Cloud point–dispersive μ-solid phase extraction of hydrophobic organic compounds onto highly hydrophobic core–shell Fe 2 O 3 @C magnetic nanoparticles

Abstract A novel two-step extraction technique combining cloud point extraction (CPE) with dispersive micro-solid phase extraction (D-μ-SPE) is presented in this work for the first time. The method involves initial extraction of the target analytes by CPE in the micelles of a non-ionic surfactant medium; then highly hydrophobic polysiloxane-coated core–shell Fe 2 O 3 @C magnetic nanoparticles (MNPs) are used to retrieve the micellar phase. In that manner, the micellar phase containing the analytes is the target of the D-μ-SPE step rather than the analytes directly. MNPs are then collected by the application of an adscititious magnetic field overcoming the need for specific steps associated …

Flow injection-chemiluminescence determination of octyl dimethyl PABA in sunscreen formulations

Abstract A sensitive flow injection (FI) procedure was developed for the determination of the UV-filter octyl dimethyl PABA in sunscreen formulations based on its chemiluminescence (CL) induced by potassium permanganate in sulfuric acid. Both second-order and log–log calibration graphs can be used to perform the analysis. Ninety injections per hour can be carried out, which means a sample throughput of 18 h −1 if five injections per solution are performed. The limit of detection (3 σ ) was 25 ng ml −1 . The interference effects of the excipient and other UV filters are studied. Sunscreen formulations containing octyl dimethyl PABA were analysed by both the proposed FI-CL method and a liquid…

Ionic liquid-based single-drop microextraction followed by liquid chromatography-ultraviolet spectrophotometry detection to determine typical UV filters in surface water samples.

Abstract A user-friendly and inexpensive ionic liquid-based single-drop microextraction (IL-SDME) procedure has been developed to preconcentrate trace amounts of six typical UV filters extensively used in cosmetic products (i.e., 2-hydroxy-4-methoxybenzophenone, isoamyl 4-methoxycinnamate, 3-(4′-methylbenzylidene)camphor, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-methoxycinnamate) from surface water samples prior to analysis by liquid chromatography-ultraviolet spectrophotometry detection (LC-UV). A two-stage multivariate optimization approach was developed by means of a Plackett–Burman design for screening and selecting the significa…

Determination of water-soluble UV-filters in sunscreen sprays by liquid chromatography.

Abstract Liquid chromatography was used for the determination of the three most used water-soluble UV filters, benzophenone-4 (BZ4), terephthalylidene dicamphor sulfonic acid (TDS), and phenylbenzimidazole sulphonic acid (PBS), in aqueous sunscreen sprays. A C 18 stationary phase and an isocratic mobile phase of EtOH–20 m M sodium acetate buffer of pH 4.6 (30:70, v/v) were used at a flow-rate of 0.5 ml min −1 . Mobile phase was also used as solvent for samples and standards. UV detection was at 313 nm. The analytical run took 5.5 min. The limits of detection were 0.5, 0.9 and 2 μg ml −1 for BZ4, TDS and PBS, respectively. The proposed method does not involve highly toxic solvents.

Carbon fibers as green and sustainable sorbent for the extraction of isoflavones from environmental waters.

Abstract Isoflavones are a group of phytoestrogens of important environmental concern due to their endocrine disrupting effects. This article presents a rapid, green, and sustainable method for determining four isoflavones (daidzein, genistein, formononetin, and biochanin A) in environmental waters complying with current trends in Analytical Chemistry. The method consists of in-syringe dispersive solid-phase extraction (DSPE) as the extraction approach, using carbon fibers as extraction material. The synthesis of carbon fibers is simple and sustainable, since it only requires a natural product such as raw cotton as precursor, which is thermally treated (600 °C for 30 min) in an inert (Ar) a…

Green determination of eight water-soluble B vitamins in cosmetic products by liquid chromatography with ultraviolet detection.

Abstract B vitamins are a group of compounds with beneficious properties for dermatologic care, and therefore they are included in the cosmetic formulations as high added-value ingredients. In this paper, an analytical method for the simultaneous determination of eight water-soluble B vitamins in cosmetic products is reported for the first time. This method is based on liquid chromatography with ultraviolet detection (LC-UV) analysis after simple water leaching of the analytes from the cosmetic matrix. No organic solvents are required, beyond the ethanol used in the chromatographic mobile phase. The proposed method has been successfully validated showing good linearity, limits of detection …

Supercritical fluid extraction and high performance liquid chromatography determination of homosalate in lipsticks

Supercritical fluid extraction of homosalate is reported for the first time. Extraction parameters such as pressure, time of extraction, use of modifier, temperature and sample mass were studied. The proposed method was assayed for the extraction of homosalate in sunscreen lipsticks. Efficient recoveries were obtained after 5 min of dynamic extraction with supercritical CO2 and 15% ethanol as modifier at 300 bar and 60°C, flow rate 4 mL min−1. Extracts were dissolved in ethanol, and homosalate determined by HPLC using water—acetic acid—ethanol mobile phase and flow rate of 1 mL min−1. UV detection was at 309 nm using homosalate in ethanol solutions as standards, limit of detection 4 μg mL−1…

Sequential injection analysis for benzophenone-4 and phenylbenzimidazole sulphonic acid in sunscreen sprays by solid-phase extraction coupled with ultraviolet spectrometry

Abstract A sequential injection UV method was developed to determine benzophenone-4 (BZ4) and phenylbenzimidazole sulphonic acid (PBS) simultaneously, these being the most commonly used UV-filters in aqueous formulations used as sunscreen sprays. The selective elution of both was performed by on-line solid-phase extraction, by retention on a SAX microcolumn and separation by varying the pH of elution. The sensitivity obtained was 0.042±0.001 ml μg −1 for PBS and 0.0159±0.0003 ml μg −1 for BZ4. The limit of detection was 1.6 μg ml −1 for PBS and 0.6 μg ml −1 for BZ4. The R.S.D. of the results was 1–6% for PBS and 1–12% for BZ4. The method was validated using commercial sunscreen formulations…

Identification of the Biotransformation Products of 2-Ethylhexyl 4-(N,N-Dimethylamino)benzoate

Nowadays, 2-ethylhexyl 4-(N,N-dimethylamino)benzoate (EDP) is one of the most widely used UV filters in sunscreen cosmetics and other cosmetic products. However, undesirable processes such as percutaneous absorption and biological activity have been attributed to this compound. The in vitro metabolism of EDP was elucidated in the present work. First of all, the phase I biotransformation was studied in rat liver microsomes and two metabolites, N,N-dimethyl-p-aminobenzoic acid (DMP) and N-monomethyl-p-aminobenzoic acid (MMP), were identified by GC-MS analysis. Secondly, the phase II metabolism was investigated by means of LC-MS. The investigated reactions were acetylation and glucuronidation …

Dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry for the determination of nitro musks in surface water and wastewater samples

A new, simple, fast and high sensitive analytical method based on dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of nitro musks in surface water and wastewater samples is presented. Different parameters, such as the nature and volume of both the extraction and disperser solvents and the ionic strength and pH of the aqueous donor phase, were optimized. Under the selected conditions (injection of a mixture of 1 mL of acetone as disperser solvent and 50 μL of chloroform as extraction solvent, no salt addition and no pH adjustment) the figures of merit of the proposed DLLME-GC-MS method were evaluated.…

Simultaneous determination of oxybenzone and 2-ethylhexyl 4-methoxycinnamate in sunscreen formulations by flow injection-isodifferential derivative ultraviolet spectrometry

Abstract A flow injection procedure was developed for the simultaneous determination of two UV filters (oxybenzone and 2-ethylhexyl 4-methoxycinnamate) in sunscreen formulations, based on the isodifferential approach. The use of the second derivative spectra allowed a selective determination of the analytes free from matrix interferences and without pretreatment of samples. Standard solutions of the analytes were analyzed by the proposed procedure in order to select the appropriate wavelengths to solve the mixture. After this, the procedure was validated using commercial sunscreen formulations the concentrations of which were determined by an HPLC procedure. The two procedures gave comparab…

Determination of free formaldehyde in cosmetics containing formaldehyde-releasing preservatives by reversed-phase dispersive liquid-liquid microextraction and liquid chromatography with post-column derivatization.

Abstract An analytical method for the determination of traces of formaldehyde in cosmetic products containing formaldehyde-releasing preservatives has been developed. The method is based on reversed-phase dispersive liquid–liquid microextraction (RP-DLLME), that allows the extraction of highly polar compounds, followed by liquid chromatography–ultraviolet/visible (LC–UV/vis) determination with post-column derivatization. The variables involved in the RP-DLLME process were studied to provide the best enrichment factors. Under the selected conditions, a mixture of 500 μL of acetonitrile (disperser solvent) and 50 μL of water (extraction solvent) was rapidly injected into 5 mL of toluene sampl…

Extraction and Sample Preparation

As everyone knows, the role played by extraction and sample preparation in the analytical sciences cannot be overemphasized. Despite tremendous advances in chromatography, detection, and other aspects of analysis, extraction and sample preparation remain a preanalysis ritual of critical importance. It has been estimated that around 50% to 70% possibly even more of the time and effort that goes into an analytical process comprises extraction and sample preparation. Sample preparation procedure can vary in the degree of selectivity, speed, and convenience, depending on the approach and conditions used, as well as on the geometric configurations of the extraction phase and conditions. Proper d…

Determination of ultraviolet filters in bathing waters by stir bar sorptive–dispersive microextraction coupled to thermal desorption–gas chromatography–mass spectrometry

In this work, a new approach that combines the advantages of stir bar sorptive extraction (SBSE) and dispersive solid phase extraction (DSPE), i.e. stir bar sorptive-dispersive microextraction (SBSDµE), is employed as enrichment and clean-up technique for the sensitive determination of eight lipophilic UV filters in water samples. The extraction is accomplished using a neodymium stir bar magnetically coated with oleic acid-coated cobalt ferrite magnetic nanoparticles (MNPs) as sorbent material, which are detached and dispersed into the solution at high stirring rate. When stirring is stopped, MNPs are magnetically retrieved onto the stir bar, which is subjected to thermal desorption (TD) to…

Fundamentals and applications of stir bar sorptive dispersive microextraction: A tutorial review

Current trends in sample preparation focus on the miniaturization of the process resulting in what is known as microextraction techniques. Among them stir bar sorptive dispersive microextraction (SBSDME) is one of the most recent techniques. It was presented a few years ago as a hybrid microextraction technique that combines the principles of stir bar sorptive extraction (SBSE) and dispersive solid phase extraction (DSPE). This novel technique introduces, into the sample solution, a bar-shaped magnet coated with a magnetic (nano)material, which is maintained on the surface by magnetism. Once stirring starts, the competitive action between magnetism and rotational force is exploited. At low …

Determination of selenium, zinc and cadmium in antidandruff shampoos by atomic spectrometry after microwave assisted sample digestion

Microwave assisted pre-treatments for atomic spectrometric determination (inductive coupled plasma-optical emission spectrometry, ICP-OES or flame atomic absorption spectrometry, FAAS) of metallic elements, usually present in antidandruff shampoos, are proposed. They are based on the digestion of the sample with HNO(3) into a closed reactor, which is irradiated at 800 W for a few minutes. Selenium was determined by ICP-OES. The limit of detection was 0.11 mg l(-1); the relative standard deviation (R.S.D.) for the selenium content in the samples was in the 0.6-3.6% range. The results obtained were in agreement with the label contents and the recovery of the proposed method was in the 100-106…

In-situ suspended aggregate microextraction: A sample preparation approach for the enrichment of organic compounds in aqueous solutions.

Abstract This work presents in-situ suspended aggregate microextraction (iSAME) as a new and expedient sample preparation method. This new concept capitalizes on the general principles of in-situ solvent formation microextraction, in the sense that extraction is carried out in a supramolecular aggregate phase, which is formed in-situ in the sample through one-step process involving ion-association between a cationic surfactant and a benzene sulfonic acid derivative. The suspended aggregate containing the analytes is then collected in the form of a thin-film on the surface of a common filter paper by suction filtration. The entrapped analytes are released by completely dissolving the thin-fi…

A sequential-injection system for spectrophotometric determination of p -aminobenzoic acid in sunscreens.

A sequential injection method is proposed for spectrophotometric determination of p-aminobenzoic acid (PABA) in cosmetic formulations. The method is based on diazotization of the analyte, coupling with 8-hydroxyquinoline, and the subsequent formation of a colored product. The experimental conditions used (coupling reagent, sandwich arrangement, volumes aspirated, propulsion flow rate, reaction coil length) were studied. Response of the sequential injection method were linearly dependent on concentrations up to 25 micro g mL(-1) and the detection limit was 2 micro g mL(-1). Throughput was 51 measurements per hour and a complete cycle, including three measurement per sample and a washing step…

Determination of N-nitrosodiethanolamine in cosmetic products by reversed-phase dispersive liquid-liquid microextraction followed by liquid chromatography.

A new analytical method for the determination of N-nitrosodiethanolamine (NDELA), a very harmful compound not allowed in cosmetic products, is presented. The method is based on a new approach of dispersive liquid-liquid microextraction (DLLME) useful for extraction of highly polar compounds, called reversed-phase DLLME (RP-DLLME), followed by liquid chromatography-ultraviolet/visible (LC-UV/Vis) determination. The variables involved in the RP-DLLME process were studied to provide the best enrichment factors. Under the optimized conditions, a mixture of 750µL of acetone (disperser solvent) and 125µL of water (extraction solvent) was rapidly injected into 5mL of toluene sample solution. The e…

Sequential injection spectrophotometric determination of oxybenzone in lipsticks

A sequential injection (SI) procedure for the spectrophotometric determination of oxybenzone in lipsticks is reported. The colorimetric reaction between nickel and oxybenzone was used. SI parameters such as sample solution volume, reagent solution volume, propulsion flow rate and reaction coil length were studied. The limit of detection was 3 microg ml(-1). The sensitivity was 0.0108+/-0.0002 ml microg(-1). The relative standard deviations of the results were between 6 and 12%. The real concentrations of samples and the values obtained by HPLC were comparable. Microwave sample pre-treatment allowed the extraction of oxybenzone with ethanol, thus avoiding the use of toxic organic solvents. E…

Determination of hydroxytyrosol and tyrosol by liquid chromatography for the quality control of cosmetic products based on olive extracts

An analytical method for the simultaneous determination of hydroxytyrosol and tyrosol in different types of olive extract raw materials and cosmetic cream samples has been developed. The determination was performed by liquid chromatography with UV spectrophotometric detection. Different chromatographic parameters, such as mobile phase pH and composition, oven temperature and different sample preparation variables were studied. The best chromatographic separation was obtained under the following conditions: C18 column set at 35°C and isocratic elution of a mixture ethanol: 1% acetic acid solution at pH 5 (5:95, v/v) as mobile phase pumped at 1 mL min(-1). The detection wavelength was set at …

Determination of alternative preservatives in cosmetic products by chromophoric derivatization followed by vortex-assisted liquid-liquid semimicroextraction and liquid chromatography.

An analytical method for the simultaneous determination of phenethyl alcohol, methylpropanediol, phenylpropanol, caprylyl glycol, and ethylhexylglycerin, which are used as alternative preservatives in cosmetic products, has been developed. The method is based on liquid chromatography with UV spectrophotometric detection after chromophoric derivatization with benzoyl chloride and vortex-assisted liquid-liquid semimicroextraction. Different chromatographic parameters, derivatization conditions, and sample preparation variables were studied. Under optimized conditions, the limits of detection values for the analytes ranged from 0.02 to 0.06µgmL(-1). The method was validated with good recovery …

Sensitive sequential-injection system for the determination of 2-phenylbenzimidazole-5-sulphonic acid in human urine samples using on-line solid-phase extraction coupled with fluorimetric detection

Abstract 2-Phenylbenzimidazole-5-sulphonic acid (PBS) is an UV-filter contained in many cosmetics as a sunscreen. A direct, selective and sensitive method to determine traces of PBS is presented. The on-line separation of this compound from urine matrix was directly coupled with fluorimetric detection in a sequential-injection system. The separation was performed using a SAX microcolumn in which the analyte was retained and eluted selectively. The determination is carried out without any derivatization reaction, by directly measuring the intrinsic fluorescence of the analyte. The wavelengths of excitation and emission were 301 and 681 nm, respectively. On-line standard addition calibration …

A rapid and sensitive gas chromatography-mass spectrometry method for the quality control of perfumes: simultaneous determination of phthalates

A rapid and sensitive analytical gas chromatography-mass spectrometry (GC-MS) method for perfume analysis to determine the phthalates banned by the European Union Regulation on cosmetic samples is presented. This method has been tested in commercial alcoholic perfume samples for the determination of the following seven phthalates: dibutyl phthalate, bis(2-ethylhexyl) phthalate, bis(2-methoxyethyl) phthalate, n-pentyl-isopentylphthalate, di-n-pentyl phthalate, diisopentylphthalate and benzyl butyl phthalate. Sample evaporation and redissolution in ethanol is carried out before GC-MS analysis, with no dilution of the sample. External calibration and standard addition calibration are compared …

Determination of UV-filters in sunscreens by HPLC.

Simultaneous determination of six internationally authorised organic UV-filters in sunscreen formulations was performed by HPLC with UV spectrophotometric detection. The filters determined were: sulisobenzone, oxybenzone, octyl dimethyl PABA, octyl methoxycinnamate, octyl salicylate and homosalate. A C18 stationary phase and a mobile phase of ethanol water acetic acid (70 : 29.5 : 0.5) were used with a flow rate of 0.5 mL/min. UV measurements were carried out at 313 nm. The time required for the analysis was 25 min and the limits of detection were between 0.2 and 2 mg/L, except for sulisobenzone, which gave a limit of detection of 20 mg/L. The procedure proposed provides an accurate, fast a…

Determination of UV filters in both soluble and particulate fractions of seawaters by dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry

An analytical method to determine the total content (i.e., not only in the soluble fraction but also in the particulate one) of eight commonly used UV filters in seawater samples is presented for the first time. Dispersive liquid-liquid microextraction (DLLME) is used as microextraction technique to pre-concentrate the target analytes before their determination by gas chromatography-mass spectrometry (GC-MS). In order to release the UV filters from the suspended particles an ultrasound treatment is performed before DLLME. The ultrasound treatment time was studied in order to achieve a quantitative lixiviation of the target analytes. The type and volume of both disperser and extraction solve…

Determination of N -nitrosamines in cosmetic products by vortex-assisted reversed-phase dispersive liquid-liquid microextraction and liquid chromatography with mass spectrometry

A new analytical method for the simultaneous determination of trace levels of seven prohibited N-nitrosamines (N-nitrosodimethylamine, N-nitrosoethylmethylamine, N-nitrosopyrrolidine, N-nitrosodiethylamine, N-nitrosopiperidine, N-nitrosomorpholine, and N-nitrosodiethanolamine) in cosmetic products has been developed. The method is based on vortex-assisted reversed-phase dispersive liquid-liquid microextraction, which allows the extraction of highly polar compounds, followed by liquid chromatography with mass spectrometry. The variables involved in the extraction process were studied to obtain the highest enrichment factor. Under the selected conditions, 75 μL of water as extraction solvent …

Introducing a new and rapid microextraction approach based on magnetic ionic liquids: Stir bar dispersive liquid microextraction

With the aim of contributing to the development and improvement of microextraction techniques, a novel approach combining the principles and advantages of stir bar sorptive extraction (SBSE) and dispersive liquid-liquid microextraction (DLLME) is presented. This new approach, termed stir bar dispersive liquid microextraction (SBDLME), involves the addition of a magnetic ionic liquid (MIL) and a neodymium-core magnetic stir bar into the sample allowing the MIL coat the stir bar due to physical forces (i.e., magnetism). As long as the stirring rate is maintained at low speed, the MIL resists rotational (centrifugal) forces and remains on the stir bar surface in a manner closely resembling SBS…

Flow injection spectrophotometric determination of lead using 1,5-diphenylthiocarbazone in aqueous micellar

A simple flow injection colorimetric procedure for determining lead was established. It is based on the reaction of lead in sulfuric acid with 1,5-diphenylthiocarbazone and sodium dodecyl sulfate, resulting in an intense red-blue complex with a suitable absorption at 500 nm. A standard or sample solution was injected into the sulfuric acid stream (flow rate of 2.0 ml min(-1)), which was then merged with sodium dodecyl sulfate stream (flow rate of 2.0 ml min(-1)) and 1,5-diphenylthiocarbazone stream (flow rate of 1.5 ml min(-1)). Optimum conditions for determining lead were investigated by univariate method. Under the optimum conditions, a linear calibration graph was obtained over the range…

Determination of the UV filters worldwide authorised in sunscreens by high-performance liquid chromatography

Simultaneous determination of organic UV filters worldwide authorised in sunscreen formulations was performed by HPLC with UV spectrophotometric detection. The filters determined were: benzophenone-4, benzophenone-3, butyl methoxydibenzoylmethane, octyl dimethyl PABA, octyl methoxycinnamate, homosalate and octyl salicylate. A C18 stationary phase and an isocratic mobile phase of ethanol-water-acetic acid (70:29.5:0.5) containing 65.4 mM of hydroxypropyl-beta-cyclodextrin, were used with a flow-rate of 0.6 ml/min. UV measurements were carried out at 313 nm. The time required for the analysis was 20 min and the limits of detection were between 1.5 and 2.3 mg/l. The procedure proposed provides…

General Review of Published Analytical Methods for Cosmetics

Current trends on the determination of organic UV filters in environmental water samples based on microextraction techniques – A review

UV filters are a group of cosmetic ingredients commonly used in a wide variety of cosmetic products to protect users from UV solar radiation. They belong to different chemical families, such as benzophenones, p-aminobenzoates, salicylates, cinnamates, benzotriazoles, benzimidazoles, camphor derivatives, triazines, etc. These cosmetic ingredients are considered as emerging contaminants since they easily reach the aquatic environment, where they are accumulated causing harmful effects in the flora and fauna despite being present at the ng L-1 level. Therefore, the development of sensitive and selective analytical methods for their environmental surveillance monitoring is of high interest. In …

Stir bar sorptive-dispersive microextraction for trace determination of triphenyl and diphenyl phosphate in urine of nail polish users

Abstract This work describes a new analytical method useful for monitoring the human exposure to the endocrine-disrupting plasticizer triphenyl phosphate (TPP) via nail polish use. The method allows trace determination of this parent compound and its main metabolite, namely diphenyl phosphate (DPP), in urine samples of nail polish users. The method is based on a novel microextraction technique termed stir bar sorptive-dispersive microextraction (SBSDME) using a magnetic composite made of CoFe2O4 magnetic nanoparticles embedded into a mixed-mode weak anion exchange polymer (Strata™-X-AW), followed by liquid chromatography-tandem mass spectrometry (LC–MS/MS). The main parameters involved in t…

Stir bar sorptive-dispersive microextraction mediated by magnetic nanoparticles-nylon 6 composite for the extraction of hydrophilic organic compounds in aqueous media.

A new and sensitive analytical method based on the recently developed approach termed stir bar-sorptive dispersive microextraction (SBSDME) using a magnetic CoFe2O4@SiO2-nylon 6 composite as sorbent material is presented for the extraction of hydrophilic organic compounds. The simultaneous determination of four hydrophilic UV filters in environmental water samples has been chosen as a model analytical application due to the increasing awareness regarding the occurrence of sunscreen residuals in natural waters. The developed SBSDME approach combines the principles and benefits of stir bar sorptive extraction (SBSE) and dispersive solid phase extraction (DSPE) but allows for lower extraction …

Essential Oils: Analytical Methods to Control the Quality of Perfumes

Cosmetic products, including perfumes, are regulated by a single law concerning important aspects, such as composition or labeling, in order to protect public health. A revision on the regulatory aspects for fragrance chemicals in cosmetics and household products is exposed here. Quality control of both, commercial perfumes and raw materials, is important for perfume manufacturers to assure that the finished perfume is the one that was formulated. On the other hand, analytical methods are necessary to assure, for safety purposes, that there are no undesired or banned compounds present in the finished product. Methods for perfume analysis are compiled and revised with special emphasis on the…

Synergistic combination of polyamide-coated paper-based sorptive phase for the extraction of antibiotics in saliva.

Abstract The development of analytical methods that allow the simultaneous determination of a wide range of analytes with different properties is one of the focuses of attention in Analytical Chemistry. This work describes a proof-of-concept of the synergistic extraction of a planar paper-based sorptive phase modified with a polyamide such as nylon. This as-prepared sorptive phase enables the extraction of six penicillin-derived antibiotics of different polarity from human saliva samples in the same analysis, since the analytes either interact with the paper or with the nylon. The synthesis of the sorptive phase is simple as it only requires dipping the paper into an organic solution of the…

Environmental Monitoring of Cosmetic Ingredients

Abstract Since the late 1990s there has been an increasing concern regarding the release and accumulation of cosmetic ingredients in the environment. These compounds reach the aquatic environment by direct sources, such as bathing activities, but also by indirect sources due to industrial activities, showering, domestic washing, etc., through wastewater treatment plants at which they are not completely removed. As a result, studies have shown that cosmetic ingredients can be found not only in the water phase but also in sediments, soils and living organisms, thus affecting the flora and fauna of the aquatic environment. In this chapter, the fundamental principles of sample preparation metho…

Effects of UV filter 4-methylbenzylidene camphor during early development of Solea senegalensis Kaup, 1858

Abstract The inclusion of organic UV filters in personal care products (PCPs) has increased in recent years. 4-Methylbenzylidene camphor (4MBC) is one of the most used UV filters, and thus it is commonly found in aquatic ecosystems, with proved negative effects on aquatic organisms. Effects on early life stages of marine vertebrates are largely unknown. Therefore, the main goal of this work was to evaluate 4MBC effects on Senegalese sole (Solea Senegalensis Kaup, 1858) larvae at different levels of biological organization. S. senegalensis were exposed to increasing concentrations of 4MBC from egg stage until 96 h. Mortality, growth, malformations, behaviour and biochemical responses, includ…

An environmentally friendly (“green”) reversed-phase liquid chromatography method for UV filters determination in cosmetics

Abstract A green procedure based on reversed-phase liquid chromatography with gradient elution using environmentally friendly solvents, has been developed to determine 18 UV filters, which are most used in Europe nowadays as sunscreen in cosmetics. Samples were weighed and dissolved in ethanol. Two aliquots were taken from the initial sample solution to prepare two solutions, so analytes could be determined chromatographically in two groups (the most fat-soluble and the easily water-soluble ones) using a different gradient elution program for each group. The mobile phases were based on mixtures of ethanol and 1% acetic acid or 1% sodium acetate buffer pH 4.75. The same C18 stationary phase …

On-line extraction coupled to liquid chromatographic analysis of hydrophobic organic compounds from complex solid samples-Application to the analysis of UV filters in soils and sediments.

This work investigates the applicability of on-line extraction (OLE) directly coupled to liquid chromatography (LC) for the dynamic extraction of hydrophobic organic compounds from complex solid samples. The method operates within the existing apparatus of the LC by replacing the valve loop with an extraction vessel comprised of an empty guard column loaded with the sample. In this manner, extraction is accomplished by the mobile phase as it flows through the extraction vessel under high pressure without the need for additional apparatus other than those comprising the LC system or additional sample pretreatment steps. The experimental parameters affecting the extraction efficiency of the m…

Determination of atranol and chloroatranol in perfumes using simultaneous derivatization and dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

Abstract A new analytical method based on simultaneous derivatization and dispersive liquid–liquid microextraction (DLLME) followed by gas chromatography–mass spectrometry (GC–MS), for the determination of the allergenic compounds atranol and chloroatranol in perfumes, is presented. Derivatization of the target analytes by means of acetylation with anhydride acetic in carbonate buffer was carried out. Thereby volatility and detectability were increased for improved GC–MS sensitivity. In addition, extractability by DLLME was also enhanced due to a less polar character of the solutes. A liquid–liquid extraction was performed before DLLME to clean up the sample and to obtain an aqueous sample …

Modified magnetic-based solvent-assisted dispersive solid-phase extraction: application to the determination of cortisol and cortisone in human saliva.

A modification of magnetic-based solvent-assisted dispersive solid-phase extraction (M-SA-DSPE) has been employed for the determination of the biomarkers cortisol and cortisone in saliva samples. M-SA-DSPE is based on the dispersion of the sorbent material by using a disperser solvent like in dispersive solid phase extraction (SA-DSPE) but a magnetic sorbent is used like in magnetic dispersive solid-phase extraction (M-DSPE). Thus, the magnetic sorbent containing the target analytes is retrieved using an external magnet like in M-DSPE. Finally, the analytes are desorbed into a small volume of organic solvent for the subsequent chromatographic analysis. To this regard, a M-SA-DSPE-based meth…

Efficient flow injection and sequential injection methods for spectrophotometric determination of oxybenzone in sunscreens based on reaction with Ni(II).

Spectrophotometric determination of a widely used UV-filter, such as oxybenzone, is proposed. The method is based on the complexation reaction between oxybenzone and Ni(II) in ammoniacal medium. The stoichiometry of the reaction, established by the Job method, was 1:1. Reaction conditions were studied and the experimental parameters were optimized, for both flow injection (FI) and sequential injection (SI) determinations, with comparative purposes. Sunscreen formulations containing oxybenzone were analyzed by the proposed methods and results compared with those obtained by HPLC. Data show that both FI and SI procedures provide accurate and precise results. The ruggedness, sensitivity and LO…

A simple novel configuration for in-vial microporous membrane liquid–liquid extraction

Abstract A novel arrangement for microporous membrane liquid–liquid extraction from the aqueous donor phase to the organic acceptor phase within a micro-vial, which is compatible with the chromatograph autosampler is presented. The device consisted of a stoppered glass micro-vial containing the organic solvent where the septum of the screw stopper was replaced by a sized piece of membrane which is hermetically assembled to the volumetric flask containing the aqueous donor solution. The placement of the membrane in alternative contact with the solutions was achieved by orbital agitation. As a preliminary study, 2-ethylhexyl 4-(dimethylamino)benzoate has been determined (limit of quantificati…

Near-critical carbon dioxide extraction and liquid chromatography determination of UV filters in solid cosmetic samples: A green analytical procedure

Near-critical carbon dioxide extraction of four UV filters used as sunscreens in lipsticks and makeup formulations is reported. Extraction parameters were optimized. Efficient recoveries were obtained after 15 min of dynamic extraction with a 80:20 CO2/ethanol mixture at 300 atm and 54 degrees C, using a 1.8 mL/min flow rate. Extracts were collected in ethanol, and appropriately diluted with ethanol and 1% acetic acid to obtain a 70:30 v/v ethanol/1% acetic acid solution. The four UV filters were determined by LC with gradient elution using ethanol/1% acetic acid as mobile phase. The accuracy of the analytical procedure was estimated by comparing the results with those obtained by methods b…

Reduced graphene oxide-based magnetic composite for trace determination of polycyclic aromatic hydrocarbons in cosmetics by stir bar sorptive dispersive microextraction

This work describes a sensitive and rapid analytical method for trace determination of polycyclic aromatic hydrocarbons (PAHs) in cosmetic samples. The proposed method is based on stir bar sorptive-dispersive microextraction (SBSDME). A magnetic composite made of CoFe2O4 magnetic nanoparticles embedded into reduced graphene oxide sheets is used as sorbent phase. After the extraction, the target analytes are desorbed in toluene and then analyzed by gas chromatography-mass spectrometry (GC-MS). The main parameters involved in the extraction procedure (i.e., composite amount, extraction time and desorption time) were evaluated and optimized to provide the best extraction efficiency. The method…

A rapid and reliable size-exclusion chromatographic method for determination of kojic dipalmitate in skin-whitening cosmetic products

A size-exclusion chromatographic method has been developed to determine the relatively novel skin-whitening agent called kojic dipalmitate (KDP) in skin-whitening cosmetic products. Preliminary experiments were carried out in order to select the solvent for standard and sample solution, and also for mobile phase composition. A PLGel Mixed-D (polystyrene/divinylbenzene co-polymer) column and isocratic mobile phase of pure tetrahydrofuran (at 1.5 mL min(-1) flow rate) were used. Detection was carried out by means of an UV/vis spectrometry detector set at 248 nm. A study of interferences reveals that KDP can be determined without interferences coming from cosmetic matrices. Most other cosmetic…

Sunscreen Products as Emerging Pollutants to Coastal Waters

A growing awareness of the risks associated with skin exposure to ultraviolet (UV) radiation over the past decades has led to increased use of sunscreen cosmetic products leading the introduction of new chemical compounds in the marine environment. Although coastal tourism and recreation are the largest and most rapidly growing activities in the world, the evaluation of sunscreen as source of chemicals to the coastal marine system has not been addressed. Concentrations of chemical UV filters included in the formulation of sunscreens, such as benzophehone 3 (BZ-3), 4-methylbenzylidene camphor (4-MBC), TiO2 and ZnO, are detected in nearshore waters with variable concentrations along the day a…

A chromatochemometric approach for evaluating and selecting the perfume maceration time.

Abstract A chemometric treatment of the data obtained by gas chromatography (GC) with flame ionization detector (FID) has been proposed to study the maceration time involved in perfumes manufacture with the final purpose of reducing this time but preserving the organoleptic characteristics of the perfume that is being elaborated. In this sense, GC–FID chromatograms were used as a fingerprint of perfume samples subjected to different maceration times, and data were treated by linear discriminant analysis (LDA), by comparing to a set of samples known to be macerated or not, which were used as calibration objects. The GC–FID methodology combined with the treatment of data by LDA has been appli…

A solid-phase extraction liquid chromatography-tandem mass spectrometry method for the percutaneous absorption assessment of 3-(4′-methylbenzylidene)camphor via human urine analysis

The UV filter 3-(4′-methylbenzylidene)camphor (MBC) is a common ingredient in sunscreen cosmetic products. However, different in vitro and in vivo studies suggest that MBC can cause endocrine disrupting effects. This report focuses on the development of an analytical method based on solid-phase extraction (SPE) prior to liquid chromatography tandem mass spectrometry (LC-MS/MS) for the determination of MBC and its main phase I metabolite, named 3-(4′-carboxybenzylidene)camphor (CBC), in urine from users of sunscreen cosmetic products containing MBC. The formation of phase II metabolites (i.e., glucuronide and sulphate conjugates) was also considered by carrying out an enzymatic hydrolysis of…

Use of green alternative solvents in dispersive liquid‐liquid microextraction: A review

Dispersive liquid-liquid microextraction is one of the most widely used microextraction techniques currently in the Analytical Chemistry field, mainly due to its simplicity and rapidity. The operational mode of this approach has been constantly changing since its introduction, adapting to new trends and applications. Most of these changes are related to the nature of the solvent employed for the microextraction. From the classical halogenated solvents (e.g., chloroform or dichloromethane), different alternatives have been proposed in order to obtain safer and non-pollutants microextraction applications. In this sense, low density solvents, such as alkanols, switchable hydrophobicity solvent…

Development of stir bar sorptive-dispersive microextraction mediated by magnetic nanoparticles and its analytical application to the determination of hydrophobic organic compounds in aqueous media

A novel microextraction technique combining the principles of stir bar sorptive extraction (SBSE) and dispersive micro-solid phase extraction (DμSPE) is presented. The main feature of the method is the use of a neodymium-core stirring bar physically coated with a hydrophobic magnetic nanosorbent. Depending on stirring speed, the magnetic sorbent either acts as a coating material to the stir bar, thus affording extraction alike SBSE, or as a dispersed nanosorbent medium for the collection and extraction of the target analytes, in close analogy to DμSPE. Once the stirring process is finished, the strong magnetic field of the stir bar prevails again and rapidly retrieves the dispersed MNPs. Al…

Development of a gas chromatography-mass spectrometry method for the determination of ultraviolet filters in beach sand samples

An analytical method for the determination of eight fat-soluble ultraviolet (UV) filters in beach sand samples is presented for the first time. The method is based on a leaching process of the target compounds from sand samples using vortex mixer agitation and further centrifugation, followed by dispersive liquid–liquid microextraction (DLLME) of the supernatant and gas chromatography-mass spectrometry (GC-MS) analysis of the DLLME extract. The variables involved in the leaching and in the DLLME processes were studied to provide the best enrichment factors. In the first case, the leaching solvent type and volume, and the vortex mixer agitation time were studied. In the case of the DLLME, th…

Determination of benzophenone-3 and its main metabolites in human serum by dispersive liquid–liquid microextraction followed by liquid chromatography tandem mass spectrometry

A new analytical method for the determination of benzophenone-3 (2-hydroxy-4-methoxybenzophenone), and its main metabolites (2,4-dihydroxybenzophenone and 2,2'-dihydroxy-4-methoxybenzophenone) in human serum is presented. The method is based on dispersive liquid-liquid microextraction (DLLME) as preconcentration and clean-up technique, followed by liquid chromatography tandem mass spectrometry (LC-MS/MS). Acidic hydrolysis and protein precipitation with HCl 6 M (1:1) (100 °C, 1 h) were carried out before extraction. The variables involved in the DLLME process were studied. Under the optimized conditions, 70 µL of acetone (disperser solvent) and 30 µL of chloroform (extraction solvent) were …

Stir bar sorptive-dispersive microextraction mediated by magnetic nanoparticles-metal organic framework composite: Determination of N-nitrosamines in cosmetic products

Abstract A new analytical method based on the recently proposed stir bar sorptive-dispersive microextraction (SBSDME) technique has been developed to determine eight hazardous N-nitrosamines in cosmetic products. As previous step, a simple clean-up is carried out with hexane to remove those highly lipophilic compounds that disturb the SBSDME step. Subsequently, SBSDME is performed by using magnetic nanoparticles–metal organic framework composite, CoFe2O4/MIL-101(Fe), as sorbent to entrap the target analytes, which are later chemically desorbed and measured by liquid chromatography–tandem mass spectrometry (LC–MS/MS). The experimental variables related to the SBSDME procedure were studied to…

Dispersive micro-solid phase extraction

Abstract Dispersive micro-solid phase extraction (D-μSPE) has gained special attention in the sample preparation process due to its simplicity, speed and efficiency. Different dispersion approaches have been used within this technique to allow a close contact between the sorbent and the donor sample solution during the entrapping step, but also between the sorbent and the solvent in the elution step. This dispersion favors the kinetics of both sorption and elution and therefore increases the efficiency of the overall extraction procedure. This technique boasts of high versatility owing to the great variety of solids available, covering a high range of chemical functionalities. This article …

A solid-phase extraction and size-exclusion liquid chromatographic method for polyethylene glycol 25 p-aminobenzoic acid determination in urine: Validation for urinary excretion studies of users of sunscreens

No previous publications about percutaneous absorption of polyethylene glycol 25 p-aminobenzoic acid (PEG-25 PABA) have been found in the literature and the expected levels to be found in human urine after sunscreens use are unknown. The method proposed here is suitable to determine PEG-25 PABA in the urine of sunscreens users in order to carry out studies on body accumulation/excretion. It is based on solid-phase extraction (SPE) with size-exclusion liquid chromatography determination. Solid-phase extraction allows the analyte to be retained and subsequently eluted for a clean-up, using a silica-based cartridge. The size-exclusion liquid chromatography of the eluted allows the rest of matr…

Determination of 3-(4′-methylbenzylidene)camphor and its metabolite 3-(4′-carboxybenzylidene)camphor in human semen by solid-phase extraction and liquid chromatography tandem mass spectrometry

An analytical method for the determination of the controversial UV filter 3-(4′-methylbenzylidene)camphor (MBC) and its metabolite 3-(4′-carboxybenzylidene)camphor (CBC) in human semen is presented. The method is based on the simultaneous hydrolysis of phase II conjugates and protein precipitation, followed by solid-phase extraction (SPE) and liquid chromatography tandem mass spectrometry (LC-MS/MS) detection. The proposed method was validated by analyzing spiked analyte-free human semen samples. Matrix-matched calibration using an analyte-free semen pool was employed. Satisfactory recoveries (92–114%) were obtained using this calibration methodology, thus showing the accuracy of the propos…

Analytical Methodologies for the Determination of Personal Care Products in Water Samples

Personal-care products (PCPs) could reach the aquatic environment and cause a great impact in the aquatic ecosystem. In this sense, the monitoring of these emerging pollutants in the environment yields valuable information. For this reason, analytical methods to determine PCPs in environmental waters are needed. Due to the low concentration of the PCPs, i.e. ng L−1, sensitive methods are needed. This required sensitivity can be achieved by using sensitive analytical techniques during the measurement step, or by employing enrichment techniques during the sample treatment step. Obviously, the combination of both sensitive analytical techniques and extraction techniques considerably improves t…

Use of Nanomaterial-Based (Micro)Extraction Techniques for the Determination of Cosmetic-Related Compounds

The high consumer demand for cosmetic products has caused the authorities and the industry to require rigorous analytical controls to assure their safety and efficacy. Thus, the determination of prohibited compounds that could be present at trace level due to unintended causes is increasingly important. Furthermore, some cosmetic ingredients can be percutaneously absorbed, further metabolized and eventually excreted or bioaccumulated. Either the parent compound and/or their metabolites can cause adverse health effects even at trace level. Moreover, due to the increasing use of cosmetics, some of their ingredients have reached the environment, where they are accumulated causing harmful effec…

Toxicity effects of the organic UV-filter 4-Methylbenzylidene camphor in zebrafish embryos

Abstract Ultraviolet (UV) filters are widely used in personal care products and due to their lipophilicity these chemicals tend to bioaccumulate in the aquatic biota. 4-Methylbenzylidene camphor (4-MBC) is one of the most used UV-filters, and it is commonly detected in freshwater fish tissues. This substance is suspected to be an endocrine disruptor due to its interaction with Hypothalamus-Pituitary-Gonadal (HPG) and HP-Thyroid (HPT)-axis. The main objective of this study was to evaluate the effects of 4-MBC on apical endpoints, biochemical markers and on genes involved in endocrine pathways in Danio rerio. Zebrafish embryos were exposed to 4-MBC (0.083–0.77 mg/l) from 0 to 96 h post-fertil…

UV filters: From sunscreens to human body and the environment

Recognition of the harmful effects of ultraviolet (UV) radiation on the skin has triggered development of organic chemicals (commonly referred as UV filters) that can absorb UV radiation and attenuate the negative effects of sunlight exposure. Depending on the properties and the intended degree of protection, a wide array of combinations is being marketed as delivering protection against most kinds of UV-induced skin damage. However, some UV filters have dermatological implications, so maximum applicable concentrations have been established. To monitor to what extent commercial products comply with the mandatory limits, several analytical methods have been used for their determination in co…

Analytical Methods for Actives used in General and Specific Skin-Care, Personal Hygiene and other Toiletry Products (Excluding those Mentioned in Previous Chapters)

Development of a sensitive method for determining traces of prohibited acrylamide in cosmetic products based on dispersive liquid-liquid microextraction followed by liquid chromatography-ultraviolet detection

Abstract According to the European Regulation on cosmetic products, the presence of acrylamide in these consumer products is not allowed due to its mutagenic and potentially carcinogenic effects. Despite this ban, acrylamide might be present in those cosmetic products containing acrylamide-based polymers. However, there is no analytical method for its determination in this type of matrices. Based on this, the development of analytical methods for the determination of acrylamide in cosmetic products is required to guarantee consumer safety. In this work, an analytical method for determining traces of prohibited acrylamide in cosmetic products is presented for the first time. The method is ba…

Green, rapid and simultaneous determination of ‘alternative preservatives’ in cosmetic formulations by gas chromatography-mass spectrometry

Abstract Some hydroxylated compounds commonly used in cosmetic formulations including short chain glycols, benzylic alcohols, and organic acids show antimicrobial activity, although they are not considered as preservatives according to the existing European legislation. These ‘alternative preservatives’ are not exempt of potential side-effects for cosmetics users. The aim of this work is to develop a simple and affordable analytical method useful for the simultaneous and green determination of fourteen compounds used as ‘alternative preservatives’ in cosmetic samples with different matrices. The proposed method allows a rapid sample preparation by simple dissolution or dispersion of the sam…

Ultraviolet Filters in Cosmetics

Abstract UV filters are used in sunscreen cosmetics to protect skin from the sunlight. Nowadays, they are also incorporated into other daily-use cosmetics. However, many concerns about their safety have been raised, because they can be absorbed through the skin, further metabolized and eventually bioaccumulated and/or excreted. These percutaneous absorption processes may result in various adverse health effects (i.e., allergic contact dermatitis) and other more serious systemic effects, such as carcinogenic and oestrogenic activity. For this reason, UV filters as well as their maximum allowed concentrations have been regulated by the legislations in force. In this sense, analytical control …

Sunscreen analysis

Although there are no official analytical methods for UV filters determination in sunscreen cosmetics, their maximum content are regulated by legislation, and then analytical methods to control these products are necessary. In this paper, analytical methods for UV filters determination in cosmetics, which can be found in the literature, are reviewed. The usefulness of the analytical methods, techniques and sample preparation is discussed. The analytical methods used for the determination of UV filters in other type of samples are commented upon. Moreover, a brief overview of the European Union legislation concerning UV filters is included.

Expanding the application of stir bar sorptive-dispersive microextraction approach to solid matrices: Determination of ultraviolet filters in coastal sand samples

This work describes a new method for the determination of organic compounds in solid samples based on the equilibrium desorption of the analytes in an aqueous phase followed by stir bar sorptive-dispersive microextraction (SBSDME). Sand samples, contaminated with UV filters due to bathing and recreational activities, were dispersed in an aqueous medium by using a coated stir bar with CoFe2O4@oleic acid magnetic nanoparticles. The UV filters were physically desorbed from the surface of the sand particles and rapidly adsorbed on the hydrophobic coating of the nanoparticles, which were retrieved by means of their magnetism after stopping the stirring. In this manner, both preconcentration of t…

Development of a selective solid phase extraction method for nitro musk compounds in environmental waters using a molecularly imprinted sorbent

A powerful analytical method for the determination of the family of the nitro musk compounds at trace level in environmental waters-river, sea, and water from a treatment plant-is presented. The method is based on the use of molecularly imprinted silica (MIS) as sorbent for solid phase extraction (SPE) used for the clean-up and the concentration step of the target analytes previous to their determination by gas chromatography-mass spectrometry. The optimized extraction procedure allowed extraction recoveries between 61% and 87% using the MIS. The comparison with a non-imprinted silica (NIS) sorbent, for which extraction recoveries between 8% and 26% were obtained, showed the high selectivit…

A reliable and environmentally-friendly liquid-chromatographic method for multi-class determination of fat-soluble UV filters in cosmetic products.

An environmentally-friendly analytical method for the simultaneous determination of 15 fat-soluble ultraviolet (UV) filters currently authorized by the European Union regulation on cosmetic products has been developed. The determination was performed by liquid chromatography with UV spectrophotometric detection. Different parameters, such as type of column, oven temperature, mobile phase composition and flow rate were studied. The best chromatographic separation was obtained under the following conditions: C18 column set at 60°C and gradient ethanol:water (containing 1% formic acid and 20mM of 2-hydroxypropyl-β-cyclodextrin) as mobile phase pumped at 1mL min(-1). 2-Hydroxypropyl-β-cyclodext…

Sensitive determination of free benzophenone-3 in human urine samples based on an ionic liquid as extractant phase in single-drop microextraction prior to liquid chromatography analysis.

Abstract Benzophenone-3 (BZ3), one of the compounds most commonly used as UV filter in cosmetic products, can be absorbed through the skin into the human body, since it can be found at trace levels in urine from users of cosmetic products that contain BZ3. Moreover, different undesirable effects have been attributed to this compound. Thus, sensitive analytical methods to monitor urinary excretion of this compound should be developed. This paper presents a selective and sensitive methodology for BZ3 determination at ultratrace levels in human urine samples. The methodology is based on a novel microextraction technique, known as single-drop microextraction (SDME). An ionic liquid (IL) has bee…

Sequential-injection determination of traces of disodium phenyl dibenzimidazole tetrasulphonate in urine from users of sunscreens by on-line solid-phase extraction coupled with a fluorimetric detector

Abstract A sensitive and selective method to determine disodium phenyl dibenzimidazole tetrasulphonate (PDT) in the urine of sunscreen users, which is suitable for studies on body accumulation/excretion is proposed. On-line solid-phase extraction allows the analyte to be retained and subsequentely eluted, using a strong anion exchange (SAX) microcolumn. Standard addition calibration was carried out with only one standard. The wavelengths of excitation and emission were 330 and 454 nm, respectively. The method allows PDT to be determined in both, spiked and unspiked human urine samples, without any pre-treatment. Results obtained for spiked urine samples (40–200 ng ml −1 ) showed the accurac…

An overview of the analytical methods for the determination of organic ultraviolet filters in biological fluids and tissues.

Organic UV filters are chemical compounds added to cosmetic sunscreen products in order to protect users from UV solar radiation. The need of broad-spectrum protection to avoid the deleterious effects of solar radiation has triggered a trend in the cosmetic market of including these compounds not only in those exclusively designed for sun protection but also in all types of cosmetic products. Different studies have shown that organic UV filters can be absorbed through the skin after topical application, further metabolized in the body and eventually excreted or bioaccumulated. These percutaneous absorption processes may result in various adverse health effects, such as genotoxicity caused b…

Environmentally friendly LC for the simultaneous determination of ascorbic acid and its derivatives in skin-whitening cosmetics

Ascorbic acid (AA), also known as vitamin C, is a very popular skin-whitening agent used in cosmetics. However, the use of AA (and also its sodium or magnesium salts) in cosmetic products is limited owing to its labile oxidative properties. In order to avoid its early degradation, different derivatives have been designed, such as ascorbyl phosphate (APH; as magnesium or sodium salts) and ascorbyl palmitate (AP), and more recently the ascorbyl glucoside (AG). Bearing in mind that all these chemicals in skin-whitening cosmetic products must be determined in order to control the efficacy of such products, this paper focuses on developing a wide-ranging LC analytical method able to determine th…

Indirect spectrophotometric determination of p-aminobenzoic acid in sunscreen formulations by sequential injection analysis

Abstract A simple indirect sequential injection spectrophotometric method for the determination of the UV-filter p -aminobenzoic acid (PABA) in sunscreen formulations is proposed. The determination is based on the reaction of PABA with hypochlorite in acidic medium and the subsequent measurement of the residual chlorine by using the well-known reaction with o -tolidine. The experimental variables involved in the sequential injection analysis (SIA) system (sandwich arrangement, volumes of sample and reagents, propulsion flow rate, reaction coil length) and adequate concentrations of reagents were studied. The SIA method has a linear range up to 20 μg ml −1 (3 s y / x / b detection limit) of …

Dispersive solid-phase extraction based on oleic acid-coated magnetic nanoparticles followed by gas chromatography-mass spectrometry for UV-filter determination in water samples.

Abstract A sensitive analytical method to concentrate and determine extensively used UV filters in cosmetic products at (ultra)trace levels in water samples is presented. The method is based on a sample treatment using dispersive solid-phase extraction (dSPE) with laboratory-made chemisorbed oleic acid-coated cobalt ferrite (CoFe 2 O 4 @oleic acid) magnetic nanoparticles (MNPs) as optimized sorbent for the target analytes. The variables involved in dSPE were studied and optimized in terms of sensitivity, and the optimum conditions were: mass of sorbent, 100 mg; donor phase volume, 75 mL; pH, 3; and sodium chloride concentration, 30% (w/v). After dSPE, the MNPs were eluted twice with 1.5 mL …

Rapid and Simple Determination of Honokiol and Magnolol in Cosmetic Products by Liquid Chromatography with Ultraviolet Detection

A rapid and simple analytical method based on liquid chromatography – ultraviolet detection has been developed and validated for the simultaneous determination of two high added-value cosmetic ingr...

Determination of hydroxylated benzophenone UV filters in sea water samples by dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

A new analytical method for the determination of four hydroxylated benzophenone UV filters (i.e. 2-hydroxy-4-methoxybenzophenone (HMB), 2,4-dihydroxybenzophenone (DHB), 2,2'-dihydroxy-4-methoxybenzophenone (DHMB) and 2,3,4-trihydroxybenzophenone (THB)) in sea water samples is presented. The method is based on dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography-mass spectrometry (GC-MS) determination. The variables involved in the DLLME process were studied. Under optimized conditions, 1000 microL of acetone (disperser solvent) containing 60 microL of chloroform (extraction solvent) were injected into 5 mL of aqueous sample adjusted to pH 4 and containing 10% NaCl…

Determination of Phenolic Endocrine Disruptors in Cosmetics by High-Performance Liquid Chromatography Mass Spectrometry

An analytical method for the simultaneous determination of bisphenol A, 4-t-octylphenol, 4-n-octylphenol, and 4-n-nonylphenol in cosmetic samples has been developed. These compounds have toxic effe...

Determination of butyl methoxydibenzoylmethane, benzophenone-3, octyl dimethyl PABA and octyl methoxycinnamate in lipsticks.

The complex composition of lipstick formulations usually needs the use of organic solvents for sample dissolution. A treatment based on dissolution of cosmetic samples in ethanol-water (70 : 30, v/v) by use of ultrasonic irradiation is proposed. A C(18) stationary phase and an isocratic mobile phase of ethanol:water:acetic acid (70 : 29.5 : 0.5, v/v/v) with a flow rate of 1 mL min(-1) and an injection volume of 20 microL is proposed for the high-pressure liquid chromatography (HPLC) determination of four UV-filters, and detection was carried out at 309 nm. The limit of the chromatographic detection was 7.0 microg mL(-1) for butyl methoxydibenzoylmethane, 1.5 microg mL(-1) for benzophenone-3…

Simple and commercial readily-available approach for the direct use of ionic liquid-based single-drop microextraction prior to gas chromatography

A simple and commercial readily-available approach that enables the direct use of ionic liquid (IL)-based single-drop microextraction (SDME) prior to gas chromatography (GC) is presented. The approach is based on thermal desorption (TD) of the analytes from the IL droplet to the GC system, by using a robust and commercially-available thermodesorption system. For this purpose, a two-glass-tube concentrically disposed system was designed. The inner tube is a laboratory-cut Pyrex tube (20mm length) that houses the ionic liquid droplet from the SDME process, and the outer tube is a commercially-available TD glass tube (187 mm length) commonly employed for stir-bar sorptive extractions (SBSE). I…

Selection From Bibliographic Resources of an Analytical Method for Cosmetic Products

Abstract This chapter is focussed on a general strategy to select an appropriate method from the scientific literature to solve an analytical problem in cosmetic analysis using useful and flexible web tools. A short introduction on the use of ScienceDirect (Elsevier), Scopus (Elsevier), SciFinder Scholar (American Chemical Society), Web of Science (Thomson Reuters) and the freely available Google Scholar is given. The main analytical features to be considered in the selection of the method, such as limit of detection, limit of quantification, linearity, precision (repeatability, intermediate precision and reproducibility), selectivity, robustness and accuracy, are briefly described. Additio…

Development of a fully automated sequential injection solid-phase extraction procedure coupled to liquid chromatography to determine free 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid in human urine

Abstract 2-Hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid, commonly known as benzophenone-3 (BZ3) and benzophenone-4 (BZ4), respectively, are substances widely used as UV filters in cosmetic products in order to absorb UV radiation and protect human skin from direct exposure to the deleterious wavelengths of sunlight. As with other UV filters, there is evidence of their percutaneous absorption. This work describes an analytical method developed to determine trace levels of free BZ3 and BZ4 in human urine. The methodology is based on a solid-phase extraction (SPE) procedure for clean-up and pre-concentration, followed by the monitoring of the UV filters by…

Trace determination of volatile polycyclic aromatic hydrocarbons in natural waters by magnetic ionic liquid-based stir bar dispersive liquid microextraction.

In this work, a novel hybrid approach called stir bar dispersive liquid microextraction (SBDLME) that combines the advantages of stir bar sorptive extraction (SBSE) and dispersive liquid-liquid microextraction (DLLME) has been employed for the accurate and sensitive determination of ten polycyclic aromatic hydrocarbons (PAHs) in natural water samples. The extraction is carried out using a neodymium stir bar magnetically coated with a magnetic ionic liquid (MIL) as extraction device, in such a way that the MIL is dispersed into the solution at high stirring rates. Once the stirring is ceased, the MIL is magnetically retrieved onto the stir bar, and subsequently subjected to thermal desorptio…

A gas chromatography-mass spectrometric method to determine skin-whitening agents in cosmetic products.

An analytical method is proposed here to determine three allowed (kojic acid, azelaic acid and arbutin) and two forbidden (resorcinol and hydroquinone) skin-whitening agents in cosmetics. The method is based on gas chromatography coupled with mass spectrometric detection, which allows the two prohibited target compounds to be identified unequivocally by means of their mass spectra acquired in full-scan mode at the retention time of these compounds. Owing to their low volatility, target analytes are derivatized using N,O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA) (containing 1% trimethylchlorosylane) prior to injection into the chromatographic system. The accuracy and precision of the pr…

Polydopamine-coated magnetic nanoparticles for the determination of nitro musks in environmental water samples by stir bar sorptive-dispersive microextraction.

Magnetic-based microextraction approaches have gained popularity in recent years due to the magnetic properties of the extraction phases allowing to handle them easier and more efficiently. This work describes a magnetic-based analytical method for the determination of the family of nitro musks in environmental water samples. These compounds have been of great concern due to their environmental impacts and potential health effects. The method is based on stir bar sorptive-dispersive microextraction (SBSDME) as extraction approach, prior to thermal desorption coupled to gas chromatography-mass spectrometry analysis (TD-GC-MS). For this purpose, polydopamine-coated cobalt ferrite magnetic nan…