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 solvents, and ionic liquids were the first and most popular replacements for halogenated solvents, which provided similar or better results than these classical dispersive liquid-liquid microextraction solvents. However, despite the good performances obtained with low-density solvents and ionic liquids, researchers have continued investigating in order to obtain even greener solvents for dispersive liquid-liquid microextraction. For that reason, in this review, the evolution over the last five years of the three types of solvents already mentioned and two of the most promising solvent alternatives (i.e., deep eutectic solvents and supramolecular solvents), have been studied in detail with the purpose of discussing which one provides the greenest alternative.

Stir bar sorptive-dispersive microextraction by a poly(methacrylic acid-co-ethylene glycol dimethacrylate)-based magnetic sorbent for the determination of tricyclic antidepressants and their main active metabolites in human urine.

A poly(methacrylic acid-co-ethylene glycol dimethacrylate)-based magnetic sorbent was used for the rapid and sensitive determination of tricyclic antidepressants and their main active metabolites in human urine. This material was characterized by magnetism measurements, zeta potential, scanning electron microscopy, nitrogen adsorption-desorption isotherms, and thermogravimetric analysis. The proposed analytical method is based on stir bar sorptive-dispersive microextraction (SBSDME) followed by liquid chromatography-tandem mass spectrometry. The main parameters involved in the extraction step were optimized by using the response surface methodology as a multivariate optimization method, whereas a univariate approach was employed to study the desorption parameters. Under the optimized conditions, the proposed method was properly validated showing good linearity (at least up to 50 ng mL-1) and enrichment factors (13-22), limits of detection and quantification in the low ng L-1 range (1.4-7.0 ng L-1), and good intra- and inter-day repeatability (relative standard deviations below 15%). Matrix effects were observed for the direct analysis of urine samples, but they were negligible when a 1:1 v/v dilution with deionized water was performed. Finally, the method was successfully applied to human urine samples from three volunteers, one of them consuming a prescribed drug for depression that tested positive for clomipramine and its main active metabolite. Quantitative relative recoveries (80-113%) were obtained by external calibration. The present work expands the applicability of the SBSDME to new analytes and new types of magnetic sorbents.

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 from bronopol also depends on the formulation, being the aqueous solution the system that allowed greater absorption. Transdermal absorption of formaldehyde, applied directly or released from DMDM hydantoin, is not conditioned by the excipients. The degree of transdermal absorption of all the preservatives tested is low and therefore the concentrations allowed by regulations are safely used. Nonetheless, since formaldehyde was detected in the receptor compartment after a long time exposure to bronopol and DMDM hydantoin it would be important to consider the possibility of limiting the use of these two preservatives to rinse off products as is the case of bronidox.

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 was added to 5 mL of n-hexane sample solution and assisted by vortex mixing during 30 s to form the cloudy solution. The method was successfully validated showing good linearity (0.5-50 ng/mL), enrichment factors up to 65 depending on the target compound, limits of detection values of 1.8-50 ng/g, and good repeatability (RSD < 9.8%). Finally, the proposed method was applied to different cosmetic samples. Quantitative relative recovery values (80-113%) were obtained, thus showing that matrix effects were negligible. The achieved analytical features of the proposed method, besides of its simplicity and affordability, make it useful to perform the quality control of cosmetic products to ensure the safety of consumers.

Vortex-assisted emulsification semimicroextraction for the analytical control of restricted ingredients in cosmetic products: determination of bronopol by liquid chromatography.

Vortex-assisted emulsification semimicroextraction is proposed as a one-step solution-extraction procedure for sample preparation in cosmetic products. The procedure allows rapid preparation based on dispersion of the sample in a mixture of 1 mL of n-hexane and 0.5 mL of ethanol, followed by the addition of 0.5 mL of water and centrifugation to obtain two separated phases. This procedure provides good sample clean-up with minimum dilution and is very useful for the determination of ingredients with restricted concentrations, such as bronopol. The procedure was applied to the determination of bronopol by liquid chromatography with UV detection. The best chromatographic separation was obtained by using a C18 column set at 40 °C and performing a stepwise elution with a mixture of ethanol/aqueous 1 % acetic acid solution as mobile phase pumped at 0.5 mL min(-1). The detection wavelength was set at 250 nm and the total run time required was 12 min. The method was successfully applied to 18 commercial cosmetic samples including creams, shampoos, and bath gels. Good recoveries and repeatability were obtained, with a limit of detection of 0.9 µg mL(-1), which makes the method suitable for the analytical control of cosmetic products. Moreover, it could be considered environmentally friendly, because water, ethanol, and only a low volume of n-hexane are used as solvents.

Trace determination of tetrahydrocannabinol (THC) in cosmetic products by stir bar sorptive dispersive microextraction followed by liquid chromatography-tandem mass spectrometry.

An analytical method for the determination of tetrahydrocannabinol (THC) at trace level in cosmetics is presented. As psychoactive compound, the presence of THC in consumer products should be avoided. However, it might be unintentionally present in cannabidiol-rich or hemp-based products by contamination or isomerization of cannabidiol. Due to the low concentrations expected, a sensitive and selective method is necessary for the analytical control of these products. In this sense, the presented method is based on stir bar sorptive dispersive microextraction (SBSDME) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). In this work, a magnetic composite made of CoFe2O4 magnetic nanoparticles embedded in a commercial reverse-phase polymer (Strata™-X-RP) was employed as magnetic sorbent material taking advantage of its affinity to the target analyte. Under the optimized conditions, the method was validated and showed good analytical features in terms of linearity (at least up to 10 ng mL-1), limits of detection and quantification (2.2 and 7.2 ng g-1, respectively) and repeatability (RSD <10%). Moreover, relative recoveries between 99 and 109% were obtained, showing matrix effects were negligible using deuterated THC (THC-D3) as surrogate. This new approach was successfully applied to ten commercially-available cosmetic samples of different matrices, thus showing it is suitable for the analytical control of THC in cosmetic products. The proposed methodology overcomes some of the drawbacks of the previous works with the same purpose, such as the higher limits of detection, time-consuming procedures, and consumption of large volumes of organic solvents.

Microsporidia infecting Apis mellifera: coexistence or competition. Is Nosema ceranae replacing Nosema apis?

Nosema ceranae has been suggested to be replacing Nosema apis in some populations of Apis mellifera honeybees. However, this replacement from one to the other is not supported when studying the distribution and prevalence of both microsporidia in professional apiaries in Spanish territories (transverse study), their seasonal pattern in experimental hives with co-infection or their prevalence at individual level (either in worker bees or drones). Nevertheless, N.ceranae has shown to present a higher prevalence at all the studied levels that could indicate any advantage for its development over N.apis or that it is more adapted to Spanish conditions. Also, both microsporidia show a different pattern of preference for its development according to the prevalence in the different Spanish bioclimatic belts studied. Finally, the fact that all analyses were carried out using an Internal PCR Control (IPC) newly developed guarantees the confidence of the data extracted from the PCR analyses. This IPC provides a useful tool for laboratory detection of honeybee pathogens.

The prevalence of Acarapis woodi in Spanish honey bee (Apis mellifera) colonies.

Acarapis woodi is an internal obligate parasite of the respiratory system of honey bees which provokes significant economic losses in many geographical areas. The main aim of this study was assess the A. woodi role in the "higher honey bee colony losses phenomenon" in Spain. Therefore, a new polymerase chain reaction (PCR) was developed to amplify the mitochondrial cytochrome oxidase I gene (COI) and so the actual prevalence of A. woodi in Spanish honey bee colonies in 2006 and 2007 was determined as part of a wider survey. The results revealed a greater prevalence than expected in most of the geographical areas studied where has been generally underestimated One problem encountered in this study was to distinguish between A. woodi and other species (Acarapis dorsalis and Acarapis externus) at the molecular level. Furthermore, the patterns of genetic divergence across sequences raised serious doubts about the current classification of these organisms.

A high-throughput magnetic-based pipette tip microextraction as an alternative to conventional pipette tip strategies: Determination of testosterone in human saliva as a proof-of-concept.

In this work, a lab-made and affordable high-throughput pipette tip microextraction strategy is presented. In this approach, a magnetic sorbent is quickly dispersed in the sample by means of a disperser solvent and the resulting dispersion is immediately aspirated into a pipette tip containing a small neodymium magnet inside, which entraps the magnetic sorbent containing the analytes. The sample is then discarded, and the subsequent cleaning and desorption steps are conducted by aspirating/dispensing the suitable solvents. This methodology provides satisfactory results when compared with previous pipette tip extraction strategies (i.e., pipette-tip solid-phase extraction and dispersive pipette extraction). Furthermore, it requires a minimum number of aspirating/dispensing cycles, thus benefiting the ergonomics for the operator, and it is not commercially dependent. This new approach has been tested by measuring testosterone levels in saliva of volunteers as a proof-of-concept. In this regard, a magnetic composite made of CoFe2O4 magnetic nanoparticles embedded in octadecyl bonded silica microparticles was employed as sorbent material. Testosterone was quantified by liquid chromatography coupled to tandem mass spectrometry. Under the optimized conditions, low limits of detection and quantification (7.5 ng L-1 and 24.8 ng L-1, respectively), good repeatability (RSD <9%) and relative recoveries between 82 and 106% were obtained with just one adsorption and two desorption cycles, which requires few seconds per sample. In order to increase even more the sample throughput, a multichannel pipette was also evaluated.

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

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 sample in ethanol using ultrasound-assisted leaching of the analytes from the cosmetic matrix. Gas chromatography coupled to mass spectrometry (GC-MS) is used for the analysis of the samples. Working conditions for the instrumental measure and the quantification of analytes were studied. The method was found to have high sensitivity and good precision (relative standard deviation below 13%) as well as low limits of detection (i.e., 0.01·10-3-2.14·10-3% w/w) and quantification (i.e., 0.04·10-3-7.14·10-3% w/w). The method was successfully applied to five commercial cosmetic samples of different composition. Recovery values near 100% were obtained. Each sample was found to contain at least three of the analytes of the study and their concentrations were determined with low standard deviations. The analytical features of the proposed method and the obtained results agree with the principles of Green Analytical Chemistry and make it a useful tool for controlling these alternative preservatives in the cosmetic industry in order to guarantee quality and safety of the products.

Development of a new three-phase membrane-assisted liquid-phase microextraction method: determination of nitrite in tap water samples as model analytical application.

A novel and simple device for membrane-assisted liquid-phase microextraction is used for the first time in a three-phase system. The device consists of a glass vial containing the aqueous acceptor phase, whose septum of its screw stopper has been replaced by a sized piece of polytetrafluoroethylene membrane impregnated with n-decane. The vial is assembled to a volumetric flask containing the aqueous donor phase, and the membrane comes in contact alternatively with both donor and acceptor aqueous phases by orbital agitation. The device has been tested for the determination of nitrite in tap water samples, which is extensively carried out in routine analysis, as model analytical application. Experimental variables, such as the organic solvent used to form the supported liquid membrane, the volumes of both donor and acceptor phases, the orbital agitation rate, and the extraction time were studied and optimized in terms of enrichment factor. Under the selected working conditions, the analytical figures of merit for nitrite determination were a linearity range up to 50 ng mL(-1), limits of detection and quantification of 0.15 and 0.50 ng mL(-1), respectively, and a good repeatability (RSD < 10%). The method has been applied to four tap water samples of different origins, and accurate and precise results were achieved. Besides, the very low volume of organic solvent used, its low cost and the no-risk of cross-contamination are significant operational advantages.

Comparison of the energetic stress associated with experimental Nosema ceranae and Nosema apis infection of honeybees (Apis mellifera).

Nosema ceranae is a relatively new and widespread parasite of the western honeybee Apis mellifera that provokes a new form of nosemosis. In comparison to Nosema apis, which has been infecting the honeybee for much longer, N. ceranae seems to have co-evolved less with this host, causing a more virulent disease. Given that N. apis and N. ceranae are obligate intracellular microsporidian parasites, needing host energy to reproduce, energetic stress may be an important factor contributing to the increased virulence observed. Through feeding experiments on caged bees, we show that both mortality and sugar syrup consumption were higher in N. ceranae-infected bees than in N. apis-infected and control bees. The mortality and sugar syrup consumption are also higher in N. apis-infected bees than in controls, but are less than in N. ceranae-infected bees. With both microsporidia, mortality and sugar syrup consumption increased in function of the increasing spore counts administered for infection. The differences in energetic requirements between both Nosema spp. confirm that their metabolic patterns are not the same, which may depend critically on host-parasite interactions and, ultimately, on host pathology. The repercussions of this increased energetic stress may even explain the changes in host behavior due to starvation, lack of thermoregulatory capacity, or higher rates of trophallaxis, which might enhance transmission and bee death.

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 method was developed using a magnetic composite as sorbent, made of CoFe2O4 magnetic nanoparticles embedded into a reversed phase polymer (Strata-XTM-RP), which exhibits affinity to the target analytes. Then, liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was used to measure both analytes in the M-SA-DSPE extract. Under the optimized conditions, good analytical features were obtained: limits of detection of 0.029 ng mL-1 for cortisol and 0.018 ng mL-1 for cortisone, repeatability (as RSD) ≤ 10 %, and relative recoveries between 86 and 111 %, showing no significant matrix effects. Finally, the proposed method was applied to the analysis of saliva from different volunteers. This new methodology allows a fast and non-invasive determination of cortisol and cortisone, and it employs small amounts of sample, organic solvent and sorbent. Likewise, the sample treatment is minimum, since any supporting equipment (vortex, centrifuge, ultrasounds, etc.) is required.

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

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 in the low µg mL-1 range (from 0.14 to 0.43 µg mL-1) and good repeatability (relative standard deviation below 11 %). The accuracy of the method has been proven by the analysis of laboratory-made samples (i.e., a cream and a gel) with known concentrations of the analytes, providing low relative errors (below 12 %). Finally, the method has been successfully applied to four commercial cosmetic samples of different formulations without significant matrix effects. The results obtained and the environmentally friendly features of the method showed its usefulness for carrying out both pre- and in-market quality control of final cosmetic products.

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 rotational speed the (nano)material is retained on the magnet reminding SBSE, whereas at high sufficiently rotational speed the rotational force surpasses magnetism so that the magnetic (nano)material is dispersed into the sample solution as in DSPE. Upon halting rotation, the magnetic field prevails again and attracts the magnetic (nano)material containing the analytes back on the surface of the stirring bar. Finally, the extracted analytes are chemically or thermally desorbed before their measurement with the appropriate analytical instrument. When compared separately to SBSE and DSPE procedures, SBSDME affords, in a single approach, advantages such as lower extraction times than SBSE and easier extraction and post-extraction treatment than DSPE. The main purpose of this tutorial review is to describe the fundamentals and the experimental variables involved in this technique, as well as to compile and critically discuss the published papers concerning analytical methods based on the use of the SBSDME approach, analyzing its evolution and future prospects.

Solid-phase extraction liquid chromatography-tandem mass spectrometry analytical method for the determination of 2-hydroxy-4-methoxybenzophenone and its metabolites in both human urine and semen.

2-Hydroxy-4-methoxybenzophenone (HMB), which is one of the most commonly used UV filters in sunscreen cosmetics to protect skin from the deleterious effects of the sun, can be percutaneously absorbed, further metabolized, and finally excreted or bioaccumulated. An analytical method for the sensitive determination of HMB and its three metabolites in both human urine and semen is developed. The presented analytical method is based on a solid-phase extraction (SPE) procedure to clean-up and preconcentrate the target analytes from the urine and semen samples followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) detection. The methodology was fully validated and the standard addition calibration method was used to quantify the target analytes in order to correct the matrix effects observed. Considering this approach, the accuracy of the method was evaluated and the recoveries ranged from 98% to 115% and from 86% to 111% in urine and semen samples, respectively, depending on the analyte. For urine samples, the limits of detection ranged between 0.027 and 0.103 ng mL(-1) and the repeatability of the method, expressed as relative standard deviation, was in the range of 7.2-9.2%, depending on the analyte. In the case of semen samples, the limits of detection ranged between 1 and 3 ng mL(-1) whereas the repeatability was in the range of 2.2-6.4%, depending on the analyte. The described SPE-LC-MS/MS method was satisfactorily applied to both urine and semen samples from a male volunteer who applied a sunscreen cosmetic product containing HMB. HMB and its metabolites were found and quantified in the low ng mL(-1) range in both urine and semen samples, although at a different extent.

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 working with rat liver cytosol and with both human and rat liver microsomes, respectively. Analogue studies with p-aminobenzoic acid (PABA) were carried out in order to compare the well established metabolic pathway of PABA with the unknown biotransformation of EDP. In addition, a method for the determination of EDP and its two phase I metabolites in human urine was developed. The methodology requires a solid-phase extraction prior to LC-MS analysis. The method is based on standard addition quantification and has been fully validated. The repeatability of the method, expressed as relative standard deviation, was in the range 3.4-7.4% and the limit of detection for all quantified analytes was in the low ng mL(-1) range.

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 was successfully validated under the selected conditions, showing a linear range of at least up to 125 ng mL-1, instrumental and method limits of detection from 0.02 to 2.50 ng mL-1 and from 0.15 to 24.22 ng g-1, respectively, and relative standard deviations (RSD) below 10 % for all the target analytes. Standard addition combined with internal standard calibration was employed for quantification. The proposed method was successfully applied to the analysis of ten PAHs in four cosmetic products of different matrix. Several analytes between 14 and 464 ng g-1 were found, some of them prohibited in cosmetic products. This work expands the analytical potential of SBSDME technique to other analytes and to the use of new sorbent phases, showing the great versatility of this approach depending on the characteristics of the analytes.

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

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 achieve the highest analytical signal. Under the most favorable conditions, the proposed method was validated providing good linearity; enrichment factors up to 62 depending on the analyte; limits of detection from 3 to 13 µg kg-1; and good repeatability values (RSD < 17.0%). Finally, the method was successfully applied to cosmetic samples composed either of lipophilic or hydrophilic matrices. Quantitative relative recoveries (96-109%) were obtained by using standard addition calibration. The present work expands the applicability of the SBSDME technique, whereas its analytical features make it useful to carry out the quality control of cosmetic samples.

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 this sense, the so-called microextraction techniques play an important role in the sample preparation of environmental water samples. The aim of this review is to compile and discuss the published papers concerning analytical methods for the determination of organic UV filters in environmental water samples based on the use of both sorbent-based and solvent-based microextraction techniques. A special emphasis has been placed on the current trends, i.e., the use of novel (nano)materials and solvents, and the application of the most advanced approaches. The increase in the number of published articles related to the use of these miniaturized techniques reflects their high potential in the determination of organic UV filters in environmental water samples.