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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 approach Open 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) SI

Different groups of emerging pollutants (EPs) were identified (drugs, pesticides, hormones, illicit drugs, and fire retardant), and the removal of four antibiotics was determined (sulfamethoxazole 62.2–94.4%, ciprofloxacin 71–83.1%, norfloxacin 82–89%, and ofloxacin 78–97.9%) in a municipal wastewater treatment plant (WWTP) in Acapulco, Gro. Mexico. The compounds were extracted from influent and effluent samples by solid phase extraction (SPE). The identification of non-target EPs was performed by liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS). The antibiotic quantification was performed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Most of the non-target compounds were detected only in the influent samples. Antibiotics levofloxacin and nalidixic acid, the anticonvulsants carbamazepine and oxycarbamazepine, the local anesthetic lidocaine, and the pesticide tridemorph were the main EPs not removed by the WWTP. In this study, it was shown that the Aguas Blancas WWTP does not manage to remove 100% of the various EPs identified in the effluent, although the elimination degree is high in most cases, despite being one of the model plants in Mexico. HIGHLIGHTS Different groups of emerging pollutants (EPs) were identified.; Detection of non-target compounds.; Removal of four antibiotics (sulfamethoxazole, ciprofloxacin, norfloxacin, and ofloxacin).; The study was carried out in a model plant in Mexico.; The non-target analysis was able to detect pesticides included in the highly dangerous pesticides (PAP) list.

Nowadays concern exists about the safety for both football players and the environment of recycled tire rubber used as infill in synthetic turf football pitches. In this study 40 target compounds, including polycyclic aromatic hydrocarbons (PAHs), plasticizers, antioxidants and vulcanization agents were determined in 50 synthetic football pitches of diverse characteristics to estimate environmental risks. This is the first study of crumb rubber sport facilities in Portugal. Analyses were performed by ultrasound-assisted extraction followed by gas chromatography-tandem mass spectrometry (UAE-GC-MS/MS). To evaluate the transfer of the target chemicals from the crumb rubber to the runoff water, water leachates collected from several football pitches were analyzed by solid-phase microextraction (SPME-GC-MS/MS). In addition, lab-scale runoff simulation experiments were performed to assess whether a persistent inflow of the target compounds from the football pitches into the runoff water wcould exist. Results revealed the presence of most of the target PAHs in crumb rubber at total concentrations up to 57 μg g−1, next to a high number of plasticizers and vulcanization agents. Runoff water collected from the football pitches contained up to 13 PAHs as well as other chemicals of environmental concern. In addition, continuous leaching of chemicals from the crumb rubber to the surrounding water was demonstrated. The transfer of target chemicals into the runoff water poses a potential risk for the aquatic environment.

Crumb rubber obtained from scrap tires is greatly employed for the construction of different facilities for sport, recreational and other uses. However, in recent years the concern about their safety and the related adult and children exposure to these surfaces is growing. This study aims a thorough chemical characterization encompassing 42 hazardous compounds, including polycyclic aromatic hydrocarbons (PAHs), phthalates, adipates, antioxidants and vulcanization agents in a wide range of crumb rubber from different surfaces. For the extraction of the target compounds, a method based on ultrasound-assisted extraction followed by gas chromatography-tandem mass spectrometry (UAE-GC–MS/MS) has been validated. Forty crumb rubber samples coming from synthetic turf football pitches, outdoor and indoor playgrounds, urban pavements, commercial tiles and granulates, and scrap tires, were analyzed. In addition, green alternative materials, such as sand and artificial turf based on cork granulate infill were included to compare the levels of the target compounds with those of crumb rubber. Most of the analyzed recycled surfaces meet the recent limits proposed by the European Commission for rubber granulates and mulches, although they exceed in several cases the maximum levels allowed for rubber consumer products. Besides, most of the other target compounds, including several of them considered as endocrine disruptors, were detected in the analyzed samples, reaching parts per million concentrations.

A rapid environmental pollution screening and monitoring workflow based on fabric phase sorptive extraction-gas chromatography-tandem mass spectrometry (FPSE-GC-MS/MS) is proposed for the first time for the analysis of 17 widespread used fungicides (metalaxyl, cyprodinil, tolylfluanid, procymidone, folpet, fludioxonil, myclobutanil, kresoxim methyl, iprovalicarb, benalaxyl, trifloxystrobin, fenhexamid, tebuconazole, iprodione, pyraclostrobin, azoxystrobin and dimethomorph) in environmental waters. The most critical parameters affecting FPSE, such as sample volume, matrix pH, desorption solvent and time, and ionic strength were optimized by statistical design of experiment to obtain the highest extraction efficiency. Under the optimized conditions, the proposed FPSE-GC-MS/MS method was validated in terms of linearity, repeatability, reproducibility, accuracy and precision. To assess matrix effects, recovery studies were performed employing different water matrices including ultrapure, fountain, river, spring, and tap water at 4 different concentration levels (0.1, 0.5, 1 and 5 µg/L). Recoveries were quantitative with values ranging between 70-115%, and relative standard deviation values lower than 14%. Limits of quantification were at the low ng/L for all the target fungicides. Finally, the validated FPSE-GC-MS/MS method was applied to real water samples, revealing the presence of 11 out of the 17 target fungicides.

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 time This 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] SI

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 formulation This 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) SI

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 reported This 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) SI

A fast, efficient, and simple air sampling methodology was developed to study a high number of volatile and semivolatile organic compounds in air above tire rubber materials and surfaces made of recycled tire rubber. The proposed method, based on active sampling (solid-phase extraction, SPE) using a small quantity of sorbent material (25 mg) followed by solid-phase microextraction (SPME) and gas chromatography-tandem mass spectrometry analysis, was developed with the aim of determining 40 organics substances including polycyclic aromatic hydrocarbons (PAHs), plasticizers, antioxidants, and vulcanization agents. An experimental design was carried out to study the influence of main factors such as type of SPME fibre, solvent addition, headspace volume, stirring, as well as the factor interactions. Method performance showed good linearity in a broad concentration range (0.05 to 200 ng m−3, for most compounds), with coefficients of determination (R2) higher than 0.9900. Whole method precision (≤ 16 %) and accuracy were also satisfactory, obtaining quantitative recoveries (mean values between 80 and 110 % in most cases). Limits of detection and quantification have also been calculated, yielding values of sub ng m−3 for most compounds. The validated method was applied to outdoor and indoor air environments including playgrounds, football pitches and warehouses showing the presence of most target compounds in the samples achieving high levels for some PAHs (concentrations up to 51 ng m−3), benzothiazole (BTZ), diisobutyl- dibutyl- and di-(2-ethylhexyl)- phthalate, among others, reaching concentrations up to hundreds of ng m−3 (BTZ). This is the first time that the combination of techniques SPE and SPME is applied for these families of chemicals, and it is also the first time that this approach is proposed for the simultaneous multiclass compound extraction of substances of different chemical families. The whole sampling and extraction procedure is performed in a short period of time (61 min) allowing high throughput. The elimination of the use of organic solvents and waste generation by using only 25 mg of sorbent and a SPME fibre than are both reused makes the method sustainable and in consonance with the principles of the green chemistry. The method can be implemented in any routine lab and easily automated using a SPME autosampler This research was supported by projects RETOS PID2019-104336RB-I00 and UNST10-1E-491 (Ministry of Science and Innovation, Spain) and ED431 2020/06 and IN607B 2019/13 (Xunta de Galicia). The authors belong to the National Network for the Innovation in miniaturized sample preparation techniques, RED2018-102522-T. 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 programs are co-funded by FEDER (EU) SI

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 differentiation This 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) SI

Microwave-assisted extraction (MAE) is a well-established automated green extraction technique, offering many advantages such as the combined reduction of the extraction time, solvent and energy consumptions, as well as the possibility of performing simultaneous multiple extractions, thus increasing the number of samples processed daily. This review provides a comprehensive description of the most relevant analytical methods and applications, proposed from year 2012, for the extraction of selected emerging pollutants, including pharmaceuticals and veterinary drugs, personal care products, as well as industrial contaminants, in environmental matrices. The novel developments and last technological trends such as the implementation of organic solvent-free extraction methods, the use of surfactants and ionic liquids, the combination with microextraction approaches or the introduction of systems that sequentially process the samples, are also addressed. Overall, MAE appears to be an excellent alternative for the determination of emerging organic pollutants, thereby enabling its application within the regulatory environmental field.

Photostability of three synthetic dyes (Carmoisine, CI 14720; Allura Red AC, CI 16035; and Patent Blue V, CI 42051) commonly used in mouthwashes was investigated for the first time. Aqueous solutions of dyes and commercial mouthwashes were submitted to simulated outdoor and indoor conditions of irradiation. All dyes demonstrated high stability in aqueous solutions but discolouration was observed in commercial products after irradiation, highlighting a strong effect of matrix composition on the dyes stability. The photochemical behaviour of dyes corresponded to a first-order reaction. Degradation half-life times of Carmoisine, Allura Red AC, and Patent Blue V under solar standard conditions of irradiation were 18.4 ± 3.3, 11.9 ± 1.6, and 6.6 ± 1.2 h respectively, for 5.0 μg mL−1 of dye spiked in a blank matrix (a mouthwash without the presence of dyes among the ingredients). Factors potentially affecting the photostability, such as temperature and the presence of oxygen, also were studied.

Solid-phase microextraction is a well-established green solvent free extraction technique with a large number of applications in different fields such as food, forensic, biomedical, and the environment. The present review comprehensively describes the most recent applications mostly reported from 2013 of SPME for the extraction of environmental pollutants including persistent organic pollutants (POPs), pesticides, and emerging pollutants such as pharmaceuticals and personal care products (PPCPs), in different environmental matrices. This review also covers the last technological developments including the use of novel extraction coatings (MOFs, CNTs, ILs), formats (e.g. TFSE), approaches (e.g. vacuum, cold fiber, and in-tube SPME), and on-site devices. The hyphenation of SPME with other techniques, especially mass spectrometry will be described, as well. The usefulness of SPME to follow (photo)degradation studies, both in target and non-target analysis, as well as to determine some of the physicochemical parameters governing the pollutant fate in the environment is also illustrated through different examples.

An effective, quick and sustainable air analysis method was developed to analyse 41 volatiles and semi volatile organic compounds present in tire rubber and crumb rubber materials. The proposed method, based on active sampling using a sorbent material followed by an ultrasound assisted extraction, was developed with the aim of obtaining a fast and simple procedure to determine polycyclic aromatic hydrocarbons, plasticizers, antioxidants and vulcanisation agents in air. A small amount of sorbent (25 mg) was used, and the analytes were recovered in only 1 mL of solvent. An experimental design was applied to study the influence of main factors such as type of sorbent and type of solvent, extraction technique (ultrasound assisted extraction and vortex extraction), extraction time, as well as the factor interactions. Under optimal conditions, no breakthrough occurs in the studied interval (up to 4 m3 ). Linearity was demonstrated in a wide concentration range. Accuracy of the total sampling-extraction analysis was evaluated obtaining satisfactory recoveries as well as good precision. The method was successfully applied to different outdoor and indoor air environments, including a recycled rubber synthetic turf football pitch. This article is protected by copyright. All rights reserved.

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 suitability This 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) SI

Although there are several works in the literature that study the presence of pharmaceuticals and personal care products (PPCPs) in surface waters, the vast majority focus their attention on pharmaceuticals and little information is found about personal care products (PCPs). Therefore, this study focused, for the first time, on the monitoring of five classes of PCPs - fragrance allergens, synthetic musks, phthalates, antioxidants, and ultraviolet-filters - in the surface water of four small-size typically pollution-impacted Portuguese rivers (Ave, Leça, Antuã and Cértima). A solid-phase microextraction (SPME) followed by gas chromatography - tandem mass spectrometry (GC-MS/MS) protocol was employed to analyse surface water samples collected in two seasonal campaigns - summer and winter (34 samples per season). A total of 22 out of 37 target PCPs were detected concomitantly at least once in one sampling point, being the most frequently detected α-isomethyl ionone, galaxolide, tonalide and cashmeran. The highest concentrations were confirmed for diethylhexyl phthalate (610.6 ng L

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&minus, 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 &beta, zearalenol, with an occurrence frequency ranging from 60% to 90%.

A simple methodology based on vortex extraction (VE) followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) has been developed for the simultaneous analysis of 22 regulated preservatives and synthetic dyes in cosmetics. The extraction procedure was performed in an Eppendorf tube allowing both extraction and clean-up in a single step, reducing sample and reagents consumption, and resulting in an effective and quick extraction. The method exhibited good linearity (R2 ≥ 0.9918) and intra and inter-day precision (%RSD ≤ 13) with LOQs lower than 0.587 µg g−1 for preservatives and 3.437 µg g−1 for synthetic dyes. Quantitative recoveries were obtained at four concentration levels in the range 2–100 µg g−1 in the cosmetic matrices. The method was successfully applied to a broad range of cosmetics, including both leave-on and rinse-off products in which 13 of the target compounds could be quantified at concentrations ranging from 0.39 to 442 µg g−1 in the case of dyes, and from 1.89 to 1335 µg g−1 for the preservatives. It can be highlighted the presence of parabens in 24 out of the 35 analyzed samples at concentrations higher than 1000 µg g−1 in a toothpaste.

Due to the high concern generated in the last years about the safety of recycled tire rubber used for recreational sports surfaces, this study aims at evaluating the presence of forty organic compounds including polycyclic aromatic hydrocarbons (PAHs), phthalates, adipates, vulcanisation additives and antioxidants in recycled tire crumb of synthetic turf football fields. Ultrasound Assisted Extraction (UAE) was successfully employed to extract the target compounds from the crumb rubber, and analysis was performed by gas chromatography-mass spectrometry (GC-MS). The transfer of the target chemicals from the crumb rubber to the runoff water and to the air above the rubber surface has also been evaluated employing solid-phase microextraction (SPME). Samples from fifteen football fields were analysed, and the results revealed the presence of 24 of the 40 target compounds, including 14 of the 16 EPA PAHs, with total concentrations up to 50 μg g−1. Heavy metals such as Cd, Cr and Pb were also found. A partial transfer of organic compounds to the air and runoff water was also demonstrated. The analysis of rain water collected directly from the football field, showed the presence of a high number of the target compounds at concentrations reaching above 100 μg L−1. The environmental risk arising from the burning of crumb rubber tires has been assessed, as well, analysing the crumb rubber, and the air and water in contact with this material, showing a substantial increase both of the number and concentration of the hazardous chemicals.

This work assesses different advanced oxidation processes (AOPs) for the elimination of 3 UV filters, ensulizole (PBSA), benzophenone-4 (BP-4) and benzophenone-3 (BP-3), in concentrations of few micrograms per liter, from synthetic and real swimming pool waters. AOPs experiments were performed in a lab-scale tubular photoreactor irradiated by UVA (λ = 360 nm) or UVC (λ = 254 nm) light. First, UVA heterogeneous photocatalysis using cellulose acetate monolithic structures coated with thin films of commercial Fe2O3 and TiO2 (P25, PC105, and PC500) nanoparticles were employed. The highest removal efficiencies values for PBSA (44%), BP-4 (90%) and BP-3 (91%) using synthetic swimming pool waters, after 30 min of irradiation, were achieved using TiO2-P25 (3 dips). The addition of H2O2 to the TiO2-P25/UVA and Fe2O3/UVA systems improved substantially the reaction rate, especially for the TiO2-P25/UVA system. The second approach consisted in the photochemical oxidation of the UV filters using a UVC/H2O2 system. The optimal H2O2 concentration obtained was 0.59 mM, resulting in removal efficiencies of 77%, 98% and 95% for PBSA, BP-4, and BP-3, respectively, after 6 min of irradiation, with photolysis half-lifes lower than 3 min. UVC (λ = 254 nm) and UVA (λ = 360 nm) photolysis showed lower degradation rates for the three target compounds when compared with the AOPs tested. Finally, heterogeneous TiO2-P25/UVA photocatalysis and photochemical UVC/H2O2 oxidation systems, under their optimal conditions, were applied to the treatment of real swimming pool waters containing simultaneously the three UV filters, reaching a complete degradation ( 50% for the recalcitrant PBSA in less than 6 min. Although several by-products, including chlorinated compounds, were identified during the oxidation process, its abundance was substantially decreased for extended period of reaction time.

Seventeen fungicides were determined in different matrices from vineyard areas, including vine leaves, soils, grapes and water, using gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). For leaf analysis, ultrasound-assisted extraction (UAE) was performed evaluating different solvents. UAE was compared with other extraction techniques such as vortex extraction (VE) and matrix solid-phase dispersion (MSPD). The performance of the UAE method was demonstrated on vine leaf samples and on other types of samples such as tea leaves, underlining its general suitability for leaf crops. As regards other matrices, soils were analyzed by UAE and microwave-assisted extraction (MAE), grapes by UAE and waters by SPE using cork as the sorbent. The proposed method was applied to 17 grape leaf samples in which 14 of the target fungicides were detected at concentrations up to 1000 μg g−1. Furthermore, the diffusion and transport of fungicides was demonstrated not only in crops but also in environmental matrices.

A dumbbell-shaped stir bar adsorbent of MIL-101 entrapped in PVA cryogel coated with poly(3,4-ethylenedioxythiophene) was fabricated to extract synthetic phenolic antioxidants in foodstuffs. The interconnected porous of cryogel allowed the entrapment of MIL-101 and enhanced the surface areas of poly(3,4-ethylenedioxythiophene) coating which facilitated multiple adsorptions. The fabricated adsorbent was characterized and measured the adsorption capacities for synthetic phenolic antioxidants. Extraction efficiency was optimized by evaluating the effect of adsorbent compositions, extraction time, stirring speed, sample pH, desorption conditions, sample volume and ionic strength. The analysis of extracted synthetic phenolic antioxidants was carried out using high performance liquid chromatography. The developed analysis method provided a wide linear range of 0.20 - 200 µg kg−1 for butylated hydroxyanisole and 0.50 - 200 µg kg−1 for tert‑butylhydroquinone and butylated hydroxytoluene. The limits of detection were between 0.05 and 0.15 µg kg−1. The developed stir bar adsorbent was utilized to extract these three synthetic phenolic antioxidants from juice, milk, infant formula and coffee creamer. Recoveries ranged from 87 to 101% with RSDs below 7%. The developed composite stir bar adsorbent was convenient to use, and good physical and chemical stability allowed efficient extraction for 12 extraction cycles.

Recycled crumb rubber (CR) is rich in compounds with unrecognized toxic potency; this study aims at the development of an analytical method that would allow identification and quantification of a very wide range of organic compounds extractable from the complex rubber matrix. The analytical set-up includes target analysis of polycyclic aromatic hydrocarbons (PAHs) and methyl-PAHs and suspect screening of raw extracts to tentatively identify primary organic compounds present, but not included in the standard target analysis of recycled rubber, followed by analytical method development and target analysis of identified compounds. Analyzed samples included weathered and new CR originating from football turf granulates, rubber mats, and end-of-life car tires (ELTs). The developed analytical method involves sonication extraction, followed by solid phase extraction (SPE) fractionation that enables simple and efficient separation of analytes with broad polarity scale. The application of SPE fractionation resolves coelution problems and simplifies the chromatograms. This analytical approach allowed to identify and quantify 46 sample specific compounds, including several heterocyclic PAHs like 2-methylthiobenzothiazole, benzonapthothiophenes, benzonaphthofuranes and aromatic amines like diphenylamine and N-phenyl-2-naphthylamine, which to our knowledge were not determined before. The PAHs concentrations determined in CR tiles purchased in Dutch and Spanish shops exceed the EU limits for articles marketed for use by the public. Furthermore, sets of methylated PAHs, dibenzothiazoles and aromatic amines were identified and quantified, and several other compounds were tentatively identified. The obtained results stress the need for expanding the list of target compounds analyzed in CR and the need for longitudinal studies on weathering processes taking place in CR SI

The photodegradation behaviour for nine widespread fungicides (benalaxyl, cyprodinil, dimethomorph, fenhexamide, iprovalicarb, kresoxim-methyl, metalaxyl, myclobutanil and tebuconazole) was evaluated in different types of water. Two different systems, direct UV photolysis and UVC/H2O2 advanced oxidation process (AOP), were applied for the photodegradation tests. For the monitoring of the target compound degradation, a method based on direct injection liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed. Several fungicide photodegradation by-products were tentatively identified by high-resolution mass spectrometry (HRMS) as well. For the photolysis studies, the efficiency of different types of radiation, UVC (lambda = 254 nm) and UVA (lambda = 365 nm), was compared. UVC photolysis provided the highest removal with a complete degradation for fenhexamide and kresoxim-methyl, and percentages between 48 and 78% for the other compounds, excluding iprovalicarb and myclobutanil with removals

Three methodologies based on miniaturized solvent extraction: vortex extraction (VE), ultrasound-assisted extraction (UAE), and matrix solid-phase dispersion (MSPD), were optimized for the gas chromatography-tandem mass spectrometry analysis of seven regulated oxidative hair dyes, including some of the most frequently used sensitizers in hair products (resorcinol, RL; 1-naphthol, 1NL), as well as their banned isomers (hydroquinone, HQ; 2-naphthol, 2NL). The use of MS/MS in combination with GC is a valuable approach that had not been applied before in the analysis of the considered compounds in hair dyes formulations. Parameters influencing the extraction efficiency were optimized for the three sample preparation techniques employing real sample. 0.1 g of sample and 1 mL of organic solvent were used in all cases, which reduced the solvent consumption compared to other methods proposed in literature. Under the optimal selected conditions, three methods were validated. Good linearity (R2 ≥ 0.991, %RSD ≤ 10) was achieved in a broad range of concentrations. In general, quantitative recoveries were obtained in real samples spiked at low, medium and high concentration levels using the three extraction techniques (ranged from 71.4 to 118% with exceptions). Good method precision (%RSD ≤ 14) and LOQ ≤ 0.13 μg g− 1 were achieved in all cases. Results demonstrated that the three methods could be implemented indistinctly. In the commercial hair dye formulations analyzed, all investigated compounds but 2-naphtol were found. Thus, hydroquinone, one of the banned hair dyes according to EU Cosmetic Directive, was evidenced in at least one formulation.

A metal organic framework material MIL-101 was developed as an effective solid-phase extraction adsorbent for the extraction of eleven UV filters compounds. The MIL-101 adsorbent was packed into a polypropylene cartridge and connected at the outlet tip with the Visiprep™ vacuum manifolds allowing process up to 12-port SPE samples, simultaneously. The extracted UV filters were quantified by gas chromatography-tandem mass spectrometry. Several parameters affecting the extraction efficiency of the target analytes, i.e. desorption conditions, sample pH, the addition of salt and sample volume were optimized by ANOVA analysis followed by a multifactorial design. The sample breakthrough volume of the developed method was also evaluated. The SPE-GC–MS/MS method was validated in terms of linearity (R2 ≥ 0.9973), accuracy (with satisfactory recovery from 82% to 105%), precision (relative standard deviation of less than 10%) and limits of detection ranging from 1.0 to 11.7 ng L−1. The validated method was successfully applied for the extraction and quantification of the target UV filters in different types of water samples, including lake, river, seawater and swimming pool waters. The most often found UV filters were octocrylene, 4-methylbencylidene camphor and homosalate that also came out with the highest concentrations, up to 4000 ng L−1, particularly in swimming pool waters.

This study focused on the determination of seven volatile methylsiloxanes (VMSs) and eleven UV-filters (UVFs) in beach sand from the Oporto's region (Portugal). A QuEChERS methodology (“Quick, Easy, Cheap, Effective, Rugged, and Safe”) was used to extract VMSs from the sand, which has never been employed before. To extract the UVFs, a solid-phase microextraction (SPME) was used. The analyses were performed by gas chromatography–mass spectrometry (GC–MS). Twenty-three beach sand samples were analysed, from two campaigns – summer/winter. VMSs were found in all the samples with concentrations ranging from 0.007 ± 0.001 to 17.8 ± 0.9 ng g−1dw, while UVFs in summer samples from 0.030 ± 0.001 to 373 ± 17 ng g−1dw. Cyclic VMSs and octocrylene (OC) were detected in higher concentrations. In general, higher levels were detected in summer than winter. Hazard quotients were determined and 3-(4′-methylbenzylidene) camphor (4-MBC), 2-ethylhexyl 4-methoxycinnamate (EMC) and benzophenone-3 (BP3) presented values >1, which may indicate that they may pose an ecotoxicological risk.

A method based on micro-matrix solid-phase dispersion (&mu, MSPD) followed by gas-chromatography tandem mass spectrometry (GC&ndash, 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 nature.

A methodology based on solid-phase-microextraction (SPME) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous analysis of 14 UV filters of different chemical nature in water. The extraction parameters (the extraction mode and temperature, the fibre coating, and the addition of salt) were optimised by means of experimental designs in order to select the best extraction conditions. The final proposed conditions were 10 mL of water sample with 35% NaCl added, extracted in the headspace mode with a polyacrylate (PA) fibre at 100 °C for 20 minutes. The SPME-GC-MS/MS method was validated in terms of linearity (R2 ≥ 0.9937), accuracy and precision, obtaining LODs in the range of 0.068–12 ng L−1. The validated methodology was then applied to the analysis of different bathing water samples including sea, river, spa, swimming pool, and aquapark water, allowing the detection of 10 of the 14 target compounds; some of them were found at concentrations up to 692 ng mL−1.

A methodology based on ultrasound-assisted emulsification microextraction (USAEME) has been developed for the simultaneous analysis of ten UV filters (2-ethylhexyl methoxycinnamate (2EHMC), 4- methylbencylidene camphor (4MBC), benzyl salicylate (BS), ethylhexyl dimethyl PABA (EHPABA), ethylhexyl salicylate (EHS), etocrylene (Eto), homosalate (HMS), isoamyl methoxycinnamate (IAMC), menthyl anthranilate (MA) and octocrylene (OCR)) in different water samples employing two detection modes, gas chromatography–mass spectrometry (GC–MS), and gas chromatography–tandem mass spectrometry (GC–MS/MS). The extraction parameters such as the extraction solvent, the temperature and the time of extraction, and the addition of salt were optimized by means of experimental design tools. Selected conditions were 100 μL of chloroform, 10 mL of sample, 2 g of salt (NaCl) and 5 min of extraction. Good linearity (R2 > 0.9910), quantitative recoveries (> 90% for most of compounds) and satisfactory precision (RSD

An analytical method based on pressurized liquid extraction (PLE) followed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed for the simultaneous analysis of fifteen different organic UV filters, both water and fat soluble, in cosmetic products. The extractions were carried out in 10 mL extraction cells and the amount of sample employed was only 100 mg. Several factors affecting the PLE procedure such as the extraction solvent and the dispersive agent used to fill the PLE cell were studied. The use of smaller cells (1 mL) and with Teflon as an inner cell coating was also evaluated. Good linearity (R2 > 0.991), quantitative recoveries (82–101%), and satisfactory precision (RSD < 12%) were obtained under the optimal conditions. LOQ values