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Herein, nano-sized covalent triazine-based framework grafted magnetic particles were synthesized by a facile Friedel-Crafts reaction between cyanuric chloride as node and biphenyl as linker. The formation of the material has been confirmed by Fourier transform infrared spectroscopy, X-ray diffraction, field emission-scanning electron microscopy, thermogravimetric analysis, and N 2 adsorption-desorption measurement. With respect to the material structure, the large number of aromatic rings in the molecular framework provided a bed for extracting aromatic ring-containing compounds through π-π stacking interactions. The applicability of the prepared material as a new sorbent for micro solid-phase extraction of parabens was investigated. The effect of key experimental parameters affecting the extraction efficiency of the analytes including sorbent amount, sample pH, extraction time and desorption conditions were investigated. High-performance liquid chromatography with UV detection was used for determining the enriched analytes. The method was successfully applied for determining parabens in human urine, breast milk, personal care products, and shower wastewater. After optimization, the linearity range of 0.1–500 μg L −1 and detection limit of 0.02 μg L −1 were obtained for all the selected parabens. The relative standard deviations and recoveries for the real sample analysis were in the range of 2.3–5.0% and 86–102%, respectively. [ABSTRACT FROM AUTHOR]

A methodology based on solid-phase microextraction (SPME) followed by gas chromatography–tandem mass spectrometry (GC–MS/MS) has been developed for the simultaneous analysis of eleven multiclass ultraviolet (UV) filters in beach sand. To the best of our knowledge, this is the first time that this extraction technique is applied to the analysis of UV filters in sand samples, and in other kind of environmental solid samples. Main extraction parameters such as the fibre coating, the amount of sample, the addition of salt, the volume of water added to the sand, and the temperature were optimized. An experimental design approach was implemented in order to find out the most favourable conditions. The final conditions consisted of adding 1 mL of water to 1 g of sample followed by the headspace SPME for 20 min at 100 °C, using PDMS/DVB as fibre coating. The SPME-GC–MS/MS method was validated in terms of linearity, accuracy, limits of detection and quantification, and precision. Recovery studies were also performed at three concentration levels in real Atlantic and Mediterranean sand samples. The recoveries were generally above 85% and relative standard deviations below 11%. The limits of detection were in the pg g −1 level. The validated methodology was successfully applied to the analysis of real sand samples collected from Atlantic Ocean beaches in the Northwest coast of Spain and Portugal, Canary Islands (Spain), and from Mediterranean Sea beaches in Mallorca Island (Spain). The most frequently found UV filters were ethylhexyl salicylate (EHS), homosalate (HMS), 4-methylbenzylidene camphor (4MBC), 2-ethylhexyl methoxycinnamate (2EHMC) and octocrylene (OCR), with concentrations up to 670 ng g −1 . [ABSTRACT FROM AUTHOR]

Personal care products (PCPs) are ubiquitous in aquatic environments owing to the continuous discharge of domestic wastewater from highly urbanized regions. These PCPs can be adsorbed by fish and thereafter usually enter the bile of the fish through biliary excretion. In this study, a sensitive method based on a combination of hybrid solvent precipitation and dispersive solid phase extraction (d-SPE) purification was developed to simultaneously extract and detect 24 PCPs, namely, 16 biocides, 4 synthetic musks, and 4 benzotriazoles, from fish bile. Hybrid precipitation on solid phase extraction (SPE) tubes was applied to remove phospholipids and proteins, and a d-SPE procedure was used for further purification. The extraction solvents for the hybrid precipitation/SPE tubes and d-SPE materials were optimized. The method performance for bile samples both with and without enzyme hydrolysis using β -glucuronidase/aryl-sulfatase were validated. The 24 PCPs in fish bile were spiked with standard concentrations of 10 ng/mL, 20 ng/mL, 100 ng/mL, and 200 ng/mL to evaluate recoveries, which ranged from 70 to 120% for 16, 16, 22, and 21 analytes with hydrolysis, respectively, and 70–120% for 14, 15, 23, and 23 analytes without hydrolysis, respectively. The quantification limits for target PCPs were in the range 0.26–7.38 ng/mL [excluding musk xylene (MX) and musk ketone (MK)] and 0.20–9.48 ng/mL (excluding MX and MK) for bile samples with and without enzyme hydrolysis, respectively. After enzyme hydrolysis, 12 PCPs were detected in bile from fish collected from the Yangtze River, with a maximum detected concentration of 460 ng/mL, for triclosan (TCS). The hydrolysis reaction indicated that high percentages of glucuronide and sulfate metabolites for some PCPs, i.e. four parabens and TCS, existed in the bile. [ABSTRACT FROM AUTHOR]

Insect repellents (IRs) are a group of organic chemicals whose function is to prevent the ability of insects of landing in a surface. These compounds have been found in the environment and may pose a risk to non-target organisms. In this study, an on-line solid phase extraction – high performance liquid chromatography-tandem mass spectrometry multiresidue method was developed using an atmospheric photoionization source (SPE-HPLC-(APPI)-MS/MS). The use of the APPI as an alternative ionization technique to electrospray (ESI) and atmospheric pressure chemical ionization (APCI) allowed expanding the range of analytical techniques suitable for the analysis of IRs, so far relied in gas chromatography. High sensitivity and precision was reached with method limits of quantification between 0.2 and 4.6 ng l −1 and interday and intraday precision equal or below 15%. The validated method was applied to the study of surface water samples from three European river basins with different flow regime (Adige River in Italy, Sava River in the Balkans, and Evrotas River in Greece). The results showed that two IRs (DEET and Bayrepel) were ubiquitous in the Sava and Evrotas basins, reaching concentrations as high as 105 μg l −1 of Bayrepel in the Sava River, and 5 μg l −1 of DEET in the Evrotas River. Densely populated areas and effluent waste waters are pointed out as the responsible for this pollution. In the alpine river Adige, only three samples showed low levels of IRs (6.01–37.8 ng l −1 ). The concentrations measured were used to perform an environmental risk assessment based on the hazard quotients (HQs) estimation approach by using the chronic and acute eco-toxicity data available. The results revealed that despite the high frequency and eventually high concentrations of these IRs determined in the three basins, only few sites were at risk, with 1 < HQs < 3.3. [ABSTRACT FROM AUTHOR]

A multiresidue method has been developed for the determination of emerging pollutants in leafy and root vegetables. Selected compounds were 6 perfluoroalkyl compounds (5 perfluorocarboxylic acids and perfluorooctanesulfonic acid), 3 non-ionic surfactants (nonylphenol and nonylphenolethoxylates), 8 anionic surfactants (4 alkylsulfates and 4 linear alkylbenzene sulfonates), 4 preservatives (parabens), 2 biocides (triclosan and triclocarban), 2 plasticizers (bisphenol A and di-(2-ethylhexyl)phthalate), 6 UV-filters (benzophenones) and 4 hormones. The method is based on ultrasound-assisted extraction, clean-up by dispersive solid-phase extraction (d-SPE) and liquid chromatography-tandem mass spectrometry analysis. Due to the diversity of the physico-chemical properties of the target compounds, and to better evaluate the influence of sample treatment variables in extraction efficiencies, Box-Behnken design was applied to optimize extraction solvent volume, number of extraction cycles and d-SPE sorbent amount. Linearity (R 2 ) higher than 0.992, accuracy (expressed as relative recoveries) in the range from 81 to 126%, precision (expressed as relative standard deviation) lower than 19% and limits of detection between 0.025 and 12.5 ng g −1 dry weight were achieved. The method was applied to leafy vegetables (lettuce, spinach and chard) and root vegetables (carrot, turnip and potato) from a local market. The highest concentrations corresponded to the surfactants reaching levels up to 114 ng g −1 (dry weight), in one of the lettuce samples analyzed. [ABSTRACT FROM AUTHOR]

Environmental exposures often occur through short, pulsed events; therefore, the ability to accurately measure these toxicologically-relevant concentrations is important. Three different integrative passive sampler configurations were evaluated under different flow and pulsed exposure conditions for the measurement of current-use pesticides (n = 19), polyaromatic hydrocarbons (n = 10), and personal care products (n = 5) spanning a broad range of hydrophobicities (log Kow 1.5–7.6). Two modified POCIS-style samplers were investigated using macroporous nylon mesh membranes (35 μm pores) and two different sorbent materials (i.e. Oasis HLB and Dowex Optipore L-493). A recently developed design, the Sentinel Sampler (ABS Materials), utilizing Osorb media enclosed within stainless steel mesh (145 μm pores), was also investigated. Relatively high sampling rates ( Rs ) were achieved for all sampler configurations during the short eight-day exposure (4300–27 mL/d). Under flow conditions, median Rs were approximately 5–10 times higher for POCIS-style samplers and 27 times higher for Sentinel Samplers, as compared to static conditions. The ability of samplers to rapidly measure hydrophobic contaminants may be a trade off with increased flow dependence. Analyte accumulation was integrative under pulsed and continuous exposures for POCIS-style samplers with mean difference between treatments of 11% and 33%; however, accumulation into Sentinel Samplers was more variable. Collectively, results show that reducing membrane limitations allows for rapid, integrative accumulation of a broad range of analytes even under pulsed exposures. As such, these sampler designs may be suitable for monitoring environmental substances that have short aquatic half-lives. [ABSTRACT FROM AUTHOR]

The stability and photochemical transformations of cosmetic preservatives in topical applications exposed to UV-light is a serious but poorly understood problem. In this study, a high throughput extraction and selective method based on pressurized liquid extraction (PLE) coupled to gas chromatography–mass spectrometry (GC–MS) was validated and applied to investigate the photochemical transformation of the antioxidant butylated hydroxytoluene (BHT), as well as the antimicrobials triclosan (TCS) and phenyl benzoate (PhBz) in an artificial skin model. Two sets of photodegradation experiments were performed: (i) UV-Irradiation (8 W, 254 nm) of artificial skin directly spiked with the target preservatives, and (ii) UV-irradiation of artificial skin after the application of a cosmetic cream fortified with the target compounds. After irradiation, PLE was used to isolate the target preservatives and their transformation products. The follow-up of the photodegradation kinetics of the parent preservatives, the identification of the arising by-products, and the monitorization of their kinetic profiles was performed by GC–MS. The photochemical transformation of triclosan into 2,8-dichloro-dibenzo- p -dioxin (2,8-DCDD) and other dioxin-like photoproducts has been confirmed in this work. Furthermore, seven BHT photoproducts, and three benzophenones as PhBz by-products, have been also identified. These findings reveal the first evidences of cosmetic ingredients phototransformation into unwanted photoproducts on an artificial skin model. [ABSTRACT FROM AUTHOR]

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

A sensitive analytical method based on liquid–liquid extraction (LLE) and liquid chromatography tandem mass spectrometry (LC–MS/MS) was developed for rapid analysis of 11 pharmaceuticals and personal care products (PPCPs) in fish plasma micro-aliquots (∼20 μL). Target PPCPs included, bisphenol A, carbamazepine, diclofenac, fluoxetine, gemfibrozil, ibuprofen, naproxen, risperidone, sertraline, simvastatin and triclosan. A relatively quicker and cheaper LLE procedure exhibited comparable analyte recoveries with solid-phase extraction. Rapid separation and analysis of target compounds in fish plasma extracts was achieved by employing a high efficiency C-18 HPLC column (Agilent Poroshell 120 SB-C18, 2.1 mm × 50 mm, 2.7 μm) and fast polarity switching, enabling effective monitoring of positive and negative ions in a single 9 min run. With the exception of bisphenol A, which exhibited relatively high background contamination, method detection limits of individual PPCPs ranged between 0.15 and 0.69 pg/μL, while method quantification limits were between 0.05 and 2.3 pg/μL. Mean matrix effect (ME) values ranged between 65 and 156% for the various target analytes. Isotope dilution quantification using isotopically labelled internal surrogates was utilized to correct for signal suppression or enhancement and analyte losses during sample preparation. The method was evaluated by analysis of 20 μL plasma micro-aliquots collected from zebrafish ( Danio rerio ) from a laboratory bioaccumulation study, which included control group fish (no exposure), as well as fish exposed to environmentally relevant concentrations of PPCPs. Using the developed LC–MS/MS based method, concentrations of the studied PPCPs were consistently detected in the low pg/μL (ppb) range. The method may be useful for investigations requiring fast, reliable concentration measurements of PPCPs in fish plasma. In particular, the method may be applicable for in situ contaminant biomonitoring, as well as bioaccumulation and toxicology studies employing small fishes with low blood compartment volumes. [ABSTRACT FROM AUTHOR]

Phthalic acid esters (PEs) were preconcentrated from cleaning products, detergents and cosmetics using ultrasound assisted extraction (UAE) in the presence of acetonitrile, and then submitted to dispersive liquid–liquid microextraction (DLLME). For DLLME, 3 mL of acetonitrile extract, 150 μL carbon tetrachloride and 10 mL aqueous solution were used. The enriched organic phase was evaporated, reconstituted with 25 μL acetonitrile and injected into a liquid chromatograph with a mobile phase (acetonitrile:10 mM ammonium acetate, pH 4) under gradient elution. Detection was carried out using both diode-array (DAD) and electrospray-ion trap-tandem mass spectrometry (ESI-IT-MS/MS) in the multiple reaction monitoring mode (MRM) of the positive fragment ions. Quantification was carried out using matrix-matched standards. Detection limits were in the range 0.04–0.45 ng mL −1 for the six PEs considered. The recoveries obtained were in the 84–124% range, with RSDs lower than 10%. Thirty three different cleaning products were analyzed. The most frequently found compound was diethyl phthalate. [ABSTRACT FROM AUTHOR]

In the present study, a sensitive and accurate isotope dilution method was developed for the simultaneous determination of 17 polar pharmaceutical and personal care product (PPCP) residues (logKow=1.40-5.74), including 14 pharmaceuticals and 3 personal care products, in biological organs and tissues. The proposed method involved enzymatic hydrolysis, followed by sequential clean-up using silica gel chromatography and gel permeation chromatography, and analysis via ultra-high-performance liquid chromatography with tandem mass spectrometry. This method yielded acceptable absolute recoveries (48-88%) and internal standard-corrected recoveries (90-130%) for 17 PPCPs. Method detection limits were between 0.0092 and 3.2ngg-1 wet weight, and the limits of quantification were between 0.020 and 8.7ngg-1 wet weight. The method can be used to readily detect the target compounds at trace levels while minimizing the required sample volume. The developed method was applied to the determination of 17 PPCPs in the liver and kidney of 17 birds collected from Japan and also in the plasma, liver, and brain of 7 cyprinoid fish from an effluent-dominated stream in Japan. Triclosan was detected in 5 of 11 fish-eating birds but not in non-fish-eating birds, suggesting the contamination of prey fish by the chemical. Non-steroidal anti-inflammatory drugs, antibacterial agents, and psychotropic agents were frequently detected in the fish tissues. In addition, 7 of the target compounds were found in fish brain. The median brain/plasma ratios of the psychotropic agents ranged from 1.6 (carbamazepine) to 12 (diphenhydramine), indicating high transportability to fish brain. [ABSTRACT FROM AUTHOR]

Highlights: [•] Free chlorine enhance degradation of targets yielding halogenated by-products in aqueous photodegradation. [•] Parents and transformation products kinetic behavior was monitored by SPME-GC/MS. [•] Brominated parabens and other hydroxybenzoates were mainly detected. [•] Halogenated phenols were identified as breakdown photochemical by-products. [Copyright &y& Elsevier]

Highlights: [•] First time GC–MS/MS implemented for fragrances and preservatives in cosmetics. [•] Twenty-five fragrances allergens and 13 preservatives including 35 regulated substances. [•] The miniaturized MSPD is rapid, low cost, and easy to implement for routine control. [•] Thirty-one of the 38 target compounds were found in personal care products. [ABSTRACT FROM AUTHOR]

Highlights: [•] Reliable contribution to the multi-preservative analysis of cosmetics based on SPME–GC–MS/MS. [•] Matrix effect compensation and chromatographic performance improvement. [•] The method is simple, rapid, low cost, and easy to implement for routine control. [•] Successfully applied in both rinse-off and leave-on cosmetic samples. [ABSTRACT FROM AUTHOR]

Highlights: [•] First time MSPD implemented for synthetic musks and plasticizers in cosmetics. [•] 18 plasticizers and 12 musks including 10 banned substances were selected as targets. [•] The miniaturized MSPD is rapid, low cost, and easy to implement for routine control. [•] Forbidden Banned phthalates and nitro musk confirmed in 62% of personal care products. [•] None of the phthalates neither the musks were included in the list of ingredients. [Copyright &y& Elsevier]

Abstract: In this work, the development of a new efficient methodology applying, for the first time, matrix solid phase dispersion (MSPD) for the determination of sensitizer isothiazolinone biocides in cosmetics and household products – 2-methyl-3-isothiazolinone (MI), 5-chloro-2-methyl-3-isothiazolinone (CMI), 1,2-benzisothiazolinone (BzI) and 2-octyl-3-isothiazolinone (OI) – is described. The main factors affecting the MSPD extraction procedure, the dispersive phase and the elution solvent, are assessed and optimized through a multicategorical experimental design, using a real cosmetic sample. The most suitable extraction conditions comprise the use of 2g of florisil as dispersive phase and 5mL of methanol as elution solvent. Subsequently, the extract is readily analyzed by HPLC–MS/MS without any further clean-up or concentration steps. Method performance was evaluated demonstrating to have a broad linear range (R 2 >0.9980) and limits of detection (LOD) and quantification (LOQ) at the low nanogram per gram level, which are well below the required limits for UE regulation compliance. Satisfactory recoveries above 80%, except for MI (mean values close to 60%), were obtained. In all cases, the method precision (% RSD) was lower than 7%, making this low cost extraction method reliable for routine control. The validated methodology was finally applied to the analysis of a wide variety of cosmetics and household products. Most of the real samples analyzed have been shown to comply with the current European Cosmetic Regulation, although the results obtained for some rinse-off cosmetics (e.g. baby care products) revealed high isothiazolinone content. [Copyright &y& Elsevier]

Abstract: Analytical improvements were developed and validated for measuring select personal care products (PCPs) and two pharmaceuticals in fish tissue. The method was validated using fortified fillet tissue for twelve PCPs including fragrance materials, alkylphenols, photo initiators, and triclosan as well as two pharmaceuticals including carbamazepine (anti-seizure) and diazepam (anti-convulsant). The analytical method utilized pressurized liquid extraction (PLE) combined with silica gel cleanup, gel permeation chromatography, and gas chromatography ion-trap tandem mass spectrometry. Silica gel cleanup was combined with the PLE to produce one automated extraction/cleanup technique. This analytical improvement served to reduce the incurred cost, time, and loss of potential target analytes associated with independent cleanup steps. The combined extraction/cleanup technique resulted in an average increase of 10% in analyte recoveries. Average triplicate recoveries and relative standard deviations for the entire method, using 2.5g of fish fillet tissue, were 92±9% (recoveries ranged from 64 to 131%). The sensitivity of the analytical methods was improved by optimizing the resonant collision induced dissociation energy to the hundredths place (0.01V). Improvements in ion production range from 24 to 122% for six of the 12 PCPs. Statistically derived method detection limits (MDLs) were also lowered on average by a factor of 8 and ranged from 1.2 to 38ng/g wet weight. MDLs for carbamazepine and diazepam were 18 and 3.7ng/g wet weight, respectively. Galaxolide and tonalide were measured in an environmental sample at concentrations of 81 and 5.5ng/g wet weight, respectively. [Copyright &y& Elsevier]

Abstract: An effective low cost sample preparation methodology for the determination of regulated fragrance allergens in leave-on and rinse-off cosmetics has been developed applying, for the first time, matrix solid-phase dispersion (MSPD) to this kind of analytes and samples. The selection of the most suitable extraction conditions was made using statistical tools such as ANOVA, as well as a factorial multifactor experimental design. These studies were carried out using real cosmetic samples. In the final conditions, 0.5 of sample, previously mixed with 1g of anhydrous Na2SO4, were blended with 2g of dispersive sorbent (Florisil), and the MSPD column was eluted with 5mL of hexane/acetone (1:1). The extract was then analyzed by GC–MS without any further clean-up or concentration step. Accuracy, precision, linearity and detection limits (LODs) were evaluated to assess the performance of the proposed method. Quantitative recoveries (>75%) were obtained and RSD values were lower than 10% in all cases. The quantification limits were well below those set by the international cosmetic regulations, making this multi-component analytical method suitable for routine control. In addition, the MSPD method can be implemented in any laboratory at low cost since it does not require special equipment. Finally, a wide variety of cosmetic products were analyzed. All the samples contained several of the target cosmetic ingredients, with and average number of seven. The total fragrance allergen content was in general quite high, even in baby care products, with values close to or up to 1%, for several samples, although the actual European Cosmetic Regulation was fulfilled. [Copyright &y& Elsevier]

Abstract: A large number of xenobiotics including pharmaceuticals and personal care products are continuously released into the environment. Effluents from sewage treatment plants are well known to be the major source for introduction of pharmaceuticals and personal care products into the aquatic system. In recent years, reliable methods have been established for residue analysis of these pollutants down to low ng/L levels. In this review, the different approaches to their trace determination are reviewed with special attention being paid to sample preparation procedures, state-of-the-art high-performance separation methods hyphenated with mass spectrometry, and immunochemical methods. [ABSTRACT FROM AUTHOR]

Abstract: A new method based on solid phase dispersion-pressurized liquid extraction (PLE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed for the determination of 26 suspected fragrance allergens (all the regulated in the EU Cosmetics Directive amenable by GC, as well as pinene and methyleugenol) in cosmetic samples. The effects of the temperature, extraction time and solvent, and dispersing sorbent, affecting the whole proposed procedure, have been evaluated using a multifactor strategy. The optima conditions after the analysis of main and second order effects entailed the extraction at 120°C for 15min, using hexane/acetone as solvent, and florisil as dispersing sorbent. The method performance has been studied, showing good linearity (R ≥0.996) as well as good precision (RSD≤10%). Detection limits (S/N=3) ranged from 0.000001 to 0.0002% (w/w), values far below the established restrictions as regard labelling in the European Cosmetics Regulation. Reliability was demonstrated through the quantitative recoveries of all the studied compounds. The absence of matrix effects allowed quantification of the compounds by calibration with standard solutions. The analysis of 10 samples (several moisturizing and anti-wrinkle creams and lotions, hand creams, and sunscreen and after-sun creams), covering very different matrices, showed the presence of suspected allergens in all the analyzed samples; in fact, half of the samples contained an elevated number of them. Although the ubiquity of these compounds was demonstrated, labelling was in all cases in consonance with the European Cosmetics Regulation. [ABSTRACT FROM AUTHOR]

Abstract: This study describes the development of a new analytical method for determining 14 personal care products (PCPs) – nine synthetic musks, four parabens and one insect repellent – in air samples. The method is based on active sampling on sorbent tubes and thermal desorption-gas chromatography–mass spectrometry analysis, and is rapid, sensitive and drastically reduces the risk of sample contamination. Three kinds of tubes and traps were tested, those filled with Tenax TA being the most suitable for this study. Method validation showed good repeatability and reproducibility, low detection limits (between 0.03ngm−3 for DPMI and 12.5ngm−3 for propyl paraben) and good linearity for all compounds. Stability during storage indicated that samples must be kept refrigerated at 4°C and analysed within 1 week of collection. The applicability of the technique to real samples was tested in different indoor and outdoor atmospheres. The total PCP values for indoor air ranged from 135ngm−3 in a pharmacy to 2838ngm−3 in a hairdresser''s, whereas the values for outdoor air ranged from 14ngm−3 for a suburban environment to 26ngm−3 for an urban environment. In general, the most abundant synthetic musks were galaxolide (5.9–1256ngm−3), musk xylene (1.6–766ngm−3) and tonalide (1.1–138ngm−3). Methyl and ethyl paraben (2.4–313ngm−3 and 1.8–117ngm−3, respectively) were the most abundant parabens. Although thermal desorption methods have been widely used for determining volatile organic compounds, they are rarely used with semi-volatile compounds. This study thus demonstrates that the thermal desorption method performs well with semi-volatile compounds and, for the first time, that it can be used for determining PCPs. [Copyright &y& Elsevier]

Abstract: The enantiomeric separation of four chiral polycyclic musks (Galaxolide, Tonalide, Traseolide and Phantolide) using CE was achieved for the first time in this work. Two chiral methodologies were developed by CD-MEKC using SDS as surfactant in a CHES buffer (pH 9.0). One methodology enabled the fast enantiomeric separation of individual polycyclic musks with analysis times lower than 10min for Tonalide, 13min for Traseolide and Phantolide, and 17min for Galaxolide. Enantiomeric resolutions obtained were higher than 1.5 using different separation media for each compound. A second methodology was also developed enabling the simultaneous enantioseparation of the four musks. In this case, the use of a dual CD system containing two neutral CDs was necessary to achieve the separation of all enantiomers from three out of four musks in 45min. Although a coelution between Galaxolide and Phantolide was observed, the use of different UV absorption wavelengths allowed the simultaneous analysis of both musks. In addition, a sweeping strategy was performed in order to increase the sensitivity of the method. Appropriate analytical characteristics (linearity, LOD and LOQ, precision and absence of matrix interferences) were obtained for conventional and sweeping methodologies. Finally, the usefulness of the method was demonstrated in the determination of the enantiomers of the polycyclic musks in personal care products as perfumes. [Copyright &y& Elsevier]

• A miniaturized aqueous biphasic system (µ-ABS) is formed with food additives. • Cholinium chloride is used as extraction phase and K 2 HPO 4 as salting-out reagent. • The solvent-free µ-ABS is applied to preconcentrate 9 personal care products. • The validated µ-ABS-HPLC-DAD has high extraction efficiency. • The method is applied for multi-residue determination in wastewater samples. A miniaturized extraction/preconcentration method based on an aqueous biphasic system (μ-ABS) was developed with reagents commonly used as food additives: cholinium chloride (ChCl) as main extraction phase, K 2 HPO 4 as salting-out agent, and water as the main component (being the sample for analyses). With the aim of obtaining high enrichment factors, miniaturization, and adequate analytical performance, a point in the biphasic region with the lowest amount of ChCl was selected, corresponding to 1.55% (w/w) of ChCl, 59.5% (w/w) of K 2 HPO 4 , and 38.95% (w/w) of water. The green μ-ABS (attending to its main elements and performance mode) was used in combination with high-performance liquid chromatography with diode-array detection (HPLC-DAD) for the determination of 9 personal care products in wastewater samples. The μ-ABS-HPLC-DAD method showed high enrichment factors (up to 100), and quantitative extraction efficiencies for those compounds containing OH groups in their structure, which can undergo hydrogen bonding with ChCl. Thus, limits of quantification down to 0.8 µg·L-1 and extraction efficiencies between 66.4 and 108% (concentration levels of 1.3 and 13 µg·L-1) were reached for the group of parabens and the UV-filter benzophenone-3. The method is characterized by the use of non-harmful reagents and the absence of organic solvents in the entire sample preparation procedure, while being simple, low-cost, easily compatible with HPLC, and highly efficient. [ABSTRACT FROM AUTHOR]

• A rapid analytical method was developed for 72 PPCPs in fish tissues. • Acidification with acetate buffer improved absolute recovery rates. • Oasis HLB and HybridSPE-Phospholipid Ultra cartridges were assessed. • Zirconia-coated silica cartridge efficiently removed analytical interferences. • The developed method is highly useful for comprehensive evaluation of PPCPs in fish. The presence of pharmaceuticals and personal care products (PPCPs) in aquatic systems has raised concern about their potential adverse effects on aquatic organisms. Considering the fact that the physiological/biological effects of PPCPs are triggered when their concentrations in the organism exceeds the respective threshold values, it is important to understand the bioconcentration and toxicokinetics of PPCPs in aquatic organisms. In the present study, we developed a convenient analytical method for the determination of 65 pharmaceuticals and 7 personal care products (log K ow = 0.14–6.04) in plasma and whole-body tissues of fish. The analytical method consists of ultrasound-assisted extraction in methanol/acetonitrile (1:1, v/v,) acidified with acetic acid-ammonium acetate buffer (pH 4), cleanup on a HybridSPE®-Phospholipid cartridge (zirconia-coated silica cartridge), and quantification with liquid chromatography-tandem mass spectrometry (LC–MS/MS). Acceptable accuracy (internal standard-corrected recovery: 70%–120%) and intra- and inter-day precision (coefficient of variation: <15%) were obtained for both plasma and whole-body tissue samples. In addition, low method detection limits were achieved for both plasma (0.0077 to 0.93 ng mL−1) and whole-body tissue (0.022 to 4.3 ng g −1 wet weight), although the developed method is simple and fast ― a batch of 24 samples can be prepared within 6 h, excluding the time for measurement with LC–MS/MS. The developed method was successfully applied to the analysis of PPCPs in plasma and whole-body tissue samples of fish collected in a treated wastewater-dominated stream, for a comprehensive evaluation of their bioconcentration properties. The analytical method developed in the present study is sufficiently accurate, sensitive, and rapid, and thus highly useful for the comprehensive evaluation of PPCP residues in fish and would aid in future exposome and risk assessment. [ABSTRACT FROM AUTHOR]

• Model plants were grown in water contaminated (spiked) with three UV-filters. • The UV-filters and several transformation products compounds were detected in plant extracts. • Combining information from chromatography, ion-mobility-, and mass spectrometry allowed proposing structures. • Concentration of UV-filters and their transformation products were monitored over time. • UF-filters and transformation products can be detected in plants treated real sunscreen. The uptake, translocation and transformation of three UV-blockers commonly employed in sunscreens, namely avobenzone, octocrylene and octisalate from water by Lemna gibba and Cyperus alternifolius was investigated. Reversed phase high performance liquid chromatography coupled to drift-tube ion-mobility quadrupole time-of-flight mass spectrometry was used for analyzing the extracts from the selected plants after incubation with the UV-blockers for one week. For avobenzone several transformation products resulting from hydroxylation, demethylation and oxidation of the parent molecule could be identified by measuring accurate mass, performing MS/MS experiments and by determining their drift-tube collision cross sections employing nitrogen as drift gas. In addition, the plants were subjected to two commercially available sunscreens, providing similar results to those obtained for the standard solutions of the UV-blockers. Finally, a kinetic study on the uptake and transformation of avobenzone, octocrylene and octisalate was conducted over a period of 216 h, revealing that the UV-filters were mostly present in their parent form and only to a smaller part converted into transformation products. [ABSTRACT FROM AUTHOR]

• A green SPME-GC–MS/MS method was developed to analyze 43 PCPs in environmental water. • Target compounds include allergens, musks, phthalates, antioxidants and UV filters. • Main experimental parameters affecting extraction were optimized by multifactor ANOVA. • The high throughput method was successfully validated and applied to real samples. • Ultratrace PCP analysis in a single extraction chromatographic run was achieved in 23 min. A methodology based on solid-phase microextraction (SPME) followed by gas chromatography–tandem mass spectrometry (GC–MS/MS) was developed for the simultaneous analysis of different families of personal care products (PCPs) including fragrance allergens, synthetic musks, phthalates, antioxidants and UV filters in continental waters. The main parameters affecting SPME procedure were optimized by an ANOVA study. The final selected conditions comprised the use of 10 mL of sample with 20% (w/v) of sodium chloride (NaCl), polydimtehylsiloxane/divinylbenzene (PDMS/DVB) fiber and 20 min of extraction time at 100 °C in the head-space mode. Good linearity (R2>0.9925), quantitative recoveries (>79%), and precision (RSD < 15%) were achieved for all compounds under the optimal conditions. Limits of quantification (LOQs) at the sub and low ng L−1 were obtained. The validated methodology was successfully applied to the analysis of river water samples from the North Portuguese coast allowing the determination of five different families of PCPs, including a total of 43 compounds in a single chromatographic run within 23 min. [ABSTRACT FROM AUTHOR]

The IL-based surfactant octylguanidinium chloride (C 8 Gu-Cl) was designed and synthetized with the purpose of obtaining a less harmful surfactant: containing guanidinium as core cation and a relatively short alkyl chain. Its interfacial and aggregation behavior was evaluated through conductivity and fluorescence measurements, presenting a critical micelle concentration value of 42.5 and 44.6mmolL -1 , respectively. Cytotoxicity studies were carried out with C 8 Gu-Cl and other IL-based and conventional surfactants, specifically the analogue 1-octyl-3-methylimidazolium chloride (C 8 MIm-Cl), and other imidazolium- (C 16 MIm-Br) and pyridinium- (C 16 Py-Cl) based surfactants, together with the conventional cationic CTAB and the conventional anionic SDS. From these studies, C 8 Gu-Cl was the only one to achieve the classification of low cytotoxicity. An in situ dispersive liquid-liquid microextraction (DLLME) method based on transforming the water-soluble C 8 Gu-Cl IL-based surfactant into a water-insoluble IL microdroplet via a simple metathesis reaction was then selected as the extraction/preconcentration method for a group of 6 personal care products (PCPs) present in cosmetic samples. The method was carried out in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The method was properly optimized, requiring the use of only 30μL of C 8 Gu-Cl for 10mL of aqueous sample with a NaCl content of 8% (w/v) to adjust the ionic strength and pH value of 5. The metathesis reaction required the addition of the anion exchange reagent (bis[(trifluoromethyl)sulfonyl]imide - 1:1 molar ratio), followed by vortex and centrifugation, and dilution of the final microdroplet up to 60μL with acetonitrile before the injection in the HPLC-DAD system. The optimum in situ DLLME-HPLC-DAD method takes ∼10min for the extraction step and ∼22min for the chromatographic separation, with analytical features of low detection limits: down to 0.4μgL -1 ; high reproducibility: with RSD values lower than 10% (intra-day) and 16% (inter-day) for a spiked level of 15μgL -1 ; and an average enrichment factor of 89. The requirement of low volumes (30μL) of a low cytotoxic IL-based surfactant allows the method to be considered less harmful than other common analytical microextraction approaches., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The photochemical transformation of widely used cosmetic preservatives including benzoates, parabens, BHA, BHT and triclosan has been investigated in this work applying an innovative double-approach strategy: identification of transformation products in aqueous photodegradation experiments (UV-light, 254nm), followed by targeted screening analysis of such photoproducts in UV-irradiated cosmetic samples. Solid-phase microextraction (SPME) was applied, using different fiber coatings, in order to widen the range of detectable photoproducts in water, whereas UV-irradiated personal care products (PCPs) containing the target preservatives were extracted by micro-matrix solid-phase dispersion (micro-MSPD). Both SPME and micro-MSPD-based methodologies were successfully optimized and validated. Degradation kinetics of parent species, and photoformation of their transformation by-products were monitored by gas chromatography coupled to mass spectrometry (GC-MS). Thirty nine photoproducts were detected in aqueous photodegradation experiments, being tentatively identified based on their mass spectra. Transformation pathways between structurally related by-products, consistent with their kinetic behavior were postulated. The photoformation of unexpected photoproducts such as 2- and 4-hydroxybenzophenones, and 2,8-dichlorodibenzo-p-dioxin in PCPs are reported in this work for the first time., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In the present study, a sensitive and accurate isotope dilution method was developed for the simultaneous determination of 17 polar pharmaceutical and personal care product (PPCP) residues (logKow=1.40-5.74), including 14 pharmaceuticals and 3 personal care products, in biological organs and tissues. The proposed method involved enzymatic hydrolysis, followed by sequential clean-up using silica gel chromatography and gel permeation chromatography, and analysis via ultra-high-performance liquid chromatography with tandem mass spectrometry. This method yielded acceptable absolute recoveries (48-88%) and internal standard-corrected recoveries (90-130%) for 17 PPCPs. Method detection limits were between 0.0092 and 3.2ngg(-1) wet weight, and the limits of quantification were between 0.020 and 8.7ngg(-1) wet weight. The method can be used to readily detect the target compounds at trace levels while minimizing the required sample volume. The developed method was applied to the determination of 17 PPCPs in the liver and kidney of 17 birds collected from Japan and also in the plasma, liver, and brain of 7 cyprinoid fish from an effluent-dominated stream in Japan. Triclosan was detected in 5 of 11 fish-eating birds but not in non-fish-eating birds, suggesting the contamination of prey fish by the chemical. Non-steroidal anti-inflammatory drugs, antibacterial agents, and psychotropic agents were frequently detected in the fish tissues. In addition, 7 of the target compounds were found in fish brain. The median brain/plasma ratios of the psychotropic agents ranged from 1.6 (carbamazepine) to 12 (diphenhydramine), indicating high transportability to fish brain., (Copyright © 2014 Elsevier B.V. All rights reserved.)