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.     

Levels of phthalates and adipates in processed foods and migration of di-isononyl adipate from polyvinyl chloride film into foods

The levels of dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEPHP), di-isononyl phthalate (DINP), di-(2-ethylhexyl) adipate (DEHA) and di-isononyl adipate (DINA) were determined in 50 processed foods (ham and sausage, fried dumpling and shao-mai, fish paste products, croquette and fried fish, bread, noodle, pickles, etc.). DBP, BBP, DEHP, DINP, DEHA, and DINA were contained at nd approximately 47.7, nd approximately 16.6, nd approximately 749, nd approximately 358, nd approximately 57.2 and nd approximately 20,200 ppb, respectively. High-level contamination of DINA was found in fish paste products, croquette and shao-mai, presumably because of migration from plasticized wrapping film using for food packaging. We studied the relationship between DINA migration from wrapped PVC film into fried croquette and its standing time after frying. When the croquette was wrapped immediately after frying, the migration from wrapping film into the croquette was highest (36,400 ng/g). On wrapping after standing for 5 min and 30 min, the migration level was reduced to 1/3.5 and 1/14 of the highest level, respectively.     

方便面和方便米线中酞酸酯的污染现状研究

目的：了解方便面和方便米线中酞酸酯(PAEs)的污染状况。方法：样品用无水甲醇超声提取,上清液经干燥脱水过0.45μm滤膜过滤,采用毛细管气相色谱技术分析。结果：在采集的56袋市售方便面、25袋方便米线中检测到的邻苯二甲酸二丁酯和邻苯二甲酸二(2-乙基己基)酯的含量分别为：方便面调味酱料：未检出～59.38mg/kg、未检出～172.15mg/kg;方便面面饼：未检出～9.28mg/kg、未检出～1.08mg/kg;方便米线调味酱料：未检出～16.52mg/kg、未检出～44.75mg/kg。结论：方便面和方便米线食品存在不同程度的PAEs污染。     

PVC薄膜中邻苯二甲酸二乙基己酯对食品迁移的研究

邻苯二甲酸二乙基己酯(DEHP)作为增塑剂能改进聚合物的性能,特别是聚氯乙烯(PVC)一般添加该物质来生产薄膜。DEHP有害身体健康。当包装材料接触到食品时候,DEHP会通过迁移污染被包装物。研究了PVC塑料膜中增塑剂DEHP迁移到几种溶液。PVC塑料膜分别浸入100%正己烷、100%大豆色拉油、20%乙醇、10%食盐水、4%醋酸、蒸馏水中,在常温(25℃)下放2h、1d、2d、3d、4d、5d,溶液中DEHP浓度用高效液相检测。PVC薄膜分别浸入到100%正己烷、100%大豆在25、4、-18℃下放置1、2、3、4、5d。小包子蒸熟后马上用PVC塑料膜包装常温放置。猪肉用PVC塑料膜包装贮藏于4℃。西兰花和绿豆发芽后种植1周,通过覆盖地膜研究PVC塑料膜中DEHP迁移到植株中。研究结果显示:PVC塑料膜中DEHP最大迁移的溶液是100%正己烷,100%大豆色拉油、20%乙醇溶液中的迁移量也比较大,10%食盐水、4%醋酸、蒸馏水溶液中迁移量很少;DEHP对100%正己烷和100%大豆色拉油的迁移都是随温度上升而增加。PVC塑料膜中DEHP在30min内迁移到热的小包子已经很多。用PVC塑料膜包装猪肉在4℃下,...     

Contents of phthalate in polyvinyl chloride toys

The presence of plasticizers in PVC toys obtained in October 1998 was investigated. Diisononyl phthalate (DINP), di-2-ethylhexyl phthalate (DEHP), di-n-butyl phthalate (DBP), dinonyl phthalate (DNP), diheptyl phthalate (DHP), and di-2-ethylhexyl adipate (DEHA) were detected. The phthalates were found in all of the 68 samples. The principal phthalate found in toys was DINP, which was present in 48 of 68 samples. The DINP content ranged from 15 mg/g to 580 mg/g, and mean content was 308 mg/g. The highest content was found in a pacifier toy. DEHP was present in 20 of 68 samples and the content ranged from 2.0 mg/g to 380 mg/g. The mean content was 162 mg/g. It was found in 60% of domestic toys.     

PVC plasticizers/additives migrating from the gaskets of metal closures into oily food: Swiss market survey June 2005

Foods with at least a few percent of free oil packed in glass jars with metal closures were analyzed for migration of additives, primarily plasticizers, from the gasket of the lid. One hundred and fifty-eight samples were collected in June 2005, i.e., some 10 months after the problem of excessive migration into oily food was communicated to the industry. In a first step, the composition of the additives in the gaskets was determined. Then the compounds found in the lid were measured in the jar content. Sixty-four percent of the gaskets contained epoxidized soy bean oil (ESBO) as principal plasticizer, 22% a phthalate, and 6% substantial amounts of di(2-ethylhexyl) adipate (DEHA). Concentrations in the food reached 1,170 mg/kg for ESBO, 270 mg/kg for diisononyl phthalate (DINP), 740 mg/kg for diisodecyl phthalate (DIDP), 825 mg/kg for di(2-ethylhexyl) phthalate (DEHP), and 180 mg/kg for DEHA. Further, elevated concentrations of plasticizers not authorized by the EU were found: diisononyl-cyclohexane-1,2-dicarboxylate (DINCH), 2-ethylhexyl palmitate and stearate, as well as epoxidized linseed oil (ELO). The few samples complying with the European rules contained little or well emulsified oil; some others were probably of very recent production (beginning of shelf life). It is concluded that there was still no lid reliably complying with the European rules (EU and national legislation).     

A simple and reproducible testing method for dialkyl phthalate migration from polyvinyl chloride products into saliva simulant

We describe a method of mechanical agitation to determine rates of dialkyl phthalate migration from polyvinyl chloride (PVC) products into saliva simulant. The method consists of rotary shaking of a sample with 30 mL of saliva simulant (pH 7.0) at 35 degrees C in a 50 mL glass tube at 300 rpm for 15 min, then measuring the amount of dialkyl phthalate in the saliva simulant by HPLC with a UV detector. The migration rates of diisononyl phthalate (DINP), di-2-ethylhexyl phthalate (DEHP) and di-n-butyl phthalate (DBP) from PVC plates containing about 45% (w/w) plasticizer (molded in our laboratory) were identical. However, the migration rates from molded plates containing 13% (w/w) DBP were almost double those of DINP and DEHP at the same ratios. In addition, the amounts of DINP that migrated in vitro after rotary shaking for 15 min were equivalent to those in vivo determined in saliva from volunteers who chewed plates for 60 min. The migration rates of dialkyl phthalates from 11 commercially available toys ranged from 15.6 to 85.2 micrograms/cm2/h [relative standard deviation (RSD), 3 to 12%].     

食品塑料袋中DEHP气相色谱检测方法的建立

DEHP是塑料中常用的增塑剂之一,直接与内装高脂食品接触时,能够从塑料中迁移到内装食品中,造成内装食品的污染。DEHP对人体系统有不良影响,具有致畸、致癌的作用。本实验对各种材质(PVC、PE、PP、PS等)的食品塑料袋中DEHP的测定进行了较为系统的研究,采用气相色谱法,FID检测器,对DEHP进行测定。本方法检出限为3.38×10-3mg/kg,加标回收率为90.7%～105.1%,能够满足各种材质食品塑料袋中低浓度至高浓度DEHP含量测定的需要。     

Eleven phthalate esters and di(2-ethylhexyl) adipate in oneweek duplicate diet samples obtained from hospitals and their estimated daily intake

Plasticizers in duplicate diet samples obtained over 1 week were analysed in order to estimate daily intake. The phthalate esters were as follows: diethyl, dipropyl, dibutyl, dipentyl, dihexyl, butylbenzyl, dicyclohexyl, di(2-ethylhexyl), dioctyl, diisooctyl (mixture of isomers) and diisononyl (mixture). Di(2-ethylhexyl) adipate was also determined. Homogenized samples of composite meals were extracted with acetonitrile, lipids were removed by extraction into n-hexane and the acetonitrile layer was cleaned using FlorisilR and R Bondesil PSA dual layer column. Phthalates were determined by GC/MS (SIM). Phthalate recovery from the fortified food mixture by this method was 62.5-140.8%. Quality assurance as assessed by three laboratories indicated coefficient of variance in the levels of detected phthalates in same lot samples as below 10%. Detection limits were 0.1-23ng/g for each phthalate. One-week duplicate diet samples provided by three hospitals in three remote prefectures of Japan were analysed as individual meals. In all 63 samples, DEHP was present at the highest level among all phthalates in the range 10-4400ng/g. The intake of plasticizers estimated from all samples was 519 µ g DEHP/day, 86 µ g DEHA/day, 65 µ g DINP/day, and 4.7 µ g BBP/day. Calculated DEHP in 2-day samples out of 21 days exceeded EU TDI for a person of 50kg body weight (1850 µ g per day). Disposable PVC gloves used during the preparation of meals were suspected as the source of the high DEHP content. One-day intake of the other phthalates and DEHA was below 7% of TDI in all cases. High concentrations of DEHP (5990ng/g) was found in baby food used in quality assurance work. The source of contamination was the PVC-tube used during production and was effectively reduced by replacing the tube by one made of stainless steel.     

白酒中塑化剂GC-MS检测方法的研究

以邻苯二甲酸二丁酯（DBP）、邻苯二甲酸二（2-乙基）己酯（DEHP）、邻苯二甲酸二异壬酯（DINP）3种邻苯二甲酸酯类塑化剂为例,通过改进气相色谱-质谱法测定条件,研究得出适合白酒中塑化剂检测的方法。并采用不同包装的6个未知酒样进行方法应用测试,测试结果显示DBP含量高达2.03mg/kg,DEHP、DINP含量均在限量范围之内。     

Phthalates and food-contact materials: enforcing the 2008 European Union plastics legislation

The migration of phthalates into foodstuffs from food-contact materials (FCM) is a well-known source of food contamination. In 2005, the European Food Safety Authority finalized its risk assessment for several of the classical phthalate plasticizers. In their risk management procedure the European Commission transformed the tolerable daily intakes established by the Authority into legislative limits for phthalates in both plastic and food simulants, while taking exposure from other sources into consideration. These limits have been into force since 1 July 2008. A detailed interpretation of the regulation of these substances was agreed upon in the European network of FCM reference laboratories. This paper reports results from a Danish control campaign of samples collected by official food inspectors and analysed by a newly validated analytical method run under accreditation. Samples were from FCM producers, FCM importers and importers of packed foodstuffs from third-party countries. Products containing phthalates above the current limits were found in several categories of FCM: conveyor belts (six of six), lids from packed foodstuffs in glasses (eight of 28), tubes for liquid foodstuffs (four of five) and gloves (five of 14). More than 20% of the samples analysed contained dibutylphthalate (DBP) or di-(2-ethylhexyl)phthalate (DEHP) above the compositional limits of 0.05% and 0.1%, respectively. Analysis of residual phthalates in metal lid gaskets instead of analysis of phthalates in the food when controlling foodstuffs packed outside the European Union proved to be an efficient and simple control method. All findings of phthalates were associated with the use of plasticized polyvinylchloride (PVC).     

三峡库区调味油脂产品中邻苯二甲酸酯类塑化剂的含量测定和分析

目的采用气相色谱-三重四极杆串联质谱法(gas chromatography-triple quadrupole tandem mass spectrometry,GC-MS/MS)测定三峡库区调味油脂产品中的邻苯二甲酸二正丁酯(dibutyl phthalate,DBP)、邻苯二甲酸二(2-乙基)己酯[bis(2-ethylhexyl)phthalate,DEHP]2种塑化剂的含量,并对污染情况进行分析。方法样品采用乙腈提取,固相萃取(solid-phase extraction,SPE)玻璃小柱净化,氮吹近干后正己烷复溶,经气相色谱-三重四极杆串联质谱法测定。结果DBP、DEHP在一定浓度范围内线性关系良好,相关系数均大于0.998,检出限分别为0.05、0.10 mg/kg,定量限分别为0.17、0.33 mg/kg,平均加标回收率为82.79%~96.70%,相对标准偏差为0.59%~1.76%。在采集的32组调味油脂样品中,DBP的检出率高达68.75%,含量范围在0.15~517.00 mg/kg;DEHP检出率为28.12%,含量范围在0.57~125.00 mg/kg,超标率分别为62.50%和-18.75%。结论三峡库区调味油脂产品中存在一定程度的邻苯二甲酸酯类物质污染,可能与生产、环境等方面的迁移污染相关,需引起重视并进行连续监测。     

Migration of phthalates from soft PVC packaging into shower and bath gels and assessment of consumer risk

Phthalates are used as plasticizers in many commodities and materials. Therefore, they are found everywhere as contaminants in food and in environmental samples. Due to their potential for developmental and reproductive toxicity, some congeners pose a health risk for consumers and their use is legally restricted with bans and limits. This, however, applies only partly to their usage in cosmetics, toys and packaging materials. Phthalates used as plasticizers in cosmetic packaging could be a previously unknown source of exposure for consumers. In market surveys of the state laboratory of Basel-City, conspicuously high levels of di(2-ethylhexyl) phthalate (DEHP) and di-iso-nonyl phthalate (DINP) were found in shower and bath gels packed in soft PVC shaped as animals or fruits. The concentrations found ranged from 0.02 to 1.3%. It could be shown that concentrations increased significantly during storage. It can therefore be assumed that the phthalates found migrated from the packaging into the gels. The estimated exposure of adults and children to DEHP and DINP of 3.5 and 4.6 μg/kg bw/day, respectively, which may result when using the tested gels does not pose a health risk for the consumer (exposure value below TDI). Regarding the high background contamination levels with phthalates in other sources, exposure from cosmetics should be kept as low as possible. The establishment of limits for phthalates in cosmetics is discussed.     

Determination of phthalates in raw bovine milk by gas chromatography/time-of-flight mass spectrometry (GC/TOF-MS) and dietary intakes

Low levels of phthalates, including di(2-ethylhexyl) phthalate (DEHP), in raw bovine milk were determined using gas chromatography/time-of-flight mass spectrometry (GC/TOF-MS). A fast and convenient process of sample treatment combined with TOF-MS analysis (medium resolution >5000), yielded good recoveries (85–125%) and low limits of detection (<0.002 mg kg^?1). The most commonly used phthalate, DEHP, was found in 15 out of 30 samples monitored in this study. DEHP concentrations in raw milk ranged from not detected to 0.154 mg kg^?1, and the mean concentration was 0.057 mg kg^?1. The dietary intake of DEHP was about 0.004 mg kg^?1 body weight day^?1 if a child (24 months, 13 kg body weight) drinks 1 L day^?1 of milk that contains the mean concentration of DEHP found in raw milk. The estimated dietary intake corresponded to 8% of the European Union tolerable daily intake (TDI) of 0.05 mg kg^?1 body weight day^?1. Dimethyl phthalate (DMP) and di-n-butyl phthalate (DBP) were found from two and 20 samples, respectively, at low levels. Diethyl phthalate (DEP), butylbenzyl phthalate (BBP), and di-n-octyl phthalate (DnOP) were not found in any of the samples.     

河南植烟土壤6种邻苯二甲酸酯污染特征分析

[目的]探索邻苯二甲酸酯(PAEs)在河南植烟土壤中的污染状况.[方法]采集了7个县区203份耕层土壤样品,气相色谱质谱法分析了邻苯二甲酸二甲酯(DMP)、邻苯二甲酸正二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸丁基苄酯(BBP)和邻苯二甲酸正二辛酯(DnOP)等...     

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。     

基于尿苷二磷酸葡萄糖醛酸转移酶1解毒通路探讨枸杞汁对邻苯二甲酸二(2-乙基己基)酯代谢的干预作用

目的:通过大鼠毒性干预实验观察枸杞汁对邻苯二甲酸二(2-乙基己基)酯(di-(2-ethylhexyl)phthalate,DEHP)染毒大鼠肝脏中尿苷二磷酸葡萄糖醛酸转移酶1(uridine diphosphate glucuronosyltransferase 1,UGT1)活性及代谢解毒的影响,探讨枸杞汁对DEHP代谢的干预效果。方法:60只雄性大鼠随机分为对照组、DEHP组和枸杞汁干预组,每组20只,DEHP组和干预组在DEHP一次染毒(3 000 mg/kg mb)后连续7 d分别灌胃生理盐水和枸杞汁,对照组则给予同等体积的芝麻油或生理盐水,期间每天收集大鼠24 h尿液。在染毒1、3、5、7 d后各组分别随机处死5只。采用试剂盒检测肝脏UGT1的活力,高效液相色谱法检测血清中的邻苯二甲酸单(2-乙基己基)酯(mono-(2-ethylhexyl)phthalate,MEHP)以及尿液MEHP和邻苯二甲酸(phthalic acid,PA)含量。结果:枸杞汁干预组大鼠第5天UGT1活性显著高于DEHP组和对照组(P0.05),且相对于DEHP组血清中MEHP含量减少而尿液中MEHP和PA含量增加。结论:枸杞汁可能通过提高UGT1活力促进了DEHP的代谢与排泄,发挥了解毒效应,将来可能作为一种预防或对抗邻苯二甲酸酯类物质或其他有毒化学物潜在危害的保健药材或功能食品用于人群的健康防护。     

Reduced migration from flexible poly(vinyl chloride) of a plasticizer containing beta-cyclodextrin derivative

The migration of endocrine-disrupting di-(2-ethylhexyl) phthalate (DEHP) poses a serious threat to public health and the environment. In this study, we successfully prepared a plasticizerwith reduced DEHP migration by directly incorporating 2,3,6-per-O-benzoyl-beta-cyclodextrin (Bz-beta-CD) into DEHP. Bz-beta-CD was prepared by esterification between the hydroxyl groups of beta-CD and benzoyl chloride. The presence of this cyclodextrin is expected to facilitate formation of stable complexes through pi-pi association with DEHP molecules. The flexible PVC was prepared with a gelation-fusion process that uses the prepared migration-resistant plasticizer, and its properties (flexibility, thermal stability, and clarity) were evaluated by carrying out DSC and tensile testing, TGA, and haze testing, respectively. No significant changes in the physical properties of the flexible PVC were observed when Bz-beta-CD was added. DEHP migration tests were carried out for the flexible PVC according to the ISO 3826:1993(E) test method, and the quantity of migrated DEHP was then determined with UV-vis spectroscopy. It was found that the addition of Bz-beta-CD decreases the levels of DEHP migration from the flexible PVC samples by almost 40%. We investigated the molecular interaction between Bz-beta-CD and DEHP using molecular mechanics simulations, and we conclude that this reduction in DEHP migration is due to the formation of stabilized pi-pi attractive association and inclusion complexes of Bz-beta-CD and DEHP in flexible PVC.     

应用气相色谱模拟分离软件快速检测火腿肠及肠衣中的塑化剂

利用气相色谱模拟分离软件,测定火腿肠及其肠衣中的塑化剂邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、 邻苯二甲酸二丁酯、邻苯二甲酸二环己酯、邻苯二甲酸二（2-乙基）己酯和邻苯二甲酸二正辛酯的含量。对比超声 提取和索式提取2 种前处理方法对样品中塑化剂的提取效果,确定了程序升温条件,采用外标法定量。结果表明： 6 种标准物质的标准曲线R2为0.996 7～0.998 8,最小检出限为0.04 mg/kg,相对标准偏差为5.0%～9.3%;索式提取 法的提取效果更显著,某些火腿肠和火腿肠肠衣中含有高含量的生殖致癌物邻苯二甲酸酯类物质。     

Survey of phthalate levels in Italian oily foods contained in glass jars with PVC gaskets

A method based on gas chromatography/tandem mass spectrometry was used to assess levels of twelve phthalates in 50 samples of oily foods packed in glass jars with metal closure obtained from a retail market. The amounts of di-methyl phthalate, di-ethyl phthalate, di-propyl phthalate, di-butyl phthalate, di-pentyl phthalate, benzyl butyl phthalate, di-cyclohexyl phthalate, di-n-octyl phthalate, di-isononyl phthalate and di-isodecyl phthalate in all samples analysed were less than the limit of quantification (LOQ). Di-(2-ethylhexyl) phthalate was detected in 20 samples in the range from 0.1 to 6 mg kg^?1 with an average of 1.0 mg kg^?1, and it exceeded the specific migration limit (SML) of 1.5 mg kg^?1 in five cases with an average of 3.0 mg kg^?1. Di-isobutyl phthalate was found in four samples at 0.1–0.4 mg kg^?1. The PVC gaskets used for the lids were negative for all tested phthalates, suggesting that the contamination of the foods originated from other sources, e.g. olive oil.