污水中6种邻苯二甲酸酯的测定

采用同时蒸馏萃取法提取水样中的邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二正辛酯、邻苯二甲酸二(2-乙基己基)酯6种邻苯二甲酸酯,用GC-MS进行定性和定量分析.对pH值、盐度和提取时间等影响因素进行优化.当pH值为2.0,NaCl加入量为5.0 g/L和提取时间为2.5 h时,目标化合物具有较好的回收率.优化条件下6种邻苯二甲酸酯的样品加标回收率为98%～105%,相对标准偏差为1.8%～5.6%,方法检出限为8.0～200.0 ng/L.方法成功应用于城市污水中该类化合物的监测.     

Determination of phthalate esters in soil by microemulsion electrokinetic chromatography coupled with accelerated solvent extraction

A novel method using microemulsion electrokinetic chromatography combining accelerated solvent extraction was developed for quantitative analysis of six phthalate esters (PAEs) including dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate, as well as dioctyl phthalate. The effect of each individual component within the microemulsions, i.e. oil phase, surfactant and co-surfactant on resolution of the analytes was systematically studied. Baseline separation of six PAEs was achieved within 26?min by using the microemulsion buffer containing a 60?mmol/L borate buffer at pH 9.0, 0.5% v/v n-octane as oil droplets, 100?mmol/L sodium cholate as surfactant and 5.0% v/v 1-butanol as co-surfactant. The purposed accelerated solvent extraction-microemulsion electrokinetic chromatography method was successfully applied to the determination of trace amount of PAEs in soil samples collected from three different fields in areas of Fujian Province and the contents of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate and dioctyl phthalate were 0.63-0.68, 0.32-0.63, 2.53-3.96, 0-1.75, 7.32-11.7 and 0-3.46mg/kg, respectively. It was validated that the results were consistent with those obtained by GC-MS method.     

Simultaneous determination of seven phthalates and four parabens in cosmetic products using HPLC-DAD and GC-MS methods

Studies on the determination of seven kinds of phthalates, i.e. diethyl phthalate, dipropyl phthalate, dibutyl phthalate, benzyl butyl phthalate, dicyclohexyl phthalate, di-(2-ethylhexyl) phthalate, and dioctyl phthalate, and four parabens, i.e. methylparaben, ethylparaben, propylparaben, and butylparaben, in 15 kinds of cosmetic products, including hair sprays, perfumes, deodorants, cream, lotion, etc., by HPLC with diode array detection and GC-MS in electron impact ionization mode with selected-ion monitoring have been carried out. Methods have been developed for both qualitative and quantitative detection of phthalates and parabens. Extraction, clean-up, and analysis procedures have been optimized. HPLC and GC-MS determinations were performed after sonication-assisted extraction with methanol and clean-up with C18 SPE. These techniques permit detection of phthalates at a level of 10.0-100.0 microg/kg and of parabens at a level of 20.0-200.0 microg/kg. Overall recoveries were 85-108% with RSD values of 4.2-8.8%. Only one of the 15 examined samples was free from phthalates and parabens. The remaining 14 samples were found to contain at least three or more of these phthalates and/or parabens. The predominant phthalates and parabens detected in the studied samples were methylparaben, propylparaben, diethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, and di-(2-ethylhexyl) phthalate. The residue level is at 1.22-5289 mg/kg.     

Phthalates determination in pharmaceutical formulae used in parenteral nutrition by LC-ES-MS: importance in public health

A method for determining a group of phthalate esters in pharmaceutical formulae used in parenteral nutrition samples (with and without vitamins) has been developed. The phthalic acid esters (PAEs) studied were dimethyl phthalate, diethyl phthalate, butyl benzyl phthalate, dibutyl phthalate, di-(2-ethylhexyl) phthalate, and dioctyl phthalate. This group of phthalates was determined by high performance liquid chromatography (HPLC)–electrospray ionization–mass spectrometry, working in positive ion mode. The phthalates analyzed were extracted from the sample using hexane and sodium hydroxide. The hexane was then evaporated, and the compounds were redissolved in acetonitrile. The compounds were separated by HPLC working in gradient mode with acetonitrile-ultrapure water starting from 5% to 75% acetonitrile in 5 min, followed by isocratic elution for 27 min. Standard calibration curves were linear for all the analytes over the concentration range 10–250 μg L⁻¹. The method was precise (with RSD from 3.3% to 12.9%) and sensitive. The proposed analytical method has been applied to the analysis of these compounds in different pharmaceutical formulae (with different compositions) for parenteral nutrition samples in order to check the presence of phthalates and determine their concentration.     

Determination of phthalates and adipate in bottled water by headspace solid-phase microextraction and gas chromatography/mass spectrometry

The performance of three fibres for the headspace solid-phase microextraction (SPME) of di-2-ethylhexyl adipate (DEHA) and eight phthalates in water was investigated systematically under different extraction conditions. Good responses on the 65 microm polydimethylsiloxane/divinylbenzene (PDMS/DVB) SPME fibre were observed for DEHA and all phthalates. The polydimethylsiloxane (PDMS) SPME fibre had very poor responses for the lighter and slightly polar phthalates, dimethyl phthalate (DMP) and diethyl phthalate (DEP), while the divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) SPME fibre had very poor responses for the heavier and non-polar adipate and phthalates. The salt (NaCl) was found to increase the partitioning of DMP, DEP, diisobutyl phthalate (DiBP), di-n-butyl phthalate, and benzyl butyl phthalate (BBP) from water into the headspace, while partitioning of heavier adipate and phthalates from water into headspace was suppressed when the concentration of NaCl was above 10%. The automated headspace SPME methods were developed and validated under two different salting conditions (30% NaCl for DMP, DEP and BBP, and 10% for DEHA, DiBP, DBP, di-n-hexyl phthalate (DHP), di-2-ethylhexyl phthalate (DEHP), and di-n-octyl phthalate (DOP)). Linearity with R(2) values better than 0.9949 was observed for DEHA and eight phthalates over the range from 0.1 to 20 microg L(-1). Method detection limits ranged from 0.003 microg L(-1) for DOP to 0.085 microg L(-1) for BBP. Good repeatability was observed for DEHA and most phthalates with relative standard deviation (RSD) values less than 10%. The methods were used to analyse bottled water samples for DEHA and eight phthalates. DMP, DHP, BBP, DEHA and DOP were not detected in any samples. Concentrations of the other phthalates were low (around sub-ppb) except for DBP in the water from a polycarbonate bottle at 1.72 microg L(-1).     

Determination of Phthalates in Milk by Ultrasound-Assisted Dispersive Liquid–Liquid Microextraction and Gas Chromatography–Mass Spectrometry

Ultrasound-assisted dispersive liquid–liquid microextraction was coupled with gas chromatography—mass spectrometry for the determination of phthalate esters in milk. Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate, and dioctyl phthalate were analyzed in five brands of pasteurized Turkish milk. The efficiencies of the extraction procedure for the analytes were between 66 and 100%. The linear dynamic ranges of the calibration curves were from 0.025 to 1.000 µg/mL with correlation coefficients exceeding 0.99. The precision of the method is acceptable with relative standard deviation values below 5%. Dibutyl phthalate and bis(2-ethylhexyl) phthalate were commonly observed in milk.     

Determination of phthalates in milk and milk products by liquid chromatography/tandem mass spectrometry

A liquid chromatographic/tandem mass spectrometric method using pneumatically assisted electrospray ionisation (LC/ESI-MS/MS) was developed for determination of dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP), di-'isononyl' phthalate (DINP) and di-'isodecyl' phthalate (DIDP) in milk and milk products including infant formulas. The phthalates were extracted by a mixture of tert-butyl methyl ether and hexane from liquid samples. DBP, BBP and DEHP were removed from fats by liquid/liquid extraction into acetonitrile while DINP and DIDP were cleaned up on deactivated silica. The phthalates were detected in positive ion mode after separation on a reversed-phase C5 analytical column. Two transition products were monitored for each compound. The detection limits related to the transition products of lowest abundance were in the range 5-9 microg/kg.     

Development of an ionic liquid-based dispersive liquid-liquid micro-extraction method for the determination of phthalate esters in water samples

Ionic liquid-based dispersive liquid-liquid micro-extraction (IL-DLLME) was coupled with high-performance liquid chromatography-ultraviolet (HPLC-UV) for the determination of four phthalate esters, including butyl benzyl phthalate, di-n-butyl phthalate, dicyclohexyl phthalate and bis(2-ethylhexyl) phthalate in water samples. The mixture of ionic liquid (IL) and dispersive solvent was rapidly injected into 10 mL aqueous sample. Then, IL phase was separated by centrifugation and was determined by high-performance liquid chromatography-ultraviolet. The factors influencing the extraction efficiency, such as type and volume of IL, disperse solvent, extraction time, centrifuging time and ionic strength, were investigated and optimized. Under the optimized conditions, the extraction recoveries by the proposed ionic liquid-based dispersive liquid-liquid micro-extraction for the four phthalates ranged from 83.0 to 91.7%. The relative standard deviations were between 7.8 and 15%. The limits of quantification for four phthalates were between 10.6 and 28.5 μg/L. The proposed method was successfully applied for the analysis of PAEs in tap, lake and treated wastewater samples.     

Fast Chromatographic Separation of Plasticizers on Thin Layers of an Inorganic Ion-Exchanger: Quantitative Determination of Di(2-ethylhexyl)phthalate

Fast and selective separation of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di(2-ethylhexyl)phthalate (DEHP), benzyl butyl phthalate, diisodecyl phthalate, dimethyl adipate, diethyl adipate, di(2-ethylhexyl)adipate, triethyl citrate, tributyl citrate, tributyl acetyl citrate and n-butyl stearate have been developed on thin layers of inorganic ion-exchanger stannic silicate using a mixture of toluene + ethyl acetate (10:1, v/v) as mobile phase. The development distance and time were 12 cm and 25 min, respectively. Quantitative determination of DEHP was made at wavelength 280 nm by Camag TLC Scanner-3. Limit of quantitation for DEHP was 0.50 μg per zone while its limit of detection was 0.05 μg per zone.     

Detection of Phthalate Esters in Environmental Water Samples-Comparison of Nylon6 Nanofibers Mat-based Solid Phase Extraction and Other Conventional Extraction Methods

In this article, a new method for simultaneous determination of six phthalate esters was developed by a combination of electrospun nylon6 nanofibers mat‐based solid phase extraction with high performance liquid chromatography‐ultraviolet detector (HPLC‐UV). The six phthalate esters were dimethyl phthalate (DMP), diethyl phthalate (DEP), butyl benzyl phthalate (BBP), di‐n‐butyl phthalate (DBP), di‐(2‐ethylhexyl) phthalate (DEHP) and dioctyl phthalate (DOP). Under optimized conditions, all target analytes in 50 mL environmental water samples could be completely extracted by 2.5 mg nylon6 nanofibers mat and eluted by 100 µL solvent. Compared with C18 cartridges solid phase extraction, C18 disks solid phase extraction and national standard method (China), nylon6 nanofibers mat‐based solid phase extraction was advantageous in aspects of simple and fast operation, low consumption of extraction materials and organic solvents. The four methods were applied to analysis of environment water samples. All the results indicated that the determination values of target compounds with the proposed method were consistent with C18 cartridges and C18 disks solid phase extraction method, and the new method was better than the national standard method in aspects of recovery, LOD and precision. Therefore, nylon6 nanofibers mat has great potential as a novel material for solid phase extraction.     

养殖鱼邻苯二甲酸酯的含量分析

目的：为了解宁波地区淡水养殖鱼PAEs污染情况。方法采用液液超声萃取-气质联用法对宁波6个不同养殖点5种淡水养殖鱼体内8种邻苯二甲酸酯含量进行分析。结果宁波地区养殖鱼主要受 DMP、 DEP、 DBP、 DEHP 和 DOP 污染，质量分数最高可达134.1、258.9、249.2、830.8和5029μg/kg；草鱼、鳊鱼、鳙鱼、鲫鱼和乌鳢邻苯二甲酸污染指数PPI分别为9.999、9.735、13.97、8.945和5.809μg/kg。结论宁波地区淡水养殖鱼鱼体邻苯二甲酸酯含量与养殖环境有关，与鱼种无关。     

A novel quantitation method for phthalates in air using a combined thermal desorption/gas chromatography/mass spectrometry application

In this study, a novel quantitation method was developed to facilitate the simple and effective sampling and analysis of phthalates in air based on a sorbent tube-thermal desorption-gas chromatography-mass spectrometry system combination. The performance of the thermal desorption-based analysis was assessed using three different sorbent combinations [1]: quartz wool (QW) [2], glass wool (GW), and [3] quartz wool plus Tenax TA (QWTN) in terms of relative recovery in reference to a direct injection method. There was no significant difference in the average recovery rate for seven target phthalates based on sorbent tube type (QW, 70.2 ± 4.28; GW, 73.2 ± 8.8; and QWTN, 72.5 ± 5.02%). However, the recovery rate of phthalates in each sorbent tube type was distingusihed by physicochemical properties of the target compound (e.g., molecular weight and boiling point). The recovery rate of the QW tube was high for dimethyl phthalate and diethyl phthalate compared to other sorbent tubes, while that of the GW tube exhibited greater values for dibutyl phthalate, benzyl butyl phthalate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) phthalate, and di-n-octyl phthalate. The simple sorbent tube-thermal desorption approach is feasible for the quantitation of seven phthalates present at 0.45–24.5 ng m⁻³ levels in actual air samples (20 L).     

毛细管气相色谱法测定化妆品中的酞酸酯

建立了用毛细管气相色谱配氢火焰离子化检测器测定化妆品中6种酞酸酯(邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸二(2-乙基己)酯(DEHP)和邻苯二甲酸二正辛酯(DOP))的方法。样品用甲醇超声提取,经高速冷冻离心,清液经干燥脱水过0.5 μm滤膜过滤,直接注入气相色谱仪进行分析。然后,经过气相色谱-电子电离-质谱检测分析,确证气相色谱-氢火焰检测的阳性检出结果。用保留时间定性,外标法定量。6种酞酸酯的回收率为82.90%～     

Comparison of different fibers for the solid-phase microextraction of phthalate esters from water

Solid-phase microextraction (SPME) coupled to gas chromatography-mass spectrometry (GC-MS) has been applied to determine six phthalate esters and one adipate ester in water. The SPME parameters were optimized for several commercially available fibers. A 65-microm polydimethylsiloxane-divinylbenzene (PDMS-DVB) was the fiber selected and was applied to analysis of water from the Ebro river and the industrial port of Tarragona. The studied compounds were found at concentrations ranging from 0.4 microg l(-1) for di-n-butyl phthalate ester (DnBP) to 3.2 microg l(-1) for bis(2-ethylhexyl) phthalate ester (DEHP). The linear range for real samples was from 0.1 to 10 microg l(-1) for most phthalates, and the limits of detection of the method were between 3 and 30 ng l(-1). Repeatability and reproducibility between days (n = 5) for 1 microg l(-1) samples were below 13 and 18%, respectively.     

Determination of phthalate esters in bottled water using dispersive liquid–liquid microextraction coupled with GC–MS

Dispersive liquid–liquid microextraction method was developed for the determination of the amount of phthalate esters in bottled drinking water samples and dispersive liquid–liquid microextraction samples were analyzed by GC–MS. Various experimental conditions influencing the extraction were optimized. Under the optimized conditions, very good linearity was observed for all analytes in a range between 0.05 and 150 μg/L with coefficient of determination (R²) between 0.995 and 0.999. The LODs based on S/N = 3 were 0.005–0.22 μg/L. The reproducibility of dispersive liquid–liquid microextraction was evaluated. The RSDs were 1.3–5.2% (n = 3). The concentrations of phthalates were determined in bottled samples available in half shell. To understand the leaching profile of these phthalates from bottled water, bottles were exposed to direct sunlight during summer (temperature from 34–57°C) and sampled at different intervals. Result showed that the proposed dispersive liquid–liquid microextraction is suitable for rapid determination of phthalates in bottled water and di‐n‐butyl, butyl benzyl, and bis‐2‐ethylhexyl phthalate compounds leaching from bottles up to 36 h. Thereafter, degradation of phthalates was observed.     

Simultaneous determination of 22 phthalate esters in polystyrene food‐contact materials by ultra‐performance convergence chromatography with tandem mass spectrometry

A method for the determination of 22 phthalate esters in polystyrene food‐contact materials has been established using ultraperformance convergence chromatography with tandem mass spectrometry. In this method, 22 phthalate esters were analyzed in <3.5 min on an ACQUITY Tours 1‐AA column by gradient elution. The mobile phase, the compensation solvent, the flow rate of mobile phase, column temperature, and automatic back pressure regulator pressure were optimized, respectively. There was a good linearity of 20 phthalate esters with a range of 0.05–10 mg/L, diisodecyl phthalate and diisononyl phthalate were 0.25–10 mg/L, and the correlation coefficients of all phthalates were higher than 0.99 and those of 16 phthalates were higher than 0.999. The limits of detection and the limits of quantification of 15 phthalates were 0.02 and 0.05 mg/kg, meanwhile diallyl phthalate, diisobutyl phthalate, dimethyl phthalate, di‐n‐butyl phthalate, and di(2‐ethylhexyl) phthalate were 0.05 and 0.10 mg/kg, and diisodecyl phthalate and diisononyl phthalate were 0.10 and 0.25 mg/kg. The spiked recoveries were in the range of 76.26–107.76%, and the relative standard deviations were in the range of 1.78–12.10%. Results support this method as an efficient alternative to apply for the simultaneous determination of 22 phthalate esters in common polystyrene food‐contact materials.     

食品包装材料中13种增塑剂的毛细管气相色谱法测定

建立了索氏提取、固相萃取净化浓缩、毛细管气相色谱法测定塑料食品包装材料中13种增塑剂的方法.优化了固相萃取淋洗剂、洗脱剂和洗脱剂体积等参数.样品经正己烷索氏提取后,用硅胶小柱净化浓缩.以正己烷-甲苯为淋洗剂,2 mL乙酸乙酯为洗脱剂.过滤后的洗脱液用气相色谱仪分析.结果显示,13种增塑剂在0.1～1000 mg/L范围...     

Simultaneous screening and determination eight phthalates in plastic products for food use by sonication-assisted extraction/GC-MS methods

Studies on determination of eight kinds of phthalates, e.g. di-ethyl phthalate (DEP), di-propyl phthalate (DPP), di-isobutyl phthalate (DIBP), di-butyl phthalate (DBP), benzyl butyl phthalate (BBP), di-cyclohexyl phthalate (DCHP), di-(2-ethylhexyl) phthalate (DEHP), di-octyl phthalate (DOP), in 25 kinds of plastic products for food use, including packaging bags, packaging film, containers, boxes for microwave oven use, sucking tubes, spoons, cups, plates, etc. by gas chromatography in combination with mass spectrometry detector (GC-MS) in electronic ionisation mode (EI) with selected-ion monitoring (SIM) acquisition method (GC-MS (EI-SIM)) have been carried out. Methods have been developed for both qualitative and quantitative analysis of phthalates. Extraction, clean-up and analysis procedure have been optimized. Determination of samples were performed after frozen in liquid nitrogen and sonication-assisted extraction with hexane, clean-up with LC-C18 SPE and analyzed by GC-MS methods. The base peak (m/z = 149) of all the phthalates was selected for the screening studies. The characteristic ions, 121, 177, 222 for DEP; 191, 209 for DPP; 57, 223 for DIBP; 104 for DBP; 91, 132, 206 for BBP; 55, 167 for DCHP; 113, 167, 279 for DEHP; 279 for DOP were chosen for quantitative studies. These techniques are possible to detect phthalates at the level of 10.0 μg/kg. Overall recoveries were 82-106% with R.S.D. values at 3.8-10.2%. Only one of the 25 examined samples was free from phthalates. The rest 24 samples were found to contain at least three or more of these phthalates. The predominant phthalate detected in the studied samples was DEHP.     

Determination of phthalate esters from environmental water samples by micro‐solid‐phase extraction using TiO2 nanotube arrays before high‐performance liquid chromatography

We describe a highly sensitive micro‐solid‐phase extraction method for the pre‐concentration of six phthalate esters utilizing a TiO₂ nanotube array coupled to high‐performance liquid chromatography with a variable‐wavelength ultraviolet visible detector. The selected phthalate esters included dimethyl phthalate, diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, bis(2‐ethylhexyl)phthalate and dioctyl phthalate. The factors that would affect the enrichment, such as desorption solvent, sample pH, salting‐out effect, extraction time and desorption time, were optimized. Under the optimum conditions, the linear range of the proposed method was 0.3–200 μg/L. The limits of detection were 0.04–0.2 μg/L (S/N = 3). The proposed method was successfully applied to the determination of six phthalate esters in water samples and satisfied spiked recoveries were achieved. These results indicated that the proposed method was appropriate for the determination of trace phthalate esters in environmental water samples.     

固相萃取-气相色谱/质谱法同时测定化妆品中的邻苯二甲酸酯和对羟基苯甲酸酯

采用超声协助甲醇提取、固相萃取净化、气相色谱/选择离子质谱联用法,同时测定化妆品中8种邻苯二甲酸酯和4种对羟基苯甲酸酯。该方法线性范围广、重现性好、快速简便、干扰小。样品的加标回收率为80%～100%;含量检测的相对标准偏差小于10%;方法的检出限为0.1~5.0 μg/kg。用该方法对15种实际样品中的12种残留物进行定量检测,结果表明除了一种样品中不含待测物外,其余样品均检测到3~7种待测物。其中以对羟基苯甲酸甲酯、对羟基苯甲酸丙酯、邻苯二甲酸丙酯、邻苯二甲酸环己酯和邻苯二甲酸乙基庚基酯为主。