Maria Celeiro

Analysis of plasticizers and synthetic musks in cosmetic and personal care products by matrix solid-phase dispersion gas chromatography–mass spectrometry

Matrix solid-phase dispersion (MSPD) and gas chromatography-mass spectrometry were used for the rapid determination of 18 plasticizers (phthalates and adipates), 7 polycyclic musks and 5 nitromusks, which makes a total of 30 targets, in both rinse-off and leave-on cosmetic formulations. The MSPD method was miniaturized and customized to avoid or minimize risks of phthalate contamination and to reduce residues and costs. The amount of sample and extraction solvent employed were 0.1g and 1mL, respectively. The procedure was optimized by means of an experimental design and under the optima conditions it showed satisfactory linearity, repeatability and intermediate precision. LOQs were, in general, in the low ngg(-1), and recoveries were quantitative for all the 18 plasticizers and the 12 fragrances. Twenty-six cosmetic products such as creams, emulsions, lotions, gels for the skin, bath and shower preparations, deodorants, hair-setting, hair-cleansing and hair-conditioning products, shaving products, and sunbathing products, were analyzed. Twenty-five out of thirty targets were detected in the samples. The most frequently found compounds were galaxolide and tonalide reaching concentrations above 0.1% (1000μgg(-1)), and diethyl phthalate (between 0.7 and 357μgg(-1)). The presence of banned substances (Regulation (EC) No. 1223/2009) such as dibutyl phthalate, diisobutyl phthalate, dimethoxyethyl phthalate, benzylbutyl phthalate, diethylhexyl phthalate, diisopentyl phthalate and dipentyl phthalate, musk ambrette and musk tibetene was confirmed in sixteen of the twenty-six personal care products (62%).

Development of a multianalyte method based on micro-matrix-solid-phase dispersion for the analysis of fragrance allergens and preservatives in personal care products☆

An effective, simple and low cost sample preparation method based on matrix solid-phase dispersion (MSPD) followed by gas chromatography-mass spectrometry (GC-MS) or gas chromatography-triple quadrupole-mass spectrometry (GC-MS/MS) has been developed for the rapid simultaneous determination of 38 cosmetic ingredients, 25 fragrance allergens and 13 preservatives. All target substances are frequently used in cosmetics and personal care products and they are subjected to use restrictions or labeling requirements according to the EU Cosmetic Directive. The extraction procedure was optimized on real non-spiked rinse-off and leave-on cosmetic products by means of experimental designs. The final miniaturized process required the use of only 0.1g of sample and 1 mL of organic solvent, obtaining a final extract ready for analysis. The micro-MSPD method was validated showing satisfactory performance by GC-MS and GC-MS/MS analysis. The use of GC coupled to triple quadrupole mass detection allowed to reach very low detection limits (low ng g(-1)) improving, at the same time, method selectivity. In an attempt to improve the chromatographic analysis of preservatives, the inclusion of a derivatization step was also assessed. The proposed method was applied to a broad range of cosmetics and personal care products (shampoos, body milk, moisturizing milk, toothpaste, hand creams, gloss lipstick, sunblock, deodorants and liquid soaps among others), demonstrating the extended use of these substances. The concentration levels were ranging from the sub parts per million to the parts per mill. The number of target fragrance allergens per samples was quite high (up to 16). Several fragrances (linalool, farnesol, hexylcinnamal, and benzyl benzoate) have been detected at levels >0.1% (1,000 μg g(-1)). As regards preservatives, phenoxyethanol was the most frequently found additive reaching quite high concentration (>1,500 μg g(-1)) in five cosmetic products. BHT was detected in eight samples, in two of them (a baby care product and a lipstick) at high concentrations (>1,000 μg g(-1)). Methyl paraben was also found at high levels (>1,700 μg g(-1)) in three leave-on samples. Finally, triclosan was found at the maximum concentration limit (0.3%) laid down by the European regulation in two deodorant samples, and the total paraben concentration was close to the maximum concentration permitted (0.8%) in one leave-on sample (body milk).

Pressurized liquid extraction-gas chromatography-mass spectrometry analysis of fragrance allergens, musks, phthalates and preservatives in baby wipes

Baby wipes and wet toilet paper are specific hygiene care daily products used on newborn and children skin. These products may contain complexes mixtures of harmful chemicals. A method based on pressurized liquid extraction (PLE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed for the simultaneous determination of sixty-five chemical compounds (fragrance allergens, preservatives, musks, and phthalates) in wipes and wet toilet paper for children. These compounds are legislated in Europe according Regulation EC No 1223/2009, being twelve of them banned for their use in cosmetics, and one of them, 3-iodo-2-propynyl butylcarbamate (IPBC), is banned in products intended for children under 3 years. Also, propyl-, and butylparaben will be prohibited in leave-on cosmetic products designed for application on the nappy area of children under 3 years from April 2015. PLE is a fast, simple, easily automated technique, which permits to integrate a clean-up step during the extraction process reducing analysis time and stages. The proposed PLE-based procedure was optimized on real non-spiked baby wipe samples by means of experimental design to study the influence on extraction of parameters such as extraction solvent, temperature, extraction time, and sorbent type. Under the selected conditions, the method was validated showing satisfactory linearity, and intra-day, and inter-day precision. Recoveries were between 80-115% for most of the compounds with relative standard deviations (RSD) lower than 15%. Finally, twenty real samples were analyzed. Thirty-six of the target analytes were detected, highlighting the presence of phenoxyethanol in all analyzed samples at high concentration levels (up to 0.8%, 800μgg(-1)). Methyl paraben (MeP), and ethyl paraben (EtP) were found in 40-50% of the samples, and the recently banned isobutyl paraben (iBuP) and isopropyl paraben (iPrP), were detected in one and seven samples, respectively, at concentrations between 0.093 and 247μgg(-1). In the case of phthalates, the forbidden phthalates dibutyl phtalate (DBP) and di(2-ethylhexyl)phthalate (DEHP) were also found in thirteen samples at low levels. All the samples contained fragrance allergens in many cases at high levels (up to 2400μgg(-1)) and three musks were detected in the samples. Excluding the banned compounds, all samples complied with the concentration limits established by the European Regulation although 25% of them did not fulfill the labeling requirements for fragrance allergens.

Positive lists of cosmetic ingredients: Analytical methodology for regulatory and safety controls – A review

Cosmetic products placed on the market and their ingredients, must be safe under reasonable conditions of use, in accordance to the current legislation. Therefore, regulated and allowed chemical substances must meet the regulatory criteria to be used as ingredients in cosmetics and personal care products, and adequate analytical methodology is needed to evaluate the degree of compliance. This article reviews the most recent methods (2005-2015) used for the extraction and the analytical determination of the ingredients included in the positive lists of the European Regulation of Cosmetic Products (EC 1223/2009): comprising colorants, preservatives and UV filters. It summarizes the analytical properties of the most relevant analytical methods along with the possibilities of fulfilment of the current regulatory issues. The cosmetic legislation is frequently being updated; consequently, the analytical methodology must be constantly revised and improved to meet safety requirements. The article highlights the most important advances in analytical methodology for cosmetics control, both in relation to the sample pretreatment and extraction and the different instrumental approaches developed to solve this challenge. Cosmetics are complex samples, and most of them require a sample pretreatment before analysis. In the last times, the research conducted covering this aspect, tended to the use of green extraction and microextraction techniques. Analytical methods were generally based on liquid chromatography with UV detection, and gas and liquid chromatographic techniques hyphenated with single or tandem mass spectrometry; but some interesting proposals based on electrophoresis have also been reported, together with some electroanalytical approaches. Regarding the number of ingredients considered for analytical control, single analyte methods have been proposed, although the most useful ones in the real life cosmetic analysis are the multianalyte approaches.

Determination of dyes in cosmetic products by micro-matrix solid phase dispersion and liquid chromatography coupled to tandem mass spectrometry

A simple method based on micro-matrix solid phase dispersion (MSPD) followed by liquid chromatography-mass spectrometry (LC-MS/MS) has been developed for the rapid and simultaneous determination of nine regulated water-soluble dyes in personal care and decorative products. The proposed miniaturized extraction procedure was optimized by means of experimental designs in order to obtain the highest extraction efficiency. Under the optimal selected conditions, the method was validated showing satisfactory performance in terms of linearity, sensitivity, and intra-day and inter-day precision. Recoveries were evaluated in different cosmetic matrices and they can be considered quantitative with average values between 70 and 120% with relative standard deviations (RSD) lower than 15%. Finally, the validated method was applied to 24 samples of cosmetic and personal care products, including decorative makeup, lipsticks, lip gloss, toothpastes, regenerating creams, shampoos, and eye shadows, among others, to cover a broad range of commercial real samples. Seven of the analyzed dyes were detected, being declared all of them in the label list of ingredients. More than 50% of the samples contained at least two dyes. Tartrazine was the most frequently found (50% of the samples) at concentration levels of 0.243-79.9μgg(-1). Other targets were found in 1-9 samples, highlighting the presence of Quinoline at high concentration (>500μgg(-1)) in a toothpaste sample.

Determination of fungicides in white grape bagasse by pressurized liquid extraction and gas chromatography tandem mass spectrometry.

Ultrasound-assisted extraction (UAE) and pressurized liquid extraction (PLE) followed by gas chromatography-triple quadrupole-mass spectrometry (GC TQ-MS) were used for the rapid determination of 11 fungicides (metalaxyl, cyprodinil, procymidone, iprovalicarb, myclobutanyl, kresoxim-methyl, benalaxyl, fenhexamide, tebuconazole, iprodione and dimethomorph) in white grape bagasse. The extractions were optimized on real non-spiked samples by means of experimental design and the optimal conditions were selected to achieve the method validation. The PLE procedure showed much higher efficiency than UAE for the target fungicides. Under the selected extraction conditions, PLE showed satisfactory linearity, repeatability and reproducibility. Recoveries for the majority of studied fungicides were higher than 80% with relative standard deviations (RSD) lower than 12%. Limits of detection (LODs) for GC TQ-MS were very low, at the sub ngg(-1) for the majority of the target fungicides, well below the European maximum residue limits (MRLs) for wine and table grapes, and vine leaves. Eighteen white grape bagasse samples were analyzed and nine out of eleven targets were detected in the samples. Seven of them were detected in more than 50% of the samples and most samples contained at least four of the target analytes. The most frequently found compounds were tebuconazole and dimethomorph with concentrations between 1.6-130 and 2.0-1788ngg(-1), respectively. Some samples showed high levels of many of the studied fungicides (high ngg(-1), even μgg(-1) for cyprodinil, fenhexamide, iprodione and dimethomorph), but all of them below the European maximum residue limits (MRLs) for wine grapes.

Determination of fourteen UV filters in bathing water by headspace solid-phase microextraction and gas chromatography-tandem mass spectrometry

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.

Investigation of PAH and other hazardous contaminant occurrence in recycled tyre rubber surfaces. Case-study: restaurant playground in an indoor shopping centre

The objective of this case study was to investigate the presence of polycyclic aromatic hydrocarbons (PAHs) and other hazardous organic chemicals in a recycled tyre playground surface (in an indoor restaurant of a shopping centre with limited ventilation). This study also aimed at underlining both the volatilisation of these compounds in the vapour phase above the sample and the partial leaching of contaminants from the playground surface to the runoff and cleaning water put in contact with the sample. Playground samples were extracted with ethyl acetate using ultrasonic energy followed by GC-MS analysis. In addition, the same samples were analysed by HS-SPME to study the volatilisation and the transfer of those organic compounds. The analysis confirmed the presence of a large number of hazardous substances. Thus, 14 of the 16 studied PAHs were identified in the extracts (including the considered most toxic PAH, benzo[a]pyrene) and nine of them were also detected in the vapour phase. Besides, nine PAHs were found in the runoff/cleaning water, yielding a total PAH concentration at the ppm level. The presence and the high concentrations of these chemical compounds in playgrounds should be a matter of concern owing to their high toxicity.

Development of novel adenosine receptor ligands based on the 3-amidocoumarin scaffold.

With the aim of finding new adenosine receptor (AR) ligands presenting the 3-amidocoumarin scaffold, a study focusing on the discovery of new chemical entities was carried out. The synthesized compounds 1-8 were evaluated in radioligand binding (A1, A2A and A3) and adenylyl cyclase activity (A2B) assays in order to determine their affinity for human AR subtypes. The 3-benzamide derivative 4 showed the highest affinity of the whole series and was more than 30-fold selective for the A3 AR (Ki=3.24 μM). The current study supported that small structural changes in this scaffold allowed modulating the affinity resulting in novel promising classes of A1, A2A, and/or A3 AR ligands. We also performed docking calculations in hA2A and hA3 to identify the hypothetical binding mode for the most active compounds. In addition, some ADME properties were calculated in order to better understand the potential of these compounds as drug candidates.

Rapid analysis of fungicides in white wines from Northwest Spain by ultrasound-assisted emulsification-microextraction and gas chromatography-mass spectrometry

A rapid, efficient and low-cost method based on ultrasound-assisted emulsification-microextraction (USAEME) and gas chromatography-mass spectrometry was developed for the analysis of several fungicides, belonging to different chemical families, in white wines. The experimental procedure was optimized using factorial design to study the influence of the solvent type, extraction time, extraction temperature, sample, pH, and salt addition on the extraction efficiency. Under the selected conditions, compounds were extracted into 200 μL chloroform from 10 mL of wine sample in only 5 min at ambient temperature. The method was validated using real wine samples, with fungicide recoveries generally ranging from 70 to 115%, good intra- and inter-day precision (relative standard deviation (RSD) values ≤12%), and limits of detection at the sub-ng per millilitre level (LOD ≤ 0.1 ng mL−1). The application of the method to varietal wines belonging to different brands showed the presence of fungicides in all samples at concentrations ranging from 1 to 700 ng mL−1, with a minimum of two and a maximum of seven chemicals per sample.