Multicomponent analytical methodology to control phthalates, synthetic musks, fragrance allergens and preservatives in perfumes

A simple, fast, robust and reliable multicomponent analytical method applicable in control laboratories with a high throughput level has been developed to analyze commercial brands of perfumes. Contents of 52 cosmetic ingredients belonging to different chemical families can be determined in a single run. Instrumental linearity, precision of the method and recovery studies in real samples showed excellent results, so that quantification by external calibration can be effectively applied. Relevant limits of detection and quantification were obtained for all the targets considered, far below the legal requirements and amply adequate for its accurate analytical control.A survey of 70 commercial perfumes and colognes has been performed, in order to verify whether these products complied with the recent changes in European legislation: regarding the maxima allowed concentrations of the ingredients and/or ingredient labelling. All samples contained some of the target ingredients. Several samples do not comply with the regulations concerning the presence of phthalates. Musks data confirmed the trend about the replacement of nitromusks by polycyclic musks; as well as the noticeable introduction of macrocyclic musks in the perfumes composition. The prohibited musk moskene has been detected in one sample in an appreciable concentration. The average number of fragrance allergens is twelve per sample; their presence must be indicated in the list of ingredients when its concentration exceeds the 0.001%, but values higher than 1% have been found in some samples. Preservatives data show that parabens, although ubiquitous in other cosmetic products, are not widely used in perfumery. In contrast, the presence of BHT is indeed widespread. The degree of compliance with the European Regulation on the labelling has been evaluated in a subset of samples, and only about the 38% of the perfumes were properly labelled for the allergens tested.     

人工合成麝香的分析方法及环境污染现状

人工合成麝香作为天然麝香的替代物被大量用于日化产品中,按其化学结构可分为硝基麝香、多环麝香和大环麝香3种。人工合成麝香的大量生产及广泛使用使之通过各种途径进入环境,而该物质亲脂性和持久性的特点,导致其在生物体内积累并产生毒理效应,故引起了广泛关注,成为一类新型污染物。该文综述了目前人工合成麝香的分类、环境污染现状及不同基体样品的分析检测方法,为今后合成麝香的风险评价研究提供参考。     

多环麝香的分子结构和香气之间的关系

本文综述了多环麝香的当前进展,并提出了系统的分类方法。对各种多环麝香(茚满型,萘满型,异色满型,氢化引达省型,苊型)香味与分子结构之间关系的研究进行了总结,还作了比较。并描述了多环分子中环上取代基的性质,数量和位置对麝香香味的影响。     

Determination of synthetic musk fragrances

Among personal care products (PCPs), musks fragrances are a chemically heterogeneous group sharing some sensory characteristics, specially related with odour aspects that have received great attention in the last decade. From a chemical point of view, synthetic musks can be divided in four groups including nitrobenzene derivatives, polycyclic and macrocyclic musks (MCMs) and alicyclic derivatives. Thus, analytically, it is necessary to apply chromatography coupled to mass spectrometry (mainly GC-MS) for the determination of musk residues with adequate sensitivity and selectivity. This review gives a critical overview of published methods for the determination of synthetic musks in different environmental and biological matrices. Methodological aspects considering the different sample preparation and instrumental parameters involved have been reviewed and summarised paying special attention to method validation results. Although GC-MS-based methods are the most abundant ones, the use of tandem MS has become an interesting alternative to improve both sensitivity and selectivity.     

Enantiomeric separation of chiral polycyclic musks by capillary electrophoresis: Application to the analysis of cosmetic samples

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 10 min for Tonalide, 13 min for Traseolide and Phantolide, and 17 min 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 45 min. 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.     

Fully automatic exposed and in‐syringe dynamic single‐drop microextraction with online agitation for the determination of polycyclic musks in surface waters of the Pearl River Estuary and South China Sea

An automatic exposed and in‐syringe dynamic single‐drop microextraction method (SDME) for the determination of five polycyclic musks in natural waters was developed using gas chromatography with mass spectrometry. Online agitation was first introduced to the automatic SDME with a magnetic mixer fixed to the bottom of the sample tray of the autosampler. A high enrichment factor (110 ～182) for the target analytes could be achieved after several parameters that affected the microextraction were optimized. The recoveries were between 84.9 and 119.5%, while the limit of detection ranged from 3.4 to 11 ng/L with relative standard deviation < 11.1% for the polycyclic musks. This new SDME mode is fully automatic with great convenience, high enrichment and good reproducibility, and no human intervention. The proposed method was, therefore, successfully applied to determine the polycyclic musks in 31 surface sea waters that were collected from the Pearl River Estuary and the South China Sea. Most polycyclic musks could be detected with the total concentrations ranging from 58.9 to 528.5 ng/L. By using spatial interpolation method of ordinary kriging, the most contaminated area was found near the cities of Dongguan and Guangzhou with local discharge via the major rivers.     

Study of the photoinduced degradation of polycyclic musk compounds by solid-phase microextraction and gas chromatography/mass spectrometry

Polycyclic musks are widely used synthetic fragrances that have been identified during the last few years in biota samples and environmental matrices. Nevertheless, there is a lack of information concerning the photodegradation behavior of these compounds. In this work, the photoinduced degradation of six polycyclic musk compounds (Cashmeran, Celestolide, Phantolide, Galaxolide, Traseolide and Tonalide) was studied using a solid-phase microextraction (SPME) fiber as support. Musk fragrances were extracted from aqueous solutions using SPME fibers that were subsequently exposed to ultraviolet (UV) irradiation for different times. To study the degradation kinetics and to tentatively identify the photoproducts generated, gas chromatography coupled to ion trap mass spectrometry was used. Aqueous photodegradation studies were also performed. The on-fiber photodegradation approach avoids the need for further extraction processes and makes the identification of photoproducts easier, due to their higher concentration on the fibers. All musk compounds were easily photodegraded, suggesting that UV irradiation could work as a decontamination tool for these musks.     

Facile preparation of stainless steel microextraction fiber via in situ growth of metal–organic framework UiO‐66 and its application to sensitive analysis of polycyclic musks

A functional stainless steel microextraction fiber easily prepared by in situ growing metal–organic framework UiO‐66 was presented and used for high‐performance analysis of polycyclic musks. Via the robust Ag‐SH bonding reaction, mercaptoacetic acid was easily anchored on Ag film to provide carboxyl group on the stainless steel fiber, then in situ grown UiO‐66 was fulfilled via the coordination reaction between Zr⁴⁺ and carboxyl group. Good characteristics including large surface area, high thermal stability, and good adsorption property were achieved. Sensitive detection limits (0.015–0.040 ng/L) were achieved for polycyclic musks by coupling with gas chromatography with mass spectrometry, and it could be stable enough for 150 extraction cycles without a significant loss of extraction efficiency. Compared with the classical commercial fibers, 2.2–11.4 times higher enhancement factors were shown. Applied to the analysis of fortified river water samples, five typical polycyclic musks were well detected with the recoveries of 90.2–101.8%, respectively. It showed a facile approach for preparing stainless steel microextraction fiber via chemically bonding in situ grown metal–organic framework for high‐performance enrichment.     

Analysis of musk fragrances in environmental samples

The methods for the determination of polycyclic and nitro-aromatic musk compounds in comparison to other fragrances such as OTNE ([1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalen-2yl] ethan-1-one) as well as those for the respective metabolites are described in this contribution. It covers instrumental aspects, as well as procedures for extraction and clean-up. Protocols for the determination of musks in water, sludge, biota, and air are summarised and discussed. Extractions by means of solid phase extraction (SPE) and liquid-liquid extraction (LLE) in case of water samples are evaluated for the diverse applications, i.e., wastewater, surface water and seawater. While LLE is preferred for the analysis of bulk for transport studies and for special process studies SPE might be worth the effort. Considering sludge, sediment and biota samples, drying and successive accelerated solvent extraction. Soxhlet extractions as well as cold column extractions are being compared. ASE has proven to be the most exhaustive and quickest to adopt method. Clean-up by means of size exclusion chromatography and silica sorption chromatography with their respective merits and problems are demonstrated. Suggestions for routine and research analysis are also given. The diverse approaches for enantioselective separations are discussed in respect to HHCB, AHTN and the metabolite HHCB-lactone. The power of two-dimensional (GCxGC) approaches is demonstrated considering the various production impurities (isomers) of the two polycyclic musks with the highest usage rates. The usage of tandem mass spectrometry and high resolution mass spectrometry for the same purpose is also discussed. The identification of an isomer of the HHCB-transformation product HHCB-lactone from wastewater treatment that has not been described in the literature before, is presented as well. Additionally some ideas to make the REACh process more efficient are discussed considering the special experiences from the development of the analysis of musk fragrances in the environment.     

Comparisons of Microwave-Assisted Extraction, Simultaneous Distillation-Solvent Extraction, Soxhlet Extraction and Ultrasound Probe for Polycyclic Musks in Sediments: Recovery, Repeatability, Matrix Effects and Bioavailability

The extraction method of pharmaceutical and personal care products (PPCPs) has become a popular issue due to the emergence of PPCPs as contaminants. In this work, polycyclic musks, a typical type of PPCPs, were selected to test various techniques including microwave-assisted extraction (MAE), simultaneous distillation-solvent extraction (SDSE), Soxhlet extraction (SE), and ultrasound probe (UP). MAE and UP proved to be more effective pretreatment techniques than SE and SDSE, with high recovery, repeatability, accuracy, efficiency, little solvent consumption, and acceptable matrix effects. Notably, the chemical methods usually did not work well for the determination of bioavailability and the environmental fate of pollutants was overestimated. In this work, wheat (Triticum aestivum L.) was used as the ecological receptor to evaluate the bioavailability of chemical pollutants. The concentrations of polycyclic musks in sediments by way of UP extraction had a significant correlation (R ²?>?0.9, P?<?0.01) with the concentrations in roots of wheat and the changes of chlorophyll, malondialdehyde and peroxidase in leaves of wheat. These changes suggest that the concentrations of polycyclic musks in sediments using UP extraction were comparable with the level of those in vivo. Through this work, it was discovered that using UP with a different solvent was suitable for determining total concentrations and the bioavailable fractions in sediments.     

Fast determination of synthetic polycyclic musks in sewage sludge and sediments by microwave-assisted headspace solid-phase microextraction and gas chromatography–mass spectrometry

One-step in situ microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) followed by gas chromatography–mass spectrometry (GC–MS) analysis is presented as a fast and solvent-free technique to determine synthetic polycyclic musks in sewage sludge and sediment samples. Six synthetic polycyclic musks (galaxolide (HHCB), tonalide (AHTN), celestolide (ADBI), traseolide (ATII), cashmeran (DPMI) and phantolide (AHMI)) were selected in the method development and validation. The effects of extraction parameters for the quantitative extraction of these analytes by one-step MA-HS-SPME were systematically investigated. The dewatered solid sample mixed with 20-mL deionized water (containing 3 g of NaCl in a 40-mL sample-vial) was efficiently extracted by a polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber placed in the headspace when the extraction slurry was microwave irradiated at 80 W for 5 min. The limits of detection (LODs) ranged from 0.04 to 0.1 ng/g, and the limits of quantification (LOQs) ranged from 0.1 to 0.3 ng/g (fresh weight). A preliminary analysis of sludge and sediment samples revealed that HHCB and AHTN were the two most commonly detected synthetic polycyclic musks; using a standard addition method, their total concentrations were determined to range from 0.3 to 10.9 ng/g (fresh weight) with relative standard deviation (RSD) ranging from 4% to 10%.     

Determination of synthetic musks in the sediment of the Taihu lake by using accelerated solvent extraction (ASE) and GC/MS

Synthetic musks, substitutes for natural musks, are widely distributed in environment. They have been detected in water, sludge, fish, shrimp, mussels and other aquatic animals, and even in human's adipose tissue, blood and breast milk. In this study, a new extraction procedure, based on the accelerated solvent extraction (ASE) and in cell clean-up technique was developed and successfully coupled with gas chromatography-mass spectrometry (GC/MS) for the analysis of musks in sediment samples. With this method, the limits of detection as low as 0.03–0.05?ng?g^?1 and the recovery rate of 86.0%–104% are achieved. When compared with soxhlet extraction (SE) and ultrasonic extraction (USE), ASE not only has the best extraction efficiency but also has advantage in extraction time and solvent consumption. Eight synthetic musks, including six polycyclic musks (Tonalide (AHTN), Galaxolide (HHCB), Phantolide (AHDI), Traseolide (ATII), Cashmeran (DPMI) and Celestolide (ADBI)) and two nitro musks (musk xylene (MX) and musk ketone (MK)), were evaluated in sediment samples collected from 15 selected locations of the Taihu lake, one of the largest freshwater lakes in China. The contents of synthetic musks in sediment samples range from 0.336 to 3.10?ng?g^?1 for HHCB, 0.184 to 1.21?ng?g^?1 for AHTN, below detection limit (BDL) to 0.349?ng?g^?1 for MX, and BDL to 0.0786?ng?g^?1 for MK. The contents of DPMI, ADBI, AHMI and ATII are below detection limit in all samples. The results reflect current status of fragrance compound pollution in this area, and provide basic data for environmental policy making.     

Determination of synthetic polycyclic musks in water by microwave-assisted headspace solid-phase microextraction and gas chromatography-mass spectrometry

This paper describes a rapid and solvent-free method, microwave-assisted headspace solid-phase microextraction (MA-HS-SPME), for the extraction of six commonly used synthetic polycyclic musks: galaxolide (HHCB), tonalide (AHTN), celestolide (ADBI), traseolide (ATII), cashmeran (DPMI) and phantolide (AHMI) from water samples prior to their determination using gas chromatography-mass spectrometry (GC-MS). The effects of various extraction parameters for the quantitative extraction of these analytes by MA-HS-SPME were systematically investigated and optimized. The analytes in a 20-mL water sample (in a 40-mL sample-vial containing 4 g of NaCl) were efficiently extracted by a polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber placed in the headspace when the system was microwave irradiated at 180 W for less than 4 min. The limits of detection (LODs) ranged from 0.05 to 0.1 ng/L, and the limits of quantification (LOQs) were less than 0.2 ng/L. A preliminary analysis of wastewater samples revealed that HHCB and AHTN were the two most commonly detected synthetic polycyclic musks; using a standard addition method, their concentration were determined to range from 1.2 to 37.3 ng/L with relative standard deviation (RSD) ranging from 2 to 6%. The results obtained using this approach are better than those from the conventional oil-bath HS-SPME.     

Odds and Trends: Recent Developments in the Chemistry of Odorants

Fragrance chemistry is, together with the closely related area of flavor chemistry, one of the few domains, if not the only one, in which chemists can immediately experience structure–activity relationships. This review presents structure–odor correlations and olfactophore models for the main odor notes of perfumery: “fruity”, “marine”, “green”, “floral”, “spicy”, “woody”, “amber”, and “musky”. New trendsetters and so‐called captive odorants of these notes are introduced, and recent activities and highlights in fragrance chemistry are summarized. The design of odorants, their chemical synthesis, and their use in modern perfumery is discussed. Our selection is guided and illustrated by creative fragrances, and features new odorants which encompassed current trends in perfumery. New odorants for grapefruit and blackcurrant, for galbanum, and leafy top notes are presented. Compounds with fashionable marine, ozonic, and aquatic facets are treated, as well as new odorants for classical lily‐of‐the‐valley, rose, and jasmine accords. Compounds with sweet and spicy tonalities are also discussed, as are the most recent developments for woody notes such as sandalwood and vetiver. We conclude with musky and ambery odorants possessing uncommon or unusual structural features. Some odor trends and effects are illustrated by microencapsulated fragrance samples, and areas where there is need for the development of new synthetic materials and methodologies are pointed out. Thus, chemists are invited to explore fragrance chemistry and participate in the design and synthesis of new odorants. This review gives the latest state of the art of the subject.     

顶空固相微萃取-气相色谱-质谱联用测定香水中5种合成麝香

建立了香水中5种合成麝香的顶空固相微萃取-气相色谱-质谱联用分析方法。实验选用65 μm的聚二甲基硅氧烷-二乙烯基苯(PDMS-DVB)萃取纤维,在磁力搅拌600 r/min条件下,考察了萃取温度、平衡时间、萃取时间、解吸时间、进样口温度和盐效应6个方面对实验结果的影响。优化后的条件为: 10 mL顶空瓶中加入适量用水稀释过的样品,于60 ℃平衡3 min后,顶空萃取20 min,随即插入气相色谱进样口,于250 ℃解吸3 min进行定性、定量分析。5种合成麝香在0.05～1.00 μg/g范围内线性关系良好,检出限(LOD)为0.6～2.1 ng/g。空白样品在3个浓度加标水平下(0.05, 0.50, 1.00 μg/g)的回收率为82.0%～103.3%,相对标准偏差(RSD)为1.8%～9.4%。本方法简便、准确、快速、灵敏,适用于香水中合成麝香的分析检验工作。     

Determination of musk compounds in sewage treatment plant sludge samples by solid-phase microextraction

Headspace solid-phase microextraction, followed by GC-MS analysis is presented as a suitable technique for the determination of musk compounds in sewage treatment plant sludge. Five polycyclic musks (celestolide, phantolide, traseolide, galaxolide and tonalide) and four nitro musks (musk xylene, musk moskene, musk tibetene and musk ketone) were considered in the optimisation of the analytical method. The influence of extraction temperature, fibre coating, agitation, pH and salting out on the efficiency of the extraction along with the extraction kinetics were studied. An extraction temperature of 100 degrees C and sampling the headspace over the stirred sludge sample using polydimethylsiloxane -divinylbenzene as fibre coating lead to effective extraction. The method proposed is very simple and yields high sensitivity, good linearity and repeatability for all the analytes with limits of detection at the sub-ng/g level. The total analysis time, including extraction and GC analysis, was only 40 min, and no manipulation of the sample was required.     

GC-MS analytical methods for the determination of personal-care products in water matrices

This article discusses the more recent methods combining gas chromatography and mass spectrometry (GC-MS) for analysis of personal-care products (PCPs) in water matrices. We describe different procedures for sample extraction and preparation as well as different instrumental methods commonly used for these compounds. GC-MS and GC-tandem MS (GC-MS²), which are complementary to liquid chromatography combined with MS (LC-MS), allow identification and quantification of PCPs belonging to different classes with the sensitivity and the selectivity necessary for environmental monitoring. The compounds investigated include fragrances (e.g., nitro and polycyclic musks), antimicrobial compounds (e.g., triclosan), ultraviolet blockers (e.g., methylbenzylidene camphor), antioxidants and preservatives (e.g., phenols and p-hydroxybenzoic acid (parabens)) and insect repellents (e.g., N,N-diethyl-m-toluamide (DEET)). We critically review data in the literature by focusing attention on analytical methods devoted to simultaneous detection and quantification of structurally diverse pharmaceuticals and PCPs.     

Dispersive Micro Solid‐phase Extraction Coupled with Ultrasound‐assisted Solvent Desorption for Determination of Synthetic Polycyclic and Nitro‐aromatic Musks in Aqueous Samples

An optimized method for the determination of five synthetic polycyclic: celestolide (ADBI), phantolide (AHMI), traseolide (ATII), galaxolide (HHCB), tonalide (AHTN), and two nitro‐aromatic musks: musk xylene (MX) and musk ketone (MK), in water samples is described. The method involves a dispersive micro solid‐phase extraction (D‐μ‐SPE) plus ultrasound‐assisted solvent desorption (UASD) prior to their determination by gas chromatography‐mass spectrometry (GC‐MS) using the selected ion storage (SIS) mode. Factors affecting the extraction efficiency of the target analytes from water samples and ultrasound‐assisted solvent desorption were optimized by a Box‐Behnken design method. The optimal extraction conditions involved immersing 10.1 mg of a typical octadecyl (C18) bonded silica adsorbent (i.e., ENVI‐18) in a 50 mL water sample. After 10.4 min of extraction by vigorously shaking, the adsorbent was collected and dried on a filter, and the target musks were desorbed by ultrasound‐assisted for 38 sec with n‐hexane (200 μL) as the desorption solvent. A 10 μL aliquot was then directly determined by large‐volume injection GC‐MS. The limits of quantitation (LOQs) were 1.2 to 5 ng/L. The precision for these analytes, as indicated by relative standard deviations (RSDs), were less than 11% for both intra‐ and inter‐day analysis. Accuracy, expressed as the mean extraction recovery, was between 74% and 92%. A preliminary analysis of the effluents from municipal wastewater treatment plants (MWTP) and river water samples revealed that HHCB and AHTN were the two most commonly detected synthetic musks; their concentration were determined to range from 88 to 690 ng/L for effluent samples, and 5 to 320 ng/L for river water samples. This is a simple, low cost, effective, and eco‐friendly analytical method.     

New analytical method for the determination of musks in personal care products by Quick,Easy, Cheap,Effective, Rugged,and Safe extraction followed by GC–MS

Synthetic musks are organic compounds used as fragrance additives and fixative compounds in a diversity of personal care products. A new method based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction followed by GC–MS for the analysis of 12 musks in personal care products was developed and validated. Some experimental parameters, such as total QuEChERS mass, sample mass/solvent volume ratio, type of extraction solvent, as well as salts and sorbents amount were investigated and optimized. The final method involves the musks extraction using acetonitrile, followed by the addition of anhydrous magnesium sulphate and sodium acetate. The clean‐up step was performed using dispersive SPE with primary and secondary amine and octadecyl–silica sorbents. This extraction procedure is fast (about 10 min) when compared to other traditional approaches. The method was robust for the matrices studied and shows a high precision (%RSD < 15%) and accuracy (average recovery of 85%), allowing the detection of musks in minimum concentrations between 0.01 ng/g (galaxolide) and 15.80 ng/g (musk xylene). The developed method was applied to the analysis of 12 samples, which revealed musks concentrations ranging from 2 ng/g (toothpaste) to 882 340 ng/g (perfumed body lotion).     

In situ acetylation dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry for the simultaneous determination of musks,triclosan and methyl-triclosan in wastewaters

A rapid and environmental-friendly analytical method for the simultaneous analysis of different personal care products (PCPs) namely synthetic musks (nitro-, polycyclic and macrocyclic musks) and the disinfectant triclosan (TCS) and its transformation product methyl-TCS in wastewater samples has been developed. The method combines dispersive liquid–liquid microextraction with in situ aqueous derivatisation using acetic anhydride (Ac2O) prior to ?gas chromatography–mass spectrometry analysis. Several parameters affecting both extraction and derivatisation efficiency (e.g. type and volume of extractor and dispersive solvents, volume of derivatising reagent, etc.) were optimised to achieve reliable conditions. Validation of the method for all compounds under study showed good linearity with coefficient of correlation > 0.9947. Limits of quantification (LOQs) ranged between 2 and 72 ng/L for musks and 28 and 31 ng/L for TCS and methyl-TCS, respectively. Accuracy, expressed as the average recoveries, ranged between 76% and 87%, and precision, expressed in terms of intraday repeatability (%RSD), was better than 13% for all analytes. The application of the method to the analysis of 24 wastewater samples enabled the detection of all the target PCPs at concentration levels up to 2.7 μg/L, being galaxolide (HHCB) and tonalide (AHTN) the more prevalent, present in 88% and 46% of the samples, respectively.