Migration Of Phthalates Research Articles

Determination of di(2-ethylhexyl) phthalate migration from toys into artificial sweat by gas chromatography mass spectrometry after activated carbon enrichment

The determination of di(2-ethylhexyl) phthalate migration was achieved in artificial sweat using gas chromatography mass spectrometry following activated carbon enrichment of samples. Response surface methodology (RSM) was used to optimise the conditions for maximum recovery and to understand the significance and interaction of the factors affecting the recovery of di(2-ethylhexyl) phthalate. The best compromise of analytical conditions for the simultaneous determination of analyte from spiked artificial sweat was found to be: pH (3.1), activated carbon amount (1.4 g L−1), adsorption time (55 min) and elution solvent (chloroform). These conditions were applied to study the migration of di(2-ethylhexyl) phthalate from different children’s toys into artificial sweat. The detection limit of the method was 13.8 μg L−1, while the relative standard deviation (%) value for the analysis of 100 μg L−1 of the analyte was below 3.7% (n = 5).

Presence of phthalate esters in intravenous solution evaluated using gas chromatography–mass spectrometry method

Di-(2-ethylhexyl) phthalate (DEHP) is a plasticizer widely used in the production of poly-(vinyl) chloride (PVC) materials. It is a reproductive and developmental toxicant in animals and a suspected endocrine modulator in humans. DEHP is not covalently bound within the PVC molecule, which is why migration into a suitable medium can be expected. Since application of infusion solutions is one of the most common medical treatments, the objective of this study was to determine the migration of phthalates from softened PVC storage bags into infusion solution in different time periods within one year from date of production using a gas chromatography-mass spectrometry method. The measured values of DEHP ranged between 0.22 and 14.00 µg l(-1) , but the unexpected presence of other phthalate esters was also detected. It was concluded that values obtained in infusion solutions match the reference data and represent a minor risk for the patient. The presence of other phthalate esters leads to the conclusion that the pharmacopeic requirement for polymer cleanness was not fully met. Since phthalate esters are among the most extensively used industrial chemicals and are widely distributed in the environment, special precautions and further monitoring should be conducted to minimize any possible health risks.

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).

Analysis of Phthalate Migration from Plastic Containers to Packaged Cooking Oil and Mineral Water

The migration of phthalates (PAEs), a class of typical environmental estrogen contaminants in food, from food packaging to packaged food attracts more and more attention worldwide. Many factors will affect the migration processes. The purpose of this study was to evaluate PAE migration from plastic containers to cooking oil and mineral water packed in authentic commercial packaging and stored under various conditions (different storage temperatures, contact times, and storage states (static or dynamic state)) and to identify a potential relationship between the amount and type of PAEs migrated and the lipophilic character of the food matrix. The samples were analyzed by a novel method of liquid chromatography combined with solid-phase extraction by an electrospun nylon 6 nanofibers mat, with PAE detection limits of 0.001 μg/L in mineral water and 0.020 μg/L in cooking oil, respectively. The results demonstrated that the cooking oil was a more suitable medium for the migration of PAEs from packages into foodstuffs than mineral water. Scilicet, the migration potential of the PAEs into foodstuffs, depends on the lipophilic characteristics of the food matrix. The results also demonstrated that migrations were more significant at higher temperature, longer contact time, and higher dynamic frequency; thus, the migration tests should be evaluated with consideration of different storage temperatures and contact times. Mathematical models with good logarithmic relationships were established to demonstrate the relationship between the PAE migration and food/packaging contact time for different storage temperatures. These established mathematical models would be expected to become a set of practical tools for the prediction of PAE migration.

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.

Migration of phthalates from plastic tank to vegetable oil as a part of feeding mixtures used for chicken broilers fattening

The concentrations of phthalic acid esters (PAEs) as di-n-butyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP) were measured in samples of rapeseed oil, which was used as a feed. First samples were collected during the production process and second after the storage in plastic tank (21 days). The results of measurements are that there is 2.93-10.10 mg PAEs.kg-1 in the oil before storage and 22.73-61.55 mg PAEs.kg-1 after storage. For the monitoring of distribution and accumulation of PAEs in animal tissues and organs (muscles, adipose tissue, skin and liver) broiler chicks ROSS 308 were used. The chicks were divided into 4 groups (50 chicks each). All the chicks were fed by commercial diets (complete feed, KKS) for broiler chicks (starter – BR1; grower – BR2 and finisher – BR3). The experimental diets were supplemented with vegetable oil (RO) with low (group N) or high (group V) phthalate content, or animal fat with high phthalate content (group Z). Neither the control diets (K) nor the grower (BR1) diets contained vegetable oil or animal fat. DBP and DEHP were found in all tissues of all chicks. The highest concentration of DBP of 1.28 1.00 mg.kg-1 of fresh sample (an average value from 8 chicks) was determined in the adipose tissue of V chicks. The highest concentration of DEHP of 3.27 2.87 mg.kg-1 of fresh sample (average of 8 chicks) was also determined in the V group.

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

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.

Analysis and Migration of Phthalates in Infant Food Packed in Recycled Paperboard

The contamination of infant food with substances from its packaging due to migration processes is still a problem. Most recently, great attention was paid to the migration of epoxidized soybean oil (ESBO) and phthalates from twist-off closures into baby food packed in glass jars. Besides, packaging made of recycled fiber materials such as paper and paperboard were found to be the source of contaminants in dry and powdery foodstuffs such as sugar, rice, and maize flour. In this study 20 infant food samples packed in recycled paperboard containers were tested for phthalates and diisopropyl naphthalenes (DIPN), known incorporated substances in recycled paper. Furthermore, the barrier function of different secondary packaging materials (paper and aluminum-coated foil) was investigated. The highest contents of phthalates (mainly diisobutyl phthalate, DiBP) and DIPN in infant food samples were found for those foods packed in inner bags made of paper. Migration experiments were performed under authentic conditions to evaluate possible transfer mechanism (gas phase, direct contact) of phthalate esters into foodstuff. It is shown that paper does not provide an appropriate barrier against migration of semipolar compounds such as phthalates. The air space itself otherwise effectively prevents migration of the less volatile phthalates under the applied conditions.

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.

Encapsulation of β-cyclodextrin by in situ polymerization with vinyl chloride leading to suppressing the migration of endocrine disrupting phthalate plasticizer

We performed the encapsulation of β-cyclodextrin (β-CD) in PVC by in situ polymerization with vinyl chloride monomer (VCM), and investigated the effect of CD encapsulation on the suppression of dioctyl phthalate (DOP) migration suspected as endocrine disruptor. β-CD was partially modified with 3-(methacryloxy)propyl trimethoxysilane and modified β-CD (MCD) was then encapsulated in PVC through suspension polymerization via radical reaction between double bonds MCD and VCM. Resulting MCD-encapsulated PVC (MCD x –PVC) exhibited the similar morphology and characteristics to commercial PVC. For MCD x –PVCs plasticized with DOP, they showed the considerably suppressed DOP migration as well as the similar optical and mechanical properties to conventionally plasticized PVC. In particular, the plasticized MCD x –PVCs exhibited the superior suppression of DOP migration compared to the plasticized PVC where MCD and DOP were introduced by conventional melt mixing. Therefore, the encapsulation of MCD in PVC is thought to be an effective approach to producing the ecological PVC material.

Effect of gamma-ray irradiation on degradation of di(2-ethylhexyl)phthalate in polyvinyl chloride sheet

The risk assessment of di(2-ethylhexyl)phthalate (DEHP) migration from polyvinyl chloride (PVC) medical devices is an important issue for patients. The aim of this study was to determine DEHP degradation and migration from PVC sheets. To this end, the method for the simultaneous determination of DEHP and its breakdown products (mono(2-ethylhexyl)phthalate (MEHP) and phthalic acid (PA)) was improved. Their migration levels from 0 to 50 kGy gamma-ray irradiated PVC sheets were determined. DEHP migration level decreased in proportion to the dose of gamma-ray irradiation, while MEHP and PA migration levels increased. The hardness and the elastic modulus of PVC sheets were examined, but no clear relationship between DEHP migration and these parameters was observed.

Extraction and gas chromatographic evaluation of plasticizers content in food packaging films

Cling films are prepared by adding (5–30% w/w) adipates, citrates, and phthalates. The adverse effects on human health of the plasticizers have been demonstrated, and then their content in food contact plastics and possible migration to foodstuffs must be carefully checked. To offer an easier tool to perform these controls, a Soxhlet extraction by ethyl acetate and a multi residue chromatography analysis, with Flame Ionization Detector, have been optimised for the application in evaluating both the real content of plasticizers in films and freezing bags, and their migrated amounts in simulants. The average extraction yield was 95 ± 10%. The chromatographic analysis was able to determine 16 different compounds, clearly separated, taking only 25 min to complete the assay. The detection limits ranged from 0.07 to 0.7% (w/w). The total amount of plasticizers in the packaging products was comprised between 3 and 10% (w/w). Extracted and migrated amounts were compared, and they resulted in good agreement. No migration of Phthalates, whose presence has been demonstrated in some samples, has been observed. It has been also demonstrated that a prolonged contact (till 60 days) did not increase the amount of migrated plasticizers, and then the risks for health.

The internal exposure of Taiwanese to phthalate—An evidence of intensive use of plastic materials

Phthalates are widely used in industry and consumer products. Di-(2-ethylhexyl) phthalate (DEHP) and di-n-butylphthalate (DBP) show the greatest potency of reproductive toxicants among phthalates. The purposes of this study are to examine the migration level of phthalate from PVC films by simulating food handling and to reveal the body burden of phthalate for Taiwanese. In order to estimate a worst-case of phthalate migration, food was covered with polyvinyl chloride (PVC) films and then microwave heated. Results show that DEHP level in food increased significantly after heating for 3 min. Under the heating condition, the calculated intake of phthalate and the percentage of the tolerable daily intake (TDI, based on body weight of 60 kg) from eating one 400-g meal were 1705.6 μg and 92.2% for DEHP. Determination of urinary metabolites from 60 subjects reveals more than 90% of samples were detectable for mono-methyl phthalate (MMP), mono-butyl phthalate (MBP) and mono-ethylhexyl phthalate (MEHP). Notably, the median value of estimated daily intake of DEHP had reached 91.6% of TDI established by the European Union Scientific Committee for Toxicity, Ecotoxicity and the Environment (CSTEE) (1998). Thirty-seven percent of the study population exceeded the TDI and 85% exceeded the reference dose (RfD) of the US EPA. We conclude that the body burden of DEHP for Taiwanese reflects the intensives use of plastic materials in the region. The regulation of PVC for food preparation is necessary.

Investigation into the migration potential of coating materials from cookware products

Twenty-six non-stick-coated cookware samples were purchased, covering a variety of products, coating/metal types and food contact applications. The polymer coatings were identified to be polyethersulphone, polytetrafluoroethylene (PTFE), bisphenol A/epichlorohydrin and one coating for which no good match was obtained with infra-red library spectra. All of the products intended for stove-top use had a polymer coating containing PTFE. The coatings were analysed as purchased and after heating at 250°C for 30 min to simulate actual conditions of use. Total solvent extractables were measured and the overall migration was determined into simulants. None of the products exceeded an overall migration limit of 10 mg dm−2. Coating materials were analysed by headspace gas chromatography–mass spectrometry (GC–MS), by liquid extraction followed by GC–MS and by liquid extraction followed by liquid chromatography–mass spectroscopy with a particle-beam interface. Benzene was detected in two samples, at 1.4 and 2.4 µg dm−2. These levels in the coatings are too low to give any detectable migration into foods. There was no detectable release of perfluorochemicals. Several other substances were identified and the worst-case migration was calculated. The origin of many of the substances detected was considered to be by pick-up from the printed packaging materials in which the cookware was sold. Potential consumer exposure was calculated. None of the substances identified had the potential to exceed their tolerable daily intake (TDI) value. To confirm these worst-case calculations, the migration of certain phthalates and of bisphenol A was measured into food simulants. Migration levels were very low.

Determination of phthalate esters from food-contacted materials by on-line microdialysis and liquid chromatography

Phthalates (endocrine disrupters) released from food-contacted plastics into aqueous solution during microwave conditioning were measured with microdialysis enrichment on-lined high-performance liquid chromatography. The released phthalates in aqueous solution were diffused through a cellular dialysis membrane into the perfusion stream and thus enriched prior to HPLC analysis. Conditions for obtaining optimum enrichment such as the hollow dialysis fiber, flow-rate and polarity modifier in perfusion stream, pH, added-salt and stirring rate in sample solution, as well as chromatographic conditions were investigated. Experimental results indicated that microdialysis enrichment with a 20-cm polysulfone hollow dialysis fiber and heptane as the perfusate at 0.10-μL/min flow-rate to collect phthalates from aqueous sample in 0.5 M KCl matrix (optional pH) at 250 rpm stirring offered the optimum enriched efficiency. The dimethyl phthalate (DMP), diethyl phthalate (DEP) and dibutyl phthalate (DBP) were well separated within 16 min by a C-18 column and eluted gradient from 40 to 90% aqueous acetonitrile (at pH 6.0) and 1.0 to 1.5 mL/min flow-rate. Detection was carried out with an UV detector at 225 nm. The enrichment factors were 14, 140 and 201 (at 0.10-μL/min perfusate flow-rate) for DMP, DEP and DBP, respectively, with less than 4% RSD. The proposed method provided a very simple, fast and eco-friendly enriched procedure to determine the extent of phthalates migration from disposable plastic materials into drinking soup.

High-throughput determination of mono- and di(2-ethylhexyl)phthalate migration from PVC tubing to drugs using liquid chromatography–tandem mass spectrometry

The risk assessment of di(2-ethylhexyl) phthalate (DEHP) that migrated from polyvinyl chloride (PVC) medical devices is an important issue for hospitalized patients. Many studies have been conducted to determine the level of DEHP migration. A recent report has indicated that DEHP in blood bags was hydrolyzed by esterase to mono(2-ethylhexyl) phthalate (MEHP). Therefore, a method for the simultaneous determination of DEHP and MEHP was developed. The migration of DEHP and MEHP from PVC tubing to drugs was examined. Although we detected MEHP in the drugs, we found no enzymatic activity involved in the migration process. Some reports have indicated that hydrolysis may have occurred during sterilization by autoclaving. However, we did not perform any heat treatment. It is speculated that the MEHP migrated directly from the PVC tubing. The simultaneous determination of DEHP and MEHP is required for risk assessment, as MEHP may be even more toxic than the parent compound.

DEHP Migration Behavior from Excessively Plasticized PVC Sheets

The quantity, process and kinetics of di-(2-ethylhexyl)phthalate (DEHP) migration in the 30/70 and 40/60 poly(vinylchloride) (PVC)/DEHP blends were investigated using gas chromatograph. A thin and flexible PVC sheet was soaked in surrounding medium (SM) of water/ethanol mixture and acetonitrile with constant stirring to release DEHP. By observed concentration of DEHP in the SM, it is found that acetonitrile is more intense in DEHP migration than water/ethanol mixture. In addition the amount of extracted DEHP is proportional to the leaching temperature and added ratio of DEHP. The behavior of DEHP migration from flexible PVC sheets was described by the Ficks's law with <TEX>$2.72-10.1\;{times}\;10^{-10}$</TEX> cm²/s of the diffusion coefficients.

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%].

Migration of phthalates from PVC toys into saliva simulant by dynamic extraction

Soft PVC children's products are usually plasticized with phthalates. As young children suck and chew on toys, they extract and ingest certain quantities of the plasticizers. Some phthalates are suspected to affect the kidneys and liver and cause testicular damage. Therefore, the EC has prohibited the sale of toys and childcare articles intended to be placed in the mouth by children <3 years of age made of soft PVC containing >0.1% by weight of six phthalates (1999/815/EC). The aim was to study the materials and plasticizers used in soft children's products. In February 2001, a market surveillance was performed in The Netherlands and 62 soft toys were sampled. Forty-seven of these toys contained plasticized PVC. Diisononylphthalate (DINP) and di(2-ethylhexyl)phthalate (DEHP) were the predominant plasticizers and were usually found in concentrations between 30 and 45% by weight. One teething ring was made of PVC plasticized with 45% by weight of DINP and was not in compliance with Decision 1999/815/EC. The DINP and DEHP migration was determined in saliva simulant using the ‘Head over Heels’ agitation method. All toys complied with the Scientific Committee on Toxicity, Ecotoxicity and the Environment (SCTEE) guidance release value of 6.7 µg min-1 10 cm-2. The DEHP migration of six toys exceeded the SCTEE guidance release value of 1.7 µg min-1 10 cm-2. Substitutes found for phthalates plasticizers are acetyltributylcitrate, tributylcitrate and diisononyladipate. In addition, other plasticizers and additives were found in minor amounts. The toxicity and the migration behaviour of these substances is less known and requires more attention. To ensure the safety of PVC toys, these substances should also be regulated.

Comparison of Diisononyl Phthalate Migration from Polyvinyl Chloride Products into Human Saliva in Vivo and into Saliva Simulant in Vitro.

Human volunteers chewed polyvinyl chloride (PVC) products under controlled conditions for 60 min (four consecutive periods of 15 min), and then the amount of diisononyl phthalate (DINP) migration into the saliva was determined by HPLC. The PVC products consisted of a molded plate containing added DINP (500 mg/g) and five types of commercial toy containing 160-583 mg/g DINP (mean value 372 mg/g). The DINP migration rates ranged from 3.8 to 32.6 μg/cm2/hr (mean value 16.4 μg/cm2/hr). The DINP contents in the toy products did not correlate with the amount of in vivo migration. The DINP migration rates during the last 15-min period (45-60 min) decreased by 38-75% compared with the first session (0-15 min). In addition, in vitro DINP migration rates from the PVC products into saliva simulant during 15 min of rotary shaking were about 3.6-4.1-fold higher than the rates in vivo over 60 min, and remained essentially fixed for each sample.