Hair Dyes in Cosmetics. Regulatory Aspects and Analytical Methods

Abstract Fragrance ingredients are extensively used in perfumes and other cosmetics, providing us with a pleasant scent. However, different fragrance chemicals and other chemicals present in perfume composition have been shown to cause undesirable side effects. The EC Regulation prohibits and limits the contents of some of them in cosmetics. Other international organizations, such as the International Fragrance Association and the Research Institute for Fragrance Materials, work on the safety of fragrance chemicals and release reports on the convenience or not of using certain fragrance chemicals in cosmetics, depending on their toxicity. This chapter is focussed on the determination of fra…

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.

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…

On-line microwave oven digestion flame atomic absorption analysis of solid samples

Abstract A manifold has been developed for on-line microwave oven digestion and flame atomic absorption spectrometric (FAAS) determination of metallic elements in solid samples. The use of a closed flow system permits sample treatment before analysis by FAAS, the direct injection of slurries avoids a filtration step and the interconnection of two conventional rotary injection valves allows the rapid introduction of samples and standards. The determination of lead in sewage sludge was employed as a test system for the proposed on-line sample digestion manifold. The procedure has a limit of detection of 0.2 μg Pb g−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 …

Extension of the dynamic range of flame atomic absorption spectrometry using flow injection analysis with variable-volume dilution chambers

Abstract A simple and inexpensive procedure is proposed for the extension of the dynamic range of flame atomic absorption spectrometry measurements using on-line dilution. The proposed methodology is based on the use of a manifold with two coupled dilution chambers and a zone injection system. The samples are prediluted in a closed system which includes a variable-volume mixing chamber (10–120 ml) and two injection valves. The samples are injected through one of these valves, and the other is employed to take 100 μl of prediluted samples which are then passed through a new dilution chamber (volume 1–10 ml) and aspirated by the nebulizer of the instrument. A third injection valve mounted in …

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…

In vitro skin penetration of bronidox, bronopol and formaldehyde from cosmetics

The objective was to evaluate the influence of the formulation in the in vitro transdermal absorption through pig ear skin of three preservatives, bronopol, bronidox and formaldehyde as well as the absorption of formaldehyde from bronopol and dimethyloldimethyl hydantoin (DMDM hydantoin). An aqueous solution, an O/W emulsion and a hydrogel were assayed. Bronidox and bronopol absorption depends on the formulation. The O/W emulsion was the system that least promoted absorption of bronidox while the absorption of bronopol was lower from the hydrogel. The aqueous solution provided maximal transdermal absorption of both preservatives. Moreover, the transdermal absorption of formaldehyde released…

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…

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…

Electrothermal Atomic Absorption Determination of Chromium in Sediments

Abstract An electrothermal atomic absorption spectrometric method has been developed to determine total chromium concentration in natural sediment samples. Samples were mineralized by dry ashing at 550°C and fused at 1100°C for 30 min with lithium metaborate. Dissolved samples were injected in graphite tubes, mineralized at 1100°C, and atomized at 2600°C. Standard addition calibration made unnecessary the use of chemical modifiers. The method provided a limit of detection from 23 to 45 ng liter −1 . The relative standard deviation for chromium determination was between 3 and 14%. Results obtained for a standard reference material agree well with the certified value. A series of natural samp…

Supercritical Fluid Extraction and Supercritical Fluid Chromatography of Vitamin E in Pharmaceutical Preparations

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…

Speciation of tetraalkyllead compounds by flow injection — atomic absorption spectrophotometry

The on-line demetallation of alkyllead compounds, with iodine, and further emulsification, provides a fast determination of total lead content in liposoluble matrices, such as gasolines. It can be carried out in a double channel manifold, using a magnetically well stirred dilution chamber for the emulsification of the samples, previous to their analysis by flame atomic absorption spectrophotometry. On the other hand, the different behaviour of tetraethyllead (TEL) and tetramethyllead (TML) can be employed for speciation of both compounds in the sample. The effect of the flow injection parameters on the sensitivity and accuracy has been studied and the figures of merit of the proposed method…

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 …

Chromium speciation in liquid matrices: a survey of the literature

A thorough review of the literature published (1983 - March 1999) on chromium speciation in liquid samples is presented, and analytical techniques used in the 404 articles are summarized. The discussion focuses on atomic spectrometric techniques, which are mainly employed for chromium speciation in liquid matrices (134 articles). Details on the type of pretreatment, species, samples, techniques and analytical features of the methodologies proposed are given.

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 …

Microwave muffle furnace assisted decomposition of vegetable samples for flame atomic spectrometric determination of Ca, Mg, K, Fe, Mn and Zn

Calcium, magnesium, potassium, iron, manganese and zinc can be accurately determined in vegetable samples by flame atomic absorption and flame emission spectrophotometry after a previous dry ashing of the sample in a microwave muffle furnace. This treatment is carried out in 45 min using a new accessory developed by us to obtain high temperatures on a domestic microwave oven. Sample ashes, obtained in the muffle, are diluted with nitric acid and the obtained slurry is introduced directly into an air-C2H2 flame for the analysis of Fe, Mn, and Zn, or injected into a double-channel FIA manifold to determine Ca, Mg and K. The obtained results agree with those certified and also with those obtai…

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…

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…

Stopped-flow Fourier-transform infra-red spectrometric speciation of glycolic and lactic acids in cosmetic formulations

The dermatological activity of cosmetic formulations containing alpha-hydroxyacids depends on their different chemical forms, and it is therefore useful to determine these species in the finished products. In the present report a new procedure for studying the protonation equilibria of glycolic and lactic acids by stopped-flow Fourier-transform infra-red (FTIR) spectrometry is described. The procedure was validated for use in the speciation of glycolic and lactic acids in cosmetic formulations, with preferential attention given to glycolic acid, which is the most widely used. Species of these alpha-hydroxyacids can be approximately determined at different pHs and the total content of each a…

Multivariate data analysis and bivariate regression studies applied to comparison of two multi-elemental methods for analysing wine samples

Two inductively coupled plasma mass spectrometry (ICP-MS) methods which permit multi-elemental analysis in wine samples have been compared following two strategies. First, a multivariate tool based on principal component analysis (PCA) was employed for a global (all analytes) qualitative comparison of the two methods. A single plot based on the confidence limits of the Q and T2 PCA model statistics corresponding to the ‘standard’ method results (calibration set) was used to check the comparability of the ‘candidate’ method (test samples). The residual matrix (after test matrix interpolation into the PCA model) gives qualitative information about the nature of the main errors. This approach …

Impairment of antioxidant enzymes, lipid peroxidation and 8-oxo-2'-deoxyguanosine in advanced epithelial ovarian carcinoma of a Spanish community.

In the present study, we describe the changes of antioxidant enzyme activities and other oxidative stress-related parameters in a mediterranean cohort of women affected with epithelial ovarian carcinoma (EOC). For that purpose, the most representative enzymatic activities, such as superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx) and the oxidized/reduced glutathione (GSSG/GSH) ratio have been analyzed in tumor tissue biopsies and compared with the normal tissue of the same patient. As oxidation products, the levels of malondialdehyde (MDA) as an indication of lipid peroxidation, and the DNA damaged base 8-oxo-2'-deoxyguanosine (8-oxo-dG) have been also measured. Ad…

Slurries Introduction in Flow Injection Atomic Absorption Spectroscopic Analysis of Sewage Sludges

Abstract The direct introduction of slurries in flow Injection-flame atomic absorption spectroscopy has been studied using a single-channel manifold. The influence of flow Injection parameters on the sensitivity and accuracy of this procedure has been established. A method has been developed for the determination of copper, manganese, and lead In sewage sludge where batch digestion of the samples In a microwave oven is carried out before dilution. Both sensitivity and limit of detection of the flow Injection analysis procedure are adequate for the analysis of actual samples (the limit of detection was 0.06, 0.05, and 0.3 ppm for copper, manganese, and lead, respectively). The accuracy of th…

Some observations on the determination of the methyl parathion-parathion ratio in binary mixtures by infrared spectroscopy

Abstract The determination of the methyl parathion/parathion ratio in binary mixtures has been carried out by infrared spectroscopy using a simple and easy model for the treatment of the spectra obtained from sample thin films using sodium chloride windows. The model is based on the use of two bands, one at 974 cm−1, characteristic of parathion, and other at 1348 cm−1, common to both compounds. From the spectra of pure parathion samples and mixtures of known composition of methyl parathion and parathion, two constants have been obtained. These constants relate the absorption of each compound at 1348 cm−1 to the absorption of parathion at 974 cm−1. Eighteen synthetic samples have been analyz…

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 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…

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…

Supercritical fluid extraction of resveratrol from grape skin of Vitis vinifera and determination by HPLC

Supercritical fluid extraction of resveratrol from grape skin of Vitis vinifera was studied. Extraction variables such pressure, modifier concentration (ethanol), and extraction time were optimised. Final extraction conditions were: 40 degrees C, 150 bar, 7.5% ethanol and extraction time 15 min. Extraction recovery and precision (variation coefficient between 0.2 and 1.0%) were calculated. The resveratrol content in the ethanolic extract was determined by HPLC with UV detection at 306 nm. Acetic acid-methanol-water was used as the mobile phase, and C-18 and C-8 columns were tested, instrumental parameters were optimised, and analytical parameters were calculated (lineal interval 0-75 mg l(-…

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 …

Flow injection flame atomic spectrometric determination of iron, calcium, magnesium, sodium and potassium in ceramic materials by using a variable-volume injector

A series of different ceramic materials, such as porcelain, feldspar, kaolin, varnish, clay and stoneware have been analyzed. Iron, calcium and magnesium have been determined in these materials by flame atomic absorption and sodium and potassium by flame emission. The use of a variable-volume injector enables one to carry out these analyses in a flow system (after fusion of samples with lithium metaborate) and does not require different dilutions for the determination of each type of sample considered, nor the use of different flow injection manifolds. The developed procedure provides a limit of detection of 100 μg/l for Na, 70 μg/l for Ca, 50 μg/l for both Fe and K and 8 μg/l for Mg. The c…

Actives for Hair Products (Excluding Hair Dyes)

Analytical methodologies for chromium speciation in solid matrices: a survey of literature

The analytical literature about chromium speciation in solid samples has been surveyed. From 451 articles published on the speciation of chromium from 1983 to 1997, the methodologies to do speciation in solids after sample pretreatment are discussed, through consideration of the types of samples and their dissolution, the analytical techniques employed for chromium measurement, and the figures of merit of the 86 papers reported in the Analytical Abstracts data base.

Hydrolysis of Phytic Acid by Microwave Treatment: Application to Phytic Acid Analysis in Pharmaceutical Preparations

Abstract The acid hydrolysis of phytic acid in a Teflon reactor using a domestic microwave oven has been studied and compared with other reported procedures. In 0.44 M HCl quantitative hydrolysis was achieved with six heating stages of 2 min each. A lower yield was obtained with H 2 SO 4 and HNO 3 . The analytical use of this hydrolysis to determine phytic acid by indirect determination of phosphate has been demonstrated by analysis of three pharmaceutical formulations. No sample pretreatment other than obtaining a homogeneous suspension was necessary.

Simple variable-volume injector for flow-injection systems

Abstract A simple and versatile variable-volume injector is described for the introduction of samples in flow-injection systems. The device delivers precisely and reproducibly (usually r.s.d.

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…

Rapid hydrolysis of benzodiazepines to benzophenones in a microwave oven

Abstract A microwave oven is used to carry out the complete hydrolysis of diazepam to the corresponding benzophenone in only 10 min, at 650 W, with good recovery. The reaction yield is evaluated by first-derivative UV spectrophotometry.

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…

Determination of essential metals in complete diet feed by flow injection and flame atomic absorption spectrometry

A prior study of different sample pre-treatments for the determination of metallic elements in complete diet feeds was performed in order to choose the most suitable for these samples. The studied pre-treatment were: acid extraction (lixiviation), wet digestion (on microwave oven) and dry ashing mineralization (calcination). Lixiviation (acid extraction) with hydrochloric acid was selected due to its accuracy, fast and simple pre-treatment procedure. Due of the different levels of concentration of the metallic elements in the samples, the same manifold was used but with small variations. Copper (with on-line pre-concentration by chelating Chelex-100 resin), calcium (with on-line dilution) a…

Microwave-assisted saponification of animal greases for cholesterol determination

Abstract An alternative method for the hydrolysis of cholesterol esters in animal grease samples has been developed. The method consists of the microwave-assisted treatment of 4 g of animal fat or oil with 40 ml of an ethanolic KOH solution inside a 115 ml closed reactor in which samples were irradiated for 2.5 min at 50% power level of an exit power of 700 W. After extraction with petroleum ether and dissolution of the unsaponifiables in toluene, total cholesterol was determined spectrophotometrically by using p-anisidine as a test reagent of the enzymatic reaction of cholesterol through a bienzymic reactor in which cholesterol oxidase and horseradish peroxidase were noncovalently immobili…

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…

Influence of the differentiation system on the analytical parameters for the spectrophotometric determination of clonazepam in urine

Abstract Electronic and mathematical differentiation of the ultraviolet visible spectra were compared from the study of the analytical parameters of the direct determination of clonazepam in urine samples. Third-order derivative spectra were used. The mathematical differentiation provides higher sensitivity, a lower limit of detection, and better accuracy and precision than the electronic one. The use of a diode array instrument provides lower sensitivity than that found using a conventional spectrometer; however, the limit of detection obtained in both cases is of the same order.

Direct FIA—AS determination of potassium and magnesium in cement samples by use of the slurries approach

A direct procedure has been developed for the flame atomic determination of potassium and magnesium in cement samples. A 50-mg sample is dispersed in 25 ml of 0.13M nitric acid; 100 mul of this slurry is injected in a double channel FIA manifold simultaneously with 100 mul of a 10% (w/v) lanthanum solution. This procedure allows the rapid extraction of potassium and magnesium by leaching of the sample; nitric acid is not necessary if only potassium must be determined and the sample can be diluted with only distilled water. Aqueous standards are used. The manifold employed includes a well-stirred mixing chamber, which provides an adequate on-line dilution of the sample, in order to obtain em…

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…

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 atomic spectrometric determination of metallic oxides in UV sunscreen creams.

In this study, methodologies for determining titanium oxide, zinc oxide and iron oxide are proposed and assayed in commercial sunscreen products. The proposed methodology for TiO2, determination in sunscreens is based on a microwave-assisted treatment for digesting the organic components in a closed teflon reactor in presence of HNO3 and HCl. Titanium is determined by inductive coupled plasma emission spectrometry (ICP-AES). The proposed methodologies for measuring ZnO and Fe2O3 are based on a sample emulsification in water with a non ionic tensioactive and IBMK, followed by Zn and Fe determination by flame atomic absorption spectrometry (FAAS). The methodologies allow a precise and accurat…

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…

Direct determination of calcium, magnesium, sodium and potassium in water by flow injection flame atomic spectroscopy, using a dilution chamber

A simple procedure to carry out the direct analysis of calcium, magnesium, sodium and potassium in water by flow injection analysis (FIA) using flame atomic absorption spectroscopy (AAS) or flame photometry (FP) has been developed, using a well stirred dilution chamber to extend the calibration range, and both a double injector and the merging zone technique to add a lanthanum solution to samples and standards. The results obtained in the analysis of real samples agree with those found by a batch flame atomic procedure. The use of the dilution chamber makes it possible to carry out the calibration using the dilution profile of a single concentrate standard for each element, and an empirical…

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)

Flow injection flame atomic absorption analysis of Fe and Mn in cement samples

A new procedure has been developed for the determination of Fe and Mn in cements. It consists in dispersing 50 mg of the solid sample in 25 ml of 0.15 mol/l HNO3 and 0.12 mol/l HCl solution. Acid slurries are heated at 50°C for 10 min and then different volumes of the slurry are injected into a water carrier stream. This previous acid treatment leaches the elements to be determined and permits the use of acid solutions as standards. For the Mn determination, the use of a single line flow injection manifold provides a limit of detection of 0.03 mgl−1 and a dynamic range up to 6 mgl−1. For the determination of Fe, the on-line dispersion of samples, using a well stirred mixing chamber, increas…

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.

Supercritical fluid chromatography in drug analysis: A literature survey

The applications of supercritical fluid chromatography to the analysis of drugs have been carefully revised from the literature compiled in the Analytical Abstracts until March 1994. Easy-to-read tables provide useful information about the state-of-the-art and possibilities offered by SFC in pharmaceutical analysis. The tables comprise extensive data about samples analyzed, pharmaceutical principles determined, solvents used and sample quantity injected, supercritical fluids and modifiers employed, injection system, instrumentation, experimental conditions for chromatographic separations (density, pressure, flow, temperature), characteristics of columns employed (type, support, length, diam…

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 …

Insulin resistance and oxidative stress in familial combined hyperlipidemia.

Oxidative stress is associated with atherosclerosis. Familial combined hyperlipidemia (FCH) is considered as a human model of primary dyslipidemia and atherosclerosis frequently associated with insulin resistance (IR), but there are few data on its possible relation to oxidative stress. The objective of this study was to evaluate oxidative stress status using different markers in subjects with FCH assessing its possible correlation with anthropometric parameters and IR. This was a cross-sectional study. A cohort of 40 FCH patients (20 with IR (HOMAor=3.2) and 20 without IR (HOMA3.2)), and 20 healthy volunteers were included, all of them non-diabetic, normotensive and non-smokers. We measure…

Supercritical fluid extraction and HPLC determination of relevant polyphenolic compounds in grape skin.

The polyphenols determined are: (+)-catechin, (-)-epicatechin, rutin, quercetin and trans-resveratrol. Suitable conditions of supercritical fluid extraction were established using ethanol as a modifier of the polarity solvent (supercritical carbon dioxide). Final extraction conditions were: 20% v/v ethanol, 60degreesC, 250 bars and flow rate 2 mL/min. Static step time and dynamic step time were established using a selected grape skin sample. The extract was collected in water; the more polar polyphenols ((+)-catechin and (-)-epicatechin) remain in solution but rutin, quercetin and trans-resveratrol precipitate in this medium, thereby the solution of the extracted polyphenols was filtered. (…

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…

Trace element determination in sediments: a comparative study between neutron activation analysis (NAA) and inductively coupled plasma-mass spectrometry (ICP-MS)

An inductively coupled plasma-mass spectrometry (ICP-MS) method has been employed for trace element determination in five real sediment samples and a standard reference material. These samples were mineralized by dry ashing at 550°C and fused at 1100°C for 30 min with lithium metaborate. Dissolved samples were measured by a semiquantitative methodology with external calibration and with Rh as an internal standard. More than 50 elements have been measured. As a reference technique, a direct analysis of the solid samples was carried out by neutron activation analysis. Results obtained by ICP-MS have been compared with those obtained by neutron activation analysis (NAA) by applying the paired …

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…

Some observations on the sensitivity of flow-injection techniques for atomic absorption spectrophotometry

Abstract Different strategies for coupling flow-injection manifolds to atomic absorption spectrometers in order to obtain better sensitivity are compared. Using a T-connector interface, different carriers and flow compensation solvents have been assayed in an attempt to improve the sensitivity of flow-injection analysis. Manganese and copper determinations in sewage sludge have been used as a test system and the analytical parameters of both batch and flow-injection methods are compared.

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…

Literature survey of the on-line preconcentration in flow-injection atomic spectrometric analysis

The literature on the use of “on-line” preconcentration in flow injection atomic spectrometric analysis is reviewed, taking into account its application both in flame and electrothermal atomic absorption methods as well as in plasma emission spectrometry. The basis of the different preconcentration approaches, such as liquid-liquid extraction, column preconcentration and “on-line” precipitation are discussed. The literature survey reveals the analytical performance of the developed methodologies.

Chromium speciation using activated alumina microcolumns and sequential injection analysis-flame atomic absorption spectrometry

Abstract A new procedure has been developed for chromium speciation in water by sequential injection analysis and flame atomic absorption spectrometry. The method involves the online retention of Cr(VI) anionic species and Cr(III) cationic species on alumina microcolumns, prepared by packing activated alumina in polytetrafluoroethylene tubes, followed by selective elution of Cr(VI) with 2 mol l −1 NH 4 OH and of Cr(III) with 0.2 mol l −1 HNO 3 . Studies were carried out on the effect of retention and elution conditions for both Cr species. The limit of detection values, established as the concentration corresponding to three times the standard deviation of blank measurements divided by the …

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…

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…

Urinary 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxo-dG), a reliable oxidative stress marker in hypertension

The potential use of oxidative stress products as disease markers and progression is an important aspect of biomedical research. In the present study, the quantification of urine 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxo-dG) concentration has been used to express the oxidation status of hypertensive subjects. 8-oxo-dG has been simultaneously isolated and assayed in nuclear (nDNA) and mitochondrial DNA (mtDNA). In addition, oxidative stress of mononuclear cells has been estimated by means of GSH and GSSG levels and GSSG/GSH ratio in hypertensive subjects before and after antihypertensive treatment. It is shown that oxidative stress decreases significantly in hypertensive patients after trea…

Direct derivative spectrophotometric determination of carbaryl and carbofuran in water samples

Abstract Derivative absorption spectrophotometry has been applied to the direct determination of carbaryl and carbofuran in water samples. The use of the third derivative for carbaryl and the fourth derivative for carbofuran reduces the matrix effect and the seventh derivative provides, in both cases, accurate results for the determination of these pesticides, even working at low dilution levels of the samples. A limit of detection of 4 ppb and a variation coefficient of 0.1% have been obtained for the determination of carbaryl. Carbofuran can be determined with a limit of detection of 5 ppb and a variation coefficient of 0.02%.

Application of the slurry technique to biological materials: a survey of literature

The literature on the application of the slurry technique to biological materials is reviewed. It is obvious from the various applications that the most frequently employed atomization method for slurry analysis in biological materials is electrothermal atomization using either graphite tube or platform atomizers. The slurry technique is particularly useful when certified reference materials are not available and when the standard addition method is to be avoided. The literature survey revealed that this technique compares favourably with other methods for the determination of trace metals in biological materials.