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

As Festas de Nossa Senhora da Lapa e de Nossa Senhora da Porta em Arcos de Valdevez

Dissertação de mestrado em Património CulturalA festa e romaria em honra de Nossa Senhora da Lapa é atualmente uma das festividades mais importantes do concelho de Arcos de Valdevez. Em Arcos de Valdevez, esta devoção começou no século XVIII e, quando esta investigação se iniciou, cria-se que as respetivas festividades tinham sido constantes até meados do século XX, altura em que deixaram de se fazer. Esta festa e romaria veio a ser retomada em 2009, passando mesmo a festa de Nossa Senhora da Lapa a titular as «festas do concelho». A festa em honra de Nossa Senhora da Porta deixou de realizar-se nos finais do século XIX. Foi retomada em 2010 como resultado de uma ação conjunta da Santa Casa da Misericórdia e da Câmara Municipal de Arcos de Valdevez. Uma vez que estas duas festas foram interrompidas durante décadas, pretendíamos saber se, atualmente, são sentidas como um retomar de antigas tradições, o que se sabe sobre a forma como cada uma delas foi celebrada no passado e se é possível encontrar similitudes entre o passado e o presente de cada uma delas.The festival and pilgrimage in honour of Nossa Senhora da Lapa is currently one of the most important festivities in the municipality of Arcos de Valdevez. In Arcos de Valdevez, this devotion began in the 18th century and, when this investigation began, it was believed that the respective festivities had been constant until the middle of the 20th century, when they stopped taking place. This festival and pilgrimage was resumed in 2009, the feast of Nossa Senhora da Lapa even becoming the title of the «municipality feasts». The feast in honour of Nossa Senhora da Porta was no longer held at the end of the 19th century. It was resumed in 2010 as a result of a joint action by Santa Casa da Misericórdia and the municipality of Arcos de Valdevez. Since these two festivals were interrupted for decades, I wanted to know if they are currently felt like a return to old traditions, what is known about how each one of them was celebrated in the past and if it is possible to find similarities between the past and the present of each one of them

Miniaturized Sample Preparation Methods to Simultaneously Determine the Levels of Glycols, Glycol Ethers and Their Acetates in Cosmetics

Two environmentally friendly methodologies based on ultrasound-assisted extraction (UAE) and micro-matrix solid-phase dispersion (µMSPD) followed by gas chromatography-mass spectrometry (GC-MS) analysis are proposed for the first time for the simultaneous analysis of 17 glycols, glycol ethers, and their acetates in cosmetics. These sample preparation approaches result in efficient and low-cost extraction while employing small amounts of sample, with a low consumption of reagents and organic solvents. The use of a highly polar column allows for the direct analysis of the obtained extracts by GC-MS without a previous derivatization step, drastically reducing the sample preparation time and residues and thus complying with green analytical chemistry (GAC) principles. Both the UAE and µMSPD methodologies were validated in terms of linearity, accuracy, and precision, providing satisfactory results. LODs were found to be lower than 0.75 µg g−1, allowing the determination of trace levels of the forbidden target compounds. Finally, the validated methodologies were applied to real cosmetics and personal care products, showing suitability, and providing a reliable and useful tool for cosmetics control laboratories

In-Vial Micro-Matrix-Solid Phase Dispersion for the Analysis of Fragrance Allergens, Preservatives, Plasticizers, and Musks in Cosmetics

Fragrance allergens, preservatives, plasticizers, and synthetic musks are usually present in cosmetic and personal care products formulations and many of them are subjected to use restrictions or labeling requirements. Matrix solid-phase dispersion (MSPD) is a very suitable analytical technique for the extraction of these compounds providing a simple, low cost sample preparation, and the possibility of performing both extraction and clean-up in one step, reducing possible contamination and analyte losses. This extraction technique has been successfully applied to many cosmetics ingredients allowing obtaining quantitative recoveries. A new very simple micro-MSPD procedure performing the disruption step in a vial is proposed for the gas chromatography-mass spectrometry (GC-MS) analysis of 66 chemicals usually present in cosmetics and personal care products. The method was validated showing general recoveries between 80% and 110%, relative standard deviation (RSD) values lower than 15%, and limits of detection (LODs) below 30 ng·g−1. The validated method was applied to a broad range of cosmetics and personal care products, including several products intended for baby care

Antioxidants Profiling of By-Products from Eucalyptus Greenboards Manufacture

Three different by-products from the Eucalyptus wood industry have been exhaustively characterized to find compounds with antioxidant properties. The industrial process to manufacture Eucalyptus greenboards is distinguished by using just wood and water, which converts the generated by-products in a highly attractive source of bioactive compounds that are originally in the raw material. The studied by-products were: the screw water, derived from the washing of the wood chips; the condensates, obtained after the evaporation and further condensation of the screw water; and finally, the concentrate of eucalyptus. For all of them and for their derived organic extracts, the total polyphenols content (TPC) and antioxidant activity (AA) have been evaluated. The chromatographic fingerprints, based on gas chromatography-mass spectrometry (GC-MS), and liquid chromatography-tandem mass spectrometry (LC-MS/MS) have been obtained to identify the main extractable organic wood components. Besides, solid-phase microextraction (SPME) has been employed to characterize the most volatile compounds. Significant differences were observed for the chromatographic profiles of the studied by-products. Up to 48 and 30 different compounds were identified in the screw water, and condensate by-products, respectively; whereas the highest number of compounds, up to 72, have been identified in the organic extracts derived from the concentrate of Eucalyptus, highlighting the presence of monoterpenes, sesquiterpenes, polyphenols, and other bioactive compounds with antioxidant properties. Therefore, these by-products could be exploited to obtain natural extracts with added value which could be reused in the food, cosmetic or pharmaceutical industry, reducing the environmental impact of the industrial activity

Miniaturized Sample Preparation Methods to Simultaneously Determine the Levels of Glycols, Glycol Ethers and Their Acetates in Cosmetics

Two environmentally friendly methodologies based on ultrasound-assisted extraction (UAE) and micro-matrix solid-phase dispersion (µMSPD) followed by gas chromatography-mass spectrometry (GC-MS) analysis are proposed for the first time for the simultaneous analysis of 17 glycols, glycol ethers, and their acetates in cosmetics. These sample preparation approaches result in efficient and low-cost extraction while employing small amounts of sample, with a low consumption of reagents and organic solvents. The use of a highly polar column allows for the direct analysis of the obtained extracts by GC-MS without a previous derivatization step, drastically reducing the sample preparation time and residues and thus complying with green analytical chemistry (GAC) principles. Both the UAE and µMSPD methodologies were validated in terms of linearity, accuracy, and precision, providing satisfactory results. LODs were found to be lower than 0.75 µg g−1, allowing the determination of trace levels of the forbidden target compounds. Finally, the validated methodologies were applied to real cosmetics and personal care products, showing suitability, and providing a reliable and useful tool for cosmetics control laboratories

Croatian Traditional Apple Varieties: Why Are They More Resistant to Plant Diseases?

This study aimed to detect, quantify and compare the amounts of chlorogenic acid, phloridzin and quercetin in Croatian traditional and conventional apple varieties by HPLC-PDA. The results showed that Croatian traditional apple varieties had significantly higher amounts of chlorogenic acid (30.29 ± 0.34 mg/100 g dw), phloridzin (3.12 ± 0.01 mg/100 g dw) and quercetin (11.68 ± 0.09 mg/100 g dw) detected for varieties Božičnica, Mašanka and Petrovnjača, respectively. The highest contents of the total phenolic acids, dihydrochalcones and flavonols were detected in Božićnica (31.94 ± 0.65 mg/100 g dw), Mašanka (3.52 ± 0.52 mg/100 g dw) and Fuji (19.11 ± 0.56 mg/100 g dw). These results present the beginning of the research on the resistance of Croatian traditional apple varieties to plant diseases

Photodegradation of multiclass fungicides in the aquatic environment and determination by liquid chromatography-tandem mass spectrometry

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 <35%, after 30 min of irradiation. Besides, the photodegradation tests were performed with different initial concentrations of fungicides, and the efficiency of two photoreactor systems was compared. In all cases, the kinetics followed pseudo-first order, and the half-life times could also be calculated. The addition of H2O2 under UVC light allowed an improvement of the reaction kinetics, especially for the most recalcitrant fungicides, obtaining in all cases removals higher than 82% in less than 6 min. Finally, in order to evaluate the suitability of the proposed systems, both UVC photolysis and UVC/H2O2 system were tested in different real water matrices (wastewater, tap water, swimming pool water and river water), showing that the UVC/H2O2 system had the highest removal efficiency in less than 6 min, for all water samples