High-Resolution Mass Spectrometry for the Comprehensive Characterization of Plant-Pigment-Based Tattoos and Dyes Formulations

There has been little research on emerging natural-pigment-based temporary tattoos and their constituents so far. This study focused on the characterization of natural henna and jagua tattoos and dyes in commercial samples. Sample manipulation and treatment were minimal to analyze natural pigments as they are marketed. The characterization of active compounds was performed by ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS). A novel untargeted characterization was also applied for these types of samples, searching for compounds ranging from the original ingredients to other additives of interest they may contain. The fact that these products may also be a source of unlabelled allergens was considered. This work showed that not all of the 34 samples analyzed contained their characteristic active ingredients, and in addition, 70 substances of a different nature were found. Therefore, a rapid and high-throughput methodology has been developed for the identification of the components of these dyes, providing a necessary approach for quality control or identification of suspicious substancesThis research was supported by projects EQC2018-005011-P (Ministry of Science, Innovation and Universities, Spain) and ED431 2020/06 (Xunta de Galicia). The authors belong to the CRETUS Strategic Partnership (ED431E 2018/01). All these programs are co-funded by FEDER (UE). L.R. acknowledges Xunta de Galicia for her predoctoral contract (ED481A-2018/227)S

Monitoring of Natural Pigments in Henna and Jagua Tattoos for Fake Detection

Temporary tattoos are a popular alternative to permanent ones. Some of them use natural pigments such as lawsone in the famous henna tattoos. Recently, jagua tattoos, whose main ingredients are genipin and geniposide, have emerged as an interesting option. This study was conducted to identify the presence and concentration of henna and jagua active ingredients (lawsone; genipin and geniposide, respectively) in commercial tattoo samples. Since natural pigments are often mixed with additives such as p-phenylenediamine (PPD) in the case of henna, PPD has been included in the study. Green and simple extraction methods based on vortex or ultrasound-assisted techniques have been tested. To determine the compounds of interest liquid chromatography (LC) with diode-array detection (DAD) has been applied; and PPD absence was confirmed by LC-QTOF (quadrupole-time of flight tandem mass spectrometry). This work demonstrated that only one out of 14 henna samples analyzed contained lawsone. For jaguas, genipin was found in all samples, while geniposide only in two. Therefore, quality control analysis on these semi-permanent tattoos is considered necessary to detect these ingredients in commercial mixtures, as well as to uncover possible fraud in products sold as natural hennaThis research was supported by project EQC2018-005011-P (Ministry of Science, Innovation and Universities, Spain. The authors belong to the CRETUS Strategic Partnership (ED431E2018/01). All these programmes are co-funded by FEDER (UE). L.R. acknowledges Xunta de Galicia for her predoctoral contractS

Multi-Target Strategy to Uncover Unexpected Compounds in Rinse-Off and Leave-On Cosmetics

The wide range and complexity of cosmetic formulations currently available on the market poses a challenge from an analytical point of view. In addition, during cosmetics manufacture, impurities coming from raw materials or formed by reaction of different organic compounds present in the formulation may be present. Their identification is mandatory to assure product quality and consumer health. In this work, micro-matrix solid-phase dispersion (μMSPD) is proposed as a multi-target sample preparation strategy to analyze a wide number of unexpected families of compounds including polycyclic aromatic hydrocarbons (PAHs), pesticides, plasticizers, nitrosamines, alkylphenols (APs), and alkylphenol ethoxylates (APEOs). Analytical determination was performed by gas chromatography-mass spectrometry (GC-MS) for the determination of 51 target compounds in a single run, whereas liquid chromatography tandem mass spectrometry (LC-MS/MS) was employed for the analysis of six APs and APEOs. Both methodologies were successfully validated in terms of linearity, accuracy, and precision in leave-on and rinse-off cosmetics. Limits of detection (LODs) were calculated in the low ng g−1, showing their suitability to determine trace levels of impurities and banned compounds with different chemical natures, providing useful tools to cosmetic control laboratories and companiesThis project was supported by project ED431 2020/06 (Xunta de Galicia). Authors belong to CRETUS Strategic Partnership (ED431E 2018/01) (Xunta de Galicia). All these programs are co-funded by FEDER (UE). L.R. acknowledges Xunta de Galicia for her predoctoral contract (ED481A-2018/227)S

Profiling the Fatty Acids Content of Ornamental Camellia Seeds Cultivated in Galicia by an Optimized Matrix Solid-Phase Dispersion Extraction

Camellia (genus of flowering plants of fam. Theaceae) is one of the main crops in Asia, where tea and oil from leaves and seeds have been utilized for thousands of years. This plant is excellently adapted to the climate and soil of Galicia (northwestern Spain) and northern Portugal where it is grown not only as an ornamental plant, but to be evaluated as a source of bioactive compounds. In this work, the main fatty acids were extracted from Camellia seeds of four varieties of Camellia: sasanqua, reticulata, japonica and sinensis, by means of matrix-solid phase dispersion (MSPD), and analyzed by gas chromatography (GC) with MS detection of the corresponding methyl esters. MSPD constitutes an efficient and greener alternative to conventional extraction techniques, moreover if it is combined with the use of green solvents such as limonene. The optimization of the MSPD extraction procedure has been conducted using a multivariate approach based on strategies of experimental design, which enabled the simultaneous evaluation of the factors influencing the extraction efficiency as well as interactions between factors. The optimized method was applied to characterize the fatty acids profiles of four Camellia varieties seeds, allowing us to compare their fatty acid compositionThis research was supported by European Regional Development Fund 2007–2013 (FEDER), and project GPC2014/035 (Consolidated Research Groups Program of Galician Government Xunta de Galicia)S

Multicomponent bioactive extract from red stage Haematococcus pluvialis wet paste: avoiding the drying step and toxic solvents

info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/EQC2018-005011-P/ESThis study provides an efficient alternative by extracting bioactive compounds from Haematococcus pluvialis via matrix solid-phase dispersion (MSPD) from its wet form, reducing one of the process steps with the greatest economic impact, the drying of the microalga. To obtain a suitable extract for nutraceutical purposes, solvents with the generally recognised as safe (GRAS) designation (ethanol, ethyl lactate, and ethyl acetate) with limitations of use (acetone) and extractants with higher toxicity such as methanol and methyl-tert-butyl ether (MTBE) are contrasted. Through the optimisation of the extractive process, ethanol, a GRAS solvent, presents the best overall recovery for carotenoid compounds and fatty acids, showing an antioxidant activity of 1.58 mmolTE g−1 DW, comparable to its synthetic alternative of petrochemical origin without the drawback of having limitations in its food use. In addition, the identification of the phenolic compounds, phloroglucinol, p-coumaric acid, gallic acid, and catechin, not previously characterised in red stage H. pluvialis, provides a response to the phenolic activity present in the extract (24.65 mmolGAE g−1 DW). Comparison of the extractive efficiency obtained with the main methods for the extraction of carotenoids and fatty acids in H. pluvialis, in contrast to the proposed method, shows a positive feasibility of this approachOpen Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This research was funded by project ED431 2020/06 (Galician Competitive Research Groups Xunta de Galicia). This work was supported by project EQC2018-005011-P (Ministry of Science, Innovation and Universities, Spain). All these programmes are co-funded by FEDER (EU). This article is based upon work from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical SocietyS

Antioxidant white grape seed phenolics: pressurized liquid extracts from different varieties

Grape seeds represent a high percentage (20% to 26%) of the grape marc obtained as a byproduct from white winemaking and keep a vast proportion of grape polyphenols. In this study, seeds obtained from 11 monovarietal white grape marcs cultivated in Northwestern Spain have been analyzed in order to characterize their polyphenolic content and antioxidant activity. Seeds of native (Albariño, Caiño, Godello, Loureiro, Torrontés, and Treixadura) and non-native (Chardonnay, Gewurtzträminer, Pinot blanc, Pinot gris, and Riesling) grape varieties have been considered. Low weight phenolics have been extracted by means of pressurized liquid extraction (PLE) and further analyzed by LC-MS/MS. The results showed that PLE extracts, whatever the grape variety of origin, contained large amounts of polyphenols and high antioxidant activity. Differences in the varietal polyphenolic profiles were found, so a selective exploitation of seeds might be possibleThis research was supported by European Regional Development Fund 2007-2013 (FEDER), and project GPC2014/035 (Consolidated Research Groups Program of Galician Government Xunta de Galicia)S

Conversión acelerada de retama negra (Cytisus scoparius) en un biofertilizante de calidad mediante vermicompostaje

Cytisus scoparius es una planta arbustiva ampliamente distribuida por todo el mundo y considerada como una amenaza para otras especies en algunos países. Las plantas del género Cytisus crecen sobre todo en áreas perturbadas y su presencia favorece, a menudo, la propagación rápida del fuego. El objetivo de este estudio fue evaluar el proceso de vermicompostaje de estos arbustos para producir un fertilizante orgánico de alta calidad y libre de polifenoles. El vermicompostaje redujo sustancialmente la biomasa de C. scoparius (en un 84%), fundamentalmente como resultado de la pérdida de sólidos volátiles, en tan sólo 6 semanas. Se obtuvo un vermicompost de calidad, que es un material similar a la turba, rico en nutrientes y microbiológicamente activo y estable, y sin la fitotoxicidad asociada a los polifenoles. Simultáneamente, la población inicial de lombrices se incrementó muy considerablemente, en un 350%. El procedimiento descrito es eficaz, simple y económico, y puede escalarse fácilmente para su aplicación industrialWild shrubs belonging to Cytisus scoparius are widely distributed throughout the world, and they are considered a threat to other species in some countries. Cytisus spp. mainly grow in disturbed areas and their presence often favours the rapid spread of fire. Theaim of this study was to evaluate whether such shrubs could be processed by vermicomposting on an industrial scale to yield high-quality organic and polyphenol-free fertiliser. Vermicomposting reduced thebiomass of C. scoparius substantially (by 84%), mainly as a result of the loss of volatile solids. After 6 weeks, the process yielded anutrientrich, microbiologically active and stabilised peat-like material without the polyphenol-associated phytotoxicity. Simultaneously, the initial population of earthworms increases remarkably, up to 350%. The procedure described is effective, simple and economical, and could easily be scaled up for industrial applicationS

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