In-Vial Micro-Matrix-Solid Phase Dispersion for the Analysis of Fragrance Allergens, Preservatives, Plasticizers, and Musks in Cosmetics

Cosmetics 2014, 1, 171-201; doi:10.3390/cosmetics1030171 cosmetics ISSN 2079-9284 www.mdpi.com/journal/cosmetics Article In-Vial Micro-Matrix-Solid Phase Dispersion for the Analysis of Fragrance Allergens, Preservatives, Plasticizers, and Musks in Cosmetics Maria Celeiro †, Juan Pablo Lamas †, Maria Llompart † and Carmen Garcia-Jares * Department of Analytical Chemistry, Nutrition and Food Science, Faculty of Chemistry, University of Santiago de Compostela, Campus Vida, E-15782 Santiago de Compostela, Spain; E-Mails: [email protected] (M.C.); [email protected] (J.P.L.); maria.llom[email protected] (M.L.) † These authors contributed equally to this work. * Author to whom correspondence should be addressed; E-Mail: carmen.ga[email protected]; Tel.: +34-881-814-394; Fax: +34-881-814-468. Received: 28 May 2014; in revised form: 7 July 2014 / Accepted: 9 July 2014 / Published: 22 July 2014 Abstract: Fragrance allergens, preservatives, plasticizers, and synthetic musks are usually present in cosmetic and personal care products formulations and many of them are subjected to use restrictions or labeling requirements. Matrix solid-phase dispersion (MSPD) is a very suitable analytical technique for the extraction of these compounds providing a simple, low cost sample preparation, and the possibility of performing both extraction and clean-up in one step, reducing possible contamination and analyte losses. This extraction technique has been successfully applied to many cosmetics ingredients allowing obtaining quantitative recoveries. A new very simple micro-MSPD procedure performing the disruption step in a vial is proposed for the gas chromatography-mass spectrometry (GC-MS) analysis of 66 chemicals usually present in cosmetics and personal care products. The method was validated showing general recoveries between 80% and 110%, relative standard deviation (RSD) values lower than 15%, and limits of detection (LODs) below 30 ng·g−1. The validated method was applied to a broad range of cosmetics and personal care products, including several products intended for baby care. OPEN ACCESS Cosmetics 2014, 1 172 Keywords: cosmetics; micro-matrix solid-phase dispersion; fragrance allergens; preservatives; plasticizers; musks; gas chromatography-mass spectrometry (GC-MS) 1. Introduction Fragrances and preservatives are common ingredients in cosmetics and personal care products. Fragrances provide nice and attractive scents and preservatives are used to prevent microbial growth because the aqueous nature of many personal care products is an optimal medium for microbial growth. European legislation [1] requires the monitoring of 26 volatile compounds, the so-called potentially allergen substances (PAS) or fragrance allergens. Their presence must be indicated in the list of ingredients when their concentrations exceed 0.01% for rinse-off products, and 0.001% for leave-on products. Of these 26 substances, 24 are chemically defined volatile compounds whereas the other two are natural moss extracts. One of these 24 fragrance allergens, lyral®, was recently proposed to be transferred to the Annex III (list of substances which cosmetic products must not contain except subject to restrictions) to Annex II (list of substances prohibited in cosmetic products). Also, pinene and methyleugenol were included in the referred study; pinene is proposed to be labelled when its concentration exceeds 0.01% for rinse-off products, and 0.001% for leave-on products, whereas methyleugenol has been banned in cosmetics and personal care products for some years, and now it is included in Annex III. Parabens are the most frequently used preservatives (their maximum concentration in cosmetics and personal care products is 0.4% for a single ester and 0.8% for mixture of esters). Its extended use is due to their broad antimicrobial spectrum and low cost [2,3]. Although these compounds are not mutagenic agents, recent studies have reported that certain parabens have been associated with genotoxicity, allergies and may also act as antiandrogens [4–6]. In recent years, another preservative, phenoxyethanol, is increasing its use as substitute of parabens. According to the European regulation [1], the maximum concentration permitted for this compound is 1% regardless of its use. However, a recent study reported by the France National Agency for Security of Medicaments (ANSM) proposed not using phenoxyethanol in products intended for children under 3 years and to reduce the maximum permitted concentration (0.4%) in other personal care products [7]. Triclosan (2,4,4′-trichloro-2′- hydroxydiphenyl ether) and the bromine-containing preservative bronidox, are also preservatives present in personal care products. Their maximum permitted concentrations according European legislation is 0.3% and 0.1%, respectively. IPBC (iodopropynyl butylcarbamate) is not permitted in products for children under 3 years of age, except in bath products, shower gels and shampoo. The antioxidants butylated hidroxyanisole (BHA) and butylated hydroxytoluene (BHT) can be used without restrictions. Synthetic musks are other chemical compounds usually present in personal care products under the term “fragrance” or “parfum”. Synthetic musks are used as an alternative for natural musks. The European regulation has forbidden the use of three nitromusks: musk ambrette, musk moskene and musk tibetene due to their bioaccumulative properties [8]. Another two nitromusks (musk ketone and musk xylene) are allowed with restrictions [1]. Cosmetics 2014, 1 173 Plasticizers (phthalates and adipates) are used in cosmetic and personal care formulations as solvents, fixer of fragrances, and to promote skin penetration. Diethyl phthalate (DEP) can be present in personal care products as solvent of the synthetic musk galaxolide. However, the European Commission on Endocrine Disruption has listed DEP as a Category 1 priority substance [9]. Other six phthalates (dibutyl phthalate (DBP), dimethoxyethyl phthalate (DMEP), diisopentyl phthalate (DIPP), dipentyl phthalate (DPP), benzylbutyl phthalate (BBP) and di(2-ethylhexyl) phthalate (DEHP)) were forbidden as ingredients in cosmetics and personal care products due to their possible carcinogenic and mutagenic effects in human health. Adipates (1,6-dimethylhexanedioate (DMA), 1,6-diethylhexanedioate (DEA) and di(2-ethylhexyl) adipate (DEHA)) are permitted without restrictions. In order to guarantee product safety, the development of analytical methods is mandatory in cosmetic quality control. In this way, several analytical methods to determine fragrance allergens, preservatives, plasticizers, and/or musks in cosmetics and personal care products have been reported. A summary of the more recent extraction and analysis techniques for the analysis of these compounds in different cosmetic matrices can be found in recent reviews [10–13]. Matrix solid-phase dispersion (MSPD) is a very suitable analytical technique for the extraction of contaminants in environmental and other matrices [14] as well as to determine fragrances, preservatives, plasticizers and musks in cosmetic samples. This technique is primarily used because of its flexibility and selectivity providing efficient and low cost extractions; the possibility of performing extraction and clean-up in one step is one of their main advantages [15–21]. Also, its miniaturizing allows reducing the amount of sample, reagents and solvents required. MSPD combines different aspects of several analytical techniques, performing sample disruption while dispersing the components of the sample on and into a solid support, thereby generating a chromatographic material that possesses a particular character for the extraction of compounds from the dispersed sample [15]. This extraction technique allowed obtaining quantitative recoveries for many cosmetic ingredients [16,19,20,22]. For very volatile compounds such as pinene and limonene, that are easily lost during extraction processes [23], MSPD can constitute a good alternative to lower analyte losses [20]. The aim of the present study is to compare the performance of two micro-MSPD procedures, performing the sample disruption in mortar and also in vial, for the gas chromatography-mass spectrometry (GC-MS) analysis of 66 compounds including fragrance allergens, preservatives, plasticizers, and musks, usually present in cosmetics and personal care products. All these families of compounds are subjected to restrictions according international regulation. 2. Experimental Section 2.1. Chemicals, Materials and Samples The analyzed compounds, their chemical names, Chemical Abstract Services (CAS) numbers, suppliers, purity of the standards and European legislation restrictions are also shown in Table 1. Deuterated methyl-4-hydroxybenzoate-2,3,5,6-d4 (MeP_d4; 98atom% D), benzyl_d7 alcohol (98atom% D) and di-(2-ethylhexyl)phthalate-3,4,5,6-d4 (DEHP_d4; 98atom% D) used as surrogate standard, were obtained from C/D/N Isotopes (Quebec, Canada), Aldrich (St. Louis, MO, USA), and Fluka Chemie GmbH (Steinheim, Germany), respectively. 2,4,6-trichlorobiphenyl (PCB-30) used as internal standard was provided by Dr. Ehrenstorfer (Augsburg, Germany). Cosmetics 2014, 1 174 Table 1. Target compounds: chemical names, suppliers, purity, CAS and European restrictions. Fragrance Allergens Chemical Names Purity (%) CAS Maximum Concentration Permitted [1] Pinene Bicyclo[3.1.1]hept-2-ene, 2,6,6-trimethyl ≥99 b 80-56-8 n.r Limonene a (4R)-1-Methyl-4-(1-methylethenyl)cyclohexene 97 b 5989-27-5 n.r Benzyl alcohol a Benzene methanol ≥99 b 100-51-6 1% (as preservative) Linalool a 3,7-Dimethyl-1,6-octadien-3-ol 97 b 78-70-6 n.r Methyl-2-octynoate a Methyl heptin carbonate ≥99 b 111-12-6 n.r Citronellol a (±)-3,7-Dimethyoct-6-en-1-ol 95 b 106-22-9 n.r Citral a 3,7-Dimethyl-2,6-octadienal 95 b 5392-40-5 n.r Geraniol a 3,7-Dimethyl-(2E)-2,6-octadien-1-ol ≥96 b 106-24-1 n.r Cinnamal a 3-Phenyl-2-propenal ≥93 b 104-55-2 n.r Hydroxycitronellal a 7-Hydroxy-3,7-dimethyloctanal ≥95 b 107-75-5 1% Anise alcohol a 4-Methoxybenzyl alcohol 98 b 105-13-5 n.r Cinnamyl alcohol a 3-Phenyl-2-propen-1-ol 98 b 104-54-1 n.r Eugenol a 2-Methoxy-4-(2-propenyl)-phenol 99 b 97-53-0 n.r Methyleugenol a 1,2-Dimethoxy-4-(2-propenyl)-benzene 99 b 93-15-2 0.01% (fine fragrance); 0.004% (eau de toilette); 0.002% (fragrance cream); 0.0002% (other leave-on products); 0.001% (rinse-off products) Isoeugenol a 2-Methoxy-4-(1-propenyl)phenol 98 b 97-54-1 0.02% Coumarin a 2H-1-benzopyran-2-one ≥99 b 91-64-5 n.r α-isomethyl ionone a 3-Methyl-4-(2,6,6-trimethyl-2-cyclohexen-1yl)-3-buten-2-one ≥85 b 127-51-5 n.r Lilial® a 2-(4-tert-Butylbenzyl)propionaldehyde ≥90 b 80-54-6 n.r Amyl cinnamala 2-Benzylideneheptanal 97 b 122-40-7 n.r Lyral® a,g Hydroxyhexyl-3-cyclohexene carboxaldehyde ≥97 b 31906-04-4 n.r Amylcinnamyl alcohol a 2-Pentyl-3-phenylprop-2-en-1-ol ≥85 b 101-85-9 n.r Farnesol a 3,7,11-trimethyldodeca-2,6,10-trien-1-ol 95 b 4602-84-0 n.r Hexylcinnamal a 2-Benzylideneoctanal ≥95 b 101-86-0 n.r Cosmetics 2014, 1 175 Table 1. Cont. Chemical Names Purity (%) CAS Maximum Concentration Permitted [1] Benzyl benzoate a Phenylmethyl benzoate ≥99 b 120-51-4 n.r Benzyl salicylate a Benzyl-2-hydroxybenzoate ≥99 b 118-58-1 n.r Benzyl cinnamate a 3-Phenyl-2-propenoic acid phenylmethyl ester 99 b 103-41-3 n.r Preservatives Bronidox 5-Bromo-5-nitro-1,3-dioxane ≥99 c 30007-47-7 0.1% (rinse-off products) Phenoxyethanol (phEtOH) 2-Phenoxyethanol 99 c 122-99-6 1% Methyl paraben (MeP) Methyl 4-hydroxibenzoate 99 b 99-76-3 0.4% as acid (for single ester) 0.8% as acid (for mixtures of esters) BHA Butylated hidroxyanisole 98.5 c 25013-16-5 n.r BHT Butylated hydroxytoluene 99 c 128-37-0 n.r Ethyl paraben (EtP) Ethyl 4-hydroxybenzoate 99 b 120-47-8 0.4% as acid (for single ester) 0.8% as acid (for mixtures of esters) Isopropyl paraben (iPrP) * Isopropyl 4-hydroxybenzoate ≥99 b 4191-73-5 0.4% as acid (for single ester) 0.8% as acid (for mixtures of esters) Propyl paraben (PrP) Propyl 4-hydroxybenzoate 99 b 94-13-3 0.4% as acid (for single ester) 0.8% as acid (for mixtures of esters) IPBC Carbamic acid, butyl-3-iodo-2-propynyl ester 97 c 55406-53-6 Prohibited in products for children under 3 years, except in bath products. Prohibited in oral and lip products. 0.02% (rinse-off products); 0.01% (leave-on products); 0.0075% (deodorants). Isobutyl paraben (iBuP) * Isobutyl 4-hydroxybenzoate ≥97 b 4247-02-3 0.4% as acid (for single ester) 0.8% as acid (for mixtures of esters) Butyl paraben (BuP) Butyl 4-hydroxybenzoate 99 b 94-26-8 0.4% as acid (for single ester) 0.8% as acid (for mixtures of esters) Cosmetics 2014, 1 176 Table 1. Cont. Chemical Names Purity (%) CAS Maximum Concentration Permitted [1] Triclosan 2,4,4′-Trichloro-2′-hydroxydiphenyl ether ≥97 c 3380-34-5 0.3% (toothpastes, hand soaps, shower gels, deodorants, face powders and blemish concealers, nail products); 0.2% (mouthwashes) Benzyl paraben (BzP) * Benzyl hydroxybenzoate 99 b 94-18-8 0.4% as acid (for single ester) 0.8% as acid (for mixtures of esters) Plasticizers DMA 1,6-Dimethylhexanedioate 99 c 627-93-0 n.r DEA 1,6-Diethylhexanedioate 99 c 141-28-6 n.r DMP Dimethyl phthalate 98 c 131-11-3 n.r DEP Diethyl phthalate 98 b 84-66-2 n.r DIBP Diisobutyl phthalate 99 f 84-69-5 n.r DBP Dibutyl phthalate 99 b 84-74-2 Prohibited DMEP Dimethoxyethyl phthalate 94 f 117-82-8 Prohibited DPP Dipentyl phthalate 99.2 b 131-18-0 Prohibited BBP Benzylbutyl phthalate 98 b 85-68-7 Prohibited DEHA Di(2-ethylhexyl) adipate 98.5 c 103-23-1 n.r DIHP Diisoheptylphthalate 99 b 41451-28-9 n.r DEHP Di(2-ethylhexyl) phthalate 99.5 c 117-81-7 Prohibited DCHP Diclohexyl phthalate 99 b 84-61-7 n.r DPhP Diphenyl phthalate 98 b 84-62-8 n.r DNOP Di-noctyl phthalate ≥ 98 d 117-84-0 n.r Musks Cashmeran 1,1,2,3,3-Pentamethyl-2,5,6,7-tetrahydroinden-4-one ≥ 95 f 33704-61-9 n.r Celestolide 4-Acetyl-6-tert-butyl-1,1-dimethylindane ≥ 98 f 13171-00-1 n.r Phantolide 6-Acetyl-1,1,2,3,3,5-hexamethylindan ≥ 98 f 15323-35-0 2% (leave-on products) Cosmetics 2014, 1 177 Table 1. Cont. Chemical Names Purity (%) CAS Maximum Concentration Permitted [1] Musk Ambrette 6-tert-Butyl-3-methyl-2,4-dinitroanisole 99 f 83-66-9 Prohibited Traseolide 5-Acetyl-3-isopropyl-1,1,2,6-tetramethylindane 99 f 68140-48-7 n.r Galaxolide 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8hexamethylcyclopenta(g)-2-benzopyran 55.5 b 1222-05-5 n.r Musk Xylene 1-tert-Butyl-3,5-dimethyl-2,4,6-trinitrobenzene 100 ng·mL−1 c 81-15-2 Prohibited in oral products. 1.0% (fine fragrance); 0.4% (eau de toilette); 0.03% (other products) Tonalide 6-Acetyl-1,1,2,4,4,7-hexamethyltetralin 98 f 1506-02-1 Prohibited in oral products. 0.2% (rinse-off products) 0.1% (leave-on products, except: 1% hydroalcoholic products; 2.5% fine fragrance; 0.5% fragrance cream) Musk Moskene 1,1,3,3,5-Pentamethyl-4,6-dinitro-2H-indene ≥99 f 116-66-5 Prohibited Musk Tibetene 1-tert-Butyl-3,4,5-trimethyl-2,6-dinitrobenzen ≥99 f 145-39-1 Prohibited Ambrettolide 17-Oxacycloheptadec-6-en-1-one ≥ 97 b 7779-50-2 n.r Musk Ketone 4-tert-Butyl-3,5-dinitro-2,6-dimethyl acetophenone ≥98 b 81-14-1 Prohibited in oral products. 1.4% (fine fragrance) 0.56% (eau de toilette) 0.042% (other products) a The presence of the substance must be indicated in the list of ingredients when its concentration exceeds 0.001% (leave-on products) and 0.01% (rinse-off products); b Sigma Aldrich Chemie GmbH (Steimheim, Germany); c Fluka Chemie GmbH (Steimheim, Germany); d Supelco Analytical (Bellefonte, PA, USA); e LGC Standards GmbH (Wesel, Germany); f Dr. Ehrenstorfer (Ausburg, Germany); g Is proposed to be excluded completely from cosmetics and personal care products; n.r: no restricted by EC No 1223/2009. * Banned from 30 July 2015. Cosmetics 2014, 1 178 Ethyl acetate was provided by Sigma-Aldrich Chemie GmbH (Steinheim, Germany). Florisil (60–100 mesh) was purchased from Supelco Analytical (Bellefonte, PA, USA) and anhydrous sodium sulphate (99%) from Panreac (Barcelona, Spain). Individual stock solutions were prepared in acetone, isooctane or methanol. Further dilutions and mixtures were prepared in acetone or ethyl acetate. Solutions were stored in amber glass vials at −20 °C. All solvents and reagents were of analytical grade. Metallic, glass, and ceramic materials; sorbents (Florisil and sodium sulphate anhydrous) and the glass wool for laboratory use (Sigma-Aldrich) were baked at 230 °C for 12 h before use to eliminate possible phthalate contamination. All materials were allowed to cool down wrapped with aluminum foil and Florisil and sodium sulphate anhydrous in desiccator. Samples of cosmetics and personal care products from national and international brands were obtained from local sources. They included leave-on and rinse-off products such as shampoo, shower gel, body milk, sunblock, among others, including products intended for babies. Until their analysis, samples were kept in their original containers at room temperature. 2.2. Micro-Matrix Solid-Phase Dispersion (MSPD) Cosmetic samples (0.1 g) were exactly weighted into a 10-mL glass vial and spiked with 25 µL of each surrogate solution (10 µg·mL−1) containing benzyl alcohol-d7, MeP-d4, PrP-d4 and DEHP-d4. Then, the sample was gently blended with 0.2 g of a drying agent (anhydrous Na2SO4), and 0.4 g of the dispersing sorbent (Florisil), into the vial or in a porcelain mortar, using a glass rod or a porcelain pestle, respectively, until a homogeneous mixture was obtained (ca. 5 min). The mixture was transferred into a glass Pasteur pipette (approximately 150 mm), with a small amount of glass wool at the bottom, containing 0.1 g of Florisil (to obtain a further degree of fractionation and sample clean-up). Finally, a small amount of glass wool was placed on top of the sample before compression with a spatula. Elution with ethyl acetate was made by gravity flow, collecting the extract into a 1 mL volumetric flask. Then, 12.5 µL of PCB-30 internal standard solution (1 µg·mL−1) was added. The micro-MSPD extracts diluted when necessary were directly analyzed by GC-MS. Fortified samples were spiked with 20 µL of the corresponding acetone solution of the target compounds to get the desired final concentration and submitted to the same process described above. The optimization of the experimental conditions (amount of sample, solvent, dispersant and volume elution) has been described elsewhere [19,20]. Figure 1 illustrates the described micro-MSPD process. Cosmetics 2014, 1 179 Figure 1. Micro-matrix-solid-phase-dispersion (MSPD) procedure. 2.3. Gas Chromatography-Mass Spectrometry (GC-MS) Analysis The analysis was performed using an Agilent 7890A (GC)-Agilent 5975C inert MSD with triple axis detector and an Agilent 7693 autosampler from Agilent Technologies (Palo Alto, CA, USA). The temperatures of the transfer line, the quadrupole and the ion source were set at 290, 150 and 230 °C, respectively. Electronic impact (EI) was used as ionization technique. The system was operated by Agilent MSD ChemStation E.02.00.493 software. Separation was performed on a ZB-5 capillary column (30 m × 0.25 mm i.d. (internal diameter), 0.25 μm film thickness) obtained from Phenomenex (Torrance, CA, USA). Helium (purity 99.999%) was employed as carrier gas at a constant column flow of 1.0 mL·min−1. The GC oven temperature was programmed from 60 °C (held 1 min) to 100 °C at 8 °C min−1, to 150 °C at 20 °C·min−1, to 200 °C at 25 °C·min−1 to 220 °C at 8 °C·min−1 and 30 °C·min−1 to 290 (held 10 min). After 1 min, the split valve was opened (75 mL·min−1), and the injector temperature was kept at 260 °C. The injection volume was 1 μL. The electron multiplier was set at a nominal value of 1553 V. 3. Results and Discussion 3.1. GC-MS Performance The chromatographic conditions were optimized to achieve an efficient separation of 66 target compounds frequently used in cosmetics and personal care products: 26 fragrance allergens, 13 preservatives, 15 plasticizers (phthalates and adipates) and 12 musks. For GC-MS analysis, the mass spectra detector (MSD) was operated in the selected ion monitoring (SIM) mode, monitoring three ions per compound. Table 2 shows the quantification and identification ions, and the retention time of the compounds. Chromatograms of a standard solution containing 200 ng·mL−1 of target compounds (DIHP, 400 ng·mL−1) are shown in Figure 2. 0.1 g sample + 0.4 g Florisil+ 0.2 g Na 2 SO 4 COSMETICS AND PERSONAL CARE PRODUCTS 0.1 g sample + 0.4 g Florisil + 0.2 g Na 2 SO 4 5 min Glass wool Florisil Ethyl acetate 1 mL GC-MS ANALYSIS Cosmetics 2014, 1 186 3.2. Analytical Method Performance Complete method quality parameters were evaluated using real cosmetic samples and the results are shown in Tables 4 and 5. In this way, recovery studies were carried out by applying the optimized method to two samples spiked at three levels of concentration: 2, 10 and 20 µg·g−1. These samples are a regenerating cream (leave-on) and a shampoo (rinse-off); they were selected for recoveries studies since the leave-on sample was labeled as perfume-free and preservative-free, and the rinse-off sample was almost free of the target compounds (only contained MeP, BHT, and PrP). In any case, previous analyses of the samples showed the presence of some of the target compounds, and these initial concentrations were taken into account to calculate the recoveries. Recoveries were higher than 90% for the most of the studied compounds (see Tables 4 and 5 for leave-on and rinse-off samples, respectively) regardless of using vial or mortar for the MSPD disruption step. In the case of the most volatile compounds, pinene recovery was 70% and 35%, for leave-on and rinse-of samples, respectively; and for limonene, recovery presented an average value of 75% employing a vial, whereas lower recoveries were obtained employing a mortar. Recovery study was extended to three other cosmetic matrices (shampoo, sunblock product, body milk) that were fortified at 10 µg·g−1. Results are presented in Table 6, and demonstrate the quantitative recovery of the compounds. Precision was evaluated attaining RSD values generally lower than 10% (see also Tables 4 and 5). Figure 3 shows a comparison of the results obtained using vial or mortar for the micro-MSPD for a real leave-on sample containing 23 target analytes (hands cream). Obtained responses are equivalent employing mortar or vial for the disruption step, excluding pinene and limonene for which responses were higher using vial. Limits of detection (LODs) were calculated as the compound concentration giving a signal-to-noise ratio of three (S/N = 3). As shown in Table 3, LOD values for the fragrance allergens ranged from 0.0118 to 0.0604 µg·g−1 (excluding farnesol, 0.700 µg·g−1), for preservatives, these values were between 0.0053 and 0.0595 µg·g−1 (excluding IPBC) and for plasticizers and musks LODs values ranged from 0.0026 to 0.1200 (excluding DIHP). Therefore, the proposed micro-MSPD method using a vial instead of a mortar for the disruption and dispersion step can be considered suitable for the determination of fragrance allergens, preservatives, musks, and plasticizers in cosmetic and personal care products. It is highly recommended to decrease losses of most volatile fragrances such as pinene and limonene during sample preparation. For these compounds, the increase of temperature in the mortar disruption step is unfavorable for their quantitative extraction, whereas for in-vial disruption the generated heat is lower, and the most volatile compounds can be extracted lossless; also, in-vial disruption reduces extraction steps, providing a quicker extraction procedure. Cosmetics 2014, 1 187 Table 4. Recoveries of fragrance allergens, preservatives, plasticizers and musks in a leave-on sample (regenerating cream) fortified at three concentration levels, analyzed by the proposed method µMSPD-GC-MS. Fragrance Allergens Recoveries (%, RSD) 2 µg·g−1 10 µg·g−1 20 µg·g−1 Mortar Vial Mortar Vial Mortar Vial Pinene 23.2 (6.4) 63.1 (3.9) 23.5 (0.24) 71.8 (13) 34.0 (0.87) 72.6 (4.3) Limonene 51.7 (2.0) 73.8 (1.1) 56.7 (7.1) 79.5 (11) 57.8 (0.016) 78.6 (10) Benzyl alcohol 97.3 (0.76) 97.3 (1.3) 98.6 (0.80) 90.4 (7.9) 113 (0.15) 110 (1.9) Linalool 105 (0.67) 82.5 (0.11) 96.7 (10) 89.3 (14) 107 (0.17) 100 (13) Methyl-2-octynoate 87.8 (1.7) 85.2 (2.9) 97.5 (10) 86.7 (14) 112 (0.90) 95.4 (11) Citronellol 101 (4.0) 89.3 (11) 97.6 (8.1) 93.1 (13) 110 (0.53) 94.8 (10) Citral 99.0 (3.7) 104 (1.8) 97.5 (14) 112 (14) 112 (1.1) 101 (10) Geraniol 114 (1.6) 82.5 (7.7) 82.0 (5.6) 81.7 (7.6) 102 (0.14) 92.7 (10) Cinnamal 90.5 (4.5) 87.8 (0.74) 91.5 (12) 84.5 (13) 104 (0.88) 96.2 (6.6) Hydroxycitronellal 81.9 (1.7) 80.1 (0.60) 101 (11) 97.8 (2.9) 114 (0.052) 101 (11) Anise alcohol 93.8 (4.5) 92.2 (2.6) 96.2 (13) 87.4 (13) 111 (0.67) 101 (6.3) Cinnamyl alcohol 96.3 (5.6) 87.3 (13) 94.0 (9.6) 87.2 (15) 110 (0.83) 98.8 (13) Eugenol 87.2 (5.2) 83.0 (4.0) 93.8 (8.7) 89.2 (15) 105 (0.96) 98.7 (12) Methyleugenol 85.8 (0.15) 83.6 (3.1) 95.5 (11) 86.7 (14) 109 (1.3) 98.7 (8.4) Isoeugenol 80.9 (15) 100 (12) 114 (9.6) 109 (14) 87.2 (1.0) 89.4 (9.1) Coumarin 91.1 (0.61) 85.2 (2.7) 95.5 (14) 87.3 (11) 109 (0.23) 100 (2.7) α-isomethyl ionone 83.6 (6.2) 86.3 (0.78) 95.7 (11) 89.6 (12) 108 (0.82) 101 (7.4) Lilial® 84.5 (3.3) 83.2 (1.4) 97.0 (11) 88.8 (15) 110 (1.7) 98.2 (10) Amyl cinnamal 89.3 (4.4) 89.5 (7.8) 94.3 (5.2) 85.8 (4.3) 111 (3.5) 95.9 (15) Lyral® 99.3 (11) 83.0 (12) 104 (6.9) 94.3 (5.4) 114 (2.8) 95.4 (14) Amylcinnamyl alcohol 108 (10) 95.2 (12) 104 (7.4) 95.9 (3.9) 112 (3.1) 102 (15) Farnesol <LOQ <LOQ 104 (2.7) 97.1 (7.6) 109 (7.5) 86.8 (7.5) Hexylcinnamal 87.7 (1.8) 107 (0.12) 107 (4.5) 103 (5.1) 115 (3.8) 97.3 (11) Benzyl benzoate 88.7 (7.6) 90.8 (6.9) 98.3 (14) 90.8 (12) 111 (0.16) 104 (4.9) Benzyl salicylate 105 (3.1) 109 (13) 97.9 (14) 90.7 (13) 112 (1.9) 106 (2.8) Benzyl cinnamate 94.5 (1.8) 102 (0.27) 102 (15) 94.2 (12) 112 (10) 108 (1.6) Cosmetics 2014, 1 188 Table 4. Cont. Preservatives Recoveries (%, RSD) 2 µg·g−1 10 µg·g−1 20 µg·g−1 Mortar Vial Mortar Vial Mortar Vial Bronidox 92.1 (1.3) 88.0 (4.4) 95.6 (12) 87.3 (13) 108 (0.89) 100 (10) PhEtOH 96.0 (3.8) 91.6 (0.87) 102 (12) 92.1 (13) 109 (0.91) 97.1 (11) MeP 95.5 (4.2) 90.2 (6.4) 97.3 (11) 93.6 (15) 107 (1.7) 96.6 (11) BHA 72.8 (6.6) 80.2 (1.2) 104 (9.4) 104 (13) 99.3 (0.53) 97.7 (7.3) BHT 82.3 (0.16) 81.4 (0.33) 116 (0.83) 115 (12) 108 (0.67) 105 (6.9) EtP 96.7 (10) 83.9 (15) 103 (13) 95.2 (14) 112 (0.36) 102 (10) iPrP 100 (4.7) 91.0 (6.5) 100 (10) 93.2 (14) 109 (1.1) 98.2 (11) PrP 111 (5.2) 87.5 (14) 99.3 (9.6) 97.5 (7.8) 109 (2.0) 94.3 (13) IPBC 106 (15) 83.0 (12) 88.4 (1.6) 101 (4.5) 113 (4.0) 89.0 (16) iBuP 113 (9.4) 92.6 (14) 103 (12) 95.2 (2.2) 111 (1.4) 98.5 (11) BuP 96.8 (7.9) 82.0 (6.7) 99 (9.2) 88.9 (2.7) 110 (2.5) 95.2 (15) Triclosan 109 (14) 112 (3.4) 100 (13) 107 (9.1) 111 (11) 108 (12) BzP 105 (14) 92.6 (1.5) 111 (13) 111 (6.8) 117 ( 11) 111 (8.4) Plasticizers DMA 93.9 (7.0) 105 (12) 116 (9.8) 108 (8.5) 103 (0.60) 97.5 (3.1) DEA 87.5 (0.038) 81.4 (2.8) 95.4 (15) 87.5 (12) 111 (0.22) 100 (5.2) DMP 81.5 (3.6) 83.3 (0.53) 98.2 (15) 90.5 (9.4) 109 (0.77) 102 (0.33) DEP 79.3 (5.2) 83.1 (0.81) 96.1 (13) 87.2 (12) 110 (0.36) 101 (2.8) DIBP 83.1 (1.2) 95.0 (2.1) 98.4 (14) 88.7 (14) 111 (0.88) 101 (3.2) DBP 91.0 (6.5) 94.8 (3.3) 100 (14) 92.1 (8.8) 114 (2.5) 110 (3.6) DMEP 90.3 (6.8) 103 (7.2) 107 (12) 99.2 (12) 114 (3.7) 108 (0.82) DPP 96.8 (11) 98.3 (0.40) 101 (14) 96.3 (10) 110 (6.6) 107 (2.6) BBP 89.7 (3.5) 83.7 (0.35) 92.0 (16) 86.7 (8.9) 103 (0.34) 96.9 (4.2) DEHA 83.9 (7.8) 84.5 (2.7) 87.8 (14) 85.2 (8.5) 86.4 (0.87) 95.0 (0.76) Cosmetics 2014, 1 189 Table 4. Cont. Plasticizers Recoveries (%, RSD) 2 µg·g−1 10 µg·g−1 20 µg·g−1 Mortar Vial Mortar Vial Mortar Vial DIHP 104 (5.3) 102 (1.1) 106 (6.3) 88.4 (6.0) 96.9 (6.2) 93.7 (5.1) DEHP 98.1 (3.6) 81.1 (0.73) 93.3 (13) 92.4 (4.8) 101 (8.8) 96.4 (3.1) DCHP 88.5 (2.4) 92.0 (5.1) 93.0 (12) 87.5 (6.4) 105 (2.4) 102 (3.4) DPhP 84.9 (4.6) 84.4 (1.3) 90.5 (0.61) 84.3 (8.6) 102 (0.29) 96.9 (4.2) DNOP 87.1 (1.2) 88.4 (2.8) 89.0 (15) 84.1 (9.2) 103 (3.6) 98.5 (2.2) Musks Cashmeran 87.4 (2.0) 82.5 (9.5) 98.0 (13) 89.1 (13) 110 (1.5) 103 (7.2) Celestolide 81.8 (5.7) 82.9 (0.80) 94.6 (9.9) 87.4 (3.1) 109 (1.9) 96.9 (9.0) Phantolide 86.3 (4.9) 90.4 (0.67) 102 (10) 94.3 (3.4) 115 (3.3) 102 (11) Ambrette 86.8 (9.3) 83.7 (14) 93.8 (0.23) 104 (7.1) 115 (6.1) 91.5 (6.2) Traseolide 88.1 (7.6) 90.7 (3.3) 99.4 (9.4) 91.0 (4.5) 114 (2.6) 97.9 (10) Galaxolide 88.9 (0.27) 94.7 (0.52) 103 (15) 95.3 (13) 114 (1.4) 105 (3.3) Xylene 81.1 (12) 82.1 (5.6) 68.3 (2.1) 79.1 (2.6) 93.3 (3.1) 80.0 (6.2) Tonalide 83.1 (1.4) 88.4 (0.72) 87.5 (14) 83.1 (8.2) 101 (0.92) 96.4 (1.4) Moskene 89.8 (13) 86.1 (15) 93.5 (7.3) 83.2 (4.4) 114 (3.7) 94.6 (15) Tibetene 103 (8.1) 109 (3.8) 100 (14) 93.0 (13) 115 (3.6) 111 (2.6) Ambrettolide 96.0 (5.6) 111 (7.9) 106 (1.1) 107 (12) 113 (3.0) 108 (8.8) Ketone 101 (14) 109 (6.1) 104 (10) 97.9 (15) 114 (5.9) 109 (6.9) Cosmetics 2014, 1 190 Table 5. Recoveries of fragrance allergens, preservatives, plasticizers and musks in a rinse-off sample (shampoo) fortified at three concentration levels, analyzed by the proposed method µMSPD-GC-MS. Fragrance Allergens Recoveries (%, RSD) 2 µg·g−1 10 µg·g−1 20 µg·g−1 Mortar Vial Mortar Vial Mortar Vial Pinene 4.08 (12) 20.8 (0.59) 5.13 (0.38) 36.5 (1.2) 9.5 (6.9) 36.8 (9.4) Limonene 28.2 (11) 64.7 (2.1) 28.1 (7.5) 75.8 (15) 38.9 (5.7) 65.9 (14) Benzyl alcohol 113 (9.3) 90.8 (13) 85.7 (1.7) 92.2 (1.5) 105 (8.7) 102 (8.9) Linalool 81.3 (9.3) 114 (6.9) 85.4 (3.6) 109 (2.5) 95.5 (14) 88.7 (0.53) Methyl-2-octynoate 92.4 (2.8) 83.2 (5.2) 94.0 (6.7) 101 (5.6) 106 (11) 88.5 (15) Citronellol 108 (1.4) 114 (5.0) 90.9 (5.0) 99.1 (3.8) 100 (14) 102 (6.8) Citral 100 (3.0) 107 (10) 83.3 (6.4) 103 (7.0) 103 (12) 97.7 (4.3) Geraniol 109 (4.0) 94.9 (13) 90.4 (11) 102 (3.4) 93.9 (13) 92.6 (0.44) Cinnamal 105 (3.6) 89.1 (11) 88.5 (5.3) 94.2 (0.88) 103 (7.2) 96.0 (15) Hydroxycitronellal 100 (14) 82.1 (5.0) 80.1 (2.7) 83.7 (4.7) 89.9 (12) 87.6 (3.7) Anise alcohol 112 (8.5) 90.1 (15) 86.6 (2.4) 97.1 (0.76) 101 (10) 91.7 (9.3) Cinnamyl alcohol 113 (7.9) 83.4 (15) 87.6 (4.3) 97.7 (0.40) 97.9 (13) 95.5 (13) Eugenol 106 (3.5) 88.6 (13) 87.5 (1.9) 99.1 (1.2) 98.6 (10) 92.1 (15) Methyleugenol 110 (10) 94.3 (1.5) 96.4 (1.2) 102 (0.33) 104 (4.4) 95.9 (10) Isoeugenol 87.9 (10) 83.8 (6.9) 107 (2.6) 119 (0.42) 96.2 (5.0) 92.7 (10) Coumarin 111 (12) 90.1 (3.8) 89.7 (1.7) 97.1 (3.5) 104 (1.7) 97.8 (7.9) α-isomethyl ionone 110 (10) 97.4 (0.76) 94.4 (0.84) 98.4 (1.2) 103 (4.3) 93.4 (6.5) Lilial® 106 (12) 91.7 (2.3) 88.2 (0.10) 93.3 (4.1) 98.9 (5.3) 88.3 (12) Amyl cinnamal 112 (5.8) 106 (9.2) 102 (3.6) 109 (4.1) 108 (11) 102 (16) Lyral® 105 (1.7) 112 (9.0) 89.2 (1.2) 99.4 (2.3) 98.8 (11) 82.6 (4.9) Amylcinnamyl alcohol 113 (8.3) 118 (5.5) 98.8 (1.8) 114 (1.0) 112 (7.7) 113 (12) Farnesol <LOQ <LOQ 97 (3.2) 111 (6.8) 95.0 (15) 108 (8.4) Hexylcinnamal 108 (1.2) 105 (5.5) 105 (3.1) 111 (4.7) 108 (9.5) 104 (11) Benzyl benzoate 111 (11) 98.4 (1.5) 92.3 (1.6) 103 (0.42) 104 (3.1) 97.6 (5.6) Cosmetics 2014, 1 191 Table 5. Cont. Fragrance Allergens Recoveries (%, RSD) 2 µg·g−1 10 µg·g−1 20 µg·g−1 Mortar Vial Mortar Vial Mortar Vial Benzyl salicylate 116 (1.2) 113 (3.7) 80.8 (0.51) 102 (4.5) 111 (8.4) 104 (10) Benzyl cinnamate 102 (12) 102 (2.1) 102 (5.4) 113 (3.9) 119 (4.4) 116 (3.3) Preservatives Bronidox 104 (2.8) 90.4 (11) 94.4 (3.2) 97 (5.3) 101 (7.7) 95.9 (16) PhEtOH 112 (10) 90.5 (2.1) 91.7 (3.1) 94 (5.5) 98.4 (12) 92.6 (11) MeP a n.c n.c n.c n.c n.c n.c BHA 106 (12) 98.4 (1.3) 105 (5.7) 110 (1.1) 100 (3.1) 100 (8.3) BHT a n.c n.c n.c n.c n.c n.c EtP 112 (1.0) 103 (1.7) 102 (2.5) 102 (0.32) 110 (3.9) 108 (10) iPrP 118 (3.2) 114 (15) 102 (1.1) 110 (3.4) 111 (6.8) 113 (7.4) PrP a n.c n.c n.c n.c n.c n.c IPBC 113 (8.7) 97.7 (14) 103 (8.0) 117 (0.50) 111 (16) 95.4 (7.9) iBuP 94.1 (15) 103 (2.4) 104 (2.9) 109 (2.3) 111 (0.13) 113 (8.4) BuP 115 (1.0) 110 (1.6) 108 (2.7) 114 (2.4) 116 (1.6) 113 (10) Triclosan 87.0 (6.9) 84.4 (6.1) 81.7 (6.7) 91 (7.8) 118 (6.4) 113 (11) BzP 87.3 (11) 104 (9.5) 81.4 (2.0) 112 (1.7) 104 (12) 103 (11) Plasticizers DMA 98.6 (5.5) 95.1 (2.7) 104 (0.65) 72.4 (0.65) 104 (1.3) 96.6 (9.4) DEA 101 (5.5) 81.3 (6.9) 94.8 (1.6) 92.8 (1.1) 103 (4.0) 91.8 (11) DMP 109 (12) 87.9 (1.5) 95.4 (2.7) 94.2 (0.72) 103 (1.4) 95.0 (7.6) DEP 105 (7.0) 92.2 (0.34) 102 (2.5) 100 (0.20) 101 (3.2) 100 (8.6) DIBP 115 (4.9) 93.3 (2.7) 94.1 (2.4) 102 (0.64) 98.9 (4.6) 102 (10) DBP 117 (12) 109 (0.69) 91.5 (2.0) 108 (1.7) 105 (5.9) 110 (9.3) DMEP 112 (10) 100 (1.6) 112 (7.9) 119 (4.9) 113 (2.3) 112 (8.7) DPP 113 (11) 88.4 (4.1) 94.7 (4.2) 107 (0.56) 114 (3.9) 115 (5.9) Cosmetics 2014, 1 192 Table 5. Cont. Plasticizers Recoveries (%, RSD) 2 µg·g−1 10 µg·g−1 20 µg·g−1 Mortar Vial Mortar Vial Mortar Vial BBP 114 (5.6) 115 (2.2) 101 (5.4) 108 (2.4) 117 (3.0) 119 (0.20) DEHA 96.9 (9.1) 105 (7.0) 101 (6.6) 108 (8.5) 112 (1.0) 107 (2.8) DIHP 98.5 (1.4) 102 (7.9) 98.1 (1.7) 102 (3.4) 99.2 (6.8) 113 (7.3) DEHP 116 (2.3) 93.4 (3.5) 103 (4.5) 101 (4.6) 109 (4.4) 103 (5.2) DCHP 116 (8.7) 107 (0.94) 107 (6.9) 107 (1.5) 112 (10) 114 (0.43) DPhP 116 (11) 105 (1.5) 95.9 (6.9) 104 (3.2) 113 (1.1) 108 (2.2) DNOP 118 (4.4) 87.8 (8.3) 96.1 (6.5) 106 (0.48) 111 (2.3) 120 (4.4) Musks Cashmeran 112 (8.9) 101 (1.8) 113 (0.77) 99 (1.2) 103 (4.0) 96.8 (11) Celestolide 113 (12) 115 (1.1) 114 (0.99) 107 (0.47) 104 (4.0) 101 (6.8) Phantolide 109 (10) 107 (3.4) 113 (1.4) 111 (4.2) 102 (10) 103 (14) Ambrette 118 (6.4) 104 (10) 118 (6.7) 118 (11) 100 (10) 106 (10) Traseolide 113 (10) 104 (7.3) 95.2 (1.4) 102 (3.8) 103 (9.2) 100 (12) Galaxolide 113 (13) 100 (2.6) 106 (2.0) 98.9 (0.011) 101 (4.0) 97.2 (8.0) Xylene 118 (2.9) 111 (8.2) 101 (5.6) 88.9 (14) 104 (7.1) 114 (4.3) Tonalide 117 (16) 113 (2.6) 90.7 (0.77) 89.8 (1.3) 101 (5.4) 98.0 (7.6) Moskene 111 (15) 96.7 (3.6) 109 (4.0) 105 (10) 103 (16) 96.0 (7.3) Tibetene 112 (12) 108 (5.7) 111 (1.7) 99.0 (6.2) 104 (10) 100 (16) Ambrettolide 115 (3.8) 111 (3.5) 99.3 (1.3) 101 82.7) 104 (6.1) 108 (14) Ketone 79.6 (4.5) 114 (13) 93.5 (0.75) 109 (4.0) 117 (8.0) 113 (11) a n.c: not calculated since initial sample concentration is higher than the spiked level. MeP, BHT, and PrP: 22, 21, and 10 µg·g-1, respectively. Cosmetics 2014, 1 193 Table 6. Recovery study in different cosmetic matrices. Spike level: 10 µg·g−1. Fragrance Allergens Recoveries (%, RSD) S3 a S6 a S8 a Mortar Vial Mortar Vial Mortar Vial Pinene 4.2 (7.3) 72.1 (1.5) 11.2 (3.1) 74.0 (0.013) 21.2 (11) 74.3 (4.1) Limonene 35.4 (5.6) 90.3 (1.7) 81.3 (3.1) 77.0 (2.1) 57.1 (2.5) 93.0 (0.87) Benzyl alcohol 115 (6.9) 109 (0.19) 114 (4.2) 91.2 (10) 113 (0.51) 116 (0.38) Linalool 102 (4.5) 117 (0.021) n.c n.c n.c n.c Methyl-2-octynoate 106 (10.4) 93.0 (3.4) 94.9 (8.6) 81.3 (9.7) 103 (3.7) 113 (6.1) Citronellol 89.8 (13) 101 (2.8) 110 (3.8) 100 (2.2) 90.0 (2.1) 100 (2.8) Citral 113 (7.1) 105 (6.7) 115 (5.0) 94.2 (4.0) 107 (2.9) 108 (8.1) Geraniol 80.4 (13) 93.4 (1.9) 107 (7.8) 92.4 (4.1) 91.2 (8.1) 98.2 (9.7) Cinnamal 98.8 (9.4) 103 (2.8) 106 (7.4) 98.2 (4.6) 101 (2.4) 108 (2.5) Hydroxycitronellal 108 (12) 102 (6.8) 93.6 (6.3) 81.0 (7.4) 112 (6.1) 111 (6.8) Anise alcohol 98.3 (13) 101 (4.2) 95.4 (5.2) 96.1 (6.2) 83.3 (6.6) 104 (0.041) Cinnamyl alcohol 81.7 (15) 96.9 (6.7) 112 (11) 91.4 (8.8) 106 (8.7) 109 (3.5) Eugenol 100 (11) 95.4 (4.2) 115 (10) 92.1 (3.6) 101 (6.1) 109 (5.9) Methyleugenol 100 (8.3) 110 (0.45) 96.4 (6.5) 96.1 (4.9) 100 (3.5) 106 (3.7) Isoeugenol 102 (9.9) 93.0 (2.9) 114 (15) 82.5 (5.3) 86.2 (3.3) 95.2 (0.45) Coumarin 107 (11) 118 (0.62) 95.8 (2.1) 81.0 (1.5) 91.3 (1.3) 97.1 (0.52) α-isomethyl ionone 98.4 (7.5) 104 (1.9) 96.8 (3.7) 94.6 (0.24) 98.8 (3.1) 103 (2.5) Lilial® 99.2 (8.6) 98.1 (1.2) 97.2 (4.5) 85.0 (0.055) 96.3 (3.7) 102 (4.2) Amyl cinnamal 106 (10) 107 (0.82) 105 (8.1) 96.4 (3.6) 98.7 (4.5) 106 (4.2) Lyral® 115 (7.3) 98.0 (1.5) 85.8 (12) 82.0 (11) 112 (6.7) 114 (7.5) Amylcinnamyl alcohol 104 (10) 98.3 (6.7) 109 (9.7) 96.5 (9.4) 111 (4.3) 111 (9.1) Farnesol 92.3 (13) 95.0 (0.29) 97.2 (1.8) 95.9 (13) 109 (8.5) 106 (12) Hexylcinnamal 107 (14) 119 (0.29) n.c n.c 105 (5.9) 112 (5.9) Benzyl benzoate 102 (9.0) 105 (0.43) 101 (2.4) 95.4 (1.2) 107 (3.8) 113 (5.1) Benzyl salicylate 112 (10) 115 (6.9) n.c n.c 113 (3.5) 114 (4.3) Benzyl cinnamate 115 (6.7) 116 (0.14) 113 (9.0) 112 (0.40) 113 (6.1) 115 (4.8) Cosmetics 2014, 1 194 Table 6. Cont. Preservatives Recoveries (%, RSD) S3 a S6 a S8 a Mortar Vial Mortar Vial Mortar Vial Bronidox 93.9 (7.5) 101 (2.7) 106 (5.2) 108 (0.94) 105 (0.72) 95.0 (5.2) PhEtOH n.c n.c n.c n.c n.c n.c MeP 112 (11) 100 (7.7) n.c n.c n.c n.c BHA 99.1 (9.6) 94.2 (0.89) 109 (6.2) 83.2 (0.91) 93.1 (3.1) 102 (2.7) BHT 98.4 (3.1) 92.0 (0.040) n.c n.c 91.2 (3.4) 100 (3.2) EtP 108 (7.7) 92.0 (9.8) n.c n.c n.c n.c iPrP 105 (11) 114 (8.5) 114 (6.3) 115 (1.2) 94.9 (3.9) 103 (3.8) PrP 115 (8.7) 115 (1.14) n.c n.c n.c n.c IPBC 106 (14) 84.2 (10) 101 (7.4) 113 (15) 110 (18) 114 (10) iBuP 105 (13) 111 (5.3) n.c n.c 112 (9.6) 106 (1.4) BuP 103 (14) 107 (0.79) n.c n.c 107 (13) 103 (6.8) Triclosan 119 (5.8) 96.0 (3.0) 114 (3.3) 106 (13) 104 (8.8) 110 (3.5) BzP 96.0 (14) 108 (7.9) 95.1 (2.8) 116 (9.0) 110 (10) 102 (3.5) Plasticizers DMA 105 (8.1) 105 (1.1) 97.0 (3.7) 84.0 (2.8) 95.1 (0.59) 98.2 (3.1) DEA 108 (6.5) 100 (2.9) 104 (5.2) 96.1 (2.4) 105 (4.6) 113 (5.4) DMP 96.4 (7.6) 104 (1.8) 95.0 (5.8) 88.3 (2.0) 95.2 (0.75) 101 (1.5) DEP 97.8 (7.4) 107 (0.41) n.c n.c n.c n.c DIBP 97.6 (10) 104 (0.24) 100 (2.5) 88.2 (1.5) 96.4 (2.5) 102 (3.1) DBP 109 (8.4) 115 (1.1) 108 (4.4) 98.7 (2.1) 106 (3.2) 112 (4.1) DMEP 113 (8.7) 119 (5.8) 98.2 (7.0) 103 (3.0) 107 (7.9) 114 (4.9) DPP 108 (7.3) 108 (0.93) 112 (3.7) 101 (0.82) 114 (2.7) 115 (2.2) BBP 97.3 (8.1) 97 (1.9) 109 (3.6) 86.0 (0.94) 103 (4.8) 110 (0.74) DEHA 112 (6.9) 83 (3.3) 83.1 (4.1) 80.2 (1.7) 96.4 (4.9) 103 (0.70) DIHP 113 (6.6) 115 (4.6) 108 (7.3) 107 (15) 101 (10) 89.0 (1.5) Cosmetics 2014, 1 195 Table 6. Cont. Plasticizers Recoveries (%, RSD) S3 a S6 a S8 a Mortar Vial Mortar Vial Mortar Vial DEHP 114 (13) 93 (1.3) 99.2 (4.4) 90.3 (2.2) 105 (2.1) 112 (2.1) DCHP 113 (14) 96 (0.80) 94.0 (8.6) 88.5 (1.5) 97.2 (8.5) 97.2 (7.5) DPhP 112 (7.6) 102 (0.13) 115 (3.0) 92.0 (5.9) 102 (3.1) 108 (3.1) DNOP 102 (8.1) 114 (0.88) 113 (2.8) 100 (0.31) 114 (1.5) 113 (2.4) Musks Cashmeran 98.4 (8.6) 96.0 (0.32) 93.0 (7.0) 88.3 (1.6) 97.2 (2.4) 103 (2.5) Celestolide 102 (8.5) 103 (1.0) 93.5 (6.9) 93.5 (1.6) 98.0 (4.8) 105 (5.0) Phantolide 100 (8.1) 102 (1.1) 96.4 (4.4) 93.9 (1.0) 101 (4.8) 107 (4.4) Ambrette 92.0 (13) 84.2 (13) 113 (6.3) 112 (15) 112 (10) 113 (11) Traseolide 98.8 (10) 100 (2.3) 105 (7.7) 101 (0.10) 105 (5.3) 113 (4.9) Galaxolide 98.0 (10) 102 (0.72) n.c n.c n.c n.c Xylene 88.2 (9.2) -- 111 (8.9) -- 86.0 (5.5) 97.4 (7.4) Tonalide 98.4 (10) 98.0 (0.83) 81.0 (2.6) 84.0 (2.2) n.c n.c Moskene 93.0 (12) 89.1 (11) 109 (11) 103 (15) 98.2 (8.1) 103 (8.6) Tibetene 107 (10) 105 (4.4) 111 (11) 106 (7.8) 104 (7.1) 109 (7.9) Ambrettolide 114 (13) 101 (0.98) 94.4 (10) 86.2 (4.8) 80.1 (10) 93.2 (3.5) Ketone 109 (11) 99.0 (7.4) 109 (13) 114 (3.7) 108 (9.5) 115 (10) a See initial concentration in Table 7. n.c: not calculated since initial sample concentration is higher than the spiked level.