at the same time, to avoid or minimize matrix effect. The most critical parameters affecting SPME (fibre coating, extraction mode and temperature) were optimized by design of experiments (DOE). The method was successfully validated in terms of linearity, precision and accuracy, obtaining recovery values between 80 and 112% for most compounds with relative standard deviation (RSD) values lower than 10%. External calibration using standards prepared in ultrapure water demonstrated suitability due to the absence of matrix effect. Finally, the simple, fast and high throughput method was applied to the analysis of real hydroalcoholic gel samples. Among the 60 target compounds, 39 of them were found, highlighting the high number of fragrance allergens, at concentrations ranging between 0.01 and 217 μg g−1. Most of the samples were not correctly labelled attending cosmetic Regulation (EU) No 1223/2009, and none of them followed the World Health Organization (WHO) recommendation for hand sanitizers formulationThis work was supported by projects UNST10-1E-491 (Infrastructure Program, Ministry of Science and Innovation, Spain) and ED431 2020/06 (Consolidated Research Groups Program, Xunta de Galicia). The authors belong to the National Network for the Innovation in miniaturized sample preparation techniques, RED2018-102522-T (Ministry of Science, Innovation and Universities, Spain). This study is based upon work from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society, and upon work from the IUPAC project No. 2021-015-2-500 ‘Greenness of official standard sample preparation methods”. All these programmes are co-funded by FEDER (EU)S

Extraction of bioactive polyphenols from grape marc by a matrix solid-phase dispersion method

A matrix solid-phase dispersion process to extract polyphenols from grape marc, a winemaking byproduct, has been optimized by Response Surface Methodology. The dependent variables evaluated were the total polyphenols content, flavanols, hydrocynnamates, and flavonoids. The performance of the extraction method in terms of linearity and precision has also been assessed. The optimized MSPD method provides good results to extract polyphenols from white winemaking byproducts, much less studied than those from red wines, requiring low solvent consumption and being low cost and fast (15 min). The analytical instrumentation is available almost everywhere, thus becoming a ready-to-use methodology for virtually any control or winery laboratory. The optimized method has been applied to a set of bagasse samples from Albariño grapes (Vitis vinifera sp) cultivated in Galicia (NW Spain) and coming from five different types of grapevine training techniques. The vine training factor was significant on the basis of the content of the different groups of polyphenols determined in the MSPD extract