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1.
A useful tool for the determination of eight UV filters in sediments which combines extraction and clean-up in a single-step has been developed. To this end, the protocol incorporates silica gel and copper powder placed directly in the pressurised-liquid extraction (PLE) cell. After extract evaporation, salicylate- and benzophenone-type UV filters are derivatised with N,O-bis-trimethylsilyltrifluoroacetamide (BSTFA). Trimethylsilylation increases the sensitivity of these UV filters about 4-10-fold when they are finally analysed by gas chromatography-mass spectrometry (GC-MS). Derivatisation conditions (temperature, time and volume of BSTFA) and PLE parameters (temperature, time, number of cycles and solvent composition) were optimised using multivariate experimental designs. Under optimal conditions, the developed procedure provides an excellent linearity, detection limits (1-5 ng g−1) and recoveries above 73% for all the compounds. Compared to the few existing methods, this analytical approach affords optimal throughput and method automation. Finally, the proposed method was applied to the analysis of three sediment samples.  相似文献   

2.
Microemulsion electrokinetic chromatography (MEEKC) has been applied to the separation of some UV filters (Eusolex 4360, Eusolex 6300, Eusolex OCR, Eusolex 2292, Eusolex 6007, Eusolex 9020, Eusolex HMS, Eusolex OS, and Eusolex 232) commonly used in sunscreen lotions. Use of a MEEKC buffer with a mixed surfactant system to stabilize the oil droplets and an organic modifier in the aqueous phase allowed separation of most of the selected analytes in a single run in a system fitted with a diode array detector recording three wavelengths (240 nm, 300 nm, and 380 nm) simultaneously. The microemulsion employed consisted of 2.25 g of SDS, 0.75 g of Brij 35, 6.6 g 1‐butanol, 0.8 g n‐octane, 17.5 g 2‐propanol, and 72.1 g of 10 mM borate buffer (pH 9.2). Detection limits from 0.65 to 6.0 μg/mL were obtained and the calibration plots were linear over at least one order of magnitude for all analytes. The developed method could be applied to the determination of UV filters in several sun protection products including lotions, milks, and oils. Comparison of the obtained data with those from an HPLC method described in the literature showed acceptable agreement.  相似文献   

3.
An analytical method based on ion-interaction chromatography with UV detection for simultaneous in-vitro estimation of the percutaneous absorption of the most used water-soluble UV filters in sunscreen cosmetics is proposed. These UV filters were phenylbenzimidazole sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, benzophenone-4, and terephthalylidene dicamphor sulfonic acid. The methodology is based on applying the sunscreen containing the target UV filters to human epidermis in a diffusion cell. Analytes are determined in the receptor solution. To ensure skin integrity, screening of the cells was carried out by analytical determination of a marker. Analytical variables such as percentage ethanol, concentration of ion-pairing agent, pH of the mobile phase, and temperature were studied in order to achieve high resolution of the chromatographic peaks in the lowest possible time of analysis. The conditions selected consisted of a mobile phase composed of 35:65 (v/v) ethanol–ammonium acetate buffer solution (pH 4, containing 50 mmol L−1 tetra-n-butylammonium bromide). The chromatographic determination was carried out with the analytical column at 50 °C. UV detection was carried out at the maximum absorption wavelength for each analyte. The limit of detection (3s y/x /b) ranged from 16 to 65 ng mL−1, depending on the analyte.  相似文献   

4.
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 20 mM of 2-hydroxypropyl-β-cyclodextrin) as mobile phase pumped at 1 mL min−1. 2-Hydroxypropyl-β-cyclodextrin was added as mobile phase modifier to achieve the complete resolution of some of the chromatographic peaks. The 15 target compounds were separated in less than 30 min. The method was satisfactorily validated by analyzing three laboratory-made cosmetic samples besides of eleven commercially available cosmetic products containing different combination of the target UV filters. Good accordance of the found levels compared with those of the laboratory-made samples and those of the commercial samples (when available) was achieved. Moreover, excellent recoveries (97–104%) and good intra-day and inter-day precision values at different concentration levels, besides limits of detection values below the μg mL−1 level, were obtained. These good analytical features, as well as their environmentally-friendly characteristics, make the presented method suitable not only for routine analysis in cosmetics industries, but also as candidate reference method for sunscreen analysis.  相似文献   

5.
A focused ultrasonic solid-liquid extraction (FUSLE) and high performance liquid chromatography (HPLC) with a diode array detector (DAD) is proposed for the determination of ten fat-soluble UV filters in packaging. FUSLE technique is relatively new and has been used for the extraction of a few analytes; such as polycyclic aromatic hydrocarbons and other organic pollutants. In this work, it has been demonstrated that FUSLE is a useful, fast and simple extraction methodology for UV filters because the complete extraction was carried out with just 6ml of tetrahydrofuran and in only one cycle of 30s. The developed method has been validated and applied to the analysis of polyethylene-based multilayer packaging samples. The FUSLE-based method allows the sensitive detection of most of the UV-filters in polyethylene, with limits of detection between 0.4 and 8.5ngmg(-1) (except for BDM). Intra and inter-day relative standard deviation values were below 5 and 14%, respectively, except for MBP. In addition, the proposed method was more efficient than tetrahydrofuran extraction under reflux for 2.5h for all the analytes except for EMT and BDM. Therefore, the developed method can be used to establish the absorption capability of different types of packaging and this information will be very useful in packaging selection.  相似文献   

6.
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.  相似文献   

7.
A low solvent consumption method for the determination of eight ultraviolet (UV) filters, displaying low to medium polarities, in freeze-dried samples of marine bivalves and fish is proposed. Matrix solid-phase dispersion (MSPD) and gas chromatography with mass spectrometry (GC-MS) were used as sample preparation and determination techniques, respectively. This work describes the influence of several parameters (type and amount of dispersant and clean-up sorbents, as well as elution solvent) on the yield and the selectivity of the MSPD extraction. Under optimized conditions, samples (0.5?g) were ground with 2?g of Florisil in a mortar with a pestle and transferred into a polypropylene syringe, which contained 1?g of C18 as clean-up sorbent. Analytes were eluted with 5?mL of acetonitrile. This extract was concentrated to dryness, re-constituted with 1?mL of ethyl acetate and injected in the GC-MS system without any further clean-up. The global average recoveries, measured for three different biota samples, spiked at three different levels (between 50 and 1000?ng?g?1), ranged from 80% to 101% with associated standard deviations below 10%. The inter-day precision of the method varied from 4% to 15% and the achieved LOQs (defined for a signal to noise ratio of 10) ranged from 4 to 28?ng?g?1, referred to the freeze-dried matrix. Octocrylene (OCR) was found in some samples of fish and mussels at concentrations between 15 and 20?ng?g?1, referred to dry mass.  相似文献   

8.
This work describes the development of a new green solid-phase extraction approach, which is based on the use of low-cost extraction discs composed of plain filter papers that are covered with a synthetic wax-like coating. The filter papers are printed in a commercial solid ink printer, which dispenses a synthetic wax-like ink on the surface of the paper, to cover the hydrophilic cellulose fibre matrix with an interface of lipophilic domains where non-polar analytes can partition through hydrophobic interactions. The modified paper filters were used to extract hydrophobic organic compounds from water samples following the customary procedure of solid-phase extraction without sorbent preconditioning and needless of high-vacuum sources. As a proof-of-concept application, a series of non-polar organic UV filters were used as model analytes to optimise the extraction parameters and evaluate the performance of the method in spiked water samples. Based on this principle, a new sample preparation platform with low environmental footprint has been developed that enables extraction to be carried out using low-cost, environmental benign and non-toxic conventional materials. The advantages and disadvantages of the method, alongside with its future prospects towards the development of custom-made ‘printed extraction kits’, are envisioned and discussed.  相似文献   

9.
Zhang PP  Shi ZG  Yu QW  Feng YQ 《Talanta》2011,83(5):5896-1715
A new method based on dispersive liquid-liquid microextraction (DLLME) in combination with high-performance liquid chromatography (HPLC) has been developed for the analysis of UV filters. A specially designed flask, which has two narrow open necks with one of them having a capillary tip, was employed to facilitate the DLLME process. By adopting such a device, the extraction and subsequent phase separation were conveniently achieved. A binary solvent system of water sample and low-density extraction solvent (1-octanol) was used for the DLLME and no disperser solvent was involved. The extraction was accelerated by magnetic agitation of the two phases. After extraction, phase separation of the extraction solvent from the aqueous sample was easily achieved by leaving the extraction system statically for a while. No centrifugation step involving in classical DLLME was necessary. The analyte-enriched phase, floating above the sample solution, was elevated and concentrated into the narrow open tip of the flask by adding pure water into it via the other port, which was withdrawn with a microsyringe for the subsequent HPLC analysis. Under the optimized conditions, the limits of detection for the analytes were in range of 0.2-0.8 ng mL−1 .The linearity ranges were 8-20,000 ng mL−1 for HB, 7-20,000 ng mL−1 for DB, 8-10,000 ng mL−1 for BP and 5-20,000 ng mL−1 for HMB, respectively. Enrichment factors ranging from 59 to 107 folders were obtained for the analytes. The relative standard deviations (n = 3) at a spiked level of 80 ng mL−1 were between 1.4 and 4.8%. The proposed magnetic stirring-assisted DLLME method was successfully applied to the analysis of lake water samples.  相似文献   

10.
Although there is increasing concern about residues from personal care products entering the aquatic environment and their potential to accumulate to levels that pose a health threat to humans and wildlife, we still know little about the extent and magnitude of their presence in the aquatic environment. In this study we describe a procedure for isolation, and subsequent determination, of compounds commonly added to personal care products. The compounds of interest include UV filters with the commercial name Eusolex (homosalate, 4-methylbenzylidenecamphor, benzophenone-3, octocrylene, butylmethoxydibenzoylmethane, ethylhexyl methoxycinnamate) and two common anti-microbial agents, clorophene and triclosan. Water samples were filtered, acidified, and extracted by use of solid-phase extraction. Extracted compounds were then derivatised before analysis by gas chromatography–mass spectroscopy. By use of our method we obtained limits of detection of 13–266 ng L−1 for UV filters, and 10–186 ng L−1 for triclosan and clorophene. Recoveries were 82–98% for deionised water and 50–98% for natural water (seawater, pool water, lake water, and river water). Samples collected in Slovenia included seventeen recreational waters (seawater, pool water, lake water, and river water; August 2004) and four wastewaters (January 2005). The most abundant UV filter was benzophenone-3 (11–400 ng L−1). Of the two anti-microbial agents studied, trace amounts, only, of triclosan were present in the river Kolpa (68 ng L−1) and in an hospital effluent (122 ng L−1).  相似文献   

11.
This work presents an effective sample preparation method for the determination of eight UV filter compounds, belonging to different chemical classes, in freeze-dried sludge samples. Pressurized liquid extraction (PLE) and gas chromatography-mass spectrometry (GC-MS) were selected as extraction and determination techniques, respectively. Normal-phase, reversed-phase and anionic exchange materials were tested as clean-up sorbents to reduce the complexity of raw PLE extracts. Under final working conditions, graphitized carbon (0.5 g) was used as in-cell purification sorbent for the retention of co-extracted pigments. Thereafter, a solid-phase extraction cartridge, containing 0.5 g of primary secondary amine (PSA) bonded silica, was employed for off-line removal of other interferences, mainly fatty acids, overlapping the chromatographic peaks of some UV filters. Extractions were performed with a n-hexane:dichloromethane (80:20, v:v) solution at 75°C, using a single extraction cycle of 5 min at 1500 psi. Flush volume and purge time were set at 100% and 2 min, respectively. Considering 0.5 g of sample and 1 mL as the final volume of the purified extract, the developed method provided recoveries between 73% and 112%, with limits of quantification (LOQs) from 17 to 61 ng g(-1) and a linear response range up to 10 μg g(-1). Total solvent consumption remained around 30 mL per sample. The analysis of non-spiked samples confirmed the sorption of significant amounts of several UV filters in sludge with average concentrations above 0.6 μg g(-1) for 3-(4-methylbenzylidene) camphor (4-MBC), 2-ethylhexyl-p-methoxycinnamate (EHMC) and octocrylene (OC).  相似文献   

12.
For the first time, an automatic sample pre-treatment/detection method is proposed for the multiclass determination of UV filters (namely, benzophenone-3, ethylhexylmetoxycinnamate, butylmethoxydibenzoylmethane and homosalate) in environmental samples. The new methodology comprises in-line solid-phase extraction (SPE) of the target analytes by exploiting the bead injection (BI) concept in a mesofluidic lab-on-valve (LOV) format, with subsequent determination by liquid chromatography (LC). The proposed microanalytical system, using a multisyringe burette as propulsion unit, automatically performed the overall SPE steps, including the renewal of the sorbent in each analytical cycle to prevent sample cross-contamination and the post-extraction adjustment of the eluate composition to prevent chromatographic band broadening effects. In order to expedite the LC separation, a C18 monolithic column was applied and an accelerated isocratic elution was carried out by using a cationic surfactant as mobile phase additive. The LOV-BI-LC method was proven reliable for handling and analysis of complex matrices, e.g., spiked swimming pool water and seawater, with limits of detection ranging between 0.45 and 3.2 μg L−1 for 9 mL sample volume. Linear calibration was attained up to 160 μg L−1 for homosalate and up to 35 μg L−1 for the other target analytes, with good reproducibility (RSD < 13%, for 5 different SPE columns). The hyphenated scheme is able to process a given sample simultaneously and within the same time frame than the chromatographic separation/determination of the formerly pre-treated sample, providing concentration values every 9 min. Hence, the sample throughput was enhanced up to 33 times when compared with previously reported off-line SPE methods. A drastic reduction in reagent consumption and effluent production was also attained, contributing to the development of an environment-friendly analyzer.  相似文献   

13.
A method for the determination of 11 UV-filter compounds in sludge has been developed and evaluated. The procedure includes the use of non-porous polymeric membranes in combination with pressurised liquid extraction (PLE). Firstly, the solid sample, wetted with the extraction solvent, was enclosed into tailor-made bags prepared with low density polyethylene. Secondly, these packages were submitted to a conventional PLE (70 °C, 4 cycles of 5 min static time). Finally, the analytes were determined by liquid chromatography–atmospheric pressure photoionisation–tandem mass spectrometry. The main advantage of this procedure is the reduction of time, solvent and labour effort ought to the combination of extraction and clean-up in a single step. Although the extraction is not quantitative (thus, standard addition is recommended for quantification) selectivity is clearly gained using the membrane as a consequence of the differences of permeation and transport through the membrane between the analytes and other sample matrix components. The optimised protocol provides limits of detection ranging from 0.3 ng g−1 (ethylhexyl dimethyl p-aminobenzoate (OD-PABA)) to 25 ng g−1 (ethylhexyl triazone (EHT)) with only 0.5 g of sludge sample. All the studied UV filters were found in the samples at concentration levels between 1.4 and 2479 ng g−1, emphasising the high adsorption potential of this kind of environmental pollutants onto solid samples such as sludge. Also, this method has permitted the determination of seven of the studied UV filters in sludge samples for the first time.  相似文献   

14.
A sensitive procedure for the determination of three UV filters: ethylhexyl salicylate (EHS), 3,3,5-trimethylcyclohexyl salicylate (Homosalate, HMS), 2-hydroxy-4-methoxybenzophenone (BP-3) and two related hydroxylated benzophenones (2,4-dihydroxybenzophenone, BP-1 and 2,2′-dihydroxy-4-methoxybenzophenone, BP-8) in water samples is presented. Analytes were first concentrated on the coating of a solid-phase microextraction (SPME) fibre, on-fibre silylated and then determined using gas chromatography combined with tandem mass spectrometry (GC-MS/MS). Factors affecting the performance of extraction and derivatization steps are thoroughly evaluated and their effects on the yield of the sample preparation discussed. Under final working conditions, a PDMS-DVB coated SPME fibre was exposed directly to 10 mL of water, adjusted at pH 3, for 30 min. After that, the fibre was placed in the headspace (HS) of a 1.5 mL vial containing 20 μL of N-methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA). On-fibre silylation of hydroxyl groups contained in the structure of target compounds was performed at 45 °C for 10 min. The whole sample preparation process was completed in 40 min, providing limits of quantification from 0.5 to 10 ng L−1 and acceptable precision (RSDs under 13%) for samples spiked at different concentrations. All compounds could be accurately determined in river and treated wastewater (relative recoveries from 89 to 115%) using standards in ultrapure water, whereas standard addition is recommended to quantify their levels in untreated wastewater. Analysis of wastewater revealed the systematic presence of BP-3 and BP-1 in raw samples with maximum concentrations close to 500 and 250 ng L−1, respectively.  相似文献   

15.
UV filters, contained in sunscreens and other cosmetic products, as well as in some plastics and industrial products, are nowadays considered contaminants of emerging concern because their widespread and increasing use has lead to their presence in the environment. Furthermore, some UV filters are suspected to have endocrine disruption activity. In the present work, we developed an analytical method based on liquid chromatography with tandem mass spectrometry for the determination of UV filters in tap and lake waters. Sixteen UV filters were extracted from water samples by solid‐phase extraction employing graphitized carbon black as adsorbent material. Handling 200 mL of water sample, satisfactory recoveries were obtained for almost all the analytes. The limits of detection and quantification of the method were comparable to those reported in other works, and ranged between 0.7–3.5 and 1.9–11.8 ng/L, respectively; however in our case the number of investigated compounds was larger. The major encountered problem in method development was to identify the background contamination sources and reduce their contribution. UV filters were not detected in tap water samples, whereas the analyses conducted on samples collected from three different lakes showed that the swimming areas are most subject to UV filter contamination.  相似文献   

16.
An analytical method for the determination of UV filters in soil and sediment has been developed and validated considering benzophenones (BP) and salicylates as target analytes. Soil and sediment samples were extracted with ethyl acetate-methanol (90:10, v/v) assisted with sonication, performing a simultaneous clean-up step. Quantification of these compounds was carried out by gas chromatography-mass spectrometry (GC-MS) after derivatization of the extracts with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA). Recoveries from spiked soil samples ranged from 89.8% to 104.4% and they were between 88.4% and 105.3% for spiked sediment samples. The effect of the residence time and soil moisture content on the recovery of these compounds was also studied. The precision, expressed as relative standard deviation, was in all cases below 6.1% and the limits of detection (S/N=3) varied from 0.07 to 0.10 ng g(-1) and from 0.11 to 0.28 ng g(-1) for soils and sediments, respectively. The validated method was applied to the analysis of five benzophenone and two salicylate UV filters in soil and sediment samples collected in different areas of Spain.  相似文献   

17.
The use of SPE coupled in‐line to CE using electrospray MS detection (in‐line SPE‐CE‐ESI‐MS) was investigated for the preconcentration and separation of four UV filters: benzophenone‐3, 2,2‐dihydroxy‐4‐methoxybenzophenone, 2,4‐dihydroxybenzophenone and 2‐phenylbenzimidazole‐5‐sulphonic acid. First, a CE‐ESI‐MS method was developed and validated using standard samples, obtaining LODs between 0.06 μg/mL and 0.40 μg/mL. For the in‐line SPE‐CE‐ESI‐MS method, three different sorbents were evaluated and compared: Oasis HLB, Oasis MCX, and Oasis MAX. For each sorbent, the main parameters affecting the preconcentration performance, such as sample pH, volume, and composition of the elution plug, and sample injection time were studied. The Oasis MCX sorbent showed the best performance and was used to validate the in‐line SPE‐CE‐ESI‐MS methodology. The LODs reached for standard samples were in the range between 0.01 and 0.05 ng/mL with good reproducibility and the developed strategy provided sensitivity enhancement factors between 3400‐fold and 34 000‐fold. The applicability of the developed methodology was demonstrated by the analysis of UV filters in river water samples.  相似文献   

18.
Nguyen KT  Scapolla C  Di Carro M  Magi E 《Talanta》2011,85(5):2375-2384
Fast liquid chromatography coupled to triple-quadrupole tandem mass spectrometry was employed for the determination of six UV filters in seawater. The separation of the analytes was achieved in less than 5 min; polarity switching was used as four of the analytes were ionized in positive mode and the remaining two in negative mode. Two ionization sources were employed and compared: atmospheric pressure chemical ionization (APCI) gave better results than electrospray ionization (ESI) for all analytes, with higher reproducibility and lower detection limits. Therefore APCI was chosen for the determination of the analytes in seawater samples using stir bar sorptive extraction-liquid desorption (SBSE-LD).Quantitative analysis was performed in multiple reaction monitoring (MRM) mode; fragmentation pathways of the analytes with regard to the formation of the MRM ions were also proposed.For the analysis of seawater samples, calibration curves were drawn using SBSE in spiked seawater. All figures of merit of the method were satisfactory; limits of detection were particularly low for the four analytes ionized in positive mode, being in the range 8-31 ng/L. The method was applied to the determination of the six UV filters in seawater samples from Liguria, Italy. Only benzophenone-3 (BP-3) and ethylhexyl methoxycinnamate (EHMC) were measured in the analyzed samples; some of the remaining analytes were also detected but always below the limit of quantitation.  相似文献   

19.
In the present study, dispersive liquid–liquid microextraction followed by high performance liquid chromatography‐diode array detection has been developed as simple, rapid, accurate, and efficient sample preparation method for simultaneous determination of seven organic UV filters in urine samples. The influence of the main effects as well as their interactions was studied through a 2(6–2) fractional factorial design. The candidate parameters were: type and volume of dispersant and extraction solvents, sample pH, and salt concentration. Under final optimal conditions, the analytes were extracted from 5 mL of samples by addition of 0.5 mL of acetonitrile (dispersing solvent) containing 70 μL of carbon tetrachloride (extraction solvent), without modifying the pH of the solution and applying the (+1) level of salt concentration (10% w/v NaCl). The assay was linear (R2 > 0.997), relative recoveries ranged from 86.9 up to 97.3% and the LOQs between 3 and 45 ng mL?1 were obtained. The intra‐ and interday RSDs were lower than 5 and 8% at the middle point of the linear range, respectively. The proposed method was successfully applied to different volunteer urine samples and it was shown that the extraction efficiency was not affected by the type of urine samples.  相似文献   

20.
In this work, a simple and reliable micellar electrokinetic chromatography method for the separation and quantification of 14 preservatives, including isothiazolinones, and two benzophenone‐type UV filters in household, cosmetic and personal care products was developed. The selected priority compounds are widely used as ingredients in many personal care products, and are included in the European Regulation concerning cosmetic products. The electrophoretic separation parameters were optimized by means of a modified chromatographic response function in combination with an experimental design, namely a central composite design. After optimization of experimental conditions, the BGE selected for the separation of the targets consisted of 60 mM SDS, 18 mM sodium tetraborate, pH 9.4 and 10% v/v methanol. The MEKC method was checked in terms of linearity, LODs and quantification, repeatability, intermediate precision, and accuracy, providing appropriate values (i.e. R2 ≥ 0.992, repeatability RSD values ?9%, and accuracy 90–115%). Applicability of the validated method was successfully assessed by quantifying preservatives and UV filters in commercial consumer products.  相似文献   

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