Migration of di(2-ethylhexyl) phthalate from polyvinyl chloride tubes used in preparation of foods

Three samples of polyvinyl chloride products for food use were examined for di(2-ethylhexyl) phthalate (DEHP) migration levels under the conditions described in the Japanese Food Sanitation Law. These samples were two kinds of tubes and one stretched film, containing 12 to 41% DEHP by weight. DEHP migration levels from them were very low, all below 0.1 ppm, into 3 kinds of food simulant; water, 4% acetic acid and 20% ethanol. However, high levels of DEHP migrated into n-heptane, 12 ppm from the stretched film sample and more than 800 ppm from the tube samples. Migration from the 2 tubes was higher than 150 ppm, the limit of residues after evaporation in containers and wraps. Though the limit of residues after evaporation is not set for equipment used in the preparation of foods, the tested tubes were considered to be unsuitable for uses in which they come into direct contact with oils, fats or oily foods.     

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.     

邻苯二甲酸二（2-乙基己基）酯在青春期小鼠体内的代谢动力学研究

研究邻苯二甲酸二（2-乙基己基）酯（di-（2-ethylhexyl）phthalate,DEHP）在青春期小鼠体内的代谢动力学,以300 mg/kg DEHP灌胃青春期小鼠,血清样品经固相萃取（solid phase extraction,SPE）提取和净化,气相色谱-质谱联用（gas chromatography-mass spectrometry,GC-MS）法测定不同时间点的血药质量浓度,以3p97软件拟合其动力学参数。DEHP在青春期小鼠体内的主要药物代谢动力学参数：药峰质量浓度ρmax为（0.476±0.028） μg/mL,达峰时间Tpeak为（2.539±0.424） h,药-时曲线下面积AUC（0-t）为（32.209±11.220） h•μg/mL,分布半衰期t1/2α为（1.886±0.480） h,消除半衰期t1/2β为（36.473±8.324） h。本方法简便快捷,其灵敏度和准确度均可满足青春期小鼠体内DEHP代谢动力学研究。DEHP在青春期小鼠体内药物代谢动力学过程符合一级吸收二室开放模型,其分布较快,代谢较慢。     

Survey of di-(2-ethylhexyl)phthalate plasticizer contamination of retail Danish milks.

An investigation of residues of di-(2-ethylhexyl)-phthalate (DEHP) in retail whole milk in samples from one German and 14 Danish dairies is reported. The investigation was performed about six months after the use of DEHP-plasticized milk tubing was banned in Denmark. The results indicate a mean concentration of DEHP lower than 50 micrograms/litre in retail whole milk. Based on these data and the Tolerable Daily Intake (TDI) for DEHP of 25 micrograms/kg body weight laid down by the EEC Scientific Committee for Food, it is concluded that the intake of DEHP from milk and milk products does not, even through a whole life, constitute a danger to health for the Danish population.     

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,...     

Uptake of di-(2-ethylhexyl)phthalate from plastic mulch film by vegetable plants

The uptake of di-(2-ethylhexyl) phthalate (DEHP) from plastic mulch film used in field cultivation by 10 vegetable plants was investigated by experiments carried out in pots. The results showed that DEHP was transferred from the mulch film to all vegetable plants. Wax gourd (Benincasa hispida) showed the greatest capacity for uptake of DEHP, while cucumber (Cucumis sativus) and pumpkin (Cucurbita moschata) could also accumulate high levels. This implies that wax gourd, cucumber and pumpkin may be sources of DEHP contamination in the human diet. Moreover, Chinese cabbage (Brassica parachinensis) also accumulated a high level of DEHP from mulch plastic film giving dietary exposure close to the daily intake limit for DEHP.     

Di-2-ethylhexyl phthalate in the fruits of Benincasa hispida

Di-2-ethylhexyl phthalate (DEHP) is a commonly used plasticizer that is harmful to human health. magnetic resonance spectroscopy from the edible fruit flesh of Benincasa hispida (wax gourd) of the plant family Curcurbitaceae. The DEHP content of seven wax gourd samples collected from southern and northern provinces in China was determined as (mean ± SD): 18.3 ± 0.43, 2.64 ± 0.44, 44.0 ± 0.34, 62.5 ± 0.48, 52.0 ± 0.42, 58.3 ± 0.55 and 75.5 ± 0.63 mg kg^-1 fresh weight, respectively, indicating that most wax gourds were severely contaminated with DEHP.     

2-Ethylhexyl tetrabromobenzoate and bis(2-ethylhexyl) tetrabromophthalate flame retardants in the Great Lakes atmosphere

Two relatively new flame retardants, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) and bis(2-ethylhexyl)-tetrabromophthalate (TBPH), were identified and quantitated in gas and particle-phase air samples collected from six sites near the shores of the Great Lakes. TBB and TBPH were detected in more than half of the samples collected from 2008 to 2010. Urban areas, such as Chicago and Cleveland, showed the highest concentrations (0.36-290 pg/m(3)), while remote areas, such as Eagle Harbor and Sleeping Bear Dunes, exhibited the lowest levels (0.050-32 pg/m(3)). The atmospheric concentrations of TBB and TBPH increased rapidly and significantly over this time period, perhaps indicating that these compounds are replacing the polybrominated diphenyl ethers (PBDEs), which have been removed or soon will be removed from the marketplace.     

白酒中邻苯二甲酸二(2-乙基)己酯荧光探针测定方法的构建

目的 构建一种塑化剂邻苯二甲酸二(2-乙基)己酯(di(2-ethylhexyl)phthalate,DEHP)含量测定的荧光探针检测方法。方法 基于芘分子满足激基缔合物的要求,本文选择以芘为荧光探针,设计合成了芘-聚氧乙烯蓖麻油体系(芘-EL体系)。结果 芘荧光探针在该体系中结合DEHP后収生荧光猝灭,且荧光强度的降低与DEHP的浓度之间存在线性兲系。荧光探针检测的最优条件为波长为374 nm, 400μmol/L芘-EL体系,相互作用时间30min。该方法对DEHP测定的线性范围为5～30μmol/L,线性方程为△F=-23.153+24.179C,线性相兲系数r=0.9929,检出限为0.063μmol/L,相对标准偏差为4.43%(n=6)。结论 本方法具有可视化、成本低、高灵敏度、高选择性、操作简便等优点,适用于白酒中DEHP的测定。     

Diffusion and accumulation in cultivated vegetable plants of di-(2-ethylhexyl) phthalate (DEHP) from a plastic production factory

Di-(2-ethylhexyl) phthalate (DEHP) concentrations in the atmosphere and in four vegetable crops including Brassica chinensis L. (bok choy), Brassica campestris L. (field mustard), Vigna unguiculata Walp. (cowpea), and Solanum melongena L. (eggplant) cultivated on land surrounding a plastic production factory were determined. The air DEHP concentrations (means) at the sites 0.2, 0.4, 0.8, and 1.6 km away from the plastic production building were about 9.4–12.8, 5.8–9.6, 1.6–5.0, and 0.04–0.27 µg m^?3 dry weight (DW), respectively. Wind direction is a key factor influencing the measurable DEHP concentration of the air, which was highest in the downwind direction and lowest in the upwind direction, and thus the vegetables accumulated the highest DEHP contents in the downwind direction and the lowest quantities in the upwind direction. The highest DEHP accumulations content of bok choy, field mustard, eggplant, and cowpea were 52.0 ± 3.1, 43.1 ± 2.2, 36.2 ± 2.8, and 19.4 ± 0.47 mg kg^?1 DW, respectively. Safety estimation on the basis of the daily intake limit referenced by the US Environmental Protection Agency (USEPA) led to the conclusion that eating vegetables cultivated 0.2 km away from the plastic production building is not a food safety problem under normal conditions. A strong positive linear correlation between atmospheric DEHP concentration and DEHP content of the vegetable crops was found. The limits for air DEHP concentration for safe vegetable cultivation are 24.0, 34.8, 40.8, and 82.8 µg m^?3 for bok choy, field mustard, cowpea, and eggplant, respectively, by calculating from the equation of linear regression between air DEHP concentration and vegetable DEHP content.     

γ-氨基丁酸对DEHP染毒大鼠焦虑行为的干预研究

目的:研究γ-氨基丁酸（GABA）对邻苯二甲酸二（2-乙基己基）酯（DEHP）染毒大鼠焦虑行为的影响。方法:将30只雄性SD大鼠随机分为5组:对照组（C）、DEHP组（500 mg/kg）、GABA低、中、高剂量干预组（L组:500 mg/kg DEHP+1 mg/kg GABA、M组:500 mg/kg DEHP+2 mg/kg GABA、H组:500 mg/kg DEHP+4 mg/kg GABA）,连续干预30 d。利用高架十字迷宫（EPM）测定干预前后大鼠行为变化,随后测定大鼠额叶皮质五羟色胺（5-HT）、去甲肾上腺素（NE）的水平。结果:干预前各组大鼠EPM指标无显著性差异（p>0.05）;干预后H组和C组总食物利用率显著高于DEHP组（p<0.05）;干预后各组大鼠入臂总次数无显著性差异（p>0.05）,DEHP组大鼠开臂时间百分比、开臂次数百分比均极显著低于对照组（p<0.01）,M组和H组开臂时间百分比及开臂次数百分比均显著高于DEHP组（p<0.05）;DEHP组5-HT和NE均显著高于C组（p<0.05）,M组5-HT及NE均显著低于DEHP组（p<0.05）,H组5-HT及NE均极显著低于DEHP组（p<0.01）。结论:DEHP可能通过升高额叶皮质5-HT、NE水平造成大鼠焦虑,GABA可以通过降低额叶皮质5-HT、NE水平起到改善焦虑的作用。      

Migration of di-(2-ethylhexyl) phthalate from PVC child articles into saliva and saliva simulant.

A simple migration test and a more complicated simulation of children's sucking and biting was used to establish migration of DEHP from PVC child-use articles into saliva and compared to a mimic test. The static migration test of a film containing approximately 30% DEHP with saliva simulant gave the lowest values of DEHP; simple shaking increased the amounts of DEHP from 25 +/- 8 to 499 +/- 153 micrograms/g film. The more complicated arrangements to simulate sucking and biting are not so suitable for standard applications. When comparing the in vitro migration tests with the mimic test the factors were 25 and 29 for the static tests (3 and 6 hours) and 1.4 for the shaking test.     

气相色谱-串联质谱法测定食用植物油中邻苯二甲酸二正丁酯和邻苯二甲酸二(2-乙基)己酯的不确定度评定

目的 评定气相色谱-质谱法测定食用植物油中邻苯二甲酸二正丁酯和邻苯二甲酸二(2-乙基)己酯含量的不确定度。方法 样品由正己烷、乙腈超声提取, 提取液由固相萃取柱净进化, 采用Rtx-5MS石英毛细管柱, 程序升温, 流速为1.0 mL/min; 进样量1 μL。依据JJF 1059-2012《测量不确定度评定与表示》, 建立不确定度评定的数学模型, 分析在检测过程中不确定度的主要影响因素。结果 在95%的置信区间下, 当邻苯二甲酸二正丁酯为1.2 mg/kg, 扩展不确定度为0.06 mg/kg (k=2); 当邻苯二甲酸二(2-乙基)己酯为1.1 mg/kg, 扩展不确定度为0.04 mg/kg (k=2)。实验过程中不确定度主要来源于测定重复性和标准曲线的拟合。结论 该方法准确可靠, 适用于气相色谱-串联质谱法测定食用植物油中邻苯二甲酸二正丁酯和邻苯二甲酸二(2-乙基)己酯的不确定度评定, 对检测结果准确度的提高与有一定的指导意义。     

Influence of temperature on the emission of di-(2-ethylhexyl)phthalate (DEHP) from PVC flooring in the emission cell FLEC

Emissions of di-(2-ethylhexyl) phthalate (DEHP) from one type of polyvinylchloride (PVC) flooring with approximately 13% (w/w) DEHP as plasticizer were measured in the Field and Laboratory Emission Cell (FLEC). The gas-phase concentrations of DEHP versus time were measured at air flow rate of 450 mL·min(-1) and five different temperatures: 23 °C, 35 °C, 47 °C, 55 °C, and 61 °C. The experiments were terminated two weeks to three months after steady-state was reached and the interior surface of the FLECs was rinsed with methanol to determine the surface concentration of DEHP. The most important findings are (1) DEHP steady-state concentrations increased greatly with increasing temperature (0.9 ± 0.1 μg·m(-3), 10 ± 1 μg·m(-3), 38 ± 1 μg·m(-3), 91 ± 4 μg·m(-3), and 198 ± 5 μg·m(-3), respectively), (2) adsorption to the chamber walls decreased greatly with increasing temperature (measured partition coefficient between FLEC air and interior surface are: 640 ± 146 m, 97 ± 20 m, 21 ± 5 m, 11 ± 2 m, and 2 ± 1 m, respectively), (3) gas-phase DEHP concentration in equilibrium with the vinyl flooring surface is close to the vapor pressure of pure DEHP, and (4) with an increase of temperature in a home from 23 to 35 °C, the amount of DEHP in the gas- and particle-phase combined is predicted to increase almost 10-fold. The amount in the gas-phase increases by a factor of 24 with a corresponding decrease in the amount on the airborne particles.     

Mono-(2-ethylhexyl) phthalate stimulates basal steroidogenesis by a cAMP-independent mechanism in mouse gonadal cells of both sexes

Phthalates are widely used as plasticizers in a number of daily-life products. In this study, we investigated the influence of mono-(2-ethylhexyl) phthalate (MEHP), the active metabolite of the frequently used plasticizer di-(2-ethylhexyl) phthalate (DEHP), on gonadal steroidogenesis in vitro. MEHP (25-100 microM) stimulated basal steroid synthesis in a concentration-dependent manner in immortalized mouse Leydig tumor cells (MLTC-1). The stimulatory effect was also detected in KK-1 granulosa tumor cells. MEHP exposure did not influence cAMP or StAR protein levels and induced a gene expression profile of key steroidogenic proteins different from the one induced by human chorionic gonadotropin (hCG). Simultaneous treatment with MEHP and a p450scc inhibitor (aminoglutethimide) indicated that MEHP exerts its main stimulatory effect prior to pregnenolone formation. MEHP (10-100 microM) up-regulated hormone-sensitive lipase and 3-hydroxy-3-methylglutaryl coenzyme A reductase, suggesting that MEHP increases the amount of cholesterol available for steroidogenesis. Our data suggest that MEHP, besides its known inhibitory effect on hCG action, can directly stimulate gonadal steroidogenesis in both sexes through a cAMP- and StAR-independent mechanism. The anti-steroidogenic effect of DEHP has been proposed to cause developmental disorders such as hypospadias and cryptorchidism, whereas a stimulation of steroid synthesis may prematurely initiate the onset of puberty and theoretically affect the hypothalamic-pituitary-gonadal axis.     

Di(2-ethylhexyl) phthalate contamination of retail packed lunches caused by PVC gloves used in the preparation of foods

Plasticizer contamination of foods sold in retail packed lunches and set lunches in restaurants was determined by GC/MS. 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. Sixteen packed lunches and ten set lunches were analysed, and in all samples the concentration of di(2-ethylhexyl) phthalate (DEHP) was the highest, at 0.80-11.8 mg/ kg in packed lunches and 0.012-0.30 mg/kg in set lunches. The DEHP content of five packed lunches exceeded 1.85 mg, which is the EU tolerable daily intake (TDI) for a person of 50 kg body weight. Foodstuffs that were components of the packed lunches were taken from the factory at each step of preparation and phthalates were determined. For example, chicken contained 0.08 mg/kg DEHP when uncooked, 13.1 mg/ kg after frying and 16.9 mg/kg after packing. Disposable PVC gloves used in the preparation of foods were apparently the source of high DEHP concentrations. The gloves used during cooking or packaging were sprayed with 68% (w/w) ethanol to sterilize them. PVC gloves from the factory contained 22 or 41% by weight of DEHP. To confirm the link with the contamination problem, samples of boiled rice, croquette and boiled dry radish were handled in the laboratory with PVC gloves containing 30% (w/w) DEHP. DEHP migration levels of 0.05 mg/kg in rice or 0.33 mg/kg in croquette, and 11.1 mg/kg in radish were found. The alcohol sprayed onto the gloves increased the migration of DEHP to 2.03 mg/kg in rice, 2.45 mg/ kg in croquette, and 18.4 mg/kg in radish.     

同位素模拟-气相色谱-串联质谱法测定邻苯二甲酸二（2-乙基）己酯在茶汤中的浸出率

在排查茶叶冲泡和样品前处理过程中邻苯二甲酸二（2-乙基）己酯（di-(2-ethylhexyl) phthalate,DEHP）背景污染基础上,采用同位素模拟-气相色谱-串联质谱法研究茶汤中DEHP的浸出率。结果表明,有机试剂、实验器皿以及旋转蒸发浓缩过程会产生DEHP污染,背景污染造成DEHP在茶汤中的浸出率偏高,为13%～400%。同位素DEHP-D4模拟冲泡实验结果表明,DEHP-D4在茶汤中的浸出率为4.5%～11.9%,浸出率与茶叶中DEHP-D4质量浓度相关性较小,但与茶叶种类、冲泡方式和冲泡次数相关。该研究结果为茶叶中DEHP风险评估提供技术支撑,为制定茶叶中DEHP最大残留限量标准提供基础数据。     

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.     

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.     

GC-MS快速测定纸制食品接触材料中邻苯二甲酸二（2-乙基己基）酯

以甲醇为萃取剂,微波辅助萃取,建立了气相色谱-质谱（GC-MS）法快速测定纸制食品接触材料中邻苯二甲酸二（2-乙基己基）酯（DEHP）含量的分析方法。考察6种不同萃取剂萃取效果,选择甲醇为最佳萃取剂,并对超声萃取的温度和时间进行试验,选择最佳试验条件。DEHP的质量浓度在0.1~20mg/l范围内与峰面积响应值具有良好线性关系,方法定量检出限为0.05mg/kg。样品加标回收率为90.2%~103.6%,相对标准偏差小于6.73%。该方法具有快速、准确度高、干扰少等优点。