Advances in the determination of degradation intermediates of personal care products in environmental matrixes: a review

In this review, recent methods developed for the determination of degradation intermediates of personal care products in environmental matrixes focusing on the extraction and determination steps are discussed. The five classes of personal care products evaluated are stimulants, fragrances, sunscreens, antimicrobials, and insect repellents. Methods are critically reviewed in terms of the analytical steps involved in the analysis, sample pretreatment, separation, and detection as well as the different confirmation strategies employed. Preconcentration from aqueous matrixes was performed by solid-phase extraction, liquid–liquid extraction, or solid-phase microextraction, allowing the simultaneous extraction of parent compounds and their degradation intermediates. Following the extraction and cleanup steps, the identification and quantification of degradation intermediates of personal care products at environmental levels (i.e., parts per trillion to parts per billion range) is usually performed by using mass spectrometry techniques such as single quadrupole mass spectrometry and more recently by time-of-flight mass spectrometry or tandem mass spectrometry. The main scope of this review is to critically evaluate the current state of the art of the analytical techniques used and to identify the research needs in the determination of degradation intermediates of personal care products in environmental matrixes.     

Current approaches to trace analysis of pharmaceuticals and personal care products in the environment

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.     

Simultaneous derivatization and air‐assisted liquid–liquid microextraction of some parabens in personal care products and their determination by GC with flame ionization detection

A simultaneous derivatization/air‐assisted liquid–liquid microextraction technique has been developed for the sample pretreatment of some parabens in aqueous samples. The analytes were derivatized and extracted simultaneously by a fast reaction/extraction with butylchloroformate (derivatization agent/extraction solvent) from the aqueous samples and then analyzed by GC with flame ionization detection. The effect of catalyst type and volume, derivatization agent/extraction solvent volume, ionic strength of aqueous solution, pH, numbers of extraction, aqueous sample volume, etc. on the method efficiency was investigated. Calibration graphs were linear in the range of 2–5000 μg/L with squared correlation coefficients >0.990. Enhancement factors and enrichment factors ranged from 1535 to 1941 and 268 to 343, respectively. Detection limits were obtained in the range of 0.41–0.62 μg/L. The RSDs for the extraction and determination of 250 μg/L of each paraben were <4.9% (n = 6). In this method, the derivatization agent and extraction solvent were the same and there is no need for a dispersive solvent, which is common in a traditional dispersive liquid–liquid microextraction technique. Furthermore, the sample preparation time is very short.     

New approach on trace analysis of triclosan in personal care products, biological and environmental matrices

Stir bar sorptive extraction and liquid desorption followed by high performance liquid chromatography with diode array detection (SBSE-LD-LC-DAD) is proposed for the determination of triclosan in personal care products, biological and environmental matrices, which is included in the priority lists, set by several international regulatory organizations. Instrumental conditions and experimental parameters that affecting SBSE-LD efficiency are fully discussed. Throughout systematic assays on 25 mL water samples spiked at the 10.0 μg L⁻¹ level, it had been established that stir bars coated with 126 μL of polydimethylsiloxane, an equilibrium time of 1 h (1000 rpm) and acetonitrile under sonification (60 min) as back-extraction solvent, allowed the best analytical performance to determine triclosan in water matrices. From the data obtained, good recovery and remarkable repeatability were attained, providing experimental average yields (78.5 ± 2.2%), although slightly lower than the theoretical equilibrium (99.7%) described by the octanol–water partition coefficients (K_PDMS/W < K_O/W). The analytical performance proved suitable precision (<3.6%), convenient detection limits (0.1 μg L⁻¹) and excellent linear dynamic range (r² > 0.9992) from 0.4 to 108.0 μg L⁻¹. The application of the present method to determine triclosan in real matrices such as commercial toothpaste, saliva and urban wastewater samples, allowed appropriate selectivity, high sensitivity and accuracy using the standard addition methodology. The proposed method showed to be feasible and sensitive with a low-sample volume requirement to monitor triclosan in personal care products, biological and environmental matrices at the trace level, in compliance with international regulatory directives.     

Simultaneous determination of multiclass preservatives including isothiazolinones and benzophenone‐type UV filters in household and personal care products by micellar electrokinetic chromatography

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

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).     

Analytical methods for the determination of persistent ingredients of personal care products in environmental matrices

Concern about the environmental fate and potential effects of synthetic organic chemicals used in soaps, lotions, toothpaste, and other personal care products continues to increase. This review describes procedures used for the analysis of five classes of these compounds–synthetic musk fragrances, antimicrobials, ultraviolet filters, insect repellents, and parabens–in water, sediment, sewage sludge, air, and aquatic biota. The primary focus is on sample extraction and preparation methods for these compounds. Instrumental methods commonly used for these compounds are also discussed. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Ultrasound‐assisted temperature‐controlled ionic liquid emulsification microextraction coupled with capillary electrophoresis for the determination of parabens in personal care products

We developed a CE and ultrasound‐assisted temperature‐controlled ionic liquid emulsification microextraction method for the determination of four parabens (methyl paraben, ethyl paraben, propyl paraben, and butyl paraben) in personal care products including mouthwash and toning lotion. In the proposed extraction procedure, ionic liquid (IL, 1‐octyl‐3‐methylimidazolium hexafluorophosphate) was used as extraction solvent, moreover, no disperser solvent was needed. Parameters affecting the extraction efficiency including volume of IL, heating temperature, ultrasonic time, extraction time, sample pH, ionic strength, and centrifugation time were optimized. Under the optimized conditions, the method was found to be linear over the range of 3–500 ng/mL with coefficient of determination (R²) in the range of 0.9990–0.9998. The LODs and LOQs for the four parabens were 0.45–0.72 ng/mL and 1.50–2.40 ng/mL, respectively. Intraday and interday precisions (RSDs, n = 5) were in the range of 5.4–6.8% and 7.0–8.7%, respectively. The recoveries of parabens at different spiked levels ranged from 71.9 to 119.2% with RSDs less than 9.5%.     

Spectrophotometric determination of trace lead in water after preconcentration using mercaptosephadex

A highly sensitive and selective spectrophotometric method for determination of trace lead in water after pre-concentration using mercaptosephadex (MS-50) has been developed, the method based on the color reaction of lead(II) with dibromohydroxylphenylporphyrin. Under optimal condition, lead(II) reacts with the reagent to form a 1:2 yellow complex in presence of TritonX-100, which has a maximum absorption peak at 479 nm. The color reaction can complete rapidly and remain stable for 24 h in room temperature. The molar absorption coefficient of the lead complex, the limit of quantification, the limit of detection and relative standard deviations were found to be 2.35×10⁵ l mol⁻¹ cm⁻¹, 4.3, 1.4 ng ml⁻¹ and 1.0%, respectively. The absorbance of the lead complex at 479 nm is linear up to 0.48 μg ml⁻¹ of lead(II). The effect of various co-existing ions in water were examined seriously. No interference was observed. Moreover, a simple pre-concentration method for trace lead in water was also studied using MS-50. It was found that trace lead in water can be adsorbed in 1.0 mol l⁻¹ HCl and dissociated from MS-50 with 4.0 mol l⁻¹ HCl quantitatively, that improves the selectivity and the sensitivity of method (its detection limit (3 s) changed into 0.2 ng ml⁻¹ of lead) obviously. The proposed method has been applied to determine trace lead in water samples with satisfactory results.     

Signal processing to evaluate parameters affecting SPE for multi‐residue analysis of personal care products

This paper discusses the development of a comprehensive method for the simultaneous analysis of personal care products (PCPs) based on SPE and GC‐MS. The method was developed on 29 target compounds to represent PCPs belonging to different chemical classes: surfactants in detergents (alkyl benzenes), fragrances in cosmetics (nitro and polycyclic musks), antioxidants and preservatives (phenols), plasticizers (phthalates) displaying a wide range of volatility, polarity, water solubility. In addition to the conventional C₁₈ stationary phase, a surface modified styrene divinylbenzene polymeric phase (Strata^TM X SPE cartridge) has been investigated as suitable for the simultaneous extraction of several PCPs with polar and non‐polar characteristics. For both sorbents different solvent compositions and eluting conditions were tested and compared in order to achieve high extraction efficiency for as many sample components as possible. Comparison of the behavior of the two cartridges reveals that, overall, Strata‐X provides better efficiency with extraction recovery higher than 70% for most of the PCPs investigated. The best results were obtained under the following operative conditions: an evaporation temperature of 40°C, elution on Strata‐X cartridge using a volume of 15 mL of ethyl acetate (EA) as solvent and operating with slow flow rate (–10 KPa). In addition to the conventional method based on peak integration, a chemometric approach based on the computation of the experimental autocovariance function (EACVF_tot) was applied to the complex GC‐MS signal: the percentage recovery and information on peak abundance distribution can be evaluated for each procedure step. The PC‐based signal processing proved very helpful in assisting the development of the analytical procedure, since it saves labor and time and increases result reliability in handling GC complex signals.     

Simultaneous analysis of select pharmaceuticals and personal care products in fish tissue using pressurized liquid extraction combined with silica gel cleanup

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 2.5 g 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 (0.01 V). 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 38 ng/g wet weight. MDLs for carbamazepine and diazepam were 18 and 3.7 ng/g wet weight, respectively. Galaxolide and tonalide were measured in an environmental sample at concentrations of 81 and 5.5 ng/g wet weight, respectively.     

银杏叶提取物中黄酮类化合物的分光光度分析研究

建立了一种银杏叶提取物中黄酮类化合物的分光光度测定方法。研究表明在NaNO2存在下,pH在13.20～13.60范围内,银杏叶提取物与Al(NO3)3形成稳定的粉红色配合物,于λmax=510nm处进行分光光度分析。标准品选用芦丁,其标准曲线在4.606～55.27μg/mL范围内服从朗伯-比尔定律,相关系数为r=0.9998。回收率为98.58%～102.80%,RSD为0.111%。可用于银杏叶提取物中黄酮类化合物的测定。     

Determination of pharmaceutical and personal care products in wastewater by capillary electrophoresis with UV detection

Capillary electrophoresis (CE) offers a fast and cost-effective alternative analytical technique to LC-MS/MS for separation and quantitation of many PPCP compounds in wastewater. In this study, we have developed a method that can simultaneously analyze eight different PPCP compounds in untreated wastewater (ibuprofen, triclosan, carbamazepine, caffeine, acetaminophen, sulfamethoxazole, trimethoprim, and lincomycin), using capillary electrophoresis with UV detection (CE-UV). The method detection limit (MDL) ranged from 1.6 to 68.7 ppb through solid phase extraction. The standard limit of quantification (LOQ) ranged from 0.63 to 7.72 ppm. Factors affecting separation and quantification of PPCPs, such as pH, electrophoretic potential, buffer strength, buffer type, and additives, were investigated and optimized. Water samples from two different wastewater treatment plants were collected and analyzed. The results obtained were comparable with those of LC-MS/MS. The technique developed in this study provides a low cost, simple, fast, and relatively sensitive method for determination of various PPCPs in wastewater samples for PPCP screening.     

固相萃取-气相色谱-质谱法同时测定水中9种药品及个人护理用品

采用固相萃取-气相色谱-质谱联用技术,建立了水体中9种药品及个人护理用品（水杨酸、萘普生、布洛芬、对乙酰氨基酚、降固醇酸、三氯生、双氯酚酸、酮洛芬和双酚A）的定量分析方法。水样品经稀盐酸调节至pH=3后,采用Oasis HLB固相萃取小柱进行富集净化;选用三甲基氢氧化硫（TMSH）为衍生化试剂,在常温条件下对目标物进行快速甲基化;以气相色谱-质谱法选择离子监测模式（GC-MS-SIM）进行检测,由2,4,5-涕丙酸为内标进行定量分析。本实验分别对固相萃取和衍生化等前处理条件进行了系统的研究。在优化的实验条件下,方法的回收率为50.7~115.4%,相对标准偏差均不高于10%,检出限为0.03~0.30 μg/L,定量限为0.15~1.50 μg/L。利用该方法对东莞市某农田灌溉水进行了分析,4种目标物在样品中有检出,最大质量浓度范围为0.176~0.998 μg/L。结果表明该方法操作简便,灵敏可靠。     

Sensitive Spectrophotometric Determination of Some Dibenzazepine Drugs with Diazotized P-Phenylenediamine Dihydrochloride

ABSTRACT

A simple, sensitive and selective spectrophotometric procedure was developed for the determination of imipramine hydrochloride, desipramine hydrochloride, clomipramine hydrochloride and trimipramine maleate belonging to dibenzazepine class of drugs. The method is based on the interaction of diazotized p-phenylenediamine dihydrochloride with the drug in sulphuric acid medium. The resulting chromophore was measured at 565 nm, and was stable for about 2.5 hr. The commonly encountered excipients and additives do not interfere with the determination. Dibenzazepine drugs can be determined in the range of 0.1-4.0 μg/ml, with a relative standard deviation of 1.92% for ten replicate measurement of 2.0 μg/ml dibenzazepine drugs. Results from the analysis of preformulations and commercial tablets by this procedure agree well with those of the official method.     

Electrochemical behaviour of triclosan at a screen-printed carbon electrode and its voltammetric determination in toothpaste and mouthrinse products

Cyclic voltammetry was used to investigate the electrochemical behaviour of triclosan (2,2,4′-trichloro-2′-hydroxydiphenyl ether) at a screen-printed carbon electrode (SPCE). It was found that a single anodic peak occurred over the pH range 6.0–12.0; this peak was considered to result from an irreversible oxidation reaction at the phenolic moiety. A plot of E_p versus pH was constructed and from the break point a pK_a value of 7.9 was obtained, thus agreeing with the literature value. Detailed voltammetric studies were performed at pH 10, where the analyte exists as an anion. It was demonstrated that, at an initial potential of 0 V, the anion underwent electrosorption prior to electrochemical oxidation. The oxidation reaction appeared to involve a one-electron transfer, as deduced from a calculated n_a value of 0.5; the same value was obtained at pH 7.0. In contrast to triclosan, triclosan monophosphate was found to be electrochemically inactive when subjected to voltammetry under the stated conditions.

The electrochemical oxidation of triclosan at a SPCE was exploited for its determination (0.3%) in commercial toothpaste and mouthrinse products using differential pulse voltammetry. The recovery and precision data indicated that this approach may have application in routine quality control analysis.     

三氯生的光降解产物分析及相关日化产品的安全性研究

采用气相色谱-质谱联用法(GC-MS)和高效液相色谱法(HPLC)(PAD检测器)对三氯生的光降解产物进行了分析,同时考查日化产品(牙膏、洗手液)中三氯生的安全性。光解反应是通过在紫外灯(UVB,15W)下直接照射三氯生溶液来完成的。HPLC的分离条件为:以Symmetry C18(5μm,4.6mm i.d.×250mm)为色谱柱,95%的甲醇溶液为流动相(H3PO4调节pH至5),外标法定量测定其降解产物2,8-二氯代二苯并-对-二口恶英(2,8-DCDD)。结果表明,2,8-DCDD在三氯生的光照溶液中被检测到,而在日化产品牙膏和洗手液中未被发现。本法可对2,8-DCDD进行定性和定量测定,便于对一些日化产品的监控。     

Diazotized reagent for spectrophotometric determination of glyphosate pesticide in environmental and agricultural samples

A new sensitive spectrophotometric method for the determination of glyphosate herbicide in environmental and agricultural samples is developed. The reaction is based on diazotization followed by coupling of glyphosate with p-dimethyl amino benzaldehyde. The resulted complex absorption spectra was observed at λ_max = 420 nm. The effects of other metal ions and pesticides were also tested for selective determination of glyphosate. The analytical parameters were optimized and have been successfully applied for determination of glyphosate in various environmental samples such as soil, water and vegetables. This method has a lower limit detection of 6 μg of glyphosate. Beer's law is obeyed over the concentration range of 6.0 μg–24.0 μg glyphosate in 25 mL of the final solution at 420 nm. The standard deviation and relative standard deviation calculated are 0.0055 and 1.023, respectively. The molar absorptivity of the colored system is 1.91 × 10¹⁰ L mol^?1cm^?1 and Sandell's sensitivity is found 0.408 × 10^?5 μg cm^?2. The proposed method is simple, sensitive, highly reproducible and time saving as compare to those complicated time consuming methods.     

电荷转移络合物分光光度法测定磺胺脒的研究

研究了电子给体磺胺脒与电子受体对苯醌之间的荷移反应。结果表明 ,在乙醇介质中磺胺脒与对苯醌能形成橙红色电荷转移络合物 ,且反应体系的pH范围较宽。络合物的最大吸收波长λmax=497.6nm ,表观摩尔吸光系数为 2 .3 5× 1 0 3L·mol- 1 ·cm- 1 ,比耳定律的线性范围是 0～ 5 0mg/L ,络合比为 1∶2。应用拟定的方法测定磺胺脒制剂的含量 ,平均回收率为 1 0 0 .4% ,可用于磺胺脒制剂的分析。     

超高效液相色谱-串联质谱法同时检测地表水中18种药物与个人护理品的残留量

采用固相萃取对水样进行预处理,建立了同时检测地表水中包括抗生素、β-阻滞剂、驱蚊剂、抗癫痫药、中枢神经兴奋剂、血脂调节剂、非甾体抗炎药、杀菌消毒剂在内的18种药物与个人护理品的超高效液相色谱-串联质谱分析方法。采用中性条件萃取水样,控制上样流速为2 mL/min,用甲醇-乙腈(1:1, v/v)溶液洗脱。纯水中的平均加标回收率为53.9%～112%,相对标准偏差为2.6%～15.3%(n=6);以地表水样加标100 ng/L为样品,目标分析物平均回收率为45.1%～156.6%,相对标准偏差为2.4%～15.7%(n=6)。结果表明,本方法可同时精确检测地表水样中的18种分析物,方法验证结果表明所建立的方法可靠。用该方法分析杭州余杭塘河水,结果检出9种分析物,其中咖啡因平均质量浓度达550.7 ng/L。结果表明该方法可靠。