Hazardous compounds in recreational and urban recycled surfaces made from crumb rubber. Compliance with current regulation and future perspectives

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

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

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

Analysis of industrial contaminants in indoor air. Part 2. Emergent contaminants and pesticides

This article reviews recent literature on the analysis of several contaminants related to the industrial development in indoor air in the framework of the REACH project. In this second part, the attention is focused on emergent contaminants and biocides. Among these chemicals, phthalates, polybrominated and phosphate flame retardants, fragrances, pesticides, as well as other emerging pollutants, are increasing their environmental and health concern and are extensively found in indoor air. Some of them are suspected to behave as priority organic pollutants (POPs) and/or endocrine disrupting compounds (EDC), and can be found both in air and associated to the suspended particulate matter (PM) and settled dust. Main literature considered for this review is from the last ten years, reporting analytical developments and applications regarding the considered contaminants in the indoor environment. Sample collection and pretreatment, analyte extraction or desorption, clean-up procedures, determination techniques, and performance results are summarized and discussed.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

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

COMPRENDO: Focus and approach

Tens of thousands of man-made chemicals are in regular use and discharged into the environment. Many of them are known to interfere with the hormonal systems in humans and wildlife. Given the complexity of endocrine systems, there are many ways in which endocrine-disrupting chemicals (EDCs) can affect the body’s signaling system, and this makes unraveling the mechanisms of action of these chemicals difficult. A major concern is that some of these EDCs appear to be biologically active at extremely low concentrations. There is growing evidence to indicate that the guiding principle of traditional toxicology that “the dose makes the poison” may not always be the case because some EDCs do not induce the classical dose–response relationships. The European Union project COMPRENDO (Comparative Research on Endocrine Disrupters—Phylogenetic Approach and Common Principles focussing on Androgenic/Antiandrogenic Compounds) therefore aims to develop an understanding of potential health problems posed by androgenic and antiandrogenic compounds (AACs) to wildlife and humans by focusing on the commonalities and differences in responses to AACs across the animal kingdom (from invertebrates to vertebrates)

Caractéristiques édaphiques des groupements à Genévrier thurifère des Atlas marocains: étude des niveaux superficiels des sols sous couvert et hors couvert

Plant communities dominated by Juniperus thurifera L. in moroccan Atlas are seriously damaged and show a near total lack of regeneration. The edaphic features of these formations had never been studied. Investigations about superficial layers of these soils, tacking into account the structural heterogeneity of these communities have been carried out. Thus, two pedological profiles have been systematically studied in each of the fourteen formations selected in the Middle and High Atlas : one beneath the tree crown and one away from canopy influence. Results show at first the utmost diversity of these soils. They also point out the microedaphism found under tree crown, related with organic matter produced by trees. This microedaphism, playing a part in the regeneration's potentials, is however dependent on Juniper vitality.Les phytocenoses dominées par le Genévrier thurifère dans les Atlas marocains sont particulièrement menacées par une dégradation intense et une absence quasi-totale de régénération. Les auteurs s'intéressent ici aux niveaux superficiels des sols de ces thurifèraies, en prenant en compte l'hétérogénéité structurelle de ces formations où les arbres ne présentent que rarement des couronnes jointives. Ainsi deux profils pédologiques : l'un sous le couvert des arbres, l'autre entre les arbres, ont été systématiquement étudiés dans chacune des quatorze formations choisies dans le Moyen et Haut Atlas. L'extrême diversité du support édaphique de ces peuplements est mise en évidence. L'existence d'un micro édaphisme sous le couvert de l'arbre lié, entre autres, à l'accumulation de matière organique générée par les couronnes, est ensuite clairement établie. L'importance de ce micro édaphisme, auquel les possibilités de régénération semblent liées, dépend cependant de la structure et de la vitalité des peuplements.Gauquelin Thierry, Dagnac Joseph. Caractéristiques édaphiques des groupements à Genévrier thurifère des Atlas marocains: étude des niveaux superficiels des sols sous couvert et hors couvert. In: Ecologia mediterranea, tome 14 n°3-4, 1988. pp. 43-56

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

Development of Analytical Methods to Analyze Pesticide Residues

Pesticides are compounds applied on crops to eliminate or control pests, diseases and weeds and it is known that their use provides unquestionable benefits in increasing agricultural production [...