反相液相色谱法测定膏状香精中邻苯二甲酸酯类

采用反相液相色谱法研究了膏状香精中邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二正丁基酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)4种邻苯二甲酸酯的萃取条件。利用正交实验对影响萃取总量的3个主要因素(正己烷用量、超声时间、水浴温度)进行了优化,确定了萃取的最佳条件:正己烷用量10mL,超声时间25min,水浴温度15℃。结果表明,该分析条件下,样品猪骨膏、牛肉膏的加标回收率为90%~94%。用乙腈-水等梯度洗脱(75∶25),4种PAEs分离较好,在0.5~20mg/L之间,色谱峰面积与4种邻苯二甲酸酯的浓度呈现良好的线性关系。     

食品塑料包装材料中邻苯二甲酸酯类物质的检测

采用固相萃取-气相色谱法测定9种不同食品塑料包装材料中的6种邻苯二甲酸酯[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-乙基己基)酯(DEHP)、邻苯二甲酸二正辛酯(DNOP)]的含量。结果表明,回收率介于83.2%~106.9%区间,相对标准偏差(RSD)介于1.6%~6.2%区间。9种抽检的食品塑料包装材料中全部检出了邻苯二甲酸酯(PAEs),其中DBP存在于所有抽检样品中,且66.67%的样品中含有DEHP,检出的邻苯二甲酸酯类物质的含量均高于欧洲规定的每天0.3 mg/kg体重的标准。     

食品中邻苯二甲酸酯类增塑剂含量的测定

采用气相色谱法测定14种食品中5种邻苯二甲酸酯[邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二乙酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二正辛酯(DnOP)]的含量.样品经正己烷溶解、超声波辅助提取、固相萃取浓缩富集等预处理,以保留时间定性,外标法定量.结果表明,该分析条件下样品的回收率为72.3%～101.5%,相对标准偏差为2.69%～5.84%,说明本方法准确可靠.14种食品中检出的邻苯二甲酸酯类约69%的含量高于欧洲规定的每天0.3 mg/kg体重的标准,表明邻苯二甲酸酯类污染物在被检食品中有较大的的迁移.     

固相萃取- 气相色谱法测定食品包装材料中邻苯二甲酸酯类物质

建立采用固相萃取-气相色谱法同时分析检测邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二环己酯(DCHP)、邻苯二甲酸丁基苄基酯(BBP)和邻苯二甲酸二-2-乙基己酯(DEHP)4种邻苯二甲酸酯类物质的方法。研究塑料包装材料中邻苯二甲酸酯类在水、65%乙醇、4%乙酸、正己烷4种模拟液中的溶出及利用固相萃取技术对浸出液进行富集的情况,考察气相色谱操作条件对4种邻苯二甲酸酯类物质分离的影响。结果表明,该方法具有良好的线性相关性,线性相关系数在0.9986～0.9994之间;回收率在80.63%～95.50%之间;DBP、BBP、DCHP和DEHP的检测限分别是0.050、0.010、0.055μg/mL和0.012μg/mL。该方法样品预处理简便,测定方法灵敏、可靠,可用于食品包装材料中邻苯二甲酸酯类的监测。     

烟台市市售白酒中16种邻苯二甲酸酯类物质污染调查

目的了解烟台市市售白酒中邻苯二甲酸酯类物质的污染水平,为强化监督和监管提供依据,保障消费者的食用安全。方法按照《2013年国家食品污染和有害因素风险工作手册》中的食品中邻苯二甲酸酯类化合物检测的操作程序,并根据GB/T 21911—2008《食品中邻苯二甲酸酯的测定》中规定的16种酸酯类化合物测定方法进行检测,本课题组对烟台市市售的35份白酒样品进行了邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二异辛酯(DEHP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二戊酯(DPP)等16种邻苯二甲酸酯类物质的检测。结果邻苯二甲酸二异壬酯(DINP)检测限为0.10 mg/kg,其余15种邻苯二甲酸酯类物质均为0.05 mg/kg,65.71%的样品中检出DIBP和DBP,其中DBP最大值为2.14 mg/kg,DMP、DEHP、DEP、DPP的检出率分别为25%、20%、8.5%、2.85%。DIBP、DBP、DEHP、DEP、DMP、DPP检出均值分别为0.404、0.396、0.216、0.206、0.104、0.0546 mg/kg,其余10种均未检出。结论白酒中普遍存在增塑剂的污染,可能是由包装材料迁移到产品中,需要加大监测和监管力度,降低消费者的健康风险。     

湖北地区市售白酒中邻苯二甲酸酯类物质的监测结果及分析

目的对湖北地区市售白酒中邻苯二甲酸脂类物质的污染水平进行分析。方法按照《国家食品污染和有害因素风险工作手册》对湖北地区9个地市销售的89份白酒样品中的邻苯二甲酸二丁酯(dibutyl phthalate,DBP)、邻苯二甲酸二(2-乙基)己酯(di 2-ethyl hexyl phthalate,DEHP)、邻苯二甲酸二异壬酯(diisononyl phthalate,DINP)等17种邻苯二甲酸酯类化合物进行监控和风险评估。结果检测的89份白酒样品中,DBP超标率为29.2%;最高浓度高达23.48 mg/kg,超出国家标准限量值(0.3 mg/kg)78倍,DEHP的浓度均未超过国家标准限量值(1.5 mg/kg),DINP均未检出,其余14种邻苯二甲酸酯类物质部分有检出。结论湖北省市售白酒中存在一定程度的邻苯二甲酸酯类物质污染,需引起重视并进行连续监测。     

2013年内蒙古地区市售植物油中3种邻苯二甲酸酯含量调查分析

目的 了解内蒙古地区市售植物油中邻苯二甲酸酯(phthalates esters, PAEs)类物质的污染情况,为加强食品安全监督管理提供依据。方法 2013年期间,在内蒙古地区各大型超市、农贸市场和食品商店等流通领域抽取不同品牌的桶装植物油共150份。采用固相萃取-气相色谱-质谱法(gas chromatography-mass spectrometry, GC-MS)测定了植物油样本中3种邻苯二甲酸酯类化合物(邻苯二甲酸二异壬酯(Dinonylphthalate,DINP、邻苯二甲酸二正丁酯(dibutyl phthalate, DBP)和邻苯二甲酸(2-乙基已基)酯(bis(2-ethylhexyl) phthalate,DEHP))的浓度。结果 在采集的150份样品中,共有46份样品检测出邻苯二甲酸酯类物质DBP与DEHP,总检出率为30.67%,其中,DBP和DEHP的检出率分别为18.67%和20.00%,最高检出浓度分别为46.50 mg/kg和0.85 mg/kg,DBP检出超标样品15份,超标率为10.00%; DINP在所有样本中没有检出。结论 在2013年期间,内蒙古地区市售植物油中3种PAEs的总体检出率不高,但是个别样本中DBP的检出值较高。邻苯二甲酸酯类属于环境激素类,被我国卫生行政部们列入可能违法添加的非食用物质和易滥用的食品添加剂名单,因此,应加强植物油生产过程的监管及食品包装材料对植物油的污染,定期开展监测工作。     

超低温冷冻除脂-气相色谱串联质谱法检测食用植物油中21种邻苯二甲酸酯

建立了超低温冷冻除脂-气相色谱串联质谱(GC-MS/MS)检测食用植物油中21种邻苯二甲酸酯(PAEs)的新方法。样品用乙腈提取,经超低温(-80℃)冷冻10 min除脂,再经减压浓缩,以正己烷复溶,采用GC-MS/MS多反应监测模式进行测定。结果表明,在考察浓度范围(1~1000 ng/mL)内21种PAEs均呈现良好线性,相关系数均大于0.999,检出限为0.10~8.52 μg/kg,定量限为0.32~28.40 μg/kg,加标回收率为74.31%~116.62%,相对标准偏差为1.21%~17.82%。对市售7类19个油样的抽样检测,显示邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二异丁酯(DIBP)、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(2-丁氧基)乙酯(DBEP)、邻苯二甲酸二正庚酯(DHP)、邻苯二甲酸二(2-乙基己)酯(DEHP)和邻苯二甲酸二正辛酯(DNOP)共9种PAEs被检出,其中DMP、DBP、DBEP、DHP和DEHP检出率均大于90%,含量范围为105.57~2156.76 μg/kg。该方法操作简便,成本低,可用于食用植物油中PAEs的有效测定。     

卷烟滤嘴中邻苯二甲酸酯的GC/MS测定

为了测定卷烟滤嘴中邻苯二甲酸酯( PAEs)的含量,考察了萃取方式、萃取溶剂、超声条件和检测条件对测定结果的影响,建立了同时测定卷烟滤嘴中17种PAEs的方法,并采用该方法检测了45个卷烟滤嘴中的PAEs.结果表明:①用水、乙醇和正己烷超声萃取30 min效果较好;②该法的回收率为87.0％～105.8％,RSD为2.6％～5.4％;③45个卷烟滤嘴样品中,有14个样品中检出PAEs,总检出率为31.11％.其中,4个样品中检出邻苯二甲酸二正丁酯,检出率8.88％;7个样品中检出邻苯二甲酸二异丁酯,检出率15.56％;8个样品中检出邻苯二甲酸二(2-乙基)已酯,检出率17.78％.该方法适用于卷烟滤嘴中PAEs的同时测定.     

食品塑料包装溶出酞酸酯DBP与DEHP的测定

采用毛细管气相色谱测定2种邻苯二甲酸酯类化合物[邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二异辛酯(DEHP)]。样品用正己烷浸泡,超声辅助提取,0.45μm滤膜过滤,进行气相色谱分析。气相色谱回收率为89.365%~117.875%,精密度RSD为0.26%~2.5%。结果表明,该方法简便、快速、灵敏,适用于食品塑料包装材料中邻苯二甲酸酯类增塑剂的测定。     

烟用水基胶中化学成分检测技术研究进展

按照目标待测物的不同,综述了烟用水基胶中的生产过程残留物、添加剂及重金属杂质等检测方法,并展望了烟用水基胶检测方法的发展方向。     

Determination of Phthalate Residues in Different Types of Yogurt by Gas Chromatography-Mass Spectrometry and Estimation of Yogurt-Related Intake of Phthalates

Phthalates are potential endocrine-disrupting chemicals, found widely in the environment, and commonly used to make plastics softer and more flexible. Little information is available about the presence of phthalates in yogurt products sold on the world market. This study aimed to develop a sensitive GC-MS method for the determination of selected phthalates in yogurt and residue levels in fruit yogurts together with the packaging materials and to estimate a yogurt-related exposure to phthalates in the Turkish population. Acetonitrile extraction followed by cleanup procedures using different adsorbents yielded relatively clean extracts. The presence as the percent of selected phthalates tested—dibutyl phthalate (DBP), diethylhexyl phthalate (DEHP), dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-octyl phthalate (DNOP), and benzyl butyl phthalate (BBP)—were determined as 76, 70, 70, 54, 20, and 8% of the samples, respectively, for the phthalates, ranging from <LOQ to 1640 μg/kg. The highest concentrations were found in cherry yogurt among the fruit yogurts, while banana and pineapple yogurts contained the least. The results indicate that the estimated daily intakes for phthalates were below tolerable daily intakes.     

Development and application of a method for analysis of phthalates in ham sausages by solid-phase extraction and gas chromatography–mass spectrometry

A gas chromatography-mass spectrometry assay was developed and successfully applied for the determination of phthalates in ham sausage migrated from packaging film. The phthalates studied were dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), benzylbutyl phthalate (BBP), bis(2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DNOP) , with dibutyl adipate (DBA) as internal standard. The sample pre-treatments included extraction with n-hexane, solvent evaporation and reconstitution with acetonitrile before and after solid-phase extraction (SPE). The extraction and cleaning up procedure was carried out with cartridges containing dimethyl butylamine groups, which showed extraction efficiencies over 87.3%. The calibration curves obtained were linear with correlation coefficients greater than 0.99. The method proved to be accurate and precise for the six phthalates used. It was successfully applied to a study on the migration of phthalates from packaging PVC film into ham sausage.     

2018年广东省酒类中三种邻苯二甲酸酯类的污染状况调查

目的 调查广东省酒类中邻苯二甲酸酯类塑化剂的污染状况。方法 采用随机采样的方法, 抽取2018 年在广东省内生产环节、流通环节和餐饮环节的酒样样本577份。采用气相色谱-质谱联用法对常见的邻苯二甲酸二(2-乙基己)酯、邻苯二甲酸二正丁酯、邻苯二甲酸二异壬酯进行监测。结果 广东省酒样中邻苯二甲酸酯类总超标率为4.68% (27/577)。生产环节、流通环节和餐饮环节的超标率分别为4.50% (15/333)、5.02% (11/219)和4.00% (1/25)。3种邻苯二甲酸酯类中邻苯二甲酸二正丁酯污染情况较多。结论 广东省酒类中在一定程度上存在邻苯二甲酸酯类污染, 应继续加强监督管理, 保障食品安全。     

Phthalate Esters in Foods: Sources,Occurrence, and Analytical Methods

ABSTRACT: Phthalates are a group of diesters of ortho‐phthalic acid (dialkyl or alkyl aryl esters of 1,2‐benzenedicarboxylic acid). Higher‐molecular‐weight phthalates, such as di‐2‐ethylhexyl phthalate (DEHP), are primarily used as plasticizers to soften polyvinyl chloride (PVC) products, while the lower‐molecular‐weight phthalates, such as diethyl phthalate (DEP), di‐n‐butyl phthalate (DBP), and butyl benzyl phthalate (BBzP), are widely used as solvents to hold color and scent in various consumer and personal care products. Phthalates have become ubiquitous environmental contaminants due to volatilization and leaching from their widespread applications, and thus contamination of the environment has become another important source for phthalates in foods in addition to migration from packaging materials. Human exposure to phthalates has been an increased concern due to the findings from toxicology studies in animals. DEHP, one of the important and widely used phthalates, is a rodent liver carcinogen. DEHP, DBP, BBzP, and several phthalate metabolites, such as monobutyl phthalate, monobenzyl phthalate, and mono‐(2‐ethylhexyl) phthalate, are teratogenic in animals. Since foods are the major source of exposure to phthalates, information on levels of phthalates in foods is important for human exposure assessment. The objective of this review is to identify the knowledge gaps for future investigations by reviewing levels of a wide range of phthalates in a variety of foods, such as bottled water, soft drinks, infant formula, human milk, total diet foods, and others, migration of phthalates from various food‐packaging materials, and traditional and new methodologies for the determination of phthalates in foods.     

Migration analysis and health impact assessment of phthalates in takeaway food packaging materials

Plasticizers are commonly utilized as packaging additives in the food service industry. The takeaway food sector provides convenience to consumers, but also raises the risk of human exposure to plasticizers. The goal of this study is to determine the amount of phthalates in takeaway food packaging and compare the migration amounts under various situations. A comprehensive health impact assessment of phthalates was conducted to provide the evaluation of human's daily exposure to phthalates. The results revealed that five phthalates (di (2-ethylhexyl) phthalate (DEHP), butyl benzyl phthalate (BBP), diethyl phthalate (DEP), dimethyl phthalate (DMP), dibutyl phthalate (DBP)) could be detected in n-hexane extract of plastic food packaging materials at room temperature. High amount of phthalates was correlated with high temperature or in an oily food simulant solvent. Phthalate contents in dietary exposure did not surpass the concentration that could represent a risk to human health, based on the dietary exposure evaluation.     

Occurrence and air-sea exchange of phthalates in the Arctic

Air and seawater samples were taken simultaneously to investigate the distribution and air-sea gas exchange of phthalates in the Arctic onboard the German Research Ship FS Polarstern. Samples were collected on expeditions ARK XX1&2 from the North Sea to the high Arctic (60 degrees N-85 degrees N) in the summer of 2004. The concentration of sigma6 phthalates (dimethyl phthalate (DMP), diethyl phthalate (DEP), di-i-butyl phthalate (DiBP), di-n-butyl phthalate (DnBP), butylbenzyl phthalate (BBP), and diethylhexyl phthalate (DEHP)) ranged from 30 to 5030 pg L(-1) in the aqueous dissolved phase and from 1110 to 3090 pg m(-3) in the atmospheric gas phase. A decreasing latitudinal trend was present in the seawater and to a lesser degree in the atmosphere from the Norwegian coast to the high Arctic. Overall, deposition dominated the air-sea gas exchange for DEHP, while volatilization from seawater took place in the near-coast environment. The estimated net gas deposition of DEHP was 5, 30, and 190 t year(-1) for the Norwegian Sea, the Greenland Sea, and the Arctic, respectively. This suggests that atmospheric transport and deposition of phthalates is a significant process for their occurrence in the remote Atlantic and Arctic Ocean.     

Quantification of Six Phthalates and One Adipate in Luxembourgish Beer Using HS-SPME-GC/MS

A simple, low-cost and sensitive method for the determination of six phthalate acid esters (dimethyl phthalate, diethyl phthalate, dibutyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate and dioctyl phthalate) and one adipate (bis(2-ethylhexyl) adipate) in beer has been developed using head-space solid-phase microextraction (HS-SPME) followed by gas chromatography coupled to mass spectrometry (GC/MS). SPME conditions were optimised, and optimum extraction parameters were found to be 95 °C at 100 min, without addition of NaCl. Matrix interference was avoided by using a deuterated internal standard (ISTD). Limits of detection ranged from 0.006 to 0.590 μg/L. The method showed good linearity with coefficients of determination ranging from 0.963 to 0.999 and satisfactory accuracy (74–101 %) and repeatability (3.56–27.86 %) values. The method was applied to 15 samples of beer from Luxembourgish breweries, stored in different containers (can, glass and aluminium bottle), and phthalates were detected in all samples with concentrations as high as 61.56 μg/L for total phthalates. The exact origins of phthalates in beer were difficult to determine from the data in this study, though the brewing and bottling process seems to be a major contributor.     

Survey of plasticizers in polyvinyl chloride toys

Plasticizers in 101 samples of polyvinyl chloride (PVC) toys on the Japanese market were surveyed. No phthalates were detected in designated toys, though bis(2-ethylhexyl)phthalate, diisononyl phthalate, diisobutyl phthalate, dibutyl phthalate, diisodecyl phthalate and benzyl butyl phthalate were detected in more than half of other toys. 2,2,4-Tributyl-1,3-pentanediol diisobutylate, o-acetyl tributyl citrate, adipates and diacetyl lauroyl glycerol, which are alternative plasticizers to phthalates, were detected. The results of structural analysis confirmed the presence of di(2-ethylhexyl)terephthalate, tributyl citrate, diisononyl 1,2-cyclohexanedicarboxylate and neopentyl glycol esters; these have not previonsly been reported in Japan. There appears to be a shift in plasticizers used for designated toys from phthalates to new plasticizers, and the number of different plasticizers is increasing.     

Contents of eleven phthalates and di(2-ethylhexyl) adipate in retail packed lunches after prohibition of DEHP-containing PVC gloves for cooking purposes

Ten samples of retail packed lunches purchased from convenience stores were determined for 11 phthalates and di(2-ethylhexyl) adipate (DEHA) in August 2000, 2 months after the prohibition of DEHP-containing PVC gloves in Japan. Each homogenized sample was extracted with acetonitrile, partitioned with n-hexane, and cleaned up using Florisil and PSA columns. Phthalates in the extract were determined by GC/MS (SIM). The limits of detection were 14.9 ng/g for di(2-ethylhexyl) phthalate (DEHP) and 18.6 ng/g for dibutyl phthalate (DBP). Levels of phthalates in packed lunch samples were 45 to 517 ng DEHP/g (198 ng/g, average), ND to 90 ng DEHA/g, and ND to 10.0 ng BBP/g. Diisononyl phthalate (DINP) was detected in one sample at 76 ng/g. Average DEHP level in ten samples was 4% of that in 1999. The contents of other phthalates were also reduced. DBP was not detected in any sample. Recovery of deuterated isomers added as surrogates was 27.9% for DNP-d4, and 40.6 to 101.5% for the other phthalates.