塑化剂处理机问世

本刊讯:塑化剂在国际塑料制品中普遍存在,塑化剂有毒,在国际食品行业中有限制标准,但在酒类行业中还没有标准。塑化剂含量不高,不会影响人体健康,但是含量过高,则会对人体造成危害。塑化剂主要有三种:邻苯二甲酸二(2-乙基)己酯(DEHP)、邻苯二甲酸二异丁酯(DIBP)和邻苯二甲酸二丁酯(DBP)。邻苯二甲酸二丁酯在塑化剂总量中     

高效液相色谱法测定白酒中的邻苯二甲酸酯

建立一种基于高效液相色谱法(HPLC)邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二戊酯(DPP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二烯丙酯(DAP)进行检测分析。以C18反相柱为分析柱,采用UV检测器对比了两种不同流动相的洗脱效果,最后选择乙腈—超纯水为流动相进行梯度洗脱,检测6种邻苯二甲酸酯类塑化剂在1~20 mg/L范围内有着良好的线性范围(R20.999 0)。在3个添加水平下,6种塑化剂的回收率在85.57%~109.90%,相对标准偏差小于5%。此方法的检出限范围为0.179~0.425 mg/L,该方法灵敏、方便且稳定,可用于食品中邻苯二甲酸酯类塑化剂的快速检测。     

食用植物油中邻苯二甲酸酯类塑化剂的分析

本文采用随机抽样的方法,抽取120份市售食用植物油样品,采用气相色谱-质谱法检测了3种邻苯二甲酸酯类塑化剂的浓度,并进行危害性评估。结果表明,120份样品中,邻苯二甲酸二丁酯(DBP)的检出率为10.8%,最高检出浓度为33.12%。邻苯二甲酸二(2-乙基)己酯(DEHP)和邻苯二甲酸二异壬酯(DINP)未检出。对当前市售食用植物油中邻苯二甲酸酯类(PAEs)塑化剂的含量进行监测,有助于了解市售食用植物油中塑化剂的污染状况,为食用植物油的安全监管提供理论依据。     

微波萃取-气相色谱-质谱法测定塑料包装材料 中的DEHP

基于气相色谱-质谱法(GC-MS)建立了检测塑料包装材料中邻苯二甲酸二(2-乙基己)酯(DEHP)的含量分析方法。比较了水浴振荡提取法、超声提取法、索氏提取法和微波辅助萃取法,试验结果表明微波辅助萃取法萃取效率最好。在选定的最优试验条件下,待测样品中邻苯二甲酸二(2-乙基己)酯加标回收率在88.9%～98.4%之间,相对标准偏差小于3.2%。该方法具有测试结果准确度高,适用于塑料包装食品中邻苯二甲酸二(2-乙基己)酯含量的分析测试。     

GC-MS/MS法测定不同香型白酒中邻苯二甲酸酯类的含量分析

采用气相色谱-三重四极杆串联质谱法（GC-MS/MS）建立了邻苯二甲酸酯（PAEs）的检测方法,并对12种不同香型白酒中的18种PAEs塑化剂的含量进行了测定。结果表明,18种PAEs的分离效果良好,检出限为0.001～0.428 mg/kg,定量限为0.003～1.426 mg/kg。邻苯二甲酸二异壬酯（DINP）的线性范围为0.403～20.150 μg/mL,其余17种PAEs的线性范围为0.020～1.106 μg/mL,相关系数（R2）均＞0.999,精密度试验结果相对标准偏差（RSD）均＜10%,回收率为82.99%～115.25%;白酒样品检出塑化剂的种类主要为邻苯二甲酸二异丁酯（DIBP）、邻苯二甲酸二正丁酯（DBP）及邻苯二甲酸二（2-乙基）己酯（DEHP）,含量分别在0.18～1.53 mg/kg、0.27～1.36 mg/kg、0.18～1.86 mg/kg,其中兼香型白酒样品的DBP含量为1.36 mg/kg,超出国标规定限值。在凤香型白酒样品和馥郁香型白酒样品中检出邻苯二甲酸二甲酯（DMP）,含量分别为0.53 mg/kg、0.45 mg/kg,在药香型白酒样品中检出邻苯二甲酸二正辛酯（DNOP）,含量为1.42 mg/kg,其余均未检出。     

气液微萃取技术联用气相色谱-质谱法快速检测包装食品中15种邻苯二甲酸酯

目的建立气液微萃取技术(gas liquid microextraction,GLME)联用气相色谱-质谱法(gas chromatography-mass spectrometry,GC-MS)快速检测包装食品中15种邻苯二甲酸酯(phthalic acid esters,PAEs)的方法。方法称取0.1 g样品放入GLME中进行萃取、净化、浓缩,加入20 ng仪器内标,定容至100μL,利用GC-MS对5种包装食品中15种PAEs的浓度进行检测。结果样品中检测出邻苯二甲酸二异丁酯(diisobutyl phthalate,DIBP)、邻苯二甲酸二丁酯(dibutyl phthalate,DBP)、邻苯二甲酸二甲氧基乙酯(dimethoxyethyl phthalate,DMEP)、邻苯二甲酸二(2-丁氧基)乙酯(bis(2-butoxyethyl)phthalate,DBEP)、邻苯二甲酸二环己酯(dicyclohexyl phthalate,DCHP)、邻苯二甲酸二(2-乙基)己酯(dioctyl phthalate,DEHP)等6种塑化剂,其中DIBP、DBP、DMEP、DCHP、DEHP等5种塑化剂的检测率达到100%。该方法可以在5 min内完成萃取、净化、浓缩等步骤,回收率为55.2%~121.9%和相对标准偏差(relative standard deviation,RSD)小于20.0%。结论本方法实现了对于包装食品中塑化剂的快速检测,为以后的现场检测塑化剂打下了坚实的基础。     

烟台市成品及散装食用油中塑化剂含量的调查

目的了解烟台市售成品及散装食用油中塑化剂的迁移情况。方法样品前处理依据GB/T21911-2008,乙酸乙酯:环己烷(1:1,V:V)提取,凝胶渗透色谱装置净化,三重串联四级杆气质联用仪进行定性及定量分析。结果成品油中塑化剂有少量检出,而散装油的检出率很高,主要为邻苯二甲酸二(2-乙基)己酯(DEHP)70%、邻苯二甲酸二丁酯(DBP)60%、邻苯二甲酸二异丁酯(DIBP)45%和邻苯二甲酸二异壬酯(DINP)20%,超标率为DEHP 35.7%,DBP 58.3%。结论市民在购买食用油时应尽量购买成品油,购买散装的食用油时尽量不要使用非食品级的塑料桶盛放。     

气质联用法测定市售白酒中18种邻苯二甲酸酯类塑化剂含量

为了进一步了解市售白酒中邻苯二甲酸酯类塑化剂的污染水平,本文随机抽检了市售的33件白酒样品,采用气质联用法(GC-MS)检测了常见的18种邻苯二甲酸酯类塑化剂的含量。结果表明,邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二戊酯(DPP)、邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基)己酯(DEHP)均有不同程度的检出,其检出率分别为30.3%、18.2%、84.8%和45.4%。DBP的检出含量分布在1.00～5.60 mg/kg之间,DEHP的含量在2 mg/kg左右。本方法中DINP的检出限为9.0 mg/kg,其余17种塑化剂的检出限为0.5 mg/kg,方法的加标回收率为85.6%～110%。因此,市场上在售的白酒中仍然存在塑化剂的污染风险,可能原因是由于其在生产或储存过程中迁移到白酒中。本研究可为食品中有害因子的风险监测提供参考。     

AB SCIEX针对白酒中塑化剂的最新检测解决方案

近日来,媒体报道某白酒公司生产的产品中共检测出3种塑化剂成分,分别为邻苯二甲酸二(2-乙基)己酯(DEHP)、邻苯二甲酸二异丁酯(DIBP)和邻苯二甲酸二丁酯(DBP),引发公众广泛关注。在此之前,卫生部规定食品中部分塑化剂限量,如DBP残留不超过0.3mg/kg,因此白酒中塑化剂的分析成为食品安全实验室的高度关注项目。目前,国家标准委员会现已发布标准《GB/T21 911-2008食品中邻苯二甲酸酯的测定》,使用气相质谱仪标准用于分析食品中塑化剂。但是考虑到气质方法中样品处理后     

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.     

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.     

气相色谱-串联质谱法测定涂布纸中邻苯二甲酸酯类增塑剂

以丙酮为萃取溶剂,采用微波辅助萃取技术提取涂布纸中的邻苯二甲酸酯类增塑剂,提取产物进行气相色谱-串联质谱法（GC-MS）测定,从而建立了一种同时测定涂布纸中多种邻苯二甲酸酯类增塑剂的快速检测方法。该方法的精密度（RSD）均小于14%,加标平均回收率为83.6%～104.1%。在信噪比为10（S/N=10）的条件下,DINP、DIDP和DMPP的定量下限分别为0.2、0.2、0.1 mg/kg,其余各组分的定量下限均小于0.05 mg/kg。采用该方法对市售涂布纸进行测定,结果在部分涂布纸中检出多种邻苯二甲酸酯类增塑剂。     

同位素稀释三重串联四级杆质谱法测定饮用水中4种增塑剂

目的建立同位素稀释-气相色谱-三重四级杆质谱法同时测定饮用水中3种邻苯二甲酸酯和己二酸二(2乙基己基)酯的方法。方法样品采用正己烷提取后,气相色谱三重四极杆质谱检测,内标法定量。结果方法具有良好线性,相关系数R均大于0.998,定量限为0.1~0.5 g/L。各组分平均回收率为92.3%~105.3%,相对标准偏差为0.4%~5.5%。实际样品中3种增塑剂有检出。结论该方法操作简单,准确度和灵敏度高,重现性好,可作为生活饮用水中增塑剂含量检测的确证方法。     

GC/MS Method for the Determination of Adipate Plasticizers in Ham Sausage and Its Application to Kinetic and Penetration Studies

ABSTRACT:  A GC/MS method was developed and successfully validated for the determination of adipate plasticizers in ham sausage migrated from polyvinylidene chloride (PVDC) packaging film. The sample pretreatment includes liquid extraction, solvent evaporation, and reconstitution before and after solid phase extraction (SPE). For the 5 adipate plasticizers studied, the SPE process with Oasis MAX cartridge showed an extraction efficiency from 85.7% to 106%, and the calibration curves are all linear in the range of 5 to 1000 ng/g with correlation coefficients greater than 0.998. The method proved to be accurate and precise; the average intraday recovery ranges from 85.4% to 114.6% with a %CV value from 2.5 to 11.3, and the average interday recovery from 83.6% to 118.5% with a %CV value from 2.8 to 15.6, respectively, for the adipate plasticizers. The method is sensitive and was effectively applied in the kinetic and penetration studies of the adipate plasticizers migrating from food-grade PVDC packaging film into ham sausage. The experimental data showed that approximately 6.8% of dibutyl adipate (DBA) in the packaging film migrated into the ham sausage in 4 mo and the migration reached the innermost portion of the sausage in 6 mo.     

Comparison of different methods for total lipid quantification in meat and meat products

This study was aimed to evaluate the efficiency of six extraction methods for the quantification of total lipid content in meat and meat products: standard Soxhlet method (with and without previous acid hydrolysis), continuous Soxhlet method (with and without previous acid hydrolysis), and those methods based in the use of a mixture of chloroform and methanol, and described by Folch, Less, and Sloane (1957) and Bligh and Dyer (1959). Lipid content was determined in nine different meat products with different fat contents and physico-chemical features: cooked turkey breast, fresh pork loin, cooked ham, dry-cured ham, mortadella, beef burger, fresh sausage, dry-cured sausage and salami. The most effective methods for determining fat content in the studied meat products were the method described by Folch et al. (1957) and the Soxhlet with previous acid hydrolysis method. The Soxhlet method without previous acid hydrolysis adequately extracted lipids only in those meat products with very high fat content. The use of the method described by Bligh and Dyer (1959) gave rise to the lowest lipid contents in all the studied meat products.     

采用超声辅助-固相萃取气相色谱串联质谱法测定废棉中的增塑剂

为开发废棉中增塑剂的高效定量分析方法,建立了超声辅助-固相萃取气相色谱串联质谱的方法,用于对废棉中18种邻苯二甲酸酯和5种己二酸酯类增塑剂的定性及定量分析。以正己烷-二氯甲烷(体积比为4∶1)作为提取剂,提取液经Alumina-N固相萃取柱纯化,采用选择离子扫描模式,用外标法进行定量。结果表明:20种增塑剂在1~20 μg/mL,邻苯二甲酸二异庚酯、邻苯二甲酸二异壬酯、邻苯二甲酸二异癸酯在5~100 μg/mL的质量浓度范围内均呈现出良好的线性关系,检出限为0.084~1.748 μg/g,定量限为0.336~6.992 μg/g;在5、10和20 μg/mL加标水平下,23种增塑剂的回收率为83.3%~104.3%,日内及日间的相对标准偏差分别为1.9%~8.1%和1.6%~8.7%,满足检测要求。该方法操作简单、干扰小,可检测出废棉中邻苯二甲酸酯和己二酸酯类增塑剂的微量残留。     

液-液微萃取结合气质联用法测定白酒中15种塑化剂含量

为考察白酒中塑化剂含量,采用表面活性剂强化乳化液-液微萃取结合气相色谱-质谱联用法测定32份不同白酒中15种邻苯二甲酸酯类塑化剂的含量。结果表明,该方法在0.008～5.00 μg/mL范围内呈良好线性关系,15种塑化剂的最低检出限在1.44～1.50 μg/L范围内,加标回收率在89.71%～117.73%之间,回收率试验结果相对标准偏差（RSD）范围为1.71%～6.82%,精密度试验结果RSD均＜2.53%,重复性试验结果RSD均＜3.60%,精密度、重复性良好,准确度高。在32份不同香型白酒样品中,9种塑化剂的检出率均＞70%,其中邻苯二甲酸二乙酯的检出率100%,检出值范围为0.001～0.740 μg/mL。主成分分析（PCA）结果表明,塑化剂含量与白酒香型相关性不显著（P＞0.05）,相关性分析结果表明塑化剂含量之间存在极显著相关性（P＜0.01）。     

Estimated daily intake of plasticizers in 1-week duplicate diet samples following regulation of DEHP-containing PVC gloves in Japan

Duplicate hospital diet samples obtained over 1 week in 2001 were analysed to estimate the daily intake of plasticizers and the results were compared with those obtained in 1999. The plasticizers quantified in this study were: dibutyl phthalate, butylbenzyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP), di(2-ethylhexyl) adipate (DEHA), diisononyl adipate (DINA) and O-acetyl tributyl citrate (ATBC). Dipropyl, dipentyl, dihexyl and dicyclohexyl phthalate were also analysed but not detected. The analytical procedure for this follow-up study was essentially the same as in the previous one. Detection limits were 0.1-15.6 ng g^-1 for each plasticizer. One-week duplicate diet samples provided by three hospitals in three remote prefectures of Japan were analysed as individual meals. DEHP was detected at 6-675 ng g^-1 in 62 of 63 meals, significantly lower levels compared with those detected in 1999. Levels of DEHA and DINP also decreased. The mean intake of plasticizers estimated from all samples was 160 μg DEHP day^-1, 12.5 μg DEHA day^-1, 4.7 μg DINP day^-1 and 3.4 μg BBP day^-1. Levels of DINA were relatively high in meals from one hospital: in those meals, the average daily intake was 1338 μg day^-1. Those of ATBC were also higher in meals from another hospital: the average daily intake was 1228 μg day^-1. The sources of DINA and ATBC can be cling-film or sausage packaging.     

Determination of phthalate esters in non-alcoholic beverages by GC–MS and optimization of the extraction conditions

A quantificational method for 7 phthalate esters in non-alcoholic beverages was developed. Dimethyl phthalate, di-ethyl phthalate, di-propyl phthalate (DPP), di-butyl phthalate (DBP), benzyl butyl phthalate, di-(2-ethylhexyl) phthalate (DEHP), and di-octyl phthalate (DOP) were extracted from non-alcoholic beverages with the optimized solid-phase extraction method, and quantification was achieved by gas chromatography–mass spectrometry with isotope internal standard of d₄-di-(2-ethylhexyl) phthalate (DEHP-d₄). The inter-day method repeatability (RSD) was 8–13 %, whereas the intra-day method repeatability (RSD) was 9–15 %. The mean spiking recoveries were 84–105 %. A wide variety of phthalate concentrations was observed in 48 non-alcoholic beverages. DEHP was the most abundant phthalate compound followed by DBP, DPP, and DOP. DEHP was found in sport drinks (0.015–0.098 mg L^?1), tea (0.016–0.123 mg L^?1), coffee (0.028–0.159 mg L^?1), and fruit juices (0.022–0.126 mg L^?1).