食品包装材料中邻苯二甲酸酯检测方法研究进展

介绍邻苯二甲酸酯的性质及其对人体的危害,综述了近几年来食品包装材料中邻苯二甲酸酯的检测方法及样品前处理方法,并对比了其优缺点。展望了食品包装材料中邻苯二甲酸酯分析方法的研究趋势。     

GC-MS法测定白酒中邻苯二甲酸酯残留量

采用正己烷提取白酒中的16种邻苯二甲酸酯类增塑剂,建立了气相色谱-质谱联用法测定白酒中污染物邻苯二甲酸酯类增塑剂残留量的检测方法。该方法对白酒中16种邻苯二甲酸酯化合物的检测限为0.05 mg/kg,方法的检测浓度线性范围为0.5~5.0 mg/L,样品的加标回收率为80.0%~95.0%,测定结果的相对标准偏差为2.1%~7.0%(n=6)。该方法可以满足白酒中污染物邻苯二甲酸酯检测的需要。     

邻苯二甲酸酯的毒性及相关限制法规

自台湾"起云剂事件"爆发以来,邻苯二甲酸酯开始为人们所知。作为一种塑料助剂,邻苯二甲酸酯广泛应用于日常生活的各个领域,特别是食品包装领域。研究发现,邻苯二甲酸酯具有致突变性、致癌性和致畸性等毒性,会对人体及动物的肝、肾等造成损伤。由于邻苯二甲酸酯与塑料分子间的作用力较弱,容易从食品包装材料中迁移到食品中,世界各国都制定了相关政策对其使用进行限制;我国也制定了一系列政策和法规对其进行控制;今后研究新的检测方法和替代品将是解决我国目前邻苯二甲酸酯问题的主要出路。     

常见食品中邻苯二甲酸酯类增塑剂含量及食品包装材料中邻苯二甲酸酯类增塑剂迁移量的测定

采用气相色谱-质谱联用(GC-MS)方法并结合液液萃取及基质分散固相萃取的样品处理方式,建立了测定饮料、牛奶、白酒3类食品中16种邻苯二甲酸酯类增塑剂的分析方法。研究结果表明16种邻苯二甲酸酯类增塑剂的检出限(LOD, S/N=3)范围为0.005~0.025 mg/L;峰面积的相对标准偏差(RSD)均小于2%。饮料、牛奶、白酒3种样品的加标回收率范围普遍在60%~110%。所建方法简便、灵敏、准确,可满足饮料、牛奶和白酒中痕量邻苯二甲酸酯类增塑剂的测定需要。此外,将该方法应用于食品包装材料中邻苯二甲酸酯类增塑剂的迁移研究,以异辛烷为油脂食品模拟物,测定了保鲜膜与保鲜袋中16种邻苯二甲酸酯类增塑剂的迁移量。结果显示保鲜膜存在显著的邻苯二甲酸酯类增塑剂迁移现象。     

南昌市农田土壤和水样中邻苯二甲酸酯污染物的分析

采用气相色谱-质谱联用的方法,研究了南昌市15处农田的土壤、地表水和地下水中4种常见邻苯二甲酸酯类物质的分布状况.结果表明,邻苯二甲酸二乙酯和邻苯二甲酸二(2-乙基己基)酯是南昌市农田的主要邻苯二甲酸酯污染物;土壤中邻苯二甲酸酯的检出率低于地表水和地下水.     

超声萃取-气相色谱-质谱法检测塑料玩具中8种邻苯二甲酸酯类增塑剂

建立了气相色谱-质谱法（GC-MS）同时测定玩具中8种邻苯二甲酸酯化合物的方法.利用四氢呋喃提取塑料玩具中邻苯二甲酸酯化合物,超声提取30 min,经乙腈沉淀,采用GC-MS外标法进行定量检测.结果表明,8种邻苯二甲酸酯线性范围为0.5~10 mg/L,相关系数均大于0.995,方法检出限为1.14~13.65 mg/kg,平均回收率为89.2%~103.8%,相对标准偏差为1.41%~4.93%.方法简单、快速、准确,可用于塑料玩具中邻苯二甲酸酯的检测.     

荧光法快速测定邻苯二甲酸酯的总量

基于邻苯二甲酸酯在浓硫酸下荧光增强的原理构建了一种测定邻苯二甲酸酯总量的荧光分析新方法。 体系的荧光强度与邻苯二甲酸酯的浓度在5.00~600 μg/L的范围内呈线性关系,方法的检出限为0.57 μg/L,回收率在91.6%~105.1%之间。 该方法简单、快速、灵敏度高、线性范围宽。 用于塑料水杯和聚氯乙烯水管中邻苯二甲酸酯总量的测定,结果令人满意。     

离子迁移谱快速筛查白酒中痕量邻苯二甲酸酯的研究

建立了离子迁移谱技术快速检测白酒中痕量邻苯二甲酸酯的方法。对迁移管温度、进样口温度进行了参数优化后,选取5种典型的邻苯二甲酸酯进行了系统研究。在迁移管和进样口温度分别为90℃和160℃的条件下,邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸二异丁酯和邻苯二甲酸二(2-乙基己)酯的检出限分别为0.14,0.06,0.14,0.44和0.02 mg/L;9次平行测量的相对标准偏差RSD<8.9%,单个样品的分析周期小于95 s。将本方法应用于5种白酒盲样的检测,成功筛查出邻苯二甲酸酯类物质。利用离子阱质谱对5种邻苯二甲酸酯标样产物离子和白酒盲样的产物离子进行了确认,结果表明,离子迁移谱的谱峰是邻苯二甲酸酯离子。这说明丙酮作为掺杂剂,可以避免白酒中背景化合物的干扰。本方法适于大量白酒样品中邻苯二甲酸酯类物质的快速筛查。     

PVC塑料玩具中邻苯二甲酸酯检测能力验证北大核心CSCD

邻苯二甲酸酯增塑剂是现代塑料工业最大的助剂品种,其主要作用是增加聚合物的塑性。增塑剂的广泛应用,导致其可能在儿童玩具中残留。邻苯二甲酸酯增塑剂对人体的肝脏、生殖系统和内分泌系统存在一定危害性。     

乙醇-K2HPO4-H2O双水相萃取体系结合GC-MS检测白酒中的邻苯二甲酸酯

本文直接以白酒中的乙醇为萃取剂,通过双水相萃取技术结合气相色谱质谱联用法,建立了一种测定白酒中邻苯二甲酸酯类化合物的方法.实验对双水相体系的形成条件进行了研究,并探讨了双水相体系对邻苯二甲酸酯类的萃取效率.实验结果表明:乙醇-磷酸氢二钾-水双水相体系对邻苯二甲酸酯类物质有较高的萃取效率,在上相萃取液中加入无水MgSO4...     

Simultaneous selective detection of organophosphate and phthalate esters using gas chromatography with positive ion chemical ionization tandem mass spectrometry and its application to indoor air and dust

A selective and sensitive method for the simultaneous determination of 14 organophosphate and six phthalate esters using gas chromatography (GC) and mass spectrometry (MS) is presented. Both of these compound classes are frequently found in the indoor environment due to their use as bulk additives in numerous polymers, consumer products and building materials. GC/MS utilizing positive ion chemical ionisation (PICI) in selected reaction monitoring (SRM) mode with isobutane as the reagent gas was found to be the best of the tested methods; it proved superior to electron ionisation (EI) in selected ion monitoring (SIM) mode and to PICI using methane as the reagent gas. The method was applied to indoor air samples collected by active air sampling using solid‐phase extraction (SPE) cartridges. Organophosphates and phthalates were simultaneously determined with method detection limits (MDLs) in the range of 0.1–47 ng m^?3. For most compounds the MDLs were ≤0.2 ng m^?3, but due to the presence of some of these ubiquitous indoor air pollutants in the blanks, significantly higher MDLs were observed for a few compounds. Finally, the method was also applied in the screening of a much more complex sample matrix, indoor dust. Copyright © 2010 John Wiley & Sons, Ltd.     

凝胶渗透色谱-气相色谱/质谱法同时测定食用油中22种邻苯二甲酸酯

建立了凝胶渗透色谱-气相色谱/质谱法同时测定食用油中22种邻苯二甲酸酯的方法。方法具有良好线性,相关系数R均大于0.999,检测限在0.09～11.83 mg/kg之间,平均回收率在81.45%～113.90%范围内,相对标准偏差为1.55%～9.41%。采用该方法对国内食用油中邻苯二甲酸酯增塑剂进行检测,实际样品中检出邻苯二甲酸二异丁酯、邻苯二甲酸二丁酯和邻苯二甲酸二(2-乙基)己酯,可满足目前食用油中邻苯二甲酸酯的检测要求。     

Investigation of feasibility of bamboo charcoal as solid-phase extraction adsorbent for the enrichment and determination of four phthalate esters in environmental water samples

This paper demonstrates, for the first time, that adsorptive potential of bamboo charcoal for solid-phase extraction of phthalate esters was investigated. The four phthalate esters, dimethyl phthalate (DMP), diethyl phthalate (DEP), butyl benzyl phthalate (BBP) and di-n-butyl phthalate (DBP), are quantitatively adsorbed on a bamboo charcoal packed cartridge, then the analytes retained on the cartridge are quantitatively desorbed with optimum amounts of acetone. Finally, the analytes in the eluant acetone are determined by high-performance liquid chromatography-ultraviolet detectior. Important parameters influencing the extraction efficiency, such as eluant and its volume, flow rate of sample, sample volume, pH, the amount of adsorbent and ionic strength were investigated and optimized in detail. Under the optimum conditions, the limits of detection were 0.35-0.43 microg/L for four phthalate esters. The proposed method has been applied to the analysis of rainwater and tap water samples. And satisfactory spiked recoveries were obtained in the range of 75.0-114.2%. All the results indicated that the bamboo charcoal has great potential as a novel adsorbent material for the enrichment and determination of phthalate esters in real environmental water samples.     

Determination of micelle/water partition coefficients and associated thermodynamic data for dialkyl phthalate esters

Micelle/water partition coefficients for three dialkyl phthalate esters — dimethyl phthalate ester (DMP), diethyl phthalate ester (DEP) and dipropyl phthalate ester (DPP) were obtained by micellar liquid chromatography (MLC). Experiments were conducted over a temperature range which led to calculation of a Gibbs free energy, enthalpy and entropy of transfer for the phthalate esters. In addition, small angle neutron scattering (SANS) experiments were conducted with no substantial change observed in micelle size before and after phthalate ester incorporation. Overall, a novel method for obtaining thermodynamic information, based on partitioning data, has been developed for dialkyl phthalate esters using micellar liquid chromatography.     

超高效合相色谱快速检测塑料制品中的15种邻苯二甲酸酯

建立了使用超高效合相色谱检测塑料中15种邻苯二甲酸酯的方法。样品经正己烷超声萃取,过0.45 μ m有机膜后上机测试。采用ACQUITY UPC² HSS C18 SB色谱柱（150 mm×3 mm, 1.8 μ m）,以超临界CO₂流体为主流动相、乙腈为流动相改性剂进行梯度洗脱,流速为1.5 mL/min。在系统背压为12.41 MPa、色谱柱温度为65 ℃、二极管阵列检测器（PDA）检测波长为220 nm的条件下,15种邻苯二甲酸酯可以在8 min内实现分离检测。实验结果表明：15种邻苯二甲酸酯的线性范围为0.5~10 mg/L,相关系数大于0.9960,检出限（S/N=3）为1.0~2.2 mg/kg,加标回收率为78.1%~122.3%,相对标准偏差为2.95%~8.26%。该方法分析速度快,为邻苯二甲酸酯类物质的检测提供了新的选择。     

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.     

Determination of phthalate esters in cow milk samples using dispersive liquid-liquid microextraction coupled with gas chromatography followed by flame ionization and mass spectrometric detection

A simple and economic method for the analysis of phthalate esters, dimethyl phthalate, diethyl phthalate, di-iso-butyl phthalate, di-n-butyl phthalate, and di-2-ethylhexyl phthalate in cow milk samples by means of gas chromatography-flame ionization detection and gas chromatography-mass spectrometry has been developed. In this work, NaCl and ACN were added to 5 mL of the milk sample as the salting out agent and extraction solvent, respectively. After manual shaking, the mixture was centrifuged. In the presence of NaCl, a two-phase system was formed: upper phase - acetonitrile containing phthalate esters -and lower phase - aqueous phase containing soluble compounds and the precipitated proteins. After the extraction of phthalate esters from milk, a portion of supernatant phase (acetonitrile) was removed, mixed with 1,2-dibromoethane at microliter level and injected by syringe into NaCl solution. After the extraction of the selected phthalate esters into 1,2-dibromoethane, phase separation was performed by centrifugation and the enriched analytes in the sedimented phase were determined by gas chromatography-flame ionization detection and gas chromatography-mass spectrometry. Under the optimum extraction conditions, low limits of detection and quantification between 1.5-3 and 2.5-11 ng/mL, respectively was observed. Enrichment factors were in the range of 397-499. The relative standard deviations for the extraction of 100 ng/mL of each phthalate ester were in the range of 3-4% (n = 6). Finally, some milk samples were successfully analyzed using the proposed method and two analytes, di-n-butyl phthalate and di-2-ethylhyxel phthalate, were determined in them in nanogram per milliliter level.     

Analytical method for urinary metabolites as biomarkers for monitoring exposure to phthalates by gas chromatography/mass spectrometry

Phthalates, widely used as plasticizers, have been detected in indoor air, but there have been few reports on methods of analyzing urinary metabolites as biomarkers to monitor exposure to di‐n ‐pentyl phthalate or di‐n ‐hexyl phthalate. Presented here is a cost‐effective and sensitive analytical method for the determination of urinary metabolites of phthalates containing these two compounds. Nine urinary phthalate metabolites were enzymatically hydrolyzed and extracted with toluene: monomethyl phthalate, monoethyl phthalate, monoisobutyl phthalate, mono‐n‐ butyl phthalate, mono‐n‐ pentyl phthalate, mono‐n‐ hexyl phthalate, monocyclohexyl phthalate, monobenzyl phthalate and mono(2‐ethyl‐5‐carboxypentyl) phthalate. After transformation to their tert‐ butyldimethylsilyl derivatives, they were analyzed by gas chromatography/mass spectrometry in the electron impact ionization mode. The calibration curves for the metabolites were linear at urinary concentrations of up to 30 μg/L, showing that they could be determined accurately and precisely (detection limits 0.1–0.4 μg/L, quantification limits 0.3–1.3 μg/L). The urine samples collected could be stored for up to 1 month at −20°C. The proposed analytical method was used to examine urine samples from seven healthy volunteers. This method should be useful for monitoring phthalate exposure in the general population.     

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 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.