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.     

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 total mercury in total diet food composites and an estimation of the dietary intake of mercury by adults and children from two Canadian cities, 1998-2000

Total mercury was measured in 259 total diet food composites from two Canadian cities. Levels were generally low, with 46% of the composites having concentrations below the limit of detection, which ranged from 0.026 to 0.506 ng g^-1. The fish category contained the highest mercury concentrations, which averaged 67 ng g^-1 and ranged from 24 to 148 ng g^-1. All composites were below the Canadian guideline for total mercury in fish of 0.5 ppm. Dietary intakes of mercury averaged 0.022 μg kg^-1 body weight/day (μg kg^-1 day^-1), and ranged from 0.012 μg kg^-1 day^-1 for females over 65 years old to 0.062 μg kg^-1 day^-1 for 0-1-month-old infants. For fish consumers, fish contributed to more than half of the ingested mercury. All intakes were well below Joint FAO/WHO Expert Committee on Food Additives Provisional Tolerable Weekly Intakes, expressed on a daily basis, of 0.71 μg kg^-1 day^-1 total mercury and 0.47 μg kg^-1 day^-1 methyl mercury, and also below a recent Health Canada recommended maximum methyl mercury intake of 0.2 μg kg^-1 day^-1 for children and women of child-bearing age.     

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.     

Analysis of plasticizers in cap-sealing resins for bottled foods

A survey of plasticizers in cap-sealing resins for bottled foods has been undertaken. During 1997-1999 di-(2- ethylhexyl)phthalate (DEHP) was found in seven out of 21 samples on the Japanese domestic market and in 10 out of 61 imported samples as well as a further two samples which contained di-(2-ethylhexyl)adipate (DEHA). In the period 1993-1999, of the other plasticizers diacetyl lauroyl glycerol (DALG) was only detected in domestic samples whereas diisodecyl phthalate (DIDP) and diisononyl phthalate (DINP) were only in imported samples. It was observed overall that DEHP and DEHA were restricted to use in cap-sealing resins for bottled foods. Whilst phthalates, DEHA or DALG were detected in samples in 1993 and 1995, the investigation in 1997-1999 showed fewer samples in which these plasticizers were found.     

Plasticizers in total diet samples, baby food and infant formulae

The plasticizers di-n-butylphthalate (DBP), butylbenzylphthalate (BBP), di-2-(ethylhexyl)phthalate (DEHP) and di-2-(ethylhexyl)adipate (DEHA) were analysed in 29 total diet samples, in 11 samples of baby food and in 11 samples of infant formulae. In all of the total diet samples the presence of one or more of the plasticizers was demonstrated. Maximum and minimum mean concentrations in the total diet samples were: 0.09-0.19mg DBP/kg, 0.017-0.019mg BBP/kg, 0.11-0.18mg DEHP/kg and 0.13-0.14mg DEHA/kg. One or more of the phthalates was also found in about 50% of the samples of baby food as well as in infant formulae. The calculated mean maximum intakes of the individual compounds from the total diet samples were below 10% of the restrictions proposed by the EU Scientific Committee for Food (SCF), and the spread in individual intakes was considerable. DEHP was the plasticizer determined most frequently and contributed the highest fraction of its tolerable daily intake (TDI). Hence, the maximum calculated intake of DEHP from single samples of the foodstuffs analysed could be up to one-third of the TDI. The calculated mean intake of DEHA was about 1% of the TDI with a maximum value of 13% of the TDI. Violations of the restrictions proposed by the EU Scientific Committee for Food (SCF) in the form of TDI values or specific migration limits were not found in this investigation.     

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.     

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).     

Cadmium intake of moose hunters in Finland from consumption of moose meat, liver and kidney

Although the average cadmium intake in Finland is about 10 μg day^-1, some risk groups can be identified. This study assessed cadmium intake from the consumption of moose meat, liver and kidneys by moose hunters. Consumption data from a postal questionnaire were combined with a representative database on moose cadmium concentrations. Cadmium intakes were calculated as point estimates for all respondents (n = 711), for those consuming moose meat, liver and/or kidneys, and for the highest decile of those. Probabilistic modelling using the Monte Carlo technique was used to simulate the distribution of dietary cadmium exposure. Of the respondents, 69% consumed moose liver and only 23% moose kidneys. The consumption of moose liver or kidneys significantly increased cadmium intake, whereas moose meat (median consumption 17 kg year^-1 person^-1) contributed only slightly (0.16 μg day^-1 person^-1) to the daily total cadmium intake. In the simulation, 10% of the moose hunters had an intake of > 8.76 μg day^-1 (14.6% of PTWI for a 60-kg person) from moose. Point estimates provided only a partial understanding of the potential exposure. Simulated distributions of intake were more useful in characterizing exposure. The study revealed that heavy users of moose organs have a relatively narrow safety margin from the levels of cadmium probably causing adverse health effects.     

Contents of plasticizers in cap-sealing for bottled food and their migration into food

Plasticizers in cap-sealing for bottled foods were analyzed. Twenty-three domestic samples and 80 imported samples, a total of 103 samples, were tested. Among them, 93 contained chloride, and 62 contained di(2-ethylhexyl) phthalate (DEHP), diisodecyl phthalate, O-acetyl tributyl citrate, diacetyllauroyl glycerol, di(2-ethylhexyl) adipate, diisononyl phthalate or dicyclohexyl phthalate. Twelve samples with DEHP-containing caps were further tested for plasticizer levels in the foods. Higher DEHP was detected in oily and fluid food specimens. However, the intake of plasticizers calculated based on usual food consumption did not exceed the tolerable daily intake level in any of the cases. A food sample containing the highest level of DEHP was stored under various conditions, and DEHP that migrated from the cap-sealing into the food was determined. Shaking the bottles increased migration of DEHP into foods.     

Migration of monomers from liquid crystalline poly(p-hydroxybenzoic acid-co-2-hydroxy-6-naphthoic acid)

Liquid-crystalline co-polyesters (e.g. a random copolyester based on p-hydroxybenzoic acid (HBA) and 2-hydroxy-6-naphthoic acid (HNA) known as Vectra A950) offer good barrier properties, but for food-contact use require overall and specific migration testing. For Vectra A950 films, the highest overall migration level obtained was 2.3 mg kg^-1 in olive oil (10 days at 40°C) well below the EC limit of 60 mg kg^-1. The highest specific migration for p-hydroxybenzoic acid was 15.2 μg dm^-2 in olive oil (2h at 175°C). For 2-hydroxy-6-naphthoic acid, the highest value obtained was 4.3 μg dm^-2 in 10% ethanol (4h at 100°C), although it was not on the EC positive and cannot yet be used for food-contact materials. At conditions considered as severe, the estimated daily intake for p-hydroxybenzoic acid was calculated as 11.9 μg/person day^-1 and for 2-hydroxy-6-naphthoic acid it was 5.3 μg/person day^-1. The results exceed the threshold of regulation of 1.5 μg/person day^-1.     

Natural co-occurrence of deoxynivalenol and fumonisins B1 and B2 in Italian marketed foodstuffs

A survey was performed to obtain the frequency and levels of contamination by deoxynivalenol (DON) and fumonisins B₁ and B₂ (FB1, FB2) mycotoxins in Italian marketed foods. Of 202 samples investigated, including raw materials and processed cereal foods (bread, pasta, breakfast cereals, biscuits, baby and infant foods), 84% were contaminated with DON at levels from 0.007 to 0.930 μg g^-1 (median 0.065 μg g^-1); 26% contained FB1 ranging from 0.010 to 2.870 μg g^-1 (0.070 μg g^-1); 35% contained FB2 at 0.010-0.790 μg g^-1 (0.080 μg g^-1). The highest levels of DON and FB1 were detected in raw cereals and wholemeal flours. The highest levels of FB2 were detected in durum wheat pasta. A widespread DON contamination was found in baby and infant foods at levels varying from 0.007 to 0.166 μg g^-1.     

Survey of total mercury in some edible fish and shellfish species collected in Canada in 2002

Total mercury was measured in the edible portions of 244 selected fish and shellfish purchased in Canada at the retail level. By species, average mercury concentrations ranged from 0.011 μg g^-1 for oysters to 1.82 μg g^-1 for swordfish. The predatory fish contained the highest concentrations of mercury: swordfish (mean 1.82 μg g^-1, range 0.40-3.85 μg g^-1), marlin (1.43, 0.34-3.19 μg g^-1), shark (1.26, 0.087-2.73 μg g^-1), and canned, fresh and frozen tuna (0.35, 0.020-2.12 μg g^-1). Levels of mercury in the fresh and frozen tuna contained a mean of 0.93 μg g^-1 (range 0.077-2.12 μg g^-1) and were substantially higher than in the canned tuna (0.15, 0.02-0.59 μg g^-1). In the canned tuna, mercury concentrations varied with subspecies, with the highest average concentrations being found in Albacore tuna (mean 0.26 μg g^-1, range 0.19-0.38 μg g^-1) and the lowest (0.047, 0.025-0.069 μg g^-1) in five samples for which the subspecies of tuna were not identified. Mean concentrations of mercury in swordfish and fresh and frozen tuna were up to three times higher than reported for the USA. Dietary intake estimations found that provided fresh and frozen tuna, marlin, swordfish or shark are consumed once a month or less, the dietary intakes of total mercury by women of child-bearing age, averaged over 1 month, would fall below the Joint FAO/WHO Expert Committee on Food Additives provisional tolerable weekly intake for total mercury. The current Canadian advisory to children and women of child-bearing age is to limit their consumption of fresh and frozen tuna, swordfish and shark to no more than one meal per month.     

Occurrence of phthalates in different food matrices: A systematic review of the main sources of contamination and potential risks

This systematic review aimed to investigate the occurrence of phthalates (phthalic acid esters [PAEs]) in different food matrices, as well as report the main sources of PAEs in food, the potential risks to the population, and the factors that influence its migration from food contact materials (FCMs) to food. Nineteen PAEs were identified, including di-(2-ehtylhexyl) phthalate (DEHP), dibutyl-phthalate (DBP), benzylbutyl phthalate (BBP), diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP) in fruits and vegetables, milk and dairy products, cereals, meat, fish, fat and oils, snacks, condiments and sauces, miscellaneous, and baby food. Fifty-seven values of PAEs were above the legal limits of countries. DEHP is the PAE with the highest incidence, with maximum concentrations above the specific migration limit (SML) for milk and dairy products, oils and fats, fish, cereals, condiments and sauces, meat, and fruits and vegetables. The risk of exceeding the tolerable daily intake (TDI) was high for DEHP and DBP in fish, fat and oils, cereals, and milk and dairy products for children and adults. Fat and oils are the most critical food for DEHP, DBP, BBP, and DINP. Comparing the estimated daily intake (EDI) with the TDI, there was a risk for “milk and dairy products” in adults and for “cereal and cereal products” in children concerning DEHP. “Cereal and cereal products” presented a risk in children and adults concerning DBP. The “fat and oils” category presented a risk in children and adults about DBP and DINP. Temperature, contact time between food and the FCM, fat percent, and acidity positively correlate with the PAE's migration. The contamination occurs in many steps of the production chain.     

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。     

Dietary intake of polychlorinated dioxins, furans and dioxin-like polychlorinated biphenyls from foods of animal origin in China

Four food groups of animal origin from the Chinese Total Diet Study (TDS) in 2000 were analysed for 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and 12 dioxin-like polychlorinated biphenyls (PCBs). The samples were from four regions, covering 12 provinces of China. PCDD/Fs, expressed as WHO toxic equivalents (TEQ), ranged from 0.02 to 0.28 pg TEQ g^-1 and dioxin-like PCBs ranged from 0.01 to 0.24 pg TEQ g^-1 (wet weight, ND = LOD), in all samples. Using food consumption data from a 3-day household dietary survey, daily dietary intake of dioxin-like compounds from foods of animal origin in China was estimated. Daily intake among regions ranged 0.09-0.59 pg TEQ kg^-1 body eight day^-1.     

Survey of furan in heat processed foods by headspace gas chromatography/mass spectrometry and estimated adult exposure

Furan is a suspected human carcinogen that is formed in some processed foods at low ng per g levels. Recent improvements in analytical methodology and scientific instrumentation have made it possible to accurately measure the amount of furan in a wide variety of foods. Results from analysis of more than 300 processed foods are presented. Furan was found at levels ranging from non-detectable (LOD, 0.2-0.9 ng g^-1) to over 100 ng g^-1. Exposure estimates for several adult food types were calculated, with brewed coffee being the major source of furan in the adult diet (0.15 µg kg^-1 body weight day^-1). Estimates of mean exposure to furan for different subpopulations were calculated. For consumers 2 years and older, the intake is estimated to be about 0.2 µg kg^-1 body weight day^-1.     

RISK21分析工具在邻苯二甲酸酯类物质膳食暴露风险评估中应用研究

目的应用RISK21框架和工具分析我国2～6岁儿童邻苯二甲酸二(2-乙基)己基酯(DEHP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)7种邻苯二甲酸酯类物质(PAEs)的膳食暴露风险,为风险管理决策提供科学基础。方法以PAEs的毒性为纵坐标,以暴露为横坐标,以暴露限值(MOE)和不确定系数为参数,应用RISK21工具中RISK PLOT模块,通过矩阵计算,以图形展示2～6岁儿童暴露于7种PAEs的风险大小和等级。应用TTC PLOT模块,分析毒理学资料缺乏的DMP、DEP、DIBP 3种PAEs的暴露风险。结果 RISK PLOT表明一般人群7种PAEs均处于风险较低的绿色区域;高食物消费量人群7种PAEs暴露风险排序为DBP、DIBP、DEHP、DMP、DEP、DINP及BBP, TTC PLOT显示我国2～6岁儿童DMP、DEP、DIBP膳食暴露风险低于相应的毒理学关注阈值(TTC)。结论 RISK21框架和工具可应用于风险评估及其后期的管理决策, RISK21分析结果表明我国2～6岁儿童7种PAEs膳食暴露风险较低。     

Content of mercury and cadmium in fish (Thunnus alalunga) and cephalopods (Eledone moschata) from the south-eastern Mediterranean Sea

Mercury and cadmium concentrations were measured in the flesh and liver (or hepatopancreas) of albacore (Thunnus alalunga) and horned octopus (Eledone moschata) to establish whether the concentrations exceeded the maximum levels fixed by the European Commission. In both species, mercury and cadmium mean concentrations were higher in liver (albacore: mercury = 2.41 μg g^-1 wet wt, cadmium = 9.22 μg g^-1 wet wt; horned octopus: mercury = 0.76 μg g^-1 wet wt, cadmium = 6.72 μg g^-1 wet wt) than in flesh (albacore: mercury = 1.56 μg g^-1 wet wt, cadmium = 0.05 μg g^-1 wet wt; horned octopus: mercury = 0.36 μg g^-1 wet wt, cadmium = 0.33 μg g^-1). Mercury concentrations exceeding the prescribed legal limit of 1 μg g^-1 wet wt were found in almost all albacore samples (flesh: 71.4%; liver: 85.7%). For horned octopus, concentrations above 0.5 μg g^-1 wet wt were observed solely in hepatopancreas, while in flesh, the concentrations were below this limit in all the samples examined. Of the flesh samples of albacore, 42.8% exceeded the proposed tolerance for cadmium for human consumption, whilst for horned octopus, the established limit was not exceeded in any sample.     

Australian survey of acrylamide in carbohydrate-based foods

A method was developed and validated for the determination of acrylamide in carbohydrate-based foods. Solid-phase extraction employing a mixed-bed anion and cation exchange cartridge in series with a C18 extraction disk was used to clean-up water extracts of food samples before analysis by liquid chromatography coupled with tandem mass spectrometry detection. The limit of detection was calculated as approximately 25 μg kg^-1 and the limit of reporting was 50 μg kg^-1. The average method recovery for 84 samples from a range of matrices reporting was 99% with a relative standard deviation of 11.2%. A survey was conducted of 112 samples of carbohydrate-based foods composited from 547 products available in the Australian market. The analytical results were used in conjunction with Australian food consumption data derived from the 1995 National Nutrition Survey (NNS) to prepare preliminary dietary exposure estimates of Australians to acrylamide through only the food groups examined. Mean dietary exposure to acrylamide resulting from consumption of the foods tested, for Australians aged 2 years and above, was estimated as 22-29 µg day^-1 (equivalent to 0.4-0.5 µg kg^-1 bodyweight day^-1) and between 73 and 80 µg day^-1 (1.4 and 1.5 µg kg^-1 bodyweight day^-1) for 95th percentile consumers. Young children (2-6 years) consuming acrylamide-containing foods had a higher acrylamide exposure on a per kilogram bodyweight basis (mean 1.0-1.3 µg kg^-1 bodyweight day^-1). The estimated exposure of Australians to acrylamide is similar to that estimated for other countries.